Advances in Carbon Capture and Utilization [1 ed.] 9811606374, 9789811606373

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Energy, Environment, and Sustainability Series Editor: Avinash Kumar Agarwal

Deepak Pant Ashok Kumar Nadda Kamal Kishore Pant Avinash Kumar Agarwal   Editors

Advances in Carbon Capture and Utilization

Energy, Environment, and Sustainability Series Editor Avinash Kumar Agarwal, Department of Mechanical Engineering, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh, India

AIMS AND SCOPE This books series publishes cutting edge monographs and professional books focused on all aspects of energy and environmental sustainability, especially as it relates to energy concerns. The Series is published in partnership with the International Society for Energy, Environment, and Sustainability. The books in these series are edited or authored by top researchers and professional across the globe. The series aims at publishing state-of-the-art research and development in areas including, but not limited to: • • • • • • • • • •

Renewable Energy Alternative Fuels Engines and Locomotives Combustion and Propulsion Fossil Fuels Carbon Capture Control and Automation for Energy Environmental Pollution Waste Management Transportation Sustainability

Review Process The proposal for each volume is reviewed by the main editor and/or the advisory board. The chapters in each volume are individually reviewed single blind by expert reviewers (at least four reviews per chapter) and the main editor. Ethics Statement for this series can be found in the Springer standard guidelines here https://www.springer.com/us/authors-editors/journal-author/journal-author-hel pdesk/before-you-start/before-you-start/1330#c14214.

More information about this series at http://www.springer.com/series/15901

Deepak Pant · Ashok Kumar Nadda · Kamal Kishore Pant · Avinash Kumar Agarwal Editors

Advances in Carbon Capture and Utilization

Editors Deepak Pant School of Earth and Environmental Sciences Central University of Himachal Pradesh Dharamshala, Himachal Pradesh, India Kamal Kishore Pant Department of Chemical Engineering Indian Institute of Technology Delhi New Delhi, Delhi, India

Ashok Kumar Nadda Department of Biotechnology and Bioinformatics Jaypee University of Information Technology Waknaghat, Himachal Pradesh, India Avinash Kumar Agarwal Department of Mechanical Engineering Indian Institute of Technology Kanpur Kanpur, Uttar Pradesh, India

ISSN 2522-8366 ISSN 2522-8374 (electronic) Energy, Environment, and Sustainability ISBN 978-981-16-0637-3 ISBN 978-981-16-0638-0 (eBook) https://doi.org/10.1007/978-981-16-0638-0 © The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2021 This work is subject to copyright. All rights are solely and exclusively licensed 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 Singapore Pte Ltd. The registered company address is: 152 Beach Road, #21-01/04 Gateway East, Singapore 189721, Singapore

Preface

This book was motivated by the current scenario of global warming and its harmful impact on the environment as well as living system. In the modern society, human beings are well aware about the climate change and the factors responsible for the same. However, our efforts to mitigate the climate change do not meet the required standard that can make significant impact to save the earth. The greenhouse gases (CO2 , N2 O, HFC and methane) are majorly responsible for the global warming. CO2 is being released from various sources, automobiles, cement industries, power plants, animals and volcanic eruptions. Every year, there is continuous rise in the CO2 level and reached around 417 ppm. The controlled emission of CO2 , capturing the emitted CO2 from atmosphere, and conversion of CO2 released from various sources are the key objectives to achieve in order to lower its atmospheric level. Naturally, plants and oceans are the ordinary sink available for the absorption and conversion of CO2 . Even after 70% of total water covered area on earth, various human activities, such as deforestation, unplanned urbanization, excessive automobiles and industrial emission, construction of highways and new cities led to the increase in CO2 level. This became a great challenge in front of environmentalists, chemical engineers as well as whole human population to minimize the CO2 quantity to a safe level on the earth. In the last two decades, researchers have focused to develop the new methods and techniques to control the release of CO2 or to capture the released CO2 from the atmosphere and convert it into value-added products. Nanomaterials including nanoparticles, nanosheets, nanomembranes, metal organic frameworks and biochar have gained more acceptance to use these as artificial CO2 adsorbents. Also, the organic solvents such as amine-based solvents have also been employed for the CO2 absorption from various sources. Various ionic liquids, eutectic solvents and organic solvents have also huge potential to absorb and convert the atmospheric CO2 and convert it into other or useful products under controlled conditions. Biologists moved toward the microorganisms to exploit their potential as CO2 converting candidates. The major advantages stabilities and efficiencies of the chemical-, biological- and material-based systems have been discussed in the respective chapters of this book. The International Society for Energy, Environment and Sustainability (ISEES) was founded at Indian Institute of Technology Kanpur (IIT Kanpur), India, in January 2014 with an aim to spread knowledge/awareness and catalyze research activities in v

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the fields of energy, environment, sustainability and combustion. The society’s goal is to contribute to the development of clean, affordable and secure energy resources and a sustainable environment for the society and to spread knowledge in the abovementioned areas and create awareness about the environmental challenges, which the world is facing today. The unique way adopted by the society was to break the conventional silos of specialications (engineering, science, environment, agriculture, biotechnology, materials, fuels, etc.) to tackle the problems related to energy, environment and sustainability in a holistic manner. This is quite evident by the participation of experts from all fields to resolve these issues. The ISEES is involved in various activities such as conducting workshops, seminars, conferences in the domains of its interests. The society also recognizes the outstanding works done by the young scientists and engineers for their contributions in these fields by conferring them awards under various categories. Fourth International Conference on ‘Sustainable Energy and Environmental Challenges’ (IV-SEEC) was organized under the auspices of ISEES from November 27– 29, 2019, at NEERI, Nagpur. This conference provided a platform for discussions between eminent scientists and engineers from various countries including India, USA, China, Italy, Mexico, South Korea, Japan, Sweden, Greece, Czech Republic, Germany, Netherland and Canada. In this conference, eminent speakers from all over the world presented their views related to different aspects of energy, combustion, emissions and alternative energy resource for sustainable development and cleaner environment. The conference presented one high-voltage plenary talk by Mrs. Rashmi Urdhwareshe, Director, Automotive Research Association of India (ARAI), Pune. The conference included 28 technical sessions on topics related to energy and environmental sustainability including 1 plenary talk, 25 keynote talks and 54 invited talks from prominent scientists, in addition to 70+ contributed talks and 80+ poster presentation by students and researchers. The technical sessions in the conference included fuels, engine technology and emissions, coal and biomass combustion/gasification, atomization and sprays, combustion and modeling, alternative energy resources, water and water and wastewater treatment, automobile and other environmental applications, environmental challenges and sustainability, nuclear energy and other environmental challenges, clean fuels and other environmental challenges, water pollution and control, biomass and biotechnology, waste to wealth, microbiology, biotechnological and other environmental applications, waste and wastewater management, cleaner technology and environment, sustainable materials and processes, energy, environment and sustainability, technologies and approaches for clean, sensors and materials for environmental, biological processes and environmental sustainability. One of the highlights of the conference was the rapid fire poster sessions in (i) engine/fuels/emissions, (ii) environment and (III) biotechnology, where 50+ students participated with great enthusiasm and won many prizes in a fiercely competitive environment. 300+ participants and speakers attended this three days conference, where 12 ISEES books published by Springer, Singapore, under a special dedicated series ‘Energy, environment and sustainability’ were released. This was third time in a row that such significant and high-quality outcome has been achieved by any society

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in India. The conference concluded with a panel discussion on ‘Balancing Energy Security, Environmental Impacts and Economic Considerations: Indian Perspective’, where the panelists were Dr. Anjan Ray, CSIR-IIP Dehradun; Dr. R. R. Sonde, Thermax Ltd.; Prof. Avinash Kumar Agarwal, IIT Kanpur; Dr. R. Srikanth, National Institute of Advanced Studies, Bengaluru; and Dr. Rakesh Kumar, NEERI, Nagpur. The panel discussion was moderated by Prof. Ashok Pandey, Chairman, ISEES. This conference laid out the roadmap for technology developments, opportunities and challenges in energy, environment and sustainability domain. All these topics are very relevant for the country and the world in present context. We acknowledge the support received from various funding agencies and organizations for the successful conduct of the Fourth ISEES Conference IV-SEEC, where these books germinated. We would therefore like to acknowledge SERB, Government of India (special thanks to Dr. Sandeep Verma, Secretary); NEERI, Nagpur (special thanks to Dr. Rakesh Kumar, Director), CSIR, and our publishing partner Springer (special thanks to Swati Mehershi). The editors would like to express their sincere gratitude to large number of authors from all over the world for submitting their high-quality work in a timely manner and revising it appropriately at a short notice. We would like express our special thanks to Anand Giri, Atul Dhar, Dr. Pravesh Chandra Shukla, Dr. Nirendra Nath Mustafi, Prof. V. S. Moholkar, Prof. V. Ganeshan, Dr. Joonsik Hwang, Dr. Biplab Das, Dr. Veena Chaudhary, Dr. Jai Gopal Gupta, Dr. Chetan Patel, Dr. Sajna Kottupvill, Dr. Aditi Banerjee, Dr. Swati Tyagi, Dr. Sikandar I. Mulla, Dr. Achlesh Davery, Dr. Rishi Mahajan, Dr. Swati Sharma and Dr. Arun who reviewed various chapters of this monograph and provided their valuable suggestions to improve the manuscripts. The chapters include recent results and more focussed on current trends emphasized on the generation of energy, fuels and products of commercial importance from CO2 using various new methods and techniques. Chapters 1 and 2 described the fundamentals of carbon capture and importance of healthy and green environment. Chapters 3 and 4 focused on the geological and soil-based carbon capture and storage. Chapter 5 described the role of nanomaterials as a potent adsorbent for CO2 capture, conversion and post-combustion technologies. The biological systems of CO2 capture have been elaborated in detail in Chap. 6. Chapter 7 highlights the simultaneous wastewater treatment, CO2 capture and bioenergy generation using electrochemical approaches. The role of ionic liquids for the CO2 capture and its absorption has discussed in Chap. 8. Chapter 9 discussed the carbon capture and smart agriculture techniques. Chapter 10 is a case study that describes the data of quantification of soil organic carbon in the Lahaul Valley of India. Biochar is one the organic materials that has been emerged as potent candidate for carbon removal which is discussed in Chap. 11. Chapter 12 discussed the use of different land sectors of Western Himalaya. The last two Chaps. 13 and 14 have focused on the generation of bioenergy and commercial products from CO2 using various new methods and techniques. Overall, the present book will cover a wide range of topics of carbon management that are being used to minimize the emission of greenhouse gases and mitigate the climate change. We hope that the book would be of great interest to

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the professionals, post-graduate students involved in chemistry, chemical, biological engineering and environmental research Dharamshala, India Solan, India New Delhi, India Kanpur, India

Deepak Pant Ashok Kumar Nadda Kamal Kant Pant Avinash Kumar Agarwal

Contents

Part I 1

General

Advances in Carbon Capture and Utilization . . . . . . . . . . . . . . . . . . . . Deepak Pant, Ashok Kumar Nadda, Kamal Kant Pant, and Avinash Kumar Agarwal

