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Environmental Chemistry for a Sustainable World 45

K. M. Gothandam Shivendu Ranjan Nandita Dasgupta Eric Lichtfouse  Editors

Environmental Biotechnology Vol. 2

Environmental Chemistry for a Sustainable World Volume 45

Series Editors Eric Lichtfouse, Aix-Marseille University, CNRS, IRD, INRA, Coll France, CEREGE, Aix-en-Provence, France Jan Schwarzbauer, RWTH Aachen University, Aachen, Germany Didier Robert, CNRS, European Laboratory for Catalysis and Surface Sciences,  Saint-Avold, France

Other Publications by the Editors

Books Environmental Chemistry http://www.springer.com/978-3-540-22860-8 Organic Contaminants in Riverine and Groundwater Systems http://www.springer.com/978-3-540-31169-0 Sustainable Agriculture Volume 1: http://www.springer.com/978-90-481-2665-1 Volume 2: http://www.springer.com/978-94-007-0393-3 Book series Environmental Chemistry for a Sustainable World http://www.springer.com/series/11480 Sustainable Agriculture Reviews http://www.springer.com/series/8380 Journals Environmental Chemistry Letters http://www.springer.com/10311 More information about this series at http://www.springer.com/series/11480

K. M. Gothandam  •  Shivendu Ranjan Nandita Dasgupta  •  Eric Lichtfouse Editors

Environmental Biotechnology Vol. 2

Editors K. M. Gothandam School of Bio Sciences and Technology Vellore Institute of Technology Vellore, Tamil Nadu, India Nandita Dasgupta Department of Biotechnology Institute of Engineering and Technology Lucknow, Uttar Pradesh, India

Shivendu Ranjan Faculty of Engineering and the Built Environment University of Johannesburg Johannesburg, South Africa Eric Lichtfouse Aix-Marseille University, CNRS, IRD, INRA, Coll France, CEREGE Aix-en-Provence, France

ISSN 2213-7114     ISSN 2213-7122 (electronic) Environmental Chemistry for a Sustainable World ISBN 978-3-030-38195-0    ISBN 978-3-030-38196-7 (eBook) https://doi.org/10.1007/978-3-030-38196-7 © Springer Nature Switzerland AG 2020 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors, and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Switzerland AG. The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland

‘Dedicated to all real sufferers for the lack of a clean environment’ Gothandam, Shivendu, Nandita and Eric

Preface

This book is the second volume on Environmental Biotechnology, published in the series Environmental Chemistry for a Sustainable World. Environmental biotechnology is a multidisciplinary approach that integrates biotechnological science and engineering knowledge to design technologies to improve the environment, for example, biotreatment of solid, liquid and gaseous wastes, bioremediation of environmental pollution, biomonitoring and preserving the environment. The main advantages of the biotechnological approach are the technical, economical and reasonable uses of natural resources. For example, using microbes to transform pollutant into harmless compounds requires few energy and nutrients. Therefore, environmental biotechnologists identify, develop, engineer and use microbes for remediation and for other environmental applications. The chapters in this volume review recent technologies such as biochar technology, biorefinery, nanobioremediation, biosurfactants, microRNAs, biomarkers, microbial omics and microbial fuel cells. The chapters also present emerging pollutants in wastewater, techniques of remediation and the use of microbial fuel cells to generate electricity from wastewater (Fig. 1). Thanks for reading.

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Fig. 1  Biological synthesis of nanoparticles using a bottom-up approach (Singh et al., Chap. 3)

Vellore, Tamil Nadu, India Johannesburg, South Africa Lucknow, Uttar Pradesh, India Aix-en-Provence, France

K. M. Gothandam Shivendu Ranjan Nandita Dasgupta Eric Lichtfouse

Contents

1 Biochar Technology for Environmental Sustainability������������������������    1 Mahesh Ganesapillai, Aruna Singh, and Dhanaraj Sangeetha 2 Biorefinery: A Concept for Co-producing Biofuel with Value-Added Products��������������������������������������������������������������������   23 Senthil Nagappan and Ekambaram Nakkeeran 3 Nanobioremediation Technologies for Potential Application in Environmental Cleanup����������������������������������������������������������������������   53 Surbhi Sinha, Tithi Mehrotra, Ashutosh Srivastava, Arti Srivastava, and Rachana Singh 4 Biosurfactant in Food and Agricultural Application����������������������������   75 Srinivasan Nalini, Rengasamy Parthasarathi, and Dhinakarasamy Inbakanadan 5 Influence of Sustainable Agricultural Practices on Healthy Food Cultivation ������������������������������������������������������������������   95 Rajesh K. Srivastava 6 Application of Microbial Fuel Cells for Treatment of Paper and Pulp Industry Wastewater: Opportunities and Challenges����������  125 Elangovan Elakkiya and Subramaniapillai Niju 7 MicroRNAs as Biomarkers for Prediction of Environmental Health and Toxicity: A Systematic Overview ��������  151 Padmanaban S. Suresh, Abhishek Shetty, Neethu Mohan, Rie Tsutsumi, and Thejaswini Venkatesh 8 Microbial Omics: Role in Ecological Studies and Environmental Control Measures��������������������������������������������������  173 Neelam M. Nathani, Riddhi H. Rajyaguru, P. Ninian Prem Prashanth, Chandrashekar Mootapally, and Bharti P. Dave ix

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9 Wastewater: Sources of Pollutants and Its Remediation���������������������  197 Raghupatruni Lakshmi Manasa and Alka Mehta 10 Biotechnological Applications of Fungal Enzymes with Special Reference to Bioremediation ��������������������������������������������  221 Madan L. Verma, Meenu Thakur, Jatinder S. Randhawa, Deepka Sharma, Akhilesh Thakur, Harmanpreet Meehnian, and Asim K. Jana Index������������������������������������������������������������������������������������������������������������������  249

About the Editors

Dr. K. M. Gothandam  is Professor in the Department of Biotechnology, School of Bio Sciences and Technology, Vellore Institute of Technology, Vellore. He earned his Ph.D. from Bharathiar University, Coimbatore, and his Postdoctoral Fellowship from the School of Life Sciences and Biotechnology, Korea University, Seoul (2002–2007). He also served as Head of the Department of Biotechnology and Dean of the School of Bio Sciences and Technology (2016–2018). His research interest includes functional genomics, plant and microbial metabolites, cancer biology, environmental biotechnology, etc. He has published over 75 scientific research and review articles in international peer-reviewed journals and also refereed many journals of high impact, authored 5 book chapters, edited 2 books and guided 10 Ph.D. theses. At present, he is guiding six scholars and is handling two funded projects funded by DBT. He completed five projects funded by DBT, DST and CSIR. Dr.  Shivendu  Ranjan  is Director at the Centre for Technological Innovations and Industrial Research, SAIARD (Certified Institute of the Ministry of Micro, Small and Medium Enterprise, Government of India). He is also serving as a Senior Research Associate (visiting) at the Faculty of Engineering and Built Environment, University of Johannesburg, South Africa. His research interests include nanotechnology, nanomedicine, science policy and diplomacy. He is Associate Editor of Environmental Chemistry Letters and Editorial Board Member of several journals of international repute. He has received many awards and xi

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honours from national and international organizations. He is Elected Fellow of several scientific societies such as Indian Chemical Society, Linnean Society (London), Bose Science Society and Indian Engineering Teachers Association. Dr.  Nandita  Dasgupta  is Assistant Professor in the Department of Biotechnology, Institute of Engineering and Technology, Lucknow, India. She has worked on mesenchymal stem cell-derived exosomes for the treatment of uveitis and has successfully engineered microvehicles for model drug molecules. Her areas of interest include nanomaterial fabrication and its applications in medicine, food and biomedicine. She is the Associate Editor of Environmental Chemistry Letters and Elected Fellow of the Linnean Society (London) and Bose Science Society. She has received several awards and recognitions from different national and international organizations. Dr.  Eric  Lichtfouse  is Geochemist and Professor of Scientific Writing at Aix-Marseille University, France, and Visiting Professor at Xi’an Jiaotong University, China. He has discovered temporal pools of molecular substances in soils, invented carbon-13 dating and published the book Scientific Writing for Impact Factor Journals. He is Chief Editor and Founder of the journal Environmental Chemistry Letters and the book series Sustainable Agriculture Reviews and Environmental Chemistry for a Sustainable World. He has awards in analytical chemistry and scientific editing. He is World XTerra Vice-Champion.

Contributors

Bharti  P.  Dave  Department of Life Sciences, Maharaja Krishnakumarsinhji Bhavnagar University, Bhavnagar, Gujarat, India Elangovan Elakkiya  Department of Biotechnology, PSG College of Technology, Coimbatore, Tamil Nadu, India Mahesh Ganesapillai  Mass Transfer Group, Department of Chemical Engineering, School of Chemical Engineering, Vellore Institute of Technology, Vellore, Tamil Nadu, India Dhinakarasamy Inbakanadan  Centre for Ocean Research (DST-FIST Sponsored Centre), MoES  – Earth Science & Technology Cell (Marine Biotechnological Studies), Sathyabama Institute of Science and Technology, Chennai, Tamil Nadu, India Asim  K.  Jana  Department of Biotechnology, National Institute of Technology, Jalandhar, Punjab, India Raghupatruni  Lakshmi  Manasa  Department of Integrative Biology, School of Biosciences and Technology, Vellore Institute of Technology, Vellore, Tamil Nadu, India Harmanpreet  Meehnian  Department of Biotechnology, National Institute of Technology, Jalandhar, Punjab, India Tithi Mehrotra  Amity Institute of Biotechnology, Amity University, Noida, Uttar Pradesh, India Alka  Mehta  Department of Integrative Biology, School of Biosciences and Technology, Vellore Institute of Technology, Vellore, Tamil Nadu, India Neethu  Mohan  Department of Biochemistry and Molecular Biology, Central University of Kerala, Kasargod, Kerala, India Chandrashekar  Mootapally  Department of Marine Science, Krishnakumarsinhji Bhavnagar University, Bhavnagar, Gujarat, India

Maharaja xiii

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Contributors

Senthil  Nagappan  Department of Biotechnology, Sri Venkateswara College of Engineering (Autonomous), Sriperumbudur, Tamil Nadu, India Ekambaram Nakkeeran  Department of Biotechnology, Sri Venkateswara College of Engineering (Autonomous), Sriperumbudur, Tamil Nadu, India Srinivasan  Nalini  Centre for Ocean Research (DST-FIST Sponsored Centre), MoES  – Earth Science & Technology Cell (Marine Biotechnological Studies), Sathyabama Institute of Science and Technology, Chennai, Tamil Nadu, India Neelam M. Nathani  Department of Life Sciences, Maharaja Krishnakumarsinhji Bhavnagar University, Bhavnagar, Gujarat, India Subramaniapillai Niju  Department of Biotechnology, PSG College of Technology, Coimbatore, Tamil Nadu, India Rengasamy Parthasarathi  Department of Microbiology, Faculty of Agriculture, Annamalai University, Annamalai Nagar, Tamil Nadu, India P.  Ninian  Prem  Prashanth  Department of Biotechnology, National Institute of Technology (NIT), Warangal, Telangana, India Riddhi H. Rajyaguru  Department of Plant Biotechnology, Junagadh Agricultural University, Junagadh, Gujarat, India Jatinder  S.  Randhawa  Centre for Environmental Sciences and Technology, Central University of Punjab, Bathinda, Punjab, India Dhanaraj  Sangeetha  Department of Chemistry, School of Advanced Sciences, Vellore Institute of Technology, Vellore, Tamil Nadu, India Deepka Sharma  Department of Biotechnology, School of Basic Sciences, Indian Institute of Information Technology, Una, Himachal Pradesh, India Abhishek  Shetty  Department of Mangalagangothri, Karnataka, India

Biosciences,

Mangalore

University,

Aruna Singh  Mass Transfer Group, Department of Chemical Engineering, School of Chemical Engineering, Vellore Institute of Technology, Vellore, Tamil Nadu, India Rachana Singh  Amity Institute of Biotechnology, Amity University, Noida, Uttar Pradesh, India Surbhi  Sinha  Amity Institute of Biotechnology, Amity University, Noida, Uttar Pradesh, India Arti  Srivastava  Amity Institute of Marine Science and Technology, Amity University, Noida, Uttar Pradesh, India Ashutosh Srivastava  Amity Institute of Marine Science and Technology, Amity University, Noida, Uttar Pradesh, India

Contributors

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Rajesh  K.  Srivastava  Department of Biotechnology, GIT Gitam Institute of Technology and Management (GITAM) (Declared as deemed to be University), Visakhapatnam, Andhra Pradesh, India Padmanaban S. Suresh  School of Biotechnology, National Institute of Technology, Calicut, Kerala, India Akhilesh Thakur  School of Agriculture, Abhilashi University, Mandi, Himachal Pradesh, India Meenu Thakur  Department of Biotechnology, Shoolini Institute of Life Sciences and Business Management, Solan, Himachal Pradesh, India Rie Tsutsumi  Department of Nutrition and Metabolism, Institute of Biomedical Sciences, Tokushima University Graduate School, Tokushima City, Japan Thejaswini  Venkatesh  Department of Biochemistry and Molecular Biology, Central University of Kerala, Kasargod, Kerala, India Madan  L.  Verma  Centre for Chemistry and Biotechnology, Deakin University, Geelong, VIC, Australia Department of Biotechnology, School of Basic Sciences, Indian Institute of Information Technology, Una, Himachal Pradesh, India

Chapter 1

Biochar Technology for Environmental Sustainability Mahesh Ganesapillai, Aruna Singh, and Dhanaraj Sangeetha

Contents 1.1  I ntroduction 1.2  T  hermo-conversion of Biomass for Biochar Production 1.2.1  Pyrolysis 1.2.2  Slow Pyrolysis 1.2.3  Torrefaction 1.2.4  Hydrothermal Carbonization 1.2.5  Gasification 1.3  Applications of Biochar 1.3.1  Soil Amendment 1.3.2  Water Treatment 1.3.3  Carbon Sequestration 1.4  International Biochar Initiative (IBI) 1.5  Biochar Economics 1.6  Challenges and Future Work 1.7  Conclusions References

 2  4  4  4  5  5  6  6  6  7  8  9  13  15  16  17

Abstract  Biochar has been indicated as an amendment to degrade soils, improve carbon sequestration and increase agronomic productivity and future carbon trading markets. Intensive research has confirmed that biochar is part of the carbon with variable properties due to the result of production, e.g. feedstock and pyrolysis conditions and other factors like storage and transportation. Agronomic benefits from biochar additions to degrade soils have been emphasized. Soils are complex mixtures of solids, liquids, gases and living organisms, and adding biochar can change

M. Ganesapillai (*) · A. Singh Mass Transfer Group, Department of Chemical Engineering, School of Chemical Engineering, Vellore Institute of Technology, Vellore, Tamil Nadu, India D. Sangeetha (*) Department of Chemistry, School of Advanced Sciences, Vellore Institute of Technology, Vellore, Tamil Nadu, India e-mail: [email protected] © Springer Nature Switzerland AG 2020 K. M. Gothandam et al. (eds.), Environmental Biotechnology Vol. 2, Environmental Chemistry for a Sustainable World 45, https://doi.org/10.1007/978-3-030-38196-7_1

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their physical, chemical and biological properties in several different ways. The research started to show which soil and biochar properties are responsible for these changes and to use them to improve crop growth and soil amendment or for environmental management. People are hopeful about the positive agronomic effects from potential biochar usage on climate impacts, but there is a lot still to be done. Biochar can be produced at scales ranging from individual farm to large industrial level making it appropriate to a variety of socioeconomic situations. Various pyrolysis technologies are commercially available that yield different proportions of biochar and bioenergy products. The bio-oil produced may be used directly for low-­ grade heating applications and as a diesel substitute after suitable treatment. Pyrolysis processes consist of two major types, fast and slow, which refer to the speed at which the biomass is altered. Fast pyrolysis, with biomass residence times of a few seconds, generates more bio-oil and less biochar than slow pyrolysis. Slow process for which biomass residence time can range from hours to days. Also biochar produced from wood shavings is likely to be different from a biochar produced from dairy cow manure. The application of biochar on a worldwide basis has been undertaken to clearly understand ramifications in adapting the biochar technology. The challenges that are unique to regions in terms of physical, economic and chemical natures are taken up to devise future plans for this fascinating innovation in soil amendment and climate mitigation. Many organizations have accepted the responsibility to change the way carbon sequestration is realized. Keywords  Biomass · Socioeconomic · Pyrolysis · Soil amendment · Carbon sequestration

1.1  Introduction Biomass such as agricultural residues is increasingly being recognized as valuable, renewable resources. Biomass is considered as one of the most abundant, clean, cost-effective and CO2 neutral feedstock for sustainable energy production (Shuttleworth et al. 2012). In lieu of this, it has attracted research interest from economic, scientific, political as well as social perspectives (Tinaju et  al. 2011; Zabaniotou and Damartzis 2007; Arshad and Ani 2011; Chungen 2012; Ganesapillai et al. 2016). The basic constituents of biomass include cellulose, hemicellulose and lignin. The pyrolysis of cellulose is thus important in understanding the more complex behaviour of lignocellulosic biomass (Ahmad and Robert 2014). Biochar, an aromatized material, is obtained by pyrolysis of biomass under little or no oxygen. The term biochar was first introduced into modern scientific literature by Harshavardhan Bapat and Stanley E. Manahan at the 215th National Meeting of the American Chemical Society in 1998. Biochar, being a highly carbonaceous charred

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organic material, can be applied as a soil conditioner to provide agricultural and environmental gains (Sohi 2012; Das and Sarmah 2015; Jeff Schahczenski 2010; Lehmann et al. 2009). In spite of the recent interest in biochar, its ancient origin and use in the systems of the past are well documented (Herrera et al. 1992; Roosevelt 1993; Roosevelt 1999; Heckenberger et al. 1999; Heckenberger 2005). The proof for this found in deposits of charcoal dating back to 9500 years has been found in the wet tropical forest soils of Guyana, 6000 years in Amazonia and 23,000 years in Costa Rica. The carbon bound in the highly fertile Amazonian ‘terra preta’ (the Portuguese term for ‘dark earth’) soils is still stable (Neves et al. 2004). In the Amazon basin, several regions with terra preta soils of up to 2 m in depth have been identified. Analyses of these dark soils have revealed high concentrations of charcoal and organic matter, such as plant and animal remains (manure, bones and fish). In an area where soil pH is generally acidic, terra preta with its good nutrient retention capacity and neutral pH allows augmentation of crop productivity. Interestingly, these soils are known to exist only in inhabited areas suggesting that humans were responsible for its creation. Biochar can be obtained via various thermochemical decomposition processes such as slow pyrolysis, fast pyrolysis, hydrothermal carbonization, flash carbonization, torrefaction and gasification (Ganesapillai et  al. 2016; Naveed et  al. 2017). These thermochemical processes transform biomass to biochar, bio-oil and syngas. The gas product syngas and the liquid product bio-oil are regarded as alternative to fossil fuels, and extensive research is being conducted on their formation, upgradation and applications (Bohon et  al. 2011). Feedstock for biochar production can include different organic materials such as plant tissue, anthropogenic sources, raw pine chips, peanut hulls, pecan shells, forage plant biomass, pine chips, poultry litter, paper mill waste, woody debris, corn stalks, macadamia shells, citrus wood, cottonseed hulls, empty fruit bunches, rubber wood sawdust, rice husks, sewage biosolids, poultry manure, goat manure, human manure, swine manure, agro-­ industrial biomass, petroleum residues, coal, peat, lignite, polymers and other solid wastes (Natasa et al. 2016). Although carbon is the main element in biochar, it also contains hydrogen, oxygen, ash and trace amounts of nitrogen and sulphur (Undri et al. 2014). The elemental composition of biochar varies according to the biomass feed and the conversion process used for its production (Bu et  al. 2011; Chen et  al. 2008). Biochar finds multiple applications in environmental protection and energy storage due to its large specific surface area, porous structure, surface functional groups and high mineral content (Srinivasan et al. 2015). During the past few years, the application of biochar for soil conditioning and amendment has drawn extensive research attention (Sohi et al. 2009; Manyà 2012; Ahmad et al. 2014; Mohan et al. 2006). In part, this has been largely due to its potential role in carbon sequestration and, subsequently, climate change mitigation. Since char production allows concentration and retention of carbon, its application in soils induces a time delay in the release of carbon back into the atmosphere as carbon dioxide.

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1.2  Thermo-conversion of Biomass for Biochar Production Thermochemical processes such as pyrolysis, torrefaction, hydrothermal carbonization and gasification convert biomass into biochar, condensable liquid (bio-oil) and noncondensable gases (syngas), under various temperature and pressure regimes in the absence of oxygen (Table 1.1).

1.2.1  Pyrolysis Pyrolysis of biomass is an attractive option for expanding the possibilities of using less desirable biomass. It is one of the few biofuel technologies that thermally decompose organic materials into syngas, bio-oil, a solid residue containing carbon (biochar) and ash, under pressure and at operating temperatures above 300 °C. The yield of the products depends on the type of pyrolyzer used and the process parameters. The reaction condition for the pyrolysis production can be engineered to change the product ratio and properties (Bridgwater 2007). Pyrolysis can be classified as slow, intermediate and fast, based on temperature, heating rate, pressure and residence time of operation. Table 1.1 provides an overview of different pyrolysis techniques and their respective product yields.

1.2.2  Slow Pyrolysis Slow pyrolysis is a thermal conversion process characterized by long residence times and slow heating rates that produce approximately equal compositions of solid, gas and liquid products. The process functions at atmospheric pressure with heat provided by partial combustion of the feed that may be produced by external heaters or hot-gas recirculation. Fast pyrolysis is characterized by short residence times greater than 2 seconds and fast heating rates greater than 2 °C per second, at temperatures ranging between 500 and 1000 °C. Fast pyrolysis provides high yields of bio-oil of 75% together with noncondensable gases up to 13% and biochar nearly Table 1.1  Overview of pyrolysis parameters and product yields for various technologies (Poritosh and Goretty 2017) Pyrolysis Slow Intermediate Fast/flash

Reaction temperature (°C) 300–550 300–450 300–1000

Heating (°C. s−1) 0.1–0.8 3–5 10–1000

Residence time 25–35 h ~10 min < 2 sec

Biochar yield percentage 25–35 25–40 10–25

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12%. This process yields higher quantity of bio-oil compared to solid products or gases. The bio-oil produced can be used directly as a renewable fuel or an efficient energy carrier. In addition, it can also be considered as a feedstock for production of chemicals.

1.2.3  Torrefaction Torrefaction is a mild thermal pretreatment process performed under anoxic conditions with a temperature range of 200–300 °C for 0.5–2 h (Svetlana et al. 2017). During torrefaction, the fibrous structure and firmness of the feedstock are destroyed; the hydroxyl groups, oxygen and water are removed through carboxylation and dehydration. The end products from the process are torrefied hydrophobic solid biomass, condensable liquids and noncondensable gases (van der Stelt et al. 2011). In essence, the process removes low molecular weight organic compounds leading to depolymerization of long polysaccharide chains and resulting in biomass with higher energy density and grind ability. Recent advances have looked towards using torrefaction for biomass pretreatment since it improves bulk and moisture properties and eases the handling of biomass (Yang et al. 2017).

1.2.4  Hydrothermal Carbonization The process is suitable for wet biomass and biowaste that undergo a number of complex physical, molecular and chemical reactions. The complex processes are hydrolysis, dehydration, decarboxylation, aromatization and recondensation to produce biochar (Acharya et  al. 2015; Kambo and Dutta 2015; Libra et  al. 2011; Wikberg et  al. 2015). Hydrothermal carbonization is typically performed in the presence of steam at moderate temperatures between 180 and 260 °C. The reaction times range from few minutes to several hours under self-generated pressures above 1 MPa (Bach and Skreiberg 2016; Ghanim et al. 2016; Reza et al. 2016). Bashir et  al. (2017) reported changes in the yield, volatile contents, heavy metals, pH, microstructure, adsorption capacity, energy density and elemental composition based on the variation in reaction conditions. The solid fuel produced via hydrothermal carbonization, commonly referred as hydrochar, has shown higher energy density, higher calorific value and better mechanical properties than torrefied material obtained at similar temperatures and treatment durations (Yunbo et  al. 2017; Maurizio and Luca 2012).

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1.2.5  Gasification Biomass gasification is a promising technology that thermally converts lignocellulosic biomass to syngas. A sequence of thermochemical reactions leave behind vaporized tars and oils. The char residue has a typical concentration of 5–10% of the original feedstock mass. Gasification can be performed either under partial oxidation or a pyrolytic process at high temperatures around 800–1000 °C (Bridgwater 2003; McKendry 2002). Briefly, the process consists of two steps: (1) pyrolysis and (2) char conversion. A large volume of gases consisting of hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), nitrogen (N2) and methane (CH4) are produced by high temperature oxidation in the presence of pure oxygen or air. However, gasification of biomass still has challenges towards large-scale development due to low gasification efficiency, low hydrogen production and high tar content in the syngas (Fermoso et al. 2009; Yanai et al. 2007; Xiaodong et al. 2016).

1.3  Applications of Biochar 1.3.1  Soil Amendment Biochar has been deliberately applied as a soil conditioner with the intent to improve soil quality and associated environmental services. Several investigations on the agronomic value of biochar addition have indicated improved crop yields following soil conditioning (Chan et al. 2007; Yadav et al. 2016). When used as soil amendment, it can enhance soil-water retention and plant availability of water, increase plant resilience in drought conditions and promote crop productivity per unit of water added (Glaser and Birk 2012; Steiner et  al. 2008). Biochar also favours increasing soil carbon storage since it is structurally resistant to decomposition due to prevalence of aromatic structures with a ratio of few functional groups oxygen/ carbon less than 0.2 (Spokas and Reicosky 2009; Ahmad et al. 2014; Renner 2007). Besides, as Lehmann (2007) estimates, carbon abatement of 1 GtC year−1 (gigatons of carbon per year) can be attained by adding biochar to soils where it is a permanent C sink with a half-life of 100 to 1000 years in lieu of its chemical persistence. Biochar typically has large pores with low skeletal density when compared to most soils (Brewer et al. 2014). The availability of large pores in biochar increases the pore fraction and surface area that allow restoration and remediation of soils contaminated by organic and inorganic pollutants (Beesley et  al. 2013; Cabrera et al. 2014; Tang et al. 2013). Pores provide space for microbial growth and increase the quantity of air and moisture, as well as the residence time of nutrients. In addition, biochar improves soil quality by neutralizing acidic soil, enhancing its cation exchange capacity and increasing the activity of soil microorganisms. Since biochar

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has phenolic, carboxyl and hydroxyl functional groups which react with H+ ions in soil, it increases soil alkalinity. Silicates, carbonates and bicarbonates in biochar can also combine with H+ to buffer the soil pH (Jin et al. 2016). Tailored chars derived from various organic wastes are being applied on agricultural soils to facilitate cation exchange, nutrient uptake and carbon sequestration (Kookana et al. 2011; Sohi et al. 2010). Biochar-improved soils release less methane and nitrous oxide, both of which are more potent greenhouse gases than carbon dioxide. Spokas et al. (2009) observed that biochar suppressed the decomposition activity of microorganisms, resulting in reduced CO2 emissions by 2–60%, depending on the area of biochar application, reduced N2O emission by 60% and reduced CH4 oxidation. They also reported that the application of 5% (w/w) of biochar to soil enhanced the sorption of atrazine and acetochlor and reduced the dissipation rate of herbicides (Jin et al. 2016). Unlike fertilizers, it is not necessary to apply biochar annually to the fields. Since biochar is stable in soils, it could be built up to an optimum level that remains in soil indefinitely. Currently, no cap is available to what extent biochar can be used. According to Virginia Tech’s Agriculture Extension Service, adding biochar up to 20% (v/v) to soil is acceptable (Lehmann, J. and S. Joseph, eds. 2009).

1.3.2  Water Treatment It is only recently that research effort has focused on the adsorption properties of biochar which are considered to be comparable to that of activated carbon. Biochar is an attractive option for use as an adsorbent for removal of aqueous contaminants due to its wide availability of feedstock, low costs and favourable physical and chemical surface characteristics attributed to the presence of several functional groups, for example, amino, carboxyl and hydroxyl groups (Tan et al. 2015; Ahmad et al. 2014). Biochar produced from rice husks, dairy manure and municipal sludge has been effective in the removal of Pb, Cu, Zn and Cd, in addition to trivalent and hexavalent Cr from aqueous solutions. This ability to adsorb heavy metals may be due to the electrostatic interactions between metal cations and carbon negative surface charge, ionic exchange between biochar surface protons and metal cations and acidic oxygen groups like carboxylic and lactonic groups, mineral impurities such as ash and metal oxides and basic nitrogen groups present in its solid matrix (Machida et al. 2006; Xu et al. 2013; Evita et al. 2014). On the contrary, the application of biochar for water treatment is also restricted due to its limited ability to adsorb contaminants from highly concentrated aqueous solutions (Ahmad et  al. 2014; Tan et al. 2015). However, Simha et al. (2016) have demonstrated through ex situ studies that base-activated biochar could have high adsorptive capacity towards immobilizing nitrogen from wastewater.

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1.3.3  Carbon Sequestration Carbon sequestration is the long-term storage of carbon that has the immediate potential to become carbon dioxide that occurs both naturally and as a result of anthropogenic activities. The growing concern of climate change due to increased carbon dioxide in the atmosphere has drawn considerable interest on the possibility of mitigation through carbon sequestration. This may be brought about by changes in land use, forestry and geo-engineering techniques, like carbon capture and storage. Biochar, produced from biomass which is in abundance, fills this void while being a form of waste disposal and recycling. By an adaptation of the current biological carbon cycle, a substantial quantity of the biochar is returned to the soil as charcoal, while the remaining may be commercially utilized as an organic fuel. The percent that is being used as a biofuel is the off syngas and oil which can be applied as energy source in transportation and industry to reduce the amount of petroleum used, thus reducing the amount of carbon dioxide emitted (Fig. 1.2). Biochar being highly resistant to breakdown when returned to the soil forms a carbon sink (artificial reservoir that accumulates and stores some carbon dioxide for a biomass dependant time period through sequestration). According to a prominent study performed by Woolf et al. (2010), the sustainable biochar implementation could offset a maximum of 12% of anthropogenic greenhouse gas emission (GHG) on an annual basis. Over the course of 100 years, this roughly amounts to 106 metric tons of CO2 equivalents. The study assessed the globally available maximum potential biomass from agriculture and forestry for technically sustainable utilization. Woolf et al. derived a biomass availability scenario for the evaluation of maximum sustainable technical potential, as well as two additional scenarios, alpha and beta, which represent lower demands on global biomass resources. Attainment of the maximum sustainable technical potential would require substantial alteration to global biomass management but would not endanger food security, habitat or soil conservation. The alpha scenario restricts biomass availability to residues and wastes available using current technology and practices, together with a moderate amount of agroforestry and biomass cropping. All three scenarios represent fairly ambitious projects and require progressively greater levels of political intervention to promote greater adoption of sustainable land use practices and increase the quantity of uncontaminated organic wastes available for pyrolysis (Fig. 1.1). The intention of the study is to investigate whether biochar could make a substantial contribution to climate change mitigation – an aspiration that certainly will not be accomplished by half-hearted measures. Figure  1.2 (courtesy of Nature Publishing Group) shows avoided emissions attributable to sustainable biochar over 100  years, relative to the current use of biomass. Three scenarios are modelled showing different degrees of demands on global biomass resources (red, maximum sustainable technical potential; blue, medium and black, low). Sustainable biochar is represented by solid lines and biomass combustion by dashed lines. The top panel shows annual avoided emissions; the bottom panel shows cumulative avoided

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CO2

CO2

Automobiles

Electricity

Power plant Alcohol plant

Tree plantation Truck transport

Truck transport

(Source: www.google.co.in/images)

Fig. 1.1  Carbon sequestration in soil resulting in net decrease in CO2 levels

e­ missions over 100 years. The model predicts that maximum avoided emissions of 1.0–1.8 Pg CO2-Ce per year are approached by mid-century, and that, after a century, the cumulative avoided emissions are 66–130 Pg CO2-Ce. Under biochar conversion scenarios, easily mineralized carbon compounds in biomass are converted into fused carbon ring structures in biochar and are placed in soils where they persist for hundreds or thousands of years. When deployed on a global scale through the conversion of gigatons of biomass into biochar, studies have shown that biochar has the potential to mitigate global climate change by drawing down atmospheric GHG concentrations.

1.4  International Biochar Initiative (IBI) According to Messrs. Wakefield Agricultural Carbon, biochar, a soil amendment, has the potential as a valuable tool for the agricultural industry with its unique ability to help build soil, conserve water, produce renewable energy and sequester carbon. A distinct effort is diverted to study these concerns with contributions from academicians, practicing agriculturists and international organizations such as the World Bank. Subsequently, the International Biochar Initiative (IBI) was formed during the World Soil Science Congress in 2006. The founders acknowledged a common concern in promoting the research and development, deployment and commercialization of biochar technology and production.

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Fig. 1.2  Avoided emissions attributable to sustainable biochar production

The relevance of biochar technology is felt across the world as envisaged by the initiative ‘The Basics of Biochar’ by the Department of Parliamentary Services in the Parliament of Australia, on 10 September 2009. The Australian parliament claimed to distinguish biochar from charcoal on the application of its purpose; it is produced as an additive to soils mainly to improve nutrient retention and carbon storage unlike charcoal that is used as alternative energy source (Lehmann and Joseph 2009). In 2012, in the University of California, Davis established long-term biochar experimental plots through the university’s Agricultural Sustainability Institute at the Russell Ranch Sustainable Agriculture Facility located near the main campus on its 300 acres of field. The long-term effect of biochar application on the yield of tomato and corn revealed that it was substantial for tomato on a 3-year

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r­ otation. Further, Flux Farm, a non-profit independent research and education foundation registered with the State of Colorado, is engaged in the research to pursue the development of biochar as a source of renewable energy and carbon sequestration in the Intermountain West, Colorado, involving academia, private industry, non-profit and local government. ‘The biochar market is still in its early stages’ says IBI’s Thayer Tomlinson, ‘Different biochars can behave differently in soils depending on the feedstock and conditions of pyrolysis’. The 2013 IBI report provides a comprehensive overview of the state of the biochar industry as recognized by surveys and other data. One of the highlights of the report is the increase in scientific research. The number of peer-­reviewed biochar-related publications increased nearly fivefold over the last few years. IBI has undertaken biochar studies over diverse geographies that include Belize, Costa Rica, Cameroon, Chile, India, Vietnam, Mongolia and other countries. In Belize, field trials were performed on crops including corn, beans, cacao, rice and citrus, by the application of biochar produced from agro-wastes primarily from cacao farming, rice cultivation and orange juice processing. The focus in the Cameroon project is on shifting cultivation, the primary system of agriculture of the local terrain. The Cameroon biochar initiative was dedicated to exploring the possibility of bundling small projects for gaining potential carbon credits, centralized energy production, trainings and future funding. These are some of the spinning effects expected to arise from using biochar techniques. Biochar is perceived as an innovative and eco-friendly technology for alleviating the regional agricultural issues in Chile. A pilot-scale pyrolysis unit was built by the University of Tarapaca to ascertain the suitability of different feedstocks to produce biochar that may be applied in field trials, whereas in Costa Rica, the main activities of biochar initiative included the production of biochar from locally available biomass; establishment of feasible technologies to produce, promote and transport biochar; and investigation through field trials and analysis of the potential economics related to carbon credits, farming gains and cost of biochar (if any). Lack of finance and health risks limit research on biochar in sub-Saharan Africa (Willis et al. 2015). Particularly, in Zimbabwe, about 3.5 Mton per year of biochar was produced from an estimated feedstock of 9.9 Mton per year, corresponding to 63% of carbon sequestered at 2.2 Mton per year of soil carbon. Besides, the World Bank selected Kenya and Senegal as a case study for biochar technologies to provide heat for cooking for subsistence farmers. The project was essentially aimed to have improved pyrolysis cook stove for each household and to apply the biochar generated to their own fields. The crop residues are collected completely from the farm during maize harvest (Torres-Rojas et al. 2011), and the remaining stover is typically applied back to the field to stop runoff due to erosion and improve mulch. Limited crop residue production and competing uses for residues on the farm are challenges for soil conservation (Unger et al. 1991). The ultimate objective was to optimize the application rate to yield better agronomic returns (Scholz et al. 2014).

