Advances in Oil-Water Separation: A Complete Guide for Physical, Chemical, and Biochemical Processes 0323899781, 9780323899789

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ADVANCES IN OIL-WATER SEPARATION

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ADVANCES IN OIL-WATER SEPARATION A Complete Guide for Physical, Chemical, and Biochemical Processes

Edited by

PAPITA DAS School of Advanced Studies on Industrial Pollution Control Engineering, Jadavpur University, Kolkata, India; Department of Chemical Engineering, Jadavpur University, Kolkata, India

SUVENDU MANNA Department of Health Safety and Environment, University of Petroleum and Energy Studies, Dehradun, India

JITENDRA KUMAR PANDEY School of Basic and Applied Science, Adamas University, Kolkata, India

Elsevier Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom 50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States Copyright © 2022 Elsevier Inc. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions. This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary. Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein. British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress ISBN: 978-0-323-89978-9 For Information on all Elsevier publications visit our website at https://www.elsevier.com/books-and-journals

Publisher: Susan Dennis Acquisitions Editor: Anita Koch Editorial Project Manager: Ivy Dawn Torre Production Project Manager: Sruthi Satheesh Cover Designer: Victoria Pearson Typeset by MPS Limited, Chennai, India

Contents List of contributors xi

3. Oil pollution and municipal wastewater treatment: issues and impact 57 Rwiddhi Sarkhel and Preetha Ganguly

A

3.1 Introduction 57 3.2 Methodology 58 3.3 Treatment methods of wastewater containing oil 59 3.4 Results 61 3.5 Conclusion 63 Acknowledgements 63 Conflict of interest 63 References 63

Overview on oil pollution and its effect on environment 1. An overview of oil pollution and oil-spilling incidents 3 Sangita Bhattacharjee and Trina Dutta

1.1 Introduction 3 1.2 Oil spill incidents 5 1.3 Case studies 6 1.4 Recovery and clean up 10 1.5 Future predictions 12 1.6 Summary 13 References 13

4. An overview of worldwide regulations on oil pollution control 65 K. Krishna Koundinya, Surajit Mondal and Amarnath Bose

4.1 4.2 4.3 4.4

Introduction 66 International laws on maritime pollution 69 1954
62 Convention and its amendments 70 International conference on marine pollution, 1973 71 4.5 MARPOL Convention—73/78 73 4.6 Oil Pollution Act, 1990 77 4.7 Conclusions 80 References 82

2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India 17 Pankaj Kumar Roy, Arnab Ghosh, Malabika Biswas Roy, Arunabha Majumder, Asis Mazumdar and Siddhartha Datta

5. Technological aspects of different oil and water separation advanced techniques 83

2.1 Introduction 18 2.2 Materials and methods 22 2.3 Methodology 24 2.4 Result and discussions 26 2.5 Dissolved heavy metal indices 42 2.6 Conclusion and recommendation 48 Acknowledgment 50 References 50

Vishal Kumar Singh, Sankari Hazarika, Robin V. John Fernandes, Ankit Dasgotra, Poonam Singh, Abhishek Sharma and S.M. Tauseef

5.1 Introduction 83 5.2 Advanced filtration materials

v

84

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Contents

5.3 Advanced absorption based materials 5.4 Sol-gel based materials 90 5.5 Conclusion 93 References 94

89

6. Impact analysis of oil pollution on environment, marine, and soil communities 99 Shipra Jha and Praveen Dahiya

6.1 Introduction 99 6.2 Composition of petroleum hydrocarbon 100 6.3 Sources and fate of oil spill 101 6.4 Oil pollution and its impact analysis 103 6.5 Future prospects and conclusion 109 References 110

7. Impact of oil exploration and spillage on marine environments 115 Ankita Thakur and Bhupendra Koul

7.1 7.2 7.3 7.4 7.5 7.6

Introduction 116 Types of pollution 116 Types of oils 118 Causes of oil pollution 119 Harmful effects of oil pollution 120 Bioaccumulation and biomagnification: marine chemistry 127 7.7 Remedies to cope up with oil pollution 128 7.8 Conclusion 132 References 132

B Physical processes 8. Superhydrophobic polymeric adsorbents as an efficient oil separator 139 Shubhalakshmi Sengupta, Priya Banerjee, Anil Kumar Nallajarla, Venkatalakshmi Jakka, Aniruddha Mukhopadhyay and Papita Das

8.1 Introduction 140 8.2 Materials used for oil/water separation 142 8.3 Polymer-based adsorbents for oil/water separation 145 8.4 Superhydrophobic polymeric adsorbents 148

8.5 Conclusion 152 Acknowledgments 152 References 152

9. Oil spill treatment using porous materials 157 Prakash Bobde, Ajaya Kumar Behera and Ravi Kumar Patel

9.1 Introduction 157 9.2 Materials and characterization 9.3 Discussion 163 9.4 Conclusion 170 Abbreviations 170 References 170

160

10. Nanotechnological advances for oil spill management: removal, recovery and remediation 175 Sougata Ghosh and Thomas J. Webster

10.1 Introduction 175 10.2 Oil pollution 176 10.3 Nanotechnology driven solutions 176 10.4 Conclusions and future perspectives 191 References 192

11. Carbon nanotube-based oil-water separation 195 Tamanna Khandelia and Bhisma K. Patel

11.1 Introduction 195 11.2 Carbon nanotube-carbon-based sorbent 196 11.3 Principles of oil-water separation by carbon nanotube 196 11.4 Structure and synthesis of carbon nanotube 197 11.5 Current applications: carbon nanotube-based oil-water separation 198 11.6 Future perspective 205 11.7 Summary 205 References 205

12. Nanocoated membranes for oil/water separation 207 Karun Kumar Jana, Avijit Bhowal and Papita Das

12.1 Introduction

208

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12.2 Nanocoated membrane technology 209 12.3 Fundamental principles behind oil/water separation behavior 210 12.4 Current application of membranes in oily wastewater treatment 213 12.5 Morphology and structure 216 12.6 Wetting properties 218 12.7 Mechanical strength 219 12.8 Antifouling method 220 12.9 Separation performance of membranes for the oil-in-water mixture 220 12.10 Summary 223 12.11 Future perspective 223 Acknowledgement 224 Conflict of interest 224 References 224

C

15. Use of chemical dispersants for management of oil pollution 263 Sunil Kumar Tiwari, Shashi Upadhyay, Vishal Kumar Singh, Ankit Dasgotra, Akula Umamaheswararao, Harsh Sharma and Jitendra Kumar Pandey

15.1 Introduction 264 15.2 Hazardous effect of oil spill and its emission 265 15.3 Use of chemical dispersant 267 15.4 Principle and mechanism of chemical dispersants 269 15.5 Effectiveness and adaptability of chemical dispersants 273 15.6 National and international regulations for using chemical dispersants 276 15.7 Applications of different chemical dispersants 277 15.8 Conclusions 278 References 279

Thermo-chemical processes 13. Chemical stabilization of oil by elastomizers 233 Sankha Chakrabortty, Jayato Nayak and Prasenjit Chakraborty

13.1 Introduction 233 13.2 Characteristics of oil spills 235 13.3 Oil spill stabilization/remediation techniques 236 13.4 Future perspective for oil stabilization through chemical process 245 13.5 Conclusions 245 References 245

14. Advances in burning process and their impact on the environment 249

16. Brief account on the thermochemical oil-spill management strategies 283 Y. Sivaji Raghav, Poonam Singh, Ankit Dasgotra and Abhishek Sharma

16.1 Introduction 283 16.2 Major oil spills incidents 284 16.3 Oil spill treating methods 286 16.4 Emulsifying agents 290 16.5 Impact of emulsion on ecosystem 16.6 Conclusion 292 References 292

292

D Biological processes

Mandira Agarwal and J. Sudharsan

14.1 Introduction 249 14.2 Principles 250 14.3 In situ burningtechniques & current application 253 14.4 Environmental and health concerns 258 14.5 Summary 260 References 261

17. Use of live microbes for oil degradation in situ 297 Ragaa A. Hamouda, Dalel Daassi, Hamdy A. Hassan, Mervat H. Hussein and Mostafa M. El-Sheekh

17.1 Introduction 298 17.2 Bioremediation of oil compounds by bacteria 299

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Contents

17.3 Role of bacterial oxygenases in the oil biodegradation 300 17.4 Oil-degrading fungi 300 17.5 Marine fungi 301 17.6 Soil fungi 302 17.7 Mycorrhizal fungi 303 17.8 White rot fungi 303 17.9 Fungal enzymes in bioremediation 304 17.10 In situ—mycoremediation 305 17.11 Bioaugmentation 305 17.12 Fungi bacteria consortium 306 17.13 Biostimulation 306 17.14 Biodegradation of crude oil by fresh algae 307 17.15 Effect of seaweeds (marine algae) in biodegradation 308 17.16 Cyanobacteria 308 17.17 Algal bacteria consortium 309 17.18 Factor affecting in biodegradations 310 17.19 Summary 311 References 311

18. Metagenomics—an approach for selection of oil degrading microbes and its application in remediation of oil pollution 319 Md Azizur Rahman, Aakanksha Rajput, Anand Prakash and Vijayaraghavan M. Chariar

18.1 Introduction 320 18.2 Microbes associated with degradation of oil 320 18.3 Metagenomics in oil degradation 321 18.4 Application 329 18.5 Metagenomics challenges 330 18.6 Conclusion 331 References 331

19. Potentiality of enzymes as a green tool in degradation of petroleum hydrocarbons 337 Uttarini Pathak, Aastha Jhunjhunwala, Sneha Singh, Neel Bajaj and Tamal Mandal

19.3 Role of algae in enzymatic degradation of petroleum hydrocarbons 343 19.4 Role of fungi in enzymatic degradation of petroleum hydrocarbons 344 19.5 Feasibility and technical applicability of enzymes in oil clean up 346 19.6 Conclusion 348 Conflict of interest 349 References 349

20. Bioremediation: an ecofriendly approach for the treatment of oil spills 353 Sudipti Arora, Sonika Saxena, Devanshi Sutaria and Jasmine Sethi

20.1 20.2 20.3 20.4

Introduction 354 Catastrophe 355 An approach to eliminate oil spills 357 Factors affecting the biodegradation efficiency 363 20.5 Role of microorganism 367 20.6 Novel approaches 368 20.7 Case studies 369 20.8 Conclusion and future prospects 370 References 370

21. Bioremediation of black tides: strategies involving genetically modified organisms 375 Sonali Mohanty and Subhankar Paul

21.1 Introduction 375 21.2 Conventional bioremediation strategies and their limitations 377 21.3 Switch to biological methods“bioremediation” 379 21.4 Genetically engineered organisms (GMOS): an in situ bioremediation approach 381 21.5 Conclusion 388 References 388

22. Microbes and marine oil spills: oil-eating bugs can cure oily sea sickness 393 Jayanta Kumar Biswas, Anurupa Banerjee and Soumyajit Biswas

19.1 Introduction 337 19.2 Role of bacteria in enzymatic degradation of petroleum hydrocarbons 339

22.1 Introduction 394 22.2 Composition of petroleum hydrocarbons

395

ix

Contents

22.3 Impact of oil pollution on marine ecosystem 398 22.4 Occurrence and distribution of oil degrading microbial communities 401 22.5 Metabolic versatilities for oil degradation by microbes 402 22.6 Factors influencing microbial remediation of oil 405 22.7 Bioremediation/biodegradation strategies for removal of oil from contaminated sites 409 22.8 Conclusions 414 22.9 Summary 414 References 415

25. Membrane bioreactors for the treatment of oily wastewater: pros and cons 469 Shibam Mitra, Riccardo Campo, Subhojit Bhowmick and Anirban Biswas

25.1 Oily wastewater: the origin and global trend 470 25.2 Oily wastewater: environmental impact 25.3 Existing oily wastewater treatment technologies 472 25.4 Conclusions 483 References 483

471

23. Hybrid biological processes for the treatment of oily wastewater 423

26. Overview on natural materials for oil water separation 489

Kulbhushan Samal, Sachin Rameshrao Geed and Kaustubha Mohanty

Somakraj Banerjee, Riddhi Chakraborty, Ranjana Das and Chiranjib Bhattacharjee

23.1 Introduction 423 23.2 Methods for oily wastewater treatment 23.3 Biological methods 424 23.4 Biological techniques 428 23.5 Hybrid biological processes 428 23.6 Summary 432 References 433

424

E Miscellaneous 24. Efficient management of oil waste: chemical and physicochemical approaches 439 Zhang Xiaojie, Kalisadhan Mukherjee, Suvendu Manna, Mohit Kumar Das, Jin Kuk Kim and Tridib Kumar Sinha

Body 440 24.1 Introduction 440 24.2 Hazardous effect of waste oil 442 24.3 Chemical constituents of waste oil 445 24.4 Recycling methods of waste oil 448 24.5 Recycling products 456 24.6 Conclusion and future prospect 460 References 461

26.1 26.2 26.3 26.4 26.5 26.6

Introduction 490 Sources of oil/water mixtures 491 Composition of oil/water mixtures 491 Major processes of oil/water separation 493 Natural materials: an alternative 496 Promising natural materials for oil/water separation 500 26.7 Conclusion and further prospects 505 Acknowledgment 506 References 506 Further reading 510

27. Extraction and separation of oils: the journey from distillation to pervaporation 511 Tathagata Adhikary and Piyali Basak

27.1 Introduction 511 27.2 Techniques in the extraction of oils 513 27.3 Emulsification/formation of emulsions 519 27.4 Oil-water separation or demulsification 522 27.5 Conclusion 530 Acknowledgment 531 References 531

Index 537

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List of contributors Subhojit Bhowmick School of Environmental Studies, Jadavpur University, Kolkata, India

Tathagata Adhikary School of Bio-Science and Engineering, Jadavpur University, Kolkata, India

Anirban Biswas Department of Environmental Science, Nabadwip Vidyasagar College, Nabadwip, India

Mandira Agarwal Department of Petroleum Engineering & Earthsciences, School of Engineering, UPES, Dehradun, India Sudipti Arora Dr. B. Lal Biotechnology, Jaipur, India

Institute

Jayanta Kumar Biswas Department of Ecological Studies, University of Kalyani, Kalyani, India; International Centre for Ecological Engineering, University of Kalyani, Kalyani, India

of

Neel Bajaj Department of Chemical Engineering, National Institute of Technology Durgapur, Durgapur, India Anurupa Banerjee Department of Ecological Studies, University of Kalyani, Kalyani, India

Soumyajit Biswas Department of Biochemistry and Biophysics, University of Kalyani, Kalyani, India

Priya Banerjee Department of Environmental Studies, Centre for Distance and Online Education, Rabindra Bharati University, Kolkata, India

Prakash Bobde Department of Research and Development, Energy Acres, University of Petroleum and Energy Studies, Dehradun, India

Somakraj Banerjee Chemical Engineering Department, Jadavpur University, Kolkata, India

Amarnath Bose Department of Health Safety and Environment Engineering, University of Petroleum and Energy Studies, Dehradun, India

Piyali Basak School of Bio-Science and Engineering, Jadavpur University, Kolkata, India

Riccardo Campo Department of Civil and Environmental Engineering, University of Florence, Florence, Italy

Ajaya Kumar Behera Department of Chemistry, Utkal University, Bhubaneswar, India

Sankha Chakrabortty School of BioTechnology and Chemical Technology, Kalinga Institute of Industrial Technology, India

Chiranjib Bhattacharjee Chemical Engineering Department, Jadavpur University, Kolkata, India

Prasenjit Chakraborty Agni College Technology, Thalambur, Chennai, India

Sangita Bhattacharjee Chemical Engineering Department, Heritage Institute of Technology, Kolkata, India

of

Riddhi Chakraborty Chemical Engineering Department, Jadavpur University, Kolkata, India

Avijit Bhowal School of Advanced Studies on Industrial Pollution Control Engineering, Jadavpur University, Kolkata, India; Department of Chemical Engineering, Jadavpur University, Kolkata, India

Vijayaraghavan M. Chariar Centre for Rural Development and Technology, Indian Institute of Technology-Delhi, New Delhi, India

xi

xii

List of contributors

University of Jeddah, Jeddah, Saudi Arabia; Department of Microbial Biotechnology, Genetic Engineering and Biotechnology Research Institute, University of Sadat City, Sadat City, Egypt

Dalel Daassi Department of Biology, College of Sciences and Arts, Khulais, University of Jeddah, Jeddah, Saudi Arabia Praveen Dahiya Amity Institute of Biotechnology, Amity University Uttar Pradesh, Noida, India Mohit Kumar Das Environment Department, Tata steel Ltd., India Papita Das School of Advanced Studies on Industrial Pollution Control Engineering, Jadavpur University, Kolkata, India; Department of Chemical Engineering, Jadavpur University, Kolkata, India Ranjana Das Chemical Engineering Department, Jadavpur University, Kolkata, India Ankit Dasgotra Department of Research and Development, School of Engineering, University of Petroleum and Energy Studies, Dehradun, India; Department of Mechanical Energy, University of Petroleum and Energy Studies, Energy Acres, Dehradun, India Siddhartha Datta Department of Chemical Engineering, Jadavpur University, Kolkata, India Trina Dutta Department of Chemistry, JIS College of Engineering, Kalyani, India

Hamdy A. Hassan Department of Biological Science, Faculty of Science and Humanity Studies at Al-Quwayiyah, Shaqra University, Al-Quwayiyah, Saudi Arabia; Department of Environmental Biotechnology, Genetic Engineering, and Biotechnology Research Institute, University of Sadat City, Sadat City, Egypt Sankari Hazarika Department of Petroleum Engineering and Earth Science, University of Petroleum and Energy Studies, Dehradun, India Mervat H. Hussein Botany Department, Faculty of Science, Mansoura University, Mansoura, Egypt Venkatalakshmi Jakka Department of Sciences and Humanities, Vignan’s Foundation for Science, Technology and Research (deemed to be University), Guntur, India Karun Kumar Jana School of Advanced Studies on Industrial Pollution Control Engineering, Jadavpur University, Kolkata, India

Mostafa M. El-Sheekh Botany Department, Faculty of Science, Tanta University, Tanta, Egypt

Shipra Jha Amity Institute of Biotechnology, Amity University Uttar Pradesh, Noida, India

Preetha Ganguly Department of Biochemical Engineering and Biotechnology, Indian Institute of Technology Delhi, New Delhi, India

Aastha Jhunjhunwala Department of Chemical Engineering, National Institute of Technology Durgapur, Durgapur, India

Sachin Rameshrao Geed Department of Chemical Engineering, Indian Institute of Technology (BHU), Varanasi, India Arnab Ghosh School of Water Resource Engineering, Jadavpur University, Kolkata, India Sougata Ghosh Department of Microbiology, School of Science, RK University, Rajkot, India Ragaa A. Hamouda Department of Biology, College of Sciences and Arts, Khulais,

Robin V. John Fernandes Department of Health Safety, Environment and Civil Engineering, School of Engineering, University of Petroleum and Energy Studies, Dehradun, India Tamanna Khandelia Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati, India Jin

Kuk Kim Department of Materials Engineering and Convergence Technology, Gyeongsang National University, Jinju, South Korea

xiii

List of contributors

Bhupendra Koul School of Bioengineering and Biosciences, Department of Biotechnology, Lovely Professional University, Phagwara, India K. Krishna Koundinya Department of Electrical and Electronics Engineering, University of Petroleum and Energy Studies, Dehradun, India Arunabha Majumder School of Water Resource Engineering, Jadavpur University, Kolkata, India Tamal Mandal Department of Chemical Engineering, National Institute of Technology Durgapur, Durgapur, India Suvendu Manna Department of Health Safety and Environment, University of Petroleum and Energy Studies, India Asis Mazumdar School of Water Resource Engineering, Jadavpur University, Kolkata, India Shibam Mitra Envirotech Kolkata, India

East

Pvt.

Ltd.,

Kaustubha Mohanty Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati, India Sonali Mohanty Department of Biotechnology & Medical Engineering, National Institute of Technology Rourkela, Rourkela, India Surajit Mondal Department of Electrical and Electronics Engineering, University of Petroleum and Energy Studies, Dehradun, India Kalisadhan Mukherjee Department of Chemistry, Pandit Deendayal Energy University, India Aniruddha Mukhopadhyay Department of Environmental Science, University of Calcutta, Kolkata, India Anil Kumar Nallajarla Department of Sciences and Humanities, Vignan’s Foundation for Science, Technology and Research (deemed to be University), Guntur, India Jayato Nayak Department of Chemical Engineering, School of Bio and Chemical Engineering, Kalasalingam Academy of Research and Education, India

Jitendra Kumar Pandey School of Basic and Applied Science, Adamas University, Kolkata, India Bhisma K. Patel Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati, India Ravi Kumar Patel UPES Council for Innovation and Entrepreneurship, Energy Acres, University of Petroleum and Energy Studies, Dehradun, India Uttarini Pathak Department of Chemical Engineering, National Institute of Technology Durgapur, Durgapur, India Subhankar Paul Department of Biotechnology & Medical Engineering, National Institute of Technology Rourkela, Rourkela, India Anand Prakash Department of Bioscience and Biotechnology, Banasthali Vidyapith, Banasthali, India Y.

Sivaji Raghav CNPC BOHAI Drilling Company (BHDC), Kuwait City, KuwaitCNPC BOHAI Drilling Company (BHDC), Kuwait City, Kuwait

Md Azizur Rahman University Institute of Engineering, Department of Biotechnology Engineering and Food Technology, Chandigarh University, Ludhiana, India Aakanksha Rajput Department of Bioscience and Biotechnology, Banasthali Vidyapith, Banasthali, India Malabika Biswas Kolkata, India

Roy

Women’s

College,

Pankaj Kumar Roy School of Water Resource Engineering, Jadavpur University, Kolkata, India; Faculty of Interdisciplinary Studies, Law & Management, Jadavpur University, Kolkata, India Kulbhushan Samal Department of Chemical Engineering, Ramaiah Institute of Technology, Bangalore, India Rwiddhi Sarkhel Department of Chemical Engineering, National Institute of Technology Durgapur, Durgapur, India Sonika Saxena Dr. B. Lal Biotechnology, Jaipur, India

Institute

of

xiv

List of contributors

Shubhalakshmi Sengupta Department of Sciences and Humanities, Vignan’s Foundation for Science, Technology and Research (deemed to be University), Guntur, India Jasmine Sethi Entrepreneurship and Career Hub, University of Rajasthan, Jaipur, India Abhishek Sharma Department of Research and Development, School of Engineering, University of Petroleum and Energy Studies, Dehradun, India Harsh Sharma Department of Mechanical Energy, University of Petroleum and Energy Studies, Energy Acres, Dehradun, India Poonam Singh Department of Chemistry, University of Petroleum & Energy Studies (UPES), Dehradun, India; School of Engineering, University of Petroleum and Energy Studies, Dehradun, India Sneha Singh Department of Chemical Engineering, National Institute of Technology Durgapur, Durgapur, India Vishal Kumar Singh Department of Mechanical Energy, University of Petroleum and Energy Studies, Energy Acres, Dehradun, India; Department of Health Safety, Environment and Civil Engineering, School of Engineering, University of Petroleum and Energy Studies, Dehradun, India Tridib Kumar Sinha Department of Materials Engineering and Convergence Technology, Gyeongsang National University, Jinju, South Korea J.

Sudharsan Doctoral Research Fellow, Department of R&D, UPES, Dehradun, India

Devanshi Sutaria Dr. B. Lal Institute of Biotechnology, Jaipur, India S.M. Tauseef Centre for Interdisciplinary Research and Innovation (CIDRI), UPES, India and Sustainability Cluster, School of Engineering, UPES, India Ankita Thakur School of Bioengineering and Biosciences, Department of Biotechnology, Lovely Professional University, Phagwara, India Sunil Kumar Tiwari Department of Mechanical Energy, University of Petroleum and Energy Studies, Energy Acres, Dehradun, India; Department of Research and Development, School of Engineering, University of Petroleum and Energy Studies, Dehradun, India Akula Umamaheswararao Department of Mechanical Energy, University of Petroleum and Energy Studies, Energy Acres, Dehradun, India Shashi Upadhyay Department of Microbiology, University of Petroleum and Energy Studies, Energy Acres, Dehradun, India Thomas J. Webster Department of Chemical Engineering, Northeastern University, Boston, MA, United States Zhang Xiaojie Department of Materials Engineering and Convergence Technology, Gyeongsang National University, Jinju, South Korea; School of Material Science and Engineering, Nanchang Hangkong University, Nanchang, P.R. China

S E C T I O N

A

Overview on oil pollution and its effect on environment

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C H A P T E R

1 An overview of oil pollution and oil-spilling incidents Sangita Bhattacharjee1 and Trina Dutta2 1

Chemical Engineering Department, Heritage Institute of Technology, Kolkata, India 2 Department of Chemistry, JIS College of Engineering, Kalyani, India O U T L I N E

1.1 Introduction

3

1.5 Future predictions

12

1.2 Oil spill incidents

5

1.6 Summary

13

1.3 Case studies

6

References

13

1.4 Recovery and clean up

10

1.1 Introduction The risk of accidental oil spill is associated with the transportation of crude petroleum or petroleum derived oil from production sources to consumption locations. Spilled oil causes severe damage to terrestrial as well as marine ecosystems and also loss to human society. Though the occurrences of major oil spills are occasional, these lead to obvious environmental damage and hence receive considerable public attention. The most significant variables those affect the dispersal and residence time of the contaminants following oil spillage in marine environment are the prevailing hydrodynamic conditions and location of spillage. The wave exposure and prevailing tides and currents during spillage affect the dispersal of oil spilt. With increasing wave exposure, the availability of mechanical mixing energy required for natural dispersal of oil increases. Increased wave exposure also increases the effectiveness of chemical dispersants (Carls et al., 2001; Owens, Robson, & Foget, 1987).

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00014-8

3

© 2022 Elsevier Inc. All rights reserved.

4

1. An overview of oil pollution and oil-spilling incidents

Depending upon timing and duration of oil spill, the effects of oil pollution can be divided into acute impact for a short duration or impact for prolonged period. The impact also depends on the number and types of organisms affected. Oil spills become an immediate source of fire hazards. Organisms get continuously exposed to different components of oil when small amounts of oil are released into sea water over long periods. These can contaminate drinking water supplies and thus may cause waterborne diseases. Point sources including leaking pipelines, natural seepages, production discharges at offshore, and nonpoint runoff from various facilities based on lands are the sources of chronic exposures. In most of the cases, there exists a strong gradient of oil concentration against distance. In the case of oil spillage from a nonpoint source for example, with land-based run-off and natural input, weak concentration gradients of oil compounds are found in the environment. More so often spilled oil gets incorporated into sediments and due to this weathering of oil is retarded. This causes a release of nearly
fresh oil to the water body for a prolonged period. Currently the prolonged impacts of acute and chronic contamination are receiving increased attention (https://www.ncbi.nlm.nih.gov/books/NBK220710/). The extent and severity of damage on the environment following crude oil spillage varies on the particular properties of the crude oil and the type of surrounding. Owing to easy absorption, these light oils act at the cellular level and cause immediate toxicity to the plants. Plants experience asphyxia as well as hindrance to gaseous exchange after getting covered by heavy oils (Pezeshki, Hester, Lin, & Nyman, 2000). In case of oil spillage in terrestrial environment, the ecosystem gets affected due to contamination of soil; in aquatic surroundings, in the littoral zone, the wind and wave action disperse floating oil on the surface of water, which affects the shoreline environment and vegetation (Pezeshki et al., 2000). Among vegetation, mangroves are highly vulnerable to oil spills. These salt-tolerant trees and shrubs breed in muddy anaerobic sediments. These plants take air through tiny pores on aerial roots. Mangroves in those areas may die due to lack of oxygen supply owing to heavy oil inundation of the root systems. However, in open aerated sediments, the toxic components mostly the light refined products of oil, interfere with the plants’ salt balance maintenance system and thus significantly affect their tolerance toward salt water (https://www.itopf.org/ knowledge-resources/documents-guides/document/tip-13-effects-of-oil-pollution-on-the-marineenvironment/#:B:text 5 Oil%20spills%20can%20seriously%20affect,their%20habitats%20to %20the%20oil). Some biological traits such as habitat/depth of the species make them more prone to be exposed to oil compared to other species; Species with canopies such as kelp and seagrass reach the water surface. Generally, as spilled oil floats along the surface of the water, most subtidal species are likely to get much less exposure to oil. In general, animals and plants are affected by oil spill either directly from the spilled oil or during cleanup operations. Owing to the presence of poisonous chemicals, spilled oil can be harmful to living things. Organisms become internally exposed to oil either by ingestion or inhalation, externally exposed via skin and eye. Following spillage, small species of fish or invertebrates get damped by oil, oil can coat feathers and fur of birds. All these lower the natural ability of birds’ and mammals’ to maintain their body temperatures.

A. Overview on oil pollution and its effect on environment

1.2 Oil spill incidents

5

There are certain sea animals as well as birds those need to traverse air-water interface intermittently to respire and hence make themselves more vulnerable to oil exposure (Peterson et al., 2003). However pelagic fish species, due to their habitat, remain minimally exposed to spilled oil (Paine et al., 1996). During oil spill disasters the intertidal zone experiences the greatest exposure as the species are brought in direct contact with the oil during regular rising and falling of tides,. Cetaceans such as whales, dolphins etc. get affected when they come to surface for breathing purpose. The floating oil may cause harm to their eyes and nasal tissues. Marine mammals like seals, otters, etc. are more prone to get damaged by floating oil as they spend time on shore. Sea birds such as sea ducks, alcids, etc. are severely affected by oil spills. The spilled area becomes uninhabitable for many bird species as their sources of food such as fishes are killed off. As their plumage gets coated, the alignment of feathers gets damaged and can provide neither waterproofing nor thermal insulation. The birds may die due to hypothermia or overheating depending upon the season as their fur matted with oil. Besides being smothered by oil the natural buoyancy gets lost and these species ultimately end up their lives into watery grave. The birds while trying to clean themselves by preening out of natural instinct, take in the sticky, toxic petroleum hydrocarbons, which damage their internal organs including lungs, livers, and intestines. Oil spillage may have severe effect on human health and society. Inhalation of crude oil vapor or ingestion of contaminated seafood may cause immediate effects including dizziness, nausea to long term effects such as development of cancers or ailment of central nervous system (Davidson, Phalen, & Solomon, 2005; Major & Wang, 2012). The tourism industry can be negatively impacted as oil spills cause harm to beaches and waterfront properties. The media coverage on oil spilling incidents causes much reduced trade activities and disruption of activities including swimming, boating, diving angling, etc. United States Department of Commerce (1983; Oxford Economics, 2010). Other subsectors of tourism such as accommodations, transportation, guides, and activities also experience economical loss (McDowell Group, 1990; United States Department of Commerce, 1983). Shopping outlets and eateries catering to the tourism industry suffers substantial economic losses (Loureiro, Ribas, Lo´pez, & Ojea, 2005; United States Department of Commerce, 1983).

1.2 Oil spill incidents Petroleum has been used by humans for a few thousand years. However the use of petroleum and its refined products had surged after industrial revolution. Due to various reasons including old and worn out equipment, manmade error and bad fortune, incidents of oil spillage occurred over years during extraction oil from underground and transportation it to petroleum refineries or other destinations. A detailed study of oil spilling incidents would reveal that a major fraction of the oil split had resulted from a few very large oil spills. In the 1990s there were 358 oil spilling incidents, each causing spillage of 7 tons or higher, which resulted in an oil loss of 1.134 3 106 tons. Only ten of such oil spilling incidents caused loss of about 73% of the total quantity of oil lost. In the 2000s, 181 oil spills each with spillage of 7 tons or higher

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were reported, causing a cumulative loss of 1.96 3 105 tons. Only 10 incidents are to be blamed for 75% of the total oil lost in 2000s. In the last decade, a loss of 1.64 3 105 tons of oil was reported, the loss had arisen from a number of oil spilling incidents out of which there have been 62 spills of 7 tons and over, 91% of the total quantity was lost only in ten incidents. About 70% of the total spilled quantity occurred only in one incident (https://www.itopf.org/knowledgeresources/data-statistics/statistics/). A single large incident of oil spillage in a particular year may significantly change the figures with respect to the total volume of spillage. This can be witnessed by considering incidents such as Atlantic Empress, in 1979, causing oil spillage of 2.87 3 105 tons; Castillo De Bellver, in 1983, 2.52 3 105 tons spillage; ABT Summer in 1991, 2.60 3 105 tons spillage (https://www.itopf.org/knowledge-resources/data-statistics/statistics/) etc. Tens of millions of gallons of oil have been released into the marine environment in largest oil spills which caused pollution of fisheries, fouling of coastlines, death and injury of wildlife, and loss of tourism revenue (https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history; How BP’s Blowout Ranks among Top 5 Oil Spills in 1 Graphic, 2015). Accidents of tanker ships carrying crude oil and refined fuel have severely affected vulnerable ecosystems in various parts of the Earth. Smaller spills even sometimes cause a severe impact on ecosystems as the remote location of the site may hamper the emergency environmental response required to protect the surrounding ecosystem. Following spill at sea, oil forms a thin oil slick which can spread over about few hundreds nautical miles, hence the spillages are more disastrous for the sea than those on land. The beaches are generally covered by a thin oil coating by the oil slick. In the case of spillage on land, the oil can be effectively contained by construction of a makeshift earthen dam. This can effectively prevent the land animals from the undesirable, toxic exposure of oil. The Indian coast is also vulnerable to oil spilling incidents. On January 27, 2018, an oil spill took place on the outer Kamarajar Port in Ennore near Chennai in TamilNadu, India (The Hindu, 2017). On the day of the accident, a tanker BW Maple suddenly made a collision with an inbound tanker namely Dawn Kanchipuram. In 2010, Mumbai oil spill happened when the outbound ship MV MSC Chitra from Nava Seva port of south Mumbai collided off with the inbound Khalija
III. Due to this incident about 200 cargo containers were thrown into the Arabian Sea (https://en.wikipedia. org/wiki/2010_Mumbai_oil_spill).

1.3 Case studies Oil spilling incidents are severe environmental catastrophes, which often lead to significant, continuing impacts on the surrounding, ecology, and socioeconomic activities of the affected area. The major oil spilling incidents are summarized in Table 1.1. The most disastrous, inadvertent oil spill was caused by an explosion on the Deepwater Horizon oil rig. The incident took place following a gush of natural gas occurred through a newly installed cement wall cap, built to seal a drilled oil well. Due to the explosion,

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1.3 Case studies

TABLE 1.1 Major oil-spilling incidents. Month & year of occurrence

Name of vessel/ platform/incident

Location

References

March, 1910

Lakeview Well

California, USA

https://www.idealresponse.co.uk/blog/ the-10-biggest-oil-spills-in-history/

March, 1978

The Amoco Cadiz,

Brittany, France

https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history

June 1979- March, 1980

The Ixtoc 1

Bay of Campeche

https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history

July, 1979

Atlantic Empress

Trinidad and Tobago islands in Atlantic Ocean

https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history

February, 1983




Nowruz oil field

https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history

August, 1983

Castillo de Bellver

Cape Town, South Africa

https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history

March, 1989

Exxon Valdez

Alaska, USA

https://www.idealresponse.co.uk/blog/ the-10-biggest-oil-spills-in-history/

January
February, 1991

Persian Gulf war

Northern Persian Gulf near Kuwait

https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history

April, 1991

Motor Tanker Haven

Genoa, Italy

https://www.idealresponse.co.uk/blog/ the-10-biggest-oil-spills-in-history/

March, 1992

The Mingbulak oil spill

Fergana valley, Uzbekistan

https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history

1994

Kolva river spill

Russian Arctic

https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history

2010

Deepwater Horizon oil platform

Gulf of Mexico

https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history

huge volumes of oil spilt into the gulf of Mexico resulting in very adverse damage to the marine environment and ecology. This incident took 11 human lives and caused injury to 17 people. Approximately 1100 miles of coastline and thousands of animals including sea turtles, mammals, and birds were killed. Among endangered species, brown pelicans, and Kemp’s ridley sea turtles (critically endangered) were included. According to some studies conducted in 2014, almost 65,000 turtles were found dead and about 800,000 birds were thought to have died due to the catastrophic oil spill (https://www.idealresponse.co.uk/ blog/the-10-biggest-oil-spills-in-history/). After this incident, oil, and soot persistently rained down on seafloor for months. In 1910, a massive disaster related to oil spill occurred when the Lakeview well of California, USA erupted releasing huge geyser of crude oil continuously spilling almost 40,000
50,000 barrels/day. In spite the workers’ effort to contain the flow of oil, it continued to spill over. Finally, after elapse of 18 months the leak got sealed as the oil caved in

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on itself. Over 378 million crude oil was lost, however the adverse effect on environment was significantly reduced due to the work carried out by the workers and volunteers. Workers built dikes to prevent the oil to contaminate the Buena Vista lake, most of the spilled oil got evaporated or got soaked into the soil (https://www.idealresponse.co.uk/ blog/the-10-biggest-oil-spills-in-history/). One of the largest oil spill occurred when on March 16, 1978, a very large crude carrier Amoco Cadiz, stocked with approximately 69 3 106 gallons of lighter crude, suddenly touched the ground below water on shallow rocks off the coast of Brittany, France. As the ship was steering through the rough seas of the English Channel, a large wave broke its rudder and hydraulic system. Inclement weather hampered the rescue operation. Despite all efforts, the vessel broke by the afternoon of March 17th, following that, the oil slicks quickly reached the coast. Unfavorable weather conditions, such as strong breeze and heavy seas, disturbed cleanup operations, causing contamination of some of the channel islands. This was the worst and largest oil spill from a tanker until that time and caused severe harm to marine ecosystem. Two weeks after the accident, numerous sea urchins, dead mollusks, and various benthic species were washed toward the shore. This spill adversely affected oyster cultivation. About 9000 tons of oysters were destroyed in order to protect market confidence. From some regions, small crustacean and echinoderm species were almost totally vanished, however fortunately many other species were found to be recovered within a year. Approximately 20,000 dead birds were recovered, most of them were diving birds. Amoco Corporation, in 1990, decided to pay $120 3 106 to French claimants, also another compensation amounting to about $35 million towards Royal Dutch Shell against lost oil was agreed upon by Amoco Corporation (https://en.wikipedia.org/wiki/2010_Mumbai_oil_spill). During the month of June, 1979, an occurrence of oil spillage from Ixtoc oil well took place in the Mexican gulf. This accident released up to 140 3 106 gallons of crude oil into the Bay of Campeche till March 1980. An explosion followed by oil spill occurred when drilling of exploration wells was taking place at a depth of about 50 m below water surface. The explosion started with an accumulation of oil and gas in pipe due to failure of circulation of drilling mud. This incident ultimately ruined the rig followed by sinking of the same. Initially approximately 30 3 103 barrels of oil/day was leaking. Rigorous efforts were made to reduce the flow and by August, 1979, the flow was reduced to about 10,000 barrels per day. It was reported by Pemex that about 50% of oil spilt got burnt upon reaching the surface, about one third of original spilled oil evaporated, and the remaining was contained or dispersed in the gulf of Mexico. In July 1979, another big oil spill known as Atlantic Empress oil spill occurred when collision took place between two fully loaded very large crude carriers-Atlantic Empress and Aegean Captain, during rainstorm while navigating in the Caribbean Sea. Leaking of oil started from the vessels after the collision. An estimated 88.3 million gallons oil spill took place. Fire broke in both the vessels and 27 crew members died. Though most of the crude oil was burnt in the fire, an oil slick of 30 miles by 60 miles was found. Though huge volume of oil spilt during the accident, very small environmental damage was observed to the beaches on nearby islands; as most of the oil was pushed out to sea. The VLCC Atlantic Empress, after burning for two weeks, finally sank in the sea on August 3, 1979.

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1.3 Case studies

9

On August 6, 1983, another major and disastrous oil spill took place at Saldanha bay, South Africa when Castillo de Bellver, a Spanish tanker was caught fire on board which resulted in the explosion and burning of the ship. The crew members left the ship, the ship subsequently got broken down dumping an estimated 78.5 million gallons into the South Atlantic ocean. An oil slick of approximately 20 miles long was formed. The spill could have created a major environmental danger by causing destruction to the seabirds rookeries and damaging productive fisheries. But as the strong wind blew the oil out to sea rather than shore, much less environmental impact could be prevented. However, more than 1500 seabirds got either injured or killed due to this spill (https://www.idealresponse.co.uk/blog/the-10-biggest-oil-spills-in-history/). Several incidents of oil spill occurred in the Nowruz oil field in the Persian Gulf. During early 1980s, the northern Persian Gulf had become a contested zone of as part of the Iran-Iraq War. In one such contest an oil spill incident took place when one Iraqi helicopter attacked a local platform of the same oil-field in March, 1983. Initially one platform above the oilfield was hit by a tanker on February, 10, 1983. In March, 1983 when Iraqi helicopters charge the platform, the spill caught fire. Due to the Iran
Iraq war, the technicians could not be able to carry out the capping operation of the well until 18 September 1983. Ultimately capping was done with cement (“Nowruz—Cedre,” 2016; Ottaway, 1983). The lives of eleven people were lost during the operation. Up to September 1983, each day after the spill, the well leaked about 1500 barrels of oil in Persian Gulf. As a result, about 733,000 barrels of oil got spilled from this platform until Iran’s capping and repair operation could get completed by May, 1983. Nine people had died during capping operation as they had to work under the fire from the Iraqis. The Norwuz oil field incidents in 1983 caused a total spill of over 80 million gallons of oil (https://www.britannica.com/list/9-of-the-biggest-oil-spills-in-history). The Gulf War oil spill, arising due to the Gulf War in 1991 was recorded as one of the largest oil spilling incident in history. The war was initiated by the aggression and invasion of Iraq under leadership of Saddam Hussein against the oil rich country Kuwait. The Persian Gulf War started by allied coalition with a massive United States-led air offensive known as Operation Desert Storm when Hussein defied United Nations Security Council demands to withdraw from Kuwait by mid-January 1991. As a strategy, the Iraqi troops deliberately open valves at the Sea Island oil terminal in Kuwait and discharged oil from few tankers into the Persian Gulf with an objective to prevent potential landing by United States Marines. An estimated 240
336 million gallons of oil have spilled in this incident. Following the spill, an oil slick of 160 km was observed, the thickness of the same was up to 13 cm. in some areas. This oil spill caused detrimental effect of surroundings and local marine ecosystems. It is evident from some study conducted after 10 years of this incident, that the ecosystem of salt marshes was still far from complete recovery. Some centuries will certainly be needed for full recovery of the salt marshes. On April, 11, 1991 a major explosion followed by spillage of oil occurred when MT Haven had been unloading a huge cargo carrying oil at the Multedo oil platform adjacent to Genoa of Italy. Five crew members were died from the violent fire resulted from the explosion. The motor tanker finally sank into the Mediterranean sea after burning continuously for three days, spilling an approximate quantity of 45 3 106 gallons of crude into seawater. The Italian authority significantly limited the scale of disaster by carrying out large cleanup operation. However, the environmental damage due to pollution seriously affected the fisheries along both the French and Italian coast.

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1.4 Recovery and clean up Clean-up of oil spills from the marine environment is a challenging task. After the oil spill phenomena, the discharged petroleum hydrocarbons may be transported, may be dispersed in the water or distributed in form of surface slick. The submerged part of hydrocarbons can also be accumulated in the sediments (Liu, Wang, Zou, Wei, & Tong, 2012; Reddy et al., 2002).The characteristics of spilled oil changed owing to weathering processes like evaporation, dissolution, dispersion, photo-oxidation and microbial degradation. Due to evaporation of light hydrocarbons, the density and viscosity of spilled oil increases in marine environment (Hussein, Amer, & Sawsan, 2009; Karana, Rengasamy, & Das, 2011). There are different clean-up strategies from shorelines, water, and sediments. For oil spills disaster management first step is very crucial to contain oil spills immediately to keep down the damage on human health, marine ecosystem and natural resources. So in oil spill clean-up, first critical step is containment which is followed by recovery. Booms are used as containment equipment to restrict spread of oil spills to shoreline and other resources as soon as possible, to protect the environment and assist in recovery. Booms concentrate oil on surface and channelize for recovery and dispersal. These are basically floating barriers either fixed structure or towed behind or alongside the vessel. These are designed to have four basic features: (1) “Freeboard” above the water surface, (2) “Floating device,” (3) “Skirt” below the water surface and (4) “Longitudinal support” at the bottom of the skirt (USEPA archive document). In situ burning can remove thick oil layers above the water surface. Its hourly cleaning capacity is around 100
300 tons (Asadpour et al., 2013). This technique should be done very quickly before remarkable evaporation takes place and minimum 2
3 mm of oil spill thickness is required for better efficacy. The recovery based oil spill treatment are broadly categorized as physical, chemical, and biological techniques (EPA, 2017). For recovery using physical technique, skimmers are used. These can recover oil films from the water surface. Skimmers may be selfpropelled, can be operated from vessels or shore. The floating oil spills above the dam and trapped inside a well, carrying least amount of water. The oil recovery can be enhanced with meshes made up of water repelling materials which keep away water and permit more oil to cross through it. Three types of skimmers are available. In case of “Weir” skimmers, the enclosure is used to trap oil from oil- water interface. It recovers fluids at a fast rate, but prone to clog by the debris floating in the water. In case of oleophilic skimmers, the oil is scrapped using disks, belts, or continuous mop chains manufactured from oleophilic materials. It is efficient to attract oil and flexible on spill irrespective of its thickness. The “suction” skimmers runs similar with a vacuum cleaner used for household purpose. It is highly efficient, but vulnerable to chocking by debris and requires continuous maintenance (USEPA archive document; https://www.bsee.gov/site-page/mechanical-containment-and-recovery). Sorbents are used to recover small-scale oil spills either by the mechanism of absorption or adsorption. It is used to remove final trace of oil after collection from skimmer or from the areas inaccessible by skimmers very efficiently. For oil recovery, sorbent should be oleophilic and hydrophobic both. Hydrophobicity prevents water

A. Overview on oil pollution and its effect on environment

1.4 Recovery and clean up

11

sorption and increases oil recovery yield. During the selection of sorbent, the characteristics like rate of absorption, oil retention and ease of application need to be considered. Whenever the sorbents are used, these require proper disposal or can be recycled. There are different types of sorbents. Natural organics sorbents are cheaper, abundant and eco-friendly. They soak up three to fifteen times of the weight of sorbents in oil but sometimes also absorb water. The examples of organic sorbents are rice straw, peat moss, hay, wood fiber, wool fiber, fibers from kapok and kenaf etc. Other examples are cotton, rice husk, bagasse, sawdust, ground corncobs, feathers, and other carbon-based products. Collection is a difficult task as few materials may sink after water absorption or dust particle may spread on water surface. The flotation device aids collection and the problem of sinking is resolved. Naturally available inorganic adsorbents are wool, sand, clay, perlite and vermiculite. They absorb oil ranging from four to twenty times of the weight of sorbents. These are also cheap and abundantly available. The synthetically produced sorbents like polyurethane, polyethylene, and nylon fibers etc. have high absorption capacity, seventy times of the weight of sorbents in oil. Sorbents cleaning is easy process and these can be used multiple times. But disposal is a major issue (USEPA archive document). In comparison among different sorbents, the cheaper, biodegradable biomass like cattail fiber, kapok fiber, bagasse, Salvinia sp., rice husk, woodchip, coconut husk have 70% greater removal efficiency than synthetic polymer-based fiber sorbents due to enough void spaces in surface structure and hydrophobicity (Khan, Virojnagud, & Ratpukdi, 2004). Different treatment methods can enhance the sorption capacity. The pyrolysis of rice husk increases adsorption capacity by breaking bonds in organic materials and silicon. The white ash obtained from pyrolysis of rice husk adsorb diesel 5.02 g/g (Vlaev, Petkov, Dimitrov, & Genieva, 2011). Alkaline treatment of rice husk removes silica. Waste from Silkworm cocoon can remove 30% more motor oil as well as vegetable oil compared to natural wool fibers. The adsorption capacity is 42 to 52 (g/g) (51%) in case of motor oil and 37 to 60 (g/g) (54%) in the case of vegetable oil (Moriwaki et al., 2009). Banana peel along with Orange peel waste enriched with cellulose removes heavy oil more efficiently than lighter oil. Hybridized peels waste adsorbs 38% lubricant oil, 32% petrol oil but only 0.58 g/g of vegetable oil (Abdullah et al., 2016). Luffa, one of the microporous agricultural wastes adsorb .85% diesel oil after treatment (Abdelwahab, 2014) and become a part for waste management. There are different particles like chitosan flakes, cellulose nanofibril and polyvinyl alcohol based aerogel microspheres show excellent absorption efficiencies in case of floating oil clean-up (Barros, Vasconcellos, Carvalho, & Ferreira do Nascimento, 2014; Zhai, Zeng, Cai, Zia, & Gong, 2016). Currently the blending of nanoparticles and polymer-based materials are getting importance for better surface property, reusability, biodegradability, and simple recovery (Fouad, Aljohani, & Shoueir, 2016). The Nanofibers acquired by blending electro-spinning process from polystyrene and polyvinyl chloride have five to nine times higher sorption capacity compared to commercial polypropylene. The comparison studied in case of peanut oil, diesel oil and motor oils (Zhu et al., 2011) (Fig. 1.1).

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1. An overview of oil pollution and oil-spilling incidents

FIGURE 1.1 Oil recovery and clean-up.

Nowadays, the external magnetic field is being used for oil separation. Magnetic nanoparticles coated quaternized chitosan reported as excellent oil-water separator at different pH values (Zhang et al., 2017). For open and deep-water oil spills, the dispersants, making up surfactant, the amphiphilic surface-active molecules are sprayed on the oil spills and breaks into smaller droplet size of ,100 μm (NOAA, 2017b). Dispersants reduce the tension of oil-water interface, also reduce coalescence with formation of stable micro-emulsions. In addition, the dispersants increase surface to volume ratio which helps in further treatment like bioremediation. Dioctyl sodium sulfosuccinate, one of the anionic surfactants used in dispersants named Corexit 9527 and Corexit 9500A during response the Deepwater Horizon oil spill (Belore, Trudel, Mullin, & Guarino, 2009). In recent trend the green surfactants or herders are getting focus as the existing chemicals are non-biodegradable and stable to stay for long time in marine environment and create toxicity effect (Place et al., 2016). The dispersants/chemicals are non-biodegradable, remains in the marine environment for long years and create further pollution. To resolve this issue the biopolymer based low-cost sorbents, different advanced materials like aerogels, inorganic meshes, foam membranes, and surface modified fabrics are getting more weightage for oil separation in the recent years. In case of bioremediation, the microorganisms and green plants are used to degrade hydrocarbons. The toxic heavy metals, and volatile organic compounds present within fossil fuels are also sequestered in this process. It is less labor-intensive, also avoids chemical or mechanical damage. It is a green way of oil spills treatment.

1.5 Future predictions Future unintentional oil spilling incidents may be prevented by adopting various methods including deployment of trained and experienced crew members, by ensuring strict

A. Overview on oil pollution and its effect on environment

References

13

fire safety regulation on board, limiting the size of individual tanks in ship to ensure smaller spill, by using vessel traffic control in congested areas to reduce risk of collision. Unintentional oil spilling incidences may also be avoided by ensuring proper mechanical maintenance of vessel including tightening of bolts which may become loose with shaking during engine use, by changing damaged hydraulic lines and fittings prior to mechanical failure. Care must be undertaken during fueling of tank at pump to avoid overflow and also to leave some room for fuel expansion. Considering the harmful impact of oil spilt on marine ecosystem, on coastlines and seafloors as well as on environment, preventive measures are to be keenly adopted to minimize future oil spilling incidents. Oil wells are to be carefully designed and maintained. Care is to be taken while carrying out various phases of work for example, drilling operation, production followed by workover and lastly abandonment. Impact on human particularly the social and economic harm of the spillage are to be properly identified. Practice of prevention of offshore oil spill and response lowers frequency of oil spilling incidents at offshore and this practice also reduces the quantity of spilled oil. In the United States, prevention contingency plans for offshore oil spilling and emergency response plans are federally mandated requirements, for all offshore oil facilities in United States In many countries, various International treaties take actions towards prevention of pollution from ships by implementing mandatory control, recording, and punishments for oil spillage from ships (American Petroleum Institute, 2010).

1.6 Summary Key variables that have influences on the severity of the consequences of oil spill are to be found out and their interactions are to be clearly defined. That framework can then be effectively utilized to understand the impact of oil spilling incidents, to identify lessons those can be transferable from other oil spills, can be used to plan properly, and perform risk analysis and policy debates with objectives to develop understanding so as to lower their vulnerability to oil spill catastrophe.

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218. Abdullah, M., Muhamad, S. H. A., Sanusi, S. N., Jamaludin, S. I. S., Mohamad, N. F., & Rusli, M. A. H. (2016). Preliminary study of oil removal using hybrid peel waste: Musa Balbisiana and Citrus Sinensis. Applied Environmental and Biological Sciences., 6(8S), 59
63. American Petroleum Institute. Spill prevention and response. Energy Tomorrow. Accessed 15.06.10. Asadpour, R., Sapari, N. B., Tuan, Z. Z., Jusoh, H., Riahi, A., & Uka, O. K. (2013). Application of sorbent materials in oil spill management: a review. Caspian Journal of Applied Sciences Research, 2(2), 46
58. Barros, F. Cd. F., Vasconcellos, L. C. G., Carvalho, T. V., & Ferreira do Nascimento, R. (2014). Removal of petroleum spill in water by chitin and chitosan. Orbital: The Electronic Journal of Chemistry, 6(1). Belore, R. C., Trudel, K., Mullin, J. V., & Guarino, A. (2009). Large-scale cold water dispersant effectiveness experiments with Alaskan crude oils and Corexit 9500 and 9527 dispersants. Marine Pollution Bulletin, 58, 118
128. Carls, M. G., Babcock, M. M., Harris, P. M., Irvine, G. V., Cusick, J. A., & Rice, S. D. (2001). Persistence of oiling in mussel beds after the Exxon Valdez oil spill. Marine Environmental Research, 51(2), 167
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Davidson, C. I., Phalen, R. F., & Solomon, P. A. (2005). Airborne particulate matter and human health: a review. Aerosol Science and Technology, 39(8), 737
749. Available from https://doi.org/10.1080/02786820500191348. EPA (2017). Oil spill response techniques, EPA’s response techniques. https://www.epa.gov/emergencyresponse/epas-responsetechniques. Fouad, R. R., Aljohani, H. A., & Shoueir, K. R. (2016). Biocompatible poly (vinyl alcohol) nanoparticle-based binary blends for oil spill. Marine Pollution Bulletin, 46
52, 112. Scientific American How BP’s blowout ranks among top 5 oil spills in 1 graphic. http://www.scientificamerican. com 20.04.15. Hussein, M., Amer, A., & Sawsan, I. I. (2009). Oil spill sorption using carbonized pith bagasse. Application of carbonized pith bagasse as loose fiber. Global Nest Journal, 11(4), 440
448. Karana, C. P., Rengasamy, R., & Das, D. (2011). Oil spill cleanup by structured fibre assembly. Indian Journal of Fibre& Textile Research, 36, 190
200. Khan, E., Virojnagud, W., & Ratpukdi, T. (2004). Use of biomass sorbents for oil removal from gas station runoff. Chemosphere, 57, 681
689. Liu, H., Wang, C., Zou, S., Wei, Z., & Tong, Z. (2012). Simple reversible emulsion system switched by ph on the basis of chitosan without any hydrophobic modification. Langmuir, 28, 11017
11024. Loureiro, M. L., Ribas, A., Lo´pez, E., & Ojea, E. (2005). Estimated costs and admissible claims linked to the prestige oil spill. Ecological Economics, 59, 48
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467. Available from https://doi.org/10.1080/ 02772248.2012.654633. McDowell Group (1990). An assessment of the impact of the ExxonnValdez oil spill on the Alaska tourism industry. McDowell Group, Juneau, Alaska. http://www.evostc.state.ak.us/Universal/Documents/Publications/ Economic/Econ_Tourism.pdf Moriwaki, H., et al. (2009). Utilization of silkworm cocoon waste as a sorbent for the removal of oil from water. Journal of Hazardous Materials, 165, 266
270. NOAA (2017b). Spill containment methods. Office of response and restoration. https://response.restoration.noaa. gov/oil-and-chemicalspills/oil-spills/spill-containment-methods.html. Nowruz—Cedre. wwz.cedre.fr. Accessed 2 August 2016. Ottaway, D. B. (30 March 1983). Gulf war blocks effort to stop large oil spill. The Washington Post, p. A25. Owens, E. H., Robson, W., & Foget, C. R. (1987). A field evaluation of selected beach-cleaning techniques. Arctic, 40, 244
257. Available from http://pubs.aina.ucalgary.ca/arctic/arctic40-s-244.pdf. Oxford Economics. (2010). Potential impact of the Gulf oil spill on tourism. London, UK: Oxford Economics. Available from http://www.ustravel.org/sites/default/files/page/2009/11/Gulf_Oil_Spill_Analysis_Oxford_Economics_710.pdf. Paine, R. T., Ruesink, J. L., Sun, A., Soulanille, E. L., Wonham, M. J., Harley, C. D. G., Brumbaugh, D. R., & Secord, D. L. (1996). Trouble on oiled waters: lessons from the Exxon Valdez oil spill. Annual Review of Ecology and Systematics, 27, 197
235. Available from https://doi.org/10.1146/annurev.ecolsys.27.1.197. Peterson, C. H., Rice, S. D., Short, J. W., Esler, D., Bodkin, J. L., Ballachey, B. E., & Irons, D. B. (2003). Long-term ecosystem response to the Exxon Valdez oil spill. Science, 302(5653), 2082
2086. Pezeshki, S. R., Hester, M. W., Lin, Q., & Nyman, J. A. (2000). The effect of oil spill and cleanup on dominant United States Gulf coast marsh macrophytes: a review. Environmental Pollution, 180, 129
139. Place, B. J., Perkins, M. J., Sinclair, E., Barsamian, A. L., Blakemore, P. R., & Field, J. A. (2016). Trace analysis of surfactants in Corexit oil dispersant formulations and seawater. Deep-Sea Research Part II, 129, 273
281. Reddy, C. M., Eglinton, T. I., Hounshell, A., White, H. K., Xu, L., Gains, R. B., & Frysinger, G. S. (2002). The west falmouth oil spill after thirty years: the persistence of petroleum hydrocarbons in marsh sediments. Environmental Science & Technology, 36, 4754
4760. The Hindu. (31 January 2017). Pollution central: in the Ennore oil spill. Accessed 27.02.17. United States Department of Commerce. 1983. Assessing the social costs of oil spills: the Amoco Cadiz case study. United States Department of Commerce, Washington, DC. https://ia600600.us.archive.org/15/items/assessingsocialc00unit/assessingsocialc00unit.pdf USEPA archive document. https://archive.epa.gov/emergencies/docs/oil/edu/web/pdf/chap2.pdf Vlaev, L., Petkov, P., Dimitrov, A., & Genieva, S. (2011). Cleanup of water polluted with crude oil or diesel fuel using rice husks ash. Journal of the Taiwan Institute of Chemical Engineers, 42, 957
964.

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Zhai, T., Zeng, Q., Cai, Z., Zia, H., & Gong, S. (2016). Synthesis of polyvinyl alcohol/cellulose nanofibril hybrid aerogel microspheres and their use as oil/solvent superabsorbents. Carbohydrate Polymers., 148, 300
308. Zhang, S., et al. (2017). Synthesis of quaternized chitosan-coated magnetic nanoparticles for oil-water separation. Materials Letters, 191, 128
131. Zhu, H., et al. (2011). Evaluation of electrospun polyvinyl chloride/polystyrene fibers as sorbent materials for oil spill cleanup. Environmental Science & Technology, 45, 4527
4531.

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C H A P T E R

2 Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India Pankaj Kumar Roy1,2, Arnab Ghosh1, Malabika Biswas Roy3, Arunabha Majumder1, Asis Mazumdar1 and Siddhartha Datta4 1

School of Water Resource Engineering, Jadavpur University, Kolkata, India 2Faculty of Interdisciplinary Studies, Law & Management, Jadavpur University, Kolkata, India 3Women’s College, Kolkata, India 4Department of Chemical Engineering, Jadavpur University, Kolkata, India O U T L I N E 2.1 Introduction

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2.2 Materials and methods 2.2.1 Study area 2.2.2 Data used

22 22 22

2.4.2 Spatiotemporal analysis of dissolved heavy metal parameter 33 2.4.3 Changes in the parameter effecting oil spill 41 2.5 Dissolved heavy metal indices 2.5.1 Enrichment factor 2.5.2 Contamination factor 2.5.3 Pollution load index and degree of contamination 2.5.4 Geo accumulation index 2.5.5 Changes in heavy metal indices 2.5.6 Quantitative variation with increased oil spill 2.5.7 Ecological impacts through BOPA index

2.3 Methodology 24 2.3.1 Spatiotemporal analysis in water quality and heavy metal concentration 24 2.3.2 Heavy metal indices analysis 24 2.3.3 Ecological impact through BOPA index 26 2.4 Result and discussions 2.4.1 Spatiotemporal analysis of water quality parameter

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00002-1

26 26

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42 42 43 43 44 45 45 47

© 2022 Elsevier Inc. All rights reserved.

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2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India

2.6 Conclusion and recommendation

48

Acknowledgment

50

References

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2.1 Introduction Oil spill is usually called the leaking process of crude natural liquid petroleum with hydro carbon from a ship, fishing boat or vessel and mixed with the water of sea, river and estuary portion (Chen, Ye, Zhang, Jing, & Lee, 2019; Wang et al., 2011). Organic compounds derived from the thousand organic materials have long been converted beneath the soil surface by pressure, heat, and chemical reactions to form a complex mixture of crude mineral oil. In addition to hydrogen and carbon, crude oil contains small amounts of metals such as sulfur, oxygen, nitrogen and nickel, iron, and vanadium (Onwurah, Ogugua, Onyike, Ochonogor, & Otitoju, 2007). When this unrefined oil is refined, these compounds retain their properties and functions, even if they are no longer there. When crude oil comes out of large ships or vessels it pollutes the environment, while various fishing vessels or trawlers accidentally throw refined oil into the water and pollute the environment. Until World War II (Campbell, Ed, & Dean, 1942), sea or water transport was dependent on coal. But since then, the use of mineral oil in water transport has been steadily increasing, and with it also the level of water pollution. Not only vehicles, but also various oil rigs, offshore platforms, from the crude oil extraction sites, crude oil leaks into the sea and pollutes the ocean environment. It can be said that human actions are entirely responsible for oil spills. Also, oil spills are often seen in ports for fishing and conservation (Mirajkar, Shinde, Sini, Nikam, & Verma, 2019). About 5 million tons of crude oil is exported to various countries by sea every year. During these exports, oil spills occur mainly due to technical problems, human nuisance, and carelessness. Oil spills also occur when the oil drilling machinery fails due to human error, carelessness, intentional actions or errors, or natural disasters or marine accidents, especially in the case of refineries or tankers carrying any type of petroleum product (Ishak, Md Arof, & Zoolfakar, 2020; Nelson & Grubesic, 2017). Spillage from refineries, dams, tankers, storage facilities and pipelines usually release vast quantities of oil into the water body and inland areas when such activities occur. The oil floats on the water and spreads rapidly over the water surface, which forms a thin layer (Bender, Shearls, Murray, & Huggett, 1980; Singh, Bhardwaj, Arya, & Khatri, 2020; Teal & Howarth, 1984). If the oil begins to disperse across the water surface, the thin coating, also referred to as an oil slick, becomes thinner and thinner. Eventually, with the appearance of a rainbow, which is often referred to as sheen, the oil slick becomes a very thin layer. The oil forms a very dense coating on the water surface as it spreads out in situations where there is spillage of large quantities of oil (Ivshina et al., 2015; Reed, Aamo, & Daling, 1995; Board, Board, & Council, 2003; Onwurah et al., 2007). Oil spills directly harm the marine animal and plant world and indirectly the human environment, health and economy (Ansari & Matondkar, 2014). The harmful effects of oil spills and ways to get rid of them have been discussed in various works before. Oil spills have the potential to destroy marine habitat, ecosystems (Camus & Smit, 2019) and

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19

accompanying human activities. Since crude oil is made up of a combination of various toxic hydrocarbons, marine fauna is easily destroyed. Oil spills have a detrimental effect on various coastal activities and are gradually affecting the various resources of the river estuarine ecosystem (Murphy & Riley, 1962; Prat et al., 1999). In most cases, crude oil causes temporary damage, which can lead to future disasters. Different effects on the environment of coastal and estuary areas are seen based on the toxicity of different chemical components of crude oil (Alexander & Webb, 1987; Baker, 1983; Beeby, 1993; Board et al., 2003; Gundlach & Hayes, 1978). Various elements of the ecosystem in coastal and estuarine regions are damaged by the physical nature or chemical composition of crude oil. Plants or animals that come in contact with crude oil during this time become endangered within a few days or immediately. The entire mammal world, including birds and fish, are affected by this oil spill. Fish gills and bird feathers, if saturated with oil, normally die. Owing also to the presence of lethal concentrations of toxic components in oil; at the spilled site, large-scale marine life mortalities are expected. Due to ingestion of oil polluted food from the river bed, biological resources on the shallow areas of the BhagirathiHooghly River as well as other benthos that feed on living resources present in the bed of the river ecosystem are impacted. The digestive system of sedentary animals within river ecosystem may also get affected due to the consumption of oil contaminated food (Al-majed, Adebayo, & Hossain, 2012; Almeda, Hyatt, & Buskey, 2014; Berry, Dabrowski, & Lyons, 2012; Zenetos et al., 2004). Those animals either die due to ingestion of toxic oils present or if survive, get contaminated with oil. Bioaccumulations of oily compounds are common in organisms that survive in such oil contaminated environment. The bio-accumulation of toxic components of the oil are common in different trophic levels of ecosystem through food chain and food web and can reach the highest trophic levels of ecosystem including human being. Thus, human beings are affected by toxic properties of oil by consuming oil contaminated fish (Banerjee, Joshi, & Jayaram, 2006; Bejarano & Michel, 2010; Je˛drzejczak, 2002). Thus, oil pollution can occur from industrial waste, blow out, collision, stranding, human failure, failure of equipment’s, or from any other possible marine accidents which can threaten human and other marine lives in the tidal & intertidal zones (Beyer, Trannum, Bakke, Hodson, & Collier, 2016). A major oil spill could affect several areas around the coast and effective combating response will call for coordinated and concerted activities by a large number of agencies. Preparation of an Oil Pollution Emergency Plan is, therefore necessary to identify the capabilities and resources of the port as well as all other mutual aid agencies towards establishing an organizational structure to combat marine pollution (Chang, Stone, Demes, & Piscitelli, 2014; Dawes, 1998). There has been a lot of work done in different countries on oil spills and their harmful effects on the environment have been discussed. Oil spills are more common in the USA (Gulf of Mexico) (Allan, Smith, & Anderson, 2012; Dı´az-Castan˜eda & Harris, 2004; Eklund, Knapp, Sandifer, & Colwell, 2019), West Coast of the UK, Canada, Germany, Netherlands, France (Fattal et al., 2010), Spain (Murphy & Riley, 1962; Prat et al., 1999a) and Portugal. Also, during the Gulf War, oil spills were observed on the Arabian coast including Iraq, Iran, Italy (Akoumianaki & Nicolaidou, 2007), South Africa, Niger Delta of Africa (Iduk & Samson, 2015; Ifelebuegu, Ukpebor, Ahukannah, Nnadi, & Theophilus, 2017), Russian Arctic (Yamamoto, Nakoka, Komatsu, Kawai, & Ohwada, 2003), Brazil (Borzone & Rosa, 2009), Venezuela, Chile, Australia, etc. The number of oil spills in Asian countries is very

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2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India

low and it is limited to China, India, South Korea, Philippines, Thailand (Abdulrazaq & Kader, 2004), Pakistan etc. In India, oil spills have been seen in Chennai’s Ennore Port (2016), Mumbai (2002
05, 2020, 2011), Goa, Andaman and Nicobar Islands (2006) before. Oil spills have had an impact on the environment in India (Ansari & Ingole, 2002; Gupta, Dhage, & Kumar, 2009; Han, Nambi, & Clement, 2018; Ingole et al., 2006; Paul, 2017; Qasim, Sengupra, & Kureishy, 1988; Sharma, 2009; Sukumaran, Mulik, Rokade, & Kamble, 2014; Singh, Pandey, Singh, & Shukla, 2017; Vaas, Mondal, Samanta, Suresh, & Katiha, 2010) and other parts of Asia. Much of the work on oil spills deals with the direct and indirect effects on ecosystems, fauna, flora and human health. Recognizing the importance of these effects, various statistical analyzes have been made in different fields to understand the harmful effects of oil spills. Different countries have developed various action plans based on these models and implemented these environmentally friendly plans over time. Risk and vulnerability assessment have also been done based on various data (Dhanakumar, Mani, Murthy, Veeramani, & Mohanraj, 2011; Wang, Fingas, & Page, 1999). In general, remote sensing and GIS play a much more effective role in determining oil spills and their effects in the estuarine region. With the change of seasons and time, changes in water quality and location of heavy metal in the estuary can be detected with the help of remote sensing and GIS (Abdunaser, 2020; Balogun, Yekeen, Pradhan, & Althuwaynee, 2020; Dutsenwai, Ahmad, Tanko, & Mijinyawa, 2017; El-Amier, Elnaggar, & Al-Alfy, 2017; Nelson & Grubesic, 2021). The effect of oil spill can be easily detected based on various parameters through the isoline. In fact, the effects of oil spills are best understood based on water quality and the presence of metal in river sediments obtained in estuarine areas. Water quality and amount of contaminated metal vary depending on the seasonal flow of the river. When crude oil is mixed with water, the amount of water pollution increases and the water quality changes. Understanding the matter on a seasonal basis, it can be seen that the water quality is changing as the flow of water in the river increases during the monsoon. In addition, when crude oil is dissolved in water, the metals that exist in it accumulate in the sediments at the bottom of the estuary and increase the presence of heavy metals. In the estuarine region, tide also plays an important role in controlling the distribution of water quality and heavy metals. At high tide, water mixed with contaminated and unrefined oil rises up the estuary, but at low tide it recedes. This changes the position of water quality and heavy metal. Industrial waste as oil spill is one of the sources for raising metallic elements in waterways (Banerjee et al., 2006; Bejarano & Michel, 2010; Je˛drzejczak, 2002; Singare, Mishra, & Trivedi, 2012). These elements are destroying the river ecosystem as well as harming human health. It isn’t right to think that we are knowingly increasing these pollutants and metals in the river every day. In India, over the past three or four decades, the level of pollution has accelerated with increasing population density and industrial habitation (Ajmal, Nomani, & Khan, 1984; Banerjee, Kumar, Maiti, & Chowdhury, 2016; Biswas, Paul, & Sinha, 2015; Dhanakumar et al., 2011; Gupta, Yadav, Kumar, & Singh, 2013; Jain, 2004; Kumar, Solanki, & Kumar, 2013; Hejabi, Basavarajappa, Karbassi, & Monavari, 2011; Marathe, Marathe, Sawant, & Shrivastava, 2011; Pandey & Singh, 2017; Prabha & Selvapathy, 1997). Heavy metals have carried in combination with deposits. Many times, these trace elements change their place with seasons. This sediment relocation in the Indo-Gangetic floodplain has been perceived from the writings of many researchers (Joshi, Kumar, & Agrawal, 2009; Rahaman, 2009; Saikia, Mathur, & Srivastava, 1988; Wang et al., 2011). Toxic substances like arsenic, nickel, copper, cadmium,

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21

zinc, lead, etc. have poisoned the river sediments in estuarine part. Many researchers have found the amount of sediment toxicity in the Ganges and other rivers in India through contamination, degree of contamination, pollution load index, enrichment factor, and geoaccumulation index (Bender et al., 1980; Chakravarty & Patgiri, 2009; Singh et al., 2020; Suthar, Nema, Chabukdhara, & Gupta, 2009; Teal & Howarth, 1984). These various parameters not only indicate the toxicity of sediments in the river but also help in understanding their mobility with the channel. The detrimental effects of oil spills on the estuarine region are most evident on the ecosystem. Ecological health in the estuarine region largely depends on the functioning of the river benthic ecosystem. The BOPA index is often used to realize this effectiveness (Dauvin & Ruellet, 2007; De-la-Ossa-Carretero & Dauvin, 2010; Gesteira & Dauvin, 2000; Gesteira & Dauvin, 2005; Hir & Hily, 2002). Bhagirathi-Hooghly river is a distributary channel of River Ganges, flowing from its bifurcation point Mithipur, Murshidabad district, West Bengal, towards the Bay of Bengal, encompassing Kolkata (Bera et al., 2019; Ghosh, Biswas Roy, & Roy, 2020). This river system is a lifeline of the southern part of West Bengal, providing irrigation, industrialization, and human habitation to a large extent (Laha, 2015). The only busiest port in the estuarine region of the Bhagirathi-Hooghly river is the Kolkata port. This port is visited by over 3000 large sea-going vessels each year which interalia comprises of oil & chemical tankers. In addition, the Bhagirathi-Hooghly river within the jurisdiction of Kolkata port is also navigated by a large number of Inland vessels/barges including Barges of Bangladesh origin plying under the Indo-Bangla protocol. Sources of oil pollution within Kolkata Port Trust jurisdiction may be categorized under four major groups: 1. Collision, fire, explosion or grounding which results in the release of oil from the ship’s bunkers and/or from the cargo tanks. 2. Industrial wastes containing oil and grease discharged to sea. 3. Accidental spills while transferring bunker or cargo from ship to ship, ship to shore or shore to ship and accidental spillage resulting from incorrect operation of valves on shipboard or at oil terminals. 4. Intentional discharge of oil or oily waste from the pumping of bilge, oily ballast water and tank washings or by any other means. In the estuarine region (Das & Tamminga, 2012; Mohiuddin, Zakir, Otomo, Sharmin, & Shikazona, 2010; Nelson-Smith, 1972; Paul and Sinha, 2013) of the Bhagirathi-Hooghly river (Kidderpore-Haldia stretch), the harmful effects of oil spills are most visible on the mangrove forests of the Sundarbans. Earlier, oil spills in Bangladesh had an impact on the Sundarbans. Therefore, it is very important to know the distribution of oil spills to reduce the impact of oil spills on the ecosystem of the Indian Sundarbans. The stakeholders of this river have increased over the last few decades with rapid urbanization and industrial growth. As a result, the amount of pollution in the estuarine part of Bhagirathi-Hooghly river has also increased. Plenty of water mixes with pesticide which flows into this river every day. Even small factories, sewage from the city continue to pollute the river. The abandonment of immersion is one of the causes of river pollution here (Roy, Halder, Nag, Roy, & Majumder, 2018). Earlier in 2012, a contingency survey was conducted at the mentioned places along this subcatchment basin and its assessment was submitted to the Environment Department of the Government of West Bengal. The same areas were

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2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India

re-surveyed in 2018 and a comparative discussion of past records with current reports is conducted. The present study tries to investigate the seasonal and spatial distribution of water quality and sediment with metal constraints on oil spill and compare it with the tidal character. Thus, the study identifies the spatial and temporal variation of oil spill effect on the surface and river bed with the help of GIS. The present study is also trying to identify the ecological significance of oil spill in the estuarine part of lower BhagirathiHooghly river (Kidderpore-Haldia stretch).

2.2 Materials and methods 2.2.1 Study area The selected subcatchment basin of the lower course of Bhagirathi-Hooghly river is up to 85 km long stretch from Kidderpore (upstream) to Haldia (downstream) comprising a portion of Kolkata, South 24 Parganas and East Medinipur district of West Bengal, India. Geologically, this area lies in the delta region, the lower portion of the ctive deltaic part of the Bengal Basin, and is composed of the recent deposit of the Pleistocene period. Initially, the area was covered by sandy clay and sand along the course of the river, and fine silt, sandy loam, and loamy soil have been found in the flat portion of the plain Fig. 2.1. The Bhagirathi-Hooghly river is connected to Bay of Bengal via coastal estuaries. The coastal zones of West Bengal are used for navigational purpose by a considerable number of vessels moorings at Kolkata and Haldia Port. The Kolkata city is situated on river Bhagirathi-Hooghly and is approximately 85 km upstream from the sea. The major water source for maintaining municipal water supply for Kolkata city is the Bhagirathi-Hooghly river’s water. There are many water treatment plants situated along the bank of river Bhagirathi-Hooghly for example, Palta, Baranagar-Kamarhati, Garden Reach, Dakhin Raipur Water Works etc. As there is risk of oil spillage in coastal areas of West Bengal as well as the river Bhagirathi-Hooghly, so there is threat of deterioration of river water quality and chances of disruption of public water supply system.

2.2.2 Data used Water samples were collected during May, June and October 2018 from fourteen different locations as presented in map from lower Bhagirathi-Hooghly river (KidderporeHaldia stretch) and estuary. A vessel was used for collection of samples for qualitative analysis. The samples were collected for both low tide and high tide condition. Some parameters were analyzed for the water quality and heavy metal samples on oil spill at the laboratory of School of Water Resources Engineering, Jadavpur University, like, oil and grease, dissolved oxygen (DO), biological oxygen demand (BOD), chemical oxygen demand (COD), turbidity, total dissolved solids (TDS) for water quality and Cadmium, Chromium, Lead, Zinc, Nickel, Mercury for heavy metal residue from sediments. The river water quality parameters for example, DO and TDS were measured at site by using Rugged Field Kit. The rest of the parameters were analyzed in the laboratory. The influence of oil pollution must be resulted from handling of crude oil/petroleum oil/diesel etc in Haldia Port/Kolkata Port and Oil Terminal Stations.

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2.2 Materials and methods

FIGURE 2.1 Study area map with sample points.

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24

2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India

2.3 Methodology 2.3.1 Spatiotemporal analysis in water quality and heavy metal concentration There is a need for spatiotemporal analysis to understand the seasonal changes in water quality (APHA, 2005) and heavy metal concentration (IOC-UNESCO, 1982; IOCUNESCO, 1984) caused by oil spills. This analysis is done through the spline method of the Spatial Analyst tool of the Arc GIS 10.4 software and the contouring verification of the 3D Analyst tool on the year 2018. This contouring has been made possible by placing data along 14 points. This helps in understanding the variation of water quality and heavy metal in 14 points. These points were previously surveyed by contingency survey in 2012 and we also compare the result of those survey with present one in later part.

2.3.2 Heavy metal indices analysis The amount of heavy metal dissolved in water has been analyzed in the water samples taken. Analysis has been done mainly on 6 types of heavy metals. Based on several factors and their analysis, it has been possible to get an idea about these heavy metals. These are, 2.3.2.1 Enrichment factor EF evaluates to assess the level of contamination and differentiates the metal based on their origin (anthropogenic or geogenic sources). EF value is measured with the help of conservative tracer elements like iron, aluminum, etc. The EF value of plotted points is measured through commonly used iron (Fe) as the reference value. The EF is calculated through (Ajmal et al., 1984; Franco-Uria, Lopez-Mateo, Roca, & Fernandez-Marcos, 2009; Liaghati, Preda, & Cox, 2003; Turekian & Wedepohl, 1961), EF 5 ðM=FeÞSample =ðM=FeÞBackground

(2.1)

where (M/Fe) is the ratio of metal and iron concentration in the sample and background of the crust, M is the concentration of metal and background value may be found in subsurface geological condition. In this discussion, the study only concentrated on the heavy metal concentration except for Fe concentration. The evaluation has considered Fe as a trace element and a part of EF evaluation for the measurement. The calculated Fe concentration has not been depicted in the article, but the calculation was made through the Fe concentration. The interpretation of EF values are classified as: , 1 means depletion, $ 1 indicates enrichment, $ 1.5 indicates the delivery of trace metal from noncrustal material or bank erosion element, and .2 means significant enhancement. In the case of calculating the background concentration, fundamental values are generally used, except in the Indian subcontinent area. So, for analyzing the background concentration of metal enrichment, the studied point value is calculated through Singh et al.’s (M. Singh, Ansari, Muller, & Singh, 2003) parameters.

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25

2.3.2.2 Contamination factor CF is used to understand the contamination level of heavy metal concentration in a specific area. CF is analyzed through (Ajmal et al., 1984; Franco-Uria et al., 2009; Liaghati et al., 2003; Turekian & Wedepohl, 1961), CF 5 C;metal =C;background

(2.2)

where, the ratio of CF understood through the relation between the concentration of metal (C,metal) and metallic concentration in sub surface element (C,background). CF value has been classified as, CF , 1 means low contamination, 1 # CF # 3 indicates moderate contamination, 3 # CF # 6 indicates considerable contamination and CF . 6 means very high contamination. 2.3.2.3 Pollution load index PLI is used to compare the total metal content of different studied points in the study area. It also provides the variation of quantity in metal concentration towards public awareness in the surrounding area. PLI is measured through (Ajmal et al., 1984; FrancoUria et al., 2009; Liaghati et al., 2003; Seshan, Natesan, & Deepthi, 2010; Tomlinson, Wilson, Harris, & Jeffrey, 1980; Turekian & Wedepohl, 1961), PLI 5 ðCF1 3 CF2 3 CF3 3 . . . CFnÞ1=n

(2.3)

where, CF is the contamination factor and n is the number of metals (here 4). PLI has been categorized into two parts that is, . 1 means pollution, ,1 indicates no contamination, and PLI 5 1 shows only a marginal level of pollutants present in the sample. 2.3.2.4 Degree of contamination DC is measured through the sum of all contamination factors in the study area. DC is calculated through (Ajmal et al., 1984; Ho¨kanson, 1980), DC 5

n X

CFi

(2.4)

i51

Where, n is the number of metals and CFi is the single contamination factor of metals. DC is evaluated through 4 categories that is , n indicates low DC, n # DC # 2n indicates moderate DC, 2n # DC # 4n indicates considerable DC and DC . 4n indicates very high DC. 2.3.2.5 Geo accumulation index To assess the anthropogenic impact on heavy metal concentration, we used Igeo, first introduced by Muller (1969). It can be measured by the following equation (Ajmal et al., 1984; Buccolieri et al., 2006), Igeo 5

log2 ðCn Þ 1:5Bn

(2.5)

Cn is the metal concentration in the sediment, Bn is the background concentration of element (Turekian & Wedepohl, 1961), and 1.5 is the compensating factor of background data

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2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India

by lithogenic effect (Taylor, 1964). This function has not been compared with the other indices’ measurement due to involvement in a log function and 1.5 background multiplication. It is categorized into seven grades (0
6) of metal enrichment that is Igeo # 0 indicates unpolluted, 0 , Igeo # 1 (unpolluted to moderately polluted), 1 , Igeo # 2 (moderately polluted), 2 , Igeo # 3 (moderately to strongly polluted), 3 , Igeo # 4 (strongly polluted) and 4 , Igeo # 5 (strongly to extremely polluted). Class 6 is an open class and comprises of the pattern of all values from the previous class.

2.3.3 Ecological impact through BOPA index The effects of oil spills on ecosystems are best understood in the benthic region below the estuary. Basically, all the heavy metals that are dissolved in water slowly settle to the bottom of the estuary and cause a lot of damage to other plant species including fish. The BOPA index is discussed to understand the effects of oil spills on benthic ecosystems (Dauvin & Ruellet, 2007; De-la-Ossa-Carretero & Dauvin, 2010; Gesteira & Dauvin, 2000; Gesteira & Dauvin, 2005; Hir & Hily, 2002). This index is formed based on the approximate percentage of the presence of opportunistic polychaetes and the amount of this index is higher in stressed zone Table 2.1. This index can be divided into five ecological quality status classes.

2.4 Result and discussions 2.4.1 Spatiotemporal analysis of water quality parameter Different parameters of water quality affect the environment in different ways. Increasing the amount of oil and grease in estuary water causes considerable damage to the environment and ecosystem in 2018. In addition, increasing the amount of BOD and COD reduces the amount of DO, which in turn harms estuarine ecosystems. Increasing the amount of turbidity and TDS increases the hardness of water which causes various physical problems in human and animal body. One thing is to be noted that, all measurements here are based on high and low tides period. Measurements of water quality have increased from low tide to high tide period, which indicates the changing course of the river at the estuary. Seasonal position change of water quality parameters with high and low tide is discussed below (Abdunaser, 2020; Balogun et al., 2020). TABLE 2.1 BOPA index classes [46]. Quality

Index

High (unpolluted sites)

0.00000 # BOPA # 0.02452

Good (slightly polluted)

0. 02452 # BOPA # 0.13002

Moderate (moderately polluted)

0. 13002 # BOPA # 0.19884

Poor (heavily polluted)

0.19884 # BOPA # 0.25512

Bad (extremely polluted)

0.25512 # BOPA # 0.30103

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2.4 Result and discussions

27

The concentration of oil and grease in river Bhagirathi-Hooghly between Khidirpur and Falta during low tide and high tide indicated less than 1 mg/L Fig. 2.2. Presence of oil and grease above 1 mg/L was found between Raichak Public Jetty and Kendamari. The concentration of oil and grease during low tide and high tide between Raichak Public Jetty and Kendamari ranged between 3.1 mg/L and 1.9 mg/L. The highest amount of oil and grease are mainly concentrated in the downstream part (Diamond Harbor to Haldia) in time of low tide. But the concentration is totally altered in time of low tide (downstream mainly surrounding Nayachar Island). In case of BOD, maximum permissible limit for discharge of wastewater in inland waterbody is 30 mg/L Fig. 2.3. As per IS 2296, the tolerance of BOD in Class C waterbody is 3 mg/L. Hence maximum tolerance limit of BOD in Class C waterbody is 10% of maximum permissible limit of BOD for discharging inland surface water. In IS 2296, there is no tolerance limit for oil and grease getting discharged in inland surface water. However, as per said IS code the tolerance limit for mineral oil in Class C waterbody is 0.1 mg/L. Considering similarity with respect to BOD, maximum tolerance limit could be considered as 1 mg/L for oil and grease. Therefore, presence of oil and grease between 3.1 mg/L and 1.9 mg/L between Raichak Public Jetty and Kendamari indicated influence of oil spill/pollution. The influence of oil pollution resulted from handling of crude oil/petroleum oil/diesel etc in Haldia Port/ Kolkata Port and Oil Terminal Stations. The study indicated risk associated with oil spill/ pollution in Hooghly river. Any accidental oil spill due to vessel collision, tanker leakage etc may cause increasing oil and grease concentration in the river and can spread upstream between Moyapur/Royapur and Kalyani where many water intakes for water treatment plants are situated. In all time, the highest amount of BOD concentration is mainly surrounded in Haldia industrial region. The COD in river Bhagirathi-Hooghly during May and October, 2018 ranged between 1.9 and 5.9 mg/L Fig. 2.4. As per IS 2296 for Class C category of inland surface water the maximum tolerance limit of COD is 3 mg/L. There is a need to take up action-oriented program for abatement of pollution of river Ganga. Higher concentration of COD (. 3 mg/L) has been recorded downstream of Falta. The number of COD is seasonally higher around the Nayachar island and Haldia industrial belt. The DO concentration as studied between May and October, 2018 indicated 4.4 and 7.1 mg/L (Fig. 2.5). Presence of DO below 5 mg/L may have been caused due to higher organic load getting discharged in the river. In fact, DO saturation around 90% was recorded between Raichak and Kendamari. But lesser saturation concentration of DO has been recorded upstream of Raichak and it could be attributed due to the discharge of untreated and partially treated sewage. Seasonally the concentration of DO is higher in downstream part (Diamond Harbor to Haldia) with tidal effect. TDS is considered as an important parameter for assessment of tidal river water quality (Fig. 2.6). The river Hooghly is a tidal river and it is influenced by the salinity entering from Bay of Bengal. Since the river Hooghly receives a good amount of discharge from Farakka, the salinity level in Hooghly around Kolkata Metropolitan Area (KMA) is normally less than 80 mg/L. Thus, TDS becomes less than 300 mg/L in the Hooghly along KMA. The water quality analysis of river Hooghly indicated lower TDS above Falta whereas downstream of Falta TDS found to be increasing at a faster rate. The TDS between 10,000 and 20,000 mg/L was monitored between Kulpi and Kendamari. TDS concentration is seasonally higher in the downstream part (Diamond Harbor to Haldia) with tidal effect. A. Overview on oil pollution and its effect on environment

28

2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India

FIGURE 2.2 Spatiotemporal seasonal distribution of oil and grease (with tidal effect). A. Overview on oil pollution and its effect on environment

2.4 Result and discussions

FIGURE 2.3 Spatiotemporal seasonal distribution of BOD (with tidal effect). A. Overview on oil pollution and its effect on environment

29

30

2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India

FIGURE 2.4 Spatiotemporal seasonal distribution of COD (with tidal effect). A. Overview on oil pollution and its effect on environment

2.4 Result and discussions

FIGURE 2.5 Spatiotemporal seasonal distribution of DO (with tidal effect). A. Overview on oil pollution and its effect on environment

31

32

2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India

FIGURE 2.6 Spatiotemporal seasonal distribution of TDS (with tidal effect). A. Overview on oil pollution and its effect on environment

2.4 Result and discussions

33

Turbidity is largely calculated as a result of measuring total suspended solids in water (Fig. 2.7). The more turbid the water, the higher the amount of turbidity. As the water flow is higher during high tide, the water content is higher and the amount of turbidity increases. Turbidity increases mainly during monsoon period. Turbidity levels are much higher near the industrial areas of Diamond Harbor, Kulpi, Haldia and Nayachar (429
801 NTU). Basically, the amount of turbidity is much higher for industrial effluents. This amount of turbid water is much higher also during the monsoon. The concentration of turbidity is same with TDS but in the seasonal period of low tide, the story is different. Highest turbidity in low tide section is found between Budge Budge to Kulpi, due to excessive pollution from urban land.

2.4.2 Spatiotemporal analysis of dissolved heavy metal parameter The amount of heavy metal concentration in the water varied in different seasons in 2018. As the river belongs to the old stage of the morphometric condition, the accumulation of sand heave is presented elsewhere over the river. Thus, the river’s flow condition is severely low, but it becomes high during monsoon time. Therefore, river transports all the sediment heave from upper to lower section, and in postmonsoon, the metallic concentration becomes higher in the lower part. River water quality was also monitored to assess the presence of metal pollution for example, Cadmium (Cd), Mercury (Hg), Lead (Pb), Zinc (Zn), Chromium (Cr) and Nickel (Ni). The presence of these metals upstream of Falta has been found to be within the tolerance limit. However, presence of metal concentrations for example, Cadmium and Lead has been found beyond permissible limit in downstream Falta (Fig. 2.8 and Fig. 2.9). In all the water samples between Khidirpur and Kendamari, Mercury concentration was found to be less than 0.0025 mg/L (Fig. 2.10). The position and amount of heavy metal dissolved in water varies with the flow of water. Although the amount of heavy metal is less during the monsoon, the presence of heavy metal can be noticed as there is no good water flow before and after the monsoon. Basically, the runoff of industrial areas, factories, sewage system etc., constantly flows into the BhagirathiHooghly river and increases the amount of heavy metal. When these elements are present in large quantities, they completely damage the estuary ecosystem. Not only that, it enters the human body through fish and other aquatic animals and causes overall harm to humans. The amount of heavy metal dissolved in water as a whole is much higher in Diamond Harbor, Kulpi, Haldia, Nayachar etc. While the amount of cadmium and mercury is higher in the Diamond Harbor area, the amount of Lead is higher in all points overall. Lead causes various diseases in the human body. In addition, the amount of Zinc (Fig. 2.11), Chromium (Fig. 2.12) and Nickel (Fig. 2.13) is much higher in Haldia than in Diamond Harbor. Basically, the location of the natural sandbar has helped a lot to increase the concentration of this heavy metal. The concentration of cadmium, zinc, mercury and nickel is higher in upstream (Kidderpore-Budge Budge) and downstream (Kulpi to Haldia) part of this subcatchment basin in pre and postmonsoon period with tidal effect. But in the monsoon, the metal floats due to the heavy flow of water and is concentrated in the lower section around Nayachar. The concentration of lead is higher in the downstream section (Diamond Harbor to Haldia) with tidal effect. Seasonally, the concentration of chromium is always higher in in the downstream section (Kulpi to Haldia) with changing tidal behavior.

A. Overview on oil pollution and its effect on environment

34

2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India

FIGURE 2.7 Spatio-temporal seasonal distribution of Turbidity (with tidal effect). A. Overview on oil pollution and its effect on environment

2.4 Result and discussions

FIGURE 2.8 Spatiotemporal seasonal distribution of Cadmium (with tidal effect). A. Overview on oil pollution and its effect on environment

35

36

2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India

FIGURE 2.9 Spatiotemporal seasonal distribution of Lead (with tidal effect). A. Overview on oil pollution and its effect on environment

2.4 Result and discussions

FIGURE 2.10 Spatiotemporal seasonal distribution of Mercury (with tidal effect). A. Overview on oil pollution and its effect on environment

37

38

2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India

FIGURE 2.11

Spatiotemporal seasonal distribution of Zinc (with tidal effect). A. Overview on oil pollution and its effect on environment

2.4 Result and discussions

FIGURE 2.12 Spatiotemporal seasonal distribution of Chromium (with tidal effect). A. Overview on oil pollution and its effect on environment

39

40

2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India

FIGURE 2.13

Spatiotemporal seasonal distribution of Nickel (with tidal effect). A. Overview on oil pollution and its effect on environment

2.4 Result and discussions

41

2.4.3 Changes in the parameter effecting oil spill It is important to compare the current reports with the information obtained since it makes it possible to understand the rate of change. Because it makes it possible to understand the rate of change. This comparison is based on changes with high and low tides. The quality of the parameters changed from 2012 to 2018 based on the contamination of crude oil in the water quality samples. Since 2012, the levels of TDS, Turbidity, BOD and COD have increased by 12%, 9%, 7.8% and 4.8% respectively in 2018. On the other hand, pollution of crude oil increased the levels of lead, cadmium, zinc and mercury in heavy metals dissolved in water by about 7.6%, 5.2%, 4.2%, and 3% in 2018. Due to the increase in the pollution of crude oil in the estuary area, the amount of these substances in the water has continuously increased (Fig. 2.14).

FIGURE 2.14 Changes in (A) water quality parameter and (B) heavy metal concentration (2012
18) by oil spill.

A. Overview on oil pollution and its effect on environment

42

2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India

2.5 Dissolved heavy metal indices 2.5.1 Enrichment factor The results of the mean annual enrichment factor in heavy metal concentration in water has been illustrated in Fig. 2.15. This figure indicates that the EF of lead and cadmium are significantly high in enrichment seasonally during both high and low tide period. The EF (Ajmal et al., 1984; Franco-Uria et al., 2009; Liaghati et al., 2003; Turekian & Wedepohl, 1961) variation of other metals is negligible, compared to cadmium and lead during both high and low tide period. According to these results, the EF value of all six studied metal is highly varied, except chromium and nickel. Chromium and Nickel are in low enrichment in the study area. Cadmium and lead enriched in this area comes from surrounding agricultural field and industrial sectors, and also for river transportation mainly in downstream location (near Haldia and Nayachar). The EF sequence for heavy metals in sediment of this subcatchment basin is in following sequencing order: Pb . Cd . Zn . Hg . Cr . Ni, which proves the enrichment of lead was higher in comparison with other metal and nickel had a lower amount of concentration. The geochemical analysis of sediment concentration depends upon the measurement of EF. The degree and source of metal contamination have been analyzed through the EF factor. Among the studied points, cadmium became the most enriched element in water seasonally in respecting tidal factor.

FIGURE 2.15

Seasonal enrichment factor (EF) with tidal effect.

A. Overview on oil pollution and its effect on environment

2.5 Dissolved heavy metal indices

43

2.5.2 Contamination factor The illustration in Fig. 2.16 indicated the CF of metal concentration seasonally with tidal effect. Location wises the CF (Ajmal et al., 1984; Franco-Uria et al., 2009; Liaghati et al., 2003; Turekian & Wedepohl, 1961) value varied with seasonal effect. In the case of the industrial sector neighboring and increasing the sewage system, it enhanced the CF value of concentration in the downstream area. Lead and Cadmium had high CF in most of the studied locations, which was significantly nearer to urban and industrial sites. The value of CF varied roughly in rust metal concentration throughout the area. The CF value of lead is highly significant and ranges from moderate to high variation in Diamond harbor, Kulpi, Haldia, Falta and Nayachar area.

2.5.3 Pollution load index and degree of contamination The illustration in Fig. 2.17 represented both seasonal PLI and DC in the study area within the subcatchment basin of lower Bhagirathi-Hooghly river (Kidderpore-Haldia stretch) with tidal effect. As the PLI values (Ajmal et al., 1984; Franco-Uria et al., 2009; Liaghati et al., 2003; Seshan et al., 2010; Tomlinson et al., 1980; Turekian & Wedepohl, 1961) of this area were ,1, so no significant level of pollution was indicated through this. But the result of DC value (Ajmal et al., 1984; Ho¨kanson, 1980) illustrated low to moderate degree of contamination, except the upstream and downstream location of the surveyed area. The degree of contamination was higher there because of industrial effused water

FIGURE 2.16 Seasonal contamination factor (CF) with tidal effect.

A. Overview on oil pollution and its effect on environment

44

2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India

FIGURE 2.17

Seasonal pollution load index (PLI) and degree of contamination (DC) with tidal effect.

and sewage system of the urban area. The concentration value has been gathered in the downstream area with industrial habitation and upstream area with high river transportation on seasonal basis.

2.5.4 Geo accumulation index The accumulation of data through Igeo of the seasonal studied samples are illustrated in both high and low tide period (Ajmal et al., 1984; Buccolieri et al., 2006). According to the classification by Muller (Muller, 1969), the representation of negative value indicated no pollution development in the subcatchment basin. For lead and cadmium, the Igeo values showed moderately toxic pollution in the downstream sections of the basin. The Igeo benefits also became uncontaminated in all over the basin area seasonally by Fig. 2.18. The uncontained concentration of rest of heavy metals has also been indicated in the mid-portion of the basin.

A. Overview on oil pollution and its effect on environment

2.5 Dissolved heavy metal indices

45

FIGURE 2.18 Seasonal Igeo with tidal effect.

2.5.5 Changes in heavy metal indices When the contingency survey was conducted in 2012, the number of metals that were dissolving in the water due to the contamination of crude oil was determined. There is a big difference between that standard and the heavy metal indices made in 2018. A difference of two years on that average measurement based on the tidal effect makes a good difference. In the case of PLI and DC, it can be said that the amount of pollution has increased by 4.2% and 3.5% in 2018 as compared to 2012. The amount of contamination has increased to increase the amount of pollution and according to the record, the contamination increased from 2012 to 2018 by about 5.4%. As a result of the increase in the number of contaminants in the water, they have become enriched rapidly in various aquatic animals and plants and the amount of enrichment has increased by about 5.6%. Due to the low velocity of the river, the pollutants have accumulated in one place and its measure has increased by about 8.2%. However, the position of accumulation during the low tide in 2012 has completely changed in 2018. It should be noted that the location of heavy metals derived from crude oil is highest from Kulpi to Haldia, which proves that most of the pollution is confined to this region (Fig. 2.19).

2.5.6 Quantitative variation with increased oil spill Most of the oil spill’s material concentration that is produced through effluent from sewage, industry, river transport and agricultural land is stored in mud and sand in the downstream

A. Overview on oil pollution and its effect on environment

46

2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India

region of subcatchment basin. Effused water discharge and velocity play an important role in this storage. Since the overall picture of the whole region has been compared between high and low tide, the oil spill’s material concentration is shown comparatively with the effused water flow in estuarine region (Fig. 2.20). The amount of effluent water from urban, industrial and agricultural areas has increased a lot in high tide than the low tide period. In addition, the polynomial coefficient of determination has been over 90% in two specific years (high and low tide), which shows an increase in the amount of oil spill in the region and water pollution because of the sewage from industrial and urban areas and also the residue from river transport amenities.

FIGURE 2.19

Changes in heavy metal indices of (A) PLI and DC, (B) CF, (C) EF and (D) Igeo (2012
18) by oil

spill.

FIGURE 2.20

Oil spill variation with flow (A) high tide and (B) low tide.

A. Overview on oil pollution and its effect on environment

47

2.5 Dissolved heavy metal indices

TABLE 2.2 Comparison of average seasonal oil spill material concentration and velocity.

High tide

Area

Time

Nature of flow (m/s)

Oil spill’s material concentration (mg/L)

Upstream

Pre-Monsoon

0.4
0.7

120

Monsoon

1.6
2.7

84

Post-monsoon

0.6
0.8

216

Pre-Monsoon

0.2
0.4

105

Monsoon

3.2
4.7

60

Post-monsoon

1
2.6

221

Pre-Monsoon

0.3
0.6

140

Monsoon

1.2
2.4

68

Post-monsoon

0.4
0.7

200

Pre-Monsoon

0.3
0.6

125

Monsoon

2.8
3.7

22

Post-monsoon

0.8
1.6

201

Downstream

Low tide

Upstream

Downstream

Also, since the whole discussion is based on seasonal changes, the oil spill’s material concentration on a seasonal basis is shown in the Table 2.2 in between high and low tide. Comparison of tidal effect shows that the concentration in the downstream region of the subcatchment basin increased during the postmonsoon season. From tidal differentiation, the amount of this concentration is much higher. The velocity of estuarine water flow in monsoon time is higher than pre and postmonsoon period. As a result, the amount of oil spill’s material washed out in monsoon time in seasonal scenario. Although flow is higher during the monsoon, the decrease in velocity in pre and postmonsoon increases the material concentration and adverse effect of oil spill continues.

2.5.7 Ecological impacts through BOPA index This stretch (Kidderpore-Haldia stretch) is full of various plants and animals, including a variety of fish and Gangetic dolphins. Oil spills have caused severe damage to the fauna and are now on the verge of extinction. Oil spills have severely damaged the entire ecosystem, including many plants and animals in the estuary (Dauvin & Ruellet, 2007; De-laOssa-Carretero & Dauvin, 2010; Gesteira & Dauvin, 2000; Gesteira & Dauvin, 2005; Hir & Hily, 2002). The extent and impact of these losses are determined by the BOPA Index (Fig. 2.21). The low BOPA index value of the study area above indicates the high ecological value of the region and is organized during or after the oil spill. It is most often organized during the monsoon, when the oil spills are washed away by the water due to the high-water flow. However, the value of BOPA index is highest before and after monsoon, when water flow is low and oil spills are not easily removed. The BOPA index is

A. Overview on oil pollution and its effect on environment

48

2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India

FIGURE 2.21

Seasonal BOPA index with tidal effect.

essentially a measure of the ecological quality of a region affected by oil spills, and is considered to be one of the relative means of changing ecosystems in the estuary. The BOPA index is based on 14 sample taken points. A review of this index based on the season and tide shows that the BOPA index value from Khidirpur to Falta is quite good. Then the BOPA value from Raichak to Diamond Harbor is fair but the BOPA index is very poor in the next part up to Haldia. The condition here is considered to be very bad due to excessive pollution.

2.6 Conclusion and recommendation Oil spill in river Bhagirathi-Hooghly or oil pollution from coastal zone entering in river Bhagirathi-Hooghly will have serious effect on a number of activities, such as, bathing, public

A. Overview on oil pollution and its effect on environment

2.6 Conclusion and recommendation

49

water supply, irrigation, fishing, recreation and religious activities. Tourism in coastal areas including Sundarban, Sagar Islands, Bakkhali, Frazergunge, Geokhali, Haldia, Diamond Harbor and other important locations will be affected. Livelihood of many people depending on tourism, fishing etc will also get affected due to oil pollution. Aquatic flora and fauna will be under stress condition due to emulsifications of oil in the river system. Dolphins, other marine mammals, reptiles, aquatic birds, aquatic life on shorelines will get affected. Oil spills have serious ecological impact on coastal activities and on those who exploit the resources of the river ecosystem. The entry of oil pollution in various river connectivity in Sundarban will have serious impact of aquatic life and mangrove. In most cases damages in coastal areas, estuary and river network are caused primarily by the physical properties of oil creating nuisance and hazardous conditions. The location of the oil spill in the estuarine region of Bhagirathi-Hooghly river (Kidderpore-Haldia stretch) is highlighted with seasonal changes and tidal effect. Remote sensing (RS) and geographical information systems (GIS) have helped to highlight the directional change in oil spills. The number of COD (10
42 mg/L), TDS (150
19300 mg/ L) and turbidity (70
810 NTU) in the water quality parameters along the entire stretch is quite high, which indicates the overall contamination of water in this region. On the other hand, as the amount of DO decreases, it becomes a barrier to survival for a particular ecosystem. Heavy metals dissolved in water also contain high levels of lead (0.02
18.7 mg/L) and cadmium (0.0008
12.456 mg/L). Also, compared to the data obtained from the contingency survey in 2012, the amount of TDS, turbidity, BOD, COD, lead, cadmium, mercury and zinc increased in 2018. At the same time, the contamination and accumulation of contaminants in the water has increased a lot. The effect of oil spill on water quality and heavy metal is most seen during high tide and monsoon. Basically, the higher the flow, the more oil spills dissolve from one place to another. But when the flow is low, the dissolved substances start to accumulate in one place. Pollution levels, including oil spills, are much higher in Falta, Diamond Harbor, Kulpi, Haldia, Nayachar and other areas. Having a sandbar near Nayachar allows oil spilled heavy metals and contaminants to accumulate there. Also, in the high tide, substances move from one place to another. The lower the slope (from Diamond Harbor to Haldia), with lowering velocity of the river, the less likely it is that oil spills will accumulate. Therefore, the lower part of the stretch is more prone to contamination than the upper part. Also, in the above oil spill prone areas due to high amount of water drained from factories, urban areas and urban sewers, the amount of pollution is much higher in this area of estuary. Of course, this part of the estuary is the busiest for river transport and large ships, vessels, fishing boats almost all pass through this area. All this increases the amount of oil spills from the oil emitted by the vehicle. The biggest impact of this oil spill is on the ecosystem of the region concerned, the amount of which we measure with the help of BOPA index. The value of the BOPA index is much higher in the 14 pointers from Diamond Harbor to Haldia, which highlights the maximum amount of pollution. This article highlights the spatiotemporal effects of oil spills. GIS mapping of different parameters has shown which regions are more limited. This will make it easier for policy makers to measure contaminated areas. It will also be possible for environmentalists to understand which areas are more prone to oil spills and to prevent the spread of oil spills by adopting specific policies in those areas. Ships or vessels at the port through the Kolkata Port Trust need to be inspected so that accidents (fire connection, sinking) do not

A. Overview on oil pollution and its effect on environment

50

2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India

occur and a special committee has to be formed for that. It is necessary to pay attention to the issue of purification of water discharged from urban areas and factories. Care must be taken to ensure that crude oil from large oil-carrying vessels does not accidentally fall into the estuary. In case of pollution within the dock the antipollution vessels need to be deployed at the site to recover oil from the dock waters. Manual cleaning simultaneously will also help to minimize the problem and accordingly private firms can be engaged by the competent authorities. Regular water quality monitoring will be needed to ascertain the extent and magnitude of oil pollution. All oil companies (IOCL, HPCL, BPCL, IBP) must be equipped with men and machine to fight the oil spillage. The all companies must draw action program for adoptions on regular basis as well as during emergencies to combat the problem arising out from oil spillage/pollution. The controlling officers of Water Supply authorities (KMC, KMW&SA, KMDA and PHED) shall be informed regarding instances of oil spillage in case the same threatens to affect their water intake facility. Under such situation they should deploy their own means to guard/encircle their intake jetty so that oil slicks do not enter the water treatment plant. If required, they must stop intake pump till such time the oils slick moves sufficient distance away from the intake jetty.

Acknowledgment Preparation of Contingency Plan in 2012 and survey on 2018 for Marine Oil Spill for the Coastal areas of West Bengal has been provided by the Department of Environment, Govt. of West Bengal. This support is highly acknowledged by the School of Water Resources Engineering, Jadavpur University for creating an opportunity to work on such an important issue. The authors are also acknowledging gratitude to the all the workers and Digital Library of School of Water Resources Engineering, Jadavpur University, for allowing to access all the GIS and statistical software.

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C H A P T E R

3 Oil pollution and municipal wastewater treatment: issues and impact Rwiddhi Sarkhel1 and Preetha Ganguly2 1

Department of Chemical Engineering, National Institute of Technology Durgapur, Durgapur, India 2Department of Biochemical Engineering and Biotechnology, Indian Institute of Technology Delhi, New Delhi, India O U T L I N E

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3.2 Methodology 3.2.1 Oil and petroleum sources in wastewater streams

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3.3 Treatment methods of wastewater containing oil 3.3.1 Some conventional treatment methods are as follows 3.3.2 Some new methods for the wastewater treatment

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3.4 Results 3.4.1 Future perspectives

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3.5 Conclusion

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Acknowledgements

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Conflict of interest

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3.1 Introduction Commercial wastewater effluent from different petrochemical, chemical, and biorefinery sites has various features in common with the municipal wastewater in term with the organic contamination content. The removal of such pollutants can be achieved by certain centralized and biological process. It has been estimated that the degradability of chemical

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3. Oil pollution and municipal wastewater treatment: issues and impact

oxygen demand (COD) in oil-based industrial wastewater is always less than that of the municipal wastewater. Oil and grease polluted wastewater effluent come from enormous resources like petrochemical industries, crude oil generation, and oil refinery (Lan, Gang, & Jinbao, 2009). The toxic substances contained in the industrial oil-based wastewater effluent are petroleum hydrocarbons, polyaromatic, and phenol which are carcinogenic and mutagenic to humans as well as equally inhibitory to animal and plant growth. There is a higher content of COD, color, and oil content in the oily wastewater (Lan et al., 2009). In the last few decades there has been an increasing world demand for the edible vegetable oil which has led to enormous increase in the commercial cultivation of different oil seeds such as oil palm and soybean (Yacob, 2008). Therefore, it can be concluded that the vegetable oil production industries are, equally, related with refining, uses and reuses, extraction and transportation. Oil containing wastewater are usually categorized as serious hazardous contaminants when disposed into aquatic bodies, and here they pose higher toxic level to the aquatic life, organisms, and ecology (Mendiola, Achutegui, Sanchez, & San, 1998). Oil and grease are generally classified as non-polar and hydrophobic compound insoluble in water. Under anaerobic environmental conditions, the hydrolysis of oils and grease to long chain fatty acids and glycerol takes place. On the other hand, municipal waste is categorized among one of the most enormous pollutants among other domestic and commercial contaminant currently present. To be precise municipal wastewater treatment is a process in which the addition of harmful waste pollutant in the water resources takes place from various resources. The main source of municipal pollutant is the domestic waste. The various methods to treat such waste ware biological, chemical, and physical methods. It is one of the main concerns to effectively treat municipal waste nowadays. The treated effluent might be utilized for the cultivation of different crops. In the case of municipal wastewater treatment systems, biological treatment processes are needed to be installed and operated downstream to the primary treatment plant. The major difference for the municipal waste effluent, is that in primary treatment comprises removal of only inert and large size materials and grit, that are very common to inflows, whereas typical municipal treatment comprises of pretreatment of industrial wastewater followed by primary treatment. In this review, the study focuses on both the major pollutants of wastewater that are oil based and municipal waste. The sources of waste are mentioned along with the treatment methodology. The impact of the wastewater on the environment and challenges is discussed in detail in this review paper. The SWOT analysis for the oil pollution and municipal wastewater is done.

3.2 Methodology 3.2.1 Oil and petroleum sources in wastewater streams Due to the large concentrations of oil, grease, petroleum, and crude oil around (4000 to 6000 mg/L) from the oil mills, factories, effluents, and petroleum refining industries, the wastewater streams get highly polluted. This results in its largest source of producing oily

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wastewater (Ahmad, Bhatia, Ibrahim, & Sumathi, 2005). Because of highly contaminated oily wastewater and the human shelf life, the aquatic life also gets hampered due to the accumulation of toxic products persists destructing the stability of the environment (Techobanglus & Franklin, 1995). This greywater can be utilized for the irrigation and agricultural purposes due to the presence of oil and grease present in it (Friedler, 2004). Various industries like dairy, meat, and food producing products produce high quantities of effluents containing oil and grease (Vidal, Carvalho, Mendez, & Lema, 2000; Cammarota & Annajr, 1998; El-Bestawy, El-Masry, & El-Adl, 2005). Also, some oil containing wastewater streams contain oil produced from the non-vegetable oil manufacturing industries such as the petroleum refining, metal forming, and textile industries (Wake, 2005). Large volumes of effluent are produced from different countries like the United Kingdom, Italy, etc. (Busca, 2004). The bilge water usually contains fuel oils, lubricating oils, hydraulic oils, and detergents (Karakulski, Morawski, & Crzechulska, 1998). Thus, a huge quantity of domestic and sewage wastewater contains oil and grease as emerging pollutants.

3.3 Treatment methods of wastewater containing oil There are different treatment methods for the separation of oil from the wastewater streams. This includes conventional as well as new emergent processes like floatation, coagulation, membrane separation, and biological treatment (Fig. 3.1).

3.3.1 Some conventional treatment methods are as follows 3.3.1.1 Floatation Flotation may be defined as the process of bubble formation due to the suspension of oil particles in water since the density for oil because of floatation is less than water (Moosai & Dawe, 2003). The process produces less sludge and high efficiency in the treatment of wastewater containing oil (Rubio, Souza, & Smith, 2002). Dissolved air flotation and flotation impeller has been widely used since its longevity time is more, but it has FIGURE 3.1 Schematic representation for the treatment methods of wastewater containing oil.

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disadvantages of repairing and manufacturing problems because of its large energy consumption. In comparison, the jet flotation method not only saves energy, but also have advantages for application features like, easy installation, operation and safety features, which creates a new development for the research. Flotation agents are used to improve flotation. These agents are used to bridge adsorptivity of the colloidal suspensions (Wang, 2007). Methods like dissolved air flotation and column flotation were applied to obtain high water oil separation efficiency (Li, Liu, Wang, Wang, & Zhou, 2007). The dissolved air flotation treatment was investigated after the addition of activated carbon (Hamia, AlHashimi, & Al-Doori, 2007). The results revealed that when the carbon content was of 50
150 mg/L, there was an increase in the removal rate of COD from 16%
64% to 72%
92.5% rise, and also a significant increase in the BOD removal rate from 27%
70% to 76%
94% (Painmanakul, Sastaravet, Lersjintanakarn, & Khaodhiar, 2010). The study inferred from the drawn with respect to the COD concentration varying the parameters. The velocity gradient (G) and a/G ratio provides the efficiency of floatation increasing the costs. 3.3.1.2 Coagulation Coagulation procedure is an eminent treatment process to remove the oil and other biodegradable polymers from wastewater containing oil (Ahmad, Sumathi, & Hameed, 2006). A coagulant composite CAX has been established for the treatment of wastewater streams containing oil, grease, and petroleum when the original oil in water concentration was 207 mg/L, COD concentration was 600 mg/L (Lin & Wen, 2003). Zeng, Yang, Zhang, and Pu (2007) studied the process of flocculation and coagulation treatments using zinc silicate (PISS) composite. This composite acts as an efficient flocculent for the oily wastewater treatment with an oil removal efficiency 99%, with suspended solids concentration less than 5 mg/L (Zeng et al., 2007). These methods progressively lead to high costs with the new trend of developing cost-effective composite materials. Cong, Liu, and Hao (2011) used the best flocculation condition with an optimal dosage of 35 mL, and a suitable range of pH is 7
8 (Cong et al., 2011).

3.3.2 Some new methods for the wastewater treatment 3.3.2.1 Membrane separation Membrane separation technology involves the utilization of a membrane as a porous material for the physical removal of contaminants (Lin, Liu, Liu, & Zhang, 2006). The pressure driven membrane separation processes have been classified into various treatment methods for the treatment of oily wastewater using membranes such as microfiltration (MF), ultrafiltration (UF), nanofiltration, and reverse osmosis (RO). Song, Wang, and Pan (2006) used the carbonization techniques involving activated carbon and membrane separation methods like MF to obtain a tubular carbon matrix with low cost, and high efficiency which has been suitable for the treatment of oily wastewater. The operating conditions require a pore size of 1.0 m, pressure of 0.10 MPa, and flow rate of about 0.1 m/s for the treatment of oily wastewater with oil removal efficiency 97%. The

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61

membrane was stable at a high permeation flux rate of about 99% in neutral or alkaline environments. It has been noticed from the recent literature surveys that as the temperature increased from 283 to 313K, the steady retention ratio decreased from 99.9% to 98.2% and the steady permeate fluxes increased from 120.1 to 153 L. Crossflow MF processes with oily wastewater with effects of variation in the parameters by the permeate flux was investigated by (Hua et al., 2007). A sensitivity analysis (SA) was also conducted to enumerate the influence of the parameters on the permeate volume. NaA zeolite MF membranes incorporated with in situ hydrothermal synthesis process for the separation and recovery from oily water were studied by (Cui, Zhang, Liu, Liu, & Yeung, 2008). It was inferred that more than 99% oil rejection was obtained. Salahi, Noshadi, Badrnezhad, Kanjilal, and Mohammadi (2013) developed a model named nanoporous membrane (PAN). It has been inferred from the results that nanoporous membrane is efficient for the treatment of petroleum refinery wastewater. The treated water can be utilized for the discharge to the environment and can be reused as agricultural water. Tomaszewska, Orecki, and Karakulski (2005) investigated the oily wastewater treatment in the hybrid technique of UF/RO system with maximum purification. The new methods with hybrid technique of membrane separations add into the emergence of different techniques better than the conventional methods to separate the oil from wastewater at a high efficiency. 3.3.2.2 Biological treatment Microorganisms play an interim part in the biological treatment process for the decontamination of the wastewater containing oil (Kriipsalu, Marques, Nammari, & William, 2007; Sirianuntapiboon & Ungkaprasatcha, 2007). Treatment methods involving activated sludge and biologically use filtration techniques. Aeration tank utilizes the method of activated sludge for the decomposition of the microorganisms on the surface of lagoons. The biological filter method is used where the microorganisms are attached to the filter, and the oily wastewater gets filtrated out thus separating the micropollutants and oil from water (Li, Tian, & Xie, 2006). Fungi effectively takes place for the high COD removal from the wastewater. Studies show (Li, Kang, & Zhang, 2005). Scholz and Fuchs (2000) assessed the oil removal rate with higher efficacy. Liu, Ye, Tong, and Zhang (2013) treated heavy oil wastewater with low nutrient of nitrogen and phosphorus by an up flow anaerobic sludge blanket (UASB) coupled with immobilized biological aerated filters (IBAFs). The ability to degrade the oil and to remove the COD was observed utilizing Yarrowia lipolytica W29 immobilized by calcium alginate (Wu, Ge, & Wan, 2009). The results inferred that the microorganisms Y. lipolytica have a great thermostability degrading the immobilized cells and can be applied to a wastewater treatment system.

3.4 Results Table 3.1

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3. Oil pollution and municipal wastewater treatment: issues and impact

TABLE 3.1 SWOT analysis for the different processes. Processes involved

Strengths

Weaknesses

1. Oil removal is more than 90%. 2. High processing capacity. 3. Less sludge production.

1. Maximum allowable concentration was less than 10 mg/L. 2. The dissolved air floatation stays there a long time.

1. Repairing problems. 2. High energy consumption.

(2) 1. Can easily remove Coagulation dissolved oil and emulsified oil. 2. High separation efficiency.

1.

(3) Membrane separation

1. Good for removing dissolved organics. 2. Use of special porous material for the physical removal of contaminants.

1.

(4) Biological treatment

1. Elimination of secondary clarifiers. 2. Reduce the capital cost.

1. Complex control systems. 2. Total organic carbon degradation efficiency was very less.

1. The oily wastewater composition was complex. 2. Suspended solid concentration was very low. 1. Treated water will be contaminated if there is no backwash. 2. Hybrid membrane separation is better than single membrane. 1. Extensive use may lead to high level of maintenance. 2. A very timeconsuming process.

(1) Floatation

2.

2.

Opportunities

1. High oil-water separation efficiency. 2. COD removal rate . 5 80%. 3. Activated carbon treatment can also be used here. Complex treatment of 1. Oil removal some biodegradable efficiency was organic polymer. greater than COD removal rate was 99%. very less. 2. Composite flocculants can be used. May lead to scaling 1. Less pollution. and corrosive issues. 2. Very costPretreatment is needed effective process. to reduce the 3. Separation concentration of process has less suspended solids. energy consumption. 1. Biological filters and activated carbon are widely used. 2. Better treatment effects. 3. UASB filters can be used.

Threats

3.4.1 Future perspectives 3.4.1.1 Environmental impact of wastewater containing oil The water bodies worldwide have been increasingly polluted with oily water which creates an indispensable effect on the ecosystem and destruct the shelf life of marine and human life. Formation of a layer of oil due to the presence of oil, petroleum, crude oil, and grease causes significant pollution problems such as reduction of light penetration and photosynthesis (Mohammadi & Esmaelifar, 2005). Effects of oil and grease in the wastewater streams consequently increase the costs of maintenance including in sewers, pipes, pumps, filters (Stams & Oude, 1997). Oil pollution in the wastewater streams has been a significant focus of research for the marine environment, and degradation of oil is the major potential issue for aquatic environment including flora and fauna. This also leads to explosion hazards in the treatment works (El-Bestawy et al., 2005). Oil and grease cause an offensive odors and taste for the municipal wastewater treatment (Baig, Mir, & Bhatti, 2003).

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3.4.1.2 Challenges and issues faced due to oil and municipal solid waste pollutants The mitigation of challenges for the separation of oil, grease, and petroleum sources from wastewater harms the industries and human population. For the unsaturated LCFA, it adversely affects the environment by the toxic products through both methanogenic and acetogenic bacteria and the application of anaerobic treatment to wastewater containing oil and grease (Rinzema, Boone, & Lettinga, 1994). The development of a new model UASB has quite improved the efficiency of treatment of wastewater containing sludges and oil (Angelidaki & Ahring, 1992). One of the challenges that mostly concerns the industrial wastewater is the amount of TDS especially chloride, sulfate, lead present in water. These can adversely affect treatment plants increasing the salinity, on the flocculation and coagulation techniques. If the chloride and sulfate concentration is high, it damages the performance of the plant thus reducing the quality of the effluent.

3.5 Conclusion Waste effluent which contains oil, grease and domestic waste are increasing sequentially in volume due to the expansion of the industrialization worldwide. This increasing pollutant averts immense negative impact on human and aquatic life as well as the ecological environment. Therefore, the treatment of this waste is essential. The traditional method for the treatment of waste effluent mainly comprises of coagulation and floatation, whereas the advance method includes membrane separation and biological treatment. The biological treatment is the best treatment plant because is produces a negligible amount of waste. This has identified oil and municipal waste as emerging contaminants of concern in waterbodies. This research paper has discussed the sources of the pollutant along with their treatment method. The strengths and weaknesses of the treatment methods are also discussed in detail.

Acknowledgements All authors are thankful to Jadavpur University for their sincere guidance and support at each level of the research. This work was financially supported by Jadavpur University.

Conflict of interest There is no conflict of interest.

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105. Angelidaki, I., & Ahring, B. K. (1992). Effect of free long-chain fatty acids on thermophilic anaerobic digestion. Applied Microbiology and Biotechnology, 37, 808
812. Baig, M., Mir, Z., & Bhatti, I. M. A. (2003). Removal of oil and grease from industrial effluents. EJEAFChe, 2(5), 577
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426. El-Bestawy, E., El-Masry, M. H., & El-Adl, N. E. (2005). The potentiality of free gram-negative bacteria for removing oil and grease from contaminated industrial effluents. World Journal of Microbiology & Biotechnology, 21, 815
822. Friedler, E. (2004). Quality of individual domestic greywater streams and its implication for on-site treatment and reuse possibilities. Environmental Technology, 25, 997
1008. Hamia, M. L., Al-Hashimi, M. A., & Al-Doori, M. M. (2007). Desalination, 216, 116
122. Hua, F. L., Tsang, Y. F., Wang, Y. J., Chan, S. Y., Chua, H., & Sin, S. N. (2007). Chemical Engineering, 128, 169
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996.

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C H A P T E R

4 An overview of worldwide regulations on oil pollution control K. Krishna Koundinya1, Surajit Mondal1 and Amarnath Bose2 1

Department of Electrical and Electronics Engineering, University of Petroleum and Energy Studies, Dehradun, India 2Department of Health Safety and Environment Engineering, University of Petroleum and Energy Studies, Dehradun, India O U T L I N E

4.1 Introduction 66 4.1.1 Maritime effects of oil spillage 66 4.1.2 Significance of oil pollution control management 68 4.2 International laws on maritime pollution

primary provisions of the 1973 convention are summarized below 71 4.4.2 Other conventions and instruments on the Regional Basis 72 4.5 MARPOL Convention—73/78 4.5.1 Annex I 4.5.2 Annex II 4.5.3 Annex III 4.5.4 Annex IV 4.5.5 Annex V 4.5.6 Annex VI

69

4.3 1954
62 Convention and its amendments 70 4.3.1 Origin and establishment of 1954 convention 70 4.3.2 1969 and 1971 Amendments 70

4.6 Oil Pollution Act, 1990 77 4.6.1 Origin of Oil Pollution Act, 1990 77 4.6.2 Progress of Oil Pollution Act, 1990 in oil pollution control 79

4.4 International conference on marine pollution, 1973 71 4.4.1 Annex I of the convention consists of the regulations for oil pollution control and prevention which are primarily focussed on modifying all the provisions of 1954/62 convention and amendments as per requirement. The

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00001-X

73 73 74 75 76 76 77

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4.7 Conclusions

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© 2022 Elsevier Inc. All rights reserved.

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4. An overview of worldwide regulations on oil pollution control

4.1 Introduction Many international organizations such as IMO, WHO, IMCO, UNESCO, IOC and other pollution control bodies jointly adopted an appropriate definition of marine pollution that “the hazardous or harmful effects which effect flora and fauna of the marine system from the causes of direct or indirect inventions of humans into the marine environment including all the marine activities” by considering various social, economic, political, and legal factors (Schachter, 1971). The global requirement of oil leads to the exploration even from oceans thus drilling, pipeline installation, and marine transportation got lifted up for global oil supply and consumption, but oil is one of the most happening forms of marine pollutants with serious consequences over marine ecosystems, wild life, and resources. Oil pollution takes place in the form of oil spills/seeps either naturally or by human activities which in general caused by any crude oil-based liquid products such as hydrocarbons with higher molecular weights, viscosities and densities and gaseous products such as non-marshal volatile hydrocarbons, polycyclic aromatic hydro carbons which structure is shown in Fig. 4.1, produced from the partial oxidation chemical reactions, metals like arsenic, lead, chromium, etc. from various pollutant source inputs (Nriagu, 2019). Various oil source inputs to the marine environment which lead to oil spill incidents to take place are reported in Table 4.1 based on offshore sources, transport sources, and land-based sources such as (National Research Council, 2003) 1. Natural seeps are caused when the underground crude and natural gas spilled into the oceans through sludge or sediments which contribute the largest proportion of marine pollution. 2. Extraction, transportation and consumption of crude derives or petroleum products. 3. Functional discharges like cargo oil, grounded vessels, fuel dumping, machineries. 4. Industrial waste water sludge on to the seafloors directly or through inland rivers & run-offs. 5. Atmospheric depositions of volatile hydrocarbons and pipe line spills.

4.1.1 Maritime effects of oil spillage The oil pollution can influence both environmental and socioeconomical aspects which result in loss of marine lives, aqua cultures, seashores, human health, etc. The oils form slick in various colors based on their properties on the surface of water and FIGURE 4.1 Polycyclic aromatic structure.

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4.1 Introduction

TABLE 4.1 Summary of some major global oil spills and their effects on the marine environment (Ji, Xu, Huang, & Yang, 2020). S No Incident/accident

Location

Oil spilled out

Reasons, results, and losses

1

The Persian Gulf War Oil Spill (1991, August 2)

Persian Gulf, Kuwait

380
520 million gallons

• Iraq burnt hundreds of Kuwaiti oil wells which continue to burn for months

2

The BP’s Horizon Oil Spill (2010, April 20 and September 17)

Gulf of Mexico

April—natural gas spilled out,September—134 million gallons

3

The Ixtoc-1 oil spill (1979 June
1908 March)

Bay of Campeche

126
140 million gallons

4

The Atlantic Empress Oil Spill (1979, July 19)

Atlantic Ocean, at the Islands of Trinidad and Tobago

90 million gallons

5

The Mingbulak or Fergana Valley Oil Spill (1992, March 2)

Uzbekistan

88 million gallons

6

The Kolva River Spill (1994)

Russian Arctic

84 million gallons

• Natural gas burst out from capsized well cap • 11 fatalities and 17 got seriously injured • 2100 km of United States gulf coast from Texas to Florida was coated with oil. • Explosion during drilling under 164 feet from seafloor which resulted in raising of mud, oil and natural gas • Loss of money, lost tourism • Reduced the commercial fishing for 5 years • Oil spilled into 16 km off the islands due to the collision of VLCC’s Atlantic Empress and Aegean Captain during a tropical storm • Ships caught fire and ignited the oil spilled • 27 sailors died and out of luck there was a less environmental damage • A well blow out spewed the oil into the valley of Fergana • Continuously burned for 2 months when fire caught • More than 88 million gallons of oil was protected from fire behind the dikes and berms • Oil spilled for almost 8 months and 72 sq. miles of Tundra and Wetlands

7

The Incidents at Nowruz Oil Filed (1983, February 10 & Iran-Iraq war period)

Northern Persian Gulf

In February, 733,000 barrels of oil and in war period, nearly 80 million gallons

8

The Castillo de Bellver Oil Spill (1983, August 6)

South Atlantic Ocean, South Africa

110,000 tons of oil

9

The Amoco Oil Spill (1978, March 16)

Coast of Brittany, France

69 million gallons

• Iranian Oil Field was struck by the tanker which resulted in corrosion and toppling of platform due to waves. • One month later the tanker collision took place, Iraqi helicopters attacked the nearby platforms resulted oil spills • 20 people died trying to cap the wells and 2/3 rd of oil spilled • Tanker broke into 2 pieces • Caught the fire & drifter to 24 miles of coast before it sank in deep water • Oil was floated on surface was caught in Benguela Current • Hydraulic system and rudder got damaged • 200 miles of French coast was polluted by oil slick • Huge loss of marine lives and contaminated the oyster beds in the zone

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4. An overview of worldwide regulations on oil pollution control

FIGURE 4.2 (A) Amoco Cadiz oil spill (The Editorial Team, 2019) (B) fire demolished LPG carriers (Maritime Herald, 2019).

migrates due to the ocean currents. The speed of currents has higher influence on migration of oil spillage when compared to the rate of oil spillage (Rafferty, 2020). The oil spillage tends to some serious accidents and two major accidents among them are shown in Fig. 4.2A and B and environmental impacts such as explosion, firing, capsizing, global warming, greenhouse gases emission, particulate emissions that form a ground level ozone layer and smog which have carcinogenic effects on the functional organs such as respiratory system.

4.1.2 Significance of oil pollution control management Apart from natural occurrence the other sources of oil pollution can be managed in order to minimize the marine pollution due to the oil seeps as a small amount and constant rate of oil spill into the inland water bodies (seas) can be assimilated to the ocean environment. From 2010 to 2019 nearly 415 incidents took place and the proportions per year are represented in Fig. 4.3. The serious need in marine, ecological, and environmental stabilization puts many international organizations together to govern the oil pollution control management by setting many laws, rules and regulations in implementation on the national basis and global basis depending upon the oil management proportions. Every country has its own policies and regulations to control the oil pollution which are derived from the worldwide regulation to analyze the social, economic, and environmental losses statistics if any maritime incident/accident occurred and to take some measures to prevent such phenomena to happen again by implementing various regulations and laws such that every maritime operation such as exploration, drilling, oil extraction, transportation, as a result the transportation of petroleum products through pipelines minimized the tankers usage as shipping activities are the primary source of marine pollution and hence the existing rules are mostly related to vessel source pollution. The factors like precautionary methods, polluter compensation concepts, vigilant technologies, and healthy environmental practices (OSPAR, 2019) should be adopted along with EPA and FRP rules while plotting a regulation.