Part II

Carbon Capture as Natural Phenomenon

2

Carbon Capture: Innovation for a Green Environment . . . . . . . . . . . Nishu Khurana, Nikita Goswami, Ranajit Sarmah, and Devanshi

3

Geological Carbon Capture and Storage as a Climate-Change Mitigation Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Riju, Anurag Linda, and H. P. Singh

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Soil Carbon Sequestration for Soil Quality Improvement and Climate Change Mitigation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Ruma Das, Avijit Ghosh, Shrila Das, Nirmalendu Basak, Renu Singh, Priyanka, and Ashim Datta

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Part III Advance Carbon Management Techniques 5

Post-combustion of Carbon Capture Technologies: Advancements in Absorbents and Nanoparticles . . . . . . . . . . . . . . . . . Ravinder Kumar, Mohammad HosseinAhmadi, Anand Bewoor, Reza Alayi, Pawan Kumar, and Venkata Manikanta Medisetty

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Carbon Bio-capturing System for Environment Conservation . . . . . Vishal Ahuja

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7

Simultaneous Wastewater Treatment and Carbon Capture for Energy Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127 Priyanka Verma, Deepshikha Pandey, Usharani Krishnaswamy, Kasturi Dutta, Achlesh Daverey, and Kusum Arunachalam

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Contents

8

Carbon Dioxide Capture by Ionic Liquids . . . . . . . . . . . . . . . . . . . . . . . 147 Kailas Wasewar

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The Climate Smart Agriculture for Carbon Capture and Carbon Sequestration: The Challenges and Opportunities . . . . 195 S. Senjam Jinus, Tracila Meinam, Koijam Melanglen, Minerva Potsangbam, Akoijam Ranjita Devi, Lucy Nongthombam, Thoudam Bhaigyabati, Helena D. Shephrou, Kangjam Tilotama, and Dhanaraj Singh Thokchom

10 Quantification of the Soil Organic Carbon and Major Nutrients Using Geostatistical Approach for Lahaul Valley, Cold Arid Region of Trans-Himalaya . . . . . . . . . . . . . . . . . . . . . . . . . . . 235 Praveen Kumar, Pardeep Kumar, Munish Sharma, Nagender Pal Butail, and Arvind Kumar Shukla Part IV Miscellaneous Techniques 11 Biochar: A Carbon Negative Technology for Combating Climate Change . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251 Meera Goswami, Gaurav Pant, Dalip K. Mansotra, Shivalika Sharma, and P. C. Joshi 12 Carbon Sequestration Potential of Different Land Use Sectors of Western Himalaya . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273 Deepa Rawat, S. P. Sati, Vinod Prasad Khanduri, Manoj Riyal, and Gaurav Mishra Part V

Value Addition Techniques

13 Progresses in Bioenergy Generation from CO2 : Mitigating the Climate Change . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297 Tanvi Sharma, Reva Bhardwaj, Rupali Bhardwaj, Anand Giri, Deepak Pant, and Ashok Kumar Nadda 14 Recent Advances in Enzymatic Conversion of Carbon Dioxide into Value-Added Product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313 Anand Giri, Suman Chauhan, Tanvi Sharma, Ashok Nadda, and Deepak Pant

Editors and Contributors

About the Editors Prof. Deepak Pant is currently Dean, School of Earth and Environmental Sciences, Central University of Himachal Pradesh, India. He is also Visiting Professor of Environmental and Chemical Science, Indira Gandhi Technological and Medical Sciences University, India. Prof. Pant is the recipient of Silver Jubilee Research Fellowship award (2003) by Kumaun University, India, UCOST Young Scientist Award 2009, INSA Visiting Fellow 2010, DST-SERC Visiting Fellow 2010, DSTSERC Young Scientist Award 2011 and Visitor Award 2017 by Hon’ble President of India for his research activities. He was conferred the 8th National Award for Technology Innovation by the Ministry of Chemicals and Fertilizers, Government of India. Prof. Pant has 5 patents in the area of waste management by green techniques and has authored 13 books and 50 research papers in various national and international journals. He has guided 6 Ph.D. scholars and 150 M.Sc. dissertations.

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Editors and Contributors

Dr. Ashok Kumar Nadda is Assistant Professor in the Department of Biotechnology and Bioinformatics, Jaypee University of Information Technology, India. He holds expertise in the field of microbial biotechnology, with research focusing on various issues pertaining to nano-biocatalysis, microbial enzymes, biomass, bioenergy and climate change. He worked as Postdoctoral Fellow at State Key Laboratory of Agricultural Microbiology, Huazhong Agricultural University, China. He also worked as Brain Pool Researcher/Assistant Professor at Konkuk University, South Korea. His research interests lie in microbial enzymes, biocatalysis, CO2 conversion, climate change issues, nanobiotechnology, waste management, biomass degradation, biofuel synthesis and bioremediation. He has published 65 research articles, 25 book chapters and 6 books. He is also a member of the editorial board and reviewer committee of the various journals of national and international repute. Prof. Kamal Kishore Pant is the Federation of Indian Petroleum Industries (FIPI) Chair Professor in the Department of Chemical Engineering at Indian Institute of Technology (IIT) Delhi, India. His research interests involve innovative studies covering both the theoretical and experimental aspects of heterogeneous catalysis for hydrocarbon conversion, green technologies for sustainable energy and the environment, biomass conversion, metal recovery from waste and water treatment. His research work on the development of green and sustainable technologies for management of plastic and electronic waste, coal and agro-waste conversion to chemicals, CO2 capture and conversion to chemicals, crude oil and natural gas to chemicals and hydrogen production is duly recognized across the scientific community. He has over 30 years of academic and industrial research experience with 150+ publications in peer-reviewed journals with over 8000 citations numerous book chapters and several patents. Prof. Pant also holds Adjunct Faculty position at the University of Saskatchewan, Canada, and CRDT, IIT Delhi as well as Honorary Faculty at the University of Queensland, Australia. Prof. Pant has been conferred CHEMCON Distinguished Speaker (CDS) award in 2019, Herdilia Award by Indian Institute of Chemical Engineers in 2017, and other honors.

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Prof. Avinash Kumar Agarwal joined the Indian Institute of Technology (IIT) Kanpur, India, in 2001, after working as Postdoctoral Fellow at the Engine Research Center, University of Wisconsin at Madison, USA. His interests are IC engines, combustion, alternate and conventional fuels, lubricating oil tribology, optical diagnostics, laser ignition, HCCI, emissions and particulate control, and large bore engines. Prof. Agarwal has published 290+ peer-reviewed international journal and conference papers, 42 edited books and 78 books chapters and has 10,000+ Scopus and 15,300+ Google Scholar citations. He is Fellow of SAE (2012), Fellow of ASME (2013), Fellow of ISEES (2015), Fellow of INAE (2015), Fellow of NASI (2018), Fellow of Royal Society of Chemistry (2018) and Fellow of American Association of Advancement in Science (2020). He is the recipient of several prestigious awards such as Clarivate Analytics India Citation Award-2017 in Engineering and Technology, NASI-Reliance Industries Platinum Jubilee Award-2012; INAE Silver Jubilee Young Engineer Award-2012; Dr. C. V. Raman Young Teachers Award: 2011; SAE Ralph R. Teetor Educational Award-2008; INSA Young Scientist Award-2007; UICT Young Scientist Award-2007; INAE Young Engineer Award-2005. Prof. Agarwal received Prestigious Shanti Swarup Bhatnagar Award-2016 in Engineering Sciences. For his outstanding contributions, Prof. Agarwal is conferred upon Sir J C Bose National Fellowship (2019) by SERB.

Contributors Avinash Kumar Agarwal Department of Mechanical Engineering, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh, India Vishal Ahuja Department of Biotechnology, Himachal Pradesh University, Shimla, India Reza Alayi Department of Mechanics, Germi Branch, Islamic Azad University, Germi, Iran Kusum Arunachalam School of Environment and Natural Resources, Doon University, Dehradun, Uttarakhand, India

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Nirmalendu Basak Division of Soil and Crop Management, ICAR-Central Soil Salinity Research Institute, Karnal, Haryana, India Anand Bewoor Mechanical Engineering Departments, Cummins College of Engineering for Women, Pune, Maharashtra, India Thoudam Bhaigyabati Institutional Advanced Level Biotech Hub, Imphal College, Imphal, Manipur, India Reva Bhardwaj Department of Biotechnology and Bioinformatics, Jaypee University of Information Technology, Waknaghat, Solan, India Rupali Bhardwaj Department of Biotechnology and Bioinformatics, Jaypee University of Information Technology, Waknaghat, Solan, India Nagender Pal Butail Department of Soil Science, CSKHPKV, Palampur, Himachal Pradesh, India Suman Chauhan Department of Environmental Sciences, Central University of Himachal Pradesh, Kangra, India Ruma Das Division of Soil Science and Agricultural Chemistry, ICAR-Indian Agricultural Research Institute, New Delhi, India Shrila Das Division of Soil Science and Agricultural Chemistry, ICAR-Indian Agricultural Research Institute, New Delhi, India Ashim Datta Division of Soil and Crop Management, ICAR-Central Soil Salinity Research Institute, Karnal, Haryana, India Achlesh Daverey School of Environment and Natural Resources, Doon University, Dehradun, Uttarakhand, India Devanshi University Institute of Biotechnology, Chandigarh University, Mohali, Punjab, India Akoijam Ranjita Devi Faculty of Agricultural Sciences, SRM Institute of Science and Technology, Kattankulathur, Tamil Nadu, India Kasturi Dutta Department of Biotechnology and Medical Engineering, National Institute of Technology, Rourkela, Odisha, India Avijit Ghosh ICAR-Indian Grassland and Fodder Research Institute, Jhansi, Uttar Pradesh, India Anand Giri Department of Environmental Sciences, Central University of Himachal Pradesh, Kangra, Himachal Pradesh, India Meera Goswami Department of Zoology and Environmental Science, Gurukul Kangri Vishwavidyalaya, Haridwar, Uttarakhand, India Nikita Goswami University Institute of Biotechnology, Chandigarh University, Mohali, Punjab, India