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Lehmann and Joseph (2009) showed that stover biochar improves crop yield in the short term more than wood biochar. A pioneering work was done by two non-governmental organizations ARTI and Janadhar in Latur, a medium-sized city in Western India and nearby towns as site for first biochar operation in the Indian subcontinent. Biochar production in villages and small towns in India using modular pyrolysis kilns is providing sustainable resources such as bagasse and organic municipal solid waste. The revolutionary work done by Dr. N. Sai Bhaskar Reddy in India on various aspects of biochar is chronicled in the book titled Biocharculture: Biochar for Environment and Development authored by him (Reddy and Seung-Mok 2014). As a general practice, the unutilized rice husks piled up at rice mills were ultimately burned in piles to generate energy in major rice-producing countries like Thailand, India, Vietnam and the Philippines. To overcome the emissions due to burning, a new biochar production technique was followed, where mounds of rice husks were covered by a layer of soil over a charge of approximately 200 kilograms of wood (Smith et al. 1991). This system presents itself as a low-risk biochar project with climate change adaptation and potentially high economic benefits for small and marginal farmers. The members of the Soils and Fertilizers Research Institute in Vietnam and other partners are working with the farmers to improve existing soils and agricultural practices, thus educating the farmers on the benefits of introducing biochar technology and biochar into the fields that are damaged by overfertilization of crops with chemicals or fresh animal manure and other environmental issues. Soil amendment studies in Laos have suggested an increase in nitrogen fertilizer use efficiency with biochar additions (Chan et al. 2007; Steiner et al. 2008; van et al. 2010). The experiments were conducted under upland conditions at ten sites, combining variations in biochar application, fertilizer application rates (nitrogen and phosphorus) and rice cultivars both improved and traditional. Biochar application augmented grain yields at sites with low P availability and better response to chemical fertilizer treatments with nitrogen and nitrogen-phosphorus (Asai et al. 2009; Jha et al. 2010). Contrarily, in Mongolia, biochar research was intended mainly to ascertain the opportunities for the cooperative marketing of carbon credits rather than agricultural uses. In Pakistan, the problem in the agriculture economy is soil degradation associated with wastewater and solid management, alkalinity and nutrient-deficient drylands lacking water holding capacity. Application of biochar produced by slow pyrolysis at 400  °C with low pH and high cation exchange capacity was found to be a better option than other amendments as it resulted in the highest values of cation exchange capacity and deemed fit for alkaline soils of Pakistan using bagasse as feedstock. In arid areas, studies showed improvement in plant growth and yield by biochar application because of biochar made from combinations of high nutritious feed source, e.g. municipal solid organic wastes and animal manures that may directly provide plant nutrients (Rasul et  al. 2017; Chen et al. 2011; Novak et al. 2009).

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1.5  Biochar Economics New technologies often have a higher associated risk than more established technologies, due to uncertainties in their development and deployment that may affect the eventual cost and effectiveness. The costs and social impacts of biochar projects have been started to be explored. Biochar is not only a time-honoured soil amendment practice but also recourse to climate change effects. Among all other applications, the agricultural segment is witnessing a strong growth rate in the global biochar market, because of the nature of biochar to improve soil quality and crop yield. The fine-grained and porous char has significantly improved agriculture in regions with inadequate supply of chemical fertilizers, organic resources and water. Agriculture being the primary industry in developed nations such as Australia, Germany, Canada and the United States, the demand for biochar is anticipated to grow at faster pace. As a result, the global market is predicted to record a healthy growth over the coming years. In addition, gardening is projected to generate the largest revenue for the application of biochar because of the need for improvement in soil texture and quality. Forestry waste is the major feedstock and is projected to continue being so till the next decade. The most important information regarding the economics of biochar is that the payback period of most of the projects is very short – within 1 year when surplus crops are monetized. The parameters that are more easily quantified include the cost of the feedstock, the capital and operating costs of the stove or kiln, transportation of feedstocks and biochar, the price of biochar, the price of surplus crop yields and the savings from reduced agricultural inputs and waste management. The global biochar market reported an estimated value of $4.27 million in 2015. As per the latest findings, it may record a compound annual growth rate of 17.1%, during 2015– 2023 (P&S Market Research, USA, 2014). Till date, the carbon credits are not associated with the biochar projects although their contribution may increase revenues as the projects progress. Overall, the economics of biochar projects analysed in the case studies are largely determined by the price farmers receive for surplus crops due to biochar additions. Pratt and Moran (2010) observed that small-scale biochar systems, such as cook stoves, are more cost-effective for greenhouse gases reductions than the fast pyrolysis systems favoured by large biochar plants. The World Bank case study in Kenya demonstrated nonmonetary benefits such as increased food security, labour savings and the crop yield. They reported that the choice of crop and the type of soil (to which the biochar is applied) play a larger role in determining the economic balance. This was supported by the Senegal experience, where a group of farmers were able to get better price on cultivating high-yielding onions. As mentioned earlier, another important factor in the economic balance is the capital and operating costs for biochar production. In the absence of research to support the optimization of biochar and its agronomic evaluation, an alternate to evaluate carbon offsets in soil management under biochar-based treatment is important.

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However, one deterrent to quantify biochar economy is the non-existing framework by which the carbon sequestered in biochar may be certified as a tradable commodity. Biochar-based schemes should offer the opportunity to trade a more noticeable offset (durability of biochar in soil) through its impact on agriculture. Individuals or non-governmental organizations outside of government are vying for a market capital currently valued in excess of $30 billion per year. Besides the International Biochar Initiative, pressure groups such as the US-based Clean Air Task Force are promoting biochar-based offsets alongside other bioenergy schemes for trading in all carbon markets (Baum and Weitner 2006). The available methods for carbon accounting are still complicated and vague; hence, the carbon reductions arising from such systems are apt to be discounted in any carbon offset crediting system. So, there is anticipation within some NGOs that the inclusion of biochar into any carbon trading scheme will ultimately put extra pressure on rural livelihoods in developing countries. As a consequence of land acquisition by corporates that are planning large projects based around dedicated biomass crops, that will not benefit agriculture but biochar. A research article by Wolf et al. (2015) indicated that each year, about 3.3 × 1015 grams of dry matter are generated as agricultural wastes worldwide. Players in the biochar market receive support from companies supplying feedstocks in addition to technologies. Another form of economy encountered in biochar application is through building and operating small- to medium-sized pyrolysis units. BioChar Engineering of Colorado has developed and put on sale a portable pyrolysis unit that can produce about half a ton biochar per day. The unit is supposed to cost about $50,000. If it is assumed that one person is required with a minimum wage of $16,300 per year to run the unit for an annual capital charges of approximately 10% amounting to $5000 and ignoring other operating costs, the production cost for biochar from this unit would be approximately $170 per ton. Pro-Natura International of France developed a larger system to produce about 4–5 tons of biochar per day for use in the developing world. To understand the economics involved, Pro-Natura has begun documenting benefits in terms of the potential carbon offsets from a system in Senegal. One finding of the field trials by Dynamotive Energy Systems of Canada reported a wind loss of 30% of the biochar during handling and transport (Husk and Major 2011). These windblown losses are a potential environmental concern as the biochar is principally black carbon – a potent climate stress factor and a loss of revenue as well. Further, the lack of understanding about the function of biochar carbon and its interaction with already complex soil processes and predicting the return to an investment in biochar between locations with reproducible benefits do not yet exist. Providing a measure of certainty to the many possible benefits in a simple formula is a key challenge to be addressed by further research.

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1.6  Challenges and Future Work One of the greatest uncertainties of biochar technologies is their durability and stability of carbon in the soil. With the current research and practice, it is possible to study the short-term impacts of biochar. The ancient terra preta soils have retained unnaturally high fertility when compared to surrounding areas (Tenenbaum 2009) for centuries. The challenge here is the inability to find the initial carbon content of the region and technology to incorporate the carbon. Hence, it is highly impossible to claim the same level of effect for the modern biochar technology (Sohi et  al. 2009). The complexity and heterogeneity of wood/fuel-related issues present policy makers with key challenges. In order to frame proper policy making and implementation in the tropical countries, it is important to understand the extent to which the production strategies for biochar as a means of long-term sequestration. Although earlier experiments indicated that modern biochars loose nearly 20% of their carbon content in the first year, the remaining carbon is locked into the soil for at least 10  years (Lehmann et  al. 2009). The heterogeneity of the biochar poses a major challenge to measure and quantify the impact of carbon content both original and biochar related (Guggenberger et al. 2008; Major et al. 2010; Rumpel et al. 2006). Further the economic sustainability of all biochar systems is dependent on the revenue of these projects, especially for those in developing countries where start­up capital and other funds are limited. In general, the amount of funds that go into research and experimentation has not reached the level needed to scale up specific biochar systems comfortably. Life cycle assessments that indicate very practical directions for low-risk biochar opportunities are only beginning to appear in developing countries due to its economics. A fully monitored methodology regarding quality data acquisition and availability of time series data for this type of exercise is a challenge considering the vast topography under assessment. Building global inventory and sharing of information among participating organizations and target region is again a challenge because of the policies of the local governments and trust deficiencies. The Global Inventory of Long-Term Soil-Ecosystem Experiments, established by the Duke’s Nicholas School of the Environment and Earth Sciences, North Carolina, is a good example of how an applied scientific approach could work. Until recently, only one developed-country biochar study was part of this network. The setting up and implementation of such a network across several different developing countries could be a concrete item for multilateral and bilateral donor support. Another way forward for future coordination is to integrate biochar into existing charcoal economies and clean charcoal efforts. Conventionally charcoal is used as a fuel in many of the developing world. In numerous cases, the charcoal made as fuel may be perfectly suited to use as biochar. An improvised approach could help address the current unsustainable production of charcoal by using residues rather than forests. A variety of cleaner technology that is far more efficient than traditional methods available in a community could maximize the benefits of biochar to that community. There is potential for synergy through introducing biochar

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t­echnology into communities at a range of scales from stoves to make biochar for household uses, namely, kitchen gardens, water filtration, sanitation, etc. to larger units to make biochar commercially, with possibilities for electricity production or heat generation for crop drying or commercial cooking, brewing and other activities. Modifications to stoves and kilns used in rural areas of the developing world today offer a low-tech, low-cost method of producing biochar by pyrolysis (FAO 2013). Biochar stoves have the added advantage of being more efficient and less smoky, improving the lives of their users greatly. Pyrolysis plants are expensive to build and run but offer greater returns in abatement potential and efficiency (Bonjour et al. 2013). Such technologies are favoured in developed nations where there is an abundance of waste biomass for feedstock and adequate infrastructure, as well as the higher possibility of start-up capital and the potential to incorporate biochar into carbon markets with particular reference to India (Dutta and Raghavan 2013).

1.7  Conclusions With global population expanding while the amount of arable land remains limited, restoring soil quality to nonproductive soils could be key to meeting future global food production, food security and energy supplies; biochar may play a role in this endeavour. Biochar economics are often marginally viable and are tightly tied to the assumed duration of agronomic benefits. Further research is needed to determine the conditions under which biochar can provide economic and agronomic benefits and to elucidate the fundamental mechanisms responsible for these benefits. Majority of the reviewed studies reported yield increases after black carbon or biochar additions. Biochar (black carbon) produced by traditional methods (kilns or soil pits) possessed the most consistent yield increases when added to soils. The universality of this conclusion requires additional evaluation due to the highly miscellaneous feedstock preferences. The World Bank report gives the following as key considerations for the challenges for biochar technologies: (a) The complexity of systems requires high levels of knowledge and skills. (b) The technology used needs to be reliable and economical. (c) Financing is mostly related to the investment required for the energy conversion equipment. (d) The increased workload makes the systems less attractive to farmers. (e) Competition between different uses of residues must be addressed. (f) Access to markets for agricultural and energy products is often a key factor to ensure economic viability. (g) Access to information, communication and learning mechanisms is as important a production factor as ‘classic’ land, labour and capital. (h) Few government policies encourage all aspects of systems. The above factors can be considered for Clean Development Mechanism as well as voluntary carbon market methodologies.

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Yadav A, Ansari KB, Simha P, Gaikar VG, Pandit AB (2016) Vacuum pyrolysed biochar for soil amendment. Resour Eff Technol 2:S177–S185 Yanai Y, Toyota K, Okazaki M (2007) Effects of charcoal addition on N2O emissions from soil resulting from rewetting air-dried soil in short-term laboratory experiments. Soil Sci Plant Nutr 53:181–188 Yang Y, Hari S, Bharat S, Sudhagar M (2017) Torrefaction of sorghum biomass to improve fuel properties. Bioresour Technol 232:372–379 Yunbo Z, Chuan P, Bibo X, Tengfei W, Caiting L, Guangming Z, Yun Z (2017) Hydrothermal carbonisation of sewage sludge for char production with different waste biomass: effects of reaction temperature and energy recycling. Energy 127:167–174 Zabaniotou A, Damartzis T (2007) Modeling the intra-particle transport phenomena and chemical reactions of olive kernel fast pyrolysis. J Anal Appl Pyrolysis 80:187–194

Chapter 2

Biorefinery: A Concept for Co-producing Biofuel with Value-Added Products Senthil Nagappan and Ekambaram Nakkeeran

Contents 2.1  I ntroduction 2.2  C  oncept of Biorefinery 2.3  Biofuel Feedstocks and Their Composition 2.3.1  Starch-Based Feedstock 2.3.2  Lignocellulosic-Based Feedstocks 2.3.3  Lipid-Based Feedstock 2.3.4  Sugar-Based Feedstock 2.3.5  Mixed Feedstock 2.4  Various Biofuel and Relevant Biorefinery Techniques 2.4.1  Bioethanol 2.4.2  Biodiesel 2.4.3  Biogas 2.4.4  Mechanical Processes 2.4.5  Chemical and Biochemical Processes 2.4.6  Thermochemical Processes 2.5  Biorefinery Products 2.6  Future Perspectives 2.7  Conclusions References

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Abstract Although biofuels are projected as promising alternative for non-­ renewable sources, the current cost of producing fuel from biomass is higher than crude oil. The biorefinery, co-production of value-added products along with biofuel, is suggested to overcome this drawback. The biomass is majorly utilized for biofuel production, while the residual biomass could be valorized for production of pigments, organic acids, amino acids, renewable chemicals, pharmaceuticals, enzymes, animal feed, etc. In the midst of wide array of biorefinery technologies, feedstocks and bioproduct availability, the main challenge remains in proper selection of these factors that can lead to both economical and environmental ­sustainability.

S. Nagappan (*) · E. Nakkeeran Department of Biotechnology, Sri Venkateswara College of Engineering (Autonomous), Sriperumbudur, Tamil Nadu, India © Springer Nature Switzerland AG 2020 K. M. Gothandam et al. (eds.), Environmental Biotechnology Vol. 2, Environmental Chemistry for a Sustainable World 45, https://doi.org/10.1007/978-3-030-38196-7_2

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In this chapter, the concept of biorefinery along with the role of economic and environmental assessment tools in determining the viability of biorefinery process is discussed. Various feedstocks available for energy generation and the role of chemical composition of feedstock in obtaining the end products of biorefinery are discussed. The processing technologies based on chemical, biochemical, thermochemical and mechanical methods for biorefinery-related production are also discussed. Value-added products generated from different feedstocks along with their application and market status are summarized. The final section discusses about the future perspectives of biorefinery. Keywords  Biofuel · Waste · Co-products · Biorefinery · Valorization · Lignocellulose · Microalgae · Bioethanol · Biodiesel · Biogas

2.1  Introduction The non-renewable fossil fuel is predicted to drain out completely by 2080. In search of renewable energy, wind, solar and biomass were identified as promising resources. The biomass in particular has the potential to not only provide energy but can also mitigate global warming by consuming carbon dioxide (John et al. 2011). Various biofuel products are obtained from biomass such as biodiesel, bioethanol, methanol, butanol, biogas, biomethane, hydrogen, syngas, bio-oil, Fischer-Tropsch liquids, bioethers and biochar (Nigam and Singh 2011). There are three generations of biofuel. The first- and second-generation biofuels are obtained from plant sources, whereas the third-generation biofuel is produced from microalgae. Successive generations have overcome the problem of previous generations. For example, the main disadvantage of first-generation fuel is food vs fuel conflict which has been overcome by second-generation fuel by using non-food crops like lignocellulosic waste and fuel-specific crops as its source (Tomei and Helliwell 2016). Similarly, third-­ generation fuel is considered to be better in comparison to second-generation fuel since the former has higher per acre energy productivity than the latter (Dutta et al. 2014). In spite of numerous advantages offered by new-generation biofuels, only 10% of the global energy demand is met by biofuel (Maity 2015). The major obstacle preventing the biofuel from commercialization is economic viability. The current production cost of biofuel is estimated to be higher than the selling cost of petroleum products (Bozbas 2008). The reason for higher production cost mainly arises from technology involved in biomass processing and nonutilization of by-­ products from biofuel. Various suggestions have been made to overcome the problem of high production cost, and biorefinery is one of the promising options available. Biorefinery is generation of various products from a single or multiple feedstocks (Kamm and Kamm 2004; Gírio et al. 2017). Two main factors that have to be considered for the biomass biorefinery are chemical composition of feedstock and

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relevant processing technologies. For instance, in the case of oil-rich feedstock like rapeseed, soybean, jatropha and microalgae, the biorefinery-based processing typically involves production of biodiesel and glycerol through transesterification production and co-production of animal feed, bioethanol, enzymes and pigments by fermentation and purification techniques (Almeida et al. 2012). Municipal waste, characterized by high organic content, is primarily used for production of biogas by anaerobic digestion, while the resulting digestate is used for the extraction of valuable minerals, elemental sulphur and biochemical intermediates such as acetate, propionate, butyrate, etc. (Santibañez-Aguilar et al. 2013). Sugarcane, constituting easily recoverable sugars, is more suitable for bioethanol production through fermentation using yeast (Cardona et  al. 2010). The sugarcane residuals remaining after bioethanol extraction are source of high-value chemicals including organic acids like levulinic acid, succinic acid and muconic acid, biopolymers, resins, animal feed and fibre products which are obtained by chemical or biological processes (Dias et al. 2013). There are also other biomass biorefinery technologies available for biofuel and associated by-product synthesis. These include pyrolysis, gasification, liquefaction, supercritical solvent extraction and combustion (FitzPatrick et al. 2010). A careful selection of biomass biorefinery technologies for appropriate feedstock becomes an essential criterion for economic viability of the process.

2.2  Concept of Biorefinery Biorefinery is the process of separation of biomass into biofuel and usable biochemicals. The word biorefinery is derived from oil refinery where the latter involves the separation of crude oil into petroleum products and the former deals with biomass separation. Biorefinery technique encompasses three main steps: first, a biomass pretreatment step; second, a biofuel conversion method; and finally, bioproduct purification step. Biomass pretreatment is primarily carried out for size reduction and depolymerization of biomass (Agbor et al. 2011). Examples include shredding, mashing, cutting and contact with acid, alkali and enzymes. Biofuel conversion method is selected depending on feedstock composition (Kurian et  al. 2013). Fermentation, transesterification and anaerobic digestion are the biofuel conversion methods widely used for production of bioethanol, biodiesel and biogas, respectively. Bioproduct purification step includes column chromatography, crystallization, precipitation, etc. (Huang et al. 2008). A single downstream technique will not suffice the entire biorefinery process; rather multiple downstream processes are usually incorporated. Identification of efficient techniques for separation of bioproducts is one of the important challenges for commercialization of biorefinery process. Biorefinery of biomass encompasses a wide array of techniques and products. The selection of bioproducts and relevant production techniques in biorefinery mode of production has a crucial role in determination of both commercial viability and environmental impact of the whole process (Ahlgren et al. 2015). In order to study the economic feasibility of biorefinery-based production, various assessment

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tools are available. One such technique is techno-economic analysis. Techno-­ economic studies indicate the commercial viability of a selected production method by using product and process metrics only. Literature reports on biorefinery-related techno-economic analysis exist for a number of biomasses including sugarcane, lignocellulosic biomass, microalgae, mango waste, woody biomass, sago palm and slaughter waste (Zhu et al. 2014; Wang et al. 2015; Kwan et al. 2015; Wan et al. 2016; Klein et al. 2017; Shahzad et al. 2017; Arora et al. 2018; van Rijn et al. 2018). A recent study reported an improved economic feasibility evaluation method called retro-techno-economic analysis which incorporates process variables in addition to product and process metrics (Longati et  al. 2018). The application of the above method on lignocellulosic bioethanol production identified enzyme loading, hydrolysis of cellulose to glucose and ethanol yield on xylose as the main process parameters. Some of the metrics used for evaluation of economic potential of biorefinery are internal rate of return, maximum selling price and payback period (Cheali et al. 2016). In general, the biorefinery process with a maximum energy generation and internal rate of return value and minimum payback period and maximum selling price value indicates economic viability (Wan et  al. 2016). The environmental impact of a biorefinery is studied using life cycle assessment. The terms associated with life cycle assessment are net energy ratio and global warming potential. Net energy ratio is defined as the ratio of direct output energy to the direct input energy (Shahrukh et al. 2015). A net energy ratio value less than 1 indicates an energetically unfavourable process. Global warming potential is calculated based on emission and utilization of carbon dioxide, methane and other greenhouse gases in biorefinery process (Husgafvel et al. 2016). An eco-friendly and economically feasible biorefinery production will have positive net energy ratio greater than 1 and lesser global warming potential value. Several studies have implemented techno-economic and environmental assessment methods for comparing different biorefinery scenarios starting with the same feedstock. For example, a study compared both economic feasibility and environmental impact on generation of electricity for ethanol production from sugarcane bagasse (Seabra and Macedo 2011). Results revealed that ethanol production from sugarcane residue was more eco-friendly than electricity generated from the same; the former process resulted in 37% lesser CO2 emission than the later (Seabra and Macedo 2011). However, in terms of economy, the return on investment related to electricity production was 7% higher than ethanol production. Techno-economic analysis also provides insight on feedstock diversion for biorefinery products based on market demand. This is exemplified by a study that compared two scenarios involving varied allocation of feedstock for sugar, butanol and bioethanol production (Mariano et al. 2013). The results from above study suggested that by allocating 25%, 50% and 25% of available sugarcane for sugar, bioethanol and butanol production, respectively was more favorable than other ratios in terms of economy. The study exhibited that 1.5% higher return on investment is achieved than conventional equal ratio of feedstock allotment for sugar and bioethanol production. These studies demonstrated the potentiality of techno-economic and environmental assessment tools for achieving optimal biorefinery production.

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2.3  Biofuel Feedstocks and Their Composition The feedstock for biofuel production is either exclusively cultivated or derived from wastes. Plants cultivated solely for biofuel purpose include corn, sugarcane, sugar beet, palm, cottonseed, sunflower, wheat, switchgrass, sorghum, rapeseed, soybean and jatropha, and microorganisms include microalgae (Slattery and Ort 2015). The sources of waste for biofuel production are forest residues, agricultural residues, industrial waste, municipal solid waste, molasses, bagasse, defatted microalgae, food waste, animal fat and used oils (Bhaskar et al. 2016). There are various factors that affect feedstock production. Foremost, a region-specific feedstock positively favours the economics of biorefinery-based industry owing to lesser logistic constraints (Igathinathane and Sanderson 2018). Other factors related to biorefinery feedstock that can influence its production are conducible climatic condition, high water table and socio-political parameters (Creutzig et al. 2015). In terms of chemical composition of feedstock, they highly vary from one crop to another. Based on dominant biomolecule fraction, feedstock for biofuel production can be categorized into five groups, namely, (1) starch-based, (2) lignocellulosic-based, (3) lipid-based, (4) sugar-based and (5) mixed feedstock.

2.3.1  Starch-Based Feedstock Starch-based biofuel feedstocks majorly comprise residues of edible crops. Although use of food staples exclusively for biofuel purpose is debatable, the Western world, in particular European and American market, is largely dominated by wheat- and corn-based biofuel production (Escobar et al. 2009). Whole cereals including barley, rice, wheat, corn, sweet sorghum, etc., cereal residues such as bran and some parts of endosperm and germ obtained by milling and tuber and root starches like sweet potato and cassava have been reported for both biofuel and biorefinery production (Koutinas et al. 2007; Ziska et al. 2009). The main constituent of cereal is carbohydrate (60–80% by dry weight) with protein (10–16%), lipid (2–7%) and fibre (3–10%) as sub-constituents (Mlyneková et  al. 2014). Starch, the dominant carbohydrate found in cereal, is a polymer comprising of multiple glucose units cross-linked to each other by glycosidic bonds (Nelson et al. 2008). Two types of biomolecules are found in starch, namely, amylose and amylopectin. Amylose is either linear or helical chain consisting of repeated glucose molecules linked by alpha-(1,4)-glycosidic bond, whereas amylopectin is similar to amylose in terms of repeated glucose units; however, it is branched and connected by alpha-(1,6)-glycosidic bond. Starch-based feedstocks typically contain 20–25% amylose and 75–80% amylopectin. Starch, as such, is not a fermentable carbohydrate; therefore hydrolysis of starch to simple sugars is prerequisite for biofuel production (de Souza 2010). Bioethanol is the major biofuel obtained from starch-based feedstock with animal feed as the popular co-product (de Jong et  al. 2012). Figure  2.1 summarizes the

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Starch based feedstock

Aerobic Fermentation

Succinic acid

Chemical Transformation 5Hydroxymethyl furfural, Levulinic acid

Itaconic acid

Anaerobic Fermentation

Biohydrogen

Syngas

Biogas

Fischer Tropsch fuel

Residue

Biopolymers and Bioplastics

Lignin

Biomethane

Methanol

Polylactic acid

Hydrocarbons

Biofertilizer

Dimethylether

Polyhydroxyalk anoate

Phenols, other Aromatic compounds

Ethanol

Bioethylene

Resins, Binders, Adhesives, Polymer extenders

Sorbitol Adipic acid Furfural Isoprene Glucaric acid Glutamic and Aspartic acid Acetone, Butanol, Ethanol

Deep eutectic solvent

Fig. 2.1  Schematic representation of various biorefinery products derived from carbohydrate-­ based feedstocks (starch and sugar)

various biorefinery products that could be derived from starch-based feedstocks. In conclusion, the achievement of starch-based feedstocks ought to be founded on flexible biomass supply chains and on the generation of a wide range of different bio-based items.

2.3.2  Lignocellulosic-Based Feedstocks Lignocellulosic-based feedstocks contribute towards second-generation biofuel. Unlike starch-based crops, lignocellulosic crops are generally not utilized for human consumption, thus avoiding food vs fuel scenario (Tenenbaum 2008). The source of lignocellulosic biomass includes but not limited to agricultural residues like rice and wheat straw, cotton and barley stalk, cereal husks, forest residues like twigs and leaves, herbaceous plant such as alfalfa and switchgrass, short rotation woody crop, industrial residues like wood waste from pulp and paper industry and bagasse and vinasse from sugarcane and sugar beet (Somerville et al. 2010). In general, lignocellulosic crops are mainly composed of lignin (20–30%) and carbohydrates such as 15–25% of hemicellulose and 20–40% of cellulose (Malherbe and Cloete 2002). The cellulose which forms the major portion of lignocellulosic biomass are not easily depolymerized due to extensive cross-linking with lignin (Tsukamoto et  al. 2013). Hemicellulose, also recalcitrant in nature, is the other dominant molecule in lignocellulosic biomass, which is primarily made up of hexose and pentose sugar

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molecules. Bagasse, an industrial by-product of both sugar production and first-­ generation bioethanol production, is a popular, widely generated and easily accessible lignocellulosic biomass (Pandey et al. 2000). The important cost factors deciding successful use of lignocellulosic biomass for biorefinery purpose are harvesting and transportation costs (Ghatak 2011). A close proximity of biorefinery plant to the source of lignocellulosic residue will be beneficial to economics of lignocellulosic biofuel production as it reduces cost associated with logistics (Ekşioğlu et al. 2010). Besides, considerable expenditure is also spent on depolymerization of biomass in order to release fermentable sugars due to recalcitrant nature of these biomasses (Lange 2007). Selection of suitable pretreatment step for biorefinery results in economic viability, desired by-products synthesis and minimum generation of inhibitors. Similar to starch-based feedstock, bioethanol is also the well-reported fuel extracted from lignocellulosic biomass (Soccol et  al. 2011). The production of bioethanol from lignocellulosic biomass differs from that of starchy biomass. The production of ethanol from recalcitrant lignocellulosic biomasses requires extensive pretreatments in order to separate fermentable sugars and remove lignin and hemicellulose from complex carbohydrate framework (Lange 2007). After pretreatment, fermentation of lignocellulosic hydrolysates containing reducing sugar by yeast produces bioethanol. Figure  2.2 presents the biorefinery products associated with lignocellulosic feedstocks. While the expense of downstream preparation for a single feedstock would be high, consolidating diverse feedstocks and coordinating them in a biorefinery model would diminish the generation cost.

Lignocellulosic based feedstock

Pretreatment

Thermochemical

Combustion Combined heat and power

Gasification

Syngas Fischer Tropsch fuel Methanol Dimethylethe r Ethanol

Pyrolysis and Liquefaction Bio-oil

Phenols

Furfural Organic acids Levoglucose none

Anaerobic process Biogas

Biomethane

Biofertilizer

Biohydrogen

Lignin Hydrocarbo ns Phenols, other Aromatic compounds Resins, Binders, Adhesives, Polymer extenders Deep eutectic solvent

Fermentation Organic acids Isoprene Glutamic and Aspartic acd Ethanol, Acetone, Butanol

Chemical transformation 5Hydroxymet hylfurfural, Levulinic acid

Sorbitol

Furfural Glucaric acid

Xylitol and Arabitol

Fig. 2.2  Schematic representation of various biorefinery products derived from lignocellulosic feedstocks

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2.3.3  Lipid-Based Feedstock Diverse lipid-based feedstock exists for biofuel production such as palm, sunflower, rapeseed, soybean, etc. Although the composition vary from one feedstock to the other, one similar aspect found in all these crops is abundant lipid content reported to be in the range of 13–50% of dry weight (Gunstone, 2011). Other components present in the lipid-based feedstocks are carbohydrates (12–28% of dry weight) and protein (2–60% of dry weight). The most promising lipid-based feedstock for biofuel production is microalgae owing to its high lipid content (20–70% by weight). Since microalgae have better per acre lipid productivity compared to any other plant, microalgae-derived biofuel is considered as third-generation biofuels (Demirbas and Demirbas 2011). Due to which, the biorefinery products from microalgae have garnered much attention in recent times (De Bhowmick et  al. 2018). Besides microalgae, oleaginous plants such as soybean, rapeseed, safflower, palm, sunflower, canola and jatropha having abundant lipids in their biomass are also cultivated globally for biofuel production (Lühs and Friedt 1994). Apart from plant-­ based sources, animal fats, waste cooking oil and used oil can also be utilized for biofuel production. The biodiesel is the chief product obtained from lipid-rich feedstock, whereas animal feed, enzymes, bioethanol and carotenoids are the resultant of residual biomass valorization (Vollmann and Laimer 2013). In the United States, soybean, corn, yellow grease, canola and white grease are primarily used for biodiesel production (Carriquiry 2007). The widespread cultivation of palm in Malaysia has led to large-scale biodiesel production in the country (Johari et  al. 2015). Jatropha and Pongamia can be grown in land with low water and agricultural inputs and thus deemed suitable for biofuel production in arid and semi-arid regions (Dwivedi and Sharma 2014). Biorefinery products can also be recovered from lipid-­ based feedstocks processed for omega-3 fatty acid production (Adarme-Vega et al. 2012). Figure  2.3 illustrates the biorefinery products derived from lipid-rich feedstocks. The lipid composition of feedstock influences biofuel properties. In case of biodiesel fuel, the degree of unsaturation, isomerism and chain length of fatty acids present in the lipid fraction of biomass determines the biodiesel property (Olmstead et al. 2013). A feedstock rich in saturated fatty acid is reported to have good combustion and oxidative property, but it suffers from poor cold flow properties, whereas a feedstock rich in polyunsaturated fatty acid could provide required cold flow properties (Jeong et al. 2008; Olmstead et al. 2013). A feedstock with abundant monounsaturated fatty acid is a better candidate as it provides good biodiesel qualities such as good combustion, oxidation stability and cold flow properties (Jeong et al. 2008).

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Lipid based feedstocks

Thermochemical

Oil Extraction

Transesterific ation Fatty acid methyl ester

Biodiesel

Omega 3 fatty acid

Saponification

Glycerol

Epichlorohydrin

Propylene glycol

Chemical modification

Pyrolysis and Liquefaction

Residue

Gasification

Pigment

Syngas

Animal feed

Fatty acid

Bioplastics

Bio-oil

Soaps

Resins

Phenols

Fischer Tropsch fuel

Biofertilizer

Detergents

Adhesives

Furfural

Methanol

Bioethanol

Organic acids

Dimethylether

Levoglucosan

Ethanol

Personal care

Fig. 2.3  Schematic representation of various biorefinery products derived from lipid-based feedstocks

2.3.4  Sugar-Based Feedstock Sugarcane and sugar beet are typical examples of sugar-based feedstock used for biofuel production. Owing to large-scale cultivation spread throughout the world, sugarcane has become the main feedstock for development of biorefinery technologies (Moncada et al. 2014). Bioethanol is the chief biofuel product of sugarcane, while organic acids, lignin, amino acids, animal feed, enzymes and renewable chemicals are the typical co-products associated with bioethanol (Dias et al. 2013). A typical composition of sugarcane is 10–16% fibre, 14–25% sucrose, 0.2–1% glucose and 0.5% fructose (Canilha et al. 2012). Sugarcane fibre consists of cellulose, pentose and lignin. Sugarcane is mainly cultivated for sugar production (Chauhan et al. 2011). Once sugar is extracted through crystallization, the remaining liquid residue, molasses, consists of high fermentable sugars. While liquid residue molasses is used for bioethanol production, the solid residue, bagasse, is majorly used for generating electricity. The other crop which is less consumed for bioethanol production is sugar beet typically containing 25% cellulose, 5% protein and 1.5% carbohydrate (Slattery and Ort 2015). Sugarcane bioethanol is the leading biofuel in the world (Guo et  al. 2015). Bioethanol is classified as first generation and second generation based on the source of fermentation. The first generation is production of bioethanol directly from sugarcane juice, whereas second generation’s source is the sugarcane stillage and molasses. While first-generation bioethanol is a well-established commercial process implemented globally, the second generation is still in the nascent stage of

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commercialization (Dias et al. 2013). The production of first-generation bioethanol does not require extensive pretreatment step and involves direct fermentation by yeast-producing bioethanol (Mariano et al. 2013). However, feedstocks of second-­ generation bioethanol, bagasse and molasses, require pretreatment similar to lignocellulosic crops before fermentation by yeast-producing bioethanol (Sigoillot and Faulds 2016). Vinasse requires a special mentioning in sugar-based feedstock used for biorefinery and biofuels. Vinasse is the liquid residue that remains after distillation of bioethanol. In terms of amount of vinasse generation, for every litre of bioethanol distilled, 15 litre of vinasse is produced (Moraes et  al. 2015). Vinasse is rich in pentoses, lignin, organic acids like acetate and lactate, alcohols and glycerol (Lazaro et  al. 2014). The attempts to produce ethanol and value-added chemicals from pentose-­rich vinasse using microorganisms had resulted in lower yields (Kaparaju et al. 2009). Moreover, the phenol and melanoidins found in vinasse inhibit certain fermenting microbes (Harada et al. 1996). Currently, genetically engineered microorganisms are being developed to address this problem (Yusuf and Gaur 2017; Zheng et al. 2015). In spite of which, the efficient utilization of vinasse remains a challenge in an industrial setup.

2.3.5  Mixed Feedstock Apart from well-defined feedstocks, mixed feedstocks in the form of municipal solid wastes, industrial wastes including bagasse, rice hulls, paper industry effluent, etc. have been reported for biofuel and biorefinery production (Fava et  al. 2015; Bhaskar et al. 2016). The magnitude of municipal solid waste generated although alarming provides excellent opportunity for biorefinery production (Mohan et  al. 2016). Typical composition of municipal solid waste is 50–55% organic matter, 15–20% recyclables, 28–32% inert waste and 46–51% moisture content (Sharholy et al. 2008). A high organic and moisture content in waste is considered as suitable for both fermentation and anaerobic digestion in order to achieve maximum biofuel yield (Ling et al. 1998). However, the presence of substantial heavy metals in waste is detrimental to the growth of organism leading to lower biofuel yield (Fernández-­ González et  al. 2017). Segregation of mixed waste, particularly in the case of municipal solid waste into organic and non-organic components at the source point, could provide benefit for not only the biofuel production but also help in recovering the recyclables (Gupta et al. 2015). Biogas, biofertilizer and minerals are the biorefinery products related to mixed feedstock.

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2.4  Various Biofuel and Relevant Biorefinery Techniques The separations of whole biomass into individual high-value components form the basis of biorefinery. In order to achieve this goal, various processes can be adopted. These processes can be grouped as four depending on the method of depolymerization. They are mechanical, chemical, biochemical and thermochemical processes. The main product obtained through the processes is biofuel.

2.4.1  Bioethanol Bioethanol is a well-documented biofuel product derived from starch-based feedstocks. The production of bioethanol from starchy feedstock involves pretreatment, followed by fermentation. Pretreatment comprises of mashing and hydrolysis. Mashing is primarily carried out for increasing the surface area of biomass (Wilkie et al. 2000). Utilization of starch for bioethanol production further necessitates a hydrolytic depolymerization process of saccharification. In case of starchy tuber and root, the saccharification involves conversion of starch into reducing sugar by two different enzymes in subsequent steps: one being calcium-based alpha-amylase enzyme with optimal pH of 6–7 for conversion of starch polymers into dextran, while the other is glucoamylase with optimal pH of 4 for conversion of dextran into fermentable sugars (Van Der Maarel et al. 2002). The acidity and alkalinity requirement for the process of enzymatic saccharification is achieved with addition of suitable chemicals such as lime, sodium hydroxide and acids (Wilkie et al. 2000). In case of lignocellulosic biomass, the saccharification is a two-step process comprising of acid pretreatment followed by enzymatic hydrolysis. After release of reducing sugar by saccharification process, the fermentation of carbohydrate hydrolysates by organisms like Saccharomyces cerevisiae, Zymomonas mobilis, etc. typically in a submerged fermenter produces bioethanol (ElMekawy et al. 2013).