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4.2 International laws on maritime pollution

[PERCENTA [PERCENTA [PERCENTA [PERCENTA GE] GE] GE] GE] [PERCENTA GE]

[PERCENTA GE]

[PERCENTA GE]

[PERCENTA GE]

[PERCENTA GE]

[PERCENTA GE] 2010

2011

2012

2013

2014

2015

2016

2017

2018

2019

FIGURE 4.3 Total number of global incidents occurred in water from 2010
19 (PHSMA, 2020).

4.2 International laws on maritime pollution After World War II, the global concern on maritime safety and security became a primary focus due to the results of military activities in Atlantic Ocean. In 1972, the Stock Holme Declaration on Human Environment stated that every required practice must be taken in order to keep the marine environment away from pollution and to protect the lives of humans, marine ecosystem, and amenities of seas and oceans in principle 7 and about liabilities & compensations regarding marine pollution in principle 22. Region wise marine pollution monitoring was implemented by “United National Environment Program” which adopted the regional seas action plans for monitoring the pollution prone regions and this could solve transboundary problems like Mediterranean region which was first covered. The general measures taken by the legal field to protect the marine environment from oil spills especially from ships have four objectives. 1. To reduce the unnecessary oil discharges by the tankers and ships for cleaning, filling purposes, etc. 2. Preventing accidents to take place as there might be a chance of oil spillage if any of the ships is carrying oil products. 3. Following various methods and implementing some viable technologies that minimize the accidents and protect marine environment. 4. To keep the sailors and those who travel through ships safe and to compensate the victims if suffered by any accident as a result of pollution. Oil Pollution was not projected as an issue in global conventions on the Law of the Sea where Geneva Conventions of 1958 focused on oil spill through pipelines and other sea

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bed activities which provoked the coastal states to establish safety zones around the offshore installations to protect the marine living resources from oil pollution.

4.3 1954
62 Convention and its amendments 4.3.1 Origin and establishment of 1954 convention In 1954 governments of United Kingdom and United Nations held an international conference in London from April 26th to May 12th 1954 with the aim to regulate the oil discharges from the tankers and ships which was the first step taken toward the reduction of global oil pollution and the respective regulations were confessed by the convention are described below. 1. The ships or tankers should not discharge any oils and their mixtures into the prohibited zones established by the convention (Curtis, 1985). 2. The violations of the rules by any ship “shall be an offense punishable under the laws of territory in which the ship was registered” (Boyle, 1985). 3. Huge penalties are imposed “if the violation of rules is done outside the territories when compared to the penalties for unlawful oil discharges in the territorial waters of the states concerned” (Mensah, 1976). 4. The convention also confessed that every ship within its jurisdiction must be well fitted in order to avoid the unwanted and excess oil spillages or leakages by passing the oils through oil-water separator (Concerning, 2010). The convention officially started or came into existence in January 1959. The convention synchronized the violations and contraventions by providing facilities for unwanted or disposed residue discharge from oil ballast and tankers into the ports by maintaining the regular records to inspect the operational discharges of ships in their territories and ports and these records followed by laws and other legislative aspects regarding conventional provisions in the state territories were sent to the Bureau of Conventions of the contracting parties. IMCO had become the depositary of this convention and again a conference was held to review the 1954 convention and adopted the amendments that extended the oil discharge prohibition zones and also the application of lesser gross tonnage ships. An article that empowered the IMCO assembly, was revised and with the support of IMCO maritime safety committee (MSC), was sent to the contracting governments for acceptance and since June 1957, the convention as amended in 1962, came into force and these provisions are currently followed by 52 states which means over 91% of the ocean ships and 95% of the world tanker fleet are being run with the provision of 1954 convention.

4.3.2 1969 and 1971 Amendments By resolving A 172 (VI) the IMCO Assembly adopted some amendments to 1054 convention and its annexes as amended in 1962 (Mensah, 1976), with following limitations. 1. Oil discharge quantity in any ballast voyage should be 1/15000 of the cargo vessel carrying capacity.

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2. The discharge rate of oil was limited to almost 60 L per mile traveled by the ship. 3. Within 50 miles of the nearest land, oil discharge into the waters is prohibited. The 1969 amendments introduced new oil record process that had concerned with the liberal observance of the convention and the ships carrying flags of respective countries should give a notice to the IMCO for delivering the particulars to other government. These amendments minimized the quantity of oil discharged into seas and achieved an appreciable progress in reducing the oil pollution. In 1971, by resolving A 232 (VII) the IMCO Assembly adopted an amendment to the convention for protecting Great Barrier Reef Area because of its uniqueness in scientific and environmental significance as by 1969, they came to a conclusion that long vision development regarding industrial aspects and maritime operations with respect to ships had introduced some problems which could not be handled with the perspective measures of 1954/62 Convention which made IMCO to propose another conference in 1973 to adopt the new international provinces and focus on contamination of not only seas and oceans but also air and land by ships, vessels, etc that are used for any maritime operation.

4.4 International conference on marine pollution, 1973 This conference aimed at a complete elimination of global intentional oil discharges and other hazardous toxic substances into water bodies along with regulating the accidental discharges that happen and this conference work is extended to all shipborne proportions of oil related pollutants.

4.4.1 Annex I of the convention consists of the regulations for oil pollution control and prevention which are primarily focussed on modifying all the provisions of 1954/62 convention and amendments as per requirement. The primary provisions of the 1973 convention are summarized below 1. The regulations regime of convention is applied both for all types of oils as “Load on Top” system prevents the unwanted oily mixtures discharge into the waterbodies and stored at the top of cargoes in the tanks where the non-polluting sediments and parts are disposed into water and for those ships which could not carry the oils at the top would be provided the receivers at the ports to discharge such polluting oils by providing an appropriate fitting with the corresponding equipment like oil discharge monitoring and control systems, tanks, pipelines and pumps (Mensah, 1976). 2. Two new requirements were added to the tanker construction where the first one was the limit of dead-weight was 70,000 tons for a new tanker or the ballast tanks are to be provided to increase the capacity of ships instead of carrying the segregated ballast water through cargo oil tanks for efficient operation of tankers and the other requirement was to enable the survival of tankers after collisions or stranding (Mensah, 1976). 3. The other important feature was provision on special areas in which the specified areas are pollution prone, oil discharges are strictly prohibited. Mediterranean Sea Area,

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Black Sea Area, Baltic Sea Area, Red Sea and Gulf areas come under the prohibited zones (Mensah, 1976). 4. The 1973 convention also prohibited the violations of requirements and based on the Law of Administration of the ship irrespective of the region of violation took place, the sanctions will be established and if the violation takes place in any jurisdiction of any parties, then the sanctions are established based on the law of that party (Bodansky, 1991). 5. If the evidence regarding or against violation that took place either in jurisdiction of a party or out of the jurisdiction, can be submitted to the convention to prove the violation occurrence. The 1973 conventions did not include some aspects such as direct release of oil during exploration, exploitation and mineral source processing but covered almost all incidents of marine pollution and to develop the convention provisions an article was incorporated in order to provide numerous methods for convention amending and its annexes (Mensah, 1976) under the guidance of IMCO got circulated to various state parties for acceptance and brought into force by the “explicit act” of a major number parties. The 1973 convention finally entered into force after one year of acceptance given by at least 15 states, not less than 50% of global shipping merchants. The 1973 Convention did not cover the spills arise due to the operations of some devices such as drilling rigs which are engaged in exploitation and exploration. There are other conventions that were established with the prime focus in preventing accidents due to the oil spills in order to promote maritime safety with higher standards. The important such conventions are 1. The International Convention on Safety of Marine lives, 1960 which adopted the amendments from 1966 to 1973 (Bleicher, 1972). 2. The international Regulations for preventing Collisions at Sea, 1960. 3. The International Regulations for Preventing Collisions at Sea, 1972 (Mensah, 1976). 4. The International Convention on Load Lines, 1966 (IMCO, 1969). 5. The International Convention on Safety of Life at Sea, 1974 (IMO, 1974). Some other instruments were designed specifically to eliminate the pollution accidents such as 1971 amendments to 1954/62 Convention and other amendment was adopted by IMCO to deal with pollution due to the substantial increase in sizes of tanker (Mensah, 1976) or vessel by giving the limitations as the size of the individual tanks were permitted to the strength up to 100,000 ton capacity of the “Torrey Canyon” because the level of pollution arise when such large dimensional designed ships involved in collisions or stranding made IMCO to have a concern on limiting the oil spills in such case of accidents or incidents, hence the 1969 Civil Liability Convention entered into force on June 19, 1975.

4.4.2 Other conventions and instruments on the Regional Basis These conventions deal with not only oil pollution but also the other pollutants that pollute marine environment to be comprehensive in scope and not confined to the oil exclusively. Some important Conventions and Instruments are; 1. The Convention in 1974 for Nordic Environmental Protection

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2. The Paris Convention on the Prevention of Land-Based Sources of Pollution. 3. The Convention on the Protection of the Marine Environment of the Baltic Area of 1974. The “Torrey Canyon” incident was the first major oil pollution which had a strong impact on the development of the international law and marine environmental legislation to step up for the formation of “International Maritime Organization” to improve the international liability and compensation for oil spillage and also established MSC to deal with environmental issues.

4.5 MARPOL Convention—73/78 MARPOL was adopted by IMO on November 2, 1973 and the prime attention of MARPOL was keen towards maritime pollutants in the form of oils, sewages, chemicals and other leakages or spills due to operations and accidents. 1978 MARPOL protocol was adopted and some measures were incorporated to prevent the tankers from polluting the maritime environment, in a conference on February after the disaster of tankers accidents in the period of 1976
1977. The Regulations of MARPOL Convention were aimed on all types of polluting sources like accidents and routine operations by interpreting six Annexes for preventing any accidents to take place which are listed in the Table 4.2. IMO introduced measures through MARPOL Convention which made a major impact on maritime pollution control by reducing the oil spillages with safe construction and operational procedures. The persistent spilled oil residues and water-in-oil emulsions will be the main threat posed to Marine mammals and reptiles, birds that could come into contact with a contaminated sea floors and also effects onshore marine life.

4.5.1 Annex I 4.5.1.1 Measures to control operational discharge of oils according to annex I Oil discharge either outside or inside the special areas from a 400 tonnage and above tankers or ships can be permitted when; 1. 2. 3. 4. 5.

There must be an installed oil filtering equipment as per the requirement of Annex Oil content of the effluent from the ships or tankers should be diluted at most to 15 ppm. Effluents should not be mixed with the oil cargo residues. Specific in Antarctic zone any kind of oil discharge is strictly prohibited. Oil Record book should be maintained with machinery space operations and Ballast operations.

4.5.1.2 Shipboard oil pollution emergency plan Oil tanker of greater than or same as 150 gross tonnage and every ship of 400 gross tonnage and above shall carry on board Shipboard Oil Pollution Emergency Plan governed by the Administration by reporting any incident or accident if occurred, determining the statistics of losses, compensations and liabilities including the plan of action to reduce the oil pollution with the governance of the national authorities in combating the oil pollution. The special areas focused by this Annex are the Mediterranean Sea area, the Baltic Sea

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TABLE 4.2 List of Annexes of MARPOL Convention (MEPC 58, 2008). Annex Point of attention and regulations

Entered into force

Revised annex entered into force

I

Regulations for the Prevention of Oil Pollution

2nd October 1983

1st January 2007

II

Regulations for the Control of Pollution by focusing on Noxious Liquid Substances in Bulk

2nd October 1983

1st January 2007

III

Prevention of Pollution by Harmful Substances packages across seas and oceans

1st July 1992

1st October 2010

IV

Prevention of Pollution by Sewage from Ships

27th September 2003

27th September 2003

V

Prevention of Pollution by Garbage from Ships

31st December 1988

1st January 2013

VI

Prevention of Air Pollution from Ships

19th May 2005

1st July 2010

TABLE 4.3 List of various Oils accidental or due to operational spills (Mensah, 1976). S No

Classification

1

Asphalt oils

Blending stocks, roofer flux, straight run residues

2

Gasoline blending stocks

Alkylates (fuel), reformates, polymers (fuel)

3

Distillates

Straight run residues and flashed feed stocks

4

Gasolines

Automotive, aviation, straight run, kerosene, fuel oil (1-D, 2, 2-D)

5

Jet oils

JP-(1, 3, 4 and 5), Turbo fuel, kerosene, mineral spirit

6

Naphtha

Solvents, petroleum, heart cut distillates

area, the Black Sea area, the Red Sea area, the Gulfs area, the Gulf of Aden area, the Antarctic area, the Northwest European waters including the North Sea, the Irish Sea, the Celtic Sea, the English Channel and part of the North East Atlantic near Ireland, the Arabian Sea near Oman and the Southern South African waters. The list of oils that were spilled in general are listed in Table 4.3.

4.5.2 Annex II 4.5.2.1 Main features of annex II of MARPOL The Annex II of MARPOL categorizes the effluents that are discharged into seas as X which has greatest threat to the marine environment, Y with moderate threat and Z with the least level of threat carried by the vessels or tankers in bulk based on their threat levels on the marine environment, amenities and human health. This Annex also interpreted some standard procedures and regulations that should be either in English or French or Spanish through the manual with respect to Cargo handling, tank cleaning, slop handling, ballasting and de-ballasting the cargos and in case if the manual is in other language then the format should be translated into any of the above three languages according to

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Appendix 4 of Annex II. The record book is the ship’s official log book in the form specified in IBC amendments of Appendix 2 of Annex II and various details such as loading/ unloading the cargo, pre wash/cleaning the cargo according to the manual provided, internal transfer, ballasting/de-ballasting and accidental or operational discharges of oils are included in the record book. 4.5.2.2 Shipboard marine pollution emergency plan for noxious liquid substances Every ship of 150 gross tonnage must have a shipboard marine pollution emergency plan for Noxious Liquid Substances approved by the Administration to report a Noxious Liquid Substances pollution incident with a detailed plan of action that to reduce or control the discharge of Noxious Liquid Substances following the incident and this must be governed by the national authorities to reduce the pollution. Antarctic zone is the special area for this Annex.

4.5.3 Annex III 4.5.3.1 Main features of annex III of MARPOL This Annex describes the requirements in detailed such as standards on packing, marking/labeling, documentation, stowage, quantity limitations, exceptions and notifications for preventing pollution from pollutants by adopting the amendments of International Maritime Dangerous Goods (IMDG) Code, which has been amended for the transportation of harmful substances including marine pollutants and every pollutant must be labeled with the standard marine pollutant mark which was made a mandatory form in May 2002 by IMO and IMDG finally entered into the force on January 1, 2004. The regulation 7 of this Annex states that “appropriate measures will be taken depending up on the physical, chemical and biological properties of pollutants and regulate the washing of leakages overboard without impairing the safety of the ships and persons on board” which has two parts of volume code as described in Table 4.4 and this Annex is applicable for all types of ships and vessels carrying hazardous materials in packaged form or road and rail carry wagons. For every two years, IMO incorporates the changes in IMDG Code with new amendments with the approval of MSC. TABLE 4.4 Parts of two volume code (MEPC 58, 2008). Volume 1

First 7 parts of the code excluding part 3

• Classification of the general-provisions, Packing & Tank Provisions, Consignment Procedures are described • Construction and Testing of packages, IBCs, portable tanks, MEGCs and road tank vehicles and their Operation

Volume 2

Part 3, appendix An and appendix B

• Harmful packages of goods, provisions including exceptions • Generic and N.O.S. Proper Shipping Names • Glossary of terms • An Index

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4.5.4 Annex IV 4.5.4.1 Main features of annex IV of MARPOL Many legal requirements are plotted by Marine Environmental Protection Committee in 2011 from the resolution MEPC.200(62) which adopted the amendments that consider the Baltic Sea as a Special Area and introduced some discharge requirements for passenger ships in the special areas. A set of regulations are provided for controlling sewage discharge into the seas from ships within a specific distance from the nearest land and also included a legal model of International Sewage Pollution Prevention Certificate which should be issued by National Shipping Organizations to ships under the government to ensure the adequate provision of facilities at ports and terminals for sewage discharge. 4.5.4.2 The revised annex IV The revised Annex for new ships on December 3, 1976 engaged in the international voyage of gross tonnage should be provided with sewage treatment plant with the international standards while IMO by Resolution MEPC.2(VI) adopted the installation, construction and calibration of sewage treatment systems is or a sewage holding tanks which are to be certified by more than 15 persons. Shipboard Sewage Pollution Sources such as drainages and other waste waters need the regulations but disposal of drainage from dishwasher, shower, laundry, bath and washbasin drains—gray water don’t require any regulations as they are not considered as pollutants. The revised Annex can be applicable for all types of passenger ships which includes new standards/tests for sewage treatment plants with the installation of Advanced Waste Sewage Treatment Systems. This Annex came into force on January 1, 2013 and from January 1, 2018 the sewage discharge in the Baltic Sea Area was prohibited.

4.5.5 Annex V 4.5.5.1 Legal requirements for the Annex V This Annex mainly focuses on the garbage that was produced from the ships which majorly affect the marine lives. Many wastes like plastics that float on water and also nonbiodegradable will be consumed by many fish and mammals of the seas by mistaking the plastic as food, trapped in the plastic covers, nets, fish gears, incinerated ashes, animal carcasses, and cargo residues. These garbage materials were added to the seas/oceans by the fishermen who throw away the unwanted and used items, people who throw the waste onshore and also through rivers and canals from cities/towns. The garbage is also produced from the ships that are passing through the oceans or seas. MARPOL aimed to eliminate the garbage generation across the seas. 4.5.5.2 Restrictions and garbage management According to Annex V the garbage includes waste food, domestic and operational waste produced from the ships by prohibiting the disposal of plastics anywhere into the sea, and restricts discharges of any garbage (that harm marine lives) from ships into coastal waters by providing the facilities at ports and terminals for the reception of garbage. IMO

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Guidelines MEPC.220(63) describe various garbage management aspects like garbage minimization, storage, collection and processing. The ships of minimum 400 gross tonnage should be verified and certified by 15 persons of respective jurisdiction. The prohibition zones for this Annex are the Mediterranean Sea, the Baltic Sea Area, the Black Sea area, the Red Sea Area, the Gulfs area, the North Sea, the Wider Caribbean Region and Antarctic Area. MEPC/Circ.317 gives Guidelines for developing the garbage management plans and an Appendix to Annex V of MARPOL to give a standard form for a Garbage Record Book.

4.5.6 Annex VI 4.5.6.1 Application This Annex can be applicable for all ships of 400 gross tons and above which must carry IAPP Certificate and ships of less than 400 gross tons should comply with legislation where applicable with appropriate measures and this Annex is complied with the following regulations. 1. 2. 3. 4. 5. 6. 7.

Regulation Regulation Regulation Regulation Regulation Regulation Regulation

12: 13: 14: 15: 16: 17: 18:

Ozone depleting substances Nitrogen oxides (NOx) Sulfur oxides and Particulate Matter (SOx) Volatile organic compounds Shipboard incineration Reception Facilities Fuel oil quality and availability

The summary on recent and upcoming worldwide regulations are discussed in Table 4.5. There are various energy efficiency regulations introduced for ships of 400 gross tons and above. They are (https://www.lr.org/en-in/marpol-international-convention-forthe-prevention-of-pollution/) 1. Energy Efficiency Design Index (EEDI)-to calculate CO2 generated per tonnage to approach the energy efficiency calculations. 2. Ship Energy Efficiency Management Plan (SEEMP)-to establish a mechanism for the optimum performance with good energy efficiency of a vessel in a cost-effective manner 3. International Energy Efficiency Certificate-Certificate that covers both EEDI & SEEMP.

4.6 Oil Pollution Act, 1990 4.6.1 Origin of Oil Pollution Act, 1990 After the spill of Exxon Valdez which carried up to 70,000 barrels of oil on March 24th, 1989 in United States; the Congress voted to pass Oil Pollution Act in 1990 (US Coast Guard, 1991) which amended the Federal Water Pollution Act and outlines to prevent, control and respond to the oil spills by introducing additional restrictions by mandating a

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TABLE 4.5 Summary on recent and upcoming regulations of MARPOL Convention (MARPOL, 1973). Annex Regulation Into force

Applicability

Progress

I

28

1st January Authority of oil tankers, chemical Requirements for oil tankers are introduced 2016 tankers and gas carriers for stability instruments for intact and damage stability

VI

13

1st January Authority, labor and other Tier III requirements are introduced to 2016 shipbuilding-related stakeholders control NOx emissions from diesel engines

VI

13.7

1st March 2016

I

12

1st January All ship owners and managers 2017

Requirements for sludge piping are introduced into Regulation 12

VI

13

1st September 2017

Requirements to record when engines are altered from Tier II operation to Tier III operation on applicable ships entering Tier III ECAs.

IV

11 & 13

1st June 2019

All ship owners and operators

Introduction of the Baltic Sea Special Area requirements until 2019 for new passenger ships and 2021 for existing passenger ships by changing the format of ISPP certificate

VI

22 A

1st March 2018

Authority of ships that are subject to air emission controls

New requirements for ships of capacity 5000 gt are introduced in order to record the report of ship fuel-oil consumption data of 2019

V

1.2

1st March 2018

Ship owners, operators, and managers

Cargo residues, including the cargo hold washing water and e-wastes are considered pollutants.

VI

14.1.3

1st January Authority of vessels subject to 2020 MARPOL VI

Ships when operating outside the existing ECA for SOx emissions, any fuel oil used on board should be limited to 0.50% sulfur content.

VI

14.1

1st March 2020

Authorities of ships that are subject to air emission controls under MARPOL Annex VI

Ships when operating outside the existing ECA for SOx emissions, any fuel oil used or carried on board should be limited to 0.50% sulfur content.

VI

13

1st January, 2021

New ships constructed from 1 January 2021 operated in European waters

Introduces two new NOx Emission Control Areas in various areas which requires Tier III engines for ships operating, which are constructed from 1 st January 2021 or have “non-identical” replacement engines or additional engines installed.

All ship owners and operators

Modified the IAPP Record of Construction format.

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double hull requirement of United States operating tank barges, newly built tanks and created a phrase out schedule for existed tanks and single hull tankers began to phased out from 1985.

4.6.2 Progress of Oil Pollution Act, 1990 in oil pollution control The United States Coast Guard was established by OPA which is supposed to consistently enforce the law, embrace the businesses and communities to comply with OPA with an effective utilization of resources and training their personnel to handle all OPA related aspects. The work was extended to authorize the Oil Spill Liability Trust Fund for which the fund was originally established in 1986. Crude oil tax on barrels produced within or imported to the U.S was the financial factor of OPA and can distribute up to one billion dollars per incident to compensate the victims of oil spills and is governed by the federal government. Various assessments such as federal, state, etc. oil spill removals and damage could be qualified to use the fund. OPA laid the penalties for companies responsible for oil spills and gave numerous guidelines on the perceptions like response and counter measures to be taken for a spill if takes place in order to minimize the oil spills and the impact of the spill and the amendments are adopted by taking the present best practices into consideration. OPA introduced the International Regulation “The Convention on Civil Liability” and other regulations but oil companies have found loopholes in the system to avoid the penalties. The OPA, promulgated by the United States Congress, introduced the double hull standards for oil tankers which was called “Draconian Legislation” which led to an idea concerning the vessel tank was familiar as in 1971 the amendments to the OILPOL have been elaborated which regulated the tank sizes of ships in order to reduce the pollution. However, ship construction industry at that time opposed this amendment proposal, hence the Amendments did not enter into force and as OPA was first enacted, major ship owners proposed only chartered vessels usage to carry oil into the United States and refused to enter certain ports. Apart from drawbacks, the OPA made a remarkable impact in United States maritime operations and on oil pollution to decline rapidly. Later many organizations were established in order to protect the marine environment. Some of such are discussed in Table 4.6 and some regional conventions are mentioned below. • Art. 8 of the Abidjan Convention, 1981 focused on protecting and developing the Marine and Coastal Environment of the West and Central African Region; • Art. 4 of the Lima Convention, 1981 focused on protecting the Marine Environment and Coastal Area of the South-East Pacific. • Art. 8 of the Jeddah Convention, 1982 focused on the conservation of the Red Sea and Gulf of Aden Environment. • Art. 8 of the Cartagena de India’s Convention, 1983 focused on protecting and developing the Marine Environment of the Caribbean Region. • Art. 8 of the Nairobi Convention mainly focused the of the Eastern African Region’s protection, management and development of the Marine and Coastal Environment. • Art. 8 of the Noume´a Convention, 1986 focused for the Protection of the Natural Resources and Environment of the South Pacific Region and related Protocols. • Art. 7 of the Barcelona Convention, 1976 focused on protecting the Mediterranean region from pollution.

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TABLE 4.6 Summary of various international organizations for global oil pollution control (International Spill Control Organization, 2013). Organization

Established Progress and working

APICOM (Association of Petroleum Industry Co-operative Managers)

1972

It is an advisory body for introducing and developing new standards, regulations and policies for preventing oil pollution in global vision

ISSA (International Social Security Association)

1997

Provides all the events, expert networks, professional standards, practical services, innovative appropriates and supplements the global advocacy for socio-security

IMO (International Maritime Organization)

1948

Shipping regulations, Plotting MARPOL convention against the oil pollutions from ships and almost all the world nations follow MARPOL with some required modifications if any

IGP&I (International Groups of P&I Clubs)

Covers all the responsibilities of ocean-going voyages globally by forming 13 clubs for compensating the international groups

IOPC (International Oil Pollution Compensation Funds)

1992

Provides pays, compensations for economic damage from the oil to tankers if any spill takes place

ISCO (International Spill Control Organization)

1984

Focuses on prevention and countermeasures for oil spills if took place

ITOPF (International Tanker Owners Pollution Federation Limited)

1968

Provides the guidelines, technical information documents, data and statistics to respond for implementing measures for spills of oils, chemicals and other harmful pollutants

UNEP (United States Environment Program)

1972

Focuses on Air, Bio Safety, Climate Change, Water sustainability develop programs, disasters and conflicts and serves as an administrative advocate for global environment

INTERTANKO (International Association of Independent Tanker Owners)

1970

Focuses on various amendments to authorities of tanks like operational and commercial aspects

Fig. 4.4 describes the statistics regarding quantity of oil spill per year after the implementation of these many laws and regulations to protect the marine environments due to oil spills.

4.7 Conclusions The chemicals carried at sea have a hazardous influence on the marine environment and the oil spills corrupt its ecosystem in numerous ways as when a few tons of oil spills into the sea it forms slicks with various thickness based on the viscosities of the oils spilled on the water surface which mostly damage marine life. Since the middle of the 20th century many global legislative measures were adopted to prevent the oil pollution and protect the marine environment by introducing many national laws and regulations which

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81

FIGURE 4.4 Plot of Oil spilled and progress of regulations in minimizing the global oil pollution (Roser, 2013).

led to the minimization of oil spills with improved tank construction, and other technological advancements like the load-on-top system in order to reduce onshore and offshore oil pollution. Oil pollution made to introduce many legal documents for marine environment protection using viable regulations and principles from international environmental law to embrace the sustainable development even in the aspect of welfare of victims by providing liability and compensation such as CLC fund if any accident takes along with the application of measures against oil pollution from ships/vessels by governing various conventions like MARPOL and Oil Pollution Act as even a little oil spilled into seas/oceans can cause irreparable loss and damage. There are many effective policies and instruments to prevent the oil pollution by clean-up operations, mechanical containment along with installation of sewage treatment plants and holding tanks. Other counter measures can be used in emergency scenarios due to their limitations during burning, sinking, grounding, etc. depending upon a situation arising in order to protect marine environment and marine lives, but still some obligations for the oil industry are seen as legislation for oil pollution which has a slow development. The international organizations modify the regulations based on the requirements and these regulations do not need to be followed by all parties around the world depending on their climate conditions, pollution stats, and many other factors. The exploration and exploitation in the oceans and seas for energy sources cause oil pollution but they are much needed for the further optimization of global energy efficiency by avoiding accidents and oil spillages in order to protect the marine environment and ecosystem.

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References Bleicher, S.A. (1972). IMCO Sales No. 1970
6, with amendments adopted by following resolutions of the IMCO Assembly: A. 108 (ES.III) 1966; A. 122 (V) 1967; A. 146 (ES. IV) 1968; A. 174 (VI) 1969; A. 205 (VII) 1971; A. 263
264 (VIII) 1973. Bodansky , D. (1991). International convention for the prevention of pollution of the sea by oil, supra note 6, at 152. Boyle, A.E. (1985). International convention for the prevention of pollution of the sea by oil, supra note 5, art III.I Concerning, C. (2010). International convention for the prevention of pollution of the sea by oil, supra note 5, art. VIII. Curtis, J.B. (1985). Cited by 50 — International Convention for the Prevention of Pollution from Ships, No- ... MARPOL 73/78, supra note 2, annex I, regulations 9, 10. Herald, M. (2019). https://maritime-zone.com/en/news/view/top-latest-maritime-accidents. International Spill Control Organization (2013). https://spillcontrol.org/2013/02/04/international-organizations/. IMCO (1969). IMCO Sales No. 1968-3 with amendments adopted by the resolutions of the IMCO. IMO (1974). International Convention or the Safety of Life at Sea (SOLAS), 1974. Ji, H., Xu, M., Huang, W., & Yang, K. (2020). The influence of oil leaking rate and ocean current velocity on the migration and diffusion of underwater oil spill. Scientific Reports, 10, Article number: 9226. MARPOL (1973). https://www.lr.org/en-in/marpol-international-convention-for-the-prevention-of-pollution/. Mensah, T.A. (1976). International convention for the prevention of pollution of the sea by oil, supra note 5, Regulation 25. Mensah, T.A. (1976). Text in Int’l Legal Materials 267 (1972). Mensah, T.M. (1976). IMCO Sales No. 1973-3 with amendments adopted by the resolutions of IMCO. Mensah, T.A. (1976). The text of the 1954/62 Convention, with the 1969 Amendments appears in 9 Int’l Legal Materials 1 (1970). Mensah, T.A. (1976). International convention for the prevention of pollution of the sea by oil, supra note 5, art. VI & art. VII. Mensah, T.A. (1976). International convention for the prevention of pollution of the sea by oil, supra note 5, Regulation 1 of Annex I. Mensah, T.A. (1976). International convention for the prevention of pollution of the sea by oil, supra note 5, Regulation 15, 16, 17 & 18. Mensah, T.A. (1976). International convention for the prevention of pollution of the sea by oil, supra note 5, art XVI. MEPC 58 (2008). IMO, ANNEX VI of MARPOL 73/78, regulations for the prevention of air pollution from ships and NOx Technical Code. National Research Council (2003). Oil in the sea III: Inputs, fates and effects, Chapter 3: Input of oil to the sea; 2003. Washington, DC: The National Academies Press. Available from https://doi.org/10.17226/10388. Nriagu, J. (2019). Oil industry and the health of communities in the Niger Delta of Nigeria by, School of Public Health, Encyclopedia of Environmental Health, pp. 758
766, published on March 2011. OSPAR (2019). http://www.ospar.org/html-documents/ospar/html/OSPAR-Convention-e-updated-text-2007.Pdf. PHSMA (2020). https://portal.phmsa.dot.gov/analytics/saw.dll?PortalPages. Rafferty, J.P. (2020). 9 of the biggest oil spills in history, https://www.britannica.com/list/9-of-the-biggest-oilspills-in-history. Roser, M. (2013). https://ourworldindata.org/oil-spills. Schachter, O. (1971). Comprehensive outline of scope of the long term and expanded program of oceanic exploration and research, U. N. Doc. A/7750, Part I
3rd November 1969. The Editorial Team (2019). The Acomo Cadiz Oil Spill, Brittany (March 1978). https://safety4sea.com/cm-amococadiz-oil-spill-the-largest-loss-of-marine-life-ever/. US Coast Guard (1991). Oil Pollution Act, by National Pollution. Fund Center. Available from https://www.uscg. mil/Mariners/National-Pollution-Funds-Center/About_NPFC/opa/.

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C H A P T E R

5 Technological aspects of different oil and water separation advanced techniques Vishal Kumar Singh1, Sankari Hazarika2, Robin V. John Fernandes1, Ankit Dasgotra4, Poonam Singh3, Abhishek Sharma4 and S.M. Tauseef 5 1

Department of Health Safety, Environment and Civil Engineering, School of Engineering, University of Petroleum and Energy Studies, Dehradun, India 2Department of Petroleum Engineering and Earth Science, University of Petroleum and Energy Studies, Dehradun, India 3 School of Engineering, University of Petroleum and Energy Studies, Dehradun, India 4 Department of Research and Development, School of Engineering, University of Petroleum and Energy Studies, Dehradun, India 5Centre for Interdisciplinary Research and Innovation (CIDRI), UPES, India and Sustainability Cluster, School of Engineering, UPES, India O U T L I N E 5.1 Introduction

83

5.2 Advanced filtration materials 5.2.1 Metal-based membranes 5.2.2 Polymer-based membranes 5.2.3 Ceramic based membranes

84 85 86 88

5.4.1 5.4.2 5.4.3 5.4.4

5.3 Advanced absorption based materials 89 5.4 Sol-gel based materials

Template based materials Micro nanomaterials Nanobased materials Nanocellulose based material

91 92 92 93

5.5 Conclusion

93

References

94

90

5.1 Introduction Mining, oil industry, food, textile, and other mass processing units all discharge traces of oil in wastewater, which pollutes the water bodies if discarded without

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© 2022 Elsevier Inc. All rights reserved.

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5. Technological aspects of different oil and water separation advanced techniques

proper treatment. The International Convention on the Prevention of Pollution by Sea Vessels had established strict regulations on marine emissions. To successfully separate oil from the sea, a petroleum water separator must be installed (United States E. P. Agency and O. of E. and C. Assurance, 2020). Porous materials like sponges (Guerin, 2002; Nguyen et al., 2017; Zhu et al., 2013), foam (Calcagnile et al., 2012; Li et al., 2020), and textiles (Li et al., 2015; Zhang and Seeger, 2011; Zhang, Zhang, & Wang, 2012) are widely used in the separation of oil from water after accidental use. Some research has recently focused on oil and water separation as it helps deal with numerous industrial wastewater problem. There are various methods using the mass transfer phenomenon to separate two distinct mixtures of immiscible liquid and a stable mixture like suspension. During this separation process, the more valuable component is collected. For example, the decantation process is used to separate the oil from water which greatly simplifies the purification process, and it is also used in the production of high-efficiency electrodes and the synthesis of highquality silver nanowire solutions. All forms of water pollution are not only a threat to our climate but also our ocean’s ecosystem. Despite technological advancements separation of oil and water poses a significant challenge. With the current technologies, there is demand for more costeffective, environmentally sustainable, and environmentally sound oil/water separation methods which are capable of large volume production. These separation methods should have efficiencies while dealing with large volumes of oil and water mixtures (Gupta, Dunderdale, England, & Hozumi, 2017). The materials used for oil water separation can be classified according to their mechanisms for filtration or absorption of oil and water separation in this chapter.

5.2 Advanced filtration materials The rapid development of membrane technologies has improved the membrane performance by the wetting phenomenon. Due to fewer complexities and its cost effectiveness, the functionalized membranes with superwettability have become an important tool for researchers to separate oil from water and are perfect candidates for practical industrial applications. However, numerous oil-water separating membranes break out of dependency on transmembrane pressure and have a particular wettability. The oil water separation materials can be classified into films, filters, membranes and meshes which is shown in Fig. 5.1. Using porous material with wettability functionality oils can be removed from the water because oil has lower surface tension than water. The pore size and porosity are two important parameters for pressure-driven separation membranes where breakthrough pressure is considered in wetting analysis (Mosadegh-Sedghi, Rodrigue, Brisson, & Iliuta, 2014). The first physical feature is a breakthrough pressure (ΔPc), defined as the highest pressure applied to a membrane before the moisture is created on the membrane pores of a liquid. This creates the first drop of liquid on the permeable side of the membrane which has small pores with liquid geometry. The

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5.2 Advanced filtration materials

FIGURE 5.1 Filtration materials for oil-water separation (Gupta et al., 2017).

breakthrough pressure can be measured as given in Eq. (5.1) using the Laplace young equation (Kim & Harriott, 1987). ΔPc 5

2γ L cosθY rp

(5.1)

where γ L and rp are the surface tension of the radius of the liquid and the maximum membrane pore. These superhydrophobic materials have contact angles of more than 100 degrees. The contact angle of the oil from the water must be more than 160 degrees to operate (optimum is 175).    4γcos 180 2 θA (5.2) P: Φ In this equation the interfacial tension is γ, θA is the contact angle of one phase in to the other and Φ is the square pore’s size (length). The highest resistance to oil will be observed when passing through a hydrophilic membrane which has a large θA and will be vice versa in small mesh size (Kwon et al., 2015). These researchers felt that it would only be feasible to generate the stable Cassie-Baxter state which is shown in Fig. 5.2 if the Young’s contact angle was bigger than the LTA. The researchers have been increasingly engaged in the identification of liquids in practical mesh and super-absorbed membranes. The filter media must be very porous for high flow and high selectivity. Super or ultrafine particles in the filtering surfaces should be light and larger in weight so that emulsions can be separated more easily (Kim & Harriott, 1987). The following are different working methods and their advantages and disadvantages.

5.2.1 Metal-based membranes Membranes are referred to as inorganic membranes, consist of oxides, nonoxides, carbon, organic metal frames, zeolites, metals, and other components (Abdel Halim, Ramadan, Shawabkeh, & Abufara, 2013). Inorganic membranes are split into two principal types based on their structure: porous and nonporous inorganic membranes. The porous membrane has a metallic surface with a pore size that varies from micro to nano level which is used for water

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FIGURE 5.2 Cassie- Baxter’s model (Kwon, Post, & Tuteja, 2015).

filtration. For example, a Palladium membrane is a form of dense metallic membranes that are being considered for hot gas separation (Adhikari & Fernando, 2006). Bioinspired membranes have lately been produced with porous metallic networks for the separation of all forms of oil-water mixtures. Although metal mesh substrates are always bigger than oil droplet sizes, they have a high separation efficiency and flux. These substrates have raw microstructures and nanostructures that have robust surfaces, hard environments resistant, and possess unique repeatability which makes them ideal for useful applications in oil-water separation (Ren et al., 2013). These membranes are created using a variety of surface modification techniques (Sun et al., 2013). Wang and Song (2006) developed aligned copper mesh membranes which are a good substrate for oil-water separation and made some electrochemical modification by adding copper microparticles on the mesh surface. The copper mesh membranes were treated with in-dodecanoic acid for 12 h. This represented that the substrate has a water contact angle (WCA) of 158 degrees and a surface angle of 2 degrees when came in contact with the oil and the contact angle was equivalent to 0 degree. This was developed as a superhydrophobic
superoleophobic membrane that was found to be an effective solution for oil and water separation. Guo, Liu, Dang, and Fang (2017) used a similar electrochemical approach to deposit a 2 mm thick layer of copper nanoparticles on the copper mesh surface. It was a measure that the WCA was 154 degrees and the oil contact angle was 0 degree after treating with n-octadecyl thiol. The prepared mesh membrane could efficiently separate a mixture of chloroform and water using only gravity. Wang et al. (2009) again experimented to produce a superhydrophobic
superoleophobic membrane by using copper mesh surface in addition to electrochemical deposition. The copper mesh was initially treated with nitric acid and modified with 1-hexadecane thiol which was a solution based immersion process with a WCA of 153 degrees, surface angle of 5 degrees and oil contact angle equivalent to 0 degree. The membrane did not prove a fast oil-water separator but has shown excellent results in a different medium of solutions.

5.2.2 Polymer-based membranes These polymer membranes have multiple advantages which include low cost, ease of operation and good processing. These membranes are made of polysulfone (Chakrabarty & Ghoshal, 2008), polysulfone (Xiong et al., 2018), polyvinylidene fluoride (PVDF) (Zhang et al.,

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5.2 Advanced filtration materials

2014) and widely used in oil treatment (Kocherginsky & Tan, 2003) to enhance hydrophilicity and centrifuge polymeric membrane using either additive or treatment approaches. Additionally, polymer chemistry offers more advanced approaches such as atom transfer radical polymerization (Zhu & Loo, 2013), in situ polymerization, and interfacial polymerization (Cao et al., 2013). During the phase inversion process, a polymer matrix can be mixed with additives such as hydrophilic polymers, amphiphilic copolymers, and inorganic nanoparticles to increase the resistance from fouling during filtration (Otitoju, Ahmad, & Ooi, 2017). These membranes are prone to initiate reaction of events such as aggregation, adherence, expansion and agglomeration of fouling agents during treatment of oil wastewater which results in fluidity declination. The surface properties can be changed by physical or chemical modification using different additives that improves the antifouling properties as shown in Fig. 5.3. Kim and Van Der Bruggen (2010). Zhang et al. (2013) used an inert solvent-induced phase-inversion technique to construct an superhydrophobic-superoleophilic polyvinylidene flouride SHB-SOL PVDF membrane capable of separating micro and nano stabilized surfactants with composite particles. The hydrophilic and hydrophobic segments are present in amphiphilic polymers and are used as additives in host polymers (Akthakul, Salinaro, & Mayes, 2004). Hester, Banerjee, and Mayes (1999) employed a comblike copolymer Polymethyl methacrylate (PMMA) as an additive and mixed with PVDF which forms amphiphilic membranes. This study indicated that the antifouling capability of the membrane may be significantly enhanced while maintaining the membrane’s structure. Since then, numerous amphiphilic copolymers, such as tri-block (Wang et al., 2005), comb-like (Revanur, McCloskey, Breitenkamp, Freeman, & Emrick, 2007), and branched copolymers (Zhao, Zhu, Kong, & Xu, 2007), have been employed as additives to increase the antifouling capabilities of host polymers. Additionally, amphiphilic copolymers containing both hydrolysis lignin (HL) and hydrophobic (HB) segments are utilized as additives to blend with host polymers. When the polymer is mixed with additives like hydrophilic polymer, amphiphilic copolymers and composite nanoparticles during the phase inversion process it improves the fouling resistance and selectivity of polymeric filtration membranes. FIGURE 5.3 Filler inserted as an additive in polymer membrane (Kim & Van Der Bruggen, 2010).

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In comparison to phase-inverted porous membranes, electrospun polymeric membranes exhibit similar excellent features, including exceptionally high flux at low operating pressure and comparatively controlled pore size and porosity (Chang et al., 2014). Conventional electrospun membranes with superhydrophobicity were used to separate oil from the emulsion (Ning, Xu, Wang, & Liu, 2021). The oil is entirely absorbed when they come into contact with the membrane’s surface forming an oil layer with a strong water repellent feature because the membrane has an evident attraction for oil due to its loose and porous structure. Where in a similar case Zhang, Tian, Lv, Na, and Liu (2015) developed a polymer membrane composed of polylactide and poly (3-hydroxybutyrate-co-4-hydroxybutyrate) using the blend electrospinning method. Modifying the surface wettability of polymeric membranes by chemical or physical means is another effective strategy for improving the performance of polymeric membranes for oil-water separation. Chemical alteration of the membrane surface might be used to securely introduce HL polymers such as poly(ethylene glycol) methyl ether methacrylate (Belfer, Purinson, Fainshtein, Radchenko, & Kedem, 1998), poly(2-hydroxy-ethyl methacrylate) (Rahimpour, 2011), zwitterionic polyelectrolyte (Zhu et al., 2013), or small molecules (Zhao, Su, Chen, Peng, & Jiang, 2012) via formation of covalent bonds. The added hydrophilic materials generate compact hydrated layers that prevent oil droplets from fouling membrane surfaces. Along with chemical processes, physical absorption may be used to directly coat hydrophilic polymers and zwitterionic polymers onto membrane surfaces. Zhao et al. (2012) did research on the grafting method of filtration membranes. He grafted a low surface free energy molecule, that is, pentadecaflourooctanoic acid on polyacrylonitrile ultrafiltration membrane which has resulted in a good antifouling membrane. Wang, Zhang, Yang, and Wang (2010) reported on the surface modification of the hydrophilic layer polyacrylonitrile nanofiber was first deposited onto a nonwoven microfiltration poly (ethylene terephthalate) substrate as a scaffold. To generate high flux for oilwater separation spin coating of chitosan was done on polyacrylonitrile weave as the hydrophilic layer which resulted in three-tier nanofibrous ultrafiltration membranes.

5.2.3 Ceramic based membranes The ceramic membranes are originated from alumina, titanium, zirconia, silicon carbide, etc. Chen et al. (2015) which are made of different porous layers. A substrate layer and above that a thin division layer, also known as the top layer which sometimes include a middle layer also which consist of a metal oxide or inorganic powder. This mixture of layer should be pressed or extruded before sintering process. The ceramic support surface should be smoothed to produce a ceramic membrane. The flat ceramic support is then usually dipped by capillary force and then dried for a certain period with a casting solution (Hyun & Kim, 1997). The permanent roughness to ceramic membranes was achieved by the coating method which brings the correct membrane structure and thickness followed by covering and drying of ceramic microcrystals which causes calcination. The surface roughness is a critical element in membrane weight because it influences membrane performance in oil-water separation. Numerous initiatives have focused heavily on the development of high-performance microfiltration and ultrafiltration ceramic membranes for

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5.3 Advanced absorption based materials

the treatment of oily wastewater (Barbosa, Barbosa, & Rodrigues, 2015). Hu et al. have reported his research (Hu et al., 2015) research which have focused on oil-water separation using ceramic membranes with surface wettability. These studies corresponded with roughness control and modifications to the membrane’s HL surface. Since ceramic membranes composed mostly of metal oxides are widely known to be hydrophilic, practically all membrane researchers have concentrated on developing ceramic membranes for oily water treatment. Because ceramic membranes composed mostly of metal oxides are widely known to be hydrophilic, practically all membrane researchers have concentrated on developing ceramic membranes for oily water treatment. In addition, the application of Al2O3 MF membrane modified with hydrophilic HL nanosized ZrO2 for oil-water separation was systematically investigated by Zhou, Chang, Wang, Wang, and Technology (2010).

5.3 Advanced absorption based materials Two-dimensional materials such as membranes and meshes have demonstrated success in a variety of industrial settings. They are less helpful for external environmental pollution treatment such as in lakes, rivers, and the open sea. However, 3D pore materials and particles avoid some of these drawbacks since they may be easily deposited on polluted regions and absorb water or oil (Hou et al., 2015; Lu et al., 2021; Wang et al., 2013). As a result, a vast variety of innovative and often hydrophobic three-dimensional porous and particulate systems with unique surface structures or chemical functions have been discovered. Separation efficiency is a measuring of the volume of oil or water as compared to that present in the original mixture by a rejection coefficient R (%), shown in Eq. (5.3):   Vp R% 5 1 2 3 100 (5.3) V0 where R% denotes the rejection coefficient in percentage, Vp is the volume of the separated liquid, and V0 is the volume of the original mixture. There are several ways for functionalizing porous materials for specific applications, including sol-gel functionalization (Zhu & Guo, 2014; Wu, Li, Li, Zhang, & Wang, 2015), dip-coating (Hou et al., 2015; Zhu & Guo, 2014), and nanoparticle addition as shown in Fig. 5.4. FIGURE 5.4 Absorption materials for oil-water separation (Wu et al., 2015; Zhu & Guo, 2014).

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A simple and cost-effective strategy is to employ preexisting foams and sponges as functional surfaces or as a support framework for further synthesis to create 3D porous oil and water separation materials. (Du et al., 2015; Wang & Huang, 2015; Zhang, Li, Liu, & Jiang, 2013; Zhu, Pan, & Liu, 2011). Wang et al. described inexpensive superhydrolphlilic sponges made from melamine which may be temporarily utilized to separate oil/water mixtures using a simple protonation procedure.

5.4 Sol-gel based materials The use of a sol-gel synthesis, since such synthesis is easily porous in particular reaction conditions, is another highly effective approach to the preparation of functional 3D porous materials. Researchers have also employed foams composed of various metals to boost resistance to mechanical and thermal damage and to facilitate manipulation using magnetic fields. Cufoams, as revealed by Zang et al., are particularly susceptible to texturing and functionalization. Mu et al. demonstrated that the one-pot synthesis of Methyltrimethoxysilane (MTMS), Dimethyldimethoxysilane, and tetraethoxysilane (TEOS) created an extremely porous, superhydrophobic silicone sponge of size 6 mm (Mu et al., 2015). The absorbent sponges preserved 95%
98% of their usefulness after 50 cycles and could be maintained at temperatures up to 200 C without losing functionality were 6
14 g/g for various organic liquids (Liang, 2013). Chen et al. presented a new strategy that focused on water-phase absorption. They created Ni-foams covered with a superhydrophilic hydrogel (Chen et al., 2015). The PAM hydrogel was successfully generated by immersing the Ni-foam in an aqueous solution of N, N’-methylenebisacrylamide, N, N’, N’-tetramethylethylenediamine, and ammonium persulfate. The metal foam enabled for magnetic manipulation on a dichloromethane surface to clean up spilt water (Gao, 2014). Hayase, Kanamori, Fukuchi, Kaji, and Nakanishi (2013) also utilized the same process to make comparable methyltrimethoxysilane-dimethyldimethoxysilane (MTMS-DMDMS) gels utilizing a variety of tri- and difunctional alcohoxylic reagents using an aqueous acidcatalytic sol-gel process with an n-hexadecyltrimethylammonium surfactant to increase the material’s porosity. This material absorbed up to 14 g/g chloroform and preserved its absorption and flexibility through a temperature range of 270 C
320 C (Hayase et al., 2013). Yu et al. have synthesized a similar “swamplike” aerogel using the surfactant hexadecyltrimethylammonium bromide by polycondensing methyltriethoxysilane (MTES) dimethyl-diethoxy silane (DMDES) (Yu et al., 2015). These gels exhibited comparable flexibility at room temperature and were also absorbed at a rate of 6.8
16.9 g/g in a variety of organic fluids. A polysiloxane aerogel was prepared using environment friendly synthesis under supercritical CO2 as shown in the Fig. 5.5 (Yu et al., 2015). Sol-gel synthesis may be utilized to generate materials, structures, and frameworks that include polymer species. Chen et al. described the preparation of a water-in-oil mixture gel using a specialized low-molecular-weight gelator, tertiary butyl methacrylate, 3aminopropyltriethoxysilanes, 3-isocyanatopropyltriethoxysilanes, and TEOS (Chen et al., 2014). They discovered that porous monolith architectures may be altered by altering the

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91

FIGURE 5.5 Polysiloxane aerogel prepared under supercritical CO2 (Zou et al., 2015).

oil/water phase ratio and silane addition amounts. Wu et al. modified polyurethane (PU) sponges with commercially available TiO2 to create a sponge with an outstanding capacity of 80
110 g/g for oil/water absorption from a variety of oil/water mixes when immersed in a n-octadecylthiol solution (Wu et al., 2014). Gao, Shi, Bin Zhang, Zhang, and Jin (2014) used single-walled carbon nanotubes and porous carbon nanotube (CNT)/ TiO2 porous nanocomposites to induce a self-reinforcing sol
gel reaction under moderate circumstances. Following calcination at 400 C, TiO2/CNT materials were calculated to be capable of separating both surfactant-stabilized and unstable oil/water mixtures from a variety of organic fluids with an efficiency of up to 99.9%, as well as exhibiting excellent self-cleaning and antifouling properties when exposed to UV light, as organic material accumulated on the substrate was successfully degraded by UV light.

5.4.1 Template based materials Template based methods have been used to synthesize porous materials by using existing framework for any material. Zhang (2013) prepared a superhydrophobic copper foam from a PU sponge using a conductive treatment method which was functionalized by immersing in n-dodecanethiol solution (Zhang et al., 2013). This foam has shown proved excellent hydrophobic nature and by absorption of 98% of oil and water mixtures. Yu et al. adopted a novel strategy by using tiny species to stabilize the emulsion polymerization template (Yu et al., 2015). Amphiphilic carbonaceous microspheres and a trace amount of surfactant was utilized to stabilize an oil-water emollience comprising dissolved PS, divinylbenzene, and an oil-phase initiator. This was utilized to synthesize two distinct kinds of very porous hydrophobic PS monoliths that absorbed toluene with a purity of 98.5% and exhibited absorption capacities of 4,7
33 g/g for a variety of biofluids, depending on the precursor proportions utilized in the synthesis. For example, poly (methyl methacrylate) particles are used as template with different diameters, with a controllable surface ruggedness which has brought a little effect on the water flow of membrane and oil to reject which was used in filtration of oily wastewater.

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5.4.2 Micro nanomaterials More advanced methods for oil and water separation employing columns and other ways have been reported with the use of microparticles or nanoparticles. Okada et al. employed glass beads ranging in size from 1 to 4 mm to create a bed capable of separating oil and water (Okada et al., 1985). These micrometer-scale beads were responsible for considerable coalescing, and the increased separation efficiency was noticed following the formation of an oil layer on the surface of the beads at room temperature due to a reaction between a vinyl-trimethoxy-silane oligomer and fluoroalkyl-capped nanoparticles constituted of vinyl-trimethoxylic/clay. The composition of these components enabled the encapsulation of guest molecules such as 2-hydroxy-4-methoxybenzophe´none, bisphenol A, propane sulfonic acid 3-(hydroxyalkyl), and perfluoro-2-methyl-3-oxahexanicacid for application to textiles, glass surfaces, and even to the PS. When utilized in a column, the composites are employed to separate surfactant-stabilized oil/water mixtures more successfully than typically employed silica gel particles (22 mm diameters) (Oikawa, 2015). In ternary systems of variable proportions each of the two fluid and solid phases of hydrophobe, hydrophilic and unmodified glass or SiO2 particles (0.7
35 mm of diameter) are used. When the particles are wetted in the fluid the aggregation is promoted by wetting the particles with a single fluid in which they form a suspension, and the fluid and particles have the same volume fraction. Thus both weight fractions and volume fractions are to be considered during the seperation of oil and water mixtures.

5.4.3 Nanobased materials The addition of nanoparticles to a porous material improves surface roughness, hydrophobicity and oleophilicity for oil and water separation. Ge et al. reported a simplified approach that used polyfluorowax and polysulfone to make a hydrophobic SiO2 nanoparticle dispersion (10
20 nm) which produced sponges with enhanced compressive strain resistance, and the absorbance capacity for different oils and solvents ranged from 7.5 to 75 g/g, with no significant change for most solvents after 10 cycles (Ge et al., 2015). Cao et al. also described in situ polymer synthesis using PU sponges containing dopamine polymerization, which was then functionalized with 1 H, 1 H, 2 H, 2H-perfluorodecanethiol, to create superhydrophobicity (Cao et al., 2013). These could absorb 15
60 g/g of diverse organic liquids and were not affected by exposure to boiling solvents or high pH solutions (pH 1
13). Carbon nanotubes have also been attached to porous surfaces. In systems with varying ratios of two fluid and solid phases, they utilized hydrophobe, hydrophilic, and unaltered glass or SiO2 particles ranging from 0.7 to 35 mm in diameter. Small particles have been utilized to separate oil and water because they promote emulsion coalescence in a column packing material consisting of glass beads of size 1
4 mm diameter were used to disperse oil and water. The oil coating on the surface of the bead was noticed, which increased coalescing efficacy. With the help of microparticle and nanoparticles, techniques for separating oil and water have become increasingly complex. A vinyl-trimethoxy-silane oligomer was formed by room temperature reaction in the presence of fluoroalkyl-clad nanoparticles consisting of vineyardtrimethoxy/tery. 2-Hydroxy-4-methoxybenzophenone, bisphenol A (3-(hydroxyalkyl),

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and perfluoro-2-methyl-3-oxahexaniccid can be encapsulated and applied to textiles, glass surfaces, and the SP of the guest molecules. The combination of columncombined PS microbeads (size 92 mm) and silica gel (s diameter 22 mm) created a surface-stabilized emulsion of oils/waters. It was shown that occur only when both particles may be partly wetted with both fluids and aggregation facilitated by wetting the particles with a single fluid where they form a suspension. Therefore weight and volume fractions are both critical for these systems using this process. Liu et al. (2015) used polyaniline deposition to build a tougher oil or water separation system. Aniline solution-based oxidation was applied to commercial sponges, stainless steel meshes, and textiles, after which hydrophobium was added to make them more hydrophobic. Gao et al. reported that the metal nanostructures on-site have nickel (Ni) substrate was utilized to build an ammonia evaporation method to produce metal nanoparticles with a diameter between 30 and 100 nm, and nanowire arrays were operationalized using fluoroalkyl siloxane (Gao et al., 2014). These foams initially separated at 99.6%, but after 10 cycles, the rate had dropped to 97%.

5.4.4 Nanocellulose based material For preparing oil-water separation aerogels, cellulose nanotropic fibers were sometimes used which was termed as “Nanofibrillated aerogels” (NFCs) from commercial softwood pulp, with principally 5
20 nm of cellulose nanofibers present (Kong et al., 2016). To carry out a solvent exchange for ethanol, the nanofibers were immersed in a monochloroacetic acid solution for 30 min, heated in a NaOH solution made up of methanol/isopropanol, and then carboxymethylated. The modified cellulose was obtained using CVD after washing, freeze-frying, and vacuum. NFC aerogels can extract waste oil and up to 45 g/g of oil while floating on water. The aerogels are prepared by mixing homogenized wood pulp in water and then freeze dried as described by Korhonen et al. (2013). For hydrophobic qualities, atomic layers were deposited on the aerogels to a 2
3 nm TiO2 layer, which was then repeated to enhance the layer’s thickness. The ice crystals growth caused cellulose fibers to form sheets which improves the stability and 20
40 g/g paraffin oil may be absorbed by the aerogel, after which the gel may be extracted into an organic solvent.

5.5 Conclusion Based on the studies and the practical implication of the materials, it can be determined that its reduction in the environment is the future goal of the researchers. The advance materials which are nanobased are more effective in the sepration of oil and water. Complex formation of nanomaterials will bring more involvement in the implementation. The absorption materials have shown more improvemnt in the absorption of oil and water mixture. More fundamental research is required to achieve better large-scale separation, recyclability, and sustainability of wetting materials. Developing ultrawetting smooth surfaces also takes substantial effort. Scale-up, simple, and cost-effective preparation

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techniques should be implemented. Only a limited number of surfaces are accessible, making separation of huge volumes of mixed oil/water possible using oil and water-repellent surfaces.

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C H A P T E R

6 Impact analysis of oil pollution on environment, marine, and soil communities Shipra Jha and Praveen Dahiya Amity Institute of Biotechnology, Amity University Uttar Pradesh, Noida, India O U T L I N E 6.1 Introduction

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6.2 Composition of petroleum hydrocarbon

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6.3 Sources and fate of oil spill 6.3.1 Weathering 6.3.2 Evaporation 6.3.3 Oxidation 6.3.4 Biodegradation 6.3.5 Emulsification

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6.4.1 Impact on aquatic and terrestrial microbial communities 6.4.2 Impact of oil pollution on fish 6.4.3 Impact on seabird population 6.4.4 Impact on marine mammals and invertebrates 6.4.5 Impact on vegetation 6.4.6 Impact on environment

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103 104 105 106 107 108

6.5 Future prospects and conclusion

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References

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6.1 Introduction Globally, with an increase in population there is an increase in industrial development which requires more energy demand, and oil is most essential fuel to fulfill energy demand. The oil spill becomes threat to human health, destroy the naturals resources and affect the economy (Anisuddiin, Al-Hashar, & Tahseen, 2005; Anthony, 1994). With the expanding technical period, developed countries have become dependent on more oil-based machinery including industrial, pharmaceuticals automobiles, and oil-based home products to enhance

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high living standards (Annunciado, Sydenstricker, & Amico, 2005). In addition to petroleum-based products, various other oil products include animal fats, vegetable oil are also being used worldwide. And these oils also contain harmful components adversely affect human health similarly as petroleum products harm (Alther, 2001). As we use immeasurable quantities, so the oil-based products are stored and transported through large vehicles or by waterways from one place to other. In the course of transporting or storing, sometimes oil spilled into water or onto land and becomes reason for environment and human health at risk (Baker, Crothers, Mulett, & Wilson, 1980). To protect environment and human from oil spill once it occurs, efforts must be made to clean promptly. During the oil spill, the major forecast is its location and quantity of oil. When the event adjacent to community and sea beach have significant economic effect including higher cost cleaning techniques. The oil spill slowly delivers with the time and harm many ways to the surrounding by breaking down of oil molecule cause risk to human population, natural resources and aquatic life (Bernard et al., 2011). There are many aspects which affect the spreading efficiency of oil includes composition, type of oil as animal fat, nonpetroleum oils, petroleum oil, chemical or physical properties, surface tension, viscosity etc. (Bott, Rogenmuser, & Thorne, 1978; Burden, 1991). Based on the release volume of oil on various environment, oil spills are categories into four types includes minor, medium, major and disaster. If crude oil releases in low amount in nature have rare effects on pollution but large quantity of soluble components of hydrocarbon includes xylol, toloul, and benzol causes high risk to land and sea water pollution (Butler, 1989; Carmody, Frost, Xi, & Kokot, 2007; Castro, Iglesias, Carballo, & Fraguela, 2010).

6.2 Composition of petroleum hydrocarbon The occurrence of hydrocarbon takes place in nature in varieties of forms and petroleum mainly composed of major and minor hydrocarbon compounds. The crude oil is formed by breaking down oil or wax into smaller molecules to form petroleum and known as black gold (Chatterjee & Gupta, 2002; Choi & Cloud, 1992). The crude oil formation started millions of years ago when in sea water aquatic animal died along with marine plants and buried, settle down in multiple layers in the form of slit, sand on bottom. With the time due to effect of pressure and heat processes varieties of hydrocarbon starts evolving (Choi, 1996; Daling & Strom, 1999). The crude oil slowly moves underground as it is in the form of liquid and to extract out from earth understanding of oil trap and oil pool is important. The reservoir of oil under the earth is termed as oil pool and when oil vapors are trap by nonporous sandstone associated with other gases to ovoid spreading of oil on earth surface then termed as oil trap (Dave & Ghaly, 2011; Descamps, Caruel, Borredon, Bonnin, & Vignoles, 2003; Etkin, 1999). The hydrocarbon is mainly composed of mixture of carbon and hydrogen containing compound along with mineral salts, minor elements oxygen, sulfur, nitrogen, trace metals includes chromium, nickel. These compounds also contain olefins, polar, aromatic and saturates compounds. The crude oil compounds containing saturates include alkanes in which each carbon is surrounded by hydrogen atoms. Olefins are unsaturated compounds

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containing carbon—carbon double bond and common in refined products. The petroleum oil accounts for about 1%
20% single ring aromatic compounds known as toluene, benzene, xylene and about 0.2%
7% polynuclear aromatic hydrocarbon (Espedal & Johannessen, 2000; Fingas & Fieldhouse, 1994). Polycyclic aromatic hydrocarbon (PAHs) includes those compounds in crude oil which have serious toxicity threat to living organisms. The resins are small polar compound and large polar known as asphaltenes which is part of petroleum industry and contribute majorly during road construction. If the crude oil containing large concentration of asphaltenes responsible to changes the oil behavior. Petroleum can be categorizing into many ways. Initially it produced in long chain kerogen form because below the ground it has not been buried at higher temperature for long term. The kerogen having long chain shows two properties (1) The crude oil made up of long straight chain are thick and molecules are tightly packed and occupies large mass per unit volume. (2) The long chain carbon makes it difficult for molecules to flow fast and pump out harder (Lemiere et al., 2005; Lessard & Demarco, 2000). If the crude oil contains sulfur is highly viscous, then it is also known as young shallow crudes because under the earth crude oil have not buried deeply for long time at higher temperature.

6.3 Sources and fate of oil spill When the spreading of liquid hydrocarbon starts in the environment due to spill event, failure of system, machinery, cleaning of oil tankers, ship safety features, etc. The region closes by hydrocarbon handling resources face the higher risk. Oil spill during various transportation activities may disperse various types of crude oil include petroleum products which acts adversely in ecosystem (Graham, 2010; Janjua et al., 2006). The reason behind oil spill toxicity is the presence of toxic compounds includes PAHs, volatile organic compound etc. Spilled oil does not mix immediately with water instead forms thick layers. The thick layers need to be removed from aquatic ecosystem as responsible to block the various pathways include oxygen, breakdown nervous system in marine animal (Masoora & Sommerville, 2009). The Fig. 6.1 shows direct and indirect impact of oil spill. There are various natural actions includes emulsification, evaporation, weathering, oxidation and biodegradation which works in aquatic environment to reduce the harmful effect of oil spill.

6.3.1 Weathering The action of weathering is the combination of synthetic and physical changes responsible to break down the oil spilled, form a thin layer of oil slick and making the water heavier. Further oil slick undergoes various degradation under the effect of simultaneous process include wave action known as oil weathering process. Once the higher quantity of crude oil spreads on sea surface, it begins to degrade. The weathering process modifies the behavior of oil slick and modifies the life cycle of aquatic biology (Ventikos & Sotiropoulos, 2014).

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FIGURE 6.1 Figure representing direct and indirect impacts of oil spill.

6.3.2 Evaporation The process of evaporation is considered as one of the essential steps for oil spills, but less work has been conducted to understand the chemistry of evaporation. Due to the problem in understanding oil evaporation process because of combination of hundreds of chemical compounds varies with time and from the source. The release lighter volatile substances of oil spill on water surface can vaporize up to 45% of the oil volume. The reason behind evaporating the lighter substance form oil spill includes refined products containing flammable properties in them. The lighter volatile substance may evaporate form water surface in few hours causing less harm to marine environment leaving behind heavier substances of oil includes animal fats, vegetable oils which gather on the water surface. The process requires understanding of mechanism that regulates the evaporation process (Palinkas, Petterson, Russell, & Downs, 2004).

6.3.3 Oxidation When oil comes in contact with oxygen and water to form water soluble compounds, the process is known as oxidation. Oxidation affects thick oil slicks which partially oxidizes, and forms sticky dense tall balls may stay in the environment (Shailaja & D’Silva, 2003).

6.3.4 Biodegradation When oil releases in the aquatic environment, soil, groundwater and rivers responsible for pollution. Biodegradation is the process when microorganisms degrade oil hydrocarbons and uses nitrogen and phosphorous for the growth. A wide range of microorganisms includes bacteria is present in the soil, water and air which actively participate in degradation process in the environment (Stefansson et al., 2016).

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6.3.5 Emulsification During oil spill, oil starts dispersing and floating on the surface of water as free form because oil and water does not easily mix. The oil pool toxicity affects marine ecosystem and wildlife. The emulsifiers include detergents when disperse with oil and water to form small droplets, the process is known as emulsification. Due to the wave action, water trapped inside viscous oil and called as chocolate mousse which stick to the environment for years.

6.4 Oil pollution and its impact analysis 6.4.1 Impact on aquatic and terrestrial microbial communities The impact of petroleum oil in aquatic environment mainly decided by factors including marine geology, temperature, biological activity of sea. During oil spill, petroleum oil disperses on sea water in three ways—a floating form, evaporative and sinking form. In aquatic ecosystem hydrocarbon become a part which disperse in water through oil spill (Wong, Lim, & Nolen, 1997). The microbial population have also adjusted themselves to live in their natural condition even in the presence of contaminant by acquired different response includes gene modification, composition and diversity of microbial population (Varela et al., 2006). Marine ecosystem is linked directly and indirectly to animals, plants and physical environment. If physical environment is affected, then other species also get affected which results in disturbance in the whole ecosystem (Burk, 1977). The result of oil spill containing poisonous substances may minimize with time when the certain poisonous substances vaporize from initial oil spill region without affecting human, plants and animals. Even though some life form may get severely affected as soon as exposed to oil spill depending upon exposure duration include short or long term. All categories of oil include petroleum or nonpetroleum have same chemical and physical properties and affect surrounding environment during oil spill (Peterson et al., 2003). For better understanding of fate of petroleum hydrocarbon in aquatic environment is to know bioavailability and bioaccumulation mechanism. The chemical substance when move or bind to cell membrane or gut lining through physical, chemical or biological processes. Deposition of petroleum oil depends on metabolic modification in entity, duration of exposure, biotic availability of oil and mainly biological and climatic availability (Peterson, 2001). Terrestrial oil spill is a threat for human health including neurological disorder, tumor, disruption of cellular function due to its lethal effect on soil sediments, underground water, fresh water and affecting whole ecosystem if remains untreated. According to research finding, responsiveness of vegetation to oil contaminant also depend on type of root system they contain. As compared to plants containing stock roots, the plants having shallow roots are affected with oil spill. Depending upon the soil composition, bioavailability of hydrocarbon compounds differs either maximum oil compounds absorbed by organic part of soil and reduce bioavailability with low effect on soil microflora. During oil spill event on soil, microflora affect in numerous ways includes mobile genetic alteration in soil contaminated microflora. And if genetic modification expressed then play important role in breaking down biological impurities. In order

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to understand more about natural oil degradation mechanism of microorganism extended research needs to be done. To find out distribution of soil microbial population with their gene activity for breakdown of oil compounds in fertilize rich soil. Table 6.1 represents the various oil spill incidents in history across the globe.

6.4.2 Impact of oil pollution on fish The aquatic environment is full of entity starting from microbes to algae and other forms of life. The primary food producers play role in transferring food to higher organisms and responsible for enriching food with vital nutrients necessary for human health. The aquatic family maintains balance between water and terrestrial food chain (Bly, Colcomb, & Reynolds, 2007). TABLE 6.1 Past incidence of oil spill in history across the globe. S. no. Country

Incident and year

Quantity (tones)

Reference

1

Indonesia

In Malacca Straits spilling crude oil Nagasaki burned out after collision with ocean blessing (1992)

12,000

2

Nigeria

Breakdown of pipeline to one of Mobil’s terminal (1998)

5456

Nnadi, El-Hassan, Smyth, and Mooney (2007a)

3

United States

Argo Merchant oil spill in Nantucket Island (1976)

24,961

Winslow (1978)

4

Trinidad and Tobago

Collision off Tabago during tropical rainfall (1979)

287,000

Hooke (1997)

5

Kuwait

Kuwait crisis after final phase of Iraqi attack (1991)

7,557,935

Quamar and Kumaraswamy (2019)

6

United Arab Emirates

Crude oil leaked after explosion between Baynunah tanker and Supertanker seki (1995)

15,900

Shriadah (1998)

7

Brazil

Oil spilled from refinery (2000)

31,491

Braz (2006)

8

Pakistan

Oil tanker broken up in Pakistan’s Arabian (2003)

10,000

Siddiqi and Munshi (2014)

9

Lebanon

At Jiyeh thermal power station oil spill (2006)

20,000

Khalaf et al. (2006)

10

United States

Oil spill in New Orleans (2008)

8800

11

Nigeria

Oil Explosion in the Niger (2010)

3246

Kadafa (2012)

12

Canada

Little Buffalo HC spill

3800

Chang, Stone, Kyle, Demes, and Piscitelli (2014)

13

United States

Arthur storage tank crude oil spill (2012)

1090

Vanea, Kima, Moss-Hayesa, Turnera, and Simon (2020)

14

United States

Crude oil spill in Magnolia (2013)

680

Juan, Saqalli, Laplanche, Locquet, and Elger (2018)

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The crude oil spill also affects water animal including varieties of fish in many ways; growth and reproduction rate, respiration, gill structure, morphological abnormalities, lethal effect on fish larva. Even at low concentration of oil can affects circulatory system of fish and may cause death in early developmental stage (Hicken, Linbo, Baldwin, Willis, & Myers, 2011). According to the studies it was found that adverse effects of oil spill in case of juvenile growing salmon showed instability and erratic swimming with low and slow movement due to changes in gene expression, tissues, or organs. The cyclic hydrocarbon also interferes with normal development, contractility defect of developing heart (Bellas, Saco-Alvarez, Nieto, Bayona, & Albaiges, 2013).

6.4.3 Impact on seabird population Seabirds are open water creatures that are highly vulnerable to oil spills. Oil spill will harm seabirds such as sea ducks, penguins, alcids, cormorants, etc. Oil spills can influence sea birds during primary oiling, secondary during release of oil and clean-up activities which ultimately results in decreased population size, lower reproductive rates, reduced habitat occupancy, reduced food supply, altered foraging behavior, emigration, and direct/indirect mortality. The primary problem is coating of bird feathers with oil. When swimming in or diving in the oil polluted water the seabirds’ feathers become oiled. The oiled feathers become matted and waterlogged which will destroy the buoyancy and insulation leading to starvation, hypothermia (death due to excessive heat loss) and ultimately drowning of birds. Oil results in alteration of the feather structure and disrupts the systematic arrangement of feather barbules and barbicelles resulting in waterlogged feathers. Preening behavior of seabirds also aggravated the impact of oil toxicity in the case of sea birds encountering polluted waters because the oil will spread to all parts of their plumage. The harmful oil is also ingested when the seabird cleans its feathers by preening. The feeding behavior of seabirds such as Calidris alba and Charadrius semipalmatus after oil spill was reported by Burger (1997). He observed that the bird soaked in oil is spending maximum time preening and is devoting very less time for foraging in comparison to the unoiled seabirds. Spill events at small doses may impact sea birds like alcids which mainly rest and also consume its feed from the sea surfaces. The insulating properties of plumage in arctic seabirds is very crucial as they live in cold conditions, so these birds are highly vulnerable to oil spill pollutions. 6.4.3.1 Toxic effect of oil Seabirds exposed to oil contaminated water will ingest oil during preening and by taking food from the polluted water mainly exposing themselves to toxic hydrocarbons in crude oil. These toxic hydrocarbons include PAHs whose ratio depends on the type of oil and level of weathering. Once ingested, the oil proves highly toxic in the body and can lead to various issues including liver damage, lung damage, affects the kidney function, hemolytic anemia (Troisi, Borjesson, Bexton, & Robinson, 2007), gastrointestinal issues, immunotoxicity (Troisi, 2013) and endocrine disruption (Fowler, Wingfield, & Boersma, 1995; Fry & Lowenstine, 1985). PAHs will enter the circulation resulting in plasma and tissue contamination (Troisi, Bexton, & Robinson, 2006). Even at low doses, the oil ingestion may influence the survival rate and reproduction capacity of seabirds (Lance, Irons, Kendall, & McDonald, 2001). The survival rate of rehabilitated oiled sea birds is observed

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to be unfortunately low in case of common guillemots. PAHs toxicity and almost no increase in weight are observed as the main reason of mortality (Grogan et al., 2012). In birds, thyroid hormone which is in control of HPT axis (hypothalamus-pituitary-thyroid) is important for weight gain, reproduction potential, metabolic activities, thermoregulation and development processes. Exposure of birds to oil may disrupt the HPT axis. Various field experiments performed have shown that slightly oiled adult birds can transfer oil to the eggs while incubation or by its feathers which will ultimately decline the hatching rate and sometimes bird embryo is killed by the contaminated parent. The oil spill will slowly undergo weathering, during which the highly toxic components are evaporated. The oil composition begins to vary with less volatile components and light and biodegradable components. Thus weathered oil is considered to be less toxic compared to fresh oil. Simultaneously, direct exposure (via preening) of seabirds to oil spills also shift towards indirect exposure via food intake. Mallard duck fed on weathered crude oil showed no significant impact on the reproduction potential, growth and survival at those concentrations. Whereas, at subsequently high concentrations of oil in diet (20 g of oil/kg), eggshell thickness and strength was significantly reduced. However, unweathered oil of highly toxic nature remained preserved in the seabed, under rock armor and in mussel beds over quite long period of oil spill incident ultimately impacting some fishes and invertebrates. These oil spills possess long term impact on the seabirds as studied by Lance et al. (2001) who reported that after 10 years of oil spill, only four bird taxa out of 17 showed recovery signs, no recovery was observed in case of nine taxa and four bird taxa showed higher impact of oil spill. This is because of the oil contaminated food available in shallow waters and intertidal zone preferred by seabirds. Increase in water temperature in the particular area may be another factor which will influence the rehabilitation of the seabird taxa (Lance et al., 2001). Some species of seabirds are found more vulnerable compared to others depending on their lifestyle and population regulation. Some birds spend maximum time on the surface of sea swimming or diving and are found to be most vulnerable in case of oil spills in comparison to others which are mostly airborne are less affected. Some birds feed at sea throughout includes diving ducks, various terns, gulls and alcids whereas, other birds feed at sea only for some part of year including grebes, some ducks, phalaropes etc. Seabird populations seriously impacted by oil pollution includes the ones with long lifespan and lower reproductive potential (e.g., alcids and fulmars). Few evidences available suggests that seabird Fulmarus glacialis can deliberately avoid settling on seabed polluted with oil.

6.4.4 Impact on marine mammals and invertebrates In coastal environment, crude oil further breaks in three different components such as volatile, floating and sinking component. Within a week, low molecular weight either dissolve, evaporates or are degraded photochemically. Due to advection and turbulence, the oil gets dispersed on the surface and form emulsion which is commonly named as “chocolate mousse.” This mousse will impact the marine mammals and also suffocate the invertebrates. Gesteira and Dauvin (2000) studied the impact of oil pollution microbenthic sp. and few important observations were made: (1) the crustaceans and amphipods showed maximum mortality rate thus were first to disappear, (2) opportunistic sp., like

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polychaetes increases in number due to increase in quantity of organic matter after 1
3 years after stress, (3) positive and negative effects on population dynamics observed. Physical smothering with oil will impact the respiration rate and movement in the case of invertebrates of benthic and pelagic zones, the extra weight added and shear forces during movement may result in the death of animals. Mussels and barnacles may survive short term impact, but they may suffocate due to a heavy layer of oil. Whereas, crustaceans were reported to move to deeper waters if possible, in case of oil pollution (Bonsdorff & Nelson, 1981). In case of oil spill initially significantly higher mortality rate was reported in all the taxa which will subsequently impact the infaunal species such as amphipods, bivalves and polychaetes. As all the rocky shores are covered by oil it will significantly impact the mobile fauna like crabs, gastropods, amphipods, and echinoderms. If the oil layer is thick it can also smother mussels or barnacles. Some jellyfish and anemones (Anthopleura and Actinia sp.) are found surviving in severe oil pollution. Whereas other Cnidaria like hydroid Tubularia are found very sensitive toward oil spill pollution even at very low concentrations. Oil pollution also impact the marine mammals present in the area of oil spill. Various marine mammals present includes whales, seals, dolphins, fins, sea otters, manatees, cetaceans, pinnipeds etc. Whales and adult seals are found less effected by oiling when compared to seal pups. As whales mainly depend on blubber layer and not its fur for insulation but seal pups depend on their fur for insulation (Geraci, 1990). The oil reaches finally to the pups from their mother seal during nursing. Amongst seals, hooded seal and harp seals are found more vulnerable to oiling than ringed seals (St Aubin, 1990a). If the oil pollution is in between ice then it whales (white and bowhead whales), seals (ringed and bearded seals) and walrus are at higher risk as they live-in ice-covered waters (Boertmann, Mosbech, & Johansen, 1998). Fur is required for insulation in case of polar bear thus the polar bears are sensitive to oil pollution. The oil can be ingested from the fur while grooming (Stirling, 1990). Ingestion of oil is highly toxic which will lead to poisoning. Oiling will subsequently result in hypothermia, drowning and smothering in these animals. Pinnipeds are severely affected due to contamination of shores by the oil. Marine mammals inhale volatile hydrocarbons evaporating from oil which contain extremely toxic benzene, xylene, toluene and aliphatic compounds. Theses toxic vapors result in congestion of lungs, pneumonia and inflammation of mucus membrane. Benzene and toluene once inhaled will enter the bloodstream which will further transfer to the lungs, brain, and liver resulting in damage of liver and neurological problems (Neff, 1988). A few sources of information are available regarding impact of terrestrial oil spills in relation to mammals. Terrestrial mammals can easily smell and see the oil spills therefore it can be easily avoided by them getting in contact with oil. Faulty pipelines break or blowouts from oil wells may lead to terrestrial oil spill, but it is mainly confined to limited area. Cases of huge oil spills are reported from Usinsk, Komi republic in Russia. There are no available reports of such oil spills and their impact on terrestrial mammals. Similarly, oil spills reported from Greenland reported minor impact on the population of caribou and muskox.

6.4.5 Impact on vegetation Phytoplankton’s reported very limited direct impact of oil spill pollution. In the Artic pelagic zone, the impact is not much visible compared to laboratory studies which shown

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response to the toxic compounds of oil. The coastal communities are found severely exposed to contamination due to oil stranding. The stranded oil and its associated toxicity enhance the barren period and reduces the recolonization of that area. Exxon Valdez oil spill, Alaska showed only few survivors like seaweeds and it took two years for polluted shores appeared recovered and gained the pre- oil spill vegetation (Dean, Stekoll, & Smith, 1996). Some studies based on freshwater ecosystems reported that perennial vegetation including emergent, submerged and floating plants are possessing better tolerance capacity and higher recovery potential from oil spills compared to annuals. The impact was even less in case of flowing water in comparison to stationary water. Oil spill is reportedly badly impacting the terrestrial vegetation in Arctic wetland plant communities which shows heavy damage to the plant tissues and similarly mosses were also totally eliminated but, sedges were observed to be the first one to recover. The oil spills will show immediate influence on vegetation cover as within few days of the spill the vegetation turns yellow or brown in color, losing chlorophyll and falling of leaves. Higher susceptibility was reported in case of forbs whereas graminoids possess resistance at mesic sites but were killed when at dry sites. Shrub Salix arctica was found to possess least susceptibility whereas, lichens were found prone to diesel oil. The complete vegetation cover in an area was found drastically reduced in dry/xeric conditions compared to wet/mesic conditions as in dry conditions oil can penetrate the roots easily. The adverse effect of heavy fuel oil pollution was studied on Salicornia fragilis, an edible species in greenhouse studies (Meudec, Poupart, Dussauze, & Deslandes, 2007). In order to analyze the effect of oil pollution on the growth and development of Salicornia, phytotoxicity assessments and PAH shoots assays were conducted. Chemical toxicity due to oil pollution was reported in the form of chlorosis, yellowing and reduction in growth. Shoot tissues showed significant accumulation of PAHs even at lower concentration of contamination which proves toxic impact of fuel oil contamination on the edible species. Huge amount of crude oil spill was reported from the area of coral reefs, mangroves and seagrasses, at the Caribbean entrance to the Panama Canal in year 1986. All the vegetation in the area were covered by the oil like mangroves, sea grasses, algae and associated invertebrates and die within some time. Subsequently at the same site, seedlings of Rhizophoram angle were planted but it failed to survive. Intertidal seagrass (Thalassiat estudinum) could not survive the oil pollution and was found to be dead and floating ashore whereas, the subtidal Thalassia was found to survive the oil spill. The subtidal Thalassia leaves turned brown and are heavily fouled by algae in areas which are heavily oiled. Tarn, Wong, and Wong (2005) reported smuggled oil spill incident and its impact on mangrove plants in Hong Kong. In year 2000, approximately 500 mangrove saplings were contaminated due to fuel oil spill incident that lead to the death of more than 80% saplings. After one year of oil spill, the effected mangrove saplings recovered and regrown from the root-zone sediments with the decreased total petroleum hydrocarbons concentrations.

6.4.6 Impact on environment Accidental oil spillage taking place at higher concentrations will pose a serious influence on the environment unless the oil is diluted/degraded. In the Arctic regions the effect

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will persist for long due to lower temperature and ice when compared to moderate conditions. Similarly, the spread and fate of oil spill in marine conditions is more as it can easily spread to sizeable areas when compared to terrestrial oil spills that are limited to the impact area only. In colder environments, the oil pollution is controlled via different biological and physical features including dispersion, hardening, biodegradation, bioaccumulation, dissolution etc. Few chemical processes like photolysis can also impact the oil pollution but it is insignificant the colder environments. The oil pollution may lead to oiling of all vertebrates, invertebrates and vegetation or ingestion of oil in the gut which will have higher level of toxicity due to low molecular weight compounds (alkanes, aromatics) and PAHs. Oil fate from the oil spill environments are vital to understand and analyze. It largely depends on the surface area covered by oil verses volume of oil. The effectiveness of fate process depends on higher ratio values and the ratio depends on the environmental conditions of that area such as average temperature, storm activity, ice and snow. Temperature is considered to be highly significant factor as it will affect the biological activity, viscosity and density of oil. The oil trapped in rock crevices where surface to volume ratio is quite less will not undergo weathering process and is leading to long term pollution but at lower doses. The fate and transport of oil spill will dictate the environmental impact. It includes (1) formation of oil slicks that are highly resistant towards degradation, during which the oil will collect on water body surface. Evaporation of volatile components will occur when the oil slick comes in direct contact with air, (2) Further with time some more soluble compounds are dissolved, (3) the above mechanisms results in the reduced effect of oil but increases the mobility of oil thus allowing the oil to spread to larger areas which will ultimately complicates the clean-up processes and (4) certain oil components becomes persistent and accumulates in living organisms available and the environment. It will negatively influence the environment as well as shows harmful effects on marine, freshwater and terrestrial life forms.

6.5 Future prospects and conclusion Oil spills can have a significant effect on the environment and various life forms present in the spill area, and thus it raises various guidelines and policy issues related to transportation of oil, remediation and restoration of spill sites in the case of accidents. There is huge risk associated with petroleum and its associated products due to their rising demands across the globe in order to fulfill the ever-growing energy needs. Accidental release of these products will release highly toxic compounds into the marine environment posing challenging conditions for the survival of biological ecosystem. To mitigate the effect of oil pollution, focus should be on effective cleaning up strategies which will limit the chances of secondary pollution. Policies related to contingency planning, mitigation measures, response team for onshore spill and efficient counter measures should be in place to protect the biodiversity and aquatic life before any accidental spill. Various researchers belonging to different domains are constantly working to develop cost-efficient, simple, and environment friendly techniques/materials to understand and resolve the major challenge of oil pollution which includes immobilized lipase enzyme,

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magnetic nanomaterials, techniques for chemical analysis of pollutants, biomarkers etc. Methodologies to analyze the diverse pollutants in the environment are continually evolving and now concentrations of toxic compounds up to parts per trillion can be analyzed. The oil contaminant responsible for causing pollution can be quantitatively analyzed via Gas Chromatography linked to Mass Spectrometry analysis. Biomarkers are used to analyze the PAHs present in animals due to crude oil pollution. Ethoxyresorufin O-deethylase activity can detect the enzyme level in liver tissues which is a highly sensitive technique for analysis of PAH exposure level. Enzyme lipase can catalyze the breakdown on oils and fats. Lipase isolated from Pseudomonas sp. was immobilized on charcoal and sawdust by adsorption which was utilized for the biodegradation of crude oil. Nanotechnology has also opened new approaches of using magnetic materials and checking its capacity as adsorbent for oil spill. The magnetic adsorbent materials are also utilized in repair work related to oil leakage. Various new strategies are coming up, but these must be scientifically proven via laboratory and field experiments. Further research is required in all the above-mentioned techniques, key variables to be incorporated in integrated models which can provide us a better insight of oil spill and its impacts in particular zones/areas. These models will consider oil dispersion as well as its impact on economy, ecology and human health. Such models can answer all critical questions related to pre and postoil spill incidents. It is of immense attention for planners and policy makers to get an insight from these models for decreasing the occurrence of oil spill events, supports immediate and effective response and recovery measures.

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C H A P T E R

7 Impact of oil exploration and spillage on marine environments Ankita Thakur and Bhupendra Koul School of Bioengineering and Biosciences, Department of Biotechnology, Lovely Professional University, Phagwara, India O U T L I N E 7.1 Introduction

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7.3 Types of oils 118 7.3.1 Group 1: nonpersistent light oils (gasoline, condensate) 118 7.3.2 Group 2: persistent light oils (diesel, no. 2 fuel oil, light crudes) 118 7.3.3 Group 3: medium oils (mostly crude oils, IFO 180) 118 7.3.4 Group 4: heavy oils (heavy crude oils, No. 6 fuel oil, bunker C) 118 7.3.5 Group 5: sinking oils (slurry oils, residual oils) 118 7.4 Causes of oil pollution 7.4.1 Natural cause 7.4.2 Anthropogenic activities

119 119 119

7.5 Harmful effects of oil pollution 120 7.5.1 Effects of oil pollution on aquatic ecosystem 121

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00018-5

7.5.2 Effects on marine flora 7.5.3 Effects on marine fauna

121 121

7.6 Bioaccumulation and biomagnification: marine chemistry 127 7.6.1 Toxins in the marine food chain 127 7.6.2 Bioaccumulation and biomagnification of hydrophobic organic compounds in fish 128 7.6.3 Biomagnification and bioaccumulation of mercury in an arctic marine food web 128 7.7 Remedies to cope up with oil pollution 7.7.1 Physical methods 7.7.2 Chemical treatment 7.7.3 Bioremediation 7.7.4 Natural recovery

128 130 130 131 132

7.8 Conclusion

132

References

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7.1 Introduction Literally, pollution relates to the entry of harmful substances (pollutants) into the environment. This term has become so common that almost everyone including kids are aware of and acknowledge the fact that pollution is rising continuously. When we talk about “pollution on Earth,” we refer to the contamination that is happening because of natural or anthropogenic activities. In an ecosystem, there could be multiple forms of contamination; streams loaded with toxic chemicals due to the discharge of industrial effluents, water-bodies overloaded with nutrients from agricultural fields, litter blowing away from landfill sites, cities enveloped in smog etc. Moreover, landscapes that seem to be natural can deteriorate due to the source of pollution located in the vicinity or even hundreds or thousands of miles away. All this is mainly caused by human activities that harm the environment in so many ways (Larramendy and Soloneski, 2015). Oil is the most indispensable commodity in the world for energy production. Due to its uneven distribution, it is transported by ships over the oceans and by pipelines across the lands. While transferring the oil to vessels, it results in several accidents, during transportation, also breaking of pipelines, as well as while drilling in the earth’s crust. As a result of an accident or human error, contamination of seawater due to an oil pour is termed an oil spill (Kaushik, 2019). An extensive amount of oil enters the coastal region by accidental spill, continuous discharge, and custom activities. It is obvious that oil is toxic for many marine organisms but the present information does not provide a clear understanding of environmental destruction that comes from oil pollution (Howarth, 1989; Gros et al., 2014) During this extensive phase of oil exploitation in the marine environment, the adverse effect of the same has been recorded in various aspects (Elmgren et al., 1983; Fukuyama et al., 2000; Kurylenko and Izosimova et al., 2016). Thus oil spills are of great concern due to the tremendous economic loss and the long-term, notable harm to marine ecosystems, regional economy, coastal society, and communities (Clark, 1982; Brussaard et al., 2016; Zhang et al., 2019). The fishing vessels, ferryboats, or recreational ships are comparatively smaller in size but are a major cause of pollution, contributing little by little. Oil is an indispensable commodity and a major revenue-generating resource for many countries with immense oil reserves. Therefore transporting oil from the sea can never be put to an end; rather we need to look for safer driveways. Moreover, we must be ready for any emergency associated with an oil spill and oil clean up from the sea. A novel approach need to be adapted that may provide a complete solution to combat oil spills (Yuan & Chung, 2012).

7.2 Types of pollution Pollution can be categorized into five major types. Table 7.1 shows the source, impact, and possible remedies for each type of pollution.

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7.2 Types of pollution

TABLE 7.1 Types of pollution along with their sources, impact, and solutions. Types of pollution Type of S. no. pollution

Sources/causes

Impacts

Solution

1.

Air pollution

Burning of fossil fuels, exhaust from factories and industries, mining operations, agricultural activities

Respiratory illnesses and allergies ranging from coughs to asthma, cancer or emphysema, Acidification

Replacing fossil fuels with alternative energies like solar, wind and geothermal, Ecofriendly transportation, green building

2.

Water pollution

Sewage, industrial waste, private waste, mining, oil leakages, dumping, fossil fuels, chemical fertilizers, pesticides, leak of sewer lines, radioactive garbage

Effects on humans, animals, plants, water animals and plants. Disruption of the food chain, diseases, eutrophication, destruction of whole ecosystems

Responsible use of fertilizer and pesticides, Discourage firms from disposing of their trash in rivers, lakes or oceans, Replace fossil fuels by renewable energies

3.

Soil pollution

Phenomena such as erosion, loss of organic carbon, increased salt content, compacting, acidification and chemical pollution

Damage to health, poorer harvests, climate change, desertification, decline in soil productivity and loss in crop diversity

Produce home compost, improve urban planning, transport planning, and wastewater treatment, improve management of mining waste, implementation and assessment of sustainable land and soil management.

4.

Noise pollution

Industrial sources, transport vehicles, household, public address system, agricultural machines, defense equipment

Noise induced hearing loss, high blood pressure, heart disease, sleep disturbances, and stress, impairments in memory, attention level, and reading skill.

Avoid of noisy leisure activities, installing noise insulation in new buildings, creating pedestrian areas, replacing traditional asphalt with more efficient options that can reduce traffic noise by up to 3 dB, among others.

5.

Thermal pollution

Water as a cooling agent in power, manufacturing and industrial plants, soil erosion, deforestation, runoff from paved surfaces, retention ponds, domestic sewage

Decrease in DO (dissolved oxygen) levels, increase in toxins, loss of biodiversity, ecological impact, affects reproductive systems, increases metabolic rate, migration

Cooling ponds, cooling towers, artificial lake, water recycling, the thermal discharge of power plants can be used in other purposes like: Industrial and space heating, soil warming, Fish culture, livestock shelters and heating greenhouses.

6.

Radiation pollution

Nuclear accidents from nuclear energy generation plants, the use of nuclear weapons as weapons of mass destruction, use of radioisotopes, mining, spillage of radioactive chemicals, tests on radiation, cosmic rays and other natural sources, nuclear waste handling and disposal

Genetic mutations, diseases, soil infertility, cell destruction, burns, effects on wildlife, effects on plants, effects on marine life

Proper method of disposing of radioactive waste, proper labeling, banning of nuclear tests, alternative energy sources, proper storage, reusing, precautions at the personal level

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7.3 Types of oils When spilled, the different types of oil can affect the environment differently. They can also be grouped as per the extent of labor/trouble required to clean up. Spill responders group oil into five primary groups. Each group oil along with its characteristics are mentioned below.

7.3.1 Group 1: nonpersistent light oils (gasoline, condensate) • • • • •

Highly volatile (evaporate within 1
2 days). Does not leave a residue behind after evaporation. High concentration of toxic compounds. Restricted, severe impacts on the water column and intertidal resources. Cleanup can be hazardous due to high flammability and toxicity.

7.3.2 Group 2: persistent light oils (diesel, no. 2 fuel oil, light crudes) • • • •

Slightly volatile; leave residue (up to one-third of spill amount) after a few days. Presence of moderate concentrations of toxic compounds. Long-term contamination potential. Cleanup can be mapped efficiently.

7.3.3 Group 3: medium oils (mostly crude oils, IFO 180) • • • •

About one-third will evaporate within 24 h. Oil contamination of intertidal zones can be severe and long-term. Oil impacts on waterfowl and fur-bearing mammals can be severe. Cleanup most efficient if managed promptly.

7.3.4 Group 4: heavy oils (heavy crude oils, No. 6 fuel oil, bunker C) • • • • •

Little or no evaporation or dissolution. Heavy contamination of intertidal areas. Severe impacts on waterfowl and fur-bearing mammals. Long-term decay of sediments possible. Shoreline cleanup is difficult under all circumstances.

7.3.5 Group 5: sinking oils (slurry oils, residual oils) • Will sink in water. • If spilled on the shoreline, the oil will behave similarly to that of heavy oils. • If spilled on water, oil usually sinks swiftly enough that no shoreline contamination occurs. • No evaporation or dissolution when immersed. • Severe impacts on animals living in bottom sediments, such as mussels.

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• Long-term contamination of sediments possible. • Can be eliminated from the bottom of a water body by dredging.

7.4 Causes of oil pollution Oil spills may originate from natural or anthropogenic activities.

7.4.1 Natural cause Oil exists in various environments and may be naturally spilled due to multiple factors. Such natural oil spills may occur in oceans due to the decaying of sedimentary rocks at the bottom of the ocean. However, the major natural cause of oil pollution is oil seep also known as petroleum seep. An oil seep is a natural leak of crude oil and gases from the depth of the ocean. Seeps occur when crude oil leaks from the crevice and sediments of the seafloor and migrate up. The seep oil varies in appearance depending upon the place, weather, condition of the sea, and rate of the flow. The consistency of the seep can be thick, sticky, tar-like in others it is dark like used motor oil. The seeped oil behaves exactly like spilled oil which is spread by the water currents and wind, which later on form mats and tar balls.

7.4.2 Anthropogenic activities Anthropogenic causes—including accidental oil spills as well as leaks and spills due to a large variety of human activities associated with oil refining, handling and transport, storage, and use of crude oil and any of its distilled products. Thus it is evident that a variety of sources for oil spills and a variety of ways the oil could be spilled exist. While numerous anthropogenic and natural sources of oil spill pollution determine the type and amount of oil spilled, as well as the location of the oil spill, the type of the oil spill pollution is important for the fate and transport of the spilled oil and its impact on humans and the environment. Moreover, numerous climate determinants and natural disturbances can generate oil spills, the main causes of oil spill pollution are usually of anthropogenic origin. The most ordinarily found anthropogenic sources are the following: 7.4.2.1 Accidental spills Accidental spills may occur in various circumstances, most often during the following activities: 7.4.2.1.1 Storage

Oil and oil products may be stored in different ways including underground and aboveground storage tanks; such containers may develop leaks over time. 7.4.2.1.2 Handling

Oil may leak/spill during transfer operations for various uses.

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7.4.2.1.3 Transportation

There could be large oil spills (up to millions and hundreds of million gallons) on water or land through accidental rupture of big transporting vessels (e.g., tanker ships or tanker trucks). For example, the Exxon Valdez spill was a massive oil spill off the Alaskan shoreline due to ship failure which happened in 1989. Major oil spillage like these have longterm effect on our environment, while several minor oil spills, through pipelines and other devices also impact significantly. 7.4.2.1.4 Offshore drilling

Offshore drilling/oil platform/offshore platform is a mechanical process of extracting petroleum and natural gas that lies in rock formation underneath the seabed. The offshore drilling equipment is a large structure that facilitates well drilling to extract, process, and store petroleum and natural gas. 7.4.2.1.5 Routine maintenance activities

The most common cause of oil spills are accidents concerning pipelines, tankers, pieces of equipment, or storage facility. Fortunately, these accidents are often preventable. Proper maintenance secures that oil-related equipment is in good working order and can also serve in cleanup endeavors. 7.4.2.1.6 Road runoff

Road runoff pollution appears when pollutants from oil spills and brake wear of vehicles build up on roads and are then washed into nearby rivers when it rains. Road runoff is a significant source of oil pollution because it includes a large number of different substances, all potentially dangerous. Trace metals, hydrocarbons and other organic pollutants carried into the river pose a significant threat to river health. 7.4.2.2 Intentional oil discharges Intentional oil discharges are not necessarily malevolent. Most of them occur in the following circumstances: (1) Through drains or in the sewer system. This includes any regular activities such as changing car oil if the replaced oil is simply discharged into a drain or sewer system, and (2) Indirectly through the burning of fuels, including vehicle emissions; they release various individual components of oils and oil products, such as a variety of hydrocarbons (out of which benzene and PAHs could pose serious health risks).

7.5 Harmful effects of oil pollution In the last few decades, the problem of oil spills and their consequences has brought significant attention. When an oil spill occurs, it causes a plenitude of problems for the environment and us. Oil spills have individual effects on the environment and the economy. On a primary level, oil spill impacts degrade waterways, marine life and plants, and animals on the land. Cleansing an oil spill is quite expensive and the expenses get circulated to government agencies, nonprofits, and the oil transport company itself. Every time

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an oil spill befalls, the public loses faith in the oil company’s capability to manage this critical but needed product.

7.5.1 Effects of oil pollution on aquatic ecosystem Oil spills can cause a wide range of impacts on the marine environment and are often portrayed by the media as “environmental disasters”. When the oil is spilled into an aquatic environment, it can harm organisms that live on, around, and beneath the water surface by both chemical toxicity and by coating and suffocating wildlife. Petroleum contamination is a thriving environmental solicitude that harms both terrestrial and aquatic ecosystems.

7.5.2 Effects on marine flora Plants most affected by the oil spills grow near the shore or in the marshes. Mangrove trees growing alongshore or in the marshes and coral reefs can suffocate in heavy pollution. Marine algae and seaweed respond variably to oil, and oil spills may result in dieoffs for some species. Algae may die or become more abundant in response to oil spills. Although oil can prevent the germination and growth of marine plants, most vegetation appears to recover after cleanup. Any effect on the marine plants weakens the entire food chain and massive loss of phytoplankton in large oil spills will have a profound effect on marine plants and ultimately on the food chain.

7.5.3 Effects on marine fauna 7.5.3.1 Impacts of oil spills on vertebrates 7.5.3.1.1 Fishes

Oil spills harm fishes in multiple ways; including increased mortality, kill or induce sublethal loss to fish eggs and larvae for example, morphological malformations, reduced feeding and growth rates, increase vulnerability to predators and deprivation, habitat degradation, loss of hatching ability of eggs, defiling of gill structures, impaired reproduction, growth, development, feeding, respiration (Rice et al., 1984; Incardona et al., 2014; Langangen et al., 2017). 7.5.3.1.2 Birds

Exposure to oil can have damaging repercussions on bird health and behavior, and when consumed can prompt harm to the lungs, liver, and kidney. One of the common results of oil on birds is the entrapping of their feathers which alters the feather microstructure. Entrapping causes the organisms to lose their floating and flying ability due to compressed plumage and permits water to contact the skin causing hypothermia and ultimately death; especially during cold weather. Birds flashed to oil experience impaired health such as ulcerations, embryotoxicity, cachexia, hemolytic anemia, and aspergillosis, etc. (Finch et al., 2011).

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7.5.3.1.3 Mammals

Marine Mammals are most exposed to oil on the sea surface and shoreline causing adenoidal tissue damage, low immunity, lung, and adrenal diseases. Sea otters have their fur soiled which blocks insulation and water repellence. Dolphins, sea turtles, and whales are known to breathe at the sea surface and ingest oil after an oil spill ending in respiratory irritation, skininflammation, emphysema/pneumonia, gastrointestinal inflammation, ulcers, bleeding, diarrhea, and may induce damage to different organs (Drabeck et al., 2014; Venn-Watson et al., 2015; Van Dolah et al., 2015). 7.5.3.2 Impacts of oil spills on invertebrates 7.5.3.2.1 Crustaceans

Marine crustaceans are divided into planktonic (open waters, free-living, ability to move) and benthic (deep sea, terrestrial, estuaries, mobile, attach to substrates and rocky areas). Crabs are often susceptible to oil toxicity due to the oil coat formation on their body surface which cause suffocation. Moreover, feasting on oil-polluted debris causes blockage in their gills. 7.5.3.2.2 Molluscs

Mussels accumulate oil in their gills through filter-feeding, which exposes their tissues to a high level of PAH (Polycyclic aromatic hydrocarbons). The constant accumulation of oil exposes mussels to change in the cell structure, decreased overall immunity, weakened development, gamete alteration, and DNA destruction. Mussels lose their nutritive value and deteriorate the marine food web as they are the major food source for other organisms in the marine ecosystem (Bellas et al., 2013). 7.5.3.2.3 Zooplanktons

Zooplankton is an important food resource, especially for whales. It can affect or constrain the primary productivity by top-down effects in return. Some zooplankton, such as copepods, euphausiids, and mysids, assimilate hydrocarbons directly from seawater and by ingesting oil droplets and oil-contaminated food. The ingestion of oil by these organisms frequently induces mortality, while the organisms that survive often show developmental and reproductive irregularities (Antonio et al., 2011; Jiang et al., 2012; Almeda et al., 2014). Due to the inefficiency of zooplanktons to move against currents, they tend to be stranded in oil-polluted waters and are prone to reduce physiological functions and mortality. Free-floating embryos and larvae that encounter oils exhibited miniaturized physiological functions such as growth, egg production, nutrition which eventually affects the health of the matured communities (Rodrigo et al., 2013). 7.5.3.3 Effects of oil pollution on wildlife Oil causes harm to wildlife through physical contact, ingestion, inhalation, and absorption. Floating oil can contaminate the plankton, which includes algae, fish eggs, and the larvae of various invertebrates. Fish feeding on these organisms can subsequently become contaminated through ingestion of contaminated prey or by direct toxic effects of oil. Larger animals in the food chain, including humans, can consume contaminated organisms as they feed on these fish. Although oil causes immediate effects throughout the entire spill area, it is the external effects of oil on larger wildlife species that are often immediately apparent.

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7.5.3.3.1 Birds

• External effects • External effects of oil are the most prominent and are the most rapidly debilitating. Oil, by disrupting the interlocking structure of feathers, damages the waterproofing properties of the external feathers and soaks the downy insulating layer. • This in turn can lead to: • Hypothermia by lessening or eliminating the insulation and waterproofing attributes of feathers. • Sinking or swamping as oiled feathers weigh more and cannot entrap sufficient air to keep the birds buoyant • Risk of predation, as feathers coated with oil decrease a bird’s ability to fly away. • Internal effects • The internal effects of oil on birds might not as visually apparent as the external effects are evenly life-threatening. Birds can ingest or gasp oil as they try to spruce oil from their feathers or dine on a tainted food source. Depending on the type of petroleum product, its weathering stage, and its toxicity, poisoning through ingestion can vary from sublethal to acute. • Ingestion of oil usually results in injury to the gastrointestinal tract, blocking the animal’s digestive system from processing food or water and prompting the animal to become progressively more vulnerable in a very short period. • Inflammation of other mucosal exteriors can be seen, such as ulceration of the eyes and the moist areas inside the mouth. • Kidney damage is believed to occur as a direct effect of the toxins in the oil and as a secondary effect of critical dehydration. As an oiled bird becomes more debilitated, its immune system is affected because of which the bird becomes susceptive to bacterial and fungal infections. • The oil may also influence the efficacy of those birds that survive the oil spill to reproduce. Breeding and incubating response, number of eggs laid, the fertility of the eggs, and shell thickness may all be affected. 7.5.3.3.2 Marine mammals

• External effects • The external effects of oil on marine mammals including sea otters, sea lions, seals, walruses, sea cows, polar bears, dolphins, porpoises, and whales, vary, depending on the species but may include: • Hypothermia in polar bears, sea otters, and fur seals pups, are caused by reduction or damage to the insulation of their thick fur. Adult fur seals have blubber and are therefore less likely to suffer from severe hypothermia if oiled. • Skin lesions are a problem for dolphins and whales that swim through oiled areas as they do not have any fur on their body • Eye irritation is a problem for all marine mammal species exposed to oil • Marine mammals, especially seal and sea lion pups, become easy prey while oil sticks their flippers to their bodies, making it hard for them to evade predators; fur seal pups can drown in this situation

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• Marine mammals lose bodyweight when they cannot serve due to contamination of their environment by oil • The scent that seal and sea lion pups and mothers rely on to recognize each other gets concealed, leading to denial, abandonment, and starvation of the pups. • Infection or poisoning in manatees and trouble eating due to oil spiking of the sensory hairs around their mouths • Abridged ability to hunt due to fouling of the baleen of surface feeding whale species • Internal effects • Internal effects further differ by species but may include: • Obstruction of lungs and impaired airways from inhaling of oil vapors and droplets • Emphysema and pneumonitis are common in most marine mammal species but a special concern is for sea otters that spend much of their time on the surface and cetaceans who come to the surface to breathe. • Kidney, liver, and brain damage, as well as anemia and immune suppression, are implied side effects of ingestion and inhaling of oil • Gastrointestinal ulceration, anemia from damaged red blood cells, and injury to mucous membranes. 7.5.3.3.2.1 Sea turtles

• External effects • Sea turtles can grow poisoned when they arise to the surface to breathe and discover themselves amid an oil slick. • During the breeding season, females may become oiled when they appear in the contaminated area or when they arrive at the seashore to lay eggs. • Juveniles may display greater risk of inhaling and ingesting the oil as they get captured in oil when they travel to sea after hatching. • Internal effects • Poisoning by ingestion of toxic ingredients through the skin, leading to damage to the digestive tract and other organs • Damage or irritation to airways, lungs, and eyes • Infection of eggs, which may inhibit their maturation • Consequence assessment results from the deep water horizon spill in the United States, which happened during sea turtle nesting and hatching season. 7.5.3.3.2.2 Seals

• External effects • Seals (true seals, sea lions, fur seals, and walruses) are flashed to oil pollution because they employ enough of their time on or nearby the water surface. They need the surface to breathe and frequently wriggle out onto beaches. • During an oil pollution incident, they are at risk both when surfacing and at hauling out. • Fur seals are more defenseless due to the possibility of oil adhering to their fur which will result in the fur losing its insulating ability. • Due to the heavy oil coating on fur seals they may exhibit diminished swimming strength and lack of movement when the seals are on land. • Internal effects

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• Seals may also get infected through the ingestion of oiled food or the inhaling of oil droplets and mists. • Light oils and hydrocarbon vapors, will strike revealed sensitive tissues. These involve mucous sheaths that envelope the eyes and line of the oral cavity, respiratory surfaces. • This can produce conditions like corneal abrasions, conjunctivitis, and ulcers. Consumption of oil-contaminated prey could guide to the accumulation of hydrocarbons in tissues and organs. 7.5.3.3.2.3 Polar bear

External effects The polar bear is an apical predator and a generic image of the Arctic. Petroleum exploration and extraction have been in motion along the coast of northern Alaska for more than 25 years. Contact with oil spills can reduce the insulating effect of the bear’s fur. They must then use more energy to keep themselves warm and balance it by increasing their caloric intake, which may be difficult. Polar bears are known to groom themselves regularly to sustain the insulating properties of their fur and an oiled bear would be expected to ingest significant quantities of oil during grooming. Oiling of fur and associated thermoregulatory stresses. Internal effects While combing an oil-contaminated fur (self-grooming) or feeding on an oiled prey, they may consume the oil which may culminate in the death of polar bears. 7.5.3.4 Impact of oil pollution on human health Oil and gas has remained the powerhouse of the world economy for more than 100 years. Notwithstanding this, we understand little regarding the health consequences of spills and purposefully executed oil waste. Studies associated with biomarkers have revealed major irretrievable harm to humans exposed to oil and gas spills. These outcomes can be grouped into respiratory damage, liver damage, lowered immunity, enhanced cancer risk, reproductive impairment, and higher levels of unspecified toxins. Webb et al. (2016), conducted a study that revealed that men who had worked cleaning up the spill had twice as mercury in their urine as did men who had not been involved in the struggle to restore the inlet in which the oil had deteriorated. Mercury damages the brain and the liver. Each time a pipeline ruptures or a waste pit drains, we can suspect that the people in the vicinity may get affected with mercury, through the contaminated water, the fish they eat, and the air they breathe (Fig. 7.1). Oil spillage is enduringly harmful to human health and as well as animals. Oladejo and Onyejiaka (2017), proclaimed that there is a relationship between vulnerability to oil pollution and the progress of health problems. Drinking water from polluted sources or consuming marine creatures such as fish, oysters, mussels, etc., automatically brings in high levels of carcinogenic chemicals. Other conditions associated with the carcinogenic chemicals include respiratory difficulties, skin diseases such as rashes or dermatitis, gastrointestinal dysfunctions, eye problems, water-borne diseases, and neuronal predicaments joined with an unhealthy diet. 7.5.3.5 Effect of oil pollution on economy Infection of waterfront areas with high convenience value is a constant trait of many oil spills. In addition to costs incurred by cleanup activities, serious economic losses can be experienced

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FIGURE 7.1 Effect of oil spill on human health.

by industries and individual’s dependent on coastal resources. Ordinarily, the tourism and fisheries divisions are where the greatest repercussions are felt. However, there are also many other business activities and sectors that can potentially suffer disruptions and loss of earnings. 7.5.3.5.1 Tourism

Separation of recreational ventures such as swimming, sailing, angling, and diving induced by oil-contaminated shores is ordinarily relatively short-lived. Once shorelines are clear, normal sales and actions would be expected to continue. Still, more long term and damaging commercial impacts can befall when the communal judgment of extended and wide-scale pollution remains long after the oil has gone. In these circumstances, it takes an even longer period for business activities to return to normal, sometimes with far-reaching consequences. 7.5.3.5.2 Fisheries and mariculture

Fishing formations can be influenced by spilled oil, both as a result of contamination of containers and by fishing bans. Oil spills can produce serious harm to fisheries and Mariculture sources. Physical poisoning can affect stocks and obstruct business ventures by staining gear or hindering access to fishing sites. The degree to which economic results will be felt by the fisheries division following an oil spill will depend on numerous factors such as the characteristics of the spilled oil, the details of the episode, and the type of fishing activity or business affected. The physical characteristics of the marine environment and coast also play a role in determining the range and extent of economic impacts.

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7.5.3.5.3 Other industries/businesses affected by marine oil spills

Heavy production that relies on seawater for common services can be at high risk, particularly if water consumptions are near to the surface. If such plants are accountable for satisfying needs on a social scale, disturbances can be far-reaching. Other types of coastal industry such as shipyards, ports, and harbors can also be disrupted both by oil spills and consequent cleanup services.

7.6 Bioaccumulation and biomagnification: marine chemistry Petroleum or crude oil is one of the most common pollutants released into the marine environment (Wang et al., 2019). Increasing global power demand has increased in the quest for and shipping of crude oil in the sea, making marine ecosystems uniquely susceptive (oil pollution cycle) to the increased risk of crude oil spills (Fig. 7.2).

7.6.1 Toxins in the marine food chain Chlorinated hydrocarbons including polychlorobiphenyls, and DDT derivatives, bioaccumulate, and biomagnify as they move up the marine food chain; from phytoplankton to copepods to fish to seals to killer whales. These hydrocarbons are fat-soluble and are not

FIGURE 7.2 Oil pollution cycle.

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generally metabolized. Rather, they collect in the blubber of aquatic creatures with the conclusion that killer whales have multiple thousands of events the level of toxins than plankton. Researchers have documented that migrating whales and inhabitant whales in the Gulf of Alaska are genetically distinct populations. While some visitors travel throughout the Gulf and prey mostly on marine mammals, citizens usually have a more limited range and prey essentially on fish.

7.6.2 Bioaccumulation and biomagnification of hydrophobic organic compounds in fish Biomagnification of hydrophobic organic compounds (HOCs) increases the ecoenvironmental hazards. Dietary uptake models influence bioaccumulation and biomagnifications of HOCs in fish. Wang et al. (2019) indicated that in addition to the well-known lipid
water partitioning, the bioaccumulation of HOCs in fish is also an irregular kinetic process created by the inconstancy of HOC concentration in the gastrointestinal tract as a result of the discrete food ingestion. The discontinuity and randomness of dietary uptake can partly explain the differences among aquatic ecosystems concerning biomagnifications for species at similar trophic levels and provides new insight for future analysis of bioaccumulation data for fish.

7.6.3 Biomagnification and bioaccumulation of mercury in an arctic marine food web Several recent studies have shown that the use of delta 15N analyses to characterize trophic relationships can be useful for tracing contaminants in food webs (Atwell et al., 1998). Most vertebrates show greater variance in mercury concentration than invertebrates, and there is a trend in seabirds toward increased variability in mercury concentration with the trophic position. Within species, no confirmation of bioaccumulation of mercury with age in the muscle tissue of clams (Mya truncata) or ringed seals are found.

7.7 Remedies to cope up with oil pollution Oil is one of the most copious pollutants in the oceans. According to marine insight, about 3 million metric tons of oil pollutes the oceans yearly. Oil spills fluctuate in their cruelty and the degree of destruction they cause. This can be charged to disparities in the oil type, the location of the spill, and the weather circumstances present. The spread and behavior of spilled oil in the seas is governed by a variety of chemical, physical, and biological processes. The first step to tackle the oil spill is to restrict the oil spill from its loading. This typically involves preparing the units and accompanying standard systems while leading the ships to the port, moving through small channels, and staying on the designated path for the course. In case of any spill, there are diverse clarifications measures based on the quantum of the spill and the area of the spill (Table 7.2 and Table 7.3).

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7.7 Remedies to cope up with oil pollution

TABLE 7.2 Methods for cleaning up spilled oil. Methods for cleaning up Sr. no. oil

Pros and cons

When to use

Inexpensive, effective, but hard to control and still poses risks on human health

Bacteria needs to be readily available, when other methods will cause harm to natural environments

1.

Bioremediation (use of biological agents to break down or remove spilled oil).

2.

Controlled burning/in situ Reduces oil but can cause wind burning pollution

Large oil slick, when human health is not at risk

3.

Dispersants (cause the oil Separates the oil slick, but still slick to break up and disband) pollutes the water

Large oil slick, bacteria needs to be readily available

4.

Vacuum and centrifuge (collects and separated the oil and water)

Effective method, but can disturb the natural environmental with heavy clean up machinery

When oil is floating, when oil can easily be collected, when location allows access

5.

Natural attenuation (method of allowing the natural environment to)

Used in ecological sensitive areas like wetlands

When other methods will disrupt the natural environment

6.

Dredging (for oil that is dispersed with detergents)

Eliminates oil by physical removal, but can only be used for oils denser than water and can disrupt the surrounding environment.

When the environment allows access, when oil has been removed from the top layer of sediment but still exists below.

7.

Skimming (traps spilled oil Effective method, but requires calm When oil is floating, easy to surround for later separation) waters at all times during the the oil, clam winds and ocean current process of skimming

TABLE 7.3 Equipment used for cleanup operations. Sr. no. Oil spill clean up equipment

Description

1.

Booms

Floating connected barriers that gather the oil for easy collection, can relocate oil floating on ocean’s surface, can be used as a sorbent as well

2.

Oil skimmers

Skims the oil floating on the ocean’s surface for Collection and separation.

3.

Oil sorbents

Large solid absorbents that absorbs oil, can be chemical and natural forms

4.

Chemical and biological agents

helps to break down the slick oil, and disperse the oil for later collection

5.

Vacuums

Removes spilled oil from fouled coastlines and Ocean surface.

6.

Shovels, tractors, bulldozers, conveyor belts, and other road equipment

Manual labor tools used to clean up/collect oil on beaches

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7. Impact of oil exploration and spillage on marine environments

7.7.1 Physical methods 7.7.1.1 Oil blooms Oil booms are the most popular and recommended equipment employed in oil cleansup due to their more simplistic design and smoother performance. These are also perceived as containment booms that confine the oil to a more petite area and check it from spreading further. Tools termed containment booms act like a barrier to prevent the oil from additional spreading or drifting away. Booms float on the water surface. 7.7.1.2 Skimmers Once the oil is surrounded by oil booms, it can be extracted or skimmed easily with the direction of skimmers or oil scoops. Skimmers are devices specifically produced to suck up the oil from the water surface like a vacuum cleaner. These skimmers are outfitted onto boats to eliminate the floating oil or oily contaminants. They are used to physically separate the oil from the water so that it can be collected and provided for reuse. 7.7.1.3 Sorbents Sorbents are substances that mop up liquids by both absorption or adsorption. Both these features make the method of cleanup much more manageable. Substances generally utilized as oil sorbents are hay, peat moss, fodder, or vermiculite. The application of sorbents is a simple method of oil cleanup. 7.7.1.4 Burning It is relative to lighting rice husk after yielding rice crop. In this way, the volatile oil is set to fire by lighting it cautiously. In this method, the oil hovering on the surface is inflamed to burn it off. It is the most skilled method of oil cleanup, as it can efficiently exclude 98% of the total spilled oil. According to Obi et al., (2008) The smallest concentration of the slick on the sea surface for each moderate effectiveness of in situ burning is 3 mm. This is because it would be very challenging to ignite a layer that is not dense enough.

7.7.2 Chemical treatment 7.7.2.1 Dispersant Dispersals are chemicals expanded above the spilled oil to begin the disintegration of oil. After disintegration, the exterior area of oil particles develops and it becomes more manageable for them to form a bond with water. This method uses the bonded particles immersed in water and makes them convenient for microbes, which deteriorate them later on. Dispersal agents, such as Corexit 9500, are chemicals that are spattered upon the spill with the help of aircraft and boats, which support the natural breakdown of oil elements. They release the oil to chemically bond with water by expanding the exterior area of each molecule. This guarantees that the slick does not move over the surface of the water, and is simpler to deteriorate by microbes.

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7.7 Remedies to cope up with oil pollution

7.7.2.2 Hot water and high-pressure washing This process is practiced to remove the captured and exposed oil from areas that are usually unavailable to machinery. Water heaters are employed to heat up water to about 170 C, which is then sprayed by hand with high-pressure rods or outlets. The oil is thus flushed to the water surface, which can be accumulated with skimmers or sorbents. 7.7.2.3 Chemical stabilization of oil by elastomizers Immediately after an oil spill, the immediate solicitude is to restrict the oil from growing and polluting the adjoining areas. While mechanical systems like handling oil booms efficiently hold the oil, they have some restrictions to their use. Very lately, specialists have been using compounds like “Elastol,” which is primarily polyisobutylene in a white powdered form, to confine oil spills. The compound gelatinizes or solidifies the oil on the water surface and thus prevents it from spreading or escaping. The gelatin is simple to recover, and this makes the method extremely efficient.

7.7.3 Bioremediation Bioremediation deals with the use of particular microorganisms to eliminate any toxic or dangerous substances onsite or off-site. There are several species of bacteria, fungi, archaea, and algae that deteriorate petroleum products by metabolizing and splitting them into simpler and nontoxic molecules. Sometimes, reagents and fertilizers may be affixed to the area. The phosphorus-based and nitrogen-based fertilizers contribute sufficient nutrients to the microorganisms so that they are capable to develop and multiply quickly. This process is usually not used when the spill has occurred in the deep seas and is increasingly put into operation once the oil starts to surround the shoreline. Table 7.4 shows different microbes used for Bioremediation of oil-contaminated water. TABLE 7.4 Different microbes used for Bioremediation. Sr. no. Microbes

Contaminants

Function

Reference

1.

Fungi

Polycyclic Aromatic Hydrocarbon

Biodegradation

Atagana (2009)

2.

Pseudomonas sp., Pycnoporus sanguineus

PAHs

Biodegradation

Arun et al. (2008)

3.

Acetobacterium paludosum, Clostridium acetobutylicum

Hexahydro-1,3,5- trinitro-1,3,5triazine (RDX)

Biodegradation

Sherburne et al. (2005)

4.

Enterobacter strain B-14

Chlorpyrifos

Biodegradation

Singh et al. (2004)

5.

Comamonas testosteroni VP44

-Mono chlorobiphenyls-

Substrate specificity

Hrywna et al. (1999)

6.

Rhzobium meliloti

Dibenzothiophene

Biodegradation

Frassinetti et al. (1998)

7.

Rhodococcus erythropolis TA421

Polychlorinated biphenyl

Biodegradation

Damaj and Ahmad (1996)

8.

P. pseudalkaligenesKF707-D2

TCE,toluene,benzene

Substrate specificity

Suyama et al. (1996)

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7.7.4 Natural recovery The most manageable way of dealing with the oil spill cleanup process is to make usage of the impulses of nature like the sun, the wind, the weather, tides, or naturally occurring microorganisms. It is deployed in several instances when the shoreline is extremely remote or distant, or the environmental influence of cleaning up a spill could possibly far exceed the advantages. Because of the reliability of these components the oil regularly evaporates or splits down into simpler components.

7.8 Conclusion Oil is exported by nearly 100 oil-trading countries of the world and the economic growth of some countries directly depends on its export. Oil explorations, transport, storage and distribution activities govern the oil price which affects both the oil-exporters and the importers. Certainly, the oil is required by every country for transportation, electricity generation, running machineries, synthesis of oil-based products, etc. But the dark side is that the oil spills (minor or major) during exploration and transport, influence the environment by damaging and debilitating the marine habitat. These spills can be disastrous because they disturb the functionality of the marine food chain and the food web as well and human as well. The oil spill affects a wide range of people, from coastal communities to a world leader as well either directly or indirectly. Since oil is an important source of energy, therefore oil exploration activities are a continuous business. However, the lessons learnt on oil-spill tragedies from the past have made it possible to clean up the oil-spills without delay, through high-tech instrumentation, materials and quick-response strategies. There are now several companies which provide quick, oil spill response solutions in case of accidental or general oil-leakage and spillage (Bashi-Azghadi et al., 2010). These solutions include a complete range of skimmers, oil booms, power- packs and pumps, workboats, landing-crafts, storage, and ancillary equipment. Apart from all this, with the alertness of the work-force during oil exploration and drilling may be instrumental in avoiding unfortunate tragedies. Moreover, adoption of biotechnologies (Erickson and Mondello, 1993) and forward technologies in oil-exploration regimes like use of uniquely balanced marine vessels and terminals, use of tankers with double hulls, use of corrosion-resistant storehouse tanks, etc. However, the responsibility for the prevention of oil spills not only lies on the engineers/workers of oil-trading companies but also on governments because the origin of oil-waste in the ocean is usually due to carelessness or purposeful, rather than accidental. Therefore efficient prevention of oil spills requires combined efforts towards sustainability and commitment towards the safe-exploration, transport, storage and distribution and utilization activities.

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8 Superhydrophobic polymeric adsorbents as an efficient oil separator Shubhalakshmi Sengupta1,*, Priya Banerjee2,*, Anil Kumar Nallajarla1, Venkatalakshmi Jakka1, Aniruddha Mukhopadhyay3 and Papita Das4 1

Department of Sciences and Humanities, Vignan’s Foundation for Science, Technology and Research (deemed to be University), Guntur, India 2Department of Environmental Studies, Centre for Distance and Online Education, Rabindra Bharati University, Kolkata, India 3 Department of Environmental Science, University of Calcutta, Kolkata, India 4Department of Chemical Engineering, Jadavpur University, Kolkata, India O U T L I N E 8.1 Introduction 8.2 Materials used for oil/water separation 8.2.1 Meshes and membranes for oil/water separation 8.2.2 Using inorganic materials 8.2.3 Using organic materials 8.3 Polymer-based adsorbents for oil/water separation 8.3.1 Plastic-based adsorbents 8.3.2 Polyurethane oil sorbents 8.3.3 Polystyrene oil sorbents 8.3.4 Polyethylene and polypropylene based oil sorbents

140

8.3.5 Oil sorbents based on the methacrylate polymers 8.3.6 Oil sorbents based on the miscellaneous polymers 8.3.7 Aerogels

148 148

8.4 Superhydrophobic polymeric adsorbents

148

8.5 Conclusion

152

Acknowledgments

152

References

152

142 142 144 145 145 146 146 146

148

146

* Shubhalakshmi Sengupta and Priya Banerjee contributed equally to this chapter.

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00010-0

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© 2022 Elsevier Inc. All rights reserved.

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8. Superhydrophobic polymeric adsorbents as an efficient oil separator

8.1 Introduction Polymeric substances revolutionized industrial history of this world ever since their introduction in the early 20th century (Al-Salem, Lettieri, & Baeyens, 2009). Various technological advancements and research has resulted in wide application of these polymeric substances in various applications like packaging, electronics, automobile industry, biomedical devices, paints, construction materials, insulators, textile, consumer goods. However, their extensive use has also led to enormous waste generation which in turn has cause both direct and indirect detrimental impacts on this planet. Moreover, plastic waste management is hugely hindered by difficulties in screening and processing processes (Baroulaki et al., 2006). Another, environmental hazard which plagues our planet every year is oil spills (AlMajed, Adebayo, & Hossain, 2014). The Erika oil spill of 1999, the Gulf of Mexico oil spill of 2010, and the South Atlantic oil spill of 2019 (de Oliveira Soares et al., 2020) are examples of such instances. Oil spills over oceans spread very quickly over water and undergo various physical and chemical processes like emulsification and degradation (Crone & Tolstoy, 2010). Presence of oils and its degraded products are extremely hazardous to the marine environment (Rogowska & Namie´snik, 2010). Few impacts of oil spills on marine ecosystems have been shown in Fig. 8.1. FIGURE 8.1 Effect of oil spill on marine organisms. (A) Oil spill on Brazilian beaches and the resulting damage to different species, leading to long-term negative consequences: (B) fish; (C) Marine turtle Chelonya midas covered with oil; (D) zooplankton (crab larvae (zoea 1) with mouth apparatus (arrows) possibly oiled) pelagic invertebrate; (E) Portuguese man-of-war Physalia physalis with its tentacles oiled, as well as macroalgae and marine plants; (F) seagrass impregnated with oil. Source: Reproduced with permission from de Oliveira Soares, M., Teixeira, C.E.P., Bezerra, L.E.A., Paiva, S.V., Tavares, T.C.L., Garcia, T. M., . . . Cavalcante, R.M. (2020). Oil spill in South Atlantic (Brazil): Environmental and governmental disaster. Marine Policy, 115, 103879 rElsevier.

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Several strategies have been adopted to prevent and remedy oil spills. However, these are not always environmentally benign. Methods that have been adopted in this regard include burning of oil layer which does help in removing the oil slicks but results in polluting the environment in return (Mullin & Champ, 2003). Booms are also used to physically contain the oil slicks allowing the skimmers to physically remove the oil layers. However, this process is very laborious, expensive, and not feasible in rough seas (Schrader, 1991). Chemical dispersants and biosurfactants produced by microorganisms result in dispersing and degrading oil spills, but sometimes addition of these chemicals might prove hazardous to the marine environment due to the toxicity imparted by them on the marine organisms. Nowadays, adsorbents of different kinds are used widely to remove oil from the seas. Natural sorbents like agricultural wastes and minerals (Saleem, Riaz, & Gordon, 2018) have been used for this purpose. Hydrophobicity is a significant parameter of these materials. Even in the case of hydrophilic materials, surface modifications are done to induce hydrophobicity (Saleem et al., 2018). With the advent of nanotechnology nanoparticles, nanowire membranes and other carbonaceous nanomaterials [e.g., carbon nanotubes (CNTs), graphene] have been used for this purpose (Gupta, Dunderdale, England, & Hozumi, 2017). Despite the availability of various sorbents, conventional polymers like polypropylene (PP) and polyethylene are widely used for oil separation owing to their economic viability (Carmody, Frost, Xi, & Kokot, 2007). Thus newer application areas and use of more ecofriendly and biodegradable polymers are sought by researchers. The desired properties which are mostly sought in oil sorbents include a good mutual solubility of the sorbent and the oil, high surface area, porous structure, and penetration ability of the oil into network structure of the sorbent (Gupta et al., 2017). Recent studies have reported superhydrophobic modification of the aforementioned porous nanomaterials for efficient oil/water separation. These engineered materials are a new approach toward oil recycling and water remediation. Surface modification of porous substances like sponge, melamine, copper mesh, polyurethrane have rendered them superhydrophobic. Moreover, superhydrophobic aerogels have been prepared using both natural and synthetic carbon materials. However, these materials, although environmentally friendly, are often not economically viable (Gupta et al., 2017; Saleem et al., 2018). Nevertheless, there is tremendous scope and potential for further research in the field of addressing oil spillage problems in our marine environment (Saleem et al., 2018). Many industries, such as metal/steel, petrochemical, mining, food, and textile produce exceptionally large volumes of oily-rich wastewater pose serious global environmental concerns (Chen & Xu, 2013). For example, a mining operation produces approximately 140,000 L oil contaminated water per day (Guerin, 2002). Frequent oil-leakages/spillages caused by water vehicles are potential threats to the marine environment and ecology (Chen & Xu, 2013). Various oil/water separation methods for example, (1) Conventional cleanup methods like Mechanical methods (Booms, skimmers) and Chemical methods (Dispersants, emulsion breakers) (Vergetis, 2002), (2) Advanced cleanup methods like bioremediation (Ventikos, Vergetis, Psaraftis, & Triantafyllou, 2004) are reported so far. However, these methods are energy-intensive. Commonly porous materials are used to absorb oil from water. However, such materials suffer from low oil separation efficiency, as they simultaneously absorb water and oil. After that various oil/water separation

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8. Superhydrophobic polymeric adsorbents as an efficient oil separator

methods are reported, most of them have advantages as well as disadvantages. In recent studies mainly focused on surface superwettabilities (Xue, Cao, Liu, Feng, & Jiang, 2014), such as superhydrophobicity, superoleophobicity, superhydrophilicity and superoleophilicity (Ragesh, Ganesh, Nair, & Nair, 2014; Wang & Gong, 2017; Wang, Liang, Guo, & Liu, 2015). Surface wettability is an inherent property of solid surface, the surface chemistry and geometric morphology solid surfaces are influence on the wetting/de wetting behaviors of examine liquids on solid surface (R.N. Wenzel., 1936). Superhydrophobicity/ superoleophilicity exhibiting “oil-removing” properties and superoleophobicity/superhydrophilicity exhibiting “water-removing” properties (Xue et al., 2011). Superhydrophobic/ superoleophilic stainless steel mesh is used for the oil/water separation which is allowing oil was first demonstrated by Jiang’s group (Feng et al., 2004) and also using hydrophilic polyacrylamide hydrogel-coated stainless-steel mesh which allows only water to permeate it (Xue et al., 2011).