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Mohammad HosseinAhmadi Departmant of Mechanical Engineering, Shahrood University of Technology, Shahrood, Iran P. C. Joshi Department of Zoology and Environmental Science, Gurukul Kangri Vishwavidyalaya, Haridwar, Uttarakhand, India Vinod Prasad Khanduri College of Forestry, Ranichauri, Tehri Garhwal, Uttarakhand, India; VCSG Uttarakhand University of Horticulture and Forestry, Bharsar, India Nishu Khurana University Institute of Biotechnology, Chandigarh University, Mohali, Punjab, India Usharani Krishnaswamy Department of Environmental Science, Bioremediation Technology, PSG College of Arts and Science, Coimbatore, Tamilnadu, India Pardeep Kumar Department of Soil Science, CSKHPKV, Palampur, Himachal Pradesh, India Pawan Kumar Department of Materials Science and Nanotechnology, Deenbandhu Chhotu Ram University of Science and Technology, Murthal, Haryana, India Praveen Kumar Department of Soil Science, CSKHPKV, Palampur, Himachal Pradesh, India Ravinder Kumar Departmant of Mechanical Engineering, Lovely Professional University, Phagwara, Punjab, India Anurag Linda Department of Environmental Sciences, Central University of Himachal Pradesh, Dharamsala, India Dalip K. Mansotra Department of Zoology and Environmental Science, Gurukul Kangri Vishwavidyalaya, Haridwar, Uttarakhand, India Venkata Manikanta Medisetty Departmant of Mechanical Engineering, Lovely Professional University, Phagwara, Punjab, India Tracila Meinam Department of Horticulture, School of Agriculture, School of Horticulture, Pandit Deen Dayal, Upadhyay Institute of Agricultural Sciences, Utlou, Manipur, India Koijam Melanglen Department of Horticulture, School of Agriculture, School of Horticulture, Pandit Deen Dayal, Upadhyay Institute of Agricultural Sciences, Utlou, Manipur, India Gaurav Mishra Rain Forest Research Institute, Jorhat, Assam, India; Indian Council of Forestry Research and Education, Dehradun, India Ashok Nadda Department of Biotechnology and Bioinformatics, Jaypee University of Information Technology, Waknaghat, Solan, India

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Editors and Contributors

Ashok Kumar Nadda Department of Biotechnology and Bioinformatics, Jaypee University of Information Technology, Waknaghat, Solan, India Lucy Nongthombam Biswanath College of Agriculture, Assam Agricultural University, Biswanath Chariali, Assam, India Deepshikha Pandey School of Environment and Natural Resources, Doon University, Dehradun, Uttarakhand, India Deepak Pant School of Earth and Environmental Sciences, Central University of Himachal Pradesh, Dharamshala, Himachal Pradesh, India Gaurav Pant Department of Zoology and Environmental Science, Gurukul Kangri Vishwavidyalaya, Haridwar, Uttarakhand, India Kamal Kant Pant Department of Chemical Engineering, Indian Institute of Technology New Delhi, New Delhi, India Minerva Potsangbam Department of Horticulture, North Eastern Hill University, Chasingre, West Garo Hills, Meghalaya, India Priyanka Division of Soil and Crop Management, ICAR-Central Soil Salinity Research Institute, Karnal, Haryana, India Deepa Rawat College of Forestry, Ranichauri, Tehri Garhwal, Uttarakhand, India; VCSG Uttarakhand University of Horticulture and Forestry, Bharsar, India Riju Department of Environment Studies, Panjab University Chandigarh, Chandigarh, India Manoj Riyal College of Forestry, Ranichauri, Tehri Garhwal, Uttarakhand, India; VCSG Uttarakhand University of Horticulture and Forestry, Bharsar, India Ranajit Sarmah University Institute of Biotechnology, Chandigarh University, Mohali, Punjab, India S. P. Sati College of Forestry, Ranichauri, Tehri Garhwal, Uttarakhand, India; VCSG Uttarakhand University of Horticulture and Forestry, Bharsar, India S. Senjam Jinus College of Horticulture and Agri-Biotechnology, FEEDS Group of Institutions, Hengbung, Kangpokpi, Manipur, India Munish Sharma Department of Soil Science, CSKHPKV, Palampur, Himachal Pradesh, India Shivalika Sharma Department of Zoology and Environmental Science, Gurukul Kangri Vishwavidyalaya, Haridwar, Uttarakhand, India Tanvi Sharma Department of Biotechnology and Bioinformatics, Jaypee University of Information Technology, Waknaghat, Solan, India Helena D. Shephrou College of Horticulture and Agri-Biotechnology, FEEDS Group of Institutions, Hengbung, Kangpokpi, Manipur, India

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Arvind Kumar Shukla ICAR-Indian Institute of Soil Science, Bhopal, Madhya Pradesh, India H. P. Singh Department of Environment Studies, Panjab University Chandigarh, Chandigarh, India Renu Singh Centre for Environment Science and Climate Resilient Agriculture, ICAR-Indian Agricultural Research Institute, New Delhi, India Dhanaraj Singh Thokchom Ethno-Medicinal Research Centre, FEEDS Campus, Hengbung, Kangpokpi, Manipur, India Kangjam Tilotama Foundation for Environment and Economic Development Services, Henbung, Kangpokpi, Manipur, India Priyanka Verma School of Environment and Natural Resources, Doon University, Dehradun, Uttarakhand, India Kailas Wasewar Advance Separation and Analytical Laboratory, Department of Chemical Engineering, Visvesvarya National Institute of Technology (VNIT), Nagpur, India

Part I

General

Chapter 1

Advances in Carbon Capture and Utilization Deepak Pant, Ashok Kumar Nadda, Kamal Kant Pant, and Avinash Kumar Agarwal

1.1 Introduction A combination of enzyme and material which jointly capture and convert the CO2 into methanol plausibly energizes the CO2 utilization (Sharma et al. 2020a). The CO2 to methanol conversion utilizes carbon better than the conventional syngas and the reaction yields fewer by-products, and the methanol produced can further be used as a clean-burning fuel, in pharmaceuticals, as a general solvent, etc. The various aspects of circular economy with present scenario of environment crisis will also be considered for large-scale sustainable biorefinery of CO2 . In this book, thirteen chapters have been included which represent the natural, conventional, and artificial systems for carbon management. The contents of the book have been divided into four sections. The natural systems of carbon sequestration have been discussed in detail in the first section of this book. Since ancient times, fossil fuels are used in huge amount to meet the energy demands across the world. In India, the emanations from fossils fuels have developed a lot, but alternative sources are not enough to fulfil the demand. D. Pant School of Earth and Environmental Sciences, Central University of Himachal Pradesh, Dharamshala, Himachal Pradesh 176215, India A. K. Nadda (B) Department of Biotechnology and Bioinformatics, Jaypee University of Information Technology, Waknaghat, Solan 173234, India K. K. Pant Department of Chemical Engineering, Indian Institute of Technology New Delhi, New Delhi 110601, India A. K. Agarwal Department of Mechanical Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, Uttar Pradesh, India © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2021 D. Pant et al. (eds.), Advances in Carbon Capture and Utilization, Energy, Environment, and Sustainability, https://doi.org/10.1007/978-981-16-0638-0_1

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The emissions from fossil fuels are considered as one of the major factors leading to climate change (Kumar et al. 2019). To limit the pace of emissions of these harmful gases, various methods and approaches like reduction of energy consumption, switching to alternative fuels, have been reported. This section emphasized on the carbon capture and storage (CCS) using geological and soil-based methods. The recent advancement in CCS technology is progressively concerned with ideal design and functioning of the CCS infrastructure collectively maintaining every strategy of CCS system throughout a certain range. The attainable quality of CCS technology would reduce the reliance on sustainable power sources. CCS system also implies transfer of atmospheric CO2 into other long-lived global pools including pedologic, oceanic, geological and biotic strata to reduce the net rate of atmospheric CO2 increase. Since industrialization in the nineteenth century, the CO2 concentration in the atmosphere has increased and an accord is there where a visible impact on world’s climate due to mankind is forming. The CO2 emissions from man-made sources have also been increasing in the same time frames which are known to produce greenhouse effect. CO2 holds 82% of all the greenhouse gases present in the atmosphere. There are various techniques where CO2 is injected into geological strata, oil wells, deep ocean, old coal mines, and saline aquifers. Furthermore, the soil is the biggest terrestrial sink of carbon (C) and store nearly three times of the atmospheric carbon pool and 4.5 times of the biotic carbon pool, and thus, maintains the global carbon cycle. Therefore, any change in the atmospheric carbon could be the result in modification of soil carbon. However, the carbon stabilization as well as subsequent sequestration in soil is greatly affected by different climatic and soil factors, such as soil type, nature of organics presents in soil, management practices, diversity of soil microorganism, rainfall, and temperature, etc. The sequestration of carbon in soil is very crucial to mitigate the effect of climate change by reducing the greenhouse gases emission and also to improve the soil quality for better crop productivity in sustainable manner (Roudi et al. 2020). Among different developed methods, biomineralization and bioinspired storage systems are not only cost-effective but also efficient in controlling global warming and CO2 emission. A microbial-enzymatic CCSU system can act as a green source of energy in form of electricity along with the utilization of wastewater by bacterial and algal biomass (Sharma and Kumar 2021). Instead of the whole-cell capturing systems, enzyme-based CO2 capturing systems have also been proved efficient for various industrial applications. Researchers are been joining their hands for the improvisation of several carbon capture materials. In the second section, superior performance of organic blended physical–chemical solvents is drawing much attention in recent times. Even some blends attained the optimal performances, advancements in the materials have not come to an end. Various types of nano-materials, nano-textured surface, and microwave regeneration techniques are being introduced to bring down the energy consumption of the setup. Amine technology for the capture of carbon dioxide has certain drawbacks including cost, energy consumption and by-products formation. Other methods such as membrane, cryogenic, biologicals are also of interest but not technically or economically feasible at large or industrial scales. In view of this,

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ionic liquids (ILs) are the one of the alternatives for the conventional and other technologies. Some other methods of simultaneous wastewater treatment and carbon capture have also been explored in the third section of this book. Conventional wastewater treatment systems are not environmentally friendly as they significantly contribute to the CO2 emission, directly as well as indirectly. It has been realized that there is an urgent need to not only reduce the emission of CO2 but also capture it to counter the negative impacts of climate change. Microbial fuel cell (MFC) has the potential of carbon capture while treating the wastewater with an additional advantage of direct electricity production (Verma et al. 2020). On the other hand, algal technology has the potential to capture and utilize CO2 for the production of algal oil, which can be utilized for bioenergy production (Kamyab et al. 2019a). Furthermore, the climate smart agriculture is one of the key tools for carbon capture which ensures the efficiency in income generation, productivity and food security; adaptation to climate change and resilience. Although sequestration of carbon and depletion in emissions of greenhouse gases can happen with various smart agricultural practices, perhaps there are numerous challenges while making these pillars of climate smart agriculture into reality. The change in soil carbon pool can directly influence the climatic conditions of any area due to its capability to store carbon twice as much of the atmosphere. The soil is one of the principle components for capturing terrestrial carbon, so the spatial distribution map developed along with the major nutrients from the study will provide an input for agricultural land evaluation for selecting appropriate land use plans for healthy carbon budgeting in the area (Kamyab et al. 2019b). The biological carbon cycles are not sufficient enough to switch the billions of metric tons of CO2 emission while the biochar (a recalcitrant organic charcoal material produced from pyrolysis of biomass under limited oxygen conditions) emerging as a considerable tool for long-term sink of carbon. Biochar has many other advantages of increasing the water absorption and water holding capacity of the soil which aids to increase the fertility. The charcoal produced by incomplete burning due to the limitation of oxygen in this system captures much more natural carbon from the biomaterial. Along with the ability to lock up additional carbon, biochar can also store CO2 in sink for thousands of years, displaces the fossil fuel use and also reduces the release of nitrous oxide (N2 O) and methane, thereby reduces the greenhouse gas emission from the atmosphere and helps in mitigating the impacts of climate change. The Western Himalayan regions are characterized by marked climatic conditions, variations in topography, soil-texture, and land-use practices. In the present scenario, the fragile landscapes of the Himalayan region are facing an ongoing concern about current and potential climate change impacts. Carbon stocks in vegetation types of western Himalayas have immense ecological significance, vital for the regional and global carbon reserves. Among the vegetation types, forests, pasture, agricultural fields, and orchards dominate in this region. The increasing human interventions, land management practices and natural ecosystem processes are the potential sources of GHGs emission in the atmosphere. Deforestation and other changes in land use cause significant exchanges of CO2 between the land and the atmosphere. The carbon