2.4.2  Biodiesel Biodiesel is a widely produced biofuel from lipid-based feedstock (Almeida et al. 2012). Typical biodiesel production from feedstock involves cultivation, harvesting, lipid extraction, lipid purification and transesterification (Ma and Hanna 1999). Microalgae are promising source of biodiesel owing to higher lipid productivity (Chisti 2007; Nagappan and Verma, 2016). In comparison to well-established methods for land-based crop cultivation, the aquatic culturing of microalgae requires special conditions. Microalgae are cultivated in aqueous medium contained either in photobioreactors, raceway or open ponds with abundance of sunlight and carbon dioxide (Chisti 2007). Harvesting is also unique for microalgae involving

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flocculation and filtration. Lipid extraction, a common step for most of the lipid-­ based feedstock, is traditionally performed using solvents like hexane, and extracted lipid is further purified by degumming, neutralization and bleaching processes (Halim et  al. 2011; Siddiquee and Rohani 2011). Transesterification is the final reaction for biodiesel production where purified lipid is mixed with an alcohol and suitable catalyst, thereby fatty acid ethyl ester is synthesized along with glycerol.

2.4.3  Biogas The typical product majorly associated with mixed feedstock is biogas (Weiland 2010). Anaerobic digestion, the biochemical process responsible for biogas synthesis, is brought by consortium of organisms. Four dominant groups of organisms, involved in this process, belong to hydrolytic, acidogenic, acetogenic and methanogenic bacteria (Mao et al. 2015). In the first step, complex organic matter is converted into simple biomolecules by hydrolysis; in turn, acidogenesis converts simple biomolecules into organic acids, alcohols, ketones, carbon dioxide and hydrogen (Azman et  al. 2015; Mao et  al. 2015). The products of acidogenesis are subsequently converted into acetic acid by acetogenesis process. The methanogenesis, the final step in anaerobic digestion, converts acetic acid, organic content and simple biomolecules into methane (Goberna et  al. 2015). Sometimes in cases where sulphur-­rich feed is used for anaerobic digestion, the sulphur-reducing bacteria convert sulphurous compounds into sulphide and hydrogen sulphide (Moraes et  al. 2015). The factors affecting anaerobic digestion are carbon load, temperature, level of macronutrients as well as micronutrients and absence of oxygen (Mao et  al. 2015). Due to acidic conditions prevailing in the anaerobic digester, an optimal pH of 6.5–8.2 is maintained by addition of suitable alkali reagents (Moraes et al. 2015). The end product, biogas, is primarily made up of methane (50–75%), carbon dioxide (25–50%), nitrogen (0–10%), hydrogen (0–1%) and hydrogen sulphide (0–3%) (Mao et al. 2015). Biomethane, a high-value marketable product, is obtained from biogas by concentrating methane portion of the biofuel (Batlle-Vilanova et al. 2015).

2.4.4  Mechanical Processes Mechanical process is the foremost step performed on a feedstock intended for biorefinery production. The application of force by milling, chipping, shredding, cutting or commuting process breaks down the structural background of biomass resulting in size reduction, change in shape and bulk density, reduced crystallinity and, to an extent, depolymerization (Ghatak 2011). Following mechanical breakdown, the size-reduced biomass becomes more amenable to secondary extraction techniques and biomass treatment steps (Yoo et  al. 2011). Generally mechanical processes are adopted in oil extraction from lipid-based feedstocks, biogas

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production from municipal solid waste and bioethanol production from sugar cane, bagasse, forestry products, agricultural residues and other lignocellulosic biomass (Agbor et al. 2011). Some of equipments used in mechanical processes for pulverization are shredder, planers, hammer mill, extruders and knife mills (Kurian et al. 2013). The major disadvantage of mechanical treatment is energy-intensive, and it is estimated that 33% of total energy spent on biofuel production is contributed by mechanical process alone (Yoo et al. 2011). However, it is the prerequisite for further chemical and biochemical treatment of feedstock.

2.4.5  Chemical and Biochemical Processes Chemical Process The chemical process is mainly implemented for pretreatment of biomass prior to biorefinery production. Chemicals like acid, alkali, organic solvents, etc. act on the feedstock by releasing the intracellular contents as well as recovering the inaccessible sugars. Ozonolysis, acid hydrolysis, alkaline hydrolysis, solvent delignification, wet oxidation and organosolvation are examples of chemical pretreatment involving ozone; acids like H2SO4 and HCl; alkali such as sodium, potassium, and calcium hydroxides; solvents; hydrogen peroxide; and organic acids, respectively (Oh et al. 2015). For example, in ozonation, the ozone reacts ideally with lignin than starches, advancing biomass destructuration and delignification, thus leading to sugar discharge by enzymatic hydrolysis. Ionic liquids are innovative solvents that have been demonstrated to improve enzymatic saccharification process; however, high solvent consumption remains a problem to be solved (da Silva et al. 2013). Alkali pretreatment is a cost-effective chemical method which generates lesser amount of fermentation inhibitors (Rabelo et  al. 2008). However, longer time of treatment is needed for this type of hydrolysis. Hydrogen peroxide is another chemical method for pretreatment of biomass, especially lignocelluloses. It is a highly efficient method with the ability to recover 100% cellulose from lignocellulosic biomass (Rabelo et al. 2008). Acid hydrolysis is performed either at a low concentration at high temperature or high concentration at low temperature. The factors deciding the concentration of acid and temperature are cost, time and inhibitor generation (Oh et al. 2015). A higher yield of cellulose in a corrosion-free reactor is achieved with dilute acid and high temperature combination (Moraes et al. 2015). Care shall be taken during high-temperature hydrolysis since by-products generated are inhibitory to fermentation; however, this problem could be avoided by choosing the combination of concentrated acid and low temperature. In case of lignin-free biomass, as in microalgae, a one-step acid hydrolysis using 10% sulphuric acid was demonstrated to be effective to extract maximum amount of the fermentable sugar from defatted biomass (Mirsiaghi and Reardon 2015). However, the drawback of acid hydrolysis is the generation of growth inhibitors like furans, weak acids and phenolic compounds and requirement of neutralization prior to downstream

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fermentation (Kurian et al. 2013). Moreover, the reducing sugar molecules, glucose and xylose, present in the biomass are lost as furfurals (Wilkie et  al. 2000). Nevertheless, acid hydrolysis methods are simple, cost-effective and widely used for biomass pretreatment. Biochemical Process Biological pretreatment of biomass for biorefinery involves either application of enzymes or whole microbes. Enzymes such as pectinase, exoglucanase, endoglucanase, hemicellulase, beta-glucosidase, cellulases and xylanases are used to break down cell wall and various polymers of biomass (Silva-Fernandes et al. 2016). For example, application of cellulase and beta-glucosidase classes of enzyme degrades firstly cellulose into cellobiose and subsequently hydrolyses cellobiose to glucose (Hasunuma et al. 2013). Lignin, one of the major fractions of lignocellulosic biomass, is degraded by enzymes, peroxidases, oxidases and laccase (Pandey and Kim 2011). In starch-based feedstocks, alpha-amylase and glucoamylase enzymes help in the breakdown of starch into fermentable sugars. The whole-cell extracts of mesophilic and filamentous fungus, Trichoderma reesei, containing significant amount of cellulase are also used for cellulose degradation in biomass (Bischof et al. 2016). Lignin degradation by white and brown soft-rot fungi, actinomycetes, can enhance the efficiency of subsequent enzymatic hydrolysis (Chen et al. 1995; Tuomela et  al. 2000). In particular, white-rot fungus, Phanerochaete chrysosporium, has been extensively studied due to higher rate of lignin degradation (Chen et al. 1995). The advantages of biological conversion process are substrate specificity and non-formation of fermentation inhibitors; however, bottlenecks such as high cost and longer time of action disallow industrial application.

2.4.6  Thermochemical Processes Thermochemical processes based on application can be classified into three categories: biofuel related, pretreatment and by-product thermochemical processes. Steam explosion belongs to pretreatment category of thermochemical process where biomass is contacted with high-pressure saturated steam for shorter duration and thereafter decreased to atmospheric pressure resulting in decompressing hydrolysis effect on biomass (Singh et al. 2015). Ammonia freeze/fibre explosion is similar to steam explosion in which biomass is contacted with ammonia at elevated temperature and pressure (Kumar et al. 2009). Carbon dioxide explosion is also similar to steam explosion in which biomass is contacted with supercritical carbon dioxide at low temperature and high pressure (Ahring et al. 2015). The biofuel-related thermochemical process includes combustion, gasification, pyrolysis and liquefaction. Due to its simplicity, the combustion is a widely used method for treatment of solid wastes involving total oxidation of organic

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components in the biomass (Nussbaumer 2003). However, the combustion of feedstock performed in presence of excess oxygen is energy efficient and suitable for adoption in a biorefinery setup (Ghatak 2011). Gasification involves heating of biomass under high temperature of 700  °C and greater with low level of oxygen (Kirubakaran et al. 2009). The product derived from biomass gasification is syngas, which comprises hydrogen, carbon monoxide, carbon dioxide and methane (Wilhelm et al. 2001). Syngas is used directly as fuel or can be intermediate reagent in the production of biorefinery chemicals such as ethanol, isobutene, dimethyl ether, methanol, organic acids, alcohols, ammonia, etc. (West et al. 2011). In general, gasification is more suitable for processing lignin-rich black liquor generated from the paper mill (Ghatak 2011). The pyrolysis involves heating of biomass at relatively lower temperature compared to gasification ranging from 300 to 600 °C in absence of oxygen (Czernik and Bridgwater 2004). The resulting main product, bio-oil and by-product, charcoal are generally used as fuel in thermal energy plants. Flash pyrolysis is a variation to conventional pyrolysis where biomass is heated to a high temperature for few seconds in the absence of oxygen; this process results in higher gas yield than conventional process (Demirbas 2007). Biomass liquefaction is a promising route for processing feedstock for biofuel which involves heating of biomass with water under high pressure (Gollakota et al. 2017). The main goal of liquefaction is to achieve high heating value by removal of oxygen from biomass. High-energy efficiency, operating at moderate temperatures ranging from 250 to 370 °C and pressures ranging from 580 to 3200 psi, provides a distinct advantage for liquefaction-based techniques over other thermochemical methods (Gollakota et al. 2017). The hydrothermal upgradation is a type of biomass liquefaction where hydrodeoxygenation catalysts like sulphided nickel-molybdenum are additionally added for efficient removal of oxygen resulting in bio-oil as the chief product. This type of liquefaction technique is especially suitable for wet biomass like harvested microalgae which contain 80% water of the total wet biomass (Singh et al. 2014). In terms of biorefinery, a study had shown that separation of grass feedstock into protein and hydrothermal upgradation fuel had better economic prospects of 17–25% internal rate of return (Goudriaan and Peferoen 1990). Fischer-Tropsch process is a catalytic upgradation of gaseous products obtained through thermochemical methods of pyrolysis, combustion and gasification. A typical example is conversion of syngas into liquid hydrocarbon Fischer-Tropsch fuel using iron or cobalt catalyst, either at low temperature of 200 °C or high temperature of 350 °C. Transesterification reaction, the basis for biodiesel production, converts lipid-based feedstock like microalgae, jatropha, etc. into fatty acid ethyl ester, also known as biodiesel and glycerol using alcohol and suitable catalyst usually at temperatures ranging between 50 and 70 °C (Ma and Hanna 1999). The current methodologies adopted for biofuel production as well as biorefinery involve toxic chemicals causing harm to human health and environment. This could be overcome by using green chemistry-oriented techniques. Examples are supercritical fluid extraction using supercritical carbon dioxide and supercritical ethanol. These solvents are non-flammable and eco-friendly (De Melo et al. 2014). Several studies demonstrated the usefulness of supercritical solvent in a biorefinery setup. A

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study showed that by utilizing the ethanol, electricity, carbon dioxide and heat generated from the bioethanol production plant in supercritical extraction of a bioactive compound, one could achieve higher energy efficiency (Santos et  al. 2014). The above study demonstrated that energy efficiency of supercritical extraction plant for extraction of β-ecdysone from ginseng roots was improved to 55% by coupling with bioethanol plant. In another example, the pretreatment of sugarcane bagasse with supercritical water generated as by-product from bioethanol plant could save 14% of the production cost (Albarelli et al. 2017a). In another study, an economically viable biorefinery process suggested that the CO2 generated from bioethanol fermentation was used for algal growth, while supercritical CO2 with suitable co-­ solvent was used for extraction of lipid and high-valued pigments from microalgal biomass (Albarelli et al. 2017b).

2.5  Biorefinery Products The chief product derived from biorefinery is a biofuel. The following are some important biofuels obtained from biomass: biogas, syngas, biohydrogen, biomethane, charcoal, bioethanol, biodiesel, Fischer-Tropsch fuels, dimethyl ether, synthesized natural gas and bio-oil. The biofuel production from biomass is environmentally safe; however, the economic viability in many cases is not promising. In spite of various government-aided initiatives in many countries, the biofuel production at large scale remains unachieved (Ghatak 2011). Residual biomass after fuel extraction could be used as the source of industrial chemicals and other high-value products (de Jong et  al. 2012; Nagappan and Verma 2018; Nagappan et  al. 2019). Therefore, effective utilization of these residues as commercial products could improve the economics of biofuel production. Table 2.1 illustrates various biorefinery products, their application and market status. Hexose and pentose sugar molecules recovered from the feedstock are used for the production of numerous high-value chemicals through intermediates (FitzPatrick et al. 2010; de Jong et al. 2012; Chew et al. 2017). Such intermediates include itaconic acid, glutamic acid, succinic acid, lactic acid, 3-hydroxy propionic acid, aspartic acid, fumaric acid, 2,5-furandicarboxylic acid, glucaric acid, glycerol, levulinic acid, sorbitol and xylitol which are obtained either by biological route or chemical conversion (Holladay et al. 2007). The economic production of succinic acid was achieved using fermentation of pretreated sugarcane bagasse by Actinobacillus succinogenes (Klein et  al. 2017). 3-Hydroxybutyrolactone is an important chiral building block for various pharmaceutical products including statin, antibiotic like Zyvox and antihyperlipidemic drug like Zetia (Martin et al. 2013). In a study, 3-hydroxybutyrolactone was obtained from succinic acid through hydroxybutyric acid-by-acid treatment using succinic acid overproducing rumen bacterial mutant Mannheimia succiniciproducens (Choi et al. 2013). Lactic acid, a versatile platform chemical having wide range of applications including medical, food, chemical and various other industries, can be produced by fermentation of

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Table 2.1  Biorefinery products, applications and their market status Biorefinery product Bioethanol

Applications Fuel and energy

Market information US$ 52.66 billion in 2016, compound annual growth rate (CAGR) of 5.3% between 2017 and 2022 Combined heat and power Fuel and energy US$ 19.62 billion in 2017, CAGR of 5.48% from 2018 to 2023 Biodiesel Fuel and energy US$ 32.87 billion in 2015, CAGR of 3.8%, from 2016 to 2021 Syngas and derivatives Fuel, FT fuel, power, 133,270 MW in chemicals 2016, CAGR of 9.5% from 2015 to 2020 Biogas Fuel, biomethane, US$ 24.5 billion in elemental Sulphur 2015, 6.5% CAGR from 2016 to 2021 Polylactic acid Bioplastic USD 1.65 billion in 2015, CAGR of 20.9% from 2016 to 2021 US$ 300 million in 2,5-Furandicarboxylic acid Bioplastic, 2016, CAGR of replacement for 8.2% from 2017 to polyethylene 2022 terephthalate Hydroxymethylfurfural – US$ 105 million in 2014, CAGR of 4.55% from 2015 to 2020 US$ 37 million in Muconic acid Nylon biosynthesis 2016, 6.5% CAGR used in textile from 2017 to 2022 industry US$ 75 million in Itaconic acid Superabsorbent 2015, 16.8% CAGR polymer, synthetic from 2016 to 2021 latex, detergents US$ 32.5 million Levulinic acid Solvents, pharmaceuticals and estimated in 2021, CAGR of 14% from cosmetics 2016 to 2021 Solvents, plasticizer, US$ 14.5 billion in Oxo alcohols (N-butanol, oil additive 2016, 4.4% CAGR 2-ethylhexanol, from 2017 to 2022 iso-butanol)

Data source www. marketsandmarkets. com

www. marketsandmarkets. com www. marketsandmarkets. com www. inkwoodresearch. com www.wastemanagement-world. com www.gminsights. com

www. marketsandmarkets. com www.rfdtv.com

www.gminsights. com www.gminsights. com www. marketsandmarkets. com www.gminsights. com (continued)

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Table 2.1 (continued) Biorefinery product Biohydrogen

Applications Fuel, ammonia, methanol, petroleum refinery

Glutamic acid

Food supplements, pharmaceuticals

Succinic acid

Market information US$ 115.25 billion in 2017, CAGR of 6.07%. From 2018 to 2023 2.9 million tons in 2014, CAGR of 7.5% from 2015 to 2020 US$ 157.2 million in 2015, CAGR 28% up to 2020

Coatings, pharmaceuticals, food industry, plasticizers, solvents, lubricants Glycerol Cosmetics, synthetic US$ 3 billion by paints, food industry 2022, CAGR of 7.9% from 2015 to 2022 US$ 1.09 billion in Sorbitol Cosmetics, 2016, CAGR of pharmaceuticals, 5.3% from 2016 to food industry, 2021 chemical US$ 750 million in Xylitol Food industry, 2015, CAGR 4% up cosmetics, to 2023 pharmaceuticals Packaging and US$ 2.66 billion in Bioplastics and biopolymers bottles 2015, CAGR of 12.0% up to 2020 Carotenoids (beta-carotene Food industry, animal US$ 1.24 billion in 2016, CAGR of and aqua feed, astaxanthin, lutein, 3.78% from 2016 to cosmetics lycopene and zeaxanthin) 2021 Omega-3 polyunsaturated Food industry, animal US$ 9.94 billion in 2015, CAGR of fatty acid and aqua feed, 13.8% from 2015 to pharmaceuticals, 2020 infant formula Animal feeds Feed for livestock, USD 125 billion in cattle, aquaculture 2017 Industrial enzymes Food industry, USD 4.61 billion in textiles, tanneries 2016 and is projected to grow at a CAGR of 5.8% from 2017 to 2022 USD 2.94 billion by Food enzymes Food industry 2021, at a CAGR of (bakery, beverages, 7.4% from 2016 to processed food) 2021

Data source www.gminsights. com

www.gminsights. com

www.gminsights. com

www. marketsandmarkets. com www.gminsights. com

www.gminsights. com www. marketsandmarkets. com www. marketsandmarkets. com www.gminsights. com

www.gminsights. com www. marketsandmarkets. com

www.gminsights. com

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lignocellulosic waste using Lactobacillus organisms (Aghbashlo et  al. 2018). Levulinic acid, another high-value building block compound, is extracted from hexose sugar through intermediate, 5-hydroxymethylfurfural by either acid or enzyme hydrolysis of lignocellulosic waste (Schmidt et  al. 2017). Important industrial chemicals including methyltetrahydrofuran, d-aminolevulinic acid, diphenolic acids and ethyl levulinate have been reportedly synthesized from levulinic acid by dehydrocyclization process (Yan et  al. 2015). Itaconic acid, considered as bio-­ replacement of acrylic acid, is used as superabsorbing polymer and resin in grating and pipes (de Jong et al. 2012). This compound is produced by Aspergillus terreus through fermentation of sugar molecules containing feedstock (Klement and Büchs 2013). Bioplastics including polylactide, nylon, polyhydroxyalkanoate, polyethylene furanoate, poly-γ-glutamic acid, polylactide, poly-butylene-succinate and polytrimethylene terephthalate were produced using carbon substrates present in various feedstock residuals (Wang et al. 2010; Park et al. 2013; Kind et al. 2014; Oh et al. 2015; Choi et  al. 2015). Biopolymers, alternan and pullulan, were produced by Leuconostoc mesenteroides and Aureobasidium species, respectively, using stillage from corn bioethanol production (Leathers and Gupta 1994; Leathers 1998). Biopolymer xylan, a hemicellulose derivative having applications in paper making, food and pharmaceutical industries, was successfully separated from sugarcane bagasse using alkaline treatment (Sporck et al. 2017). Since one-third portion of the lignocellulosic crop is made of lignin, significant amount of lignin waste is generated from paper and other lignocellulosic feedstock-based industries (Kouhia et al., 2015; Schutyser et al. 2018). The manufacture of paper from lignocellulosic crops requires delignification. Moreover, lignin forms the major part of lignocellulosic residuals during bioethanol production. Value-added chemicals such as phenol and furan resins have been reportedly extracted from lignin-containing feedstocks (Schutyser et al. 2018). Resins are organic polymer used in the production of adhesives, plastics and varnishes and in food industry as well. Deep eutectic solvents, synthesized using lignin, were capable of extracting sugar from lignocellulosic biomass (Kim et al. 2018). Lignin-derived aromatic compounds serve as precursor for synthesis of value-added chemicals, muconic acid, which could replace benzene and cyclohexane for production of various biopolymers (Johnson et  al. 2016). Besides, lignin is finding use as phenol replacement in adhesives, precursor for low molecular weight aromatic compound synthesis and adsorbent in polymer formulation (Schutyser et al. 2018). Biofuel extracted from biomass are potential source of pigments, nanomaterials, levoglucosenone, plant hormones and food oil. Astaxanthin, a carotenoid pigment, is used in food industry as colouring agent as well as in diagnostics as labelling agent. Enhancement of astaxanthin production using cane molasses was demonstrated in yeast, Phaffia rhodozyma (Wilkie et al. 2000). Defatted microalgal biomass obtained from biodiesel production is known to contain a variety of pigments with high commercial value including phycoxanthin, phycobilins, β-carotenoids and astaxanthins (Chew et al. 2017; Haznedaroglu et al., 2016). Microalgal biomass is also potential source of high-value pharmaceutically important omega-3 fatty

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acids including eicosapentaenoic acid, docosahexaenoic acid and alpha-linolenic acid (Chew et al. 2017). The protein-rich residue typically found in biofuel-extracted feedstock is predominantly used as animal and aquaculture feed (Ghatak 2011). However, amino acid profile of the residual biomass recovered from biofuel production could be suitable for animals and aquatic species consumption (Boisen et al. 2000). Nanocellulose, a material with wide range of applications including food industry and medicine, was extracted as value-added product from the residue of lignocellulosic bioethanol production (Oksman et al. 2011; Tsukamoto et al. 2013; Le Normand et al. 2014). High-value compound, levoglucosenone, and its derivatives are obtained from cellulose by acid catalyst and used as toxic solvent replacements in pharmaceutical industry, batteries and water purification (De Bruyn et al. 2016). The production of plant hormones, cytokinin, indoleacetic acid, abscisic acid and gibberellic acid by white-rot fungi, Funalia trogii and Trametes versicolor, was improved using diluted stillage obtained from brewery and olive oil mill (Yürekli et al. 1999). Corn bioethanol residues were used for the production of oil with low cholesterol and also high-value fibre gum (Wang et al. 2015). The gluten of corn, rich in protein, is used as adhesive and coating materials in industries related to cosmetics, textiles and biodegradable plastics. Acetone-butanol-ethanol fermentation is a promising biorefinery route for the co-production of solvents such as acetone, butanol and ethanol from reducing sugar molecules recovered from feedstocks. Clostridium species are the responsible organism for ABE fermentation (Mariano et al. 2013). In particular, biobutanol is a fuel with growing marked demand in automobile sector and also gaining attention as aviation type fuel (Zheng et al. 2015). The widely generated biofuel in developing world is biogas, which is synthesized by anaerobic digestion and is the source of various biorefinery products. A valuable by-product that could be recovered from a biogas with high hydrogen sulphide content using microaerators is elemental sulphur (Díaz et al. 2011). Other value-added products that could be recovered from a biogas plant are purified acetate, propionate and butyrate (Ghatak 2011). Moreover, the digestate from biogas production can be used in the formulation of fertilizer (Ghatak 2011). Table 2.2 presents information about biorefinery-related industries, feedstock used and derived products.

2.6  Future Perspectives The main aim of biorefinery process is economic viability. Production of high quantity of pure biofuel along with highly valued co-products will be the key for the economic success. Moreover, if the biorefinery plant is self-sustainable, it would be an added advantage. For instance, the utilization of bagasse produced during sugar or bioethanol production for cogeneration of electricity can effectively meet the energy demand of the whole plant. Also, biorefinery plant integrating multiple feedstocks and wastes from industrial processes widens the spectrum of value-added chemicals production and simultaneously improves the sustainability of the plant.

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Table 2.2  Biorefinery-related industries, feedstock used and derived products Industry DuPont cellulosic ethanol – USA, 30 MGY (million gallons per year) Golden cheese company of California – USA, 5 MGY Archer Daniels Midland co.– USA, 300 MGY Cargill, Inc. – USA, 210 MGY

Feedstock Cellulosic biomass

Marquis energy – USA, 300 MGY

Corn

SEKAB – Sweden Alkol biotech and bioforever – European Union, 500,000 tons of biomass Abengoa – USA, 25 MGY Renewable energy group – Grays Harbor USA, 100 MGY Neste oil OYJ – Singapore, 850,000 metric ton of crude palm oil AltAir and Honeywell UOP – USA

Wood biomass GM sugarcane

Valero energy Corp – USA, 135 MGY BP Vivergo – UK, 420 million litre per year Kaidi – Finland, 200,000 ton of biofuel per year Total – La Mede – France, 500,000 ton per year feedstock Praj industries – India, one million litre per annum Chempolis, Fortum and Numaligarh refinery ltd. – India, 300,000 tons of bamboo (upcoming)

Cheese whey Corn Corn

Lignocellulosic waste Low free fatty acid feedstocks Palm oil Nonedible animal fats and oils Corn residues Wheat

Products Bioethanol, animal feed, renewable chemicals Bioethanol, animal feed, renewable chemicals Bioethanol, animal feed, renewable chemicals Bioethanol, animal feed, renewable chemicals Bioethanol, animal feed, renewable chemicals Bioethanol, lignin, biogas Furan dicarboxylic acid, enzymes, resin acid, butanol Bioethanol, electricity Biodiesel, naphtha, glycerin Biodiesel and value-added chemicals Biodiesel, aviation fuel Bioethanol, animal feed Bioethanol, animal feed

Wood biomass

Biodiesel, biogasoline

Rapeseed, animal fat, used oil, palm oil Agricultural and food residues Bamboo

Biodiesel, aviation fuel, fuel additives, Bioethanol and value-added chemicals Ethanol, biocoal, furfural, acetic acid, combined heat and power

Establishment of technology assessment programme similar to the established Brazilian Bioethanol Science and Technology Laboratory in every country is the need of the hour. This would analyse and match the regional productivity of various feedstocks with market demands of by-products. New efficient tools like multi-­ criteria method have to be developed to assess the sustainability of novel biorefinery concepts in order to make policy-oriented, economical and environmental decisions (Gnansounou et al. 2017). An emerging problem faced by biorefinery industry is the difficulty in the transportation of lignocellulosic biomass throughout a biorefinery facility due to its varied size, shape and surface property. In such cases, appropriate size-reduction techniques and change in biomass surface characteristics can lead to the possible solution for logistics-associated problem (Miao et al. 2012). A recent

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study suggested by lowering the cost of feedstock and increasing the size of biorefinery plant, economic production of cellulosic biofuel is possible (van Rijn et al. 2018). The innovative technologies aimed for the improvement of bioproduct separation and process related to biofuel and by-product synthesis, together with identification of new value-added products that could be produced from the feedstock, boost the biorefinery process economics and lessen the environmental impact.

2.7  Conclusions The current use of non-renewable fuel resources leads to increased emission of carbon dioxide which in turn contributes to global warming. Biofuel derived from biomass could replace these non-renewable resources and rescue the environment from adverse effects of global warming. Biofuel production could become an economically viable option if the residual biomass is used after energy extraction. For this purpose different technologies are available for obtaining marketable products from residual biomass in pure form. A careful selection of these techniques to obtain the desired products will be the key to the success of biorefinery. The need for biorefinery has garnered more attention in recent times due to increased dependence of fossil fuel and failure of biofuel to penetrate the oil market. But biorefinery is still in nascent stage as there is no large-scale demonstration of the processes. The upcoming biorefinery-based research should focus on environmental impacts. The industrial-scale applications of toxic solvents, carbon footprint and energy requirements should be generally minimized or possibly avoided. The future success of biorefinery will depend on the types of product obtained from biomass, value of purified product and cost incurred by different downstream processes involved in refining the biomass. Acknowledgements Authors thank Prof. M.  Sivanandham, Secretary, SVEHT and SVCE Management for their support and encouragement.

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Chapter 3

Nanobioremediation Technologies for Potential Application in Environmental Cleanup Surbhi Sinha, Tithi Mehrotra, Ashutosh Srivastava, Arti Srivastava, and Rachana Singh

Contents 3.1  I ntroduction 3.2  C  urrent Treatment Technologies for the Removal of Pollutants 3.3  Nanotechnology 3.3.1  Nanoparticles 3.3.2  Properties of Nanoparticles 3.4  Synthesis of Nanoparticles 3.4.1  Nanoparticles Synthesized by Plants 3.4.2  Nanoparticles Synthesized by Bacteria 3.4.3  Nanoparticles Synthesized by Fungi and Yeast 3.4.4  Nanoparticles Synthesized by Algae 3.5  Nanobioremediation 3.6  Conclusion References

                                      

54 55 56 57 57 58 59 60 62 62 63 64 66

Abstract  Increased population density and demands of urban environment together with industrialization has caused environmental pollution which ultimately has adverse effects on human health. Maintaining a clean environment by using a sustainable, eco-friendly and cost-effective technologies is one the arduous challenge of twenty-first century. Nanobioremediation is an advanced rapidly emerging technology for the removal of contaminants from the environment using biologically synthesized nanoparticles. These nanoparticles show unique physical, chemical and biochemical properties and thus have received considerable attention from S. Sinha · T. Mehrotra · R. Singh (*) Amity Institute of Biotechnology, Amity University, Noida, Uttar Pradesh, India e-mail: [email protected]; [email protected] A. Srivastava · A. Srivastava Amity Institute of Marine Science and Technology, Amity University, Noida, Uttar Pradesh, India e-mail: [email protected] © Springer Nature Switzerland AG 2020 K. M. Gothandam et al. (eds.), Environmental Biotechnology Vol. 2, Environmental Chemistry for a Sustainable World 45, https://doi.org/10.1007/978-3-030-38196-7_3

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researchers globally in different fields of environmental sciences including bioremediation. Biologically synthesized nanoparticles have been found to be significant in modifying and detoxifying pollutants which ruin the environment. Moreover, these also have the capability for extensive environmental cleanup at lower price and reduced toxic by-products. The present chapter summarizes the biological synthesis of nanoparticles from plants, algae, yeast, fungi and bacteria and recent developments in the nanobioremediation technology for environmental cleanup along with the future prospects. The technique of nanobioremediation is found to be efficient and economic and proved to be a superior and innocuous substitute to the available traditional methods providing a sustainable environment. Keywords  Environmental cleanup · Nanotechnology · Nanoparticles · Biosynthesis · Plants · Bateria · Algae · Fungi · Nanobioremediation

3.1  Introduction Human activities in the past decade have caused severe concern associated with the environment and its conservation. Water scarcity, water pollution, air pollution, soil degradation, poor management of waste and loss of biodiversity are some of the environmental issues that have caused long-term health impacts not only on human beings but also on animals and plants (Mounika et al. 2019). Moreover, the development in industrialization as well as science and technology has led to the multiplication of waste and toxic materials in the environment making the situation worse. Thus, the degradation and diminution of natural resources must be circumvented to achieve a sustainable environment. The traditional physicochemical methods employed for the restoration of the natural environment were found to be inappropriate for this purpose due to cost, lower efficiency and non-specificity. Therefore to overpower these limitations, biological methods involving the use of microorganisms were utilized for the remediation of pollutants from the environment, and the process was termed as ‘bioremediation’ (Sherry et al. 2017). The bioremediation has the advantage of high competence and selectivity towards the pollutant, reduced sludge generation and low cost (Volesky and Kratochvil 1998). However, if the concentration of the pollutant is very high, then there are chances that the biological organism may get destroyed. Therefore, to repress these problems, biological methods were amalgamated with the nanotechnology-based physiochemical methods by the process known as ‘nanobioremediation’. So, broadly, nanobioremediation can be defined as the process that makes use of biologically synthesized nanoparticles for bioremediation or to remove pollutants from the environment. These biosynthesized nanoparticles not only have the peculiar capacity to remediate hazardous contaminants from the surroundings but also enhance the activity of the biological

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agents subsequently accelerating the entire process of environmental cleanup (Konishi et  al. 2006). So, herein the chapter summarizes the existing physical, chemical and biological methods for the treatment of pollutants along with their merits, demerits and the application of nanotechnology in the bioremediation of contaminants. The chapter primarily focuses on the synthesis of nanoparticles using different biological agents, sizes and shapes of biosynthesized nanoparticles and their applications in the treatment of different pollutants. This nanobioremediation approach for the dismissal of toxicants from the environment is the most reliable and propitious technology with respect to cost and efficiency corresponding to the socio-economic conditions of the developing nations.

3.2  C  urrent Treatment Technologies for the Removal of Pollutants Because of the toxicity and recalcitrant nature of the pollutants, they have been considered hazardous to the environment. The treatment of these pollutants in an environmentally safe manner is mandatory before they are being discharged. The physical, chemical and biological methods are some of the current treatment technologies utilized for the removal of pollutants from the environment (Lim et al. 2014). Physical methods include processes like adsorption, reverse osmosis and electrodialysis. A large number of pollutants are being released into the environment, out of which some are very difficult to be treated by the conventional physical methods (Tore et al. 2012). To overcome the constraints of physical methods, some of the chemical processes like precipitation, ion exchange, electroflotation, coagulation, flocculation, reduction, etc. were employed for the removal of pollutants from the ecosystem. Although the chemical methods utilized are efficient and rapid and can nearly remove all kinds of pollutants, their use is limited by high cost and sludge disposal problem (Luo et al. 2014). Moreover, high energy and a large number of chemicals are also required. Keeping all the above constraints in mind, biological methods involving the use of microorganisms were employed for the purging of toxicants from nature (Singh and Sinha 2013). This process is termed as ‘bioremediation’ (Asha and Sandeep 2013). The process of biological remediation is economically attractive as well as environment-friendly. Also, there is an advantage of minimum sludge generation, revival of biosorbent and possibility of metal retrieval (Yadav et al. 2017a, b). However, some difficulties in utilizing microorganisms as remediation entity were also established. The processes are slow; additional nutrition and maintenance are required. Moreover, the pollutants sometimes itself become toxic to the microorganisms involved in the process. Each of these methods has their own merits and demerits which make them inadequate to deal with the problem of pollutant removal from the environment. The merits and demerits of some of the physical, chemical and biological methods are summarized in Table 3.1.

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Table 3.1  Some of the conventional methods used for environmental cleanup Conventional methods Chemical precipitation Membrane filtration

Electrochemical treatment Coagulation and flocculation

Merits Simple, low-cost and non-metal selective Removal of suspended solids, organic compounds and heavy metals Metal selective, high treatment capacity Less sludge produced, meal selective Simple and non-metal selective

Biological methods

Cost-effective, non-toxic

Ion exchange

Demerits A large amount of sludge production, poor settling The flow rate is less, high cost

References Kousi et al. (2007) Gunatilake (2015)

Maintenance cost

Dizge et al. (2009) Gunatilake (2015) Lopez-­ Maldonado et al. (2014) Zeyaullah et al. (2009)

High cost and pH sensitive A large amount of sludge production and transfer of toxic compounds into the solid phase A slow process, necessary to create an optimal favourable environment, maintenance and nutrition requirement

3.3  Nanotechnology The existing traditional physicochemical methods and biological methods were not very efficient and effective in cleaning up the environment. Therefore, a new technology named ‘nanotechnology’ can be applied for restoration of the environment. The term nanotechnology is a derivative of a Greek word which means ‘dwarf’ (El Saliby et al. 2008). It can be defined as the science of micro-engineering, a technique dealing with the manipulation of the particles smaller than 100 nanometres. Nanotechnology, first conceptualized by Richard Feynman (Feynman 1960), is now one of the rapidly growing areas of scientific research and technology development globally (Yadav et al. 2017a, b). Currently, nanotechnology is frequently introduced as ‘Next Industrial Revolution’ as in future it is going to reduce the production costs in industries by reducing the consumption of energy, diminishing environmental pollution and enhancing the production efficiencies in developed countries (Roco 2005). It can skillfully and smartly amalgamate along with other technologies and rework or simplify any scientific theory, that is why it is also called as ‘platform’ technology (Schmidt 2007). Additionally, nanotechnology may prove useful in developing countries to tackle socially important problems such as the requirement of pure and aseptic water and cure from epidemic diseases (Fleischer and Grunwald 2008). Nanotechnology offers a large number of environmental benefits in remediation and pollution prevention and contributes a lot in developing smaller, more accurate sensing and monitoring devices (Savage et  al. 2008). The capability of nanotechnology to curtail pollutants is in a progression which could potentially bring about the most revolutionary changes in the pollution abatement (Watlington 2005).