8.2 Materials used for oil/water separation 8.2.1 Meshes and membranes for oil/water separation Over the past few decades, researchers have been using functionalized meshes and membranes with superwettability to separate oil from water. Due to their simplicity and low cost, they are ideal candidates for wide scale applications. Functionalization and mechanism of action of these devices have been explained in the following section. 8.2.1.1 Mechanism of action Woven metal-wire meshes have been functionalized with various chemicals to create an oil/water separating mesh having necessary properties. The majority of meshes reported so far is of hydrophilic in nature. They allow the passage of water and are referred to as “water selective” meshes and smaller proportion of meshes reported is oleophilic in nature which allow the passage of oil and are referred to as “oil selective” meshes (Gupta et al., 2017). Although it is possible to create an oil/water separation mesh which can be programmed to shift between water-selective and oil-selective performance, they are of rare occurrence (Dunderdale, England, Sato, Urata, & Hozumi, 2016). A mesh having pore size ,1 μm is referred to as a membrane (Gupta et al., 2017). However, these two names are often used interchangeably. Oil/water separation membranes have been reported with pore diameters larger than some of the reported oil/water separation meshes. However, irrespective of pore size, the mechanism of action is same for both. In comparison to other oil/water separation devices, meshes can separate large volumes of oil water in a given time, due to its large pore diameters. Membranes are able to separate emulsions of oil and water due to their smaller pore sizes. But meshes are limited by the fact that can only separate oil droplets larger than their mesh size. Nevertheless, meshes are simple and cost effective and low pressure required to drive liquid through them Moreover, often gravity is sufficient to provide the low pressure required to drive liquid through them.

B. Physical processes

8.2 Materials used for oil/water separation

143

8.2.1.2 Functionalization of meshes and membranes Several methods of surface functionalization have been used to alter the surface wetting properties of woven metal meshes to enable them for oil/water separation. The advantages and disadvantages of using different types of functionalizations have been discussed herein. Some examples of functionalized meshes and membranes are summarized in Table 8.1. TABLE 8.1 Typical filtration
based oil/water separation materials fabricated by different methods. Substrates/materials

Surface modification method

Chemicals/materials for surface modification

Metal meshesCu mesh/CuO or Cu (OH)2

Chemical etching

NaOH and (NH4)SO8Potassium peroxydisulfateAmmonia vapor

Particles

Electrodeposition

0.1 M CuSO4, 1 M H2SO4

Thermal treatment

_

Deposition

Polyelectrolytes or polymers Mixed with SiO2 particles TiO2 particles

Nanotubes

_

Carbon nanotubes Halloysite nanotubes

Inorganic materials

_

Graphene oxide Silica zeolite Silver

Polymers

Atom transfer radical polymerization

Polymer brushes

Electrostatic deposition

Poly (dimethylamino ethyl methacrylate)

In situ oxidative polymerization

Poly (3-ehylenedioxythiophene)-b-poly (styrene sulfonate)

Grafting polymerization

Polyacrylic acid

Spray drying

PTFE(Poly(tetrafluoroethane)) Poly (dimethyl siloxane) based polyurethane

Gels

SAMs

Dip coating

PTFE

Phase inversion

Polyethersulfone/cellulose acetate

In situ polymerization

Polydopamine

Photoinitiated polymerization

Hydrogel (Polyacrylamide)

Chemical vapor deposition

Sylgard184

Self-assembly from solution

Thiols Stearic acid Organosilanes

Biomaterial

Cross linking with glutaraldehyde

Chitosan

Source: Reproduced with permission from Gupta, R. K., Dunderdale, G. J., England, M. W., & Hozumi, A. (2017). Oil/water separation techniques: A review of recent progresses and future directions. Journal of Materials Chemistry A, 5(31), 16025
16058.

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8.2.2 Using inorganic materials The growth of nanostructured copper oxides [CuO or Cu(OH)2] on mesh surface is the most common type of surface functionalization carried out using inorganic materials (Gupta et al., 2017). Prior to functionalization, the mesh surface was highly hydrophilic and worked as a water selective mesh. The structured surface is created by etching Cu meshes with sodium hydroxide and ammonium persulfate to yield a mesh covered with Cu(OH)2 nanowires. These are used to purify water from a range of oil/water mixtures (including n-hexane, isooctane, petroleum ether, diesel, and soybean oil) to have oil content around 25 ppm (Zhang et al., 2013). Another selective wettability mesh is Cuo-covered Cu surface created through an etching with potassium peroxydisulfate (Liu et al., 2016) functionalized stainless steel meshes with a solution made of CuCl2 and hydrochloric acid for different periods of time. This treatment resulted in the formation of Cu crystal like structures on the mesh surfaces (Liu et al., 2016). Titanium dioxide (TiO2) is also used to functionalize both metal meshes and membranes (Gondal et al., 2014). Schematic representation of fabrication of polyvinylpyrrolidone—TiO2 nanowire coated metal mesh is shown in Fig. 8.2 (Pan, Cao, Li, Du, & Cheng, 2019). Materials like graphene oxide (GO) is also used to create superhydrophilic meshes that selectively separate water from oil/water mixtures (Dong et al., 2014; Liu, Zhang, Fu, & Sun, 2015). Incorporation of CNTs into membranes also change the surface morphology (Gu et al., 2014; Yu et al., 2014; Zhang, Li, Li, & Wang, 2016). In another study, silver nitrate has been used to coat stainless steel meshes with a layer of silver which in turn increased surface roughness (Wang, Lei, Xu, & Ou, 2015). This mesh performed as a water-selective mesh without any further functionalization.

FIGURE 8.2 Schematic illustration of the fabrication of polyvinylpyrrolidone-TiO2 NWs coated stainless steel membranes with special wettability for oil/water separation. Source: Reproduced with permission from Pan, Z., Cao, S., Li, J., Du, Z., & Cheng, F. (2019). Anti-fouling TiO2 nanowires membrane for oil/water separation: Synergetic effects of wettability and pore size. Journal of Membrane Science, 572, 596
606 r Elsevier.

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8.3 Polymer-based adsorbents for oil/water separation

145

8.2.3 Using organic materials The anionic or cationic polyelectrolytes like poly (2-dimethylamino ethyl methacrylate) (Cao et al., 2014), block copolymers of poly (methyl methacrylate)-b-(vinyl pyridine) (Li, Zhou, & Luo, 2015), and poly (ethylene di oxy thiophene)-b-poly (styrene sulfonate) (Teng et al., 2014) coated meshes are used to create hydrophilic water-selective meshes or membranes. Both polyethylene imine and polydopamine (PDA) are used to convert hydrophobic PP membranes to hydrophilic ones (Raza et al., 2014). These functionalized meshes or membranes are superhydrophilic in aqueous environments that is they selectively remove water from oil/water mixtures. Wang, Pan, Li, and Cao (2014) used polyvinylidene fluoride membranes which were rendered hydrophilic through ozone-induced grafting polymerization of acrylic acid. A recent study has reported the synthesis of hydrophilic poly(vinylidene fluoride) membranes exhibiting underwater superoleophobicity (Zhao et al., 2019). Surface modification of these membranes was carried out using thiolated hyperbranched zwitterionic poly (sulfobetaine methacrylate). Schematic representation of this membrane surface functionalization has been shown in Fig. 8.3.

8.3 Polymer-based adsorbents for oil/water separation In the past few decades, polymeric adsorbents have been emerging as highly effective (Pan et al., 2009) due to their wide variation in porosity and surface chemistry. Generally, polymeric adsorbents are used to collect the omnipresence organic pollutants such as Phenols (Abburi., 2003), Organic acids (Yang, Shim, Lee, & Moon, 2003), alkanes, and their derivatives (Lee, Jung, Kwak, & Chung, 2005). Recently, polymeric adsorbents have also used for oil sorbents. Here, mentioned the polymeric adsorbents that are used in oil/water separation processes. FIGURE 8.3 Schematic representation of poly(vinylidene fluoride) membrane functionalization using hyperbranched zwitterionic poly. Source: Reproduced with permission from Zhao, J., Li, D., Han, H., Lin, J., Yang, J., Wang, Q., . . . Chen, L. (2019). Hyperbranched zwitterionic polymer-functionalized underwater superoleophobic microfiltration membranes for oil-in-water emulsion separation. Langmuir: The ACS Journal of Surfaces and Colloids, 35(7), 2630
2638 r 2019 American Chemical Society.

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8.3.1 Plastic-based adsorbents The oil sorbents that are derived from plastics are prepared using single or mixture of plastics (Atta et al., 2013; Guo, Zhou, & Lv, 2013). Generally, plastics are classified as thermo plastic and thermoset plastics. Thermoplastics include PP, low density polyethylene, High density polyethylene, polyethylene terephthalate (PET), poly methyl methacrylate, polyamide/nylon, polystyrene (PS), etc., that softens on heating and hardens on cooling. These plastics can be recycled. Thermoset plastics including polyester resin, epoxy resin, polyurethane, urea formaldehyde, melamine formaldehyde, phenol-formaldehyde/bakelite, etc., harden on heating and cannot be recycled (Saleem et al., 2018). Different types of plastics reported as potential oil sorbents have been enlisted in Table 8.2.

8.3.2 Polyurethane oil sorbents Polyurethane foams used as oil adsorbents have been grafted by PS (Tanobe et al., 2009). Polyurethane sponge material treated with silica sol and gasoline reportedly exhibit an adsorption capacity of 100 g/g for motor oil (Wu et al., 2014). Oleophilic polyurethane foams formed by graft copolymerization reportedly demonstrate an oil sorption capacity of 47 and 41 g/g for diesel and kerosene respectively (Li, Liu, & Yang, 2013). They also have excellent oil/water selectivity (Wang & Uyama, 2016). Some studies have reported how absorption capacity of polyurethane foams vary with their pore size (Pinto, Athanassiou, & Fragouli, 2016). Chemical functionalization of foams also reportedly increase selectivity and sorption performance of these foams. According to a recent study, polyurethane sponges coated with graphene sheets exhibit excellent sorption efficiency for the continuous separation of oil/water mixture (Kong, Wang, Lu, Zhu, & Jiang, 2017).

8.3.3 Polystyrene oil sorbents Nanoporous PS fibers have been synthesized via an electro spinning process for oil spill remediation (Lin et al., 2012). A recent study reported magnetic PS foam having high oil removal efficiency. Electrospun fibers of both PS and polyacrylonitrile exhibited high buoyancy and adsorption capacity (B195 g/g) for pump oil (Li et al., 2015). In another study, electrospun PS films showed an adsorption capacity of 131 and 112 g/g for motor oil and peanut oil respectively (Wu et al., 2012).

8.3.4 Polyethylene and polypropylene based oil sorbents Oil sorbent films prepared from ultrahigh-molecular-weight polyethylene and other polyethylene wastes reportedly exhibits high sorption capacity and oil uptake capacity (B100 g/g) (Saleem & McKay, 2016). Membranes prepared from electrospun PP fibers have been found to be superhydrophobic with water contact angles greater than 150 (Feng et al., 2002; Ma, Hill, & Rutledge, 2008). This membrane efficiently separated water from diesel (Patel & Chase, 2014). Fiber assemblies have also been prepared with PPs, kapok and milkweed fibers that possess high sorption capacities (Rengasamy, Das, & Karan, 2011). Performance of the PP based oil sorbent materials reportedly on depend on pore

B. Physical processes

TABLE 8.2 Application of different plastics as oil sorbents. S. no Oil sorbents type

Product

Origin

Discussion

References

1

Polyurethane foams

Polyurethane foams used as mattresses

Polyurethane foam grafted by polystyrene; oil uptake (19
58 g/g) Retention values (50
18 g/g)

Tanobe, Sydenstricker, Amico, Vargas, and Zawadzki (2009)

Polyurethane sponge material treated with silica sol and gasoline successively

Polyurethane

The absorption capacity was 100 g/g sorbent for motor oil. After 15 successive sorptionsqueezing cycles, about 70% sorption capacity was left.

Wu et al. (2014)

2

3

4

5

Polyurethane based oil sorbents

Polystyrene based oil sorbents

PP and PE based oil sorbents

Acrylates based oil sorbents

Oil sorbents based on miscellaneous polymers

Treated polyurethane sponges

Polyurethane

High sorption capacity and excellent oil/water selectivity.

Wang and Uyama (2016)

Oil sorbent fibers

Polystyrene

Submicron fibers from polystyrene waste. Oil uptake measurements not presented.

Wu et al. (2012)

Polystyrene fibers

Polystyrene

Polystyrene fibers fabricated by a facile electrospinning method. The absorption capacity for PS fibers: about 7 g/g (diesel)82 g/g (silicon oil), 112 g/g (peanut oil) and 131 g/g (motor oil).

Gong, Qiu, Zhang, and Wei (2011)

Magnetic polystyrene foam

Polystyrene

The foam possessed high efficiency for the removal of oil from the surface of the water.

Oil absorbent foam

Extruded polyethylene EPE used in packing

Oil uptake (30 g/g)

Saleem and McKay (2016)

Oil sorbent film

Waste high density polyethylene bottles

Oil uptake capacity, 100 g/g

Patel and Chase (2014)

Polypropylene fibrous membrane

Syndiotactic polypropylene

Electrospun material was superhydrophobic with water contact angles greater than 150. The material successfully removed water from diesel (ULSD) samples.

Feng and Xiao (2006)

Butyl methacrylate-lauryl methacrylate copolymeric (CPMA) fibers

Butyl methacrylate and lauryl methacrylate

Hydroethyl methacrylate was used as a cross-linker. The maximum absorption capacities of the fibers were about 8 g/g (Kerosene), 15 g/g (toluene), and 35 g/g (chloroform).

Duan, Bian, and Huang (2016)

Macroporous ST/BMA copolymer Styrene and butyl methacrylate

The macroporous resin possessed oil absorbency (about 9 g/g) to crude oil.

Duan et al. (2016)

Stearyl methacrylate-butyl acrylate copolymer

Stearyl methacrylate and butyl acrylate

Porous oil-absorbent microsphere possessed above 95% oil retention for four organic liquids (toluene, gasoline, diesel and chloroform). The material can be used at least 12 times with little decrease in oil absorbency capacity.

Bukharova, Tatarintseva, and Ol’Shanskaya (2015)

Oil sorbent powder

PET

Oil uptake capacity, 1.5
2.5 g/g

Xu, Cao, and Lu (2016)

Nylon 6,6 Nonwoven Fabric

Nylon

The absorption capacity for low area mass density spun bond nylon: 16 times absorbent mass in low viscosity crude oil.

Electrospun copolymer of styrene and butyl acrylate

Styrene and butyl acrylate

The produced fibrous material possessed large specific surface area and fast oil absorption rate.

148

8. Superhydrophobic polymeric adsorbents as an efficient oil separator

diameter, porosity and oil adsorbing properties of PP (Wei, Mather, Fotheringham, & Yang, 2003).

8.3.5 Oil sorbents based on the methacrylate polymers Butyl methacrylate-lauryl methacrylate copolymeric fibers have demonstrated maximum adsorption capacities of 8, 15 and 35 g/g for kerosene, toluene and chloroform respectively (Feng & Xiao, 2006). The oil adsorption capacity of macroporous styrene and butyl methacrylate copolymer was found to be 9 g/g for crude oil (Duan et al., 2016). Porous oil-absorbent microsphere of stearyl methacrylate-butyl acrylate copolymer reportedly exhibited 95% retention of toluene, gasoline, diesel and chloroform (Duan et al., 2016). This material was successfully reused for 12 consecutive cycles.

8.3.6 Oil sorbents based on the miscellaneous polymers PET exhibited an oil uptake capacity of 1.5
2.5 g/g (Bukharova et al., 2015). Though this value is less in comparison to other oil sorbents, this process involves utilization of waste plastic. In another study, electrospun copolymer of styrene and butyl acrylate having a large specific surface area exhibited rapid rates of oil adsorption (Xu et al., 2016). Nylon bags have also been used for separating contaminated gear oil from the oil-in-water emulsions.

8.3.7 Aerogels An aerogel is a 3-dimensional porous polymeric gel having high sorption capacity. Generally, aerogels are foam or sponge like structures having high surface area and pore structure (Pinto et al., 2016). Various polymeric aerogels like poly dimethyl siloxane sponge (Choi et al., 2011), polyurethane (Ruan, Ai, Li, & Lu, 2014), PS foams (Yu et al., 2017), PP sponge (Wang, Elimelech, & Lin, 2016) have been used for the oil adsorption. A recent study reported fluorinated PDA/chitosan/reduced GO composite aerogel having high oil/water separation efficiency. Schematic representation of facile synthesis of this aerogel has been shown in Fig. 8.4 (Cao et al., 2017).

8.4 Superhydrophobic polymeric adsorbents Superhydrophobic materials are widely used due to their superhydrophobicity, high sorption capacity, and selectivity for oil recovery (Gao et al., 2016; Mi, Jing, Politowicz, et al., 2018; Shuai et al., 2015). Superhydrophobic materials having applications like selfcleaning, corrosion resistance, antiicing and drag reduction (Chen, Li, Li, & Sun, 2015; Rao et al., 2017; Si & Guo, 2015; Wang et al., 2014; Zhu et al., 2018). They can easily absorb oil from water due to their porous sponge-like structures (Wang et al., 2016). Surface modification of polyurethane sponge have been carried out to make the same superhydrophobic (Li et al., 2016; Wang, Wang, et al., 2015).

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8.4 Superhydrophobic polymeric adsorbents

149

FIGURE 8.4 Schematic illustration of facile synthesis of fluorinated polydopamine/chitosan/reduced graphene oxide composite aerogel. Source: Reproduced with permission from Cao, N., Lyu, Q., Li, J., Wang, Y., Yang, B., Szunerits, S., & Boukherroub, R. (2017). Facile synthesis of fluorinated polydopamine/chitosan/reduced graphene oxide composite aerogel for efficient oil/water separation. Chemical Engineering Journal, 326, 17
28. r 2017 Elsevier.

However, the dissociation of particle is a potential threat to environment when long term using of modified sponges are considered as degraded polymeric particles can have other environmental impacts (Cong, Ren, Wang, & Yu, 2012). Ultralight carbon-based aerogels having high absorption capacity and low density are another type of superadsorbent material (Wang et al., 2017; Zhang, Gu, et al., 2016). These are normally fabricated by pyrolysis of natural materials and polymer foams (Das & De, 2015; Feng, Nguyen, Fan, & Duong, 2015; Li, Hu, Sun, Zhang, & Wang, 2017) and cellulose (Mi, Jing, Xie, Huang, & Turng, 2018). Nevertheless, these methods of fabrication have high cost and less durability. Recently, researchers have reported conventional low-cost processing methods for the preparation of superhydrophobic porous polymeric materials, the most used method is phase inversion (Yuan, Meng, Hao, Wang, & Zhang, 2015). However, materials synthesized by these method have low hydrophobicity and absorption capacity. Another method is supercritical gas foaming. It is used in the fabrication of superhydrophobic polymer foams. This is cost-effective and environment-friendly but often produces foams having lower hydrophobicity and absorption capacity. The composite of poly(tetrafluoroethylene) (PTFE) with PP prepared using twin-screw extrusion was formed in presence of supercritical CO 2. The special PP/micro or nanoparticles of PTFE foam having multidimensional hierarchical structure was created by using nanoparticles and microparticles of PTFE. The resultant superhydrophobicity was retained even when the composite was cut, fractured, or sanded. The PP/mnPTFE composite reportedly has a high water contact angle (WCA) and low contact angle hysteresis of 156.8 and 1.9 respectively. Nanoporous polydivinylbenzene (PDVB) is also used for the adsorption of organic pollutants from air and water (Ha¨ der, Kumar, Smith, & Worrest, 1998;

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8. Superhydrophobic polymeric adsorbents as an efficient oil separator

Jones, 1999; Godduhn & Duffy, 2003). PDVB has high surface area with large pore volume and controllable average pore size (Fuertes, Marban, & Nevskaia, 2003). They exhibit specific selectivity for organic compounds. The synthesis material is in the form of PDVB-x, where x is the solvent used in the starting solutions. Solvent and sufficient time of solvothermal process are significant parameters guiding the formation of porous structure. Acetone, benzene, THF (Tetrahydrofuran), Dimethylformamide, ethyl acetate, etc., are considered as most suitable solvents for the synthesis of nanoporous PDVB. For example, PDVB synthesized using THF as a solvent (under a temperature of 60 C
100 C for 3
48 h) was found to have a contact angle of 156, indicative of the superhydrophobic nature of the same. It also showed the immediate adsorption of oil droplet in contact with its surface, indicating the superoleophilicity. The sample showed a hierarchical nanoporous structure and great adsorption property. This superhydrophobic polymer could also be recovered by using low-pressure distillation and reused. Nanocellulose aerogel is also used for the adsorption of oil and organic pollutants from water. Nanocellulose based adsorbents have attracted more attention than other adsorbents due to its complicated fabrication processes, environment incompatibility and insufficient buoyance. However, the nanocellulose aerogels are flexible, light in weight, have high adsorption capacity, are environmentally friendly, biodegradable, and extremely sustainable (Chen et al., 2004; Paakko et al., 2008). Moreover, hydrophobic cellulose aerogels have higher oil/water selectivity and porous structure in comparison to hydrophilic ones. In a recent study, Wang and Liu (2019) reported the synthesis of superhydrophobic cellulose aerogels (shown in Fig. 8.5) having high oil retention capability from raw cotton fibers. Several methods have been used for synthesis of hydrophobic cellulose aerogels from hydrophilic ones including chlorosilanes using chemical vapor deposition (Klemm, Heublein, Fink, & Bohn, 2005), triethoxyl(octyl)silane through vapor deposition, diffusion of the vapor of methyltrimethoxysilane into the aerogel skeleton to get hydrophobic surface (Wang, Peng, et al., 2015), etc. However, but by using these methods, a homogeneous grafting distribution is not obtained in the aerogels (Chaudemanche & Navard, 2011). To solve this problem, freeze-drying of a nanocellulose suspension treated by methyltrimethoxysilane is carried out (Zhang et al., 2014). This process yields hydrophobic nanocellulose aerogels but the properties and structure of aerogels are altered. Surface of nanocellulose easily can be modified by simply immersing the microfibrillated cellulose aerogels (MFCAs) in ethanol/methyltriethoxysilane (MTES) solution, and vacuum-dried the product to obtain superhydrophobic and oleophilic MFCAs (HMFCAs). The MTES solubilized in the ethanol had uniformly diffused into the pores of the HMFCAs. This method is simple and environmentally benign. The HMFCAs have a WCA of 151.8 degrees. Hence, it may be concluded that formation of the polysiloxane on the surface of the HMFCAs as a result of the silanization reaction is responsible for the superhydrophobicity of the HMFCAs. These HMFCAs exhibited an oil absorption capacity of up to 159 g/g from oil/water mixtures (Zhou, Li, & Luo, 2016).

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8.4 Superhydrophobic polymeric adsorbents

151

FIGURE 8.5 (A) Schematic representation of fabricating superhydrophobic cellulose aerogels; (B) photographs of superhydrophobic cellulose aerogels with different fiber concentration; (C) photographs of superhydrophobic cellulose aerogels (density: 0.041 g/cm3) obtained under different scale of preparation; (D) flexibility of the cellulose aerogel (8 3 1.2 cm) containing 3.5 wt.% of raw cotton fiber. Source: Reproduced with permission from Wang, J., & Liu, S. (2019). Remodeling of raw cotton fiber into flexible, squeezing-resistant macroporous cellulose aerogel with high oil retention capability for oil/water separation. Separation and Purification Technology, 221, 303
310 r 2019 Elsevier].

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8.5 Conclusion Separation of oil from water is an area of research which is progressing very fast. Since oil pollution, oil spillage in oceans are crucial environmental hazards that are detrimental to the aquatic ecosystems, newer methods and technologies have been developed for solving these problems (de Oliveira Soares et al., 2020). One such method is using adsorbents for this purpose. Although there are a variety of materials available, often polymeric materials are used for this purpose (Al-Majed et al., 2014). Among recent materials known to mankind, superhydrophobic materials are gaining huge importance due to their applicability in self-cleaning, corrosion resistance, antiicing and drag reduction to mention a few (Gao et al., 2016). This property of higher capacity of repelling water can be used effectively in separating oil from water. Such superhydrophobic materials formed from synthetic polymers like PDVB, PTFE and natural polymer like nanocellulose are now being used by scientists for oil/water separation purpose (Godduhn & Duffy, 2003; Wang & Liu, 2019). Thus these novel superhydrophobic polymeric materials have a huge potential for oil/water separation purposes.

Acknowledgments Shubhalakshmi Sengupta and Venkatalakshmi Jakka would like to acknowledge DST (SEED div) Government of India for the financial support they are receiving from of their DST (SYST) project (SP/YO/2019/1283) during the tenure of writing the chapter.

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C H A P T E R

9 Oil spill treatment using porous materials Prakash Bobde1, Ajaya Kumar Behera2 and Ravi Kumar Patel3 1

Department of Research and Development, Energy Acres, University of Petroleum and Energy Studies, Dehradun, India 2Department of Chemistry, Utkal University, Bhubaneswar, India 3 UPES Council for Innovation and Entrepreneurship, Energy Acres, University of Petroleum and Energy Studies, Dehradun, India O U T L I N E 9.1 Introduction

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9.1 Introduction Oil contamination is a significant environmental problem that is increasing in accordance with the development of petroleum production. In the last decade, an estimated 196,000 tons of transportation caused significant oil leakage, despite the fact that the world utilizes 30 billion barrels of petroleum each year, with up to five million tons of oil shipped daily via sea routes. Since the 20th century, oil leaks have been a major threat to the atmosphere and sea life (Nelson, 2000). Oil pollutants are a complex blend of aliphatic (CnH2n12), naphthenic (i.e. cycloalkanes), and aromatic hydrocarbons (Muir & Bajda, 2016). In the water there are several sources of oil. Natural gas seeps from the seabed and ocean floor, drilling in the ocean floor, leakage from oil extraction and transportation facilities, inland and marine navigation, emergency floods (e.g., tanker collisions or breakdowns), road and air transport, waste petroleum-

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00005-7

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based industrial installations, and storm water from urban areas are the most important of ´ these (Gutteter-Grudzinski, 2012; Polkowska & Bła´s, 2010). The devastating effects of oil spills onto water have resulted in the implementation of many strategies for eliminating such toxins from the marine environment. The first steps needed to prevent the harmful impacts of oil spills is the observation and monitoring of the source of pollution, as well as the preservation of human health and security. The phrase “response actions” refers to procedures, facilities, processes and practises used to recover pollutants from spills and reduce their possible impact (Fingas, 2016). Oil pollution treatment usually involves combustion and collection. Of these, burning due to additional pollution is not desirable. In comparison with the former system, however, the benefits of the collection process are quick oil recovery, no secondarily contaminated contamination and fast purification. Common techniques for preventing oil spills in seas and coasts (Fig. 9.1A) involve (Adebajo, Frost, Kloprogge, Carmody, & Kokot, 2003; Fingas, 2016): Oil stains are frequently removed using a combination of methods. Their decision is based on the extent of the leak, the quality of the water, and the temperature, although there are no uniform deoiling systems that can be used in all circumstances. The use of porous materials, such as sorbents, is a method that deserves special attention because they are readily available, easy to use, inexpensive, and, most importantly, nontoxic to the environment. Sorption is a physical form of oil removal that involves the absorption and adsorption of the oil (Fig. 9.1B) (Dı´ez, Jover, Bayona, & Albaige´s, 2007). The most popular sorbents

FIGURE 9.1 (A) Oil spill controlling strategies (B) Efficiency of sorbents for oil removal.

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being used clean up oil leaks are classified as follows (Adebajo et al., 2003; Bandura, Franus, Panek, Woszuk, & Franus, 2015): 1. inorganic mineral materials (e.g., diatomites, diatomaceous earth, perlites, clay minerals, zeolites, fly ash, activated carbons or silica gel); 2. organic mineral materials (e.g., peat, sawdust, wood, waste bark, cellulose from paper production, cotton, kapok and rice husks); 3. synthetic organic polymers (e.g., polypropylene, polyethylene, polyacrylate, polystyrene or polyurethanes). Oil spills are handled by hydrophobic sponges, which absorb oil in water and can be recycled through squeezing or distillation (Balat & Balat, 2009). Furthermore, the ideal adsorption material must have a large adsorption space, a high adsorption rate, as well as a superhydrophobic capacity. Glass wool falls under the category of inorganic mineral products, birch bark and cork fall under the category of organic mineral materials, and polyurethane foam (PUF) falls under the category of synthetic organic polymers. Fig. 9.2A

FIGURE 9.2 (A) preparation schematic diagram and (B) oil-water separation mechanism diagram. Source: Adapted with permission Zhang, Y., Zhang, Y., Cao, Q., Wang, C., Yang, C., Li, Y. & Zhou, J. (2020). Novel porous oilwater separation material with super-hydrophobicity and super-oleophilicity prepared from beeswax, lignin, and cotton. Science of the Total Environment, 706, 135807.

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depicts the preparation line representation of the biomass-based porous materials with super-hydrophobicity and super-oleophilicity. Fig. 9.2B depicts the oil-water segregation process schematic of biomass-based porous materials with super-hydrophobicity and super-oleophilicity. Porous materials are becoming increasingly popular in gas sorption, catalysis, water treatment, separation, electrochemical energy storage, sensing, proton conduction, biomedicine, and optoelectronics (Wu et al., 2019). Porous materials are empty spaces within a structured framework, resulting in high surface areas for interaction with atoms, ions, or molecules in the environment. Controlling the porous architecture and functionalizing it to enhance interactions, on the other hand, represents a problem (Ci et al., 2017). To ensure that it selectively absorbs oil rather than water, the ideal porous material for oil-water separation must be super-hydrophobic and super-oleophilic (Chen & Zheng, 2014).

9.2 Materials and characterization Different types of materials were used for the oil water separation. These include aerogel, foam, sponge, graphene. Yuan et. al. synthesized biomass carbon @SiO2@MnO2 aerogel and modified and to increase the hydrophobicity of the material, the surface of aerogel was altered by grafting the hydrophobic group on the surface of aerogel. The wettability of the biomass carbon @SiO2@MnO2 aerogel and modified biomass carbon @SiO2@MnO2 aerogel was studied utilizing contact angle measurement. Yuan et. al. was observed that water molecule could pierce into the pristine biomass carbon @SiO2@MnO2 aerogel within 1 s. and water contact angle (WCA) was 0 degrees which was found due to the hydrophilicity and intrinsic high surface energy of metallic oxides whereas water molecule could not pierce into the modified biomass carbon @SiO2@MnO2 aerogel within 30 s. and WCA was 155 degrees which showed that the hydrophobicity of the material (Yuan et al., 2018). Cellulose based aerogels (CBAs) were synthesized and characterized for the wettability. MTMS-modified CBAs showed the WCA and oil contact angle were 154 and 0 degrees which indicated the combined hydrophobicity and oleophilicity. CBAs showed the high absorptivity (98.6%
99.6%) and low thickness (0.0055
0.021 g/cm3) belong to the light weight material, indicated the material could float on the surface of water after absorbing oil (Yin, Zhang, Liu, Li, & Wang, 2016). Cellulose membrane showed the WCA 20 degrees and by coating the silane onto the surface of cellulose membrane the WCA enhanced from 20 to 140 degrees. The WCA further enhanced to 160 degrees due to the grafting of myrcene (block copolymer) onto the cellulose membrane surface. This indicated that the block copolymer successfully polymerized onto the cellulose membrane (Kollarigowda, Abraham, & Montemagno, 2017). Eggshells modified by ethanol, stearic acid and ZnO for the absorption of oil from the water. The modified eggshell particles were characterized for the WCA and slide angle for the detecting of hydrophobicity of the material. Modified eggshell particles showed the WCA more than 150 degrees which indicated the material hydrophobicity. Modified eggshell particles were exposed under UV light for 12 h for checking the UV-durability of the hydrophobic material. After 12 h of irradiation, the surface already had a WCA greater than 150 degrees and a SA less than 10 degrees, indicating exceptional UV-strength. The WCA and SA demonstrated no discernible difference

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after continued irradiation, showing that the as-prepared superhydrophobic material has excellent UV light resistance (He et al., 2018). CEC/Fe3O4/PFOS material showed the high absorptivity (83.53%) and low thickness (0.487 g/cm3) belong to the light weight material, indicated the material could float on the surface of water after absorbing oil. The WCA for CEC and CEC/Fe3O4/PFOS was found to be 51.3 and 150.1 degrees, respectively. This revealed the hydrophobicity of CEC/Fe3O4/ PFOS than CEC (Sun et al., 2020). Polydimethylsiloxane-functionalized melamine sponge (Ms) showed the high porosity (99.4%) and low density (0.008
0.026 g/cm3). The WCA of polydimethylsiloxane-functionalized Ms was found to be larger than 150 degrees, indicated the hydrophobic nature of material (Chen, Weibel, & Garimella, 2016). FOC-TiO2 modified sponge revealed the WCA 161.1 degrees, indicated the high water repellency (Cho, ChangJian, Hsiao, Lee, & Huang, 2016). Feng et al. synthesized furfuryl alcohol (FA) modified Ms and studied the surface wettability of the material. When the water and oil were drizzled on the surface of unmodified Ms and FA modified Ms, both water and oil were absorbed on the surface of pristine Ms in 1 s. while on the contrary oil got absorbed on the superficial of FA modified Ms and water maintained a stable spherical shape on the surface of FA modified Ms. Though the FA modified Ms was divided into two sections, newly divide face still exhibited a high water repellence. The WCA was estimated to be between 138 and 145 degrees. The findings reveal that after FA alteration, both the internally and externally surfaces were chemically modified, and Ms has a hydrophobic property (Feng, Wang, Wang, & Yao, 2017). Pristine Ms exhibited absorption bands at 818, 1546, and 3394/cm, which are attributed to triazine ring twisting, C 5 N stretching, and N-H stretching, respectively. Bands at 1341 and 1471/cm were also representative of -CH- bending. Furthermore, C-H stretching was due to two small peaks at 2800
2900/cm. These absorption band groups verified the chemical structure of the Ms. Because of the attribute motions of Si-O-Si stretching, new absorption bands at 1048 and 1086/cm emerged after SiO2 adsorption and silanization procedures. Furthermore, the peak attributed to N-H stretching was significantly red-shifted to 3381 and 3362/cm, as a result of the integrating reaction of amino groups on the sponge structure in the course of silica nanoparticle adsorption and the silanization process (Gao et al., 2018). The WCA of the ODS SAM-modified sponge was 91 degrees and after modification by PODS the same was increased to 153 degrees. This indicated the PODS-modified sponge exhibited the superoleophilicity (Ke, Jin, Jiang, & Yu, 2014). The specific surface area of the (Al2O3/PUF) foam sponge was found to be 214.79 m2/g and the aperture diameter ranged from 15
40 nm. The high specific surface area and pore diameter of (Al2O3/PUF) foam sponge was beneficial for the increased absorption efficiency. Fig. 9.3 showed the WCA measurement of Al2O3 sphere, hydrophobic Al2O3, PUF, and (Al2O3/PUF) foam sponge. WCA of Al2O3 sphere, hydrophobic Al2O3, PUF, and (Al2O3/PUF) foam sponge was found to be 0, 136, 127, and 144 degrees. This indicated the hydrophobicity and oleophilicity of (Al2O3/PUF) foam sponge (Kong et al., 2018). The polyurethane sponge overlayed with KH-570-improved graphene had a high WCA; which was inflated apart from the polydimethylsiloxane (PDMS)- overlayed PU sponge (140 degrees) (Wang & Lin, 2013), PU foam (152.2 degrees) (Su, 2009), and conjugated microporous polymers (150 degrees) (Li et al., 2011). Water molecules were nearly adsorbed by the primary sponge, but stayed intact on the substrate of the polyurethane sponge overlayed with KH-570-improved graphene. In 1 s, a drop of diesel oil dyed with

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FIGURE 9.3

WCA of void Al2O3 spheres (A), Al2O3 (B), PUF (C) and Al2O3/PUF (D) foam sponge. Source: Adapted with permission Kong, L., Li, Y., Qiu, F., Zhang, T., Guo, Q., Zhang, X., . . . Xue, M. (2018). Fabrication of hydrophobic and oleophilic polyurethane foam sponge modified with hydrophobic Al2O3 for oil/water separation. Journal of Industrial and Engineering Chemistry, 58, 369
375.

Sudan I was totally adsorbed into the spaces of the polyurethane sponge treated with KH570-overlayed graphene, and no CA could be detected. An impacting water column bounced off the polyurethane sponge overlayed with KH-570-improved graphene surface; this further showed the superhydrophobicity of the polyurethane sponge overlayed with KH-570-improved graphene. Superhydrophobic surfaces are typically created by combining sufficient surface harshness with hydrophobic substances. As a result, two variables, roughness and poor surface energy, led to the superhydrophobicity (Preda et al., 2013). The sponge was covered with graphene, which improved its harshness. The substrate energy of all the graphene and the sponge decreased after they were altered with KH-570. The formed polyurethane sponge layered with KH-570-improved graphene turned superhydrophobic as a result. However, it remained more superoleophilic than the initial sponge (Li et al., 2015). CS-SiO2-PU sponges were synthesized and utilized for the oil/ water separation. Contact angle calculations were used to assess the hydrophilicity of the initial and CS-SiO2-PU sponges. As demonstrated in the CA of a water (dyed with methylene blue) particle on the unmodified PU sponge is 100 6 2 degrees, whereas the CA of a kerosene (dyed with oil red O) particle is around 0 degree. Nevertheless, the CS-SiO2-PU sponge shows superhydrophobicity and superoleophilicity at the same time. When a kerosene molecule was released on the layer of the CS-SiO2-PU sponge, it was automatically drained, whereas a water molecule remained on the layer of the pristine sponge and retained its spherical form. The WCA on the CS-SiO2-PU sponge is up to 155 6 2 degrees and the SA is as low as 7 6 2 degrees. As a result, the water was annihilated by the pristine sponge, while the oil easily pervaded into it (Li, Zhao, et al., 2017). Surface chemical composition of synthesized PU@Fe3O4@PS sponge was investigated from XRD and FTIR characterizations. These results indicated that PS and Fe3O4

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163

nanoparticles were grafted on the surface of sponge successfully by means of dip-coating and photopolymerization (Zhou et al., 2019). The PDA covering on the CF layer was responsible for the minor difference in hardness of the CF-PDA. The CF-PDA-Ag, or AgNO3-treated CF-PDA, retained its initial 3D void structure and displayed clear micro/nano framework owing to the Ag NPs and agglomerates formed by the reducing response among the PDA surface and Ag1 ions. Furthermore, the centralized micro/nano frameworks on the CF-PDA-Ag substrate did not alter significantly during the corresponding NDM dipcoating operation. This suggested that the PDA surface on the CF serves an important part in shielding the CF’s 3D framework from degradation induced by the diffusion interaction among Cu and Ag1, which enabled the production of Ag NPs and their trapping into the CF-PDA-Ag substrate (Zhou, Li, Wang, Chen, & Lin, 2017). The unmodified CF had WCA 79.6 degrees showing hydrophilicity of the material. CF-PDA and CF-PDA-Ag showed lower WCA than unmodified CF due to both of the revised CF structures showed varying rates of wettability transition. The improved CF structures, synthesized by binding with NDM to get CF-PDA-NDM and CF-PDA-Ag-NDM, revealed high powerful hydrophobicity. CF-PDA-Ag-NDM revealed WCA 153.1 degrees indicated the material superhydrophobic nature (Zhou et al., 2017). PDMS sponge showed superhydrophobic nature with WCA 151.5 degrees. Due to the void framework and superhydrophobic nature, PDMS sponge could levitate on the top of water. When a sponge is submerged in water by a physical pressure it is covered by an air covering and has a silver mirror-like appearance. The pliability and superhydrophobicity of the PDMS sponge were investigated by keeping in liquid nitrogen and in an oven at 250 C for 24 h, but PDMS sponge showed very high WCA 151.2 and 150.2 degrees, respectively. TGA characterization of PDMS sponge was carried out to identify mass drop at different temperatures. No mass drop was observed at less than 322 C. 37.83% mass drop was observed between 322 C
800 C which was attributed to the methyl group decay (Zhao, Li, Li, Zhang, & Wang, 2014). The WCA of magnetic foam was found to be 110 6 1.1 degrees, stipulated the hydrophobic nature of material. The hydrophobicity of the magnetic foam was increased by incorporating titanium dioxide and increasing the concentration of titanium dioxide. WCA of magnetic titanium dioxide foam was found to be 152.1 6 1.2 degrees, showed the superhydrophobic material. In comparison, oil particles scattered and absorbed entirely into magnetic titanium dioxide foam in less than 1.2 s, demonstrating that magnetic titanium dioxide foam was both superoleophilic and superhydrophobic (Yu, Zhou, & Jiang, 2016). WCA of carbon hybridized ZnO on polymeric foam was found to be 137 degrees, showed the superhydrophobic material. The control finding demonstrated that ALD accumulation of ZnO, which has a reasonable surface energy, is a standardized method for imparting hydrophobicity to originally hydrophilic porous foams on the one side, and conclude that ALD accumulation of ZnO is a flexible method for changing the substrate wettability of porous substrates based on its particular surface properties on the other (Xiong, Yang, Zhong, & Wang, 2018).

9.3 Discussion Yuan et. al. used modified biomass carbon @SiO2@MnO2 aerogel to observe the oil water separation. The material showed the maximum absorption capacity for the separation of

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164

9. Oil spill treatment using porous materials

carbon tetrachloride and minimum absorption capacity for the toluene from water. Reusability and durability of the modified biomass carbon @SiO2@MnO2 aerogel was also checked and found that the material showed very high absorption capacity after the 9th cycle of reuse (Yuan et al., 2018). Effect of cellulose content and PAE concentration on the different oil sorption capacity of CBAs was investigated. The absorption capacities for all the oils were decreased as the cellulose content increased from 0.35 to 1wt.%. As the PAE concentration was increased from 10 to 60wt.%, the absorption capacities for crude oil, diesel oil and lubricating oil was reduced WCA of CBAs after 16th cycle were found to be 113.1
128.8 degrees indicated that the recycled CBAs had very low absorption capacity for water (Yin et al., 2016). Crude oil showed the maximum absorption capacity for the block copolymer cellulose membrane. The WCA was observed for the block copolymer cellulose membrane after using five times and it was found that 160 degrees which indicated that the hydrophobicity and oleophilicity of the material after using several times (Kollarigowda et al., 2017). Bi et al. synthesized carbon microbelt (CMB) aerogel and used for the absorption of oils and organic solvents. Pump oil and chloroform from various oils and organic solvents showed the higher absorption capacity for CMB aerogel. CMB aerogel shows the higher absorption capacity than wool-based nonwoven (Radeti´c, Joci´c, Jovanˇci´c, Petrovi´c, & Thomas, 2003), nanowire membrane (Yuan et al., 2008), magnetic exfoliated graphite (Wang, Sun, Zhang, Fan, & Ma, 2010). Nitrogen doped graphene foam (Zhao et al., 2012), ultraflyweight aerogels (Sun, Xu, & Gao, 2013) and cellulose nanofibers aerogels (Wu, Li, Liang, Chen, & Yu, 2013) showed the higher absorption capacity than the CMB aerogel, but the synthesis method of CMB aerogel is simpler and the raw material used for the synthesis for CMB aerogel is also very cheap than all the other material. From this point of view CMB aerogel is the cost effective and promising sorbent for the organic pollutants (Bi et al., 2014). Twisted carbon fibers (TCF) aerogel was synthesized and utilized for the absorption of oil and organic solvents from water. The TCF aerogel’s 3D porous structure, strong mechanical properties, and surface hydrophobicity made it an excellent candidate for the elimination of contaminants like oils and organic solvents. The results revealed that the pump oil and chloroform absorbed higher onto the TCF aerogel. TCF aerogel could uptake oils and solvents at 50
192 times its own weight (Bi et al., 2013). Lignin modified aerogel was investigated for the absorption of organic solvents and oils. Oils and organic solvents could be absorbed by a lignin-modified aerogel at rates of 20
40 times their own weight. These findings showed that the synthesized improved aerogel had distinct absorption capacities against various oils and solvents based on their densities, and that the absorption ability of the improved aerogel could be changed by regulating its density by adjusting the feed solution concentration. This distinguishing feature assured that the modified aerogels could be used in a wider range of applications. In the case of determining the reusability of the aerogel by physically pressing, chloroform was used as an oil evocative. To achieve absorption equilibrium, the improved aerogel was first dipped in chloroform. Following that, the saturated aerogel was pressed and the desorbed oil was extracted. The desorbed improved aerogel was then utilized in some other loop. The absorption capacity of the second cycle preserved 82.16% of the first cycle, and the absorption capacity of the third cycle retained approximately 83.1% of the first cycle. The reduction in absorption potential may be attributed to the residual oil in the biomassderived aerogel. Many functional groups in the biomass-derived aerogel aided in oil

B. Physical processes

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165

absorption; in other words, oil was easily combined with the biomass-derived aerogel. When physically pressing was insufficient, a minimal%age of absorbed oil could remain in the aerogel, resulting in a reduction in absorption ability for the following run. The fourth cycle’s absorption capacity decreased further, reaching roughly 68.55% of the first step, although following cycles’ absorption capacity remained constant. After ten cycles, the improved aerogel’s absorption potential maintained approximately 73.71% of the first cycle, indicating strong absorption efficiency and recyclability (Jiang, Zhang, Zhan, & Chen, 2017). Modified eggshell particles could uptake oils at 14
34 times its own weight. The separation efficiency was decreased from 93% to 83% after 10 cycles of oil separation, indicated the reusability of the modified eggshell particles (He et al., 2018). Comparison of adsorption capacities of various materials in the previous studies are given in Table 9.1. Chloroform, n-hexane, dichloromethane, motor oil, diethyl ether, cyclohexane, soybean oil and rapeseed oil were investigated for the separation from water by CEC/Fe3O4/PFOS material. The adsorption capacities of CEC/Fe3O4/PFOS material are different for eight oils or organic reagents (from 49.97 to 140.90 g/g). Out of these, chloroform showed the higher absorption capacity than others. The adsorption potential of the CEC/Fe3O4/PFOS content is greater than those of other biomass charcoal compounds. However, only the adsorption potential of an aerogel component exceeds that of the CEC/Fe3O4/PFOS content. Because of the relatively low intensity of aerogel materials, many cellulose is employed as an adsorbent, however plant natural resources as an oil adsorbent medium have been rarely utilized (Sun et al., 2020). Lee et al. (Lee, Lee, Koo, & Choi, 2019) created a magnetic adsorption medium (Ms-PDMS) from sponges and Fe3O4 nanoparticles; the product is capable of oil/water isolation and adsorption (34.837.9 g/g). The CEC/Fe3O4/PFOS content outperforms Ms-PDMS in the oil/water isolation method. The oil adsorption potential of the CEC/Fe3O4/PFOS content (49.97
140.90 g/g) is far higher than that of Ms-PDMS samples (34.8
37.9 g/g), indicating that it is effective for oilwater isolation. The WCA of the CEC/Fe3O4/PFOS material is greater (150.1 degrees) than that of the PLA/γ- Fe3O4 composite molecules (148 degrees) and Ms-PDMS samples (141 degrees) (He et al., 2018; Lee et al., 2019; Sun et al., 2020). Hexane, toluene, octadecene, silicone oil and motor oil was investigated for the separation from water by the polydimethylsiloxanefunctionalized Ms. The material revealed the high absorption capacity for all the pollutants. Polydimethylsiloxane-functionalized Ms had the absorption capacity 45.4, 71.5, 55.4, 61.4, and 46.3 g/g for the hexane, toluene, octadecene, silicone oil and motor oil, respectively. The absorption capacity of polydimethylsiloxane-functionalized Ms with different oils remained undiminished after 20 cycles. This indicated the usability of the material for the oils (Chen et al., 2016). Fig. 9.4A depicted images of the separation operation of organic solvent (toluene) from the water layer through FOC-TiO2 sponge. Fig. 9.4B showed the organic solvent (chloroform) fell in the base. Methanol, ethanol, hexane, DMSO, DMF, acetone, chloroform, THF, pump oil and motor oil were investigated for the separation from water by the FOC-TiO2 modified sponge as seen in Fig. 9.4C. Based on the, thickness, viscosity, and surface tension of the absorbed solvents, FOC-TiO2 improved sponge has an outstanding absorption potential in the vicinity of 37.2
88.1 g/g to its original weight. Absorption reusability of the FOC-TiO2 improved sponge for chloroform, pump oil and hexane was also studied and indicated after 20 cycles, there was no discernible difference, suggesting outstanding reuse efficiency (Cho et al., 2016). Turpentine, hexane, cyclohexane, paraffin oil, methyl silicon oil, CCl4, toluene, and chloroform have absorption amounts of 102.1, 78.0, 85.2, 95.9, 82.4, 159.6, 91.5, and 160.0 g/g,

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TABLE 9.1 Comparison of adsorption capacities of various materials in the previous study. Separation capacity (g/g)

Reference

Oil/water separation

60
120

Yuan et al. (2018)

Cellulose based aerogel

Oil/water separation

58.06
101.14

Yin et al. (2016)

Ms-PDMS

Oil/water separation

34.8
37.9

Lee et al. (2019)

Cellulose hybrid biomembrane

Oil/water separation

5
20

Kollarigowda et al. (2017)

Carbon microbelt aerogel

Oil/water separation

56
188

Bi et al. (2014)

Carbon fiber aerogel

Oil/water separation

50
192

Bi et al. (2013)

Lignin modified aerogel

Oil/water separation

20
40

Jiang et al. (2017)

Modified eggshell particles

Oil/water separation

14
34

He et al. (2018)

CEC/Fe3O4/PFOS material

Oil/water separation

49.97
140.90

Sun et al. (2020)

Polydimethylsiloxane-Functionalized Melamine Sponge

Oil/water separation

18
75

Chen et al. (2016)

FOC-TiO2 modified sponge

Oil/water separation

37.2
88.1

Cho et al. (2016)

Furfuryl alcohol modified melamine sponge

Oil/water separation

78
160

Feng et al. (2017)

Ms@SiO2@VTMS

Oil/water separation

60
109

Gao et al. (2018)

PODS-modified sponge

Oil/water separation

42
68

Ke et al. (2014)

(Al2O3/PUF) foam sponge

Oil/water separation

10
37

Kong et al. (2018)

polyurethane sponge coated with KH-570modified graphene

Oil/water separation

10
38

Li et al. (2015)

CS-SiO2-PU sponges

Oil/water separation

18
65

Li, Zhao, et al. (2017)

compressible and conductive carbon aerogels

Oil/water separation

33
70

Li, Li, et al. (2017)

Carbon fiber aerogels

Oil/water separation

100
170

Liu et al. (2018)

Material

Type of use

Biomass carbon @SiO2@MnO2 aerogel

(Continued)

B. Physical processes

167

9.3 Discussion

TABLE 9.1 (Continued) Separation capacity (g/g)

Reference

Oil/water separation

60
150

Oribayo et al. (2017)

PU@Fe3O4@PS sponge

Oil/water separation

30
105

Zhou et al. (2019)

CF-PDA-Ag-NDM

Oil/water separation

95.0
98.3

Zhou et al. (2017)

PDMS sponge

Oil/water separation

500%
2100%

Zhao et al. (2014)

Magnetic titanium dioxide foam

Oil/water separation

35.23
64.31

Yu et al. (2016)

ALD of ZnO

Oil/water separation

85
162

Xiong et al. (2018)

Material

Type of use

Formaldehyde-Melamine-Sodium Bisulfite Copolymer Foam

respectively. The reusability of improved Ms was investigated using turpentine, n-hexane, and cyclohexane as instances. The ingested oil and solvents into the Ms framework can be quickly retrieved using a basic pressing process, and the removal efficiency for turpentine oil, n-hexane, and cyclohexane reduced by 14.0, 5.1, and 5.2 g/g, respectively, after 10 iterations of absorption and desorption, and prevailed nearly constant in the last few sessions. Furthermore, despite 10 cycles of absorption and desorption, the WCA of improved Ms remained in the 138
145 degrees region (Feng et al., 2017). Several organic solvents and oils commonly employed in laboratories and factories were required to test the absorption potential of the Ms@SiO2@VTMS sponges. In fact, the analyzed oils/solvents were easily absorbed by the sponge in a matter of seconds, indicating good absorptivity (Liu et al., 2013). In the field of oil extraction and water/oil isolation processes, the material’s renewability or extensibility is often an important attribute to remember. A continuous absorption-compressingdehydrating procedure with hexane as the immersing solvent was used to measure the recyclability of the improved sponge (Arslan, Aytac, & Uyar, 2016). The sponge retained its normal structure throughout the method, as predicted, and the disappearance of hexane in the sponge during soaking operation was verified by mass restoration of the sponge. The hydrophobic sponge’s hexane absorption ability was tested up to 12 loops. During every loop, an essentially stable absorption potential of B60 g/g was discovered, illustrating the hydrophobic sponges’ strong recyclability (Gao et al., 2018). The absorption capacities for methyl silicon oil, toluene and light petroleum in the range 42
68 g/g. These absorption capacities maintained after 50 cycles (Ke et al., 2014). Chloroform, hexane, tetrachloromethane, bean oil, methylbenzene and diesel oil were investigated for the separation from water by (Al2O3/ PUF) foam sponge. The absorption capacities found in the range 10
37 g/g. Chloroform, soybean oil and methylbenzene were selected to assess the recyclability of the (Al2O3/PUF) foam sponge. The absorption capacity for chloroform, soybean oil and methylbenzene are 37.0, 6.8, and 15.8 g/g, respectively (Kong et al., 2018). Soybean oil, diesel oil and pumping oil were

B. Physical processes

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9. Oil spill treatment using porous materials

FIGURE 9.4 The oil absorption execution of FOC-TiO2 improved sponge. (A) The image of the reduction action of organic solvent (toluene) flow on the water surface by utilizing FOC-TiO2 sponge; (B) and the organic solvent (chloroform) fell in the base; (C) absorption capacity of the FOC-TiO2 improved sponge on different organic liquids and oils. Source: Adapted with permission Cho, E.-C., Chang-Jian, C.-W., Hsiao, Y.-S., Lee, K.-C. & Huang, J.-H. (2016). Interfacial engineering of melamine sponges using hydrophobic TiO2 nanoparticles for effective oil/ water separation. Journal of the Taiwan Institute of Chemical Engineers, 67, 476
483.

investigated for the separation from water by polyurethane sponge overlayed with KH570-improved graphene. Pumping oil shows the high absorption efficiency than soybean and diesel oil. The maximum absorption capacity of the polyurethane sponge overlayed with KH-570-improved graphene for various oils did not reduce when the polyurethane sponge overlayed with KH-570-improved graphene was reused more than 120 times. The recyclability of the polyurethane sponge overlayed with KH-570-improved graphene was ample superior apart from other oil absorbents, together with the GN-based sponge (five cycles) (Nguyen, Tai, Lee, & Kuo, 2012) and the decreased GO-overlayed PU sponge (50 cycles) (Liu et al., 2013). As a result, after 120 iterations of recycle, the oil-absorbent capacities of the KH
GN sponge barely reduced. Moreover, the mass of the sponge after 5
120 iterations of desorption revealed no improvement, including a small rise during the first five iterations. The mass of the KH
GN sponges rose by 1.6
1.9 g after five iterations with the three types of liquid. The absolute amount of adsorption capability may have decreased somewhat. It had no impact, though, on the overall adsorption capability for oil. These findings indicate that the KH
GN sponge with superhydrophobicity not only had a strong absorption potential for various oils,

B. Physical processes

9.3 Discussion

169

but it was also rather recyclability (Li et al., 2015). For a number of oils and solvents, comprising toluene, tetrachloroethane, petroleum ether, kerosene, hexane, heptane, gasoline, and chloroform, CS-SiO2-PU sponges demonstrated outstanding absorption capacities of up to 18
65 times their self-weight. The discrepancy in absorption potential was most likely caused by the thickness and gel strength of the oils or organic solvents. During the oil/water isolation cycle capillary forces push oil into the sponge’s interior while repelling water from the exterior (Li, Zhao, et al., 2017). The compacted and conductive carbon (3C) aerogels with high voids (B86%) demonstrated extremely high absorption potential for a variety of commonly experienced oils. Depending on the characteristics of the oils, the absorption capacity is 33
70 g/g, which is better than superhydrophobic polyurethane sponges with absorption capacities of 13
45 g/g (Wu, Li, Li, Zhang, & Wang, 2015) and silicone sponges with absorption capacities of 6
18 g/g (Hayase, Kanamori, Fukuchi, Kaji, & Nakanishi, 2013; Li, Li, Wu, Zhao, & Zhang, 2014). Even though absorption potential of the 3C aerogel is marginally smaller than that of the some of the aerogels developed from bacterial cellulose, CNTs, and graphene (Sun et al., 2013; Wu et al., 2013) its versatility and cheap price rendered it an attractive substrate for specific oil/water isolation between all of these 3D porous components. Furthermore, the absorption of the oils by the 3C aerogel is extremely smooth. For a 1 cm3 piece of 3C aerogel, the absorption maximum could be achieved in 5 s. Furthermore, the 3C aerogel could be employed several occasions for oil absorption with no improvement in absorption potential observed (Li, Li, Sun, & Zhang, 2017). Zhou et. al. synthesized PU@Fe3O4@PS sponge and utilized for the absorption of various oils and organic solvents. Among all oil and organic solvents, chloroform and carbon tetrachloride showed high absorption capacity. Absorption capacity for castor oil, toluene, diesel and chloroform on the PU@Fe3O4@PS sponge was evaluated for 20 cycles. Less than 5% of initial absorption capacity for particular oil or solvent was decreased after 20 cycles which shoed high reusability of the PU@Fe3O4@PS sponge (Zhou et al., 2019). CF-PDA-Ag-NDM was investigated for the absorption efficiency on the different types of oil or organic solvent and water system. All oil or organic solvent and water system showed high absorption efficiency due to the superhydrophobic nature of CF-PDA-Ag-NDM. Among all the systems, dodecanewater system revealed 98.3% absorption efficiency. In realistic implementations the material’s reliability, in comparison to isolation capacity and invasion strain, should be investigated. Despite 30 iterations of application with the dodecane/water combination, CF-PDA-Ag-NDM retains a large isolation performance (higher than 98%) and superhydrophobicity, demonstrating the reliability of the wettability and isolation performance (Zhou et al., 2017). All oil or organic solvent and water system showed high absorption efficiency due to the superhydrophobic nature of magnetic titanium dioxide foam. The separation capacity was found in between 35.23
64.31 g/g for all oil and organic solvent. The explanation for this trend was that titanium dioxide were essential in the oil absorption process, and additional titanium dioxide resulted in increased absorption to a certain amount (Yu et al., 2016). Nevertheless, additional increases in mass content had virtually no effect on absorption ability; however, the excess titanium dioxide softened the structure of the foam, which somewhat reduced absorption capacity (Wenzel, 1936). ALD of ZnO was investigated for the absorption efficiency on the carbon tetrachloride, vegetable oil, liquid paraffin, lubricate oil, cyclohexane and diesel oil. Among all the systems, carbon tetrachloride-water system revealed 162 g/g absorption efficiency. Despite 20 runs, almost 90% of the original absorption potential is retained, showing

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170

9. Oil spill treatment using porous materials

the ZnO-deposited foams’ outstanding reusability. The ultrathin ZnO coating, which barely absorbs any porous structure of the pure foams, is responsible for the large absorption potential and outstanding recyclability. Furthermore, the ultrathin ZnO layer’s binding to the foam surfaces was quite powerful. The ZnO-deposited foams withstand a rugged ultrasonication obstacle and retain their high hydrophobicity and potential to efficiently absorb oil from water for at most 8 months while kept in ambient conditions (Xiong et al., 2018).

9.4 Conclusion The standard materials and techniques used in the current production of superhydrophobic-superoleophilic, superhydrophilic-superoleophobic, superhydrophilicunderwater superoleophobic, adjustable super-wetting polymeric oil/water isolation porous materials like sponge, foam, and aerogels were briefly examined in this review. The optimal wettability for working with the specific oil/water mixtures was established by analyzing the impact of wettability on oil/water isolation. Using related methods, different polymers may be utilized to manufacture super-wettable porous materials. Owing to their distinct functions in distinguishing particular oil/water mixtures, the conditions for wettability are not the same. Low surface energy polymers and nanomaterials can be used to monitor surface wettability. The roughness of the used nanomaterials was greatly increased, which improved wettability and isolation efficiency. Furthermore, the nanomaterials that have been integrated can be used to enhance the mechanical strength of porous materials. Organic
inorganic nanomaterials alteration coatings have a lot of promise for producing high-performance porous materials to fulfill today’s and tomorrow’s oily wastewater management needs.

Abbreviations ALD CEC CF CS Ms MTMS NDM ODS PDA PDMS PFOS PU PUF WCA

atomic layer deposition carbonized eichhornia crassipes copper foam candle soot melamine sponge methyltrimethoxysilane N-dodecyl mercaptan octadecylsiloxane polydopamine polydimethylsiloxane 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane polyurethane polyurethane foam water contact angle

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C H A P T E R

10 Nanotechnological advances for oil spill management: removal, recovery and remediation Sougata Ghosh1 and Thomas J. Webster2 1

Department of Microbiology, School of Science, RK University, Rajkot, India 2Department of Chemical Engineering, Northeastern University, Boston, MA, United States O U T L I N E

10.1 Introduction

175

10.2 Oil pollution

176

10.3 Nanotechnology driven solutions 10.3.1 Nanosensors 10.3.2 Nanofluids 10.3.3 Nanocomposites

176 177 178 182

10.3.4 Nanocoating 10.3.5 Nanomembranes 10.3.6 Nanocatalysts

185 189 191

10.4 Conclusions and future perspectives

191

References

192

10.1 Introduction A multidisciplinary approach of nanotechnology has led to its applications in various fields like medicine, food, electronics, agriculture, and even cleaning the environment. Attractive physicochemical properties of nanoparticles with a high surface area and exotic shape have made them the most preferred agents in catalysis, adsorption, coatings, and carriers. Recently, nanotechnology has found its applications also in the oil industry and refineries. The most important aspect of nanotechnological advances in oil recovery and spill management is promising from an environmental remediation perspective (Franco, Zabala, & Corte´s, 2017).

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00025-2

175

© 2022 Elsevier Inc. All rights reserved.

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10. Nanotechnological advances for oil spill management: removal, recovery and remediation

More research is being carried out to ensure enhanced oil recovery (EOR) and thus several polymer coated nanoparticles are being developed and investigated for their efficiency toward the same. A high surface area-to-volume ratio, thermal and chemical stability, and dispersibility makes the nanostructured materials the most promising agents for oil recovery and removal. Various nanofilms and nanofibers play a significant role in energy storage and conversion (Peng et al., 2018). In this chapter, hazard of oil pollution is discussed. Further, an elaborate account on nanotechnological advances in several steps in the oil industry that include drilling, refining, recovery, production and damage control is furnished.

10.2 Oil pollution One of the major concerns of water pollution is due to discharge of oil refinery effluents that are mostly loaded with hazardous components that include hydrocarbons, ammonia, phenol, and sulfides. These pollutants have a grave impact on aquatic lives of algae, fish, plankton and crustaceans. Oil pollutants can kill the aquatic organisms due to poisoning, coating and asphyxiation, with sensitive juveniles being the most susceptible. Moreover, oil can cause stress and can be a sublethal apart from being mutagenic and carcinogenic. Physiological effects due to oil pollution may also result in alterationa of behavioral patterns. Other hazards include the reduced productivity of phytoplankton and/or algae that can have notable adverse effects on higher crustaceans and fish that feed on them. Inhabiting the oil contaminated niche may result in the development of resistant genotypes replacing the native population that can lead to alteration in the community structure. Such pollution can lead to selection of dominant species as it has been observed that the fresh water species are more tolerant to marine/estuarine species. Reproductive impairment is also observed in aquatic species like Ceriodaphnia that produces fewer young on growing in refinery wastewater. Likewise, a reduction in egg production and the number of broods in the estuarine crustacean Mysidopsis bahia was also noticed. High mortality in fish due to oil pollution is mainly associated with respiratory distress, surfacing and secretion of mucus (Wake, 2005). It is important to note that the severity of oil pollution can be controlled and the area of impact can recover upon the reduction of toxicity of the effluent. However, the time taken for the remediation and recovery depends on the effectiveness of the strategy and the area. Recently various nanoscale materials are being developed and used in the oil industry for ameliorating the deleterious effects of oil pollution which is discussed in the following section.

10.3 Nanotechnology driven solutions Nanomaterials play a multifunctional role in the exploration of refining and drilling as well as the completion of production due to their smaller size, attractive surface properties and high stability. There are several types of nanoscale materials that are used in various processes in the oil industries.

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10.3.1 Nanosensors Remote sensing is now a preferred strategy for detecting oil spills and designing the response for remediation. Further, remote sensing can play a vital role to trace illegal discharge from ships that is the chief cause for mortality and morbidity of seabirds, fishes, turtles and other aquatic fauna. Highly effective nanosensors are comprised of highly miniaturized electromechanic integration as the main component. The nano-size enables these sensors to evade the micro pores for sensing oil spills (Fingas & Brown, 2014). Several nanosensors that are manufactured using carbon nanotubes, graphene and also other associated piezoelectric material are resistant to extreme temperature and pressure. Nano-developer and nano-signal enhancers are nano-robots that can easily move into the cracks and crevices of the reservoir along with the flow of the fluid. This enhances the local electric, magnetic and acoustic behaviors of the reservoirs. This further increases electric logging, nuclear magnetic logging and microseismic logging due to an efficient differentiation degree of oil layers and water layers. Such a phenomenon helps in generating a more detailed information on reservoir porosity, permeability and oil saturation. However, it is important to note that the efficiency of a nanosensor largely depends upon the physicochemical and optoelectronic properties of the nanomaterials (Liu, Jin, & Ding, 2016). Paramagnetic nanoparticles can be used for monitoring the distribution of immiscible fluids on the subsurface. This is achieved upon inducing their mobility due to the imposition of a magnetic field. Such nanoparticles can be directed for selective adsorption at the oil-water interface. Moreover, monitoring of their prolong stability in dispersion with a low retention in the porous medium can be traced to exploit interfacial movements for external detection. Ryoo et al. (2012) reported surface modified iron oxide nanoparticles (IONPs) for oil detection which was measured by phase-sensitive optical coherence tomography as illustrated in Fig. 10.1. The individual

FIGURE 10.1 Schematic diagram of phase-sensitive optical coherence tomography experimental setup. The approximate diameters of the cylindrical well, glass slide holder and solenoid are 4, 38 and 50 mm respectively. The solenoid iron tip is 0.9 mm wide and is 0.2 mm from the glass slide (Ryoo et al., 2012). Source: Reprinted with permission from Ryoo, S., Rahmani, A. R., Yoon, K. Y., Prodanovi´c, M., Kotsmar, C., Milner, T. E., . . . Huh, C. (2012). Theoretical and experimental investigation of the motion of multiphase fluids containing paramagnetic nanoparticles in porous media. Journal of Petroleum Science and Engineering, 81, 129
144. Copyright r 2011 Elsevier B.V.

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nanoparticles in the ferrofluid were between 3 and 5 nm, while the citrate functionalized magnetic nanoparticles were 13 nm in size at pH 8. This novel material can be used for developing a magnetic field-based method for an accurate, non-invasive determination of multiphase oil distribution in a reservoir rock.

10.3.2 Nanofluids Although there are effective methods for oil mining, still abundant crude oil residue remains which are generally extracted by conventional methods like steam flooding, chemical flooding or gas flooding. Nanofluid flooding has emerged as a promising alternative due to its low cost and environmentally benign nature (Luo et al., 2016). More recently, Chen, Jiang, and Zhen (2021) employed temperature sensitive iron oxide (TSIO) nanoparticles for an EOR process. Initially IONPs were synthesized by a hydrothermal method where iron (III) chloride hexahydrate was reacted with sodium acetate trihydrate (NaAc) and polyvinylpyrrolidone (PVP) at 200 C for 18 h. The IONPs were recovered and further reacted with N-isopropylacrylamide (NIPAM), potassium persulfate, and sodium pstyrenesulfonate (SSS) at 80 C for 12 h resulting in the synthesis of TSIO that was dispersed in into brine or water to obtain the nanofluid. The IONPs with a comparatively thicker coating comprised of PNIPAM with styrene sulfonic acid group were irregular in shape with particle sizes smaller than 100 nm. The agglomeration of TSIO into bigger particles was attributed to the polymer chain around the IONPs. Interestingly, with a rise in temperature up to 50 C, the particle size of TSIO decreased from 225.3 to 175.6 nm. The temperature dependent modulation of particle size was due to the temperature sensitive polymer, PNIPAM. The nanofluid was further used for EOR using a microscopic oil displacement strategy as illustrated in Fig. 10.2. The experimental device was comprised of five parts that included a fluid reservoir, injection pump, glass holder, analytic system and receiver. The fluid reservoir could store fluids like water, nanofluid and crude oil that was used for flooding the glass plate fixed at the glass holder, which was made by etching the holes. Initially, crude oil was used to saturate the glass plate followed by injection of water into it simulating secondary water flooding. Next, the nanofluid was injected into the glass plate to drive the residual crude oil after water flooding that could be effectively recorded by a camera. The TSIO facilitated oil recovery was attributed to the altered wettability of the rocks as well as a decreased interfacial tension (IFT) of the oil and water. The oil recovery at room temperature was remarkably enhanced from 65.78% to 74.15% while at 50 C, the recovery rate further increased up to 84.02%. In another study, Sagala, Hethnawi, and Nassar (2020) reported hydroxyl-functionalized silicate-based nanofluids for EOR where nano-pyroxene was used to influence the wettability, IFT and asphaltene aggregation. The triethoxy (octyl) silane was anchored on the nanopyroxene (NPNP) surface to synthesize the fully hydroxylated NPNP nanoparticles. The nanofluid was dispersed in synthetic brine with a pH adjusted to 10. The hydrodynamic size was approximately 10 nm at a high pH while at a neutral pH, the size was found to be 300 nm indicating aggregation and reduced stability. Interestingly, the presence of nanoparticles reduced the aggregate size of the n-C7 asphaltenes and IFT in a concentration dependent manner. Fig. 10.3 illustrates the core flooding set up assembly for oil recovery using the nanofluid. Further, the

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FIGURE 10.2 Schematic of the microscopic oil displacement experimental device(Chen et al., 2021). Source: Reprinted with permission from Chen, Q., Jiang, X., & Zhen, J. (2021). Preparation and characterization of temperature sensitive iron oxide nanoparticle and its application on enhanced oil recovery. Journal of Petroleum Science and Engineering, 198, 108211. Copyright r 2020 Elsevier B.V.

contact angle and wettability index measurements indicated that nanoparticles from the nanofluid adsorbed on the rock surfaces changing the wettability from intermediate wet to stronger water-wet in the absence and presence of initial water films. In the presence of irreducible water saturation during wettability index measurements, depending on the brine composition and pH, initial alteration with aging resulted in a mixed or intermediate wet that changed to stronger water-wet with an increase in the NPNP concentration. Although IFT was reduced with a rise in NPNP concentration, it did not alter the ultra-low range that can remobilize trapped oil due to higher capillary forces. In another study, Sharma, Iglauer, and Sangwai (2016) reported a silica (SiO2) based nanofluid for EOR. The polyacrylamide (PAM) was used as a dispersant in which SiO2 nanoparticles were added followed by sonifaction for 2
3 h during preparation of the nanofluid. Two types of nanofluids were prepared, one with nanoparticles (N) dispersed only in the aqueous PAM solution (NP) and the other with an aqueous surfactant 2 polymer (sodium dodecyl sulfate) denoted as NSP formulations. The average nanoparticle aggregate size in the NP nanofluid was larger for 1.5 wt.% SiO2 (4.12 μm) and 2.0 wt.% SiO2 (4.54 μm) than for 1.0 wt.% SiO2 (3.54 μm), and their size further increased in the presence of SDS (5.54 μm for 1.5 wt.% SiO2 and 6.17 μm for 2.0 wt.% SiO2) as seen in Fig. 10.4. The IFT of the crude oil-SP system (4.9 mN/m on the 1st day and 5.13 mN/m on the 27th day) was lower compared to the crude oil-P system (18.03 mN/m on the 1st day and 17.02 mN/m on the 27th day) which might be attributed to

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10. Nanotechnological advances for oil spill management: removal, recovery and remediation

FIGURE 10.3 Displacement test diagram: (1) carbon dioxide cylinder, (2), manometer gauge, (3), (4), and (5) transfer cells for oil, brine, and nanofluids respectively, (6) valves, (7) pressure transducer, (8) core holder, (9) data acquisition computer, (10) back pressure regulator, (11) collector, (12) ISCO pump, (13) overburden pressure gauge. (Sagala et al., 2020) Source: Reprinted with permission from Sagala, F., Hethnawi, A., Nassar, N.N. (2020). Hydroxylfunctionalized silicate-based nanofluids for enhanced oil recovery. Fuel, 269, 117462. Copyright r 2020 Elsevier Ltd.

the adsorption of the surfactant at the crude oil 2 water interface. Further, the IFT of both the crude oil-NP/NSP systems showed minimum IFT values at 1.0 wt.% SiO2. At higher temperatures, the application of the SiO2 nanofluids remarkably increased oil recovery owing to IFT reduction, fluid viscosity increase, and wettability alteration (from intermediate-wet to strongly water-wet). Recently, Zhou et al. (2020) developed a strategy for oil recovery using a nano-composite comprised of polymer nanoparticles (PolyNPs) and a betaine-type zwitterionic surfactant. A nano-precipitation method was employed to fabricate the PolyNPs where Poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(1,4-benzo-{2,10 ,3}-thiadiazole)] (PFBT) and Poly (styrene-co-maleic anhydride), cumene terminated were dissolved in tetrahydrofuran (THF) followed by ultrasonication. The PolyNPs were recovered by the evaporative removal of THF. In the next step, the nanofluids were prepared by adding different amounts of PolyNPs into the betaine surfactant solution in 15% simulated brine as illustrated in Fig. 10.5. Interestingly, in the presence of the nanofluid the water
oil IFT of the Bakken crude oil decreased by 99.49% and the contact angle increased by 125.73%. Also, the total oil recovery by the nanofluid was enhanced by 9.32% which was attributed to the dynamic displacing processes. Ehtesabi, Ahadian, Taghikhani, and Ghazanfari (2014) used anatase and amorphous TiO2 nanoparticles (TiO2NPs) for heavy oil recovery from sandstone cores. At first, the titanium tetraisopropoxide, H2O2, and H2O were mixed at the volume ratio of 12:90:200, respectively. Further, the TiO2NP solution was refluxed for 10 h to promote crystallinity. After injecting a double pore volume of 0.01% anatase structure into solution, 80% of the oil was recovered. The rock wettability changed from oil-wet to water-wet conditions after treatment with nanoparticles as confirmed by contact angle measurements. A homogeneous deposition of nanoparticles into the core plug surface along with some nanorods

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181

FIGURE 10.4 SEM images of (A) NP and (B) NSP nanofluids (1.0 wt.%wt.% SiO2) in the presence of aqueous PAM and SDS-PAM at 30 C, (C) and (D) are SEM images of sand grains, taken from inlet and outlet ends of sand packs flooded by the NP nanofluid (Sharma et al., 2016). Source: Reprinted with permission from Sharma, T., Iglauer, S., Sangwai, J.S. (2016). Silica nanofluids in an oilfield polymer polyacrylamide: Interfacial properties, wettability alteration, and applications for chemical enhanced oil recovery. Industrial & Engineering Chemistry Research, 55, 12387 2 12397. Copyright r 2016 American Chemical Society.

with a diameter about 60 nm was seen. An increase in the nanorod concentration with the same diameter resulted in enhanced plugging, facilitating more oil recovery. More recently, several biogenic routes were developed for synthesizing novel metal and alloy nanoparticles for diverse applications (Ghosh, 2018). Green routes using extracts of medicinal plants like Dioscorea oppositifolia, Barleria prionitis, Gloriosa superba, Gnidia glauca, Litchi chinensis, Platanus orientalis, and Plumbago zeylanica are considered as environmentally benign rapid and efficient methods (Bhagwat et al., 2018; Ghosh, Chacko, et al., 2016; Ghosh, Gurav, et al., 2016; Ghosh, Harke, et al., 2016; Ghosh, Patil, et al., 2016; Jamdade et al., 2019; Rokade et al., 2017; Rokade et al., 2018; Shende et al., 2017; Shende et al., 2018; Shinde et al., 2018). Biologically synthesized nanoparticles do not involve any hazardous, toxic or corrosive chemicals during synthesis or stabilization. Hence, the biogenic nanoparticles are more biocompatible and environmental friendly (Ghosh, Jagtap, et al., 2015; Ghosh, More, Derle, et al., 2015; Ghosh, More, Nitnavare, et al., 2015; Ghosh, Nitnavare, et al., 2015; Kitture et al., 2015; Salunke et al., 2014; Sant et al., 2013).

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FIGURE 10.5

Schematic diagram of the designed nanofluid. (A) Polymer PFBT. (B) Polymer poly (styrene-comaleic anhydride). (C) Self-assembled polymer nanoparticle. (D) Polymer nanoparticle augmented surfactant nanocomposite. (E) The nanofluid formed by dissolving the nanocomposite in brine. (F) The application of the nanofluid for oil recovery (Zhou et al., 2020). Source: Reprinted with permission from Zhou, Y., Wu, X., Zhong, X., Reagen, S., Zhang, S., Sun, W., . . . Zhao, J.X. (2020). Polymer nanoparticles based nano-fluid for enhanced oil recovery at harsh formation conditions. Fuel, 267, 117251. Copyright r 2020 Elsevier Ltd.

Zargar et al. (2020) grafted titanium oxide NPs (TiO2NPs) synthesized by Euphoria condylocarpa extract on quartz surface to fabricate a green nanocomposite (NC) for EOR. The plant extract was reacted with a TiO(OH)2 solution to obtain a dark brown greenish precipitate that was recovered by filtration and heated up to 600 C which was further washed and dried to get pure TiO2NPs. After mixing the biogenic TiO2NPs with quartz powder, the resulting mixture was refluxed for 3 h at 80 C. The TiO2/quartz NC was suspended in sea water and distilled water to obtain a nanofluid which could effectively minimize the IFT and contact angle between crude oil and water on the surface of carbonate rocks. Significantly, the TiO2/Quartz-nanofluid exhibited an additional oil recovering capability of 21% original oil in place (OOIP) that was attributed to the reduction in IFT from 36.4 to 3.5 mN/m. Moreover, the nanofluid improved the rheological behavior and altered wettability that facilitated a stronger water-wet system from 103 to 48 degrees contact angles. Similarly, Table 10.1 presents various other nanoparticles were used for the preparation of nanofluids to ensure EOR.

10.3.3 Nanocomposites Various graft polymers used in nanocomposites are used effectively for oil recovery due to their high thermal and shear stability owing to the attachment of PAM chains onto the rigid polysaccharide backbone. Singh and Mahto (2017) reported a graft polymer

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TABLE 10.1 A summary of previous work on effects of various nanofluid categories on interfacial tension (IFT), contact angles (CA) and oil recovery. IFT [mN/m] Nanomaterial

Dispersion media

NP conc. [wt.%]

Rock type

Clean

With NP

CA [degree] Clean

With NP

EOR [%OOIP]

Al2O3

Propanol

0.05
0.3

Sandstone

5.7

2.3

56.6

76.8

19.4

Al2O3

DIW

0.05

Limestone

18

13.4

55.8

65.7

9.9

CuO

Polyethyl glycol

0.1
0.2

Glass

47.9

1.5

9

1.8

15

Fe2O3










6.3

2.7

56.6

73.9

17.1

Fe3O4/chitosan

Brine

0.01
0.03

Sandstone

30

17.3

127

92

10.8

SiO2

Ethylene glycol

0.277

Glass

43

8.8

66

25

17

SiO2

PAM

1
2

Sandstone

27

10.2







24.7

SiO2

Xanthan gum

0.1
0.5

Sandstone

17.8

6.4

86

20

7.81

SiO2

Ethanol

0.4

Sandstone

26.3

1.7

55

78

23

SiO2










5

1.5

56.6

79.1

21.6

SiO2

Brine

0.05

Sandstone

19.2

12.8

33

26

17

SiO2










16.7

11

54.8

57.7

2.9

SiO2

Brine

0.1

Sandstone

17.5

7

12

40

28

SiO2

LoSal water

0.1

Sandstone













7

SiO2/prop-2-enamide




0.6
1.2

Sandstone

28

7

87

28

21

0.1

Sandstone

27

14

85

62.2

9.9

SiO2/Poly2(DMAEA)

0.1
0.2

Sandstone

47

35







5.2

TiO2










17.5

12.5

55.3

61.9

6.6

ZnO

SDS

0.05

Carbonate

2.8

3.5

22.5

72.2

0

ZnO

SDS

0.05
0.5

Calcite

27.4

18.6




11.8

11

ZnO/SiO2/xanthan

LoSal water

0.05
0.2

Carbonate

31.8

2.016

137

34

19.3

SiO2/2-Poly(MPC)

Source: Reprinted with permission from Zargar, G., Arabpour, T., Manshad, A.K., Ali, J.A., Sajadi, S.M., Keshavarz, A., Mohammadi, A.H., 2020. Experimental investigation of the effect of green TiO2/Quartz nanocomposite on interfacial tension reduction, wettability alteration, and oil recovery improvement. Fuel, 263, 116599. Copyright r 2019 Elsevier Ltd.

nanocomposite hydrogel system composed of a PAM graft starch/clay nanocomposite and chromium (III) acetate (crosslinker). At first, a gelatinized starch (St) graft PAM sodium montmorillonite nanocomposite (PAAm-g-St/MMT) was fabricated employing a free radical polymerization technique in an inert atmosphere of nitrogen using potassium persulphate as an initiator. Then, the graft polymer nanocomposite hydrogel was prepared by reacting the polymer with chromium(III) acetate in brine. As seen in Fig. 10.6, starch exhibited a granular morphology that was distorted to a fibrillar structure grafted with PAAm. Further, the incorporation of MMT altered the fibrillar structure of PAAm-g-St to a coherent and near co-continuous structure in PAAm-g-St/MMT. The clay particles were

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FIGURE 10.6 FESEM images of (A) starch; (B) PAAm; (C) PAAm-g-St; and (D) PAAm-g-St/MMT (Singh and Mahto, 2017). Source: Reprinted with permission from Singh, R., & Mahto, V. (2017). Synthesis, characterization and evaluation of polyacrylamide graft starch/clay nanocomposite hydrogel system for enhanced oil recovery. Petroleum Science, 14, 765
779. Copyright r The Author(s) 2017. (Open Access).

40
100 nm in size that formed layers and were well dispersed within the polymer matrix. The PAAm-g-St/MMT hydrogel exhibited an undulant surface due to the inclusion of a nanoclay into the hydrogel. In sand pack flooding experiments, the concentration of the PAAm-g-St/MMT was set at 0.5 wt.%, while the crosslinker concentration varied at 0.4 wt. % and 0.2 wt.% and also in the conventional gel system [PAM and Cr(III) acetate gel], the PAM concentration was 1.0 wt.% and the crosslinker concentration was 0.4 wt.% and 0.2 wt.%, respectively. These parameters enhanced the plugging capacity of the graft polymer nanocomposite indicating its promise for water shutoff treatments required for EOR from oilfields. In another similar study, Tongwa, Nygaard, and Bai (2013) prepared a hydrogel where hydrolyzed PAM was mixed with brine following its addition into completely exfoliated nanoclay Laponite XLG to obtain a nanocomposite gel. The resulting product was cut into smaller sizes, and dried in an oven at 40 C overnight. The hydrogels exhibited high mechanical toughness, tensile moduli, and tensile strength. An increase in clay concentration was directly proportional to gel strength.

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Similarly, Tongwa and Bai (2014) reported that the incorporation of nanomaterials increased hydrogel strength up to 394%. Additionally, swelling performance, postdegraded gel viscosity, and long-term thermal resistance of a nanocomposite gel increased by several orders of magnitude compared to hydrogels with no nanomaterial. Initially, acrylamide was dissolved in which 0.2% XLG was supplemented and stirred vigorously for complete exfoliation of the clay nanomaterial. In this reaction mixture, PEG-200 (crosslinker) was mixed and kept for 10 h at 40 C for complete gelation. After cutting the elastic gel into small pieces, they were soaked in water for 3 days, dried at 60 C and pulverized to get the preformed particle gels of 80 and 100 mesh (180
250 mm) sizes. Fig. 10.7 shows that the nanocomposites had 3D networks with a viscosity of 4437cp unlike the individual hydrogel (170cp). The degradable laponite XLG nanocomposite hydrogels can be further used for secondary polymer flooding due to their high post-degradation viscosity under anaerobic conditions. The nanocomposite can sweep out oil from regions with low permeability as it can act as a conformance control agent that can plug water-thief zones and channels. Moreover, after injection into a reservoir, with time, the nanocomposite would degrade into a more viscous polymer that would enter deeper regions of the reservoir and mix with the flood water. This in turn would lead to better water and polymer flooding processes due to enhanced water sweep efficiency, thereby enhancing oil recovery.

10.3.4 Nanocoating Although various nanostructures are used in the process of separation of oil from water, a nanocoating is considered to be an attractive alternative for its high efficiency for EOR. Recently, Gharibshahi, Omidkhah, Jafari, and Fakhroueian (2020) reported the synthesis of a novel multiwalled carbon nanotube (MWCNT)-Fe3O4 nanohybrid (weight ratio of 3:1) employing a coprecipitation method as illustrated in Fig. 10.8. The synthesized Fe3O4 nanoparticles were spherical with 30 nm size which were distributed on the surface of the tubular MWCNT. Some aggregation was also noticed which might be attributed to the loading percent of Fe3O4 nanoparticles to MWCNT (3:1 wt.%). The resulting nanohybrids were surface modified with 3-AminoPropylTriEthoxySilane, citric acid (CA), and polyethylene glycol (PEG 6000) to ensure effective dispersion into the water. The coated nanomaterials were magnetic and a significant rise in temperature was observed with an addition of even 0.1 wt.% of MWCNT-Fe3O4 nanohybrids modified with citric acid after being subjected to microwave radiation for 180 s. An enhancement of the microfluidic oil recovery up to 30.3%, and 43.9% was achieved with Fe3O4 @ CA, and Fe3O4-MWCNT @ CA with the use of 400 W microwave radiation. In another interesting study, Hosseini, Sadeghi, and Khazaei (2017) fabricated a stable hydrophilic coating on a superhydrophobic surface of carbonate rock using TiO2/ SiO2 hybrid nanoparticles. Firstly, the TiO2/SiO2 nanoparticles were synthesized by a modified sol-gel method which increased surface hydrophilicity due to specific functional groups. TiO2 nanoparticles were synthesized reacting titanium isopropoxide (TTIP) dissolved in ethanol with HNO3 for 2 h at 60 C for hydrolysis. Next, a mixture of tetraethyl orthosilicate (TEOS), ammonia and EtOH, was added to the hydrolyzed TTIP solution and reacted for another 2 h at 60 C until an opaque suspension with high viscosity was

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FIGURE 10.7 Before-degradation environmental scanning electron microscopy (ESEM) micrographs of: (A) A pure LXLG nanomaterial. (B) A pure polyacrylamide (PAM) polymer. (C) 3-D micrograph of a bulk LXLG nanocomposite hydrogel. (D) A hydrogel with no nanomaterial. A fine, smooth network structure is observed. (E) A LXLG nanocomposite hydrogel swelled in 1% brine as the solvent. The presence of brine almost caused the porous network to close up. (F) A LXLG nanocomposite hydrogel swelled in distilled water as the solvent. A denser, thicker, and corrugated network structure is observed. (G) An extremely stretched, thin section of LXLG nanocomposite hydrogel (Tongwa and Bai, 2014). Source: Reprinted with permission from Tongwa, P., Bai B., (2014). Degradable nanocomposite preformed particle gel for chemical enhanced oil recovery applications. Journal of Petroleum Science and Engineering, 124, 35
45. Copyright r 2014 Elsevier B.V.

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FIGURE 10.8 A schematic of the surface modification of a synthesized Fe3O4-MWCNT nanohybrid (Gharibshahi et al., 2020). Source: Reprinted with permission from Gharibshahi, R., Omidkhah, M., Jafari, A., & Fakhroueian, Z. (2020). Hybridization of superparamagnetic Fe3O4 nanoparticles with MWCNTs and effect of surface modification on electromagnetic heating process efficiency: A microfluidics enhanced oil recovery study. Fuel, 282, 118603. Copyright r 2020 Elsevier Ltd.

produced. The resulting viscous suspension was dried at 100 C for 24 h followed by annealing at 600 C for 4 h to form TiO2/SiO2 nanoparticles. These nanomaterials were amorphous spheres with some agglomeration that might be attributed to the calcination process mediated growth in particle size. The size of the TiO2/SiO2 nanoparticles was 20 nm. Adsorption of nanoparticles on the rock surface converted the superhydrophobic rock surface to superhydrophilic. Hence, the nano-coatings with a high thermal stability and moderate mechanical stability can be used for altering wettability leading to increased oil wet carbonate rock for EOR. Kim et al. (2019) developed a continuous ZIF-8/reduced graphene oxide (RGO) nanocoating by growing ZIF-8 on a RGO-coated polyurethane (PU) foam as depicted in Fig. 10.9. The PU foam was immersed in a GO solution for surface modification which was then subjected to thermal treatment at 150 C for 4 h converting the GO layer into RGO layer. Then, 2-Methylimidazole (99%, 2-MeIM) and zinc nitrate hexahydrate were mixed in water to form a solution in which the RGO coated PU foam was immersed. The resulting zeolitic imidazole framework (ZIF-8) growth was conducted at 50 C for 1 h. Fig. 10.9B shows that the PU foam was covered by a continuous ZIF-8/RGO coating with well distributed N (yellow) and Zn (green) atoms throughout the surface of the PU foam (Fig. 10.9C). The synergy between the hydrophobic/oleophilic properties of RGO and ZIF-8 enabled selective oil absorption of the PU foam with an absorption capacity of 15
35 g/g which was viscosity dependent. An ultrafast selective hexane flux up to 800,000 Lm22/h confirmed the selective organic solvent filtering ability of the ZIF-8/RGO coated PU foam. Another study by Shi, Li, Cheng, Zhao, and Wang (2021) on a similar line reported that a multifunctional nanocoating comprised of nano-Fe3O4 and RGO with photothermal conversion ability and non-flammable nature, could be effectively deposited on the polymer

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FIGURE 10.9

(A) Schematic illustration to coat a ZIF-8/RGO film on PU foam. (B) Photographic image of a ZIF-8/RGO/PU foam. (C) SEM image and corresponding EDS mapping images of a ZIF-8/RGO/PU foam. (D) SEM image obtained from a skeleton of a ZIF-8/RGO/PU foam. Inset is an SEM image of the neat PU foam. (E) Top and cross sectional SEM images of ZIF-8/RGO/PU foam, respectively. (F) Schematic illustration exhibiting the interaction between ZIF-8 and RGO (Kim et al., 2019). Source: Reprinted with permission from Kim, D.W., Eum, K., Kim, H., Kim, D., de Mello, M.D., Park, K., Tsapatsis, M., 2019. Continuous ZIF-8/reduced graphene oxide nanocoating for ultrafast oil/water separation. Chemical Engineering Journal, 372, 509
515. Copyright r 2019 Elsevier B.V.

foam skeletons employing a facile coprecipitation and dip-coating processes. The selective superior absorption of various oils and organic solvents by the composite foam was attributed to its high hydrophobicity, robust morphology and low density. Interestingly, the temperature of the nanoscale coating material could rapidly rise with at a rate of 103.5 C/min upon irradiation due to the double photothermal conversion effects of nano-Fe3O4 and rGO. The foam displayed a high absorption capacity of 75.1 times its weight. Also, a faster absorption rate of 9000 g/m2/min for highly viscous oil was achieved upon irradiation. The novel material is unique and advantageous owing to its properties like high flame retardancy, elasticity, and magnetism. The material is, thus, reusable and recyclable that can be controlled

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magnetically for effective clean up thereby addressing oil spill mediated environmental pollution.

10.3.5 Nanomembranes Oil mixed with water can exist in complex forms that include floated oil, dispersed oil, stable emulsions (droplet diameter , 20 μm), and dissolved oil (Bouchemal, Briancon, Perrier, & Fessi, 2004). Since conventional methods, such as sedimentation, flotation, and centrifugation are unable to separate oil/water emulsions, particularly surfactant-stabilized oil-in-water emulsions (SSEs), newer techniques using membranes have emerged as promising alternatives. Microfiltration membranes made from poly (tetrafluoroethylene), poly (vinylidene fluoride), and cellulose are being used for the separation of industrial emulsions. More recently, Li, Gao, Wang, Chen, and Yu (2021) synthesized a flexible silica nanofiber/ nanobead (SNB) membrane by combining electrospinning and electrospraying techniques. Firstly, a poly(vinyl alcohol) (PVA) solution and silica sol (prepared using TEOS) were mixed in different proportions for 4 h. The resulting silica networks were entangled with PVA chains by hydrogen bonds, increasing the viscosity of the precursor solutions. Eventually the SNB membrane was prepared by electrospinning the precursor at a high voltage of 20 kV at 22 C 2 25 C followed by calcination at 800 C. The dimensions of the nanofibers were dependent upon the proportion of the precursor components used. Smooth surfaces with 185 nm diameter of the nanofibers were obtained when the precursors were mixed at a ratio of 10:10 (polymer and silica sol). However, the nanofibers were spindle shaped with numerous beadon-string structures when the precursor ratio was altered to 2:10 and 1:10. The bead diameters varied from 50 nm to 2 μm which were connected by ultrathin fibers with a diameter of about 30 2 60 nm. Properties like superhydrophilicity and underwater superoleophobicity (oil contact angle of 162 degrees), small sliding angles (2.5 degrees), and a small oil adhesion force (0.4 mN) were displayed by the membrane that was composed of nanofiber-supported bead-on-string structure. Further, the superwettability and hierarchical pore structure of the SNB membranes were advantageous for good separation performance toward SSEs with high efficiency ( . 98.8%) and permeate flux (2237 L/m2/h) under low pressure (,10 kPa). Such nanomembranes not only possessed robust mechanical properties but also exhibited superior antifouling properties, and excellent reusability. In another study, Tai, Gao, Tan, Sun, and Leckie (2014) reported a novel free-standing and flexible electrospun carbon 2 silica composite nanofibrous (NF) membrane for oil water separation. Initially, a spin dope for SiO2 2 carbon composite was produced by mixing polyacryonitrile (PAN), and TEOS, in dimethylformamide (DMF)/acetic acid (volume ratio of 15/1) at 90 C. The SiO2 2 PAN NF mat was prepared by electrospinning the aforementioned spin dope at 0.6 2 0.8 kV/cm electric field strength which were further oxidized (stabilized) at 280 C in air for 2 h and carbonized at 900 C in nitrogen for 2 h. Fig. 10.10 shows that the nanofibers with an average diameter of 481 6 57 nm were entangled with the membrane rendering it a 3D macroporous network that facilitated the liquid permeation rate across the membrane due to the decreased mass transfer resistance. Further, Fig. 10.10B shows the wrinkles on the nanofiber surface making it rough in appearance. Maintaining the SiO2 concentration below 2.7 wt.% could enhance the

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FIGURE 10.10

Characterization of electrospun composite nanofibers. (A) Top view of electrospun composite nanofibrous mat; (B) Surface morphology of a single composite nanofiber; (C) XRD pattern showing amorphous carbon and silica in pristine CNFs and the composite nanofibers; (D) Flexibility of the composite nanofibrous mat, which can be easily cut into a desirable shape, as shown in the inset (Tai et al., 2014). Source: Reprinted with permission from Tai, M. H., Gao, P., Tan, B. Y. L., Sun, D. D., & Leckie, J. O., (2014). Highly efficient and flexible electrospun carbon 2 silica nanofibrous membrane for ultrafast gravity-driven oil 2 water separation. ACS Applied Materials & Interfaces, 6, 9393 2 9401. Copyright r 2014 American Chemical Society.

mechanical strength, toughness and flexibility of the nanomembrane. The wettability was intact at an elevated temperature up to 300 C in highly acidic or basic conditions. A surface-coating with silicone oil for 30 mins made the composite membrane ultrahydrophobic with superoleophilic properties which was indicated by the water and oil contact angles of 144.2 6 1.2 degrees and 0 degrees, respectively. Wu et al. (2018) reported a facile and green route for fabricating a hydrophilic NF membrane that could effectively separate oil-in-water emulsions. This process is advantageous as the nanomembrane could be reused and recycled. The hydrophilic polymer filtration

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membranes was synthesized employing in situ cocrosslinked polymer 2 nanoparticle networks by using hydrophilic poly(N-isopropylacrylamide-co-N-methylolacrylamide) (PNIPAm-co-NMA) as the polymeric nanofiber matrix, and biobased nanoparticles, that is, chitin nanowiskers (ChNWs) as the reinforcement and cocrosslinked hub. The resulting cocrosslinked P(NIPAAm-co-NMA)/ChNWs nanofiber was structurally very stable with uniform, smooth, continuous and bead-free nanofibers without any adhesion among the adjacent nanofibers. This was attributed to the ability of the ChNWs to disperse homogeneously among the nanofibers. The random 3D nonwoven porous network obtained due to dense entanglement of the components with each other was ideal for emulsion separation with a separation flux of 1100 2 1300 L/m2/h resulting in a separation efficiency of .99.5%. Interestingly, for up to five cycles, the membrane could be reused and recycled without any notable difference in its activity indicating its promising role in addressing oil spills, industrial oily wastewater treatments and oil recovery.

10.3.6 Nanocatalysts Various nanocatalysts have promising applications in the oil industry owing to their high aspect ratio and unique catalytic properties. Metallic nanoparticles with unique optical, magnetic, electronic, and chemical properties were reported to offer better control of chemical processes, like the Fischer-Tropsch process. Nanoscale metals like cobalt, iron, nickel, and ruthenium can catalyze the series of chemical reactions involved in the aforementioned process responsible for converting carbon monoxide and hydrogen into liquid hydrocarbons. Polyvinylpyrrolidone stabilized rhodium (Rh), ruthenium (Ru), platinum (Pt), and cobalt (Co) tested for catalytic activity for the Fischer-Tropsch reaction revealed that PVP-Co was remarkably active enhancing the reaction. Likewise, iron or cobalt nanoparticles dispersed in PEG also effectively catalyzed the Fischer-Tropsch reaction. Interestingly, the catalyst could be recovered after the reaction due to the ferromagnetic properties of iron nanoparticles. Similarly, carbon based nanocatalysts could significantly reduce (4%) the high viscosity of heavy oil under microwave heating. Nanomaterials are also used for downstream processing in oil industries. Engineered Co-Mo catalyst on MCM-41 mesoporous materials facilitated the hydrodeoxygenation reaction associated with pyrolysis that increased the heating value reducing the high oxygen content (Peng et al., 2018). However, optimization is required for rationally employing nanocatalysts in various processes in the oil industry.

10.4 Conclusions and future perspectives Attractive physicochemical and optoelectronic properties have made nanoparticles one of the most important types of materials for applications in managing oil spills and further recovery and removal. Nanosensors are used for the detection of oil deposits underneath the Earth’s crust by creating a detailed and accurate 3D/4D seismic view of the deep wells. Likewise, nanofluids, which are mostly used during the drilling process, help in the stabilization of the well bore, improve rheology and reduce filter loss. Nanofluids are

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attractive materials that can alter the wettability of the porous surface, enhance thermal stability and reduce viscosity of heavy oils. Another group of nanomaterials, called nanocomposites, are used for manufacturing the equipment used in oil industries. They reduce fluid invasion into shales. Similarly, nanocoatings provide durability and long life to the equipment by making them corrosion resistant. Additionally, they can be used for flooding applications as they improve rock surface properties. Nanoparticle impregnated membranes, popularly termed as nanomembranes, help in the separation of the drilled oil from the impurities, CO2 capture and also in storage. Last, but not the least, nanocatalysts also play a vital role in pyrolysis and associated processes that enhance both refining efficiency and capacity. Also these nanomaterials can play an important role in the up-gradation of heavy oil. However, there are several factors that limit applications of nanotechnology in thee oil and gas industry. Firstly, the nanomaterials are expensive, which is a major drawback in their large scale application. Moreover, the activity of nanostructures is dependent on their size and shape. Hence, it is critical to design optimized processes for the fabrication of tailor-made nanoparticles with desired morphological features. On the other hand, toxicological aspects should be considered carefully before field applications as they may persist for a long duration in the environment and affect the flora and fauna. The nanomaterials may percolate through the soil and enter the ground water affecting its quality and potability. Similarly, the property of the nanostructures under salinity, temperature, and pH should be checked before field applications. Careful investigation of the structural features under simulated natural conditions will provide an insight to the overall fate of the nanostructures during field applications. The degradation of the nanostructures after use should be checked to predict the time required for their complete removing from the environment. Similarly, functionalization of the nanomaterials should be rationally undertaken in order to ensure the safe and biocompatible nature of the nanoparticles before subjecting them to field applications. Biologically synthesized nanoparticles can provide biocompatible nanoparticles for successful applications in the oil industry. In view of this background, a thorough investigation of the engineered nanomaterials should be conducted before they enter the oil industry as a promising alternative for the management of oil spills, oil recovery, removal and remediation.

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C H A P T E R

11 Carbon nanotube-based oil-water separation Tamanna Khandelia and Bhisma K. Patel Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati, India O U T L I N E 11.1 Introduction

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11.2 Carbon nanotube-carbon-based sorbent

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11.3 Principles of oil-water separation by carbon nanotube

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11.4 Structure and synthesis of carbon nanotube 197 11.4.1 Structure 197

11.4.2 Synthesis

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11.5 Current applications: carbon nanotube-based oil-water separation

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11.6 Future perspective

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11.7 Summary

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References

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11.1 Introduction The field of oil-water separation is highly significant as it has direct implications in solving the problems of oil spilling, which is a serious threat to the ecosystem (Gupta & Tai, 2016). The tremendous development of industries especially petrochemical and marine industries in the past decades is the major cause of oil-spilling, thereby disturbing the ecosystem. Leakages during storage and transportation of oil have caused many accidents all over the world (Xue, Cao, Liu, Feng, & Jiang, 2014). Above this, the planned disposal of oily wastewater into water bodies by mankind is very menacing. Oil-spill in water bodies is more dangerous than on land as oil floats over water blocking large surface area of the water body, leading to the death of many marine life and disturbing the marine ecosystem. Separation of oil-water emulsion is even more important, as emulsions are very stable and a challenging task for scientists

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00019-7

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all over the world. Emulsions may be of various types, including oil-in-water (O/W) emulsion, surfactant stabilized or surfactant free and of various sizes (micrometer or nanometer). Among many enormous oil spill incidents, the dreadful aftermath of the Persian Gulf War oil spill incident in 1991 urges us to learn important lessons from it. Miserably, it was not an accident but a filthy deed of mankind. Approximately, 4 million barrels of oil were released into the northern Persian Gulf. The oil penetrated deep down, and it persists to date, thereby affecting lives mercilessly. The adverse effects of oil-spill, particularly oilwater emulsion demands extensive research to be done in this field (Gupta & Tai, 2016). Appreciatively, commendable research has been carried out in this field. Jiang et al. in 2004 first introduced the idea of combining both superhydrophobicity and superoleophilicity of a material for the separation of oil and water (Feng et al., 2004). They developed a stainless steel mesh coated with an emulsion prepared using polytetrafluoroethylene as a precursor and successfully separated diesel oil and water.

11.2 Carbon nanotube-carbon-based sorbent The development of various carbon-based materials including carbon dots, graphene, carbon aerogels, fullerene, carbon nanotubes (CNTs), carbon nanofibers among many others have been widely explored in various fields like gas purification, wastewater treatment, oil-water separation, cleaning of drinking water, etc. Gupta, Dunderdale, England, and Hozumi (2017), considering the economic and environmental aspects, the development of CNTs have shed a bright light on gloomy disasters caused by oil spillage and industrial oily wastewater drainage. CNT was first discovered by Iijima and Ichihashi and Bethune et al. independently in 1993 in carbon arc chambers. CNTs are generally chiral and semiconductors with a moderate band gap, while a few achiral SW-CNT are metallic. The superhydrophobic and superoleophilic property of CNT makes it an ideal tool for oil-water separation. Moreover, CNT is laden with many distinguishing physicochemical properties viz. high surface area, low density, chemical stability, excellent mechanical properties, large pore volume, environment-friendliness and high sorption capacity. The absorption capacity of CNT sponge is exceptionally high and ranges between 15
50 times their own mass and can be reused by repeated heating and mechanical squeezing.

11.3 Principles of oil-water separation by carbon nanotube The theoretical aspect of oil-water separation revolves around the subject matter of contact angle (CA) θ. CA is the angle measured through the liquid, where the liquid-vapor interface meets the solid surface. It gives a quantitative measurement of the wettability of a surface via the Young equation: γ 2 γ SL cosθ 5 SV γ LV Here, γ SV, γ SL, and γ LV denote the interfacial tension between solid-vapor, solid-liquid and liquid-vapor respectively as shown in Fig. 11.1.

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11.4 Structure and synthesis of carbon nanotube

FIGURE 11.1

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Contact angle (θ).

The value of CA categorizes a surface into hydrophilic, hydrophobic, and superhydrophobic. With the water CA (WCA) less than 90 degrees, a surface is defined as hydrophilic, when it is in between 90 and 150 degrees then it is hydrophobic and above 150 degrees it is superhydrophobic. The same description is applicable for all liquids including oil. The phenomenon of non-wettability has been inspired by nature. Since time immemorial, the superhydrophobic nature of lotus leaves and butterfly wings have inspired researchers all around the world. It is the topography and chemical composition of the surface that imparts the superhydrophobic nature to a surface. Artificial superhydrophobic surfaces have been developed by introducing roughness (chemical modification) to them. In the scenario of oil-water separation, the idea of combining the property of superhydrophobicity and superoleophilicity is a boon to mankind and the idea has been implemented very successfully. Since the major problem faced by human beings is the spillage of oil in water or oil-water emulsion; materials with both the properties combined, have the potential to absorb oil besides repelling water.

11.4 Structure and synthesis of carbon nanotube 11.4.1 Structure As the name suggests, CNT has cylindrical structure (infinitely long) with a diameter in the range of 0.4
40 nm. It has a hollow one-dimensional structure with rolled up graphene layers; graphene has a two-dimensional layered structure with carbon atoms arranged in a hexagonal manner. The diameter of CNT is constrained to a narrow range as the carbon-carbon bond length is fixed. CNT may be both single walled CNT (SWCNT) or multiwalled (MWCNT). In MWCNT the SWCNTs are nested together bonded by weak Van der Waals interaction in a tree-ring like fashion. There are two main configurations of CNT: (1) Zigzag: In the zigzag configuration, a zigzag path can be defined along a direction perpendicular to the length of the CNT. The path turns 60 degrees alternatively left and right, after stepping through each bond (Fig. 11.2A). (2) Armchair: In an armchair configuration an armchair type of path can be encircled along the diameter of the CNT. The path takes two left turns of 60 degrees followed by two right turns every four steps (Fig. 11.2B). The large surface area of CNT, combined with its oleophilic properties makes it a perfect fit for oil-water separation. The typical nanostructure of CNT and the carbon-carbon

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(A)

FIGURE 11.2

(B)

(A) Zigzag configuration (B) Armchair configuration.

bond strength imparts it exceptional properties including electrical conductivity and semiconductivity, tensile strength, thermal conductivity. It is because of these properties, CNT has gained remarkable position in optics, electronics, nanotechnology and many other applications in materials chemistry. In addition, the structure of CNT can be chemically modified for superior results. Functionalization of CNT improves the solubility of CNT in various solvents.

11.4.2 Synthesis CNTs can be synthesized by various techniques including arc discharge, laser ablation, chemical vapor deposition (CVD) and high pressure carbon monoxide disproportionation (Prasek et al., 2011). Among these technique, the CVD is much popular as this method has control over the length, diameter and morphology of the CNT together with producing high yields. CVD may be assisted by various sources including oxygen assisted CVD, radiofrequency assisted, hot filament assisted CVD, water-assisted CVD, microwave plasma enhanced CVD, thermal and plasma-enhanced CVD (PECVD). Transition metal catalysts like Ni, Fe, or Co are commonly used in the technique. The role of these catalysts in CVD is to decompose the carbon source through the energy of plasma irradiation in PECVD, heat in thermal CVD, etc. The carbon sources which have been most commonly used here are hydrocarbons- ethane, methane, ethylene, acetylene, xylene, isobutane, and ethanol.

11.5 Current applications: carbon nanotube-based oil-water separation In order to increase the efficiency of CNTs, proper functionalization of the CNT wall is required. This lowers the surface energy and imparts proper roughness to CNTs. Superhydrophobic CNT films may be produced by the following two main approaches: (1) Adsorption of low surface energy chemicals onto the CNT surface (bounded by Van der Waals or π-π interactions) (2) Covalent attachment of hydrophobic groups. CNTs are used to fabricate many membranes, as the CNTs impart tensile strength, electrical and thermal conductivities, etc. to the membrane. To date, many applications of CNTs have been made for the successful separation of oil-water mixtures and emulsions (Bu et al., 2017; Hu, Li, & Dong, 2018; Peng & Guo, 2016; Zhang et al., 2016).

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In 2013, Wang et al. coated polyurethane (PU) sponge with the superhydrophobic and superoleophilic CNT and polydimethylsiloxane (PDMS) (Wang & Lin, 2013). PU sponge has been widely used in the field of oil-water separation as it is easily available commercially and has the ability to absorb both oil and water. Fabrication of the sponge with various materials can tune its absorption property according to requirements. Upon fabrication of CNT/PDMS layer onto PU sponge, the wettability of PU sponge changed from hydrophilic to superhydrophobic nature; thereby repelling water and absorbing oil and organic solvents. Owing to the robust nature of the prepared CNT/PDMS-PU sponge, it can be used in conjugation with a vacuum pump for simultaneous removal of oil from water. The CNT/PDMS-PU sponge could separate micrometer sized surfactant-free waterin-oil (W/O) emulsions with very high efficiency (99.97 wt.%). The method of preparation of the CNT/PDMS-PU sponge is as follows: A dip-coating method was used to deposit CNT/PDMS suspension on the PU sponge, which was then heated at 120 C in an oven. The prepared CNT/PDMS-PU sponge had a WCA of 162 6 2 degrees (superhydrophobic) and CA of n-hexane, n-hexadecane, and gasoline were all close to 0 degrees (superoleophilic). The fabricated sponge could separate oil up to 35,000 times of its own weight. In 2013 Jin et al. reported a method of separating both micrometer and nanometer sized surfactant stabilized and surfactant free W/O emulsions via a free standing ultrathin SWCNT network film (Shi et al., 2013). The film could separate W/O emulsion with a flux of about 100,000 L/m2/h/bar and separation efficiency of 99.95 wt.%. The procedure of synthesis is as follows: The ultrathin SWCNT film was prepared via vacuum filtering of the SWCNT suspension through a cellulose ester (MCE) filter, followed by releasing it from the filter. The thickness of the film could be controlled by the volume of the SWCNT suspension which was to be filtered. The prepared freestanding SWCNT was used as a filtering tool for the separation of the W/O emulsion. It was placed on a ceramic membrane and the W/O emulsion was filtered via suction. The film possessed high mechanical strength and good flexibility. When the W/O emulsion was allowed to pass through the SWCNT film oil droplets permeated through the film, leaving behind the water content, thereby de-emulsifying the emulsion. In 2015, Jin et al. focused on separating O/W nanoemulsions. Nanoemulsions or nanosized oil provides a new challenge to scientists as they cause serious damage to the environment and public health (Gao, Zhu, Zhang, & Jin, 2015). They fabricated SWCNTs with polydopamine (PD) and polyethyleneimine (PEI) to prepare a SWCNT/PD/PEI composite membrane of nanometer sized pores. The thickness of the composite film is 158 nm and has a pore size of B10 nm. The film can separate O/W nanoemulsions in an ultrafast manner with a permeation flux of # 6000 L/m2/h/bar. The film is stable in adverse pH conditions, which makes it suitable for treating O/W nanoemulsions in all pH ranges. The procedure of synthesis of SWCNT/PD/PEI composite film is as follows: Initially, a PD layer was coated on SWCNT to prepare the SWCNT/PD dispersion. The thickness of the PD layer upon SWCNT is controlled by the reaction time. The pore size of the SWCNT/ PD composite film is 10 6 5 nm and a thickness of 154 nm. The SWCNT/PD film was further immersed in a solution containing PEI to graft a layer of PEI onto the SWCNT/PD composite film to produce the final SWCNT/PD/PEI composite film. The final thickness of the SWCNT/PD/PEI film is 158 nm. The WCA of the raw SWCNT membrane is 120 degrees whereas the prepared composite film displays superhydrophilic and underwater

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superoleophobic property. The film has a WCA of nearly zero and an oil CA of 162 degrees. The same group in 2015, reported a photothermal responsive, SWCNT membranebased oil-in water separation technique (Hu, Gao, Ding, et al., 2015). The pore sizes of the membrane were controlled by light. They prepared an Au nano-rod (ANR)/poly(N-isopropylacrylamide-co-acrylamide) (pNIPAm-co-AAm) cohybrid SWCNT membrane. The pNIPAm-co-AAm layer imparts a hydrophilic property to the SWCNT network film. The pNIPAm based copolymer also acts as a chemical valve for the membrane which is triggered by heat, thereby tuning the pore radius of the membrane. On the other hand, Au nanoparticles add a photothermal response to the membrane. The procedure for synthesis is as follows: The photothermal-responsive nanoporous membrane was prepared via three main steps: (1) Coating of the SWCNT with PD. (2) Functionalization of the PD modified SWCNT with pNIPAm-co-AAm. (3) Decoration of prefunctionalized SWCNT with ANR. The mechanism of O/W separation is based on the size-sieving effect and the wettability of the membrane. It is the underwater oleophilicity, hydrophobicity and the nanometer sized pores that brought about the separation. The membrane displayed a separation efficiency of . 99.99%. In 2014, Wang et al. also fabricated a superhydrophobic and superoleophilic PU with CNTs for discriminatory removal of oil from water (Wang et al., 2015). Apart from superhydrophobicity and superoleophilicity, the prepared sponge had marvelous properties including excellent mechanical strength and elasticity, stability in a temperature range of 50 C to 100 C and selective absorption of oil with a sorption capacity up to 34.9 times of its own weight. A simple squeeze removes all the absorbed oil and the material may be reused for up to 150 times with intact efficiency. The procedure for synthesis is as follows: Being inspired by the adhesive property of dopamine, they coated CNTs with dopamine film; the dopamine modified CNTs (CNT-PDA) were then anchored on PU sponge through the self-polymerization of dopamine (PDA). Further, a chemical reaction was carried out where the PDA film was conjugated to octadecylamine to give the resultant sponge. In 2014, Chen et al. developed a CNT based material for separation of oil/water emulsions (Gu et al., 2014). It is well known that the separation of oil droplets with small diameters (in the range of μm and nm) as in surfactant stabilized oil-water micro emulsion is a challenging task and materials with better efficiency are highly desired. The salient features of CNTs attracted them to modify CNTs by covalently linking superhydrophobic polystyrene (PS) to it thereby preparing PS/CNT hybrid membrane. The prepared PSCNTs membrane could be reused and had a sorption capacity of up to 270 times its own weight. The hybrid membrane could separate oil-water emulsion with very high flux (5000 Lm22h21bar21). The synthesis procedure is as follows: A uniform layer of CNTs ethanol dispersed solution was spread over Al2O3 membrane. The superhydrophobic PS were allowed to covalently attach on the -OH or -COOH functional groups on CNTs via self-initiated photo grafting and photo-polymerization. The prepared hybrid membrane drastically changed the WCA of CNT from 62 to 152 degrees. In 2015, Jin et al. also developed an ultrathin superwetting bilayer membrane based on SWCNT for a pressure responsive separation of oil-water emulsions (Hu, Gao, Zhu, et al., 2015). The membrane exhibits asymmetric wettability toward the continuous phase and

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the dispersed phase throughout the membrane thickness. Simple modulation of the applied pressure brings about the separation of surfactant stabilized W/O and O/W emulsions. The pressure driven separation was carried out in such a manner that the applied pressure allows the permeation of the continuous phase selectively; the pressure is such that Pcontinuous phase (intrusion pressure of continuous phase) , Papplied , Pdispersed phase (intrusion pressure of dispersed phase). The bilayer membrane has emerged as a very efficient tool for practical use as they exhibit ultrahigh permeation flux and separation efficiency. The procedure for synthesis is as follows: An ultrathin layer of the PD was coated over SWCNTs which was further fabricated onto a mixed cellulose ester filter substrate via a vacuum filtration technique. In order to avoid any fouling issues, the underlying MCE substrate was dissolved in anhydrous acetone. The free standing SWCNT/PD bilayer was then transferred to a chemically inert porous ceramic membrane. In 2015, the group of Chen et al. also proposed a controlled functionalization of CNTs for efficient separation of oil-water mixtures (Gu, Xiao, Huang, Zhang, & Chen, 2015). They were inspired by the natural water repellent properties of the lotus leaf. Thorough research in this area led them to modify the -OH functionalized CNTs with fluorine bearing organosilanes. The strong Si-O bond motivated them to attach 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane (PFDTS) onto the -OH functionalized CNTs. They successfully separated W/O emulsion using this PFDTS/CNT hybrid. A brief discussion of the synthesis of the PFDTS/CNT hybrid: On simply mixing CNT and PFDTS in the proper ratio, PFDTS spontaneously forms layers onto CNTs. It is the ratio of PFDTS: CNT which determine the characteristics of the hybrid material. They successfully separated W/O emulsion which were surfactant stabilized with high efficiency even under adverse conditions including all temperature and pH ranges. Also, the PFDTS layer imparts a flame retardant nature to the PFDTS/CNT hybrid. In 2016, Chen et al. focused on the simultaneous separation of O/W emulsions and removal of harmful bacteria from water (Gu et al., 2016). They utilized the bactericidal effect of Ag nanoparticles (Ag NPs) which has been known since ages. They combined the antibacterial property of Ag NPs and the superhydrophilic-superoleophobic property of polyacrylic acid (PAA) grafted CNTs to reach their desired goal. The Ag/PAA-CNTs exhibited superhydrophilicity and underwater superoleophobicity in a three phasic (oil/ water/solid) system and has a very high flux. The procedure for synthesis is as follows: The preparation involves a two-step procedure: (1) Firstly, polyacrylic acid (PAA) was grafted upon CNTs via a free radical polymerization using benzoyl peroxide as the radical initiator. (2) Next, Tollens reagent was added to the PAA/CNTs suspension under gentle stirring to reduce the Ag NPs on the surface of PAA-CNT. (3) The final Ag/PAA-CNT membrane was obtained by filtrating it on the hydrophilic PVDF membrane. The prepared membrane could separate surfactant stabilized W/O emulsion with a flux of 3000 L/m2/ h/bar. The reported method is a new technique and a potential tool for oil-spill cleanup. In order to check the bactericidal effects of the Ag/PAA-CNT membrane, they performed a disk diffusion experiment. Ag NPs were expected to inactivate the microorganism’s cells by rupturing their cell membrane and inhibiting DNA replication. It was clearly visible that the bacterial growth was inhibited. Also, morphological studies of the bacteria were carried out before and after incubation with the Ag/PAA-CNT membrane, which clearly reflects the bactericidal activity of the Ag/PAA-CNT membrane.

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In 2016, Sue et al. developed a simple method of fabricating MWCNTs with long chain alkyl-pyrenes for highly efficient oil-water separation (Huang et al., 2016). With the goal of synthesizing a superhydrophobic and superoleophilic film in a very simple and commercial way, they ended up in noncovalent functionalization of MWCNT sidewalls. They synthesized alkyl-pyrene by the classic aldehyde-amine coupling reaction which was further purified by recrystallization from ethanol. The electron rich π-stacked pyrene rings were covalently absorbed on the sidewalls of MWCNT in organic solvents. The long alkyl chain attached to the pyrene rings added roughness to the surface, thereby reducing the surface energy of the MWCNT. The WCA of the resulting MWCNT film increased to 158 6 2 degrees, leading to a superhydrophobic and superoleophilic film. The film allows oil to pass through it while repels water. In the process, they tried to avoid complex synthetic procedure including acid oxidation of the CNTs (which damages the CNTs) and multiple step functionalization. In 2017, Montemagno et al. developed a gas-switchable CNT/PDEAEMA hybrid membrane which could reversibly switch from hydrophobic to hydrophilic upon absorption of carbon dioxide and nitrogen gases respectively, for the separation of oil and water (Abraham, Kumaranab, & Montemagno, 2017). The inspiration behind their discovery was the voltage dependent potassium channel of the biological cell membranes. Both carbon dioxide and nitrogen gases being “greenhouse” gases need to be utilized effectively, in order to cut down their detrimental effects on the environment (global warming). In this regard, CO2 needs special attention as its emission is increasing at an alarming rate. They coated CNT walls with an ultrathin film of poly(N,N-diethylaminoethylmethacrylate) (PDEAEMA). The PDEAEMA layer acts as a chemical valve, triggered by CO2 or N2 which changes its conformation to adjust the pore sizes of the membrane and selectively manages the permeability and selectivity. Synthesis of the hybrid membrane: Initially, they functionalized CNTs with carboxylic acid groups. The carboxylic acid derived CNTs were further functionalized with 2-hydroxyethyl-2-bromoisobutyrate to develop a CNT grafted atom transfer radical polymerization initiator. This was followed by the development of PDEAEMA brushes by mixing N,N0 -diethylaminoethyl methacrylate (DEAMA) in a methanol solution (4:1) and CuBr, PMDETA and a CNT macroinitiator (0.05% DEAEMA) at 80 C for 16 h to yield the CNT/PDEAEMA hybrid membrane. The WCA of the hybrid membrane drastically changed from 113 6 5.0 degrees to 10 6 8.0 degrees upon exposure of the membrane to CO2 gas; whereas on passing N2 gas the original WCA was obtained. This clearly indicates that CO2 turns the membrane to hydrophilic. In 2018, Qiu et al. developed an underwater superoleophobic membrane to separate O/W emulsion (Yue, Zhang, Yang, Qiu, & Li, 2018). They were inspired by the underwater hydrophilic and superoleophobic property of the fish scales, which helps the fish to remain clean in water. Various hydrophilic materials such as hydrogel, cellulose or metal oxides like ZnO, TiO2 have been studied in this respect, but there were some shortcomings. Polymers like cellulose or hydrogel were water soluble whereas metal oxides were easily corroded, which made them unfit for oil-water separation. The exceptional thermal, mechanical, and electrical properties of CNTs have attracted them to use it for oil-water separation. CNTs have been bestowed with excellent properties including low density and high porosity, which makes them a perfect fit for oil-water separation. Moreover, CNT can be easily fabricated on a surface to form a film. They chose MW-CNT over SW-CNT

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because of the high price of SW-CNT, which would encumber their large scale applications. They fabricated the dispersed MW-CNT on a MnO2 nanowire suspension through a sand-core filtration system to develop the MW-CNT/UL-MnO2-NWs hybrid membrane. The method of preparing the hybrid membrane is as follows: Initially the dispersed MW-CNT suspension was prepared by treating the MW-CNTs with HNO3 at 140 C for 4.5 h, which was followed by sonication. The UL-MnO2-NWs were obtained by a hydrothermal route. The dispersed MW-CNTs and UL-MnO2-NWs were then mixed together and vacuum filtered to obtain the final (MW-CNT/UL-MnO2-NWs) membrane. The membrane could separate both surfactant-stabilized and surfactant free O/W emulsions with permeation up to 4900 L/m2/h/bar and a separation efficiency greater than 99.7%. The MW-CNT/UL-MnO2-NWs membrane had a WCA of 0 degree and displayed underwater superoleophobicity with an oil CA of 152 degrees. In 2018, Xu et al. also focused on the separation of surfactant stabilized O/W emulsions (An, Yang, Yang, Wu, & Xu, 2018). They have reported that it becomes difficult for a general hydrophilic or hydrophobic membrane for effective separation of O/W or W/O emulsion. They took help of the Janus membrane, which is a special type of 2-dimensional membrane having two or more distinct physical properties. The two different property allows the Janus membrane to act differently on each side in different conditions. It could separate both W/O and O/L emulsions, on the basis of its sieving effect. For separating O/W emulsion, the hydrophilic side of the Janus membrane is set upwards and the lower hydrophobic layer easily allows water to pass through it; whereas for separating the W/O emulsions, the membrane can simply be flipped to make the hydrophobic side face upwards. But there is a chance of accumulation of the rejected oil which decreases the efficiency of the membrane. In order to overcome this problem, the pore size of the membrane can be made sufficiently large to allow the permeation of oil through it. Also, the thickness of the hydrophilic layer needs to be precisely managed. However, complicated preparation steps lead to uncontrolled thickness of the layer. Further, to get rid of this problem, they fabricated the hydrophilic layer of the Janus membrane with positively/negatively charged CNTs, which could tune the surface wettability and the de-emulsifying feature of the Janus membrane. Fabrication of the membrane with CNTs allows frictionless movement of oil or water through the membrane. The prime reason of the positive charge of CNT is to demulsify the emulsions which are stabilized by negatively charged surfactants before the penetration of oil and vice versa. Also, the thickness of the hydrophilic layer can be tuned easily by regulating the concentration of CNTs in aqueous dispersion. The separation efficiency of the membrane reaches its maximum as the WCA and the underwater oil CA (UOCA) are around 90 degrees on the CNT-coated surface. The prepared membrane could separate both light oil and heavy oil from O/W emulsion. In 2018, Freger et al. took advantage of the electrical conductivity of CNTs for oil-water separations (Tankus, Issman, Stolov, & Freger, 2018). They converted the CNT mats from hydrophobic to hydrophilic via electrooxidation (EO). The wetting behavior of the CNT mats was irreversibly changed to allow the permeation of water and rejection of oil. The electro oxidation of the CNTs under anodic potential generates oxygen containing polar groups in a similar way as graphene is converted to graphene oxide (GO) upon oxidation. Here, MWCNT is preferred over SWCNT as MWCNT is less vulnerable to electrotreatment preserving its mechanical and electrical characteristics. The membrane allows complete separation of oil-water mixtures (including surfactant stabilized oil-water emulsions).

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The EO preserves the morphology and porosity of the membrane. The procedure for synthesis is as follows: The electro oxidation of CNT mat was performed in situ within an airpressurized Amicon filtration cell fitted with a platinum counter. In order to overcome the competition with water-splitting, high-voltages were required to be applied. In 2019, Lu et al. designed an extremely durable and self-healing superhydrobhobic MWCNT film for efficient separation of oil-water emulsion (Ye et al., 2019). They chose MWCNT over SWCNT as MWCNT has greater stability and diameter compared to SWCNT. Also, it is cheaper as compared to SWCNT. They modified the MWCNT layer by fabricating it with a polydivinylbenzene (PDVB) layer followed by a 1-H,1-H,2-H,2-H-perfluorooctyltriethoxysilane (POTS) layer. PDVB was chosen as it is easy to prepare, stable under a range of conditions and possesses nanoporous superhydrophobic properties. The POTS layer was chosen for its self-healing property, which enables the film to recover from damages and increases its durability. The self-healing mechanism involves migration of an alkyl chain in the presence of water. The procedure for synthesis is as follows: Initially, a free standing MWCNT film was prepared by attaching the MWCNT film to a copper mesh. This was followed by: (1) PDVB modification of the film: The PDVB layer was introduced via a solvothermal route. The solvothermal reaction cross links and polymerizes DVB monomer to form a polymer network under the action of AIBN (initiator). (2) POTS modification of the layer: The self-healing, low energy layer of POTS was introduced upon the PDVB layer. The POTS modification was carried out via CVD. The prepared MWCNT film showed a WCA of 151.4 6 0.7 degrees, whereas oil was absorbed within 100 Ms. This confirms the surface to be superhydrophobic and superoleophilic. In 2020, Feng et al. developed a CNT/poly(N-isopropylacrylamide) modified membrane for the separation of double emulsions (Qu et al., 2020). Double emulsions (oil-in-W/O emulsion or W/O-in-water emulsion) are much more difficult to separate as compared to simple emulsions (oil in water or water in oil emulsions). They combined the photo-thermal conversion of CNTs and the thermal isomerization properties of poly(N-isopropylacrylamide) (PNIPAAm) and fabricated them to a poly(vinyldenefluoride) membrane to create an IR responsive superwetting switchable material. Both PNIPAAm and CNTs being cheap reagents, proved to be an economical selection. The prepared sandwich structured PNIPAAm/CNT@PVDF material could separate different types of emulsions simultaneously, thereby saving energy and simplifies the separation process. Theoretical evaluation of wettability reveals that the phenomenon is guided by intermolecular and intramolecular hydrogen bonds. Initially, the surface temperature of the PNIPAAm/CNT@PVDF layer was lower than that of the lower critical solution temperature (LCST), and the N-H and C 5 O groups of PNIPAAm molecular chain formed intermolecular hydrogen bonds with water molecules, making the membrane superhydrophilic. Upon exposure of the material to IR (800 nm), the CNTs generated a large amount of heat (ST . LCST) and the molecular chain of PNIPAAm formed intramolecular hydrogen bond, making the material hydrophobic. After removing the IR source, the material returned to its original hydrophilic state. The procedure of synthesis is as follows: The PNIPAAm/ CNT@PVDF was prepared via a twostep procedure. Initially, a CNT layer was dispersed over a pre-treated PVDF substrate via a hydrothermal reaction. Further, the CNT layer was fully covered by PNIPAAm to form the required sandwich structured membrane. The prepared PNIPAAm/CNT@PVDF material exhibited WCA of 10.3 degrees whereas upon exposure to IR source, the WCA changed to 142.4 degrees (superhydrophobic).

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11.6 Future perspective CNT based oil-water separation holds immense potential for practical use. With the ongoing usage, many challenges of the future can be successfully dealt with proper application of CNTs. CNTs have high flux rates compared to the conventional membranes, which makes it a perfect weapon for any accidental oil spillage in future.

11.7 Summary Carbon-based carbon nanotube has flourished as a remarkable tool for oil-water separation in today’s revolutionary world. Being environmentally friendly and biodegradable, it has been widely accepted. SWCNTs and MWCNTs can either be coated on polymer sponge or functionalized for efficient oil-water separation. The superhydrophobic and superoleophilic property of CNTs along with its reusability makes it a superior entity. The CNT mesh or CNT grafted material can absorb oil up to 37,000 times of its own weight. This field demands more research to be done, for smarter and convenient separation of oil-water mixtures and emulsions. In this book chapter, recent applications and developments of CNT as a tool for oil-water separation have been briefly summarized.

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10815.