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stock storage and climate change mitigation cannot be easily achieved in the highaltitude Himalayan regions, because of the type of land use available, cold climate, and the land holding capacity of the people (Sharma et al. 2020b). The sustainable management regimes for these land uses can increase their potential to act as a sink for long-term carbon storage along with providing livelihood opportunities and vulnerability of natural resources to climate change can be reduced through adoption of these management practices. Anthropogenic CO2 discharges are viewed as the significant patron of ozone-depleting substance outflows around the world. Conversion of CO2 into fuels or energy-rich compounds is very beneficial as it is cheaper to produce, less inflammable, can be produced from biomass and is discussed in the last section. Also, it is advantageous to many automobiles, power plants, and other industries like pharmaceuticals, fine chemical, and food production units. Methanol is gaining popularity as an alternative to petroleum-based fuels and is beneficial for a safer and cleaner environment. The enzymatic method for CO2 conversion has attracted much attention due to its improved selectivity and yields under mild reaction conditions. CO2 can be reduced through different methods like physical, chemical, electrochemical, photochemical and biological or enzymatic methods. Among these potential approaches, biological or enzymatic methods offer viable, effective, green and potent alternative of CO2 conversion into value-added products because of high stereo specificity and region/chemo-selectivity of enzyme. The development in global carbon management strategies becomes the mandate of all educational and research bodies. In fact, the public awareness and inclusion of climate change topics at elementary education is also equally important. We should focus on the techniques and methods to minimize the emission of excessive greenhouse gases. Alternatively, more green and sustainable methods should be developed to generate the energy for transport and industrial applications. The protection and conservation of natural ecosystem forest, lakes, rivers, wild fauna and flora should be increased to elevate the biotic carbon level and minimize the atmospheric release. Thus, in this monograph various developmental strategies for carbon management in our ecosystem have been highlighted in respective chapters. Specific topics covered in the monograph include: • Carbon capture: Innovation for a green environment • Geological carbon capture and storage as a climate-change mitigation technology • Soil carbon sequestration for soil quality improvement and climate change mitigation • Post-combustion of carbon capture technologies: Advancements in absorbents and nano-particles • Carbon biocapturing system for environment conservation • Simultaneous wastewater treatment and carbon capture for energy production • Carbon dioxide capture by ionic liquids • The climate smart agriculture for carbon capture and carbon sequestration: The challenges, risks and opportunities • Quantification of the soil organic carbon and major nutrients using geostatistical approach for Lahaul valley, cold arid region of Trans-Himalaya

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Biochar: A carbon negative technology for combating climate change Carbon sequestration potential of different land use sectors of Western Himalaya Progresses in bioenergy generation from CO2 : Mitigating the climate change Recent advances in enzymatic conversion of carbon dioxide into value-added product.

The topics are organized in four different sections: (i) carbon capture as natural phenomenon; (ii) advance carbon management techniques; (iii) miscellaneous techniques, and; (iv) value addition techniques.

References Kamyab H, Chelliapan S, Kumar A, Rezania S, Talaiekhozani A, Khademi T et al (2019b) Microalgal biotechnology application towards environmental sustainability. In: Gupta SK, Bux F (eds) Application of microalgae in wastewater treatment: volume 2: biorefinery approaches of wastewater treatment. Springer, Cham, pp 445–65 Kamyab H, Chelliapan S, Lee CT, Khademi T, Nadda A, Yadav KK et al (2019a) Improved production of lipid contents by cultivating Chlorella pyrenoidosa in heterogeneous organic substrates. Clean Technol Environ Policy. https://doi.org/10.1007/s10098-019-01743-8 Kumar A, Sharma T, Mulla SI, Kamyab H, Pant D, Sharma S (2019) Let’s protect our earth: environmental challenges and implications. In: Kumar A, Sharma S (eds) Microbes and enzymes in soil health and bioremediation. Springer, Singapore, pp 1–10 Roudi AM, Kamyab H, Chelliapan S, Ashokkumar V, Kumar A, Yadav KK et al (2020) Application of response surface method for total organic carbon reduction in leachate treatment using Fenton process. Environ Technol Innov 19:101009. https://doi.org/10.1016/j.eti.2020.101009 Sharma T, Kumar A (2021) Efficient reduction of CO2 using a novel carbonic anhydrase producing Corynebacterium flavescens. Environ Eng Res 26(3):200191. https://doi.org/10.4491/eer.202 0.191 Sharma T, Sharma S, Kamyab H, Kumar A (2020a) Energizing the CO2 utilization by chemoenzymatic approaches and potentiality of carbonic anhydrases: a review. J Clean Prod 247:119138. https://doi.org/10.1016/j.jclepro.2019.119138 Sharma T, Sharma A, Sharma S, Giri A, Pant D, Kumar A (2020b) Recent developments in CO2 capture and conversion technologies. In: Kumar A, Sharma S (eds) Chemo-biological systems for CO2 utilization. CRC Press, Taylor and Francis Group. https://doi.org/10.1201/978042931 7187-1 Verma P, Arunachalam K, Kumar A, Davery A (2020) Microbial fuel cell – a sustainable approach for simultaneous wastewater treatment and energy recovery. J Water Process Eng 101768. https:// doi.org/10.1016/j/jwpe.2020.101768

Part II

Carbon Capture as Natural Phenomenon

Chapter 2

Carbon Capture: Innovation for a Green Environment Nishu Khurana, Nikita Goswami, Ranajit Sarmah, and Devanshi

2.1 Introduction The moment after sunlight enters into the earth’s atmosphere, more than half of its actual amount is confined in its envelope and is absorbed by the geosphere, and the remaining proportion is reflected in space. Eventually, the globe warms up because of the absorbed radiations. Thermal emissions and ultraviolet rays radiate this solar energy that results in cooling up the earth’s atmosphere as it propagates straight out into the space. Although, a minimum amount of those expelled emissions is re-assimilated in the earth’s atmosphere by certain gases known as the greenhouse gases which includes carbon dioxide, methane, nitrous oxide, chlorofluorocarbons, carbon monoxide, etc., and is emitted down on the earth itself (Umair 2015). As the earth emits most of its energy in the infrared spectrum of 10 µm wavelength of the electromagnetic spectrum, it makes CO2 opaque under this range of the spectrum. This opaqueness further reduces the volume of heat eliminated, contributing to global warming (Newell 1971; Hileman 1989). The emission of greenhouse gases (GHGs) into the earth’s atmosphere or surrounding is the major reason for greenhouse effect and global warming, which are ultimately deteriorating earth’s health at a higher rate via climate change, sealevel rise and other major environmental changes (Lallanilla 2015a). Due to the increased production of these gases, less heat escapes the planet causing an increase in global warming (Umair 2015). Different sectors are responsible for such an overproduction of these greenhouse gases, which includes fossil fuel incineration, industrial processes, agricultural by-products (crop residue burning) and transportation fuel, producing pollutants to the air (Lallanilla 2015b; Bhuvaneshwari et al. 2019). Various studies have suggested that the CO2 gas signifies major role, i.e. 63% as N. Khurana (B) · N. Goswami · R. Sarmah · Devanshi University Institute of Biotechnology, Chandigarh University, Mohali, Punjab, India e-mail: [email protected]; [email protected] © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2021 D. Pant et al. (eds.), Advances in Carbon Capture and Utilization, Energy, Environment, and Sustainability, https://doi.org/10.1007/978-981-16-0638-0_2

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compared to the other GHGs, which is why it needs to be standardized to prevent the mother nature (Zhang and Da 2015; Parry et al. 2007). This CO2 can be generated by natural as well as artificial activities, such as volcanic eruption, the decay of organic materials and numerous anthropogenic deeds (Giri and Pant 2018; Pant et al. 2017; Winter et al. 2019). As the warming trend of the past 100 years has increased up to twice in the present 50 years, it clearly depicts that there is an increase of CO2 level in the atmosphere (Yu et al. 2008). The increasing CO2 level is not only affecting the aquatic ecosystem but also the terrestrial ecosystem, raising the major concern to stop or control this issue before we reach a point where it becomes impossible to curb the damage caused by these emissions (MacDonald 1982). In account to prevent the massive CO2 production, countries, like India using its action plan, have contributed in diminishing the number of environmental changes through various power generation programs, green energy generation initiatives and sustainable technologies (Bhuvaneshwari et al. 2019). India, being a part of 24 developing countries, is carrying out research in the field of carbon capture and storage with the help of some research institutes majorly from Tamil Nadu, Maharashtra and Delhi (Sood and Vyas 2017; Gupta and Paul 2019). Switching to alternative or renewable energy resources like biomass, hydro, wind and solar systems, etc., can really help in improving earth’s condition and is a promising technology that would not disturb the ecological balance of the earth in the coming years (Umair 2015). However, shifting to these techniques may not be possible completely due to the dependence of industries on classical tools for energy production (Baena-Moreno et al. 2019). Therefore, some more sustainable methods can be used to reduce the level of CO2 such as carbon fixation technique used in pharmaceutical drugs, construction material, fuel formation and few inorganic applications of CO2 (Yu et al. 2008; Winter et al. 2019). Similarly, the capturing of carbon produced at the site of initiation and saving it somewhere away from the atmosphere for future use can resolve the issues associated with carbon emissions. This process of capturing, compressing, transporting, storing and utilizing when needed is gaining attractions worldwide (Orr 2009). The raised CO2 emissions led us to the main aim of this communication that is carbon capture, its utilization, advantages and disadvantages, its current status and practical applications. As India is one of the dominant emitters of carbon alongside China, USA, Russia, Europe and Japan (Melillo et al. 2017), much of its investments are going on in activities like CO2 capture, utilization and storage. For example, carbon capture for fertilizer production having recycling quality is utilized in India (Gupta and Paul 2019). The proper use of capturing and storing approach will help in scaling the carbon out for better environmental fortune (Mishra et al. 2019). The carbon capture method includes different routes like chemical adsorption, membrane technology, cryogenic separation, etc., that has great advantages such as low waste production, thermal as well as environmental stability and separationcapture efficiency (Li et al. 2008; Hunt et al. 2010; Pires et al. 2011; Wang et al. 2011; Lam et al. 2012). Along with it, certain combustion techniques for the capture of CO2 like post-combustion, pre-combustion, oxy-fuel combustion help in separation of CO2 from other elements (Orr 2009). The storage of the captured carbon may have

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the proficiency to rejuvenate depleted oil and increase stacking strength under bare grounds, etc. (Kovscek and Cakici 2005; White et al. 2013; De Silva et al. 2015). This storage mechanism for retention of CO2 like capillary trapping, dissolution, adsorption and mineralisation is safe if deployed with the proper surface as well as pressure monitoring techniques (Orr 2009). The current gap of carbon capture, utilization and storage with already developed techniques can be filled by research and development of new crop strains that maximize the carbon absorption. The field of research can also be widened by acquiring the knowledge based on the location of a specific site and physio-chemical process through the development of techniques that will reveal stored volume of CO2 and locate the source of emission/storage (Goel 2012).