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3.3.1  Nanoparticles The basic integrant of nanotechnology is very small particles called the nanoparticles varying between 1 and 100 nm in size that can intensely alter their physicochemical properties as compared to the bulk material. Nanoparticles are made up of carbon, organic matter, metal or metal oxides, and their behavior depends on the chemical composition, size and shape of the particles. They can be spherical, cylindrical, tubular or flat in shape. Their surface can be even or uneven, while some are crystalline to amorphous with single or multi-crystal solids either loose or agglomerated. These nanoparticles are very reactive and mobile in nature. The nanoparticles are broadly categorized into inorganic, organic and carbon-­ based. Inorganic nanoparticles are not made up of carbon. They generally comprise metal and metal oxide nanoparticles. Commonly used metal and metal oxide nanoparticles are aluminium, copper, gold, iron, iron oxide, aluminium oxide, magnetite, etc. (Dreaden et al. 2012). Organic nanoparticles include liposomes, ferritin or dendrimers that are non-toxic, biodegradable and are also responsive towards thermal and electromagnetic radiations like heat and light, making them perfect choice for drug delivery (Tiwari et al. 2008). Carbon-based nanoparticles are completely made up of carbon like graphene, fullerenes or carbon nanotubes (Saeed and Khan 2016).

3.3.2  Properties of Nanoparticles The unique chemical, physical, optical, thermal and electrical properties (Panigrahi et  al. 2004) of nanoparticles can be utilized in various fields like drug delivery (Horcajada et al. 2008), medical imaging (Lee et al. 2008), optical receptors (Dahan et al. 2003), biolabelling (Liang et al. 2006) and antimicrobial agents (Sanpui et al. 2008). Apart from these, there are other significant properties of nanoparticles that make them highly useful in the bioremediation like its tiny size which leads to an increase in the surface area per unit mass. Due to the small size, a large amount of nanoparticle can directly interact with the surrounding medium, ultimately affecting its reactivity. Lower activation energy is needed to make the chemical reactions feasible as nanoparticles produce quantum effects. Nanoparticles show a remarkable property of surface plasmon resonance which helps in the detection of toxic contaminants present in the environment. Additionally, the properties of nanoparticles also make them suitable for the development of electrochemical sensor as well as a biosensor (Peng and Miller 2011) for the detection of mycotoxins and algal toxins in drinking water (Selid et al. 2009). Researchers have also developed nanosensors for the detection of auxin and oxygen distribution in plants (Koren et al. 2015). Nanoparticles have been recommended as an efficient, economical and ecofriendly substitute to the present treatment technologies, not only in resource conservation but also in environmental remediation (Dastjerdi and Montazer 2010).

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3.4  Synthesis of Nanoparticles Nanoparticles can be synthesized by different methods and approaches that include physical, chemical and biological techniques as portrayed in Fig.3.1 (Luechinger et al. 2010). Conventionally, these particles were synthesized by physicochemical methods that enabled them to be produced in abundance with definite shape and size in a very short time; howbeit, these techniques are expensive, ineffective and complicated, utilize hazardous chemicals, require high energy and generate toxic byproducts that are environmental hazards (Li et  al. 2011; Rodriguez-Sanchez et al. 2000). Recently, the interest has been focussed on the synthesis of cheap and eco-­ friendly nanoparticles that do not produce any kind of toxic and hazardous by-products during manufacturing (Chauhan et al. 2012). Hence, lately, the nanoparticles are being synthesized using a biological approach that involves microorganisms, plants and their by-products with the help of some biological tools. Biologically synthesized nanoparticles have remarkable and exceptional advantages over physical and chemical methods like the production methodologies which are cheap, rapid and eco-friendly. Moreover, the nanoparticles synthesized by biological route do not require any further stabilizing agents as microorganisms and plants themselves act as capping and stabilizing agents (Makarov et al. 2014). Biological synthesis of nanoparticles is a bottom-up approach where reducing and stabilizing agents help in synthesizing the nanoparticles (Fig.  3.2). The plant phytochemicals or microbial

Fig. 3.1  Different methods and approaches for synthesizing nanoparticles

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Fig. 3.2  Biological synthesis of nanoparticles using a bottom-up approach

enzymes with reducing features are usually accountable for the reduction of metal compounds into their biosynthesis of various nanoparticles using plants and microorganisms like bacteria, algae, fungi and yeast which are compiled below.

3.4.1  Nanoparticles Synthesized by Plants Biological synthesis of nanoparticles by plants is getting a lot of attention these days because of its simple, stable, rapid, cheap and an eco-friendly method (Mittal et al. 2013). Additionally, plants are abundant, safe to use and have a wide variety of metabolites that help in reduction. Plant extracts constituting bioactive alkaloids, phenolic acids, polyphenols, proteins and sugars play an essential role in first reducing the metallic ions and further stabilizing them (Castro et  al. 2011). Table  3.2 compiles the information on a large number of plants being employed for the synthesis of varied nanoparticles, and it is clear from the information that the synthesis of nanoparticles, their size and application all vary from plant to plant. Table 3.2 reveals that a hefty number of plants have been utilized for the synthesis of various kinds of nanoparticles; still, there is a need for research to unravel the physiological, biochemical and molecular mechanisms of plants with respect to nanoparticles.

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Table 3.2  List of various plants used for the synthesis of nanoparticles Nanoparticles Plant Gold Papaver somniferum Citrus maxima Dillenia indica Butea monosperma Musa paradisiaca

Silver

Titanium

Palladium

Platinum

Garcinia mangostana Cleome viscosa

Size 77 nm 25.7 5–50 nm 10– 30 nm 50 nm 32.96

20– 50 nm Origanum vulgare L. 2–25 nm Allium cepa 10– 23 nm Azadirachta indica 65 nm Prunus persica 40– 98 nm Aloe vera 5–50 nm

Shape Spherical Rod and spherical Spherical Spherical

References Wali et al. (2017) Yu et al. (2016) Sett et al. (2016) Patra et al. (2015)

Spherical to triangular Vijayakumar et al. (2017) Spherical Lee et al. (2016) Spherical Spherical Spherical

Lakshmanan et al. (2018) Shaik et al. (2018) Gomaa (2017)

Spherical Spherical

Roy et al. (2017) Kumar et al. (2017)

Octahedron

Logaranjan et al. (2016) Abdul Jalill et al. (2016) Shimpi et al. (2016) Sankar et al. (2015)

Curcuma longa

50–110

Spherical

Murraya koenigii Azadirachta indica

2–15 124

Psidium guajava

32.58

Spherical Spherical and interconnected Spherical

Garcinia pedunculata Roxb Camellia sinensis Glycine max Fumariae herba

~2–4 nm Spherical to non-spherical 11 nm Spherical 15 nm Spherical 20– Hexagonal 30 nm

Santhoshkumar et al. (2014) Hazarika et al. (2017) Azizi et al. (2017) Petla et al. (2012) Dobrucka (2019)

3.4.2  Nanoparticles Synthesized by Bacteria Among the biological agents, bacteria have always attracted lot of attention from researchers globally as a means for synthesizing a variety of nanoparticles such as zinc, silver, gold, cadmium sulphide, palladium and so on. These prokaryotes are considered to be a great option for synthesizing nanoparticles as they are abundantly present in the environment and also they have the capacity to adjust to any harsh conditions. Moreover, bacteria grow very fast, they are easy to manipulate, and very less cost is required for their cultivation. Growth conditions of bacteria like

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temperature, incubation time, aeration and agitation can be easily controlled and maintained in the culture medium. The marked ability of the bacterial cells to bind to metals and S-layers make these biological entities useful for application in the field of nanobioremediation (Yadav et  al. 2017a, b). Table  3.3 lists the various nanoparticles of different sizes and shapes synthesized by different bacteria.

Table 3.3  List of some nanoparticles synthesized by bacteria Nanoparticles Gold

Silver

Cadmium sulphide

Palladium

Bacteria Geobacillus sp. strain ID17 E.coli K12

Size 5–50 nm and 10–20 nm 50 nm

Stenotrophomonas maltophilia Pseudomonas fluorescens Klebsiella pneumoniae

40 nm

Escherichia coli

20–25 nm

Pseudomonas aeruginosa Salmonella typhimurium Pseudomonas fluorescens Bacillus stearothermophilus Bacillus cereus

15–30 nm

Pseudomonas aeruginosa

13 nm

Arthrobacter gangotriensis (MTCC 690) Bacillus subtilis

3.6–22.8 nm

Escherichia coli

2–5 nm

Klebsiella aerogenes

20–200 nm

Spherical, occasionally triangular Spherical, elliptical Spherical

Desulfovibrio desulfuricans NCIMB8307

~50 nm

–

50–70 nm 35–65 nm

87 ± 30 nm 85.46 nm 14 ± 4 nm 20–40 nm

5–50 nm

Shape References Quasi-hexagonal Correa-Llantén et al. (2013) Circular Srivastava et al. (2013) Spherical Sharma et al. (2012) Spherical Rajasree and Suman (2012) Spherical Nangia et al. (2009) – Deplanche and Macaskie (2008) – Husseiny et al. (2007) – Ghorbani (2013) Irregular Silambarasan and Jayanthi (2013) Spherical El-Batal et al. (2013) Spherical Silambarasan and Abraham (2012) Spherical Kumar and Mamidyala (2011) Spherical Shivaji et al. (2011) Saifuddin et al. (2009) Sweeney et al. (2004) Holmes et al. (1995) Yong et al. (2002)

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3.4.3  Nanoparticles Synthesized by Fungi and Yeast The study on the significant role of fungi in the nanotechnology and nanobioremediation cannot be ignored. Lately, the use of fungi in the production of nanoparticles has gained rapid fascination because of being tolerant and having the capacity to bioaccumulate metals (Sastry et al. 2003). An extensive amount of enzymes can be produced by fungi since they are magnificent secretors of extracellular enzymes, which subsequently influence the synthesis of nanoparticles (Castro-Longoria et al. 2012). Fungi are considered superior to bacteria in the synthesis of nanoparticles as these fungi secrete large volume of proteins which directly gets translated to nanoparticles leading to higher productivity. Proteins isolated from fungi also have great potential in the synthesis of nanoparticles. Additionally, a number of fungal species grow very fast, making their maintenance in the laboratory very simple (Castro-Longoria et al. 2011). In a similar way, easy maintenance of yeast production in the laboratory, its rapid growth and use of simple nutrients are some of the remarkable advantages of yeast over bacteria for the mass production of nanoparticles (Skalickova et al. 2017). Fungi and yeast have supremacy over other biological systems because of their wide diversity, simple culture methods, less time and low cost which successively leads to an eco-friendly approach for the synthesis of nanoparticles. Some of the fungal and yeast species successfully utilized for the production of the nanoparticles are documented in Table 3.4.

3.4.4  Nanoparticles Synthesized by Algae In the past few years, the use of algae for the biosynthesis of nanoparticles has become quite frequent due to their easy access and efficiency (Ogi et  al. 2010). Currently, they are also referred to as ‘biofactories’ for the synthesis of nanoparticles, since they are an excellent source of biomolecules (Manivasagan and Kim 2015). These biomolecules like proteins, pigments, carbohydrates, nucleic acids, fats and secondary metabolites like alkaloids constituting the algal cell wall act as the reducing agents which ultimately leads to the reduction and fabrication of metallic nanoparticles at ambient conditions (Siddiqi and Husen 2016). Additionally, seaweeds have a clear advantage over other reductants due to their high metal-­accumulating capacity, low cost, macroscopic structure and anti-biological fouling properties (Davis et al. 2003). Moreover, seaweed extracts that have both inhibitory and anti-inflammatory properties can be used to treat different medical conditions and suppress some forms of cancer (Fawcett et al. 2017). Biogenic fabrications of various nanoparticles using different algal species are presented in Table 3.5.

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Table 3.4  List of some nanoparticles synthesized by fungi and yeast Nanoparticles Fungi and yeast Gold Penicillium spp.

Silver

Size 45 nm

Mariannaea sp. HJ

37.4 nm

Pycnoporus sanguineus

29.30 nm

Magnusiomyces ingens LH-F1 Aspergillus sp. WL-au

10–80 nm 4–29 nm

Ganoderma enigmaticum

15–25 nm

Rhizopus stolonifer

9.47 nm

Raphanus sativus

4–30 nm

Saccharomyces cerevisiae

1–10 nm

Shape Spherical

References Sandhya and Suvarnalatha Devi (2017) Spherical, Pei et al. hexagon, irregular (2017) Shi et al. Spherical, (2015) pseudospherical, triangular Triangle, hexagon, Zhang et al. pentagon (2016) Spherical Shen et al. (2017) Spherical Gudikandula et al. (2017) Spherical Rahim et al. (2017) Spherical Singh et al. (2017) Spherical Marquez et al. (2018) Spherical Zahran et al. (2013)

Saccharomyces cerevisiae, 2.5–20 nm Rhodotorula glutinis and Geotrichum candidum Arthroderma fulvum 15.5 ± 2.5 nm Spherical Copper carbonate Cadmium sulphide

Neurospora crassa

10–20 nm

Spherical

Candida glabrata and Schizosaccharomyces pombe

2 nm

Spherical

Xue et al. (2016) Li and Gadd (2017) Dameron et al. (1989)

3.5  Nanobioremediation Salient feature of nanotechnology is the art of exploiting and controlling matter at the atomic and molecular level, which remarkably provides the formed materials in the nano range (1–100 nm) to have the requisite capacity to improve environmental quality and sustainability through various ways, such as prevention of pollution and bioremediation processes (Gopinath et al. 2013). The use of nanotechnology in bioremediation has become extensive because of varied reasons. Firstly, the nanoscale size helps in increasing the surface area, thereby enhancing the reactivity rate. Secondly, less activation energy is needed to make chemical reactions attainable as the nanoparticles portray quantum effect. Surface plasmon resonance (SPR) is another feature displayed by the nanoparticles that can be used for the detection of

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Table 3.5  List of some nanoparticles synthesized by algae Nanoparticles Gold

Silver

Zinc oxide Aluminium oxide Iron oxide Copper oxide

Algae Sargassum myriocystum Chlorella vulgaris Turbinaria conoides Ecklonia cava

Size 60 nm

Shape Spherical

2 to 10 nm 2–19 nm

Spherical

References Ismail et al. (2018)

Annamalai and Nallamuthu (2015) Spherical and triangular Vijayan et al. (2014)

30 nm

Spherical and triangular Venkatesan et al. (2014) Spatoglossum 20–46 nm Spherical to oval Ravichandrana et al. asperum (2018) Gelidium amansii 27–54 nm Spherical Pugazhendhi et al. (2018) Amphiroa anceps 10–80 nm Spherical Roy and Anantharaman (2018a) Sargassum 10 to Spherical, cubical and Roy and ilicifolium 80 nm hexagonal shaped Anantharaman (2018b) Laminaria 20 nm Spherical- to Kim et al. (2017) japonica oval-shaped Ulva lactuca 15 nm Asymmetrical Ishwarya et al. (2018) Sargassum 20 nm Spherical Koopi and Buazar ilicifolium (2018) Ulva flexuosa 12.3 nm Cubo-spherical Mashjoor et al. (2018) Bifurcaria 96–110 Spherical Abboud et al. (2014) bifurcata

toxic materials. Cleanup of environmental pollutants like organic/inorganic waste and heavy metals from the affected sites by the use of nanomaterials synthesized by plants, bacteria, yeast, fungi and algae is called nanobioremediation (Yadav et al. 2017a, b). Application of green technology has been escalated in the arena of nanomaterials for bioremediation due to increased efficiency, reduced cost in large-­scale remediation and shortened time for the cleanup. Different biologically synthesized nanomaterials used for bioremediation are discussed in Table 3.6, which show high level of remedial versatility like the removal of various kinds of wastes including solid waste, groundwater and wastewater, hydrocarbons, soil remediation, uranium remediation and heavy metal removal.

3.6  Conclusion Nanotechnology is gaining momentum all over the world for successfully removing the pollutants from the environment. The unique properties of nanoparticles and their confluence with the present-day technologies offer great opportunity to

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Table 3.6  Overview of nanomaterials used to remediate varied pollutants Nanomaterials Gold/carbon nanodots Gold Gold

Aspergillum sp. WL-Au Aromatic pollutants Bacillus marisflavi YCIS MN 5 Congo dye

Iron

Chlorella sp. MM3

Brewery wastewater

Iron oxide nanoparticle Silver

Padina pavonica; Sargassum acinarium Bacillus pumilus, Bacillus paralicheniformis and Sphingomonas paucimobilis Penicillium citreonigrum Dierckx and Scopulariopsis brumptii Salvanet-Duval Ocimum sanctum and Artemisia annua Cobweb

Lead

Copper

Biological agent Allium cepa leaves

Ficus benghalensis

Palladium oxide Dictyota indica seaweed Titanium dioxide

Bacillus amyloliquefaciens Ageratina altissima

Zinc oxide

Garcinia mangostana fruit pericarp Coriandrum sativum

Pollutants treated Hg2+ ions

Malachite green

Exhibited antibacterial activity

References Venkateswarlu et al. (2019) Qu et al. (2017) Nadaf and Kanase (2016) Subramaniyam et al. (2016) El-Kassas et al. (2016) Allam et al. (2019) Hamad (2019)

Antimicrobial activity

Khatoon et al. (2018) Rhodamine B Azeez et al. (2018) Methylene blue Agarwal et al. (2016) Cadmium Yazdani et al. (2018) Reactive Red 31 Khan and Fulekar (2016) Methylene blue, alizarin Ganesan et al. (2016) red, crystal violet and methyl orange Malachite green Aminuzzaman et al. (2018) Anthracene dye Hassan et al. (2015)

revolutionize environmental cleanup. Biological synthesis of nanoparticles synergistic with the bioremediation can go a long way in attaining a sustainable environment. Synthesis of nanoparticles by biological means aids in diminishing the usage of toxic chemicals and moreover makes the entire process comparatively cheap, time-saving, easy and simple. Researchers, around the globe, have synthesized different types of nanoparticles using various biological agents. Bacteria, because of their high growth rate and easy manipulation, are considered superior to other biological agents for the synthesis of nanoparticles. Alternatively, fungi have the capability to secrete proteins that lead to higher productivity of nanoparticles. Mycelia in many fungal species have a higher surface area as compared to bacteria that could help in the association of metal ions and fungal reducing agent consequently intensifying the transformation of ions to metallic nanoparticles. Plants and algae are also

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considered as good producers of nanoparticles. Recently, they have been used quite frequently for the synthesis of nanoparticles due to their easy access and efficiency. In the coming years, research should be focussed to exploit the detailed mechanism, fate of bioavailability and thereby sustainability of these biologically synthesized nanoparticles. Besides, polymeric nanoparticles, single-enzyme nanoparticles and nano-biosensors developed using biological agents can have successful future application in nanobioremediation. The field of bioremediation amalgamated with nanotechnology is quite new and not explored much; however, it displays great potential in the sector of biotechnology. Acknowledgements  The authors are grateful to Amity Institute of Biotechnology and Amity Institute of Marine Science and Technology, Amity University, Noida, Uttar Pradesh.

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Chapter 4

Biosurfactant in Food and Agricultural Application Srinivasan Nalini, Rengasamy Parthasarathi, and Dhinakarasamy Inbakanadan

Contents 4.1  4.2  4.3  4.4  4.5  4.6  4.7  4.8 

 Introduction Biosurfactant as Emulsifier Biosurfactant in Bakery and Ice Cream Industry Biosurfactant as Food Additives Biosurfactant as Flavouring Agent Biosurfactant as the Stabilizing Agent Biosurfactant as an Anticorrosive Agent Biosurfactant as an Antiadhesive Agent 4.8.1  Risk of Biofilm Formation in Food Industries 4.8.2  Biomedical Application of Biosurfactant by Its Antimicrobial Potentiality 4.9  Biosurfactant Extending the Shelf Life of Food Products 4.10  Probiotic Biosurfactant 4.10.1  Biosurfactant-Producing Probiotic Strains 4.11  Food Sanitation 4.12  Biosurfactant in Agriculture 4.12.1  Mode of Action of Biosurfactant 4.13  Conclusion References

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Abstract  Biosurfactants are synthesized majorly by microbes like bacteria and fungi (yeast) and known to decrease the interfacial and surface tension between immiscible liquids. Other properties such as detergency, wettability and foaming properties make biosurfactant suitable for different applications. Recently, biosurS. Nalini · D. Inbakanadan (*) Centre for Ocean Research (DST-FIST Sponsored Centre), MoES – Earth Science & Technology Cell (Marine Biotechnological Studies), Sathyabama Institute of Science and Technology, Chennai, Tamil Nadu, India e-mail: [email protected] R. Parthasarathi Department of Microbiology, Faculty of Agriculture, Annamalai University, Annamalai Nagar, Tamil Nadu, India © Springer Nature Switzerland AG 2020 K. M. Gothandam et al. (eds.), Environmental Biotechnology Vol. 2, Environmental Chemistry for a Sustainable World 45, https://doi.org/10.1007/978-3-030-38196-7_4

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factants are gaining attraction as potential alternate for chemically synthesized surfactant for current development for industrial and ecological sustainability. ­ According to WHO and FAO, ‘probiotics’ are live microorganisms that when consumed is believed to produce medical benefits to the consumer. LAB (lactic acid bacteria) are most documented to yield several antimicrobial compounds like biosurfactant, bacteriocin, hydrogen peroxide and carbon peroxide that inhibit the growth of pathogens. Predicting biofilm development on surface and use of biosurfactant would lessen the contamination, decrease damages and, in turn, decline costs to the food processing industries. Biosurfactants produced from different microbes are known to have antimicrobial activity against plant phytopathogens and shown to be a promising biocontrol agent for achieving sustainable agriculture. The most reported biosurfactants as biocontrol agent are rhamnolipid and lipopeptide. Biosurfactant demonstrated antagonist effect on zoosporic plant phytopathogen that has acquired resistance to commercial pesticides, thus initiating their use as biocontrol agent. Biosurfactant can likewise excite immunity of the plant which is considered as an alternate approach to decrease the disease caused by phytopathogens. The present chapter covers and reviews the aspects of biosurfactant in food and agriculture applications. Keywords  Biosurfactant · Emulsifier · Antiadhesive · Stabilizing agent · Flavouring agent

4.1  Introduction The food industry is more concerned about the quality of the food product along with the texture, consistency, aroma, taste and safety. Addition of different kinds of synthetic or artificial compounds or food additive begins to decline slowly as more awareness has been implicated among the public. Biosurfactant is one among the naturally synthesized amphiphilic components from microorganism. As there are different groups of biosurfactant, owing to the lipid moiety, they are classified into glycolipids, lipopolysaccharides, lipopeptides, phospholipids, fatty acids, polysaccharide-­ protein complexes and neutral lipids (Hamme et  al. 2006; Vasconcellos et al. 2011; Hoskova et al. 2013; Moya et al. 2015; Bezerra et al. 2018). Biosurfactant put forwards various advantages when compared to the chemical surfactant as they are less toxic, highly biodegradable and eco-friendly and have high foaming capacity, high sensitivity and specificity at extreme pH, temperature and high salinity. The overall biosurfactant production contributes 3–5% to food and agriculture and has started to create their own commercial demand with a compound annual growth rate forecast of 8–9% (Mulligan and Gibbs 2004; Markets and markets 2016). Despite the chemical structure, surface-active compounds are capable of reducing the interfacial and surface tension between immiscible liquids, which serves as a key factor for many potential applications in various fields

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including agriculture and food industry. More promisingly, biosurfactant has also been successfully implemented in food sanitation and cleaning purposes (Sharmaa and Saharan 2016; Rautela and Cameotra 2014). The potentiality of biosurfactant as biological control was pioneered by Stanghellini and Miller (1997), who evidenced that rhamnolipid biosurfactant can disrupt the zoospores of plant phytopathogens. Various biosurfactants from microorganisms have antimicrobial activity against phytopathogens and are proven to be a promising biocontrol molecule for achieving sustainable agriculture. The rhamnolipid biosurfactant from Serratia rubidaea SNAU02 revealed removal of 92% of used engine oil from the contaminated soil sample (Nalini and Parthasarathi 2013). The biosurfactant also has potential application in enhancing oil recovery and bioremediation. Biosurfactant has been reported in food products for its emulsifying, demulsifying, antiadhesive, antimicrobial and food preservation activities (Nitschke and Costa 2007; Boruah and Gogoi 2013; Mnif and Ghribi 2016). However, these properties are related to the amphiphilic nature of the biosurfactant (Merchant and Banat 2012). At present, commercialization of the biosurfactant was made available in the online market by certain private sector as per the needs and different commercial applications corresponding to the website https://www.marketsandmarkets.com/ Market-Reports/biosurfactant-market-163644922.html. This present chapter covers and concentrates on the overview of the application of biosurfactant in food industries and agriculture.

4.2  Biosurfactant as Emulsifier The emulsifier is the agent used to mix or emulsify various food components to make it a desirable product in the food industry. Due to its amphiphilic nature, biosurfactant is efficient in enhancing them to dissolve polarity of two immiscible liquids by reducing their surface tension (Smyth et al. 2010). Daverey and Pakshirajan (2010) reported the ability of sophorolipid to solubilize ghee and soybean oil, suggesting its potential application in the food industry. In most of the food products, emulsification plays a key role in the texture, consistency, phase dispersion and solubilization of atoms. An emulsifier function is to stabilize the emulsion by controlling the globular clustering and stabilizing aerated systems. Butter, cream, mayonnaise, salad dressing, chocolates and hot dogs are examples of emulsioned processed food (Campos et al. 2013). Torrego-Solana et al. (2014) reported the ability of rhamnolipids produced from P. aeruginosa 47 T2 to emulsify isopropyl myristate, soybean oil, Casablanca oil and olive oil. Uzoigwe et al. (2015) reported the emulsifier property of certain specific biosurfactants such as Alasan from Acinetobacter radioresistens KA53, Mannoproteins from Saccharomyces cerevisiae and Kluyveromyces marxianus,  Uronic acid bioemulsifiers from Halomonas eurihalina and Klebsiella species. The usage of biosurfactant in the food and beverages is diagrammatically illustrated in Fig. 4.1.

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Fig. 4.1  Diagrammatic representation of the usage of biosurfactant in food and beverages

4.3  Biosurfactant in Bakery and Ice Cream Industry In bakery and ice cream industries, biosurfactants are used to extend the freshness, control the consistency and solubilize flavour oils. The rhamnolipids improve the stability of dough and texture, volume and preservation of bakery products (Muthusamy et al. 2008). An emulsion is a heterogeneous system that possesses at least one immiscible liquid thoroughly dispersed in another phase in the form of droplets. The addition of emulsifiers imparts the texture and enhances the creaminess of dairy products, especially in low-fat products (Rosenberg and Ron 1999). Biosurfactants also improve organoleptic properties in bakery and ice cream formulation and also act as fat stabilizers by cooking the fats (Kosaric 2001).The study of Haesendonck et al. (2004) insists that rhamnolipids can be used to control consistency in ice cream and bakery formulations as they stabilize fats, solubilize flavour oils and retard staling. Biosurfactant is also used in bakery and ice cream industry especially to attain the stability of the food products (Campos et al. 2014).

4.4  Biosurfactant as Food Additives The earlier study of Irfan-Maqsood and Seddiq-Shams (2014) suggest the usage of rhamnolipid biosurfactant to enhance the properties of cream, butter, croissants and frozen confectionery products. Other food items implement the usage of rhamnolipid as food additives like in bread, hard and soft rolls, hamburger buns, baguettes, pizza, croissants, cake and sponge cake to improve their dough or batter stability and preserve the food from microbial contaminations (Nitschke and Costa 2007). Some food additives like pentosanases, enzymes (amylases, lipases, hemicellulasses) and hydrocolloids are being used effectively to enhance the texture and

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consistency of food. Additional benefits from additives include freshness and increased shelf life of the food (Mnif et al. 2012).

4.5  Biosurfactant as Flavouring Agent The study of Linhardt et al. (1989) highlights the implementation of the rhamnolipid type of biosurfactant produced from Pseudomonas aeruginosa, which is being hydrolysed to obtain L-rhamnose which acts as the precursor for excellent flavour ingredient like Furaneol (trademark of Firmenich SA, Geneva). Federici et  al. (2009) reported that rhamnolipid could serve as a source of L-rhamnose, a compound used commercially in the production of high-quality flavour compounds.

4.6  Biosurfactant as the Stabilizing Agent The usage of artificial or chemically produced compounds alters the originality of the food including its flavour, texture and nature (Parthasarathi and Subha 2018). Biosurfactants are likewise employed as anti-spattering agent and fat stabilizer in food industries when cooking food products with oil and fat (Shoeb et al. 2013). Biosurfactant controls the fat globule agglomeration and enhances the texture and shelf life of starch-containing food products. Furthermore, it modifies the rheological properties of wheat dough and improves the consistency and texture of fat-based products (Fakruddin 2012).

4.7  Biosurfactant as an Anticorrosive Agent Corrosion has become an immense challenge to all kinds of industrial production, especially in the food industry. Corrosion makes the surface irregular that allows microbial adherence and causes unhygienic conditions during food processing. Further, it results in the attachment of L. monocytogenes to stainless steel as reported by Mai and others (2006). Though bacteria are probably ignored in the literature as a cause of corrosion in the food processing industry due to other major causes such as acids, salts and food components itself, there are certain study insisting on the anticorrosive property of the biosurfactant (de Araujo et al. 2013) suggesting its use as surface coating agent by inducing chromium oxide and reducing the iron oxide (change in the chromium content of alloy during corrosion/anticorrosion) to prevent corrosion thereby minimizing microbial colonization too.

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4.8  Biosurfactant as an Antiadhesive Agent Implementing the biosurfactant to the solid surface may prevent the adsorption of pathogenic and/or spoilage-causing microorganisms in food surface, equipment, pipeline and other food processing materials, thereby preventing the contamination in food industries to a great extent. In reference to the report of McLandsborough et al. (2006), a surface-active agent interferes with the biofilm matrix and reduces the interfacial tension among solid surface and biofilm, thereby eliminating the biofilm. An effective approach to decrease the microbial adhesion and combat colonization by pathogenic microorganism on the solid surface may be through adsorption of biosurfactant, not only implemented in biomedical field but also in food industries (Nitschke and Costa (2007). Preconditioning of stainless steel utensil with biosurfactant for to its antiadhesive property has also been suggested. There are many studies confirming the antiadhesive properties of the biosurfactant against different pathogens (Singh et  al. 2007; Falagas and Makris 2009; Gudina et al. 2010b). However, in the study of Gudina et al. (2010b), biosurfactant produced from Lactobacillus paracasei has exhibited effective antiadhesive property towards Staphylococcus aureus, Staphylococcus epidermis, Staphylococcus agalactiae, Escherichia coli, Candida albicans and Pseudomonas aeruginosa, while the study of Rodrigues et al. (2004) has evidenced two biosurfactants producing probiotic strain, Lactococcus lactis and Streptococcus thermophilus, that inhibit the biofilm development of Staphylococcus epidermidis, Streptococcus salivarius, Staphylococcus aureus, Rothia dentocariosa, Candida albicans and Candida tropicalis. Earlier study has also evidenced that rhamnolipids (at the concentration of 100  mM) can disrupt the biofilm formation by B. pumilus (Dusane et  al. 2010). Rufisan produced by Candida lipolytica UCP0988 displayed antiadhesive activity of the biosurfactant at the concentration ranging from 3 to 50 mg/ml against bacteria, yeast and filamentous fungi (Rufino et al. 2011). Adsorption of a surface-active compound to a substratum alters the hydrophobicity of the surface, by interfering in the adhesion as well as in desorption process of microbes. Thus the antiadhesive properties of biosurfactant have been an essential step in controlling the microbial colonization and proving to the consumers that the products are safe, especially in food industries.

4.8.1  Risk of Biofilm Formation in Food Industries Biofilm formation or its attachment either to the food substances or the utensils used in the food industry is one of the major problems the food industry faces today. The antiadhesive property of the biosurfactant creates a serious impact in the food and biomedical field. Food spoilage can be reduced to a wide extent by preventing the biofilm formation of pathogens in food products. It is therefore essential to control

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the biofilm formation over the food substances to pave the way for food safety and control strategy (Sharmaa and Saharan 2016). Food industries are facing repeated contamination or spoilage of food due to pathogenic bacteria on the food themselves or the formation of biofilms on industrial equipment (Jahid and Ha 2012). Among the different food sectors, dairy industries occupy the most troubles due to the adherence of spores of Bacillus cereus to industrial surfaces that serve as a conditional film promoting the rapid attachment of bacterial cells inducing the pipelines and surfaces of other processing equipment including stainless steel, rubber, plastics etc. (Marchand et  al. 2012; Steenackers et al. 2012). The pathogens dominating the food industries include Acinetobacter, organisms belonging to Enterobacteriaceae, Aeromonas, Shewanella, Psychrobacter, Sphingomonas, Bacillus, other spore-forming bacteria, Staphylococcus, Micrococcus, Salmonella, Pseudomonas, etc., from fresh vegetables, meat and poultry products (Moretro and Langsrud 2017; Chen et al. 2010). Furthermore, psychrotrophic bacteria like L. monocytogenes complicate the storage of dairy products as they can thrive at refrigeration temperatures. The psychrotrophic organisms also influence the spoilage of enzymes acquired from Mucor michei (Rennilase, Hannilase, Marzyme) and Mucor pusillus lindt (Emporase) implemented for milk coagulation (Cameotra and Makkar 1998). The spoilage causing biofilm formers can grow even at low temperature on the walls of the milk cooling tank and pipelines and often secrete heat stable enzymes with proteolytic and lipolytic activity, which leads greatly to milk spoilage.

4.8.2  B  iomedical Application of Biosurfactant by Its Antimicrobial Potentiality Biosurfactant has been reported by Rodrigues et al. (2006) as the safe alternative biological components due to its antimicrobial property. The antimicrobial/antiadhesive activity of the biosurfactant is presented in Table 4.1. The study of Kim et al. (2002) has established the antimicrobial activity of sophorolipid towards Propionibacterium acne and has also suggested that sophorolipid increased the permeability nature of the membrane present in Gram-positive bacteria, while the lipopeptide type of biosurfactant molecule may penetrate the cellular membrane, resulting in the leakage of cytoplasmic material and leading to cell lysis (Naruse et al. 1990; Ocheretina and Scheibe 1997). Biosurfactants obtained from L. paracasei sp. A20 has shown the antimicrobial activity against C. albicans, S. aureus and S. epidermidis as reported by Gudina et al. (2010a). The study of Kim et al. (2002) revealed the antifungal activity of sophorolipid against the fungal pathogen, Botrytis cinerea. Several earlier studies have reported the biosurfactant with antimicrobial activity against various microorganisms including sophorolipids obtained from Starmerella

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Table 4.1  Antimicrobial/antiadhesive activity of the biosurfactant Biosurfactant Source Glycolipid Lactobacillus fermentum Glycolipid Lactobacillus paracasei ssp. paracasei A20 Sophorolipid Candida bombicola ATCC 22214 Rhamnolipids Jeneil biosurfactant Inc. (Saukville, Wisconsin) Sophorolipids MG Intobio co ltd. (Incheon, southKorea) Rhamnolipids Pseudomonas aeruginosa Iturin

Bacillus subtilis K1

Inhibitory organism Candida albicans ATCC 70014

References Gomaa (2013)

Candida albicans, Staphylococcus aureus and Staphylococcus epidermidis Botrytis cinerea

Gudina et al. (2010a) Kim et al. (2002)

Bacillus subtilis NCTC 10400, Staphylococcus aureus ATCC 9144

Mayri et al. (2016)

Pseudomonas aeruginosa PAO1, Escherichia coli NCTC 10418, Bacillus subtilis NCTC 10400, Staphylococcus aureus ATCC 9144 Aspergillus Niger, Gliocladium virens, Penicillium chrysogenum, Botrytis cinerea, Rhizoctonia solani Antifungal

Mayri et al. (2016)

Rhamnolipids Pseudomonas aeruginosa

Staphylococcus aureus, Staphylococcus epidermidis, E. coli

Surfactin

Enterococcus faecalis CI 068, Staphylococcus aureus CI311, Pseudomonas aeruginosa CI 3, Escherichia coli CI18

Bacillus subtilis R14

Kitamoto et al. (2002) Arrebola et al. (2010) Vijayakumar and Saravanan (2015) Fernandes et al. (2007)

bombicola can inhibit Gram-positive bacteria (Banat et al. 2014; Rienzo et al. 2015), surfactin exhibits its activity towards Gram-negative bacteria (Ahimou et al. 2000), and rhamnolipids have been reported to show its activity against Bordetella bronchiseptica (Irie et al. 2005). Lipopeptide biosurfactant extends its electrostatic activity due to the amphiphilic nature and binds to the lipopolysaccharides and lipoteichoic acid membrane of the bacterial cell wall as well as fungal cell wall to disintegrate them, exhibiting detergent-­like mechanism (Yao et al. 2012). However, the structure of rhamnolipid is having some kind of similarity towards the detergent, with which it alters the cell permeability of the lipid bilayer of the microbial cell wall and also intercalates with the confirmation of protein (Banat et al. 2010). Usually, food manufacturers use preservatives with low pH to prevent food spoilage as they have been validated as alternative preservatives since they exhibit prominent antimicrobial activity and are also not susceptible to proteases. The chemical ring peptide structures of the surfactin, iturin, fengycin and other lipopeptides also contribute strikingly to resist proteases (Mandal et al. 2013). The biofilms are the prompt source of transmission of diseases from food industries and the risk of

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nosocomial infection transmission by multidrug-resistant pathogens, which has been a great challenge in biomedical surface (Vandecandelaere and Coenye 2015).