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C H A P T E R

12 Nanocoated membranes for oil/water separation Karun Kumar Jana1, Avijit Bhowal1,2 and Papita Das1,2 1

School of Advanced Studies on Industrial Pollution Control Engineering, Jadavpur University, Kolkata, India 2Department of Chemical Engineering, Jadavpur University, Kolkata, India

O U T L I N E 12.1 Introduction

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12.5.1 Surface morphology 12.5.2 X-ray photoelectron spectroscopy 12.5.3 FTIR

12.2 Nanocoated membrane technology 209 12.2.1 Organic-based membranes 209 12.2.2 Inorganic-based membranes 210 12.3 Fundamental principles behind oil/ water separation behavior 210 12.3.1 Superhydrophobic-superoleophilic membrane 211 12.3.2 Superhydrophilic-superoleophobic membrane 212 12.3.3 Underwater superoleophobicity membrane 213 12.4 Current application of membranes in oily wastewater treatment 213 12.4.1 Zwitterionic membranes 213 12.4.2 Biomimetic thin membranes 215 12.5 Morphology and structure

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00008-2

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12.6 Wetting properties

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12.7 Mechanical strength

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12.8 Antifouling method

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12.9 Separation performance of membranes for the oil-in-water mixture

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12.10 Summary

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12.11 Future perspective

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Acknowledgement

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Conflict of interest

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References

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12.1 Introduction During industrial or other oil-related activities processing, (e.g., paper, textile, metalworking, food processing, and pharmaceutical), a mixture of oil-water is produced in our daily life (Abadi, Sebzari, Hemati, Rekabdar, & Mohammadi, 2011; Cheryan & Rajagopalan, 1998; Ezzati, Gorouhi, & Mohammadi, 2005; Kong & Li, 1999; Shannon et al., 2008). Therefore, several studies have also been recently introduced on the improvement of effectively distinct the oil from water-oil mixtures for worldwide oil spillage recovery and pollution control. To remove emulsified oil, dispersed oil, and free oil (Bengani-Lutz, Zaf, Culfaz-Emecen, & Asatekin, 2017; Huang, Ras, & Tian, 2018; Painmanakul, Sastaravet, Lersjintanakarn, & Khaodhiar, 2010) from water, many methods tested so far. Various conventional water treatment processes, such as absorption, chemical coagulation, air flotation, biological oxidation, and gravity separation (Cheryan & Rajagopalan, 1998; Kusworo & Utomo, 2017; Peng, Guo, Wen, Yang, & Guo, 2017; Xue, Li, Li, Zhu, & Guo, 2017) are utilized to remove much smaller droplet size emulsified oil. On the other hand, dispersed and free oil can be cleaned up mechanically (Ivshina et al., 2015). Moreover, the efficiency of using freshwater could be improved by recycling oily wastewater (Chakrabarty, Ghoshal, & Purkait, 2008). Membrane-based materials bearing superior wettability have received more attention in oily wastewater treatment fields from both private industry and academia. The operation of the membrane is very simple, a low defect rate, fouling resistance, high separation efficiency, can be prepared without additional agents and chemicals (Padaki et al., 2015). Ceramic membranes (Ashaghi, Ebrahimi, & Czermak, 2007), polymeric membranes (Salahi, Gheshlaghi, Mohammadi, & Madaeni, 2010), mixed-matrix membranes (Wan Ikhsan et al., 2018), and biomimetic thin membranes (Wang, Liang, Guo, & Liu, 2015) are the famous forms of membrane technology for separating oil from oily water because of their capability to well eliminate the droplets of oil from water vis-a`-vis recent conventional technologies (Ong, Lau, Goh, Ng, & Ismail, 2014). Membrane separation techniques are one of the most promising methods for an extensive range of oil/water mixtures. Nevertheless, one of the key problems which arise in the separation industries is membrane fouling. When organic, inorganic, and colloid particles are physically adsorbed into the membrane pores or deposited membrane surface with cake formation, this reduces permeation flux permanently and shortens the life of the membrane (Obaid, Tolba, et al., 2015; Wei, Qi, Gong, & Zhao, 2018). To avoid the fouling problems, researchers have developed some alternative new nanohybrids membrane (Karimnezhad, Rajabi, Salehi, Derakhshan, & Azimi, 2014) and bio-inspired superwetting membrane (Yang et al., 2017) that will lend the material looked-for antifouling qualities, such as hydrophilicity, self-cleaning, photodegrading, and photocatalytic properties. Back-washing, chemical cleaning, or hydraulic cleaning drops reversible fouling, whereas irreversible fouling arises when the foulant is chemisorbed by the pores of the membrane surface causes the flux to be enduringly reduced (Bhattacharya & Misra, 2004; Vasanth, Pugazhenthi, & Uppaluri, 2013). Conventional nanohybrid membranes, nanometer dimension fillers having high surface areas fall into one of the four significant classifications: (1) organic material; (2) inorganic material; (3) hybrid material, and (4) biomaterial with two or additional material types. To date, a variety of advanced nanomaterials could be resolved the issues involving water

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quality, particularly in cleaning up oil spills because of their oleophilic and hydrophobic characteristics (Campos, Oliveira Filho, Nobreg, & Sant’Anna, 2002; Feng & Jiang, 2006; Nasrollahi, Aber, Vatanpour, & Mahmoodi, 2019; Zhang & Seeger, 2011). Advances in engineering and nanoscale science propose that zinc oxide nanostructure coated membrane is one of the key points for separation technologies because they facilitate the important enhancement of the superhydrophilicity, underwater superoleophobicity, and excellent separation ability for oil/water separation application concerning commercial glass fiber membrane (Chen & Xu, 2013; Zhu, Tu, Wee, & Bai, 2014). Porous or meshes superhydrophobic-superoleophilic membranes has an oil contact angle (OCA) near 0 degrees and water contact angle (WCA) has beyond 150 degrees can effectively discrete the oil from water-in-oil emulsions by repelling water whereas let oil passes through a membrane (Xue et al., 2011). On the other hand, a superhydrophilic-underwater/ superoleophobic membrane is appropriate to treat a variety of oily wastewater, here to let water permeate from the membrane surface and prevent the oil (Darmanin & Guittard, 2014). Typically, superhydrophilic/superoleophobic (i.e., water removing) or superhydrophobic/superoleophilic (i.e., oil removing) are special kinds of wettability materials, can selectively be dispersed and separate oil or water (Pernites, Ponnapati, & Advincula, 2011). While some smart responsive oil-water separation materials having switchable special wettability facilitate both “water-removing” and “oil-removing” methods.

12.2 Nanocoated membrane technology Nano-coated membranes with nanoscale pores are used with the resolution mainly the removal of contaminants for example biological, physical, and chemical from drinking water (Humplik et al., 2011; Sorribas, Zornoza, Te´llez, & Coronas, 2014; Yin & Deng, 2015). Many different types of nanometer-size filler having high surface area and their oleophilicity have become a chief point, which led to the production of membranes with high permeation flux and “oil-removing” property. Engineered nanoporous membranes having pore size lies between 1 and 100 nm are being explored to enhance the thermal stability, mechanical strength, higher water flux compared with other conventional membranes (Zhang et al., 2012; Zhao et al., 2011). The membranes can be classified into two types depending on their materials and operating temperature.

12.2.1 Organic-based membranes Organic membrane fabrication technology and polymer choice depend on a variety of factors, including stereoisomerism, chain interactions, chain rigidity, and functional group polarity (Abraham, Kumaran, & Montemagno, 2017; Prince et al., 2016; Saadati & Pakizeh, 2017). It is significant to determine what kind of polymer or membrane is most appropriate for their practical application in oily wastewater treatment. Generally, the polymeric/ organic membranes consist of two kinds of materials synthetic and natural polymers. Samples of synthetic polymers, for example, poly(vinylidene)fluoride (PVDF), poly(ethylene terephthalate), polycarbonate, and polyacrylonitrile (PAN) whereas cellulose, wool, and rubber are made of natural polymers (Jana et al., 2015; Jana, Lue, Huang, Soesanto, &

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Tung, 2018; Saxena et al., 2020; Tiwari, Jana, Singh, Avasthi, & Maiti, 2011). At present, polymeric membranes (both hydrophilic and hydrophobic) alter the successful separation performance in the treatment of oil-water mixture. Hydrophilic membranes display superior antifouling properties vis-a`-vis hydrophobic membranes presumably due to the permit water droplets toward transfer from side to side the membrane and prevent oil droplets (Rahimpour & Madaeni, 2007). In contrast, hydrophobic material surfaces resist water and permit droplets of oil easily, and it mainly shows fouling problems (Feng, Zhang, et al., 2004). On the way to progress separation performance of the organic membranes including separation efficiency, electrochemical and antifouling properties, engineered nanoparticles are of the range of nanometer-scale such as metal oxides Al2O3, TiO2, SiO2, ZnO (Chena et al., 2018; Vatanpour, Madaeni, Moradian, Zinadini, & Astinchap, 2012; Yi et al., 2011; Yu, Xu, Shen, & Yang, 2009), carbon-based materials carbon nanofibers, carbon nanotube, and graphene (Ao et al., 2017; Jana, Patel, Rana, & Maiti, 2014; Moslehyani, Ismail, Othman, & Matsuura, 2015) are usually incorporated into the membrane matrix. Numerous techniques have been used to prepared hybrid systems regarding interfacial polymerization (Zhao et al., 2012), phase inversion (Akin, Zor, Bingol, & Ersoz, 2014), cross-linking (Deng et al., 2019), electrospinning (Asmatulu, Ceylan, & Nuraje, 2011), melt route (Jana et al., 2016), solution casting (Tiwari et al., 2013), and chemical grafting (Jana, Ray, Avasthi, & Maiti, 2012).

12.2.2 Inorganic-based membranes Researcher attempts have focused on developing inorganic membranes made of materials such as various oxides (alumina, titania, zirconia), ceramic, silica, carbon, zeolite, and metals for example silver, palladium and their alloys for aimed at increasing fouling resistance, sustainable water purification, and captivating permeation flux for the period separation of oil-in-water mixture (Lin, 2006; Sun et al., 2018). Among different commercial inorganic membranes, porous membranes have driven significant attention in recent years. Microporous inorganic membranes having pore dimensions lesser than 2 nm are always equipped as thin films reinforced on good quality porous inorganic supports with oil content, strong cleaning agents, and higher resistance to high temperature (Zhang et al., 2018; Zhang, Zhang, et al., 2013). There are some advantages about inorganic membranes for example high thermal and chemical stability, withstanding harsh chemical cleaning, frequent backwashing, inertness to microbiological degradation as compared to polymeric membranes (Kokotov & Hodes, 2010; Wang, Han, et al., 2017). Nowadays, significant R&D efforts are prepared porous inorganic membranes include crystalline and amorphous membranes, but one key disadvantage for inorganic membranes is more expensive vis-a`vis organic membranes (Wang, Yiming, Saththasivam, & Liu, 2017).

12.3 Fundamental principles behind oil/water separation behavior Surface engineering developed the design of super wetting materials, which have harvested efficient processes for industrial emulsion wastes treatment and environmental

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12.3 Fundamental principles behind oil/water separation behavior

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cleanup. So far, superoleophobic or superhydrophobic membranes for oil 2 water emulsion separation are adopted as oil and water have different surface tension, which directly intermingles with super wetting behavior (Ge et al., 2017; Gu et al., 2014; Huang, Chen, et al., 2018). The surface wettability of membranes was depending on their surface geometrical structure and free energy (Adebajo, Frost, Kloprogge, Carmody, & Kokot, 2003). Although in the presence of surfactant the super wetting materials are always difficult to distinct immiscible oily wastewater and turn into ineffective intended for oil-water emulsions (Ichikawa, 2007). Especially, three types of separation materials have been classified into (1) superhydrophobic-superoleophilic, (2) superhydrophilic-superoleophobic, and, (3) underwater superoleophobicity membrane.

12.3.1 Superhydrophobic-superoleophilic membrane The superhydrophobic/superoleophilic separation materials are typically oil removal membranes, it is easily separate oil from dispersed oil-in-water emulsions (Ke, Jin, Jiang, & Yu, 2014; Zhou & He, 2018). Nevertheless, this process shows lowered surface-tension liquid towards barrier both phases (water and oil), decreasing both separation efficiency and flux when oils willingly foul these oleophilic surfaces (Shang et al., 2012). The superhydrophobic/superoleophilic membranes having a low contact angle for oil while exhibiting a larger contact angle for water and can fascinate oil from mixing of water and oil (Zhang, Shi, et al., 2013). There are two categories of superhydrophobic/superoleophilic materials: (1) two-dimensional (2D) materials built on a metal mesh membrane, which are basically “filter type” oil separation materials, and (2) three-dimensional (3D) materials with the porous structure for example foam, and aerogels, which are primarily “adsorption type” separation materials (Zhu, Pan, & Liu, 2011). The porous structure of the superhydrophobic/superoleophilic poly(vinylidene fluoride) membranes prepared by the phase-inversion method has been presented in Scheme 12.1 (Zhang, Shi, et al., 2013). In this method, the addition of inert solvent additive like ammonia water into the poly

SCHEME 12.1 Schematic representation of phase-inversion method for the development of a poly(vinylidene) fluoride membrane (Zhang, Shi, et al., 2013).

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(vinylidene fluoride) solution forming the polymer clusters in the solution. It is noteworthy to see the effectiveness of membranes for separating various Oil-in-Water Emulsions with surfactant-free dispersed.

12.3.2 Superhydrophilic-superoleophobic membrane It was found that superhydrophilic-superoleophobic membrane in oil spill wastewater is an extraordinary membrane for filtering or absorbing water and oil retention in the separation process (Brown, Atkinson, & Badyal, 2014). It is essential to build a hydrophilic oleophobic surface, construct a low-surface-energy than oil (Cheng et al., 2011). The superhydrophilic-superoleophobic membranes are a benefit of antifouling by oil when dealing with oil spill wastewater (Wang & Gong, 2017). During the separation process, this kind of membrane is easily contaminated by oil because of its oleophilic properties, which might be a decrease in secondary pollution and separation efficiency (Wang, He, et al., 2015). The water removal processes of separation membranes have been made by using a variety of materials including graphene oxide, hydrogels, and zwitterionic polymers, which have the design of superhydrophilic surfaces that display superoleophobicity (Yang et al., 2012). As shown in Scheme 12.2, perfluorinated thiol-acidic acrylate UV photopolymerization was employed to fabricate the rapid superhydrophilic/superoleophobic membrane with a hydrophilic silica nanoparticle via spray deposition method, which showed the treatment of spilled oil and industrial daily waste (Xiong et al., 2018).

SCHEME 12.2 Hydrophilic silica nanoparticles loaded with hybrid organic-inorganic thiol-acrylate resins via photopolymerization and spray-deposition process (Xiong et al., 2018).

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12.3.3 Underwater superoleophobicity membrane The underwater superoleophobicity membrane is used extensively in the treatment of oil-in-water emulsions and achieved the real oily wastewater samples from water (Teng, Xie, Wang, Zhu, & Jiang, 2016). The membrane surface has displays good separation efficiency and low fouling, to avoid fouling problems of the membrane it should be prewetted with water (Yong et al., 2018). It is notable to see a superhydrophilic/underwater superoleophobic membrane appropriate for cleaning up water from water-in-oil emulsions when the water tends to produce a barricade among the membrane surface and oil. Sawai, Nishimoto, Kameshima, Fujii, and Miyake (2013). Fig. 12.1A shown a PAN membrane by a hydroxylamine-induced phase-inversion method for diesel oil/water emulsion separation (Zarghamia, Mohammadia, Sadrzadeha, & Bruggend, 2019). The hydroxylamine hydrochloride accumulated into a clotting bath leads to the hydroxyl and amine groups into polyacrylonitrile chains through amidoximation of PAN membranes. As exposed in Fig. 12.1B, the WCA and Underwater OCA (UOCA) of the modified membrane are about 1 and 156 , correspondingly.

12.4 Current application of membranes in oily wastewater treatment Numerous applications can affect the efficiency of water-in-oil emulsions by membranes and can be approximately classified into Zwitterionic and Biomimetic thin membranes.

12.4.1 Zwitterionic membranes The development of zwitterionic materials is of current attention globally and the zwitterion-coated membrane has excellent antifouling ability and greater flux recovery rate. But different from poly (ethylene glycol) byproducts as they produced ionic interactions with water molecules, making it tight and stable (Venault et al., 2016). It has come mostly from amino acids, which contain ammonium and a carboxylate group through a

FIGURE 12.1 (A) Development of a polyacrylonitrile membrane via hydroxylamine-induced phase-inversion method, (B) Photo of the modified membrane showing a water contact angle of ,1 degrees (left) and a UOCA of 156 degrees (right) (Zarghamia et al., 2019).

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kind of intramolecular acid/base reaction (Davenport, Lee, & Elimelech, 2017). Selfcleaning zwitterionic nanofibrous membranes are one of the major industrial applications in oil/water separation performance and display great chemical stability in acid, alkaline and salty environments owing to their can resist not only crude oil fouling but also bacteria adhesion and reduce biofilm formation (Yu, Cao, et al., 2009). Membrane surfaces grafted or coated with zwitterionic polymers for example polycarboxybetaine, polysulfonbetaine, and polyphosphobetiane are proven to be more resistant against the adsorption of biological and organic components (Dizon & Venault, 2018). In recent times, several zwitterionic polymers have been explored as surface modifiers of some substrates, and the third generation of low fouling materials for oil/water separation, these modifications have enhanced the membrane antifouling properties (Sin et al., 2017). The zwitterionic and pseudozwitterionic materials are the tendency to bind a strong bond with the water molecules through hydrogen bonding and electrostatic interactions, and well inhibit the oil adhesion on membrane surface (Li et al., 2008). A schematic has been presented where the zwitterionic polymer blended PVDF membrane is prepared via an in situ crosslinking through nonsolvent phase separation followed by sulfonation reaction (Scheme 12.3) (Zhu, Xie, Zhang, Xing, & Jin, 2017). The reaction was performed between the PVDF matrix and zwitterionic polymer, which resolves the matter of poor compatibility and is altered into a zwitterionic polyelectrolyte by functionalization/sulfonation. The prepared membrane demonstrated outstanding performance to discrete oil from the oil-in-water mixture, in addition to a possible upgraded of the oil-fouling and high water flux recovery (98%) of the membrane.

SCHEME 12.3 Schematic illustration of Zwitterionic poly(vinylidene)fluoride-PSH-blend membrane through a mutual method of in situ cross-linking of random copolymer PDH as an additive, for the duration of phase separation and subsequently membrane was sulfonated (Zhu et al., 2017).

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12.4.2 Biomimetic thin membranes The biomimetic thin membranes having superwetting property making from the superwetting microorganisms used for water-in-oil emulsions, particularly several oily wastewaters, have attracted much attention because of their high separation efficiency and fouling resistance (Pengab & Guo, 2016). Biomimetic and bioinspired membranes have high porosity and stability/resistance can be applying for separation purpose, and healthcare (Chen, Chen, Yin, Ma, & Jiang, 2009). Biomimetic membrane material improved by the engineered/modified or natural proteins, with the desired separation and sensing properties of bioderived additives (Li, Wang, Wu, Wang, & Jiang, 2012). Biomimetic membranes with superwetting property, primarily connecting superhydrophilic/underwater superoleophobic, superhydrophobic/ superoleophilic, superhydrophilic/superoleophilic (superamphiphilicity), and superhydrophilic/superoleophobic membranes show a principal role in separating an oil/water mixture (Zhang et al., 2014). Fig. 12.2 illustrates the schematic diagram of an innovative strong biomimetic and ultra-robust porous ceramic membrane (Liu et al., 2020). The lightweight and hierarchically membrane were fabricated through hydrophobic coating linking and self-assembly of the Al2O3 powder and used for oily wastewater separation with high efficiency (99.98%). Initially, propionic acid was used for modifying the Al2O3 ceramic powder (I), and afterward, oil and PVA were quickly added to form the ceramic wet emulsion (II). A biomimetic hierarchically macroporous ceramic was gotten after the drying and sintering process (III), and lastly, the PDMS coating period (IV) goes to superoleophilic and superhydrophobic.

FIGURE 12.2 Schematic design displaying the creation method of the hierarchically macroporous ceramic membrane by a mixture of (A) emulsion-assisted self-assembly of the altered Al2O3 powder and, (B) the ceramic membrane after hydrophobic PDMS coating (Liu et al., 2020).

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12.5 Morphology and structure 12.5.1 Surface morphology The surface microstructure has been demonstrated through AFM surface topography of both isotropic and anisotropic polyethersulfone (PES) membranes as exposed in Fig. 12.3 (Abdel-Aty et al., 2020). The root means square roughness values (Sq) of both the membranes provided a detailed comparison from the 2D and 3D AFM morphology. During the phase inversion process surface roughness is influenced by several issues, for example, the altercation rate amongst solvent and nonsolvent (Sadeghi, Aroujalian, Raisi, Dabir, & Fathizadeh, 2013). The Sq of the anisotropic PES membrane is 16 nm, while the Sq of isotropic PES improves to 71 nm. The smaller roughness in anisotropic PES membrane vis-a`vis isotropic membrane is presumably owing to the creation of a compact skin layer that shows average pore diameter and lower surface porosity. It is notable to mention that, the increased roughness in anisotropic PES membrane is sturdily connected to the creation of skinless porous structure and the increase in average pore diameter and membrane surface porosity.

FIGURE 12.3 Two-dimensional and three-dimensional AFM topograph of PES membranes: (A) Anisotropic and (B) Isotropic (Abdel-Aty et al., 2020).

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12.5.2 X-ray photoelectron spectroscopy X-ray photoelectron spectroscopy (XPS) can detect the elemental composition that exists within a material. XPS analysis spectra of the pure cotton fabric (CF), VPOSS@CF, and CPOSS@CF are shown in Fig. 12.4A indicating two distinguished peaks C1s and O1s, corresponding to a surface of neat CF, whereas more or less different peaks at 227.8 eV (S2s), 163.9 eV (S2p), 154.4 eV (Si2s), 103.0 eV (Si2p) respectively, have appeared after functionalization in the VPOSS@CF and C-POSS@CF membranes, are accredited to the sign of S and Si element (Zhou et al., 2021). The high-resolution C1s spectrum of virgin CF is clear from the deconvoluted peaks, which are allocated to the CaC (284.7 eV), CaO (286.3 eV), and CQO (288.1 eV) bond, correspondingly as exposed in Fig. 12.4B. The intense bond at CQC (288.6 eV) and CaSi (284.1 eV) of the VPOSS@CF sample are detected, indicating grafting of VPOSS-MPTMS (Fig. 12.4C) with the surface of cotton fiber. Fig. 12.4D has shown the high-resolution C1s spectrum, which can be split CaS (287.6 eV) bond in CPOSS@CF. In the meantime, CaO and CQO bond their peak intensities are reinforcing as compared to the VPOSS@CF. Nevertheless, the comparative content of C, O, Si, and S elements have been quantified using deconvolution of XPS peaks and found to be 35.2, 23.9, 36.5, and 4.4 wt%, correspondingly in VPOSS@CF. The content of C, O, and S elements increases after the grafted 2-mercaptoacetic acid followed by thiolene functionalization amongst surface vinyl groups

FIGURE 12.4 (A) XPS spectra of the pure cotton fabric (CF), VPOSS@CF, and C-POSS@CF. C1s spectra of the pure CF (B), VPOSS@CF (C), and C-POSS@CF (D) (Zhou et al., 2021).

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of the cotton fiber and 2-mercaptoacetic acid and found to be 45.6, 29.1, 16.5, and 8.8 wt% for C-POSS@CF.

12.5.3 FTIR Infrared spectra testing is particularly useful to a determination of the chemical composition existing in polymeric, organic, and in some cases, inorganic materials. Fig. 12.5 displays ATR-IR patterns of neat PVDF membrane and TA-Fe@PVDF nanohybrid membranes and confirms the existence of dissimilar functional groups because of surface coating technology. The peaks at 3300 cm21 are accredited to OaH stretching vibration for the PVDF membrane (Yanga et al., 2020). A characteristic peak at around 1612 cm21, which could be ascribed to the stretching vibration of the CQC bond, and the peaks at 1202 cm21 are attributed to the C-F stretching vibration. Moreover, after coating of TAphenolic complexes, the TA-Fe@PVDF nanohybrid membranes shown a band at 1714 cm21, which assigned to the stretching vibration of the CQO bond in the TA molecules (Xie et al., 2016).

12.6 Wetting properties Fig. 12.6A shows the WCA of the APM-260 membrane in the air (Li et al., 2015). The CA is 0 degrees due to the intrinsic hydrophilicity of as-calcined TiO2 nanotubes (Balaur, Macak, Taveira, & Schmuki, 2005) and the porous architecture. The membrane demonstrating superhydrophilicity, because within several seconds the droplet of water can permeate through the porous membrane rapidly. On the other hand, the APM-260 membrane displays the UOCA, which was resolute to be B156.7 degrees using 2 μL of dichloromethane as an oil probe (Fig. 12.6B) (Li et al., 2015). The porous APM-260 membrane was FIGURE 12.5 FTIR spectra of the neat PVDF and TA-Fe@PVDF nanohybrid membranes (Yanga et al., 2020).

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FIGURE 12.6 (A) The CA of APM-260 membrane, (B) The OCA of APM-260 membrane. The membrane was shown a maximum pore size of 260 mm. Li et al. (2015).

FIGURE 12.7 (A) Tensile stress-strain curves for different membrane, (B) membranes showing similar Young’s modulus (Mousaa et al., 2020).

immersed in the aqueous environment, water takes place in the pores in place of air and it prevents the infiltration of oil to be the pores.

12.7 Mechanical strength A perfect separation of oil spill wastewater membrane should be a free-standing film with adequate durability, and processability (Pandey, Jana, Aswal, Rana, & Maiti, 2017). The Young’s modulus of the polysulfone (PSF)-based nanofiber membrane has been corroborated using a tensile tester machine. The tensile curves of the fabricated membranes are existing in Fig. 12.7A displaying decreased strain for iron acetate and three times increased the tensile stress as compared to pure PSF membrane (Mousaa, Alfadhel, Ateiac, Abdel-Jabera, & Gomaa, 2020). Besides, the comparable magnitude of Young’s modulus is shown in Fig. 12.7B indicating considerably without alterations in the elastic performance of the PSF composite. These results can be accredited to the membrane porosity and the nanofiber diameters (Obaid, Barakat, et al., 2015). In contrast, the polyamide (PA) layer illustration a distinctive higher Young’s modulus and tensile stress in mutually cases are primarily owing to the polymer matrix and its nanohybrids interfacial interaction through a novel hydroxide group of PA layer (Huang et al., 2017). On the other hand, membranes make brittle behavior and higher mechanical strength when the strain rate was decreased.

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12.8 Antifouling method The fouling affects the membrane lifetime and efficiency, which forms the surface of the membrane throughout the operation and afterward leads to flux worsening. The antifouling capacity of the modified membranes was evaluated using the emulsion flux decay ratio (Dr) and flux recovery ratio (FRR) of oil-in-water emulsion (Ahmad, Majid, & Ooi, 2011). To remove the size factor of the channel, merely Dr and FRR values of PSF-1 and PSF-3 which have actual near channel dimensions were calculated. The matrix PSF is functionalized by blending in presence of SiO2 nanoparticles and promotes the membranes’ antifouling properties. The Dr and FRR were resolute from the following equations (Ahmad et al., 2011).    (12.1) DR 5 Jw1 2 Jp =Jw1 3 100%   FRR 5 Jw2 =Jw1 3 100% (12.2) where, Jw1 is the flux of water which was calculated through assessing the permeated water and the pressure was compact near 0.1 MPa, Jp is the flux which was calculated in the same way as Jw1, Jw2. The cleaned membranes were washed with distilled water for 30 min underwater flux, which was also calculated in the similar mode of Jw1. The ultrafiltration experiment was measured at room temperature and a stirring high speed of 400 rpm. The lower Dr value in membrane suggests a superior antifouling property shows in modified membranes. It should also be mentioned that a better antifouling property has been displayed in the membrane for the higher FRR value. The antifouling properties of blended membranes are reported in Table 12.1 (Ahmad et al., 2011). The Dr value reduced from 98.28% down to 86.55% for the SiO2 content of blended composition with PSf improved from 1.0 to 3.0 g. Hence, oil droplet’s adsorption and deposition have reduced on the advanced membrane surfaces vis-a`-vis pure membrane presumably owing to the incorporation of SiO2 nanoparticles along with enhancement of hydrophilicity. Interestingly, the FRR value has increased from 10.34% to 34.01% showing better oil droplets cleaned from the SiO2 surrounded membrane with respect to virgin PSF membrane. These results demonstrated that blending of PSf/SiO2 was performed in template system via 2D nanoparticle and its larger antifouling properties.

12.9 Separation performance of membranes for the oil-in-water mixture At present, porous membranes with superwetting behavior, which interact with borders of the solid phase, water phase, and oil phase was developed for manageable separation of oily wastewater (Feng, Feng, et al., 2004). The water-in-oil emulsions sources are TABLE 12.1 The PSF/SiO2 membranes showing antifouling properties (Ahmad et al., 2011). SiO2 content (g)

Dr (%)

FRR (%)

1.00

98.28

10.34

3.00

86.55

34.01

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12.9 Separation performance of membranes for the oil-in-water mixture

221

universal for example tannery, and petroleum industries (Feng et al., 2002). The oil/water mixture can be classified into dissolved oil (,0.1 μm), emulsified oil (0.1
2 μm), dispersed oil (10
100 μm), and oil slick ( . 100 μm), as said by the form of oil in water (Deng et al., 2020). Throughout the separation process of oil and water, the common corrosive constituents for example acids, alkaline, or salts are frequently contaminated on the surface of the membrane to make the defeat its superhydrophobicity (Fang et al., 2020). Dispersing a few percentages of nanoparticles into materials, it is usually anticipated to effectively isolated water and oil because of the economic and environmental demands (Feng, Sun, & Ye, 2017). There are various functional materials with extraordinary wettability to separating oil/water mixtures. In the latest decades, many researchers have developed membranes for the oil/water separation field, using numerous techniques, amongst them membrane filtrations were the greatest prime. It has been observed that application of conventional filtration membrane in oily wastewater treatment have a propensity size-sieving outcome motivated by pressure as the droplets of oil have to not permitted to pass through the channels of the membrane. Usually, for the treatment of oil-in-water mixture, we should deliberate the systematic design of porous materials by two critical physical characteristics, (1) the breakthrough pressure (i.e., pore size) and, (2) surface structure (i.e., porosity). The maximum pressure is called the breakthrough pressure (ΔPC), which is practical on the surface before the assumed fluid infuses into the channels (Mosadegh-Sedghi, Rodrigue, Brisson, & Iliuta, 2014). For the cylindrical geometry of the pores, ΔPC can be resolute using the YoungLaplace equation (Kim & Harriott, 1987) ΔPC 5 2

2γL cosθ rp

(12.3)

Anywhere, the surface tension of the fluid is denoted by γ L, θ represents the intrinsic contact angle, and rp signifies the radius of the pore. This is to mention that the breakthrough pressure can considerably be affected by the wettability of a material. Separation of membrane for oil/water separation has great impact because of its lower price, high efficiency, and simplicity of procedure (Chen, Weng, Mahmood, Chen, & Wang, 2019). Fig. 12.8 illustrates the water permeation flux and separation performances of the membranes

FIGURE 12.8 The experimental setup and separation method of oil and water of the membranes after 8 h sintering: (A) photographs of the oil (dyed red) and water (dyed blue) mixture, (B) photographs of oil and water on the surface of membrane displaying different wettability, (C) photographs viewing the mixture was transferred into the upper tube, (D) photographs presenting oil and water were separated (Qing et al., 2017).

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12. Nanocoated membranes for oil/water separation

for a mixture of oil and water into a custom-made separation module apparatus (Qing et al., 2017). When the membrane surface was absorbed by an oil droplet, however a droplet of water trying to retain its circular shape on the surface (Fig. 12.8B). The membrane fluid (water) entrance pressure were approximately 193.5 6 2.1 kPa, which outcomes in the superhydrophobic-superoleophilic membrane. Fig. 12.8B illustrates the separation cell toward the upper tube, where the mixture of oil-water has been poured. This is to mention that the membrane is fully wet by oil for quite some time after oil permeate was performed throughout the membrane toward the foot tube. The separation has been completed after only 3.5 min exhibit two stages of water separation were retained into the upper tube whereas oil was separated to the bottom tube (Fig. 12.8D). Underneath the gravity/driven condition in the separation process the membrane’s average permeate flux was about 1143 6 69 L/m2/h1 without external driven force. Furthermore, the membrane has the characteristics of good separation efficiency of oil-in-water mixture presumably due to the blue colored that is water was not found in the bottom tube. For oil/water separation, some mixtures of oil and organic solvents were poured into distilled water in addition to oil/water emulsions added onto the zwitterionic nanogels modified polyacrylonitrile nanofibrous (ZPAN) membranes for evaluating the separation performance. A milky emulsion which was obtained by mixture stirred vigorously, is stable for the period of emulsion separation without demulsification as shown in Fig. 12.9C (Zang, Zheng, Wang, Ma, & Sun, 2020). It is seen through optical microscopy, the state of oil droplets from equipped oil/water emulsion (inserted photograph in Fig. 12.9A). Simultaneously, the dynamic light scattering in the emulsion was also measured and this data illustrates the size of oil droplets, which fluctuates from nanometers to micrometers (near to hundred) range (Fig. 12.9A). The ZPAN membrane has been stationary at a dead-end into the filtration module (before the separation test) and the pre-wetted membrane surface is covered by milky emulsion has been shown in Fig. 12.9B. For the ZPAN membrane, the liquid height of about 10 cm is obtained at a constant gravitational

FIGURE 12.9 (A) Image of the optical microscopy (interleaved photo) and oil size distribution of oil/water emulsion, pictures of (B) the filtration instrument, and (C) the oil/water emulsion containing oil and organic solvents were added to deionized water, and (D) the equivalent filtrate, (E) Image from optical microscopy of the filtrate from experiment (Zang et al., 2020).

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12.11 Future perspective

223

pressure of 1 kPa. This is worth mentioning that such microfiltration membrane having low driving pressure shown less fouling primarily due to the membrane channel-filling by oil droplets and saving energy, as compared to the conventional ultrafiltration and nanofiltration methods. This outcome shows that the electrospun ZPAN membrane with superhydrophilic outward has to capture water molecules. In the meantime, our membrane surface formed the hydration layer which can resist surfactant-free oil droplets. Oil droplets tend to move on the surface probably because of the short adhesive surface and it is coalescing into bigger droplets leading to additional demulsification. Moreover, the prominent microporous structure in the ZPAN membrane indicates greater interconnected water channels. Therefore, below capillary and gravity force the apprehended water effortlessly passed through the membrane (Ge et al., 2017) is shown in Fig. 12.9D. No oil drops were observed in the filtrate as exposed by the optical microscopy image (Fig. 12.9F).

12.10 Summary The separation process with a nanocoated membrane for oil-in-water emulsions has been presented in this chapter. The present revision for producing organic-based and inorganic-based membranes was discussed. The nature of three kinds of superwetting materials has been progressing oil-in-water emulsions separation and their proper modifications required to analyze the current research status. In the meantime, membrane applications comprising zwitterionic and biomimetic thin membranes also play significant factors in the separation performance among oil and water. As well as the superwetting property, there is an improvement in other properties like surface morphology, structure by the use of nano-coated membrane systems. Consequently, a summary of the important characterization in the next-generation membranes (wetting behavior, antifouling properties, mechanical strength, etc.) and an explanation of the steps for oil/water separation technologies is explained well. Finally, a comprehensive survey of all varieties of the oilin-water mixture in different membranes and their separation performance was studied.

12.11 Future perspective So far, a molecular level phenomenon containing structural and morphology have exposed that the lead to the production of organic and inorganic multifunctional membranes with high surface areas. Spilled oil samples and different types of nano-coated raw material are the motivation for future achievements. All of these outcomes resourcefully regulate the surface hydrophilicity and structural alteration of membranes for controllable oil-water separation. Therefore, the altered (nano-coated) membranes show better wetting behavior, higher mechanical strength, superior antifouling properties, and higher separation performance vis-a`-vis pristine membranes. More studies are still needed to improve polymeric, ceramic, and mixed matrix membranes for water treatment application. Moreover, the recent literature has been focused on the low-cost membrane with outstanding separation performance in the removal of oily wastewater treatment.

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Many challenges still remain for achievements regarding the new membrane materials with lower production cost and water purification application. Accordingly, there are some challenges to be talked about in this area may include the subsequent parts: Initial, nano-coated membrane should be less fouling resistance and easy to backwash for the purification process. Second, ceramic membranes with lower cost are very crucial and more effective for study the oil/water separation processes. Third, various multifunctional membranes with high prospective and innovation have been used for the oily wastewater treatment research field. Lastly, a control surface modification method is necessary to increase the efficiency of the membrane.

Acknowledgement The authors are thankful for the award of the Post-Doctoral Fellowship of JU-RUSA 2.0, India.

Conflict of interest The authors confirm that there is no conflict of interest for this publication.

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C H A P T E R

13 Chemical stabilization of oil by elastomizers Sankha Chakrabortty1, Jayato Nayak2 and Prasenjit Chakraborty3 1

School of Bio-Technology and Chemical Technology, Kalinga Institute of Industrial Technology, India 2Department of Chemical Engineering, School of Bio and Chemical Engineering, Kalasalingam Academy of Research and Education, India 3Agni College of Technology, Thalambur, Chennai, India O U T L I N E 13.1 Introduction

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13.2 Characteristics of oil spills 13.2.1 Physical characteristics 13.2.2 Chemical characteristics

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13.3 Oil spill stabilization/remediation techniques 13.3.1 Physical stabilization process 13.3.2 Adsorbent materials 13.3.3 Thermal remediation process

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13.3.4 Bioremediation method 240 13.3.5 Oil stabilzation by chemical based elastomizers 241 13.4 Future perspective for oil stabilization through chemical process 245 13.5 Conclusions

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13.1 Introduction From the initiation of the global industrial uprising, high turnover aimed market outlook in fully competitive production strategies, enabled extreme exploitation of fossil fuels. Year-by-year, the amplified human population density accustomed with the modern sophistication, forced to uprise the demand for electrical power on the power production houses. Along with the booming of manufacturing sectors, the tuning of urbane

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00022-7

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commodities from luxury items to basic needs, and the upsurging of transportation sectors triggered the increased production of earth oils for continuous fuel supply. Due to increased demand and global financial analyses, fuel oil production, selling import-export, and earning of revenue by any country is identified as one of the greatest pivotal factors of a country’s economic standpoint (Wang et al., 2020). Eventually, the extraction of crude oil got amplified along with the petroleum and petrochemical production sectors to cater to such demand and to maintain global financial dignity for a country. In the current times, the largest extractors of crude oil extraction companies are ExxonMobil, BP, Sinopec Group, Royal Dutch Shell, Valero, Gazprom, Phillips 66, Kuwait Petroleum Corp., Pemex., Chevron Corporation, National Iranian Oil Co, Total, etc. With the exponential growth in oil extraction, about 5.6 billion/m3 of impure oil mixture (crude oil, shale oil, and liquid content of natural gas) was extracted in 2019, from where, about 4.8 billion m3 of usable oil in different forms were produced (Garside, 2020). World-widely, the crude fuel oil is extracted from the sea-shore or gulf regions of a country employing huge investments for oil extraction. In fact, specially design machinery and skilled manpower are involved to control and maintain the safety and security of a floating crude oil extraction unit. But, unwanted spilling of crude oil is now a major concern of the marine environment that cannot be avoided. In fact, the spill could be arrested only to a partial fraction even if highly skilled professionals are involved. Spilled oil is basically waste from an offshore crude oil extraction unit because it could be hardly recovered. Because of its low density than seawater, leaked or spilled oil volume keeps floating on the water surface. Along with that, it is proved to be crucially harmful to marine aquatic eco-systems because it breaks the oxygen transfer from the atmosphere to water. Thus, the biotic communities of the marine ecosystem or the ecosystems dependent on it are facing critical issues of survival regarding the oil spillage problem. But, during the current decades, the emergence of ecologically sensible legislative actions are getting stricter with prompt actions on extraction sectors (Elliott, 1999; Osuji & Chukunedum, 2006). The most adopted conventional and emerging technologies for oil spill control are the use of oil booms, skimmers, absorbent or adsorbent or dispersant materials, burning in situ, hot water and high-pressure washing, manual cleaning, bioremediation, and stabilization by Elastomizers. Along with that, priorities are being given to the use of alternative materials for spilled oil capture and separation which would be low-cost and environment-friendly. This has started to give more encouragement to the industrialists and global research communities while fostering novel research towards the exhaustive reviews, material development, analyses, and testing. Indeed, such advanced materials are the need of the hour that can capture/immobilize and stabilize the spilled oil effectively at a low cost (Czarnecki, 2009). Moreover, the concern should be towards the use of a low content of mas which is efficient in arresting spilled volume to mix further with the marine aquatic system. Therefore newer routes are getting opened focusing on the growth of clean technologies for a wide plethora of stabilizing chemicals which leads the crude oil extraction process towards the least environmental degradation by waste oil-spilling (MI News Network, 2020; Younis, AliMaitlo, Lee, & Kim, 2020). Immediate to the spilling of oil, as it becomes essential to prevent the spreading and contamination of it in the adjacent regions of the origination spot. In fact, mechanical technologies e.g., oil booms come up with certain demerits. Oil booms are like fences preventing the spread of oils, and found to be

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effective for single-spot spillage which could be accessed within a short time of occurrence. This technology is not successful for large spillage areas or regions with heavy marine waves, air-flow speeds, or unstable tides. Skimming machines work as same as vacuum cleaning apparatus, suck up the spilled into the in-built collection chamber but the process suffers due to quick clogging. In the case of adsorption, it is a must to repossess the spent adsorbents which is an extremely tough task. Ineffective collection imposes a high risk to aquatic life because of leachate formation. In situ burning produces hazardous smoke and temperature difference in the marine aquatic layer. By using dispersing agents, tiny tarballs are formed which get mixed with seawater and sands, which may travel towards the seashores. During the use of hot water and highpressure cleaning, hot water at about 170 C, is flushed through high-pressure nozzles. This high temperature is extremely dangerous for the living species present in the flushing zone. Manual cleaning process of spilled oil debris could be applied on small scale in the shorelines because it is labor-intensive and time-inefficient. Though lots of researches are going on green bioremediation of spilled oil, the process is highly timeconsuming with a high possibility of formation of undesirable algal or fungal species, that in-turn decreases sunlight and oxygen availability in deep seawater. Thus, the use of such technologies also could be proved as counter-productive to marine life (Eie, 1995; MI News Network, 2020). But, currently, with the use of “Elastol,” which are the compounds of amorphous poly iso-butylene is being analyzed to capture and stabilize spilled crude oil. Gelatinous formations of solidified oil on the water surface arresting it from spreading or escaping, the technology used to be extremely effective with a typically fast reaction process with ideal reactivity within an hour. Such proposed compound is nonhazardous but, it should be removed immediately after application to restrict the suffocation of marine animals. In the regions where the oil contamination is very high with a thick layer formation, the other methods typically fail inefficient removal/capturing/stabilization of oil. Elastomizers increase the speed of recovery rate and efficacy of oil removal by capturing oil into the polymer matrix, lessening the contacts with air and water (Eie, 1995; USEPA, 2011c). But, a lot of researches are extremely required to gain confidence in such a stabilization process with such novel polymers, which will foster the implementation of an economic and environmentfriendly process.

13.2 Characteristics of oil spills The spill of oil in the marine ecosystem has been a major threat to the environment in current days. The release of various petroleum products, crude oil, waste oil, and bunker fuel into the marine environment is a key concern for the pollution of the ocean ecosystem. The oil spill effect asperity mainly confides in the oil amount and its physicochemical properties which affect different transformation processes such as emulsification, evaporation, dissolution, spreading, and sedimentation (Holakoo, 2001). The chocolate mousse, several oxygenated products, and tarball formation occur in the various transformation processes which results in tough recovery of the oil (Daling & Strøm, 1999).

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13.2.1 Physical characteristics There are different oil physical properties like surface tension, color, viscosity and specific gravity. The change of oil spill characteristics reliant on the oil category released in the marine atmosphere. Usually, depending on the oil’s physical properties, the oil color may transform to yellow, red or green color from the black or dark brown oil color (Holakoo, 2001). The various characteristics specific gravity, surface tension, and viscosity are the key factors for spreading capability of oil spill. Oil with high viscosity has fewer propensity to outspread (USEPA, 1999a). It has been reported by Payne and Philips (1985) that chocolate moss has been formed due to high viscous oil spill as degradation of chocolate moss is very tough (Payne & Philips, 1985). The density of fuel oil is reduced 0.88 kg/ dm3 to 0.855 kg/dm3 with increased temperature of 10 C
50 C and also viscosity decreased from 5000 to 200 cSt (Nordvik, Simmons, Bitting, Lewis, & Strom-Kristiansen, 1996). The resistance of oil flow is reduced which increases the spreading capability of oil. The effect of temperature on surface tension of oil can be accredited to the fact that in hot water, dispersion tendency of oil spill increases than in less warm waters. The rapid spreading capability has been observed for low surface tension oil even without any wind or flows. The oil floats on the ocean water surface and horizontally disperses as the density of the marine water is higher than the density of the oil. The oil’s lighter element evaporates which raises the oil specific gravity permitting weightier oils to sink. Oil tar balls are generated that might be attached with bottom water sea rocks or sediments.

13.2.2 Chemical characteristics Boiling point, melting point, molecular weight, flash point, partition coefficient, solubility, explosivity limits, and flammability limits are the oil’s chemical properties. The oil type is related to chemical properties (ASTDR, 1995). The oil contains hydrocarbon with some composite chemical compositions and also comprises a few metals oxygen, nitrogen, and sulfur. Alkanes containing mainly saturated carbon and hydrogen atoms which are hydrocarbon’s mildest form. Whereas, unsaturated carbon and hydrogen molecules with double or triple bonds named Alkenes and Alkynes. There are four major groups of oil are aromatic, saturated, unsaturated, and polar groups. Crude oil includes 50% naphthene, 30% alkanes or paraffin, 15% aromatics, 5% nitrogen, oxygen comprising compounds and sulfur. The key hydrocarbons groups observed in gasoline are aromatics, paraffin, naphthenes, and olefins.

13.3 Oil spill stabilization/remediation techniques Control and removal of the oil spill from marine water are very critical which is one of the most contentious matters for the researcher as total removal of the oil spill from ocean environment is not possible. Remediation methods have been recognized as an imperative approach for oil spill cleaning from marine water. Various remediation methods are physical technique, chemical technique, thermal and biological technique (Larson, 2010).

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13.3.1 Physical stabilization process Physical remediation techniques are usually employed for controlling oil spills in marine water. These methods are mostly used to resist the oil spill dispersion in water as a barrier without varying chemical and physical properties of oil spill. Different barriers are employed for oil spill spreading consisting adsorbent materials, booms and skimmers (Fingas & Fieldhouse, 2011; Vergetis, 2002). 13.3.1.1 Booms Booms are typical kind of equipment used for oil spill remediation. It prohibits oil spill spreading through creating a barrier to flow of oil that can enhance oil recovery by different response methods or skimmers. Three types of booms, such as (1) fence boom (2) fireresistant boom and (3) curtain boom are there for oil spill separation from contaminated water (Potter & Morrison, 2008). 13.3.1.2 Fence booms Fence booms are floating type fence making of solid and lightweight materials with vertical screen as 60% of the boom stays under the water and 40% stays above the water level. The height of the boom parts is normally 300, 600 or 800 mm and length is 15 m. Different boom parts with specific connectors may be attached together. Fence booms are prepared with PVC or PU fabric which is light weight. The booms having limited storage area, easy to operate, prevent deformation, fresh and stock are extremely consistent in steady waters. Less constancy in heavy winds and tides, minor proficiency in high waves and less towing flexibility are some drawbacks of fence booms (Potter & Morrison, 2008; Ventikos, Vergetis, Psaraftis, & Triantafyllou, 2004). 13.3.1.3 Curtain booms Curtain booms are impermeable, and floating type system having a huge foam-filled circular chamber that stays above water and a malleable skirt that endures underwater. These booms are built with polystyrene, polyurethane, and bubble cork material. The width of the chamber ranges from 100
500 mm and the length of the skirt varies from 150
800 mm. Curtain booms are dependable in seawater in the offshore condition having great towing flexibility. The performance of curtain booms is higher than fence boom through cleaning and storage are very tough in these booms (OSS, 2010; Ventikos et al., 2004). 13.3.1.4 Fire-resistant boom Fire-resistant metal has been used to make fire-resistant booms that focus on adequate oil quantity to competently burn at a temperature of 1093 C. These booms are employed in accordance with techniques for in situ burning (Ventikos et al., 2004). Stainless-steel booms, Water-cooled booms, ceramic booms, and heat-resistant booms are different forms of booms that are accessible as fire-resistant booms. Approximately, 1500 m2 of burn area may produce by 200 m of fire boom length. In marine water, they are effective and have tremendous ability to save the coastline against the effects of a sea oil fire. However, these booms are costly and hard to tow as their huge in size and weight.

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13.3.1.5 Skimmers Skimmers are a general type of equipment used for oil recovery from the surface of the marine water combined with booms. Skimmers can be reused and recovered as it operates without varying its properties. It comprises drums, disks, brushes, and belts (Hammoud, 2001; Larson, 2010). These devices may be vessel-operated or shore-used and selfpropelled. Three types of skimmers are (1) suction, (2) weir and (3) oleophilic (Nomack & Cleveland, 2010). The skimming achievement depends on the oil spill width and type, climate situations and the place, the contaminant volume in the seawater. Skimmers are productive in marine waters and congestion may occur due to floating contaminants. 13.3.1.6 Wier skimmers Weir skimmers capture the floating oil from the surface of marine water through gravity action and perform as a dam. The captured oil is transported from the central weir sink to storage tanks using a pump or through gravity. High efficacy in fast oil recovery and large static constancy in tides are significant features of skimmers (Hammoud, 2001). They provide good performance in low density, nonemulsion oil, and less viscous oil. Skimmers have suggestively less productivity with oil emulsion and are often congested and blocked through floating debris (Jensen, McClimans, & Johannessen, 1995). 13.3.1.7 Oleophilic skimmers Oleophilic skimmers contain disks, ropes, drums, belt and brushes type skimmers. Oleophilic properties materials are used to make all categories of oleophilic skimmers. The oil complies with material surface that may rubbed from the surface and stored in a tank. Oleophilic nature of the skimmers can be restored 90% of the oil in marine water. Oleophilic skimmers are flexible and operative on any thickness spills, fewer affected by waves and well perform with uneven ice or debris (Nomack & Cleveland, 2010). These skimmers are not capable of dealing with dispersants mixed oil and separation of waste is carried out by hand (OSS, 2010). 13.3.1.8 Suction skimmers The role of suction skimmers is connected to the vacuum pump’s air venture scheme that extracts oil via large floating heads and moves it to storage tanks. These skimmers are very active while conducting an oil viscosity of extensive variety. They can also be obstructed by debris and necessitate trained operators. Suction skimmers are very competent to collect oil residues and are most frequently used to extract oil from beaches, restricted areas, or oil exclusion from the surface of the soil. They run successfully in offshore areas in combination with the boom in ocean water. However, for use of inflammable oil goods, these skimmers are not worthwhile due to an explosion may occur (Ventikos et al., 2004).

13.3.2 Adsorbent materials Oil spills reduction can be accomplished by hydrophobic type adsorbent material which acts as an ultimate cleaning stage of residual oil after the skimming process. For the

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complete oil removal, they promote the transfer of liquid to the semisolid stage (Adebajo, Frost, Kloprogge, Carmody, & Kokot, 2003). The numerous sorbent materials for oil spill removal are synthetic materials, natural inorganics, and natural organics. 13.3.2.1 Natural organic adsorbents Sawdust, kapok, peat moss, vegetable fibers, straw, and milkweed are the common natural organic sorbent. Banerjee, Joshi, and Jayaram (2006) examined the maximum sorption capability of sawdust and oleic acid affixed sawdust which was 3.6 g/g and 6 g/g respectively in 5 min (Banerjee et al., 2006). It has been reported by Choi and Cloud (1992) that 74%
85% of crude oil has been absorbed by cotton fibers and milkweed from crude oil comprising fabricated marine water bath surface (Choi & Cloud, 1992). Peat moss’s maximum sorption capacity was found to be 6.7 g/g by Ghaly, Pyke, Ghaly, and Ugursal (1999). Various advantages of natural organic adsorbents are easy availability, well sorption capacity of 3
15 times of their weight, and cost effectiveness (Ghaly et al., 1999). There are key drawbacks of these sorbents which are sinking occur due to their sorption of oil along with water, difficulty on an assortment of sorbents after dispersion on the oil spill water which is essential to discard for their use and they are labor-intensive (Nomack & Cleveland, 2010; USEPA, 1999b). 13.3.2.2 Natural inorganic adsorbents Natural inorganic adsorbents are glass, clay, wool, volcanic ash, and sand (Holakoo, 2001). Teas, Kalligeros, Zanikos, Stournas, and Lois (2001) exposed that for recovery of oil spill hydrophobic perlite have presented similar sorption capacity with conventional organic materials (Teas et al., 2001). Clay minerals like pillared and smectites interlayer clays are employed as sorbents for organic materials in a liquid state in the composed agrochemicals discharge (Ding, Kloprogge, Frost, Lu, & Zhu, 2001). Alther (2002) stated that sorption of 50 categories of oil by quats with modified clays performs better than activated carbon. Absorption capacities of these sorbents are 4
20 times their weight, they are less expensive and easily available (Alther, 2002). The main limitations of these sorbents are that they are not recommended for the surface of the water, application in windy environments is very tough, inhalation of this adsorbent may responsible for possible health risk, and vermiculite and clay type natural inorganic sorbents are weak material (USEPA, 2011a). 13.3.2.3 Synthetic adsorbents The most frequently used trade sorbents are synthetic sorbents. Polypropylene, polystyrene, and polyester foam are employed in synthetic adsorbents. These adsorbents are accessible in rolls, bars, booms and also applied as a powder to the surface of the water (Teas et al., 2001). Teas et al. (2001) explored that polypropylene has maximum oil (light gasoline oil, light cycle oil) sorption capacity of 4.5 g/g. The hydrophobic and oleophilic nature of synthetic sorbent provides sorption capability of 70
100 times of sorbents weights in oil. Some natural sorbents may be reused many times (Teas et al., 2001). Jarre et al. inspected that open-cell polyurethane foams and ultralight have been efficiently adsorbed oil from oil-water mixtures of 100 times their weight.

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Nonbiodegradability and storage problems are the main drawbacks of these adsorbents (Choi & Cloud, 1992; USEPA, 2011a).

13.3.3 Thermal remediation process The thermal method of remediation of oil spills is in situ burning process which is fast and easy that can ensue with nominal specialized instruments like igniters and fireresistant boom with higher oil exclusion efficacy rates. In situ burning is extensively used for removing oil spills, snow of pipeline and storage container, jet fuel in ice-enclosed waters since 1960. This method has been also used to decrease ship accidents in European countries and also in the Canada and United States (Buist, McCourt, Potter, Ross, & Trudel, 1999). In situ burning process of oil spill remediation is competent in quiet wind conditions and fresh oil spills which rapidly burn without producing marine life at any risk. An underground water source can be sunk and covered by the remaining of this process. Residue reduction can be accomplished by the mechanical way (Davies, Lewis, Lunel, & Crosbie, 1998). An effective burning process depends on oil thickness and adequate oxygen supply (Buist et al., 1999). Oil combustion sustaining and sufficient oxygen supply to fire can be conducted through two agents which are burning agents and wicking agents. Burning agents comprise light crude oils, gasoline, and several commercially existing products and wicking agents consist of wood, straw, silica, and glass beads (Fingas, Duval, Stevenson, & Galenzoski, 1979). However, in situ burning is a competitive process for the removal of oil spills. The key limitations of this method are (1) catching risk in the environment and human health due to the burning by-product (2) worried of secondary fires (Buist et al., 1999). Burning may affect flora and marine life subsequent to site and also affects the long-term modification of flora and fauna. The most effective remediation technique is in situ burning if implemented directly after the spill of oil has appeared.

13.3.4 Bioremediation method In bioremediation method, degradation of microorganisms and metabolize of chemical material have been occurred which improve the quality of the environment. The purpose of this technique is to enhance the natural attenuation method where organic molecules are incorporated to cell biomass by microorganisms and production of water, carbon dioxide, and heat as by-products has been appeared (Atlas & Cerniglia, 1995). Microorganisms have the capability to degrade hydrocarbons which is widespread in natural oil spill site for marine oil spill. Various type of microorganisms with several rate of degradation can degrade aromatic and paraffinic hydrocarbons. Over all petroleum products the utmost simply degraded hydrocarbons are aromatics of lowmolecular-weight and alkanes with 10
26 carbon train. In marine environments, bacteria are the leading degraders of hydrocarbon. Several bacterial species that degrade hydrocarbons such as Achromobacter, Pseudomonas, Alcaligenes, Acinobactor, Bacillus Brevibacterium, Arthrobacter, Flavobacterium, cornybacterium, Nocardia, Vibrio, and Pseudomonas have been reported (Atlas & Cerniglia, 1995). Numerous microorganisms leading at various bioremediation stages in which shifting of microbial populations to

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aromatic hydrocarbons from alkanes are ensued and easily degraded hydrocarbons are removed (Sugai, Lindstrom, & Braddock, 1997). The oil spill biodegradation in the aquatic climate is mostly influenced through the oil concentration, nutrients bioavailability, degree of time in which the environmental biodegradation has been conducted (Atlas & Cerniglia, 1995; Zahed, Aziz, Isa, & Mohajeri, 2010a). In aquatic ecosystem, nutrients like phosphorus and nitrogen are consistently in low concentrations has been essential for the hydrocarbon-degraders development. The natural attenuation process of oil spills is not performed at a feasible rate due to the insufficient nutrients (Atlas & Bartha, 1973; Atlas & Cerniglia, 1995). In addition, the high initial oil spilled content has a detrimental impact on the method of biodegradation producing a substantial 2
4 weeks lag phase (Zahed et al., 2010a). Microorganisms require minimum of one week to accustom in the environment after biostimulation, and it can take months and even years for the whole bioremediation method to accomplish (Zahed et al., 2010a). Oxygen and temperature are the significant environmental factor where microorganism’s metabolic rate affected by dissolve oxygen and crude oil viscosity affected by temperature (Yang, Jin, Wei, He, & Ji, 2009). In order to increase the natural degradation method rate, immunization of polluted ocean water with microorganisms of degradation of hydrocarbon and fertilizers incorporation or biostimulation are required for successful bioremediation of oil spill. One of the alternatives for marine oil spill bioremediation is screening of the microorganisms responsible for petroleum hydrocarbon degradation from earlier polluted area and immunizing them to the polluted marine water. The extensive variety of bacteria and fungi that degrade hydrocarbons develops a serious competition among native species and those in the culture media. Several studies reported that bioaugmentation has not a been a feasible substitute for bioremediation of oil spill (Atlas & Cerniglia, 1995). The application of fertilizers as substitutes of nutrients (nitrogen and phosphorous) has been observed a successful performance for marine oil spills, while the widely efficacy of bioremediation of degraded oil is restricted. The dispersant or surfactants application has been stated to be efficacious since they improve the oil bioavailability to degraders of hydrocarbon (Zahed et al., 2010a). The phosphorus and nitrogen inclusion to the aquatic body resulted eutrophication has been inspected. The algal blooms would not be induced by using oleophilic fertilizers has been reported by Atlas and Bartha (1973).

13.3.5 Oil stabilzation by chemical based elastomizers In accordance with physical approaches for ocean oil spill recovery, chemical methods are used as they minimize the propagation of oil spills and assist to defend shorelines and fragile marine ecosystems. Several chemical compounds are employed for oil spills treating as they have abilities to modify of oil chemical and physical properties (Vergetis, 2002). Solidifiers and dispersants are used as chemicals for oil spills controlling. 13.3.5.1 Dispersants In accordance with physical approaches for ocean oil spill recovery, chemical methods are used as they minimize the propagation of oil spills and assist to defend shorelines and fragile marine ecosystems. Several chemical compounds are employed for oil spills

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treating as they have abilities to modify soil chemical and physical properties (Vergetis, 2002). Solidifiers and dispersants are used as chemicals for oil spills controlling. Dispersants comprise surfactants immersed in one or more solvents. The oil slick has been imparted effectively into small droplets by dispersants and quick dilution and easy degradation occur in the marine water column (Lessard & Demarco, 2000). Dispersants are typically employed through spraying of the chemical and water mixer and by proper mixing has been confirmed by wind or the boat propeller (Sitting, 1974). Chemical compounds which were formerly used are more toxic and less effective than recent existing dispersants (Lessard & Demarco, 2000). Corexit 9500, Corexit 9600, Corexit 8667, Slickgone NS, SPC 1000, Neos AB3000, Nokomis 3-F4, Nokomis 3-AA, Finasol OSR 52, Saf-Ron Gold, ZI400 are the concentrated dispersants used for oil spill control in water (USEPA, 2011b). Siang (1998) stated that dispersant Corexit 9500 removed oil spill in 3 weeks which was a record and created history in Singapore (Siang, 1998). In another study, Corexit 9500 used as a dispersant where 50%
75% of No. 5 bunker slick of oil was dispersed (Davies et al., 1998). Holakoo (2001) reported that 90% of the oil spill has been treated proficiently by dispersants which were cost-effective compared to physical methods (Holakoo, 2001). Dispersants could be able to use on uneven seas where mechanical recovery is impossible and heavy winds are present. In these methods fast treatment is allowed, delay the development of oil-water emulsions which provide less possibility to stick the oil to the surfaces and speed up the normal biodegradation rate by enhancing oil droplet surface area. Dispersants’ suitability depends on the temperature, oil categories, sea environments, and speed of the wind (Nomack & Cleveland, 2010). Though, most of the dispersants have inflammable nature which causes possible marine life damage and health risks of humans during operations. Dispersants are also accountable for drinking water source pollution and shorelines fouling. 13.3.5.2 Solidifiers Solidifiers are also used for oil spill remediation which are hydrophobic polymers and dry granular type materials. The reaction between oil and solidifiers transforms to a solid rubber state from a liquid state which could simply eliminate oil through a physical process. Several forms of solidifiers like semisolid materials which comprise cakes, pucks, balls, sponge designs, and dry particulate can be used. Pillows, booms, socks, and pads are different forms of solidifiers (Dahl, Lessard, & Cardello, 1996; Delaune, Lindau, & Jugsujinda, 1999). In relatively rough marine water, solidifiers can also be employed as the sea waves produce the mixed energy that consequences in higher solidification (Nomack & Cleveland, 2010). The solidifier efficacy depends on oil type composition. Previously, they have not been employed widely due to the recovery of the huge amount of oil mass 16%
200% by weight is required after solidification and comparatively their lower competence than dispersants (Fingas, Stoodley, & Laroche, 1990). 13.3.5.3 Stabilization by low cost chemical stabilizers/surfactants Polyglycerol polyricinoleate and lecithin were the two basic surfactants having a low molecular weight and mostly used in oil stabilization. Fig. 13.1A and B show the mechanism of oil stabilization by surfactants and behavior of particle attachment to the oil surface respectively.

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FIGURE 13.1 (A) Schematic diagram of a W/O emulsion droplet showing different interfacial stabilization by surfactant, biopolymers or particles. (B) The three-phase contact angle is related to the balance of surface free energies at the particle-water, particle-oil and water-oil interfaces (Zembyla, Murray, and Sarkar, 2020). Source: Copyright is taken from Zembyla, M., Murray, B. S., & Sarkar, A. (2020) Water-in-oil emulsions stabilized by surfactants, biopolymers and/or particles: A review. Trends in Food Science & Technology, 104, 49
59.

Killian and Coupland (2012) had reported maximum 30 wt.% oil stabilization through the utilization of water droplets in soyabean oil. Oil stabilization by the mixture of polyglycerol polyricinoleate and stabilized water droplets was found more stable than the stabilization by the mixing of lecithin. This was attributed to the cognition of PGPR to form elastic interfaces that slow down the rate of a coalition between several droplets (Killian & Coupland, 2012; Marquez, Medrano, Panizzolo, & Wagner, 2010). The properties of a mixture of surfactant and stabilized water-oil emulsions were powerfully mutualist on the lipid and emulsifier type used. The higher chemical affinity between the hydrophobic moieties of the emulsifier and the oil made the solution more stable hydro droplets. Ushikubo and Cunha (2014) reported a study for the stabilization of water-oil emulsions in which 30 to 40 vol% of water is present, they carried out the study with three different surfactants (namely PGPR, lecithin, and Span 80) and three different types of oils (such as, soybean oil and hexadecane) (Ushikubo & Cunha, 2014). Higher kinetic stability ( . 14 days) and smaller-sized water droplets (1
4 μm) based emulsions were found best to stabilize the oil with the mixing of PGPR or hexadecane with Span 80. In another study, three different types of salts (like NaCl, CaCl2 up to 0.25 M) were used to raise the kinetic stability of PGPR and stabilized emulsions to the coalition, reducing the rate of Ostwald ripening between oil and water phases (Israelachvili, 2015). Marquez et al. (2010) reported a study regarding the stabilization and the effects of different salts on stabilization efficiency. A higher degree of stabilization was found in presence of calcium salts which is basically reduced the attractive force between water droplets. In addition to that higher adsorption density of the emulsifier, evident by a lower interfacial tension (Marquez et al., 2010). Israelachvili (2015) found maximum attractive force between two water droplets in the oil continuous phase due to the same refractive indices and/or the dielectric constants of the two phases (Israelachvili, 2015). Therefore the addition of calcium salt into the water phase would reduce the attractive force between water droplets, reducing the collision frequency (Israelachvili, 2015; Marquez et al., 2010). Advantages and disadvantages of all the remediation methods has been shown in Table 13.1.

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TABLE 13.1 Advantage and disadvantages of booms, Skimmers, and physical remediation technique of oil spill of marine. Booms

Advantages

Disadvantages

Curtain booms

Oil recovery is possible, handle with all types of oil, prevent abrasion, towing flexibility

Complex process, labor intensive, expensive, more treatment requires for collected oil, lower efficacy in high waves, difficulty in storage and cleaning Mainly comprise oil and essentially used with different technologies, high cost, labor comprehensive, lower constancy in strong wind and currents, minor flexibility for towing

Fence booms Easy handling, storage and cleaning, handle with all types of oil, probability of oil recovery, Prevents abrasion Fire-resistant Shoreline protection from the oil fire effect at boom sea, all types of oil can be used

Lower efficacy in high waves, high cost, labor comprehensive, low towing flexibility, oil collected are directly burned off, difficulty in storage and cleaning

Skimmers

Advantages

Disadvantages

Suction skimmers

Handle with all types of oil excluding inflammable, probability of oil recovery, efficiently collect residue of oil

Lower efficacy in high waves, high cost, complex process, labor comprehensive, more treatment requires for collected oil, impossible to use with inflammable oil products, maintenance is needed

Wier skimmers

Probability of oil recovery, high wave stability, applied in low viscous, low density and nonemulsion oil

More treatment requires for collected oil, complex process, labor intensive, lower oil emulsion efficacy, high cost, clogging due to floating debris

Oleophilic skimmers

Work well with debris or rough ice, possibility of 90% oil recovery effective on any thickness of oil spill in relative to water

Clogging probability due to floating debris, high cost, further treatment requires for collected oil, complex process, high maintenance desirable, unable to deal with dispersants mixed oil, labor comprehensive

Advantages

Disadvantages

Adsorption

Simple and easy process, polypropylene or polyurethane based synthetic adsorbent have decent hydrophobic and oleophilic properties, all type of oil is effective as final clean up step, maintenance is not mandatory

Selected weather conditions, labor comprehensive, require to dispose with guidelines, biodegradability is problematic for synthetic adsorbents, moderate costly

Booms

Probability of all types of oil recovery

Mainly comprise oil and essentially used with different technologies, high cost, complex process, effective in selected weather situations, labor comprehensive

Skimmers

Probability of all types of oil recovery except inflammable oil

Complex process, effective in selected weather situations, more treatment requires for collected oil, labor intensive, costly, clogging probability due to floating debris

Physical remediation method

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13.4 Future perspective for oil stabilization through chemical process Nanotechnical engineering on emerging materials could be one of the brightest futuristic development to combat for such oil stabilization issues. Such super fine nanostructured minute materials which are commercially employed in computational devices, can find its applicability in cleaning of spilled oil volume because of its promising capability in absorbing oil while repelling water. Spongy materials developed from Carbon nanotubes (CNT) could be a strongly cited for such purposes, which looks similar as those used in kitchens with about 1 foot length. National Nanotechnology Initiative (2016) Unlike the kitchen sponges, such CNT sponges possess the excellent ability in repelling water molecules but reasonably high selective adsorbing efficiency towards oil, which is even about 24 times their weight within a 1/4 hour. Where the conventional adsorbents, e.g., plastic fibrous or woolen materials show the adsorbing capacity of only about 8
9 times of their mass, CNT sponges open up whole new possibilities in capturing spilled volume of oils. This is why it has grabbed the attention of global technical and scientific research communities. Moreover, through different types of engineering modifications like the magnetic CNT materials have also been proved to be effective in efficient isolation and removal of oily compounds from water (Zhao et al., 2011). But, modification of CNTs in some cases could be costly, because of which, researchers are putting immense efforts on creating less expensive, magnetic, Fe-integrated nanostructured materials. By the addition of minute structured magnetized constituents with coconut oil, a suspended liquid or nanofluid was created which exhibited more than 90% effectiveness in eliminating motor oil from water (Nabeel Rashin, Kutty, & Hemalatha, 2014). Such nano-oils adsorbs on to the target oils, where the magnetic constituents help in removal of the magnetic particles, oil, and coconut oil from the water.

13.5 Conclusions Rigorous literature reviews highlight that the elastomizers could be an efficient alternative in the removal of oil spillage from marine water. With the ability to quickly capture and immobilize spilled shells or crude oils, it can show a route toward ecofriendliness in an economic way. Though a lot of surveys are extremely required to amplify the confidence regarding the use of such elastomer, it could be assured that the polymeric chain is tight enough to guarantee complete binding by arresting oil droplets. Through quick capturing of spent polymers, the spilled oil volume could be reduced from the seawater allowing proper air and sunlight mixing with marine ecosystems. Thus, the overall sustainability could be maintained from the point of view of economics and ecology by the wise implementation of elastomizers in the treatment of oil spills from extraction sites.

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C H A P T E R

14 Advances in burning process and their impact on the environment Mandira Agarwal1 and J. Sudharsan2 1

Department of Petroleum Engineering & Earthsciences, School of Engineering, UPES, Dehradun, India 2Doctoral Research Fellow, Department of R&D, UPES, Dehradun, India O U T L I N E

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14.2 Principles 250 14.2.1 In situ burning operation 250 14.2.2 Factors affecting in situ burning 251 14.3 In situ burningtechniques & current application 253 14.3.1 Selection of in situ burning equipment and operation 253 14.3.2 Ignitors 256

14.3.3 Treating agents and combustion additives 258 14.4 Environmental and health concerns258 14.4.1 Air quality 259 14.4.2 Water quality 260 14.5 Summary

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14.1 Introduction In situ burning (ISB) is a controlled burning process of hydrocarbon vapors arising from oil spills. ISB technique is able to remove a larger volume of oil spill in a cost effective manner that can save the cost of collection, storage, transport, and disposal of oil which is a typical requirement of all other oil spill response techniques (Barnea, 1995). As it cleans up a major amount of oil quickly, it helps to restrict the oil spreading into shoreline and prevents threats to human and animal lives. In frozen arctic conditions, ISB is an effective technique rather than mechanical and chemical methods because the ice acts as natural barrier to prevent oil spreading and oil emulsification that allows to sustain the

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thickness of oil slick for longer time without any support of boom containment in order to accomplish continuous burning. In situ burning can easily achieve oil removal efficiency more than 90% from the water surface with maximum removal rate of 2000 m3/h. Residue oil from ISB is less toxic compared to other oil spill responses as well as volume leftover residue oil is also low (1%
10% of original volume) (Buist et al., 1999; Buist et al., 2003; Mabile, 2012). It also reduces the long term impact toxicity of oil spill on flora and fauna in the sea. The generated fire remains safe and absolutely controllable throughout ISB process (Walton et al., 1999). Environmental Protection Agency (EPA) has stated that ISB has been utilized to eliminate around 310,000 bbl of oil immediately in the area of Gulf of Mexico after the major oil leakage into the sea environment by Deepwater Horizon (DWH) spill in 2010 (Lubchenco et al., 2010; Schaum et al., 2010). United States Govt. provides more importance to ISB technique for oil spill response in the sea essentially and few locations in the inland according to National Oceanic and Atmospheric Administration (NOAA) (Ekperusi et al., 2019; Mabile, 2012). Earlier attempts of using ISB could not produce desirable results because of poor understanding of the process. In 1967, the attempt of using ISB technique at Torrey Canyon incident was unsuccessful due to higher emulsification rate of oil on the surface of water. Since then a lot of research work is being carried out to understand the burning behavior of oil spill. The study shows ISB technique is able to remove oil contained with boom can be in the order of 50%
99% (Allen, 1990). Decision makers demand a complete understanding and assessment of ISB such as resources, feasibility, environmental conditions, and safety considerations to make a successful operation.

14.2 Principles 14.2.1 In situ burning operation 14.2.1.1 Ignition requirement To burn the spilled oil on the surface of water, there must be three components viz., fuel, oxygen and ignition source. The air should be heated to the extent at which sufficient hydrocarbons get vaporized for combustion in the air above oil slick causing the burning of hydrocarbon vapors but not the oil spill directly, A continuous supply of vapors are needed in order to achieve an uninterrupted burning. 14.2.1.2 Rate of heat transfer During the burning of oil spill, Most of the heat is escaped through the combusted gas to the environment. However small portion of heat (around 1%) must have been present in the oil slick that will radiate the oil slick and able to vaporize them partially. This process is helpful to obtain steady state of hydrocarbon vapors quickly for the continuous burning. 14.2.1.3 Flame temperature The temperature of flame over the oil slick must be around 1200 C and the temperature in the interface of oil slick and water should not above the boiling point of water. Optimum temperature of the oil slick ranges between 350 C and 800 C (Fingas et al., 1995).

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14.2.1.4 Thickness of oil slick If the oil slick is thicker, it can able to hold the high temperature for longer periods of time throughout the oil spill and reduce the heating loss by preventing contact of the water beneath the oil slick and this phase is referred as “hot zone.” When the oil slick becomes thinner, the oil slick will lose its isolation and start to contact the water that will stop the oil burning. 14.2.1.5 Final stage of burning In the calm water environment after attaining hot zone phase, the thinner oil zone will burn remaining oil droplets over the water surface quickly because the lost heat from oil slick zone to water will keep the temperature of interface of oil slick and water above the boiling point of water. It leads to the burning vigorously and allows remaining oil droplets into the flame. This is called as “vigorous burning phase” and this phenomenon is not possible if the towed boom has been used as water beneath the oil doesn’t stay longer to get and maintain the temperature above boiling point.

14.2.2 Factors affecting in situ burning 14.2.2.1 Ignition of oil slick The following conditions in the oil slick is needed for effective in situ burning: • For a fresh and volatile type of oil spill, thickness of oil spill must be minimum, about 1 mm. • If the oil spill is aged and emulsified (mostly diesel), the thickness of oil slick must be around 3 to 5 mm. • If the oil belongs to residual oil or Bunker “C” (fuel of electric power, space heating etc.,) or No. 6 fuel oil (fuel for ships), the thickness requirement of oil slick is 10 mm. Once 1 m2 area of oil spill is ignited, it is considered that ignition has been accomplished successfully. 14.2.2.2 Other factors affecting ignition of oil slick The other prime factors that affect the ignition in addition to the type of oil are emulsification, the speed of wind and its direction, ignition strength, surrounding ambient temperature and sea waves. The wind speed must not be exceeding more than 12 m/s for a successful ignition. If the oil spill is weathered and oil—water emulsion is in stable condition, it can ignite up to 25% of water whereas more water content can be ignited for meso—stable crude (paraffinic crude) (Fingas & Fieldhouse, 1997). When the surrounding temperature is more than the flash point of oil, the ignition will happen immediately and the flame will be spreading rapidly. 14.2.2.3 Rate of in situ burning The rate of oil spill burning is denoted as thickness per unit time (mm/min) which depends on type of spilled oil, fire diameter, thickness of oil slick, sea and ambient

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conditions. The diameter of fire for unemulsifed crude and diesel/jet fuel are 3.5 and 4 mm respectively. The oil removal efficiency is influenced by the following three factors. 1. The thickness of oil slick before the ignition. 2. The thickness of remaining residue after the in situ burning. 3. How much area is covered by the flame. The following parameters are required for the effective oil burning: • The thickness of residue for the unemulsified oil pools must be less than 5 mm. • When the oil spill pool is large and thicker, residue of thickness maybe higher than 5 mm. • If the crude oil is lighter and volatile, the thickness of residue must not be exceeded 1 mm. • When wind speed as low as 2 m/s, it is able to herd the oil to the thickness that can support combustion. • If the current is uniform, it can upsurge the burning efficiency and reduce the oil residue. Excessive waves and currents over wash the oil slick that impacts the burning efficiency adversely by increasing density and viscosity of the burn residues. 14.2.2.4 Characteristics of oil slick residue In the case of efficient in situ oil burning (more than 85% burning efficiency) of 10
20 mm thick oil slick, the produced residue looks like tar. When the oil slick is thicker about 150
300 mm, the burnt residue appears as almost solid (Ross, 1996). 14.2.2.5 Tendency of flame spreading The flame must spread efficiently to cover a large area of oil slick and the following two ways can yield high oil removal efficiency. • The fire point of combustion environment can be maintained across the oil spill by radiating the heat from flames to adjacent liquid (radiant heating). • The hot liquid beneath oil slick can transfer the heat to cold fuel to enhance the surrounding temperature. The velocity of flame spreading will be reduced when oil evaporation increases or the thickness of oil slick is reduced. If the wind speed increases, the downwind flame spreading will be also increased. Flame spreading toward upward is always slow even though the barrier or edge breaks the cross wind speed. The regular waves do not affect flame spreading and the steep waves restrain the flame spreading. 14.2.2.6 Flame heights Fires with less than 10 m of diameter will produce the flame height that is almost double the fire diameter. When the fire is larger than 10 m, the almost the same size of flame heights will be generated. If the fire is too large, the height of the flame is not possible to estimate due to generation of high quantity of thick smoke.

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14.2.2.7 Impact of emulsification Oil spills in water environments are less likely to be combusted if emulsified and this happens due to the presence of water in the emulsion. The water content of emulsions is usually between 60%
80% and up to 90%. The oil in the emulsion cannot exceed a temperature of more than 100 C unless the water is either boiling or eliminated. The heat from the igniter or the adjoining burning oil is mostly used to boil the water instead of heating the oil to its fire point. A two-stage process is required for emulsion burning: 1. Emulsion breaking—boiling off water to produce a floating unemulsified oil layer on the emulsion slick. 2. Eventual burning of the oil layer—performed by chemicals commonly known as “emulsion breakers.” The burning rate decreases significantly with rising water content for stable emulsions. The impact of the water content on the removal efficiency of the oil water emulsions can be outlined as below: • Low water contents up to 12.5% by volume, have no impact on oil removal efficiency (i.e. residual thickness); • Water contents over 12.5% percent have a noticeable drop in burning efficiency, which is more prominent for weathered oils. • Emulsion slicks with water contents of 25% or more have zero burn efficiency, but Some paraffinic crudes form meso-stable emulsions burn well at far higher water content (Fingas & Fieldhouse, 1997) The composition of ISB team and their work responsibilities are summarized in Table 14.1. 14.2.2.8 In situ burning best safety practices The best safety practices in ISB operations is attained by following the prescribed safety protocol and safety rules and regulations. The ISB team members are required to undergo appropriate safety training so that the team members are able to respond immediately for a specific situation, the working personnel can be at risk from fire or flame, proximity to excessive amounts of particulate matter, or other health and safety problems, such as operating under extreme temperatures.

14.3 In situ burningtechniques & current application 14.3.1 Selection of in situ burning equipment and operation This section describes the different forms of major equipment that are used to respond to oil spill for in situ burning viz., containment booms, ignitors, various treating agents, etc. This section also describes the selection of equipment with respect to a particular situation.

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TABLE 14.1 An outline of in situ burning burning operation and personnel responsibilities.

ISB Coordinator (Responsible for the entire burning operation)

Responsibilies of personnel

Controlling burn (Monitoring the entry of personnel, vessel etc, and ensuring their safety)

Boom Commander (Controlling over the booms where it must be placed)

Traffic Control (intimating nearby the local airport, mariners and updating them about the burn)

Communications Unit Head (Coordinating all ISB operations)

Locating vessels (location and movement of vessel must be pre planned and observed for the safer burn)

Aircraft Operation (Igniting the burn via Helicopter)

Initiation of Ignition (Deploying the appropriate ignitor according to the condition of oil spill)

Safety Boat (Monitoring all vessels and be ready with firefighting Extinguisher)

Early and Secondary fire (Avoid to ignite unnecessarily)

Operaon during the insitu burning in the field

and organizaon

Health & Safety Officer (Responsible of all personnel’s safety)

Planning burn (Planning the type of vessel and ignitor deployment, sea condition and verifying operation checklists

Termination of Burn (Extinguishing the fire if it harms the personnel or public health)

14.3.1.1 In situ burning without containment When ISB team ignite an uncontained slick, they must take safeguard that there is no connection between the oil to be burnt and the source of the oil, such as the tanker or oil and gas platform to keep away the fire from the source. When the oil spill occurs from a platform or other fixed location, the part of the slick to be burnt must be kept away from the source and the slick around the source must be separated using the containment boom. In remote locations, shorelines, coastal sandbars or ice may also be used to contain oil for combustion. To avoid fire spread, the shorelines must comprise of cliffs, rocks and gravels, or sandy slopes having a reasonable gap between the burning oil and other combustible objects such as wooden objects, forests, or vegetation cover.

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14.3.1.2 Oil containment methods Booms are used to contain the oil which also helps to maintain or increase the oil slick thickness for the effective combustion. The various types of commercial booms are discussed in this section. 14.3.1.2.1 Conventional booms

Conventional booms cannot be used directly in burning oils because the components of these booms are either get burnt or melted. The deployment of this boom is faster and cheaper compared to fire resistant booms. Conventional booms may be used to restrain oil slick before a fire resistant boom is acquired. However the boom does not stay unchanged for a very long time once the oil starts burning. Once the boom collapses, the slick may expand that deteriorates thickness of oil slick immediately and make them incapable to burn. Some floating materials like logs may be used at times as temporary booms for immediate respond. 14.3.1.2.2 Fire-resistant booms

Fire resistant booms are made of ceramic and stainless steel materials that prevent escaping oil along with the movement of water. They are used to contain large spills in a restricted area to burn the oil in a controlled way eliminating spilled oil spread. The top portion of boom floats and prevents the oil escaping from the top and the bottom portion of boom prevents the oil movement beneath water. A portion of the boom which floats on the surface of the water prevents oil from escaping over the top, and the portion below the surface prevents oil from escaping below the boom. The design of the boom, wind and also wave size determine the effectiveness of the boom containing the oil. Fire Resistant booms can mainly be categorized into four types such as Ceramic booms, stainless steel booms, thermally resistant booms and water cooled booms. The biggest disadvantage of these type of booms is storing the heat for longer periods of time that enables to abrade the portion of equipment. For example, during the burning of Exxon veldez oil spill, it has been observed that flotation legs of the boom with the height of 2 m are completely eroded due to withstand of high temperature for longer periods of time (Smith & Diaz, 2005). In 1994, four fire-resistant booms (the American Marine (3M) Fire Boom, the Applied Fabrics PyroBoom, the Kepner Plastics SeaCurtain FireGard, and the Oil Stop Auto Boom Fire Model) were tested at sea by the Marine Spill Response Corporation (MSRC) (Nordvik & Simmons, 1995). These tests aimed at evaluating the link between the boom strength and buoyancy-to-weight, towing speed and maritime condition. At towing speeds between 0.25 and 1.25 m/s the boom were towed in a U configuration (0.5 and 2.5 knots). It has been observed that Mechanical failure was discovered on three out of the four fire resistant booms. It was stressed that technical stability of the booms, ease of deployment, and recovery must be enhanced for efficient oil containment. The USCG (United States Coast Guard) and USMMS (United States Mineral Management Services) in a test tank, assessed the containment behavior of current fire resistant booms and correlated their performance to previous at sea performance (Bitting, 1997; Nash et al., 2000). The study calculated the tow speeds at which the booms started to lose oil for the initial time (“first loss”) and the speed at which, subsequent loss occurred

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(“gross loss”). The study also calculated the rate of loss of oil at particular tow speeds and the tow speed at which the boom physically collapsed and submerged. The fire resistant booms presently in market are described as below. a. American Fire Boom: Its floating components are composed of rigid ceramic foam that are surrounded by two sheets of knitted mesh of stainless steel, a ceramic textile fabric that resists high temperatures and an outside cover of PVC which also form the skirt. b. Auto Boom Fire Model: It’s an inflatable boom with in-built water-cooling-system. A ceramic blanket with a stainless steel mesh is used to insulate the flotation chamber and polyurethane cloth is used for the skirt. This type of boom can be stored and a reel may be used for its deployment. The water cooling system must be connected on a large, flat area before the boom is placed in the water. c. FESTOP Fire Boom: The boom is made up of stainless steel that can withstand temperatures up to 1260 C. d. The Hydro-Fire Boom: It is inflatable and water cooled 150 m long boom that can be stored on a reel with 30 m sections and deployed from the reel. e. PyroBoom: This is a fence boom, with a freeboard built of a patented refractory component that is highly resistant and a skirt made of urethane coated material. Either side of the fence is connected with hemispheric stainless steel floats. This boom can be deployed from a reel system which is stored in a container else the boom may be stored in a container and deployed from a large flat area. f. SeaCurtain FireGard (Kepner Plastics): The flotation parts of the boom are formed by a heavy stainless steel coil that has been protected by a high-temperature refractory material. A polyurethane-coated polyester or nylon cloth is used to make the skirt. During deployment, the stainless steel coil allows the boom to self -inflate, but recovery requires manual compacting. At present, the boomer is not actively used. 14.3.1.2.3 Backup booms

Backup booms must be set at least 200
300 m behind the fire resistant booms to contain any entrained or spilled oil during the burning. It has been noticed that oil flow out of the fire-resistant boom will in general pool behind the boom due to eddies developed in this region. Usually, this oil remains in this region for some time and may thus can be ignited for the combustion. If this oil leakages from this place, it would become too thin to withstand combustion and in this case, backup boom may be used to collect the leaked oil.

14.3.2 Ignitors A variety of ignition techniques have been used to ignite the oil slick. However the methods of igniting oil on water have not been broadly documented (ASTM F1990
07,

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2007; McKenzie, 1994). An ignition system must have basically two parameters in order to be effective. The first parameter is that it should produce sufficient heat to generate enough oil vapors to ignite the oil and then maintain it burning and the second parameter is that it must be safe to use. Thicker, volatile and less weathered oil can be ignited quickly and easily whereas the heavy oil, unstable emulsions take longer time to ignite to achieve the enough vapors. Propane and butane torches were successfully used in the past to ignite oil spills in the past. They are more successful on dense slicks, though, as the torches likely to blast the oil away from the flame on thin slicks, thereby hindering ignition. 14.3.2.1 Helitorches The most advanced industrial devices used for ignition of oil slicks are helitorch igniters. These ignitors are suspended from helicopter that dispense packets of burning and gelled fuel, resulting a fire with 800 C lasting up to 6 min (Allen, 1986; ASTM F1990
07, 2007). The helitorch fuel is a mixture of a powdered gelling agent along with either jet fuel or diesel/gas or gasoline. In general, Aluminum soap is used as gelling agent. When planning to use a helitorch, the gelling agent and the fuel must be combined in a safe environment away from any ignition source. In the specialized barrels with the raised hatch opening, the fuel is mixed with the gelling agent. The appropriate ratio between the fuel and the gelling agent mainly depends on the fuel type and air temperature. If the flash point of oil slick is low, less volume of gelling agent is needed. In general, unleaded gasoline is commonly used as fuel because it is readily available. For ignition, it is recommended to hook the torch in right angle to the frame so that it helps the pilot to track the ignition cap. 14.3.2.2 Noncommercial ignitors The other ignition techniques are use of rags, sorbent or paper soaked in oil to ignite the oil slick (ASTM F1990
07, 2007), for example, plastic bags containing gelled fuel was used to ignite the oil during Exxon valdez spill. The bag was fired and thrown out of the boat towards the slick. Diesel becomes a better choice when compared with gasoline for soaking materials as it burns slowly. Combustion of heavy oils is best accomplished using a diesel fuel and kerosene, and a tiny wick such as a sorbent or a cardboard (Fingas et al., 2003). These Igniters comprise of gelled fuel, gelled kerosene cubes and solid propellants or mixture of these compounds that can provide fire ranging between 1000 C and 2500 C lasting from 30 sec to 10 min (ASTM F1990
07, 2007). 14.3.2.2.1 The kontax igniter

It is self-igniter unit that was tested and in use since 1970 (ASTM F1990
07, 2007). The device was made of a calcium carbide filled cylinder with a sodium metal bar that passes through the center. When it was dropped into the oil slick, sodium from the bar react with the water to produce heat and hydrogen. Furthermore, acetylene was generated when water and calcium carbide are reacted together. The flames from burning acetylene was maintained long enough to heat the oil and to generate the vapors that were eventually ignited. The main disadvantage of this ignitor is that it may cause blasting, if it is exposed with water molecules.

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14.3.2.2.2 A hand-held igniter

This type of ignitor was used for in situ burning experiments conducted in 1996 in the coast of Great Britain (Guenette & Thornborough, 1997). This igniter consists of a bottle of 1-L “Nalgene” polyethylene packed with gasoline gel. The gel is prepared by combining 1 L of gasoline with 10 grams of gelling agent. This container and a traditional hand-held flare are held in two polystyrene foam rings. The flare is ignited and placed onto the slick and it burns about 60 s until the plastic container is melted and the gelled fuel is burned to ignite the oil slick. This device is simple and easy to deploy in the field.

14.3.3 Treating agents and combustion additives The various type of combustion supporting materials that are used to enhance in situ burning have been listed in the Table 14.2.

14.4 Environmental and health concerns The main environmental and health issue linked to in situ burning is the pollution caused by spilled oil and its combustion. Thus, the most important concern during the oil spill response is ensuring the health and safety of the people, the response crew and the aquatic environment. Human, marine and terrestrial life are exposed to the impacts of ISB operation mainly through inhalation of burnt particulates, ingestion and skin adsorption TABLE 14.2 List of Additives used for ISB operation. Classification S. No of additives

Function of the additive

Examples

Description of the additives

1

Ignition promotors

Used to enhance ignitibility and spreading of flame to unignited oil slick area.

Fresh crude, aviation gasoline, gasoline, kerosene and diesel.

Must have lighter density that would minimize the safety hazard.

2

Combustion promotors

Used to improve the oil removal efficiency during the combustion.

Peat moss

Acts as a wick or the insulator between oil slick and water.

3

Smoke suppressants

Added in oil slick to reduce the smoke.

Lead, magnesium, manganese, copper, iron, nickel, boron, cobalt and barium

Must be nontoxic

4

Sorbents as wicking agents

Used in smaller oil spill where it Polypropylene sorbent must have the access of manual sheets and pads. application of sorbent.

Must be nontoxic

5

Emulsion Breakers

Used to break the oil—water emulsion in situ and remove water molecules.

Highly oil specific and surfactant dependent.

Gamelin EB439, Vytac DM, and Breaxit OEB-9,

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from the spilled oil and burned residue. Particulates emanated from ISB is majorly classified as PM10 (mixture of liquid droplets and solid particles 0
10 μm diameter) and PM2.5 (finer particles of # 2.5 μm). The particulates less than 10 μm diameter can be easily inhaled and reached the lungs causing its damage. The United States Occupational Safety and Health Administration developed a detailed training method for oil spill responders under the Hazardous Waste Operations and Emergency Response Standard in 29CFR 1910.120.

14.4.1 Air quality ISB operation for oil spills causes air emission that include smoke, particulate matters, organic and nonorganic gases produced from combustion, unburned residue at the oil spill site. This section focuses on the volume and the rate of air emission after an ISB operation. The primary concern is the smoke considered as toxins that is produced during ISB operation. The major emission compounds from ISB has been listed in the Table 14.3. TABLE 14.3

List of various compounds emitted to air from ISB combustion.

S. No Name of the compound

Description

1

Particulate matter/soot

Particulate matter emission from oil slick is at least four times higher than burning diesel. Particulates in the form of soot contains 10%
15% of smoke plume. Density of particulate matter is more than 150 mg/m3 at the ground level.

2

Polyaromatic hydrocarbons (PAHs)

It can be seen in the residue post ISB in the form smoke or particulates. It may harm the skin and lungs when its concentration is more than 0.2 mg/m3.

3

Volatile organic compounds (VOCs)

More than 140 different types of VOCs have been recognized from various ISB operation and experiments. Because of its low concentration, it does not pose a major human and environmental threat.

4

Carbon monoxide

Incomplete combustion produces CO which displaces oxygen from the blood affecting hemoglobin molecules in the red cell and decreases the oxygen level of cells immediately. The average CO level in the smoke plume has been found to be 1
5 ppm in some test burns for over a period of 15
30 mins and 150 m downwind from the burns,

5

Sulfur dioxide

It is toxic and irritate eyes and affect the respiratory system when its concentration exceeds 5 ppm in the atmosphere. In few test burns, the average level sulfur dioxide has been found less than 2 ppm in the plume (100
200 m downwind). It has been concluded that there is not much threat for population from SO2 caused by ISB operations because of low concentration.

6

Nitrogen oxide

It also affects the lungs and eyes similar to SO2. Even a smaller dose of it can cause pulmonary edema as it is less soluble than SO2 and can reach the deep part of the lungs.

7

Carbon Dioxide

Around 500 ppm concentration of CO2 emission has been noted nearby oil burn. However this range does not impact much to any species/human kind

8

Dioxins and Dibenzofurans

They are highly toxic and they are generated from the crude oil that possess chlorine and not found in other type of crude oil like Diesel etc.

9

Carbonyls

They are partially oxidized materials and are produced from oil burns. They are found in very low concentrations and causes no threat even near the oil burn. Its concentration gets higher in case of fuel containing alcohol.

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14.4.2 Water quality The impact of ISB operation on marine environment is very minimal and causes almost zero threat. Most of the heat produced during a burn moves upward and outward resulting a very negligible absorption of heat by the underlying water below the oil burn. Most of the controlled burns remove maximum amount of oil and leave only low quantity of oil as tar like floating residue that can be easily collected and stored in a temporary storage. However threats to the aquatic lives are extremely low for residues either thermally soluble on water or in case they sink beneath water surface. Research has demonstrated that in situ oil burning would not release more oil components or by-products of combustion into the water column than are present if the oil is left without burning on the water surface (Fingas & Li). Test results for the water taken from burned-out oil field show that it does not contain any organic compounds or may contain very ignorable volume of hydrocarbon which is not harmful to any sea plants and species (Daykin & Kennedy PA, 1995; Fingas & Li, Fingas et al., 2005), no PAH or toxicity have been detected in the samples. The oil burned residue consists mostly of volatile oil (Fingas et al., 1997; Fingas et al., 2000) since the burning phase removes most of the nonvolatile materials. The residues may possess a significant amount of metals (typically 10 to 40 ppm nickel, vanadium and chromium) (ASTM F1788
08, 2008). Several researches have proved that burned oil residue is less toxic than other weathered oil or fresh oils of the same kind which is more harmful to marine life. Sinking of burnt residue is the major toxic pollutant to the species. But fortunately it happened in very few burns 2 in 200 burns only (Compilation, 1997) The residues can be easily collected by skimmers and sorbents. Studies show that there is no noticeable rise in water temperature even in shallow water because the oil slick layer itself insulates the water zone. The density of burnt residue is always higher than density of oil in its spilled condition. To understand the behavior of burnt residue, the burnt residue sample of Haven oil spill and fire 1991 have been investigated and the results showed that the sample resembles the characteristics of heavy oil and the burnt residues were mainly composed of highly concentrated asphaltenes, resins and metals (Moller, 1992). Sometimes residue may contain pyrogenic and Poly aromatic hydrocarbon compounds. ISB technique has been in use to remove the oil from some major oil spill incidents for number of years. The oil removal efficiency of ISB has been described in Table 14.4.

14.5 Summary This chapter has deliberated the principles of ISB, its equipment used during combustion and also highlighted the environmental impacts on air and water quality caused by ISB operations. Though the public believes that ISB technique is not always practically possible but the oil removal efficiency by ISB can be more effective and efficient if the spilled site condition is well monitored and preplanned prior to conduct of the operation. It should be kept in mind that an ISB operation can only be successful if it can assure the safe working condition for the response personnel. More research studies need to be carried out in developing the strategy to increase the performance and deployment of

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References

TABLE 14.4

Major oil spills and in situ burning responses.

S. No Name of the oil spill incident

Date of incident

Type of oil

Spilled volume

Oil removal volume by in situ burning

1

Trans-Alaska Pipeline, Fairbanks, Alaska

15 February 1978

Prudhoe Bay crude oil (API gravity 5 29 degrees)

16,000 bbls

500 bbls

2

Exxon Valdez Test Burn

24 March 1989

North Slope crude oil (API 5 29 degrees)

257,000 bbls

350
700 bbls

3

Chiltipin Creek, Texas

7 January 1992

South Texas Light crude oil

2950 bbls

1150 bbl

4

Brunswick Naval Air Station, Brunswick, Maine

26 March 1993

JP-5 aviation fuel

1512 bbls

500 bbls

5

Newfoundland Offshore Burn Experiment, Newfoundland, Canada

12 August 1993

Crude oil (API 5 36 degrees)

970 bbls

970 bbls

6

Refugio County, Texas

12 May 1997

Light and giddings steam crude

500
1000 bbls

Not exactly known (90% volume burned)

7

‘Mosquito Bay, Louisiana

5 April 2001

Condensate (a very light crude oil)

.1000 bbl .500 bbls

river—fire resistant booms and improving the safety of hand held ignitors such as delaying to spark time that will allow the response personnel to move comfortably after ignition. ISB is one of the best suitable technique in artic and polar regions and able to achieve 99% oil removal efficiency in the shortest time in the offshore. USCG has also appreciated the efforts of ISB that the environmental threat is almost eliminated after conducting the ISB rather than leaving oil over the water surface.

References Allen A.A. (1986). Alaska clean seas survey and analysis of air-deployable igniters. In Arctic and Marine Oilspill Program (AMOP) technical seminar, 9th proceedings. Ontario, Canada, vol. 2, no. NIST SP, pp. 353
373. Allen, A. A. (1990). Contained controlled burning of spilled oil during the Exxon Valdez oil spill. Spill Technology Newsletter, 15(2), 1
5. ASTM F1788-08. (1788). Standard guide for in-situ burning of oil spills on water: environmental and operational considerations. West Conshohocken, PA: ASTM International. ASTM F1990-07. (1990). ASTM standard guide for in-situ burning of oil spills ignition devices (pp. 1990
1997). Conshohocken, PA: ASTM. Barnea, N. (1995). Health and safety aspects of in-situ burning of oil. Seattle, WA: National Oceanic and Atmospheric Administration, p. 9. Bitting, K. R. (1997). Oil containment tests of fire booms. AMOP, p. 735. Buist, I., Dickins, D., Majors, L., Linderman, K., Mullin, J., & Owens, C. (2003). Tests to determine the limits to in situ burning of thin oil slicks in brash and frazil ice. Proc. Seventh Annual Arctic Marine Oilspill Program Technical Seminar, Environmental Protection Service, Environment Canada, 26(2), 629
648. Buist, L., McCourt, J., Potter, S., Ross, S., & Trudel, K. (1999). In situ burning. Pure and Applied Chemistry. Chimie Pure et Appliquee, 71(1), 43
65. Available from https://doi.org/10.1351/pac199971010043. Compilation of physical and emissions data (1997). Newfoundland Offshore Burn Experiment (NOBE) report. Environment Canada.

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Daykin, M.M., Kennedy, P.A., A. Tang (1995). Aquatic toxicity from in-situ oil burning Newfoundland Offshore Burn Experiment (NOBE). Ottawa. Environment Report. Ekperusi, A. O., Onyena, A. P., Akpudo, M. Y., Peter, C. C., Akpoduado, C. O., & Ekperusi, O. H. (2019). In-situ burning as an oil spill control measure and its effect on the environment. In Society of petroleum engineers—SPE Nigeria annual international conference and exhibition 2019, NAIC 2019, doi: 10.2118/198777-MS. Fingas, M., & Li, K. The Newfoundland offshore burn experiment-Nobe Working on new dispersion model view project oil fates view project. doi: 10.7901/2169
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C H A P T E R

15 Use of chemical dispersants for management of oil pollution Sunil Kumar Tiwari1,2, Shashi Upadhyay3, Vishal Kumar Singh1, Ankit Dasgotra1,2, Akula Umamaheswararao1, Harsh Sharma1 and Jitendra Kumar Pandey4 1

Department of Mechanical Energy, University of Petroleum and Energy Studies, Energy Acres, Dehradun, India 2Department of Research and Development, School of Engineering, University of Petroleum and Energy Studies, Dehradun, India 3Department of Microbiology, University of Petroleum and Energy Studies, Energy Acres, Dehradun, India 4School of Basic and Applied Science, Adamas University, Kolkata, India O U T L I N E 15.1 Introduction

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15.2 Hazardous effect of oil spill and its emission 265 15.2.1 Need for controlling oil pollution 266 15.2.2 Oil spill remediation 266 15.3 Use of chemical dispersant

267

15.4 Principle and mechanism of chemical dispersants 269 15.4.1 Impact of chemical dispersants 270 15.4.2 Toxicity of chemical dispersants 273

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00004-5

15.5 Effectiveness and adaptability of chemical dispersants

273

15.6 National and international regulations for using chemical dispersants 276 15.7 Applications of different chemical dispersants 277 15.8 Conclusions

278

References

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15.1 Introduction Oil pollution in general terms can be explained as a release of oil or petroleum hydrocarbons in an open environment which causes disparities in an ecosystem. Mostly oil pollution is seen in aquatic ecosystems in the form of oil spills. Major sources of oil pollution/oil spills are accidents in vessels, leakage from ships, accidents near oil exploration areas, etc. As petroleum hydrocarbon is one of the most important sources of revenue, the majority of petroleum producers transport oil/petroleum via sea, oceans, and other water bodies. While TABLE 15.1 Major oil spills from 1967 to 2010 (Aguilera, Me´ndez, Pa´saroa, & Laffona, 2010; Jackson et al., 1989; Laffon, Pa´saro, & Valdiglesias, 2016; Osuagwu & Olaifa, 2018; Saadoun, 2015). S. no.

Year

Amount

Location

1.

1967

119,000 tons

Cornwall, United Kingdom

2.

1972

115,000 tons

Gulf of Oman, Oman

3.

1975

88,000 tons

Portugal

4.

1976

100,000

La Coruna, Spain

5.

1976
96

2 million barrels

Niger Delta, Africa

6.

1978

231,000 tons

Brittany Bay, France

7.

1979

287,000 tons

Off Tobago, West Indies

8.

1979

94,000 tons

Bosphorus, Turkey

9.

1980

100,000 tons

Navarino, Greece

10.

1983

252,000 tons

Off Saldanha Bay, South Africa

11.

1985

70,000 tons

Off Kharg Island, Iran

12.

1986

8 million liters

Caribbean Coast, Panama, America

13.

1988

132,000

Nova Scotia, Canada

14.

1989

40 tons

Alaska, United States

15.

1989

70,000 tons

Atlantic Coast, Morocco

16.

1991

6 million barrels

Gulf of Mexico, Mexico

17.

1991

260,000 tons

Angola

18.

1991

144,000 tons

Genoa, Italy

19.

1992

74,000 tons

La Coruna, Spain

20.

1992

67,000 tons

Off Maputo, Mozambique

21.

1993

85,000 tons

Shetland Island, United Kingdom

22.

1996

72,000 tons

Milfold Haven, United Kingdom

23.

1999

20,000 tons

Brittany, France

24.

2002

77,000 tons

Spain

25.

2003

37,000 tons

Karachi, Pakistan

26.

2007

2.7 million gallons

South Korea

27.

2010

4 million barrels

Gulf of Mexico, Mexico

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15.2 Hazardous effect of oil spill and its emission

265

transportation, oil spill (if occurs due to shipwreck, etc.) in water bodies not only harm aquatic life, it also has an adverse effect on plants and humans (Tuan Hoang, Viet, Pham, & Nam Nguyen, 2018). It damages lungs and other internal organs of aquatic animals; it also causes air pollution once it gets evaporated; it damages plants growth and their life if it comes into their contact. Some of the most well-known oil spills are shown in Table 15.1. Looking into the hazardous effect of oil spill on living species and nonliving things there is a great need of oil spill removal and its management. The most valuable and risk-free approach to fight against the oil spill is to remove it via physical and mechanical methods which includes removal of oil spill water zone by pumping or to stop its further physical containment. Due to the limited availability of advanced machinery and equipment, mechanical methods covers a short part of affected spill area which results in retrieval of about 20% of leaked oil (Lessard & DeMarco, 2000). Moreover, if this method is not acceptable due to sea/ ocean/water bodies conditions, then there comes the need of oil spill treatment. Since 1960, dispersants have been used to control and treat oil spill in water bodies. Dispersants are a kind of detergents which are spread on the oil spilled surface to separate and/or disperse oil from water. The major concern with use of dispersants in oil spill is their toxic nature and nonrecovery of spilled oil. But according to research council of United States, the major concern of toxicity for aquatic animals was with spill oil droplets not with dispersants used (Lessard & DeMarco, 2000). Several researchers have worked on using dispersants for oil spill remediation, and they have also gotten better results in terms of oil water separation to prevent water pollution. This chapter reflects the use of chemical dispersant for oil spill treatment and management.

15.2 Hazardous effect of oil spill and its emission It is well known that most of the crude oil contains hydrocarbons whose spill in waterbodies can lead to damage both aquatic and terrestrial network. Petroleum oils containing low hydrocarbons like aromatics and alkanes evaporates in the atmosphere quickly due to their high vapor pressure (Afshar-Mohajer, Fox, & Koehler, 2019). Concentration of these organic compounds in oil spill zone decreases, as it is time dependent but on the other hand it releases aromatics like xylene, toluene, benzene, ethylbenzene, etc., which are very harmful in terms of health impacts. As per air quality guidelines WHO 2000, these exposed fumes and chemicals cause headache, eye irritation, and can also lead to lung cancer and mental disturbances to humans if inhaled or due to dermal interaction (Solomon & Janssen, 2010). Once the oil is spilled, its impact on marine and human life depends upon the fate and nature of oil spill dispersion. If oil is not dispersed in water, it remains suspended on the surface of water and flows towards the coastal areas due to the impact of water current resulting in harming coastal organisms including mammals and birds. In the case that the oil gets dispersed in water, its toxic nature can harm aquatic animals if they swallow it (Saadoun, 2015). The major effect of oil spilled in the marine environment is narcosis which is caused due to oil reaching to the cells of nervous tissue and cell membrane of aquatic animals. Moreover, cleanup operation in regard of oil spill is also responsible for affecting marine life (Saadoun, 2015). Some of the reports on impact of oil spill on aquatic life and human health have been shown in Table 15.2.

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TABLE 15.2 Effect of oil spill on aquatic and human life. Source

Effect on aquatic and human life

Evaporated volatile organic compounds from oil

Throat irritation, respiratory irrigation, depression in humans, mammals and birds

Benzene

Causes Leukemia in humans

Toluene

Malformation of an embryo in humans

Naphthalene

Causes cancer to humans, nasal tumors and cancer to animals too

Hydrogen sulfide

Acute and chronic effect on central nervous system

Heavy metals

Acute and chronic effect on central nervous system

Physical contact with spilled oil

Defatting and skin infections, also causes edema, erythema, etc., to birds and furred mammals.

15.2.1 Need for controlling oil pollution Petroleum oil contains a chain of hydrocarbons which is harmful for aquatic animals if spilled in marine environment. As it is toxic in nature it can cause death to aquatic animals and indirectly affect human health as aquatic animals are a part of the food chain. Its smoke and fumes, when evaporated; cause air pollution too. Their contamination with other water bodies puts aquatic life and farmlands in danger. Looking into the hazardous effect of oil spill on human health, aquatic animals, and the ecosystem, many researchers have worked on preventing and controlling oil spills in the marine ecosystem (Ji, Xu, & Wang, 2016; Teal & Howarth, 1984; Tuan Hoang et al., 2018). They have used different physical and mechanical approaches to remove spilled oil from water. But these methods are not too efficient to be used so that effectiveness can be seen in short period of time. Some of the researchers have used different biological and chemical dispersants to treat oil spill. It has been reported that use of chemical dispersants too has adverse effect on the living organisms. As chemical dispersants are toxic in nature, they indirectly affect human health. So looking into the oil spill treatment and management it has been suggested to use cellulose nanocrystals instead of chemical dispersants (Parajuli et al., 2020).

15.2.2 Oil spill remediation Due to the unwanted contamination of oil spill with ecosystem, it is very important to remediate (Prendergast & Gschwend, 2014). Selection of methods to treat oil spill to promote remediation depends upon nature of oil spill, oil spill location, government regulations associated with the location, type of oil and behavior of water spilled zone. The most common remediation approaches studies by researchers are mechanical methods, use of chemical dispersants, and in situ burning of oil. Studies have revealed that physical and mechanical methods are the best adopted approach to control and prevent oil spill but it lacks in efficiency and is time taking too. Chemical dispersants have good efficiency but are restricted in local areas by government and also contribute to the chemical contamination of water for long time and thus harms aquatic lives (Sakthivel, Reid, Goldstein, Hench, & Seal, 2013). Carmodi et al., have confirmed that use of organoclays is able to

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267

15.3 Use of chemical dispersant

treat oil spill because of its hydrophobic nature, retention capacities and hydrocarbon sorption property (Carmody, Frost, Xi, & Kokot, 2007). Chhatre et al., have explained that use of bacterial consortium has resulted in better oil spill treatment as it shows effective degradation of crude oil.

15.3 Use of chemical dispersant The main aim of using chemical dispersants is to remove the spilled oil from the surface of sea water. When the chemical dispersants come in contact with spilled oil, the surfactants present in the chemical dispersant significantly decreases the force of attraction between the oil and water molecules (Wilkinson et al., 2017). This reduction in interfacial force is achieved by positioning the interaction of hydrophobic shells with oil and hydrophilic shells with water, which automatically forms a stable microemulsion (Marzuki, Wahab, & Hamid, 2019). This enhances breaking of oil into tiny droplets, which increases the biodegradation of oil in sea-water (Tremblay et al., 2017). Some other studies also stated the effects on using chemical dispersants for oil spill treatment up the marine ecosystem (Kleindienst, Paul, & Joye, 2015). This formation of microemulsion mainly depends on the structure and type of surfactant used as shown in Fig. 15.1. According to Doshi, Sillanpa¨a¨, and Kalliola (2018) there are four types of microemulsion as listed Table 15.3. Chemical dispersants mainly consist of surfactants, solvents, and stabilizer. Surfactants generally decreases the formation of oil in water emulation, to spread and Classification of surfactants used for oil spill treatment

Bioremediation of spill oil

Surfactant Dispersants

Break the spill oil into smaller droplets

Chemical herders Thicken or contract the spiil oil that can be collected

Bioemulsifiers Enanhance the biodegrdation of oil by microbes

Biosurfactants Enanhances the solubility

FIGURE 15.1 Classification of surfactants used for oil spill treatment (Doshi et al., 2018). TABLE 15.3

Different types of microemulsion with their principle (Doshi et al., 2018).

Types

Principle

Type I

Oil in water microemulsion were formed in which surfactant is soluble in water but insoluble in oil phase.

Type II

Water in oil microemulsion were formed in which surfactant is soluble in oil but insoluble in water phase.

Type III

Three phase system in which middle of oil and water phases a surfactant phase will be formed that will result in oil in water or water in oil microemulsion.

Type IV

A micellar solution with single phase which formed upon addition of sufficient amount of surfactant with alcohol.

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15. Use of chemical dispersants for management of oil pollution

improves the biodegradation and consists of dioctyl-sodium-sulfosuccinate (DOSS), Tween80, Tween85, dioctyl-sodium-sulfosuccinate (DOSS) hydrolysis product α-/βethylhexyl sulfosuccinate and Span8 (Place et al., 2016). Solvent’s function is to decreases the viscosity of surfactant, dilute the compound of chemical dispersants and optimizes the concentration of chemical dispersants and solvents consists of petroleum distillates, petroleum hydrocarbons, kerosene and fuel oil. Stabilizers are used for controlling corrosion, exact color and exact pH value (Dave & Ghaly, 2011). The size of oil droplet has an important impact for reduction of interfacial force between oil and water. A sample of Macondo oil premixed with COREXIT 9500 dispersant and coastal Norwegian seawater shows that 10 μm sample is faster biodegradable than 30 μm dispersion (Brakstad, Nordtug, & Throne-Holst, 2015). Fig. 15.2, shows different types of chemical dispersants. Usually, COREXIT 9500 An and COREXIT 9500 were used as dispersants in Deepwater horizon oil spill and they contain dioctyl-sodium-sulfosuccinate (DOSS) as a main surfactant component (Gray et al., 2014). COREXIT 9500 was the improved version of COREXIT 9527 as the COREXIT 9527 is too toxic (Mitchell & Holdway, 2000). COREXIT holds different components including polyethoxylated sorbitan, isosorbide, fatty-acid core groups, and their monoesters, diesters, triesters, and tetraesters (Chang, 2019). An explosion on April 20, 2010 (28 5501200 N, 88 2301400 W) resulted in the leakage of crude oil into the Gulf of Mexico at an estimation of 11.2 million liters of oil. Which leads to the large oil spill in the coastal waters of United States of America. A wide range of chemical dispersants were sprayed on surface and subsurface waters, approximately 3.7 million liters of chemical dispersants were used in the response of oil spill. Among those COREXIT EC9500A is the mostly commonly used chemical dispersant (Noirungsee et al., 2020). By using etherification of octadecylamine along with tetraethylene glycol and quaternization with p-toluene sulfonic-acid an amphiphilic ionic liquid was synthesized and this synthesized amphiphilic ionic liquid showed an oil spill dispersant efficiency around 80% at a ratio of surfactant/oil- 1:25 (Atta, Al-Lohedan, Abdullah, & ElSaeed, 2016). Slickgone-NS is one of the most commonly used and approved chemical dispersant across European countries for oil spill response. Slickgone-NS has a dispersant to oil ratio of 1:25 (Brakstad, Ribicic, Winkler, & Netzer, 2018). Generally, the chemical dispersants having LC-50 more FIGURE 15.2 Different types of chemical dispersants (Nnadozie et al., 2017).

Chemical dispersants

Conventional hydrocarbon base

Generally used in undiluted form at a ratio of 1 part chemical dispersant to 2-3 part of oil

Water dilutable concentrate

Dilution with seawater in the ratio of 1:10 and then used at a ratio of 1 part chemical dispersant to 2-3 part of oil

Concentrate

Chemical dispersants containing higher concentraction of surfactants

Combination

These are new type of chemical dispersants synthasized both for water dilutable and concentrate

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15.4 Principle and mechanism of chemical dispersants

269

TABLE 15.4 Different chemical dispersants with their optimized ratio of dispersant/oil (Dave & Ghaly, 2011). Chemical dispersant

Optimized ratio of dispersant and oil

COREXIT-7664

1:3

COREXIT-9500

1:10
1:50

COREXIT-9527

1:20
1:30

COREXIT-9550

1:20

ARDROX-6120

1:25

TERGO-R40

1:20

Shell VDC

1:20
1:30

Neos-AB3000

1:20

Slickgone-NS

1:25

than 1000 mg/L are assumed as very less toxic. Sea-Green-805 (LC-50 5 8900 mg/L), Hytron-3 (LC-50 5 1500 mg/L) and Neos-AB3000 (LC-50. 12500 mg/L) are the commonly used chemical dispersants for oil spill response in the diamond grace, Tokyo Bay, 1997 these chemical dispersants have LC-50 more than 1000 mg/L (Holley, Lee, Valsaraj, & Bharti, 2021). Some of the chemical dispersants commonly used now a day are listed in Table 15.4. Due to the development in science and technology the chemical dispersants, which are available are more effective and less toxic in nature. The most widely used and accepted by many environmental organizations chemical dispersants are COREXIT-9500, COREXIT-9500A, COREXIT-9580, ARDROX-6120, Slickgone-NS, Slickgone EW, Slickgone LTSW, Neos-AB3000, SPC-1000, Hytron-3, Finasol-OSR-52, Shell VDC, Enersperse 700, Nokomis 3-AA, Nokomis 3-F4, TERGO-R40, Sea-Green-805 (Brown, Fieldhouse, Lumley, Lambert, & Hollebone, 2011).

15.4 Principle and mechanism of chemical dispersants Oil slicks are broken up into fine droplets that settle naturally in the sea using chemical dispersants, which are liquid mixes of surfactants and solvents. Surfactants, which are surface-active agents with molecules consisting of opposing polarity and solubility groups; that is, surfactants typically have both an oil-soluble hydrocarbon chain and a watersoluble group, are used in dispersants. Surfactants are also used extensively in the cosmetics and food industries. The surfactant molecules in oil spill dispersants achieve their lowest energy state by placing themselves at oil
water interfaces, lowering the oil
water interfacial stress and significantly lowering the energy needed to produce oil droplets in water due to their dual existence. Furthermore, dispersant-generated droplets are usually much smaller than those produced by the sea’s natural energy. Synthetic surfactants may be anionic, cationic, nonionic, or amphoteric; however, crude oil dispersants are only used

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with anionic or nonionic surfactants. Sorbitan esters of fatty acids, polyalkoxylated sorbitan esters of fatty acids, polyalkoxylated fatty alcohols, polyethylene glycol esters of oleic acid, and tall oil esters are among the nonionic forms. Salts of dialkyl sulfosuccinates and alkyl benzene sulfonic acid are examples of anionic surfactants. Sorbitan monolaurate, ethoxylated sorbitan trioleate, ethylene/propylene oxide condensates, ethoxylated tridecylphosphate, sodium dioctyl sulfosuccinate, sodium lauryl sulfate, and isopropylamine dodecyl benzene sulfonate are some examples of surfactants used. Other chemical agents, such as solvents, are often added to surfactant mixtures to improve the surfactant’s dispersing efficiency (Application, Data, & Group, 1995; Cowell, 1977). Moreover, chemical surfactants are amphiphilic compounds that accumulate at the surface of immiscible fluids to minimize surface and interfacial tensions and improve the solubility and mobility of hydrophobic or insoluble organic compounds. Chemical surfactants can make petroleum components more pseudo soluble in water (Chapman, Purnell, Law, & Kirby, 2007). The detailed mechanism for the functioning of chemical dispersants is shown in Fig. 15.3. On the oil slick, dispersant is sprayed as fine droplets. The dispersant is best used neat (undiluted) for maximum effectiveness, but it can also be used in aqueous carrier systems like those used on boats. The solvent’s action and the droplet spray’s momentum help the dispersant droplets penetrate and blend into the slick. The surfactant molecules scatter around the oil
water interface as the dispersant enters the lower part of the oil slick, lowering the interfacial stress. Small droplets of oil break free and scatter into the upper layers of the water column. Additional surfactant in the oil process replenishes the sticky oil
water interface as surfactant is carried away with the oil droplets. As a result, as droplets break away and more surfactant enters the interface, the oil slick steadily depletes. The surfactant layer stabilizes the scattered oil droplets, preventing coalescence and resurfacing. For application efficiency and slick coverage, neat dispersant drops in the 300
800 μm range are usually considered to be optimal. Winds can blow finer droplets off-target, and larger droplets can smash through the oil slick too easily, causing them to mix inefficiently. More oleophilic dispersant formulations can more readily coalesce and blend with the oil slick, resulting in a higher overall application performance. Water-based carrier systems are less efficient because of their lower affinity for oil slicks and consequent loss to sea water, and are best used on recently spilled and low viscosity oils (Kleindienst et al., 2015; The International Tanker Owners Pollution Federation Limited I, 2011).

15.4.1 Impact of chemical dispersants The impact of chemical dispersants on microbial community, marine wildlife, salinity and their composition and activity have been studied in brief. Mulkins-Phillips selected four chemical dispersants (Corexit 8666, Gamlen Sea Clean, G. H. Woods DegreaserFormula 11470, and Sugee 2), and were tested individually and in combination with Arabian Crude Oil (1:1) for their effects on the growth of bacteria native to local marine waters, bacterial population composition, and crude oil biodegradation (Mulkins-Phillips & Stewart, 1974). It has been found that the dispersants used alone supported good microorganism development, but the dispersant-oil combinations caused qualitative population shifts. Depending on the dispersant used, the degree of degradation of the crude oils

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15.4 Principle and mechanism of chemical dispersants

271

FIGURE 15.3 Detailed mechanism of chemical dispersants (Kleindienst et al., 2015; The International Tanker Owners Pollution Federation Limited I, 2011).

272

15. Use of chemical dispersants for management of oil pollution

n-alkane fraction differed. Only Sugee 2, which had the lowest emulsifying potential, supported n-alkane degradation in these tests as compared to the values obtained by using crude oil alone. Rahsepar et al. reported that the use of Corexit on crude oil resulted in a higher solubility of the oil’s aromatic compounds in sea water. This resulted in higher concentrations of these aromatic compounds, which inhibited oil biodegradation, especially when there were no aromatic compounds degrading culture (Rahsepar, Smit, Murk, Rijnaarts, & Langenhoff, 2016). Jawasim presented that the bacterial population structure in salt marsh sediments was substantially altered in response to Corexit 9500A plus crude oil treatment, and it differed from that of Corexit 9500An or crude oil treatment alone. The addition of Corexit 9500A to crude oil had several effects on the bacterial population and increased biodegradation rates by increasing the diversity and richness of hydrocarbondegrading species (Al-jawasim, 2020). The effects of three dispersants, Pars 1, Pars 2, and Gamlen OD4000, on oil removal in two Persian Gulf provinces water were compared. A total of 16 stations were chosen. The growth rate of isolated bacteria and fungi was determined using the Well process. It has been found that the growth of microorganisms on Pars 1 or Pars 2 dispersants, or their mixtures with oil, had the highest growth rate. However, the culture containing Pars 1 microorganisms had higher BOD and COD than the other two dispersants (9200 and 16800 vs 500 and 960, respectively). The highest BODs and CODs were found in mixtures of oil and Pars 2 dispersants, as well as oil and Pars 1 dispersants (Zolfaghari-Baghbaderani et al., 2012). The toxicity, effects, and efficacy of dispersants were studied before they were applied to spilled oil in nearshore environments before the oil drifted into marshes. The result shows that the marsh plant Sagittaria lancifolia was 20
80 times more resistant to the recently marketed dispersant JD-2000 than the normal test species Menidia beryllina and Mysidopsis bahia, respectively. A small number of studies on the impact of dispersants on plants have been performed, ranging from salt marshes to freshwater marshes. According to some reports, dispersants like BP1100WD, Corexit 9527, and BP Enersperse 1037 were ineffective at cleaning oiled salt marshes and had a greater negative impact on salt marsh plants like Spartina anglica, Salicornia spp., Spairtina alterniflora, and Aster spp. than oils without dispersants (Lin & Mendelssohn, 2005). Liu built a Bayesian network in the German Bight, to determine and visualize the possible benefits of using chemical dispersants to combat oil spills (Liu & Callies, 2019). The BN focuses on the physical effect of dispersion, which alters drift paths by shielding oil from additional wind drag. The BN offers a brief description of the major interactions between environmental factors such as winds, tides, and residual currents, as well as the effects of using chemical dispersants. Moles et al. found that dispersant efficiency is influenced by weathering condition, temperature, and salinity, which are all significant but not always predictable factors. Temperature and salinity affected the ability of surfactantbased dispersants to increase petroleum dispersion in the water column (Moles, Holland, & Short, 2002). Chandrasekar et al. investigated the effects of salinity on dispersion effectiveness in conjunction with three environmental factors: temperature, oil weathering, and mixing energy and found that for almost all oil-dispersant combinations, salinity played an important role in deciding the impact of temperature and mixing energy on dispersant effectiveness (Chandrasekar, Sorial, & Weaver, 2006). Later on, researchers also developed some efficient and environmentally sustainable dispersant for oil spill cleanup that can maintain excellent emulsifying capability under varying conditions. The interaction

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between lecithin and Tween 80 is critical for improving the dispersant’s emulsifying capability. Both a modeling experiment and a molecular-level analysis were used to investigate the mechanism of this dispersant on the oil/water interface (Jin et al., 2019). Without a question, the best method for reacting to an oil spill is to prevent it from occurring in the first place. It is much better to prevent a polluting incident/accident than to contend with the resulting negative effects (Ventikos, Vergetis, Psaraftis, & Triantafyllou, 2004).

15.4.2 Toxicity of chemical dispersants Chemical dispersants are made up of a combination of different surfactants and solvents. The majority of dispersants are proprietary, and the exact composition is rarely disclosed. Following the 2010 Deepwater Horizon oil spill in the Gulf of Mexico, chemical dispersants used for cleanup and containment of crude oil toxicity became a major concern. The possible toxicity of chemical dispersants to humans and marine animals has been called into question as a result of this crisis, as it is unknown if their use is reasonably healthy (Wise & Wise, 2011). In 1997, strong C-oil spilled from the tanker “Nakhodka” severely contaminated the long coastal line facing Japan-Sea. The impact on the early life stages of Japanese flounder and round nose flounder were studied in the laboratory. Exposure to oil suspended in seawater at unusually low concentrations of oil caused larvae to deform and expand insufficiently. The dispersant was not particularly toxic in the absence of oil, but it became extremely toxic in the presence of oil (OP). Since benthic species that are not harmed by oil may be exposed to the harmful effects of dispersants, the possible ecotoxicological effects of this transition is examined (Epstein, Bak, & Rinkevich, 2000). When dealing with the destructive agents of oil and oil dispersants, the fragile coral reefs, and especially their building blocks, the scleractinan corals, require extra caution. The toxicity values of different chemical dispersants on acute life are shown in Table 15.5. Finally, oil detergents and dispersed oil are especially harmful to corals. As a result, decisionmakers should carefully consider these findings when considering the use of oil dispersants as a method for reducing oil emissions near coral reefs. The findings of this and previous studies suggest that any oil dispersant should be avoided in coral reefs and their environments. Chemical dispersants can only be used in extreme cases, such as when oil slicks have reached the shore and are threatening to suffocate the reef flats (Shafir, Van Rijn, & Rinkevich, 2007).

15.5 Effectiveness and adaptability of chemical dispersants Chemical dispersants are mainly used to enhance the breaking of oil into tiny droplets, which increases the biodegradation of oil in sea-water (Nnadozie et al., 2017). There are many novel and conventional chemical dispersants used up to now based on the requirements. Due to the development of science and technology new dispersants are being synthesized to fulfill the requirements and to minimize the impact on marine environment. A chemical dispersant will be only given permission to use when it gets approval from the Swirling Flask Test (SFT), complete details of the test is given in Environmental Protection

C. Thermo-chemical processes

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15. Use of chemical dispersants for management of oil pollution

TABLE 15.5 Toxicity level of chemical dispersants on acute life (Brown et al., 2011; Koyama & Kakuno, 2004). S. no

Dispersant name

1.

BP 1002

Exposed for 24 h while testing on fry of sole and plaice organism; attains the value of LC50 , 100 mg/L

2.

Slipclean

Exposed for 24 h while testing on fry of sole and plaice organism; attains the value of LC50 , 100 mg/L

3.

Berol TL 198

Exposed for 96 h while testing on cod organism; attains the value of LC50 5 850 mg/L

4.

BP 1100 X

Exposed for 96 h while testing on cod organism; attains the value of LC50 . 688 mg/L

5.

BP 1100 X

Exposed for 24 and 96 h while testing on fingerling mullet organism; attains the value of LC50 5 153 and 151 μL/L, respectively.

6.

Corexit 7664

Exposed for 96 h while testing on cod organism; attains the value of LC50 5 130 mg/L

7.

Corexit 8666

Exposed for 96 h while testing on cod organism; attains the value of LC50 . 940 mg/L

8.

Polycleans TS Exposed for 96 h while testing on cod organism; attains the value of LC50 . 984 mg/L 7

9.

Conco-K

Exposed for 24 and 96 h while testing on fingerling mullet organism; attains the value of LC50 5 5.4 and 4.6 μL/L, respectively.

10.

Foremost

Exposed for 24 and 96 h while testing on fingerling mullet organism; attains the value of LC50 5 54.3 and 52 μL/L, respectively.

11.

Corexit 7664

Exposed for 96 h while testing on grass shrimp organism; attains the value of LC50 . 100 mg/L

12.

Hytron #3A

Exposed for 24, 48 and 96 h juvenile red sea bream organism; attains the value of LC50 5 1500, ,870 and ,870 (mg/L), respectively.

13.

Sea green

Exposed for 24, 48 and 96 h juvenile red sea bream organism; attains the value of LC50 5 8900, 7650 and 5150 mg/L respectively.

14.

Corexit 9500

Exposed for 96 h while testing on Oncorhynchus mykiss organism; attains the value of LC50 5 354 mg/L

15.

Corexit 9500

Exposed for 96 h while testing on Photobacterium phosphoreum organism; attains the value of LC50 5 0.065%

16.

Corexit 9527

Exposed for 96 h while testing on grass shrimp organism; attains the value of LC50 . 1000 mg/L

17.

Corexit 9527

Exposed for 96 h while testing on Daphnia magna organism; attains the average value of LC50 5 37 mg/L

18.

Corexit 9527

Tested on Gasterosteus aculeatus organism and exposed for 96 h, attains the average value of LC50 5 77 mg/L

19.

Corexit 9527

Exposed for 96 h while testing on Oncorhynchus mykiss organism; attains the value of LC50 5 108 mg/L

20.

Finasol OSR52

Exposed for 96 h while testing on Salmo gairdeni organism; attains the value of LC50 5 71 mg/L

Description

(Continued)

C. Thermo-chemical processes

15.5 Effectiveness and adaptability of chemical dispersants

TABLE 15.5

275

(Continued)

S. no

Dispersant name

Description

21.

NEOS AB3000

Exposed for 24, 48 and 96 h while testing on juvenile red sea bream organism; attains the value of LC50 . 8900, 5 11100 and 5 680 mg/L, respectively.

22.

NEOS AB3000

Exposed for 96 h while testing on Gasterosteus aculeatus organism; attains the average value of LC50 5 320 mg/L

23.

NEOS AB3000

Exposed for 96 h while testing on Salmo gairdeni organism; attains the value of LC50 . 5 320 mg/L

24.

Nokomis 3

Exposed for 96 h while testing on Salmo gairdeni organism; attains the value of LC50 . 5 110 mg/L

25.

Enersperse 700

Exposed for 96 h while testing on Daphnia magna organism; attains the average value of LC50 5 50 mg/L

26.

Corexit CRX8

Exposed for 96 h while testing on Daphnia magna organism; attains the average value of LC50 5 15.6 mg/L

27.

Dispersant G. Exposed for 96 h while testing on Oncorhynchus mykiss organism; attains the value of E. LC50 5 35 mg/L

28.

Dispersant G. Exposed for 96 h while testing on Oncorhynchus mykiss organism; attains the value of P. LC50 5 200 mg/L

29.

Dispersant G. Exposed for 96 h while testing on Oncorhynchus mykiss organism; attains the value of T. LC50 5 8 mg/L

30.

Dispersant G. Exposed for 96 h while testing on Oncorhynchus mykiss organism; attains the value of W. LC50 5 2 mg/L

31.

Dispersant G. Exposed for 96 h while testing on Oncorhynchus mykiss organism; attains the value of Y. LC50 5 0.71 mg/L

32.

Pennyworth

Exposed for 96 h while testing on Salmo gairdeni organism; attains the value of LC50 5 44 mg/L

33.

Shell dispersant

Exposed for 96 h while testing on Salmo gairdeni organism; attains the value of LC50 5 71 mg/L

Agency—Federal Register References—(Ederal & Ection, 2011) FR 47458, 1994 Appendix C-Part 300 (Terminal United States E Route, 2005). SFT is performed to find the effectiveness of chemical dispersant. In general the relative effectiveness of a chemical dispersant depends on viscosity of oil, temperature, and dispersant to oil ratio. As the viscosity of oil increases the effectiveness of chemical dispersant will decrease. Particularly CORE XIT9500 and Slickgone-EW shows decrease in effectiveness when temperature decrease and viscosity increase (Stevens & Roberts, 2005). An experimental result of mean effectiveness of eighteen different chemical dispersants are determined by two different testing, SDT and Baffled Flask Test and concluded that the overall mean effectiveness of the SFT was 19.7% compared to 64.6% with Baffled Flask Test. This study was also given a pass or fail criteria for selection of chemical dispersant (Sorial, Koran, Holder, Venosa, & King, 2005).