2.2 Carbon Capture (CC) Routes Carbon capture (CC) technology is a very promising and developing technology that is trying to solve the major issue of the environment by capturing CO2 . This technology has several routes to capture CO2 from the ambient atmospheres.

2.2.1 Absorption In the process of absorption, a sorbent is employed that helps in separating or isolating the CO2 from the flue gas. The sorbent used (liquid or solid) can also be restored through a stripping or regenerative methodology by warming and/or decompressing. This method is believed to be the most developed process for CO2 separation (Bhown and Freeman 2011). There is a major energy saving in case of solid sorbents because they do not require water in huge amount to warm and then cool continuously to restore the solvent solution (Figueroa et al. 2008). This solid sorbent research aims to diminish the expense of CO2 capture by structuring tough sorbents with productive materials dealing with plans, expand the limit of CO2 holding ability, lowering the restoration energy condition, quicker response rates and least weight drops (Folger 2013). An absorbent should possess high reactivity and absorptivity for CO2 capture, low vapour pressure, simple restoration, high thermal and chemical reduction durability, low ecological effect (green) and affordable (Sreenivasulu et al. 2015). For the process of CO2 capture through solvents, the standard sorbents used are monoethanolamine (MEA), diethanolamine (DEA) and potassium carbonate (Hendriks 1995). MEA has the ability to remove high fraction of CO2 due to quick response rate with acid gases such as CO2 , even when the concentration of CO2 in flue gas streams is low. (Folger 2013). Monoethanolamine (MEA) is an amine-based separation where different types of amine solvents can be used such as simple alkanolamines, primary, secondary, tertiary, hindered amines, mildly hindered primary,

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moderately hindered and cyclic diamines that are relevant for low-CO2 partial pressure streams and give a high restoration rate up to 98% as well as 99% of the purity of the finished product (Miller 2010). Amines have been effective since the 1930s to generate food-grade CO2 from gas streams with somewhere in the range of 3 and 25% CO2 (Breeze 2015). Immobilized amines and CO2 may exhibit similar reactions to liquid amines in the classic process of absorption (Saha et al. 1995) with the additional benefit that solids can be handled easily, and there is no issue of corrosion caused by the movement and spreading of very basic solutions (Veawab et al. 1999). In the recent years, the other sorbents that have gained attention and are used in the absorption process are anion-functionalized and piperazine ionic fluid (Gurkan et al. 2010). It has been seen that piperazine reacts a lot faster than MEA, but it is not the most preferred solvent because of its high cost due to its larger volatility than MEA. It is still under progress to be more cost effective (Bougie and Iliuta 2011). Sorbents are being used in different processes such as in natural gas (sweetening), gasification of coal, syngas production, petroleum refining and production of hydrogen (Sreenivasulu et al. 2015). A substitute to MEA is an ammonia-based solvent from which it is possibly simpler to discharge carbon dioxide once it has been caught (Breeze 2015). Aqueous ammonia has been utilized as a solvent because of its high CC efficiency along with high retention limit, low recovery costs, simple accessibility, capacity to evacuate SO2 , NOx alongside CO2 at the same time and the value-added salts that could be utilized as manures (Yeh and Bai 1999; Choi et al. 2009; Abass and Olajire 2010; Pellegrini et al. 2010; Puxty et al. 2010; Gouedard et al. 2012; Zhao et al. 2012). Ammonia-based systems are gaining its attention towards separation of CO2 because ammonia is cheap and practically could function with a portion of the energy price of amines. Added to it, the volatility of ammonia is also greater than MEA, and thus it can be discharged efficiently into the flue gas stream in the time of the absorption step (Folger 2013). In ammonia-based separation process, CO2 from the flue gas is being captivated by reacting CO2 with ammonium carbonate and hence ammonium bicarbonate is formed in the absorber column (Miller 2010). A crystalline product is formed in the absorber as the ammonium bicarbonate partially precipitates out. As such, the absorption process is accelerated, and the CO2 concentration is augmented (Kather et al. 2008). Among the other systems, alkali carbonate-based systems are also being studied for CO2 capture. Carbonate systems depend on the capacity of a soluble carbonate to undergo reactions with CO2 in order to form a bicarbonate, which when heated discharges CO2 and inverses back to a carbonate. At the present time, this technique is not widely used and more advancements and research are going on to remove CO2 from flue gas using carbonate (Miller 2010). The routes are listed in Fig. 2.1.

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Fig. 2.1 Different routes of carbon capture (CC) technology (Nanda et al. 2016)

2.2.2 Adsorption Adsorption is also a different method for CO2 separation and capture. A high pressure is applied in the system where CO2 particularly gets adsorbed on the surface of a solid adsorbent, and then the pressure is gradually shifted to low pressure, i.e. atmospheric pressure to desorb the adsorbent and thus CO2 is discharged for the next step of the process, i.e. transport (Leung et al. 2014). The process involves the use of sorbents, and to make this technology efficacious and cheap, sorbents should have different properties such as quick adsorption and desorption flow, high selectivity, high working limit, chemical stability and recycling ability (Wilcox et al. 2014). A significant advantage of adsorption is that adsorbent redevelopment can be done very easily by pressure or thermal adjustment and post-combustion CO2 capture can be done with reduced energy consumption (Songolzadeh et al. 2012). An adsorption process can be done by two different methods, i.e. by physisorption which is done physically involving weak van der Waals forces and chemisorption which is done chemically involving covalent bonding or electrostatic attraction (BenMansour et al. 2015). In comparison with physisorbents, chemisorbents display high isosteric heats of adsorption with predominant selectivity. Added to it, high CO2 adsorption measure can be achieved at reasonably lower CO2 partial pressures. This can be done by the introduction of basic pore–surface performance to react with acidic CO2 (Wilcox et al. 2014). Considering physical sorbents and inorganic porous materials (e.g. carbonaceous materials and zeolites, respectively), lesser energy is required as compared to chemical sorbents reason being no new bond formation occurs between the sorbate and sorbent. Thus, the energy requirement is very less for CO2 regeneration (Ben-Mansour et al. 2015). Some of the common physical adsorbents are carbon nanotubes (CNTs), hydrotalcites, activated carbon, zeolite, coal, etc. Activated carbon has great adsorption measure for CO2 , the property of repelling water is high, cheap, and energy requirement for restoration is very low and is unaffected by moisture (Ben-Mansour et al. 2015). Zeolites have an advantage of higher selectivity, but their efficacy is affected in the existence of water and shows lower CO2 loading (Li et al. 2011a, b). The principle properties of the adsorbent

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influencing CO2 capture by adsorption were tentatively explored by comparing 17 different types of activated carbon based on their different pore size dispersion and thickness of the adsorbent at a designated pressure (Marco-Lozar et al. 2014). As of now, carbon nanotubes (CNTs) are being used in the field of CO2 capture technologies because of their high thermal and electrical conductivity, encouraging physical and chemical properties and their ability to alter their surfaces by adding a chemical functional group (chemical process), resulting in high adsorption storage volume (Iijima 1991; Ebbesen and Ajayan 1992; Kiang et al. 1995; Thess et al. 1996; Journet and Bernier 1998; Jung et al. 2003; Srivastava et al. 2003; Harris 1999; Abuilaiwi et al. 2010). In recent times, it has been experimented that amine modified TiO2 nanotubes and TEPA modified metal–organic frameworks (Mg-MOF74) show the highest adsorption volume along with satisfactory cyclic constancy (Su et al. 2014; Cao et al. 2013). Relying upon the regeneration approaches, a few adsorption procedures can be adopted for CO2 separation such as temperature swing adsorption (TSA), vacuum and pressure swing adsorption (VSA and PSA), electric swing adsorption (ESA), purge displacement and simulated moving bed (SMB) (Li et al. 2011a). Adsorption selectivity and CO2 function capacity are the two major components affected in PSA system (Krishna and van Baten 2012). The adsorption step in PSA is operated at very high pressure, whereas in VSA, it is done at atmospheric pressure or lowers (Chue et al. 1995; Krishna 2012). In temperature swing system (TSA), hot gas or steam is used in the adsorption bed. After the heating is done, regeneration process is started followed by cooling of the bed using cold gas steam prior to the next adsorption step (Clausse et al. 2004; Mason et al. 2011). Among the two techniques, PSA is considered to be better than VSA (Clausse et al. 2004) because of its low-energy requirement, cheap and easy to handle with variety of applications with temperature and pressure (Ben-Mansour et al. 2015). It has been experimented that a huge improvement in the CO2 adsorption capacity can be achieved by the PSA process using MCM-41 material which was saturated with polyethyleneimine (Xu et al. 2005). Different materials are being studied to check their ability for CO2 adsorption. The microporous and mesoporous solid adsorbents have also displayed a great prospective for CO2 capture in a broad way (Sreenivasulu et al. 2015). A support with immobilization of amine such as poly (methyl methacrylate) has displayed great adsorption capacities (Lee et al. 2008). Apart from these methods, fixed bed (single or multiple columns), normal, bubbling and ultra-sound-assisted fluidized beds and moving bed contactors are also being used in different ways because they are very easy to operate and plan. It is seen that adsorption capacity declines with temperature (Sreenivasulu et al. 2015). Metal–organic frameworks (MOFs) are also being experimented to check their ability for CO2 adsorption and gas separation (Li et al. 2011b).