4.9  Biosurfactant Extending the Shelf Life of Food Products In recent times, biosurfactant has been established in numerous food products for extending its shelf life, thereby accounting for profitability in the food industries and better health of consumers. The rhamnolipds are currently approved for use in the food industry by the US Environment Protection Agency (EPA). The rhamnolipids in synergistic action with niacin extend the shelf life of UHT (ultrahigh temperature) soymilk by inhibiting haemophilic spores. Furthermore, the similar combinations of niacin with rhamnolipids have also been implemented in salads as well as cottage cheese to increase its shelf life and to inhibit the growth of mould, bacteria and spore formers as stated by Haesendonck et al. (2004). Multifunctional properties or usage of biosurfactant in various sectors of food industries is schematically illustrated in Fig. 4.2.

4.10  Probiotic Biosurfactant ‘Probiotics’ are live microorganisms/live microbial preparation which when administered in sufficient amounts confer a health benefit on the host (FAO/WHO 2002). This term is often quoted with ‘synbiotic’, which indicates a mixture of ‘probiotics’ and ‘prebiotics’. Certain probiotic strains are capable of producing biosurfactant (Moldes et  al. 2013; Saravanakumari and Mani 2010; Thavasi et  al. 2011; Kermanshahi and Peymanfar 2012). Lactic acid bacteria are beneficial bacteria and widespread genera of LAB species have been involved in fermentation of the dairy products. LAB are extensively found as commensal flora in human intestine and have potential application in dairy fermentation (Vaughan et al. 2005). Currently the investigation on microbes of probiotics has gained attention worldwide in biomedical application. Most of literatures have reported that the probiotic microbes might have a vital role in reducing the antibiotics-related diarrhoea, preventing bacterial vaginosis and urinary tract infections and improving immunological defence response (Falagas et  al. 2006; Falagas and Makris 2009). Probiotic microbes are known to synthesize various antimicrobial compounds like bacteriocin, carbon peroxide, biosurfactants, organic acids, hydrogen peroxide, low molecular weight antimicrobial substances and diacetyl, and growth of pathogens is also prevented (Ceresa et al. 2015). Probiotic biosurfactant is preferred in many applications in recent years owing to the property of the probiotic strain than other pathogenic ones (Sharma et al. 2016). Their antimicrobial and antiadhesive property makes them more effective in the biomedical application aspect. The antiadhesive property of Lactobacillus

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Cleaning & washing - Antiadhesive - Anticorrosive - Antimicrobial - Used as disinfactant

Raw Materials

Storage

- Removal of pesticides - Removal of wax )

Primary Processing - Grading - Cutting & slicing Cleaning & washing - Antiadhesive - Anticorrosive - Antimicrobial - Used as disinfactant

Main Production - Product production

Packaging

Additive Storage - Preservatives - Emulsifiers - Stabilizer - Foamers / Antifoamers - Flavoring agent - Anti-spatting agent

Storage

- Antimicrobial - Preservative in packaging materials

Marketed

Fig. 4.2  Schematic diagram representing the multifunctional properties/usage of biosurfactant in various sectors of food industries

plantarum and Lactococcus lactis preventing the microbial colonization has been demonstrated in the study of Fatena et al. (2016) and Rodrigues et al. (2004). There are certain factors that determine the efficacy of the biosurfactant-­ producing probiotic strain, which include acid and bile tolerance, proteolytic resistance, and antagonist properties against pathogenic microbes, providing a better environment for the beneficial microbes. Typically, lactic acid bacteria (probiotic strain) have established a substantial interest for their potential use in establishing the competitive environment towards pathogenic microbiota. However, Lactobacillus species shows evidence of antioxidative activity, thereby decreasing the risk of accruing reactive oxygen species on food products (Kullisaar et al. 2002).

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4.10.1  Biosurfactant-Producing Probiotic Strains The report of Sharma et al. (2016) highlighted the different species of the probiotic strains with its application and source from which they are obtained. Some of the few quoted biosurfactant-producing probiotic strains are Lactococcus paracasei subsp. paracasei A20 (Gudina et al. 2010a), Lactobacillus fermentii, Lactobacillus rhamnosus (Brzozowski et al. 2011), Lactobacillus pentosus (Rodriguez-Pazo et al. 2013), Lactobacillus reuteri (Salehi et al. 2014) and Lactobacillus brevis (Ceresa et al. 2015).

4.11  Food Sanitation Maintaining food sanitation has evolved for the past few decades to reach the goal of quality food products. The implementation of Good Manufacturing Practice (GMP) and Hazard Analysis and Critical Control Point (HACCP) in each food processing operation involves several aspects such as aseptic processing, handling techniques, grading as well as cleaning of the raw materials and equipment, disinfecting the production area, health of labours has to be ensured at all stages. The report of Coughlan et  al. (2016) affirms that all these procedures are well documented to attain CIP (clean-in-place), thereby reducing the load of microorganisms including biofilm formers. Thus food sanitation approach eliminates the microbial population from the food processing surfaces, tools and utensils to provide a better environment devoid of unwanted microbes.

4.12  Biosurfactant in Agriculture Various biosurfactants from microorganisms have antimicrobial activity against phytopathogens and proven to be a promising biocontrol molecule for achieving sustainable agriculture. The purified mono- and dirhamnolipid were found to highly effective against three zoosporic plant pathogens, Pythium aphanidermatum, Phytophthora capsici and Plasmopara lactucae-radicis at a concentration ranging from 5 to 30 mg/L, which caused lysis of the entire zoospore population in less than 1 min (Stanghellini and Miller 1997). Rhamnolipid mixture obtained from P. aeruginosa AT10 exhibited inhibitory activity against the bacteria, namely, Escherichia coli, Micrococcus luteus and Alcaligenes faecalis, at the concentration of 32 mg/ml whereas Serratia marcescens and Mycobacterium phlei at the concentration of 16 mg/ml. An excellent antifungal activity was displayed against Chaetomium globosum, Penicillium chrysogenum and Aureobasidium pullulans at a concentration of 32 mg/ml and Aspergillus niger at 16 mg/ml, respectively (Abalos et al. 2001). Nielsen and Sorensen (2003) reported

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the antifungal properties of biosurfactant produced by strain P. fluorescens. The Pseudomonas sp. aborts the growth of pathogenic fungi Pythium ultimum (damping off) and Rhizoctonia solani (several plant diseases) by production of viscosin and viscosinamid (Andersen et  al. 2003). In agriculture, biosurfactants are used to improve the antagonistic activities of microorganisms and microbial products (Kim et al. 2004). The growth of harmful algal bloom of algae species, Heterosigma akashiwo and Prorocenterum dentatum, was inhibited by rhamnolipid biosurfactant at a concentration ranging from 0.4 to 10.0 mg/l (Wang et al. 2005). De-jonghe et al. (2005) reported rhamnolipid (25% formulation in oil) can be used against brown root rot disease as a preventive measure. The rhamnolipid biosurfactant was very efficient in controlling the spread of brown root rot disease (caused by Phytophthora cryptogea) which is a zoospore-producing pathogen in the hydroponic system of witloof chicory. Bacterial wilt disease of tomato caused by Ralstonia solanacearum was actively suppressed by Pseudomonas fluorescens strain PfG32R, and the antifungal activity against Fusarium oxysporum f. sp. radicis-lycopersici and Fusarium graminearum was inactivated by mutation in GacS/GacA two-component regulatory system (Susanta and Takikawa 2006). Singh et al. (2007) reported that application of biosurfactant and chemically synthesized surfactant in agriculture facilitates plant growth-promoting microbes which are involved in the biocontrol mechanism like induced systemic resistance. The biosurfactant synthesized by Pseudomonas sp. plays a key role in inhibition of Verticillium sp. viability in vitro (Debode et al. 2007). Rhamnolipid form the rhizosphere bacterium Pseudomonas sp GR3, was isolated from the central Himamalya region could effectively control the damping off plant pathogens (Phythium aphaniermatum and Phytophthora nictotianae). The disease was spread by propagule of the oomycetes, which is particularly sensitive to interaction with surfactant, as it lacks cell wall. The proposed mechanism of biosurfactant action is by means of disruption of the plasma membrane. As rhamnolipid biosurfactant is involved on the lysis of zoospore fungi of the plasma membrane, the application of biosurfactant could facilitate in controlling the damping-off pathogens (Sharma et al. 2007). Hultberg et al. (2008a) demonstrated the inhibition of rhamnolipid biosurfactant of zoospore-forming plant pathogens that have developed resistance to the commercially available chemical pesticides. The Pseudomonas sp. with the biosurfactant-­ producing ability was demonstrated as a biocontrol agent against of Verticillium wilt in potatoes (Hultberg et  al. 2008b). The surfactin biosurfactant produced by Brevibacillus brevis strain  HOB1 exhibited strong antibacterial and antifungal activity against phytopathogens (Haddad 2008). Rhamnolipid biosurfactant plays a key role in triggering the plant defence responses and resistance to Botrytis cinerea (necrotrophic fungus) in grape wine

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(Varnier et al. 2009). The authors demonstrated that rhamnolipids exhibited antifungal activity by inhibiting the mycelium growth of B. cinerea and spore germination. Rhamnolipids were also acting as microbe-associated molecular patterns (MAMPs) and protect against grey mould disease in grapevine. Vatsa et al. (2010) demonstrated that rhamnolipid can stimulate plant immunity which is an alternative approach to decrease the infection by plant pathogen. The surface-active compound produced by Bacillus subtilis, isolated from soil, controlled the anthracnose on papaya (Kim et al. 2010). Ren et al. (2010) isolated a bacterial strain P. aeruginosa R219 that exhibited strong algicidal activity against the dominant bloom-forming species of Microcystis aeruginosa. About 90% of algicidal activity was exhibited by the strain R219 at a concentration of 50 μl/ml against the mixed species of bloom-forming cyanobacteria, and low concentration was used in controlling the harmful algal blooms in the field as biocontrol agent. There are a few studies that reported the use of glycolipid biosurfactant as biopesticides for the insects and control of mosquito invasion. The rhamnolipid produced by P. aeruginosa LBI 2A1 exhibited the larvicidal potency against Aedes aegypti larvae (Silva et al. 2014). Kim et al. (2011) reported insecticidal activity of rhamnolipid biosurfactant isolated form Pseudomonas sp. EP-3 against Myzus persicae (green peach aphid). The application of dirhamnolipid displayed dose-­ dependent activity against aphid with 50% mortality at 40 μg/ml and 100% mortality at 100  μg/ml. The treated aphids with the rhamnolipid revealed the insecticidal mechanism as cuticle membrane damage (microscopic analysis). The surfactin and iturin A biosurfactants isolated from Bacillus strain from the Amazon exhibited inhibition of several phytopathogenic fungi such as Fusarium sp., Aspergillus sp. and Bipolaris sorokiniana (Velho et al. 2011). Ghribi et al. (2011) evaluated the insecticidal activity of this biosurfactant against the Egyptian cotton leaf worm (Spodoptera littoralis) and displayed toxicity with an LC50 of 251 ng/cm2. The histopathological changes occurred in the larval midgut of S .littoralis treated with SPB1 biosurfactant were formation of vesicle in the apical region, cellular vacuolization and damage of epithelial cells. The rhizospheric isolates of Bacillus and Pseudomonas that produced biosurfactant exhibited biocontrol of soft rot caused by Dickeya sp. and Pectobacterium (Krzyzanowska et al. 2012). The lipopeptide produced by Bacillus amyloliquefaciens Q-426 exhibited significant inhibitory activity against Curvularia lunata Boed even at extreme temperature, pH and salinity condition and also could grow well in the presence of Fe2+ ions below 0.8 ML−1 (Zhao et al. 2013). Nalini and Parthasarathi (2014) reported Serratia rubidaea SNAU02, a rhamnolipid producer, as a biocontrol agent against plant phytopathogens. Phytophthora sojae is the main damaging oomycete pathogen of soybean. Soltani et al. (2016) found that the antimicrobial effects of rhamnolipid produced by P. aeruginosa were very effective against zoospore and mycelia of Phytophthora sojae. In pot culture

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study, application of rhamnolipid biosurfactant from strain SNAU02 at the concentration of 250 μg/ml was effective against Fusarium wilt of eggplant, which minimize its yield loss and completely inhibit its disease severity. This investigation revealed that application of rhamnolipid biosurfactant from SNAU02 could be a promising biocontrol agent (Nalini and Parthasarathi 2018).

4.12.1  Mode of Action of Biosurfactant The proposed mechanism of action is that biosurfactant had the ability to release the intracellular contents by causing lysis or disruption of the cells of targeted pathogens (Banat et al. 2010; Cameotra and Makkar 2004). They target the pathogens by disrupting the protein cell membrane and lipid content, thus changing the osmolarity of the cell and changing the cell wall configuration which lead to the increase in their toxicity on the pathogens (Mawgoud et al. 2010).

4.13  Conclusion Biosurfactants are unique microbial products showing advantageous features and may become future substitutes for chemically produced ones. Most of the disinfectant currently used is synthetic chemicals, which are replaced by biosurfactant in disinfectant formulation for improved cleaning and disinfection of food processing environment, where the choice of the measure depends on characteristics of the site and the targeted bacteria. Public awareness has also pushed the food sectors to look into quality products to serve as natural substitutes like biosurfactant as it possess multifunctional activity for various purposes. Interesting features of biosurfactants have made its application in various sectors a success, especially in food leading, which could lead to its possible commercialization. The high predominance of biosurfactant and biosurfactant-producing microorganisms in the rhizosphere is a positive indication of its potential key role in sustainable agriculture. The functional metagenomics, a modern approach, is needed for the discovery of novel green surfactants. The green surfactant is a preference to avoid the usage of synthetic surfactant. In agriculture, biosurfactant can be used to eliminate the plant pathogens and increase the bioavailability of nutrients for beneficial plant-associated microbes. Biosurfactants can be widely useful in agriculture, for example, increasing the soil quality by soil remediation. Acknowledgements  Dr. Nalini. S acknowledges the Science and Engineering Research Board (SERB), Department of Science and Technology (DOST), Govt. of India, New Delhi, for the award of the National Post-Doctoral Fellowship program (PDF/2016/000989). The authors  are greatful for facilities provided by the DST-FIST (SR/FST/ESI-145/2016) towards Centre for Ocean Research.

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Chapter 5

Influence of Sustainable Agricultural Practices on Healthy Food Cultivation Rajesh K. Srivastava

Contents 5.1  I ntroduction 5.2  S  tatus of Food Production in Global Agriculture 5.3  Food Variety and Agriculture 5.3.1  Wheat 5.3.2  Rice 5.3.3  Maize or Corn 5.3.4  Sugarcane as Food 5.4  Sustainable Agriculture Practices in Developing Countries 5.5  Practices of Sustainable Agriculture 5.5.1  Utilization of Cover Crops for Protection and Enrichment of the Soil 5.5.2  Soil Enrichment Practices for Crops 5.5.3  Utilization of Natural Pest Predators for Crops 5.5.4  Bio-intensive Integrated Pest Management for Agriculture 5.6  Food Cultivation via Sustainable Agriculture Methods 5.6.1  Enhanced Environmental Conservation 5.6.2  Ensuring Consumer Safety and Public Health 5.6.3  Reduction in Environmental Pollution 5.6.4  Reductions in Food Grain Costs, Price and Energy 5.6.5  Reduction in Biodiversity Losses 5.6.6  Favorable Animal Health 5.6.7  Economically Favorable to Farmers by Enhanced Crop Cultivation 5.6.8  Favorable Situations for Equality in Society 5.6.9  Enhanced Conditions for Protection of the Environment 5.7  Conclusion References

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Abstract  Sustainable agricultural systems aim to use technologies that do not cause any adverse effects to environmental goods and services. To solve the problem of food insecurity due to the increasing global population, modern agricultural practices are used by food cultivators in many countries to maximum their crop R. K. Srivastava (*) Department of Biotechnology, GIT Gitam Institute of Technology and Management (GITAM) (Declared as deemed to be University), Visakhapatnam, Andhra Pradesh, India © Springer Nature Switzerland AG 2020 K. M. Gothandam et al. (eds.), Environmental Biotechnology Vol. 2, Environmental Chemistry for a Sustainable World 45, https://doi.org/10.1007/978-3-030-38196-7_5

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yields. Modern agricultural practices use mechanized equipment for irrigation, tilling and harvesting along with hybrid seeds. However, they also use synthetic or chemical fertilizers, pesticides and herbicides that deplete soil fertility and are harmful to the environment. Modern farming has evolved with technology such that irrigation is done mainly through tube wells, sprinklers and dripping systems, which has caused decreases of the water table. In addition, modern technologies are highly mechanized and lead to increased use of non-renewable sources of energy. Modern agricultural practices are responsible for genetic erosion and the extinction of germplasms of crop seeds, which leads to less variability and a loss of indigenous varieties of crop plants. Sometimes, genetically modified food can create health issues, causing fear among consumers with regard to such food and its products. It is necessary to create awareness about healthy soils that produce healthy food systems, which is only possible through the use of sustainable agricultural practices. Fertile soils can be maintained by supplementing essential nutrients, water, oxygen and root support, which is essential for allowing food-producing plants to grow and flourish. This chapter discusses recent developments in crop production from sustainable agricultural practices that maintain healthy agricultural soil conditions. Keywords  Soil fertility · Crop variability · Fertilizer · Environmental pollution · Food security · Sustainable agriculture

Abbreviation AfDE African Dark Earths AS Adjacent soils BIPM Biointensive integrated pest management practices CRC Conventional rice-crab coculture FAI Food Animal Initiative FM Fish monoculture GDP Gross domestic product GHGs Greenhouse gases GM Genetically modified IPM Integrated pest management MDGs Millennium Development Goals MG Marigold MMT Million metric tons MY Marketing year NEP New Economic Policy ORC Organic rice-crab coculture PyC Pyrogenic carbon RC Rice-crab coculture RF Rice–fish co-culture system

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RM SDGs SH SPAD TaASN VGGTs WSPA

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Rice monoculture Sustainable Development Goals Sunn hemp Soil-plant analysis development Triticum aestivum asparagine synthetase Voluntary Guidelines on the Responsible Governance of Tenure of Land, Fisheries and Forests World Society for the Protection of Animals

5.1  Introduction A country’s capability for food production can provide the basic support for food security, which is a key determinant of food availability in that country. In India, the agricultural sector has played a vital role in the production of different types of food grain (e.g., wheat, rice, maize, millets, and sorghum as cereal and pulse crops), vegetable and fruit crops; in addition, it is a major contributor to the Indian economy, such as total gross domestic product (GDP). The agricultural sector is the backbone of India and other countries, such as China and Canada. These countries have also shown a high capability for farming crops with animal husbandry, pisciculture and agroforestry. In India, the agricultural sector supports approximately 58% of rural households; in addition to farming, fisheries, forestry and other allied sectors account for approximately 14% of the total Indian GDP. The Indian government has proposed many initiatives to its farmers to increase the productivity of their crops, including investments for technology development, the introduction of the best crop varieties, the intensive application of inputs and a focus on modern and effective agricultural practices, including irrigation infrastructure, price support and procurement. In India, total grain demand was reported to be 201 million tons in the year 2000; this is expected to reach approximately 291 and 377 tons by 2025 and 2050, respectively, with continued increases in demand in the future (Khatkar et al. 2016). Different types of crop cultivation are uniquely suited to India’s particular weather and soil conditions. Recently, food grain production in India achieved a new record high of 277.49 million tons in the years 2017–2018, with more output of pulses and rice (Time of India report 2018). A food-based approach (via food and nutrition security) has been found to help the world’s malnutrition problem (which is common among families living in poverty and tribal people) in an economically and socially sustainable manner. At the international level, India is the third largest producer of cereal crops after China and the United States. At the international level, India is also the leader in milk production, third in fish production and second in inland fisheries production. Approximately 11 million people are actively involved (full time or part time) in fish production, with high utilization of subsidies in this sector. India is ranked first in the domestication of

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cattle and buffalo (for milk or meat), second in goat cultivation (for milk or meat), third in sheep cultivation (for meat or wool), and seventh in poultry cultivation (for meat or eggs). Nearly 90 million people in India work in the livestock sector (Kisan 2006). In addition, 18 million people (including 9.8 million people at the primary level and 8.6 million people with subsidiary advantages) work in the dairy industry, which provides employment opportunities in sales, reprocessing, transport and the supply of animal products in the secondary market (Bhat 2002). In the ancient Vedic period, agriculture was based on involvement in religious-­ social activities at all ancillary levels from soil worship to weather forecasting. The agricultural spirit among ancient people was especially conciliated with worship at the time of seed sowing, reaping and storing of foods at threshold levels. In those periods, agricultural practice had improved with the development of new and high-­ yielding crops varieties, as well as with more practices for animal domestication. In those periods, agricultural practices were focused on the following activities: (1) development of fertile soil and land with village establishment and settlement, (2) development of adapted manure processing practices, (3) breeding of crop varieties with plant protection measures or strategies as well as implementing agricultural technology, (4) irrigation systems for agricultural crop cultivation, (5) breeding of animals for better milk or meat and (6) technology developments to improve meteorological observations in relation to crop growth (Roy 2009). In the last few decades, modern technology has been adopted for its broad applications, utilization and contributions to improved agricultural crop development. Modern agricultural technology, planters and harvesters can be made better than their predecessors by slightly tweaking ancient practices to improve agricultural crops. Report has shown that US$250,000 of worth has still spent today for the cutting, threshing and separating processes of food grains in a similar manner to ancient times. However, modern technology developments have changed the methods of farmers through machines such as global positioning system (GPS) locators, computer-­ based monitoring systems and self-steer programs in tractors with advanced technology. Still, it is necessary to implement precise practices for agricultural purposes with minimal waste generation from a decreased use of fuel, fertilizer or seed (Rehman et al. 2016). Some useful machines, such as geographic information systems (GIS), crop model designs and remote sensing systems, can provide more data on crop cultivators for the development of precise agriculture practices. Decisions can be made on matching inputs based on real yields of different portions or parts of farming fields. These agricultural-based tools play important roles in agriculture practices for crop production and in the management of wildlife (Kijima et al. 2011). In 1960, a green revolution forced us to reexamine unsustainable agriculture practices with the increased use of chemical fertilizers for crop cultivation. This revolution also resulted in enhanced or high-yield crop varieties of two main staple cereal food grains – rice and wheat – because of better irrigation facilities, fertilizers, pesticides and crop practice management. The high-yield crop varieties required more applications of chemical fertilizers at subsidy policy utilization.. These attempts opened up the economy to private sector industries with globalization

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trades via implementation of the New Economic Policy (NEP), with more promotion of the agricultural sector for the commercial production of crops by orienting to the export market (Punith Kumar and Indira 2017). An analysis of per capita food grain availability in an agriculture system in India examined the growth of its economy with shared agriculture practices in the Indian GDP. Highly declining trends were found for some agricultural products or food crop productivities in the current period in India compared with the United States, China and other countries (Gavhale 2017). Advances in science and technology have generated some disruptive results for nature. In certain periods, ancient human populations had been unaware of the damage to nature or the environment. Initially, the harmful activities of humans were not considered on healthy nature due to its renewability nature. Furthermore, with increased harm from the human population to the environment, renewability capability of environment has initiated for decaying or collapsing process due to fast spread of polluting condition. Harmful human activities are associated with unplanned and rapid industrial development, urbanization and organic or inorganic waste generation. Environment pollution also may increase from the unplanned use of agricultural lands with improper agricultural practices, increased pesticides or chemical fertilizers, and increased irrigation, tillage and plant hormone use. Other improper human activities such as stubble burning, burning, cropping or planting without rotation and non-suitable animal waste development, may cause further environmental damage (Önder et al. 2011). Sustainable agriculture practices can help with the healthy production of plant or animal products, including food. Sustainable farming techniques can be developed while protecting the environment, public health and animal welfare. Sustainable agricultural techniques can help to produce healthy foods without compromising the ability of future generations to use the same resources of the earth. Sustainable agriculture practices can maintain the proper balance between the need for food production and the preservation of environmental ecosystems. Sustainable agricultural practices can improve economic conditions with stability for farm lands and farmers by increasing their quality of life. They can help to generate the biggest employment opportunities (approximately 40% or more) for the world’s population. This chapter focuses on recent developments in sustainable agriculture practices.

5.2  Status of Food Production in Global Agriculture A wide range of external agricultural inputs is used to maximize the production of food, including eco-friendly farming and crop cultivation, sustainable agriculture practices, organic or biological farming and regeneration cropping practices. They are mostly beneficial to modern, advanced or high external input food systems. High-tech systems may also be used for the storage, transportation, processing and selling of food items or products. Modern food systems consist of farms, firms and traders, which are typically specialized and operate at large or industry scales.

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Today, consumers are able to purchase processed, transformed or packaged foods and food products, which are produced worldwide on a large scale and sold in large stores. The coordination of contracts, standards and vertical integration has helped to maintain market relations (Westhoek et al. 2016). Table 5.1 shows the different food production capabilities worldwide. With regard to food production, food security is an important issue for all countries. Food security can be best assured for every individual when food is produced at the local level in sufficient quantities and made available on a continuous or chain scale basis with affordable prices depending on climatic or other variations. Food security can help to solve the famine and chronic malnutrition problems, which are closely associated with the need for improved agricultural food production with management of natural resources or services, environmental protection and implementation of trade policies (Gahukar 2011). Table 5.1  Food capabilities of large producer countries using modern agriculture practices Food Wheat

Paddy rice Maize/corn

Sugarcane

Sorghum

Barley grain

Pulses

Rapeseed Fruits and vegetables Fruits

Vegetables

Production (million metric tons) 1.52 × 102 1. 29 × 102 0.98 × 102 2.10 × 102 1.65 × 102 3.70 × 102

References Statista Report on wheat (2018)

0.075 × 102 0.074 × 102 0.17 × 102 0.09 × 102 0.087 × 102 0.17 × 102 0.052 × 102 0.051 × 102 0.076 × 102 2.83 × 102

Country EU China India China India United States China Brazil Brazil India China United States India Nigeria Russia Ukraine France India Myanmar Canada India India

1.54 × 102 0.83 − 0.86 × 102 0.37 × 102 1.69 × 102

China India Brazil India

The Times of India (2016)

1.63 × 102 0.51 × 102 7.20 × 102 2.77 × 102 1.11 × 102 0.11 × 102

Statista Report on paddy rice (2017) Statista Report on corn (2018) and Keshrinandan Enterprise report (2017)

Crop Nutrition report on sugarcane (2010) Worldatlas report (2017)

Worldlistmania report (2011)

Joshi and Rao (2017) and Rediff report on pulses (2007) Vora (2014) The Times of India (2016)

APEDA report (2015)

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The crop production practices of most countries are very unsustainable, often due to the increasing pressure of population growth on finite land resources for agricultural crop cultivation. In addition, climatic changes, public distribution from government policies, marketing of food grains or a lack of participatory approaches can decrease food availability or storage (Gahukar 2007). The food balance can be maintained by aligning the growth rates of food availability and population. Food security should not affect the matter of aggregation (per capita) of food availability. A closed economy is dependent principally on food production and stocks at all levels, whereas an open economy is dependent on the food trading capability of any country (FAO report 2001). The capability of food security system depends on several important factors, such as participation in household decision with distinguishing between capability of system and functioning effort for food security of any country. These capability approaches may directly evolve from entitlement approaches or other theoretical frameworks that operate in the field of food security systems (Burchi and Muro 2016). Food security policies are based on a theoretical micro-economic model and have been developed using direct or indirect measures that can ensure food security in developing countries. These policies are based on direct interventions and involve structural changes in relative prices and targeted food subsidies. Indirect measures or strategies (e.g., improved agriculture infrastructure, the general economic environment, providing new technology to farmers) aim to improve food production capacity (Boratyńskaa and Huseynov 2017). A variety of foods and products from agriculture practices can provide specific nutrient combinations or functional ingredients to fulfill the nutritional requirements of humans by boosting the immune system, increasing stamina, helping to prevent chronic diseases and delaying the aging process. Innovative food technology plays an important role in translating nutrient information to consumer products, thus promoting their well being, happiness and active lifestyles (Soriano and Huarng 2013).

5.3  Food Variety and Agriculture Easily available and high-quality agriculture inputs (e.g., suitable land, water, seeds and fertilizers) can be used to access agriculture credits and crop insurance, assure remunerative prices for agriculture produce or products and promote storage facilities and marketing infrastructure. Several other factors can determine agricultural productivity. India’s food grain production has increased every year, with the country becoming a leading producer of several crops, including wheat, rice, pulses, sugarcane and cotton. As discussed earlier, India is ranked first in the world for milk production and second for fruit or vegetable production. In the year 2013, India contributed the following quantities of food grains on the worldwide level: 25% of pulses, 22% of rice and 13% of wheat production. In addition, 25% of cotton production occurs in India, which is the second highest cotton exporter country. Table 5.2 shows the productivity capacity for food grains by country. Some of the crops are discussed in the following sections and are shown in Fig. 5.1.

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Table 5.2  The productivity of some food varieties in their cropping land worldwide

Food species 1-JP 61 and JP Karishma-100 2-JP 64 and JP 81 3-JP 61 (un-irrigated) 4-winter wheat, Oakley variety

Production (quintals per acre) 15–16 25–30 2–4 66.90

5-wheat KWS Kielder

58.0

Country India India India New Zealand UK

1-JP 72 2-JP 80 3- hybrid rice -Xiang Liangyou 900 variety 4- Rice grown by Sumant Kumar, Bihar with only farmyard manure and without any herbicides Mustard 1-JP Vishwajit 2-genetically modified (GM) DMH-11 mustard variety 3-RP-09 4-Sitara Sringar Pigeon pea 1-annual JP 7, JP 9 and ICPL 87 2-perennial JP 5, JP 6, 3-ICPH 2740 hybrid 4-RV ICPH 2671

24–25 25–26 69.6

India India China

91.6

India

6-7 10.52

India India

Singh (2009) Bera (2017)

16.2 12.1–14.1 5–10 10–15 12.14 14.17

India India India India India India

Feed barley 1-Blackman agriculture bred variety 776 2-Azad (K.125), Vijaya, Amber 3-RS-6 4-Karan 201, 231 and 264 4-Neelam Pulse crops IPU 94-1- black gram from India Amar- Pigeonpea Pragatee- chickpea-chana Pusa 9531 -Mung bean PHG 9-Horsegram V 585, GC 3-cowpea Guar-RGC 1003 IPA-203- Arhar ((tur) variety by ICAR

55.7

New Zealand India India India India India India India India India India India India

Bera (2017) Bera (2017) Singh (2009) Singh (2009) Rao (2014) The Hindu Business-line report (2011) Cronshaw (2015)

Food Wheat

Paddy rice

12.14–13.4 16.2 15.4–18.6 20.2 0.405 0.89–1.012 1.012 0.405–0.48 0.36 0.402 0.041 8.1

References Singh (2009) Singh (2009) Singh (2009) Bayer Global report (2017) Strutt and Parker report (2013) Singh (2009) Singh (2009) Xinhua-report (2016) The guardian report (2013)

Kumar (2012) Kumar (2012) Kumar (2012) Kumar (2012) Your article library report (2013)

Indiaagronet (2014)

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Fig. 5.1  Critical food crops grown in agriculture fields using modern practices

5.3.1  Wheat Wheat is an important staple food grain and is a major food ingredient in Indian food. This crop has large quantities of sulphur, which can affect acrylamide formation. However, crop management tools can help with controlling the potential for acrylamide formation in wheat products (Curtis et al. 2014). Consistently, low concentrations of the free form of asparagine have been identified in wheat, and some genotypes within the healthy wheat grain population are found in more stable forms with respect to free asparagine concentrations than other forms over multiples years. The food industries now need more varieties of wheat that can be relied upon to produce grains with consistently low free asparagine concentrations over a range of environmental conditions and harvesting years (Corol et al. 2016). The concentration of the free form of asparagine is a determining factor for acrylamide formation potential in cereals, especially in wheat; this has been measured in different wheat crops grown in field trials in the United Kingdom in the years 2011–2012 and 2012–2013. The study reported on 25 and 59 varieties of wheat crops, which contained various concentrations of asparagine amino acid in 2012  in 2013, respectively. The trials used a split-plot mode; one half was supplemented with sulphur, whereas the other half was not. The varietal mean (m. mole/kg) was studied for free concentration of asparagine in the sulphur led wheat grains, ranging from 1.5 to 2.7 during 2011–2012 to 0.71 to 11.3 during 2012–2013. Around eight varieties of wheat grain were reported to have consistently low free asparagine concentrations (Curtis et al. 2018). Asparagine is found as a free amino acid in crops like wheat and is known to be a nitrogen-containing storage and transport molecule. The accumulation of asparagine in food products creates a safety issue because it is a precursor acrylamide formation during cooking and food processing. The synthesis of the asparagine compound occurs by asparagine synthetase enzyme via amidation of aspartate and

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asparagine synthetase enzyme gene (TaASN) expression capacity, which is determined by wheat cropping conditions such as the use of sulphur. The expression capability of the three genes of TaASN1-3 has been studied in different tissues of wheat crops in response to nitrogen or sulfur compound supplies. The highest expression rate of the TaASN-2 gene was reported in the embryo and endosperm tissues of the wheat plant during the mid to late periods of wheat grain development. TaASN1 and TaASN2 gene expression was reported to increase its rate during grain development as well as in the grains of field-grown plants in the mid period of development in response to sulphur deprivation or removal. TaASN1 gene activity was reported to be affected by the supply of nitrogen or sulphur in a pot-based study, which proved the specific complex tissue behavior and developmentally changing responses (Gao et al. 2016). The production of harvested cereals in EU countries was 317 million tons (i.e., 12.5% of the total global cereal production) in 2015, according to a report from the United Nations Food and Agriculture Organization (UNFAO). Worldwide cereal consumption in 2016–2017 was 2.546 million tons, which is slightly (0.9%) above the rate for 2015–2016 (Swaminathan and Bhavani 2013). Wheat cereal in the agriculture sector is the most (i.e., directly or indirectly) grown and consumed crops grain in the world today. It trades more at the global level than other crops. Wheat grain is used for food, feed and seed purposes; processed wheat commodities may be used as fuel. Variations in wheat strains are found worldwide, which has enhanced its ability to grow globally in different growing conditions. It has been grown in more acreage and exhibited more traceable value than other crops; however, its price is affected by climate, yields, oil prices, lagged prices, and imports (Enghiad et al. 2017). Canada is the largest exporter (around 15 million tons) and sixth-largest producer of wheat (annually more than 25 million tons) (Deshpande 2017). Modern varieties of wheat include winter wheat and spring wheat; ancient wheat varieties include spelt, emmer, and faro types known as wild grass species. The necessary conditions for a healthy wheat yield include mild temperature, nutrient-­ rich soil, adequate water or rainfall and suitable topography. Wheat has been cultivated for thousands of years using information from experience, natural evolutions and scientific modification to obtain healthy wheat plants. Various wheat strains have been modified and improved for maximum yield with grain output, dietary contents and diversity of use (Ramankutty et al. 2004).

5.3.2  Rice Rice is a staple food, especially in India, is a food ingredient for more than half of the world’s population. Annually, 480 milli-tons of milled rice is consumed; China and India account for 50% of rice growth and consumption. Rice is critical for solving the food security issue worldwide, as it provides up to 50% of the dietary caloric supply to millions of people living in poverty in Asia. It is also an important food in Latin America and Africa. Rice production increased at record levels during the

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Green Revolution in India. It is a protected food commodity in world trade markets. However, rice is a poor source of vitamins and minerals, as most are lost during the milling process. Therefore, vitamin and mineral deficiencies can occur when rice is a major component of an individual’s diet. Improved technologies can help to fortify rice and thus solve these deficiency problems, which are connected to severe, adverse health effects. To implement rice fortification in countries with nutrient deficiencies, multispectral approaches may be used to obtain nutritious rice (Muthayya et al. 2014). Rice grains of the Ciherang variety have a thinner shell and higher hardness level compared to grains of the Inpari 10 variety. These can result in more milled rice and head rice with less broken rice and groat content. The physical quality of rice is not affected by the planting system or process, but it is significantly affected by the rice variety. In addition, the planting system and rice variety do not have significant effects on the nutritional quality of rice. New technology can help to overcome problems with rice cultivation systems. Some parameters of rice varieties have been studied, including the physical quality of the grain, the milled rice quality, the physical quality of rice, and rice nutrition. The determination of the physical and nutritional quality of grain and milled rice from two varieties has been reported using several planting systems (Arief et  al. 2018). In both seasons, Sakha 101 rice variety with significantly improved growth capacity was reported by the application of three tested micronutrient models as single or combination forms. When rice crops absorbed more micronutrients from enriched soil compared with control rice, those plants exhibited greater leaf area indexes and chlorophyll content (SPAD value), significantly greater plant height and panicle length, as well as increased dry matter production. It can help to increase rice and straw quantity yield, the harvest index and the yield of other components (panicle numbers or weight, filled grains or panicles and 1000 rice grain weight). A combination of Zn+2, Fe+2, and Mn+2 has shown the highest values in rice grain cultivation; these are studied in most varieties of rice as compared by a foliar spray experiment. The application of micronutrients in soil (especially through left foliage under saline soil conditions) was reported to be more beneficial for rice crop growth with high yield under saline soil conditions (Zayed et al. 2011). The utilization of traditional agriculture practices contributes to the security of food and livelihoods. Rice production in north China region has used a rice-crab co-culture system as an eco-agriculture process for farmers. Soil fertility recognition is used to develop novel sustainable agriculture practices. Soil carbohydrates are used to determine soil fertility in different culture modes. This has been a­ nalysed under three culture modes: rice monoculture (RM), conventional rice-crab coculture (CRC) and organic rice-crab co-culture (ORC). Soil organic carbon and carbohydrates content were determined in these three cultures. Soil carbohydrate content was significantly higher in the ORC than in RM. Carbohydrates were more sensitive to Rice crab culture (RC) mode culture and manure amendment than to soil organic carbon content. The (Gal+Man)/(Ara + Xyl) ratio was found to decrease in all RC mode cultures, which indicated a relative enrichment in plant-derived carbohydrates due to the input of crab feed and manure compared with RM culture (Yan et al. 2014).