C. Thermo-chemical processes

276

15. Use of chemical dispersants for management of oil pollution

TABLE 15.6 Mean percentage of effectiveness of different chemical dispersants at 15 C at dispersant to oil ratio-1:25 using Warren Spring Laboratory WSL LR 448 protocol on Crude oil and Heavy Fuels from different sources around world (Stevens & Roberts, 2005). Mean percentage effectiveness at 15 C at dispersant to oil ratio of 1:25 Crude oil source

CORE XIT-9500

CORE XIT-9527

Slickgone-EW

Slickgone-LTSW

TERGO-R40

Gamlen-OSD-LT

Kutubu

11

11

15

13

25

22

Barrow Island

13

15

11

17

22

22

Kuwait

45

52

34

38

17

16

Labuan

10

8

15

11

26

22

Oman residue

46

38

25

18

30

25

Taiwan

66

54

61

25

24

21

Brazil

76

63

81

11

29

25

Antwerp

39

14

41

3

1

1

New Zealand

35

15




15

9

4

Cristobel

59

56

62

7

15

17

Japan

66

48

61

16

19

17

Nagoya

58

38

58

10

6

4

Singapore

62

35

59

22

6

8

Rotterdam

51

37

49

6

5

5

Heavy fuels source

Percentage effectiveness of different chemical dispersants at different locations has been shown in Table 15.6.

15.6 National and international regulations for using chemical dispersants The Indian Coast Guards (ICG) which come under the Government of India, Ministry of Defense, is the elected National Authority for oil spill response in Indian sea-water under the National Oil Spill Disaster Contingency Plan
NOS_DCP. The purview for NOS-DCP is handled by National Disaster Management Authority, Ministry of Home Affairs, Government of India. The ICGs is responsible for proper functioning of NOS-DCP and also act as central coordinating agency to fight against oil pollution in different spilled zones. Every chemical dispersant will undergo for different trials by National Institute of Oceanography (NIO) and important information related Chemical dispersant can be found at NIO. Some of the important policies and guidelines being followed by ICG have been shown in Table 15.7. Registration, Evaluation, Authorization and Restriction of Chemicals and Toxic Substances Control Act of 1976 are the authorized agency of European Union regulation and United States respectively for chemical dispersants approval. Every chemical

C. Thermo-chemical processes

15.7 Applications of different chemical dispersants

TABLE 15.7

277

Important policies and guidelines given by Indian Coast Guards (Response).

Policy

Description (National-India)

Policy-1

Only the chemical dispersants which are listed and approved should be used.

Policy-2

Sea oil spills should leave to biodegradable naturally unless they may cause damage to marine environment

Policy-3

A chemical dispersant can only be used after thorough analysis on advantages and disadvantages by Net Environmental Benefit Analysis and documented.

Policy-4

No chemical dispersants should be used in any sensitive areas or protected bays and inlets.

Policy-5

All stake holders, ports, oil handling companies, shipping companies, Coastal Refineries and Oil Exploration and Production Organization, shall recover oil from oil spill.

Guidelines

Description (National-India).

Guideline-1

Hydrocarbon based chemical dispersants shall not be used.

Guideline-2

Water biodegradable concentrate chemical dispersants can be used in the ratio 1:2 for dispersant: oil, which are spray by boats.

Guideline-3

Concentrate chemical dispersants can be used in the ratio 1:20 or 1:30 for dispersant: oil, which are spray by aircrafts.

Guideline-4

Concentrate chemical dispersants can also be used with a proper authorization and advice when they should be spray by boats.

Guideline-5

If in a case of light distillate fuels, no chemical dispersant should be used.

Guideline-6

No chemical dispersants should be used on weathered viscous emulsions at sea water.

dispersant should be gone through different test and should get approved, tests listed as Swirling Flask Dispersants Effectiveness Test, Revised Standard Dispersant Toxicity Test, Bioremediation Agent Toxicity Test effectiveness test and toxicity test are two main most requested tests for many countries (Ederal & Ection, 2011). International Petroleum Industry Environmental Conservation Association (IPIECA) is a global oil and gas industry association for environmental and social issues. IPIECA gives the guideline, polices and approval for using different chemical dispersants. International Tanker Owners Federation approved chemical dispersants are widely used and accepted by many countries (Coolbaugh, Varghese, & Li, 2017).

15.7 Applications of different chemical dispersants 1. Dispersants are scattered for oil spillage purposes on slicks for removing oil from the surface of the sea, and for its dispersion in the water body. In addition, these chemical dispersants reduce the influence on the surroundings of the split oil while spillage remover process from the waterbody.

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278

15. Use of chemical dispersants for management of oil pollution

2. Dispersants decrease the quantity of surface oil, thus decreasing the personnel reaction possible subjection to dangerous composites in the oil and reducing the amount of oil met by aqueous species. 3. Dispersants augment the breaking up of the oil, helps it in removal from the aqueous phase in the water columns as mini drops that can dilute quickly and biodegraded. 4. Dispersants can speedily and efficiently, reduce the harmful effects of pollutants to water animals and some profound coastal sources. 5. Corexit 9500 is a kind of chemical dispersant that have catastrophic influences on freshwater ecologies by upsetting the crucial foodstuff chain net (doi, 2016). 6. Pars 1 and Pars 2 are the most efficient dispersants, having higher depravity. These are highly appropriate composites for the removal of oil spillage from offshore modules, having lesser subordinate contamination (https://www.science.gov/topicpages/w/ water 1 dispersant 1 effectiveness). 7. DISPERSIT SPC 1000 is a kind of chemical dispersant that can be utilized by some conservative techniques as aerial and boat spraying. Two to ten gallons per acre is recommended as an application rate, and this is also reliant on the kind of oil, weather and temperature conditions. Timely utilization guarantees the higher chances of effective dispersal of the spillage (https://www.epa.gov/emergency-response/ dispersit-spc-1000tm#:B:text 5 Concentration%2FApplication%20Rate%3A,4840% 20square%20meters)%20is%20suggested). 8. MARE CLEAN 200 is a kind of chemical dispersant that is utilized at an application rate of 53 to 66 gallons per ton of oil. It is an efficient dispersant for liquors hydrocarbons (https://www.epa.gov/emergency-response/ mare-clean-200).

15.8 Conclusions Critical conclusions drawn from the above studies have been mentioned below: 1. Oil spill has hazardous effect on aquatic animals, human health, and plants. 2. Evaporation of oil from oil spilled zones releases fumes and smokes which causes air pollution. 3. Looking into the toxic nature of chemical dispersant and its long contamination duration it is advised to follow mechanical, physical, and biological methods. 4. Widely used chemical dispersants for oil spill remediation are COREXIT 9500 and COREXIT 9527. Results have revealed that COREXIT 9500 shows good effectiveness as compared to COREXIT 9527 and is less toxic too. 5. COREXIT 9527 is a more toxic chemical dispersant tested till date. 6. Pars 1 and Pars 2 are efficient dispersants that can be used in oil spill treatment. 7. In some cases, use of chemical dispersants increases the toxicity of water bodies which adversely affects the marine ecosystem. 8. It is always recommended to use chemical dispersant according to national and international regulations.

C. Thermo-chemical processes

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2808. Available from https://doi.org/10.1038/ismej.2017.129. Tuan Hoang, A., Viet, V., Pham., & Nam Nguyen, D. (2018). A report of oil spill recovery technologies. International Journal of Applied Engineering Research, 13(7), 4915
4928, [Online]. Available. Available from http://www.ripublication.com. Ventikos, N. P., Vergetis, E., Psaraftis, H. N., & Triantafyllou, G. (2004). A high-level synthesis of oil spill response equipment and countermeasures. Journal of Hazardous Materials, 107(1
2), 51
58. Available from https://doi. org/10.1016/j.jhazmat.2003.11.009. Wilkinson, J., et al. (2017). Oil spill response capabilities and technologies for ice-covered Arctic marine waters: A review of recent developments and established practices. Ambio, 46(s3), 423
441. Available from https://doi. org/10.1007/s13280-017-0958-y. Wise, J., & Wise, J. P. (2011). A review of the toxicity of chemical dispersants. Reviews on Environmental Health, 26 (4), 281
300. Available from https://doi.org/10.1515/REVEH.2011.035. Zolfaghari-Baghbaderani, A., et al. (2012). Effects of three types of oil dispersants on biodegradation of dispersed crude oil in water surrounding two Persian Gulf provinces. Journal of Environmental and Public Health, 2012. Available from https://doi.org/10.1155/2012/981365.

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16 Brief account on the thermochemical oil-spill management strategies Y. Sivaji Raghav1, Poonam Singh2, Ankit Dasgotra3 and Abhishek Sharma3 1

CNPC BOHAI Drilling Company (BHDC), Kuwait City, KuwaitCNPC BOHAI Drilling Company (BHDC), Kuwait City, Kuwait 2Department of Chemistry, University of Petroleum & Energy Studies (UPES), Dehradun, India 3Department of Research and Development, School of Engineering, University of Petroleum and Energy Studies, Dehradun, India O U T L I N E 16.1 Introduction

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16.2 Major oil spills incidents 284 16.2.1 Exxon Valdez oil spill (1989), and Amoco Cadiz oil spill (1978) 284 16.2.2 Deepwater horizon oil spill 284 16.3 Oil spill treating methods 286 16.3.1 Physical remediation methods 286 16.3.2 In situ burning 288

16.3.3 Bioremediation 16.3.4 Chemical methods 16.4 Emulsifying agents

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16.5 Impact of emulsion on ecosystem 292 16.6 Conclusion

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16.1 Introduction Nowadays, petroleum and other fuels are in great demand. The increase in global demands for oil transportation and other uses leads to major environmental issues. One of these environmental impact is an oil spill in seas during transportation. Despite several significant measures taken to bring down these oil spill incidents with different regulations and advancements in this subject, an oil spill can occur due to a fuel leakage,

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lubricating oils, undissolved gases, or any accident during transportation of petroleum products or crude oil. The release of oils, gases, and wastes from industries into marine leads to marine pollution. The impact of these spills can be multidimensional, which also depends upon the chemical composition and properties of oil spilt. The properties and behavior of individual components and their reaction with marine components can lead to vary diverse effects on marine life and its ecosystem. When such oil spill incidents hit the ocean, different treating agents can be used to minimize or compromise the effects that tend to appear. According to studies, oil spill treating agents can be classified based on their actions like solidifiers, demulsifying agents, surface washing agents, and dispersants. Any of these treating agents must fulfill the basic criteria. They must have long shelf life, must be nontoxic, non-polluting, biodegradable, highly active, and non-corrosive and must be easy to apply from different mode of applications like boats, ships, helicopters, etc.

16.2 Major oil spills incidents Many oil spill incidents happen in the course of history, that is the Amoco Cadiz oil spill (1978), the Allantil empress oil spill (1979), Exxon Valdez oil spill (1989), the Deepwater Horizon oil spill (2010), etc. There had been a huge number of oil spill incidents, that happened in different corners of the ocean, are subjected to major discussions so far. Till 2020, approximately ten oil spill incidents have been reported, and some of the major spill incidents have been opted for case discussion in this chapter.

16.2.1 Exxon Valdez oil spill (1989), and Amoco Cadiz oil spill (1978) It is one of the major spill incidents that happened in 1989 (Peterson et al., 2003). The spill released from 42,000 tons of crude, affected marine life and ecosystem of a very large area of around 28000 km2 (Zhang et al., 2018). As this incident happened in the remote high-energy area, oil was dispersed quickly. Amoco Cadiz incident happened in France coastal area (1978), caused extensive contamination in marine life, as it was carrying 223,000 ton of crude oil. Lots of measures were taken to remove emulsion from sand and rocks (Swannell, Lee, & McDonagh, 1996) and some of them were: 1. 2. 3. 4.

Cleaning compounds to restore oil from oil, Chemical fertilizers, Talc treated with 0.1% surfactant, Bacterial and other biological remediation.

16.2.2 Deepwater horizon oil spill It is considered to be the one of the biggest incidents that happened in the history of the petroleum industry, in which around 500,000 ton oil got released. This incident occurred in April 2010 and affected 180,000 km 2 area of ocean. In this spill incident, extensive interaction of oil spilt and seawater formed plumes and spread

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throughout deep water. While having cleansing measures, 25% of the oil that spilled got collected, 13% dispersed naturally, 23% of it got evaporated, and 13% of oiltreated using chemical methods. But despite all measures taken, 50%
55% of volume remained in the water and affected marine lives, as well as shorelines. Biodegradation and chemical dispersants were used to minimize the effect and also showed minimum contamination in seafood (Zhang et al., 2018). These incidents affected the ecosystem, seafood industry, economy, future marine and shoreline life too. Study of such events, after effects and damages caused by them, prepare researchers to be able to deal with future incidents in term of precaution to minimize the impact caused by them. Fig. 16.1 shows the systematic operation and measures of an oil spill events, reveals about the key determinants (Singh, Bhardwaj, Arya, & Khatri, 2020). It shows that factors like marine physical environment (movement of tides, connecting waterways, water currents, etc.), oil spill event/occurrence (time, date, location, etc.), characteristics of spilt oil (concentration, composition, nature of oil, etc.), marine biodiversity (effects on fisheries, birds, planktons, etc.), cleanup methods and response strategies (physical remediation, chemical remediation, in situ burning, bioremediation, etc.) and economic, social, and health impacts (fisheries, aquaculture, tourism, recreation, etc.) are the main key determinants of an oil spill event.

FIGURE 16.1 Systematic operation and measures of an oil spill event (Chen, Ye, Zhang, Jing, & Lee, 2018; Singh et al., 2020).

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16.3 Oil spill treating methods Oil spill remediation involves a great number of techniques in order to address the issue: physical techniques, chemical techniques, thermal remediation, and biological remediation

16.3.1 Physical remediation methods This includes manual controlling of spread of oil spilt without changing chemical or physical properties. Some of the physical techniques are discussed below like (1) Boom (2) skimmers (3) sorbents. 1. Boom helps to prevent the oil from spreading, so that oil can be removed using other techniques like skimmers. Booms can be in fence-like structure that remains vertical. It is noted that 60% of boom remains underwater and 40% remains above the surface, but they are pretty unstable against strong wind, high waves and prove to be less efficient in such cases. Another type of boom is curtain boom, they are flexible, foam-filled and arranged circularly but they are also efficient in calm water bodies. Booms are also available in fireresistant types made up of fireproof material, they have great reliability to protect the shoreline. Booms usually functional in river, streams and lake water columns (Ghaly & Dave, 2011; Sutherland & Kendall Melville, 2015). Pictorial illustration of different configuration of booms for oil collection is shown in Fig. 16.2. 2. Skimmers are used in recovering oil from the oil spill site. The working of skimmers depends on the quantity of oil spilt, its properties as well as weather conditions. According to the

FIGURE 16.2 Pictorial illustration of different configuration of booms for oil collection (Azizian & Khosravi, 2019; Fingas, 2011).

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working techniques of skimmer, they can be of different types like weir skimmers as they collect oil spilt using gravity actions. Skimmers show efficient results as they show stability even in the presence of high waves and collect oil pretty quickly. Oleophilic skimmers consist of oleophilic properties, resulting as they can recover up to 90% of oil, but can not function if mixed with dispersant. Suction skimmer work for a collection of oil-based on suction principle. Its functional range is a bit wide as it can also function to recover oil from beaches and land area. Skimmers are more effective when the oil layer is thick and its efficiency is affected by the viscosity of oil, wind and the current condition of oil in the water body (Zhang et al., 2018). Pictorial depiction representing working of different types of skimmers is shown in Fig. 16.3.

FIGURE 16.3 (A)
(D). Pictorial depiction of workings of different types of skimmers (Azizian & Khosravi, 2019). (A) Weir skimmer, (B) suction skimmer, (C) elevation skimmer, (D) submersion skimmer.

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3. Sorbents are materials that absorb or adsorb oil from the ocean. These materials can be natural or synthetic depends on the uses. They are usually functional in coastal areas, ports and harbors to protect noncleanable area like pathways. Though sorbents are useful but their excessive use can be problematic for further use of skimmer and also they are harmful for the environment (Zhang et al., 2018). Natural adsorbent like mass milk ward and cottonseed reported to absorb 85% of crude oil as per experiment, and natural absorbent are economically more feasible. Synthetic adsorbents include polypropylene, polyester and polystyrene, etc. Polypropylene reported to have the highest capacity. Some of them are reusable but being synthetic, they are non-biodegradable (Ghaly & Dave, 2011).

16.3.2 In situ burning In this method of cleaning up, controlled burning of oil in the presence of specialized equipment are involved. It is simple to implement, economic and highly efficient to use in freshwater, salty water as well as other water bodies. This method has many benefits like low waste, low cost and efficient elimination of oil but also have a negative side like elements from burning can be toxic for the environment and this method can be used just when a layer of spilt oil is thick enough to ignite. Concerning these issues, gasoline and other such light crude products can be used for combustion (Sahai et al., 2007; Zhang et al., 2018). Some more disadvantages of this method are that there are chances of catching secondary fire affected by wind, byproducts and smoke that also rises the risk of toxicity for the environment and human life. Despite these disadvantages, it is a potential technique to be used in remote or restricted area (Ghaly & Dave, 2011).

16.3.3 Bioremediation Bioremediation is the process in which microorganisms from marine ecology are used to simulate the rate of natural biodegradation. There are lots of species in the marine ecosystem that can work for the decomposition of organic and other chemical components. For organic compounds present in the oil, the local microbial of the ocean do the job but for crude oil, only consortium microbes can break them. The bioremediation method has some limitation like availability of oxygen, certain temperature, PH and constituent matter is required. Usually, the natural rate of degradation is very slow but it can be enhanced up to six times by the addition of fertilizers. Similarly, in the case of Exxon Valdez oil spill event, nitrogen-based fertilizer was used for the growth of microbes for the degradation of hydrocarbon. Dispersants also help in degradation of oil because it provides greater surface area for microbes to work on a faster rate. Different components of oil decompose at a different rate by a set of microorganisms (Singh et al., 2020). For the bioremediation, process to occur in marine system Nitrogen and phosphorus are required for the growth of microbes. It is recorded that the use of fertilizers does not cause eutrophication or toxicity in the medium; in fact toxicity of petroleum, hydrocarbon can be removed through bioremediation. This process is more economic than most other remediation methods (Ghaly & Dave, 2011). Dispersion of oil can be done through biodegradation as well sorption, which is demonstrated in Fig. 16.4.

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FIGURE 16.4 Mechanism of oil spill cleaning through chemical dispersion (Azizian & Khosravi, 2019).

FIGURE 16.5 Chemical dispersion process (Zhang et al., 2018): (1) water and oil are immiscible, (2) when dispersants are applied in the system, they align themselves in order to interact with both water and oil, and (3) reduction in interfacial tension results in oil dispersion and formation of small droplets.

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FIGURE 16.6

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Role of different materials in oil dispersion of oil during oil spill incidents (Doshi et al., 2018).

16.3.4 Chemical methods Dispersants can be counted in the category of surfactants work to create slurries by preventing settling, most importantly for the collection purpose (Fink, 2015; Muizis, 2013). The working of dispersants is to break the slick of oil into minute droplets to promote easy degradation of the marine system. To ensure that they mix well in the medium, Arial spraying using aircraft is the best way of application. Despite being an economic method, dispersants prove to be more capable to treat spilt oil comparatively. But one of the drawbacks is that they are hazardous for human, marine life as well as contaminate shoreline and drinking water (Ghaly & Dave, 2011). Mechanism of oil spill cleaning through chemical dispersion, and chemical dispersion process is shown in Figs. 16.5 and 16.6.

16.4 Emulsifying agents When seawater mixed with the oil spilt in the ocean, it forms emulsion which encouraged by surface turbulence. Usually, asphaltenes present in the oil is the key reason for emulsion formation, which can last for several months. Surface turbulence breaks oil layers into smaller droplets and this disturbance on the surface helps them to mix to form an emulsion (Azizian & Khosravi, 2019). If heated under sunlight under calm condition, emulsified oil and water can be separated. The formed emulsion can be stable, if they are in 60%
80% of water in an oil slick, semistable in 40%
60% of water and unstable when

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30%
40% water is present in the oil slick. The emulsion can be formed with 70% of water in it, which can lead to noticeable changes in the chemical and physical properties of the oil. Crude oil is more likely to emulsify rather than other light oils (Zhang et al., 2018). Thermodynamically emulsions are unstable system. Talking about oilfield emulsions, they can be classified according to their kinetic stability (Fink, 2015): (1) loose emulsions are very unstable that cannot even sustain for few minutes. (2) Medium emulsion- they are semistable and can exist for up to 10 minutes. (3) The tight emulsion can sustain for hours, a week and even for a month. Invert emulsion is water in oil emulsion and they have desirable suspension properties. In this case, the affinity of surfactant can be changed and can be converted into regular emulsion, changing PH or just by protonating the surfactant (United States Patent USOO7703527B2, 2007). Water in water emulsion is formed when two polymers, each having aqueous solubility but no thermodynamic compatibility are dissolved together in an aqueous medium. They are also defined as an aqueous two-phase system. These aqueous polymer systems can be used to create low viscous prehydrated for vigorous mixing of polymer to achieve low viscous polymer fluid (Fink, 2015). Oil in water emulsion work to enhance the oil recovery along with that these emulsions give stability and thinning characteristic to the system even more than water in oil emulsion could provide. According to the reports and forming condition, these emulsions used to enhance recovery operations. Contrary to oil in water emulsions, these emulsions are prepared by dispersing oil in water emulsion in second oil. Oil in water surfactant lower dispersant effectiveness unlike water in oil emulsion, which increase dispersant effectiveness (Doshi, Sillanpa¨a¨, & Kalliola, 2018). Microemulsion has a small droplet the shape ranging 10
300 nm in size. This thermodynamically stable emulsion would break back into oil and water over a period of time. They come into action by increasing the dispersibility of oil based on chemicals. These emulsions can be broken by providing a change in temperature and the addition of chemicals (Fink, 2015; Yang, 2009). Solid stabilized emulsion—Some solid compounds (particles) having the oleophilic character or possessing oil external emulsion can be used to stabilize the emulsion. These particles must be oleophilic in nature to support external emulsions. These particles are majorly effective to stabilize crude oil emulsion. The standard of solidification of the emulsion can be enhanced by pretreatment of it using sulfonating agents before emulsification. Similarly, chemical treatment of solidifying particles can be done to acquire oleophilic or hydrophilic character (Fink, 2015). Bio treated emulsion—To stabilize the water in oil emulsion they can be treated biologically before emulsification. Same as solid stabilization this is another pretreatment using oil-degrading microorganism. For the growth of these microorganisms, nitrogen and phosphorus-containing nutrients are used in the presence of a sufficient amount of oxygen at 20 C
70 C (moderate temperature). In this process aliphatic components oil are oxidized to give polar ketones or acid of aliphatic chain. Because of the surface-active properties of aliphatic components, they help in the stability of the emulsion. This also results in changes in the aqueous phase, which after bioreaction used to make water in oil emulsion and enhance the stability of the emulsion (Stability enhanced water-in-oil emulsion & method for using same, 2007).

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16.5 Impact of emulsion on ecosystem Huge amount of oil spilled in the ocean, will definitely hit economically as well as environmentally. The impact of materials spilled varies on the amount of oil released in an accident and on the properties and nature of oil spilt. The amount of energy also would get disturbed in the immediate environment because of hydrocarbon breakdown (Zhang et al., 2018). Biodegradable dispersants possess low toxicity and prove to be highly efficient from an environmental point of view as they consist of non-ionic components and less toxicity. Though dispersants and emulsifiers are recommended to cure the after effects, and to recover oil. According to the status of the incidents, emulsification could possibly increase toxicity in water and create pollution in the water body (Fink, 2015). Accidents while transportation is very common. Most of these incidents occur due to unexpected weather condition but ultimately it will affect marine life for very long upcoming years. Along with that, it brings different challenges and complications regarding the environment, marine, and human life. The thickness of the layer of oil spilt one of the major factors to be considered and affect in many ways, the toxicity of oil depends on its sources and properties. All crude oils contain many heavy metals and PAHs, which lead to toxicity of human and marine life (Zhang et al., 2018). These challenges also can be addressed to some extent using different mitigation methods.

16.6 Conclusion Technically, methods like booms and skimmers are not as effectively independent for oil mitigation, dispersants, surfactants, and other surface-active agents are required to support these methods. As per the environmental aspect, it is always preferable to remove the oil from ocean water, but economically these methods are costlier than the rest of the other methods popular for the same purpose. But on the other hand, extracted oil and surfactants can be used again after processing, these surfactants from biobased resources prove to be a better option from an economic and environmental point of view as they are more feasible in terms of biodegradability and nontoxic, and can be regenerated.

References Azizian, S., & Khosravi, M. (2019). Advanced oil spill decontamination techniques. Interface science and technology (pp. 283
332). Elsevier B.V. Available from https://doi.org/10.1016/B978-0-12-814178-6.00012-1. Chen, B., Ye, X., Zhang, B., Jing, L., & Lee, K. (2018). Marine oil spills-preparedness and countermeasures. World seas: An environmental evaluation volume III: Ecological issues and environmental impacts (pp. 407
426). Elsevier. Available from https://doi.org/10.1016/B978-0-12-805052-1.00025-5. Doshi, B., Sillanpa¨a¨, M., & Kalliola, S. (2018). A review of bio-based materials for oil spill treatment. Water Research, 135. Available from https://doi.org/10.1016/j.watres.2018.02.034. Fingas, M. (2011). Physical spill countermeasures. Oil spill science and technology (pp. 303
337). Elsevier Inc. Available from https://doi.org/10.1016/B978-1-85617-943-0.10012-7. Fink, J. (2015). Petroleum engineer’s guide to oil field chemicals and fluids. Ghaly, A. E., & Dave, D. (2011). Remediation technologies for marine oil spills: A critical review and comparative analysis. American Journal of Environmental Sciences, 7, 423
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Muizis, A., (2013). Evaluation of the methods for the oil spill response in the offshore arctic region. In Date evaluation of the methods for the oil spill response in the off-shore Arctic Region (52 pp. 1 2 Appendices). Metropolia Ammattikorkeakoulu. Peterson, C. H., Rice, S. D., Short, J. W., Esler, D., Bodkin, J. L., Ballachey, B. E., & Irons, D. B. (2003). Long-term ecosystem response to the Exxon Valdez oil spill. Science (New York, N.Y.), 302. Available from https://doi. org/10.1126/science.1084282. Sahai, S., Sharma, C., Singh, D. P., Dixit, C. K., Singh, N., Sharma, P., . . . Gupta, P. K. (2007). A study for development of emission factors for trace gases and carbonaceous particulate species from in situ burning of wheat straw in agricultural fields in india. Atmospheric Environment (Oxford, England: 1994), 41, 9173
9186. Available from https://doi.org/10.1016/j.atmosenv.2007.07.054. Singh, H., Bhardwaj, N., Arya, S. K., & Khatri, M. (2020). Environmental impacts of oil spills and their remediation by magnetic nanomaterials. Environmental Nanotechnology, Monitoring and Management, 14. Available from https://doi.org/10.1016/j.enmm.2020.100305. Stability enhanced water-in-oil emulsion and method for using same, (2007). Sutherland, P., & Kendall Melville, W. (2015). Field measurements of surface and near-surface turbulence in the presence of breaking waves. Journal of Physical Oceanography, 45, 943
965. Available from https://doi.org/ 10.1175/JPO-D-14-0133.1. Swannell, R. P., Lee, K., & McDonagh, M. (1996). Field evaluations of marine oil spill bioremediation. Microbiology and Molecular Biology Reviews: MMBR, 60, 342
365. United States Patent USOO7703527B2, 2007. Yang (2009). Microemulsion containing oil field. United States Patent. Zhang, B., Matchinski, E. J., Chen, B., Ye, X., Jing, L., & Lee, K. (2018). Marine oil spills-oil pollution, sources and effects. World seas: An environmental evaluation volume III: Ecological issues and environmental impacts (pp. 391
406). Elsevier. Available from https://doi.org/10.1016/B978-0-12-805052-1.00024-3.

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17 Use of live microbes for oil degradation in situ Ragaa A. Hamouda1,2, Dalel Daassi1, Hamdy A. Hassan3,4, Mervat H. Hussein5 and Mostafa M. El-Sheekh6 1

Department of Biology, College of Sciences and Arts, Khulais, University of Jeddah, Jeddah, Saudi Arabia 2Department of Microbial Biotechnology, Genetic Engineering and Biotechnology Research Institute, University of Sadat City, Sadat City, Egypt 3Department of Biological Science, Faculty of Science and Humanity Studies at Al-Quwayiyah, Shaqra University, AlQuwayiyah, Saudi Arabia 4Department of Environmental Biotechnology, Genetic Engineering, and Biotechnology Research Institute, University of Sadat City, Sadat City, Egypt 5Botany Department, Faculty of Science, Mansoura University, Mansoura, Egypt 6Botany Department, Faculty of Science, Tanta University, Tanta, Egypt O U T L I N E 17.1 Introduction

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17.1 Introduction In the present world, anthropogenic activities such as growth, biological, physical, economic, industrial, infrastructure growth, science, technological growth, etc., revolve around energy. Apart from traditional sources of energy like firewood, wind power, solar power, etc., petroleum hydrocarbons continue to be used as the principal and adaptable form of energy. The most important strategic resource of any country is its crude petroleum resources (Sun, 2009). All human activities are counting on the petrochemical industry to meet their energy needs. However, these crude petroleum compounds’ use seems to have a deteriorating effect on our environment (Xue, Yu, Bai, Wang, & Wu, 2015). Oil pollution is one of the most important pollution affecting the world these days. Even polar regions are not excluded from its harmful effects (Ruberto, Vazquez, Lobaldo, & MacCormack, 2005). The sudden introduction of massive amounts of these xenobiotic chemicals into the environment can affect the recipient ecosystem’s self-cleaning capacity, hence resulting in the accumulation of these pollutants to a problematic level. Bioremediation in crude petroleum, microorganisms are employed to reduce the concentration of toxic petroleum hydrocarbon compounds. Not all microorganisms have the capability to degrade all the different petroleum hydrocarbon compounds as a result of different environmental factors, which exhibit crucial roles in biodegradation and then the bioremediation of these compounds (Varjani & Upasani, 2017), at the presence of suitable environmental conditions for petroleum hydrocarbon bacterial degraders in the lab, it will increase its capability to degrade petroleum compounds (Head, Jones, & Ro¨ling, 2006). Due to the increase of petroleum hydrocarbon compounds in the environment, the indigenous bacteria ultimately used most of these compounds as a sole carbon source to meet their energy requirements to fulfill their physiological activities. This is the reason why these bacteria are found in the oil spill contamination sites, also, longer aged oil-contaminated sites, the more numbers of microorganisms (Varjani & Gnansounou, 2017). In recent years, detoxification of contaminated sites by applying one or more fungi species as natural agents is called “Myco-remediation.” It has become prevent, economical, and efficient in converting toxic wastes into not/or less toxic end products or carbon dioxide and water (Yamada, Mukumoto, Katsuyama, & Tani, 2002). Fungi have advantages over other microorganisms in that they are characterized by a robust morphology, large hyphal network, adaptability to extreme conditions, and tolerance to a high concentration of pollutants (Prasad, 2017). Furthermore, fungi are rapidly incorporated into the pollutants and grow in environments with low nutrient concentrations, acidic pH, and low activity water (Mancera-Lopez et al., 2008). Also, fungal species can produce versatile extracellular enzymes such laccases, peroxidases, and integral-membrane enzymes like cytochrome 450 and oxidoreductases (Ostrem Loss & Yu, 2018), which interact with

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various structures of hydrocarbons with a fairly high degree of nonspecific activity (Martı´nkova´, Kotik, Markova´, & Homolka, 2016). So that, the diversity of habitats and the ability for secreting a multitude of specific and no specific enzymes makes fungi potential candidates in treating a wide spectrum of petroleum hydrocarbons structures (Cerniglia & Sutherland, 2010). Mycoremediation implicates fungal cultures’ specific augmentation to enhance the biodegradation of spilled oil in situ or ex situ remediation. Saprophytic fungi perform a vital role in the decomposition of organic pollutants such as petroleum spilledoil. These fungi yield various extracellular enzymes and acids that act and catalyze native polymers such as cellulose, hemicellulose, lignin, keratin, chitin, and pectin (Lamar & White, 2001). A widespread of fungal species have shown their possibility to degrade petroleum hydrocarbon from contaminated spill oil areas. The most common fungal strain recorded as a biodegrading belongs to the following genera: Talaromyces, Talaromyces, Amorphoteca, Neosartorya, Penicillium, Aspergillus, Fusarium, Paecilomyces, Graphium, Sporobolomyces, and Cephalosporium (Das & Chandran, 2010; Varjani, 2017). Organic pollutants can be biomonitoring, controlling by various algae from aquatic ecosystems (Chekroun, Sa´nchez, & Baghour, 2014). Algae can degrade organic pollutants, which is referred to as “phycoremediation.” Phycoremediation is a promising biodegradation technology due to ecofriendly approaches for cleaning polluted areas and are environmentally sustainable (Baghour, 2019). Phycoremediation is a safe technology, nonintrusive, and worthwhile in which the prospective macro- or microalgae are used to handle a huge group of pollutants (Gupta, Ranjan, & Gupta, 2019). Suresh and Ravishankar (2004) investigated that algae positively affect the hyperaccumulation of heavy metals and xenobiotics’ degradation. Using microalgae in the elimination of colored wastewater and bioremediation of heavy metals have gained attention due to their fundamental role in carbon dioxide fixation. Algae’s biomasses have a vital feedstock for biofuel production and are useful for environmental sustainability (Ellis, Hengge, Sims, & Miller, 2012). Algae can absorb light and assimilate CO2 into chemical energy (transformations) and can grow ampler than other plants, resulting in ampler removal or biotransformation of pollutants; also, algae can good survive under stress condition, so the possibility of treatment of polluted site by algae is further sustainable for natural resource controlling (Gupta et al., 2019).

17.2 Bioremediation of oil compounds by bacteria The remediation using physical and chemical methods is costly and not environmentally friendly (Rosenberg, 1993). These methods cause raising different gas levels in the atmosphere, such as carbon-dioxide (CO2), sulfur, and nitrogen- oxide. Increasing CO2 is the main reason for global warming. However, these methods remove some petroleum oil contaminants but remain serious unpredictable hazards (Johnson & Affam, 2019). Mechanical and chemical methods for the remediation of oil contaminates become limited and expensive (Das & Chandran, 2010). Bioremediation of crude oil polluted compounds using microorganisms becomes the ideal solution because of relatively low-cost technology, public acceptance, and often carried out on-site (Brakstad & Bonaunet, 2006). Using N- and P- compounds for fertilizing oil-polluted sites are high frequent than other used methods (Varjani & Upasani, 2017). Self-cleaning of oil-polluted sites is oil-removal by the flora microorganisms in locations without using any additional

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supplements. Although the concentration of polluted oil in the contaminated sites reached 20% or more (McKinnon & Vine, 1991), only the studies reported 1%
6% of crude oil were removed by bioremediation (Siles & Margesin, 2018). As a result of damaged wells, the oil spilled and filled varying dimensions 50 oil-lakes, thus cause high oil concentrations and lead to high toxicity for organisms, where their life becomes nearly impossible in these conditions (Zio´łkowska & Wyszkowski, 2010) Bioremediation functions depend on biodegradation either to transfer the complex hydrocarbon compounds into simpler compounds or by transferring into inorganic compounds, cell protein and mainly carbon dioxide and water this what is called complete mineralization (Das & Chandran, 2010), which is cheaper than other remediation technologies (Leahy & Colwell, 1990). The factors influencing oil degradation the limited availability to microorganisms, where oil compounds bound to soil components, with difficulty to be released or degraded as polycyclic aromatic hydrocarbons (PAHs) some of these compounds not be degraded at all (Atlas & Bragg, 2009). Temperature is a significant factor for biodegradation, where the temperature affects the chemistry of oil compounds and then affects the microbial flora on the contaminated sites. By decreasing the temperature delayed the biodegradation of oil compounds (Foght, Westlake, Johnson, & Ridgway, 1996). Nutrients, especially nitrogen, phosphorus, and sometimes iron, are necessary elements for increasing biodegradation of oil pollutants (Cooney, 1984). As a result of oil spilled in water, either marine or freshwater, carbon increased, and the biodegradation becomes affected by nitrogen and phosphorus (Atlas, 1985). Additions of the nutrients could be vital to increase the oil pollutants biodegradation (Kim, Choi, Sim, & Oh, 2005), whereas the extreme concentrations of these nutrients could be the reason for inhibition of biodegradation (Chaillan, Cha^ıneau, Point, Saliot, & Oudot, 2006). Many bacterial strains can degrade different types of aromatic compounds, as in Table 17.1.

17.3 Role of bacterial oxygenases in the oil biodegradation Oxygenases either monooxygenases and dioxygenases play a vital role in the biodegradation and bioremediation of oil compounds especially the aromatic compounds by increasing their water solubility and their reactivity and also added one or two oxygen molecules to cleave the aromatic ring, where monooxygenase added one oxygen atoms and dioxygenases incorporate two oxygen atoms into the aromatic substrates. Oxygenases are broadly spread in nature and indispensable for the aerobic bacterial degradation of aromatic compounds by hydroxylation of the aromatic ring into cis-diols compounds using NADH or NADPH as a cofactor (Eltis and Bolin, 1996), for example, the conversion of benzene to cis
benzendihydrodiol (Fig. 17.1). Dioxygenases involved in ring cleavage (Weelink, 2008) (Fig. 17.1).

17.4 Oil-degrading fungi The hydrocarbon-degrading fungi are ubiquitously distributed in various habitats, including fresh or marine environment and the affected soil matrix. In oil-polluted areas, PAHs can be susceptible to the fungal transformation when the fungi can use the petroleum compounds for their growth and reproduction. Indigenous isolates are susceptible to the biodegradation of petroleum-contaminates sites (Das & Chandran, 2010).

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301

17.5 Marine fungi

TABLE 17.1

Bacteria degrading simple aromatic compounds in oil.

Microorganism

Substrate

Reference

Alcanivorax sp. HA03

Benzene and toluene

Hassan, Nashwa, Hefnawy, and Ahmad (2012)

Pseudomonas sp. HA10Pseudomonas sp. HA12Pseudomonas sp. HA140

BTEX

Hassan and Aly (2018)

Pseudomonas sp. HB01

Hassan, Eldein, and Rizk (2014)

Rhodococcus sp. strain HA01

Dibenzofuran

Aly, Huu, Wray, Junca, and Pieper (2008)

Pseudomonas putida F1

Benzene and toluene

Parales, Ditty, and Harwood (2000)

Ralstonia picketti PKO1Burkholderia cepaciaPseudomonas mendocina KR1P. putida PaW15P. putida F1

Benzene, toluene, and phenol

Reardon, Mosteller, and Rogers (2000)

Burkholderia sp JS150

Toluene and phenol

Rogers and Reardon (2000)

Bacillus sp

Toluene, ethylbenzene, and oxylene

Amor, Kennes, and Veiga (2001)

Ralstonia sp. strain PHS1

Toluene, ethylbenzene, o xylene, m-, and o-cresol

Lee and Lee (2001)

P. putida and Pseudomonas fluorescens

Benzene, toluene, ethylbenzene, and xylene isomers

Shim, Shin, and Yang (2002)

Paecilomyces variotii and Exophiala oligosperma

Toluene

Estevez, Veiga, and Kennes (2005)

P. putida

Phenol and 4-chlorophenol

Loh and Ranganath (2005)

Pseudomonas sp. Strain H12

Benzene, toluene, hexyl benzene, xylene and butyl benzene

Amer, Nasier, and ElHelow (2008)

P. variotii E. oligosperma

17.5 Marine fungi Marine-derived fungi are important microbial resources for mycoremediation applications. Those fungi are tolerant of saline conditions, which can be used in the degradation of PAH polluted environments, such as ocean and marine sediments. Hydrocarbon degradation using fungi from marine origin was reported by many authors (Barnes, Khodse, Lotlikar, Meena, & Damare, 2018; Vieira, Magrini, Bonugli-Santos, Rodrigues, & Sette, 2018); however, their application still poorly studied.

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Ring hydroxylating dioxygenasesv H

OH

OH

OH O2

NADH

H2O

+ NAD OH

OH

H

O2

NADH

OH

+ NAD OH

OH OH

OH

HO

ROC

OH OH HO

OH

OH

OH

OH

COOH

R

FIGURE 17.1 Initial attack on Benzene by oxygenases. Monooxygenases incorporate one atom of oxygen of O2 into the substrate and the second atom is reduced to H2O. Dioxygenases incorporate both atoms into the substrate.

From marine habitat contaminated with oil spill (Gulf of Mexico), fungal isolates were performed in the crude oil biodegradation. The isolated fungi belong to Aspergillus niger with higher activity, followed by Penicillium documbens, Cochliobolus lutanus, and Fusarium solani. A. niger recorded the highest weight loss of 8.6%, P. documbens (7.9%), and C. lutanus (4.7%), whereas Fusarium demonstrated the lowest weight loss solani strain 421502 (1.9%). Vieira et al. (2018) studied the isolation of three marine-derived basidiomycete fungi and selected Marasmiellus sp. CBMAI 1062 for Pyrene and benzo(a) pyrene (BaP) detoxification/degradation. Also, Barnes et al. (2018) reported the isolation of ten fungal isolates from select marine substrates with an ability to degrade crude oil. The mainly genera of isolates are Aspergillus with six strains, Acremonium with two strains, Fusarium, and Penicilium.

17.6 Soil fungi Soil fungi are mostly considered preferment Petroleum hydrocarbon-degrading, and their consortia with other species ensure effectiveness biodegradation in soil-remediation. Soil consists of a wide vary of fungi in phyla Chytridiomycota Ascomycota and Zygomycota. Most of them are nonligninolytic saprophytes and have excellent cellulose-decomposing capacity in nature.

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17.8 White rot fungi

303

Generally, the most frequent soil fungal strains belonged to Allescheriella, Aspergillus, Acremonium, Alternaria, Cladosporium, Beauveria, Cunninghamella, Fusarium, Engyodontium, Geomyces, Mortieralla, Microsporum, Paecilomyces, Phlebia, Penicillium, Rhizopus, Trichoderma, and Stachybotrys (Zafra, Moreno-Montan˜o, Absalo´n, & Corte´s-Espinosa, 2014). Several authors have made lists containing indigenous fungi genera that can degrade a broad spectrum of PAHs, proceeding from petroleum polluted soil. Burghal, Abu-Mejdad, and Al-Tamimi (2016) investigated the abilities of indigenous fungal flora isolated from polluted soil to degrade crude oil. In this study, four fungi species were isolated indigenously contaminated soil for crude oil biodegradation. The species fungi belong to A. niger, Candida glabrata, Candida krusei, and Saccharomyces cerevisiae. The study of Zheng and Obbard (2003) reported the performance of Penicillium sp. 06 to oxidize different structure of petroleum hydrocarbons in contaminated soils. More than 75% of fluroanthene, acenaphthene, and fluorine were oxidized using Penicillium sp. 06 after 30 days of treatment. The same fungus was able to oxidize 89% of phenanthrene presents in oily effluents from the petrochemical refining industry after 28 days of remediation.

17.7 Mycorrhizal fungi Mycorrhizae fungi have a symbiotic relationship with plant roots that have a critical role in phytoremediation by increasing nutrition and water uptake and improved tolerance to environmental stress at contaminated-sites (Małachowska-Jutsz & Kalka, 2010; Prasad, 2017). Several authors investigated the application of Mycorrhizal fungi genera in the bioremediation of petroleum-contaminated soil. Małachowska-Jutsz and Kalka (2010) investigate the efficacy of Mycorrhizal fungi associated with plant cultivation on petroleum-contaminated soil.

17.8 White rot fungi White-rot fungi (WRF) show promise for petroleum hydrocarbon remediation. These are the first to be applied in mycoremediation studies by 30% of the total researches (Singh, 2006). WRF effectively suppress lignin within lignocellulosic substrates by releasing extracellular Lignin-Modifying enzyme (LME). The enzymes present in the system employed for degrading lignin include lignin-peroxidase (LiP), manganese peroxidase (MnP), various H2O2 producing enzymes laccase (Pointing, 2001). This ligninolytic enzymatic cluster is characterized by a low substrate-specificity that can act upon several classes of pollutants with a similar structure to lignin. In previous studies, the extracellular oxidative ligninolytic enzymes of Phanerochaete chrysosporium was well studied as effective enzymatic tool of bioremediation in the removal of xenobiotic organic pollutants (Paszczynski & Crawford, 1995). Other genera of WRF (e.g., Trametes versicolor, Pleurotus ostreatus, Bjerkandera adusta, Irpex lacteus, and Lentinula edoles) are additionally recognized to degrade a wide range of petroleum hydrocarbons (Singh, 2006). Recently Li, Wang, Ni, Bao, and Zhang (2020) studied the in situ remediation of Carbofuran-Contaminated Soil by Immobilized WRF.

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17.9 Fungal enzymes in bioremediation Fungi are suited for bioremediation of crude oil in polluted sites owing to their diverse metabolic activities. They can secrete a broad range of ligninolytic and nonligninolytic enzymes to use petroleum hydrocarbons as a carbon and energy source and assimilate into fungal biomass (Peixoto, Vermelho, & Rosado, 2011). Many organic pollutants enter to fungal cell through the permeable cell membrane, where its internal enzymes break them down, for example, reductive dehalogenases (Stella et al., 2017), cytochrome P450 (Ostrem Loss & Yu, 2018), and nitroreductases (Tripathi et al., 2017), into simpler metabolites. Theses metabolites are followed by further metabolism, such as β-oxidation and entry into the tricarboxylic acid (TCA) cycle (Varjani, 2017). Van Beilen and Funhoff (2007) reported the implication of alkane oxygenases, like cytochrome 450 enzymes, integral membrane di-iron alkane hydroxylases (e.g., alkB), and membrane-bound copper-containing methane monooxygenases and soluble di-iron methane monooxygenases, in the biodegradation of petroleum hydrocarbons. Ligninolytic enzymes from WRF containing laccase (EC 1.10.3.2), manganese peroxidase (MnP, EC 1.11.1.13), and lignin peroxidase (LiP, EC 1.11.1.14) (Lee & Lee, 2001) have been investigated extensively as a biotechnological tool for spilled
oil bioremediation. This ligninolytic enzymatic system makes WRF able to completely mineralize PAHs to CO2 (Pointing, 2001). Fungal laccases are the main enzyme involved in petroleum hydrocarbons’ bioremediation (Unuofin, Okoh, & Nwodo, 2019). However, lipases have been significantly less studied on bioremediation of PAHs (Haritash & Kaushik, 2009). The research of Ugochukwu, Aghaand, and Ogbulie (2010) reported the presence of the enzyme lipase as an indicator of microbial degradation of crude oil using indigenous and exogenous soil microorganisms. Among the fungal isolates, A. niger showed the highest lipase activity of 4.00 μ/mL. Balaji, Arulazhagan, and Ebenezer (2014) investigated various fungal species’ ability to secrete extracellular enzymes, like laccase, lipase, protease, and peroxidase. Enzyme-based remediation offers several advantages over the application of microbial cells (Torres, Bustos-Jaimes, & Le Borgne, 2003). Enzymatic mycoremediation is simpler than using the whole fungi, especially in extreme environments. Furthermore, enzymes can avoid the implication of genetically modified organisms or exotics in the native surroundings (Dacco` et al., 2020). Other advantages including the enzyme specificity and efficacy can be improved and managed in the laboratory (Sutherland et al., 2004). Both whole cell competitiveness and toxic byproduct generation do not occur during enzymatic bioremediation (Setti, Lanzarini, & Pifferi, 1997). Moreover, fungi’ enzymatic system has been recorded as a biodegrader of hydrophobic or poorly soluble xenobiotics in aqueous solutions like PAHs. Enzymatic oxidation can occur in the presence of organic solvents. Thus the fungal enzymatic bioremediation can give a solution to the insolubility and the bioavailability of hydrocarbons during the cleanup bioprocess. Despite the advantages of enzymatic bioremediation, enzymes must be stable, adapted to environmental variations, and produced at less cost. All those restrict the widespread application of extracellular enzymes for oil spills remediation (Eibes, Arca-Ramos, Feijoo, Lema, & Moreira, 2015). Fungal enzymes are typically involved in the ex situ remediation of petroleum contaminants.

D. Biological processes

17.11 Bioaugmentation

305

17.10 In situ—mycoremediation Mycoremediation is considered as an environmentally biotechnological application of such species of fungi for in situ (at the area of contamination) and ex situ (on contamination removed from the original site) restoration and cleanup of Petroleum-contaminated areas (Strong & Burgess, 2008). Using fungi in the area of contamination provides the ability to implement in situ biological treatments without disturbing the native ecosystem compared to physical and chemical remediation methods (Mirdamadian, Emtiazi, Golabi, & Ghanavati, 2010). In many Petroleum hydrocarbon-contaminated sites, even though suitable native microbial populations may be available for biodegradation of organic contaminant, environmental conditions may restrict this process (Margesin, Zimmerbauer, & Schinner, 2000). In such cases, the addition of nutrients (biostimulation) of the degrading potential of intrinsic microbial populations and/or the addition of selected degrading microorganisms to contaminated soil (bioaugmentation) have been effective at enhancing hydrocarbons metabolism (Das, 2012; Chandra & Singh, 2019).

17.11 Bioaugmentation Bioaugmentation enhances the intrinsic population in the contaminated site by supplementing potential microbes to suppress pollutants (either indigenous or exogenous microorganisms). This approach is often used at high concentrations of spilled oil, where natural degrading microbes are absent or insufficient (Crawford, 2006). Indeed, hydrocarbons compounds can delay or inhibit microbial proliferation and activities, so for effective in situ biodegradation, bioaugmentation is important (Purohit, Chattopadhyay, Biswas, & Singh, 2018). Employing an indigenous microorganism consortium ensures that the organisms have a higher tolerance to the toxicity of aromatic hydrocarbon and are resistant to variations in the environment (Ezekoye, Chikere, & kpokwasili, 2018). Exogenous microbes are useful with more complex hydrocarbons structures, where the rates of intrinsic biodegradation will be the slower of hydrocarbons degradation (Barbeau, Descheˆnes, Karamanev, Comeau, & Samson, 1997). Therefore bioaugmentation approaches are necessary to enhance indigenous microbial populations’ performance several folds through the introduction of microbes with specific metabolic activities for effective in situ remediation of polluted areas (Ezekoye et al., 2018). Conventionally, the bioavailability of pollutants, the tolerance of microorganisms to environmental stress in oil-polluted areas, and their catabolic activities are essential for the bioaugmentation approaches (Heinaru et al., 2005). For instance, when bioaugmentation with the soil-isolated fungi: Penicillium funiculosum and Aspergillus sydowii strains in the hydrocarbons—polluted soil, an increase of 16% of the total petroleum hydrocarbons was reported, compared to the treatment carried out using biostimulation treatment without the addition of fungi (Mancera-Lopez et al., 2008). Accordingly, Garon, Sage, Wouessidjewe, and Seigle-Murandi (2004) reported that more than 90% of fluorene was removed after 288 h during the augmentation of a soil slurry

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system with A. Cylindrospora, while not bioaugmentated system required a longer time for removing fluorine from polluted-soil. The study of Byss, Tˇr´ıska, and Baldrian (2008) demonstrated that the bioaugmentation of creosote-contaminated soil by two fungal strains, P. ostreatus and I. lacteus newly isolated from wood-preserving plan, slightly improve the decontamination of soil. A removal rate of 67% PAHs was observed in P. ostreatus treatments, and 36% PAHS removal was observed in I. lacteus treatments during 120 days.

17.12 Fungi bacteria consortium The removal of hydrocarbons from highly polluted sites is a great challenge. Some researchers suggested the use of microbial consortia to enhance the biodegradation rates (Rodriguez-Rodriguez et al., 2014). Recent studies reported using living monofungus or mixed-fungal cultures (Ezekoye et al., 2018) and fungal-bacterial consortia (Ma et al., 2018) that could enhance biodegradation efficiency, especially on high concentrations of oil. Indeed, bioremediation of complex hydrocarbons usually requires the cooperation of more than a single species because the individual microorganism can metabolize only a limited range of hydrocarbon substrates (Al Nasrawi, 2019). Therefore the assemblages of mixed populations with overall broad enzymatic capabilities are required to bring the rate and extent of petroleum hydrocarbon degradation much faster (Zhong, Luan, Lin, Liu, & Tam, 2011). Atlas and Cerniglia (1995) suggested that although the fungi can metabolize some hydrocarbons, they do not have the enzymes required for transforming the cooxidation products. This removal value increased up to twofold with the biostimulation treatment. Still, the PHAs remotion was even 16-, 7- and eightfold times higher when bioaugmentation treatments with Rhizopus sp., P. funiculosum, and A. sydowii were applied, respectively. Although some studies showed an effective degradation in the initial phase by bioaugmentation treatment, then slow removal rates were showed over time, probably due to organisms’ competitiveness (Sabate, Vinas, & Solanas, 2004) and nutrient depletion. According to Ellegaard-Jensen et al. (2014), the inoculation with single or consortium of microbes (bacteria and/or fungi), had not shown improvements in the biodegradation efficiency in the high-level crude oil contaminated-sites.

17.13 Biostimulation Biostimulation is one of the adapted strategies in situ-remediation for increasing the petroleum hydrocarbons removal rates in contaminated areas (Garon et al., 2004). This approach consists of stimulating the growth and the activities of the intrinsic microbial population in the crude oil-contaminated—site by the amendments of nutrients such as organic biostimulants, carbon, nitrogen, and oxygen (the electron acceptor) According to Breedveld and Sparrevik (2000), inorganic nitrogen and phosphorous stimulated microbial growth and improved the PAHs degradation efficiency in creosote— contaminated soil in Norway.

D. Biological processes

17.14 Biodegradation of crude oil by fresh algae

307

For instance, the amendments of crude oil-contaminated soil by nutrients (nitrogen, phosphorus, and potassium) considerably improved the biodegradation efficiency with 62% of removal hydrocarbons compared to not amended contaminated-soil that where 47% of removal rate was recorded (Chaineau, Rougeux, Yepremian, & Oudot, 2005). In the same context, Zafra et al. (2014) studied the efficiency of the biostimulation approach using sugarcane bagasse during the remediation of PAH-contaminated soils by Trichoderma asperellum H15. The amount of phenanthrene degradation accomplished by T. asperellum was 78.3% in contaminated soils with 1,000 mg/Kg after 14 days. Alternatively, several agricultural byproducts (sugarcane bagasse, cowdung, and sawdust) are used as support and biostimulants for enhanced the bioremediation of petroleum-contaminants (Zafra et al., 2014) Also, some researchers reported that mycoremediation’s effectiveness might also be stimulated by generating an optimal balance of physical factors such as aeration, temperature, and buffering of environmental pH by altering the redox state and electrokinetics state of contaminated samples (Kuppusamy, Palanisami, Megharaj, Venkateswarlu, & Naidu, 2016). Various abiotic and biotic factors can influence the effectiveness of spilled oil decontamination, including the potential and the metabolic activities of petroleum-degrading microorganisms in the environment, competitiveness, availability, and concentration of petroleum and nutrients, salinity, and temperature, among others (Santos et al., 2011) Many studies showed the influence of the combined biostimulation-bioaugmentation approach. Biostimulation is more effective used in combination with bioaugmentation methods. While evaluating the performance of biostimulation methods compared with bioaugmentation and natural attenuation, biostimulation’s kinetic efficiency was relatively slow compared to the bioaugmentation process (Li et al., 2020). Recently, Li et al. (2020) studied carbofuran’s catabolism by the cobioaugmentation of WRF (Phlebia sp., Lenzites betulinus, and I. lacteus). Corn stover, wheat straw, peanut shells, wood chips, and corn cobs were used as biostimulants and carriers to immobilize the fungal strains

17.14 Biodegradation of crude oil by fresh algae Petroleum-degrading Achlorophyllous alga including Prototheca zopfii have been frequently studied to degrade Louisiana crude oils (Walker, Colwell, Vaituzis, & Meyer, 1975; b). Chlamydomonas sp. proved significant hydrocarbon degradation when grown in acetate without light (Jacobson & Alexander, 1981). Chlamydomonas reinhardtii can eliminate some of the iso-octane from diesel particulate exhaust (Liebe & Fock. 1992). Petroleum hydrocarbon can be faster degraded by Scenedesmus obliquus (green alga), meanwhile, n-alkanes can be better removed by Nitzschia linearis (Ibrahim & Gamila, 2004). Chlorella sp. could proficiently utilize petroleum hydrocarbons as a carbon source through mixotrophic conditions in oil field formation water (Das & Deka, 2019). The green alga Monoraphidium braunii can remove bisphenol A, and high levels of contaminations present on the surface of the water (Gattullo et al., 2012). The green algae S. obliquus and Chlorella vulgaris can grow normally in wastewater containing 40% oil products (Dogadina, Logvinenko, & Steblyuk, 1970). Uzoh et al. (2015) reported the potentiality of Closterium sp.

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in biodegrading crude oil in the oil-polluted water at location 1 of Shell Petroleum Development Company at Ukwugba village in Ohaji Egbema L.G.An of Imo State harbors. Samuel, Gerald, and Joseph (2020) investigated the bioremediation activity of C. vulgaris, which was isolated from a pond in Uwani, Enugu State. The alga utilized the following forms of oil, crude oil heavily, kerosene moderately, and petrol minimally, as demonstrated by the varying degree of turbidity produced during the growth in mineral salts—oil medium. El-Sheekh, Hamouda, and Nizam (2013) documented that C. vulgaris and S. obliquus showed a greater amount of crude oil degradation in aqueous solutions.

17.15 Effect of seaweeds (marine algae) in biodegradation Seaweeds can grow in polluted water by crude oil and hence can degrade crude oil. Marine organisms containing phytoplankton can uptake and collect several chlorinated hydrocarbons, resulting in decreased concentrations (Harding & Phillips, 1978). The green and brown seaweeds Enteromorpha and Fucus grew well on granite that is heavily contaminated by oil, and also Prophyra and Ulva were growing well in the same site (Tendron, 1968). Endocldia muricata and Gigartina cristata were grown well in the second season after coated with crude oil (Chan, 1973). Iridaea flaccida, Enteromorpha intestenalis, and Urospora penicilliformis were grown well after coating with oil (Chan, 1972). The pentachlorophenol PCB was accumulated in the macroalgae such as Fucus vesiculosus in as little as 24 h (Lauze & Hable, 2017). Marine red alga Portieria hornemannii can eliminate Trinitrotoluene from the seawater (Cruz-Uribe & Rorrer, 2006). S. obliquus was the best alga that degraded oxamyl in soil among the other tested algae (El-Ansary, Hamouda, & Ahmed-Farid, 2020).

17.16 Cyanobacteria Various studies have demonstrated the potential of cyanobacteria of oxidizing organic constituents, as Agmenellum quaduplicatum, and Oscillatoria sp. which revealed oxidizing capability naphthalene to 1-naphthol as documented by (Cerniglia, Gibson, & Van Baalen, 1980). Additional studies reviewed oxidation of biphenyl to 4-hydroxybiphenyl by Oscillatoria sp., strain JCM as well as metabolizing phenanthrene into trans-9,10-dihydroxy-9,10-dihydroxyphenanthrene and 1-methoxy-phenanthrene by A. quadruplicatum (Narro, Cerniglia, van Baalen, & Gibson, 1992). Both Cyanobacteria and eukaryotic microalgae were capable of biodegrading naphthalene to a nontoxic product (Cerniglia, Gibson, & Van Baalen, 1979; Cerniglia et al., 1980). Cyanobacteria is already present in the ocean which helps clean it and prevents the oil spill from accumulating, so cyanobacteria are economical sources for cleaning oceans (Turchyn, Scanlan, Smith, & Christopher, 2015). The pesticide tricyclazole was removed faster in soils when treated with cyanobacteria (Kumar, Abbas, & Aster, 2017). Significant growth of Skeletonema costatum, Dicrateria sp., and Phaeodactylum tricornutum was obtained when treated oil spill-polluted seawater and improved the bioremediation (Pi et al., 2015). Sanchez, Diestra, Esteve, and Mas (2005) suggested that cyanobacteria’s dominance to many polluted sites, including the polluted shores of the Arabian Gulf, could be

D. Biological processes

17.17 Algal bacteria consortium

309

accountable for the biodegradation of oil components. Ichor, Okerentugba, and Okpokwasili (2016) documented cyanobacteria’s potentiality isolated from crude oil polluted habitat, which utilizes it as carbon and energy sources. Al Hasan, Sorkhoh, Al Bader, and Radwan (1994) studied the performance of the dominant cyanobacterial pollution in the spilled crude oil from Arabian Gulf coasts. Microcoleus chthonoplastes showed the ability to degrade individual n-alkanes, whereas Phormidium coriurn growth was proportional to n-nonadecane (C19). Successful bioremediation of oil spills was achieved by Oscillatoria salina, Plectonema terebans, Aphanocapsa sp. And Synechococcus sp., which grew as mats in aquatic environments (Cohen, 2002). El-Sheekh and Hamouda (2014) reported that Streptomyces platensisand Nostoc punctiforme could grow heterotrophically in deferent crude oil concentrations and can biotransfear aliphatic compounds to aromatic compounds.

17.17 Algal bacteria consortium Numerous studies investigated that bacterial-algae consortia are more efficient in remediating petroleum hydrocarbons than single algal culture. Many studies reported that algae transfer more oxygen so as to enhance bacterial growth which effectively accelerates algal biomass (Gupta et al., 2019). Microalgae are produced O2 through the photosynthesis process required by acclimatized bacteria to biodegrade hazardous contaminants such as phenolics, organic solvents, and aromatic hydrocarbons (Mun˜oz, Guieysse, & Mattiasson, 2003). Numerous studies proved that algae
bacteria consortium can be employed to treat aromatic pollutants (Borde et al., 2003). Indigenous algae
bacteria consortium was considered as a possible biological method for eliminating total acid-extractable organics and toxicity reduction (Mahdavi, Prasad, Liu, & Ulrich, 2015). Subashchandrabose, Ramakrishnan, Megharaj, Venkateswarlu, and Naidu (2013) investigated that cyanobacteria and microalgae can degrade organic pollutants and monitor organic pollutant degradation. Macroalga, a bacterial consortium, including S. obliquus, eliminated efficient quantities of crude oil’s aromatic hydrocarbons (Tang et al., 2010). The efficient removal of phananthrene by a consortium of Chlorella sorokiniana (green alga) and Pseudomonas migulae in phototrophic conditions without an external supply of oxygen has been observed by Mun˜oz et al. (2003). Sanchez et al. (2005) reported that the cyanobacterium M. chthonoplastes lived in consortium with heterotrophic bacteria inhabited the polysaccharide sheath since Microcoleus introduced habitat and an oxygen source and organic matter. However, this consortium possesses the ability to grow in the presence of crude oil, decomposing aliphatic heterocyclic organo-sulfur compounds in addition to alkylated monocyclic and PAHs. Various prokaryotes constitute a microbial consortial relationship with other prokaryotic and eukaryotic microorganisms according to their nutrient requirements, as interpreted by Raghukumar, Vipparty, David, and Chandramohan (2001) found that marine cyanobacteria O. salina, Plectonema terebrans, and Aphanocapsa sp. possess the ability to decompose Bombay High crude oil though, about 45%
55% of crude oil. Within ten days, 5% polar compounds, 14% aromatics, 50% aliphatics, 31% waxes, and bitumin were removed in the presence of these cultures. Hamouda, Sorour, and Yeheia (2016) reported Chlorella

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kessleri, Anabaena oryzae, and its consortium can grow mixotrophically and promote crude oil biodegradation.

17.18 Factor affecting in biodegradations The interaction of the organic contaminating substance that contributed to their chemical composition and the decomposing potential of microorganisms in addition to the different environmental factors that affect activities of microorganisms as well as the absence of metabolic inhibitors which may certify some active microbial populations having the capability of utilizing these hydrocarbon environmental pollutants (Chikere & Ekwuabu, 2014). The oil biodegradation process proficiency may be controlled by many aspects such as nutrient concentration, oxygen, substrates, environment sensitivity, and the richness of oil-degrading microorganisms themselves (Rodriguez-Blanco, Antoine, Pelletier, Delille, & Ghiglione, 2010). And also, temperature, pH, bioavailability, and toxicity of end-products, the temperature has a substantial effect on the in situ microorganisms’ ability to degrade PAHS in the most contaminated site (Bamforth & Singleton, 2005). The degradation of PAHS was increased by increasing temperature (Margesin & Schinner, 2001). Also, pH can influence biodegradation of PAHS in situ, Burkholderia cocovenenas isolated from a petroleum-contaminated soil can degrade Phenanthrene in liquid culture at pH 5.5 (Wong, Lai, Wan, Ma, & Fang, 2002). Biostimulation, by adding nitrogen, phosphorus, and surfactants, bioaugmentation by adding microorganisms, have been employed to develop and promote bioremediation efficiency (Al-Mailem, Sorkhoh, Salamah, Eliyas, & Radwan, 2010). The specific growth rate of C. vulgaris BS1 increased with an increase in inoculums concentration when inoculated in oil field formation water (Das & Deka, 2019). EL-Sheekh, El-Naggar, Osman, and Haider (2000) demonstrated that the low concentrations of crude oil motivated the growth, protein, and nucleic acids; however, the higher concentrations reduced the growth and protein content of two Chlorella species. The results of (Talebi et al., 2016) clear that after 25 days of incubation Dunaliella salina in different dilutions of oil field produced water and seawater as 1:1, 1:2, 1:3 and seawater (control), the biomasses increase with increasing oil field, and also the same results were obtained by Nocardiopsis salina CCMP 1776 when cultivated in the oil field (Graham, Dean, & Yoshida, 2017). The nutrients and dissolved organic compounds influence marine microalgae and marine ecosystems’ growth (Subashchandrabose et al., 2013). Wang et al. (2020) investigated the influence of exogenous nitrogen supplementation on the cyanobacterial abundance in oil-polluted sediments in a microcosm study, the outbreak of cyanobacterial blooms in the oil-contaminated group amended by nitrogen was significantly delayed compared with that group without nitrogen supplementation. The Pollution by petroleum hydrocarbons emphasizes the requirement for environmental decontamination by effective clean-up of the polluted-sites. Physic-chemical techniques had been extensive used to eliminate hydrocarbons from oil-contaminated sites (soil or water) such as air stripping, chemical precipitation, oxidation
reduction, and electrochemical treatments, all of physicochemical techniques are not completely effective, costly

D. Biological processes

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which makes them nearly abandoned and with limited prospects. Bioremediation by living or dry organisms has become a promising biological treatment for restoring petroleum contaminated areas. It has been established as one of the efficient, economic, versatile, and environmentally ecofriendly.

17.19 Summary Large numbers of living organisms such as bacteria, fungi, and algae had been used for metabolic breakdown of hydrocarbon and organic contaminants. Generally, microorganisms are selected on the basis of their metabolic diversity and performance to remove or reduce contaminant levels. Microorganisms are extensively used for degradation of pollutants, but there are limiting factors that affect biodegradation processes such as concentrations of pollutants, low temperature, concentrations of nutrients, and these factors had negative effects on the degradation processes by microorganisms. A biodegradation can be efficient only where the natural conditions permit microbial growth and results in the pollutants degrade. Biodegradation has been used in different contaminated areas with various degrees of success. Further studies are needed on biodegradation in situ by different microorganism’s bacteria, fungi, algae, and its consortium, and discover new strains that adapt to natural conditions and able to degrade contaminants in situ.

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228. Yamada, K., Mukumoto, H., Katsuyama, Y., & Tani, Y. (2002). Degradation of long-chain alkanes by a polyethylene-degrading fungus, Penicillium simplicissimum YK. Enzyme and Microbial Technology, 30, 828
831. ´ . E., & Corte´s-Espinosa, D. V. (2014). Degradation of polycyclic aroZafra, G., Moreno-Montan˜o, A., Absalo´n, A matic hydrocarbons in soil by a tolerant strain of Trichoderma asperellum. Environmental Science and Pollution Research, 22, 1034
1042. Zheng, Z., & Obbard, J. P. (2003). Oxidation of polycyclic aromatic hydrocarbons by fungal isolates from an oil contaminated refinery soil. Environmental Science and Pollution Research, 10(3), 173
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C H A P T E R

18 Metagenomics—an approach for selection of oil degrading microbes and its application in remediation of oil pollution Md Azizur Rahman1, Aakanksha Rajput2, Anand Prakash2 and Vijayaraghavan M. Chariar3 1

University Institute of Engineering, Department of Biotechnology Engineering and Food Technology, Chandigarh University, Ludhiana, India 2Department of Bioscience and Biotechnology, Banasthali Vidyapith, Banasthali, India 3Centre for Rural Development and Technology, Indian Institute of Technology-Delhi, New Delhi, India

O U T L I N E 18.1 Introduction

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18.2 Microbes associated with degradation of oil 320 18.3 Metagenomics in oil degradation 18.3.1 Sampling 18.3.2 Isolation of genome 18.3.3 Modeling 16S rRNA and 18S rRNA 18.3.4 Amplification by polymerase chain reaction technique

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00003-3

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18.3.5 Sequencing 18.3.6 Phylogenetics

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18.4 Application

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18.5 Metagenomics challenges

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18.6 Conclusion

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References

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18.1 Introduction Energy resources are subjected to nonrenewable resources that are finite. Regular usage and dependency on them causes rapid decrease in their presence. Furthermore, an increase in the human population demands a great amount of energy consumption. Development of any national economy is highly influenced by crude oil and uneven distribution of oil and allied products creates huge differences in oil availability. The crude oil demand influences the transport of several metric liter of oil to the consumer countries via different modes of transportation. Inappropriate industrial and domestic use of oil, crude oil spill incidents, oil degradation issues, and many natural and anthropogenic causes magnify oil contamination and oil pollution in environment. A major portion (about 13%) of oil spills is due to transportation of oil (Chen et al., 2019). The release of untreated commercial and domestic oil in ground, water and air become risk to marine and human life (Rathi & Yadav, 2019). Nowadays much attention is paid to these issues, as its adverse effect influenced nature. Extant crude oil reservoirs affect more than 600 million humans and possibly influence environment and health (Johnston, Lim, & Roh, 2019). Various techniques, methods, and treatments are used to overcome the incidents caused by oil spillage and associated pollution. Oil booms and oil skimmer (as mechanical approaches), use of surface collecting and surface washing agents (as chemical approaches), and bioremediation (as biological approaches) are used as promising tools. (Safiyanu, Isah, Abubakar, & Rita Singh, 2015). Among all these approaches biological techniques are the most effectual as nature has the tremendous properties to heal itself. Existing microorganisms and enzymes have great potentiality to remove or degrade the pollutants. Various anaerobic and aerobic bacterial materials degrade oil contaminants naturally. For the efficiency enhancement, pathway modification and better outcomes of these bacterial resources, metagenomics is a very relevant, effective, and a fruitful tool. Through metagenomics, microorganisms are directly extracted from their original domain, cloned and modified for better results, as this approach not only help to make an account of known microbes but also give us specific knowledge about the unknown microbes. The metagenomics approach conquers the existing hurdle in evolution of diversity, proper procedure is developed, that capture undiscovered microbial diversity. For the detection of unique biocatalysts new screening approaches have been drafted which choose to select particular functional genes within metagenomic libraries. For proper understanding of entire gene or operon clusters, numerous vectors containing fosmid, bacterial artificial chromosomes, and cosmid are developed. For better and advance approaches of microbial diversity bioinformatics tools and databases are adjoined (Singh et al., 2009).

18.2 Microbes associated with degradation of oil Microbes with enormous potential to degrade the oil are used as a potent cleanup tool in the elimination of hydrocarbon contaminants from nature (Hazaimeh, Abd Mutalib, Abdullah, Kee, & Surif, 2014). The microbial process used for clean up or curing the nature is broadly placed under bioremediation. Bioremediation is defined as a natural therapy for healing the nature. The native microorganisms and enzymes neutralize or degrade hazardous pollutants

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into less toxic forms (Xu et al., 2018). The microbial degradation process is a very appropriate, appealing, easeful and economical approach for hydrocarbon degradation. This approach is not a new notion; it was traceable since the 1940s. Though in the past environmental microorganism resolve this issue, but by the passing time contamination issue become very serious and complicated for the nature to take care of it. In the recent past efficient microbes and enzyme have been discovered by the biologist and ecologist that have great potential for degradation of oil and its allied. To name a few, Aeromonas, Arthrobacter, Aspergillus, Atinetobacter, Bacilli, Beijerinckia, Brevibacterium, Burkholderia, Candida, Chrobacteria, Corynebacteri, Cyanobacteria, Flavobacteria, Fusarium, Gordonia, Mucor, Moraxella, Modococci, Mycobactena, Nocardia, Penicillium, Pseudomonas, Rhodotorula, Sporobolomyces, Streptomyces are some examples of common species that perform degradation under diverse environmental conditions (Tanzadeh & Ghasemi, 2016). For the degradation of complex hydrocarbons microbial consortium has been advocated to be more suitable than individual species as hazardous compounds cannot be converted into end product (i.e CO2 and H2O) by the single microorganism. The development of microbial consortia had proved to surpass the limitations of single microbial application. Microbial consortia were developed with multiple microbial species working in synergistic manner for efficient degradation of contaminants (Poddar, Sarkar, & Sarkar, 2019). Microbial consortia are developed by combining either various bacterial species together or a cocktail of bacteria with fungus or algae. Microorganisms that show more growth were used in the construction of hydrocarbon degraders. For construction of consortia, efficiency of two or more different bacteria or bacteria with algal and fugal was analyzed and assure for their abilities of degradation. A consortium made by comprising various microbes such as Bacillus sp., Corynebacterium sp., Flavobacterium sp., Micrococcus sp. and Pseuudomonas sp. proved to be more efficient (up to 78%) in degradation of crude oil with compared to single isolates, which had 41%
66% degradation rate (Hamzah, Phan, Abu Bakar, & Wong, 2013). An efficacious mixed consortium of fungal and bacteria showed high efficiency rate to degrade polycyclic aromatic hydrocarbon (PAH) contamination in soils. These microbial consortiums contain five native bacterial strains: Bacillus cereus, Klebsiella pneumoniae, Klebsiella sp., Pseudomonas aeruginosa, Stenotrophomonas maltophilia and four fungal strains: Aspergillus flavus, Aspergillus nomius, Trichoderma asperellum, Rhizomucor variabilis (Zafra, Taylor, Absalo´n, & Corte´s-Espinosa, 2016).

18.3 Metagenomics in oil degradation Diverse nature replete with influential microorganism, some of them have been acknowledged for oil degradation and many more remain to be recognized. The undiscovered or complex microbes which had not been reported in laboratory culture could also influence the degradation (Singh et al., 2009). Metagenomics, a recent tool, had been developed for the discovery of unrevealed, mysterious, novel, and more effectual microbial communities. The tool adds on as evolutionary technique for bioremediation for the elimination of oil pollutants and hazardous hydrocarbons from the water and soil. Through metagenomics nonfamiliar microorganism had been identified and their efficiency accelerated by alteration and modification in metabolic pathways of microbes. For the cleanup treatments of oil contaminants and pollutants in water and soil various case studies

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elucidate that metagenomic applications are extensively used (Devarapalli & Kumavath, 2015). Variety of biograders was traced by this novel approach which decomposed hydrocarbons in reservoirs of petroleum (Sierra-Garcia et al., 2014). Through the latest format of metagenomics, it can be possible to have wide perspective of complex pathways correspondence to hydrocarbons degradation and surfactant production (Oliveira et al., 2017). This appealing approach is followed in a chronological order in which initially sample is isolated collectively, then DNA is obtained from selective community of microorganism, followed by sequencing of gene is done and further analyzed by comparing with sequences available in the gene libraries (Jurkowski, Reid, & Labov, 2007). On completion of entire process a proficient metagenomic libraries is constructed and many unknown sequences are retrieved from the environment (Panigrahi, Velraj, & Rao, 2019) (Fig. 18.1).

18.3.1 Sampling Sampling is the first and very deciding step in metagenomics process unlike the other protocol where specific culturable specimens are isolated, in this process sampling of bulk communities is isolated. The nucleic acids in microbial community form the basic unit of reference as it further leads to the identification of species which are present in the sample and its relationship with other microbes of the collected sample. Extracted DNA samples contains whole genome of all possible microbial cells present in the sample material (Thomas, Gilbert, & Meyer, 2012). Major precautions should be given to the isolated samples as they are the main sources of the process, viability of the cell is main focal point. Different depths of the sites are suggested to isolate the samples. Furthermore they are recommend to freeze

FIGURE 18.1

Basic schematic representation of metagenomic process in oil degradation.

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immediately at 280 C after collection, and temperature can be increased up to 220 C. Freezing prevent changes in the communities of microbes until the further action perform. Sample can also be preserved for two hours at room temperature in a stabilizing buffer, but quick freezing is recommended if RNA is extracted, as RNA samples easily get denatured at room temperature. Sampling method should be selected by considering various criteria like availability, efficiency, high recovery, price range, suitability, usage, and compatibility with other methods (Me´ndez-Garcı´a, Bargiela, Martı´nez-Martı´nez, & Ferrer, 2018).

18.3.2 Isolation of genome Beside the isolation of specific DNA, whole community of genome is targeted for isolation in metagenomics aspect. Many conventional isolation methods have been followed to get highest DNA yields in an appropriate time. In first step, extraction buffer is used to disrupt the microbial cell wall for the cellular content is released in the buffer solution. Selection of the extraction buffer depends on the required quantity and purity of the DNA ´ (Felczykowska, Krajewska, Zielinska, & Ło´s, 2015). For the removal of humic contaminants, CTAB is a great option and used in buffer for SDS (Sodium dodecyl sulfate) based DNA extraction (Zhou, Bruns, & Tiedje, 1996). Proteinase enzyme is also added to extraction buffer and incubate in a controlled temperature for a particular duration.The pellet thus recovered after centrifugation contains DNA, is precipitated by adding Polyethylene glycol (Verma & Satyanarayana, 2011). Collected pallet is further washed, air dried and dissolved in TE buffer (Verma, Singh, & Sharma, 2017). Quantitative and qualitative properties of extracted metagenomic DNA are evaluated by various method such as electrophoresis, fluorometer (Guerra et al., 2018) and purity were analyzed by Nano-Drop spectrophotometer (Kimes et al., 2013). For the development and modernization of the isolation process, various procedural aspects are adapted. Numerous isolation kits and advance methods has been developed and available in the market that assure the accuracy of the extraction procedure and time saving. Some of the different isolation kits for extraction of metagenomic DNA from oil spillage sites are listed below. • Microbial DNA Isolation Kit (MoBio Laboratories) (Guerra et al., 2018) • ZR bacterial DNA mini prep extraction kit (Inqaba South Africa) (Ezekoye, Chikere, & Okpokwasili, 2018) • ZR fungal/bacterial DNA Kit (Zymo Research) (Kachienga, Jitendra, & Momba, 2018) • Nucleospin kit (Appolinario et al., 2019) • PowerMarxSoil (MoBio, Carlsbad, CA, United States) DNA isolation kit (Moreno-Ulloa et al., 2019) • Meta-G-Nome DNA isolation kit (Epicenter) (Sierra-Garcia et al., 2020) • FastDNA Spin Kit for Soil (MP Biomedicals, LLC, Irvine, CA, United States) (Viggor et al., 2020) • DNeasy Power Soil Kit (Qiagen, Hilden, Germany) (Pacwa-Płociniczak, Biniecka, Bondarczuk, & Piotrowska-Seget, 2020) • Power soil DNA extraction kit (Qiagen) (Auti, Narwade, Deshpande, & Dhotre, 2019) • UltraClean MegaPrep (MoBio Laboratories, Inc.) (Me´ndez-Garcı´a et al., 2018) • G’NOME DNA Extraction Kit (BIO101) (Me´ndez-Garcı´a et al., 2018)

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18.3.3 Modeling 16S rRNA and 18S rRNA Extracted samples contain massive category of genomics DNA of organisms, grouping of organism DNA is done on the basis of kingdom with 16S rRNA & 18S rRNA sequencing method. Specific primers are designed for disclosure of gene (primer: small single-stranded DNA sequence found in two forms- Forward primer [F] for initiation and Reversed primer [R] for expulsion). 18S gene primers covered a wide range detection of eukaryotic cells while 16S covered prokaryotic cells (Wang, Tian, Gao, Bougouffa, & Qian, 2014). Designing of primer is influenced by the amplification of gene of interest. 16S rRNA gene found in bacterial sources can be analyzed by using various hypervariable regions like V1/V3 or V3/V5 or V4 regions and amplified by commonly used bacterial primers like 515F & 806R (Mason et al., 2014) and universal primer 530R (50 -CCGCGGCKGCTGGCAC-30 ) and E8F (50 -AGAGTTTGATCMTGGCTCAG-30 ). For targeted level analysis 338R (50 -TGCTGCCTCCCGTAGGAGT-30 ) and 27F (50 -AGAGTTTGATCCTGGCTCAG-30 ) primers are recommended (Me´ndez-Garcı´a et al., 2018). For 18S rRNA gene analysis universal reverse primers 50 -TGATCCTTCYGCAGGTTCAC-30 or 50 CTGGTTGATCCTGCCAG-30 and forward primer 50 -GACGGGCGGTGTGTACA-30 are used (Kachienga et al., 2018). Some commercial kits are also used for taxonomic analysis of 16S rRNA & 18S rRNA genes like Ion 16S Metagenomics Kit (A26216; manual: MAN0010799, TermoFisher) (Moreno-Ulloa, et al., 2019), Nextera XT DNA Sample Preparation Kit (Illumina, San Diego, CA, United States) (Appolinario et al., 2019), DYEnamic ET Terminator Cycle Sequencing Kit (GE Healthcare) (Paixa˜o et al., 2010). Selected genome and engineered primer further used in PCR for amplification.

18.3.4 Amplification by polymerase chain reaction technique Combination of specific DNA and primer further proceed to amplification DNA template. PCR is considered desirable technique for the amplification. Various model of PCR are manufactured for the particular or preferable outcome, out of which Real-Time PCR (Yergeau, Sanschagrin, Beaumier, & Greer, 2012) is the most acceptable category in the case of hydrocarbons. In Real time PCR, SYBR green fluorescent dye is used for bacterial quantification of gene copies in QuantStudio 5 real-time PCR (Thermo-Fisher, USA) (Roy et al., 2018). PCR is conducted with the proper arrangement of temperature and time duration of Annealing, Denaturation and Extension followed by particular number of cycles (Kohno, Sugimoto, Sei, & Mori, 2002). Reaction carries both forward and reverse primer in master mix (blend of reaction buffer, Taq DNA polymerase, dNTP (Deoxynucleoside triphosphates) and MgCl2) with DNA template and nuclease free water through a tailored program. Later on quality of PCR product is checked by agarose gel (An et al., 2013).

18.3.5 Sequencing The PCR product is subjected to decoding of DNA nucleotide through sequencing techniques that are switched according to the modification of process. Over the past decade advancement in sequencing had moved to Next generation sequencing from traditional Sanger sequencing method (Thomas et al., 2012) for the achievement of more sequenced base pairs. Through the sequencing process libraries are generated via cloned nucleotides

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and vectors. Length of base pairs is considerable tool to analysis of quality, minimal length of base pairs approx. 200
250 is the indication of high quality. Miscellaneous techniques and computational tool are utilized for trimming or filtering of the sequence, assemble the sequence for the validation, analysis of assembled sequence and genome, comparison of genome sequences, detection of GC content regions, establishment of Phylogenetic trees and database submission. Basic Local Alignment Search Tool (BLAST) is applied for recognition of the novel and oriented organisms (Kimes et al., 2013) (Table 18.1). 18.3.5.1 Trimming or filtering In the generated sequences both high- and low-quality base pairs are incorporated, so that trimming and filtration is applied to low quality parameter genome. Fastx toolkit trimmer is used for the trimming of k-mer contaminants and heterogeneous GC-content areas. Metagenomes having less than 100 sequences are discarded from the final sequence. Now appropriate sequences will be assembled and validated by different software (Mason et al., 2012). 18.3.5.1.1 Sequence assembly and validation of assembled sequence

After going through process of trimming/filtering, nucleotides are managed and further processed to validation. For base calling, vector sequence removal from sequences and quality management BioMake software is used. PHRAP assembly tool is applied for sequence assembly; genome sequence finishing is performed by CONSED/AUTOFINISH software. Validation of assembled sequence is carried out by BACCardI tool in which mapping of sequences is done onto the genome sequence. 18.3.5.2 Analysis of assembled sequence and genome Having the assembled sequence, process moves towards analysis of observed sequence/genome. Annotation system GenDB40 is utilized for selection and annotation of genome. GLIMMER and CRITICA help in gene prediction. For each predicted gene various database along with InterPro, KEGG, Pfam, SWISS-PROT, TIGRFAM, and TrEMBL is used for automatic annotation that performed before the manual annotation. Eventually by COG (Clusters of Orthologous Groups) number every gene is practically classified (Schneiker et al., 2006). 18.3.5.2.1 Alignment

Further two steps of alignment are setup for quality evaluation, which is performed parallel one, is domain-based database against BioSurfDB and another is generic sequence database against the RefSeq. At this platform some specific conditions are preliminary considered: 18.3.5.2.2 RefSeq

RefSeq is surplus database that incorporate sequences from numerous sources, such as complete set of nonredundant protein sequences can be downloaded. Program LAST is performed for alignment of designate sequence as it align speedy repeat-rich datasets than traditional approach BLAST and also very much appropriate data size issues. In RefSeq database metagenome that are aligned use the default parameters for the LAST aligner.

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TABLE 18.1 Detailing of various sequencing techniques. Sr. no

Sequencing technique

01

Description

References

Next-generation sequencing technologies

NSG also known as high-throughput sequencing which cover the sequencing range from singlegene targeted sequencing to whole-genome sequencing and also effective for analysis of degradation, wastewater quality, diffusion of pathogens and to detoxify the environmental pollutants.

Kim et al. (2013)

02

Illumina sequencing

Also known as DNA sequencing, used to determine base pairs series in DNA, methylation profiling, sRNA discovery, region and whole genome sequencing. Method involved reversible dye-terminators by which multiple strands are sequenced at once that enhance sequence. More over this method only uses DNA polymerase instead of expensive and multiple enzymes.

Deng et al. (2016), Hong et al. (2017), Ma et al. (2015), Wang et al. (2013)

03

Pyrosequencing

Pyrosequencing rely on luminometric detection of Fakruddin, Chowdhury, Hossain, pyrophosphate (released by primer-directed Mannan, and Mazumda (2012), DNA polymerase catalyzed nucleotide Peng, Zi, and Wang (2015, 2014) incorporation) and suitable for DNA sequencing up to 100 bases and elaborate depiction of nucleic acids. This technique has fringe benefit like flexibility, accuracy, automated functioning and parallel processing. Even more it do not required gel electrophoresis and labeled nucleotides and primers.

04

SOLiD sequencing

SOLiD sequencing show high speed and accuracy Rosselli et al. (2016) and is the only platform that use ligation-based sequencing relies on probe recognition method.

05

Ion torrent semiconductor sequencing

In this technique DNA sequencing is done by detection of hydrogen ions (released during the polymerization of DNA). Successfully applicable in bacterial community characterization, filamentous bacterial communities in wastewater treatment systems and microbial communities in nitrifying activated sludge.

Cao, Lou, Huang, and Lee (2016), Gwin, Lefevre, Alito, and Gunsch (2018), Salipante et al. (2014)

06

Nanopore sequencing

This technology include significant advantages of nanopores include low material need, high throughput and ultra-long reads. No need of chemical labeling and PCR amplification is required for sequencing of single molecule of RNA or DNA. Electrophoresis is used to transport unknown sample via an orifice, also applied for characterization of carbapenemaseencoding plasmids isolated from wastewater treatment plant.

Feng, Zhang, Ying, Wang, and Du (2015), Ludden et al. (2017), Xia et al. (2017)

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MEGAN (version5) followed by RefSeq and KEGG maps databases is used for functional and taxonomic Binning (Tatusova, Ciufo, Fedorov, O’Neill, & Tolstoy, 2014). Use of RefSeq in taxonomic analysis: Clusters which have been formed by water or terrestrial metagenomes are arranged by RefSef on the basis of earlier studies that provide their influencing factor. If metagenomes have alike biotic and abiotic conditions (such as temperature, sunlight, redox and osmotic potential and oxygen level) to previous available metagenomes then the supply of nutrients and pH should be similar. 18.3.5.2.3 BioSurfDB

BioSurfDB is an informative system in bioremediation field, with a focal point on biosurfactant and biodegradation production organisms. It contain tools that helps in alignment of metagenomes against a number of protein sequences, total 46 sample of each metagenome can be uploaded to the BLASTx tool and BioSurfDB system. From different pathways approximately 3956 protein sequences are in the BioSurfDB database. This system automatically performs functional and taxonomic binning, but taxonomic prediction may be biased as BioSurfDB is a domain specific database. Use of BioSurfDB in functional analysis: By the help of BioSurfDB, genes that followed pathway of hydrocarbon degradation accompanying gene involved in biosurfactant synthesis are analyzed. One of the main causes is miscibility effect of biosurfactant on hydrophobic material that favored biodegradation. 18.3.5.3 Comparison of genome sequences After the alignment of resultant sequences, comparison of chromosomal sequences is done with the available sequences in GenDB. This availability is generated by previous cluster analysis. 18.3.5.3.1 Cluster analysis

By the RefSeq and BioSurfDB analysis all the alignment are obtained from metagenomes and uploaded to MEGAN to evaluate Principal Coordinates Analysis and UPGMA trees. The computational metagenomics tools involves metabolic pathways, scripts to cross the BLASTx results, database tree and proteins. For normalization these tables are uploaded to Genesis, followed by the calculation of hierarchical clustering for both metagenomes and pathways. 18.3.5.4 Detection of GC content regions From yeast to humans in various organisms high percentage of meiotic recombination is correlated with GC richness and also some mismatches like A-C, A-G, T-C or T-G are fixed by a G-C pair formation. High GC genes also have significantly increased meiotic and mitotic recombination rates (Kiktev, Sheng, Lobachev, & Petes, 2018). Sliding window is the tool for the detection of genomic regions with unusual GC content. Usually 2000 base pair window size and 1000 base pair step size is used for the purpose (Oliveira et al., 2017). GC content parameter is an important influencer to genome evolution.

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18.3.5.5 Phylogenetic trees establishment Among the various taxa evolutionary relationships are diagrammatically represented via Phylogenetic trees establishment. By BLAST analysis homologs are identified and ClustalX 1.83 tool (Thompson, Gibson, Plewniak, Jeanmougin, & Higgins, 1997) is used in rooted neighbor joining phylogenetic trees construction. Furthermore visualization is done by TreeExplorer software MEGA package49 (Kumar, Tamura, Jakobsen, & Nei, 2001). 18.3.5.6 Submission of database Results are assembled in a metadata file and uploaded to STAMP to determine correlation between the production and hydrocarbon degradation by performing the statistical tests between metagenomes to Graphpad Prism (Schneiker et al., 2006). Now the evaluated results are submitted to GenBank under a particular accession number, which is used for analysis and comparison of undiscovered genome.

18.3.6 Phylogenetics Phylogenetic assignment is a very important step in metagenomic analysis to introduce functional properties of uncharacterized microorganisms that are encrypted by the DNA fragments to the phylogeny (Sierra-Garcia et al., 2014). Phylogenies reflects the progressive journey of species development by flow of time and phylogenetics is the study of that phenomenon. Phylogenetics covers comparative genomic study ranging from ancient time to current time. The evolutionary relationship displays via a branching or treelike representation (i.e. phylogenetic tree). Construction of Phylogenetic tree is done by neighbor joining method and Jukes & Cantor Model is used to calculate the distance matrixes for single nucleotide substitution (Chikere, Surridge, Cloete, & Okpokwasili, 2011). Phylogenetic tree is composed of nodes and branches, one branch can only connected to two nodes and outer nodes show the leave or the operational taxonomic units (Fig. 18.2). Innumerable computational tools are proposed for the formation and analysis of phylogenetic tree such as: by using Phylo F3 software 16S rRNA bacterial gene sequences observed from NCBI database (Olukunle, 2019) and Phylogenetic inference sister taxa

Branch Internal node

sister taxa

Root Internal node

FIGURE 18.2

OUTs/ Leaves: - Can be populaon, genes, species, protein sequences

Outgroup

Basic schematic representation of phylogenetic tree formation.

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package is used to determine the phylogenetic relationships of sequences observed from dominant Denaturing gradient gel electrophoresis bands. The PhyloPythia software used for the observation of all metagenomic clones. Further by using BLAST, analyzed data will be compared with the available data in the Gen-Bank database that is available at http://www.ncbi.nlm.nih.gov/blast/ (Kubota, Koma, Matsumiya, Chung, & Kubo, 2008).

18.4 Application In ecological matrix, metagenomics is an approachable, effective, and beneficial tool to observe and explain the configuration and dynamics of microorganisms. It also plays a wonderful role to capture potent microbial degrader and modify detoxification and degradation properties toward the inorganic and organic contaminates at polluted sites by altering their metabolic pathways (Zwolinski, 2007). With respect to this many effective, promising, and novel microbial community can be recognized and preserved for the future perspective. Numerous environmental microorganisms have effective whole genome sequences availability which is relevant to explain the gene pool of enzymes that are participants in anthropogenic pollutants degradation (Galva˜o, Mohn, & de Lorenzo, 2005). Metagenomics is an efficacious practice to overcome the complications of cultivation-dependent research, as isolation of nucleic acids is done directly from environmental samples (Desai, Pathak, & Madamwar, 2010). Newly, DNA microarrays are applied for monitoring the novel population of microorganism and utilize their potency in bioremediation (Bae & Park, 2006). A large number of researches are successfully reported and recorded to the data base that reveals various novel microbial category and metabolic pathways. Some of these resultant novel microorganisms and their application are given below: Metagenomics has paved the way to new age classification and application of microbes for anthropogenic pollutant degradation. In a research Kim et al. (2006) used integrated approach rely on cleavable isotope-coded affinity tag analysis, to recognize and investigate catabolic pathways in Pseudomonas putida KT. For the advancement and modification of technologies researchers foreground by introducing new approach like “metabolomics” beyond the available approaches such as proteomics, genomics, and transcriptomics. A lot of studies and researches recently used metabolome analysis in the biodegradation of anthropogenic pollutants. The microbial communities which are utilized to enhance biological phosphate removing efficiency by Candidatus Accsumulibacter phosphatis (a dominant polyphosphate accumulating organism) was decoded by Martı´n et al. (2006) via generating the metagenomic libraries, they also construe metabolic and ecological activities of these microbial communities. Metatranscriptomics/Transcriptomic approaches are preferable to observe functional understating of environmental microbial communities activities by examining their mRNA transcriptional status. By implementing transcriptomics research on a cis-dichloroethene (cDCE) strain Jennings et al. (2009) identify the category of genes that are updated by cis-dichloroethene through DNA microarrays. When microorganisms contact with anthropogenic pollutants,

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the identification of proteins (present in microorganisms) that are involved in physiological response are completed by proteomics-depended investigations and also are used to determine composition alteration and richness of proteins. A study is explained by Keum, Seo, Li, and Kim (2008) which disclose the comparative metabolome observation of Sinorhizobium sp. through the phenanthrene degradation. Tang et al. (2009) work on Shewanella sp. which possesses cometabolic pathways for bioremediation or degradation of halogenated organic compounds, toxic metals and radionuclides.

18.5 Metagenomics challenges Besides the incredible response of metagenomics in hydrocarbon degradation, technique also retain some gaps that should be traced and fixed rapidly, so that modified techniques give required outcomes to resolve the issues. Since the metagenomics techniques fall in environmental domain which also has a bundle of limitations such as: Selectivity: Nature is excessively embedded by the variety of microbial population that have different functionality toward the different aims (Aislabie, Balks, Foght, & Waterhouse, 2004), but it is a challenge for researchers to screen out the desired microorganism that can give right directions and results so that screening techniques required more advancement and modification (Ghosal, Ghosh, Dutta, & Ahn, 2016). Time duration: Technique in Metagenomics is aiming towards the novel species so no previous information is available in most cases which lead to more time consumption in every step for verification. Cost: Various software and data tools are needed to includes new organism category and their pathways. This needs sufficient funding and expertise brain. Till now, the issues of the occupancy of unlike coverage over species, very alike sequences and constant sequences due to horizontal gene transfer, are still to be resolved through dedicated software (Bharti & Grimm, 2021). Manpower engagement: For implementing the metagenomics studies, new design, collection and observation of metadata and conversion of data into appropriate information required skilled and experience statistician and bioinformatician which makes it more complex and highly specialized field. Moreover, many specialized members are needed for performing specific steps in the whole metagenomic analysis (Handelsman, 2004). Result failures: The procedure has many sections to reach the final result and generate the libraries, so the failure of any step spoils the entire process. Other Challenge is to verify the mechanism of correct gathering as subsequent downstream observation will hang on its result (Pandey & Singhal, 2021). In conclusion, at present time metagenomics is most remarkable, structured and relevant approach for hydrocarbon degradation and is proving to be the most preferred method for researchers to introduce novel species category and pathways but it called for some addition and deletion for the betterment of method (Alves et al., 2018). Current metagenomics challenges decode by addressing two main tools: 1. Growth of novel bioinformatics tools 2. Creation of novel molecular tools

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18.6 Conclusion Every year a heavy load of hydrocarbons (as an alarming pollutant) are exposed to the environment due to various anthropogenic activities such as incomplete combustion of fossil fuels, petroleum spills, and by industrial waste (Jacques, Bento, & de Oliveira Camargo, 2007) and many more; for the cleanup of this troublesome mess researchers have turned to nature. As some microorganisms present in nature involve in hydrocarbon degradation through the various reactions, for discovery of such reactions, pathways, unknown microorganism and display their availability records metagenomics is a perfect platform (Nazir, 2016). By using metagenomic approach effective category of gene and their metabolic pathways are captured that associated in phenol and other aromatic compounds degradation of sludge sample that are collected from a petroleum refinery wastewater treatment system (Silva et al., 2013). Although the ratio of oil contaminated water and degradation rate is very imbalanced as anthropogenic activities pointing towards the environment safety, so there is an emergency requirement of a combine action that is control the contamination action and speedy modification to discover microbial degraders and improve the pathways.

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C H A P T E R

19 Potentiality of enzymes as a green tool in degradation of petroleum hydrocarbons Uttarini Pathak, Aastha Jhunjhunwala, Sneha Singh, Neel Bajaj and Tamal Mandal Department of Chemical Engineering, National Institute of Technology Durgapur, Durgapur, India O U T L I N E 19.1 Introduction

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19.2 Role of bacteria in enzymatic degradation of petroleum hydrocarbons

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19.3 Role of algae in enzymatic degradation of petroleum hydrocarbons 343

19.5 Feasibility and technical applicability of enzymes in oil clean up 346 19.6 Conclusion

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19.4 Role of fungi in enzymatic degradation of petroleum hydrocarbons 344

19.1 Introduction Petroleum and its products are in huge demand currently. The availability of oil in only some countries has enabled them to monopolize the oil industry thereby making oil a costly and much in demand commodity. In today’s industrialized world most of the activities are heavily dependent on oil and hence the occasional oil spill and effluents are a major concern. The seepage of these components in soil leads to both water and soil pollution (Holliger et al., 1997) Contamination of the soil by these activities leads to the

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infiltration of these pollutants into plants and animals which may lead to death or mutation of the species (Alvarez & Vogel, 1991). The traditional method of cleansing the soil is costly, ineffective, and harder to carry out on large areas all at once, hence washing, evaporation, and mechanical methods are discarded. Bioremediation is the usage of microorganisms to eliminate the pollutants attributing to their specific structural metabolism and is a promising arena for the degeneration of various pollutants affecting the environment and the components and effluents released from petroleum drills as well. Bioremediation consists of various biochemical reactions, involving all biotic and abiotic natural bioattenuation processes to deflate the contamination levels. It is a good alternative as well as the primary mechanism for reducing biodegradable toxicants and with a favored economic effectiveness. But it is a slow mechanism where its kinetics are subjected to factors like salinity, microbial diversity, temperature, etc. However, a wide variety of petroleum hydrocarbon remediating strains and their enzymatic metabolic pathways encourages the biodegradation approach. The occurrence of bioremediation takes place by the following ways: 1. Naturally 2. Bioaugmentation (whole cell introduction) 3. Biostimulation (utilization of nutrients for stimulation of the native microbial community) Also, usage of microorganisms is nonthreatening and cost-effective (April, Foght, & Currah, 2000). Hence bioremediation can be seen as a promising avenue that will mitigate the problems the petroleum industry poses with its ecofriendly and effective outcomes (Ulrici, 2000). During the infamous Exxon Valdez oil spill in 1989 (Atlas & Bartha, 1998) located in the Gulf of Alaska, bioremediation came as a breakthrough as its use to clean up the oil spill was successful which leaded to people’s interests in this arena that could open up more greener avenues and search for bioremediation technologies increased. Many of the present studies have focused on understanding the parameters affecting oil bioremediation and favored tests through laboratory studies (Mearns, 1997). In the peerreviewed literature only a limited number of field trials are believed to yield promising results for bioremediation technology (Prince, 1993; Swannell, Lee, & Mcdonagh, 1996; Venosa, Suidan, & Suidan, 1996; Venosa et al. 2002). The avenue for current application of bioremediation is specifically bounded by a fact that majority of the research focuses on large scale oil spills. Aerobic degradation is a faster metabolic process with the advantage of having oxygen availability, the latter acting as an electron acceptor. Oxidation of saturated aliphatic hydrocarbon gives acetyl-CoA as the final product which is further catabolized during citric acid cycle producing electrons as a result in the electron transport chain. The repetition of the chain leads to formation of CO2 as the final product. Aromatic hydrocarbons like benzene, napthalene are also degraded under aerobic conditions. Here the first product formed by degradation is catechol, which is further degraded to CO2 by being introduced in citric acid cycle. Since it has been mentioned earlier that aerobic degradation is a faster process compared to anaerobic digestion, it is also important to note that the latter is a crucial factor to bioremediation process. The reason is that there are several limitations to oxygen availability conditions as that in aquifers and sludge digester systems. The anaerobic metabolism of aromatic compounds results in formation of Benzoyl-CoA. Nitrates, sulfates act as terminal electron acceptors which can be used based on

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19.2 Role of bacteria in enzymatic degradation of petroleum hydrocarbons

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FIGURE 19.1 Schematic diagram for aerobic degradation of hydrocarbons by microorganisms (Das & Chandran, 2011).

environmental conditions (Das & Chandran, 2011; Peixoto, Vermelho, & Rosado, 2011). Fig. 19.1 showcases the mechanism of aerobic degradation of hydrocarbons by microorganisms. Apart from using microbes, enzymes too are seen as a promising arena due to their added advantages. Enzymes cannot be rendered inactive by inhibitors of microbial metabolism. They also come handy in extreme conditions where microbes’ effectiveness decreases. Enzymes are efficient even at low pollutant concentrations and also in the presence of microbial predators. They act against a given substrate and are more active than microorganisms because of their miniature dimension (Peixoto et al., 2011). These added advantages make enzymes environmental-friendly catalysts. Fig. 19.2 gives a schematic view of the enzymatic reactions during hydrocarbon degradation. This paper aims to provide detailed research on degradation driven by microorganisms of effluents released from petroleum products and oil spill pollution using bacteria, fungi, and algae incorporating enzymatic technology that would work for a better study on the future of bioremediation technology and a step toward an ecofriendly globe (Table 19.1).

19.2 Role of bacteria in enzymatic degradation of petroleum hydrocarbons Microbial degradation is a prominent mechanism by which the hydrocarbon pollutants of the environment containing petroleum can be cleaned. Bioattenuation of alkyl aromatics

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FIGURE 19.2

19. Potentiality of enzymes as a green tool in degradation of petroleum hydrocarbons

Schematic diagram of enzymatic reactions during hydrocarbon degradation (Das & Chandran, 2011).

in marine segments by organisms such as Arthrobacter, Burkholderia, Rhodococcus have been studied by a few scientists. Efficiency of biodegradation has been found to range from 0.13% to 50% for soil bacteria, 6%
82% for soil fungi, and 0.03%
100% for marine bacteria (Nakamura, Tomita, Abe, & Kamio, 2001) Bacteria have been found to be the most active agent in degrading the spilled oil in the environment. Few specific bacteria have been found to feed exclusively on hydrocarbons. Isolated bacterial species such as Aeromicrobium, Brevibacterium, Burkholderia, Dietzia, Gordonia, and Mycobacterium found from petroleum contaminated soil emerged to be effective for hydrocarbon degradation (Nannipieri et al., 1991). However, bacteria have the potential of degrading different petroleum components under different aerobic and anaerobic conditions at varied pH and salinity. A sequential enzymatic metabolism is responsible for petroleum degradation. In this process, the genes involved are either located on chromosomes or on Plasmid DNA (Nicell, 2001). Through various research studies, it has been found that Pseudomonads are one of the best bacteria which are capable of utilizing hydrocarbons and producing surfactants. Pseudomonads and P. aeruginosa has been widely studied for producing glycolipid type biosurfactants. These bio surfactants tend to increase the oil surface area. The role of Pseudomonas sp. in bio surfactant production during uptake of hydrocarbons has been represented in Fig. 19.3. Another bacterial species of the genus Bacillus are also of great use because of their capability of producing endospores, which enables them to remain in dormant state when the environment is not favorable.

D. Biological processes

19.2 Role of bacteria in enzymatic degradation of petroleum hydrocarbons

341

TABLE 19.1 A summary of enzymes responsible for degradation of petroleum hydrocarbons by bacterial and fungal species. Name of the enzyme

Bacterial species

Fungal species

References

Soluble methane Monooxygenases

Methylococcus Methylosinus Methylocystis Methylomonas Methylocella




McDonald et al. (2006)

Dioxygenases

Acinetobacter sp.




Maeng, Sakai, Tani, and Kato (1996)

AlkB related Alkane Hydroxylases

Pseudomonas Burkholderia Rhodococcus Mycobacterium




Jan et al. (2003)

Bacterial P450 Oxygenase system

Acinetobacter Caulobacter Mycobacterium




Van et al. (2006)

Eukaryotic P450

Candida maltosa Candida tropicalis Yarrowia lipolytica

Iida, Sumita, Ohta, and Takagi (2000)

Cytochrome 450 hydrolases

Candila apicola C. Tropicalis C. Maltose

Cerniglia, Gibson, and Van Baalen (1980), Gamila et al. (2003)

Apart from the species mentioned above, the third important one is Rhodococcus. A member of this species, including both pathogens and non pathogens can be found in soil and marine ecosystems and are found to metabolize harmful environmental pollutants like various hydrocarbon compounds. The reason for their degradation capacity getting enhanced is that their hydrophobic surface can get attached to the hydrocarbon chains (Rubilar, Diez, & Gianfreda, 2008; Sa´nchez, 2009). Species like esterases, anudases, and proteas are capable of breaking down esteric, amidic and peptidic bonds which leads to formation of nontoxic products. For example, bacterial hydrolases such as carbamate have been successfully used in transformation of pollutants such as carbofuran, coumaphos, etc. (Sheldon & Van, 2004). Several bacteria are also capable of producing carbohydrases, proteases which helps in the transformation of insoluble materials like carbohydrates, plastics, and proteins. A few examples of hydrolases are anudases and proteases. Obligate hydrocarbonoclastic bacteria (OHCB) are the bacteria that use hydrocarbons as carbon source (Atlas, 1981). They have a low abundance in sea water. When due to any reason, hydrocarbon input increases in the seawater, OHCB increases in abundance, the reason being that they have higher efficiency in utilizing hydrocarbons as their carbon source. Hence, they have an important role to play in eliminating the water body of such pollutants. Examples of OHCB are Marinobacter, Cycloclasticus. Both aliphatic and aromatic compounds bioremediation can occur under the conditions mentioned above (Atlas, 1984). The aerobic degradation is catalyzed by oxygenase enzymes which introduce oxygen atoms in the hydrocarbons, while the anaerobic one is catalyzed by sulfur reducing bacteria.

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342

FIGURE 19.3

19. Potentiality of enzymes as a green tool in degradation of petroleum hydrocarbons

Role of Pseudomonas sp. in bio surfactant production during uptake of hydrocarbons (Das &

Chandran, 2011)

Different petroleum contaminated sites have been found to be restored by bioaugmentation and biostimulation processes (Atlas & Bartha, 1992). They minimize the impact of petroleum spills. However, like every other process, these also come with their advantages and disadvantages. For example, the competitiveness of inoculated strains is the main factor to the success of bioaugmentation in different environments. Petroleum degradation efficiency can also be increased by genetically modified organisms. Environment where indigenous petroleum hydrocarbon degrading microorganisms exist, biostimulation comes handy. Research will find alternative biological strategies to enhance the effectiveness in the environment. New improvements in the development of products and methods by reducing industrial costs have been opened by biocatalysis. Enzymatic remediation is a simpler process than working with whole organisms (Foght & Westlake, 1987; Vandermeulen and Hrudey, 1987). Toxic by products are not formed when isolated enzymes are used. PAH detoxification is an example of enzymatic bioremediation involving the use of laccases (Mearns, 1997). Organic solvents are the prime agents for the occurrence of enzymatic oxidation. This is an advantage in case of xenobiotic enzymatic bioremediation which are mainly hydrophobic or poorly soluble in PAH. However, the disadvantage is that they can be unstable in organic solvents. A recent study based on an enzyme based product like TrzN showed that this strategy can effectively detoxify aquatic systems contaminated with herbicides (Prince, 1993).

D. Biological processes

19.3 Role of algae in enzymatic degradation of petroleum hydrocarbons

343

Rhoder is a mixed hydrocarbon degrading bacteria consisting of R. Ruber and R. Erythropolis showing 99% and 94% efficiency for aquatic and land surfaces respectively (Swannell et al., 1996). It can even grow in a low oxygen concentration environment because of their microaerophilic respiration capacity. The main aspect to be kept in mind for selection of an enzyme for bioremediation is that it should have the capability to degrade the pollutant to less or nontoxic products. Secondly, it should not depend on cofactors as that would inflate the process expense from the commercial point of view. The third stage comprises of identification of the gene that encoded the selected enzyme, and to improve enzymatic production (Venosa et al., 1996). On a large scale, these are produced by fermentation where the unwanted cells are eradicated during downstream processing.

19.3 Role of algae in enzymatic degradation of petroleum hydrocarbons “Phycoremediation” is the process of elimination and degradation of organic contaminants by algae. In addition to being sustainable, ecofriendly, and cost effective the process generates byproducts with useful applications. Biofuels generated as part of this bioremediation process serve as a sustainable source of bioenergy which has the potential to meet the demands for energy in the future (Vassilev & Vassileva, 2016). There are two major processes by which algae eliminate intoxicants: Biosorption: a passive process where the pollutants bind to nonliving biomass from an aqueous solution and Bioaccumulation: an active process where organic pollutants are removed by an organism’s metabolic activity (Ben et al., 2014; Baghour, 2017; Davis, Volesky, & Mucci, 2003) Algae adopt other strategies for bioremediation as well, these include biodegradation, biotransformation and biomineralization (Baghour, 2019; Martinez et al. 2019) In recent times algae have been seen to play a promising role in the degradation of organic compounds due to their low environmental impact, fast growth rate, low water intake, land requirements and adaptability. Both microalgae and macroalgae fall under the umbrella term algae. Microalgae are unicellular algae that constitute the bulk of the existing algal species. Macroalgae are multicellular algal species that are classified on the basis of the pigment coloration as brown, red and green seaweed respectively (Baghour, 2019). Arthrospira, Botryococcus, Chlamydomonas, Chlorella, Cyanothece, Desmodesmus, Phormidium, Nodularia, Oscillatoria, Scenedesmus, Spirulina, etc., are few of the species of microalgae used for remediation of organic compounds (Dubey, Dubey, Mehra, Tiwari, & Bishwas, 2013; Rawat, Kumar, Mutanda, & Bux, 2011) Ulva lactuca, Kappaphycus alvarezii, etc., are some macroalgal species used for detoxification. It is observed from literature that the studies related to the accumulation of organic xenobiotics and degradation in the green algae have come to be of much significance due to the widespread occurrence of the species in agricultural regions causing it to be a major issue in the marine ecosystem (Jin et al., 2012) There has been a recent surge in the usage of algae for water quality assessment via biomonitoring. Biomonitoring involves the deployment of organisms as bioindicators to evaluate a change in the environment. Seaweeds possess great potential as bioindicators due to their widespread distribution, availability in polluted media, physical properties which

D. Biological processes

344

19. Potentiality of enzymes as a green tool in degradation of petroleum hydrocarbons

make them easy to identify, ability to accumulate pollutants, rapid growth rates and short life spans make them well suited to study short term impacts (Omar, 2010). Algal remediation is one of the many methodologies used to treat petrochemical wastewater. The hydrocarbons serve as the carbon and energy source for metabolic activity of algae, thereby rendering the toxic contaminants harmless by their degradation. Literature suggests that Chlorella vulgaris and Scenedesmus obliquus thrive in heterotrophic conditions and efficiently degrade low concentrations of oil. Further Scenedesmus obliquus can be used for biodegradation of crude oil by means of an artificial microalgal-bacterial consortium (El-Sheekh, Hamouda, & Nizam, 2013). Thus algae provide a potential solution for removal of pollutants either by directly bringing about the transformation of the contaminant or by acting as a catalyst and expediting the degradation. They lower the carbon dioxide levels in the atmosphere, thereby reducing the effects of global warming. The biomass generated from this process has a wide variety of applications such as use as animal feed, extraction of products such as carotenoids, production of renewable energy in the form of biofuel in addition to providing reusable clean water thereby minimizing the use of fresh water (Rawat et al., 2011). Fig. 19.4A and B represents the biotransformation of napthalene and phenol by algal species.

19.4 Role of fungi in enzymatic degradation of petroleum hydrocarbons The fungi species used for the degradation of hydrocarbons depend on the nature of the hydrocarbon. Some fungi such as Amorphotheca, Aspergillus, Graphium Cunninghamella, Fusarium, Neosartorya, Penicillium, Paecilomyces, Talaromyces are used for degradation of recalcitrant pollutants. Several other species as reported in the literatures have been represented in Table 19.2. Bioremediation of pollutants is governed by several environmental factors, the most important being the restricted availability of microbes in the environment. The activity of these microbes is affected by other factors such as temperature, pH, bioavailability, salinity, oxygen, and nutrients. The hydrocarbons act as the source of both carbon and energy for their own biodegradation. Further the degradation of the hydrocarbon is also dependent on the medium, that is, there is distinction between the degradation of hydrocarbons in soil and degradation in water. Oil spills call for remediation in water. The biodegradation is recumbent on the chemical and physical properties of oil and the particle nature which in turn depends on the mobility and dispersion of oil in water (Al-Hawash et al., 2018). The mechanism of interaction of fungal cell with the various complex hydrocarbons has been outlined in Fig. 19.5. The rate of degradation of hydrocarbons is impacted by the temperature being directly proportional in nature. Due to reduced enzymatic activity at low temperatures, degradation is lower at lower temperatures and higher at higher temperatures (Bisht et al., 2015). Oxygen level and the presence of nutrients are also regulators of biodegradation. Oil spills often lead to increased carbon levels in the aquatic environment thus resulting in lower concentrations of nitrogen and phosphorus, thereby resulting in the need for addition of nutrients to promote biodegradation. At the same time an excess of nutrients isn’t conducive to the microbes as well (Hesnawi & Adbeib, 2013). Salinity adversely affects the bioremediation process; this is due to its impact on microbial activity, i.e., metabolic rate of enzymes decreases with increase in salinity of the surrounding medium. Furthermore it can be observed from literature that most

D. Biological processes

19.4 Role of fungi in enzymatic degradation of petroleum hydrocarbons

345

FIGURE 19.4 (A) Mechanism of biotransformation of Napthalene by algal species as proposed by Semple, Cain, and Schmidt (1999), (B) Mechanism of biotransformation of phenol by Ochromonas danica as proposed by Semple et al. (1999).

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346

19. Potentiality of enzymes as a green tool in degradation of petroleum hydrocarbons

TABLE 19.2 Degradation of petroleum hydrocarbons by different fungal species (Li, Liu, & Gadd, 2020).

Species

Hydrocarbons Formula Structure

Removal efficiency (%)

Penicillium sp.

Decane

C10H22

49.0

28

Govarthanan, Fuzisawa, Hosogai, and Chang (2017)

Aspergillus sp.

N-hexadecane C16H34

86.3

10

Al-Hawash, Dragh, et al. (2018)

Fusarium sp.

N-octadecane

C18H38

89

60

Hidayat and Tachibana (2013)

Phomopsis liquidambari

Phenanthrene

C14H10

77.4

10

Fu et al. (2018)

Irpex lacteus

Anthracene

C14H10

60

25

Drevinskas et al. (2016)

Pleurotus ostreatus

Anthracene

C14H10

56

23

Drevinskas et al. (2016)

Ganoderma lucidum

Pyrene

C16H10

99.6

30

Agrawal,LVerma, and Shahi (2018)

C18H12

65

30

Hadibarata, Tachibana, and Itoh (2009)

Polyporus sp. Chrysene

Treatment length (d)

Reference

enzymes prefer to thrive in a neutral to alkaline environment. Although fungi in general are tolerant to acidic conditions the neutral conditions with sufficient availability of water allow the microbes to flourish thereby favoring biodegradation (Pawar, 2015). Thus the degradation of hydrocarbon pollutants is influenced by a variety of biotic and abiotic factors which promote the growth of the biological species and thereby expedite biodegradation (Fig. 19.6).

19.5 Feasibility and technical applicability of enzymes in oil clean up The existing treatment techniques for oil clean up involve the introduction of deleterious chemical agents into the environment, whereas the technology described in this work provides a safer and more environmental friendly alternative. The enzymatic agent itself is biodegradable; therefore this process produces no harmful remnants and doesn’t waste energy. This process relies on the natural biological cycle of certain microorganisms to clean up oil spills. The enzymes present within the microorganism break down the toxic pollutants into nontoxic substances, thereby rendering them harmless. Bioremediation is flexible in nature and can be carried out both in-situ and ex situ. In situ remediation involves making use of the indigenous microorganisms which naturally occur at the site, whereas ex situ treatment involves transportation of the contaminated material to a treatment site different from where the pollution takes place (Atlas & Philp, 2005). Bioaugmentation and biostimulation methodologies are currently seen as methods that could aid in restoring various sites that are currently contaminated with petroleum and thus can reduce the effects of petroleum spills. These varied options should be carefully

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19.5 Feasibility and technical applicability of enzymes in oil clean up

347

FIGURE 19.5 Mechanism of fungal cell enzymatic interaction with petroleum hydrocarbons (Li et al., 2020).

FIGURE 19.6 Growth potentiality of fungal species under different concentrations of crude oil (Mohsenzadeh, Chehregani, & Akbari, 2012).

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348

19. Potentiality of enzymes as a green tool in degradation of petroleum hydrocarbons

researched and planned for specific types of contaminant and environmental conditions, as they come with their own set of pros and cons. For example, effectiveness of bioaugmentation is seen to depend on the competitiveness of the inoculated strains in different environments and biostimulation can be meticulously used in environments where indigenous petroleum-degrading microorganisms are found (Durkee, 2016). Researching on alternative bioremediation pathways is vital to increase their effectiveness manifolds and applications at varied locations. Bioaugmentation is another organic treatment methodology wherein nonindigenous microorganisms are procured and added to the contaminant site. Bioremediation has a wide variety of applications in the present day. In addition to being implemented to treat oil spills, it can be used for treating industrial wastewater, mines, groundwater, contaminated soils, and fly-ash disposal sites. Although the search for an alternative strategy to bioremediation is crucial, their effectiveness can be increased. Bio catalysis has reduced industrial costs, and improved product development. It is contributing to minimize the fossil fuel damage. It has a favorable cost-benefit ratio. This is because of the recent application of molecular tools to it. Enzymatic biodegradation is different because it works in a systematic way, and is not prone to conditions. The enzyme, in this process works by itself, without the need of any chemical. Research and lab testing data have shown that once the biodegradation starts, it finishes with the complete reduction of toxins and bacteria. Once the decontamination is done, the enzyme starts biodegrading itself, and eventually no toxic substance is leftover. Considerable success has been achieved by researchers and scientists to break down harsh toxic pollutants with the help of bioremediation. Bioremediation involving enzymes finds use in metal biorecovery and in the production of useful biominerals. However, bioremediation often involves the degradation of crude by a combination of different bacterial species, since each group acts on certain specific hydrocarbons only (Kohli, 2019). Further bioremediation cannot be put to use at sites with high concentrations of chemicals that are toxic to most microorganisms. These can sometimes prove to be a bottleneck in the application of microorganisms for waste treatment. Enzymatic degradation due to its versatile nature can often be combined with other treatment methodologies such as electro kinetics to find solutions for enhanced removal of hard to remove compounds such as herbicides, byproducts in chemical manufacturing, petroleum by products, etc. Thus bioremediation due to its ability to provide a cost effective and viable environmental friendly solution is gaining ground fast.

19.6 Conclusion The use of enzymes for removal of intoxicants in the form of petrochemical oil has come to be of much importance in recent times due to its sustainable nature. Bioremediation using enzymes secreted by microbes such as bacteria, fungi, and algae have gained prevalence due to their environmental friendliness, cost effectiveness, and their role in reducing the effects of global warming; the enzymes regulate the carbon dioxide levels in the atmosphere by using it as a source of energy for their metabolic activity. Furthermore they have a pivotal role to play in recovering the marine ecosystem such as the endangered and sensitive coral reefs. In addition to providing clean water, bioremediation provides for byproducts such as biofuels which are renewable sources of energy and

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References

349

mitigate the use of exhaustible fossil fuels. However, this process relies heavily on the availability of microbes. Further analysis could be carried out to study the efficiency of different microbial species in treating oil spills.

Conflict of interest On behalf of all authors, the corresponding author states that there is no conflict of interest.

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C H A P T E R

20 Bioremediation: an ecofriendly approach for the treatment of oil spills Sudipti Arora1, Sonika Saxena1, Devanshi Sutaria1 and Jasmine Sethi2 1

Dr. B. Lal Institute of Biotechnology, Jaipur, India 2Entrepreneurship and Career Hub, University of Rajasthan, Jaipur, India O U T L I N E

20.1 Introduction 20.1.1 Oil spills

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20.2 Catastrophe 20.2.1 Hydrocarbon pollution

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20.3 An approach to eliminate oil spills 357 20.3.1 Bioremediation and its techniques 358 20.4 Factors affecting the biodegradation efficiency 363 20.4.1 Nutrient availability 364 20.4.2 Temperature 365 20.4.3 Oxygen limitations 365 20.4.4 pH 365

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00012-4

20.4.5 Bioavailability of hydrocarbon 366 20.4.6 Restriction of physical contact between microorganism and oil spills 366 20.5 Role of microorganism

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20.6 Novel approaches 20.6.1 Substance addition 20.6.2 Genetic engineering

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20.7 Case studies

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20.8 Conclusion and future prospects

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References

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© 2022 Elsevier Inc. All rights reserved.

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20.1 Introduction Industrialization is the backbone of the country’s growth, but industry-induced pollution is a major concern worldwide. Globally, pollution from crude oil and its derivatives have become an important environmental issue. Due to its widespread usage and its related disposal operations and accidental spills, environmental pollution by crude oil is relatively common. The term petroleum refers to a highly complex mixture of a large range of hydrocarbons of low and high molecular weight. It has been estimated that at least 0.08%
0.4% of the oil produced globally has been released into the aquatic environment as pollutants. Increasing amounts of spilled oil are often received annually by the terrestrial and atmospheric ecosystems, imagining how severe this environmental problem is. Petroleum hydrocarbons, polynuclear aromatic hydrocarbons (such as naphthalene and benzopyrene), and solvents are among the most common chemicals involved in oil pollution. Inadvertent or intentional discharge of crude oil and its derivatives pose problems of increased magnitude (Okoh & Trejo-Hernandez, 2006). Furthermore, these problems are more aggravated because of the expensive disposal methods (Rahman et al., 2003; Das & Mukherjee, 2007).

20.1.1 Oil spills Oil spill refers to the release of liquid petroleum hydrocarbon into the environment, especially on water which could be due to the climatic factors or natural disturbances or anthropogenic activities causing environmental pollution. This problem is of major concern in sea and fresh water bodies like rivers, land, lakes etc. The main anthropogenic sources of oil spills over the natural waters include the following: 20.1.1.1 Accidental spills during 1. Storage Oil and oil products may be stored in a variety of ways including underground and aboveground storage tanks (USTs and/or ASTs, respectively); such containers (especially USTs) may develop leaks over time. 2. Handling During transfer operations and various uses, oil leakage or spillage may occur and pollute the land or water. 3. Transport During the transportation oil spills (up to million and hundreds of million gallons) on water or land through accidental rupture of big transporting vessels (e.g., tanker ships or tanker trucks) are often observed. For example, Exxon Valdez spill was a massive oil spill off the Alaskan shoreline due to ship in late 1980s (Jain et al., 2011). Smaller oil spills through pipelines and other devices also happen in large numbers and their impact is huge. 4. Offshore drilling The world is currently experiencing the massive oil spill in the Gulf of Mexico with its hard to predict consequences on environment, marine life and humans as the spill continues since April 22, 2010 and it may take a while until a solution is implemented.

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5. Routine maintenance activities Routine activities like cleaning of ships may release oil into navigable waters. This may seem insignificant, however due to the large number of ships even few gallons spilled per ship maintenance could build up to a substantial number when all ships are considered. 6. Road runoff Oily road runoff adds up especially on crowded roads. With many precipitation events, the original small amounts of oil from regular traffic would get moved around and may build up in our environment 7. Intentional oil discharges Intentional oil discharges such as those through drains or in the sewer system includes regular activities such as changing car oil, if the replaced oil is simply discharged in a drain or sewer system. 8. Indirectly through burning of fuels, including vehicle emissionsIt would release various individual components of oils and oil products such as variety of hydrocarbons.

20.2 Catastrophe The first oil spill occurred in 1907 and, as a result, 7400 tons of paraffin oil reached the United Kingdom’s sea and coastline. After that, about 140 big spills occurred, and a total of seven million tons of oil reached the atmosphere. More than 90% of oil emission, however, is either natural, such as runoff from land-based sources, or has anthropogenic sources, such as regular ship activity and deballasting and tank washing (not necessarily accidents) (Mapelli et al., 2017). The Gulf War, Deepwater Horizon (DWH), Ixtoc 1 oil well, Amoco Cadiz, and other prominent oil spills occurred in the sea in the largest oil spills in history (Lim, Von Lau, & Poh, 2016). In 1978, the Amoco Cadiz disaster dumped 227,000 tons of crude oil and bunkers into the sea and polluted 320 km of shoreline length to a depth of 20 inches (Lim et al., 2016). In 1988, the Ashland oil spill happened when a four million gallon diesel oil tank collapsed and the oil was spilled into the Monongahela River (Miklaucic & Saseen, 1989). In 1989, when an Alaska reef crashed by a tanker that poured thousands of tons of oil into the sea, the Exxon Valdez oil spill occurred (Jain et al., 2011). Pollution of the water and coast resulted in substantial environmental impact to the local inhabitants (Atlas, 1995). More than 250 thousand seabirds have been estimated to have died as a result of the leak. The largest inland oil spill happened in Uzbekistan’s Fergana Valley in 1992, when an oil well spewed 88 million gallons of oil onto the countryside. This spill was absorbed by the earth, and there was no way to clean it up. In 2002, the sinking of tankers and affected kilometers of the coastline caused a prestige tragedy, resulting in a loss of up to 66% of the region’s species richness (Bovio et al., 2017). The DWH accident that took place during the drilling rig explosion in the Gulf of Mexico in 2010 was one of the most prominent oil spills. More than 700,000 tons of crude oil was released into the Gulf of Mexico during this catastrophe (Mapelli et al., 2017). The biodiversity of the vertebrates and metazoan

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TABLE 20.1 History of oil spills. Year Event

Reference

1978 The Amoco Cadiz disaster dumped 227,000 tons of crude oil and bunkers into the sea and polluted 320 km of shoreline length to a depth of 20 inches.

Lim et al. (2016)

1988 The Ashland oil spill, a four million gallon diesel oil tank collapsed and the oil was spilled into the Monongahela River.

Miklaucic and Saseen (1989)

1989 Alaska reef crashed by a tanker that poured thousands of tons of oil into the sea, the Jain et al. (2011) Exxon Valdez oil spill. 1992 Uzbekistan’s Fergana Valley inland oil spill, 88 million gallons of oil was released into the land from an oil well. This spill was absorbed by the ground, and no cleaning was possible.

Tan (2009)

2002 the sinking of tankers and affected kilometers of the coastline caused a prestige tragedy, resulting in a loss of up to 66% of the region’s species richness

Bovio et al. (2017)

2010 The Deepwater Horizon (DWH) accident during the drilling rig explosion in the Gulf of Mexico where more than 700 thousand tons of crude oil released.

Mapelli et al. (2017)

meiofauna was diminished by this event. It was estimated that the cleaning expense of that spill was 10 billion USD (Alessandrello, Toma´s, Raimondo, Vullo, & Ferrero, 2017). The world witnessed this as the worst oil spill in history (Ng et al., 2015). The table below shows the history of oil spills (Table 20.1).

20.2.1 Hydrocarbon pollution Oil pollution occurs as a result of oil exploration, extraction, refining, transportation, and storage in both terrestrial and marine environments. Oil spills have become a global concern since the early 1900s, when the oil industry first emerged. The risk of accidental and purposeful spills has increased as the oil industry and worldwide demand have grown. Petroleum is a dangerous combination of organic chemicals, heavy metal traces, and hydrocarbons, which includes numerous persistent volatile organic compounds and polycyclic aromatic hydrocarbons (PAHs). Oil exposure harms critical activities in organisms, such as reproduction, physiological and chemical process regulation, and organ function. Crude oil is a highly complex combination of tens of thousands of hydrocarbons (aliphatic and aromatic) and nonhydrocarbons (sulfur, nitrogen, oxygen and a number of hydrocarbons) and metals from trace. The oil composition varies according to its sources (Singh, Kumari, & Mishra, 2012). There are different groups of hydrocarbon which is responsible for the contamination in oil spills are described below with the Fig. 20.1. 20.2.1.1 Aliphatic group Hydrogen and carbon, which can be linear, branched or cyclic, are made up of aliphatic hydrocarbons. It is possible to saturate or unsaturate the aliphatic compounds. There are many forms, including alkanes, alkenes, and alkynes, of aliphatic hydrocarbons. The most common components in crude oil are alkanes which are the first ingredient to be degraded.

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FIGURE 20.1 Different group of hydrocarbons responsible for contamination in oil spills.

20.2.1.2 Aromatic group PAHs are a category of approximately 10,000 air, water, and surface contaminants comprising one or more aromatic rings (Hassanshahian, Abarian, & Cappello, 2015). Benzene, toluene, and xylene have been well established and studied among monoaromatic compounds. PAHs are highly resistant to deterioration and remain persistent in the environment due to their complex structure such as naphthalene, anthracene, and phenanthrene (Ghosal, Ghosh, Dutta, & Ahn, 2016). 20.2.1.3 Heterocyclic group Heterocyclic compounds are recalcitrant organic compounds containing at least one heterocyclic ring which consists of compounds having common heteroatoms incorporated (oxygen, nitrogen, and sulfur) into an organic ring structure in place of a carbon atom. It includes polar compounds such as nitrogen (quinolines), sulfur (dibenzothiophenes) and oxygen (xanthene) atoms.