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2.2.3 Membrane Membranes are permeable materials that can be utilized to specifically separate CO2 from different segments of a gas stream (Folger 2013). It utilizes porous or semiporous materials that take into account the particular separation and transport of CO2 from flue gas (Miller 2010). Membrane technology provides the prospect of changing energy-inefficient division approaches that are limited thermodynamically (Luis et al. 2012). Membrane-based technology exhibits better performance compared to other systems, and the inherent issues of CO2 capture in association with pre-combustion and post-combustion are overpowered to meet the desired mechanism (Criscuoli and Driol 2007; Drioli and Curcio 2007; Van Gerven and Stankiewicz 2009). A membrane should possess different properties in order to be used for CO2 capture. This includes resistance to heat and chemicals, resistance to ageing, cheap, selectivity to high CO2 and N2 , permeable to CO2 , resistance to plasticisation and the capability to be constructed into distinctive membrane modules (Powell and Qiao 2006). Along with it, permeability and pore size of the membrane are also to be considered because higher membrane permeability gives higher-quality production (Khaisri et al. 2009; Ismail and Mansourizadeh 2010; Mansourizadeh et al. 2010; Zhang et al. 2010) and porosity of the membrane also exhibits the quantity of the substance that can be moved for particular pressure variation (Zhao et al. 2010). Membrane-based technology is an appealing preference for CO2 separation due to the very smaller molecular size of the membrane compared to other gases (Ebner and Ritter 2009). Comparing with other separation techniques for CO2 capture, membranes have shown different advantages such as membranes are cheap, and there is no requirement of regeneration, which makes the heat-exchange systems more simpler, solvents are not required for the process, making them more eco-friendly, requires less set-up space and shows great efficacy in separation techniques (Wilcox et al. 2014). Membrane-based technology uses different materials for the separation process. Polyimides, a class of polymer, is considered to have exquisite thermal and chemical durability along with extensive range of CO2 porosity, good assembly variations and efficiency in membrane development (Powell and Qiao 2006). An immobilized liquid, i.e. poly (amidoamine) (PAMAM) dendrimer is considered to show extraordinary CO2 and N2 selectivity at normal atmospheric pressure (Kovvali et al. 2000; Kovvali and Sirkar 2001). In recent times, hybrid membranes or mixed matrix membranes (MMMs) are being used in membrane technology. It is developed by mixing two different materials with distinctive properties. And these MMMs are further divided into three other classes based on the material filled, i.e. solid, liquid and solid–liquid (Liu et al. 2008). Facilitated transport membrane is also a different variety of membrane which is associated with movement of gas molecules with the help of membrane through reversible reaction and is used in membrane technology (Míguez et al. 2018). Added to these membranes, carbon molecular sieves membranes are also gaining attention due to its appealing performance in CO2 separation approaches (Brunetti et al. 2010).

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Membranes being the most preferred material or method for CO2 separation, they are also used in cases where absorption process could not be carried out with conventional absorbers. As such ceramic membranes are used in those cases (Sreenivasulu et al. 2015). Membrane-based absorption uses amine solutions as solvents because the selectivity is confirmed and the capacity is not restricted by the equilibrium (Luis et al. 2012). Other than this method, gas absorption membranes are extensively studied due their applications. In this method, CO2 -laden flue gases reach one side of the membrane and a fluid solvent (amine-based solvent) contacts the opposite side (Folger 2013). Most of the research and patents being carried out in the field of membrane technology are polymeric membranes, silica, metal oxides and ceramic membranes (Quintella et al. 2011).

2.2.4 Chemical Looping The concept of chemical-looping combustion (CLC) was first proposed by Lewis and Gilliland in 1950s. They also gave the idea of copper oxide reacting with syngas producing CO2 (Lewis and Gilliland 1954). Chemical looping is a very productive clean technology that has been created for CO2 capture where flue gas is reduced by CO2 dilution. This process consists of a cyclic method (two steps) where flue gas such as solid/liquid/gas is burnt in the existence of metal oxides that act as oxygen bearer within the fuel reactor (FR) (Sreenivasulu et al. 2015). The metals such as iron, copper, cobalt, nickel and manganese act as oxygen bearers in the system where natural gas is used as fuel (Mattisson and Lyngfelt 2001). Preferably, any oxygen carrier should be fast and show stable reaction kinetics so that the redox reaction is completed to allow passage of materials in high reactor and downstream gas separation can be avoided (Najera et al. 2011). The performance of the metal oxides can be improved with the help of support inert materials depending upon the type of the metal oxide used in the process (Adánez et al. 2004). Selection of metal oxides that are thermodynamically convenient and the reactor design play a very critical role for efficient functioning of the process (Lee et al. 2006; Adanez et al. 2012). The CLC system is made out of two reactors, i.e. an air and a fuel reactor (Johansson et al. 2006). The process begins as the metal is oxidized in one of the reactor (first) followed by reduction as it comes in contact with a fuel in the other reactor (second). The liquid waste that comes out of the other reactor (second) is considered as the pure mixture of CO2 and steam as well as the condensation of the steam at high pressure, sequestration, prepared CO2 steam is achieved in the process (Ishida and Jin 1994). The major advantage of using CLC technique is because of its flameless nature, less NOx development even at low temperature and separation of CO2 by the condensation of water can also be done using very minimal energy consumption (Dennis 2009; Solunke and Veser 2011; Chiu and Ku 2012). During the previous two decades, fundamental advancements in chemical-looping combustion have occurred regarding oxygen carriers, fuels and reactor designs (Richter

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and Knoche 1983; Lewis and Gilliland 1954; Ishida and Jin 1994; Jin et al. 1998; Fan et al. 2008). Despite being so efficient technology, it has several challenges to overcome from diverse factors that include selection of materials that possesses high oxygen capacity, strong restoration ability and fast reactivity. Along with it, designing improved reactor that has high efficacy, commercially practical and compatible with different industries as well as very low failure risks which are certain challenges faced by CLC system (Zhao 2012). An alternative to chemical-looping combustion (CLC) is chemical-looping dry reforming (CLDR). In this process, air or steam is not utilized but CO2 is used as an oxidant (Najera et al. 2011). Dry reforming method is one of the more settled pathways for CO2 use. An experiment carried out with methane and CO2 at higher temperatures (>700 °C) in the presence of a catalyst such as nickel or a noble metal for producing syngas gives maximum H2 or CO ratio of 1. This process was a typical methane dry reforming method (Vernon et al. 1992; Fan et al. 2009) which shows that dry reforming method can also be used for CO2 separation. The major fundamental advantage of chemical-looping dry reform method is its flexibility, i.e. CO2 reduction and fuel oxidation steps can be separated into half reactions leading to fuel flexible. This provides us with the advantage that it can be employed with fossil and renewable fuels and also in diluting CO2 as well as other streams. Thus, chemical-looping dry reform method can also be considered or hypothesized that focuses on diluting CO2 streams (Najera et al. 2011).

2.3 Direct Capture from Air The concentration of CO2 has gradually risen up to 400 ppm from 270 pm prior industrial time (Eisenberger et al. 2009). To cope up this issue, CO2 released from different industries is directly captured (removed) from the atmosphere and stored in a different locations (Okesola et al. 2018). In contrast to different CCS innovations, direct air capture (DAC) works differently and is not designed to capture a specific gas stream (Chen and Tavoni 2013). In fact, it can also be compared to sunlight-based photovoltaics, wind energy, aspiring environmental change alleviation, batteries and electrolysers (Breyer et al. 2019). The CO2 captured from the air can also be converted into a chemical yield but the marketable quantity will not be disturbing the environment (Bhown and Freeman 2011). Materials or methods to be used for CO2 capture play a vital role in the process. In order to perform direct air capture at a large scale, materials should possess mainly two different properties or capabilities such as the working capacity of the materials must be high as well as the regeneration energies must be low. These two properties measure values totally in divergent directions (Sculley and Zhou 2012). Initially, an aqueous solution of NaOH was used for the air capture method (Lackner 2003; Keith et al. 2006). But later on, another approach was developed to capture air with the use of solid sorbents (Lackner 2009). Materials like solid sorbents are considered to operate in minimal cost and minimal energy along with

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applications in broad range of scales (Keith et al. 2018). Physical sorbents such as activated carbons, zeolites and metal–organic frameworks (MOF) show weak binding capacity with CO2 , low absorption capacity and low selectivity of CO2 from the air (Bollini et al. 2011). As compared to physical sorbents, chemical sorbents which are immobilized with amines involving support from materials like cellulose (Gebald et al. 2011; Sehaqui et al. 2015), Al2 O3 (Sakwa-Novak et al. 2016; Potter et al. 2017), SiO2 (Belmabkhout et al. 2010; Serna-Guerrero et al. 2010) are considered to show great endurance to atmospheric moisture (Serna-Guerrero et al. 2008), stability (Sayari and Belmabkhou 2010) and have good CO2 selectivity (Belmabkhout et al. 2010) to carry out DAC method (Jones 2011; Didas et al. 2015). Further, permeable metal–organic materials (MOMs) (Perry et al. 2009) and hybrid ultra-microporous materials (HUMs) (Mohamed et al. 2012, 2013; Nugent et al. 2013; Shekhah et al. 2014, 2015; Scott et al. 2015) are newly found materials that show various eligible properties such as storage of gas (Sumida et al. 2012; Suh et al. 2012; He et al. 2014), separation of small molecules (Cychosz et al. 2010; Li et al. 2012; Qiu et al. 2014; Van de Voorde et al. 2014) and purification of gas (Barea et al. 2014) to function in direct air capture method in the form of physisorbents (Kumar et al. 2015). Various studies and research have put forward some major techniques for direct air capture such as carbonation (Nikulshina et al. 2016), hybrid sorbents of organic–inorganic amines sustained in permeable adsorbents (Okesola et al. 2018), etc. Aminebased adsorbents are found to be applicable for this process because amines have good selectivity with atmospheric CO2 even at normal temperature and pressure. Consequently, pure CO2 can also be obtained when heated to 100 °C (Choi et al. 2011). Added to it, capturing high concentration CO2 from the air is possible with the use of amine fibre sorbents. This experiment is demonstrated by vacuum-assisted desorption studies (Sujan et al. 2019). Another system or technique of capturing CO2 directly from the air at low temperature and at reasonable cost is by using temperature swing adsorption (TSA) method, which is considered to be the most appropriate adsorbent that shows maximum fulfilment (Okesola et al. 2018). This direct CO2 capturing method works more efficiently with a low volatility polymer, i.e. polyethylenimine or PEI (Lively and Realff 2016). It is very clear that the concentration of atmospheric carbon dioxide (CO2 ) from the air can be minimized with use of direct air capture (DAC) technique by using various materials such as sorbents. This method will be more beneficial if the captured CO2 is properly stored in specific location for long term so that it is available to us for future use. More research and experimental studies are required to carry out in this field (Sanz-Perez et al. 2016).

2.3.1 Hybrid Capture Technology To enhance the CO2 capture performance, a different type of approach, i.e. hybrid capture, is used which combines two different methods of separation, e.g. a very

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productive method for CO2 capture is by combining membrane and cryogenic separation methods in post-combustion step to form a hybrid technology. In this process, CO2 pre-concentration of the beginning step is combined with a membrane process and then CO2 concentration as well as compression of the next step is combined with the cryogenic process, thus forming a hybrid process (Belaissaoui et al. 2012). Added to it, different experiments were carried out with respect to hybrid capture technology for CO2 capture by combining oxygen-enriched air combustion and membrane technology which was performed on dry flue gas. The results obtained from the fusion of oxygen combustion and post-combustion capture were very interesting, and in order to analyse the whole process, the utmost thing to do is to distinguish the linkage of oxygen mole fraction on the feed side with CO2 mole fraction of the dry flue gas present in the downstream area (Favre et al. 2009). Thus, the hybrid technology is a very promising technology that needs to be explored more to be very productive in the field of fossil fuels and natural gas as well as to know its capabilities of using this technique with different methods and areas. Two different methods combined for a single operation can really be an advantage to the whole process, and it would be beneficial in different aspects also.