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A traditional rice–fish co-culture system (RF) has been used in some parts of world. It was found to efficiently use water and land resources, and it can help by providing food security to local people without any harm. A small scale with low fish yield can be enhanced without increasing the loss of nitrogen (N) into the surrounding environment (i.e., minimal risk of N- pollution) by proper management of N inputs. Traditional or ancient methods of RF (with fertilization or with very low fish feed) with fish monoculture (FM; without fertilization or with very low fish feed), and rice monoculture (RM; with fertilization or without fish feed) have been used to compare the rice yield; these have shown equivalent rice yields in traditional RF and RM methods with their fish yields. In addition, relatively low yields in both FM and RF mode were found. Traditional RF released very low N concentrations into the environment compared with RM but released more N than FM (Hu et al. 2013). Food crisis issues may become challenging in the future. More research is required to clarify the future relationship of rice supply and rice demand; this can be intimately connected with countries on the Asian continent. Rice production worldwide increased at a rate of 1.3–1.9% between 1984 and 1994; supply had been predicted to reach 424 million tons with demand reaching 422 million tons by 2005 worldwide. Sometimes, research can have a negative impact on the future supply and demand of rice due to improper data. At the worldwide level, the predicted rice consumption was 482 million tons in 2010, with rice consumption of 19 million tons in industrial countries and 463 million tons in developing countries (Kubo and Purevdorj 2004). Yield and consumption of rice is determined by the production capability in any country; rice production variations can be approximately 90%. A country’s population as a long-term driver has promising predictive power with the remaining independent variables. All varieties of rice production, is used for human consumption as well as within region-wise consumption, area is used for harvesting and areas in country consumption as proxy variables can be become dominant variables. The future of rice production is closely related to population growth and declining per capita rice consumption in a number of Asian or developing countries. Other factors include climatic changes, which are the biggest challenge affecting new or high-­ yielding rice varieties, which are resistant to flood and drought conditions. However, they need wetting and drying methods to utilize alternate lands and more responsible use of fertilizers and pesticides with increased rice cultivation (Milovanovic and Smutka 2017).

5.3.3  Maize or Corn Maize or corn (Zea mays L.) is cultivated on a large scale in India. It ranks third after wheat and rice. The maize crop is cultivated in all states or regions of India throughout the year and has been used for different purposes (i.e., fodder or green cobs for

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animals, sweet or baby corn and popcorn). India has an average productivity of approximately 2.43 tons per hectare. However, the United States accounts for 35% of the total world production (>9.6 tons per hectare) (Parihar et  al. 2011). Diversification practices for agriculture have been found in upland areas of India. For the past few years, this crop’s cultivation has expanded to approximately 6.2 million hectares to meet the demand for food or feed, especially for the booming livestock and poultry producing sectors in India and other countries. The intensification and commercialization of current maize production systems has helped to achieve the future increased supply of maize in various countries (Tripathi et al. 2016). Hybrid seeds of corn/maize are found in Nizamabad, Guntur and West Godavari as districts of India. They consist of three stages: breeder’s, foundation and certified seed. They are cultivated on approximately 0.3 million hectares of land area in Andhra Pradesh state, especially in the districts of Karimnagar, Warrangal, Nizamabad, Adilabad, Medak and Ranga Reddy; in these districts, the yellow variety of maize is preferred with flint grain. This crop is cultivated for food grain purposes in urban areas, with its raised value and year-round uses for green cobs or fodders. Maize seed production is influenced by the following factors: planting ratio, non-synchronization of flowering, genetic drift, detasseling, mutation, mechanical admixtures, rouging, physiological maturity, seed size and storage (Corn India 2008).

5.3.4  Sugarcane as Food Sugarcane (Saccharum officinarum L.) is an important food crop for obtaining sugars and bio-energy worldwide. A semi-perennial nature of sugarcane was found in Brazilian cropping fields with relatively minimal soil loss. The same plant can be grown back many times after cutting and can be extracted for cane juice. Sugarcane cultivation only requires replanting every 6 or 7 years. The yield of sugarcane is approximately 85 tons per hectare. Brazilian industry has helped with farming techniques for preserving soil stability (Sugarcane org report 2018). The sugarcane plant is indigenous to India. Its production has the highest value by holding an enviable position in India compared to all other commercial crops. Sugar, gur and khandsari are made from sugarcane juices. India has utilized about two-thirds of the total produced sugarcane to make gur and khandsari; sugar factories used only one third of it. Sugarcane also serves as a raw material for manufacturing alcohol. India is the second largest sugarcane cultivator in the world, after Brazil. A dramatic increase in sugarcane production was reported: 93% from 1951 to 1961 due to diversification of agriculture. India’s sugar production was 25.8 million metric tons in marketing year 2017–2018, which was an increase of 18% more quantity. The largest producer of sugar in India is Uttar Pradesh state (38.6%), followed by Maharashtra (22%). The major causes in India for low yields of sugarcane are fertilizer deficiency, unsuitable weather conditions, inadequate water supplies

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for irrigation, poor quality of cane variety, small or fragmented holdings and outdated cultivation methods (Mondo 2013; Aradhey 2017). Sugarcane planting is an important and labour-intensive operation. It is affected by sugarcane germination, whereas the yield of sugarcane is dependent on planting material, layout, plant population, method of planting and placement of bud etc. Planting can be achieved by vegetative propagation such as whole cane, setts having a single bud to six buds, settling prepared from tissue culture or single buds in the nursery. Commercially, sett planting, flat planting, ridges and furrows or the ring pit method are common methods. Setts with two buds have a germination capacity of 65–70% and better yield (Nalawade et al. 2018). Large setts have shown approximately 70% germination with better survival under bad weather. Single budded setts can be protected with chemical treatment for higher cane yield. Single budded setts has been achieved through higher seed rates or through a distribution of a suitable sugar cane variety. Maintenance of the sugarcane population to an optimum level is achieved by planting approximately 4–8 tons per hectare materials with interrow space (0.9–1.5 m) (Moshashai et al. 2008). The width and rate at most economical levels are decided by choosing the sugar varieties, planting periods, soil fertility and climatic conditions of the area in any country. Planting of sugarcane is done by unit operations, such as harvesting and de-trashing seed sugar cane, seed preparation methods, and placement of the planting materials into well prepared seed beds. It can be done by semi or fully mechanized planting systems. Sugarcane cultivation has reported in the United States, Brazil, Australia (50%), and in India (more than 80%; Patel and Patel 2014). Extreme weather events with increased frequency and intensity have been found due to increased greenhouse gases (GHGs) emissions and global warming for climatic change effects. These incidents/effects may be due to the production of sugarcane crop from its residue burning around the world. In developing countries, very poor or relatively low adaptive capacity are found, along with high vulnerability to natural hazards, poor forecasting systems and a lack of mitigating strategies. Sugarcane production may have negative impacts on the environment and be responsible for the high frequency and intensity of extreme or adverse environmental conditions (Gilbert et al. 2007). The geographic location and adaptive capacity of any area can also determine the degree of climatic change with an impact on the cultivation of sugarcane crops. Several different countries have responded to climate change events and challenges have been found for sugarcane production. They can be minimized by adopting proposed strategies, including the planting of drought-tolerant varieties, investing in suitable irrigation infrastructure with improved efficiency and adding drainage systems. Further cultural and management practices are needed to mitigate the negative impacts of climatic changes by improving the sustainable mode of sugarcane production at a profitable level (Zhao and Li 2015).

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5.4  S  ustainable Agriculture Practices in Developing Countries The green revolution in developing countries started in the 1960s and 1970s and dramatically enhanced the yield of wheat and rice in Asian countries. It helped to nullify the fatigue in productivity gains. Soil health losses and depleted freshwater resources with agro-biodiversity have been reported due to the overexploitation of intensive agriculture practices without consideration for scientific principles and ecological aspects. Gradually, arable lands have been diverted for nonagricultural purposes, which creates a big challenge for feeding the growing population worldwide. Non-sustainable agricultural practices have induced for adding more forest lands with depletion the rest of natural life (Chhetri and Chaudhary 2011). Food availability through production/procurement has helped millions on the margins farming capacity, fishing activity and landless rural families, who earn very little money due to a lack of income-generating livelihoods with insufficient access to food (Gauchan et al. 2005). Approximately 200 million rural adults and children with poor economic conditions in India are facing problems due to declining food availability. In this situation in a developing country like India, the evergreen revolution has successfully boosted productivity by increasing connections to nature and supporting women and the poor with employment-oriented eco-agriculture practices. The ‘biovillage paradigm’ is an eco-friendly sustainable agriculture practice that has been created to promote non-farm eco-enterprises using the sustainable management of natural resources. Modern or advanced Information and Communication Technologies (ICT)-based centers of village knowledge provide time- or location-specific data as well as demand-driven information, which are required for eco-technologies to achieve a successful evergreen revolution. Farming as well as marine products bio-synthesis by masses or bulk manner is reported as the twin goals or objectives of eco-agriculture and eco-livelihoods modes and has been proposed with proper addresses (Lobell et al. 2008). The following approaches have been proposed to attain sustainable agriculture (CFS-2016): • Coherent policies to ensure food security and nutrition. • Suitable working conditions and services for people, with proper nutrition and food safety. • Gender equality and women’s empowerment in the agricultural sector. • Youth empowerment for sustainable agricultural practices. • Enhanced protection of the environment with promotion of sustainable management for the efficient use of natural resources. • Resilience against risks and variability. • Cooperative and collaborative activities in innovative research and development to find solutions to current challenges • Improved animal health and welfare.

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• Sustainable resource management with recognition, protection and support of the pastoral system for beneficial livelihoods. • Proper support of sustainable grazing systems as well as mixed systems. • Promotion of the sustainability of intensive systems for human and animal populations.

5.5  Practices of Sustainable Agriculture Sustainable agriculture practices use the principles of ecology that are dependent on the relationship between occupying organisms and their natural environments. This method of agriculture requires an integrated system for plant or animal production in long-term utilization of site-specific applications. Sustainable agriculture has helped in the production of plant and animal products for food using innovative and natural farming techniques, which protect the environment, public health and animal welfare. It has helped with the production of healthy food products without compromising the ability of future generations to enjoy similar needs or services. Sustainable agriculture practices develop a balanced condition between the need for food production and the preservation of the environmental ecosystem. These efforts promote the economic ability of farmlands while improving the quality of life of farmers by providing the biggest contribution (40%) to employment sectors. Some sustainable practices are discussed in the following sections.

5.5.1  U  tilization of Cover Crops for Protection and Enrichment of the Soil In sustainable agriculture, crop rotation is a powerful technique that avoids the negative effects of plaining the same crop in same soil for many years.. It also prevents pest problems, as many pests prefer specific crops. If a pest has access to a steady food supply, then the pest can increase in population size. Crop rotation techniques can break the pest reproduction cycles. In crop rotations, farmers can plant certain or different types of crops to replenish plant nutrients. These crop rotations can reduce the need for chemical fertilizers; the benefits are shown in Fig. 5.2. For sustainable cultivation practices, farmers have to develop a habit of planting crops at all times without barren land. Barren land can cause unintended consequences for their crops. Clover or oat cultivation can prevent soil erosion, suppress weed growth and improve soil quality. This crop growth can reduce the need for chemical fertilizers. Cover crops have been shown to protect or enrich the soil with short-term economic gains. Cover crops have the capacity to turn soil into green manure in a reasonably interchangeable manner (Hutchinson and McGiffen 2000). Strip-tilled cover crop growth that follows live mulch practices can enhance beneficial nematodes and

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Fig. 5.2  Benefits of sustainable agriculture practices

other soil meso-fauna with suppression of weed growth during two vegetable cropping seasons. The cultivation of sunn hemp (Crotalaria juncea) and French marigold (Tagetes patula) was performed for a 3-month period with seedlings of bitter melon (Mamordica charantia). These crops were transplanted into tilled strips as an experiment conducted twice in seasons 1 and 2. This mode of French marigold cropping reduced broad-leaved weed growth prior to cash crop planting in season 2; this weed growth suppression did not last beyond the initial cash crop cycle (Marahatta et al. 2010).

5.5.2  Soil Enrichment Practices for Crops The central component of agricultural ecosystems is soil. Healthy soil is a good source of life, which can be harmed by the overuse of pesticides. Increased yields with more robust crops have seen in good soils. Healthy soils can be maintained by leaving or dropping crop residues in the cropping fields after harvesting, along with composted plant materials and animal manure. This helps to enhance the quality of soil in many ways (Lehmann et al. 2008). Cover crops help to improve the productivity of subsequent row crops by improving the soil properties via physical, chemical or biochemical means. Crop practices have potential benefits and drawbacks for the cultivation of annual crops with ­maintained soil quality. Cover crops have some desirable attributes with the ability to establish rapidly in less than ideal conditions. They provide sufficient dry matter or sill cover with atmospheric nitrogen fixation in their deep roots. Cover crops

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allow nutrient uptake from lower soil depths with a supply of organic matter and low-­residue carbon or nitrogen (C/N) ratios due to phytoxic or allopathic effects on subsequent crops (Zwetsloot et al. 2015). Leguminous or non-leguminous plants are cover crops. In particular, leguminous crops have the capability for biological N-fixation in substantial amounts for primary crops as well as ease of decomposition due to their low C/N ratios (Fageria et  al. 2005). In West Africa, current indigenous soil management targets waste deposition on agricultural or cultivation soils with a transforming ability in extreme weather conditions for nutrient- and carbon-poor tropical soil into the fertile, carbon-­rich black soils named African Dark Earth (AfDE). AfDE has shown more capacity to store more organic carbon (200–300%) as well as morepyrogenic carbon (PyC; 2- to 26-fold) as compared with adjacent soils (AS). PyC has maintained soil fertility for longer periods than other types of organic carbon, which is important for long-term carbon storage and fertility in soil. The strong acidic nature and poor nutrient content of AS is shown in its pH range (from 4.3 to 5.3). AfDE has reported pH values of 5.6 to 6.4 with a slightly acidic nature, ideal conditions for crop plant growth, 1.4- to 3.6-fold greater cation exchange capacity, 1.3- to 2.2-fold greater available nitrogen and 5- to 270-fold greater phosphorus content. AfDE is an ideal model for improvement of fertility in highly degraded soils in socially and environmentally appropriate methods for regions with poor natural resources and food insecurity. AfDE is known as a “climate-­smart” technique. It is found in soils with sequestered carbon processes and enhances mitigation of climatic change effects from poor carbon in tropical soils (Solomon et al. 2016).

5.5.3  Utilization of Natural Pest Predators for Crops Effective control over pests can be accomplished by promoting the growth of many bird species and other natural predators to agriculture pests in the agricultural ecosystem. Increasing these pest predators’ populations is an effective and sophisticated technique. The chemical nature of pesticides can lead to the indiscriminate killing of pest predators. Biological control of insect pests has been reported using traditional/natural methods in Taiwan by focusing on research, development and its applications. This pest control approach has been used for rice, soybean, sweet potato, vegetable and fruit crops against coconut leaf beetle, citrus psyllids, and crucifer vegetable insect pests (Yang et al. 2014). Eco-friendly pest predator management has been adapted for rice insects with minimal use of insecticides or pesticides. Advanced non-chemical technologies for pest control have been reported in China for rice cultivation (Hong xing et al. 2017).

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5.5.4  B  io-intensive Integrated Pest Management for Agriculture Integrated pest management (IPM) uses biological objects rather than chemical methods for pest control. It emphasizes the importance of crop rotation in pest control management. An example of a biocontrol agent is sterile male ladybird beetles. Bio-intensive pest management has been used for some fruit crops, including mango, citrus, litchi, guava, olive, apple, pear and peach. It has capacity for survey and surveillance, proper and accurate identification, sampling and pest population forecasting with field monitoring, scouting and threshold level determination (Kaul et al. 2009). A bio-intensive IPM system consists of a biopesticide-derived system of microbial, parasitoid, botanical, conventional and non-chemical strategies for pest control. It has shown the maximum benefits in Indian farming using a transition phase with gradual adaption of pest control management for sustainable agriculture practices by reducing chemical pesticide dependency and ecological deterioration. It has been applied for many vegetable crops in India (Dhandapani et al. 2003).

5.6  Food Cultivation via Sustainable Agriculture Methods In a sustainable food system, agricultural products can be easily and safely processed for consumers without damaging the health of the ecosystem in the long term. An optimal food system can provide ample, accessible, diverse and nutritious food to consumers in the present generation without compromising the ability of future generations to fulfill sustainability needs.. Sustainable food production can be used for biomass and non-food energy crop production. Non-sustainable food production practices can increase competition for fertile crop lands with more likelihood for increased food prices in the future. However, sustainable systems for food production can help to maintain the balanced production of food or food grains between food crop cultivation and energy-rich crop production. Obtaining a greater quantity of food is only possible by utilizing every drop of water and piece of lands, then saving these resources for our future generations by creating food systems that are sustainable. By transforming food waste or food scraps into manure or rich biofertilizer, the sustainability of agriculture practices and quantity of cultivated crops can be increased (Hobbs 2007). Some applications of the sustainable cultivation of food are discussed in the following sections.

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5.6.1  Enhanced Environmental Conservation The production of nutrient-dense food or food products is very challenging using sustainable agriculture practices, with an increased need for food for future generations due to the increasing population (Bruce 2011). Crop production cannot be easily improved or increased for food shortages using increased land acreage or past agricultural-intensive strategies. The capacity of food productivity can be enhanced (double or triple fold) by applying more chemical fertilizers or pesticides with more irrigation. All expenditures have greater environment costs. For the future, nutrient-­ rich food production can be achieved by next-generation crop production with the help of advanced technologies that require less chemical fertilizers or pesticides for maintaining a sustainable agriculture system. Cover crops and plant-beneficial microbial systems can promote sustainable and next-generation production of small food grains, tomatoes and rapeseed oil (Roberts and Mattoo 2018). Food and fibre productivity has been increased by new or advanced technologies with mechanical power and increased chemical uses with the implementation of specialized policies and government subsidies that favor increased food production. New government subsidies can ensure the sustainability of agriculture with improved yield of foods to meet demand without compromising the integrity of environment or public health. The objective of poverty reduction can be achieved by increased agricultural production with environmental sustainability by minimizing emerging pressure and resource constraints (Abubakar and Attanda 2013).

5.6.2  Ensuring Consumer Safety and Public Health Sustainable agriculture practices can be achieved with by avoiding the use of hazardous pesticides or fertilizers. This can increase the production of fruits, vegetables and others crops while ensuring safety for consumers, workers and surrounding communities. With careful and proper waste management, sustainable modes of cropping can protect humans from exposed pathogens, toxins or other hazardous pollutants while also mitigating climatic changes. Greater food security can be achieved by sustainable farming with monitoring strategies in near-real time at regional, national or international levels. In a sustainable agriculture system, infrastructure can be created for distinct groups of stakeholders coming together and working hand in hand to solve economic, social and environmental challenges. Sustainable agriculture for food cultivation aims to provide nutritious food that can be easily accessed by all people while managing the natural resources, maintaining ecosystem function and supporting the needs of present and future human populations (Umesha et al. 2018). Farming with sustainable strategies is more economical, viable, environmentally sound and socially beneficial by preserving natural resources without depletion of soil, polluting water, or biodiversity losses for impoverished rural communities.

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Improved food security governance is dependent on sustainable food cultivation with a sound or equitable nature by providing more benefits from modern information utilization. Sustainable or equitable agricultural technologies should be used in each country of the world to achieve the Sustainable Development Goals (SDGs) (Pérez-Escamilla 2017).

5.6.3  Reduction in Environmental Pollution Sustainable agriculture can help to transform or convert any waste that remains inside the soil ecosystem into useful farm produce without causing pollution. Government services and facilities around the world should commit to sustainable development as a policy goal for agriculture practice. The intended outcomes of environmental policies should be based on economic, political and communication factors. Environmental policies should be focused on economic development. Objectives should be communicated to key stakeholders to contribute to the ability to attain environmental sustainability (Howes et al. 2017). A sustainable environment has the capability to return all components, including waste, in a recyclable way by converting the waste into useful or valuable products while maintaining a biotic or abiotic relationship for an aesthetic, healthy equilibrium and ideal environment. Biological approaches to environmental sustainability have been investigated using various types of biotechnological tools or techniques for current as well as future applications. The degree of sustainability in the physical environment is symbol of the well-being of people with maintenance of entire components in a healthy environment (Ezeonu et al. 2012). An Environmental Sustainability Index (ESI) has been developed and used to evaluate environmental sustainability relative values for countries. The Environmental Performance Index (EPI) can be used for outcome-oriented indicators for work performance as a benchmark index, which can be easily used by policymakers, environmental scientists, advocates and the general public (Yale Center report 2008).

5.6.4  Reductions in Food Grain Costs, Price and Energy Sustainable modes of agriculture practices can reduce fossil fuels usage with significant cost savings for purchasing and transporting during farming. Recently, high and unstable prices of food and agricultural commodity have been found due to high population growth, increased per capita food demand, and more environment constraints. It is necessary to prioritize agriculture and food production on national and international political, policy and research agendas (Pretty et al. 2011). The fundamental links between agricultural cropping sustainability and real food prices have to be evaluated in current policy analysis. Relevant and accessible

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i­ndicators are used to monitor the sustainability of agricultural cropping productivity with real food prices. Indices from historical series are used for the estimation of the strengths, weaknesses and potential values of selected regions or countries in the world for improved sustainable agriculture development and food security indicators in successors to the current Millennium Development Goals (MDGs) (Dorward 2013). The role of agronomic inputs has been reported to improve cereal yields with consequences on the structural changes of countries’ processes. Suitable fertilizers, modern seeds and water can boost the yield of food in world. The respective empirical links between agricultural yields and economic growth share good labor of tasks for values of agriculture and non-agriculture purposes. The identification strategies are used as novel instrumental variables for exploiting the unique economic geography for compatible fertilizer production and transport costs to the agricultural heartlands of the country. Half tonnes staple food yields, can generate the higher value of GDP (14–19%) per capita and lower labor share (4.6–5.6%) are reported in agriculture sector in last 5 years. The strong role of agricultural productivity has been reported as a driver of structural changes in world (McArthur and McCord 2017).

5.6.5  Reduction in Biodiversity Losses Sustainable farming for the production of a wide variety of plants or animals can help increase the number of biodiversity varieties. In crop rotation processes, plants are seasonally rotated for improvements in soil enrichment, prevention of diseases and pest outbreak processes. Soil biodiversity has the capability to maintain a variety of lives below the soil with interactions between plant and small animal populations as a web of biological activity. Different types of biological activity can improve the entry and storage of water with resistance to soil erosion processes, more plant nutrition, and pest or disease control performances for more recycling of organic matter in the soil. Soil biodiversity can be a good driver of healthy soil for sustainable crop production or cultivation, and land use change can affect the soil biodiversity with determination of above-ground biodiversity in Kenya or other countries (Wachira et al. 2014). Sustainable practices, such as minimal tillage and better fertilizer, are required as timing need. Governments can help to create conditions for environmental service markets to function. Additional regulations can help to increase diversity on our farmlands. There are many reported problems faced by organic farmers, including weather-related production losses, organic matter certification costs, achievement of organic price premiums, high input costs and lack of organic marketing networks. In addition, the high costs of labor, weed-related production losses and production losses due to pests or diseases are also problems of organic farmers. Sustainable agriculture can contribute more productivity than provided food, fibres, energy and timbers for many functions and services. It can potentially produce a wide range of outputs or services for the sequestering carbon process, enhance wildlife animals,

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provide value-added landscapes with preserving wetlands can help in reduction of floods, enhance biodiversity and increase rural employment opportunities (Dobbs and Kellogg 2008).

5.6.6  Favorable Animal Health Sustainable agriculture practices can provide better care for animals in addition to humans. It can increase the understanding of the natural behavior of all living animals with grazing or pecking by allowing them to develop in natural ways. Sustainable farmers and ranchers have implemented livestock husbandry practices for the protection of animal health. Human farming methods protect rural livelihoods and human or animal health in the natural environment. In this regard, two main agencies in China – the World Society for the Protection of Animals (WSPA) and the Food Animal Initiative – have helped farmers to improve the welfare and productivity of chicken, particularly by organically improving the fertility of land and the market value for the product (WSPA report-2009).

5.6.7  E  conomically Favorable to Farmers by Enhanced Crop Cultivation By engaging in sustainable farming methods, most farmers will receive a fair wage for their agriculture products with a great reduction in dependency on government subsidies; in addition, the economic conditions of rural communities are strengthened. An organic mode of farming typically requires 2–3 times less labor expenses compared with factory farming, with a 10-fold increase in profits or benefits. IPM utilization has addressed the broad and widespread misuse of synthetic pesticides in cabbage and other food crops through initiatives on the optimal use of pesticides, complementary weed control, and alternative cultural or biological pest control. It has generated economic benefits via improvements in water quality, food safety, safe pesticide applications, and long-term or sustainable pest control systems. Sustainable agricultural development protects the environment, whereas unsustainable agricultural production practices have caused negative impacts on the environment due to the negative effects of pesticide use. IPM can help to protect our environment (Shamsudin et al. 2010). Policy approaches for sustainable agricultural development can maximize economic benefits by maintaining environmental quality. This has promoted capital-­ intensive farming by encouraging new scientific developments. Economic incentives are used for the development and adaptation of precise technology with minimal residue generation and environmental damage. Reliable taxation with trading permissions are reported to be desirable policies for achieving the best

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solution in c­ onditions of heterogeneity or a lack of information (Zilberman et al. 1997). Sustainable agricultural development has many positive effects with minimum risk in farming via significant costs. It is associated with minimal or very decreased topsoil depletion, groundwater contamination and air pollution. In addition, greenhouse gases, declining performance of family farms, neglect of living and working conditions of farm laborers, new threats to human health and safety due to the spread of new pathogens have been reported with economic concentrations in food and agricultural industries and the disintegration of rural communities (Brodt et al. 2011).

5.6.8  Favorable Situations for Equality in Society Sustainable agriculture techniques can provide benefits to workers by providing more competitive salaries and health benefits. This can provide humane and fair working situations with a safe work environment, adequate food, and adequate living conditions. Women and men have not been receiving equal benefits due to enhanced market opportunities for agriculture commodities with more chances of foreign investments in the agriculture sector (Semedo 2014). In agriculture, gender inequalities are more persistent; this trend can be exacerbated by trade and foreign investment. More sustainable trade and more responsible investment can be easily made in sustainable agriculture. The private sector can make an array of voluntary sustainability standards (VSS), such as fair trade labels. Governments can issue a multitude of guidelines on responsible investment opportunities in the agriculture sector with the implementation of Voluntary Guidelines on the Responsible Governance of Tenure of Land, Fisheries and Forests (VGGTs) (Bledsoe et al. 2015).

5.6.9  Enhanced Conditions for Protection of the Environment Sustainable agriculture practices have the capability to minimize the use of non-­ renewable resources by providing many benefits to our environment. Quantification of the production capacity of different types of foods on current farming lands can help to estimate food yield gaps through calculations of differences between current yields and their potentials, which can be achieved with good management of crops and soils. Analysis of food yield gaps can help to identify the regions with the best potential for higher yields. Increased demand for agriculture products in the current market can occur in emerging economies in the most populous countries of Asia and Sub-Saharan Africa, which expands and intensifies agriculture practices. These can destroy the broader environmental values of forests, wetlands and marine system with their associated biodiversity (Sayer and Cassman 2013).

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Current agriculture practices place a lot of pressure on the natural environment from changes in land use, loss of nutrients from pesticides in the soil and water, as well as biodiversity changes with effects on flora and fauna and their habitats. They have influenced the emission of greenhouse gases with air pollutants (i.e. NH3 gases) but can be minimized by the application of sustainable agriculture practices (DAFM 2016).

5.7  Conclusion Due to increasing worldwide populations, modern agricultural practices are focused on increasing the production of food quantities and varieties by applications with mechanized equipment for irrigation, tilling and harvesting along with hybrid seeds. The excessive use of synthetic fertilizers, pesticides and herbicides has been also reported in modern agricultural practices, which are responsible for climatic change in world. Current agricultural practices have also depleted soil fertility and caused harmful effects to the environment. Irrigation methods have evolved with technology through tube wells, sprinklers and drip systems, which are often responsible for decreases in the water table. A variety of agricultural foods have helped the world by providing specific sets of nutrients and functional food ingredients for improving the nutrition of the human population. These foods can boost the immune system by increasing stamina and have helped to prevent chronic diseases with a delayed process of aging. Innovative food technologies play important roles in the translation of nutrient information in food products for consumers. Most modern consumers can purchase processed or packaged foods around the world due to the production and sales strategies of large food industries and large stores. The coordination of contracts, standards and vertical integration has helped to maintain market relations. It has enhanced food security with more viable approaches by highlighting the important factors, including participation in household decisions, empowerment, and the ability to distinguish between the capability and functioning of a food-secure system in any country. Innovative food security policies are based on theoretical micro-economic modeling developed for direct or indirect strategies to ensure food security in developing countries. Sustainable agricultural systems use technologies and practices that do not cause any adverse effects on environmental goods and services. Worldwide, India is ranked first in the cultivation of cattle and buffalo populations, second in goat domestication and cultivation, third in sheep populations and and seventh in poultry populations. The country provides nearly 90 million employment opportunities for people in the livestock sector. Sustainable agriculture practices have been promoted with more stable economic conditions and better quality of life for farmers. India also has generated the most employer opportunities (around 40% or more) for the world’s population without any adverse effects to the environment.

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Chapter 6

Application of Microbial Fuel Cells for Treatment of Paper and Pulp Industry Wastewater: Opportunities and Challenges Elangovan Elakkiya and Subramaniapillai Niju

Contents 6.1  I ntroduction 6.2  P  rocess of Paper Manufacturing and Waste Generation 6.2.1  Virgin Paper Production Process 6.2.2  Recycled Paper Production 6.3  Major Pollutants Present in Paper Mill Wastewater 6.3.1  Lignin 6.3.2  Tannins 6.3.3  Resin Acids 6.3.4  Fatty Acids 6.3.5  Chlorophenolic Compounds 6.3.6  Dioxins 6.3.7  Heavy Metals 6.4  Solid Waste Generated from Paper Mills 6.5  Atmospheric Emissions 6.6  CPCB Limits for Paper and Pulp Industries 6.7  Existing Wastewater Treatment Technologies 6.7.1  Physicochemical Methods 6.7.2  Biological Methods 6.8  Requirement of Novel Sustainable Wastewater Treatment Technology 6.9  Microbial Fuel Cells 6.9.1  Exoelectrogens Isolated from Paper and Pulp Industry Wastewater 6.9.2  Paper and Pulp Industry Wastewater in MFC 6.9.3  Integration of MFC into Existing Wastewater Treatment 6.10  Challenges and Future of Microbial Fuel Cell in Wastewater Treatment Plants 6.11  Conclusion References

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E. Elakkiya · S. Niju (*) Department of Biotechnology, PSG College of Technology, Coimbatore, Tamil Nadu, India e-mail: [email protected] © Springer Nature Switzerland AG 2020 K. M. Gothandam et al. (eds.), Environmental Biotechnology Vol. 2, Environmental Chemistry for a Sustainable World 45, https://doi.org/10.1007/978-3-030-38196-7_6

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Abstract  Paper and pulp industries play vital role in socio-economic development of India. These units are present in both small scale and large scale providing employment to millions. Paper production process is water-intensive and also produces huge amount of wastewater. Due to the toxicity of pollutants and quantity of waste produced Central Pollution Control Board classifies them into red category industries. Wastewater from these units primarily consists of organic compounds from raw material processing and inorganic compounds used in production process. These units currently employ a combination of physicochemical and biological treatment methods to attain the prescribed discharge limits. These methods are energy-intensive and costly and produce secondary pollutants. Added to these a worldwide call for sustainable waste treatment technology emphasizes on energy efficiency. Anaerobic treatment for biogas production is the only available technology to harvest energy from wastewater. Though anaerobic treatment is capable of being energy positive, its lower treatment efficiency requires tertiary treatment. Hence a novel treatment technology capable of energy generation and better treatment efficiency is the future of wastewater treatment plants. Microbial fuel cells are wastewater treatment technology capable of simultaneous energy recovery. The energy recovered is in the form of electricity which is an added advantage. Though MFC confers various advantages over other treatment process, it is still experimented in laboratory scale. Extensive research is required to scale up this system to practical scale. Previous studies on MFC treating paper industry wastewater could attain higher COD removal than anaerobic treatment. In an another study the redox compounds present in paper industry wastewater mediated electrons to anode resulting in high power production. An elaborate and extensive research with MFC treating paper and pulp industry wastewater would open up strategies, feasibility and challenges in scaling up these processes. In this chapter we will be focusing on (1) various paper making processes, (2) waste generated from these units, (3) current treatment process, (4) drawbacks of these processes, (5) feasibility of using MFC for treatment of paper and pulp industry wastewater, (6) current status of MFC for paper industry wastewater treatment and (7) the possibility of integrating MFC into existing wastewater treatment plants. Keywords  Pollutants in paper industry waste · Power production · COD removal · Sustainable wastewater treatment

6.1  Introduction World Health Organization describes the ecosystem to be “the combination of physical and biological components of environment where the organisms form a complex relationship and function as a unit interacting with physical environment”(WHO-Ecosystem goods and services for health 2017). Human beings

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with a self-centric approach have exploited natural resources at an aggravated rate without due concern to the fellow living being and environment. Air, water and soil have been extensively polluted due to dumping of untreated toxic wastes produced by various industrial processes. This has disrupted the balance in ecosystem threatening the existence of living form on earth. Anthropogenic activities like industrialization, modernization and transportation are the major cause of air and water pollution. Exploitation of existing natural resources has reached the threshold causing undesirable effect on human health and ecosystem. Nations have formulated stringent laws to curb industrial pollution in view of environmental protection. In India the Ministry of Environment, Forest and Climate Change has formed a statutory body, Central Pollution Control Board (CPCB), under the Water Act of 1974 to monitor and control pollution from various industries. It serves as a field formation and also provides technical services to the Ministry of Environment and Forests and climate change “Principal Functions of the CPCB, as spelt out in the Water (Prevention and Control of Pollution) Act, 1974, and the Air (Prevention and Control of Pollution) Act, 1981, (1) to promote cleanliness of streams and wells in different areas of the States by prevention, control and abatement of water pollution, and (2) to improve the quality of air and to prevent, control or abate air pollution in the country” (CPCB 2017). Paper and pulp industries are one of the rapidly developing sectors in India. There is an increasing demand for paper production due to increasing literacy rate and population. Paper industries are one among 35 industries influencing the socio-­ economic development of the country (Technology Compendium On Energy saving Opportunities Pulp and Paper Sector 2013). These units produce large amount of wastewater and sludge and emit reduced sulphur compounds into the atmosphere (Balabanič et al. 2017). The effluent from paper and pulping units is characterized with dark colour, foul odour, high organic load and low biodegradability. The main compounds present are lignin, lignin-degraded products, resin acids, unsaturated fatty acids, chlorinated phenols and aromatic unsaturated compounds (Lindholm-­ Lehto et al. 2015). When let untreated into the environment, it is toxic to the existing flora and fauna. Hence paper mills are forced to treat the wastewater and sludge before disposal into the environment. Wastewater treatment plants have been erected with sole aim of pollutant load reduction to attain prescribed discharge limits. A combination of physicochemical and biological methods is being currently used. Biological components play important role in controlling pollution, and the field of study dealing with biological components for controlling pollution is known as environmental biotechnology. Biological treatment includes combination of both aerobic and anaerobic process to control water pollution (Pokhrel and Viraraghavan 2004). The current global scenario has transformed wastewater treatment plants to energy-efficient units. Energy efficiency recommends both reduced energy inputs and maximal energy recovery. Anaerobic treatment produces biogas which has to be converted to thermal or electrical energy for end use. This conversion process poses inherent power losses and requires installation and maintenance of sophisticated

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infrastructure. A simple yet efficient treatment process combining high power production would gain sustainability in wastewater treatment. Microbial fuel cells are bioelectrochemical devices capable of converting the chemical energy in wastewater to electrical energy with simultaneous bioremediation. It employs exoelectrogenic bacteria in anode chamber which utilizes the organic compounds in wastewater as substrate (Venkata Mohan et al. 2014). They are self-sufficient technologies which integrate bioremediation and electricity generation in a single cell (Singh et  al. 2018). Better treatment efficiency could be attained due to integration of biological and electrochemical treatment in single cell. Lignin and its derivatives are complex and recalcitrant to biological degradation. Work on lignin-rich wastewater in MFC has reported higher lignin removal to other biological treatments (Zang et al. 2010; Li et al. 2017). This chapter reviews the paper production process, the effect of produced waste on environment, current methods of treatment, their advantages and drawbacks and feasibility and advantages of using MFC in paper industry wastewater treatment.