20.3 An approach to eliminate oil spills The rapid deployment to the spill leads to a better chance of avoiding and stopping leakage (Helmy & Kardena, 2015). Rather of controlling pollutants and allowing natural

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attenuation, the purpose of the reaction to the oil spill is to minimize the spill’s negative impacts. The primary concern in reacting to an oil spill is to regularly monitor the source and prevent the oil from spreading. The solution might be any policy, technique, technology, or equipment for managing the spill and resolving its negative consequences. Stewardship, in addition to swift action, is necessary to track and forecast the movement of oil. Mechanical spill recovery equipment such as skimmers, booms, barriers, and sorbents, as well as dispersants and controlled in situ burning, are among the reaction approaches (Walker, 2017). Environmental treatments and remediation techniques are aimed at degrading and transforming pollutants into less toxic and even harmless compounds; treatment is carried out, if not necessary, by restricting the movement and migration of contaminants to avoid their dissemination to uncontaminated areas. The toxicity of pollutants do not improve with this method, but the likelihood of their further distribution to the ecosystem is decreased. There are many therapies and solutions to oil spills, including physical, chemical, and biological strategies (Jain et al., 2011). While physical and chemical methods are often used to extract spilled oil (Kuiper, Lagendijk, Bloemberg, & Lugtenberg, 2004; Wang, Zhang, Li, & Klassen, 2011), they are mostly neither cost-effective nor environmentally friendly. Incineration contributes to air pollution, for instance, and land-filling leads to groundwater contamination. The spilled oil is simply burned for incineration, with the result of raising levels of ambient carbon dioxide, nitrogen oxide, and sulfur oxide. It is understood that the present issue of global warming is due to CO2 accumulation in the atmosphere. It can be argued that bioremediation often contributes to bacteria releasing CO2. In fact, only one portion of the oil’s carbon is released by bacteria during energy (ATP) processing, while the other portion is retained as bacterial cell content in the soil. The acidic rain due to nitrogen and sulfur oxides is known to degrade the quality of land and water while affecting the aquatic ecosystems and groundwater table. Land-filling of the contaminants has been reported to generate dangerous leachates in the form of gases and liquids that can toxify groundwater (Radwan, 2008; Sverdrup, Nielsen, & Krogh, 2002). Certainly, these methods have contributed in the elimination of a large proportion of the spilled oil with the unpredictable risks associated and undoubtedly severe obstacles to their implementation (Johnson & Affam, 2019). Therefore there is a need of such techniques which are ecofriendly and cost-effective and can play a vital role in sustainable development.

20.3.1 Bioremediation and its techniques The term bioremediation refers to the degradation of environmental pollutants using biological agents like bacteria and fungi for the breakdown of complicated chemical molecules into simpler ones. Bioattenuation is a term used to describe naturally occurring bioremediation (Mrozik & Piotrowska-Seget, 2010). Natural attenuation, but after an oil spill, is typically too retarded to satisfy the immediate needs of the environment. It is based on the catabolic activities of microorganisms and their ability to convert pollutants into less or nontoxic compounds by converting them into carbon and energy sources. Depending on many variables, such as site conditions, form and concentration of contaminants, various bioremediation techniques are implemented. The physical removal of the polluted land for

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the treatment process requires ex situ approaches. In situ procedures, however, include handling the infected substance in place. Therefore by various improved methods, attempts have been made to increase the productivity of the method. Bioremediation methods have often been referred to as biorestoration (Testa & Winegardner, 1991; Wilson, Leach, Henson, & Jones, 1986). This include land-farming, composting, bioreactor use (Zouboulis, Moussas, & Psaltou, 2019), bioventing/biosparging, pumping and treatment strategies, bioslurping, biostimulation, and bioaugmentation (Boopathy, 2000). Compared to other oil spill management methods, bioremediation is often considered to be a cost-effective (involves the use of ubiquitous oleophilic microbes) and ecofriendly (which breaks down crude oil into nontoxic products and intermediates) clean-up process (Furukawa, 2003; Okoh & Trejo-Hernandez, 2006; Pieper & Reineke, 2000). Bioremediation has often received criticism of being ineffective in cleaning up heavy crude oil components and is often constrained by abiotic factors such as availability of nutrients, temperature, and concentration of oxygen (Boopathy, 2000). This present review is therefore intended to define the key challenges associated with the use of bioremediation to clean up crude oil emissions in terrestrial and marine ecosystems, as well as to establish guidelines that are likely to form the basis for new lines of research on how to resolve these challenges. Several chemical and physical hydrocarbon treatment approaches have been investigated such as incineration, chlorination, UV oxidation, and solvent extraction (Ghosal et al., 2016), but are often ignored due to lower removal efficiency and higher environmental and health associated risks. The biological approach, meanwhile, are more efficient in hydrocarbon removal and can be distinguished into (1) phytoremediation strategy which uses plants for decontamination purposes and (2) bioremediation which involves the use of microbial population for the cleanup of contaminated sites. There are two broad approaches of the bioremediation viz, In situ and Ex situ as illustrated in Fig. 20.2. The in situ method of treating is based on site excavating while Ex situ is treating contaminant off site (Boopathy, 2000). The bioremediation efficiency depends mainly on the microbial structure, the sites to be decontaminated and the environmental conditions. The natural bioremediation process is influenced by physicochemical conditions like temperature, pressure, pollutant surface area, oxygen content, nutrient availability, pH, salinity, oil composition, etc. There are two main approaches available when applying bioremediation as a response to the oil spill, which are biostimulation (increasing the availability of nutrients, mostly nitrogen and phosphorus, to initiate growth and speed up biodegradation) and bioaugmentation (inoculation of microorganisms with enhanced ability to degrade petroleum hydrocarbons in order to facilitate the process). There is also a new approach, however, which is bioaugmentation with genetically engineered microorganisms (GEM bioaugmentation) (Jafarinejad, 2017; Lahel et al., 2016). It has been reported that bioaugmentation effects can be observed much more quickly than biostimulation (Pontes et al., 2013). The most promising approach, however, is to combine biostimulation and bioaugmentation with additional of biosurfactants. 20.3.1.1 Bioaugmentation Bioaugmentation is an approach that is used when pollutant mixtures like petroleum are insufficient to be degraded by the native microbial populations. This method is opted

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FIGURE 20.2

20. Bioremediation: an ecofriendly approach for the treatment of oil spills

Approaches to bioremediation.

when the degradation process is limited by the number of hydrocarbon degrading bacteria or the absence of such bacteria. Polynuclear aromatic hydrocarbons, for example, are usually hard to degrade (Jafarinejad, 2017). In this approach, to supplement the naturally available microbes, microorganisms with enhanced biodegradation ability are added to the polluted environment. It is commonly used to add nonindigenous microbes from other polluted environments to the target site (Jafarinejad, 2017). Alternatively, in laboratory conditions in bioreactors, microbes from the target site are separated, mass cultured and are used as an inoculum to the target site. This technique is called autochthonous bioaugmentation and refers to cases where bioaugmentation is performed after enrichment by the native microbes of the contaminated site to be reapplied to the site (Lim et al., 2016). The selection criteria for the microbes added are based on their physiology and metabolic capacity (Lim et al., 2016). In order to start biodegradation, the seeding of microorganisms at the contaminated site can reduce the lag time. The adaptation problem is avoided when the seeding is carried out by the enhanced indigenous organisms taken from the target site (Jafarinejad, 2017). Under controlled conditions, bioaugmentation has been successfully performed on the bench scale. It must, however, be considered that conditions may be uncontrollable in real fields (Jafarinejad, 2017). It has been suggested that prior to in situ application of the microorganisms, primary laboratory tests for microorganism selection may increase the chance of successful bioremediation. In the work of Szulc et al. (2014), in addition to Xanthomonas sp., Gordonia sp., Stenotrophomonasmaltophilia, and Rhodococcus sp., the most effective consortium (Pseudomonas fluorescens and Pseudomonas putida mixed with Aeromonashydrophila and Alcaligenesxylosoxidans) for bioaugmentation was selected in the laboratory based on the quantity of CO2 and dehydrogenase activity (Szulc et al., 2014). Researchers claim that, taking into account the specific nutritional needs and limitations,

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commercial bacterial blends can be produced with customized properties for each specific site and type of spill pollution. 20.3.1.2 Biostimulation Biostimulation is the process of nutrient-enhanced bioremediation to improve the indigenous rate of biodegradation of petroleum hydrocarbons, particularly organic pollutants, by providing the contaminated medium with the limiting nutrient material (Soleimani, Farhoudi, & Christensen, 2013). The nutrients include carbon, phosphorus, and nitrogen, and some other cosubstrates that limit growth. During biostimulation, it is also possible to modify the conditions, including temperature and aeration. All of these operations are carried out in order to accelerate the growth and activity of oil degraders. This strategy can be called fertilization or the enrichment of nutrients (Jafarinejad, 2017). Due to the supply of nutrients, microbial metabolic activity is enhanced. Electron acceptors and donors can be used to activate the oxidation and reduction mechanisms. Their inclusion, however, must be managed carefully. The nutrients must be readily available and in touch with microbes (Balba, Al-Awadhi, & Al-Daher, 1998). The circumstances for increasing natural biodegradation may be altered by altering numerous parameters such as the administration of fertilizers, nutrients, biosurfactants, and biopolymers. Biostimulation is the manipulation of all of these characteristics in order to increase natural bioremediation (Lim et al., 2016). The bioventilation process, which is the application of oxygen to porous soil in order to improve the growth of microorganisms and the metabolism of organic matter by providing aerobic conditions, is another practice used to improve conditions, especially aeration. Bioventilation has been shown to increase the bioremediation rate to 85% from 64% in the natural attenuation process (Lim et al., 2016). In marine environments or generally open systems, it is quite difficult to add Nitrogen and Phosphorous. Uric acid, which is the waste product of animals, is thus added instead (birds, reptiles, insects, etc.). Low water soluble, uric acid can bind to petroleum hydrocarbons and can be used by bacteria as a source of nitrogen or both nitrogen and carbon. It has been observed that nitrate addition is more effective than ammonia in seawater for light crude oil degradation, whereas ammonia addition is more effective than nitrate in salt-marsh soil. Fortunately, nitrogen supplementation has not shown any adverse effects, such as algal blooms (Jafarinejad, 2017). Using this approach, good results have been obtained on the cost of sediments contaminated after the Exxon Valdez spill in Alaska, and the biodegradation rate increased three to five times by the addition of fertilizers such as iron, phosphorus, and nitrogen. 20.3.1.3 Biosparging In biosparging, air is introduced into the pollutant site to promote the microorganisms’ degradation efficiency. In contrast to bioventing, the air inside the saturated area is incorporated, causing volatile pollutants to move upwards. The efficacy of biosparging relies on the permeability that determines the availability of pollutants to microorganisms and the biodegradability of the pollutant (Godheja et al., 2019). Biosparging has been widely applied to the treatment of aquifers polluted by oil derivatives, mainly kerosene and diesel, which have good biodegradation of the BTEX group and naphtalenes (Kao, Chen, Chen, Chien, & Chen, 2008). It is possible to use aerobic bacteria to break down mineral

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oils, BTEX, and naphthalene. The deepest layers of soil and groundwater, however, are principally anaerobic. Oxygen is injected into the soil and groundwater by injection filters to promote the development of aerobic microorganisms. This direct supply of bacteria with oxygen increases their efficiency to degrade these contaminants. 20.3.1.4 Phytoremediation In order to promote biological, biochemical, physical, microbiological, and chemical interactions to attenuate the toxicity of contaminants, phytoremediation refers to the use of plants in polluted sites (Godheja et al., 2019). It occurs through various mechanisms depending on the type of pollutant, namely biodegradation, vaporization, filtration, among others. Elemental contaminants, such as heavy metals or radioactive elements, are mainly extracted, processed and sequestered, whereas organic contaminants are mainly removed by rhizodegradation, biodegradation, vaporization or stabilization (Kuiper et al., 2004). 1. Phytoextraction: The use of plant or plant part (e.g., root, stem or leaf) by accumulation or extracting out the pollutant from the soil (Sidhu, Bali, Singh, Batish, & Kohli, 2018). 2. Phytotransformation or Phytodegradation: The toxic components are transformed or degraded by the plants (Park, Kim, Kim, Kang, & Sung, 2011). 3. Phytovolatilization: The plant removes the pollutant from the soil and then manages to convert it into a volatile product, releasing it into the atmosphere. 4. Phytostimulation: The enhancement of soil microbial activity for the degradation of organic contaminant (Borriss, 2020). 5. Phytostabilization: This process consists in the immobilization of pollutants in the soil, thus avoiding erosive processes and allowing the association with humus and lignin (Shackira & Puthur, 2019). 6. Rhizofiltration: The adsorption or precipitation of dissolved compounds onto plant roots or absorption into the roots. Rhizofiltration usually addresses contaminated groundwater (Awa & Hadibarata, 2020). 7. Rhizodegradation: The degradation of the organic pollutant by the means of the root (Cristaldi et al., 2020). 20.3.1.5 Landfarming Landfarming is a soil bioremediation approach that includes mixing hydrocarboncontaminated soil. Biodegradation is also used for biological, physical, and chemical processes in the soil. The technique has been used since the 1980s due to its simplicity and cost-effectiveness. It is a “low-tech” oil spill remediation procedure designed for oilpolluted top soil surfaces (Genouw et al., 1994). It can be carried out in situ or ex situ, but it is more common to use the latter method. Contaminated soil is often transferred to a treatment site where aerobic microbial degradation is spread over a prepared soil surface and periodically tilled to occur (Zouboulis et al., 2019). This simple technology, however, faces inherent challenges, such as the inhalation of hydrocarbon volatiles by humans and the risk of other hydrocarbon contaminants leaching into the groundwater region through the soil profile.

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This challenge has been managed in recent times by providing the treatment site with a layered polythene material about 250 μm in thickness, which is laid at the bottom of the topsoil in order to prevent the leachates from seeping to the groundwater zone. In addition, by building a greenhouse to limit the extent of diffusion, the dispersed hydrocarbon volatiles have been controlled (Maila & Cloete, 2004). A number of hydrocarbon compounds have been successfully degraded by land farming as most oleophilic microbes are confined to the superficial soil layer, 15
30 cm deep. The major challenges faced during land farming are that it is a very slow process of biodegradation and has been unsuccessful in degrading PAHs with high molar mass. However, in terms of the biodegradation of light PAHs, a number of successes have been recorded. For example, Picado et al. reported a 63% reduction of mostly low molar mass PAHs after three months of landfarming; Bossert and Bartha, 1986 recorded an 80%
90% reduction of low molar mass PAHs after three years. Although the latter report is quite dated compared to the former, the fact that landfarming is indeed a very slow process of bioremediation is still revealed. The nonavailability of petroleum hydrocarbons to the oleophilic soil biota has been attributed to the slow nature of land farming. The use of surfactants such as detergents has therefore been suggested to help improve bioavailability. Adsorbents such as straws can, on the other hand, help mop up the soil’s nonbiodegradable heavy hydrocarbon residues (Maila & Cloete, 2004). 20.3.1.6 Bioslurping Bioslurping is a relatively new in situ bioremediation strategy that combines bioventing with a free-product recovery system. This method of remediation achieves two aims simultaneously—aerobic microbial biodegradation of the vadose zone through air injection and soil vapor extension and the removal of the light nonaqueous phase liquid saturates (NAPLS—free-phase petroleum pollutants) from the capillary fringe and water table via dual-pumps (through gravity-gradient, the first pump forces the flow of petroleum from the vadose zone into the well and the second pump skims off the petroleum to the surface). 20.3.1.7 Bioreactor A bioreactor comprises of a reaction chamber equipped with a mixing mechanism, oxygen and nutrient supply system, influential and effluent pumps. It is an ex situ bioremediation technology that provides the direct control of environmental/nutritional factors (such as oxygen, moisture, nutrients, pH and even microbial population) that control biodegradation (Zouboulis et al., 2019). Hydrocarbon-polluted soils are incorporated to the bioreactor chamber and mixed along with the periodic input of oxygen and nutrients to boost biodegradation. This makes the technology more accurate than most bioremediation in situ technologies in which it is not easy to control the variables affecting bioremediation at the spill site.

20.4 Factors affecting the biodegradation efficiency The rate of hydrocarbon degradation is affected by diverse physical and chemical factors. The nature and quantity of hydrocarbons, the type of polluted matrix (soil, sediment,

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water and effluent), the environmental conditions, and the activity of the microbial community can be cited among many. The environmental factors include nutrient availability, temperature, water or humidity content, oxygen, pollutant bioavailability, and pH as shown in Fig. 20.3 (Breedveld & Sparrevik, 2000; Haritash & Kaushik, 2009; Silva-Castro et al., 2012).

20.4.1 Nutrient availability For microbial metabolism, inorganic sources such as nitrogen, phosphorus, potassium, hydrogen or oxygen are essential and affect the growth and activity of microorganisms, whereas micronutrients such as zinc, manganese, iron, nickel, cobalt, molybdenum, copper, and chlorine are necessary. The carbon/nitrogen or carbon/phosphorus ratios are considered to be a determining factor in biodegradation rates and are high in contaminated hydrocarbon sites that limit and affect the rate of degradation (Garon, Sage, Wouessidjewe, & Seigle-Murandi, 2004). Significant effort has been made to develop nutrient delivery systems that overcome the washing problems characteristic of open sea and intertidal environments; the use of slow-release fertilizers and/or oleophilic nutrients can provide polluted environments with a continuous source of nutrients. Slow release fertilizer typically consists of solid-form inorganic nutrients coated with a hydrophobic compound such as paraffin or vegetable oil. Oleophilic biostimulants are a successful alternative that solves the problem of rapid dilution and washing out of water-soluble

FIGURE 20.3

Factors affecting bioremediation.

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nutrients containing nitrogen and phosphorus. Oleophilic additives remain dissolved in the oil phase and are thus available at the oil-water or oil-sediment interface, where bacterial growth and metabolism are enhanced.

20.4.2 Temperature The hydrocarbon degradation capacity of microorganisms is significantly affected by temperature. Solubility, bioavailability, distribution of hydrocarbons and diffusion rate are increased at high temperatures, promoting the capacity of microbial biodegradation and improving the rate of biodegradation. Very high temperatures, on the other hand, decrease oxygen solubility and limit the biodegradation of aerobic microbes (Leahy & Colwell, 1990). In addition, Boopathy (2000) confirmed that pollutant degradation is better and more efficient at mesophilic temperatures than very low or high temperature degradation. However, it was reported that microorganisms are able to metabolize PAHs at extreme temperatures: for example, a high degradation rate of PAHs occurred in seawater at low temperatures (low as 0 C) and at 50 C. Bargiela et al. (2015) have derived the correlation between the relative percentage of genes encoding enzymes involved in biodegradation and temperature at oil-polluted sites.

20.4.3 Oxygen limitations The initial steps in the catabolism by bacteria and fungi of aliphatic, cyclic and aromatic hydrocarbons involve the oxidation of the substrate by oxygenases for which molecular oxygen is needed. Although it has been shown that anaerobic biodegradation occurs in various ecosystems, including marine environments, its ecological significance has generally been considered to be minor and the rate of biodegradation is rather low (Ghosal et al., 2016). In aquatic sediments and soils, oxygen restriction conditions normally exist. Oxygen depletion can occur in the presence of easily utilizable substrates that increase microbial oxygen consumption. In several instances, the concentration of dissolved oxygen can be close to zero, leading to practically zero aerobic biodegradation rates. Although oxygen can be successfully delivered (in various forms) to soils and groundwater polluted with hydrocarbons, boosting biodegradation rates, this is not the case in marine environments, as such deployment is very difficult to execute technologies. Thus oxygen represents a very significant and potential factor which limits the rate of hydrocarbon degradation.

20.4.4 pH In aquatic environments, the pH variations are not commonly observed, and most hydrocarbon-degradable bacteria and fungi require a neutral pH. Microbial activity is, in general, affected by extremely low or high pH. Bamforth and Singleton et al. (2005) have reported that for Burkholderia cocovenenans, 40% of phenanthrene degradation was observed at pH 5.5. The degradation at neutral pH, however, was 80% under the same conditions. Furthermore, Leahy and Colwell (1990) reported that microbial degradation of

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naphthalene decreased at pH 5.0, compared with the highest rate of degradation observed at pH 7.0. In addition, the efficacy of some microorganisms, such as Pseudomonas, to degrade hydrocarbons at alkaline pH has been described in other reports. PAH degradation has been reported by indigenous microorganisms in an acid-contaminated environment (pH 2). The suitable pH depends on the microorganisms that are to be used for the process of bioremediation.

20.4.5 Bioavailability of hydrocarbon The bioavailability is defined as the rate of substrate mass transfer into the microbial cells. It is regarded as one of the most important parameters for the rate of degradation of hydrocarbons. PAHs are characterized by low bioavailability as a result of their low aqueous solubility. That is why they are reported to be resistant and environmentally persistent to the degradation process. Unsuccessful remediation of PAH-contaminated sites has been reported due to the low bioavailability of PAHs. Hydrocarbon bioavailability has been reported to decrease over time (Ghosal et al., 2016). Although the photooxidation increases the biodegradation of petroleum hydrocarbon by increasing its bioavailability, hence promoting microbial activity (Maki et al., 2003). Hydrocarbons, and particularly PAHs, become more bioavailable when dissolved or evaporated. The bioavailability of pollutants in contaminated environments may be increased through the application of surfactants.

20.4.6 Restriction of physical contact between microorganism and oil spills The rate of biodegradation in the environment is generally limited due to the hydrophobicity and low water solubility of most petroleum hydrocarbons. This is because the first step in the petroleum oil degradation process often requires the involvement of bacterial membrane-bound oxygenases, which require direct and effective contact between bacterial cells and substrates of petroleum hydrocarbons. The primary factors restricting the biodegradation efficiency of petroleum hydrocarbons are: (1) limited bioavailability of petroleum hydrocarbons to bacteria, and (2) the fact that bacterial cell contact with hydrocarbon substrates is a requirement before introduction of molecular oxygen into molecules by the functional oxygenases. However, countermeasures against petroleum contaminants have been developed by bacteria, such as improving the cell’s adhesion capacity by altering its surface components and secreting bio emulsifiers in order to improve their access to target hydrocarbon substrates. Bacteria with such functions are often tested for use as environmental remediation agents, accelerating the removal from the environment of petroleum hydrocarbon pollutants (Krasowska & Sigler, 2014). The efficient biodegradation of hydrophobic hydrocarbon substrates requires bacterial surface properties. Although bacterial adherence may improve hydrophobic hydrocarbon biodegradation, it is not necessary to attach bacterial cells to targeted substrates. This is because bacteria with high surface hydrophobicity are easily aggregated and biofilms are formed in some instances, creating potential risks such as diseases. Indeed, not only hydrophobic bacteria can biodegrade hydrophobic pollutants; several solvent-resistant hydrophilic bacteria are

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also capable of metabolizing such pollutants (Heipieper, Neumann, Cornelissen, & Meinhardt, 2007), which can be attributed to the modification of lipopolysaccharides or porines of the outer membrane of the bacterial surface (Krasowska & Sigler, 2014) also reported the first colonization and dominance of solvent-resistant bacteria for pollutant removal. This is due to the fact that bacteria with a high surface hydrophobicity can easily combine and biofilms can form in some cases, posing health dangers. Several solvent-resistant hydrophilic bacteria can also biodegrade hydrophobic contaminants (Heipieper, Neumann, Cornelissen, & Meinhardt, 2007), which can be linked to the change of lipopolysaccharides or porines of the bacterial surface (Krasowska & Sigler, 2014) was also the first to report the colonisation and domination of solvent-resistant bacteria in the pollutant removal process. Hydrophilic microorganisms appear to be more useful than hydrophobic microorganisms in the remediation of hydrocarbon contaminants (Obuekwe, Al-Jadi, & Al-Saleh, 2009). To enhance the bioavailability of petroleum hydrocarbons, one promising approach is the application of surfactants (Kleindienst et al., 2015), which may enhance dissolution or desorption rates leading to the solubilization or emulsification of petroleum hydrocarbon pollutants. Chen and Li (2007) found that Bacillus sp. adhered to in the presence of rhamnolipids, hydrocarbon DQ02 increased 44% and n-hexadecane degradation increased 11.6% compared to treatment in the absence of rhamnolipids. However, certain surfactants, such as Corexit 9500, have been reported to have adverse effects on oil-degrading bacteria (Kleindienst et al., 2015) because of surfactant toxicity and competition with hydrocarbon substrates. Hence, the selection of suitable surfactant is crucial for the remediation of pollutants while preventing secondary pollution. Bioemulsifier-producing bacteria, which have attracted much attention, generally have the following two physiological aspects: (1) the ability to enhance the complexation and solubilization of nonpolar substrates, thereby promoting the bioavailability of substrates, and (2) the ability to improve affinity between cell surfaces and oil-water interfaces through metabolism, promoting deformation of the oil-water interface film. Ayed et al. (2015) reported that the bio surfactant produced by Bacillus amyloliquefaciens An6 was an alternative to chemically synthesized surfactants because it showed a high efficiency of solubilization towards diesel oil (71.54% at 1 g/L) better than SDS and Tween 80 and could improve the efficiency of the An6 strain degradation of diesel oil. However, not all the biosurfactants produced by bioemulsifier-producing bacteria can effectively enhance the degradation rate of pollutants. Indeed, whether various bio surfactants stimulate or inhibit the bioremediation of pollutants is dependent on the physicochemical properties of the surfactants, types of pollutants and physiological characteristics of the functional microorganisms. Therefore a database of petroleum hydrocarbon pollutants and bio emulsifier-producing bacteria must be established, which is conducive to the targeted selection of suitable petroleum hydrocarbon treatment bacteria.

20.5 Role of microorganism More than 200 different bacterial, fungal, and yeast species have been reported to be able to degrade petroleum hydrocarbons. Naturally, these microorganisms can be found in the sea, freshwater and soil. The biodegradable compounds of hydrocarbons range from methane

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compounds to C40 compounds. Nearly 79 bacteria, 9 cyanobacterial genera, 103 fungi, 14 algae, and 56 leaves are capable of degrading hydrocarbon pollutants for classification (Jafarinejad, 2017). Various compounds of petroleum hydrocarbons can be degraded by different groups of indigenous soil bacteria. These bacteria comprise soil-isolated Pseudomonas strains and reservoirs to degrade PAHs (Atlas, 1995). Other microorganisms with the ability to degrade petroleum hydrocarbons are Yokenella sp., Alcaligenes sp., Alcanivorax sp., Microbulbifer sp., Sphingomonas sp., Micrococcus sp., Cellulomonus sp., Dietzia sp., Roseomonas sp., Stenotrophomonas sp., Gordonia sp., Acinetobacter sp., Corynebacterium sp., Flavobacter sp., Streptococcus sp., Providencia sp., Sphingobacterium sp., Capnocytophaga sp., Bacillus sp., Enterobacter sp., and Moraxella sp. (Jain et al., 2011). Alcanivorax sp. bacteria and Cycloclasticus sp. can use aliphatic and aromatic hydrocarbons, as their carbon source, respectively. Some bacteria can help to produce biosurfactants which can enhance the bioremediation by reducing surface tension and increase of crude oil uptake. However, factors such as supply of nutrients and nature of oil impurities are influential in degrading the petroleum hydrocarbons (Bovio et al., 2017). Some fungi are also capable of degrading hydrocarbons from petroleum. However, for effective degradation, they need more time. Fungus from Aspergillus sp., Amorphoteca sp., Penicillium sp., Graphium sp., Neosartorya sp., Paecilomyces sp., Fusarium sp., and Talaromyces sp. They are among the microorganisms capable of degrading hydrocarbons from petroleum. Compounds such as polychlorinated biphenyls (PCBs) and PAHs are reported to be able to degrade white rot fungi. Some yeasts including Candida sp., Pichia sp., and Yarrowia sp. also reported to have the potential to degrade the compounds available in oil contaminants (Jain et al., 2011). Some researchers suggest that in specific circumstances, fungi can degrade petroleum better than bacteria (Bovio et al., 2017). However, for fungal bioremediation of marine contaminated sites, there really is not much information available. Genetic manipulation of microorganisms to enhance their ability of oil degradation still requires investigation.

20.6 Novel approaches Current research into the bioremediation of oil spills focuses mainly on new materials addition for biostimulation, using genetically modified microorganisms for bioaugmentation and integration of different physicochemical and biological approaches for oil spill treatment. The new methods for the bioremediation of oil spills are enlightened in the following section.

20.6.1 Substance addition In novel approaches biowastes, inorganic materials, polymeric materials, etc. are added to enhance the bioremediation. Another material that has recently gained attention in the bioremediation studies of oil spills is the addition of biosurfactants. Biosurfactants are produced by various microorganisms, including leaves, bacteria, and filamentous fungi, extracellularly or as part of the cell membrane. Microbial activity in the case of biosurfactant is due to the enhancement of extracellular biosurfactant (e.g., trehalose lipids produced by Rhodococcus species) or cellular biosurfactants (e.g., mycolic acids) which cause the microbial cells to be linked to hydrophobic phases. There is a broad structural diversity of biosurfactants, including lipopeptides, glycolipids, fatty acids, lipoproteins, neutral lipids,

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phospholipids, and polymeric biosurfactants. Two groups of biosurfactants, which are lowmolecular-weight surface active materials with the ability to lower the tension (both surface and interfacial) efficiently and polymers with high molecular weight (bioemulsifiers) that are used for stabilization of emulsions (Bezza & Chirwa, 2015) are available. Biosurfactants have less toxicity, biodegradability, and ecological acceptability than chemical surfactants. In comparison to chemical ones, biosurfactants act more effectively at different pH, temperature, and salinity (Bezza & Chirwa, 2015) with superior biodegradability and ecofriendly nature (Szulc et al., 2014). For bioremediation, especially for the biodegradation of hydrophobic compounds, biosurfactant-producing microorganisms are of interest.

20.6.2 Genetic engineering In 1970, the first GEM was developed with the name “superbug” and was capable of degrading oil. This was done with plasmid transfer to utilize some toxic hydrocarbons including hexane, octane, toluene, xylene, camphor. After improving genetic engineering methods and thorough research on the metabolic capabilities of microorganisms, the development of GEMs became more significant in the early 1980s. It was in 1981 that the first two genetically modified strains were patented. The two strains containing genes that give them the ability to degrade naphthalene, salicylate, and camphor are Pseudomonas aeruginosa (NRRL B-5472) and P. putida (NRRL B-5473). The development of GEMs with enriched capacity for biodegradation of organic compounds is possible since the degradative method, the enzymes, and the relevant genes are documented and biochemical reactions are thoroughly explained. The limitation of this method is, on the one hand, the survival of GEMs in the environment and, on the other hand, public acceptance, which hampers their broad application (Jafarinejad, 2017). Different genetic engineering methods are available for bioremediation purposes, including improving the specificity and affinity of the enzyme, the design and regulation of the metabolic pathway, and the expansion of the substrate range for existing pathway, preventing the accumulation of waste intermediates that inhibit the carbon flow redirection pathway, improving the genetic stability of catabolic activities, identifying genetically modified bacteria by marker gene in the polluted environment, and using biosensors for monitoring specific chemical compound. The most common method for creation of GEMs is engineering of one gene or operons and construction of pathways and modification of the existing genetic sequence.

20.7 Case studies An unintentional oil spill due to the rupture of crude oil trunk line was reported near the city of Gujarat (western India) in June 2008. The oil spill site was also immediately barricaded by the oil company and the spread of crude oil was also stopped. The oil company recovered large amounts of crude oil collected at the spill site in a low lying field. After these primary actions by the oil company themselves, they approached ONGC TERI Biotech Ltd which is a joint venture company between ONGC and TERI (New Delhi, India), http://www.otbl.co.in.

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The contaminated site was treated with Oil zapper (crude oil degrading bacterial consortium of four species) for the degradation of TPH in oil polluted soil after dumping of oil-soaked soil in a protected bioremediation trap. The nutrient formula was also sprayed on oil-soaked soil after application of Oil zapper (74.5 tons) and then tilling of oil- soaked soil was performed at regular intervals. Samples from the bioremediation site were collected and checked in the laboratory to monitor the rate of degradation. After completion of bioremediation (TPH reduced to 5000 ppm), toxicity of bioremediated soil was checked in laboratory approved by Ministry of Environment and Forest, Government of India. After fish toxicity test, soil after bioremediation is used in green belt development.

20.8 Conclusion and future prospects The occurrence of oil spills is not a new issue and has been a problem for more than a century. Whether it occurs in water or soil, this problem is a huge threat to the ecosystem, fauna, and flora. Due to their high toxicity to human and environmental health, petroleum hydrocarbons are one of the most alarming pollutants. Bioremediation of petroleum hydrocarbon-degrading bacteria is widely considered to be environmentally friendly and effective. A large amount of bacterial species with petroleum hydrocarbon-degrading ability have been exploited and applied in bioremediation. Nevertheless, different problems that slow down the effects of biodegradation have been identified during the practical application process. Bioremediation is a more efficient approach without disrupting the polluted environments compared with physicochemical methods (application of skimmers, booms, barriers and sorbents, dispersants, and controlled in situ burning). This method is based on the presence of catabolic genes and enzymes, which allow microorganisms to utilize hydrocarbons as carbon and energy source. There are various factors that affect the effectiveness of bioremediation, such as oxygen, pH, temperature, and the availability of nutrients. Although several aspects of this approach have been studied by various researchers and a relatively high rate of hydrocarbon removal has been reported, particularly on a laboratory scale, real-field applications are still under review (Sihag, Pathak, & Jaroli, 2014). New fields of research for the bioremediation of oil spills are still a topic of research including the addition of novel materials, the use of GEMs and the integration of electrochemical strategies with biological methods for a better removal of toxins from the contaminated sites.

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C H A P T E R

21 Bioremediation of black tides: strategies involving genetically modified organisms Sonali Mohanty and Subhankar Paul Department of Biotechnology & Medical Engineering, National Institute of Technology Rourkela, Rourkela, India O U T L I N E 21.1 Introduction

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21.2 Conventional bioremediation strategies and their limitations 21.2.1 Physical methods 21.2.2 Chemical methods 21.2.3 Thermal method

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21.3 Switch to biological methods“bioremediation” 21.3.1 Bioaugmentation 21.3.2 Biostimulation 21.3.3 Biosparging 21.3.4 Phytoremediation

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21.4 Genetically engineered organisms (GMOS): an in situ bioremediation approach 381 21.4.1 Current applications of potential GEMs for bioremediation of oil contaminants 384 21.4.2 Technical applicability of GEMs in oil cleanup 386 21.5 Conclusion

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21.1 Introduction The rapid spreading of oil quickly on water surfaces to form a thin flimsy layer is called an oil spill. As the oil keeps spreading, the layer gets more and more slender finally turning into a thin layer called sheen, which basically resembles a rainbow. This is of frequent

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occurrence, due to the regular utilization of oil-based commodities by man and this represents a multifaceted issue as of now bothering oil-producing communities globally. Oil spillage is the frequently occurring man made environmental disaster, that occurs either accidentally or deliberately, affecting coastal waters as well as land, which has become a matter of global concern. Spillage of oil is a controversial part involved in exploration of oil reserves, leakage in pipeline carrying oil, vandalization, while transportation of oil in big haulers. Oil industries pay serious attention to both offshore and onshore oil slick. (Ndimele et al., 2018). Oil industry faces frequent issues due to spillage or leakage of contaminants such as petroleum and its derivatives in the marine environment. Hence requirement for remediation has become obligatory and environmental control agencies charge penalty on violation of corporate responsibility. Polycyclic aromatic hydrocarbons (PAHs) released from the spills are a matter of serious concern due to their hazardous effect on human health, consequently requiring explicit remediation measures. Researchers reported the oil spill can form about 5 3 106 m2 slick on the water surface and this eventually blocks O2/CO2 exchange, resulting in O2 depletion and pH alteration in the water body. This also affects the water evaporation and precipitation rate, which is indicated by desertification caused in most marine environments followed by spillage accidents (Quintella, Mata, & Lima, 2019). Furthermore, oil spill accidents seriously affect the marine environment and human wellbeing indirectly, for example creation of anaerobic conditions in the water bodies induces death of marine organisms. Other chief impacts include hypothermia in mammals and marine birds by obliterating the insulating capacity of the furs in mammals and plumage of birds. The poisonous constituents of crude oil may cause toxicity or kill aves, vertebrates, fishes, and other marine life forms. It could also harm the delicate submerged life forms causing a serious misbalance on the ecological food chain, ultimately affecting human health by harming interior organs, like kidneys, lungs, and liver. The spillage may also damage marine plant growth and coastal vegetation by obstructing optimum light and exchange of gases. It was assessed that 50% of the total coastal wetland loss inferred was brought about by oil spillage. Finally, the spillage accidents in marine environment is the reason for critical revenue losses in the related industries like tourism and other marine asset ventures, like fishery and salt industry, marine chemical industry, etc. (Xue, Yu, Bai, Wang, & Wu, 2015). In comparison to regular physical and chemical remediation techniques, bioremediation process for contaminant removal is more economic (can save 50%
70% of remediation costs) and effective for restoration of marine natural habitat, accompanied with additional benefits. The significance of bioremediation lies in the fact that crude petroleum contaminants are rendered harmless by converting them into CO2 and H2O during the microbial digestion, effectively re-entering the biogeochemical cycle. While the use of conventional physicochemical remediation methods involve conversion of chemical structure of petroleum into complex synthetic compounds other than CO2 and H2O. Simultaneously, secondary contaminations could be created during this process, which could harm the marine climate. Many of the previous studies reported the use of genetically altered oildegrading microbes for in situ bioremediation under natural conditions (Das & Chandran, 2011). Thus it is a better option for the future studies to shift their focus on in situ bioremediation using GMOs.

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21.2 Conventional bioremediation strategies and their limitations

21.2 Conventional bioremediation strategies and their limitations Oil spill incidents have created havoc over the marine environment over the years. Various conventional physical, chemical, and biological remediation techniques have been developed to decrease the toxic effects of oil contaminants on aquatic life.

21.2.1 Physical methods Physical methods also known as mechanical methods don’t involve any chemical treatment of the wastes. These methods are mainly in the form of barriers that control oil spillage without actually altering the physical or chemical characteristics of oil spillage in a water environment. Various barriers are used to contain oil spills, including: (1) booms, (2) skimmers, and (3) adsorbent materials (Hoang, Duong, Nguyen, Viet, & Nguyen, 2018).

21.2.2 Chemical methods Chemical techniques are used in combination with other strategies for marine oil spill remediation as they limit the spreading of oil and help to secure the shorelines and delicate marine natural surroundings. Different synthetic substances are utilized to treat the crude oil as they have capacities to change its physical and chemical properties. The type of chemicals generally used for cleanup purposes include solidifiers and dispersants. The chemical methods for remediating the marine climate don’t just impede the spreading of the oil spill, yet additionally ensure protection of the coastline and susceptible marine territories. These strategies are, hence, the best amongst conventional remediation methods accessible for both coastal as well as seawards (Hoang et al., 2018).

21.2.3 Thermal method Thermal method is an in situ bioremediation process where the spilled oil is burned with a specially designed equipment like fire-resistant boom or igniters. This process is most effective if immediately carried out after the spillage. Calm water and steady wind flow is the best environmental condition for this method to work effectively. The thermal remediation method is best relevant for refined oil items consumed rapidly without threatening marine life. Great care has to be taken before conducting this process, like ensuring that there are no floating vessels close by like boats, speedboats, and oil tankers (Tewari & Sirvaiya, 2015). Conventional methods Physical methods (Chatterjee, 2015; Dave & Ghaly, 2011; Ventikos, Vergetis, Psaraftis, & Triantafyllou, 2004)

Classification of methods 1. Booms

Description

Types

Disadvantages

Booms include floating physical barriers and skirt or curtains which sinks down, slowing down the flow of oil by keeping it contained.

Fence boom

It is inconvenient to clean and store them after use.

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Conventional methods

Classification of methods

Description

Types

Disadvantages Low stability in strong winds and currents, low flexibility

Skimmers

Adsorbents

Chemical methods (Mapelli et al., 2017; Tewari & Sirvaiya, 2015)

Skimmers can be boats, vacuum machines, sponges or oil-absorbent ropes that removes spilled oil from the water’s surface.

Sorbent materials adsorb oil to varying degrees with some of them swelling more than 50%.

Fireresistant boom

Direct burning of collected oil, they are very expensive and hard to tow owing to their huge dimensions

Wier skimmer

Very often jammed by floating trash and debris

Oleophillic Skimmer

It is inefficient in dealing with oil mixed with dispersants and trash has to be separated by hand.

Suction skimmer

They are not convenient for use with inflammable contaminants that may lead to explosion

Natural organic

Using them involves intensive labor, they also absorb water along with oil and which leads to sinking and makes their collection difficult.

Natural inorganic

Common inorganic adsorbents, for example, mud and vermiculite being light material and hard to apply in unsteady wind flow and cause breathing hazards.

Synthetic

The inconveniences involve difficulty in storage and nonbiodegradability after use.

Dispersants

These are surfactants that by the action of water currents break the spilled oil into smaller droplets(100 μm).

Associated with toxicity and gets accumulated in sea foods.

Solidifiers

Solidifiers are hydrophobic polymeric

The issue of recovery after solidification large

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21.3 Switch to biological methods-“bioremediation”

Conventional methods

Thermal methods (Tewari & Sirvaiya, 2015)

Classification of methods

In situ burning

Description

Types

Disadvantages

materials that on reacting with oil, change its state into rubber like state that can be effectively eliminate by physical methods.

amount is required (16%
200% by weight of oil mass) and they have a relatively lower efficiency than dispersants.

Controlled burning of oil at the spillage site to decrease the spread of oil.

Fire mishap leading to destruction of coastal vegetation cover, and human health risks due to gases released via combustion.

21.3 Switch to biological methods-“bioremediation” Bioremediation is an environment friendly, cost effective process of degrading hydrocarbons via selected microorganisms. Those microbial species or specific strains can process hydrocarbons and use the subsequent compound carbon as their food and carbon source for development and generation. Subsequently the complex organic hydrocarbon is hydrolyzed into simpler and nontoxic inorganic forms for example, CO2 and H2O, with microbial biomass accumulation, through oxidation under aerobic conditions. In specific situations, some anaerobic microbes degrade hydrocarbons by reduction. For example, Flavobacterium sp. (DS-711), which is a benzene tolerant strain, segregated from remote ocean sediments of 1945 m degraded nearly 90% of n-alkanes in kerosene (Adams et al., 2015). Bioaugmentation and biostimulation are two significant kinds of bioremediation strategies.

21.3.1 Bioaugmentation Bioaugmentation refers to the addition of oil-degrading bacteria in a general population of bacteria near the oil spill site. This methodology & reasoning is that the native microbial population may not be capable of fully degrading the complex composition of petroleum or maybe in stress due to the oil spill. According to the remediation process, like remediation of petroleum hydrocarbons, the microorganisms introduced can be isolated from a historical site, contaminated site, or genetically engineered (Adams, Tawari-Fufeyin, Okoro, & Ehinomen, 2015).

21.3.2 Biostimulation By restricting the supplement material to the contaminated medium we can enhance the rate of natural biodegradation of oil hydrocarbons, especially organic pollutant, thus it can be called a supplement mediated bioremediation cycle. The supplement includes phosphorous, carbon, and nitrogen. Other conditions that are altered or changed include

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temperature and the amount of supplied air. All the conditions are made as such to increase the oil degrader’s activity and development (Baniasadi & Mousavi, 2018).

21.3.3 Biosparging Biosparging is somewhat similar to bioventing, where petroleum products present in the soil or dissolved in groundwater are remediated using wild microorganisms located in the site of pollution. In this method, wild microorganisms found at the contaminant saturated zone are provided with nutrients and oxygen to enhance their metabolism which speeds up the remediation process (Azubuike, Chikere, & Okpokwasili, 2016).

21.3.4 Phytoremediation Phytoremediation refers to the green strategy to remediate the ecological contaminations, primarily pesticides, and oil hydrocarbons. It involves plants and their related microbial population, which breaks down the toxins in an agronomic pattern. The plants help in degrading the pollutants in various ways like, accumulating toxins in roots, translocation of pollutants from roots to shoots or leaves for transpiration, photo degradation, metabolic degradation using enzymes secreted by plants. With the improvement in genetic engineering, various transgenic plants are used in bioremediation processes. For instance, the introduction of reductase enzyme-coding genes in Arabidopsis thaliana helped absorb mercury from the soil for remediation purposes (Suresh & Ravishankar, 2004).

21.3.5 The oil eating microbes The petroleum crude oil usually consists of mainly carbon(83%
87%) followed by hydrogen(10%
14%), nitrogen(0.1%
2%), oxygen(0.1%
1.5%), and traces of sulfur, and other metals. The principal hydrocarbons are theoretically degradable but the elements present in traces are matter of concern. Crude oil is a mixture of aliphatic and aromatic hydrocarbons that include paraffin ranging about 15%
60%, naphthalene(30%
60%), aromatics(3%
30%) and 6% asphaltic by weight. Therefore, screening and isolation of microbial strain is carried out by supplying crude petroleum or any crude component in particular, and the selective strain is checked for utilization of that component, as carbon source, with mineral nutrients essential to build up the microbial biomass (Wang, Zhang, & Klassen, 2011). The oil degrading strains of the marine habitat include (e.g., Oleiphilus, Alcanivorax, Neptunomonas, Cycloclasticus, Marinobacter, etc) most efficiently degrade alkanes and aromatics. Branched chains and n-alkanes are significantly broken down by Alcanivorax strains while aromatic hydrocarbons are very well degraded by Cycloclasticus species (McGenity, Folwell, McKew, & Sanni, 2012). Pseudomonas, Bacillus, and Corynebacterium were isolated from the Liao he oil-field’s residual oil which could break petroleum compounds into byproducts that constituted: 80% of aromatic hydrocarbon; 53% bitumen; 37% aliphatic hydrocarbon; and 30% nonhydrocarbon. Tropicibacter naphthalenivorans degrades naphthalene, phenanthrene, C1-alkyl naphthalene, and C2-alkyl naphthalene, with the

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exception of two alkyl benzothiophene, alkyl phenanthrene, and alkyl fluorine (Harayama, Kasai, & Hara, 2004). Slow degradation of contaminants by natural microorganisms is one of the main limitations of bioremediation. Apart from that, the toxicity of organic pollutants in microorganisms due to diversity in pollutants causes more complications in the bioremediation process. Bioremediation is difficult for new complex human-made contaminants because of the primitive metabolic pathway of microorganisms. Hence improving genetic engineering becomes essential to improve the genetic frame of microorganisms using processes that include using GEMs for fast and effective degradation of specific pollutants. Knowledge of microbiological information combined with ecological and biochemical mechanisms like biochemical paths, operon arrangement, microbes, and contaminants is the key to a proper GEM design with important genetic parameters (Kulshreshtha, 2013).

21.4 Genetically engineered organisms (GMOS): an in situ bioremediation approach There has been a paradigm shift toward the use of genetically engineered organisms in wide variety of applications for the bioremediation purpose. The genetic design of these microorganisms makes them valuable for biodegradation, biosorption biotransformation, and bioaccumulation. The basic blue print for GMO production incorporating the gene encoding for biodegradative proteins in the chromosomal and extra-chromosomal DNA of such microorganisms. Some widely used methods for achieving the above target includes PCR, site directed mutagenesis, anti-sense RNA technology, electroporation, biolistics, particle bombardment, etc. The biotechnology equipped with recombinant DNA is currently the most potential method tuning the bioremediation strategies by enhancing contaminant degradation through use of microorganisms via strain improvement and regulatorymetabolic genetic alterations (Xu & Zhang, 2016). Genes contain information required to make proteins. The construction of genetically modified bacteria (GMBs) or GMOs is carried out utilizing the above concept. There are two broad category of genes utilized for this purpose of bioremediation which includes degradative and reporter genes. The major type is degradative genes which contain directions to make proteins that separate, breakdown, or degrade contaminants. These proteins form essential biomolecules such as enzymes which assume a wide range of jobs in living things, from aiding make new strands of DNA, to separating huge atoms to extricate energy from them or to render them nontoxic. The second type is the reporter gene that is used to monitor or help screen levels of contamination. This kind of gene in a genetically engineered organism does it by any characteristic change, for example, a gene that makes a microbe express a green fluorescent protein (GFP). GFP acts as a marker that makes it simple to later recognize and screen these creature’s movement in natural environmental samples, for example, water, soil, or biofilms (Das & Chandran, 2011) (Table 21.1). Based on the above gene constructs different methodologies have been deduced for constructing GEMs (Kulshreshtha, 2013). The first methodology is the identification of organisms with required genes and suitable properties for adaptation in particular habitat. For example, soil microorganisms

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TABLE 21.1 Application of genetically modified organisms (GMOs) in measuring the contaminant degradation efficiency. GMOs

Indicators

Application

References

Pseudomonas fluorescens- HK44

Reporter gene- LUX

Monitoring naphthalene degradation pathway

Saxena, Kishor, Saratale, and Bharagava (2019)

P. fluorescens 10586 s pUCD607

Reporter gene- LUX

Toxicity assessment of benzene and its metabolites

Boyd, Meharg, Wright, and Killham (1997)

Alcaligenes eutrophus H850

luxAB reporter genes

Monitoring PCB-degradation pathway

Van Dyke, Lee, and Trevors (1996)

Acinetobacter baumannii S30

luxCDABE

Monitoring total petroleum hydrocarbon (TPH) degradation

Mishra, Sarma, and Lal (2004)

Pseudomonas putida TVA8

tod-luxCDABE fusion reporter

Monitoring benzene, toluene, ethylbenzene, and xylene(BTEX) degradation

Applegate, Kehrmeyer, and Sayler (1998)

Pseudomonas cepacia (BRI6001L)

luxAB and lacZY gene system

Monitoring the bacterial strain in 2,4dichlorophenoxyacetic acid (2,4-D)degradation

Masson, Comeau, Brousseau, Samson, and Greer (1993)

Escherichia coli W3110 gyrB-lacZ reporters

Monitoring stress tolerance of E. coli strain Sousa, De Lorenzo, and W3110 in naphthalene biodegradation Cebolla (1997)

Pseudomonas strain Shk1

Shk 1 bioreporter

Monitoring toxicity of 2, 4-dinitrophenol hydroquinone

Kelly, Lajoie, Layton, and Sayler (1999)

Stenotrophomonas 3664 & A. eutrophus 2050

Lux reporter

End point analysis of nonpolar narcotics

Layton, Gregory, Schultz, and Sayler (1999)

struggle to thrive in aquatic habitat and hence can’t be effectively utilized. Similarly, microorganisms of aquatic environment can be utilized to create GEMs for bioremediation in water bodies. The utilization of such organisms would reduce the maintenance cost by avoiding the extra supply of nutrients in the inoculated environment. Anabena species and Nostoc ellipsosporum were modified by introducing gene linA (from Pseudomonas paucimobilus) along with fcbABC (from Arthrobacter globiformis). linA is responsible for biodegradation of lindane while fcbABC degrades fcbABC. Hence combined use of the two genes involves efficient bioremediation of the later contaminants together. The subsequent methodology is the pathway development, extension, and further regulation. GEMs are constructed in way, so as to enhance and improvise the catabolic pathways or to extend them in a such way that leads to the degradation of xenobiotics which was impossible in the case of the wild types. The entire catabolic pathway is governed either by a single microbe, or by a group, each participating in at least one of the phases of bioremediation. The constructed GEMs hence have the combined degradation abilities of several microbes, and the modification of certain genes further improves the productivity and adequacy of the catabolic pathways. The third methodology is to modify enzyme substrate affinity and specificity. The enzymes that mediate each step of particular pathway to occur are the product of

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21.4 Genetically engineered organisms (GMOS): an in situ bioremediation approach

transcription and translation of genes, and these genes are altered in GEMs which are developed to change the specificity of enzyme for the substrate. These gene clusters in fact are designed to encode the compound having improved transformation capability. Escherichia coli strain was genetically transformed through modified hybrid gene cluster for efficient trichloroethylene (TCE) degradation. Fourth methodology is monitoring and controlling the bioprocess improvement, along with sensing via bioreporters for the detection of toxicity and end point analysis. The use of lux gene to monitor the progress in biodegradation is the most advantageous, since bioluminescence can be effortlessly detected and don’t need costly equipment or addition of synthetic elements. The chemical sensors present in the GEMs also helps in evaluating bioavailability of toxins along with detection of pollutant. Bioluminescence created assists in finding out the spread of microorganisms in the contaminated zone and end point of the process is evaluated (Table 21.2). Friello et al. constructed a multiplasmid strain of Pseudomonas capable of degrading aliphatic, aromatic, polyaromatic and terpenic hydrocarbons. Pseudomonas putida containing XYL, NAH, and a hybrid plasmid (formed by joining parts of OCT and CAM) easily TABLE 21.2 Principal strategies involved in construction of genetically modified organisms for bioremediation purposes. Genetically modified bacteria (GMBs)

Plasmids used Modifications Genes of interest Degraded oil contaminants

Pseudomonas putida PaW85

pWW0 plasmid

Pathways




Petroleum

Saxena et al. (2019)

P. putida

TOL plasmid

Pathways

xylS gene and xylE gene

4-ethylbenzoate

Ramos, Wasserfallen, Rose, and Timmis (1987)

P. putida KT2442

Pathways

Transposon mini- Toluene/benzoate Tn5 with xylE/ npt portion deleted

Panke, Sa´nchezRomero, and DE Lorenzo (1998)

Pseudomonas B13 derivative FR1

pFRC20P Pathways plasmid (ortho cleavage pathway)

xyLXYZ, xyIL, xylS

Methyl phenols and methyl benzoates

Top (2002), Rojo, Pieper, Engesser, Knackmuss, and Timmis (1987)

Pseudomonas sp. LB400

pGEM456
335 Substrate specificity

bphA gene

Polychlorinated biphenyls

Erickson and Mondello (1993)

Comamonas. testosteroni VP44

pPC3 and pE43

Substrate specificity

Chlorobenzoate (CBA) dehalogenase genes

o-, p-monochlorobiphenyls

Hrywna, Tsoi, Maltseva, Quensen, and Tiedje (1999)

Hybrid pseudomonas strainsPseudomonas pseudoalcaligenes (KF707- D2) & P. putida(KF715-D5)

pJHF101 pASF101

Substrate specificity

todC1 gene

Chloroethenes

Suyama et al. (1996)

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21. Bioremediation of black tides: strategies involving genetically modified organisms

degraded naphthalene, octane, camphor, and salicylate and was very efficient in processing oil contaminants than any other single plasmid. (Sayler & Ripp, 2000). P. putida is also called a superbug or oil eating bug. Plasmid WWO of P. putida is one amongst the bunch of plasmids currently named as TOL (for toluene and xylene) plasmid (Tahri Joutey, Bahafid, Sayel, & El Ghachtouli, 2013).

21.4.1 Current applications of potential GEMs for bioremediation of oil contaminants The advancement in research in the 1980s and 1990s led to the development of genetically engineered microorganisms for bioremediation. This led to a boost in the number of companies carrying out bioremediation, and also, in the number of researchers cultivating the field of genetic engineering and microbiology. Indian-born microbiologist and genetic engineer, Prof. Ananda Mohan Chakraborty, created the first genetically engineered microbe in 1971, and the patent of it got approved by the United States Supreme Court in 1980 (Pandey & Arora, 2020). The specialty of the microbe, a variant of the genus Pseudomonas, was its ability to breakdown the constituents of crude oil. He found that four strains of the common Pseudomonas bacteria possessed enzymes that could carry out the decomposition of different hydrocarbons. It was determined that the genes encoding those enzymes were carried by the extra-chromosomal elements, known as plasmids. Those plasmids were combined together into a strain of Pseudomonas to yield a synergistic effect. Due to high levels of petroleum hydrocarbons in the environment, GMOs have been finding extensive usage in research. Oil has a variety of components associated with it, along with possessing interconnected metabolic pathways, which makes it difficult to be degraded. The scanty research with GMOs can be attributed to their low acceptance by regulatory bodies, which have strong reservations against GMOs and this has been aggravated by the recent decline in funding of bioremediation research projects (Fox, 2011). This restricts our interpretation to a few studies. Cycloclasticus strain A5 can grow on dibenzothiophene, phenanthrene, naphthalene, and fluorine, irrespective of alkyl substitution. The genes, phnA1, phnA2, phnA3, and phnA4, that encode the an and b subunits of an iron
sulfur protein, a ferredoxin, and a ferredoxin reductase, were isolated from the strain. Phenanthrene, naphthalene, methylnaphthalene, dibenzofuran, and dibenzothiophene were successfully converted into their hydroxylated forms by transformed E. coli cells containing the phnA1, A2, A3, and A4 genes. In addition to that, the E. coli cells also transformed biphenyl- and diphenylmethane, the usual substrates of biphenyl dioxygenases (Kasai, Shindo, Harayama, & Misawa, 2003). The broad substrate specificity of Cycloclasticus makes it critical in oil-contaminated sea water. Bacterial hydrocarbon degradation is facilitated by a constant supply of nutrients from bacteriophages by means of phage-mediated biomass yield. Phages, in conjunction with plasmids, are also crucial in the distribution of important genetic material, including the genes responsible for the breakdown of hydrocarbons and the generation of novel catabolic pathways via lateral gene transfer. Phage mediated gene transfer studies can be used as an appropriate means for the transfer of genes into wild strains. The detoxification of polyaromatic hydrocarbons is also feasible via laccase enzyme. Considering this, laccase

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from Myceliophthora thermophila (MtL) was expressed in Saccharomyces cerevisiae via directed evolution for the purpose of bioremediating petroleum spills (Bulter et al., 2003). Genetic manipulation techniques have been used extensively to enhance the oil-degrading capacity of microbes, on land as well as in sea, with the purpose of creating more efficient petroleum-degrading microbes than the ones naturally in existence. An example of genetic modification is the multi plasmid P. putida strain, which possesses the ability to degrade light alkanes and aromatics, simultaneously (Jafarinejad, 2016). The role of GEMs, specifically, “metagenomic clones” was tested on simulated seawater to analyze the degradation of crude oil components. DNA from microbes inhibiting oilcontaminated environments is inserted into genetically modified microorganisms. Using aerobic and anaerobic bacteria derived by metabolic machinery, three metagenomic clones combined the metabolic pathways to replicate that found in nature. A comparative analysis was conducted between the results obtained for biodegradation of petroleum hydrocarbons by genetically modified bacteria and those obtained by naturally-occurring bacterial strains found in reservoirs. 31% and 47% of saturated hydrocarbons were degraded by two metagenomic clones while 99% was degraded by naturally-occurring bacteria. On the contrary, for aromatic hydrocarbons, the degradation was higher under the influence of metagenomic clones which had 94% efficiency as compared to the natural strains, which showed 63%
99% efficiency (Dellagnezze et al., 2014). The DNA diagnostic method developed by Kim et al. involves microarrays that help in identifying the genes which break down hydrocarbon compounds(aliphatic and aromatic). Following that, bioslurping, a sophisticated dewatering technology meant for the bioremediation of soil and water, was executed to carry out the bioremediation of the contaminated site. This system facilitates a high reduction in the discharge of groundwater and soil (Kim, Krajmalnik-Brown, Kim, & Chung, 2014). Genome sequence analysis, was performed by Das et al. (2015) using Pseudomonas aeruginosa N002, isolated from oil tainted soil, with high hydrocarbon degradation efficiency. Using shot gun sequencing, it was found that, the catabolic genes encoding the enzymes responsible for the proper functioning of the hydrocarbon degradation pathways were, alkM from Acinetobacter sp. strain, alkane monooxygenase of P. putida, catechol 2,3-dioxygenase of P. putida, alkane monooxygenase from Rhodococcus sp., pyrene dioxygenase from Mycobacterium sp. strain PYR-1, and naphthalene dioxygenase of P. putida (Das et al., 2015). 21.4.1.1 Genetically modified organisms in phytoremediation Phytoremediation is the designed utilization of plants along with related micro biota for the detoxification and removal of organic and inorganic contaminants from the polluted soil/water to protect the climate and human health. Initially, plants produced by genetic engineering were employed for removal of heavy metals via phytoremediation (Misra & Gedamu, 1989). Explosives and halogenated organic compounds were phytoremediated by tobacco, the first plant to be genetically modified. (Doty et al., 2007). Genetically manipulated plants are designed by incorporating the gene of interest which is associated with the digestion of xenobiotics and offer increased protection from contaminants (Abhilash, Jamil, & Singh, 2009). The objective of utilizing genetic modifications in phytoremediation is for enhancing functional attributes of toxin degradation. With the incorporation of human gene that

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codes for cytochrome P450 IIE1 (responsible for degradation of halogenated compounds like vinyl chloride, tetrachlorocarbon, ethylene bromide, chloroform and TCE) into tobacco, the transgenic plant degraded TCE 640 times quicker than wild strains. Around 400,000 vascular plants have been reported on record to have metabolic ability to debase contaminations. The secondary metabolism of plants varies from species to species. It could be expected, when more plants are researched, even more efficient variety for phytoremediation will be discovered (Alkorta & Garbisu, 2001). 21.4.1.2 Genetically engineered fungi for mycoremediation Genetic engineering approaches have proven to be quite advantageous in adding favorable traits in metabolic pathways or enzymes. With the rampant increase in molecular toolboxes and genome sequences, the process of manipulating fungal strains has become substantially easier. Mycotransformation is best understood when studied with respect to the genes of fungi. Metabolic engineering has paved the way for the design and regulation of gene alterations. Mycoremediation, the technology utilizing fungi with the purpose of decontaminating polluted areas, has a plethora of objectives that are met with the help of cloned fungal genes. Specific enzymes of special importance overproduced by certain fungal mutants can be engineered, and the processes involving those mutants can be developed and implemented for the treatment of pollutants. Processes related to mycoremediation can be controlled using fungal protoplast. Currently, there have been feeble attempts made to increase the flux through specific pathways. The future of metabolic engineering holds extreme potential, but the area of the metabolic network requires more extensive understanding before the implementation of bioengineered yeast or fungi in the field of mycoremediation (Deshmukh, Khardenavis, & Purohit, 2016). The mineralization of Polychlorinated Biphenyls (PCB) by fungi has been facilitated by several improvements in the field of biotechnology in recent times. Lignin peroxidaseencoding genes from 30 fungal species have been screened which have allowed for new ways of PCB degradation to be successful, and the sequence relationship among 32 fungal peroxidases has been illustrated with the help of a dendrogram (Janusz et al., 2017). The area of genetic splicing holds tremendous potential which will aid in piecing together pathway fragments responsible for constructing a novel white-rot fungus that has the ability to use PCBs as the sole carbon source.

21.4.2 Technical applicability of GEMs in oil cleanup In Europe, three potential ways are recognized for utilizing GMOs, in particular, a contained use, release of GMO into the climate, and marketing or commercialization of GMOs. The contained use of GMOs is the development of those GMOs in a closed reactor system unanimously accepted by the public. Various investigations have demonstrated a high bioremediation capability of genetically altered microorganisms and plants. Nonetheless, because of potential risks and less public acknowledgment, the uses of GMOs for remediation advancements are still scant (Halecky & Kozliak, 2020). In 1996, the first field test was conducted in the United States releasing Pseudomonas fluorescens strain HK44 into the environment for detection and biodegradation of PAHs.

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The PAHs (consists of at least two benzene rings fused together having two or more carbons in common) are the major constituent of crude as well as refined petroleum oil items. The recombinant strain HK$$ was constructed by combining plasmids of parental strain P. fluorescens, pKA1 and an additional DNA from Photobacterium fischeri and E. coli. The product strains containing plamid pUTK21 were released into lysimeters. These containers were built up at Y-12 site of Department Of Energy’s, OAK Ridge National laboratories, Tennessee. University of Tennessee in collaboration with OAK Ridge National laboratories got the approval for the release of biosensor strain HK44 under Toxic Substances Control Act (TSCA) authority of the United States Environmental Protection Agency. The strain HK44 was designed to degrade PAHs as well as functions as biosensor, that produces visible light on sensing bioavailable PAHs. This method of oil contaminant detection is less expensive as compared to other chemical means such as gas chromatography, electrophoresis, or mass spectroscopy. The light producing genes introduced into the genetically engineered organisms produce light directly proportional to the concentration of pollutants in soil or water (Ripp et al., 2000). 21.4.2.1 Construction of hybrid pathways through genetic engineering for degradation of oil contaminants Genetic manipulation allows for combination of several degradative pathways inside a single host for bioremediation of hydrocarbons, which are the major contaminant in the case of oil spillage. For instance, two genes are responsible for complete degradation of PCB, and are not present in a single organism. The reason for incompatibility is the catecholic intermediate of both the pathways which inhibit each other. Hence a hybrid organism was constructed by combining Pseudomonas pseudoalcaligenes KF707 and Burkholderia cepacia LB400 for bph genes that give rise to a complementary pathway, containing biphenyl benzoate and chlorocatechol genes from a parental strain. This hybrid strain resulted in complete degradation of PCB, along with efficient degradation of other aromatics like toluene, benzene which are at first a poor substrate for enzyme biphenyl dioxygenases in the original strain (Kumamaru, Suenaga, Mitsuoka, Watanabe, & Furukawa, 1998). 21.4.2.2 Use of DNA probes and biosensors for oil pollutant detection Developing DNA probes prepared from PCB degrading genotypes, used for recognition of PCB degrading strains in polluted environment. Biosensors consists of regulatory elements which on sensing particular pollutant, induces the expression of biodegradative operon. These operons are located in the upstream of the reporter element, which often creates bioluminescence, on being expressed, and hence the pollutant could be easily detected. In all the biosensor strains for PAHs, PCBs, Cd or Pb detection lux reporter gene is fused, for instance, nahG-lux, bphA-lux, todCl-lux etc. (Dua, Singh, Sethunathan, & Johri, 2002). 21.4.2.3 Use of biosurfactants to increase bioavailability of oil contaminants Biosurfactants are amphiphillic products formed as a result of biodegradation by microorganisms that use water immiscible substances as substrates thus enhancing the bioavailability of organic pollutants. Biosurfactants are mostly utilized for cleansing of large oil tankers, for oil spill clean up in oceans, for increased oil recovery and in bioremediation of

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hydrocarbon polluted environment. A rhamnolipid biosurfactant was capable of solubilizing hydrophobic α-HCH in water, resulting the degradation of HCH. This biosurfactant was released by Pseudomonas Ptm1 strain, which was formed by a genetic recombination in-vivo that occurred during the bioremediation process. Later the genes responsible for the biosurfactant formation were discovered and the detailed study was carried out on the molecular mechanism and the pathways involved (Sullivan, 1998). Many organizations and research labs are involved in the formation of bioremediation products, but a few companies and laboratories use genetic modifications to produce bioremediation products commercially. There has been a significant development in the use of GMOs for remediation purposes over the past decade. Bioremediation of petroleum contaminated systems has also become conceivable in India, with the development of oil zapper for oil polluted sites by Tata Energy Research Institute (New Delhi). However most of the studies involving GEMs for the purpose of remediation have been successful in laboratory, but not in real ecosystems pertaining to the lack of environmental conditions like spatial heterogeneity, competition between species, availability of nutrients, and prevailing climatic conditions (Jain & Bajpai, 2012).

21.5 Conclusion With the increase in the complexity of the pollutants introduced into the environment, and employing GMOs for the cleanup purposes requires deep understanding of how the transgene may function under added stress. The incorporation of genetic engineering for developing recombinant microorganisms has increased the efficiency of bioremediation by several folds. The principal target in bioremediation is the degradation of aromatic compounds. Hence manipulation of genes in an organism is done by manipulating or altering the gene sequences of the host organism that speeds up the process of degradation. Even though genetic engineering has many advantages, its limitations are often difficult to overcome. The survivality and efficacy of GEMs is also an important issue as artificial gene transfer may not be that effective as horizontal gene transfer that occurs naturally. At present, lack of knowledge about the effect of GEMs on the environment and human health makes its use in bioremediation a debatable topic. A broad and extensive GMO body is needed to regulate its proper use. Various monitoring and detection methods in combination with a biosafety regulatory framework becomes a necessity to keep the environmental and health threats in check and open a platform for the future development of these organisms in the field of bioremediation.

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C H A P T E R

22 Microbes and marine oil spills: oileating bugs can cure oily sea sickness Jayanta Kumar Biswas1,2, Anurupa Banerjee1 and Soumyajit Biswas3 1

Department of Ecological Studies, University of Kalyani, Kalyani, India 2International Centre for Ecological Engineering, University of Kalyani, Kalyani, India 3Department of Biochemistry and Biophysics, University of Kalyani, Kalyani, India O U T L I N E 22.1 Introduction 22.2 Composition of petroleum hydrocarbons

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22.3 Impact of oil pollution on marine ecosystem 398 22.3.1 Sources of oil pollution in marine and coastal environment 399 22.3.2 Fate of oil contaminants in marine ecosystems 399 22.3.3 Toxicity and hazardous consequences 400 22.4 Occurrence and distribution of oil degrading microbial communities 401 22.5 Metabolic versatilities for oil degradation by microbes 22.5.1 Aerobic degradation 22.5.2 Anaerobic degradation

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00023-9

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22.5.3 Enzymes involved in PH degradation

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22.6 Factors influencing microbial remediation of oil 405 22.6.1 Temperature 406 22.6.2 pH 406 22.6.3 Salinity and pressure 407 22.6.4 Oxygen 407 22.6.5 Composition and properties of substrates 407 22.6.6 Nutrients availability 408 22.6.7 Microbial communities 408 22.6.8 Bioavailability 409 22.7 Bioremediation/biodegradation strategies for removal of oil from contaminated sites 22.7.1 Principles and or strategies for PH bioremediation

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22.7.2 Applications 22.8 Conclusions

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22.1 Introduction Remediation and restoration of environment contaminated with hazardous substances has received increasing attention and global awareness over the past few decades in view of the potential detrimental effects of pollutants on public health and habitat (Ghosal, Ghosh, Dutta, & Ahn, 2016). Amidst the several pollutions caused by the varying range of pollutants, petroleum hydrocarbon (PH) pollution has become one of the most serious global concerns. PH pollutants have been listed as priority pollutants due to their high stability, toxicity, and recalcitrant nature (Costa et al., 2012; Varjani, 2017). Petroleum oil serves as the paramount source of energy and also as a raw material in petroleum oil refineries and petrochemical industries for several commodities such as fuel, synthetic polymers, and petrochemicals (Varjani, Rana, Jain, Bateja, & Upasani, 2015). Continuous use of petroleum and its products results in large scale environmental deterioration (Xu et al., 2018; Xue et al., 2015). PH pollution is a direct consequence of several anthropogenic activities such as municipal and industrial run-offs and effluent release (AlHawash et al., 2018; Varjani, 2017). Wide-scale petroleum production, its storage, transportation, coastal oil refining, shipping activities, offshore oil production, and accidental spilling pose direct or indirect effect of PH pollution on the environment and its life forms (Al-Hawash et al., 2018; Arulazhagan, Vasudevan, & Yeom, 2010; Sajna, Sukumaran, Gottumukkala, & Pandey, 2015). Marine environment has become the largest sink and ultimate site for PH pollutants (Varjani & Srivastava, 2015; Varjani, 2017). Oil leaks into the marine ecosystem due to operating problems in oil drilling platforms and exploration boreholes, damage in oil ships or wreckage incidents (Anh, 2019; Guo, Liu, & Xie, 2013; Zhao et al., 2018). A huge amount of oil transportation occurs through waterways resulting in a significant impact on marine habitat from oil-related accidents (Anh, 2019). PH pollutants not only possess direct harm to the marine flora and fauna but also impacts human health through food chain enrichments (Lei et al., 2015). Moreover, severe pollution of the marine bed sediments results from the evaporation and dissolution of oil floating on marine water surfaces forming a thick layer of scattered ions which further agglomerates or gets adsorbed onto other particulate matter and finally settles down (Yavari et al., 2015). Owing to the toxicity, carcinogenicity, neurotoxicity, and recalcitrant nature of PH pollutants it has become imperative to remove such pollutants from the environment. Application of physical and chemical methods to remove such pollutants can impose detrimental consequences on the aquatic life and ecosystem (Kujawinski et al., 2011; Zhao et al., 2018). Utilization of living organisms could be a well accepted alternative for removing oil pollution. Bioremediation involves the use of microorganisms to remove and/or degrade hazardous pollutants to nonhazardous end products (Varjani & Upasani, 2012; Zhao et al., 2011). Although the metabolic versatilities of naturally occurring microorganisms possess incredible bioremediation abilities, several biotic and abiotic factors limit their biodegradability potentials. Paucity of specialized indigenous microbes with complementary substrate specificity necessary for degrading different hydrocarbons at oil

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polluted sites restricts biodegradation possibilities (Ron & Rosenberg, 2014; Varjani, 2017). Several reports on the metabolic versatilities of mixed cultures and the superiority of mixed cultures to pure cultures have proven that catabolic cooperation between various groups of microorganisms in the course of bioremediating PH pollutants is highly relevant (Das & Chandran, 2011; Li et al., 2008; Varjani et al., 2015; Wang, Nomura, Nakajima, & Uchiyama, 2012). New advancements in biotechnological processes have helped to evaluate the genetic make-up of overall microbial communities (Sana, 2015). This further leads to the development of novel strains of microorganisms with desirable characteristics for PH degradation (Varjani & Upasani, 2016a). The application of biosurfactants, immobilized microbial cells, and/or their enzymes has proven to be highly beneficial in the case of marine oil spill remediation (Shen et al., 2015; Zhang et al., 2016). This chapter will provide knowledge on the fate and toxicity of PH pollutants in the marine environment. The microbial metabolic pathways for degradation of PH pollutants are discussed. Details on the exploitation of natural indigenous as well as biotechnologically improved microbes for the cleanup of marine ecosystem have also been focused on.

22.2 Composition of petroleum hydrocarbons The word petroleum is derived from the Latin for “rock” (petra) and “oil” (oleum). Petroleum consists of mixtures of liquid (crude oil), gaseous (natural gas), solid hydrocarbons (condensate), which have been formed within sediments through thermocatalytic alterations when organic matter was exposed to extreme pressure and temperatures. In general all petroleum contains different relative proportions of similar types of compounds (Microbial Genomics of the Global Ocean System, 2020) (Figs. 22.1
22.4). PHs can be differentiated into following four different fractions: 1. Saturates: This fraction consists of nonpolar compounds (Aliphatic hydrocarbons which are saturated or unsaturated and linear or branched open-chain structures such as nalkanes, iso-alkanes, cyclo-alkanes (naphthenes), terpenes and steranes alkanes, paraffins, and naphthenes) as well as natural gases (such as methane, other alkanes up to six carbon compounds, and condensates that exist in the gas phase under reservoir conditions). n-Alkanes can be further classified into four molecular weight groups (1) gaseous alkanes, (2) aliphatic hydrocarbons possessing lower molecular weight (C8C16), (3) aliphatic hydrocarbons having medium molecular weight (C17
C28), and (4) aliphatic hydrocarbons with high molecular weight ( . C28) (Abbasian, Lockington, Mallavarapu, & Naidu, 2015). Biomarkers (such as hopanes, steranes, and steroids) are also included in this fraction. 2. Aromatic hydrocarbons (arenes): This fraction includes ringed hydrocarbon molecules. These hydrocarbons can be classified into (1) monocyclic aromatic hydrocarbons (such as benzene, toluene, ethylbenzene, and xylene [BTEX]) (Costa et al., 2012; Farhadian, Vachelard, Duchez, & Larroche, 2008) and (2) polycyclic aromatic hydrocarbons (PAHs), PAHs can be further divided into high molecular weight PAHs which are made up of four rings or above such as pyrene and chrysenes (four-ringed), fluoranthene and benzo[a]pyrene (five ringed) (Costa et al., 2012; Farhadian et al., 2008; Macaulay & Rees, 2014); and low molecular weight

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FIGURE 22.1

Composition of petroleum hydrocarbons.

FIGURE 22.2

Impact of oil spill on marine ecosystem.

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FIGURE 22.3 Schematic representation of the biodegradation pathways for petroleum degradation by microorganisms (Varjani, 2017).

PAHs containing two or three cyclic rings forming hexagon chains with double bonds such as naphthalene (two-ringed), phenanthrene and anthracene (threeringed) (Wilkes, Buckel, Golding, & Rabus, 2016). 3. Resins: This is a much more polar fraction of crude oil, having nitrogen, sulfur, oxygen, and trace metals that are dissolved in oil (Speight, 2007). Resins consist of aromatic compounds with long alkyl chains and are soluble in n-heptane and n-pentane (Chandra, Sharma, Singh, & Sharma, 2013; Jada & Salou, 2002; Parra-Barraza et al., 2003). Structurally they resemble surface-active molecules in crude oil and act as peptizing agents (Chandra et al., 2013; Jada & Salou, 2002). 4. Asphaltenes: Asphaltenes are like resins containing numerous polar functional groups. They are colloidally dispersed in saturates and aromatics and are dark brown, large and complex molecules (Speight, 2007). The components of this fraction are soluble in light aromatic hydrocarbons such as benzene and toluene (Parra-Barraza et al., 2003). Asphaltenes are viscous and high molecular weight compounds which are composed of polycyclic clusters, substituted variably with alkyl groups, this complex structures contributes to resistance to biodegradation of PHs (Chandra et al., 2013). Peptizing agents like the resins keep asphaltenes in suspension which helps to maintain the stability of crude oil (Chandra et al., 2013; Parra-Barraza et al., 2003).

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FIGURE 22.4

22. Microbes and marine oil spills: oil-eating bugs can cure oily sea sickness

Bioremediation technologies employed in response to petroleum hydrocarbon pollution.

These components and/or fractions of PHs arrange in a way that crude oil, saturates form the outermost layer, while asphalthenes form the innermost portion of oil because of its greater molar mass. Highly condensed aromatics, cycloparaffinic structures, and asphaltic materials possess high molecular weights and high boiling points (Amodu, Ojumu, & Ntwampe, 2013; El-Tarabily, 2002). The biodegradability of the PHs is strongly affected by the unique chemical behavior of each of the component (Costa et al., 2012). Crude petroleum oil obtained naturally can be of use only if it is refined and transformed to other products (Fumoto, Tago, Tsuji, & Masuda, 2004; Lucia, Argyropoulos, Adamopoulos, & Gaspar, 2006). Refined crude oil products obtained are compounds such as petroleum naphtha, jet fuel, gasoline, diesel fuel, heating oil, petrochemical feedstocks, kerosene, asphalt, lubricating oil, waxes and liquefied petroleum gas, etc. (Fumoto et al., 2004; Lucia et al., 2006; Varjani, 2017). Majority of these products pose a load on the environment during their use and at the end of their life cycle (Waigi, Fuxing, Carspar, Wanting, & Yanzheng, 2015).

22.3 Impact of oil pollution on marine ecosystem Transportation of oil from the site of production to the area of consumption poses a major threat to the marine environment due to the risk of accidental oil spills (Adzigbli & Yuewen, 2018). Oil spills cause severe and decade long devastation on marine and coastal ecosystems along with the organisms that sustain them (Joye, 2015).

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22.3 Impact of oil pollution on marine ecosystem

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22.3.1 Sources of oil pollution in marine and coastal environment Oil enters the marine ecosystem through a variety of sources including both natural and man-made sources. The most prominent and visible cause of oil pollution of the marine environment is the accidental or deliberate and/or operational discharges of oil from ships, tankers, offshore platforms, and pipelines (Issa & Vempatti, 2018). Major anthropogenic activities leading to oil pollution include drilling, manufacturing, storing, and transportations. Activities such as well blowouts, breakage in pipelines, ship collisions or groundings, overfilling of gas tanks and bilge pumping from ships, leaking underground storage tanks, and oil-contaminated water runoff from streets and parking lots during rain storms are responsible for oil pollution in the marine and costal ecosystems (Al-Hawash et al., 2018). PHs can enter the marine environment not only as wet (oil) products but also as gaseous air pollutants. Hydrocarbon vapors obtained at different stages from oil extraction to consumption during hydrocarbon loading and unloading can enter the marine ecosystem causing oil pollution (Saadoun, 2015). Sources of input of oil into marine environment can be divided into four main categories: natural seeping of oil, extraction of oil, transportation of oil, and consumption of oil. The oil pollution caused by consumption of oil can be further divided into sea-based and land-based sources. Sea-based sources of marine oil pollution include: (1) Accidental oil spills from tankers, other commercial vessels, grounded and abandoned vessels, oil platforms (blowouts), and pipelines; (2) Deliberate, operational discharges of oil from all kinds of commercial vessels (ship- or cargo-related discharges), oil platforms and pipelines; (3) Emissions of non-methane volatile organic compounds and PAHs from tankers and from oil extraction. Land-based sources of marine oil pollution include: (i) Discharges of untreated or partially treated municipal sewage and urban runoff; (ii) Discharges of untreated or partially treated waste water from coastal industries; (iii) Accidental or operational discharges of oil from coastal refineries, oil storage facilities, oil terminals, and reception facilities; (iv) Emissions of gaseous hydrocarbons from oil-handling onshore facilities (terminals, refineries, filling stations) and from vehicles.

22.3.2 Fate of oil contaminants in marine ecosystems Once the crude oil and petroleum are spilled in the marine ecosystem the presence of wind and water current spreads the oil and moves on the water surface as a slick few millimeters thick (Saadoun, 2015). This oil and petroleum distillate products released in the marine system are immediately subjected to a variety of physical, chemical and biological changes. These changes are collectively termed as weathering (Saadoun, 2015). The weathering can be abiological weathering such as evaporation, dissolution, dispersion, water-in-oil emulsion formation, photochemical oxidation, and adsorption onto suspended particulate material. Biological weathering involves ingestion by organisms and/or microbial degradation (Al-Majed, Adebayo, & Hossain, 2012; Souza, Vessoni-Penna, & Oliveira, 2014). Weathering processes depends on environmental factors such as temperature, ocean currents and weather conditions (Atlas, 1981; Widdel & Rabus, 2001). In the initial 48 h evaporation is most predominant where low medium weight oil components having lower boiling points volatilize (Cappello, Gabriella, & Vivia, 2004). As evaporation proceeds the

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specific gravity and viscosity of the oil increases. The material left behind after evaporation is mostly rich in metals, waxes, asphaltenes. The other abiological weathering processes do not contribute to the significant mass lost from the oil spill (Cappello, Crisari, et al., 2012; Saadoun, 2015). Dissolution involves the solubilization of crude oil fractions (such as light aromatic compounds) which can be highly toxic and impose great threat to marine environment. Dispersion of oil spill refers to the breaking up of oil and the transportation of these oil fractions as smaller particles from the surface of the water to the depths of water column. The process of dispersion is largely controlled by the surface turbulence, greater the turbulence higher is the dispersion. Oil particles which have been dispersed are more susceptible to biological weathering of oil due to the greater exposed surface area (Cappello, Genovese, et al., 2012). Water and oil emulsions also termed as “mousses” are formed when marine water bodies get entrained with insoluble components of oil due to heavy action of waves. The most stable mousses are formed by the heavier or weathered crudes with high viscosities (Cappello, Santisi, Calogero, Hassanshahian, & Yakimov, 2012). Mousse formation is considered as the major limiting factor in petroleum biodegradation. This is because of low surface area of the mousse and low flux of oxygen and mineral nutrients necessary for oil degradation by microorganisms (McGenity, Folwell, McKew, & Sanni, 2012; Saadoun, 2015). The biological weathering involves the action of living organisms specifically microbes for transforming the oil components. Natural biodegradation is ultimately one of the most important means by which oil is removed from the marine environment, especially the nonvolatile components of crude or refined petroleum (Varjani, 2017). The effectiveness of natural biodegradation however is much less, so man-made bioremediation processes have been evolved (Cappello, Santisi, et al., 2012; McGenity et al., 2012; Saadoun, 2015).

22.3.3 Toxicity and hazardous consequences PH pollutants cause extensive and/or permanent damage to ecosystems owing to their recalcitrant, persistent nature and biomagnification abilities (Chandra et al., 2013). PHs is highly toxic because of the presence of components such as BTEX and PAHs which are hemotoxic, carcinogenic and teratogenic (Meckenstock et al., 2016; Souza et al., 2014). Several researches has documented that oil toxicity is highest at the initial stages of oil spill (Adzigbli & Yuewen, 2018; Gros et al., 2014). As a result even smaller spills can cause prolonged impacts and threat to marine ecosystem health. The marine ecosystem is a home of many life forms from microorganisms, plants and algae, invertebrates (such as corals, mollusks, crustaceans, echinoderms etc.) to vertebrates (such as fishes, birds, mammals, turtles etc.). These organisms are exposed to varying degrees of impact during oil pollution. Acute or chronic as well as direct/indirect effects include suffocation, anoxia, stunted growth, metabolic and hormonal disturbances in life forms (Souza et al., 2014; Walker, 2006). Toxicity pathways are different in different species such as ingestion of oil, accumulation of contaminants in tissues, DNA damage, impacts to immune functioning, cardiac dysfunction, mass mortality of eggs and larvae, for example, in fish, loss of

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buoyancy and insulation for birds, and inhalation of vapors (Aguilera, Me´ndez, Pa´saro, & Laffon, 2010; Judson et al., 2010; Major & Wang, 2012). PH pollution results in both long and short term impacts on marine life. Development of abnormalities in marine animals such as jaw reductions, lack of pigmentation and unfused skulls belong to the long term effect (Alonso-Alvarez, Munilla, Lopez-Alonso, & Velando, 2007; Varjani, 2014). Some of the short term impacts on marine life involve acute necrosis mortality, hypothermia, smothering, drowning, and ingestion of toxic compounds during preening (Desforges et al., 2016; Varjani, 2014). Other effects include increased mortality or as sub-lethal injury, impaired feeding and reproduction and avoiding predators on fish communities, estuarine communities, mammals, birds and turtles, deep-water corals, plankton and microbial communities. These toxicological impacts result in changes in species population or community and as a result it affects the entire ecosystem. Not only is the marine world affected by PH pollution, several consequences have been reported in humans also. Crude oil component specifically PAHs have potential to induce malignant tumors which primarily affect skin and other epithelial tissue as they have a great affinity for nucleophilic center of macromolecules like RNA, protein and DNA (Costa et al., 2012; Desforges et al., 2016; Perez-Cadahia et al., 2007)

22.4 Occurrence and distribution of oil degrading microbial communities Microorganisms (most effectively bacteria) which have evolved more than three billion years ago, possess strategies for utilizing almost every compound to obtain energy (Ghosal et al., 2016). Microorganisms play a crucial role in maintaining ecosystem and biosphere to develop sustainable environment (Varjani & Srivastava, 2015; Widdel & Rabus, 2001). Microbial bioremediation has come up to be a widely used technique for treating PH pollution in both terrestrial and aquatic ecosystems (Abbasian et al., 2015). Most of the PHs encountered in the environment has been observed to be degraded or metabolized by indegenous microflora (Hazen et al., 2010; Kleindienst, Paul, & Joye, 2015). Several studies have reported the existence of a large number of hydrocarbon degrading bacteria in environments rich in oil such as oil spill areas and/or oil reservoirs (Hazen et al., 2010; Yang et al., 2015). One of the most common and important microbial adaptation of microbes to survive and grow in such harsh conditions is the organization of biofilms. The formation of microbial biofilms has been observed in the presence of crude oil (Pannekens, Kroll, Mu¨ller, Mbow, & Meckenstock, 2019; Raghukumar, Vipparty, David, & Chandramohan, 2001). Microorganisms dwelling in polluted areas adapt themselves according to environment, gradually in subsequent generations’ genetic mutations results and thereby organisms become hydrocarbon degraders with passage of time (Watkinson & Morgan, 1990; Varjani, 2017). The occurrence and abundance of such oil degrading microbes are closely related to the types of PHs and also the environment in which they are present (Fuentes, Barra, Caporaso, & Seeger, 2015; Varjani & Gnansounou, 2017). In general microbial degradation of oil is limited by the availability of electron acceptors, since hydrocarbons cannot be degraded without hydrogen and acetate scavenging process (Pannekens et al., 2019).

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However, microbes can conserve energy only if they have direct contact to both electron acceptors from the water phase and electron donors from the oil phase (Ridley & Voordouw, 2018). Such optimum situation is found at the oil-water transition zone (OWTZ) present beneath the oil leg, thus being the hotspot for microbial growth and oil degradation. This OWTZ water phase provides habitat for microbes and oil phase acts as electron donors. Thus, the rate of oil biodegradation depends on the size of oil-water interface (Pannekens et al., 2019). Recent studies have isolated and identified greater than 79 genera of bacteria capable of degrading PHs (Tremblay et al., 2017). Several of such bacterial strains namely Achromobacter, Acinetobacter, Alkanindiges, Alteromonas, Arthrobacter, Burkholderia, Dietzia, Enterobacter, Kocuria, Marinobacter, Mycobacterium, Pandoraea, Pseudomonas, Staphylococcus, Streptobacillus, Streptococcus, and Rhodococcus have been found to play vital roles in PH degradation (Nie, Liang, Fang, Tang, & Wu, 2014; Sarkar et al., 2017; Varjani & Upasani, 2016a; Varjani, 2017; Xu et al., 2017). Unexpectedly certain rare soil microbial taxa such as Alkanindiges sp. has also been reported to exhibit degradation abilities in diesel pollution (Fuentes et al., 2015). Certain obligate hydrocarbonoclastic bacteria (OHCB) such as Alcanivorax, Marinobacter, Thallassolituus, Cycloclasticus, Oleispira etc. showed a hike in their population in areas contaminated with petroleum oil (Xu et al., 2018; Yakimov et al., 2007). These bacterial strains use limited carbon sources with a preference for PHs. For example, Alcanivorax strains grow on n-alkanes and branched alkanes, but cannot use any sugars or amino acids as carbon sources. Similarly, Cycloclasticus strains grow on the aromatic hydrocarbons, naphthalene, phenanthrene and anthracene, whereas Oleiphilus and Oleispira strains grow on the aliphatic hydrocarbons, alkanoles, and alkanoates (Hassanshahian & Cappello, 2013) It is highly crucial to assess biodegradation in light of a multidomain community in order to understand complete metabolic potential of indigenous microbial community (Widdel & Rabus, 2001). Such type of observations lead to a clear picture and understanding of the crucial role played by the microorganisms in the degradation of PH pollutants and that they significantly influence the transformation and fate of PHs in the environment (Xu et al., 2018).

22.5 Metabolic versatilities for oil degradation by microbes Microbial biodegradation of any pollutant requires the involvement of several enzymes and is completed in a series of different steps (Abbasian et al., 2015). Hydrocarbons can selectively be metabolized by individual strain of microorganism or consortium of microbial strains belonging to either same or different genera (Boopathy, 2000; Varjani & Upasani, 2016a). There are reports showing that n-alkanes are preferred more by microorganisms for biodegradation as compared to polyaromatic hydrocarbons (Abbasian et al., 2015; Zhang et al., 2011). Methyl branching generally increases the resistance of hydrocarbons to microbial attack (Abbasian et al., 2015; Atlas, 1995). Areas of petroleum spillage contain highly persistent compounds such as hopanes, pristines, and phytanes (Ron & Rosenberg, 2014; Varjani et al., 2015). During the biodegradation process microorganisms obtain energy or assimilate hydrocarbons into their cell biomass (Peixoto, Vermelho, & Rosado, 2011;

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Varjani, 2017). The simpler components of PH pollutants can be degraded by a wide variety of bacteria, but the ability to degrade complex compounds (such as PAHs, resins, and asphaltenes) is found only in very few species. In the majority microorganisms enzymes for biodegradation are encoded on plasmids. Biodegradation of PH pollutants involve metabolic reactions catalyzed by a variety of enzymes (Peixoto et al., 2011). The genes for these enzymes are encoded in various plasmids such as Q15, OCT, TOL, NAH7, pND140, and pND160 with the presence of genes alkA, alkM, alkB, theA, LadA, assA1, and assA2 and nahA-M (Abbasian et al., 2015; Wilkes et al., 2016). Biological degradation of PHs by microorganisms and the metabolic pathways has been well documented (Abbasian et al., 2015; Hasanuzzaman et al., 2007; Leahy & Colwell, 1990; Meckenstock et al., 2016; Wilkes et al., 2016). Microorganisms are capable of utilizing PH pollutants by three possible ways: (1) Phototrophic, anoxygenic; (2) Chemotrophic, aerobic; and (3) Chemotrophic, anaerobic. Several reactions such as oxidation, reduction, hydroxylation, and dehydrogenation are common for both aerobic and anaerobic pathways of microbial degradation of PH pollutants (Abbasian et al., 2015; Wilkes et al., 2016).

22.5.1 Aerobic degradation Aerobically PH pollutants can be degraded by various pathways such as terminal oxidation, sub-terminal oxidation, β-oxidation, etc. (Abbasian et al., 2015; Rahman et al., 2003; Salleh, Ghazali, Rahman, & Basri, 2003). The key step involved in hydrocarbon degradation is the addition of one or two oxygen atoms to the hydrocarbon molecule resulting in alkanol formation in the case of aliphatic hydrocarbon molecule and phenol in the case of aromatic molecules. The incorporation of oxygen is the enzymatic key reaction catalyzed by oxygenases and peroxidases (Abbasian et al., 2015; Peixoto et al., 2011). The enzyme monooxygenase transfers one oxygen atom to the substrate, and forms water by reducing the other oxygen atom (Das & Chandran, 2011; Van Herwijnen et al., 2003). Dioxygenases incorporate both the oxygen atoms of the reaction into products (Abbasian et al., 2015; Das & Chandran, 2011). Degradation of alkanes commonly occurs by monoterminal oxidation (Rahman et al., 2003; Salleh et al., 2003). The primary alcohol formed after oxidation of methyl group in the first step is further oxidized to aldehydes and fatty acids (Hassanshahian & Cappello, 2013; Varjani, 2017). The fatty acid formed undergoes β
oxidation resulting in the formation of short two-carbon atom compound (Hassanshahian & Cappello, 2013; Varjani, 2017) thereby converting organic compounds step by step into intermediates of central intermediary metabolism for example, the tricarboxylic acid (TCA) cycle. In di-terminal pathway, oxidation of both ends of alkane molecule takes place through omega-hydroxylation of fatty acids resulting in the formation of a dicarboxylic acid which is further processed by β-oxidation (Abbasian et al., 2015). In sub-terminal oxidation pathway alkanes are oxidized to secondary alcohol and then to its corresponding ketone and ester, this ester is further hydrolyzed to generate alcohol and fatty acid (Rojo, 2009). The aromatic hydrocarbons containing benzene rings are comparatively less biodegradable than saturated hydrocarbons. Bacterial metabolic pathway for aromatic hydrocarbon

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degradation involves formation of diol, followed by cleavage of the ring and formation of di-carboxylic acid. On the other hand fungal species and eukaryotic organisms use monooxygenases for aromatic hydrocarbon degradation forming trans-diols (Zhang et al., 2011). The cleavage of benzene rings is carried out by microorganisms by ortho-or meta cleavage pathways. Both these pathways leads to the formation of central intermediates such as protocatechuates and catechols which are further converted to TCA cycle intermediates (Abbasian et al., 2015). Metacleavage genes are found to be located on plasmids; while ortho cleavage genes are mostly located on chromosome, however genetically modified orthogenes are located on catabolic plasmids also (Varjani, 2017). Cyclic alkanes represent a component of crude oil which is resistant to microbial attack. For example in case of cyclohexane primary attack becomes difficult due to the absence of an exposed terminal methyl group (Trower, Buckland, Higgins, & Griffin, 1985; Varjani, 2014). Cyclic alkanes are converted to cyclic alcohols and further converted to ketones by oxidase systems. Cyclohexane biodegradation pathway is initiated by monooxygenase which oxidizes cyclohexane to cyclohexanol. Cyclohexanol is subsequently processed by dehydrogenases and hydrolases enzymes resulting in the formation of adipic acid (Trower et al., 1985), Adipic acid then through β-oxidation enters in intermediary metabolism (Varjani & Upasani, 2016b). Alkenes on the other hand are reacted upon by (1) terminal oxygenase, (2) sub-terminal oxygenase, (3) oxidation across double bond to corresponding epoxide and (4) oxidation across double bond to corresponding diol (Varjani, 2017; Watkinson & Morgan, 1990).

22.5.2 Anaerobic degradation Since many decades it was assumed that biological degradation of hydrocarbons were only aerobically feasible. However, reports on anaerobic degradation of aromatic compounds by Evans and Fuchs (1988) and anaerobic mineralization of hexadecane by sulfate reducing bacterium (Aeckersberg, Bak, & Widdel, 1991) shifted the concept and since then, a great deal of work has been done on the anaerobic degradation of aliphatic and aromatic hydrocarbons. For anaerobic biodegradation initial activation of hydrocarbons is fundamental, and four general enzymatic reactions are involved: (1) Formation of aromatic-substituted succinates by fumerate addition, catalyzed by a glycyl radical enzyme (Callaghan, 2013; Wilkes et al., 2016), (2) methylation of unsubstituted aromatics (Callaghan, 2013), (3) hydroxylation of an alkyl substituent via a dehydrogenase (Mbadinga et al., 2011; Meckenstock et al., 2016) and (4) direct carboxylation (Heider, 2007). These reactions ultimately result in ring saturation, β-oxidation and/or ring cleavage reactions, which produce metabolites (e.g., benzoyl-coA) at can incorporated in biomass or completely oxidized (Meckenstock et al., 2016). The rate of biodegradation of the BTEX compounds is found to be similar for both aerobic and anaerobic degradation pathways (Abbasian et al., 2015). Nitrate, ferrous iron, manganese or sulfate ions are reported to act as electron acceptors for anaerobic degradation of PHs (Callaghan, 2013; Foght, 2008; Gieg, Fowler, & Berdugo-Clavijo, 2014; Widdel & Rabus, 2001; Abbasian et al., 2015). Under anaerobic metabolism the aromatic compounds initially undergo oxidation to phenols or organic acids, and then transformed to long-

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chain volatile fatty acids, which are finally metabolized to CH4 and CO2 (Abbasian et al., 2015; Heider, Spormann, Beller, & Widdel, 1999; Wilkes et al., 2016). There are instances suggesting that in many anaerobic ecosystems syntrophism plays a key role in PH degradation (Gieg et al., 2014; Heider, Spormann, Beller, & Widdel, 1998). There are reports on the abilities of anoxygenic photosynthetic bacteria to utilize hydrocarbons as carbon and electron sources (Mbadinga et al., 2011; Meckenstock et al., 2016). Several laboratory based studies on sulfate reducing, denitrifying and methanogenic cultures acting on aliphatic and aromatic substrates have identified formation of succinates. As initial metabolites in biodegradation process succinates are formed by the addition of fumarate either to a sub-terminal carbon of an alkane or to an alkyl substituent of an aromatic hydrocarbon (Callaghan, 2013; Heider, 2007; Meckenstock et al., 2016; Wilkes et al., 2016). Biodegradation of both saturated and aromatic hydrocarbons in anoxic zones of petroleum-contaminated aquifers have also confirmed the presence of succinates (Aeckersberg et al., 1991; Heider et al., 1998).

22.5.3 Enzymes involved in PH degradation The biodegradation of PH pollutants through the diverse metabolic pathways requires the involvement of different enzymes. The most important group of enzymes participating in the degradation of PHs, chlorinated hydrocarbons and other compounds is cytochrome P450 hydroxylases which constitute a family of ubiquitous Heme-thiolate Monooxygenases (Unimke, Mnuoegbulam, & Anika, 2018; Van Beilen & Funhoff, 2007). Diverse groups of membrane bound as well as soluble alkane oxygenases (such as integral membrane di-iron alkane hydroxylases, membrane-bound copper-containing methane monooxygenases and soluble di-iron methane monooxygenases) has been isolated from different prokaryotic and eukaryotic species which are actively involved in aerobic degradation of alkanes (Al-Hawash et al., 2018; Van Beilen & Funhoff, 2007). The enzymes produced are expressed from the different genes which are either present in the plasmid or in the microbial chromosomes. Some of the major genes which has been recognized for microbial degradation of PH are alkB gene, xylE gene and nahAC gene for alkane monooxygenase, catechol dioxygenase and naphthalene dioxygenase respectively (Hendrickx et al., 2006; Varjani, 2017; Wilkes et al., 2016).

22.6 Factors influencing microbial remediation of oil Biological degradation of PHs is indeed a tough job to commence. Microorganisms respond highly sensitively to the alterations in their surrounding growth environment (Boopathy, 2000; Varjani, 2017). The most significant factor that restricts the biodegradability of oil contaminants is the poor diversity and/or availability of efficient indigenous microflora with adequate supplementary substrate properties necessary for the degradation of various hydrocarbons present in contaminated sites (Al-Hawash et al., 2018; Ron & Rosenberg, 2014). The rate of biodegradation of PH pollutants is influenced by several factors which are both biotic and abiotic in nature. The influential factors involve: (1) environmental factors such as temperature, pH, pressure, salinity, water activity (in terrestrial

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ecosystem), and oxygen availability (Aislabie, Saul, & Foght, 2006; Atlas, 1991; Boopathy, 2000; Chandra et al., 2013; Varjani et al., 2015), (2) substrates and its properties include the availability, type, and length of hydrocarbons, dispersion into aqueous phase and volatilization (Beskoski et al., 2011; Chandra et al., 2013; Chaudhry, Blom-Zandstra, Gupta, & Joner, 2005; Rojo, 2009). (3) Nutritional factors include the adequate availability of nutrients (4) biological factors include the availability of microbes, the cell metabolic pathways, and their abilities to biodegrade PHs (Baldwin, Nakatsu, & Nies, 2003; Meckenstock et al., 2016; Rocha, Pedregosa, & Laborda, 2011). (5) Bioavailability of PH pollutants to microorganisms. It is important to consider all these factors before biodegradation of PHs can be conducted (Okoh, 2006).

22.6.1 Temperature Temperature is an important factor influencing the biodegradability potentials of PHs as it affects both the physical and chemical state of the PHs and also the growth rate of microbes, gas solubility’s, and microbial metabolism (Chandra et al., 2013; Megharaj, Ramakrishnan, Venkateswarlu, Sethunathan, & Naidu, 2011). Rise in temperatures results in increased biodegradation possibilities due to the increase in solubility of hydrophobic pollutants, decrease in viscosity, enhanced diffusion and transfer of long chain n-alkanes from solid phase to water phase (Aislabie et al., 2006; Varjani & Gnansounou, 2017). Conversely low temperatures results in decline of PH biodegradation due to rise in viscosity of oil, reduction in volatilization of toxic short-chain alkanes and their low solubility in water further delay onset of biodegradation (Leahy & Colwell, 1990). Reduced enzymatic activity rates at low temperature also hinder PHs biodegradation (Bisht et al., 2015). Although the biological degradation of PH can occur at wide range of temperatures, the rate of hydrocarbon metabolism reached the maximum level in high temperatures ranging from 30 C
40 C (Al-Hawash et al., 2018). Reports also show that crude oil degradation through mixed cultures of marine bacteria is possible at 30 C (Al-Hawash et al., 2018; Colwell, Mills, Walker, Garcia-Tello, & Campos-P, 1978).

22.6.2 pH Alterations in pH can affect the biodegradability potentials of the microorganisms involved. pH affects processes such as cell membrane transport and catalytic reaction balance as well as enzyme activities (Bonomo, Cennamo, Purrello, Santoro, & Zappala, 2001). Most of the heterotrophic bacteria prefer to grow in a neutral to alkaline pH in contrast to the pH of the most aquatic ecosystems, which can highly vary, ranging from 2.5
11. Several reports suggest a varying rate in PH degradation at varying pH ranges. Hambrick, DeLaune, and Patrick (1980) found that at a pH of 6.5 microbial mineralization of naphthalene and octadecane was possible. Rates of octadecane mineralization increase remarkably when pH increases from 6.5 to 8.0, whereas the mineralization rate of naphthalene remained unchanged. Thavasi, Jayalakshmi, Balasubramanian, and Banat (2007) found that the maximum biodegradation of crude oil by Pseudomonas aeruginosa in water was at pH 8.0.

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22.6.3 Salinity and pressure While working with marine ecosystem the factors salinity and pressure is of great importance. Salinity has a major influence on the bioremediation and biodegradation of PHs and it also affects the microbial growth and diversity (Qin, Tang, Li, & Zhang, 2012). Salinity has an adverse influence on the activity of some key enzymes involved in the process of hydrocarbon degradation (Ebadi, Khoshkholgh Sima, Olamaee, Hashemi, & Ghorbani Nasrabadi, 2017). Hydrocarbon pollutants when reaches the deep-ocean environment is subjected to increase in hydrostatic pressure. Studies indicate that an increase in pressure lowers PH degradation (Unimke et al., 2018). Thus, the PH pollutants which reach deep benthic zones of the oceans are biodegraded very slowly by the PH degrading microorganisms and therefore the pollutants persist there for long time may be years or decades (Unimke et al., 2018).

22.6.4 Oxygen The oxygen concentration has been considered as rate limiting variable for PHs degradation in environment (Al-Hawash et al., 2018). Oxidation of substrate by the enzyme oxygenases in the catabolism of all aliphatic, cyclic and aromatic compounds by microorganisms is considered a key step in the biodegradation process (Meng, Li, Bao, & Sun, 2017). Oxygen acts as electron acceptor and increases bioremediation activity thereby enhance aerobic biodegradation process (Abbasian et al., 2015). However, provision of an adequate oxygen supply to enable mineralization of the PH pollutants to take place completely is frequently problematic and expensive (Boopathy, 2000). Biodegradation of PHs in anaerobic conditions was slow as compared to degradation in aerobic conditions (Grishchenkov et al., 2000). The flux rate of oxygen through water is about 1/10,000 times less than its rate through air. However, in some marine habitats the limits to oxygen diffusion can be offset by the increased solubility of oxygen at colder temperatures and increasing atmospheric pressures. Thus for the very deep ocean, the oxygen concentration actually increases with depth, even though the air/water interface is literally miles away. On the other hand, tropical lakes and summertime-temperate lakes may become oxygen limited only meters below the surface. In this case, aerobic microbes consume the surfaceassociated oxygen faster than it can be replenished (Willey et al., 2009).

22.6.5 Composition and properties of substrates Degradation and mineralization of PHs is inherently influenced by its concentration and composition. Biodegradability of hydrocarbons can be ranked as: linear alkanes . branched alkanes . low-molecular-weight alkyl aromatics . monoaromatics . cyclic alkanes . polyaromatics . . asphaltenes (Varjani, 2017; Xu et al., 2018). Under suitable conditions kerosene is totally biodegradable as it consists of medium chain alkenes (Atlas, 1981). While, crude oil having major constituent as saturates and/or aromatics is biodegradable, but for heavy asphaltic-naphthenic crude oils approximately 11% may be biodegradable within a reasonable time period under favorable growth conditions for microorganisms (Ghazali, Rahman, Salleh, & Basri, 2004). High PH concentration is

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lethal for microbial communities and their degradation abilities (Admon, Green, & Avnimelech, 2001). Rate of biodegradation of PH rises as the complexity of chemical structure and molecular weight of PH decreases (Varjani, 2014). Physicochemical properties of crude oil and polluted sites are also essential for successful bioremediation process (Varjani & Upasani, 2013). These factors have direct influence on type, number and metabolic activities of microflora of any ecosystem (Admon et al., 2001; Ghazali et al., 2004).

22.6.6 Nutrients availability Microorganisms require adequate amount of nutrient such as carbon, nitrogen, phosphorous etc. for proper growth, survival and functioning. Type and concentration of different nutrient sources used in culture medium plays vital role for microbial growth (Dias et al., 2012; Varjani & Upasani, 2016b; Varjani, Thaker, & Upasani, 2014; Zhao et al., 2011). The availability of optimum concentration and composition of nutrients within the same area of hydrocarbons is critical (Atlas, 1981; Ron & Rosenberg, 2014). The most adequate C:N:P to promote microbial growth is 100:10:1 (Beskoski et al., 2011; Dias et al., 2012; Zhao et al., 2011). In marine and freshwater environments, oil spills cause a dramatic increase of carbon levels and a decrease of nitrogen and phosphorus levels which can affect the biodegradation process. In marine environments, nitrogen and phosphorus levels are low, and the wetlands are unable to provide the nutrients because of strong demands of nutrients by the plants. Walworth et al. (2005), reported that treating petroleum polluted site with nitrogen increases cell growth rate as well as hydrocarbon degradation rate by decreasing lag phase of microbial growth and maintaining microbial populations at high activity levels. Thus, nutrients addition was necessary to promote the biodegradation of contaminants (Hesnawi & Adbeib, 2013). On the other hand, the concentration of excess nutrients can also inhibit the activity of biodegradation (Al-Hawash et al., 2018; Atlas, 1985). Excessive nutrient concentrations especially high concentration of NPK levels inhibits biodegradation activity of hydrocarbon pollutants (Boopathy, 2000; Souza et al., 2014; Varjani, 2017). Apart from this, high concentrations of nutrients in polluted sites disturb C: N: P ratio which leads to oxygen limitations (Sihag, Pathak, & Jaroli, 2014).

22.6.7 Microbial communities Bacteria, fungi, algae, protozoa and viruses are reported to be the major groups of microbial communities that have been used in bioremediation of hydrocarbon pollutants (Zhao et al., 2011; Waigi et al., 2015; Varjani, 2017). Bacteria are the most abundant group playing fundamental role in biodegradation of PHs (Varjani & Upasani, 2013; Zhao et al., 2011; Zhao et al., 2016). One of the main factors impacting PHs degradation is the availability of microorganisms that can catabolize pollutants. The poor biodiversity of local microbes and/or the scarcity of local specialized microbes with supplementary substrate properties required for the degradation of various hydrocarbons present in contaminated sites often limit the biodegradability of sites contaminated with PHs (Ron & Rosenberg, 2014). In marine environments hydrocarbon-degrading microorganisms usually exist in very low abundance. Pollution by PH, however, may stimulate the growth of such

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organisms and cause changes in the structure of microbial communities in the contaminated area. Addition of pure and/or consortia of native microorganisms with petroleum crude utilizing capabilities microorganisms or genetically modified microorganisms with high biodegrading potentials on the site of PH pollution could result in a solution for such inadequacy.

22.6.8 Bioavailability Bioavailability of PH pollutants to microbes plays key role in bioremediation process (Saeki, Sasaki, Komatsu, Miura, & Matsuda, 2009; Souza et al., 2014). Amount of a substance that is physicochemically accessible to microorganisms is referred to as bioavailability (Varjani & Upasani, 2016b; Varjani, Rana, Bateja, Sharma, & Upasani, 2014). Studies show that similar compounds present in different pollutants can be degraded to different extents by same organisms/consortium, due to the bioavailability of a particular compound and not it’s chemical structure (Sugiura, Ishihara, Shimauchi, & Harayama, 1997; Varjani et al., 2015). Pollutant bioavailability depends on its chemical properties such as hydrophobicity and volatility; environmental conditions and biological activities (PilonSmits, 2005; Varjani, Rana, et al., 2014; Yalcin et al., 2011). The solubility and dissolution rates play critical role in bioavailability of pollutants (Kavitha, Mandal, & Gnanamani, 2014). The bioavailable part of the hydrocarbons is the area accessible to microorganisms. PHs has low bioavailability and is classified as hydrophobic organic pollutants (chemicals having little water solubility, which makes them resistant to photolytic breakdown and chemical biological) (Semple, Morriss, & Paton, 2003). The pH, the microbial community and the extent of deterioration of the hydrocarbon can be significantly affected by the restrictions in the bioavailability of hydrocarbons (Al-Hawash et al., 2018).

22.7 Bioremediation/biodegradation strategies for removal of oil from contaminated sites Whenever oil spill occurs in a marine environment the initial combat strategy is to contain and recover the oil using different types of booms, barriers and skimmers along with this several natural or synthetic sorbent materials are also employed. Depending upon the type of oil contamination the physical methods for oil removal also alters (Mapelli et al., 2017). Conventional in situ and ex situ technologies for petroleum pollution remediation are very expensive, slow acting and also environmentally unsustainable (Asemoloye, Ahmad, & Jonathan, 2017; Cole, 2018; Dacco et al., 2020). To get an ecofriendly solution the scientific world has explored and optimized several biological treatments for oil remediation (Dacco et al., 2020). Microbial bioremediation being noninvasive and relatively cost-effective has evolved to be a widely used technique for treating PH pollution in both terrestrial and aquatic ecosystems (Yuniati, 2018). Any bioremediation techniques rely on the exploitation of microbial metabolism and co-metabolism for obtaining innocuous products (such as CO2, CH4, H2O) from hazardous organic pollutants (Ron & Rosenberg, 2014).

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22.7.1 Principles and or strategies for PH bioremediation To develop and optimize a bioremediation intervention strategy it is highly essential to acquire the accurate knowledge about the metabolic potential of the microorganisms and the environmental factors which govern the interactions, viabilities and degradation activities (Mapelli et al., 2017). To get a better insight into the microbial abundance, distribution, their abilities and potentials of specific or groups of microorganisms and also to evaluate the overall community profiles several molecular biology and metagenomic analyses are performed (Ron & Rosenberg, 2014; Varjani, 2014). Molecular biotechnological techniques such as denaturing gradient gel electrophoresis, reverse sample genome probing, restriction fragment length polymorphism, 16S rRNA genetic sequence analysis, oligonucleotide matrix array hybridization etc. have been used to study microbial diversity from petroleum reservoirs (Gieg et al., 2014; Liu et al., 2015; Ron & Rosenberg, 2014; Yang et al., 2016). Several novel strains of microorganisms has been recovered from a wide variety of habitat including pelagic and coastal ocean systems, soils and sediments, hot springs, and terrestrial subsurface environments from the 16S rDNA and rRNA analysis (Liu et al., 2015; Ron & Rosenberg, 2014). Studying the microbial diversity of oil reservoirs and thereby exploiting their potential in remediating PH pollutants is highly important in PH bioremediation. Bioremediation technologies that can be used for responding to marine oil spills are: Application of individual and/or microbial consortium (Bioaugmentation); Bioaugmentation with genetically engineered strains (GES); Enrichment of the nutrients (biostimulation); Use of immobilized cells and application of biosurfactants.

22.7.2 Applications 22.7.2.1 Applying indigenous individual and/or microbial consortium (bioaugmentation) The addition of PH pollutants into the marine environment results in ecological succession of microbial communities starting from aliphatic PH degraders (for e.g., Alcanivorax spp.) to aromatic PH degraders (e.g., Cycloclasticus spp.) (Kimes, Callaghan, Suflita, & Morris, 2014; Rodriguez-R et al., 2015). The activities of the autochthonous microbial communities in an oil spill environment rely on the community’s initial functional diversity and also on the local environmental conditions. Studies conducted on chronically polluted marine sediments and freshly pollutes samples indicate that there exists a higher and wider catabolic diversification and potentials in microbial communities of chronically polluted marine samples that allow them to respond more promptly to oil spills as compared to the fresh samples (Bargiela et al., 2015). The cleanup of PH pollutants requires enrichment of specialized microorganisms that can degrade different classes of PHs. Discovering a single strain of microbial species with abilities to degrade all the different hydrocarbons is highly desirable but results show that use of consortia of microorganisms (bacterial and or bacteria-fungi) shows better result (Dacco et al., 2020; Medina-Bellver et al., 2005). The synergistic co-metabolic activities of microbial consortia help to attenuate and gradually remove PH pollutants from the site of pollution (April, Foght, & Currah, 2000; Dacco et al., 2020; Ghosal et al., 2016). Genomes assembled from metagenomic data sets following

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stable isotope probing of the surface spills indicates that combination of degradation capabilities and pathways of different microbial community members is required for PH degradation (Dombrowski et al., 2016). The metagenomic studies thus indicate that the degradative and metabolic pathways distributed in the different members of microbial communities can work cooperatively and coordinately to carry out PH degradation (Mapelli et al., 2017). Biodegradation technologies involve the seeding/inoculation (Bioaugmentation) of microorganisms to the polluted site to increase the rate of degradation. The inoculums added can be a mix of non-indigenous microbes isolated from different polluted environments, specially studied for their oil degradation capabilities or they may be a combination of oil-degrading microbes selected from the site to be remediated and has been masscultured in the laboratory or in on-site bioreactors. The necessity for adding microorganisms to a spill site is that the autochthonous microbial populations on the pollution site may not include the diversity or density of oil degraders needed to efficiently degrade the many components of a spill (Hassanshahian & Cappello, 2013). Successful remediation of PH in polluted sites augmented with microorganisms can only be possible when the introduced microbes can survive and degrade better than the indigenous microbes while competing with the natural environment, predator species and cope with such factors to which the native organisms are likely to be well adapted (Hassanshahian & Cappello, 2013). To achieve best results proper choice of microbial strains and controlling the factors (such as keeping cells moist and in contact with the oil; protecting them from excess ultraviolet light; providing adequate nutrients; and controlling temperature, pH, and salinity) is highly essential. 22.7.2.2 Application of genetically engineered strains The advancement of biotechnological and genetic engineering techniques along with the intensive study on metabolic potentials of varying PH degrading microorganisms has resulted in the designing of GES of microorganisms (Peixoto et al., 2011; Pieper & Reineke, 2000; Sana, 2015; Varjani & Upasani, 2013; Varjani & Upasani, 2017; Unimke et al., 2018). Artificial consortia (or GES) with PH bioremediating capabilities can be prepared in research laboratories with the help of molecular biological techniques such as transferring necessary genetic material (either in form of plasmids or from chromosomes) from exogenous to indigenous microorganisms (Varjani &Upasani, 2017; Unimke et al., 2018). Application of GES of microorganisms on PH polluted sites can be alternative solution to degrade PH. In the early 70’s Prof. Ananda Mohan Chakrabarty developed a GES of Pseudomonas putida (“an oil eating bacteria” also known as “superbug”) capable of digesting two thirds of hydrocarbon present in oil spill area at a rate faster (about one or two orders of magnitudes) than any previously existing strains of oil degrading microbes (Pandey & Arora, 2020). The research got notable recognition on such GES, and a new method of genetic cross-linking to transfer genes required for degradation of oil using plasmid transfer technique was invented (Chakrabarty, Mylroie, Friello, & Vacca, 1975; Pandey & Arora, 2020). The new organism contained genes for naphthalene, salicylate and camphor degradation, Chakrabarty called it as a “multi-plasmid hydrocarbon-degrading Pseudomonas.” The construction of this “superbug” included plasmid genes from E. coli, Pseudomonas sp. able to degrade naphthalene and P. putida with gfp gene localized in

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chromosome (Unimke et al., 2018). This scientific invention paved the biological way for removing PH pollutants during disastrous oil spills and leakages in marine ecosystems by utilizing GES. The problems associated with the introduction of laboratory cultured microorganisms in natural environment include their survival, persistence and compatibility. So, the formation of new GES in laboratory must be genetically stable and competent enough to survive and act in the new environment. The strategies include construction and regulation of novel pathways, proper substrate utilization and expansion of existing pathways without producing harmful metabolites, catabolic enzyme specificity and increase in bioavailability of pollutants (Peixoto et al., 2011; Urgun-Demirtas, Stark, & Pagilla, 2006; Varjani & Upasani, 2017). The release of GES in the natural environment must be well assessed on their potential biosafety and environmental risk measures (Varjani, 2014; Varjani & Upasani, 2017). 22.7.2.3 Enrichment of the nutrients (biostimulation) The rate at which PHs can be biologically degraded in marine environment is highly limited by the availability of adequate and balanced nutrient supply (Hassanshahian & Cappello, 2013; Liu et al., 2015). While in the marine environment the microorganisms are well suited to their ecological niche but the release of oil/PH pollutants in the marine environment causes an imbalance in the C:N:P ratio, and microbes lose their efficiency of degrading PHs due to lack of sufficient nutrients (such as nitrogen, phosphorous etc.) (Agarry & Owabor, 2011; Fodelianakis et al., 2015). Therefore the addition of sufficient nitrogen, phosphorus, and other nutrients (Biostimulation) further allow the biodegradation of PH to proceed at the optimal rate (Hassanshahian & Cappello, 2013). The challenge imposed on the biostimulation process is the rapid leaching of the supplied nutrients along the water column. The solution to such a problem can be the immobilization of the nutrients by the process of microencapsulation, which will result in slow release of nutrient molecules at the site of biostimulation. Microencapsulation can be achieved by the use of less toxic polymers such as polyurethane
polyurea co-polymers, alginates and chitosans (Dellagnezze et al., 2016; Shan et al., 2016). Recent study on microencapsulating nutrients demonstrated that synthesis of alginate beads obtained by a microinjection technology has raised the load capacity and slow release of N and P nutrients (Mapelli et al., 2017; Shan et al., 2016). Metagenomic data analysis also showed a positive response towards biostimulation, where addition of different sources of nitrogen favored the metabolic pathways of different hydrocarbons without altering the taxonomic structure of the microbial community (Bargiela et al., 2015; Mapelli et al., 2017). 22.7.2.4 Use of immobilized cells The process of immobilization involves an imposition of restriction on movement of a molecule or microbial cells in a particular space either completely or to a smaller limited region by attachment to a support (Unimke et al., 2018). An immobilized molecule or microbial cell possesses longer operating capacities, extended stability and survival. Such advantages resulted in the advancement of new technology of immobilization in environmental cleanup. Different types of carrier molecules such as sodium alginate, chitosan, chitin, wood chips and wheat straw, biochar and mollusk shells can be used to immobilize

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the microbial cells (Zhang et al., 2016; Varjani & Upasani, 2017). The act of immobilization of PH degrading microbial cell and its application in bioremediation of PH contaminated site has proved to be successful and has received considerable attention in bioremediation technologies (Lu, Zhang, Yu, & Zhu, 2009; Tong, Zhang, Liu, Ye, & Chu, 2013). Research conducted by Diaz, Boyd, and Grigson (2002) showed that immobilization of bacterial cells enhanced the biodegradation rate of crude oil significantly as compared to free-living cells. In nature too, the use of the process of immobilization in bioremediation of PH is evident. There are reports from gulf coast where biofilm (of oil degrading bacteria) covered microalgal samples helped in degrading hydrocarbons in seawater (Radwan, Al-Hassan, & Salamah, 2002). The immobilized cell systems provide a lot of advantages such as providing high biomass, cell reuse and thereby reducing the cost of cell recovery and cell recycle and also eliminate cell washout problems. Apart from this immobilized cell systems provide high resistance to pH, temperature, toxic chemicals, solvents and heavy metals (Antai, Unimke, & Agbor, 2014; Diaz et al., 2002). The utilization of immobilized cells can help in enhancing PH bioremediation and come up as an advanced technology for PH bioremediation. 22.7.2.5 Applications of biosurfactants Direct interaction between oil pollutants and microorganisms is highly essential for proper bioremediation abilities (Souza et al., 2014; Uad, Silva-Castro, Pozo, GonzalezLopez, & Calvo, 2010). The PH contaminants must penetrate into microbial cells as submicroscopic droplets in order to be degraded (Varjani, 2014; Varjani & Upasani, 2017). This close contact interaction between microorganisms and insoluble substrate is favored by the activity of surfactant and surface hydrophobicity (Kavitha et al., 2014; Varjani & Upasani, 2016a). Studies show that presence of surface active agents favor solubilization of oil and oil droplet formation in water, thereby helps in raising the bioavailability of PH pollutants for bioremediation (Mapelli et al., 2017). Surface active agents are molecules which are amphiphatic in nature possessing hydrophilic and hydrophobic portions which can act in between fluids differing in their polarities. Thereby such surface active agents are capable of bringing about a reduction in surface tension, an increase in the area of contact of insoluble compounds and the enhancement of the mobility, bioavailability and biodegradation of hydrophobic substrates such as PHs (Aparna, Srinikethan, & Hedge, 2011; Biswas et al., 2020; Mapelli et al., 2017; Unimke, Mmuoegbulam, Bassey, & Obot, 2017). Biosurfactants refers to the biologically produced surface active compounds which facilitates the translocation of insoluble substrates across cell membranes (Campos et al., 2013; Kapadia & Yagnik, 2013). There are evidences showing that biosurfactants producing oil degrading microorganisms are more effective in oil degradation as compared to the oil degrading potentials of non-biosurfactants producing oil degraders (Peixoto et al., 2011; Zhao et al., 2016). Strains of Acinetobacter, Bacillus, Pseudomonas, Alcanivorax capable of producing glycolipid biosurfactants have been successfully isolated from oil-contaminated marine surface waters worldwide (Mapelli et al., 2017). Biosurfactants that are produced by PH degrading microbes can be firmly attached to cell surface or released extracelullarly into the environment (Sajna et al., 2015; Varjani & Upasani, 2017). The application of biosurfactants in oil contaminated sites has several other advantages over chemical dispersants owing to their environmental compatibility, low toxicity, high biodegradability, high

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surface, and emulsification activities, high selectivity due to the presence of specific functional groups and activity under extreme conditions of temperatures, pH, and salinity (Mapelli et al., 2017; Unimke et al., 2017). The positive impact of biosurfactants on PH biodegradation has resulted in the application of potent biosurfactants or biosurfactants producing organisms not only in PH polluted sites but also in oil recovery reservoirs, oil transportation pipelines, and to production of emulsified fuels (Mapelli et al., 2017).

22.8 Conclusions Marine pollution by PHs is increasing at an alarming rate and the negative impact on the marine ecosystem requires a sincere attention. The advancements in the PH bioremediation strategies has resulted in some positive results in removing PHs, but the fact that every PH polluted site is unique and a clear assessment on the implementation of the type of bioremediation strategy is highly necessary. There have been developments on identifying the biodegradability pathways for PH pollutants from diverse phylogenetic groups of microorganisms and methods for producing novel genetically modifying bioremediating strains which also have evolved, yet there are constraints on the complete removal of PH pollutants from environment. Although the utilization of immobilized microbial cells and/or application of biosurfactants producing microorganisms have proved to be successful, a lot of research work is still necessary on pilot- scale and further on a large-scale basis in order to receive promising results.

22.9 Summary This chapter highlights multifarious aspects of PH pollution with a special insight on marine oil spill and marine oil pollution. The constant exploitation of PHs has intensified accidental spills and chronic oil pollution in marine ecosystems. The hazardous, toxic consequences and recalcitrant nature of PH pollutants makes it imperative to remove such pollutants from the environment. Bioremediation of pollutants from environment has received greater socioeconomic acceptance as compared to physicochemical treatments of pollutants. The occurrence, distribution, and versatile metabolic pathways of PH degrading microorganisms have showed the way to design effective strategies for bioremediating PH pollutants from contaminated sites. Furthermore the advancements and breakthrough research by Prof. Ananda Mohan Chakrabarty have resulted in the discoveries of genetically modified microbes with potent PH degradation abilities. Effective bioremediation of PH pollutants also rely on several biotic and abiotic factors such as optimum nutrition, physical conditions of PH pollutants, diversity of microbial communities involved and bioavailability of substrates. Applications of biosurfactants and immobilized PH degrading microbial cells have shown positive impactful result on removing PH pollutants from contaminated areas. Despite such significant advancements there remains certain constraint which still remains unaccomplished. Novel discoveries in microbial ecology and physiology associated with PH pollution in marine ecosystems will certainly lead to a developing a sustainable solution to marine oil pollution.

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C H A P T E R

23 Hybrid biological processes for the treatment of oily wastewater Kulbhushan Samal1, Sachin Rameshrao Geed2 and Kaustubha Mohanty3 1

2

Department of Chemical Engineering, Ramaiah Institute of Technology, Bangalore, India Department of Chemical Engineering, Indian Institute of Technology (BHU), Varanasi, India 3 Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati, India O U T L I N E

23.1 Introduction

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23.2 Methods for oily wastewater treatment

424

23.3 Biological methods 424 23.3.1 Microbe isolation 425 23.3.2 Analysis of microbial community composition 425 23.3.3 Microbes for degradation of oily wastewater 425 23.3.4 Biodegradation systems: free cell, immobilized and continuous bioreactor 426

23.3.5 Mechanism and kinetics 23.3.6 Effect of oil toxicity on degradation

426 427

23.4 Biological techniques

428

23.5 Hybrid biological processes

428

23.6 Summary

432

References

433

23.1 Introduction Due to industrial development a huge amount of oily wastewater is generated through various industrial processes activities (Jamaly, Giwa, & Hasan, 2015). This oily wastewater has turned out to be a global problem. Oily contents present in waste water form emulsions which are a highly

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00021-5

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hazardous pollutant. This oily wastewater has mainly threatened aquatic, animal, and human life and causes harms to the ecosystem (Bayat, Mahdavi, Kazemimoghaddam, & Mohammadi, 2016). The main source of this pollutants are releases of effluent wastewater from petrochemical plants, refineries, metal industries, transportations and other industries (Barbu, Vilanova, Meneses, & Santin, 2017). Due to the water crisis, after the treatment of oily wastewater, this treated wastewater is able to be reused in a variety of ways such as usage in agriculture, washing purposes, and industrial plant utilities. There are several conventionally methods available to treat oily wastewater as discussed below.

23.2 Methods for oily wastewater treatment Currently several physicochemical methods are available to treat oily waste water from environment. The physicochemical methods include adsorption, flotation, coagulation/flocculation, membrane separation, and advanced oxidation process. The adsorption process uses different types of adsorbents for accumulation of contaminants on its surface by physisorption or chemisorption. Nevertheless, desorption of pollutant is required to regenerate the adsorbent which is again a tedious task to do. In addition, the requirement of costly synthetic adsorbents makes the process economical unsuitable. Flocculation is the formation of floating oil layer on water by means of tiny air bubbles. The oily substance adheres to air bubbles that float due to less density than water. The main disadvantages of flocculation are that it requires heavy equipment and their repairing results in an energy intensive process. Moreover, emulsification is required to assist water-oil separation. Coagulation is another mature technology for oily wastewater treatment. In recent years composite coagulants were developed to address the problems due to complexities in composition of oily wastewater. This method has limitations of requirement of high cost chemicals and causing secondary pollution that needs subsequent processing. Membrane technology has also shown potential in treating the oily wastewater, and their application is limited due to fouling of the membrane resulting into decline in permeate flux and increased energy demand. Moreover, these discussed physicochemical methods require complicated equipment designing and high processing cost, or produce a large amount of toxic sludge and toxic waste as intermediates. The conventional treatment methods are not frequently efficient enough or economical to treat oily wastewater and cannot satisfy the effluent discharge standard. In order to make the process economical and enhance the treatment efficiency of oily wastewater, several biological methods have been tested in the past. The biological methods have shown an advantage over the other mentioned techniques. Biological processes use microbial species metabolism to degrade hazardous substances in water into harmless products. The biological process has been discussed in this chapter with an emphasis on hybrid biological treatment of oily wastewater.

23.3 Biological methods In the biological methods, the microbes play an important role for the degradation of pollutants. The treatment efficiency of biological processes mainly depends on the microbes metabolism and interactions with highly diverse community present in organic

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waste (Ma et al., 2015). Therefore recent literature has shown interest regarding the biodegradation potential of microbes for targeted organic pollutants.

23.3.1 Microbe isolation In any biological process microbes’ identification and selection is the most crucial role. Once microbial species are identified, the microbe that shows the better efficiency to treat the targeted organic pollutant is selected. In the treatment of oily wastewater using any biological methods the microbial species plays an important role. Hence, identification of microbial species for targeted pollutants from contaminated site has great importance. The isolation of microbial species is a similar exercise reported in various literature that follows standard protocols proposed by Bergey’s Manual of Systematic Bacteriology and the methodologies. The sediment samples are first collected from selected polluted sites. These sediments are subjected to some pretreatment processes such as heat treatment, depending on the requirements. Further, after serial dilutions incubated with suitable nutrient media and environment. The microbial species which is most consistent in all samples is identified as the most surviving microbe. There are a variety of microbial species that have potential in treating oily wastewater. Mazumder, Das, Sen, and Bhattacharjee (2020) have used hydrocarbonoclastic bacterium Rhodococcus pyridinivorans F5 for degradation of hydrocarbons from oily wastewater. The maximum 79(0.03)% percentage degradation of hydrocarbon was achieved. They used an isolated strain in free bacterial suspension state. Further, they observed that degradation percentage increased up to 86(0.028)% when the cell entrapped alginate bead was used without activated carbon as the doped agent (Mazumder et al., 2020). Bashandy, Abd-Alla, and Dawood (2020) found that the elevation of toxicity of oily wastewater used aromatic hydrocarbon biodegrading bacterium Stenotrophomonas maltophilia-SR1 (Bashandy et al., 2020). The microbial communities in the functional areas of a biofilm reactor with anaerobic aerobic process were used to treat oily wastewater (Li et al., 2017a). Li et al. (2017a) observed that the Proteobacteria, Nitrospirae, and Acidobacteria are the three most abundant microorganisms that degraded oily wastewater.

23.3.2 Analysis of microbial community composition In the last few years, in order to analyze the microbial community compositions in organic waste, the several molecular biological techniques have been used for 16S rDNA sequence. This molecular biological techniques are denaturing gradient gel electrophoresis (Yeung et al., 2015), clone library (Das & Kazy, 2014), terminal restriction fragment length polymorphism (Duran et al., 2015), high-throughput sequencing technology (Cai et al., 2018) were used to give new insights into the microbial diversity and structure.

23.3.3 Microbes for degradation of oily wastewater The treatment efficiency of biological wastewater treatment process mainly depends on the microbial metabolism activities and interactions with the oily contaminant.