2.3.2 Methods of Carbon Capture Emission of CO2 is generally through oil refineries, fossil fuel power plants and production of biogas, ethylene oxide, cement, iron and steel industry. As the sources for CO2 emission are diverse, therefore, only one technology would not be feasible for capturing CO2 emitted from different sources. The options for capturing CO2 are broadly classified as follows: pre-combustion capture, post-combustion capture and oxy-fuel combustion (Leung et al. 2014).

2.3.2.1

Pre-combustion Capture

It is the technologies in which natural gas or syngas is used and solid waste is converted into gaseous fuel, i.e. hydrogen and carbon monoxide at high pressure and heat in the presence of oxygen and steam. The syngas thus produced is used as a fuel to generate electricity. The capture of carbon is done before the syngas is combusted in the gas turbine. For increasing the hydrogen production and to facilitate carbon capture, the syngas is passed through water gas shift reaction to produce more hydrogen and for converting carbon monoxide to carbon dioxide. For the conversion of hydrogen and carbon dioxide, pre-combustion capture emphasizes advanced solvents, membrane systems and solid sorbents under high temperature and pressure. In a solvent-based system, the CO2 is chemically or physically adsorbed into a liquid carrier and the adsorbed liquid is regenerated by increasing the temperature or reducing the pressure to break the CO2 and the adsorbent bond. The sorbent-based

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system is still under development (Theo et al. 2016), and the major aim of this technology is to maintain high adsorption loading and show resistance to multiple regeneration cycles and to develop a system which removes the need of reheating of syngas. For membrane systems, organic and porous membranes are being developed having high CO2 selectivity and uptake (Khaisri et al. 2009; Ismail and Mansourizadeh 2010; Mansourizadeh et al. 2010; Zhang et al. 2012).

2.3.2.2

Post-Combustion Capture

The efficiency of capturing CO2 depends on the concentration of carbon dioxide within the flue gases of a power plant. Post-combustion capture involves removal of CO2 from flue gases emitted from power plants and other sources. In a distinctive coal-fired boiler, the concentration ranges between 12 and 14% of the flue gas by volume. At this concentration, the most efficient way of entrapping carbon dioxide is to use a reagent that chemically bonds with the gas containing carbon. The chemical solvent eliminates a large portion of CO2 as the bond between the absorbent and the gas is strong, releasing the gas again is a tedious task. In situations where the carbon dioxide is in much higher concentration, it is possible to employ a physical solvent into which the carbon dioxide simply dissolves. Post-combustion capture can be considered as an extension for the treatment of flue gas for removal of SOx and NOx . Although many methods have been deployed for the post-combustion capture but chemical absorption is the most widely used technology (Gruenewald and Radnjanski 2016). In this, reagents capable of capturing CO2 are used (Breeze 2015). The most widely used liquid sorbent for capturing CO2 is MEA (Monoethanolamine) (Sodiq et al. 2014). The chemical absorbent is made to react with CO2 . In a counter current manner, the absorbent receives the CO2 -loaded flue gas from the bottom and aqueous or non-aqueous liquid absorbent solution from above. The absorbent forms a bond with CO2 releasing the streams free of CO2 in the atmosphere. The CO2 -enriched sorbent is exposed to high temperature by which the bond between the sorbent and CO2 is broken and CO2 free of absorbent is collected. The absorbent is recycled. The desorbed CO2 is compressed for easy transportation. For post-combustion capture, the commonly accepted liquid absorbent system application is 30 wt% MEA in water (Abu-Zahra et al. 2016). Post-combustion capture is a process which is capable of removing about 90% of CO2 present in the exhaust gases (Breeze 2015).

2.3.2.3

Oxy-Fuel Combustion

Traditionally in coal combustion air was used in which 79% of the nitrogen diluted the concentration of CO2 present in the flue gas (Buhre et al. 2005). The main idea for using oxy-fuel combustion in a coal-fired power plant is to produce flue gas with very elevated concentrations of CO2 and water vapour, to separate the CO2 from the flue gas under low temperature.This method of capturing CO2 from diluted mixture using amines is a costly method. In oxy-fuel combustion, a combination of 95%

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pure oxygen and recycled flue gas is used for combustion of the fuel. Gas consisting mainly of CO2 and water is generated, after recycling of flue gas which is now ready for confiscation without removal of the CO2 from the gas stream.

2.4 Advantages and Disadvantages of Carbon Capture Techniques The whole progression of capturing carbon from different sources, processing the captured carbon and then transporting it to the storage site has been cited as an answer to decrease the carbon outflows from fossil fuel-based power plants and other related activities. CCS is instituting a significant change that will outline the climate change with the reduction in greenhouse gases. CCS technology may sound easy to capture carbon, transport and storage, but actually, it involves commonsensical realization and flavours of diverse technologies. CCS has been positioned as a greener solution that can reduce carbon emissions from 50 to 85% and can be easily accustomed to existing plants (Viebahn 2014). Apart from bridging the gap between emissions and low carbon economy, CCS technology requires additional energy (around 25%) for capturing carbon, which adds additional cost for the owner/operators of the fossil fuel plants. Apart from this, the technology has some safety concerns over the storing of captured CO2. There is a risk of leakages and environmental contamination (microbial contamination). Natural calamities (like an earthquake) or man-induced activities always risk the leakage from underground reservoirs. Though CCS technology is few years old but is not mature enough as it is not capable of handling emissions from agricultural activities, transportation, other heating and power generation methods (Wang et al. 2017; Porter et al. 2017).

2.5 Barriers Human beings are contributing constantly towards the emission of GHGs in the atmosphere. Power sector, petrochemical industries, refineries, oil and gas processing industries, iron and steel industries and cement production are among the major troupe in CO2 emission (Metz et al. 2012). The IPCC has cited in its third assessment report that no sole technology will be able to provide way out to the overall emission reduction (IPCC 2001). Different countries, in order to achieve the GHG emission reduction target, are implementing numbers of technologies (as shown in Table 2.1) which include use of clean and green fuels, improving energy efficiency and conservation and implementation of the technology according to their state of affairs. Among different technologies, the capture technologies are growing exponentially every year.

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Table 2.1 Advantages and disadvantages of different carbon reduction methods S.

Method

Advantages

Disadvantages

1

Use of clean fuel

Natural gas emits around Higher fuel cost for 40–50% less carbon dioxide conventional natural gas and efficiency is also higher. Amount of other emissions is also reduced

2

Use of clean coal technologies

Lower emissions

Higher fuel cost is involved

3

Use of renewable energy

No GHG and other toxic gases in emissions

Depends on the local resources available and high cost is involved

4

Development of nuclear power

No emissions

Restricted usage, handling is also critical, and high cost is involved

5

Afforestation and reforestation

Simple approach to create natural carbon sinks

Restricts usage of land for other activities

6

Enhancing energy Saves energy efficiency and conservation of energy

CCS technology is not fully mature

7

Carbon capture and storage Vast reduction in the CO2 emissions

Involves high capital investment in installation of energy-saving devices

No.

Carbon capture and storage are budding technology, which is deficient of R and D. It has been observed that CCS requires some energy input externally and in country like India which is struggling for fulfilling its own power need, and extra power/energy is a burden. Setting additionally separate plant will add to the cost of energy and lead to political instability also. International aid in terms of finance may play an important role (Sood and Vyas 2017).

2.6 Conclusions CCS is a complex process and requires expertise from different discipline. Many institutions are also doing research on this technology to reduce the GHG emissions but anticipation of private sectors can be a game changer. CCS is a well-known process but its demonstration and commercialization still need to be explored. The evaluation of point sources of emission and storage capacity is essential. Apart from various technological, environmental and economical aspects, we need to focus on safety and sustainability of the technology also. Utilization of captured carbon in a more sustainable way is one of the challenges. It can be converted to biofuel that, in turn, reduces the dependence on fossil fuels. So

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the combination of technologies can lead to more sustainable solution with reduced GHGs emission and accelerate the rate of industrialization, without pollution.

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Umair S (2015) Global warming: causes, effects and solutions. Durreesamin J 1(4) Van de Voorde B, Bueken B, Denayer J, De Vos D (2014) Adsorptive separation on metal–organic frameworks in the liquid phase. Chem Soc Rev 43(16):5766–5788 Van Gerven T, Stankiewicz A (2009) Structure, energy, synergy, time. The fundamentals of process intensification. Ind Eng Chem Res 48(5):2465–2474 Veawab A, Tontiwachwuthikul P, Chakma A (1999) Corrosion behavior of carbon steel in the CO2 absorption process using aqueous amine solutions. Ind Eng Chem Res 38(10):3917–3924 Vernon PDF, Green MLH, Cheetham AK, Ashcroft AT (1992) Partial oxidation of methane to synthesis gas, and carbon dioxide as an oxidising agent for methane conversion. Catal Today 13(2–3):417–426 Viebahn P, Vallentin D, Holler S (2014) Prospects of carbon capture and storage (CCS) in India’s power sector—an integrated assessment. Appl Energy 117:62–75 Wang Q, Luo J, Zhong Z, Borgna A (2011) CO2 capture by solid adsorbents and their applications: current status and new trends. Energy Environ Sci 4(1):42–55 Wang Y, Zhao L, Otto A, Robinius M, Stolten D (2017) A review of post-combustion CO2 capture technologies from coal-fired power plants. Energy Procedia. 114:650–665 White DA, Pagarette A, Rooks P, Ali ST (2013) The effect of sodium bicarbonate supplementation on growth and biochemical composition of marine microalgae cultures. J Appl Phycol 25(1):153–165 Wilcox J, Haghpanah R, Rupp EC, He J, Lee K (2014) Advancing adsorption and membrane separation processes for the gigaton carbon capture challenge. Annu Rev Chem Biomole Eng 5:479–505 Winter F, Agarwal RA, Hrdlicka J, Varjani S (2019) Introduction to CO2 separation, purification and conversion to chemicals and fuels. In: CO2 separation, purification and conversion to chemicals and fuels. Springer, Singapore, pp 1–3 Xu X, Song C, Miller BG, Scaroni AW (2005) Adsorption separation of carbon dioxide from flue gas of natural gas-fired boiler by a novel nanoporous “molecular basket” adsorbent. Fuel Process Technol 86(14–15):1457–1472 Yeh AC, Bai H (1999) Comparison of ammonia and monoethanolamine solvents to reduce CO2 greenhouse gas emissions. Sci Total Environ 228(2–3):121–133 Yu KMK, Curcic I, Gabriel J, Tsang SCE (2008) Recent advances in CO2 capture and utilization. ChemSusChem Chem Sustain Energy Mater 1(11):893–899 Zhang W, Li J, Chen G, You W, Jiang Y, Sun W (2010) Experimental study of mass transfer in membrane absorption process using membranes with different porosities. Ind Eng Chem Res 49(14):6641–6648 Zhang X, Zhang X, Dong H, Zhao Z, Zhang S, Huang Y (2012) Carbon capture with ionic liquids: overview and progress. Energy Environ Sci 5(5):6668–6681 Zhang YJ, Da YB (2015) The decomposition of energy-related carbon emission and its decoupling with economic growth in China. Renew Sustain Energy Rev 41:1255–1266 Zhao B, Su Y, Tao W, Li L, Peng Y (2012) Post-combustion CO2 capture by aqueous ammonia: a state-of-the-art review. Int J Greenhouse Gas Control 9:355–371 Zhao L, Riensche E, Blum L, Stolten D (2010) Multi-stage gas separation membrane processes used in post-combustion capture: energetic and economic analyses. J Membr Sci 359(1–2):160–172 Zhao Z (2012) Rotary bed reactor for chemical-looping combustion with carbon capture. Doctoral dissertation, Massachusetts Institute of Technology