6.2  Process of Paper Manufacturing and Waste Generation Paper is produced from cellulose fibres obtained from wood and agro-waste processing and is recycled from old paper. Paper production process varies according to the raw material used, final product requirement and water available for processing, and hence the wastewater generated from these units also varies in characteristics and pollutant load (Kamali and Khodaparast 2015). Table  6.1 shows the difference in wastewater generated from various paper mills. Though water recycling reduces the total amount of water utilized, it tends to produce wastewater with high concentration of pollutants. In the following section, we will look into process of paper production from wood (Chandra et al. 2011) and agro-residues raw materials (Mahesh et al. 2006) and paper recycling process (Toczyłowska-Mamińska 2017).

6.2.1  Virgin Paper Production Process Virgin paper pulp is made from cellulose fibre obtained from raw materials like wood and agricultural residues. In India nonwood raw materials like bagasse, cereal straw, bamboo, jute and flax are extensively used due to limited availability of wood-based raw materials (Rainey and Covey 2016; Bajpai 2011). Virgin paper manufacturing process can be classified into four major steps including raw material preparation, pulping, bleaching and paper making (Bajpai 2011). Raw material preparation involves debarking and chipping of wood into small pieces which can be easily cooked for pulp production. Wastewater from these units mainly consists of soil, dirt, wood chips and fibres (Pokhrel and Viraraghavan 2004).

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Table 6.1  The characteristics of wastewater generated from different paper mills

Parameter pH Colour COD BOD TDS Conductivity TS Total volatile solids TSS Total alkalinity Lignin Total phenols Sulphate Phosphate K+ Na+ Nitrates TKN NH3-N NO3-N Chlorides Calcium Heavy metals Cd Cr Cu Fe Ni Zn

Rayon grade paper manufacturer (Chandra et al. 2011) 9 ± 0.2 6100 ± 3.5 (Co.pt) 18,700 ± 440 7360 ± 153 1402 ± 1.5 – – –

Agro-based units (Mahesh et al. 2006) 6.86–7.12 1750 (Pt-Co units) 2000–2100 615–670 1760 0.746–0.791 2100 1200

Paper recycling units (Toczyłowska-Mamińska 2017) 5.93 ± 0.08 1990 ± 30 (Pt-Co units) 11,415 ± 15 7155 ± 23 – 6.08 ± 0.5 mS/cm 11,140 ± 520 –

– – 1000 ± 1.1 38.5 ± 2.8 1800 ± 14 BDL 12.2 ± 1.33 102 ± 11 3 ± 4.5 – – – – – – BDL BDL 0.105 ± 0.013 3.99 ± 0.47 2.84 ± 0.38 1.5 ± 0.17

40 380–410 – – 0.241–0.0.269 – – – – – – – 48–62 – – – – – – – –

127 ± 30 2380 ± 150 – – – 7.9 ± 1.8 – – – 80 ± 1.5 12 ± 3 20 ± 2 448 ± 50 2074 ± 55 – – – – – – –

Cellulosic pulp is obtained from raw materials by both chemical and mechanical means. Pulping process removes lignin from cellulose in plant material; the cellulose is further processed to produce paper. The choice of pulping process is decided based on the final requirement of quality of pulp and economic considerations. Mechanical pulping involves grinding of raw material to loosen the fibres to remove lignin; though the pulp yield is higher (nearly 90%) and the process is economical, the quality of product is low having lower strength and discolourations as ageing progresses. Hence mechanical pulping is used to manufacture newsprint. Chemical pulping is the most commercially exploited method of pulping; though the yield of cellulose fibre is low, ranging from 45 to 50%, the final quality of paper makes it as an attractive choice. This process involves chemical digestion of non-pulp materials.

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Pulp washing and chemical recovery are important steps of paper making process. Chemically treated pulp is washed, and the chemicals are recovered for future use. Efficient washing is required to improve chemical recovery and reduce bleaching chemicals, as high amount of cooking liquor in bleaching step would aggregate with bleaching chemicals and result in increased chemicals used. Chemical recovery reduces the pollution load in wastewater. The main aim of bleaching process is to remove residual lignin in the pulp by alkali dissolving of lignin. This step essentially uses various chemicals such as oxygen, hydrogen peroxide, ozone, peracetic acid, sodium hypochlorite, chloride oxide and chlorine to convert lignin to soluble form. Bleaching process can be divided into two categories based on the chemicals used as TCF (total chlorine free) which uses oxygen in the initial stages and ECF (elemental chlorine free) which uses chloride dioxide. Pulp is blended by beating and refining; the quality of final product is based on various proportion of pulp blended. The latter furnish is treated with chemicals to improve strength; fillers and sizing agents are added to improve optical properties and penetration control of liquids which will improve printing properties. In the final stage, pulp mainly consisting of water is dewatered by pressing and drying for paper making (Kamali and Khodaparast 2015). Waste Generated from Virgin Paper and Pulp Mills Virgin paper mills produce huge amount of wastewater and solid sludge and release gaseous emissions; these units are the sixth largest producers of pollutants after oil, cement, leather, textile and steel industries. Amount of waste generation and characteristics depend on the raw material used, technology implemented for paper production and the final product requirement (Kamali and Khodaparast 2015), though various technological advancements have been made to reduce the waste generation and the nature of waste generated requires intensive treatment to meet discharge limits. Paper and pulp mill wastewater has dark colour, foul smell with high COD and low biodegradability index (Soloman et al. 2009). It mainly consists of wood-­ derived organic matter like lignin, resin acids, modified form of lignin, tannins and organic impurities which include the chemicals used for processing (Lindholm-­ Lehto et al. 2015). When discharged untreated into the water bodies the dark colour of the wastewater blocks light penetration affecting flora of receiving ecosystem, the undesirable effects include scum and slime formation, thermal impacts, toxicity and aesthetical issues (Kamali and Khodaparast 2015).

6.2.2  Recycled Paper Production Paper production from recycled fibre has gained considerable importance due to the difficulties in obtaining raw materials. Office waste, corrugated containers and old newspapers have been used as raw material for recycled fibre production. The pro-

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duction process involves three steps: pulping, screening and deinking. In the pulping stage, the waste paper is dispersed in water to prepare them for deinking. In screening stages the high- and medium-sized particles such as staples and clips are removed. Deinking is the important step where the ink particles are separated from cellulose fibres. Though chemical deinking is used widely, enzymatic deinking is more efficient and is used to remove persistent compounds (Kamali and Khodaparast 2015). Waste Generated from Recycled Paper Mill The wastewater generated from these units is different from paper and pulp mill producing virgin fibres. The wastewater mainly consists of surfactants present in paints and inks and chemical additives used in deinking process such as caustic soda, sodium silicate, hydrogen peroxide and soap. It also contains short fibres and fibre-like particles. The pollutants present and the load in wastewater depend on the source of paper used for recycling. In India, most of the small-scale mills use waste paper as raw material for paper production (Kamali and Khodaparast 2015; Bajpai 2015). Small-scale units do not employ chemical recovery in production process; hence these units tend to produce more concentrated wastewater.

6.3  Major Pollutants Present in Paper Mill Wastewater In the following section, we will have a brief overlook of the pollutants present in paper mill wastewater and their effect on environment. The treatment process has to be designed based on the chemical characteristics of wastewater and final effluent quality requirement. The wastewater characteristics vary widely, and hence customized treatment process would enable efficient treatment. Table 6.1 enumerates the wide variation in wastewater generated from various units. The wastewater characteristics tend to change with changing seasons and water availability; hence wastewater treatment plant must be capable of tolerating the variations.

6.3.1  Lignin Lignin is a complex plant polymer second most abundant after cellulose. Lignin in wastewater from paper and pulp industry originates from the plant-based raw materials used. Lignin contributes to the dark colour of the wastewater. It is depolymerized and modified by the chemicals used in pulping and bleaching process. Hence wastewater from paper mills consists of complex mixture of lignin and its derivatives. Lignin is considered to be biologically inert in natural form due to its large size, but its derivatives are considered to be toxic to living being. In particular,

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chlorinated lignin derivatives are responsible for toxicity of wastewater (Lindholm-­ Lehto et al. 2015). 1,2-dihydrobenzene a product of lignin oxidation is considered to be mutagenic. The fate of chlorinated lignin is not entirely known, but it is degraded very slowly and may release toxic biologically active compounds. It has an adverse effect on wheat germination, and though on long term, plants get adapted to these compounds (Deeba et al. 2018).

6.3.2  Tannins Tannins are polar phenolic compounds which are highly reactive with proteins. Tannins add colour to wastewater and absorb more heat and light and maintain low oxygen. They show methanogenic toxicity to microorganisms reducing the biogas yield in anaerobic treatment (Deeba et al. 2018).

6.3.3  Resin Acids Resin acids are hydrophobic, non-volatile, unsaturated, tricyclic, diterpenic carboxylic acid which is commonly found in the bark of trees. Resin acids present in paper and pulp industry wastewater include abietic acid, neoabeitioc acid, dehydroabietic acid, pimaric acid, isopimaric acid, palustic acid, levopimaric acid and sandaracopimaric acid (Lindholm-Lehto et al. 2015). Resin acids are harmful to animals and humans. Resin acids are toxic to invertebrates and fishes. They accumulate in the liver and bile and also decrease the level of reproductive hormones. Though at lower quantity hormonal imbalances do not occur, it accumulates in the liver and causes hormonal disturbances in the long run (Deeba et al. 2018).

6.3.4  Fatty Acids Paper and pulp mill wastewater consists of unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid. They cause toxicity to fishes especially salmonids. Long-chain fatty acids inhibit methanogens and slow down methane production reducing the energy harvesting capacity from anaerobic reactors (Deeba et al. 2018).

6.3.5  Chlorophenolic Compounds Cholorophenols are volatile, lipophilic compounds. They are formed during the pulping process of paper making. They are toxic chemicals with estrogenic, mutagenic and carcinogenic properties. They are the precursors of dioxins and furans.

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Due their lipophilic properties, they tend to accumulate in soils and sediment (Lindholm-Lehto et  al. 2015). It affects both the flora and fauna. It inhibits ­photosynthesis in blue-green algae and diatoms. On long-term intake, it causes necrosis, dermal inflammation, enlarged liver and gastrointestinal irritation (Deeba et al. 2018).

6.3.6  Dioxins Polychlorinated dibenzodioxins, polychlorinated dibenzofurans and dioxin-like polychlorinated biphenyls are structurally and chemically related halogens. They are persistent in nature and resistant to chemical and biological degradation. It causes cancer, affects reproduction and causes sterility (Deeba et al. 2018).

6.3.7  Heavy Metals Heavy metals such as lead, nickel, chromium, mercury, cadmium and cobalt cause birth defects and tumours. These toxic metals possess potential hazards to life forms and bioaccumulation in the food chain causing life-threatening illness as well as damage to vital body system (Deeba et al. 2018).

6.4  Solid Waste Generated from Paper Mills Solid waste is generated in both production process and wastewater treatment. The amount of solid waste produced is based on the raw materials used and production process. The amount of solid waste is high when recycled fibre is used due to the unrecyclable fillers present in it. This issue arises mainly when office paper is used as raw material. Solid wastes produced by recycling paper mills consist of lumps of fibre, staples, metals, sand, plastic, glass, fillers, sizing agents and chemical additives. Screen rejects consist of small fibres which may disturb paper production process if not removed. Deinking process also produces waste which comprises of fillers, coating, small fibres, ink particles and additives. Ink particles may be potential source of heavy metal contamination. Sludge low in moisture content are dewatered, incinerated and disposed off in landfills (Deeba et al. 2018). Solid waste generation from paper mills using virgin fibres for production is relatively low, and the amount is based on the pulping process used. Chemical pulping produces relatively higher solid waste than semi-chemical or mechanical pulping. Rejects from these units mainly consist of sand, bark and wood residues. Usually these rejects are combusted in boiler for energy recovery. Green liquor sludge, dregs and lime mud which arise from the chemical recovery unit comprised of inorganic waste are dewatered and incinerated (Kamali and Khodaparast 2015).

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Primary wastewater treatment involves sedimentation and flotation. Sludge from this process consists of both organic and inorganic waste. The sludge handling is comparatively easy and can be easily dewatered. Secondary wastewater treatment utilizes biological remediation, and the sludge from these units mainly consists of organic matter. It is difficult to dewater and hence difficult to handle. It can be used to improve soil fertility if chlorinated compounds are not present (Kamali et  al. 2016; Deeba et al. 2018). The solid waste is dewatered and dumped in landfills.

6.5  Atmospheric Emissions Paper and pulp industries are fourth largest emitter of greenhouse gases in the manufacturing sector. CO2, SO2 and NOx are produced during combustion for energy generation, and CH4 is released from biological treatment of wastewater. Paper mills also produce considerable amount of VOC which combine with NOx to produce ozone which is common cause for smog and causes lung irritation. Total sulphur-­reduced compounds arise during the kraft pulping stage and are the main reason for distinct odour of kraft pulping mills. Chloroform and other organochlorides are released during chlorine bleaching which are highly toxic. Table 6.2 provides the major pollutants present in paper mill wastewater and their effect on receiving environment (Deeba et al. 2018).

6.6  CPCB Limits for Paper and Pulp Industries CPCB classifies industries into four categories based on the pollution load. Each industry is given a pollution index based on emissions (air pollutants); effluents (wastewater) and hazardous waste generated; the quality, quantity and type of hazardous waste; and consumption of natural resources. Nearly 60 industries are classified into red category; paper and pulp industry is one among them. Industries under red category are to be monitored closely for pollution, and discharge from these units needs to be treated before its release into the environment. Paper and pulp industry is given a pollution index of 60. In particular these units are scored 20 for hazardous waste which signifies the requirement of special care and treatment of waste before disposal. The limits for disposal of wastewater have been prescribed for small- and large-scale mill separately. The standards have been listed in Table 6.3 (CPCB 2017).

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Table 6.2  Major pollutants from paper and pulp industry and their effect on receiving environment S. no Pollutants 1 Lignin

Form in waste Depolymerized and derivatives 1,2-dihydrobenzene Chlorinated lignins Phenolic compounds

2

Tannins

3

Resin acids

Abietic acid, neoabietic acid, dehydroabietic acid, pimaric acid, isopimaric acid, palustic acid, levopimaric acid and sandaracopimaric acid

4

Fatty acid

Oleic acid, linoleic acid and linolenic acid

5

Chlorophenolic compounds

6

Dioxins

7

Heavy metals

8

Solid waste

Polychlorinated dibenzodioxins, polychlorinated dibenzofurans and polychlorinated biphenyls Lead, nickel, chromium, mercury, cadmium and cobalt Primary sludge

Secondary sludge

9

Gaseous emission CO2, SO2 and NOx VOC and NOx Chloroform and organochlorides

Effect on human health and environment Mutagenic Affects wheat germination Toxic to methanogens; affects anaerobic treatment Harmful in animals, humans and fishes Accumulates in liver and bile. Causes lowering of reproductive hormones Toxic to fishes Inhibits methanogens and slows down methane production Estrogenic, mutagenic and carcinogenic properties Inhibits photosynthesis in aquatic flora Causes necrosis, dermal inflammation, enlarged liver and gastrointestinal irritation. Causes cancer, affects reproduction and causes sterility Life-threatening illness and damage to vital body system Consist of chemicals used in production usually sent to landfill From biological waste treatment plants used as fertilizers in absence of chlorides Leads to acid rain Leads to smog formation Highly toxic

Lindholm-Lehto et al. 2015; Deeba et al. 2018; Kamali and Khodaparast 2015

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Table 6.3  CPCB limits for wastewater discharge from paper mills (CPCB 2017) Standards (concentration in mg/l Industry Effluents except pH) Large paper mills of capacity of and above 24,000 MT/ year Large pulp and newsprint/rayon grade plants (capacity of and above 24,000 MT per annum) pH 7–8.5 BOD 30 COD 350 Suspended solids 500 Absorbable organic halogen 1 kg/ton of product produced in effluent 200 cum/ton of paper produced Flow rate 150 cum/ton of paper produced  (i) Large pulp and paper.  (ii) Large rayon grade newsprint. Small paper mill of capacity below 24,000 MT/year Small pulp and paper industry Discharge into inland pH 5.5–9 surface water Suspended solids 100 BOD 30 Discharge into land pH 5.5–9 Suspended solids 100 BOD 100 Sodium absorption ratio 3 kg/ton of paper produced Adsorbable organic halogens 2 kg/ton of paper produced 200 cum/ton of paper produced Flow rate 75 cum/ton of paper produced  (i) Agro-based.  (ii) Waste paper-based.

6.7  Existing Wastewater Treatment Technologies The high pollution load, dark colour and toxicity of wastewater released from these units require proper treatment before disposal. Current treatment methods include both physicochemical and biological methods (Pokhrel and Viraraghavan 2004). Physicochemical treatment is used in primary treatment to reduce the load to secondary biological treatment. It is also used in the tertiary treatment to meet final effluent quality. The physicochemical treatment is energy-intensive and not economical; biological treatment methods are inefficient in treating recalcitrant pollutants. Hence it is required to integrate various treatment methods to attain highest possible treatment economically. In this section we will review various biological treatment methods available and the drawbacks (Kamali et  al. 2016). Figure  6.1 presents the points of waste generation, the current methods employed in waste handling, treatment and discharge.

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Fig. 6.1  Waste production and management in India paper mills

6.7.1  Physicochemical Methods Physicochemical methods include floatation, sedimentation, coagulation (Teng et  al. 2014), precipitation, various membrane technologies (Nataraj et  al. 2007), adsorption and various advanced oxidation processes (Merayo et al. 2013). These methods are energy-intensive, though high treatment efficiency can be attained. Hence a trade-off between treatment efficiency and economy is required (Kamali et al. 2016). Small-scale units are unable to exploit these methods due to the cost of operation and energy requirement involved.

6.7.2  Biological Methods Biological treatment method includes the exploitation of microorganisms in oxidizing the pollutants in wastewater. It is used both as stand-alone technology and in combination with existing physicochemical methods. Biological agents such as bacteria, algae and fungi are used in paper and pulp industry wastewater treatment (Pokhrel and Viraraghavan 2004).

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Fungal System Fungi have been extensively researched for treatment of paper and pulp mill wastewater due to its capability to produce extracellular enzymes degrading phenolic and lignin-based compounds. They are capable of surviving at high effluent load, but the major drawback is their high sensitivity to pH and oxygen limitation (Kamali and Khodaparast 2015). The widely studied fungi species used for paper mill wastewater treatment include Phanerochaete chrysosporium, Trametes vesicolor, Fusarium sambucinum and Emericella nidulans (Asgher et al. 2008). Algal Treatment Recently algae-based treatment of paper mill wastewater has gained considerable importance due to capability of algae to degrade phenol-based compounds. Tarlan, Dilek and Yetis (2002) have experimented the ability of mixed cultures of algae in treating paper and pulp industry effluent and have found that algae had the potential to reduce pollutants in paper mill wastewater. The colour removal was by metabolic degradation of organic matter rather than adsorption defining the sustainability of the system in practical scale. Usha et al. (2016) employed a mixture of two microalgae species of Scenedesmus and have found nearly 85% of pollutant removal. Microalgae-based wastewater treatment includes benefits of CO2 sequestration, and algal biomass finds application in energy sector for biofuel production. These treatment technologies are still in infant stage, and immense research would provide us with numerous advantages over existing systems. Bacteria-Based Treatment Bacterial system is advantageous over fungal system due to the flexibility in operating pH and the treatment efficiency they can render. Both aerobic and anaerobic treatment of paper and pulp industry wastewater are exploited in paper industries (Pokhrel and Viraraghavan 2004). In the following section, we will be focusing elaborately on anaerobic digestion due to the energy recovery option with simultaneous treatment (Chinnaraj and Venkoba Rao 2006). Aerobic Treatment Aerobic treatment is widely used in treatment of paper and pulp industry wastewater. The main drawback of these systems is the requirement for aeration which increases energy input. The increased sludge production also increases the cost of sludge treatment. Various reactors and configuration have been experimented to increase treatment efficiency. Aerobic reactors such as aerated lagoons, stabilized bed reactor and membrane reactors have been studied and used. Aerobic granulation

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is the recent technology used in aerobic treatment of paper and pulp industry wastewater. In paper and pulp industry, aerobic and anaerobic treatment are used in combination (Kalathil et al. 2011). Anaerobic Digestion Anaerobic digestion is defined as the biological degradation of organic compounds by microbial consortia in absence of oxygen into different end products such as methane, carbon dioxide, nitrogen and hydrogen. The gas produced is known as biogas and has energy value in it. Anaerobic digestion is advantageous over aerobic treatment due to low sludge production and low energy requirements. Energy recovery in the form of biogas is the major factor attracting industries in setting up anaerobic treatment plants. The low sludge production is another advantage over other microbial treatment systems. Anaerobic digestion has been extensively studied, and considerable COD removal has been attained. Key factors affecting anaerobic treatment are the pH of the system, temperature, inhibitory compounds present, nutrients and trace elements, hydraulic retention time (HRT) and volatile fatty acids loading (Kamali et al. 2016). Temperature is important factor for influencing biogas production and treatment efficiency. The temperature optimum for anaerobic operation is mesophilic (35–40 °C) and thermophilic (50–55 °C). It is important to maintain temperature as constant in industrial-scale reactors to attain high biogas yield. Thermophilic operation of reactors is considered advantageous as it yields higher biomass hydrolysis leading to high degradation efficiency and favors growth of methanogens resulting in high biogas generation. The major disadvantage of this process is increased energy requirement and instability in the process (Bajpai 2017). The pH of the system is usually maintained at near neutral pH to aid joined digestion of various groups of microbes in the treatment plant. Methanogens are more sensitive to pH, and at acidic pH methanogens growth is retarded, and acidogens grow at faster rate producing high molecular weight volatile fatty acids which further reduces the pH, and the condition is known as SOUR and STRUCK (Bajpai 2017). To avoid this condition, external buffering system is provided (Lindholm-­ Lehto et al. 2015). The presence of toxic compounds inhibits methanogens growth which may lead to system failure (Kamali et al. 2016). The toxic compounds include sulphur compounds, hydrogen peroxide, low molecular weight compounds, heavy metals and resin acids. Nutrient availability and trace elements are essential for methanogenic growth apart from carbon, nitrogen and phosphorous. The trace elements requirement includes Ni, Co, Fe, Mo, Se, Ba, Ca, Mg and Na (Bajpai 2017). Hydraulic retention time is one of the important factors contributing to treatment efficiency of the system. Increased HRT increases the treatment efficiency, but it also increases the capital cost and reactor volume. Hence it is important to optimize the HRT to attain highest treatment without increasing the total cost of the system (Bajpai 2017). Variety of system configurations are used in anaerobic treatment

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which includes anaerobic filters (AFs), up-flow anaerobic sludge bed reactor (UASB) and anaerobic membrane reactors (AnMBRs) (Kamali et al. 2016).

6.8  R  equirement of Novel Sustainable Wastewater Treatment Technology Wastewater treatment plants in the past have been installed and operated with a sole aim of effluent treatment. The current energy scenarios across the globe with increasing energy price have set an alarm for industries to move to energy-sufficient and energy-efficient processes. Current wastewater treatment technologies adopted by paper mills for waste treatment are energy-intensive and costly (Kamali and Khodaparast 2015). The physicochemical methods such as flocculation, coagulation and membrane filtration generate secondary pollutants more toxic than the primary form (Toczyłowska-Mamińska 2017). Reduction of number of unit operations in wastewater treatment plant would reduce the cost of installation and energy requirement. Microbial fuel cells provide anaerobic and micro aerobic environment enhancing the treatment efficiency. Replacement of MFC with the existing biological treatment process would reduce the energy requirements for aeration, and energy recovery in the form of electricity will widely benefit the industry and society (Gu et al. 2017).

6.9  Microbial Fuel Cells MFCs are robust technology combining biological and electrochemical treatment of wastewater into a single unit. It primarily consists of two chambers, the anode and the cathode chamber, separated by a cation exchange membrane. Exoelectrogens are group of bacteria capable of transferring electron to external electron acceptor (Aelterman et al. 2006). Exoelectrogens present in the anode chamber oxidize the organic matter in wastewater to produce protons and electrons. Electrons are transferred to anode by direct electron transfer through conductive pili or by redox mediators present in wastewater or metabolites produced by bacteria (Logan 2009). The protons produced pass through the cation exchange membrane to reach the cathode chamber. In the cathode chamber protons, electrons combine with oxygen to produce water (Rabaey and Verstraete 2005). The basic working of dual-chambered MFC has been represented in Fig. 6.2. Unlike other treatment methods, MFCs have very low environmental footprints. The combination of biological and electrochemical treatment improves the treatment efficiency favouring pollution control (Kim et  al. 2015). The electrical energy produced is the most attractive feature of this treatment method. Researchers working with MFC focus on improving power

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Fig. 6.2  Working of typical dual-chambered microbial fuel cell

p­ roduction by modifying reactor configuration and improving electron transfer to anodes (Li et al. 2017).

6.9.1  E  xoelectrogens Isolated from Paper and Pulp Industry Wastewater One of the most important factors influencing power generation in MFC is the bacteria present in anode chamber. Bacteria in anode chamber must be able to utilize pollutants in paper and pulp mill wastewater and must be capable of extracellular electron transfer. Ketep et al. (2013) have isolated exoelectrogens from bioanodes in MFC operating with paper and pulp mill effluent. The exoelectrogens isolated include Pelobacter propionicus, Geobacter metallireducens and Desulfuromonas acetexigens. Exoelectrogens play important role in electron transfer and power production. Geobacter metallireducens consist of c-type cytochromes, OmcB and OmcE, involved in electron transfer. Desulfuromonas sp. have been earlier isolated from sediment MFC and are capable of power production. The questionability of bacteria capable of extracellular electron transfer and paper mill effluent treatment can thereby be positively answered. These studies open up a new arena of study involving isolating and enriching bacteria capable of both paper mill wastewater treatment and extracellular electron transfer.

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6.9.2  Paper and Pulp Industry Wastewater in MFC The low biodegradability and complex nature of organic compounds present in paper and pulp industry wastewater are two most important reasons making bacterial treatment undesirable for wastewater treatment. Very few studies are available on MFC treating paper and pulp industry wastewater. In the coming section, we will be comparing and discussing the various studies pertaining to MFC using paper and pulp industry wastewater as substrate. Table 6.4 lists the work performed until date and the inferences observed. Paper Recycling Wastewater in MFC As we have seen earlier, the recycled paper mill effluent mainly consists of cellulose. Bacteria find it difficult to degrade cellulose in wastewater. Cellulose degradation is the slowest step, and it affects both the power production and treatment efficiency. Huang and Logan (2008) have studied the feasibility of using paper recycling wastewater in MFC power generation. MFC when operated with paper recycling wastewater modified with phosphate buffer system yielded higher power of 501  mW/m2 which was 245% from plain wastewater, and wastewater treatment increased from 29% of total COD to 76%. The increase in power production was due to the increase in conductivity of wastewater. It was found that cellulose degradation was difficult for bacteria and hence it led to reduced power generation and treatment efficiency. Velasquez-Orta et al. (2011) have studied the factors affecting power production and the treatment efficiency in MFC using various industrial wastewaters as substrate including paper and pulp industry wastewater. Four different wastewaters were collected from various industries including paper recycling, brewery, bakery and dairy industries; similar setup was used in all the studies. Surprisingly the paper recycling effluent previously regarded as very complex for MFC operation showed higher current generation of 125  mA/m2 which was five times higher than other wastewater. As stated earlier conductivity was one of the factors influencing power production; a twofold increase in power was observed with sevenfold increase in conductivity. The paper and pulp industry wastewater showed highest power, and a cyclic voltammetry analysis revealed presence of redox compound with redox potential at -135 mV vs normal hydrogen electrode. It is hypothesized that the compound could be similar to quinone and is capable of shuttling electrons between bacteria and anode. The presence of inherent electron-mediating compound in wastewater increases the total power production.

Single-­ chambered

Single-­ chambered

2

3

S. MFC no configuration 1 Single-­ chambered

Electrodes Anode-carbon brush electrodes Cathode Pt loaded carbon cloth Anode-carbon cloth attached to steel wire Cathode-carbon paper with platinum loading supported on steel mesh Anode-graphite plate Cathode-graphite plate 55%

Sludge from anaerobic treatment

Power density 45 mW/m2

Paper and pulp industry wastewater

78%

Current density 125 mA/m2

Paper recycling Bacteria wastewater present in wastewater

COD removal % 76%

Power generation Power density 501 mW/m2

Wastewater type Inoculum Paper recycling Bacteria wastewater present in wastewater

Table 6.4  MFC operating with paper and pulp industry wastewater

References Huang and Logan (2008)

MFC followed by chemical coagulation was similar to electrocoagulation

Krishna et al. (2014)

Quinone-based compounds present Velasquez-­ in paper industry wastewater could Orta et al. (2011) act as redox mediator resulting in high power generation

Observations Cellulose degradation was the slowest and was the main reason for reduced power generation and treatment

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Virgin Paper Mill Effluent Treatment in MFC Virgin paper mills using both wood and agro-residues as raw material produce large amount of wastewater containing lignin and other plant-derived organic compounds. The wastewater is very complex and hence requires integrated treatment of biological and physicochemical methods. Studies on MFC treating virgin paper mill wastewater elaborate the complexity and its influence on wastewater treatment. Comparative study on MFC and anaerobic system has been made by Krishna, Sarkar and Venkata Mohan et al. (2014). Very low COD removal of 55% and 51% could be attained respectively. Hence combination of MFC with chemical coagulation and anaerobic treatment followed by chemical coagulation has been attempted. Better COD removal of 95% was made after chemical coagulation of MFC-treated wastewater, whereas anaerobic treated wastewater could only be treated to 69%. The difference in coagulation efficiency was due to the generation of charged chemicals species in MFC-treated wastewater mimicking electrocoagulation. The low biodegradability of paper mill effluent has been one of the important parameters pertaining to low treatment efficiency in biological process. Shankar et al. (2016) have evaluated the feasibility of using electrocoagulation to improve the biodegradability of paper mill effluent. The electrocoagulated wastewater was used as substrate for MFC operation. The study highlights that the electrocoagulation could improve biodegradability of wastewater from 0.1 to 0.3. The integrated system of electrocoagulation followed by MFC treatment could yield high treatment efficiency, and energy recovery was also high. The scum from electrocoagulation was tested for the calorific value and could be used as fuel. The study emphasizes the possible ways of improving energy recovery from waste stream.

6.9.3  Integration of MFC into Existing Wastewater Treatment Wastewater generated from paper and pulp industry is very complex and contains various organic and inorganic compounds; hence a stand-alone wastewater treatment is not capable of treating wastewater to prescribed limits. Combination of various treatment processes is essential to attain wastewater of quality prescribed by CPCB.  Physicochemical methods are widely used in the primary treatment and rarely in the final polishing step, biological treatment (aerobic and anaerobic) are usually placed in the secondary stages. MFC is wastewater treatment technology which integrates biological and electrochemical treatment and is capable of oxidizing recalcitrant pollutants in wastewater. The integration of MFC with existing treatment plants would provide electrical energy as supplementary product, raising the economic benefit to industries. The advantages of using MFC for wastewater treatment are:

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1. The integration of electrochemical and biological treatment (Krishna et  al. 2014). 2. Existence of aerobic and anaerobic micro atmosphere in single reactor (Li et al. 2013). It has been found the bioelectrochemical system had better treatment capacity than anaerobic treatment and was able to remove recalcitrant pollutants with higher efficiency. The combination of aerobic and anaerobic treatment in the reactor enhances pollutant removal and aids degradation of recalcitrant organics and metals, which are otherwise difficult to be degraded. Identifying, isolating and exploiting exoelectrogens capable of recalcitrant pollutant degradation would increase the treatment efficiency. Figure 6.3a describes the existing wastewater treatment plant, and Fig.  6.3b illustrates the feasibility of replacement of aerobic and anaerobic treatment in existing wastewater treatment plants with MFC. The lower sludge production in MFC reduces the energy required to treat secondary sludge gaining credits for reduced energy input. The low carbon foot-print and supplementary power production are the attractive features making MFC sustainable replacement to existing treatment methods (Li et al. 2017).

6.10  C  hallenges and Future of Microbial Fuel Cell in Wastewater Treatment Plants MFC research is still in the nascent stage, and lower power production hinders practical-­ scale installation (Janicek et  al. 2014). Current research focuses on improving the material properties, used in MFC. Anode and cathode play major role in deciding the total power produced. Studies enumerate the surface modification of anode for increased surface area, and bacterial attachment could enable higher energy recovery (Li et  al. 2017). Cathode side reaction is the slowest and rate-­ limiting step in MFC power production. Employment of noble metals as catalyst increases the rate of reaction positively impacting power generation. The downside of using these cathodes is on long-term operation, there is a decline in MFC performance (Santoro et al. 2017). Operating factors such as pH, loading rate, shear stress and temperature have been optimized for high power production (Janicek et  al. 2014). Cation exchange membrane currently used is Nafion which is very costly. Search for alternative low-cost material with considerable proton transfer and reduced oxygen permeability has led to development of ceramic membranes (Pasternak et al. 2016). Improvements on all facets of MFC development will aid in scaling up MFC to wastewater treatment plants.

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Fig. 6.3 (a) Unit operations in current wastewater treatment plants (b) Possible integration of microbial fuel cell into existing wastewater treatment plant

6.11  Conclusion Sustainability in wastewater treatment is the distant dream of environmentalist. Though existing treatment methods are capable of reducing pollution load in waste stream, the risk of secondary pollution generation and expenditure incurred for maintenance is very high. Microbial fuel cells offer greater advantages over other biological wastewater treatment technology. MFCs are energy-positive technologies generating electrical energy from waste stream. The combination of electrochemical and biological treatment inside a single unit confers higher treatment efficiency. Paper and pulp industry impacts the country’s economy and provides employment to rural population. As these industries already face economic con-

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straints in raw material sourcing, installation and wastewater treatment plants are considered as further burden. Hence technologies which could generate energy or economy would be encouraged among industrialist.