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However, many researchers focused on the biodegradation of oily wastewater using microbial species. There are several literatures available reporting the biological treatment of oily wastewater using microbial species. For the efficient treatment of oil containing organic pollutants the targeted isolated microbial species were used. The specific microbial species that have been isolated and tested for biodegradation of petroleum contaminated oily wastewater and have shown promising results are Janibacter sp. SB2, Bacillus sphaericus, Mycobacterium sp., Pseudomonas mendocina, Ralstonia pickettii, Burkholderia cepacia, Rhodococcus rhodochrous, Pseudomonas fluorescens, Psudomonas putida out of which P. putida was found to be the most common bacterial species reported by different researchers. The performance of bioreactor enhances significantly using selected targeted microorganism for the targeted organic oil containing component. A few researchers have also used mixed microbial culture (consortia) (Firmino et al., 2015; Simantiraki, Kollias, Maratos, Hahladakis, & Gidarakos, 2013) and filamentous fungus Metarhizium robertsii (Szewczyk et al., 2014). The microbial species such as Pseudomonas sp., Bacillus sp., Rhodococcus sp., Proteobacteria, Nitrospirae, Acidobacteria, Klebsiella sp., and Alcaligenes sp., etc.were used to treat oil containing compounds (Li et al., 2017a; Mohanakrishna, Abu-Reesh, & Al-Raoush, 2018).

23.3.4 Biodegradation systems: free cell, immobilized and continuous bioreactor The performance of bioreactor enhances significantly using good microorganisms but further enhancement is only possible by selecting the best reactor system along with optimized process parameters. Researchers have used different types of reactors such as batch with free cell system, immobilized batch, and continuous bioreactors. Batch free cell reactors are the most common (Kim, Choi, Choi, Mahendran, & Lee, 2005; Lin, Chen, I, & Lai, 2010; Liu et al., 2010; Padhi & Gokhale, 2017; Simantiraki et al., 2013). Some researchers have also evaluated batch immobilized reactors (Singh & Fulekar, 2010; Tsai, Lin, Wu, & Shen, 2013). Degradation in the immobilized system was found to be better in general keeping other parameters the same (Robledo-Ortı´z et al., 2011). The batch systems are simple in nature, cost effective, easy to operate, but not suitable for real time applications. Limited studies are available on bioremediation of oily wastewater in continuous immobilized systems such as two-phase partitioning, USAB, fibrous bed and hybrid bioreactor etc. Luo, He, and Zhang (2020) have studied the degradation of oily sludge using continuous aeration and stirred bioreactor. They optimized the process parameters for example stirring speed and aeration rate and observe that the degradation rate of oily sludge can be enhanced (Luo et al., 2020). These systems have shown a better rate, however have several limitations like a cell in excess of growth, striping difficulties to maintain the consistent aeration, etc.

23.3.5 Mechanism and kinetics In biological process for oily wastewater treatment, the metabolism of microbial species is used to degrade the organic oily contents. The bacterial species degrade hazardous oily contaminants and produce less harmful metabolites which are mainly bio-surfactant. The

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bacterial species interact with oily wastewater to degrade it and form O/W emulsion. Moreover, some bacterial species are directly used as demulsifiers to destabilize the emulsion. The proteins and lipids present in bacterial cell surface plays important role in demulsification process (Cai, Zhu, Chen, & Zhang, 2019). For the microbial growth kinetic study Monod model was used. Monod model was modified and used for the biodegradation kinetic of oily wastewater was tested by first order chemical reaction kinetic Eq. (23.1) and calculated the rate constant (Asemoloye, Ahmad, & Jonathan, 2017; Tian et al., 2018) log

C 5 2 kt C0

(23.1)

where, C is mass concentration of oil at time t, C0 is initial mass concentration of oil and k is first order rate constant. The biodegradation half-life method was calculated using Eq. (23.2) (Asemoloye et al., 2017) t1=2 5

ln2 k

(23.2)

where,t1/2 is the Half-life, k is the biodegradation rate constant Luo et al. (2020) have reported degradation kinetics of oily sludge by bioreactor using the strain Pseudomonas aeruginosa (NY3). They analyzed the transient kinetics model considering the both the gas-liquid-solid multiphase flow model and mass transfer reaction. Mazumder et al. (2020) have also presented kinetic analysis and parametric optimization for oily wastewater degradation using bacterial species R. pyridinivorans F5 (Mazumder et al., 2020). Kurian, Nakhla, and Bassi (2006) studied the kinetic parameters of the volatile fatty acids, acetic acid, and propionic acid as substrate of wastewater. Monod kinetic model was used to obtain yield coefficient, maximum substrate removal, half-saturation constant, and death phase decay coefficient were determined. The half-saturation constant to be 181, 271, and 806 mg/COD and rate constants were 1.89, 1.08, and 0.85 mg COD/mg VSS/h for volatile fatty acids, acetic acid, and propionic acid wastewater, respectively (Kurian et al., 2006).

23.3.6 Effect of oil toxicity on degradation Kim et al. (2005) have investigated the process efficiency of full-scale wastewater treatment plant and microbial communities using petroleum refining wastewater containing toxic hydrocarbon contaminants. The full-scale wastewater treatment plant showed a stable process with efficiencies greater than 70% for both soluble chemical oxygen demand and benzene removal. Poi, Aburto-Medina, Mok, Ball, and Shahsavari (2017) have reported the commercial scale biodegradation of a soil contaminated with processed petroleum oil contaminants using microbial consortium. Kachieng’an and Momba (2018) have studied the synergistic effect and toxicity of a consortium of protozoan species (Paramecium sp., Vorticella sp., Epistylis sp. and Opercularia sp.) throughout the biodegradation process of contaminated petroleum oily wastewater. They have calculated the synergistic indices and the toxicity of petroleum oil hydrocarbons and

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their degradation products present in wastewater were tested, in terms of LD50 at 24 h. They observed that the individual isolates were able to biodegrade approximately greater than 65% with a consortium having biodegradation efficiency of greater than 70%.

23.4 Biological techniques In order to enhance the treatment efficiency of oil contaminated wastewater, a variety of biological methods such as biological filter, activated sludge (Aerobic activated sludge process, Activated sludge process), bioreactor, have been used during the last few decades (Rastegar, Mousavi, Shojaosadati, & Sheibani, 2011; Shokrollahzadeh, Azizmohseni, Golmohammad, Shokouhi, & Khademhaghighat, 2008). Various bioreactors have been designed by researchers and tested for oil degradation using isolated microbial species. The most common types of reactors are batch reactor, continuous reactor, biological aerated tank reactor, membrane bioreactor, anaerobic baffled reactor, anaerobic-aerobic-biofilm reactor, and moving bed bioreactor. Karray et al. (2020) reported that the performance of the continuous stirred tank bioreactor system for the treatment of highly toxic petroleum refinery wastewaters. It was observed that reduction of the COD, BOD5, phenols, and the total petroleum hydrocarbon reached 82.10%, 85.87%, 91.63%, and 81.11%, respectively. Ismail and Khudhair (2018) used spouted bed bioreactor for the real biotreatment of petroleum contaminated oily wastewater using non-acclimated immobilized mixed bacterial cells. They obtained the percentage removal of COD and total petroleum hydrocarbons in the real-field petroleum wastewater which were 61.7% and 66.6%, respectively. The biological processes have some problems while treating oily wastewater such as slow biodegradation rate, toxicity problem, cannot work at a high organic loading, and selection of targeted microorganisms. These limitations of biological process can be overcome by using hybrid biological process.

23.5 Hybrid biological processes The increasing concern about the potential accumulation of micropollutants in the aquatic environment triggered many investigations about their biological degradation in wastewater treatment systems (Stackelberg et al., 2007). Some mechanisms such as adsorption on activated sludge flocs or photolysis have been studied for the removal of micropollutants during water treatment processes (Radjenovi´c et al., 2009). However, current wastewater treatment plants using conventional biological processes are not specifically designed to eliminate recalcitrant TrOCs. Thus, due to their persistence, many of these molecules are able to pass through wastewater biological treatment processes. This recalcitrance has often been linked to their molecular properties, which define their biodegradation abilities by a given strain of microorganism under given operating conditions (Tahri et al., 2013). For instance, Kim et al. (2005) suggested that the presence of chlorine in the molecular structure, and a relatively

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complex aromatic structure are the reasons for the low degradation rates observed in the case of clofibric acid. The biological processes have some limitations. First, growth inhibition to microbial species at high concentration of organic pollutant, sometimes biological system get failed at high concentration load. Second, the rate of degradation of the biological process is slow, it required too much time to treat the pollutant. Third, the microbial species causes blocking due to overgrowth, channeling in the bioreactor the system and inefficient to treat the pollutant. In order to overcome these limitations of biological processes hybrid biological process is used. Hybrid treatment processes can be a combination of various conventional processes to improve the wastewater effluent quality. The primary process may be utilizing physical or chemical processes to prepare the wastewater for the next stage of treatment comprises a biological treatment processes. The selection of hybrid process depends on the types of pollutants that is present in the wastewater. Normally, biological processes are required for degradable organic compounds, nitrogen, phosphorus, volatile organics, and refractory toxic organics from the wastewater. Hybrid biological processes are a combination of biological process with the conventional physicochemical process. Hybrid biological processes are a combination of the two or more processes in which, at least one should be biological process and other can be any one of the physicochemical treatment process. Nowadays hybrid biological process has a great importance to treat industrial effluents. Different hybrid processes have been reported in literature for the treatment of oily wastewater. The biological process in combination with another biological process, adsorption process, chemical oxidation process, and electro-coagulation is among frequently reported hybrid processes. A few reported studies on the oily wastewater are discussed. Das et al. (2021) reported that steel plant generated wastewater treated using biological oxidation hybrid process. The pharmaceutical compounds present in the wastewater were removed through a hybrid biological and adsorption process (Ferrer-Polonio, Ferna´ndezNavarro, Iborra-Clar, Alcaina-Miranda, & Mendoza-Roca, 2020). El-Naas, Alhaija, and Al-Zuhair (2014) used bioreactor in combination with adsorption and electro-coagulation process for the treatment of refinery wastewater. They obtained 97% of COD removal efficiency for initial COD of 3600
5300 mg/L of wastewater. Pirieh and Naeimpoor (2019) have used hybrid two-phase process and studied the discrimination of chemical and biological sulfide oxidation. Liang, Mai, Tang, and Wei (2019) have reported treatment of petroleum wastewater using hybrid granular sludge bed bioreactor coupled with activated sludge process. They obtained 85% COD reduction in 62.8 h of retention time for initial COD of 4600
5300 mg/L. Mohanakrishna et al. (2018) studied the biological anodic oxidation and cathodic reduction of petroleum refinery wastewater using bio-electrochemical hybrid treatment process. Razavi and Miri (2015) have tested the hollow fiber membrane bioreactor for refinery wastewater treatment and reported a COD removal of 82% for 36 h of retention time. Razavi and Miri (2015) have been used the fenton and sequencing batch reactor for petroleum refinery wastewater treatment. Huo et al. (2018) were studied a hybrid photo-bioreactor-oxic/anoxic process to treat petrochemical wastewater and reported 71% removal efficiency. Li et al. (2017b) have demonstrated biofilm reactor with anaerobic
aerobic process (Fig. 23.1) for oily wastewater treatment. The field scale biofilm reactor was used with anaerobic
aerobic process for degradation of oily contaminated in

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FIGURE 23.1 A simple schematic diagram of the field-scale A/O biofilm reactor reflux process. (1) Raw water storage, (2) Thermostatic water bath, (3) Peristaltic pump, (4) Anaerobic biofilm reactor, (5) Aerobic biofilm reactor, (6) Air Pump, (7) Discharge water storage (Li et al., 2017b). Source: Li, J., Sun, S., Yan, P., Fang, L., Yu, Y., Xiang, Y., . . . Zhang, Z. (2017b). Microbial communities in the functional areas of a biofilm reactor with anaerobic
aerobic process for oily wastewater treatment. Bioresource Technology, 238, 7
15.

the wastewater. They observed 93.2% COD removal and 82.8% total nitrogen removal in aerobic step. The further reduction in COD and nitrogen was achieved in the anaerobic biofilm reactor. The COD and total nitrogen reduction of 95% and 99%, respectively was observed in the second step. Ahmadi, Benis, Faraji, Shakerkhatibi, and Aliashrafi (2019) have demonstrated the performance of a membrane bioreactor in their study. The membrane bioreactor as shown in the Fig. 23.2 used. In this study, the oily wastewater was treated using mixed liquor suspended solids. They have reported maximum 97% COD removal with the 8.5 g/L of mixed liquor suspended solids and 24 h of retention time. Sambusiti et al. (2020) examined pilot scale flat sheet submerged membrane bioreactor for treatment of oil and gas wastewater. The Fig. 23.3 shows the process diagram of pilot scale flat sheet submerged membrane bioreactor process. The studied biological process was efficient in treating the oily wastewater. The heavy metals removal of 29%
97% was achieved. The phenols, BTEX compound, PAHs compound removal was achieved up to 100% and total organic carbon removal was upto 96%
98%. In the pilot scale membrane bioreactor outlet toxicity tests was also performed and reported complete absence of toxicity. Elleuch, Hammemi, Khannous, Nasri, and Gharsallah (2014) examined the efficiency of hybrid biological processes for the treatment of bottle oil washing wastewater. They have studied the combined coagulation and flocculation

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FIGURE 23.2 Membrane bioreactor used for the treatment of oily wastewater (Ahmadi et al., 2019). Source: Ahmadi, M., Benis, K. Z., Faraji, M., Shakerkhatibi, M., & Aliashrafi, A. (2019). Process performance and multi-kinetic modeling of a membrane bioreactor treating actual oil refinery wastewater. Journal of Water Process Engineering, 28, 115
122.

process followed by activated sludge treatment as well as the combination of coagulation and flocculation process. They observed that COD removal of oily wastewater using combined coagulation and flocculation process followed by activated sludge treatment was more as compared to combination of coagulation and flocculation process (Elleuch et al., 2014). In the recent past, most of the researchers have focused on the removal of oily pollutants by hybrid processes. The influence of the physicochemical process parameters is significant on the hybrid biological process. It reduces the organic pollutant concentration in the effluent such a way that the biological process can be used as next treatment step to increase the removal efficiency and it mineralizes the intermediate product formed. The toxic effect of organic pollutant have shown adverse effect on the performance of the hybrid processes. To minimize the toxic effect pollutants advanced physicochemical processes such as oxidation, fenton, ozonation, etc. is required in hybrid process to reduce the organic load of wastewater. The incorporation of physicochemical process improves biological activities of microorganism in biological treatment step. Further, the stable biofilm formation on the packing media can also improve the biodegradation potential of organic pollutant. In most of the hybrid biological processes studied, activated sludge was used for the treatment of oily wastewater. The activated sludge contains several bacterial species in which the combined effect of consortia is observed, the specific microbes targeted specific compound or one microbes can break down two or more compound hence enhance the efficacy of overall process.

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FIGURE 23.3 Shows the submerged flatsheet membrane bioreactor: PIN 5 inlet pump; FIN 5 inlet flow meter; PF 5 filtration pump; FF 5 filtration flowmeter; F 5 air flowmeter; PBW 5 backwash pump; FBW 5 backwash flowmeter; pH 5 pHmeter; P 5 pressure transmitter; DO 5 DO-meter; L 5 level sensor; CA 5 compressed air (Sambusiti et al., 2020). Source: Sambusiti, C., Saadouni, M., Gauchou, V., Segues, B., Ange Leca, M., Baldoni-Andrey, P., & Jacob, M. (2020). Influence of HRT reduction on pilot scale flat sheet submerged membrane bioreactor (sMBR) performances for oil & gas wastewater treatment. Journal of Membrane Science, 594, 117459. https://doi.org/10.1016/j.memsci.2019.117459.

23.6 Summary Removal of oily contents from wastewater is important and challenging in wastewater management. Various innovative methods have been tested aiming for the economical treatment of oily wastewater. This chapter gives brief insights on biological treatment process of oily wastewater in emphasizing hybrid biological processes. It was found that microbes has an important role in biological process. Among the microbial species P. putida was found most common bacterial species for oily wastewater degradation. The individual biological process has limitation of slow process and sometime lower removal rate. The limitation of individual biological process can be overcome by appropriate hybrid biological process. However, there is few literature reporting hybrid biological processes for oily wastewater. Therefore, more research work is required for developing an economical hybrid biological process for oily wastewater treatment.

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52. Available from https://doi.org/10.1016/j.jclepro.2018.04.141. Padhi, S. K., & Gokhale, S. (2017). Treatment of gaseous volatile organic compounds using a rotating biological filter. Bioresource Technology, 244, 270
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17715. Available from https://doi.org/10.1007/s11356-015-4947-z.

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C H A P T E R

24 Efficient management of oil waste: chemical and physicochemical approaches Zhang Xiaojie1,2, Kalisadhan Mukherjee3, Suvendu Manna4, Mohit Kumar Das5, Jin Kuk Kim1 and Tridib Kumar Sinha1 1

Department of Materials Engineering and Convergence Technology, Gyeongsang National University, Jinju, South Korea 2School of Material Science and Engineering, Nanchang Hangkong University, Nanchang, P.R. China 3Department of Chemistry, Pandit Deendayal Energy University, India 4Department of Health Safety and Environment, University of Petroleum and Energy Studies, India 5Environment Department, Tata steel Ltd., India O U T L I N E Body

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24.1 Introduction

440

24.2 Hazardous effect of waste oil 24.2.1 Soil 24.2.2 Water 24.2.3 Air

442 442 443 443

24.3 Chemical constituents of waste oil 445 24.3.1 Waste cooking oil 445 24.3.2 Waste lubricating oil 447 24.4 Recycling methods of waste oil 24.4.1 Physical treatment of waste oil (2
7)

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00027-6

448

24.4.2 Chemical treatment of waste oil451 24.5 Recycling products 24.5.1 Plasticizers 24.5.2 Biofuel 24.5.3 Animal feedstuff 24.5.4 Polymer 24.5.5 Converting waste lubricating oil into useable oil

456 456 457 458 459

24.6 Conclusion and future prospect

460

References

461

459

448

439

© 2022 Elsevier Inc. All rights reserved.

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Body

24.1 Introduction Waste oils, particularly the lubricants (e.g., engine oil, transmission oil, and hydraulic and cutting oils) obtained as unusable after their end of life from various machineries, and the cooking oils after their thermal aging, because of the structural alteration of the chemical components, and formation of undesired by-products, are known to be hazardous for human health as well as the environment. Waste oil may exhibit a carcinogenic, mutagenic, and reproductive effect to the human body, whereas it may be responsible for polluting the water and soil, climate change, and disturbing the ecosystem. Thin liquid film of lubricants in the interfaces of moving surfaces provides longevity and better performance of the engines or machineries by reducing friction and wear, removing the in-built heat therein, preventing the corrosion, keeping cleanness, and so on. After a time-intervals, the lubricant, because of long-term mechanical or thermal agitation, loses their virgin properties, and needs to be changed. Consequently, the waste lubricants, in addition to the asphaltic compounds resulted due to the thermomechanical degradation, contain various contaminants, for example, metal powders, ash, gum, varnish, carbon residues, etc. (Whisman, Ml, Jw, & Jw, 1978). The consumption of lubricants followed by its rejection as wastage is large in amount. For instance, it is nearly 1.7
3.5 million tons/year in case of Europe and America. The common practices to discarding the waste lubricants includes discharging it to the land or water, burning as low-grade fuel, etc., which causes serious hazardous impacts to health and environments (Pinheiro, Pais, Quina, & Gando-Ferreira, 2018). In addition, if the cost of the lubricants is considered, the discarding of the reusable waste lubricants can be said also as a huge economical drainage worldwide. It is predicted that the global market value of lubricants is going to be more than 180 billion US dollar by 2025. To meet the fast-growing societal demand, more than half of the total lubricants is being consumed by the automobile industry. According to the recent available data, considering the total volume consumption, the China has been found as global

E. Miscellaneous

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441

lubricants market leader, followed by the United States and India with a consumption of 7.3, 6.05, and 1.7 million tons in the year of 2019 (N. So¨nnichsen, 2021). Nearly 20 million tons of lubricants are being wasted worldwide which is about 50% of total lubricants consumed per year. Thus it is being attempted to enable the “trash-to-treasure” and to promote the “circular economy” by regenerating the usable oil from the waste. For instance, up to 30% and 22% oils are regenerated from the waste in Asia and North America, respectively. According to the statistics of European commission, approximately 3 million tons of waste oil is being afforded to manage every year in the European Union (EU) (Hamawand, Yusaf, & Rafat, 2013). In addition to the lubricants, another form of waste oil is the waste cooking oils which are in general oils or fats used for cooking or frying in various food processing industries, restaurants, street food centers, and public houses (Tsoutsos & Stavroula, 2013). The basic material of the cooking oil includes mainly the lipids which are either plant-based (such as corn oil, margarine, coconut oil, palm oil, olive oil, soybean oil, grape seed oil, canola oil, etc.) or animal-based (such as butter, ghee, kermanshahi oil, fish oil, etc.) (Yaakob, Mohammad, Alherbawi, Alam, & Sopian, 2013). Herein, the structural alteration of the constituent materials happened through several temperature induced physicochemical mechanisms such as hydrolysis, oxidation, cracking, etc. (Cvengroˇs & Cvengroˇsova´, 2004). As a consequence of oxidation, hydroperoxide is primarily produced which may further produce various reactive and toxic chemicals such as 4-hydroxy-2-alkenals (Choe & Min, 2006; Kulkarni & Dalai, 2006). Based on the increasing demands of foods to maintain the highly grown human population, waste cooking oil is found to have rapidly increased (Chen et al., 2009; Phan & Phan, 2008). According to the following table (Table 24.1), although many countries are attempting to recover and reuse to waste cooking oil, nearly 60% of its total global consumption is being disposed inappropriately (Hamze, Akia, & Yazdani, 2015). For example, South Africa yearly regenerates 60,000 tons of waste cooking oil whereas nearly 200,000 tons are remained uncollected. This huge amount of waste oil and its improper discarding practices worldwide, because of its hazardous effects, has become a major concern to be well managed for our socioeconomic and environmental sustainability. TABLE 24.1 Estimated waste cooking oil collected in a year (De Feo, Di Domenico, Ferrara, Abate, & Sesti Osseo, 2020; Yaakob et al., 2013). Country

Million tons/year

Year

United States

10

2007

China

5

2020

England

1.6

2011

European

0.7
10

2012

Japan

0.45
0.57

2006

Malaysia

0.5

2006

Ireland

0.153

2012

Canada

0.12
0.135

2008

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So, there is an urgent need to manage the waste oil to support the circular economy and sustainable green environment by means of developing proper disposal technique, recycling of this waste trash to treasure, or modifying the waste oil to be reused. In this regard, throughout this decade, some techniques have been developed to tackle the problems associated with waste oils. These include conversion of waste to energy or other value-added materials (Reddy, 2011). This chapter presents and discusses the current situation and way of recovery of the waste oil.

24.2 Hazardous effect of waste oil Proper disposal of waste oil is a cost intensive factor. Because of this cost factor, illegal ways like discarding the waste oil into sewers and the sea can be attempted by irresponsible waste oil producers. Considering the hazardous effects of waste oil such as toxicity, non-biodegradability, etc., it can be said that the improper disposal of waste oil may pose serious problems for ecosystems including the soil, water, and air (Speight & Exall, 2014).

24.2.1 Soil Improper disposal, leakage from the engines or pipelines cause the contamination of soil with the waste lubricating oil. As a consequence, the physical, chemical, and microbiological properties of soil are being deteriorated from its normal condition. Nature of soil, its porosity and organic matter in the soil control the fate of oil released into the soil. Soil containing high organic matter absorb the oil and prevents its downward flow whereas the permeable soil containing lesser amount of organic matter allows the oil to flow and contaminating the ´ groundwater (Klamerus-Iwan, Błonska, Lasota, Kalandyk, & Walig Rski, 2015). The rest of the oil remaining in soil degrades slowly via volatilization, hydrolysis and/or microbial degradation (Speight & Exall, 2014). The presence of oil in the soil significantly affects the living organisms particularly those are involved in the nitrogen cycle. Oil fills the pores in the soil, hinders the oxygen to pass through, induces significant number of anaerobic zones, and causes changes in metabolic activity of both the aerobic and anaerobic microorganisms (John, Itah, Essien, & Ikpe, 2011). The heavy metals in waste oil can strongly inhibit the primary productions in soil, for example, mineralization and transformations of carbon, sulfur, phosphorous and nitrogen (Srivastava et al., 2017). The pollution laid by waste oil causes deviation in the normal accumulation of both the essential (e.g., K, Mg, Ca, Fe, Co, Ni, Cu, Zn, etc.) and nonessential elements (e.g., Al, Pb, and Cd) elements soil and their translocation into the plant tissues (Vwioko, Anoliefo, & Fashemi, 2006), affecting the metabolism and growth of the plants, and causes a harmful effect on the food chain (because of high amount of toxic metals accumulation) (Kayode, Olowoyo, & Oyedeji, 2009; Morkunas, ´ Wo´zniak, Mai, Rucinska-Sobkowiak, & Jeandet, 2018). Moreover, plants may uptake the low molecular weight polycyclic aromatic hydrocarbons (PAH) from the oil polluted soil, which are readily translocated within the above-ground plant tissues (Klamerus-Iwan et al., 2015), causing severe to moderate toxic effects (50
1000 mg/kg body weight) on oral health, reproduction and immunity (Jahromi, Kannan, Zakaria, & Aris, 2014).

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24.2.2 Water Waste oils because of their unconventional dumping practices, and water dragging from streets, roads, and vehicle-parks into the various watercourses seriously contaminate the water resources and threaten our sustainable livelihood (Vazquez-Duhalt, 1989). The hydrocarbons in the oils or lubricants, because of their obvious property form a low-density organic film over the water surface, and prevent the adequate oxygen needed for the aquatic living beings. The other constituents of the waste oil transforms into their different forms via different slow processes such as volatilization, emulsification, agglomeration, photodegradation, biodegradation, etc. resulting in a bad impact on the physical and chemical features of the normal water which on the other hand shows serious health hazard effects to all the living organisms in the ¨ zbay, 2016). Bioavailability of the hydrocarbons (aliphatic and aromatic) through world (O their various forms depend on their solubility in water (Swigert, Lee, Wong, & Podhasky, 2014). Studies indicate that the solubility of carbon chains (containing C $ 10) in water is limited to ,1 mg/L, enough to cause the toxicity (ECHA, 2008). Similar to the soil, these hydrocarbons mainly affect the aquatic environment which then transfers to the other the community of microorganisms and seriously damages the sustainability of whole ecosystem. Although various microorganisms are found to be capable to bio-degrade the low molecular weight hydrocarbons (Deshpande et al., 2018), they may inhibited by the other constituents (e.g., metals) present the in waste oil (especially lubricants) (Kapoor et al., 2015). A recent study showed that the lubricants even after their photodegradation can have serious health hazard effects on the living organisms in the aquatic ecosystem. Morphological defects (especially tail fin fold defect) of olive flounder (Paralichthys olivaceus) embryos were found to be evaluated in the presence of trace amounts of lubricant with or without its photodegradation under exposure of UV-irradiation (Shankar et al., 2020). Thus waste lubricating oil is being considered as one of the most important mutagenic agents in the aquatic environment (Salam, 2016). It has been observed that the hydrocarbons compared to the other organic constituents of waste oil are highly resistance toward the biodegradation. Thus in addition to the environmental parameters (and their variation), the degradation rate of waste oil is highly influenced by its hydrocarbons content, and the rate decreases with increasing the hydrocarbons. The degradation efficacy of hydrocarbons depends on their chemical structure and chain length, and varies from short-chain-to-branched-to-aromatics (Xue, Yu, Bai, Wang, & Wu, 2015). In brief, it can be said that the oil contaminated water can have adverse effects on human health and natural ecosystems (Speight, 2016).

24.2.3 Air Because of low cost and petroleum like heat of combustion (i.e., nearly 40,000 kcal/kg), waste lubricating oils are being considered as primary or supplemental fuel for industrial boilers, domestic oil burners, rotary cement kilns, waste disposal incinerators, etc. (Arpa, Yumrutas, & Demirbas, 2010). However, as mentioned above, the waste lubricating oil accumulates various contaminants including metals, which during combustion may transform to various toxic gases and pollute the air (Speight & Exall, 2014). It has been found that nearly 800 mg of Zn and 30 mg of Pb can be exposed to the air after combustion of 1 L waste lubricating oil which is 50- to 100-folds increase compared to the burning of

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24. Efficient management of oil waste: chemical and physicochemical approaches

normal oils (Boughton & Horvath, 2004). Again, it has been reported that combustion of waste lubricating oil releases more than 50% of its lead, cadmium, chromium and zinc particles to the air (United States Department of Energy, 2006). Thus demetalization is needed before the combustion of waste oil. In addition to the toxic metals, combustion may produce various harmful compounds, for example, dioxins, oxides of sulfur, nitrogen and phosphorus, hydrochloric acid, etc. For example, cutting oil and metal processing oil because of their chloride contaminant produces HCl into the air during combustion (Audibert, 2002). Beside the aforementioned particulates, emission of carcinogenic hydrocarbons (mainly polycyclic type) are also reported during combustion of waste oils (especially waste lubricants) (Abadin, Ashizawa, Llados, & Stevens, 2007). In case of waste cooking oil, the observable problem is its bad odor in the air. Considering, the chemical constituents of cooking oil their solubility in water, it is anticipated that 1 L of waste cooking oil may pollute 500,000 L of natural water. Herein, the waste oil not only increases the organic load of natural water but also causes formation of thin layer over the water surface responsible for shortage of dissolved oxygen concentration required for the underwater living beings (Stoytcheva & Montero, 2011). Improper disposal of cooking oil into the kitchen sinks is found block the sewer pipes due to formation of solids formed possibly through the formation of emulsion. To resolve the problems (i.e., to degrade the blocks), some chemical and physical treatments are needed which results in corrosion of metals, concrete etc. and further pollution of water (Refaat, 2010). On the other hand, the collection of the waste cooking oil from the drainages and repacking them (without considering their health hazard effects) for selling to mitigate the public, nowadays becomes a serious issue for our society. Recently, this unethical and improper dumping practices of waste cooking oil into the sewers has become an issue of public awareness in China and Taiwan. It was revealed that some dishonest companies for their huge profit, were collecting the waste cooking oils from the sewers through some very simple treatment procedures and selling among the public markets (Li, 2010). These “badly-refined” cooking oils mainly contain various undesirable substances such as PAHs and heavy metals (e.g., nickel and lead) which are known to be poisonous for human health (Yang, Chen, Lu, Luo, & Wang, 2014). In this regard several governments are imposing various strict rules. For instance, the recycling of waste cooking oil as an animal feedstock is strictly prohibited in the EU (Cvengroˇs & Cvengroˇsova´, 2004). In addition to the above discussion, following Table 24.2 summarizes some of the harmful chemicals in waste cooking oil and their effects. Thus there must be standard protocols for discarding the waste oils such as, pretreatment of waste oils before their combustion/incineration which may better work out without or minimizing the environmental pollution. It has been observed that the direct combustion without any pretreatment can lead to the release of many toxic and hazardous residues such as metal and metalloid particles, chlorinated compounds, PAHs, etc. causing a serious impact on the health and environment (Diphare, Pilusa, Muzenda, & Mollagee, 2013). Also, the formation of greenhouse gases (e.g., CO2) during combustion that contributes to the severe deterioration in climate, is also a big concern to realize a sophisticated way for the disposal of waste oil (Lam & Chase, 2012). Thus the development of an ecofriendly, safe, sustainable, socially acceptable, and cost-effective remediation for the treatment, recovery, and disposal of waste oil should be considered as a primary task for the sake of our sustainability (Stehlı´k, 2009).

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24.3 Chemical constituents of waste oil

TABLE 24.2

Some harmful chemicals in waste cooking oil and their effects (Awogbemi, Onuh, & Inambao, 2019).

Chemical

Effects

References

1-Hexanol (C6H14O)

• Harmful if consumed or touches the skin • Causes severe eye irritation

National Center for Biotechnology Information (2018b)

1-Heptene (C7H14)

• Highly combustible • Supposed to be dangerous if swallowed and enters airways • Poisonous to aquatic life • Causes skin, eye, and respiratory irritations • Harmful if inhaled • Extremely poisonous to aquatic life • Toxic to aquatic animals and wildlife habitat • Causes eye and skin irritations and lung injury • Long-term destructive effects to the human health • Highly toxic if inhaled • Causes acute skin, eye and respiratory irritations • Harmful to aquatic life with long-lasting effects • Causes skin, eye, and respiratory irritations • The possibility of causing long-lasting damaging effects on aquatic life • Harmful if ingested • Causes severe eye irritation

National Center for Biotechnology Information (2018e)

Cis-9-Hexadecenal (C16H30O)

i-Propyl 14-methylpentadecanoate (C16H32O2)

Palmitic acid (C16H32O2)

Linoleic acid (C18H32O2)

2,3-Dihydroxypropyl elaidate (C21H40O4)

National Center for Biotechnology Information (2018e) Santa Cruz Biotechnology (2009)

National Center for Biotechnology Information (2018c)

National Center for Biotechnology Information (2018d) National Center for Biotechnology Information (2018a)

24.3 Chemical constituents of waste oil 24.3.1 Waste cooking oil Waste cooking oil is obtained after several times of frying the edible vegetable oils such as palm, sunflower, and corn oils (Campanelli, Banchero, & Manna, 2010). The frying processes make many physical and chemical changes of oil and thus it loses the edible features for the human consumption. Physiochemical changes in color, odor, viscosity, calories count are notable when the cooking oil is fried several times (Lam, Lee, & Mohamed, 2010a). Waste oil also contains an increased amount of particulate matter as well as total polar solids and polymeric molecules (Cvengroˇs & Cvengroˇsova´, 2004; Kulkarni & Dalai, 2006) as mentioned in Table 24.3. The use of waste cooking oil may cause serious gastrointestinal disorders in the human body. The chemical and physical properties of a typical waste cooking oil sample collected by Wen et al. (Wen, Yu, Tu, Yan, & Dahlquist, 2010) is summarized in Table 24.4. The frying conditions, such as temperature and cooking time often influence the physical and chemical features of waste cooking oil. With the increase in the amount of heat and water during the frying process, the hydrolysis of triglycerides increases and eventually the Fatty Acid (FA) percentage in the waste cooking oil (Carlini, Castellucci, & Cocchi,

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24. Efficient management of oil waste: chemical and physicochemical approaches

TABLE 24.3 Chemical changes occur in cooking oil after frying. Chemical reactions

Reaction causes

Change in chemical composition

Thermal degradation

Anaerobic and high temperature degradation of triglyceride

Produces alkanes, alkenes, symmetric ketones, oxo propyl esters, COx, etc.

Oxidation

Reaction with atmospheric oxygen

Formation of Oxides, hydroperoxides, etc., which in particular hydroperoxides may change the content of conjugated dienes and trienes

Hydrolysis

During frying of food at high temperature, interaction, and reaction of water in food and atmospheric moisture with the oil

Increase in concentration of total polar molecules, production of free fatty acids, glycerol, etc.

Polymerization Reactions with unsaturated fatty acyl groups at high temperature

Production of polymerized triacylglycerides

TABLE 24.4 Physical and chemical properties of a typical waste cooking oil. Property

Value

Palmitic acid (wt.%)

8.5

Stearic acid (wt.%)

3.1

Oleic acid (wt.%)

21.2

Linoleic acid (wt.%)

55.2

Linolenic acid (wt.%)

5.9

Others (wt.%)

4.2

Water content (wt.%)

1.9

3

Density (g/cm )

0.91 

2

Kinematic viscosity (40 C, mm /s)

4.2

Saponification value (mg KOH/g)

207

Acid value (mg KOH/g)

3.6

Iodine number (gI/100g)

83

Sodium content (mg/kg)

6.9

Peroxide value (meg/kg)

23.1

2014) enhances. Kumar and Negi (2015) have studied the FA composition of vegetable oil before and after repeated use. They have reported that repeated use of vegetable oil alters the composition and produces various polymerized derivatives, hydrocarbons, and glyceride molecules, which make the oil unsafe for human consumption and disposal to the environment. Moreover, many volatile compounds are generated during deep frying in presence of oxygen at high temperature (Saguy & Dana, 2003; Ziaiifar, Achir, Courtois,

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447

Trezzani, & Trystram, 2008). Knothe and Steidley (2009) have analyzed the FA profile, viscosity and acid value of the fresh and used vegetable oils collected from 16 restaurants. They have observed that oxidative degradation during high-temperature frying alters both the physical and chemical features of fresh vegetable oils. The content of saturated FA and monounsaturated FA in waste oil increases as compared to the presence of polyunsaturated FA. In addition, the exposure of foods and frying utensils during frying promote leaching as well as increase in the amount of particulate matters, metal traces, spices, and other organics (Pokorny, 1989). A complex mixture of aldehydes, alcohols, dienes, and heterocycles are identified when the volatile fraction of waste cooking oil is analyzed. Mannu et al. have analyzed commercial sunflower oil prior to and after several cycles of frying (Mannu et al., 2019b). Various chemicals such as hexanal, heptanal, limonene, furan, 2pentyl-, nonanal, 1-octen-3-ol, furfural, cyclohexanol-dimethyl-2, benzaldehyde, 2-nonenal, 2-furan-methanol, 2-decenal, 2-undecenal, and 2,4-decadienal are identified depending on the frying conditions that also include the type of food and tools being exposed. The low degree of degradation and presence of little contamination while is enough to declare oil unfit for food applications, it can be utilized easily to produce value-added products through recycling process (Li, Cai, Sun, & Liu, 2016; Mannu et al., 2019a). The waste cooking oil can be used as main raw materials in several industrial processes, such as biolubricant (Karmakar, Ghosh, & Sharma, 2017), fuel production (Chrysikou, Dagonikou, Dimitriadis, & Bezergianni, 2019; Hazrat, Rasul, Khan, Ashwath, & Rufford, 2019), additives for asphalts (Ahmed & Hossain, 2020), preparation of animal food, etc. (Tres et al., 2013). Depending on the chemical compositions, waste cooking oils can further be used for the production of bio-plasticizers, syngas, adsorbents for volatile organic compounds, etc. (Mannu, Ferro, Pietro, & Mele, 2019c).

24.3.2 Waste lubricating oil Nowadays, a variety of lubricants are being used in modern machines, which operate under various normal to harsh environments. Mineral oil-based lubricants remain popular to the consumers mainly because of their easy availability and low cost (Mang & Dresel, 2007). Report predicts that the market size for global synthetic lubricants were valued at USD 4.40 billion in 2018 and it is expected to grow at a compound annual growth rate of 5.1% from 2019 to 2025 (Global synthetic lubricants market size report, 2019). Lubricating agents mainly consist of two ingredients which are the base oil and chemical additives. The nature of chemical additives influences the performances of lubricating oils. Table 24.5 summarizes different types of additives that are blended with base oil to achieve the lubrication properties. Lubricating oil undergoes various physical and chemical transformations during operation and it continues after being released into the environment. Waste lubricating oil is a complex mixture of paraffinic, naphthenic, and aromatic petroleum hydrocarbons. Different ingredients of waste lubricating oils include carbon deposits, sludge, aromatic and nonaromatic solvents, water, glycols, wear metals and metallic salts, antifoaming agents, fuels, polynuclear aromatic hydrocarbons, etc. (Speight & Exall, 2014) The chemical changes that occur in oil depend on the nature of original base oil, refining process used, additives used, application type, time of service, etc. (Totten, Westbrook, & Shah, 2003). The elemental contamination may be caused in the base oil due to the

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TABLE 24.5 Typical composition of lubricating oil (Mohammed et al., 2013). Component

Wt.%

Base oil

71.5
96.2

Metallic detergents

2.0
10.0

Ashless dispersants

1.0
9.0

Oxidation inhibitor (zinc dithiophosphate)

0.5
3.0

Antioxidant/antiwear

0.1
2.0

Friction modifier

0.1
3.0

Pour point depressant

0.1
1.5

Antifoam

2
15 ppm

deterioration of additives and addition of external moieties. The lubrication properties of oils may be lost due to the presence of water, chlorine and polychlorinated biphenyls (PCB), PAH and particulate metals (Audibert, 2011). Metals are often found in waste lubricating oil as particulate matter or in their elemental form (Speight & Exall, 2014). Waste lubricating oil may also be comprised of soot and carbons which are derived from incomplete combustion and causes characteristic black color of the used oil. In addition, many other chemicals, sludge, varnish, dust, dirt, solvents, antifreeze agents, coolants are also may be found in waste lubricating oil (Francois, 2006). Table 24.6 compares the compositions of typical virgin lubricating oil and their used counterpart.

24.4 Recycling methods of waste oil 24.4.1 Physical treatment of waste oil (2
7) Mainly three kinds of physical treatments (as stated below) are considered to remove the undesired products and regenerate the reusable part from the crude waste oil (Mannu, Garroni, Ibanez Porras, & Mele, 2020). The physical routes are technically various separation methods (as pointed below). (1) Solvent extraction (2) Filtration (3) Distillation 24.4.1.1 Solvent extraction In this case, a thumb rule of organic chemistry that is “like-likes-like” is followed. Basically, various organic solvents of polarity (i.e., polar, or nonpolar) similar to the desired components of crude waste oil are chosen for their extraction. Selective separation of unwanted aromatic components using a suitable organic solvent is followed to retain the saturated hydrocarbons (having more oxidative stability) enriched treated oil

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TABLE 24.6 Comparison among the properties of virgin and waste lubricating oil (Pinheiro et al., 2020; Rosli et al., 2002). Properties

Virgin lubricating oil

Used lubricating oil

Physical properties 3

Density (kg/cm )

817
953

0.82
324

4
491

324.0

Kinematic viscosity (100 C), cst

1
86




Sediments (wt.%)

0

0
50.4

Water (wt.%)

0

0
14.6

Viscosity index

-13 to 314




Surface tension (mN/m)




22.4
33.2

Ash content (wt.%)

0.94

1.3




175.6

-37

-37

Kinematic viscosity (40 C), cst 



Flash point ( C) 

Pour point ( C)

Chemical properties Saponification number (mg KOH/g)

0
64

2.12
21.8

Total acid number (mg KOH/g)

0
5.35

0.26
4.6

Sulfur (wt.%)

0
2.2

0
1.1

Lead (ppm)

0

3700
14,000

Calcium (ppm)

38
8750

90
4468

Zinc (ppm)

48
1664

24
16,70

Phosphorus (ppm)

0
1500

57
1220

Chlorine (ppm)

9
675

0
6012

Barium (ppm)

37

297

Iron (ppm)

0
3

20
1210

Chromium (ppm)

0

5
24

Aromatics

0
19.3

0
7.87

Paraffinics

23.9
75.4

34.1
62.1

Naphthenics

21.3
46.27

29.9
65.8

Carbon content

(Rincon, Canizares, & Garcia, 2005). Currently, instead of direct (or conventional) solvent extraction, different physical or chemical treatment are being conducted before or after the solvent extraction such as thermal degradation of waste oil in alkaline condition followed by solvent extraction (Pilusa, Muzenda, & Shukla, 2013), combination of solvent extraction

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and adsorption (Mohammed, Ibrahim, Taha, & Mckay, 2013), etc. These kinds of hybrid solvent extraction techniques are found to be advantageous toward selective separation of the unwanted components and regeneration of the usable oil having high oxidative stability. Though the solvent extraction seems to be a flexible and potential technique, the use of high volume of organic solvents, their hazardous and inflammable nature, huge financial investment for establishing an extraction plant assembled with high pressure sealing system limit the wide applicability of this technique in waste oil recovery. 24.4.1.2 Filtration Mainly three types of filtration technologies, that is membrane filtration, conventional filtration and activated filtration are being pursued to regenerate the waste oil. Various solid materials are used as filter in all this filtration process which play a crucial role to determine the quality (i.e., performance) and cost of the recycled product, and the sustainability of recycling process. In case of vegetable oil, the membrane filtration, mainly because of its low energy consumption, and ability to retain the nutrient components in recycled product, has received an increasing attention since last two decades (Ladhe & Kumar, 2010). Membranes are the semipermeable barriers, which allow the passage of the desired components (with or without the applied pressure) keeping retained others undesired (e.g., undesired carbon soot and metal particles). Basically, the membranes are made of either ceramics and metals or polymer hollow fibers of various polymers such as polyethersulphone (PES), polyvinylidene fluoride, polyacrylonitrile, etc. In case of polymerbased membrane filters, the hydrophobicity of the base materials is considered as the main important factor. Thus in some cases surface modification is being carried out to improve the efficacy of the filter. For example, Tur et al. (Tur, Onal-Ulusoy, Akdogan, & Mutlu, 2012) have reported the surface modification of PES membrane with hexamethyldisiloxane followed by radio frequency plasma treatment to improve the hydrophobicity of the membrane for the filtration of waste frying oil. For cooking oil, surface having more hydrophobicity is supposed to efficient for selective removal of inhibit the polar components present in the waste oil. Tur et al. (2012) have found the selective filtration of the polar components along with the free FAs by the modified PES membrane, resulting in extraction of lower viscosity and reusable frying oil from its waste. Apart from the high efficiency, although, the membrane filtration process has various advantages such as low processing temperature (i.e., less than 50 C) and pressure (i.e., nearly 0.1 MPa), it suffers from several drawbacks such as high cost, less damage resistance against the large particles, and possibility of retention of the undesired components (e.g., PAHs) in the recovered oil (as the membrane allows the removal of only polar components and FAs), which limit the wide and large-scale applicability of the filtration technique (Dang, 1997). Conventional filters, normally made of metal screened cellulose fiber pads are not only cost-effective but also highly efficient compared to the other filters. For example, cellulose filter paper has been reported to remove up to 79% of solid particles from Colombian waste cooking oil through a facile and standardized process (Casallas et al., 2018). Although the cellulose pads are economic, but they adsorb a considerable amount of the filtered oil, have very low mechanical strength, which limits their usability for multiple filtration cycle. Also, it only can separate the solid particles having dimension higher than 1

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micron. On the other hand, the metal screen, generally stainless steel can be reused for indefinite times but limited to remove the solid particles larger than 80 μm only. In this regard, efficacy of the conventional filters are being attempted to improve by depositing various powdered filter aids (e.g., diatomaceous earth, clays, silicates, activated carbons, etc.) over the surface of conventional filters which not only increase the active surface area of the filter and enhance the retention of smaller particles (around 1 μm) but also participates in active filtration through the plausible chemical interaction or electrostatic bonding of the contaminants (particularly FAs) with the adsorbents or neutralizing agents present in the filter aids. Previously, free FAs and colors have been attempted to remove by the use of silicates of calcium and magnesium filter aids respectively over the conventional filter (Weisshaar, 2014). In last 20 years, new materials such as blends of silicates with the oxides of magnesium and aluminum have been attempted to include in cooking oil treatment during the frying operations (Bertram, Abrams, & Kauffman, 2002; Muraldihara, Jirjis, & Seymour, 1996). Similar attempts have been pursued with the filters composed with the synthetic fibers of polyester, polypropylene, and nylon, etc. which have been found to be very much efficient to remove up to 93%
98% of FAs from the used cooking (Bivens & Clark, 2007; Bivens & Clark, 2011). Although the conventional, powdered, and fiber filters are found to be high performing, they are still inefficient to remove the smaller (,0.5 μm) undesired particles. 24.4.1.3 Distillation Distillation of waste oil is one of the simplest processes for removing water and volatile compounds from crude waste oil. Many small-scale oil-recycling distillation units are being produced for such applications. This small-scale distillation unit is advantageous due to low processing time, small dimension, and low processing temperature. Also due to low requirement of energy such process is considered to be economic. It is possible to estimate a consumption of 1.583 kWh to produce 25 tons of purified oil, which corresponds to an overall energetic cost of approximately 7 h (euros) per ton of purified oil, based on the average energy prices in Europe for nonhousehold consumers (0.11 h/kWh) (Mannu et al., 2020) The recycled oil can be utilized as lubricating oil. The lubricating market is fast growing (Luzuriaga, 2017). With further modification like addition of antioxidants and transesterification of the recycled oil can be used as chainsaw lubricants or as solvents (Tulashie & Kotoka, 2020). The recycled vegetable oil also can be modified to form poly(esteramide), alkyds, poly(etheramide), epoxies, polyurethane (PU), and glycerol for blending application like biodegradable coatings and paints (Alam, Akram, Sharmin, Zafar, & Ahmad, 2014). In addition to the aforementioned treatment procedures toward the reusability of oil wastes, centrifugation method is also considered in the oil industries.

24.4.2 Chemical treatment of waste oil 24.4.2.1 Transesterification Alcoholysis or transesterification is considered to be another route for further refining of waste oil [Eq. (24.1)]. In this process, transformation of an ester to another ester via interchanging of the alkyl moieties with the alcohol in presence of different catalysts such

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as acids (e.g., H2SO4, HCl), bases (e.g., NaOH, KOH), or enzymes (e.g., lipase) is optimized (Lam et al., 2010a). The type of catalyst is determined by the amount of free FA content in the waste cooking oil (Knothe, Krahl, & Van Gerpen, 2015). For example, waste cooking oil with high amount of free FAs are transesterified efficiently in the presence of acidic catalysts (Zhang, Dube, Mclean, & Kates, 2003) whereas the less free FAs containing waste cooking oils are transesterified more efficiently in the presence of basic catalysts (Narasimharao, Lee, & Wilson, 2007). It has been observed that the bases can react with FA leading to formation of soap which could retired the catalysis process and resulting in low yield of desirable product (i.e., alkyl ester) (Kulkarni & Dalai, 2006; Yan, Salley, & Ng, 2009). In contrast, there is no chance of soap formation in case of acid catalysis which could led to high yield (up to 90%) production of the desirable product (Wang, Ou, Liu, Xue, & Tang, 2006). However, acid-catalyzed transesterification requires longer reaction time (10 to 70 h) (Wang et al., 2006) than that of the base-catalyzed, and thus the basecatalyzed transesterification is commercially preferable. In comparison to both the acidand base-catalysis, enzyme-catalyzed transesterification could be a better alternative as this process has no such effect of free FA content in the waste cooking oil. However, high operational cost and expensive enzymes are the main drawback for enzyme-based transesterification (Bajaj, Lohan, Jha, & Mehrotra, 2010). Commercialized biodiesel production from waste vegetable oil and animal fats via transesterification between the triglycerides (present in the wastes) and alcohol (usually methanol) is already reported [as schematically shown in Eq. (24.1)], and this biodiesel is found to exhibit nearly similar properties to that of the diesel with respect to its cetane number, density, and heating value (Demirbas, 2009).

Although this process is already commercialized, it needs high amount of alcohol, and the final product could have lower oxidation stability leading to poor storage efficacy. 24.4.2.2 Hydrotreating Hydrotreating is a well-established and industrially acceptable process to refine the crude petroleum and production of transportation fuels. In this process, a high volume of hydrogen gas is used for the removal of the undesired impurities (e.g., sulfur, nitrogen, oxygen, etc.) in crude petroleum to reduce the emission of pollutant

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gases (e.g., SOx and NOx) during its consumption, and also for enhancing the quality of various fuels (e.g., diesel and gasoline) by increasing the cetane number. Recently, this process has been attempted to enhance the oxidative stability of the tranesterified biodiesel by making them oxygen-free (Holmgren, Gosling, Marinangeli, Marker, & Faraci, 2007; Madsen, Christensen, Fehrmann, & Riisager, 2011; Sebos, Matsoukas, Apostolopoulos, & Papayannakos, 2009; Zhang et al., 2014). However, requirement of large amount hydrogen gas makes this process cost intensive. Eqs. (24.2)
(24.5) represent the stoichiometric chemical equations involved in common hydrotreating processes for the removal of undesired impurities in crude petroleum which implies that the hydrodenitrogenation (i.e., the removal of nitrogen) is more cost-intensive as it requires more hydrogen than the other impurities.

24.4.2.3 Gasification Gasification is a process to convert any carbonaceous material (e.g., coal, biomass, waste oils, and natural gas) into fuel gases alias synthesis gas (or syngas) (eg., CO, CO2, H2, CH4, etc.). The syngas (H2 and CO) can be used as a precursor for diesel-like fuel production via Fischer-Tropsch synthesis pathway. Guo et al. (2014) found that the cogasification of waste engine oil with the bio-oil obtained via pyrolysis of corn-straw could yield a remarkable amount of hydrogen gas. The gasification technique is found to be utilized to produce electricity from internal combustion engines. Thus it can be said that the gasification technique is towards producing electricity from the waste. However, requirement of high processing temperature (B1600 C), limits its wide applicability (Biomass Energy Center, 2011). 24.4.2.4 Pyrolysis Pyrolysis (i.e., heating in absence of oxygen) is a promising technique to convert the biomasses (e.g., cellulose, hemicellulose, lignin, etc.), waste oils, waste animal fats, etc. into various combustible gases, waxy liquids (can be used for developing different chemical feedstocks) and charcoal via their thermal decomposition without any combustion (Grundas, 2011). Alteration of the process parameters mainly temperature and time may vary the content of pyrolysis products (i.e., gas, liquid or solid). Thus these process

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parameters can be optimized to maximize the desired product (Onwudili, Insura, & Williams, 2009). For example, production of gases are promoted via increasing the processing temperature and time; condensable liquid oil are produced by increasing the temperature while decreasing the time (i.e., “flash pyrolysis”), and the char are produced at a low processing temperature and low heating rate (Dominguez et al., 2007). The mixture of pyrolysis products are separated and purified (for their further utilization) via various distillery and refinery facilities. By exploiting the pyrolysis technique, the sewage sludge has been transformed into tar-free fuel gas (Zhang et al., 2014) and polyaromatic hydrocarbons (Dai et al., 2014). Similarly, various wastes such plastic wastes, catechol, acetylene, ethylene, scrap tires, etc. are being attempted to transformed various value-added products via pyrolysis or copyrolysis (Sa´nchez, Callejas, Millera, Bilbao, & Alzueta, 2012; Scheirs & Kaminsky, 2006; Uc¸ar, Karago¨z, Yanik, Saglam, & Yuksel, 2005). The pyrolysis can be mainly two types, conventional and microwave. 24.4.2.4.1 Conventional pyrolysis of waste oil

In case of conventional pyrolysis, the electrical heating (Arpa, Yumrutas, & Demirbas, 2010; Go´mez-Rico, Martı´n-Gullo´n, Fullana, Conesa, & Font, 2003; Nerı´n et al., 2000) has been used for the recovery of waste biomass (e.g., waste cooking oil) (Fortes & Baugh, 2004; Idem, Katikaneni, & Bakhshi, 1996). Generally, the waste oils containing long-chain, saturated, and unbranched hydrocarbons show similarity (according to the hydrocarbon contents) with the diesel fuel (Knothe, Dunn, & Bagby, 1997). Consequently, various attempts are being taken to convert the waste vegetable oils (e.g., sunflower oil) to biodiesel and bio-gasoline via pyrolysis (Dandik, Aksoy, & Erdem-Senatalar, 1998). Instead of conventional pyrolysis, recently electric arc pyrolysis employing different heating mode is being examined to pyrolyze the waste oil (Song, Seo, Pudasainee, & Kim, 2010) toward producing valuable gaseous fuels (e.g., hydrogen, acetylene) and different “usable” carbonaceous residues (or chars). Due to the possibility of presence of the various undesired impurities (e.g., PAHs, metals), the pyrolysis technique to recover the waste oil needs further investigation and optimization (Williams & Besler, 1994). 24.4.2.4.2 Microwave pyrolysis

Instead of conventional pyrolysis comprising with electrical or electrical arc heating, the microwave pyrolysis or microwave-assisted pyrolysis involves microwave dielectric heating arises from the interaction of electromagnetic wave with the dipoles of the material similar to the heating of food in microwave oven. In this case, heat is generated within the material being heated resulting in its homogenous heat distribution and more efficient heating compared to that of the conventional surface heating process. In addition easy heating control, availability of high temperature with higher heating rates (Ludlow-Palafox & Chase, 2001), make the microwave heating more efficient (Osepchuk, 2002). As a consequence, the microwave pyrolyzed products (e.g., hydrocarbons, olefins, aliphatics, and syngas) are found to be light weight, and very much potential to be used as a gaseous fuel and chemical feedstock (Bai, Chen, Li, & Li, 2006). The hydrogen obtained from the syngas is being potentially used as second-generation clean fuel. Steam-reformation of hydrogen from CO of syngas, direct use of other gaseous product or their upgradation to hydrogen, extraction of light weight hydrocarbons for various

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chemical feedstock are the most possible and potential applications of the microwave pyrolyzed products. In addition, production of nearly contaminant free liquid oil (B88%) containing various light weight aliphatic and aromatic hydrocarbons [e.g., benzene, toluene, xylene (BTX)] is also a value-added production of microwave pyrolysis (Lam, Russell, & Chase, 2010b) which is found to exhibit commercial gasoline like fuel properties (Lam, Russell, & Chase, 2010c; Moliner, Suelves, La´zaro, & Moreno, 2005). Again, the oily product of microwave pyrolysis can be added to the petroleum refinery to produce useful industrial chemicals and products. Further investigations are still needed to explore the possibility of this oil to be upgraded as transport grade fuel quality. 24.4.2.5 Incineration The incineration is a rapid combustion of a substance in presence of oxygen or destruction of a substance via burning. For waste oil management, this method can be preferred when the oil is highly contaminated with various hazardous materials such as PCB, polychlorinated terphenyls, etc. Waste oil containing no such hazardous waste incinerators, is recommended its incineration at the cement factories assembled with cement kilns having a temperature range of 2000 C
2400 C which is enough to destroy the organic and acidic contaminants of waste oil (Arnaout, 1997). Considerable reduction of heavy metals at their low quantity is also possible here. However, it is highly required to ensure the air quality standard during the incineration process, and thus continuous monitoring is needed (ElFadel & Khoury, 2001). In the industries, all of the aforementioned physical and chemical processes are investigated to realize their synergistic influence to improve the oil waste treatment efficacy. For instance, Figs. 24.1 and 24.2 schematically represent the industrial treatment process of various oil waste (e.g., used oil and waste oil). Table 24.7 summarizes the advantages and limitations of the current techniques in recovery of usable parts from the waste oil. The limitations are attributed to the high

FIGURE 24.1 General processing steps for used oil refining.

FIGURE 24.2 General processing steps for waste oil (fuel) refining.

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TABLE 24.7 Advantages and limitation of various techniques in recovery of waste oil. Technology

Advantages

Disadvantages

Membrane technology

Low processing temperature (40 C) and pressure (0.1 MPa) Improve the liquidity and flash point of recovered oil

The membrane could be expensive, easily damageable, and can be fouled by large particles (Dang, 1997)

Solvent extraction

Selective separation Enhanced oxidation stability of recovered oil (Rincon et al., 2005) Transesterification Selective production of desired fatty acid Transformation of by-product (glycerol) into ethanol (Emptage, Haynie, Laffend, Pucci, & Whited, 2003), polyglycerol (Gholami, Abdullah, & Lee, 2014), and act as fuel additives (Mota, Da Silva, Rosenbach, Costa, & Da Silva, 2010) Hydrotreating High product recovery High oxidation stability of product (Sebos et al., 2009)

High investment cost The use of hazardous or flammable solvents

Gasification

High yield of hydrogen gas

High process temperature (1600 C)

Conventional pyrolysis

High feedstock flexibility Simple system and inexpensive to construct (Onay & Koc¸kar, 2004) Production of potential gasoline range oil products (Dandik & Aksoy, 1999; Dandik et al., 1998) Fast and selective heating lead to shorter reaction time Less PAHs compounds produced More environmentally friendly with less greenhouse gases emission Products possessed many potential uses

The need for high process temperature (usually up to 1000 C) Slow heat transfer leads to longer reaction time Production of PAHs compounds as by-product (Domen˜o & Nerı´n, 2003) Not all materials used are conducive to microwave absorption Reactor design, microwave cavity, microwave magnetron yet to be optimized Possibly high cost of the whole system set-up Limited information available on key process parameters (e.g., microwave power, heating rate, catalyst, microwave absorbent) Air emissions, although minimal, still need to be addressed Opposition by regulatory and government institutions (Diphare, Muzenda, Pilusa, & Mollagee, 2013)

Microwave pyrolysis

Incineration

Economically feasible at lower processing volumes Cement factories are willing to procure the waste oil Less capital intensive than the previous options Concentrates waste oil disposal to limited sites that can be more easily regulated and controlled

High processing cost due to the use of large volume of alcohol consumption Final product possesses low oxidation stability and leads to a short storage period

High operation cost due to the need for large volume of hydrogen gas

operation cost, use of large amounts of reagents and solvents, low yield, and undesired components in the final products. Considering all the pros and cons of the available techniques employed in waste oil recovery, it can be said that many more investigations and optimization are yet to be needed to make them feasible for waste oil treatment and recovery.

24.5 Recycling products 24.5.1 Plasticizers A mixture of three unsaturated FAs namely oleic, linoleic, and linolenic acid is the main chemical constituent of waste cooking oil (Mcnutt, 2016). The carbon-carbon double bonds

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and the acidic groups of these chemicals can be exploited to develop several building blocks usable in polymer chemistry. In this regard, waste cooking oils have been recently reported as the precursor material to develop the bio-plasticizer. Instead of commercially available plasticizers associated with some serious controversies such as migration of phthalate ester (a commercial and widely used plasticizer) from the polymer matrix to the surrounding environment followed by its bioaccumulation, the bioplasticizer are essential to play its extensive role as polymer additives for processing plastic, rubber and adhesives with no risk/less risk to the environment (Greco, Ferrari, & Maffezzoli, 2017; Jia et al., 2018). It is noteworthy to mention here that the commercial plasticizers because of their harmful effects have been banned in several countries particularly in fields of toys, food packing and medicine (Feng et al., 2018). In this scenario, bio-based plasticizers obtained via modification of edible oil are being considered as the best alternative. In this regard, epoxidized soybean oil and its different derivatives, acetylated forms of castor oil, tall-oil fatty esters, etc. have been synthesized and examined their performances (Jia et al., 2017; Li et al., 2017). Because of high cost and possibility of negative impact on the food and feed chain, the use of bioplasticizers is still limited (Suzuki, Botelho, Oliveira, & Franca, 2018). Some very recent reports are found to propose the indispensable usability of bioplasticizer in polymer industries. For example, use of epoxidized waste cooking oil as plasticizer for PVC has been proposed by a recent work (Zheng et al., 2018). Although after a prolonged use, the bioplasticizer Nevertheless after prolonged times some degree of migration of the bioplasticizers are found to migrate from the matrix (e.g., PVC) (Chen et al., 2016), possibility of covalent boding of the bioplasticizer to the polymer back bone has been reported to mitigate the problem (Jia et al., 2018). For instance, Mannich base of waste cooking oil methyl ester was synthesized as a nonmigrating plasticizer for PVC. In this case, no migration from the plasticized PVC in n-hexane, ensures the long-term usability of the PVC products.

24.5.2 Biofuel The extraction of biofuel (i.e., biodiesel) from used vegetable oils, expansion of related manufacturing units and cultivation of oleaginous plants are being considered emerging as primary concern in various countries to mitigate the issues related to the depletion of fossil fuel from the earth crust, ever increasing cost of the traditional fuels, the environmental pollution laid by the combustion of these fuels. Following figure (i.e., Fig. 24.3) schematically represents the brief description about extraction of bio-disel from waste cooking oil. The vital step in this development is the transesterification of the oil with a catalyst (e.g., methanol) to release its esters (e.g., methyl ester) and glycerin. Corresponding chemical reaction can be represented as follows: Triglyceride (waste cooking oil) 1 3 methanol 5 3 fatty acid methyl ester 1 glycerin Herein the following stages are mainly considered: • Transformation of acid functionalities of the triglycerides into ester (i.e., biodiesel) through reacting with the methanol, and by-production of a glyceride mixture.

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FIGURE 24.3

General outline for obtaining biodiesel.

• Separation of the biodiesel and glyceride by decantation, and removal of residual methanol by distillation. • Filtration to separate the insoluble biodiesel residue to obtain a clean and homogenous product. The transesterification is a low-temperature (between 20 C and 50 C) reaction that occurs in an alkaline environment in presence of base such as sodium hydroxide, potassium hydroxide, sodium methylate, etc. The reaction can be proceed continuously or discontinuously using two stages (before and after cleaning). To proceed the reaction continuously, the by-product glycerin is separated out by the settling tanks, while for the discontinuous processes, sedimentation deposition technique is used. The glycerin stage is treated with various acids such as sulfuric acid, acetic acid or phosphoric acid, where the following type reaction occurs. Alkaline glycerin 1 sulfuric acid 5 glycerin 1 fatty acid 1 potassium sulfate The re-neutralized glycerin is evaporated, the FA is again subjected to esterification, and corresponding efficiency is further optimized.

24.5.3 Animal feedstuff Although the oils regenerated using the aforementioned treatment procedures from its waste, are already being used in animal feedstuff, the regeneration of its large quantity having higher utility level can be accomplished via the process described below which is in the experimental stage and has been successfully attempted in pilot plant. The process enables to deliver two fractions: (1) one fraction (i.e., 70% of the used oil) having nearly similar specifications corresponding to the oils used in human foodstuff, and (2) the rest (i.e., 30% of the used oil) suitable to use as fuel. Herein, the preliminary goal is to recover the nontransformed oil from its waste which is mainly made up of the triglycerides and unsaponifiable compounds. Its separation is carried out using carbonic acid gas as an extracting solvent at a low temperature range of 40 C
60 C. The low temperature is considered to prevent further chemical reactions.

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The use of gaseous carbonic acid as an extracting medium has the flowing positive aspects. • It enables elimination of the polar compounds responsible for the toxicity of the waste cooking oils. • It reduces the contamination taken place by the mineral oils mixed with the vegetable oil.

24.5.4 Polymer During production of biodiesel, crude glycerol (CG) is formed as a low-cost byproduct (nearly 1 wt.% if the biodiesel) (Kongjao, Damronglerd, & Hunsom, 2010) containing various impurities such as alcohols, water, salts, and soap (Johnson & Taconi, 2007). The refining of the CG can be considered important for its sustainable supply chain to the industries of foods and beverages, pharmaceuticals, cosmetics, textiles, etc. However, the refining processes is cost-intensive (Werpy & Petersen, 2004), especially for small- and medium-sized biodiesel plants (Pachauri & He, 2006). Thus CG becomes a potential financial and environmental liability for the biodiesel industries (Johnson & Taconi, 2007). Several biological and chemical methods are being approached to convert the CG into various value-added products, such as 1,3-propanediol (Mu, Teng, Zhang, Wang, & Xiu, 2006; Oh, Seo, Choi, & Kim, 2008), citric acid ´ (Rywinska & Rymowicz, 2010), hydrogen (Sabourin-Provost & Hallenbeck, 2009), poly (hydroxyalkanoates) (Mothes, Schnorpfeil, & Ackermann, 2007), succinic acid (Scholten, Renz, & Thomas, 2009), polyols, and PU foams (Luo, Hu, Zhang, & Li, 2013). Dang, Luo, Wang and Li (2016) proposed a sustainable process for the valueadded conversion of waste cooking oil and used PET bottles (via integrating the CG and PET) into the biodiesel and PU foams (Fig. 24.4). The other usable recycled products from the waste cooking oil can be classified as follows: • Manufacturing of industrial lubricants. • Manufacturing of surfactants to be used in production of soap and detergent. • Preparing mixed combustion fuel having calorific value higher than 8500 kcal/kg.

24.5.5 Converting waste lubricating oil into useable oil Various impurities such as dirt, metal scrapings, water, or other chemicals are accumulated with the lubricants after a period of its application which deviates its virgin properties and limits its further usability. Thus various analytical characterizations are pursued to ensure the waste lubricant quality to be used in the re-refining process. After that comparative quality of the end products obtained from the refined oil are checked with that of the premium product (i.e., virgin oil). Herein, the environmentally correct refining processes are considered. After overall satisfactorily standardization, the waste oils are allowed to be recycled or reused in various ways. Recycling of such contaminated oil is supposed to be beneficial for the cost reduction of engine oil as well as for the sustainability of the environment. Recycling of waste oils can be satisfactorily carried out via appropriate physical and chemical treatments. Certain types of used oils (particularly the lubricants) can be directly used after processing. Otherwise, the recovered oils can be used

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FIGURE 24.4 The value-added conversion of waste cooking oil and post-consumer PET bottles into biodiesel and PU foams.

as clean fuel, or a lubricating oil base stock. In fact, the recycled oils are used to reprocess the fuel oil. If the reprocessed oil is failed to qualify as a fuel, it can be used as heating fuel oil (by blending with crude oil) in various industries such as asphalt plants, cement companies, steel mills, etc.

24.6 Conclusion and future prospect Proper management over the improper disposal of waste oil not only minimizes the adverse effect to the environment and health but also boosts the economic sustainability. This chapter aimed to provide the conceptual idea toward the oil waste recycling for our socioeconomic and environmental sustainability. Instead of improper disposal causing a high risk to ecosystems, the holistic circular economy approach ensuring the “trash-totreasure” can be considered the best way of waste oil management. In this regard, the governmental effort for establishing a mass awareness toward realizing the profitable aspects of the oil waste management is highly needed. On the other hand, many scientific and technical developments in this area are yet to explored. Because of depletion of fossil fuel and related environmental pollutions, various alternative energy resources are being attempted to establish. Efforts are being paid to develop bio-based fuels from the agriproducts and their wastes in addition which is very much encouraging to the farmers for their economic sustainability. However, energy in various forms (e.g., thermal, and mechanical) are being wasted during the processing, transportation, and recycling of the oils. These waste energies can be recovered simply by employing different new techniques and related materials engineering. For instance, the use of pyro-/thermoelectric devices for

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harvesting the huge amount of waste heat energy (during various processing of oils) to the electricity can be explored further. On other words, this approach will be beneficial to reduce the global warming. The friction force (waste mechanical energy) during transportation or processing of oil can be recycled via the piezo-/triboelectric approaches. On the other hand, the soil or water quality can be protected from being polluted by the discarding of oil wastes, if the waste products can be biodegraded. In this regard, although some positive efforts are reported, research and further developments are yet to be done. Even the established ways for waste oil treatment can be further improved by making these fast, facile, and less hazardous. So, a humble united effort from every corner of our society becomes crucial to well manage the wastage of oil toward developing a healthy atmosphere (in respect to environment, health, and economy) for our future sustainability.

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So¨nnichsen, N. (2021). Global demand for lubricants from 2000 to 2019. ,https://www.statista.com/statistics/ 411616/lubricants-demand-worldwide/.. Speight, J., & Exall, D. I. (2014). Refining used lubricating oils. CRC Press. Speight, J. G. (2016). Environmental organic chemistry for engineers. Butterworth-Heinemann. Srivastava, V., Sarkar, A., Singh, S., Singh, P., De Araujo, A. S., & Singh, R. P. (2017). Agroecological responses of heavy metal pollution with special emphasis on soil health and plant performances. Frontiers in Environmental Science, 5, 64. Stehlı´k, P. (2009). Contribution to advances in waste-to-energy technologies. Journal of Cleaner Production, 17, 919
931. Stoytcheva, M., & Montero, G. (2011). Biodiesel: Feedstocks and processing technologies. BoD
Books on Demand. Suzuki, A. H., Botelho, B. G., Oliveira, L. S., & Franca, A. S. (2018). Sustainable synthesis of epoxidized waste cooking oil and its application as a plasticizer for polyvinyl chloride films. European Polymer Journal, 99, 142
149. Swigert, J. P., Lee, C., Wong, D. C., & Podhasky, P. (2014). Aquatic hazard and biodegradability of light and middle atmospheric distillate petroleum streams. Chemosphere, 108, 1
9. Totten, G. E., Westbrook, S., & Shah, R. (2003). Fuels and lubricants handbook: Technology, properties, performance, and testing. ASTM International, 10.1520/MNL37WCD-EB. Tres, A., Bou, R., Guardiola, F., Nuchi, C., Magriny, N., & Codony, R. (2013). Use of recovered frying oils in chicken and rabbit feeds: Effect on the fatty acid and tocol composition and on the oxidation levels of meat, liver and plasma. Animal, 7, 505
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184. Zhang, Y., Dube, M., Mclean, D., & Kates, M. (2003). Biodiesel production from waste cooking oil: 1. Process design and technological assessment. Bioresource Technology, 89, 1
16. Zheng, T., Wu, Z., Xie, Q., Fang, J., Hu, Y., Lu, M., . . . Ji, J. (2018). Structural modification of waste cooking oil methyl esters as cleaner plasticizer to substitute toxic dioctyl phthalate. Journal of Cleaner Production, 186, 1021
1030. Ziaiifar, A. M., Achir, N., Courtois, F., Trezzani, I., & Trystram, G. (2008). Review of mechanisms, conditions, and factors involved in the oil uptake phenomenon during the deep-fat frying process. International Journal of Food Science & Technology, 43, 1410
1423.

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C H A P T E R

25 Membrane bioreactors for the treatment of oily wastewater: pros and cons Shibam Mitra1,*, Riccardo Campo2,*, Subhojit Bhowmick3,* and Anirban Biswas4,* 1

Envirotech East Pvt. Ltd., Kolkata, India 2Department of Civil and Environmental Engineering, University of Florence, Florence, Italy 3School of Environmental Studies, Jadavpur University, Kolkata, India 4Department of Environmental Science, Nabadwip Vidyasagar College, Nabadwip, India O U T L I N E 25.1 Oily wastewater: the origin and global trend

470

25.2 Oily wastewater: environmental impact

471

25.3 Existing oily wastewater treatment technologies 472 25.3.1 Application of membrane bioreactor as the advanced treatment technology 473

25.3.2 Membrane bioreactor for the treatment of oily wastewater 473 25.3.3 Fouling as the main drawback of membrane bioreactor treating oily wastewater 479 25.3.4 Methods for fouling mitigation treating oily wastewater 481 25.4 Conclusions

483

References

483

* All the authors contributed equally to this chapter.

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00007-0

469

© 2022 Elsevier Inc. All rights reserved.

470

25. Membrane bioreactors for the treatment of oily wastewater: pros and cons

25.1 Oily wastewater: the origin and global trend Waste generation in urbanized and industrial environment are obvious facts and wastewater comprises major part which includes wastewater mixed with oils or oily wastewater. Oil and grease (O&G) are common pollutants generated from several industries and domestic sewages. Millions of cubic meters of oil containing wastewaters are generated daily from metal working, primary metal operations, petroleum refineries, petrochemical, textile, waste collection and transportation (Cheryan, 1986) and also by the food industry and restaurants, etc. Therefore oil-contaminated wastewaters not only contain mineral and synthetic oils, but also vegetable oils and esters. The chemical compositions of oily wastes are very complex which contain organic (fats, lubricants, cutting liquids, heavy hydrocarbons tars, grease, crude oils and diesel oil), light hydrocarbons (kerosene, jet fuel and gasoline) (Sokolovi´c et al., 2014; Srinivasan & Viraraghavan, 2010) and inorganic compounds, with about 20% of all the known chemical elements. Yavuz et al. (2010) reported the phenol and chemical oxygen demand (COD) concentrations to be 192.9 and 590 mg/L, respectively, in a petroleum refinery wastewater in Turkey. Another petroleum refinery wastewater in China was found to generate around 1021 mg/L of COD (Yan et al., 2011). A raw biodiesel wastewater in Thailand was reported with having COD concentration of 312,000
588,800 mg/L and O&G concentration of 18,000
22,000 mg/L (Jaruwat et al., 2010; Jamaly et al., 2015). The toxic substances present in the oily wastewater as mentioned above, are inhibitory to plant and animal growth, equally, mutagenic and carcinogenic to human being. Similarly, oily wastewater contains high oil content, COD and color (Alade et al., 2011; Lan, Gang, & Jinbao, 2009). Table 25.1 summarizes the O&G concentrations in effluents of selected industries. Saline produced water, which contains different kinds of organic and inorganic components, is the largest waste stream generated by the oil and gas industries (Fakhru’l-Razi et al., 2009). Bilge water is also considered to be one of the biggest waste streams concerning oily wastewaters produced from naval and commercial vessels. According to the Act on Environmental Protection in Maritime Transport (1672/2009) in Finland, it is prohibited to discharge oil or oily mixtures not only from ships in Finnish waters or in Finland’s exclusive economic zone, but also from Finnish ships outside. Oil spills also produce waters containing oil with the volumes in the marine environment around 7 metric tons, and data concerning them is incomplete due to the inconsistent reporting of smaller incidents worldwide. However, data concerning larger spills of 7 tons and above tends to be more reliable, ITOPF (2015). The quantity of total oil discharged in 2010 with refinery effluents from reporting 98 European oil refineries, was 798 t/year (Karhu, 2015). The growing awareness of environmental protection has led to impose more stringent limitations on pollutant concentrations before wastewater discharge. The fish canning, petroleum, petrochemical and tannery industries are of particular concern when considering specific activities producing saline wastewater that might be characterized by highly recalcitrant, toxic and slowly biodegradable compounds (De Temmerman et al., 2008; Sharghi et al., 2014; Zhang et al., 2014). An important issue in this context is represented by the treatment of wastewater produced during shipboard activities (bilge water or slops), which usually features high oily and saline concentrations (Di Bella et al., 2015; Sun, Leiknes, Weitzenbock, & Thorstensen, 2010). It is worth noting that the International Maritime Organization (IMO) has prohibited the direct

E. Miscellaneous

471

25.2 Oily wastewater: environmental impact

TABLE 25.1 Oil and grease concentrations in effluents of selected industries (Cheryan & Rajagopalan, 1998; Patterson, 1985). Industrial source

Oil and grease concentration (mg/L)

Steel-rolling mills Hot rolling

20

Cold rolling

700

Cold rolling coolant

2088
48,742

Aluminum rolling

5000
50,000

Can production (forming)

200,000

Food processing

3830

Food processing (fish)

520
13,700

Rendering

14
3551

Wool scouring

1605
12,260

Tanning waste, hide curing

40
200

Metal finishing

4000
6000

Petroleum refinery

10
3200

discharge of wastewater from ships (MARPOL 73/78, 1997). IMO regulations have limited the hydrocarbon concentration in oil and oil residue discharged in wastewater streams less than 5 ppm. As per APPS/MARPOL’s guideline the oily wastewater on ships must be processed by a properly working oily water separator and oil content monitor and that any discharge contains no more than 15 parts per million of oil (Marine Defender, 1978). The permitted O&G limits for treated produced water discharge offshore in Australia are 30 and 50 mg/L, respectively, for daily average and instantaneous discharge (Neff, 2002). The United States Environmental Protection Agency has regulated the daily maximum discharge for O&G at 42 mg/L that of for monthly at 29 mg/L (USEPA, 2021). Considering the significant environmental concern, many countries have implemented more stringent regulatory standards for discharging produced water. The monthly average limits of O&G and COD of oily wastewater prescribed by the Peoples Republic of China are 10 and 100 mg/L, respectively (Tellez, Nirmalakhandan, & Gardea-Torresdey, 2002). The Convention for the Protection of the Marine Environment of the North-East Atlantic (OSPAR Convention), sets the annual average limit for discharge of dispersed oil for produced water into the sea is 40 mg/L (Ahmaduna et al., 2009; OSPAR Commission, 2005).

25.2 Oily wastewater: environmental impact The oily wastewater is harmful to the environment considering the following aspects: (1) it affects drinking water and groundwater resources, and dangerous to

E. Miscellaneous

472

25. Membrane bioreactors for the treatment of oily wastewater: pros and cons

aquatic resources; (2) it directly affects the human health; (3) it pollutes the local atmosphere; (4) it affects crop production; (5) the destruction of landscape (Hou et al., 2003; Poulopoulos et al., 2005; Yu et al., 2013). Prehydrocarbons are priority pollutants due to their high polycyclic aromatics contents, which are toxic persistent in the environment (Mrayyana & Battikhi, 2005; Wake, 2005). Decreased productivity of algae observed for prehydrocarbons receiving water bodies have been attributed to such effects (El-Naas et al., 2009b; Pardeshi & Patil, 2008). This pollutants also reduce the dissolved oxygen concentration (,2 mg/L) rendering the water body unfavorable for the aquatic organisms to survive and also create fouling smell and color (Alade et al., 2011; Attiogbe et al., 2007). O&G are sticky in nature and tend to aggregate, clogging drain pipes and sewer lines, causing unpleasant odors and corroding sewer lines under anaerobic conditions. The operation of municipal wastewater treatment plants get hampered as oils float as a layer on the top of the water, not only that, due to their stickiness the strainers and the filters in the treatment plant gets choked (Chen et al., 1999; Xu & Zhu, 2004). Phenolic compounds are extremely toxic to the environment due to their extreme toxicity, stability, bioaccumulation, and ability to remain in the environment for long periods causing considerable damage and threatens the ecosystem in water bodies along with human health (Abdelwahab et al., 2009; Kavitha & Palanivelu, 2004; Lathasree et al., 2004; Pardeshi & Patil, 2008; Yang, 2008). The ammonia and hydrogen sulfide compounds are too very toxic in nature (Altas & Bu¨yu¨kgu¨ngo¨r, 2008). Particularly, sulfide has a high oxygen demand of 2 molO2/L which contributes significantly to oxygen depletion (Poulton et al., 2002) and leads to mass fish mortality at a threshold limit of 0.5 mg/L for freshwater or saltwater fish (Altas & Bu¨yu¨kgu¨ngo¨r, 2008; Diyauddeen et al., 2011).

25.3 Existing oily wastewater treatment technologies Gravity separation is the most common primary treatment of oily wastewater, but it does not meet required discharge limits, so secondary treatments are used to lower the levels of dissolved, emulsified and dispersed oils. Breaking of emulsions with chemicals, followed by dissolved air flotation (DAF) or sedimentation, is then used to remove additional oil. Chemical emulsion breaking is effective process but it produces large volumes of sludge, the equipment has a large footprint, and the operating costs are high enough. Thermal treatment (evaporation and incineration) is more universal and perhaps more suitable but require high energy costs and loss of entrained oils in the vapors from the evaporator, making it necessary to treat the condensate (Beisinger, Vining, & Shell, 1974; Gardner, 1972; Katnik & Pavilcius, 1978; Lash & Kominek, 1975; Nebolsine, 1970). Coalescers and precoat filtration are more effective in reducing high levels of O&G in the suitable particle size range but the problem arises in coalescers due to gradual adsorption of material on the coalescing media leading to its poisoning and loss of effectiveness. The large volume of sludge production is an associated problem with precoat filtration and electrocoagulation (Cheryan & Rajagopalan, 1998).

E. Miscellaneous

25.3 Existing oily wastewater treatment technologies

473

25.3.1 Application of membrane bioreactor as the advanced treatment technology Generally, biological treatment of wastewater is the most cost-effective alternative compared to other treatment technologies. A membrane coupled biological process as a separation step is able to retain microorganisms in the bioreactor and as a result has many advantages including high effluent quality, small footprint, high mixed liquor suspended solids (MLSS) concentration, good disinfection capability, and high volumetric loading (Kang et al., 2003; Le-Clech et al., 2006; Pendashteha et al., 2011). With new advances in membrane design and technology, the MBR processes appear to have a promising future in oily wastewater treatment (Cicek et al., 1998). Although a number of reviews on MBR technology were published in the last few years, most of these reviews focused on municipal wastewater treatment with MBRs (Judd, 2004; Liao et al., 2006; Ng & Kim, 2007) reviewed anaerobic MBR progress by focusing on applications for treatment of municipal and some industrial wastewaters. Similarly, (Cicek et al., 1998) reviewed the applications of MBR technology for agricultural wastewater treatment. Previous reviews did not cover most of the recent studies regarding various industrial wastewater treatments with MBR systems. So far there is no summary on the application of MBR for the treatment of oily wastewater generated from different sources. With the rapid development of MBR technology for industrial wastewater treatments, a detailed analysis and review of past academic research progress on industrial wastewater treatments would be valuable (Mohammedadela, 2016).

25.3.2 Membrane bioreactor for the treatment of oily wastewater The application of MBR has been studied extensively for its ability to treat oily wastewater. It has numerous advantages over the other mentioned technologies available for the treatment of oily wastewater. It also encounters some problems when operated to treat oily wastewater. Below is the summary of the previous literatures which studied the performance of MBRs at different operating conditions to treat oily wastewater. Table 25.2 summarized the outcomes of different studies on MBR treating oily wastewater. It was mentioned before that better sludge concentration in the MBR leads to better removal of the industrial pollutants. This was further proved in a study in which a bench scale MBR was installed to compare the effect of two different MLSS concentration ranges. It is worth noting that the MLSS was found to grow rapidly (within 6 days of operation) from 0.5
5 and 1
7.8 g/L. The MBR was fed with the wastewater brought from Al-Daura refinery, Bagdad having influent COD concentration of 235 mg/L and O&G concentrations of 14 mg/L. The results showed that the COD and oil content removal efficiency of the MBR were influenced by the concentration of MLSS as better oil and COD reductions (71% and 100% of COD and oil reductions, respectively) were achieved at higher MLSS value (1
7.8 g/L) (Alsalhy et al., 2016). Similarly, another group of researchers studied the effect of MLSS (3
5 g/L) on the treatability of a petroleum refinery which was characterized by a very high oil and COD concentration (B160000 and 370,000
2,300,000 mg/L of oil and COD concentrations, respectively). A cross flow membrane bioreactor (CF-MBR) was operated with intermittent feeding of the refinery wastewater (2 min in every 2 h at 1.24
2.66 L/h flow rate). The CF-MBR efficiently removed more than 93% and 99% of

E. Miscellaneous

TABLE 25.2

Various MRR configuration and their treatability.

Membrane bioreactor (MBR) configuration

MBR features

Operating condition

Reactor volume (L)

Wastewater type

Biomass concentration (MLSS/VSS) (g/L)

Treatability

Inf. COD/TOC (mg/L)

Inf. O&G/oily derivatives (mg/L)

HRT (h)

SRT (d)

Flux (L/m2/h)

%COD/ TOC red

% Oil red




12.64

71

100

Alsalhy et al. (2016)

65
140

COD93
95

99

Rahman and Al-Malack (2006)

Reference

• • • • • •

HF-MBR Pore size (μm): 0.12 Surface area (m2): 11.3 Ceramic CF-MBR Pore size (μm): 0.2 Surface area (m2): 0.019

20

Oil refinery wastewater

0.5
51
7.8

235

14

5

20

Petroleum refinery wastewater combined with synthetic wastewater

MLSS 3.0
5.0

370,000
2,300,000 (2 min in every 2 h at 1.24
2.66 L/h flow rate)

160,000

17
34

•

External CF UF MBR

11

Synthetic wastewater combined with fuel oil lubricant

MLSS:48

COD: 1464
7877

HCs: 500
3000

6.7
13.3




73
85

COD93
98

99.9

Scholz and Fuchs (2000)

•

SMBR with HF external membrane module Origin water Co., Ltd., China) Pore size (μm): 0.1 Surface area (m2): 0.05 Bench MSBR Tubular crossflow UF membrane modules (MIC-RO 240, PCI membrane systems, UK), Pore size (μm): 0.45. Surface area (m2): 0.012 MSBR-RO (MSBR/RO) Pore size: not mentioned Surface area (m2): 0.024 HMBR-RBC hybrid reactor Pore size: not mentioned Surface area (m2): 0.0128 Internal submerged UF PAC-MBR hybrid reactor (module STERAPOREMitsubishi Rayon Co., Ltd., Japan) Pore size (μm): 0.1 Surface area (m2): 0.42 Anaerobic MBR with external submerged HF membrane module (Micronet R,Porous Fibers, Spain) Pore size (μm): 0.4 Surface area (m2): 2 The bench scale MB-MBR was filled with LINPOR soft polyurethane sponges as biocareer. HF-MBR Pore size (μm): 0.04 Surface area (m2): 0.093 MB-MBR HF membrane module (Zee-Weed01) Pore size μm (μm): 0.04 surface area (m2): 0.093

11.8

Vegetable oil processing plant effluent

MLSS 5.3
10.7

COD-1355
1987

Oil-413
667

16
23

. 120

10.0
14.6

COD-86.1, TOC-88.9

94.8

(Ma et al., 2015)

5

Synthetic oily wastewater

MLSS 1.5
7.9

COD-562.5
6750

O&G-87.5
1050, 48 HYDROCARBON204.5
2456

Complete SRT

40

COD94.3
99.5 Pendashteha 93.26
96.97 et al. (2012)

5

Oilfield produced water

MLSS: 1.44
5.9

COD-1,240, 540

O&G-15

20

38

COD-90.9

91.5

Razi et al. (2010)

18

Synthetic oily wastewater

MLSS: 1.5
3.0

COD-1000

TPH:700

18
24

88

COD- 97.3

TPH: 99

Safa et al. (2014)

6

Synthetic wastewater

MLSS 8.34
10.02

COD-971

O&G: 300

4

3.57

COD 95
97.5

98.3
99.9 (Tri et al. 2006)

UASB: Snacks factory discharge 760 LMBR:180 L

VSS 28 g/L

COD-8200
22000

O&G-4400
6000

6.5
8.0

COD-97

100

Diez et al. (2012)

15

Synthetic oily wastewater

MLSS 3.5
8

COD-695
980

As TPH B11.1
115

12
15

Complete SRT

B16.13

B89
96.2

,5
B50

(Bella et al., 2015)

14

Synthetic wastewater combined with slops

MLSS 7
8

COD-1092
1487

TPH 0
31.4




22
28

12
15

COD84
90

8
70

Campo et al. (2016)

• • • •

• • • • • • • • •

• • •

• • •

• • • • • •

50

•

UF-Aerobic anoxic hybrid MBR (Zenon Zeeweed, ZW 10) Pore size (μm): 0.04 Surface area (m2): 0.98 Polypropylene HF membrane module (H-filtration, China) Pore size (μm): 0.2 Surface area: not mentioned

Anoxic tank: 45 L Aerobic tank: 224 L

Synthetic shipboard slops

MLSS 4

COD-350

TPH-20

16




Synthetic oily wastewater




COD-500
1000

TOG-10
23

10
15

20

Synthetic shipboard slops

TOC-21

Diesel Oil-170

48

40

Petroleum refinery wastewater

COD-580




25
36




0.846
1.205 COD: 82

Petroleum refinery wastewater

COD-475










COD-81

• • • • • • • • •

MB-MBR containing HF membrane module (Zee-Weed01) Pore size (μm): 0.04 Surface area (m2): 0.1 HF-MBR (Pishtaz Polymer Sepahan Co., Iran) Pore size (μm): 0.1
0.2 Surface area (m2): 0.39 SIEMEN’s petro MBR with added GAC Pore size (μm): not mentioned Surface area (m2): not mentioned KONSOLIDATOR system with FEG PLUS membranes Pore size (μm): not mentioned Surface area (m2): not mentioned UF-MBR Pore size (μm): not mentioned Surface area (m2): not mentioned

75708

Die lube wastewater, glycol wastewater, wastewater

COD: 20,000
40,000













Oily wastewater from the barge wash down

COD: 1000

O&G:165

• • • • • • •

CFMBR Pore size (μm): 0.1 Surface area (m2): not mentioned CFMBR Pore size (μm): 0.1 Surface area (m2): not mentioned HF-MBR (Zee Weed 10; Zenon)

COD-267
549

O&G:27
57

COD-180
267

• • • • • • • • • • • •

MLSS 3
6.6

21

COD: 90

7




88

Mannina et al. (2016)

100

Soltani et al. (2010)

33
82

Cappello et al. (2016)

Razavi and Miri (2015)




(William & Cunningham, 2014) (Koch Membrane, 2020)

COD: 99.5

COD-70

100

Peeters (2005)

7.92

COD: 90
94

85
91

Shiraishi (2015)

O&G:20
65

35

COD: 51
59

98.4
99.5

COD-129
960

O&G: 10.3
29.5

13
25

COD-86

65

Food factory effluent

COD-797
2912

O&G: 20.9
264

COD88
91

66
73

Port runoff water

COD-485
738

O&G: 4.3

COD38
56

96

Oil refinery wastewater

MLSS 7.0

Oilfield injection wastewater Paper mill effluent

MLSS: 11

16

Galil and Levinsky (2007)

476

25. Membrane bioreactors for the treatment of oily wastewater: pros and cons

COD and oil concentrations, respectively at both the MLSS concentrations showing not much beneficial effects of elevated MLSS concentration above 3 g/L (Rahman & AlMalack, 2006). In another study the MLSS concentration was maintained as high as 48 g/L in a MBR treating oily wastewater combined with surfactants (Scholz & Fuchs, 2000). It was observed that at different loading stages the MBR showed around 99.9% removal of fuel-oil as well as lubricating oil. The average removal of COD was found to be in the range of 93%
98% (Scholz & Fuchs, 2000). A bench-scale external submerged hollow fiber (HF) MBR was used in another study to treat vegetable oil plant wastewater at an average 8.6 g/L of MLSS concentration. High removal of total oil was achieved (B94.8%) associated with significant level of COD removal (88.9%) (Ma et al., 2015). The above mentioned studied are depicting the performance of the conventional MBR systems treating oily wastewater but the MBR technology has always been a subject of up gradation or hybridization in recent years. For example, an external UF unit was coupled with a sequential batch reactor (SBR) forming a membrane sequencing batch reactor (MSBR).The MSBR was found to be excellent in treating highly oil contaminated wastewater showing around 97.2% and 98.9% of COD and O&G, respectively (Pendashteha et al., 2012). Another improvisation on MSBR was done in another study where the MSBR was coupled with a RO system to form MSBR-RO process and was evaluated in terms of biodegradation of O&G wastewater water with high COD (1240 mg/L) and O&G concentrations (15 mg/L).The MSBR/RO system significantly removed COD (90.9%) and O&G (91.5%) from the oily wastewater and was suitable for re-use (Razi et al., 2010). A novel implementation of a hybrid MBR has been studied which utilized a combination of rotating biological contractor (RBC) and an external membrane, as a new biological system for oily wastewater treatment. RBC requires a secondary settling tank which was accomplished by adding a membrane to the system. The highest removal efficiency of COD and total petroleum hydrocarbon (TPH) was 97.3% and 98.8%, respectively at an influent COD and oil concentrations of 1167 and 700 mg/L, respectively, (Safa et al., 2014). Activated carbon has been extensively studied for its ability to adsorb different pollutants from the wastewater stream (Jeirani, Niu, & Soltan, 2016). Taking that advantage an experimental investigation on the treatability of oily wastewater from gas stations using a MBR system which was added with powdered activated carbon particles (PAC) (2 g/L) with a view to obtain simultaneous physical adsorption on the surface of PAC, biodegradation and membrane separation. The system revealed that the MBR system could achieve removal efficiency to the extent of 97.5% and 99.9% of COD and O&G, respectively, with stability against shock loading. It was anticipated that adding PAC in the MBR could help to adsorb the oils. A bench scale application of an anaerobic MBR (An MBR) could be cited as another up gradation over the conventional MBR process for the treatment of high strength oily wastewater discharged from a snacks factory containing 4400
6000 mg/L of O&G and8200
22,000 mg/L of COD concentration. After eight weeks of operation the An MBR achieved 97% of COD removal and around 100% of O&G removal which suggested that the modification of MBR is very much effective for the treatment of oily wastewater from different sources (Diez et al., 2012). Some other examples could be cited on the improvisation of MBR configuration to obtain better results particularly to treat such oily wastewaters which are characterized by

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high level of salinity and hydrocarbons in it. In a recent study a comparative research was carried out between two bench scale MBRs, one of which is a MBR and another one is a moving bed membrane bioreactor (MB-MBR) and their ability was tested in terms of hydrocarbon biodegradation in presence of high salinity as total dissolved solids (TDS). The MB-MBR system was characterized by the presence of soft polyurethane sponges as carrier material for biofilm growth. The two plants were initially fed with synthetic wastewater characterized by an increasing salinity (B120
6475 mg Cl/L), in order to enhance the biomass acclimation to salinity. Subsequently, they were fed with a mixture of synthetic wastewater and real shipboard slops (with an increasing slops percentage up to 50% by volume). The MB-MBR showed slight improvement over the MBR in terms of TPHs removal (51.3% and 47.4% respective for MB-MBR and MBR). The authors suggested that the improvement in TPHs biodegradation in MB-MBR system over the MBR system was due to the formation of the biofilm on the sponge carriers as the sponge carriers provided a very good shelter for the growth of the microorganisms into it Di Bella et al. (2015). The advantages of the application of sponge biocarriers in MBR was further investigated in a different study where the MB-MBR was employed to treat saline wastewater contaminated by hydrocarbons from washing of oil tankers with seawater (slops).The MB-MBR was operated in a gradual increasing mode of influent salinity (216
23919 mg Cl/L) and TPHs (0
31.4 mg/L) during six experimental phases each characterized by a decreasing slop dilution factor in order to allow microorganisms acclimation (Phase I: no slop addition, Phase II: 5% slop volume, Phase III: 10% slop volume, Phase IV: 30% slop volume, Phase V: 50% slop volume, Phase VI: 100% slop volume).The MB-MBR showed significant improvement in the TPHs removal efficiency from about 8% of Phase III up to about 35% in Phase IV and till 70% in Phase VI, highlighting the good acclimation of the bacteria to the hydrocarbons (Campo et al., 2016). The gradual improvement in COD reduction (8%
70%) at different phases of the operation also confirms the better acclimation of the bacteria to high strength slop (Campo et al., 2016). In a quite similar work with a simple improvisation, an external submerged membrane unit was installed in combination with anoxic and an aerobic tank to treat synthetic shipboard slops. The experimental campaign was divided in to two phases: salinity acclimation up to 20 g NaCl/L (Phase I) and TPH dosing of concentration 20 mg/L (Phase II).The reactor showed a very good performance in terms of total COD and TPH removals during the experiments with an average value near to 91% and 88%, respectively. However, the biological COD removal was affected (64%) by the feeding salt rate and the hydrocarbon addition, showing a significant reduction in terms of organic pollutants removal (Mannina et al., 2016). Bacterial acclimatization to high saline oily wastewater in a MBR was also carried out in another study where different samples from sea sediment in Bushehr (south of Iran) were analyzed and different groups of bacteria were isolated and adapted for surveying under high salinity conditions. The TDS, COD and O&G concentration was varied from 370
1000, 500
1000 and 10
22 mg/L, respectively, at different phases of the study. The result showed around 100% removal efficiency of O&G in advanced stages of the experiment (Soltani et al., 2010). It is worth noting that the MBR performed well at medium strength of wastewater (TDS and COD concentrations were 1000 and 700 mg/L, respectively). Further increase in the COD level (1000 ppm) lead to decrease in the oil removal efficiency of the MBR (fig. 2). The authors concluded that the bacteria belong to

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halo tolerant group with activity at low and high salt concentrations (Soltani et al., 2010) but they did not identify the species involved in oil degradation in MBR. Now the question comes which types of bacterial species are responsible for the biodegradation of the oily compounds in the MBR under very saline environment. Notably there are very limited numbers of works carried out to identify the bacterial species in MBR treating oily wastewater. One good example of such study can be referred in this regard. A collection of 42 strains were obtained during microbiological screening of a MBR for the treatment of saline oily wastewater originated from marine transportation. The diversity of the bacterial collection was analyzed by amplification and sequencing of the 16S rRNA gene. Taxonomic analysis showed high level of identity with recognized sequences of 7 distinct bacterial genera (Alcanivorax, Erythrobacter, Marinobacter, Microbacterium, Muricauda). The biotechnological potential of the isolates was screened considering an important factor such as the biosurfactant production. In particular, 14 biosurfactant producing bacteria were selected and further tested, for growth on crude oil and hydrocarbon degradation. Data obtained from this study confirmed the high activity of the isolated bacteria mentioned above have the possible application in remediation of saline oily wastewater in MBR (Cappello et al., 2016). The application of MBR system to treat oily wastewater has not been limited in the lab scale studies rather it has been successfully employed in pilot scale or as real field full scale MBR plants. Some of the good examples could be cited in this regard. The capability of a pilot scale HF-MBR for real petroleum refinery wastewater treatment in Iran was studied. The HF-MBR was operated for 160 days with high COD (500 mg/L) and TDS (21,000 mg/L) concentrations. Though the authors did not mention about the changes in the O&G concentration with time but they found very good treatability in terms of COD (82%) (Razavi & Miri, 2015). A trial at a refinery at Aramco refinery, Saudi Arabia, using MBR technology combining the granulated activated carbon with microbiology has been found to be effective after a run over 319 days. Even though the article did not mention about the changes in the O&G concentration but reported about 91% and 96% of COD and ammonia removals at an influent concentrations of 475 and 16 mg/L of COD and ammonia concentration, respectively. The treated water was fed to RO equipment and was reused for cooling tower (William & Cunningham, 2014). In an another trial in Metaldyne’s Twinsburg, Ohio aluminum die casting plant a MBR with a pretreatment unit which was comprised of tubular UF membranes was found to be very effective to produce a steady MBR permeate. It was found to reduce COD concentration by around 99.5%. The O&G removal efficiency of that MBR was not mentioned in that article (Koch Membrane, 2020). Marathon Ashland petroleum marine repair terminal, Catlettsburg, Kentucky installed a MBR system of capacity 50,000 gpd for the treatment of oily wastewater generated from the barge wash down and was under operation for around 1 year. Around 95% removal of benzene, toluene and xylene (BTX) compounds and almost 100% removal of O&G were achieved by the system (inf. Average BTX compounds and O&G compounds were 10 and 165 mg/L, respectively). The COD (1000 mg/L) reduction was fair (70%) and found to meet the wastewater discharge criteria. The MBR was also able to cope up with the wastewater flow and composition variations. The treated wastewater was found to be of reuse quality (Peeters, 2005). Meiden developed a ceramic flat sheet (CF) MBR for a full scale MBR which was installed

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for two different types of oily wastewaters in Japan: (1) oil refinery wastewater and (2) oilfield injection water. At the influent COD and O&G concentration range of 267
549 and 27
57 mg/L, respectively. The CF membrane showed healthy performance in terms of COD (94%) and oil reductions (91%).While treating the oilfield injection water the CF membrane bioreactor showed more than 98.5% of oil removal when operated at influent oil concentration of 20
65 mg/L. The COD reduction was found to be 51%
59% at an initial COD concentration range of 180
267 mg/L (Shiraishi, 2015). A full scale treatment plant in a paper mill in Israel includes equalization, raw solids separation by straining, anaerobic biotreatment followed by activated sludge. The operation of the existing activated sludge is characterized by often disturbances, mainly bad settling, and voluminous bioflocs, followed by wash-out of the biosolids. In order to improve the aerobic biotreatment, it was suggested to upgrade the activated sludge by adopting a MBR. A pilot plant based on HF membrane was operated during 4 months. The MBR brought down the COD value from 960 to 130 mg/L and total oil from 29.5 to 10.3 mg/L suggesting 86 and 65% for COD and total oil removals, respectively. The MBR could save the need for further filtration. The high effluent quality has already promoted a project for the reuse of the effluent within the paper mill for various production processes (Galil & Levinsky, 2007). Similarly, a food factory is located in the Haifa Bay industrial area, specializing in the production of margarine and soups. The existing wastewater treatment includes gravity separators, chemical flocculation and DAF. A MBR was included in the existing system. One of the raw wastewater streams in this factory is characterized by high concentrations of organic matter (COD 797
2912 mg/L), especially oil (20.9
264 mg/L) which came up with a reduction of 88%
91% of COD and 66%
73% of O&G (Galil & Levinsky, 2007). Oil and Energy Infrastructure operates the Fuel Division in the Port of Haifa. The wastewater includes ballast, bilge and run-off water in the rain season. The wastewater has to be treated and the effluent is discharged to the sea, according to the governmental regulation. The examination of wastewater treatment by chemical
physical procedures by flocculation and DAF indicated some improvement of wastewater quality, however this processes did not provide the required reliability for achieving the effluent quality, especially in cases when gasoline fractions in raw wastewater increased. In order to prevent environmental violations it was decided to adopt biological treatment. For this purpose, the MBR process was adopted. Ballast and bilge wastewater have been separately treated for three months each, by a 500 L/day MBR pilot. The results indicated in both cases good removals of organic matter and oil. The COD and O&G reductions were found to be around 56% and 96%, respectively (Galil & Levinsky, 2007).

25.3.3 Fouling as the main drawback of membrane bioreactor treating oily wastewater Although MBR technology has many advantages mainly linked to high removal efficiencies, it has some drawbacks due to economical-technical reasons. The utilization of membrane for wastewater treatment imply capital costs, due to the employed materials and to the realization of membrane, and operational costs mainly due to fouling of fibers caused by cake deposition of the activated sludge during the filtration period

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(Judd & Judd, 2011). Furthermore, fouling is the first cause of membrane deterioration, causing flux decline, performance reduction, the need for membrane cleaning and replacement. For this reason, the research of MBR all over the world is focused on fouling causes and mitigation. Some factors such as MLSS concentration, viscosity, particle sizes of the mixed liquor and extra cellular polymeric substances can have significant influence on membrane fouling (Le-Clech et al., 2006). So, several studies investigated the effect of oily wastewater on fouling in MBR, observing that the effect of the increase of salinity and oily hydrocarbons towards the microorganisms, resulted in a more consistent fouling (Campo et al., 2016). More in detail, a significant production of extracellular polymeric substances, provoked the increase of the irreversible fouling contribution. Furthermore, if mobile carriers are employed, the collisions of the supports in a hybrid MB-MBR, implied a significant slowing of membrane fouling attributable to the action of mechanical stress exerted by the mobile carriers that have repeatedly bumped against the membrane’s fibers. However, when a high concentration of salinity and hydrocarbons was registered, a sudden increase of the resistance to filtration, was registered, denoting a high sensibility of the system to the environmental shock. Pendashteh et al. (2011) studied the membrane foulants in an MBR treating hypersaline oily wastewater composed by a complex mixtures of hydrocarbons and various organic compounds (aromatics, phenols, alcohols) where alkanes were the most abundant constituents in the wastewater. The authors encountered that the cake layer resistance was the major contributor to the total resistance and the foulant properties changed during time. For example, at the early stage the foulants were mainly composed of low-molecular weight substances such as amino acids and aromatic proteins, where as in the long period the foulant characteristics changed to high molecular weight substances, such as biopolymers and a variety of others components e.g., microorganisms and various inorganic and organic substances. Looking at the chemical components of the cake layer, elemental analysis by means of EDX (Pendashteh et al., 2011) revealed that aluminum, silica, and iron have significant impacts on the formation of the membrane cake layer (An et al., 2009; Meng et al., 2007; Wang et al., 2008). Moreover, also PVDF could be detected, as it is the main component of membrane material (Lee & Kim, 2009). When industrial wastewaters are treated, such as oily wastewater, the contribution of metals in fouling was found to be more than organic materials (You et al., 2006). In this case, a considerable amount of fouling is due to scaling phenomena which is more difficult to remove even by chemical cleaning. This effect could be due to crystallization and hydrodynamic transport (Lee & Lee, 2000). A possible explanation of inorganic fouling was reported by Meng et al. (2009) that discovered that this kind of fouling could principally form through two chemical and biological precipitation. Chemical precipitation of cations and anions (such as Ca21, Mg21,Al31, Fe31, CO322, SO422, PO432, OH2) occurs when the chemical species concentration exceeds the saturation concentrations due to concentration polarization, and this is typical in high salt concentrations environments. Biological precipitation is linked to microorganisms and their products, hydrocarbons constituents, biopolymers which contain ignitable groups such as COO2, CO322, SO422,PO432, OH2 (Sheikholeslami, 1999) and it occurs when metal ions are captured by these negative ions (Al-Amoudi & Lovitt, 2007; ITOPF, 2015). Similar results were also obtained in another research (Reza et al., 2011) where the accumulation of organic matter (hydrocarbon components and microorganisms

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products) and inorganic salts (NaCl and CaCO3) on the membrane surface may affect the membrane performance (Fakhru’l-Razi et al., 2010).

25.3.4 Methods for fouling mitigation treating oily wastewater Since fouling represents the first cause of membrane deterioration, various technical were applied during time, to limit fouling deposition and to remove the deposited substances from membrane surface. The most widely used techniques are physical cleaning and chemical cleaning (Le-Clech et al., 2006). Physical cleaning could be applied cyclically on-line by means of permeate backwashing through membrane hollow fibers after the filtration time, or off-line with a manual washing of each fiber. The first one to remove reversible cake, the second one to remove the irreversible cake deposition. Chemical cleaning is a particular washing of membrane fibers with acid solutions (such as NaOCl, HCl) to remove the membrane foulants and, in particular, to reduce the pore blocking. When polarization concentration is the main cause of fouling, a reduction of membrane fouling rate could be achieved by controlling inorganic and organic concentrations in feed water and bioreactor. Inorganic anion and cation concentrations, as well as oil concentrations, can be reduced by pretreatment of wastewater (Hansen, 1994). The control of organic matters (colloidal and soluble) in bioreactor can be achieved by two approaches: optimization of operation parameter (i.e., sludge residence time, hydraulic residence time, DO, temperature, cross flow velocity) and addition of coagulants, filter aids or adsorbents. Another technique to reduce membrane fouling and fouling rate is represented by membrane relaxation. It is defined as temporary cessation of the permeate withdrawal whilst the air flow is scouring the membrane (Judd & Judd, 2011) and, compared to back washing, relaxation has the advantage of less energy consumption and no permeate loss (Wang et al., 2014; Yusuf et al., 2016). Pajoumshariati, Zare, and Bonakdarpour (2017) tried to confirm the fouling mitigation effect of membrane relaxation and they performed two successive cycles, one employing membrane relaxation and one not employing this mode of operation. Membrane relaxation, according to the protocol employed, resulted in around one third reduction in the membrane fouling rate in the MBR treating real petroleum refinery oily wastewater. Furthermore, since previous work with MBRs has suggested that relaxation mainly removes reversible fouling (Christensen et al., 2016), the fairly high efficacy of relaxation in membrane cleaning during operation with produced wastewater suggests that the dominant mechanism of membrane fouling has been cake layer formation. To confirm this fact, at the end of the reactor run, experiments were carried out with the fouled membrane to determine the values and the contributions of the various resistances to membrane fouling. So, the relative contribution of the cake layer, pore blocking and irreversible fouling to the overall resistance was determined as 59.6%, 18.19%, and 8.6%, respectively. These results confirmed that cake layer resistance played a dominant role in membrane fouling during the operation of the MBR treating real petroleum refinery oily wastewater, with pore blocking having a less significant contribution. Regarding to the use of some flocculants to decrease fouling rate in MBRs, it has been found that Fe31 and Al31 salts, organic polyelectrolyte and inorganic polymeric matters are able to alleviate membrane fouling (Koseoglu et al., 2008; Lee et al., 2009; Wu et al., 2006). Furthermore, (Ji et al., 2010) observed that addition of inorganic (FeCl3) and organic

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(Chitosan) flocculants was able to modify the properties of mixed liquor suspension in MBR and reduce fouling rate. Pendashteh et al. (2011) tried four different flocculants (Chitosan, FeCl3, PAC, Alum) at constant trans membrane pressure of 2 bar. The impact of Chitosan and FeCl3 on membrane fouling rate was more than Alum and PAC. It can be seen that the order of effect of different flocculants was Chitosan . FeCl3 . PAC . Alum. A similar trend was observed in a submerged MBR treating a synthetic low salt and nonoily wastewater at short and long term experiment (Ji et al., 2010). Also, other authors like Lee et al. (2009) observed that membrane fouling mitigation effect of FeCl3 was more than PAC in a textile wastewater treatment. The effect of the organic polymer on decreasing fouling rate was more than inorganic flocculants and the effect of Alum and PAC flocculants on filtration time was not significant. A possible explanation for membrane fouling alleviation in the organic flocculants, was due to decreasing SMP, because it was absorbed into the flocs aggregates, and increasing mean particle size of mixed liquor, while for inorganic flocculants this phenomenon is due to decrease of SMP concentration and increase of relative hydrophobicity in mixed liquor (Ji et al., 2010). Generally, the results showed that the effect of the flocculants on decreasing rate of fouling in hypersaline conditions were less than that in low salinity wastewaters. A possible explanation for this difference is that only 37% of the foulant cake layer is belong to organic matters while inorganic matters are main contributor of the fouling cake layer and added flocculants may have less effect on concentration and/or composition of inorganic matters. Another alternative technique for membrane fouling control is the sonication with ultrasound. This technique can enhance membrane permeate flux and decrease the development of membrane fouling (Kobayashi et al., 1999). Pengzhe et al., (Sui et al., 2008) used ultrasound to control the membrane fouling in an anaerobic MBR treating nonsaline and nonoily synthetic wastewater and observed that the sound can control fouling effectively. Sonication is the use of high energy, ultrasonic pulses to bombard and loosen particles from the membrane, therefore remove the cake from the surface (Lim & Bai, 2003). In the preliminary study, it was concluded that 15 min of sonication was an appropriate duration and shorter and longer sonication duration did not improved cleaning. At high ionic strength, the foulant
foulant and foulant
membrane interactions are less repulsive and attribute to compression of the double layer and formation of a dense fouling cake (Faibish et al., 1998). Ultrasonic cleaning did not appear to be strong enough to overcome these particle
particle and particle
membrane interactions. Analysis of the foulant cake layer after sonication showed that the percentages of the organic and inorganic matters were 58.4 and 41.6, respectively. The cleaning mechanism of the sonication is removing of the loosely attached particles and/or dissolving readily dissolvable matters. The results showed that during sonication, the inorganic matters dissolved and removed more than organic matters. Average flux recovery after sonication was almost 50% of the initial flux. After each sonication cleaning cycle, the initial flux decreased. This result showed that sonication was able to remove cake layer from membrane surface and was not effective in flux recovery for membrane fouling due to other mechanisms such as pore blocking (Meng et al., 2009). So, after a long period of cleaning with sonication, chemical cleaning was necessary to control the irreversible fouling. Finally, another technique which allows to indirectly control fouling is represented by the possibility to put mobile carriers into membrane compartment, to physically obstacle

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cake deposition and/or to remove the deposited cake. So, the collision of mobile carriers with the membrane’s surface may result in a significant slowing of membrane fouling, maintaining an almost constant permeability and transmembrane pressure. This effect is attributable to the action of mechanical stress exerted by the spongy carriers that repeatedly bump against membrane’s fibers that, effectively, minimize the fouling rate (Campo et al., 2017).

25.4 Conclusions With the continuous improvement in environmental requirements, the quality of oily wastewater treatment effluent is required to improve. Among other available treatment technologies the MBR system has been found to be one of the more effective alternatives in treating oily wastewater from different sources. MBR has certain drawbacks, and membrane fouling is one of the major constraints. The fouling control mechanisms renders it less economical and hinders its widespread application. Researchers all over the world are trying to improve the MBR system to elevate the MBR performances both in terms of its treatability and its effectiveness as well. Further indepth study of oily wastewater degradation mechanism in MBR (with detailed microbiological studies involved in biodegradation of O&G), to improve oily wastewater treatment efficiency would provide a solid theoretical foundation.

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C H A P T E R

26 Overview on natural materials for oil water separation Somakraj Banerjee, Riddhi Chakraborty, Ranjana Das and Chiranjib Bhattacharjee Chemical Engineering Department, Jadavpur University, Kolkata, India O U T L I N E 26.1 Introduction

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26.2 Sources of oil/water mixtures

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26.3 Composition of oil/water mixtures 491 26.3.1 Chemical composition 492 26.3.2 Physical properties of oily wastewater 492 26.4 Major processes of oil/water separation 26.4.1 Physical-mechanical methods 26.4.2 Chemical methods 26.4.3 Biological treatment

493 493 495 496

26.5 Natural materials: an alternative 26.5.1 Sorbent materials 26.5.2 Particles 26.5.3 Surfactants 26.5.4 Aerogels

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Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00009-4

26.6 Promising natural materials for oil/ water separation 500 26.6.1 Kapok fibers 500 26.6.2 Rice husk/straw 501 26.6.3 Vegetable residue wastes 502 26.6.4 Nutshells 502 26.6.5 Wood sheets 503 26.6.6 Barley straw 504 26.6.7 Cotton fiber 504 26.6.8 Sugarcane bagasse 505 26.7 Conclusion and further prospects 505 Acknowledgment

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26.1 Introduction The process of technological advancement and industrial growth has made compromising damages to various aspects of the environment. One of the major contributors to this damage is oil in various forms mixed in water. With an ever increasing energy demand, oilspill accidents and industrial oily wastewater discharge have become tremendous sources of concern. An oil spill is an accidental or deliberate deposition of oil into the marine ecosystem. Oil pollution of seawater occurs from land runoff, pipelines leakages, crude oil extraction in sea and production processes, and illegal water discharges (Lucas & MacGregor, 2006). Oil spills on the surface of ocean can get drifted by wind and water current. The spilled oil creates a slick on the water surface which undergoes evaporation, dissolution, photolysis, biodegradation. The spilled oil sometime forms an emulsion, or gets deposited in the sediments after submerging (Liu et al., 2012; Reddy et al., 2002). Ambient weather, salinity of seawater, pH, waves also affect the oil dispersion and weathering rates. Water-oil emulsion formation causes noticeable variations in oil viscosity, density, and water-oil interfacial tension. Various oxygenated products are formed as a result of photolysis of the spilled oil such as, aromatic, aliphatic, benzoic and naphthanoic acids, alcohols, phenols, and aliphatic ketones (Hussein, Amer, & Sawsan, 2009). Major oil-spill incidents include the 1989 Exxon-Valdez oil spill where 11 million gallons of oil was spilled (Exxon Valdez oil spill—Wikipedia). In 2002, the tanker ‘Prestige’ faced a storm at sea and spread 20 million gallons of heavy fuel oil onto Spanish coasts (Prestige oil spill—Wikipedia). In 2010, Deepwater Horizon offshore drilling rig caused the Gulf of Mexico oil spill which spilled 200 million gallons of crude oil into the sea. These were the worst ever oil-spill incidents in history. An estimated 5.71 million tons of oil was spilled due to tanker related oil spills in between 1970
2010 (White, 2000). Oil spills damage marine ecosystem, marine life by causing significant physical and chemical changes in the water body. These oil-spills also affect humans by inhalation of harmful evaporated gases, and also cause skin and eye infections. These oil-spill incidents along with oily wastewater discharge have become a recurring problem and a serious global environmental issue. Besides causing serious ecological damages these oil spill incidents also cause a lot of economic burden. Oil/water separation is usually done using various physical/mechanical, chemical, and biological methods. Mechanical processes employed for oil-spills are booms, barriers and skimmers, etc. Physical methods include sorption, filtration-membrane separation, flocculation, gravity settling, and so on. Chemical processes include usage of coagulants, dispersing agents, gelling agents, and solidifiers. Biological remediation methods include use of microbes with nutrients and/or oxygen to stimulate the bacterial growth and biodegradation process (Azubuike, Chikere, & Okpokwasili, 2016). The estimated mean cost of treating a crude oil spill is $2730 per barrel (Davis DW, 1996). Selecting the optimum method or material for oil/water treatment depends on the characteristics of the oily wastewater, weather condition, environmental variables like wind, currents, waves, oil viscosity, amount of the debris and effect on marine life. The methods mentioned above have certain drawbacks while handling oil/water separation such as lack of separation efficiency, need for external energy input, generation of secondary waste materials. As for example, in situ burning releases greenhouse gases in the environment, porous absorbing materials like foams, clothes, textiles absorb both oil and water resulting in poor selectivity

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and removal efficiency. These absorbing materials also end up contaminating recovered oil and are majorly nonrenewable. Due to the nonrenewable nature of synthetic materials, secondary waste formation becomes imminent. The above limitations necessitate the search for alternative materials which are environmentally friendly, renewable, and low-cost bio/natural-materials for oil/water separation. This chapter deals with such materials/methods used in both oil recovery and oil degradation from oil/water mixtures. In recent years, advanced materials like aerogels, inorganic meshes, foam membranes and surface modified, superwetting (superhydrophobic—superoleophilic) porous materials, textiles, fabrics have been hugely used for oil/water separation (Sabir, 2015). This chapter discusses the source and characteristics of the oil/water mixtures, conventional separation processes, and the ecofriendly nature-based and natural materials as sorbents, particles, gelling agents, surfactants, and separators for oil/water separation.

26.2 Sources of oil/water mixtures Oil/water mixtures are produced as a waste by various industries like gas & oil, food, shipping, tanning, textile, metal and machining industries. Oil spills can happen in the process of offshore crude extraction, oil exploration, marine transport and infrastructure development processes like storage, etc. In a 2002 report by USNRC it was published that, 1.3 million tons of oil is being deposited in sea water every year from conventional sources. Approximately 250 million barrels/day of oily wastewater is generated all over the world for every 80 million barrels of oil (Diya’uddeen et al., 2015). In 2003, offshore facilities released 800 million m3 of oily wastewater globally which brought the water-oil ratio to a sensational 3:1 (Ahmad, Guria, & Mandal, 2020). Water is used abundantly in the food (meat, poultry, seafood), drink and milk industry. As a result, a major portion of emulsified wastewater is generated by these industries. These oily discharges show a very high organic carbon content. In the metal processing industry, a conventional coolant and flushing fluid is cutting oil. The emulsified wastewater generated from mixing with cutting oil consists oil, water and various compounds like fatty acids, surfactants, etc. (J. Paul Guyer, 2013). In short, oil/water mixtures from various sources are chemically and physically complex. These create environmental hazards and removal/recovery is needed with appropriate treatment technology.

26.3 Composition of oil/water mixtures The components of oily wastewater vary widely depending on their sources. For example, in petroleum refinery, the composition of waste material depends on the nature of crude oil used, the process involved, and the end product. Though industrial wastes are lower in volume, the concentration of pollutants is usually pretty high. The oily wastewater is a mixture of organic and inorganic elements but mainly constitutes of oil and grease. There can be four forms: free droplets (diameter . 150 mm), dispersed droplets (diameter: 20
150 mm), emulsified (droplets with diameter , 20 mm), and dissolved oil (not in the form of droplets) (Pintor et al., 2016).

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26.3.1 Chemical composition Major pollutants in oily wastewater are inorganic oils such as hydraulic, turbine, lubricating, cutting and motor oils, organic aliphatic, aromatic, asphaltene hydrocarbons from petroleum. With these pollutants, metals like nickel, cadmium, lead, vanadium; organometallic complexes, oily sludges, and particulate matters are also present in oil/water mixtures. Organic pollutants occur in oil/water mixtures as dispersion, emulsions, or in dissolved state while the inorganic pollutants occur in floatable or settleable state (Ikhsan et al., 2020). In petroleum refinery wastewater hydrocarbons like benzene, toluene, ethylbenzene, and xylenes, naphthalene, phenanthrene, dibenzothiophene, polyaromatic hydrocarbons, methyl tertiary butyl ether, polycyclic aromatic hydrocarbons, phenols, naphthalenic acid, sulfides, and metals derivatives are found (Liu et al., 2014). Oxygen demand of waste water is a measure of organic content. Oxygen demand is the amount of oxygen needed to completely oxidize, or break down, its components. High organic material containing wastewater requires 2 mg/L dissolved oxygen to sustain aquatic life and if it is discharged into water bodies, it causes high consumption of oxygen by the microorganisms (Henze, 1989). Thus, presence of a certain amount of dissolved oxygen is required, otherwise the products of chemical and biochemical reactions often give rise to unfamiliar colors, tastes and odors to water. Inorganic compounds include cations such as Na1, K1, Ca21, Mg21, Ba21, Sr21, Fe21, anions such as Cl2, SO422, CO322, HCO32, heavy metals and radio-active materials. Cations anions affect the buffer capacity, salinity, scale potential of wastewater. Sulfate concentration of produced water is lower than sea water. Salt concentration of oily wastewater from oil & gas industries ranges from a few parts per million (ppm) to about 300,000 ppm, 1000
250,000 mg/L (Chang, Chiang, & Yuan, 2005). Apart from the heavy metals mentioned before, oily wastewater also contains naturally occurring radioactive compounds 226Ra and 228Ra. In the North Sea, these radioactive elements were found in concentrations ranging from under the detectable limit of 0.3
1.3 becquerel per liter (Bq/L) to 16 and 21 Bq/L, respectively (Fakhru’l-Razi et al., 2009).

26.3.2 Physical properties of oily wastewater The physical properties of oily wastewater are characterized by mainly color, odor, temperature, surface tension, viscosity, type of oil, etc. Extent of an oil spill spread depends on physical properties like surface tension, specific gravity and viscosity. Lower values of surface tension lead to quick spread in the absence of external environmental factors (wind, current, etc.). Surface tension is dependent on the temperature, so in warmer climates, oil spill spread is higher. Due to its low density most oil float on the water surface but in some cases due to evaporation of lighter components, oil gets heavy and sinks. It has been reported that an increase in temperature of 10 C
50 C can decrease the density from 0.88 to 0.855 kg/dm3 and the viscosity from 5000 to 200 cSt (Nordvik et al., 1996). Higher viscosity of oil spills form chocolate moss which is not easy to degrade (Payne & Phillips, 2018). Oil/water mixtures can be broadly divided into four types according to their physical state which are, oil-in-water emulsions, water-in-oil emulsions, total dissolved solids

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(TDS), and suspended solids. Oil-in-water emulsion is droplets of oil dispersed throughout water where water is the dispersion medium that is, the continuous phase, while oil is in the dispersion phase. In this type of emulsions, oil inside the water is usually waste oil, so the primary task is to recover the water. Water-in-oil emulsions are droplets of water dispersed in the oil. In this case water is the byproduct and must be removed to recover the oil. TDS is small particles dispersed throughout the oily wastewater which cannot be removed with filter paper. Similar to colloidal suspension, suspended solids consist of particles floating in the water, rather than dispersed.

26.4 Major processes of oil/water separation Because of harmful effects and rigorous regulations on discharge of oily wastewater, various treatment methods have been applied to minimize its toxicity and recover oil or water. It is not possible to decontaminate waste water by a single treatment process. Series of processes are required for desired quality of water. There are three stages of wastewater treatment—primary, secondary, and tertiary. At first in primary stages, oil is separated from water by different kinds of floatation chambers, equalization tanks, etc. Gravity separation, dissolved air floatation, filtration, sedimentation are the primary stages to reduce suspended and floating solids, oil and gas mechanically. Then wastewater is treated by secondary and tertiary processes to remove other organic, inorganic components to achieve desired excretion limit. Secondary treatments (biological treatment) consist of biological degradation of dissolved oil and other pollutants by microorganisms which oxidize the pollutants into simple compounds like CO2, H2O, CH4, etc. Major processes are of three types: physical-mechanical, chemical, and biological process.

26.4.1 Physical-mechanical methods 26.4.1.1 Sedimentation Sedimentation is a physical separation method that utilizes gravity to separate the suspended solids from water. The particles that settle out at the bottom of tank as a thick layer are known as sludge and it needs periodical removal. Sometimes coagulates are used to facilitate the settling process. Technologically this process is simple, economically advantageous, efficient to adapt high pollutant loads. 26.4.1.2 Dissolved air floatation It is often used after gravity separator to treat water polluted with particles in a range of 10
100 μm. In this process, at first, air is dissolved under pressure in wastewater. The removal is done by causing air bubbles in floatation tank after releasing the pressure of the dissolved air. The bubbles then get attached to the solids, oil droplets and lift them to surface of water. Skimming devices are employed to remove this. DAF method works faster to remove suspended solids in comparison to the sedimentation process which is economically favorable from the engineering point of view (Jafarinejad, 2016).

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26.4.1.3 Coagulation-flocculation These two processes can remove most of the colloids. In coagulation, positive ions i.e., coagulants such as iron or aluminum salt are added to the water. Similar charges of coagulates repel each other and prevent them for settling quickly. These positive charges neutralize the negative charges present on the surface of the suspended and dissolved solids and bind together or coagulate. Coagulation causes particle destabilization and flocculation facilitates transport of those destabilized particles to collide with floc. Various synthetic flocculants like zinc silicate and anionic polyacrylamide composite (Zeng et al., 2007), poly aluminum zinc silicate chloride (Cong, Liu, & Hao, 2011), CAX have been used with favorable results but these are not cost-effective and they also create secondary pollution of water bodies. 26.4.1.4 Sorption It is a physicochemical method as well as a surface phenomenon used to remove inorganic and organic contaminates from wastewater. When a solution containing adsorbable constituents come across with highly porous solid surface (adsorbent), some of the solute particles get deposited on the surface of adsorbent due to liquid solid intermolecular attraction force. Adsorbents used are selective in nature. High thermal stability, small pore diameter which results in high surface area and high capacity are must have characteristics for a sorbent. Natural and synthetic adsorbents are used in various wastewater treatment plants such as charcoal, zeolite, ores, and clay minerals. Various sponge-based porous materials with superwetting properties, sponges, aerogels, fibers, cottons have been used to selectively absorb oil from water. 26.4.1.5 Mechanical containment Containment and recovery are the main two steps used as barrier to control oil spills. The varieties of barriers are booms and skimmers. Mechanical containment is done to limit the spread of oil spill with booms so that the oil can be recovered and treated in time without letting the oil spill get out of control. Equipment called containment boom acts like a fence to prevent spills from further spreading. Booms can be of several basic types like fence boom, round or curtain boom, fire-resistant boom, and inflated booms (Booms | Emergency Response | United States EPA). Once the oil has been confined in boomers, skimmers can be deployed to remove contaminates without altering their properties. They are mainly categorized into oleophilic, weir skimmers, and suction. 26.4.1.6 Thermal and electrical treatment One type of thermal remediation method involves in situ burning of oil. It requires a boat, fire-resistor boom, and an ignition element. This treatment is effective for fresh spill or refined products which can be burnt quickly without harming marine life. The obvious downside to this process is production of different aromatic hydrocarbons, burn residue and minor amount of CO, SO2, NOX, etc. Another thermal demulsification method is microwave heating. By increasing temperature in a controlled way, it reduces interfacial tension and viscosity of oil which promotes coalescence.

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The electrical treatment of electrocoagulation destabilizes the charges of suspended, emulsified and dissolved particles in a dispersion medium by employing an electric current causing electrode dissolution. Metal ions emerged from anode dissolution followed by hydrolysis work as coagulants which helps to weaken the charged pollutants and results in creating a floc. Aluminum and iron are widely used as electrodes. Al electrodes can result of 70% of COD removal whereas Fe electrodes cause 71.3% of the same (Hakizimana et al., 2017). 26.4.1.7 Filtration One of the most economical processes for removing oil droplets smaller than B10 μm is membrane filtration. The advantages of membrane-based processes are their high selectivity and separation efficiency, low carbon footprint, no need for external chemical, less waste, and external energy demand. The key downside is membrane fouling due to cumulative retention of oil on the surface and pores of the membrane. Another problem with membrane processes is lower throughput, increasing the total cost. Besides membrane filtration various meshes, sand beds, stone bed, anthracite-sand, resin bed-sand, activated carbon-sand have also been used as filter media to remove oil from water. In sand filtration, wastewater flows vertically through a fine bed of sand or gravel. Contaminates are removed by absorption or physical encapsulation. Natural filter media will be discussed later in the chapter.

26.4.2 Chemical methods 26.4.2.1 Chemical precipitation In chemical precipitation counter ions are added to remove ionic constituents and reduce the solubility. A precipitation reagent is needed to enhance the process of conversion. The precipitated solid can be separated by sedimentation, filtration, etc. It is used for removing metallic cations as well as anions such as fluorides, cyanides and organic compounds too. 26.4.2.2 Dispersants and solidifiers Dispersants are surfactants dissolved in various solvents and/or stabilizers. The function of a dispersant is to break the oil slick into smaller droplets which can be diluted and degraded easily in later stages. The most used dispersants are Slickgone NS, Neos AB3000, Corexit 9500, Corexit 8667, Corexit 9600, SPC 1000, Finasol OSR 52, Nokomis 3-AA, Nokomis 3-F4, Saf-Ron Gold, ZI-400, Finasol OSR 52 (United States EPA). Gelling agent or Solidifiers are hydrophobic polymers in dry granular state. These chemicals transform the oil into a rubbery form which is easier to separate by physical means. Solidifiers are used as dry particulate and semisolid materials like pucks, cakes, balls, sponge designs. 26.4.2.3 Chemical oxidation This process involves the transfer of electron from an oxidizing agent to a compound being oxidized. Residual COD reduction and treatment of nonbiodegradable compounds, trace

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organic compounds are the goals of chemical oxidation. Generally, oxygen, ozone, hydrogen peroxide, chlorine dioxide are used as oxidizing agents. Chemical oxidation works better for small streams where natural biooxidation processes do not happen. In short, wastewater with high recalcitrant compounds like dissolved aromatic compounds, is treated with chemical oxidation because these compounds are not suitable for biological degradation. Fenton oxidation process is another effective oxidation method for abatement of organic pollutants like volatile phenol, benzene, benzene derivatives which are generally toxic in nature and hard to remove by other conventional processes. In this process poly ferric sulfate is used as flocculant for settling period. There are some other conditions that need to be satisfied which are, pH value between 3
4, 30% of H2O2, Fe13 to H2O mass ratio of 4%, oxidation time 120 min, adsorption time 120 min, active carbon dose 4000
5000 mg/L (Diya’uddeen et al., 2015).