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Krishna KV, Sarkar O, Venkata Mohan S (2014) Bioelectrochemical treatment of paper and pulp wastewater in comparison with anaerobic process: integrating chemical coagulation with simultaneous power production. Bioresour Technol 174:142–151. https://doi.org/10.1016/j. biortech.2014.09.141 Li W-W, Yu H-Q, He Z (2013) Towards sustainable wastewater treatment by using microbial fuel cells-centered technologies. Energy Environ Sci 7(3):911–924. https://doi.org/10.1039/ C3EE43106A Li S, Cheng C, Thomas A (2017) Carbon-based microbial-fuel-cell electrodes: from conductive supports to active catalysts. Adv Mater 29(8):1–30. https://doi.org/10.1002/adma.201602547 Lindholm-Lehto PC et  al (2015) Refractory organic pollutants and toxicity in pulp and paper mill wastewaters. Environ Sci Pollut Res 22(9):6473–6499. https://doi.org/10.1007/ s11356-015-4163-x Logan BE (2009) Exoelectrogenic bacteria that power microbial fuel cells. Nat Rev Microbiol 7(5):375–381. https://doi.org/10.1038/nrmicro2113 Mahesh S et al (2006) Electrochemical degradation of pulp and paper mill wastewater. Part 1. COD and color removal. Ind Eng Chem Res 45(8):2830–2839. https://doi.org/10.1021/ie0514096 Merayo N et al (2013) Assessing the application of advanced oxidation processes, and their combination with biological treatment, to effluents from pulp and paper industry. J Hazard Mater 262:420–427. https://doi.org/10.1016/j.jhazmat.2013.09.005 Nataraj SK et  al (2007) Membrane-based microfiltration/electrodialysis hybrid process for the treatment of paper industry wastewater. Sep Purif Technol 57(1):185–192. https://doi. org/10.1016/j.seppur.2007.03.014 Pasternak G, Greenman J, Ieropoulos I (2016) Comprehensive study on ceramic membranes for low-cost microbial fuel cells. Chem Sus Chem 9(1):88–96. https://doi.org/10.1002/ cssc.201501320 Pokhrel D, Viraraghavan T (2004) Treatment of pulp and paper mill wastewater – a review. Sci Total Environ 333(1–3):37–58. https://doi.org/10.1016/j.scitotenv.2004.05.017 Rabaey K, Verstraete W (2005) Microbial fuel cells: novel biotechnology for energy generation. Trends Biotechnol 23(6):291–298. https://doi.org/10.1016/j.tibtech.2005.04.008 Rainey, Thomas J., Covey, G., 2016. Pulp and paper production from sugarcane bagasse, in: O’Hara, I.M., Mundree, S.G. (Eds.), Sugarcane-Based Biofuels and Bioproducts. John Wiley & Sons, Hoboken, New Jersey, pp. 259–277 Santoro C et al (2017) Microbial fuel cells: from fundamentals to applications. A review. J Power Sour 356:225–244. https://doi.org/10.1016/j.jpowsour.2017.03.109 Shankar R et  al (2016) Simultaneous treatment and energy production from PIW using electro coagulation & microbial fuel cell. J Environ Chem Eng 4(4). https://doi.org/10.1016/j. jece.2016.10.021 Singh HM et al (2018) Microbial fuel cells: a sustainable solution for bioelectricity generation and wastewater treatment. Biofuels 7269:1–21. https://doi.org/10.1080/17597269.2017.1413860 Soloman PA et al (2009) Augmentation of biodegradability of pulp and paper industry wastewater by electrochemical pre-treatment and optimization by RSM. Sep Purif Technol 69(1):109–117. https://doi.org/10.1016/j.seppur.2009.07.002 Tarlan E, Dilek FB, Yetis U (2002) Effectiveness of algae in the treatment of a wood-based pulp and paper industry wastewater. Bioresour Technol 84(1):1–5. https://doi.org/10.1016/ S0960-8524(02)00029-9 Technology Compendium On Energy saving Opportunities Pulp & Paper Sector (2013) Confederation of Indian Industry Teng TT, San Wong S, Wei Low L (2014) Coagulation-flocculation method for the treatment of pulp and paper mill wastewater. In: The role of colloidal systems in environmental protection, pp 239–259. https://doi.org/10.1016/B978-0-444-63283-8.00010-7 Toczyłowska-Mamińska R (2017) Limits and perspectives of pulp and paper industry wastewater treatment – a review. Renew Sust Energ Rev 78(May):764–772. https://doi.org/10.1016/j. rser.2017.05.021

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Chapter 7

MicroRNAs as Biomarkers for Prediction of Environmental Health and Toxicity: A Systematic Overview Padmanaban S. Suresh, Abhishek Shetty, Neethu Mohan, Rie Tsutsumi, and Thejaswini Venkatesh

Contents 7.1  I ntroduction 7.2  R  elationship Between Environmental Toxicants and miRNA Expression Profiles 7.2.1  Polychlorinated Biphenyls 7.2.2   Bisphenol A 7.2.3   Dichlorodiphenyltrichloroethane 7.2.4   Arsenite 7.2.5   Cadmium 7.2.6   Aluminium 7.2.7   Carbon Tetrachloride 7.2.8   Dioxin 7.2.9   Diethylstilbestrol 7.2.10  Hexahydro-1,3,5-Trinitro-1,3,5-Triazine 7.2.11  Cigarette Smoke 7.3  Conclusion and Future Perspectives References

 152  159  159  160  161  162  163  163  164  164  165  165  165  167  167

P. S. Suresh (*) School of Biotechnology, National Institute of Technology, Calicut, Kerala, India A. Shetty Department of Biosciences, Mangalore University, Mangalagangothri, Karnataka, India N. Mohan · T. Venkatesh (*) Department of Biochemistry and Molecular Biology, Central University of Kerala, Kasargod, Kerala, India R. Tsutsumi Department of Nutrition and Metabolism, Institute of Biomedical Sciences, Tokushima University Graduate School, Tokushima City, Japan © Springer Nature Switzerland AG 2020 K. M. Gothandam et al. (eds.), Environmental Biotechnology Vol. 2, Environmental Chemistry for a Sustainable World 45, https://doi.org/10.1007/978-3-030-38196-7_7

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Abstract  MicroRNAs regulate gene expression, and their diverse roles in the field of biomedicine are established and progressively increasing along with advancements in molecular biology techniques. The environment affects human health via genetic and epigenetic alterations. The study of cellular or circulating biomarkers offers help in the management of environmental toxicology by predicting environmental risk factors of any nature, such as air, metals and pesticides and other chemicals. Here, we review on the relationship of microRNAs as biomarkers and the toxicology of environmental agents. Concerning the effects of toxic agents in the environment and prediction of human exposure by biomarkers are still ongoing processes. It demands further researches using advanced research tools. Moreover, the studies dealing with toxicology-related miRNA changes and biomonitoring of environmental xenobiotics with altered miRNA expression will be highlighted in this review. Keywords  MicroRNAs · Polychlorinated biphenyls · Bisphenol A · Metal toxicity

7.1  Introduction The human transcriptome consists of protein-coding genes and noncoding RNAs (ncRNAs). ncRNAs play an important role in the gene regulation at the transcriptional/post-transcriptional level. The roles of ncRNAs in health and disease have been extensively studied in eukaryotes in the last decade (Venkatesh et  al. 2015, 2016). Broadly, ncRNAs are classified into two main groups: the short ncRNAs (200 nucleotides). MicroRNAs (miRNAs) are small, single-stranded ncRNAs of 19 to 22 nucleotides in length and regulate gene expressions in animals and plants. They are encoded by eukaryotic nuclear DNA.  The sequences in miRNAs base-pair with complementary sequences to mRNA molecules, which results in gene silencing via translational repression or degradation (Hou et  al. 2011). The human genome encodes over 1000 miRNAs, which may target about 60% of mammalian genes (Hou et al. 2011). miRNAs are mostly transcribed by RNA polymerase II as primary miRNA (pri-miRNA), which are processed further to precursor miRNA (pre-miR). Mature miRNAs are derived from precursor miRNAs. In animals, the first step occurs in the nucleus, where the RNase III Drosha acts upon pri-mRNAs, generating a pre-miR, which is a small RNA duplex of approximately 65–70 nucleotides in the hairpin conformation (Hou et al. 2011). The pre-miRs are then exported to the cytoplasm by a nuclear transport receptor complex, exportin-5-RanGTP. Pre-miRs are then processed by Dicer into ~22-nt mature miRNA-miRNA∗ duplexes. In the miRNA-miRNA∗ duplexes, miRNA is described as antisense/guide/mature strand and in other miRNA∗ is the sense/passenger strand (Krol et al. 2010). Drosha and Dicer are assisted by a number of cofactors or accessory proteins (Krol et al. 2010). They base-pair with target mRNAs and induce translational repression, deadenylation or degradation (Krol et  al. 2010). They can be convergently transcribed from both DNA strands of a single locus, giving rise to two miRNAs with distinct seed sequences (Stark et al.

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2008). miRNAs regulate their own transcription through single-negative or double-­ negative feedback loops with transcription factors. For example, PITX3 and miR133b form a negative autoregulatory loop in neuronal differentiation (Kim et al. 2007). These mechanisms lead to precise spatiotemporal expression of miRNAs for physiologically optimal effects. miRNAs can also act as activators of translation. For example, miR-10a stimulates ribosomal protein translation (Orom et al. 2008). They are reasonably stable molecules; their turnover is differentially regulated under various conditions. For example, miR-20b decays faster in cycling cells than in arrested cells. Viral infections can regulate miRNA stability. Addition of adenosine or uracil at the 3′ end also regulates miRNA decay. XRN1, SDN1, SDN2 and SFN3 (small RNA degrading nucleases) are examples of enzymes that degrade miRNAs (Krol et al. 2010). The genesis of microRNAs along with factors involved is represented in Fig. 7.1. Better assessment of progression of health effects induced by environmental toxicants is dependent upon the evaluation of various biomarkers. The most recent and

Fig. 7.1  Biogenesis of microRNAs (canonical pathway). miRNAs are transcribed as primary miRNAs (pri-miRNAs) from DNA by RNA polymerase II in the nucleus. These pri-miRNAs undergo further modification by Drosha-RNAse type 3 enzyme and RNA-binding protein DGCR8 to form pre-miRNA (~70 to 120 nucleotides length precursor form). These pre-miRNAs are transported to cytoplasm by exportin-5 and cleaved by Dicer into mature miRNAs (~18 to 23 nucleotides length). Dicer-miRNA complex associates into RISC (RNA-induced silencing) complex along with other proteins in which one strand (passenger strand) gets degraded. The other strand (guide strand) in RISC complex is guided to the 3′untranslated region of the target mRNA and mediate degradation if complete match between miRNA and target mRNA, otherwise translational repression. Readers are requested to refer to the content for more details

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exciting findings in RNA biology add complexity to the understanding of several ncRNAs, including miRNAs, as potential biomarkers in various diseases. Among these biomarkers, miRNAs serve as better indicators because of their stability in cells and circulation, species-dependent regulation, chemical uniformity and the availability of standard assay methods to quantify miRNA (Valencia-Quintana et al. 2014). Exogenous environmental stressors alter and/or induce gene expression, and this can lead to deleterious health effects. Environmental exposure to cigarette smoking, heavy metals, bisphenol A and air pollution can lead to chronic diseases associated with changes in gene and altered miRNA expression. The hazardous potential of various agents in altering gene expression through miRNAs has been studied by various investigators. Studies examining a few of the most important environmental agents and their corresponding biological assays to measure changes in miRNAs are discussed in this review. Endocrine-disrupting chemicals affect the endocrine system at certain doses and can cause cancerous tumours, developmental anomalies, etc. A few of the most important examples are dichlorodiphenyltrichloroethane (DDT), polychlorinated biphenyls (PCBs), bisphenol A (BPA), polybrominated diphenyl ethers (PBDEs) and a variety of phthalates. Among the phthalates, butyl phthalate and di(2ethylhexyl) phthalate are the two most extensively used phthalates. Butyl benzyl phthalate is an endocrine-disrupting chemical that alters the differentiation of endometrial mesenchymal stem/stromal cells through the miR-137-PITX2 axis and alters epigenomic balance to increase adipogenesis (Chen et al. 2017; Sonkar et al. 2016). Biomonitoring of environmental xenobiotics including phthalates has revealed changes in selected inducible and constitutive genes related to the endocrine system, cellular stress response and ribosomal machinery in the freshwater macroinvertebrate Chironomus riparius (Planello et al. 2011; Herrero et al. 2018). Mono-(2-ethylhexyl) phthalate, a well-known endocrine disruptor, induces oxidative stress and apoptosis through oxidative stress-­responsive miRNAs (miR-17-5p, miR-155-5p and miR126-3p) and apoptosis-­related miR-16 in HTR8/SVneo, a first trimester placental cell line, in a dose- and time-dependent manner (Meruvu et al. 2016). These observations, describing potential mechanisms of endocrine-disrupting chemicals in a cell line through miRNAs, were also observed in placental miRNAs, miR-142-3p, miR15a-5p and miR-185, from a cohort of US women with prenatal phenol and phthalate exposure (LaRocca et al. 2016). Nonylphenol is an endocrine-disrupting chemical and is specifically a xenoestrogen. Comprehensive analysis of miRNA/mRNA expression profiles in mouse TM4 Sertoli cells after nonylphenol treatment revealed differential expression of 186 miRNAs and altered pathways, including the Wnt/beta-catenin signaling pathway (Choi et al. 2011). Few of the most important studies described the above changes in microRNA expression following exposure to environmental toxicants. This warrants a systematic overview and catalogue of those miRNAs differentially expressed following exposure to toxicants, and therefore this review will focus on the studies describing the effects of toxic agents on microRNA expression in suitable models. The purpose of this review is to delineate the growing evidence for miRNAs as candidate biomarkers following exposure to environmental toxicants. Most of the studies showing relationship between environmental toxicants and miRNA expression profiles discussed in this review are also presented in Table 7.1.

S. no 1

Human choriocarcinoma cell line (JAR and human endometrial cancer cell line Ishikawa) Human endothelial cells Sprague Dawley rats

Human Zebrafish

miR-21, 31, 126, 221, 222 ↑

miR-132 ↑

miR-193a-3p, 152, 31-5p, 34a-5p

miR-21

PCB mixture Aroclor 1260

PCB 95

Persistent organic pollutants including PCBs PCB 1254

Human peripheral blood mononuclear cells Human placental tissues

Model system studied P19 mouse embryonal carcinoma cells differentiated into cardiomyocytes

miR-30d ↓

let-7c (inverse association)

miR188-5p (positive association)

miRNAs studied Upregulated Mmu-miR-99a, 214, 345-5p, 126-5p, 762, 324-5p, 181a, 302b, 155, 33, 208a, 10a, 154, 500 Downregulated 29a, 302c, 302b, 293, 294, 295, 7a, 302a, 1949, 21, 494, 20b, 200b, 136, 141, 194, 29b, 32 miR-191 ↑

PBDE High-brominated congener 209 PBDE Low-brominated congener 99 PCB mixture Aroclor 1254

PCB 169, a coplanar congener

Environmental toxicants including its derivatives Polychlorinated biphenyls

Table 7.1  Summary of dysregulated miRNAs following exposure to different environmental toxicants

CREB-miR132, p250GAP (negative regulator of synaptogenesis) Cancer pathways including p53 and Wnt Skeletal defects and altered calcium metabolism) BMPRII ↓

Cardiac injury

Epithelial-mesenchymal transition regulator Snai1

(continued)

Krauskopf et al. (2017) Ju et al. (2017)

Wahlang et al. (2016) Lesiak et al. (2014)

Cai et al. (2016)

Associated with therapeutic Guida et al. abortion due to foetal malfunction (2013) Association study with exposure Li et al. (2015)

Target genes/pathways associated References Wnt1 and GSK3beta Zhu et al. (2012)

Environmental toxicants including its derivatives PCB mixture Aroclor 1250

Bisphenol A

Dichlorodiphenyltrichloroethane (DDT)

Arsenite

S. no

2

3.

4.

Table 7.1 (continued)

Human endometrial cancer RL95–2 cells Rats Rats White leghorn chick eggs and EAhy926 cell Human bronchial epithelial cells (p53 knockout)

↓ miR149 miR107 ↑ miR221, 222, 205, 126a, 429

miR-21 ↓

miR-9, 181b, 124, 10b, 125b ↓

miR-200 family members ↓

Mice

Malignant transformation

Neuropilin-1

Pancreatic islet insulin secretory dysfunction ARF6, CCNE2, p53 and hedgehog signalling factors Pten, Dicer1, Esr1, Pgr, Ccnd1, Cyp19a1 Acat1, Armcx1, Pten

Wang et al. (2011)

Chou et al. (2017) Kalinina et al. (2017) Chanyshev et al. (2017) Cui et al. (2012)

Wei et al. (2017)

Target genes/pathways associated References Increased viral infection Waugh et al. (2018) Michele Decreased cell proliferation, Human SV40 transformed Avissar-Whiting increased susceptibility to placental cell lines 3A, et al. (2010) DNA-damaging agents TCL-1, HTR-8 Human placental tissues Therapeutic abortion associated De Felice et al. with foetal malformations (2015) Human MCF7 breast cancer Breast cancer genes Tilghman et al. cells (2012) Human MCF7 breast cancer Breast cancer genes Tilghman et al. cells (2012) Renaud et al. Zebrafish Histone modifications, DNA (2017) methylation and downstream gene regulatory networks

Model system studied Chicken embryo fibroblasts

↑ miR-430a-3p, 430b-3p, 430c-3p, 202-5p, 122, 499-5p, 458-3p, 725-3p, 193a-3p, 184, 499-5p, 205-5p, 133a-3p, 724 ↓ miR-189 miR338

↓ miR-21(ER positive)

↑ miR-21 (ER negative)

miR-146a ↑

miR-146a ↑

miRNAs studied miR-155 ↓

Environmental toxicants including its derivatives

Cadmium

Aluminium

Carbon tetrachloride

Dioxin

S. no

5.

6.

7.

8.

Human Human lung epithelial BEAS-2B cells (as-T cells) Non-malignant human keratinocytes (HaCaT) Human placenta Rat Chicken

miR-21 ↑

miR-222 ↑

miR-21, miR-200a, miR-141 ↑

miR-21, miR-192, miR-29a/b/c

miR-33-5q ↓

↑ miR-122, 125a, 127, 145, 199a, 379, 451, 126, 143, 298, 486 ↓ miR-31, 34a, 181c, 700, 671, 669, 500, 491, 466, 466c, 449a, 134a, let-7b, let-7c

Mice, embryonic kidney 293 cells and mouse hepatoma cells Mouse foetal thymocytes

Mice

↑ miR-9, 125b, 146a

miR-29

Human neural cells

miR-146a

miR-26a ↑

Human

Model system studied Human embryo lung fibroblast cells Pluripotent P19 mouse embryonic carcinoma cells

mir-9, mir-199 ↓ miR92a, 291a, 709 ↑ miR466–669 cluster ↑ miR-29a ↑

miRNAs studied miR-21 ↑ Liu and Bain (2018)

Thymic atrophy and dysregulation in T cell differentiation

(continued)

Singh et al. (2012)

Chatterjee et al. (2018) Banerjee et al. (2017) Cell proliferation, migration, tube Wang et al. formation, etc. (2016a) Pathways leading to melanoma Gonzalez et al. (2015) TGF-beta pathway Brooks et al. (2016) Chronic renal injury Chen et al. (2016a, b) AMPK, NF-kappa B, P-JNK/ Chen et al. JNK, autophagy-related pathways (2018) Reactive oxygen species Pogue et al. pathways (2009) Neurodegeneration Pogue et al. (2017) NF-kappa pathway Zhang et al. (2012)

Beta-catenin/peripheral myelin protein 2 PTEN and PDCD4

Regulation of neurogenic transcription factors

Target genes/pathways associated References ERK/NFKB pathway Ling et al. (2012)

Diethylstilbestrol

9.

10. Hexahydro-1,3,5-trinitro-1,3,5-­ triazine 11. Cigarette smoke

Environmental toxicants including its derivatives

S. no

Table 7.1 (continued)

miR-217 ↓

miR-487b ↓

↓ let-7, miR-10, 26, 30, 34, 99, 122, 123, 124, 125, 140, 145, 146, 191, 192, 219, 222, 223 miR-294 ↑ miR-16, miR-21 and miR-146a ↓

↑ miR-21, 200a, 200b, 200c, 29a, 29b, 429, 141 ↓ miR-181a, miR-133a ↑ miR-71, 27ab, 98

miR-101a, miR-122

miRNAs studied miR-146b-5p

Cell cycle regulation, immunomodulation and growth in placenta Lung cancer cell and normal Cancer pathways human respiratory epithelia KLK7 (kallikrein-2) Immortalized esophageal epithelia, esophageal adenocarcinoma cells

Human placenta

Model system studied Target genes/pathways associated SK-N-SH cells, human-­ Neural toxicological effects derived neuroblastoma cells Mouse COX-2, cFos, enhancer of zeste homolog 2 Hamster uterus Pathways in cancer and adherens junction, regulation of cell cycle and apoptosis Rat brain tissue POLE4, C50RF13, SULF1, ROCK2 Rat lungs Stress response, apoptosis, proliferation, angiogenesis

Xi et al. (2015)

Xi et al. (2013)

Maccani et al. (2010)

Deng et al. (2014) Izzotti et al. (2009)

Yoshioka et al. (2011) Padmanabhan et al. (2017)

References Xu et al. (2018)

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7.2  R  elationship Between Environmental Toxicants and miRNA Expression Profiles 7.2.1  Polychlorinated Biphenyls PCB is an organic chlorine compound with the formula C12H10−xCl. PCBs are classified as probable human carcinogens and can cause potent toxic effects through the environment. Most of the toxicity is related to their similarity with dioxins in terms of structure and mode of action, including endocrine-disrupting activities. Because of its toxic nature, the production of PCBs was banned by the federal law of the United States in 1978 (Porta and Zumeta 2002). Exposure to environmental pollutants including PCBs can lead to congenital heart defects, embryo malformation leading to miscarriage, defective implantation of embryos and skeletal deficiencies. Mechanisms by which PCBs cause the above effects were addressed by several investigators using cell line models and animal and human studies. By addressing the mechanisms, the following studies added a new set of biomarkers induced by exposure to PCBs in the respective tissues/cells/organs. Experiments on cardiomyocyte differentiation after treatment with PCBs (2.5 μmol/L) identified the differential expression of miRNAs and their target genes Wnt1 and GSK3beta. This study suggested that exposure to environmental agents such as PCBs can lead to cardiac developmental defects through the axis of miRNAs and their target genes (Zhu et al. 2012). A particular PCB, 3,3′,4,4′,5,5′-hexachlorobiphenyl (PCB 169, a coplanar congener), is shown to upregulate miR-191. There is a strong correlation between circulating concentrations of PCB and miR-191 expression in human peripheral blood mononuclear cells. In fact, pregnant women living in environments of PCB pollution underwent therapeutic abortion due to foetal malformations and showed increased levels of miR-191  in peripheral blood mononuclear cells (Guida et  al. 2013). In this regard, several studies documented the association of failure in embryo implantation and embryo defects when women were exposed to environmental toxicants such as PCBs. However, the mechanisms of action through the miRNA axis in reproductive tissues including endometrial cells and the placenta are being unravelled. Several miRNAs are differentially regulated in the placenta, a principal regulator of the in utero environment, after exposure to various environmental toxicants. In a study by Li Q et al., the data suggested a strong positive correlation between PBDEs and miR-188-5p expression and an inverse correlation between PBDE 99 and let-7c in the placenta. This study did not find any correlation between placental miRNA expression and DDE or BPA levels (Li et al. 2015). Upon incubation with environmentally relevant concentrations (2.5, 12.5 and 62.5 μM) of PCB mixture Aroclor 1254 in human choriocarcinoma cell line JAR and the human endometrial cell line Ishikawa, there was an impairment in endometrial receptivity and activation of epithelial-mesenchymal transition in endometrial cells through downregulation of miR-30d (Cai et  al. 2016). Analysis of miRNA expression in human endothelial cells after incubating with commercial PCB mixture Aroclor 1260 by Affymetrix GeneChip® miRNA 4.0 arrays for high-throughput detection

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identified a total of 557 out of 6656 miRNAs that were altered after exposure. Furthermore, this study revealed an association with vascular diseases of 21 miRNAs from the differentially regulated miRNAs after PCB exposure (Wahlang et al. 2016). Exposure to non-dioxin-like (NDL) polychlorinated biphenyls (PCBs) can lead to neurodevelopmental disorders, and mechanisms that can relate to the disease process act through the upregulation of miR-132 (Lesiak et al. 2014). Human blood miRNA signature is greatly affected by exposure to persistent organic pollutants (POP) such as PCBs, hexachlorobenzene and DDT, which are often carcinogenic. In a very recent study, 93 miRNAs were differentially regulated in blood and were found to be strongly associated with POP exposure. More detailed analysis of the transcriptome profile suggested a relationship with oncogenes and cancer, such as through the Wnt and p53 signaling pathways (Krauskopf et al. 2017). The mechanisms leading to skeletal diseases/deficiency after exposure to PCB were studied in zebrafish embryos. Induction of miRNA-21, a negative regulator of bone morphology protein receptor II in zebrafish embryos following exposure to PCB1254, revealed mechanisms that cause skeletal diseases/deficiencies (Ju et al. 2017). PCBs can also dampen the immune system by downregulating miRNAs, and recently, the increased viral infection was found to be associated with the deregulation of miR-155 after PCB exposure (Waugh et a1. 2018). This study suggested the mechanism linking exposure to PCBs and sustained viral infections or increased viral-induced mortality through miR-155. Thus the induction of miRNAs by PCBs along with its role in various diseases is toxicologically significant.

7.2.2  Bisphenol A BPA toxicity studies in human placental cytotrophoblast cells identified miR-146a as a specific target among the miRNAs that decreased proliferation and increased sensitivity to DNA-damaging agent bleomycin (Avissar-Whiting et  al. 2010; De Felice et al. 2015). Some endocrine disruptors such as BPAs can potentiate the transcriptional activity of the estrogen receptor in breast cancer cells and thereby augment the disease burden. To investigate this, Tilghman et al. screened ER-positive MCF7 cells for changes in transcriptome and miRNAs after BPA and DDT treatment. This study identified global changes in miRNA expression, including oncomiR-21 expression, after BPA and DDT treatment. The study suggested that BPA and DDT have an important role in breast carcinogenesis apart from their estrogenic activity (Tilghman et al. 2012). Study of zebrafish models to understand the toxic effects of BPA has further enhanced our understanding by suggesting that BPA can modulate miRNAs and thereby the epigenome in favour of progression to cancer phenotype. Recently, Renaud et al. (2017) observed the differential expression of 15 miRNAs in the livers of zebrafish after BPA treatment. They also studied the expression of genes associated with non-alcoholic fatty liver disease, oxidative phosphorylation and mitochondrial and cell cycle dysfunction (Renaud et al. 2017). Association of non-alcoholic fatty liver disease with BPA exposure was

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mechanistically explored through the miR-192-SREBF-1 axis. In a study, male mice exposed to 50 μg/kg/day of BPA by oral gavage for 90 days exhibited a nonalcoholic fatty liver disease (NAFLD) like phenotype which is associated with decreased expression of miR-192, upregulation of sterol regulatory element-binding transcription factor 1 (SREBF1) and a series of genes involved in de novo lipogenesis (Lin et  al. 2017). The significance of BPA in disrupting pancreatic islet function and glucose homeostasis was strengthened by the observations of elevated pancreatic and duodenal homeobox 1 (PDX1) gene and the associated decrease in miR-338 expression in mice through suppression of glucagon-like peptide 1 receptor (Glp1r) (Wei et al. 2017). BPA exposure in endometrial cancer cell lines identified miR-149 and miR-107 as specific targets, whose target genes influence cell cycle regulation and hedgehog signaling. This explains the underlying epigenetic mechanisms related to the risk of endometrial carcinogenesis after BPA exposure (Chou et al. 2017). The deleterious effects of BPA are synonymous to the effects caused by bisphenol F (BPF) and bisphenol S (BPS), which are BPA structural analogs used in marketed products (Verbanck et  al. 2017). BPS and BPF have been detected in everyday products including food and food packaging products, personal care products, paper products, pipe linings, industrial floors, lacquers, varnishes, adhesives, etc. (Rochester and Bolden 2015). Many researchers have studied the correlation between the detrimental effects of BPA through miRNAs; miR21a-5p was identified to reverse BPA-induced obesity by targeting map2k3 through MKK3/p38/MAPK in 3 T3-L1 cells, suggesting a potential therapeutic strategy for BPA-induced obesity (Xie et al. 2016). The protective effects of curcumin in breast cancer are caused by the reversal of BPA-induced upregulated oncogenic miRNAs (miR-19a and miR-19b) in breast cancer cells; this study suggested that many therapeutic agents can nullify the BPA-induced effects through miRNAs (Li et al. 2014). The pluripotency in mouse embryonic stem cells and embryoid bodies is also disturbed by a decrease in miR-134 (Chen et  al. 2013). Thus BPA alters miRNA expression in plethora of tissues.

7.2.3  Dichlorodiphenyltrichloroethane The insecticide DDT is a non-mutagenic xenobiotic compound that can exert estrogen-­like effects and change the expression of its downstream target genes. Studies conducted over recent years have suggested the involvement of DDT in the control of miRNA expression (Kalinina et al. 2017). Female rats treated with DDT showed altered miRNA expression in their liver and ovaries, which regulated the CYP1A and CYP2B genes post-transcriptionally (Chanyshev et  al. 2014). Administration of DDT in oil via an intraperitoneal route for 12 weeks at different doses, 50 and 10  mg/kg, resulted in the altered expression of various miRNAs including miRNA-221, miR222, miR-205, miR-126a and miR-429. These miRNAs were involved in the regulation of genes such as Pten, Dicer1, Esr1, Pgr, Ccnd1 and Cyp19a1, which are involved in pathways of hormonal carcinogenesis (Kalinina

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et al. 2017). Substantial changes in the expression of miR-21 were noted in the livers of DDT-treated rats, suggesting the post-transcriptional regulation of genes by DDT (Chanyshev et al. 2017). It is interesting to note from a recent study that DDT differentially regulates miRNAs in DDT-resistant Drosophila melanogaster (91-R strain) that target the genes involved in detoxification. This study suggests a role for miRNAs in detoxification of DDT in the resistant strain of D. melanogaster (Seong et al. 2018).

7.2.4  Arsenite Arsenic is a metalloid and is mainly found as a sulphide in over 200 mineral species that contain a mixture of metals including silver, lead, copper, nickel, cobalt and iron (Beck et  al. 2017). According to the US Environmental Protection Agency (EPA) and the Agency for Toxic Substances and Disease Registry (ATSDR), arsenic is in the top priority list of hazardous substances in the United States (Beck et al. 2017). Exposure to inorganic arsenic compounds leads to serious health effects in humans. Low-dose chronic exposure to arsenic in drinking water is a global public health concern associated with risks such as metabolic and cardiovascular diseases, hypertension, atherosclerosis and cancer (Beezhold et al. 2017). Arsenic causes diseases via multiple targets. Arsenic compounds target angiogenesis by altering the expression of miRNAs and their cognate mRNA targets in endothelial cells lining the blood vessels. To understand arsenite-induced toxicity, fertilized eggs were injected via the yolk sac with 100  nM sodium arsenite, and microarray analyses were performed in chick embryos. A massive decrease in miRNA-9, miR-181b, miR-124, miR-10b and miR-125b was noted, and subsequently, experiments confirmed their target to be neuropilin-1, which has a profound influence in the process of angiogenesis (Cui et al. 2012). In another cell line experiment, malignant transformation of immortalized, p53-knocked down, human bronchial epithelial cells by low levels of arsenite was associated with reduced levels of the miR-200 family members. Further mechanistic studies indicated that oncogenic transformation is caused by induction of epithelial to mesenchymal transition-inducing transcription factors (Wang et al. 2011). miR-21 was upregulated in human embryo lung fibroblasts after arsenite exposure. The miR-21 upregulation was associated with the activation of the extracellular signal-regulated kinase (ERK)/nuclear factor-κB (NF-­ κB) signal pathway by induced reactive oxygen species (Ling et al. 2012). Some of the most important adverse effects of chronic arsenic exposure include developmental effects involving cognitive function and decreased locomotor activity and birth weight. When pluripotent P19 mouse embryonal carcinoma cells were exposed to 0.5 μM arsenic, several miRNAs involved in differentiation of cells were found to be altered, including members of the miR-466-669 cluster and their target gene NeuroD1 (Liu and Bain 2018). A study conducted on individuals that were exposed and unexposed to arsenic from India suggested that arsenic exposure can alter the expression of senescence-associated miRNAs and cause peripheral neuropathy through the miR-29a/beta-catenin/PMP22 axis (Chatterjee et al. 2018). Upregulation

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of miR-21 was found to contribute to arsenic-induced skin lesions in the same population (Banerjee et al. 2017). Arsenic-transformed human lung epithelial BEAS-2B cells (As-T cells) showed increased expression of miR-222 (Wang et al. 2016a, b). Laboratory studies have shown that arsenic-treated keratinocytes expressed more miR-21, miR-200a and miR-141. These miRNAS are part of melanoma pathways (Gonzalez et  al. 2015). In vivo experiments performed in Sprague Dawley rats exposed to various concentrations of sodium arsenite (0, 0.1, 1, 10 and 100 mg/L) for 60  days revealed changes in miRNAs that alter the balance of antioxidant defence and oxidative stress (Ren et al. 2015).

7.2.5  Cadmium Cadmium metal toxicity occurs via multiple sources, including contaminated food and water, as well as cigarette smoke. Many studies have reported the involvement of miRNAs in cadmium toxicity in plants, which have not been reviewed in this paper. Although the kidney is the major organ affected by cadmium exposure, many studies have unravelled its association with dysfunction in different organ systems. Exposure to toxic metal has been linked to alterations in epigenetic landscape and genomic instability; cadmium exposure is correlated with placental toxicity and dysregulation. Experiments utilizing clinical samples and in vitro experimentation in placental trophoblast cells have identified cadmium-responsive miRNAs, miR-­26a and miR-155. These miRNAs are associated with preeclampsia and are predicted to regulate the members of the TGF-beta pathway (Brooks et al. 2016). Laboratory studies showed altered renal function after exposing rats to 250 mg/L cadmium chloride through drinking water (Chen et al. 2016a, b). The affected renal function was correlated with a change in specific miRNAs (miR-21, miR-192 and miR-29a/b/c) and oxidative stress (Chen et al. 2016a, b). Epigallocatechin-3-gallate effectively reversed these changes caused by cadmium in drinking water (Chen et  al. 2016a, b). Another agent, selenium, potentially antagonizes the cadmium-­ induced apoptosis via a mitochondrial pathway in LLC-PK1 cells through the miR-­125a/b axis (Chen et al. 2016a, b). Cadmium promotes malignant transformation of human bronchial epithelial cells through miRNAs, and various miRNAs have been catalogued in this context (Liu et al. 2015). A very recent study has further suggested that cadmium induces autophagy in chicken spleen through deregulation of the miR-33-AMPK (5′AMP-activated protein kinase) axis (Chen et al. 2018).

7.2.6  Aluminium Brain cells express and maintain distinct populations of miRNAs that support various vital roles. Expression of miRNAs is affected by various toxicants, and a laboratory study has demonstrated the effect of aluminium sulphate on the miRNA profile

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in human neural cells (Pogue et al. 2009). In this study, researchers have shown that upon treatment of human neural cells with aluminium sulphate, miRNA-146a is upregulated, and complement factor is downregulated, and these processes are NF-κB-sensitive (Pogue et al. 2009). Complement factor is a repressor of inflammation, and this study underscores the importance of aluminium-induced toxicity characteristics of neurodegenerative diseases (Pogue et  al. 2009). Furthermore, there was upregulation of a triad of pro-inflammatory miRNAs (miRNA-9, miRNA-125b and miRNA-146a) in mice serum after they were exposed to a standard diet that included aluminium sulphate in the food and drinking water (Pogue et al. 2017). The actions of aluminium are synergistic with iron sulphates, and studies performed in human astroglial cells have demonstrated the role of metals in contributing to Alzheimer’s disease through the miRNA axis (Pogue et al. 2009).

7.2.7  Carbon Tetrachloride Carbon tetrachloride (CCL4) is an organic compound previously used in fire extinguishers as a precursor to refrigerants and as a cleaning agent. CCL4-induced hepatic fibrogenesis is mediated through miRNAs, and it has been shown that three members of the miR-29 family (miR-29a, miR-29b and miR-29c) are significantly downregulated in CCL4-treated mice (Roderburg et al. 2011). The actions of CCL4 to induce hepatic fibrogenesis are reversed by estradiol through induction of hepatic miR-29 (Zhang et al. 2012) and single systemic injection of a miR-29a-expressing adeno-associated virus (AAV) (Knabel et al. 2015).

7.2.8  Dioxin Dioxin (2,3,7,8-tetrachlorodibenzo-para-dioxin; TCDD) belongs to the family of structurally and chemically related polychlorinated dibenzo-para-dioxins and polychlorinated dibenzofurans. They are highly toxic and can affect a number of organs and systems by changing the expression of numerous genes through the aryl hydrocarbon receptor. They cause hepatotoxicity, teratogenicity, cancer, severe anorexia-­ like wasting and death (Moffat et al. 2007). Exposure to TCDD has been shown to cause thymic atrophy and alterations in T cell differentiation. Experiments were conducted to analyse the change in miRNAs in mouse thymocytes post-exposure to TCDD. Data analysis of those experiments revealed changes in 78 miRNAs (>1.5-­ fold) and 28 miRNAs (>two-fold) in foetal thymocytes post-TCDD exposure when compared to vehicle controls (Singh et  al. 2012). Experiments conducted in SK-N-SH cells, a human-derived neuroblastoma cell line, revealed upregulation and enhanced promoter activity of miR-146-5p following dioxin treatment. These observations suggest that dioxin-mediated neural toxicological effects occur through miR-146-5p (Xu et  al. 2018). Exposure to TCDD is also associated with the

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dysregulation of the expression of miR101a and miR122 that causes liver damage in mice (Yoshioka et al. 2011).

7.2.9  Diethylstilbestrol Diethylstilbestrol, otherwise known as stilbestrol, is a previously used estrogen medication for a variety of purposes. It is used to support pregnancy in women with a history of recurrent miscarriage, hormonal therapy after menopause or in estrogen deficiency and treatment of prostate cancer in men. Prenatal exposure to diethylstilbestrol causes a variety of disorders, and the molecular mechanisms affecting gene expression are associated with change in the expression of miRNAs. When mice were exposed to diethylstilbestrol, there were alterations in miRNA profiles of thymocytes in both the mother and foetuses on postnatal day. These miRNAs regulate several cellular processes including apoptosis, autophagy, toxicity and cancer (Singh et al. 2015). Neonatal diethylstilbestrol-induced dysplasia/neoplasia in hamster uterus also altered miRNAs (upregulated miR-21, miR-200a, miR-200b, miR-­200c, miR-29a, miR-29b, miR429 and miR-141; downregulated miR-181a) (Padmanabhan et al. 2017).

7.2.10  Hexahydro-1,3,5-Trinitro-1,3,5-Triazine Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) gets contaminated in soil and groundwater due to military and manufacturing activities. A series of studies has concluded that exposure to RDX can cause neurotoxicity and immunotoxicity in humans and animals (Deng et al. 2014). RDX induces miR-71, miR-27ab, miR-98 and miR-135a expression in brains of RDX-treated rats; this could reduce the expression of genes POLE4, C5ORF13, SULF1 and ROCK2, thus causing neurotoxicity (Deng et al. 2014). Brain and liver tissues of RDX-treated B6C3F1 mice showed altered expression patterns of 13 miRNAs (10 upregulated, 3 downregulated, p