26.4.3 Biological treatment This method uses bacteria, nematodes, protozoa, microorganisms to breakdown organic pollutants and removes wastewater biochemical oxygen demand (BOD) up to 95% (Freire, Cammarota, & Sant’Anna, 2001). Microorganisms stick together to create flocculant and allow the organic matter to settle down as sludge. Biodemulsification can happen in two major methods one is microbial metabolism where pollutants are degraded into harmless compounds like in activated sludge process; another method is biological filters where the microorganisms are attached to a filter medium and the wastewater is passed through that. Mainly biological methods are divided into two categories according to their type of metabolism, aerobic and anaerobic. 26.4.3.1 Aerobic methods Aerobic treatment processes include aerobic tank, activated sludge, oxidation ditches, spray aeration, lagoon-based treatment, etc. Oxygen is fed to the effluent and microorganisms use that dissolved oxygen to degrade organic components to carbon dioxide and biomass. Air stripping is also used for conversion of ammonified organic nitrogenous compounds into ammonia and nitrite to form nitrate, known as nitrification. 26.4.3.2 Anaerobic methods In absence of oxygen, anaerobic organisms treat high polluted effluent (i.e., BOD . 500 mg/L) and create excess sludge. Aerobic treatment of these wastewaters is problematic because the elevated oxygen demand increases the oxygen expense. Biogas is produced in degradation process which consists of methane, CO2, trace amount of H2S, nitrogen and oxygen.

26.5 Natural materials: an alternative Existing materials for oil/water separation, as discussed before are hardly environmentally sustainable due to the formation of secondary waste, nonbiodegradable nature, and

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synthesis methods which are also not environmentally-friendly. All of these brings the search for alternative materials in light. The materials discussed in the following sections are mostly natural or nature derived sorbents, nanoparticles, aerogels, surfactants, etc., used in both oil recovery and oil removal.

26.5.1 Sorbent materials The process of adsorption and absorption together is called sorption. In adsorption, the sorbate molecules are accumulated on the adsorbent surface. Oil molecules diffuse on the adsorbent surface, gets attached by chemical bonding or Van der Waals forces and gets entrapped in capillaries in the adsorbent surface causing agglomeration. On the other hand, absorption is a physical/chemical phenomenon where sorbate molecules are absorbed into the bulk phase of the absorbent. The surface chemistry and morphology are important for a good sorbent. Surface morphology dictates the wettability of the surface and the measure of wettability is the water contact angle. A contact angle under 90 degrees demarks hydrophilicity, contact angle in between 90 and 150 degrees is characterized as hydrophobicity and a contact angle greater than 150 degrees is characterized as superhydrophobicity. Similarly, oleophobic, superoleophobic materials can be classified. A superhydrophobic sorbent shows very little water adsorption and thus, is a better sorbent for oil. An example of a superhydrophobic surface is the surface of lotus leaves. Superhydrophobic surfaces can be created by surface modification, chemical corrosion and other chemical methods but these methods create toxic waste. To be a perfect sorbent for oil/water separation, the material has to have good porosity, high surface area and high selectivity towards oil. Kapok fiber, cotton, rice straw, rice husk, banana peels, potato peels, walnut shells, hybrid fruit peels, silkworm cocoon waste, and wood sheets are some examples of natural sorbents for oil/water separation. These materials can remove oil from gas station effluent with 70% higher oil removal capacity in comparison to the polymeric sorbents (Khan, Virojnagud, & Ratpukdi, 2004). The drawbacks of these natural materials are their poor hydrophilicity, buoyancy and low selectivity (Maleki, 2016). Various modifications have been done to surpass these drawbacks keeping native properties of the natural materials intact.

26.5.2 Particles Separation properties of a particle depends on its size, porosity, functional groups and whether it undergoes adsorption or emulsion. In an emulsion system a particle comes in contact with both the dispersed phase and the continuous phase. If a particle is strongly hydrophilic it only gets wetted by water and gets dispersed in the continuous phase; the opposite happens in case of a strongly hydrophobic particle. That’s why the particles need to be amphiphilic to adsorb oil/water from the interface of oil, solid and water. If the three-phased contact angle is greater than 90 degrees the particle is better suited for oil-in-water emulsion and a contact angle less than 90 degrees is favorable for water-in-oil emulsion (Aveyard, Binks, & Clint, 2003). Particles adsorb in the interface and create a stable emulsion by resisting coagulation and coalescence. Separation happens when the interfacial tension between oil/water phase increases. Due

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to their hydrophilic nature, natural particles for oil/water demulsification takes up excessive water and performs poorly. Research is going to remedy this by adding hydrophobic parts to these natural particles. Solid particles which adsorb onto the interface between the two phases can stabilize the emulsions similar to a surfactant. These emulsions are called Pickering emulsions. Cellulose contains poly-β-(1 4)-D-glucosyl chains which forms fiber-like structures that give rise to its hydrophilicity. Cellulose nanocrystals have been used to remove marine diesel by forming emulsified creaming through Pickering emulsions (Laitinen et al., 2017). Desorption of these particles adsorbed in the interface are more difficult than surfactants. O/w pickering emulsions can be stabilized using particles with thermoresponsive copolymers. The destabilization is done by simple heating (Zoppe, Venditti, & Rojas, 2012). Ojala et al. synthesized bifunctionalized rod-like cellulose nanocrystals which could stabilize oil in water emulsions containing up to 3.5% salinity (Ojala, Sirvio¨, & Liimatainen, 2016). Another natural particle of interest is Chitosan. Crab shell derived hydrophilic carboxymethyl chitosan have been used as a destabilizer that performed under the seawater salinity and alkalinity (Doshi et al., 2017). Microspheres of chitosan synthesized by ionic gelation of chitosan showed 90% oil separation while used in packed columns (Da Silva Grem et al., 2013). Magnetic separation of oil adsorbed nanoparticles is another potential method for oil removal. Quaternized chitosan with magnetic nanoparticle coating could (Zhang et al., 2013) separate oil/water in a wide pH range, and retain its separation capacity up to eight cycles. Shrimp shells show underwater oleophobicity, from that observation Zhang et al. they used chitosan derived from chitin, found in shrimp shells, to coat metal meshes. This mesh showed over 99% separation in a broad range of pH and high saline water conditions. (Zhang et al., 2013). Another natural particle that can be used as oil/water mixture separation material is sand. Sand particles show high water absorption capacity that suggests strong hydrophilicity and underwater superoleophobicity. A sand layer shows macro, micro and nanoscale rough microstructure and a size between 130
270 μm (Yong et al., 2016). Major component of sand is silicon dioxide, some metals like Na, Mg, Al, K, Ca, Fe and hydroxyl groups—all of these contribute to its hydrophilicity. A water droplet can easily pass through a sand layer where an oil particle cannot due to the oleophobicity of the wetted sand layer. Cassie wetting state is created by these prewetted sand layer in contact with oil droplets in this three-phase system. The rough microstructure of sand particles entrap water on the surface which prevents oil particles to come in contact with the sand layer. Yong et al. designed a separation device based on these properties of sand particles. A 1 cm thick sand layer stuffed between two plastic tubes was used as the separation layer, to avoid sand particle loss with a cloth was used. This setup separated oil-water with great efficiency. A sand layer of 0.5 cm can produce almost 9648 LMH water flux and can withstand over 39 cm of petroleum ether. Sand particles have also been employed to treat emulsified oil/water mixtures. Li et al. successfully separated oil/water from a Span 80 stabilized water-in-diesel emulsion by directly pouring it on sand layer without prewetting (Li et al., 2017). This study suggested that sand layers have the potential to separate surfactant stabilized w/o emulsions and the removal efficiency got better with the increase in sand layer thickness. Sand particles need support structures to retain its structure and stop material loss. Since sand is in abundant supply from desserts, it can be used as a potential material for separating both immiscible and emulsified oil/water mixtures.

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26.5.3 Surfactants Surfactants are amphiphilic surface-active molecules with a hydrophilic and a hydrophobic part. These molecules orient their hydrophilic part with the water phase and the hydrophobic part with the oil phase forming stable microemulsions and preventing coalescence. Surfactants are the main components of the dispersants used in oil spill cleanup which breaks the oil slick into smaller droplets. Corexit 9527 and Corexit 9500An are two main chemical dispersants which were used for various oil spill responses like the deep horizon oil spill. These dispersants contained anionic surfactant dioctyl sodium sulfosuccinate (Belore et al., 2009). Another type of surface-active molecules used in oil spill cleanup by contacting and thickening the slick are herding agents. Existing chemical dispersants and herding agents are chemically stable and effective but stay in the marine environment for a long time and are nonbiodegradable (Gray et al., 2014), that’s why further research is going on for utilizing natural materials for synthesizing biodegradable, low-cost surface active compounds. Muhammad et al. treated crushed eggshell powder with hexadecyl-trimethylammonium-bromide (HDTMA-Br) to produce a surfactant for oil/water separation. At an equilibrium dose of 1600 mg/L, the surfactant took 5 min to remove 91.21% of the oil and complete removal (194 mg/L) was done in 25 min (Muhammad, Aliyu El-Nafaty, & Isa Makarfi, 2015). In another work, phosphatidylinositol (PI) and phosphatidylcholine were found by fractionation of soyabean lecithin using ethanol. This PI was further hydroxylated to alter the hydrophilic-lipophilic balance. Athas et al. reported that mixing lecithin and Tween 80 in ethanol solvent can be effective as an emulsifier for oil water separation (Athas et al., 2014). Phytol is a plant-based small amphiphilic molecule, its hydrophobic tail consists of a terpenoid (isoprenoid) with isoprene units and the polar group was esterified with a cation (1-methylimidazolium/pyridinium). It is a part of the chlorophyll molecule that occurs naturally and abundantly in the marine biota. Phytol modified herding agents have been observed to hydrolyze rapidly after herding in comparison with commercial herders based on silicon (Gupta et al., 2015).

26.5.4 Aerogels Aerogel is a porous gel material. In this material, the liquid phase has been replaced by air or a gaseous component without significant change in the gel structure. This results in a highly porous (B99%) solid structure with very low density (around 10 mg/mL), high surface area ( . 100 m2/g), and low thermal conductivity. These properties can be very useful for oil absorption applications—high porosity can provide higher absorption and low density can facilitate floatation on water surface. It has been reported that mass absorbency increases in the case of higher density oils. The main upsides of using aerogel sorbents are that they can be recycled successfully and the recovery of the oil is satisfactory. Different kinds of recovery methods have been applied like extraction, distillation, and mechanical squeezing (Doshi, Sillanpa¨a¨, & Kalliola, 2018). Aerogels are prepared by freeze-drying the biomaterial dispersed in aqueous phase which is putting the material through low temperature under vacuum. Cellulose based natural materials are usually amphiphilic which makes it a sorbent for water and oil both,

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so, the task is to make it more hydrophobic so that it only absorbs oil. This can be done by chemical treatment and pyrolysis. Pyrolysis along with freeze drying is an environmentfriendly way to modify the hydrophobicity of the aerogels. Pyrolysis improves the mechanical strength, chemical, thermal durability of the aerogels and increases hydrophobicity by formation of saturated carbon chains. Yuan et al. used bamboo pulp fibers to prepare a carbonaceous aerogel using freezing drying and pyrolysis at up to 800 C temperature. This material demonstrated excellent surface area of 379.39 m2/g, low density of 5.65 mg/mL and 50
150 g/g sorption capacity with reusability up to 5 cycles (Yuan et al., 2017). A twisted carbon fiber aerogel was prepared by pyrolyzing raw cotton at 800 C. The material showed 12 mg/mL density, 50
192 g/g sorption capacity up to 5 cycles (Bi et al., 2013). Li et al. prepared 3-D carbon aerogel from winter melon, it could absorb 16
50 times its own weight and a recyclability over cycle (Li et al., 2014). Zhang et al. used kapok fiber to prepare ultralight microfibrillated cellulose aerogel which showed 104
190.1 g/g sorption capacity and ultrahigh porosity of 99.58% (Zhang et al., 2021). A carbon aerogel from waste pomelo peels was prepared by Zhu et al. through hydrothermal carbonization, freeze drying, and pyrolysis which showed a sorption capacity of 5 and 36 g/g for castor and sunflower oil, respectively (Zhu et al., 2017). However, the process of manufacturing aerogels is costly due to the huge energy demand of both free-drying and pyrolysis process (Maleki, 2016), scaling up the freezedrying process to an industrial level is still a difficult task. Moreover, aerogels lack mechanical strength and are brittle in most cases (Maleki, 2016) which creates problem with the recyclability of the material. Lack of mechanical strength may also cause degradation of the aerogel structure causing a decrease in sorption capacity.

26.6 Promising natural materials for oil/water separation In recent years a new class of environmentally-friendly alternative materials with high absorption capacity, high porosity, surface area has been developed from natural materials and their modifications. These materials reduce waste handling problems faced with conventional oil/water separation materials and show excellent recyclability. Some of these promising materials, their working mechanisms, and various modifications have been discussed below.

26.6.1 Kapok fibers Kapok fiber is a natural sorbent found from the fruits of silk-cotton tree—the lightest fiber tree in the world. The fiber contains 64% cellulose and 13% lignin (Reddy & Yang, 2009). Its high hollow structure and natural hydrophobic characteristic makes it a good candidate for oil/water separation. The hollow lumens have low density of 290 kg/m3 which contribute to its sorption capacity (Quek, Ngadi, & Zaini, 2019) and smooth layer of surface wax contributes to its hydrophobic nature (Zheng et al., 2015). Oil gets entrapped in the hollow gaps by Van der Waals forces and hydrophobic interactions (Choi & Moreau, 1993). The wax layer helps oil particles to diffuse into internal hollows and the

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adhesive-cohesive interactions cause capillary action. Raw kapok fiber showed an absorption capacity of 30 g/g for low viscosity diesel oil, 40 g/g for medium viscosity vegetable and 50 g/g for high viscosity lubricating oil (Kartina & Suhaila, 2012). Kapok fiber is produced abundantly in tropical countries worldwide. According to studies this material can be reused up to 15 cycles (Lim & Huang, 2007) which makes this a sustainable, environment-friendly alternative material for oil/water separation. 1 g of Kapok fiber can absorb 200 g of refined palm oil (Quek et al., 2014) and with acetylation this performance gets enhanced for diesel and soyabean oil sorption (Wang, Zheng, & Wang, 2013). In that study the sorption capacity for diesel was found to be 30.5 g/g for raw kapok fiber which increased to 36.7 g/g after acetylation. Enhancement seen in case of soyabean oil sorption was from 47.4 g/g to 52.2 g/g. Kapok fiber can absorb 40.2 g/g chloroform which increases to 51.8 g/g after HCl treatment. Solvent treatments make the surface of the fiber rougher which increases the oil sorption. Wang et. al., made modified superhydrophobic Kapok fiber using polybutyl methacrylate and silica nanoparticle coating with silanization. This increases the sorption capacity up to 85 g/g and had a great reusability of 8 cycles (Wang, Zheng, & Wang, 2012). In another work, Fe3O4 nanoparticle coated and dopamine treated kapok fiber showed great reusability of 16 cycles and sorption capacity up to 51 g/g for toluene, gasoline and diesel (Wang, Yu, Sun, & Ding, 2016). In NaClO2 treatment, the waxy layer of the fiber gets removed and the finer fibril structures gets exposed. Though it is perceived that hydrophobicity is a determining factor in sorption capacity, increase in surface roughness increases the surface area, oil adhesion capacity and overall oil sorption (Annunciado, Sydenstricker, & Amico, 2005). Alkali treatment of kapok fiber collapses the hollow lumens of the fiber, creates finer fibril structures and broken holes in the fibers which enhances the oil-fiber interaction probability. Moreover, formation of cracks and holes in the fiber increases the available area for sorption, increasing overall sorption capacity.

26.6.2 Rice husk/straw Rice husk is an agriculture-based waste biomass which has potential as a sorbent for oil/water separation. Rice husks make approximately 20% of the annual gross of rice in the world (545 million metric tons) (Mansaray & Ghaly, 1998). Rice husk as a sorbent material can be useful due to its granular structure, hydrophobicity, chemical stability, high mechanical strength, and its abundance as agowaste. The husk has a bulk density of 34
40 kg/m3 and contains lignin (28.25%), hemicellulose (18.59%) and cellulose (31.13%) (Wang et al., 2015). Another effective upside is, rice husk and its ash are not needed to be recycled due to do their low cost. Thus, use of rice husk solves the waste management problem and the need for a natural sorbent. The presence of carboxyl, silanol, etc., functional groups in rice husk and rice husk ash facilitates adsorption. Rice husk contains almost 20% silica, pyrolysis of brown rice husk ash breaks the bonds between silicon and organic materials which increases its hydrophobicity and sorption capacity up to 5.02 g/g for diesel and 6.22 g/g for crude oil (Vlaev et al., 2011). The oil adsorption capacity depends on the granulometric composition or the C/SiO2 weight ratio, bulk density, surface structure and the oleophobicity of the sorbent. Alkaline treatment of rice husk

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increases the adsorption capacity for diesel up to 19 g/g by removing silica and reducing its bulk density which allows internal diffusion of oil particles (Bazargan et al., 2014). The rice husk leftover with adsorbed oil can further be used as a fuel. Acetylation of rice husks can be done through catalytic or noncatalytic process. Noncatalytic acetylation led to 11.2% increase in sorbent weight and a sorption capacity up to 20 g/g whereas, catalytic acetylation increases 15.4% sorbent weight and shows sorption capacity up to 24 g/g (Nwadiogbu et al., 2014).

26.6.3 Vegetable residue wastes Another low-cost, biodegradable alternative biomass sorbent group is vegetable/fruit peels such as banana, orange and pomelo. These peels contain cellulose and are potentially viable for removing heavy oil effectively (Abdullah et al., 2016). It has been reported that 0.3625 mm banana peel particles are able to show a sorption capacity of 5.31 g/g for gas oil, 6.35 g/g for 1-day weathered oil and 6.63 g/g for 7-day weathered oil (Alaa El-Din et al., 2018). Raw orange peels contain limonene and linalyl acetate which contributes to the surface oleophilicity. Raw orange peels show a sorption capacity of 2.38
5.23 g/g for diesel, used oil and weathered crude oil with a reusability up to 5 cycles. Thermal treatment of raw orange peels at 500 C makes previously smooth and homogeneous structure rough and highly porous, which increases its sorption capacity (El Gheriany et al., 2020). Lam et al. synthesized a biochar adsorbent from pyrolysis of banana and orange peels at 400 C
500 C for sorption of palm oil mill effluent (POME). This biochar, with a surface area of 105 m2/g and a mesoporous structure showed a 57% reduction in BOD, chemical oxygen demand COD, total suspended solid and oil and grease of POME under the predetermined standard (Lam et al., 2018). Cellulose-rich materials like fruit peels are voluminous and show low bulk density and higher sorption capacity for marine fuel without any need of much treatment. Pomelo peels contain 46.22% cellulose, 18.84% hemicellulose and 10.24% lignin. After acetylation it shows a sorption capacity of 18.91 and 26.36 g/g for diesel and lubricating oil, respectively. The sorption capacity becomes 16.50 and 19.39 g/g after styrene treatment for same oil samples. Zou et al. prepared a modified pomelo peel with magnetic properties by a solvothermal process which showed maximum uptake of 27.98 g/g and good reusability. The sorbent retained 41.8% of its capacity after 10 cycles (Zou et al., 2016). A hybrid fruit peel adsorbent prepared with banana and orange peels after treating with NaOH. Banana peel contains high cellulose contain of 82% which is ideal for retaining lubricating oils and the orange peels contain less cellulose which makes it ideal for sorption of lighter oils.

26.6.4 Nutshells Nut Shell media is another agriculture-based potential sorbent material for oil/water separation. An abundant source of this material is the walnut processing industry. Walnut shells, especially black walnuts and Pecan shells, hazelnut shell, coconut shells are commonly used because of their suitable characteristics for oil removal in the oil & gas industry. Due to its strong adsorption, interception capability, antioil immersion, high hardness, good abrasion resistance, low ash content, nutshells can produce hydraulic rebound without significant

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backwashing. This type of pressurized bed filters is frequently used to filter contact cooling water, preventing the water from becoming dirty. Structural components of walnut shells are most common hydrophilic compounds like lignin and cellulose which contains a lot of active groups (OH2 and -COO2). While Coconut shells are made of environment-friendly compounds like, glucan, xylan, klason-lignin, with mass percentage of 29.30%, 25.92%, and 24.36, respectively, which makes the surface hydrophilic in nature (Li et al., 2018). Various chemical groups like carboxyl, hydroxyl, amide, acetamido, etc., are also present in the nutshells. Walnut shell media filters have low media gravity (Yang, Zhang, & Wang, 2002) which have the mechanical strength to retain their size during backwashing. This decreases the possibility of material loss from the sorbent bed (Rahman, 1992). In the study by Srinivasan et al. the walnut shell media sorbent showed 0.56, 0.58, 0.74 sorption capacity for standard mineral oil, vegetable oil and DoALL Bright-Edge oil, respectively (Srinivasan & Viraraghavan, 2008). Li et al. worked on waste coconut shell powder (WCSP) which has a porosity of approximately 85.8%. A single particle of this WCSP shows a layered structure with apertures on the layer surface. The WCSP layers show superamphiphilicity due to hydrophilic chemical properties and a rough surface that gives rise to hydrophobicity. WCSP showed separation efficiency up to 99.99% and had a recyclability of 50 cycles.

26.6.5 Wood sheets Wood has been introduced in oil wastewater treatment because of its strong water affinity and capturing of water, providing it with superoleophobicity and very low oil affinity under water. The morphology of wood consists of aligned tracheids that forms a 3D hollow fibrous structure. The cell wall of wood is composed by 40%
50% w/w cellulose nanofibrils, 20%
30% w/w lignin and hemicelluloses. This large lignocellulosic content makes wood very hydrophilic, on top of that the highly porous 3D structure suggests that wood can be used as a material for oil/water separation. When the wood is immersed in water, the water molecules penetrate the cell wall, enters the internal fibrous structure and gets stabilized by capillary forces. This makes the wood surface hydrated, forming a thin film of water. This film of water prevents any oil droplet to come in contact of the wood surface resulting in underwater oleophobicity. Vidiella et al. demonstrated free oil/water mixture separation using a prewetted wood disk of 1 mm thickness cutting the tree perpendicular to the trunk (Vidiella del Blanco, Fischer, & Cabane, 2017). The wood sheet showed almost 99.9% separation efficiency for hexadecane. Moreover, porous hollow fibrous structure of wood sheet facilitated a water flux of 3500 LMH (1 mm sheet). Yong et al. worked with balsa wood sheet cut along the trunk direction. In this cutting, the microgrooves of the surface get exposed. Wetted balsa wood contains almost 50.3% water. This high water-content makes it superoleophilic under water (Yong et al., 2018). Guan et al. synthesized a cellulose based anisotropic wood sponge from natural balsa wood for oil sorption. In this synthesis lignin and hemicellulose was removed from the wood by chemical methods to break the thin cell walls and then freeze-dried create a lamellar structure with wave like layers. Great selectivity for oil/water absorption and a high uptake of 41 g/g was found with this wood sponge. The absorbed oil was easy to extract by simple mechanical squeezing (Guan, Cheng, & Wang, 2018). Wood has high mechanical strength,

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1 mm wood sheet could support a breakthrough pressure of 2.64 kPa (Yong et al., 2018) and it can be made into preferable shapes and structures which makes it a potential material for many practical applications.

26.6.6 Barley straw Another agriculture derivative product that has potential to be oil sorbent is barley straw. It has a top layer covered by a film of wax and a layered structure. This top layer is called cuticle and the wax layer gives it hydrophobic property (Wi´sniewska et al., 2003). Pyrolysis has been applied to various fibers to enhance their properties by carbonization. 200 C
500 C pyrolyzed barley straw fibers show 5.9
7.6 g/g sorption capacity for diesel and 8.1
9.2 g/g sorption capacity for heavy oil (Husseien et al., 2009). The carbonized barley straw pads were able to absorb oil at higher rates than commercial polymeric pads. Though carbonization reduced its reusability to two cycles where the raw fiber could be used up to four cycles. The absorbed oil could be recovered by manual squeezing. Ibrahim et al. synthesized a modified barley straw with caustic soda and hexadecylpyridinium chloride monohydrate. It showed uptake capacity up to 0.613 g/g for canola oil (Ibrahim, Ang, & Wang, 2009). Tijani et al. investigated the oil sorption performance of barley straw and various different Canadian biomass and found the highest sorption capacity of 6.07 g/g (Tijani, Aqsha, & Mahinpey, 2016).

26.6.7 Cotton fiber Cotton fiber contains 91% cellulose, 7.85% water and 0.55% potassium pectin wax, rest fatty substances and mineral salts. High percentage of cellulose which constitutes its secondary wall contributes to its sorption capacity and the waxy primary layer gives rise to oleophilicity. This wax layer gives it oleophilicity by nonpolar mechanism (Carmody et al., 2008). Modifications have been done on raw cotton fiber to enhance its sorption capacity. Acetylation of cotton fiber increases the maximum sorption capacity from 23 to 30 g/g for vegetable oil, mineral oil, fuel oil and crude oil (Deschamps et al., 2003). The oil could be extracted by manual squeezing up to 10 cycles. However, the raw cotton retained higher sorption capacity after 10th cycle than the treated cotton. Low-micronaire raw cotton fibers have been reported to show uptake capacity up to 30.5 g/g due to the low cellulosic morphology of the fibers (Singh et al., 2013). The same group worked on aligning of raw unprocessed cotton fiber to synthesize low-density, sustainable cotton batt which showed maximum sorption capacity of 50.27 g/g (Singh et al., 2014). A modified raw cotton fiber was prepared using stearic acid, with 4-(dimethylamino) pyridine and N, N’-dicyclohexylcarbodiimide. This improved the reusability of the sorbent and the sorption capacity was almost unchanged up to 10 cycles (Hoai, Sang, & Hoang, 2016). A superhydrophobic cotton fabric with superior reusability was prepared by Zhou et al. using vapor phase deposition of polyaniline and fluorinated alkyl silane. This modified material showed a maximum of 97.8% removal efficiency and retained sorption capacity up to 30 cycles in various extreme conditions (Zhou et al., 2013). The high sorption capacity through various modifications can be attributed to the interaction between oil and the waxy layer, interfiber capillary action and hollow lumen structures.

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26.6.8 Sugarcane bagasse Sugarcane bagasse is the residue fiber obtained from the cane sugar processing. It is the waste product that remains after the sugar is derived from the pressed sugarcane. Being another lignocellulosic biomass, sugarcane bagasse contains 42.8% cellulose, 25.8% hemicellulose, and 22.1% lignin (Wanderley et al., 2013). In the works of Behnood et al., raw sugarcane could absorb up to 8 g/g of crude oil (Behnood et al., 2013). It was further reported that a lower particle size gives higher sorption capacity due to increase in surface area. To increase the hydrophobicity of the sorbent, acetylation was done in a solvent-free method using N-bromosuccinimide as a catalyst. Acetylation significantly increases the oleophilicity of the material. The acetylated sugarcane bagasse showed sorption capacity up to 20.2 g/g which is almost twice the capacity of industrial polypropylene (Sun, Sun, & Sun, 2004). Another chemical modification of sugarcane bagasse by grafting stearic acid to add a hydrophobic envelope was done by Said et al. Though raw bagasse showed higher oil absorption capacity, it also absorbs water which was remedied by grafting stearic acid (Said, Ludwick, & Aglan, 2009).

26.7 Conclusion and further prospects Frequent oil spill incidents, volume of oil in water, and emulsions have increased over the years causing serious environmental damage and economic loss. Various materials with specific characteristics like superwettability, high surface area, fibrous structure, etc., have been employed to tackle oil-spill, oily wastewater, and emulsions. The greatest challenges with these materials are their waning performance with increasing oil and emulsion density because gradual evaporation and emulsification causes change in viscosity. The biomass derived sorbents, particles, aerogels discussed in this chapter are generally costeffective, abundant and encourages sustainable circular economy by utilizing many waste products. The possibility of oil-recovery from these materials is another lucrative quality. Low hydrophobicity is a fairly discussed drawback of these materials which have been addressed through various modifications like acetylation, alkali treatment, pyrolysis, and various environment friendly chemical modifications. Aerogels are perfect oil/water separation materials due to their high sorption capacity originating from high surface area and low density. Aerogel synthesis is easy and environment friendly. Though processes like freeze-drying and pyrolysis have a substantial energy demand, research is ongoing to scaleup the production of aerogels to bring it to an industrial level of usage. Preparation of aerogels by nanoscale biomaterial stabilized air-drying of foams is an energy efficient option instead of freeze-drying. We have discussed a few of natural materials which can be applied successfully to separate oil/water mixtures but the range of available materials is still small, as there are a lot of potential materials in nature and further research has to be done in identifying and using them. There are some materials like dandelion seeds, milkweed, silk fiber, wool fiber, bamboo fiber, coconut fiber, chicken and avian feathers, human hair, pineapple leaves, etc., which are being studied by researchers to come out with even better and varied alternatives for conventional materials for oil/water separation. Further research is

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needed to understand the fundamental interactions between oil-water-particle surface like underwater oleophobicity, the dynamic interaction of oil/water mixtures with a superwetting surface. To conclude, most of these materials producing satisfactory oil sorption/ recovery characteristics are still in lab scale research. In the future, significant research is necessary to put these materials in real conditions to pave their way to the market to actually replace conventional materials in use.

Acknowledgment The authors acknowledge Department of Science and Technology, Govt. of India sponsored project entitled “Center for Technological Excellence in Water Purification (CTEWP)” under Water Treatment Initiative (WTI) (vide sanction letter no DST/TM/WTI/WIC/2K17/84(c) dated 21.02.2019), for providing necessary support and facilities during the preparation of this chapter.

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Further reading Daling, P. S., & StrØm, T. (1999). Weathering of oils at sea: Model/field data comparisons. Spill Science & Technology Bulletin, 5(1), 63
74. Available from https://doi.org/10.1016/S1353-2561(98)00051-6. Nyankson, E., Decuir, M. J., & Gupta, R. B. (2015). Soybean lecithin as a dispersant for crude oil spills. ACS Sustainable Chemistry and Engineering, 3(5), 920
931. Available from https://doi.org/10.1021/acssuschemeng.5b00027.

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27 Extraction and separation of oils: the journey from distillation to pervaporation Tathagata Adhikary and Piyali Basak School of Bio-Science and Engineering, Jadavpur University, Kolkata, India O U T L I N E 27.1 Introduction

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27.2 Techniques in the extraction of oils513 27.2.1 Mechanical extraction of oils 513 27.2.2 Steam and hydrodistillation 514 27.2.3 Chemical extraction of oils 515 27.2.4 Ultrasound and microwave-assisted extraction 517 27.2.5 Optimizing the extraction process 518 27.3 Emulsification/formation of emulsions 519 27.3.1 Types of emulsions 520 27.3.2 Properties relating to emulsions and emulsifiers 521

27.4 Oil-water separation or demulsification 27.4.1 Chemical demulsification 27.4.2 Biological demulsification 27.4.3 Thermal demulsification 27.4.4 Microwave demulsification 27.4.5 Electrical demulsification 27.4.6 Ultrasonic demulsification 27.4.7 Mechanical demulsification 27.4.8 Membrane demulsification 27.4.9 Pervaporation

522 523 524 526 526 527 527 528 528 529

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Acknowledgment

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References

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27.1 Introduction The ever-increasing pollution and its serious impact on the environment have motivated the scientific community to develop new technologies combating these challenges in

Advances in Oil-Water Separation DOI: https://doi.org/10.1016/B978-0-323-89978-9.00026-4

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our everyday life. A huge quantity of a mixture of oil and wastewater stands as a major threat that primarily pollutes groundwater affecting agriculture and drinking water supply. In context to the arising environmental issues relating to oily wastewater from industries such as mining, petroleum, food and textile industry, oil-water separation or demulsification has earned the attention of the researchers and industrialists (Yu, Han, & He, 2017). Found its diverse application in phytotherapy and related industries, essential oils derived from medicinal plants constitute more than 200 compounds including both volatiles and nonvolatiles. The volatile fraction consists of mono- and sesquiterpenes, several oxygenated derivatives, alcohols, aliphatic aldehydes, and esters. The nonvolatile fraction accounts for 1%
10% (w/w) of the extracted essential oil comprising carotenoids, fatty acids, flavonoids and waxes (Hussain, Anwar, Hussain Sherazi, & Przybylski, 2008). The yield of essential oils is likely to be below 1% and the composition of it after extraction largely depends on the chosen protocol of extraction. Advanced techniques in oil extraction (such as supercritical fluid extraction, ultrasound or microwave-assisted extraction) present some leading edge in terms of increased oil extraction rate, less extraction time and improved purity of oil when compared to conventional oil extraction methods (like solvent extraction and mechanical extraction). Lately, oilseeds are exploited as a raw material in alternative fuels and biodiesel production (Bhuiya et al., 2015). Apart from the oil content of the raw material used, oil extraction techniques (mechanical, chemical or biochemical) largely influence the quantity of oil produced and the composition of impurities (i.e. its purity) (Gnansounou & Raman, n.d.). In the petroleum industry, the process of extraction of crude oil is divided into primary, secondary, and tertiary phases. In the primary phase of oil recovery (e.g., using pumps or gravity drainage), approximately 10% of the oil is extracted. In the secondary phase, water or gas is injected into the well. This in turn displaces the oil and creates a production well. Water flooding can increase extraction efficiency by up to 40%. Finally, the tertiary phase in the extraction makes use of thermal energy or chemicals to achieve a yield value of up to 60%. Water is also introduced in the desalting tank of crude oils (Zolfaghari, Fakhru’lRazi, Abdullah, Elnashaie, & Pendashteh, 2016). This coproduction of water and crude oil by different stages of industrial processing and refining of oils has encountered some challenges. The formation of stable emulsion presents undesirable effects in the subsequent stages of the industrial process. Proper demulsification strategies are needed to be employed for the following reasons (Thompson, Taylor, & Graham, 1985): maintain the purity, reduce corrosion in production units (pipes, pumps, distillation columns etc.), increase the pumping efficiency, combat the concerns related to increased oil viscosity due to the presence of water globules, 5. ease in transportation and commercialization of crude oil production. 1. 2. 3. 4.

Lately, wastes (from industrial processing) and by-products from multiple industries are utilized as substrates for microbes to produce biodemulsifiers. This technique of biological demulsification tackles the question of environmental pollution arising from these wastes and also provides a cost-effective approach for the bulk production of demulsifiers (Sabati & Motamedi, 2018). The nature of surfactants/emulsifiers (like ionic/nonionic,

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hydrophilicity/lipophilicity, its concentration) together with physical parameters like salinity, temperature and pH determine the stability of the emulsion and its appropriate demulsification technique. Prior to the discussion of demulsification techniques, this chapter introduces the concept behind emulsification and the stability of emulsions owing to the challenges in demulsification.

27.2 Techniques in the extraction of oils The crisis for non-renewable energy sources and the increasing global energy demand make alternative fuels a matter of great importance because of its renewable and biodegradable nature (thus impacting less on our environment and climate changes). Biofuels, particularly biodiesel, proved to be promising in this regard and calls for researchers worldwide to address the challenges faced in its development and commercialization (Bhargavi, Nageswara Rao, & Renganathan, 2018). In the production of biodiesel, one encounters extraction of lipids (from various feedstocks acting as sources of oil) and subsequently the process of esterification/transesterification. Manufacturing biodiesel, which is mono-alkyl esters of long-chain fatty acids, involves triacylglycerols/triglycerides (a constituent of animal or vegetable fat) as a basic component in its production process (Durrett, Benning, & Ohlrogge, 2008). The extraction process can be mechanical, chemical, or biological, each with its own advantages and disadvantages in oil extraction.

27.2.1 Mechanical extraction of oils The primitive technique in extracting oils from oleaginous feed includes mechanical processes using presses or expellers (hydraulic or screw presses) operated by a motor (Fig. 27.1). In all the mechanical ways of oil extraction including ram press, bridge press, plank press, cage press, wedge press, scissor press, hydraulic press, ghani, or continuous screw press, oil is extracted forcefully by applying pressure slowly and gradually increasing it (Head et al., 1995). Although these mechanical techniques do not use any additives/chemicals, require cheap machinery setup, comparatively less energy, low maintenance cost and labor skills for producing high standard edible oils instantly, they fall back in terms of yield and efficiency with a significant proportion of unextracted oils in the cakes, limiting its profitability in industries (Pighinelli & Gambetta, 2012). In order to understand the mechanism underlying the mechanical extraction of oils, let us consider the ram press. Karl Bilenberg provided the design of ram press in 1985 that essentially consists of a hopper where the raw material is fed, one long pivoted lever to control the movement of a piston, and a cylindrical cage where the oilseeds are pressed. At one piston’s stroke, the forward movement allows the entry of feed from the hopper to the press cage through a small opening, while its backward movement blocks the opening and creates a pressure. This pressure causes the oil to get extracted and can be regulated with the help of an adjustable restriction cone. Finally, the extracted oil passes through the holes in the cage to get collected while the compressed feed is rejected through the gap between the cage and the restriction cone (Uziak & Loukanov, 2007). The use of ram press is largely seen in rural areas to extract oil from sunflower seeds and reported to have an efficiency of 57%
62% (Otto, 1992).

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FIGURE 27.1 Blueprint of ram press. Source: Bhargavi, G., Nageswara Rao, P., & Renganathan, S. (2018). Review on the extraction methods of crude oil from all generation biofuels in last few decades. IOP Conference Series: Materials Science and Engineering, 330, 012024. https://doi.org/10.1088/1757899x/330/1/012024.

The magnitude of compression pressure and duration of its application affects the yield of soybean oil and is reported to exhibit a linear graph between oil yield and magnitude or time of the applied force (Gikuru & Moriasi, 2007).

27.2.2 Steam and hydrodistillation Steam distillation, primarily used in the purification of organic compounds, is the most primitive technique applied in extracting essential oils from aromatic plants. The herbal material is heated by passing steam which subsequently breaks the pores to release intracellular components and essential oils. The vapor with the volatile fraction is condensed and the mixture of essential oil and water is separated. In order to increase the yield, this technique can be operated under pressure. Allowing solely the steam to interact with the feed without mixing the plant material with the boiling water is reported to cut the volume of wastewater generated in the process (Masango, 2005). Hydrodistillation can be considered as a type of steam distillation in which the essential oils are evaporated by boiling a concoction of plant material in water. Finally, the condensate is collected for isolating essential oils. However, these techniques tend to have a poor yield, decompose the majority of thermolabile organic compounds and add oxidation products in the purified extract (Rassem, Nour, & Yunus, 2016). The essential oil extracted from Rosmarinus officinalis L. by hydrodistillation yielded a volatile fraction of 0.31%

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only (Okoh, Sadimenko, & Afolayan, 2010). Hence there was a need for alternative techniques to aid the process of extraction of essential oils on a commercial scale.

27.2.3 Chemical extraction of oils Chemical extraction is often referred to as solvent extraction, majorly involving organic solvents. Sometimes it is coupled with mechanical treatments like ultrasound or microwave-assisted extractions to increase the efficiency in separating oil and fats. Solvent extraction has a higher yield value with respect to mechanical extraction and can utilize the residual cake generated from mechanical extraction as a raw material for further oil extraction (Bargale, Sosulski, & Sosulski, 2000). The major parameters of the extract that determine the choice of the extracting solvent are solubility, hydrophobicity or hydrophilicity, vapor pressure, molecular weight and acid dissociation while particle size of feed, degree of mixing and operating temperature play a vital role in the efficiency of extraction process (Sample Preparation Techniques in Analitycal Chemistry, n.d.). The first reported protocol for extracting and separating lipids takes the solvent system as a mixture of chloroform and methanol in the ratio of 1:2 (v/v) whereby lipids are isolated from the chloroform phase. The use of 1M NaCl has been found to increase the efficiency of extraction of lipids by preventing the formation of bonds between acidic lipids and denatured lipids. Simultaneously, adding 0.2M phosphoric acid and HCl reduces the time involved in lipid extraction from microalgae (Ranjith Kumar, Hanumantha Rao, & Arumugam, 2015). In a study, Calophyllum Inophyllum oil seeds are subjected to mechanical oil extraction employing screw press and solvent extraction using n-hexane. It is found that the feed with a moisture content of 15% exhibited the highest yield value of around 51% and 25% in solvent extraction and mechanical extraction respectively. Mechanical extraction proved to be more ineffective when the feed sample has a moisture content of 25% with an oil yield of less than 5% only (Jahirul et al., 2013). 27.2.3.1 Soxhlet extraction After the name of its inventor Baron Von Soxhlet, this technique is traditionally used for separating volatile components or oils from the feed material and is often regarded as a reference while comparing different extraction methods. It is a semicontinuous method where the extraction of oils and fats from the feed material is done by repeatedly mixing it with a chosen solvent (e.g., hexane or petroleum ether) under reflux. The raw material in a porous thimble is placed in the extraction chamber (fixed between the solvent flask and condenser). Solvents preferably hexane, ethanol, methanol, hexane, chloroform, 2-propanol, and toluene or their mixtures are heated to the boiling point and vaporize to pass through the sidearm. After passing the condenser, the liquid solvent is collected in the extracting chamber and covers the thimble. The chamber is designed in such a way that the solvent is drained back to the flask through the siphon beyond a certain overflow level (Fig. 27.2). This cycle is repeated till the extraction is completed and extracted

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FIGURE 27.2 Schematic diagram showing apparatus setup in Soxhlet extraction. Source: From https://commons.wikimedia.org/ wiki/File:Soxhlet_extractor.png.

compounds get accumulated in the flask (Wang & Weller, 2006). Soxhlet extraction introduces fresh solvent (i.e. extractant) to the sample material in each of its cycles thereby increasing the efficiency of extraction. Also, there is no need for filtration after the leaching step and the sample throughput can be easily improved. On the downside, it includes longer extraction time, high solvent consumption, proper disposal of extractant waste (considering environmental effects), restricted to solvent selectivity, lack of agitation, high temperature of extraction that can possibly decompose thermolabile compounds, and hazards encircling boiling solvents (Lo´ pezBasco´ n & Luque de Castro, 2019). Hexane is predominantly used in oil extraction because it is highly miscible with oils and can be recovered easily, but the Environmental Protection Agency, United States has listed n-hexane among 189 air pollution causing dangerous solvents, hence requires careful handling in industries (Mamidipally & Liu, 2004). Modern advancements in this technique reported the use of a high-pressure Soxhlet extractor (extractor placed inside an autoclave), and application of auxiliary energy (as seen in ultrasound-assisted and microwave-assisted extractions). 27.2.3.2 Supercritical fluid extraction The disadvantages associated with solvent extraction, many of which affecting the environment, have made U.S E.P.A to encourage green chemistry in preventing pollution. This has led to the development of supercritical fluid extraction that utilizes gases at their supercritical state. Because of this state, the intermediate properties of the fluid including

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diffusivity, liquid-like density and gas-like viscosity enhances the selectivity, flow rate and mass transfer in the extraction process (Berger, n.d.; Herrero, Mendiola, Cifuentes, & Iba´n˜ez, 2010). Some commonly used supercritical fluids in the extraction are CO2 (critical temperature and pressure are 31.1 C and 73 atm), propane (96.6 C and 42.5 atm), ethane (32.2 C and 48.8 atm), ethylene (9.5 C and 50.7 atm), propylene (91 C and 46.1 atm), methanol (234.4 C and 78.9 atm), nitrous oxide (36.7 C and 70.1 atm) and water (374 C and 220 atm) (Capuzzo, Maffei, & Occhipinti, 2013). CO2 possesses certain properties owing to which it has found its use predominantly in oil/lipid extraction. The list includes acceptable critical values, cheap, nonflammable, nontoxic nature, highly solubilizes nonpolar compounds, high affinity towards oxygencontaining organic compounds whereas less likeliness towards proteins, polysaccharides and other salts (Sahena et al., 2009). Supercritical CO2 is allowed to come in contact with the oleaginous material where it penetrates and solubilizes the oils in it. After the extraction, the solvent is collected and the pressure is reduced. As a consequence it changes the solubility and hence the extracted compounds leave the solvent while fresh CO2 is again circulated for further extraction. Adsorbents namely silica, celite, or synthetic resins are often adopted in supercritical fluid extraction to efficiently separate soluble lipids from the solvent. Like solvent extraction, parameters like temperature, pressure and time determine the yield and purity of the oil. Despite its advantages compared to conventional solvent extraction techniques, its limited industrial use is due to high investments associated with setup, operation and maintenance (Pighinelli & Gambetta, 2012). In extracting oils from sunflower seeds by supercritical fluid extraction, the oil yield exhibited an increase with the increase in temperature at 40 MPa whereas it decreases as the temperature rises at 20 MPa. The effect of pressure was reported to be maximum at the temperature of 70 C and minimum at 40 C (Roy, Sasaki, & Goto, 2006).

27.2.4 Ultrasound and microwave-assisted extraction Incorporation of ultrasound and microwaves in conventional extraction techniques involving solvents reported to a gain an upper hand by increasing the overall efficiency. The application of microwave makes the cells absorb energy and on dissipation, it increases the temperature of the system. As the moisture inside the cells struggles to evaporate, the extensive pressure generated stimulates swelling and rupture the cells, subsequently releasing the intracellular components (like fats, lipids, essential oils etc.) (Ekezie, Sun, & Cheng, 2017). The oil content of cottonseed extracted by Soxhlet extraction for 16 h using n-hexane is found to be 34.7% whereas the optimum time to get a yield value of 32.6% using microwave-assisted extraction is 3.5 min (Taghvaei, Jafari, Assadpoor, Nowrouzieh, & Alishah, 2014). Ultrasonic systems (both bath and probe systems) essentially consists of a transducer to generate ultrasonic waves and a cooling system connected to a temperature controller. Plant cells being sensitive to ultrasonic waves break and facilitate the release of intracellular components in the solvent by diffusion or osmosis. Ultrasonication is based on the principle of acoustic cavitation as a consequence of alternative high-pressure/low-pressure cycles created when ultrasound waves (of frequency 2 to 100 MHz) travel through the solvent. When high frequency (20 kHz) ultrasound waves

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are pulsed into the sample containing solvent medium, bubbling occurs throughout the medium. The cavitation bubbles with negative pressure implode on the exterior of the material and cause micro-jets and interparticular collision. This in turn produces stress (responsible for surface peeling, erosion, and sonoporation), macro-turbulences and micromixing (due to the shock waves generated during cavitation bubble implosion). Some of the factors that regulate the efficiency of ultrasound extraction are temperature, frequency and time of exposure of ultrasound (Dzah et al., 2020). Ultrasound-assisted Soxhlet extraction of oil from rapeseed reduced the extraction time from 4 h to 1.5 h at 800 kHz (Ibiari, El-Enin, Attia, & El-Diwani, 2010). Even though these strategies improve the time of extraction, the quantity of solvent required for extraction remains the same as that of conventional solvent extraction.

27.2.5 Optimizing the extraction process Multiple parameters namely extraction time, feed (by wt) to solvent (by vol) ratio, physicochemical properties of the raw material and solvent, extraction temperature, pH and particle size strongly influence the overall efficiency of the extraction process. Performing experimental trials by varying only one variable at a time and analyzing the data to get the optimum value of each parameter is often time-consuming and tedious involving a huge number of experimental runs to be conducted for optimization. This method of single parameter optimization is also inaccurate and tends to have a shift in the optimized value of one parameter when other parameters are varied slightly since it does not take into account the interactions between the factors/variables (Avram, Stroescu, StoicaGuzun, & Floarea, 2015). Statistics can intervene in this matter to decipher the understanding of interactions between the variables and optimize the extraction process with fewer experimental data (Masime, Ogur, Mbatia, Aluoch, & Otieno, 2017). Response surface methodology (RSM) is a widely used mathematical and statistical method to study a process involving two or more variables and reach an optimal solution. The regression equation (generally a second-order polynomial) so obtained portrays the individual effects of each parameter and their interactions on the chosen response. In most of the cases, the oil yield value is the response, but factors affecting the quality of the yield such as free fatty acid, saponification value, specific gravity, refractive index, moisture content, peroxide values, total phenolic and flavonoid content are some of the chosen output variables (Dang & Nguyen, 2019). Prior to RSM, screening of variables is important to discard the nonsignificant factors (involved in the extraction process) from the model (Fuad & Don, 2016). The central composite design (including central composite rotatable designs and faced centered composite design) and the Box-Behnken design are predominant RSM models exploited in the optimization. In a study, central composite design is used to optimize three factors namely temperature, compression force and mass of feed, ranging from 40 C
200 C, 550
750 kN and 20
100 g respectively. The factors at 5 different levels are investigated and 20 experimental runs are conducted to optimize the process of mechanical extraction of castor oil. It reported a maximum yield value of 31.01% with 45 C, 745.38 kN and 99.88 g as the optimal values of each factor (Ogunleye, Babatunde, & Agbede, 2015).

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Model validation is often done by the values of regression coefficient R2, adjusted R2 and absolute/standard error of deviation. At the optimized condition, experimental validation should be done to compare the predicted values (given by the model) with the actual values of experiments. Commonly used software encountered by the researchers for performing RSM are Design Experts, Sigma plot, the statistical package IBM SPSS, MATLAB and Minitab (Bhattacharjee, Singhal, & Tiwari, 2007; Nde & Foncha, 2020).

27.3 Emulsification/formation of emulsions Emulsions by definition consist of two immiscible liquids (e.g., oil and water). One liquid acts as the continuous phase where the globules/droplets of another liquid (having 20 $ diameter $ 0.5 μm) are dispersed as the sparse phase (Pal, 1994). They are considered as thermodynamically metastable systems but are kinetically stable and can maintain their stability for years. Emulsions are inevitably formed during crude oil production and must be treated to remove them from the dispersed medium. Added to the emulsions generated during the production process, transportation of oil through pipelines provides the necessary shear force required for the formation of emulsions (Thompson et al., 1985). Apart from the widespread use of chemical demulsification, others such as biological, thermal, membrane, electrical, microwave and ultrasonic-assisted demulsification techniques and their combinations have found their place in the petroleum sector. Emulsions can be produced by using homogenizer, mill, applying shear stress, chemical means or by temperature mediated nucleation process. The extracted crude oil often contains water, sediments and hydrocarbons like asphaltenes, waxes, resins and carboxylic acids. Some of these impurities act as a natural emulsifier that facilitates the development of a stable film surrounding the globules, further inhibiting the globules to coalesce (Biniaz, Farsi, & Rahimpour, 2016). In other words, these natural surfactants lower the interfacial tension that exists between oil and water and subsequently forms an interfacial film. Hence in the presence of emulsifying agents and adequate agitation, the film provides the mechanical durability required to form stable emulsions (Souas, Safri, & Benmounah, 2020). An emulsifier can be structured as a hydrophilic/lipophobic head attached to a hydrophobic/lipophilic tail. Its head attracts the water molecules and its tail easily interacts with oil molecules, forming the interfacial layer and acting as the stabilizing agent (Roodbari, Badiei, Soleimani, & Khaniani, 2016). The properties of an emulsifier like its degree of hydrophilicity/lipophilicity, ionic/nonionic nature and concentration greatly influence the stabilization of an emulsion. The composition of natural surfactants in the crude oil greatly influences the nature of emulsions formed. Thus the content of asphaltene, resin, acidic compounds like naphthenic acids and other emulsifiers directs the process of emulsification (Schramm, 1992). The trace elements such as nickel, iron, vanadium, nitrogen and sulfur present in the crude oil also impact the stability of emulsions by forming hydrogen bonds and polar interactions between the asphaltene components. Asphaltenes and resins facilitate to form stable emulsions due to the presence of hydrophilic functional groups in them. The stability is reported to be greater in the case of asphaltenes than resins. In fact, their dispersion state (i.e. whether molecular or colloidal), resin-to-asphaltene ratio and the

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number of polar groups present play a crucial part in the stability of emulsions. As in the case, the resin-to-asphaltene ratio beyond a certain value will lead resin molecules to eventually disturb π-π and polar interactions that exist between asphaltene monomers, and hence destabilize the emulsion (Schorling, Kessel, & Rahimian, 1999). Some oilsoluble nonionic surfactants that are functionally analogous to asphaltenes are alcohol ethoxylates, alkylphenols, and alkylolamides (Chistyakov, 2001). Industrially, nonionic surfactants like Spans (i.e. sorbitan esters) and Tweens (i.e. ethoxylated sorbitan esters) are widely used in combination or alone for emulsification. In addition to the properties of surfactants, other parameters controlling the stability of emulsions are the size of emulsions, the ratio (v/v) of oil to water, temperature, pH, trace elements and salt concentration (Schramm, 1992). Surface-active organic compounds that act as emulsifiers to stabilize the interfacial film, preventing the droplets to coalesce, contribute its stabilizing effect mainly by hydrogen bonding of N, O or S holding groups, or with Si-OH and Si-O- groups (Zolfaghari et al., 2016).

27.3.1 Types of emulsions Emulsions can be classified as oil-in-water (o/w), water-in-oil (w/o), and multiple emulsions [like water-in-oil-in-water (w/o/w) and oil-in-water-in-oil (o/w/o)] (Fig. 27.3). The maximum water content in w/o emulsions is 50%, while it is generally more than 80% in o/w emulsions. The stability mechanism of emulsions varies with the type of emulsion. o/w emulsions are observed to be stabilized by both steric and electrostatic repulsion while steric forces form the basis of stabilization in w/o emulsions (Ushikubo & Cunha, 2014). This is because w/o emulsions do not exhibit a positive conductivity test due to oil being the continuous phase is a poor conductor of electricity (Khan et al., 2011). Considering thermodynamics and kinetics, o/w emulsions possess added stability when compared to w/o emulsions, accounting for the high conductivity of the continuous medium in o/w emulsions [50]. One will notice that o/w emulsions (for e.g., a bitumenin-water emulsified fuel known as Orimulsion) are nongreasy while w/o emulsions are greasy in nature. On basis of their stability, emulsions can further be classified as stable, meostable, entrained and unstable emulsions. In stable emulsions, the viscosity remains unchanged for more the four weeks, meostable emulsions are stable for one week and entrained for less than one week. In o/w pickering emulsions, the stability is related to the FIGURE

27.3 Schematic diagram showing types of emulsions.

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size and contact angle of fine solid particles present in it. The particle size directs the equilibrium position of a particle at the oil-water interface whereas the contact angle relates the wettability of a particle by a phase in the emulsion (Yan, Kurbis, & Masliyah, 1997). In case of water drops dispersed in an oil phase, hydrophilic solids with a contact angle below 90 degrees aid in stabilizing o/w emulsions, while hydrophobic solids having a contact angle greater than 90 degrees is used in the stabilization of w/o emulsions (Binks & Lumsdon, 2000). During the production of crude oil, oily sludge waste generated can be considered as a w/o emulsion. It is stabilized by fine particles which account for 10%
12% (w/w) of oily sludge waste. Factors namely density, viscosity, temperature, water/oil content and chemical composition that contribute to the stability of the emulsions should be reviewed while choosing the protocol of sludge treatment (Hu, Li, & Zeng, 2013).

27.3.2 Properties relating to emulsions and emulsifiers 1. Rheology: Rheology is the analysis of the flow and deformation of a material when it experiences shear stress. The rheological property of emulsions is influenced by the following factors (Mikula & Munoz, 2000): a. surface phase viscosity b. indoor stage viscosity c. division of the droplet volume in the continuous part d. size and concentration of the sparse/dispersed phase e. type of emulsifying agent used f. shear rate. Shear viscosity is also an important consideration while studying emulsions and their behavior. Shear viscosity can be defined as the coefficient of proportionality between the shear stress and shear rate and is a quantitative measure of the internal fluid friction. Viscosity shoots up with the increase in the sparse phase fraction as a result of more interactions among the globules. Two prime factors controlling shear viscosity are temperature and sparse phase concentration, while others include viscosity of the continuous phase and sparse phase, shear rate, average size and size distribution of globules (Tadros, 1994). 1. Phase inversion temperature: In emulsions, the occurrence of phase inversion is often witnessed where the continuous and sparse fractions rapidly interchange their phases, for example, a transition from o/w to w/o. The choice of the sparse phase largely depends on the relative affinity of an emulsifier for each phase. Alterations in temperature can cause certain surfactants to change their affinity for one phase such as shifting their solubility from oil to water. Phase inversion temperature exists for a system (for e.g., surfactant-water-oil system) involving nonionic emulsifiers since ionic emulsifiers are not so sensitive to temperature (Izquierdo et al., 2002; Shinoda & Arai, 1964). 2. Hydrophilic-lipophilic balance: This is a dimensionless quantity and can have a value between 0 and 20. It classifies emulsifiers based on their solubility in water. Emulsifiers having a value less than 10 are suitable for w/o emulsions while hydrophilic-lipophilic balance exceeding 10 gives rise to o/w emulsions. This is “The Rule of Bancroft” which

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states that the phase having more affinity towards the emulsifiers becomes the continuous phase in the formation of emulsion (Go´mora-Figueroa, Camacho-Vela´zquez, Guadarrama-Cetina, & Guerrero-Sarabia, 2019). However, it does not reflect the influence of other parameters like temperature, salinity, concentration and properties of emulsifiers. Another quantifier called relative solubility number, applicable to nonionic emulsifiers, quantifies the combined inclination of the hydrophilic and lipophilic groups of an emulsifier to oil or aqueous phase: its higher value indicates more hydrophilicity of the emulsifier (Zolfaghari et al., 2016). 3. Steric Effect: It takes into consideration the spatial arrangement of the demulsifier molecules (i.e positional isomers) and influences their demulsifying property/efficiency (Zolfaghari et al., 2016). 4. R-ratio: This indicator is the ratio of the net molecular interaction energy (calculated per unit area of the interface) between the emulsifier molecule (adsorbed at the interface) and the oil molecule to that between the emulsifier and the aqueous phase. It is given by (Winsor, 1954): R 5 ðEðeoÞ 2 EðooÞÞ=ðEðewÞ 2 EðwwÞÞ where E (eo), E(oo), E(ew), and E(ww) refer to the net interaction energy between emulsifier and oil phase, between two oil molecules, between emulsifier and aqueous phase, and between two water molecules respectively. In the case of R , 1, Winsor type I phase behavior is observed where emulsifier in the water phase is higher than the oil phase leading to the formation of o/w emulsion. When R . 1, Winsor type II phase behavior is observed with the formation of w/o emulsion. In the former case (i.e. R , 1), the emulsifier layer is convex towards the water phase, while for R . 1 the convexity is towards the oil phase. The emulsion is least stable for R 5 1 where the interactions of emulsifier with both oil and aqueous phases are balanced leading to the formation of a bicontinuous microemulsion (Winsor type III phase behavior) (Pen˜a, Hirasaki, & Miller, 2005).

27.4 Oil-water separation or demulsification Opposite to emulsification, demulsification is the process in which emulsions are broken down into their constituent phases distinctly. It aims to minimize the stability of interfacial film/emulsion, causing the two immiscible phases to separate. Added to the importance of oil-water separation in accidental oil spills and oily wastewater management, demulsification is widely exploited in different industries as a part of their production process, for example, in petroleum industries removal of water from crude oil prior to refining is necessary. One can opt for chemical, biological or physical treatments to achieve demulsification. Briefly, chemical treatment makes use of synthetic surfactants whereas biological methods use microorganisms instead of surfactants to separate the emulsion in distinct phases. Physical demulsification includes gravitational separation, heat or electrical treatment (i.e. thermal or electro-coalescence), skimming, cycles of freezing/thawing, adjusting pH and

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membrane separation. The thermochemical approach is often seen to be practiced in industries that involves thermal treatment and the addition of demulsifiers simultaneously (Martı´nez-Palou et al., 2013). Each technique has its own advantages and challenges with a huge scope of advancements. The choice of the technique is directed by temperature, pH, salinity, the composition of emulsion (e.g., oil:water ratio, presence of salt, emulsifiers, alkali and polymer), emulsification condition and its age (Strøm-Kristiansen, Lewis, Daling, & Nordvik, 1995).

27.4.1 Chemical demulsification It employs the addition of chemicals (referred to as emulsion breakers) that are capable of neutralizing the charge on the emulsified globules. Proper demulsification by chemicals requires an adequate amount of demulsifying agents, good mixing and sufficient residence time for settling of demulsified globules (Zhang, Xu, Wang, Dong, & Li, 2004). Two approaches are established: coagulation and flocculation. In coagulation, the emulsifying property of the emulsifier is destroyed whereas flocculation targets the globules to agglomerate into bigger units that are easily separable. Both of these methods aim to amplify the coalescence of droplets. Some examples of coagulants that are frequently used as a demulsifying agent are iron, aluminum and ferric salt (Zhong, Sun, & Wang, 2003). The efficiency of a demulsifier however relies on the size distribution of droplets, occurrence and composition of solids present in the oil and oil viscosity (Mikula & Munoz, 2000). In a study, the efficiency of 37 demulsifiers (including anionic, cationic and nonionic) in demulsifying Marpol oil waste is investigated. It is reported that with the operating temperature set at 70 C for 30 h, anionic and nonionic samples showed good oil-water separation (Yau, Rudolph, Ho, Lo, & Wu, 2017). Magnetic graphene oxide can also be used as a demulsifying agent. It exhibited its effect within a short time interval and managed to achieve an efficiency of 99.98% even after recycling 6
7 times (Liu et al., 2017). Several parameters that are vital in demulsification and alters the stability of emulsions are (Fortuny et al., 2007): 1. Water or oil content in emulsion: It is one of the most important parameters that control the coalescence efficiency, affecting the stability of emulsions. A rise in the water content will narrow the separation between the globules in w/o emulsions. This in turn increases the probability of their collisions, eventually enhancing the demulsification efficiency. 2. pH: In an indirect fashion, the pH of an emulsion controls the fate of emulsion stability by regulating the properties of surfactants. The hydrophilicity of an emulsifier increases with the increase in pH, owing to which w/o emulsion is likely to be developed in acidic pH while o/w emulsion prefers basic pH to develop. Interfacial films stabilized by asphaltenes are most stable in acidic medium and are weakly stable or unstable in a basic environment, whereas it’s vice-versa is observed for the films stabilized by resins. Optimal pH for best demulsification of asphaltene (i.e. amphoteric emulsifier) stabilized emulsions is found to be 7. It is worth noting that some nonionic emulsifiers (having no charge) can act as ionic emulsifiers in acidic or basic pH. For example, in acidic pH polyethylene oxides are in cationic form, and long-chain carboxylic acids are anionics in basic pH (Mo¨bius, Miller, & Fainerman, 2001).

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3. Temperature: It affects the stability of emulsions in a number of ways. Higher temperatures decrease the viscosity of the oil, increase the collisions between droplets and broaden the difference in density between different phases. This leads to weakening the mechanical strength of the interfacial film (surrounding the droplet) and enhances the demulsification efficiency. With the rise in temperature, the relative solubility of the nonionic emulsifiers in water reduces, in contrast, it increases for anionic emulsifiers. Hence the adsorption of anionic emulsifiers at the interface of an o/w emulsion diminishes, compromising emulsion stability and easing demulsification (Hirasaki et al., 2011). 4. Salinity: It decreases the hydrophilicity of emulsifiers due to the “salting out” effect, by virtue of which the interaction between the emulsifiers and water molecules get reduced. An increase in the salinity (i.e. NaCl content) of o/w emulsion will increase the action of demulsifiers while demulsification efficiency decreases in the case of w/o emulsion (due to the reduced affinity of emulsifiers to water molecules) (Fortuny et al., 2007). Generally, the effect of salinity is found to be more in anionic emulsifiers than nonionic emulsifiers. Demulsification of o/w emulsion is easier in presence of salts with divalent cation rather than with monovalent cation (Kuo & Lee, 2009).

27.4.2 Biological demulsification This technique came into existence in the 1980s when researchers found that microorganisms can use the hydrocarbons present in the emulsion as its nutrients’ source and hence can replace chemical demulsifying agent. Two methods are adopted utilizing biodemulsifiers that is microorganisms in the demulsification process: activated sludge and biological filter. Microbial demulsifiers are preferred over chemical ones because of their nontoxic nature, cost-effectiveness, biodegradability and recycling ability. Essentially, the adsorption of biodemulsifier molecules at the oil-water interface displaces the emulsifier molecules with the loss of emulsion stability. Biodemulsifiers can be cell-bound or extracellular, that is present on the cell surface or in the culture supernatant. From industrial aspects, extracellular biodemulsifiers provide extra ease in the recovery process, but cell-bound biodemulsifiers are reported to have improved demulsifying ability (Wei, Wan-Jing, & Xiao-Guang, 2014). Rhamnolipid is a bioproduct belonging to the class of glycolipid. It is produced by various microbes (e.g., Pseudomonas aeruginosa) and has found its use as a bacterial surfactant. It is reported to achieve a performance efficiency of 90% in treating waste crude oil to remove water (Long et al., 2013). Acinetobacter calcoaceticus is studied for producing biodemulsifiers and its efficiency in breaking w/o emulsions. The extracellular components act as a demulsifying agent and reduce the surface tension to 38.6 mN/m. This facilitates the destabilization of 95% of the surfactant-mediated emulsions (Abed, Abdurahman, Yunus, Abdulbari, & Akbari, n.d.) α-amylase (produced by organisms and microorganisms such as aquatic bacteria, fungi and actinomycetes) is also established as a potent bio-demulsifier and at optimal conditions (of α-amylase concentration, salinity and temperature) it significantly accelerates the demulsification process (Jiang et al., 2018).

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Since with the growth of microbes demulsification is achieved, factors relating medium quality (like carbon source, nitrogen source, pH, salinity) and operating conditions like temperature play a key role in the rate of demulsification. Let us go through the parameters that one needs to consider in biological demulsification: 1. Cell concentration: Half-life of an emulsion is the time required for the emulsion to decay to half of its primary volume and reflects the stability of the emulsion (as a low value of half-life will indicate increased decay rate of the emulsion). A study reported a drop in half-life value of o/w emulsion with the increase in the cell concentration of an isolated Micrococcus strain, while reversely half-life increased in case w/o emulsion. The hindrance in demulsification for the case of w/o emulsion due to increased cell concentration is hypothesized to be due to the formation of a defensive layer around the droplets that prevent them to coalesce (Das, 2001). 2. Cell washing: Washing the cells postharvest with lipid-solubilizing solvents influence the demulsification process. Some commonly used solvent systems are n-pentane (removes neutral lipids), n-hexane (removes certain glycolipids), chloroform-methanolwater (removes total extractable lipids) and kerosene (a combination of n-alkanes that removes lipids). It is observed that unwashed cells improved the rate of demulsification followed by pentane, kerosene and hexane. Cells washed with chloroform-methanolwater exhibited the slowest demulsification due to the removal of the majority of lipids from the cell wall (Das, 2001; Kates, 1972). 3. Substrate: Carbon source for microbial growth is also related to the effectiveness of biological demulsification. The substrate type regulates the chemical composition on the cellular surface. As an example, microbial growth supplemented by petroleum hydrocarbon substrates (like crude oil and diesel) showed significant demulsification efficiency. On the contrary culture media supplemented by nonpetroleum substrates (like starch and glucose) act as a good source for microbial growth but fails to disturb the emulsion stability due to the changes in the composition of cellular components (that function as biodemulsifiers) (Nadarajah, Singh, & Ward, 2002). In general, biodemulsifiers are produced more in presence of hydrophobic carbon sources than hydrophilic sources. 4. Nitrogen source: Similar to a carbon source, the nitrogen source of the culture medium affects the production and composition of biodemulsifiers, hence a synergism between these two sources directs the microbial growth. Ammonium nitrate when used as a nitrogen source in addition to paraffin (a hydrophobic carbon source) for Alcaligenes sp. S-XJ-1, it reported good demulsification, whereas poor demulsifying ability is seen in the case of ammonium nitrate with sodium citrate (a hydrophilic carbon source). In the case of Alcaligenes sp. S-XJ-1, the surface tension of the media decreases more when ammonium nitrate is used instead of sodium nitrate, while the reverse is true for Brevibacilis brevis HOB1 (Juan Liu et al., 2017). 5. pH and temperature: The pH of the media is a key factor determining the microbial growth and production of biodemulsifiers. A pH of 7 (or close to 7) is recommended in the majority of the cases for producing biodemulsifiers, for example, producing biodemulsifier from Paenibacillus alvei ARN63. The growth and demulsifying ability of Alcaligenes sp. S-XJ-1 is observed to prefer an alkaline environment. Generally, the

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highest production of biodemulsifiers and efficient demulsification is established to be around 35 C
40 C. In a study utilizing Bacillus mojavensis XH1 for producing biodemulsifier, it is found that demulsification efficiency is considerable up to 75 C and upon increasing the temperature from 75 C to 120 C the efficiency deteriorated greatly (Li et al., 2012, 1992). 6. Culture age: Hydrophobic nature of the cell surface expresses with culture age. Increasing hydrophobicity improves the demulsification efficiency of o/w emulsions. Contrarily, the hydrophilicity of young cultures facilitates the demulsification of w/o emulsions (Gray, Stewart, Cairns, & Kosaric, 1984). Similar to chemical demulsification, other parameters including agitation speed, residence time and phase volume ratio play a key role in the process of biological demulsification.

27.4.3 Thermal demulsification As the name suggests, it involves the application of heat energy to achieve demulsification. At higher temperatures, the rate of collision of globules in the emulsion increases. The stability of the interfacial film gets compromised which facilitates the phenomenon of demulsification. In addition, heating recuses the viscosity and promotes the lighter compounds to escape thereby directing gravitational separation (Sztukowski, 2005). Thermal demulsification is often used synergistically with other treatments such as chemical demulsification. This significantly reduces the time required for demulsification to complete with increased performance efficiency. In a wax-stabilized water-in-oil emulsion, the influence of temperature on demulsification is studied. It exhibited an increase in the rate of coalescence with the application of thermal energy. This temperature-mediated increase is the result of fusing, melting and varnishing of the wax particles thereupon allowing the droplets to come closer and combine, eventually leading to the separation of phases (Binks & Rocher, 2009).

27.4.4 Microwave demulsification Wolf in 1986 first introduced the use of microwaves to achieve demulsification. In comparison to the conventional way of heating like hot plate heating, microwave heating has gained its popularity as it consumes less energy without compromising the separation efficiency (Evdokimov & Losev, 2014). Two parameters that need to be optimized in this technique are microwave power and duration of exposure. Irradiation of microwaves in w/o emulsions will initiate molecular rotation and ionic conduction of the sparse phase, by virtue of which internal heating occurs. This in turn reduces the viscosity of the oil phase and thinning of the interfacial films. The thermal effect is responsible for the demulsification by microwaves. A comparative study was performed to establish the efficiency (in terms of separation rate) of microwave and bath heating in demulsifying o/w emulsion. Salt content and the presence of chemical emulsifiers are considered while determining the rate of separation of oil and water. The extent of demulsification is reported to be more in microwave

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heating. As the microwave power and salt concentration are increased, it exhibited improved demulsification of o/w emulsions (Martı´nez-Palou et al., 2013). A similar study compared demulsification by microwave and hot-plate heating and documented that microwave-assisted breakdown of w/o emulsions is more efficient in terms of time and energy. The possible reason, as stated, can be the heating pattern by microwaves that volumetrically heat the material on basis of its dielectric property (Abed et al., n.d.).

27.4.5 Electrical demulsification It is an energy-efficient technique compared to other demulsification approaches like thermal or centrifugal demulsification. Upon application of an electric field, the droplets in emulsions deform and generate an attractive force between them. This forms the principle behind electrical demulsification. Hence electrical demulsification can be considered as a three-step process: initially, the droplets approach towards each other, followed by thinning of interfacial films and finally film disruption for the droplets to coalesce. Some established mechanisms to decipher electrical demulsification are chain formation of droplets, development of intermolecular bonds, dipole-dipole coalescence, electrophoresis, dielectrophoresis, random collisions and electrorefining (Eow, Ghadiri, Sharif, & Williams, 2001). In w/o emulsions, exposure to an electric field will readily fuse water globules into a larger droplet. The deformation of the droplets (often becomes elongated) during their migration aids in rapid coalescence with each other (Abed et al., n.d.). A major downside of electrical demulsification is the formation of secondary smaller droplets during the process of coalescence. Apart from the discussed factors (like temperature, shear rate, water/oil content and residence time), the extent of loss of stability of w/o emulsions upon exposure to alternating current depends on parameters of the electric field including field strength, waveform (square, sinusoidal or triangular) and frequency (Lesaint, Glomm, Lundgaard, & Sjo¨blom, 2009; Zolfaghari et al., 2016). The optimum value of frequency for maximum demulsification is determined by the dielectric, rheological and electrical properties of continuous phase and size of droplets in the emulsion. It is reported that when the electrolyte concentration is decreased or the content of ionic emulsifiers is decreased, improved electrical demulsification is observed. Emulsions stabilized by nonionic emulsifiers do not support this technique as their stability is due to the steric effect of the adsorbed molecules and not by the electrostatic interactions (Ichikawa & Nakajima, 2004).

27.4.6 Ultrasonic demulsification In recent years, this technique has gained interest due to its ease in operation and potential to enhance the efficiency of the demulsification process. A study on ultrasonic demulsification investigated the influence of input power, ultrasound irradiation time, injected water volume and temperature on its performance efficiency for removing salt and water from crude oil. At the optimized value of 57.7 W, 100 C and 6.2 min, the desalting and dehydration efficiencies were calculated to 84% and 99.8% respectively. Using

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low-frequency ultrasonic waves in conjunction with chemical demulsifiers, the required dose of demulsifying agents in crude oil processing can be greatly reduced. Considering ultrasonic field intensity, initial water content and irradiation time as the factors controlling the rate of separation, it is reported that the concentration of demulsifiers can be halved, yet achieving complete demulsification (Khajehesamedini, Sadatshojaie, Parvasi, Rahimpour, & Naserimojarad, 2018).

27.4.7 Mechanical demulsification It lists all the methods that use mechanical forces to disintegrate the physical barrier and takes into account the difference in density between the water and oil phase to accomplish separation (Auflem, 2002). It includes separation by centrifugation and gravitational separation using gravity settling tanks. Commercial application of centrifugation for demulsifying turns out to be expensive with a small capacity for processing the feed (Boyd, Parkinson, & Sherman, 1972).

27.4.8 Membrane demulsification It is one of the most important domains of oil-water separation that is extensively researched nowadays. In membrane demulsification, the membrane acts as a sieve or aids the droplets to coalesce. In the sieving effect, the size of the globules in the emulsion and the pore size of the membrane regulates the separation process. A membrane can also allow the droplets to interact with its material and triggers the coalescence of droplets. Among the advantages, membrane demulsification does not involve the use of any chemicals, ensures homogeneity in the properties of the permeate irrespective of the feed properties, effective in separating small droplets, has high separation efficiency, costeffective and compact in nature. Despite its potential in oil-water separation, its use is restricted for certain reasons. Membrane demulsification involves polymeric membranes that foul and degrades with time. Also, it has a comparatively low separation rate while handling huge volumes of effluent and tends to be sensitive to chlorinated and polar solutions (Hong, Fane, & Burford, 2002). Hence the primary concern in membrane demulsification is to optimize the permeate flux and minimize membrane fouling. Membranes used in ultrafiltration and reverse osmosis have good rejection capability for oil, total organic carbon and total surface charge from o/w emulsions. Microfiltration membranes are used in demulsifying o/w emulsions whereas porous glass membranes are suitable w/o emulsions (Kocherginsky, Tan, & Lu, 2003; Sun, Duan, Li, & Zhou, 1998). A work on demulsification employing ultrafiltration, chemical treatment and shear force simultaneously in an anaerobic/aerobic biofilm reactor claimed that improved oilwater separation was attained with CaCl2 than any other inorganic salts. It was further observed that chemical pretreatment before initiating demulsification proved to improve the efficiency of membrane filtration (Z. Zhang et al., 2004). The rejection capability of a membrane depends on membrane material, pore size distribution, operating parameters (like cross-flow velocity and temperature) and the capillary pressure of emulsified globules in its porous structure (Lee, Aurelle, & Roques, 1984). The

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fabrication material of a membrane is responsible for its surface properties such as surface tension, surface charge and surface energy. The percentage separation efficiency of a membrane (also called oil rejection coefficient) for o/w emulsion is given by (Zolfaghari et al., 2016): % R 5 (oil content in feed-oil content in permeate)/(oil content in feed). Fouling of membranes causes the pores to plug due to the accumulation of solid components in the feed. Fouling alters the wettability of a membrane and makes it more hydrophobic (i.e. oil-wet). One can get rid of reversible fouling by backflushing/backwashing the membrane, but cleaning techniques fail for irreversible fouling (caused by pore adsorption). Backwashing for membrane regeneration/cleaning is often done by hot water, alkaline wash or alkaline wash followed by an acidic wash. Care should be taken as extreme cleaning techniques can modify the porosity, pore size and surface area of a membrane (J. Liu et al., 2017). In order to synthesize antifouling membranes, one can opt for hydrophilization, zwitterionic polymer coating, photocatalytic decomposition, and electrically enhanced antifouling techniques. Some examples of materials used in the fabrication of microfiltration membranes are ceramic coated with hydrophilic nano- TiO2, hydrophilic NaA zeolite on the porous ceramic tube and ZrO2 membrane on asymmetric Al2O3 support. For ultrafiltration membranes, the materials reported are polysulfone, ceramic-supported polymer composite, and hydrophilic cellulose hollow fiber (Zolfaghari et al., 2016).

27.4.9 Pervaporation The technique of fractional distillation to purify and separate essential oils is energetically expensive. Moreover, distillation tends to degrade thermolabile components. Recent advancements in this domain led rise to a technique known as pervaporation for separating essential oils and terpenes. It refers to permeation and evaporation simultaneously. The operational setup of pervaporation allows the separation to accomplish at temperatures below 30 C, hence suitable for thermolabile compounds. It is a thermodynamically irreversible process and employs a membrane for separating liquid mixtures. The membrane has a dense layer that allows the passage of molecules through the sorption-diffusion mechanism, also known as solution-diffusion. The steps involved in pervaporation are: (1) diffusion of the molecules through the liquid boundary layer to the membrane surface; (2) sorption/ transport of adsorbed molecules through the membrane according to Fick’s law; (3) desorption at the permeate side into the vapor phase. There is a selectively permeable membrane (controls the sorption-diffusion selectivity) in pervaporation that separates the components of the feed. Unlike conventional filtration, it is capable of isolating miscible solutions (Figoli et al., 2006). The performance of a membrane used in pervaporation can be judged by its transmembrane flux, nature of selectivity, permeance, the extent of swelling, chemical resistance and microscopic structural properties (Cheng et al., 2017). Sorption and preferential sorption in pervaporation rely on the affinity of compounds towards membranes. Compounds having stronger interactions with the pervaporation membrane get sorbed to a greater extent. Principles of thermodynamics and intermolecular forces direct this process of preferential sorption. It restricts the compounds having lesser affinity to pass into the permeate stream (Jyoti, Keshav, & Anandkumar, 2015). Considering the thermodynamics of

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diffusion, preferential sorption eases the exit of compounds and tries to reduce the membrane swelling (caused by the sorption of molecules in the internal structure of a membrane). To evaporate the sorbed molecules, a vacuum is applied downstream to the membrane. The concentration gradient between the surface of the membrane in contact with feed and the membrane surface on the vacuum side determines the diffusion direction (Dawiec-Li´sniewska, Szumny, Podstawczyk, & Witek-Krowiak, 2018). Based on selectivity, pervaporation membranes can be hydrophilic, organophilic or targetorganophilic. Hydrophilic membranes having a strong affinity towards water are exploited for dehydration purposes that is separation of water from organics whereas organophilic membranes are designed to remove organic compounds from water. Target-organophilic membranes are used to separate a specific compound from a mixture of organic compounds (Van der Bruggen & Luis, 2015). The recent studies on hybrid membranes have gained the interest of researchers due to their capability to alter the selectivity and chemical resistance of the pervaporation membrane based on the type of carrier present in the polymer matrix (Lecaros et al., 2019). Instead of being a standalone technique, pervaporation can be conjugated with other methods in a hybrid system to achieve higher separation efficiency at lower costs. Pervaporation is often encountered in the recovery process of essential oil compounds from hydrolates, aqueous, or hydroalcoholic solutions. As an example, pervaporation using organophilic membranes is predominantly used in citrus fruit processing for separating essential oils from its juice (i.e. the hydrolate here) (Aroujalian & Raisi, 2007; Basile, Figoli, & Khayet, 2015). Contrasting to the techniques of oil-water separation discussed before in this chapter, pervaporation is costly and does not aim to address oily wastewater treatment but is exploited in industries to separate compounds/essential oils with high purity.

27.5 Conclusion The continuous urge for development in science and technology to counteract the environmental pollution arising from industrial oily wastewater or oil spills has led to innovate new strategies in oil-water separation. With the recent advancements, new solutions ponder upon a few goals. These strategies should have appreciable separation efficiency, be energy-efficient, environmentally friendly, and compact in nature. Extraction of oil from natural resources demands for suitable techniques each with its own advantages and disadvantages in oil extraction. Emulsions are inevitably formed during crude oil production and must be treated to remove them from the dispersed medium. Added to the emulsions formed during the production process, transportation of oil through pipelines provides the necessary shear force required for the formation of emulsions. Apart from the widespread use of chemical demulsification, others such as biological, thermal, membrane, electrical, microwave, and ultrasonic-assisted demulsification techniques and their combinations have found their place in the petroleum sector. Emulsions can be produced by using homogenizer, mill, applying shear stress, chemical means, or by temperature mediated nucleation process. An effective demulsification technique targets to minimize the stability of the interfacial films for separating two immiscible liquids.

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This chapter attempts to provide an overview of different oil extraction techniques, optimization using RSM, emulsification, and demulsification techniques along with a glimpse of cutting-edge ongoing researches in specific domains.

Acknowledgment The authors are thankful to TEQIP-III, Jadavpur University for providing the manpower, necessary resources, and support.

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E. Miscellaneous

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Index Note: Page numbers followed by “f” and “t” refer to figures and tables, respectively.

A Absorption, 497 advanced absorption based materials, 89
90 Accidental spills, 119
120, 354
355 handling, 119 offshore drilling, 120 road runoff, 120 routine maintenance activities, 120 storage, 119 transportation, 120 Achromobacter, 402 Acidic compounds, 519
520 Acinetobacter, 402 Acremonium, 303 Activated filtration, 450 Adsorbent materials, 238
240 natural inorganic adsorbents, 239 natural organic adsorbents, 239 synthetic adsorbents, 239
240 Adsorption, 146, 424, 497 Advanced absorption based materials, 89
90 Advanced filtration materials, 84
89. See also Sol-gel based materials ceramic based membranes, 88
89 metal-based membranes, 85
86 oil-water separation, 85f polymer-based membranes, 86
88 Advanced oxidation process, 424 Aerobic degradation, 338
339, 403
404 Aerobic methods, 496 Aerogels, 148, 499
500 Aeromicrobium, 340 Aeromonas, 320
321 Ag nanoparticles (Ag NPs), 201 Agmenellum quaduplicatum, 308 Air hazardous effect of waste oil on, 443
444 quality, 259 Alcanivorax, 380
381, 402 Alcoholysis, 451
452 Algae, 408
409 role in enzymatic degradation of petroleum hydrocarbons, 343
344

Algal bacteria consortium, 309
310 remediation, 344 Aliphatic group, 356 Alkanindiges, 402 Allescheriella, 303 Alternaria, 303 Alteromonas, 402 Amendments, 70 American Fire Boom, 256 Amino acids, 213
214 3-AminoPropylTriEthoxySilane, 185 Amoco Cadiz oil spill, 284 Amorphoteca, 298
299 Amorphotheca, 344 Amplification by polymerase chain reaction technique, 324 Anaerobic degradation, 404
405 Anaerobic MBR (An MBR), 476 Animal feedstuff, 458
459 Anthropogenic activities, 298 Antifouling method, 220 Anudases, 341 Aphanocapsa sp., 309 Aquatic animals, effect of oil spill on, 264
266 Aquatic ecosystem, oil pollution effects on, 121 Aquatic microbial communities, impact on, 103
104 Arabidopsis thaliana, 380 ARDROX-6120, 268
269 Aromatic compounds, 270
273 Aromatic group, 357 Aromatic hydrocarbons, 338
339 Arthrobacter, 320
321, 339
340, 402 A. globiformis, 381
382 Arthrospira, 343 Ascomycota, 302 Ashland oil spill, 355
356 Aspergillus, 298
299, 303, 320
321, 344 A. flavus, 320
321 A. niger, 302 A. nomius, 320
321 A. sydowii, 305
306 Asphaltenes, 101, 397, 519
520

537

538 Assembled sequence analysis and genome, 325
327 validation, 325 Atinetobacter, 320
321 Atlantic Empress oil spill, 8 Atomic layer deposition (ALD), 163 Au nano-rod (ANR), 200 Auto Boom Fire Model, 256 Autochthonous bioaugmentation, 360

B Bacilli, 320
321 Bacillus B. amyloliquefaciens, 367 B. cereus, 320
321 Backup booms, 256 Bacteria(l), 408
409 bioremediation of oil compounds by, 299
300, 301t hydrocarbon degradation, 384
385 oxygenases role in oil biodegradation, 300 role in enzymatic degradation of petroleum hydrocarbons, 339
343 Barleria prionitis, 181 Barley straw, 504 Basic Local Alignment Search Tool (BLAST), 324
325 Beauveria, 303 Beijerinckia, 320
321 Benzene, 100
101 Benzene, toluene, ethylbenzene, and xylene (BTEX), 395
397 Benzene, toluene and xylene compounds (BTX compounds), 478
479 Benzopyrene, 354 Bhagirathi-Hooghly river, spatiotemporal distribution of oil spill effect in, 21 dissolved heavy metal indices, 42
48 ecological impact through BOPA index, 26 materials and methods, 22
23 data, 22
23 study area, 22, 23f methodology, 24
26 result, 26
41 Bilge water, 470
471 Bio treated emulsion, 291 Bioaccumulation, 127
128 of hydrophobic organic compounds in fish, 128 of mercury in arctic marine food web, 128 Bioattenuation of alkyl aromatics, 339
340 Bioaugmentation, 305
306, 359
361, 379, 410
411 Bioavailability of hydrocarbon, 366 influence on microbial remediation of oil, 409 Biochemical oxygen demand (BOD), 496

Index

Biodegradable dispersants, 292 Biodegradation, 102, 267 crude oil by fresh algae, 307
308 half-life method, 427 seaweeds effect in, 308 systems, 426 Bioemulsifier-producing bacteria, 367 Biofuel, 457
458 Bioinspired membranes, 86 Biological degradation of PHs, 405
406 Biological demulsification, 524
526 Biological methods, 424
428 analysis of microbial community composition, 425 biodegradation systems, 426 mechanism and kinetics, 426
427 microbe isolation, 425 microbes for oily wastewater degradation, 425
426 oil toxicity effect on degradation, 427
428 Biological oxygen demand (BOD), 22 Biological techniques, 428 Biological treatment, 58, 61, 496 aerobic methods, 496 anaerobic methods, 496 Biological weathering, 400 Biomagnification, 127
128 of hydrophobic organic compounds in fish, 128 of mercury in arctic marine food web, 128 BioMake software, 325 Biomass carbon @SiO2@MnO2 aerogel, 160
161, 163
164 Biomimetic thin membranes, 215 Bioreactor, 363 Bioremediation, 131, 240
241, 288
289, 298
299, 338, 379 approach to eliminate oil spills, 357
363 case studies, 369
370 catastrophe, 355
357 conventional bioremediation strategies and limitations, 377
379 factors affecting biodegradation efficiency, 363
367 bioavailability of hydrocarbon, 366 nutrient availability, 364
365 oxygen limitations, 365 pH, 365
366 restriction of physical contact between microorganism and oil spills, 366
367 temperature, 365 fungal enzymes in, 304 GMOs, 381
388 novel approaches, 368
369 genetic engineering, 369 substance addition, 368
369 of oil compounds by bacteria, 299
300

Index

oil spills, 354
355 role of microorganism, 367
368 switch to biological methods-“bioremediation”, 379
381 bioaugmentation, 379 biosparging, 380 biostimulation, 379
380 oil eating microbes, 380
381 phytoremediation, 380 and techniques, 358
363 Bioremediation/biodegradation strategies for oil removal, 409
414 applications applying indigenous individual and/or microbial consortium, 410
411 of biosurfactants, 413
414 genetically engineered strains, 411
412 nutrients enrichment, 412 use of immobilized cells, 412
413 principles and or strategies for PH bioremediation, 410 Biorestoration, 359 Biosensors for oil pollutant detection, 387 Bioslurping, 363 Biosorption, 343 Biosparging, 361
362, 380 Biostimulation, 306
307, 361, 379
380, 412 Biosurfactants, 413
414 used to increase bioavailability of oil contaminants, 387
388 BioSurfDB, 327 Bioventilation process, 361 Birds, 121, 123 Booms, 141, 237, 286 BOPA index, 20
21, 47
48 ecological impacts through, 26, 47
48 Botryococcus, 343 Breakthrough pressure, 84
85 Brevibacterium, 320
321, 340 Burkholderia, 320
321, 339
340, 402 B. cepacia LB400, 387 B. cocovenenas, 310 Burning, 130

C Cadmium (Cd), 33 Calidris alba, 105 Calophyllum Inophyllum oil seeds, 515 Candida, 320
321 Carbon, 356 Carbon microbelt aerogel (CMB aerogel), 163
164 Carbon nanotubes (CNTs), 141, 196, 245 armchair configuration, 197

539

carbon nanotube-based oil-water separation, 198
204 carbon nanotube-carbon-based sorbent, 196 future perspective, 205 principles of oil-water separation by, 196
197 structure and synthesis, 197
198 zigzag configuration, 197 Cassie-Baxter’s model, 84
85, 86f Catastrophe, 355
357 CEC/Fe3O4/PFOS material, 161 Cellulose based aerogels (CBAs), 160
161 Cephalosporium, 298
299 Ceramic based membranes, 88
89 Ceriodaphnia, 176 Charadrius semipalmatus, 105 Chemical constituents of waste oil, 445
448 Chemical demulsification, 519, 523
524 Chemical dispersants, 266
267 applications, 277
278 effectiveness and adaptability, 273
276 impact, 270
273 national and international regulations for using, 276
277 principle and mechanism, 269
273 toxicity, 273 use, 267
269 Chemical extraction of oils, 515
517 Soxhlet extraction, 515
516 supercritical fluid extraction, 516
517 Chemical methods for oil spill remediation, 290 for oil/water separation chemical oxidation, 495
496 chemical precipitation, 495 dispersants and solidifiers, 495 Chemical oxygen demand (COD), 22, 57
58, 470 Chemical stabilization of oil by elastomizers, 131 characteristics of oil spills, 235
236 future perspective for oil stabilization through chemical process, 245 oil spill stabilization/remediation techniques, 236
244 Chemical treatment of waste oil, 451
456 gasification, 453 hydrotreating, 452
453 pyrolysis, 453
455 transesterification, 451
452 Chlamydomonas, 343 Chlamydomonas reinhardtii, 307
308 Chlorella, 343 C. vulgaris, 344 Chlorinated hydrocarbons, 127
128 Chocolate mousse, 106
107 Chrobacteria, 320
321

540 Chromium (Cr), 33 Chytridiomycota, 302 cis-dichloroethene (cDCE), 329
330 Citric acid (CA), 185 Cladosporium, 303 Clean up, 10
12 Cluster analysis, 327 Clusters of Orthologous Groups (COG), 325 Coagulation, 60, 424 Coagulation-flocculation, 494 Cobalt (Co), 191 Cochliobolus lutanus, 302 Consortium algal bacteria, 309
310 fungi bacteria, 306 Consumption of oil, 399 Contact angle (CA), 196, 197f Containment boom acts, 494 Contamination factor (CF), 25, 43 Continuous bioreactor, 426 Conventional bioremediation strategies and limitations, 377
379 chemical methods, 377 physical methods, 377 thermal method, 377
379 Conventional booms, 255 Conventional filtration, 450 Conventional pyrolysis of waste oil, 454 Conventional treatment methods, 59
60 coagulation, 60 floatation, 59
60 Corexit 8666, 270
273 COREXIT 9500 An, 268
269 Corexit 9500, 130, 268
269, 278 COREXIT 9527, 268
269 COREXIT EC9500A, 268
269 COREXIT-9500A, 268
269 COREXIT-9580, 268
269 Corynebacteri, 320
321 Cotton fabric (CF), 217, 504 Crude glycerol (CG), 459 Crude oil, 100, 290
291, 320, 354, 356, 380, 399
400 biodegradation by fresh algae, 307
308 extraction, 512 Crude petroleum oil, 398 Crustaceans, 122 CS-SiO2-PU sponges, 161
162 CTAB, 323
324 Cunninghamella, 303 Curtain booms, 237 Cyanobacteria, 308
309, 320
321 Cyanothece, 343 Cyclic alkanes, 404

Index

Cycloclasticus, 380
381, 402 Cyclohexane biodegradation pathway, 404 Cyclohexanol, 404

D

DEAMA. See N,N0 -diethylaminoethyl methacrylate (DEAMA) Decay ratio (Dr), 220 Deepwater Horizon spill (DWH spill), 250, 284
285, 355, 490 Degree of contamination (DC), 25, 43
44 Demulsification, 522
530 biological, 524
526 chemical, 523
524 electrical, 527 mechanical, 528 membrane, 528
529 microwave, 526
527 pervaporation, 529
530 thermal, 526 ultrasonic, 527
528 Desmodesmus, 343 Dietzia, 340, 402 Dimethyl-diethoxy silane (DMDES), 90 Dimethylformamide (DMF), 189
190 Dioctyl-sodium-sulfosuccinate (DOSS), 12, 267
269 Dioscorea oppositifolia, 181 Dispersals, 130 Dispersants, 12, 130, 241
242, 290. See also Chemical dispersants Dispersed droplets, 491 DISPERSIT SPC 1000, 278 Dissolved air flotation (DAF), 472, 493 Dissolved heavy metal indices, 42
48 Heavy metal indices analysis changes in heavy metal indices, 45 contamination factor, 43 ecological impacts through BOPA index, 47
48 enrichment factor, 42 geo accumulation index, 44 pollution load index and degree of contamination, 43
44 quantitative variation with increased oil spill, 45
47 Dissolved oil, 491 Dissolved oxygen (DO), 22 Distillation, 451 DNA diagnostic method, 385 DNA probes for oil pollutant detection, 387 Draconian Legislation, 79
80

E Ecological quality, 47
48 Economic process, 233
235

Index

Ecosystem, emulsion impact on, 292 Elastol, 131 Elastomizers, 233
235 Electrical demulsification, 527 Electrooxidation (EO), 203
204 Emulsification, 103, 253. See also Demulsification emulsification/formation of emulsions, 519
522 properties relating to emulsions and emulsifiers, 521
522 types, 520
521 Emulsified droplets, 491 Emulsifiers, 521
522 Emulsifying agents, 290
291 Emulsion breakers, 523 impact on ecosystem, 292 Endocldia muricata, 308 Energy Efficiency Design Index (EEDI), 77 Energy resources, 320 Enersperse 700, 268
269 Engyodontium, 303 Enhanced oil recovery (EOR), 175
176 Enrichment factor (EF), 24, 42 Enterobacter, 402 Enteromorpha intestenalis, 308 Environment, petroleum oil impact on, 108
109 Environmental catastrophes, 6 Environmental Protection Agency (EPA), 250 Enzymatic degradation of petroleum hydrocarbons algae role in, 343
344 bacteria role in, 339
343 fungi role in, 344
346 Enzymatic mycoremediation, 304 Enzymatic remediation, 342 Enzymes enzymatic degradation of petroleum hydrocarbons algae role in, 343
344 bacteria role in, 339
343 fungi role in, 344
346 feasibility and technical applicability of enzymes in oil clean up, 346
348 in PH degradation, 405 Essential oils, 511
512 Esterases, 341 Euphoria condylocarpa, 182 Evaporation, 102 Extracellular enzymes, 298
299 Extraction of oil, 399 Exxon Valdez oil spill, 284, 338, 355
356

F Fatty acid (FA), 445
447 Fence booms, 237

541

Fenton oxidation process, 496 FESTOP Fire Boom, 256 Filtering, 325 Filtration, 450
451, 495 Finasol-OSR-52, 268
269 Fire-resistant boom, 237, 255
256 Fish, oil pollution impact on, 104
105, 121 Fisheries, 126 Flame heights, 252 Flame spreading, tendency of, 252 Flame temperature, 250 Flavobacteria, 320
321 Flavobacterium sp., 379 Floatation, 59
60 Flocculation, 424 Flotation, 424 Flux recovery ratio (FRR), 220 Food chain, 121 Fouling, 208 as main drawback of MBR treating oily wastewater, 479
481 methods for fouling mitigation treating oily wastewater, 481
483 Free cell, 426 Free droplets, 491 Fresh algae, crude oil biodegradation by, 307
308 FTIR, 218 Fucus vesiculosus, 308 Fungal enzymes in bioremediation, 304 Fungal species, 298
299 Fungi, 408
409 bacteria consortium, 306 role in enzymatic degradation of petroleum hydrocarbons, 344
346 Fusarium, 298
299, 303, 320
321, 344 F. solani, 302

G G.H. Woods Degreaser-Formula 11470, 270
273 Gamlen Sea Clean, 270
273 Gasification, 453 GC content regions detection, 327 GenDB40, 325 Genetic engineering, 369 Genetically engineered fungi for mycoremediation, 386 Genetically engineered microorganisms (GEM), 359, 381
388 current applications of potential GEMs for oil contaminants bioremediation, 384
386 genetically engineered fungi for mycoremediation, 386 genetically modified organisms in phytoremediation, 385
386

542

Index

Genetically engineered microorganisms (GEM) (Continued) for oil contaminants bioremediation, 384
386 technical applicability in oil cleanup, 386
388 biosurfactants used to increase bioavailability of oil contaminants, 387
388 construction of hybrid pathways through genetic engineering for oil contaminants degradation, 387 DNA probes and biosensors for oil pollutant detection, 387 Genetically engineered strains (GES), 410
412 Genetically modified bacteria (GMBs), 381 Genetically modified organisms (GMOs), 382t in phytoremediation, 385
386 Genome, 325
327 comparison of genome sequences, 327 cluster analysis, 327 isolation, 323 sequence analysis, 385 Geo accumulation index, 25
26, 44 Geographical information systems (GIS), 20
21, 49 Geomyces, 303 Gigartina cristata, 308 Gloriosa superba, 181 Gnidia glauca, 181 Gordonia, 320
321, 340, 360
361 Graft polymers, 182
184 Graphene oxide (GO), 144, 203
204 Graphium, 298
299 G. cunninghamella, 344 Gravity separation, 472 Green fluorescent protein (GFP), 381 Greenhouse gases, 444 Gulf War oil spill, 9

H 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane (PFDTS), 201 1-H, 1-H, 2-H, 2H-perfluorooctyltriethoxysilane (POTS), 204 Hand-held igniter, 258 Hazardous effect of waste oil, 442
444 air, 443
444 soil, 442 water, 443 Heat transfer rate, 250 Heavy metals, 20
21 indices analysis, 24
26 CF, 25 DC, 25 EF, 24 geo accumulation index, 25
26 PLI, 25

Heavy oils, 118 Helitorches, 257 Heterocyclic group, 357 Hexadecyl-trimethylammonium-bromide (HDTMABr), 499 High-pressure washing, 131 Hot water, 131 Hybrid biological processes for oily wastewater treatment, 428
431 biological methods, 424
428 methods for oily wastewater treatment, 424 Hydro-Fire Boom, 256 Hydrocarbon bioavailability of, 366 hydrocarbon-degrading fungi, 300 pollution, 356
357 aliphatic group, 356 aromatic group, 357 heterocyclic group, 357 Hydrodistillation, 514
515 Hydrogen, 356 Hydrolysis lignin (HL), 87 Hydrophilic membranes, 529
530 Hydrophilic-lipophilic balance, 521
522 Hydrophobic organic compounds (HOCs), 128 bioaccumulation and biomagnification of, 128 Hydrophobic sponges, 159
160 Hydrophobicity, 10
11, 141 Hydrotreating, 452
453 Hydroxyl-functionalized silicate-based nanofluids, 178
179 Hytron-3, 268
269

I IBM SPSS, 519 Ignition of oil slick, 251 factors affecting, 251 requirement, 250 Ignitors, 256
258 helitorches, 257 noncommercial ignitors, 257
258 Immobilization, 412
413 Immobilized biological aerated filters (IBAFs), 61 Immobilized bioreactor, 426 Immobilized cells, 412
413 Impact analysis of oil pollution, 103
109 impact on aquatic and terrestrial microbial communities, 103
104 impact on environment, 108
109 impact on marine mammals and invertebrates, 106
107 impact on seabird population, 105
106

Index

toxic effect of oil, 105
106 impact on vegetation, 107
108 oil pollution impact on fish, 104
105 In situ bioremediation approach, 381
388 In situ burning (ISB), 240, 249
250, 288 best safety practices, 253 without containment, 254 environmental and health concerns, 258
260 factors affecting, 251
253 operation, 250
251 principles, 250
253 rate of, 251
252 techniques & current application, 253
258 ignitors, 256
258 selection of in situ burning equipment and operation, 253
256 treating agents and combustion additives, 258 Incineration, 358, 455
456 Indian Coast Guards (ICG), 276 Industrialization, 354 Industries/businesses affected by marine oil spills, 127 Innumerable computational tools, 328
329 Inorganic compounds, 492 Inorganic materials, 144 Inorganic membranes, 85
86 Inorganic oils, 492 Inorganic-based membranes, 210 Intentional oil discharges, 120 Interfacial tension (IFT), 178 International conference on marine pollution, 71
73 conventions and instruments on Regional Basis, 72
73 regulations for oil pollution control and prevention, 71
72 International laws on maritime pollution, 69
70 International Maritime Dangerous Goods Code (IMDG Code), 75 International Maritime Organization (IMO), 470
471 International Petroleum Industry Environmental Conservation Association (IPIECA), 276
277 Intertidal seagrass (Thalassiat estudinum), 108 Invert emulsion, 291 Invertebrates, impact on, 106
107 Iridaea flaccida, 308 Iron oxide nanoparticles (IONPs), 177
178

J Jukes & Cantor Model, 328

K Kapok fibers, 500
501 Kappaphycus alvarezii, 343 Kidderpore-Haldia stretch, 47
48

543

Klebsiella pneumoniae, 320
321 Kocuria, 402 Kolkata Metropolitan Area (KMA), 27 Kontax igniter, 257

L Land-based sources of marine oil pollution, 399 Landfarming, 362
363 Laplace young equation, 84
85 Lead (Pb), 33 Lecithin, 242 Lignin modified aerogel, 164
165 Lignin-Modifying enzyme (LME), 303 Lignin-peroxidase (LiP), 303 Litchi chinensis, 181 Live microbes for oil degradation algal bacteria consortium, 309
310 bacterial oxygenases role in oil biodegradation, 300, 301t bioaugmentation, 305
306 biodegradation of crude oil by fresh algae, 307
308 factor affecting in, 310
311 bioremediation fungal enzymes in, 304 of oil compounds by bacteria, 299
300 biostimulation, 306
307 cyanobacteria, 308
309 fungi bacteria consortium, 306 marine fungi, 301
302 mycoremediation, 305 mycorrhizal fungi, 303 oil-degrading fungi, 300 seaweeds effect in biodegradation, 308 soil fungi, 302
303 WRF, 303 Local texture angle (LTA), 84
85 Loose emulsions, 290
291 Lower critical solution temperature (LCST), 204

M Macondo oil, 267
268 Mammals, 122 Manganese peroxidase (MnP), 303 Mangroves, 4 MARE CLEAN 200, 278 Mariculture, 126 Marine fauna, effects on, 121
127 oil pollution effects on economy, 125
127 effects on wildlife, 122
125 impact on human health, 125 oil spills impacts

544

Index

Marine fauna, effects on (Continued) on invertebrates, 122 on vertebrates, 121
122 Marine flora, effects on, 121 Marine fungi, 301
302 Marine mammals, 123
125 oil pollution impact on, 106
107 Marine oil spills bioremediation/biodegradation strategies for oil removal, 409
414 composition of petroleum hydrocarbons, 395
398 factors influencing microbial remediation of oil, 405
409 bioavailability, 409 composition and properties of substrates, 407
408 microbial communities, 408
409 nutrients availability, 408 oxygen, 407 pH, 406 salinity and pressure, 407 temperature, 406 metabolic versatilities for oil degradation by microbes, 402
405 occurrence and distribution of oil degrading microbial communities, 401
402 oil pollution impact on marine ecosystem, 398
401 Marine pollution, 66 Marine Spill Response Corporation (MSRC), 255 Marinobacter, 380
381, 402 Maritime effects of oil spillage, 66
68 Maritime safety committee (MSC), 70 MARPOL Convention, 73
77, 78t Annex I, 73
74 measures to control operational discharge of oils, 73 shipboard oil pollution emergency plan, 73
74 Annex II, 74
75 features, 74
75 shipboard marine pollution emergency plan for noxious liquid substances, 75 Annex III, 75 features, 75 Annex IV, 76 features, 76 revised Annex IV, 76 Annex V, 76
77 legal requirements, 76 restrictions and garbage management, 76
77 Annex VI, 77 application, 77 MATLAB, 519 Mechanical containment, 494 Mechanical demulsification, 528 Mechanical extraction of oils, 513
514

Medium emulsion, 290
291 Medium oils, 118 MEGA package49, 328 Melamine sponge (Ms), 161 Membrane bioreactor (MBR), 473 application as advanced treatment technology, 473 for oily wastewater treatment, 473
479 Membrane sequencing batch reactor (MSBR), 476 Membrane(s), 84 coupled biological process, 473 demulsification, 528
529 filtration, 450 membrane-based materials, 208 separation, 60
61, 208, 424 Mercury (Hg), 33 bioaccumulation and biomagnification in arctic marine food web, 128 Meshes and membranes for oil/water separation, 142
143 functionalization, 143 mechanism of action, 142 Metabolic versatilities for oil degradation by microbes, 402
405 Metagenomics, 320, 329 application, 329
330 challenges, 330 microbes associated with oil degradation, 320
321 in oil degradation, 321
329 amplification by polymerase chain reaction technique, 324 isolation of genome, 323 modeling 16S rRNA and 18S rRNA, 324 phylogenetics, 328
329 sampling, 322
323 sequencing, 324
328, 326t Metal-based membranes, 85
86 2-Methylimidazole (2-MeIM), 187 Methyltriethoxysilane (MTES), 90, 150 Methyltrimethoxysilane (MTMS), 90 Micro nanomaterials, 92 Microbe(s) associated with oil degradation, 320
321 isolation, 425 metabolic versatilities for oil degradation by, 402
405 aerobic degradation, 403
404 anaerobic degradation, 404
405 enzymes in PH degradation, 405 for oily wastewater degradation, 425
426 Microbial biodegradation, 402 Microbial bioremediation, 401 Microbial communities, 103
104, 408
409 composition analysis, 425 Microbial degradation, 320
321, 339
340

Index

Microcoleus chthonoplastes, 308
309 Microemulsion, 267, 291 Microencapsulation, 412 Microfibrillated cellulose aerogels (MFCAs), 150 Microfiltration (MF), 60
61 Microorganism, 61, 401 consortium, 305 role in oil spills treatment, 367
368 Microsporum, 303 Microwave demulsification, 526
527 pyrolysis, 454
455 Microwave-assisted extraction, 511
512, 517
518 Mineral oil-based lubricants, 447 Minitab, 519 Mixed liquor suspended solids (MLSS), 473 Model validation, 519 Modococci, 320
321 Molecular biotechnological techniques, 410 Molluscs, 122 Monocyclic aromatic hydrocarbons, 395
397 Monod model, 427 Monoraphidium braunii, 307
308 Moraxella, 320
321 Mortieralla, 303 Mousses, 400 Moving bed membrane bioreactor (MB-MBR), 476
477 Mucor, 320
321 Multiple emulsions, 520 Multiwalled carbon nanotube (MWCNT), 185, 197 Municipal solid waste pollutants, 63 Municipal waste, 58 Municipal wastewater treatment, 58 methodology, 58
59 results, 61
63 challenges and issues faced due to oil and municipal solid waste pollutants, 63 environmental impact of wastewater containing oil, 62 future perspectives, 62
63 treatment methods of wastewater containing oil, 59
61 Myceliophthora thermophila (MtL), 384
385 Mycobactena, 320
321 Mycobacterium, 340, 402 Mycoremediation, 298
299, 305 genetically engineered fungi for, 386 Mycorrhizal fungi, 303 Mysidopsis bahia, 176

N

N,N0 -diethylaminoethyl methacrylate (DEAMA), 202 N-isopropylacrylamide (NIPAM), 178

545

Nano-developer, 177 Nano-precipitation method, 180 Nano-signal enhancers, 177 Nanobased materials, 92
93 Nanocatalysts, 191 Nanocellulose aerogel, 150 Nanocellulose based material, 93 Nanocoated membrane technology, 209
210 antifouling method, 220 current application of membranes in oily wastewater treatment, 213
215 FTIR, 218 fundamental principles behind oil/water separation behavior, 210
213 future perspective, 223
224 inorganic-based membranes, 210 mechanical strength, 219 organic-based membranes, 209
210 separation performance of membranes for oil-inwater mixture, 220
223 surface morphology, 216 wetting properties, 218
219 XPS, 217
218 Nanocoating, 185
189 Nanocomposites (NC), 182
185 Nanofibers, 11 Nanofibrillated aerogels, 93 Nanofibrous membrane (NF membrane), 189
190 Nanofiltration, 60
61 Nanofluids, 178
182 Nanomaterials, 176 Nanomembranes, 189
191 Nanopyroxene (NPNP), 178
179 Nanosensors, 177
178 Nanotechnology, 175 driven solutions, 176
191 oil pollution, 176 Naphthalene, 354 National Institute of Oceanography (NIO), 276 National Oceanic and Atmospheric Administration (NOAA), 250 Natural adsorbent, 288 Natural gas, 157
158 Natural inorganic adsorbents, 239 Natural materials, 496
500 aerogels, 499
500 particles, 497
498 sorbent materials, 497 surfactants, 499 Natural organic adsorbents, 239 Natural recovery, 132 Natural seeping of oil, 399 Natural sorbents, 141

546 Neighbor joining method, 328 Neos-AB3000, 268
269 Neosartorya, 298
299, 344 Neptunomonas, 380
381 Nickel (Ni), 33, 93 Nitrogen oxides (NOx), 77 Nitzschia linearis, 307
308 Nocardia, 320
321 Nodularia, 343 Nokomis 3-AA, 268
269 Nokomis 3-F4, 268
269 Non-wettability, 197 Noncommercial ignitors, 257
258 hand-held igniter, 258 kontax igniter, 257 Nonpersistent light oils, 118 Nonvolatile fraction, 511
512 Nostoc punctiforme, 309 Nutrient(s) availability, 364
365, 408 enrichment, 412 Nutshells, 502
503

O Obligate hydrocarbonoclastic bacteria (OHCB), 341, 402 Offshore drilling, 120 Oil and grease (O&G), 470 Oil biodegradation, bacterial oxygenases role in, 300 Oil contact angle (OCA), 209 Oil extraction, 511
512 chemical extraction of oils, 515
517 emulsification/formation of emulsions, 519
522 mechanical extraction, 513
514 oil-water separation or demulsification, 522
530 optimizing extraction process, 518
519 steam and hydrodistillation, 514
515 techniques in, 513
519 ultrasound and microwave-assisted extraction, 517
518 Oil pollution, 18
19, 176, 264
265, 298
299 causes of, 119
120 anthropogenic activities, 119
120 natural cause, 119 1954
62 Convention and amendments, 70
71 1969 and 1971 amendments, 70
71 origin and establishment, 70 harmful effects, 120
127 impact on marine ecosystem, 398
401 oil contaminants in marine ecosystems, 399
400 oil pollution sources in marine and coastal environment, 399 toxicity and hazardous consequences, 400
401

Index

international conference on marine pollution, 71
73 international laws on maritime pollution, 69
70 maritime effects of oil spillage, 66
68 MARPOL Convention, 73
77 need for controlling, 266 remedies to cope up with, 128
132 bioremediation, 131 chemical treatment, 130
131 natural recovery, 132 physical methods, 130 of seawater, 490 significance of oil pollution control management, 68 worldwide regulations on oil pollution control, 66 Oil Pollution Act, 77
80 international organizations, 80t origin, 77
79 progress, 79
80 Oil sorbents based on methacrylate polymers, 148 based on miscellaneous polymers, 148 Oil spill(s), 3, 18, 99
100, 159
160, 195
196, 283
284, 354
355, 375
376. See also Marine oil spills accidental spills during, 354
355 approach to eliminate, 357
363 bioremediation and techniques, 358
363 case studies, 6
9 changes in parameter effecting, 41 characteristics, 235
236 chemical, 236 physical, 236 countries on, 19
20 disasters, 5 effect on aquatic and human life, 266t future predictions, 12
13 hazardous effect of oil spill and emission, 265
267 history, 356t hydrocarbon pollution, 356
357 incidents, 5
6, 7t recovery and clean up, 10
12 remediation, 266
267 sources and fate, 101
103 stabilization/remediation techniques, 236
244 timing and duration, 4 treating methods, 286
290 bioremediation, 288
289 chemical methods, 290 physical remediation methods, 286
288 in situ burning, 288 Oil spillage, 5, 120 Oil stabilization by chemical based elastomizers, 241
244 dispersants, 241
242 solidifiers, 242

Index

stabilization by low cost chemical stabilizers/ surfactants, 242
244 Oil-in-water emulsion (O/W emulsion), 195
196, 492
493, 520 Oil-in-water-in-oil emulsion (o/w/o emulsion), 520 Oil-water transition zone (OWTZ), 401
402 Oil/water separation, 160, 490
491, 522
530 composition of oil/water mixtures, 491
493 chemical composition, 492 physical properties of oily wastewater, 492
493 major processes of, 493
496 biological treatment, 496 chemical methods, 495
496 physical-mechanical methods, 493
495 materials, 84 advanced absorption based materials, 89
90 advanced filtration materials, 84
89 sol-gel based materials, 90
93 materials used for, 142
145, 143t natural materials, 496
500 polymer-based adsorbents for, 145
148 promising natural materials for, 500
505 barley straw, 504 cotton fiber, 504 Kapok fibers, 500
501 nutshells, 502
503 rice husk/straw, 501
502 sugarcane bagasse, 505 vegetable residue wastes, 502 wood sheets, 503
504 sources of oil/water mixtures, 491 Oil(s), 118
119 blooms, 130 containment methods, 255
256 conventional booms, 255 fire-resistant booms, 255
256 contaminants in marine ecosystems, 399
400 contamination, 157 degradation metagenomics in, 321
329 microbes associated with, 320
321 eating microbes, 380
381 emulsions, 400 genetic engineering for oil contaminants degradation, 387 oil-degrading fungi, 300 and petroleum sources in wastewater streams, 58
59 pollutants, 157
158, 176 seep, 119 selective meshes, 142 slick, 18, 269
270 residue characteristics, 252

547

stains, 158 toxicity effect on degradation, 427
428 transportation, 398 trap, 100 in water emulsion, 291 weathering process, 101 Oilfield emulsions, 290
291 Oily wastewater, 423
424 current application of membranes in Oily wastewater treatment, 213
215 biomimetic thin membranes, 215 zwitterionic membranes, 213
214 environmental impact, 471
472 existing oily wastewater treatment technologies, 472
483 fouling as main drawback of MBR treating oily wastewater, 479
481 membrane bioreactor application as advanced treatment technology, 473 membrane bioreactor for oily wastewater treatment, 473
479 methods for fouling mitigation treating oily wastewater, 481
483 origin and global trend, 470
471 Olefins, 100
101 Oleiphilus, 380
381, 402 Oleispira, 402 Oleophilic skimmers, 238, 286
287 Operation Desert Storm, 9 Organic materials, 145 Organic pollutants, 298
299, 492 Organic solvents, 342 Organic-based membranes, 209
210 Organizations, 66 Original oil in place (OOIP), 182 Orimulsion, 520
521 Oscillatoria, 308, 343 O. salina, 309 Oxidation, 102 Oxygen, 407 demand of waste water, 492 limitations, 365 Oxygenases, 300

P Paecilomyces, 298
299, 303, 344 PAM sodium montmorillonite nanocomposite (PAAmg-St/MMT), 182
184 Pandoraea, 402 Paramagnetic nanoparticles, 177
178 Pars 1, 278 Pars 2, 278 Particles, 497
498

548

Index

Penicillium, 298
299, 303, 320
321, 344 P. documbens, 302 P. funiculosum, 305
306 Persian Gulf, 9 Persistent light oils, 118 Pervaporation, 529
530 Petroleum, 5, 101, 283
284, 337
338, 354, 376, 399
400 oil, 394 petroleum-degrading Achlorophyllous alga, 307
308 seep, 119 Petroleum hydrocarbon (PH), 264
265, 354, 394 algae role in enzymatic degradation of, 343
344 bacteria role in enzymatic degradation of, 339
343 composition, 100
101, 395
398, 396f compounds, 298
299 enzymes in PH degradation, 405 fungi role in enzymatic degradation of, 344
346 principles and or strategies for PH bioremediation, 410 Phanerochaete chrysosporium, 303 Phase inversion temperature, 521 Phlebia, 303 Phormidium, 343 P. coriurn, 308
309 Phosphatidylcholine, 499 Phosphatidylinositol (PI), 499 PHRAP assembly tool, 325 Phycoremediation, 298
299, 343 Phylo F3 software, 328
329 Phylogenetics, 328
329 trees establishment, 328 PhyloPythia software, 328
329 Physical remediation methods, 286
288 Physical smothering, 107 Physical stabilization process, 237
238 booms, 237 curtain booms, 237 fence booms, 237 fire-resistant boom, 237 oleophilic skimmers, 238 skimmers, 238 suction skimmers, 238 wier skimmers, 238 Physical treatment of waste oil, 448
451 distillation, 451 filtration, 450
451 solvent extraction, 448
450 Physical-mechanical method for oil/water separation, 493
495 coagulation-flocculation, 494 dissolved air floatation, 493

filtration, 495 mechanical containment, 494 sedimentation, 493 sorption, 494 thermal and electrical treatment, 494
495 Physicochemical methods, 310
311, 424 Phytodegradation, 362 Phytoextraction, 362 Phytol, 499 Phytoremediation, 362, 380 genetically modified organisms in, 385
386 Phytostabilization, 362 Phytostimulation, 362 Phytotransformation, 362 Phytovolatilization, 362 Pickering emulsions, 498 Pinnipeds, 107 Plasma-enhanced CVD (PECVD), 198 Plasmids, 384 Plastic-based adsorbents, 146 Plasticizers, 456
457 Platanus orientalis, 181 Platinum (Pt), 191 Plectonema terebans, 309 Plumbago zeylanica, 181 Polar bear, 125 Pollution, 116
117 along with sources, impact, and solutions, 117t Pollution load index (PLI), 25, 43
44 Poly(ethylene terephthalate), 209
210 Poly(N,N-diethylaminoethylmethacrylate) (PDEAEMA), 202 Poly(N-isopropylacrylamide-co-acrylamide) (pNIPAm-co-AAm), 200 Poly(N-isopropylacrylamide-co-N-methylolacrylamide) (PNIPAm-co-NMA), 190
191 Poly(N-isopropylacrylamide) (PNIPAAm), 204 Poly(tetrafluoroethylene) (PTFE), 149 Poly(vinyl alcohol) (PVA), 189 Poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(1,4-benzo{2,10 ,3}-thiadiazole)] (PFBT), 180 Polyacrylamide (PAM), 179
180 Polyacrylic acid (PAA), 201 Polyacrylonitrile (PAN), 189
190, 209
210, 450 Polyamide (PA), 219 Polycarbonate, 209
210 Polychlorinated Biphenyls (PCB), 386 Polycyclic aromatic hydrocarbon (PAH), 101, 122, 299
300, 320
321, 356, 376, 395
397, 442 Polydimethylsiloxane (PDMS), 161
162, 199 Polydivinylbenzene (PDVB), 149
150, 204 Polydopamine (PD), 145, 199
200 Polyethersulfone (PES), 216

Index

Polyethersulphone (PES), 450 Polyethylene based oil sorbents, 146
148 Polyethylene glycol (PEG 6000), 185 Polyethylene terephthalate (PET), 146 Polyethyleneimine (PEI), 199
200 Polyglycerol polyricinoleate, 242 Polymer, 459 Polymer nanoparticles (PolyNPs), 180 Polymer-based adsorbents for oil/water separation, 145
148 aerogels, 148 oil sorbents based on methacrylate polymers, 148 miscellaneous polymers, 148 plastic-based adsorbents, 146 polyethylene and polypropylene based oil sorbents, 146
148 polystyrene oil sorbents, 146 polyurethane oil sorbents, 146 Polymer-based membranes, 86
88 Polymerase chain reaction technique (PCR), 324 amplification by, 324 Polymethyl methacrylate (PMMA), 87 Polynuclear aromatic hydrocarbons, 354 Polypropylene (PP), 141 based oil sorbents, 146
148 Polystyrene (PS), 146, 200 oil sorbents, 146 Polysulfone (PSF), 219 Polyurethane (PU), 199 oil sorbents, 146 PU@Fe3O4@PS sponge, 169
170 Polyurethane foam (PUF), 159
160 Polyvinylidene fluoride (PVDF), 86
87, 209
210, 450 Polyvinylpyrrolidone (PVP), 178 Porous materials, 160. See also Adsorbent materials materials and characterization, 160
163 Portieria hornemannii, 308 Powdered activated carbon particles (PAC), 476 Pressure, 407 Protease, 341 Prototheca zopfii, 307
308 Protozoa, 408
409 Pseudomonas, 320
321, 402 P. aeruginosa, 320
321, 524 P. paucimobilus, 381
382 P. pseudoalcaligenes KF707, 387 P. putida, 383
384, 411
412 PyroBoom, 256 Pyrolysis, 453
455 conventional pyrolysis of waste oil, 454 incineration, 455
456 microwave pyrolysis, 454
455

549

Q Quantitative variation with increased oil spill, 45
47

R R-ratio, 522 Ram press, 513, 514f Recovery, 176 Recycling methods of waste oil, 448
456 chemical treatment of waste oil, 451
456 physical treatment of waste oil, 448
451 products, 456
460 animal feedstuff, 458
459 biofuel, 457
458 converting waste lubricating oil into useable oil, 459
460 plasticizers, 456
457 polymer, 459 Reduced graphene oxide (RGO), 187 RefSeq, 325
327 Registration, Evaluation, Authorization and Restriction of Chemicals and Toxic Substances Control Act of 1976, 276
277 Remediation, 176 Remote sensing, 20
21, 177 Resin, 519
520 “Response actions”, 158 Response surface methodology (RSM), 518 Reverse osmosis (RO), 60
61 Rhamnolipid, 524 Rheology, 521 Rhizodegradation, 362 Rhizofiltration, 362 Rhizomucor variabilis, 320
321 Rhizophoram angle, 108 Rhizopus, 303 Rhoder, 343 Rhoder Erythropolis, 343 Rhoder Ruber, 343 Rhodium (Rh), 191 Rhodococcus, 339
340, 360
361, 402 R. pyridinivorans F5, 425 Rhodotorula, 320
321 Rice husk/straw, 501
502 Rotating biological contractor (RBC), 476 “Rule of Bancroft”, 521
522 Ruthenium (Ru), 191

S 16S rRNA modeling, 324 18S rRNA modeling, 324 Saccharomyces cerevisiae, 384
385 Salicornia fragilis, 108

550 Saline produced water, 470
471 Salinity, 407 Salix arctica, 108 Sampling, 322
323 Saprophytic fungi, 298
299 Scenedesmus, 343 S. obliquus, 307
308, 344 Sea birds, 5 Sea turtles, 124 Sea-based sources of marine oil pollution, 399 Sea-Green-805, 268
269 Seabird population, impact on, 105
106 SeaCurtain FireGard, 256 Seals, 124
125 Seaweeds effect in biodegradation, 308 Sedimentation, 472, 493 Sensitivity analysis (SA), 60
61 Separation efficiency, 89 performance of membranes for oil-in-water mixture, 220
223 Sequence assembly, 325 Sequencing techniques, 324
328, 326t analysis of assembled sequence and genome, 325
327 alignment, 325 BioSurfDB, 327 RefSeq, 325
327 comparison of genome sequences, 327 GC content regions detection, 327 phylogenetic trees establishment, 328 submission of database, 328 trimming or filtering, 325 Sequential batch reactor (SBR), 476 Shear viscosity, 521
522 Sheen, 18, 375
376 Shell VDC, 268
269 Ship Energy Efficiency Management Plan (SEEMP), 77 Shipboard marine pollution emergency plan for noxious liquid substances, 75 Shipboard oil pollution emergency plan, 73
74 Silica (SiO2), 179
180 Silica nanofiber/nanobead (SNB), 189 Single walled CNT (SWCNT), 197 Sinking oils, 118
119 Skimmers, 130, 238, 286
287 Slickgone EW, 268
269 Slickgone LTSW, 268
269 Slickgone-NS, 268
269 Sodium acetate trihydrate (NaAc), 178 Sodium dodecyl sulfate (SDS), 323
324

Index

Sodium p-styrenesulfonate (SSS), 178 Soil fungi, 302
303 hazardous effect of waste oil on, 442 Sol-gel based materials, 90
93 micro nanomaterials, 92 nanobased materials, 92
93 nanocellulose based material, 93 template based materials, 91 Solid stabilized emulsion, 291 Solidifiers, 242 Solvent extraction, 448
450 Sonication, 482 Sorbents, 10
11, 130, 288 materials, 497 Sorption, 158
159, 494, 497 Soxhlet extraction, 515
516, 516f Spatiotemporal analysis of dissolved heavy metal parameter, 33
40 in water quality and heavy metal concentration, 24 of water quality parameter, 26
33 SPC-1000, 268
269 Spillage of oil, 375
376 Spirulina, 343 Sponge, 160
161 Sporobolomyces, 298
299, 320
321 Stabilization, 233
235 by low cost chemical stabilizers/surfactants, 242
244 Stabilizers, 267
268 Stachybotrys, 303 Staphylococcus, 402 Starch (St), 182
184 Steam distillation, 514
515 Stenotrophomonas maltophilia, 320
321, 360
361 S. maltophilia-SR1, 425 Steric effect, 522 Stock Holme Declaration on Human Environment, 69 Streptobacillus, 402 Streptococcus, 402 Streptomyces, 320
321 S. platensis, 309 Substance addition, 368
369 Suction skimmers, 238 Sugarcane bagasse, 505 Sugee 2, 270
273 Sulfur oxides (SOx), 77 Super wetting materials, 210
211 Supercritical CO2, 517 Supercritical fluid extraction, 511
512, 516
517 Superhydrophilic-superoleophobic membrane, 212 Superhydrophobic capacity, 159
160

Index

551

Superhydrophobic polymeric adsorbents, 148
151 materials used for oil/water separation, 142
145 polymer-based adsorbents for oil/water separation, 145
148 Superhydrophobic-superoleophilic membrane, 211
212 Superhydrophobicity, 196, 497 Superhydrophobic
superoleophobic membrane, 86 Superoleophilicity, 161, 196 Surface-active organic compounds, 519
520 Surfactant-stabilized oil-in-water emulsions (SSEs), 189 Surfactants, 269
270, 499 Suspended solids, 492
493 Swirling Flask Test (SFT), 273
276 SWOT analysis, 62t Synechococcus sp., 309 Synthetic adsorbents, 239
240, 288

Tourism, 126 Toxic Substances Control Act (TSCA), 386
387 Toxicity and hazardous consequences, 400
401 Toxins in marine food chain, 127
128 Trace elements, 519
520 Transesterification, 451
452, 458 Transportation of oil, 399 Treating agents, 283
284 Tricarboxylic acid (TCA), 304 Trichloroethylene (TCE), 382
383 Trichoderma, 303 T. asperellum, 320
321 Triethoxy silane, 178
179 Trimming, 325 Tropicibacter naphthalenivorans, 380
381 Twisted carbon fibers aerogel (TCF aerogel), 163
164 Two-dimensional materials (2D materials), 89, 211
212

T

U

Talaromyces, 298
299, 344 Target-organophilic membranes, 529
530 Temperature, 299
300, 406 affecting biodegradation efficiency, 365 Temperature sensitive iron oxide (TSIO), 178 Template based materials, 91 TERGO-R40, 268
269 Terrestrial microbial communities, impact on, 103
104 Terrestrial oil spill, 103
104 Tetraethyl orthosilicate (TEOS), 185
187 Thalassiat estudinum.. See Intertidal seagrass (Thalassiat estudinum) Thallassolituus, 402 Thermal demulsification, 526 Thermal remediation process, 240 Thermochemical oil-spill management strategies emulsifying agents, 290
291 emulsion impact on ecosystem, 292 major oil spills incidents, 284
285 Amoco Cadiz oil spill, 284 Deepwater Horizon oil spill, 284
285 Exxon Valdez oil spill, 284 oil spill treating methods, 286
290 Thermodynamically emulsions, 290
291 Thickness of oil slick, 251 Three-dimensional materials (3D materials), 211
212 Tight emulsion, 290
291 Titanium dioxide (TiO2), 144 NPs, 180
181 Titanium isopropoxide (TTIP), 185
187 Titanium oxide NPs (TiO2NPs), 182 Toluene, 100
101 “Torrey Canyon” incident, 73 Total dissolved solids (TDS), 22, 492
493 Total petroleum hydrocarbon (TPH), 476

Ultrafiltration (UF), 60
61 Ultrasonic demulsification, 527
528 Ultrasonication, 517
518 Ultrasound-assisted extraction, 511
512, 517
518 Ultrathin ZnO coating, 169
170 Ulva lactuca, 343 Underwater OCA (UOCA), 203, 213 Underwater superoleophobicity membrane, 213 United National Environment Program, 69 United States Coast Guard (USCG), 255
256 United States Mineral Management Services (USMMS), 255
256 Up flow anaerobic sludge blanket (UASB), 61 Uric acid, 361 Urospora, 308

V Vegetable residue wastes, 502 Vegetation, impact on, 107
108 Vigorous burning phase, 251 Viruses, 408
409 Volatile fraction, 511
512

W Waste coconut shell powder (WCSP), 502
503 Waste cooking oil, 445
447 Waste lubricating oil, 447
448 Waste oils, 440
441 chemical constituents of, 445
448 waste cooking oil, 445
447 waste lubricating oil, 447
448 hazardous effect of, 442
444 recycling methods of, 448
456 recycling products, 456
460

552

Index

Wastewater hydrocarbons, 492 Water, 512 emulsions, 400 oil in, 291 water in, 291 hazardous effect of waste oil on, 443 quality, 260 selective meshes, 142 water-oil emulsion formation, 490 Water contact angle (WCA), 86, 149, 160
161, 197, 209 of CBAs, 163
164 of magnetic foam, 163 Water-in-oil emulsions (W/O emulsions), 199, 492
493, 520 Water-in-oil-in-water emulsion (w/o/w emulsion), 520 Weathering, 101 Wettability, 84
85, 208, 497 White-rot fungi (WRF), 303 Wier skimmers, 238 Wood sheets, 503
504

X X-ray photoelectron spectroscopy (XPS), 217
218 Xanthomonas sp., 360
361 Xylene, 100
101

Y Yarrowia lipolytica W29, 61 Young equation, 196 Young shallow crudes, 101

Z Zeolitic imidazole framework-8 (ZIF-8), 187 Zinc (Zn), 33 Zooplanktons, 122 Zwitterionic membranes, 213
214 Zwitterionic nanogels modified polyacrylonitrile nanofibrous membranes (ZPAN membranes), 222
223 Zygomycota, 302