Chapter 3

Geological Carbon Capture and Storage as a Climate-Change Mitigation Technology Riju, Anurag Linda, and H. P. Singh

3.1 Introduction The most important greenhouse gas (GHG) is CO2 , and it is the vital component of fossil fuels on which the world economy depends. Global cycling of carbon dioxide gives the overall index of health of the biosphere that makes it an essential attribute of life. Carbon dioxide is the most commonly produced greenhouse gas. CO2 emissions from fossil fuels and industry power generate around 36.2 gigatons of CO2 per year (IPCC 2018). Interchange of C (carbon) occurs in the middle of mainly four reservoirs, i.e., terrestrial biosphere, atmosphere, sediments, and oceans which are involve in the global carbon cycle. Knowledge of various biological processes that regulate the movement of carbon from one reservoir to another is important and central to control the methane (CH4 ) and carbon dioxide (CO2) emissions, required for mitigating climate change. Also C budget accounts the balance of exchange of C among the various reservoirs. This checks the amount of C coming in and going out from different reservoirs at a particular time. When the input (source) exceeds the output (sink), there is increase in the amount of reservoir. Also the C cycle determines the overall budget which is observed at a particular time. But currently, there is an imbalance of global C budget with more accumulation of C in the atmosphere in the form of carbon dioxide and methane since the beginning of the industrialization. Due to anthropogenic interventions, earth is getting warmer than ever. An imbalance has been caused in the natural C cycle due to human activities that has resulted into greenhouse effect thus global warming. Burning of fossil fuels for power generation, transportation, manufacturing, etc., results in emission of more carbon dioxide than it Riju (B) · H. P. Singh Department of Environment Studies, Panjab University Chandigarh, Chandigarh, India A. Linda Department of Environmental Sciences, Central University of Himachal Pradesh, Dharamsala, India © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2021 D. Pant et al. (eds.), Advances in Carbon Capture and Utilization, Energy, Environment, and Sustainability, https://doi.org/10.1007/978-981-16-0638-0_3

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is being removed naturally in the atmosphere resulting in global warming and climate change (Giri and Pant 2018, 2019). It is a global threat that needs an urgent action around the global community. It has been found that earth’s average temperature has increased by 1.4 °F over the past century, and it is projected that it will further likely to increase another 2–11.5 °F over next century (NCAR). Methane (CH4 ) and nitrous oxide (N2 O) concentrations have also increased steadily over the period of time (Prather et al. 2001), which are potent greenhouse gases. Since industrialization, the radiative forcing has increased by 1.94 W m−2 (NOAA 2015). Stabilization of abundant atmospheric CO2 and other GHG is of strong interest in order to mitigate the risks of global warming (Walsh 2007). Various strategies can be used for lowering the CO2 emissions for mitigating climate change which are reduction of global energy usage, development of less-carbon fuel, and sequestering carbon dioxide from the atmosphere or point source through engineered and natural processes.

3.1.1 The Global Carbon Cycle Global carbon cycle delineates the interchange of C between fossil fuels, land, oceans, and earth’s atmosphere where both the sources of sink and emission contain carbon and movement of carbon between land, atmosphere, and oceans with numbers of anthropogenic inputs and natural fluxes of carbon in gigatons per year. Sink of carbon and its source on the earth’s surface results from direct human impact including deforestation from grazing, agriculture, forestry, etc., and changes in environment. As global warming is changing landscapes, it is still unclear how much these changes are going to affect global carbon budget. C (carbon) cycle plays a vital role in functioning and wellbeing of earth. Earth’s climate is being controlled by concentration of CO2 in the atmosphere where carbon cycle plays a crucial role globally. It is also essential as it contributes to greenhouse effect where there is generation of heat from solar energy at surface of earth. Heat is then trapped by certain gases which in turn prevent it to escape through atmosphere. Greenhouse naturally is a perfect phenomenon, and without it, earth would have been a colder place. But an unnatural buildup of greenhouse gases (GHGs) leads to increase the temperature of the planet unnaturally. After water vapor, carbon dioxide and methane are the second and third most important greenhouse gases. These have a strong influence on radiative forcing. A concentration of carbon dioxide and methane has increased over the period 1880–2014. Due to this, the average ocean and land surface temperature has increased by 0.85 ± 0.21 °C (IPCC 2014). This has been shown by various scientists that the increase in GHGs is a result of anthropogenic activities including the deforestation and overexploitation of fossil fuels. As carbon dioxide is a GHG, the increase in its concentration is believed to be a main factor of causing a rise in global temperatures. This is the main reason for increasing interest in the carbon cycle as it is a primary cause of global warming. Earth’s soil, atmosphere, crust, and oceans consist of carbon. These components are referred to as carbon pools when

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considered earth as a system. These act as storage houses for large amounts of carbon thus are sometimes called as reservoirs and stocks. Carbon movement between these reservoirs is called a flux. These fluxes connect different reservoirs all together to create cycles in an integrated system. Globally, these processes transfer huge amounts of C from one pool to another pool, e.g., in terrestrial ecosystem, there is transfer of carbon from one pool, i.e., the atmosphere, to another pool, i.e., plants. With the passage of time, these plants become dead and decay which are then burned either for wildfires or energy or harvested by humans. These all processes are fluxes where C is cycled in various pools within an ecosystem and in due course releases back into the atmosphere. Likewise, these cycles are linked to various other ecosystems, i.e., rocks, oceans, etc. (DOE, Department of energy, USA, 1995). Plants take C from the atmosphere through photosynthesis and release it back to the atmosphere by respiration. This process occurs in shortest time scale, i.e., seconds to minutes. But on a larger time scales, carbon from dead and decayed plant materials is incorporated in the soils where it might live in for centuries, decades, and years. There is a continuous movement of carbon between plants, soil, and atmosphere through decomposition, harvesting, fire, photosynthesis, and respiration. Organic matters which are protected from decay are buried into deep sediments, slowly altered into deposits of oil, coal and natural gas (fossil fuels which are being used today). After burning these substances, carbon is released that has been stored for millions of years again into to the atmosphere in the form of CO2 . Earth’s carbon reservoirs naturally act as both sinks and sources where there is addition of carbon and removal of carbon from the atmosphere. A carbon cycle is said to be in equilibrium when all sources are equal to all sinks and there is no change in the size of the pools over time. A steady amount of carbon dioxide in the atmosphere helps in maintaining stable average temperatures globally. Due to deforestation and overexploitation of fossil fuels, the increased carbon dioxide in the atmosphere have caused the size of atmospheric carbon pool to increase. This is what has been responsible for the present buildup of carbon dioxide and is believed to cause the observed trend of increasing global temperatures. Energy-supply systems would be replaced by additional point sources that would be amenable to capture.

3.1.2 Source of Carbon More than 40% of energy-related CO2 emission is accounted by coal, and also it accounts for almost 40% of electricity generation (IEA, International energy agency 2019). Major portion of carbon dioxide emission results from oxidation of carbon when fossil fuels are burnt. Global coal demand was highest in 2018 although estimated coal power generation was declined in the year 2019. Coal is currently a dominant fuel in various power sectors. Almost 38% of coal was accounted in power generation in the year 2000, with natural gas 17.3%, hydro power for 17.5%, nonhydro renewable 1.6%, and nuclear for 16.8% (IPCC 2001). After two decades, coal still remains the dominant fuel in the power generation sector which is around 36%

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where natural gas surpassed hydro power that has become the second-largest source (IEA 2019). But biomass as a fuel is still limited in the power sector. In India, coal trade on international desk central government suggests the zeroimport policy for thermal coal. But even if government retains the policy, still India will need import of 50 metric tons of steam coal because of its demands from the import-based power plants. Tables 3.1 and 3.2 represent the estimated coal imports and production under 2 °C scenarios. The scenario suggests that by the year 2050 renewable energy could potentially provide as much as half of the world’s energy needs. Mainly, the target is to decrease global carbon dioxide release to around 10 gigatons per year in 2050 which shall limit the rise in global average temperature to 2 °C that can avoid menacing interference through anthropogenic inputs with climate system (Krewitt et al. 2007). The overall demand of coal shall reduce by 8% because of cut down of overall demand of steam coal in 2 °C conventional and 59% in 2 °C_sustainable scenario over INDC scenario (Garg et al. 2018). There are sector-specific fuel selection in the industries, like in steel and iron sector, coke and coal are primarily used in blast furnaces for primary steel production (IPCC 2001; IEA GHG 2000), whereas gas and oil are primary fuels for chemical and refining sectors. In cement industries, all fuels are used but with dominance of coal usage in many countries like India, China, and USA (IEA GHG 1999). And Table 3.1 Coal production and import estimates (conventional scenario) Production

Import

Year

Cooking*

Non-cooking** (steam coal)

Cooking*

Non-cooking** (steam coal)

2020

18

684–734

62

50–100

2030

20

584–634

64

50–100

2040

23

770–820

71

50–100

2050

25

771–821

97

50–100

Source Garg et al. (2018) *Estimated numbers, **Assumed numbers

Table 3.2 Coal production and import estimates (sustainable scenario) Production

Import

Year

Cooking*

Non-cooking** (steam coal)

Cooking*

Non-cooking** (steam coal)

2020

18

673–723

62

50–100

2030

20

709–759

64

50–100

2040

23

376–426#

72

0

2050

25

365–415#

80

0

Source Garg et al. (2018) **Estimated numbers, *Assumed numbers #Domestic producers may try to maintain the current large production levels, but due to global climate pressure, it would be difficult to find export markets on coal phase out; thus, domiciliary demand of coal is projected to go down in such scenario

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countries like Mexico, gas and oil are in dominant usage (Sheinbaum and Ozawa 1998). Trend in European countries for cement manufacturing is to use non-fossil fuels. Mostly chemical waste mixtures, tires, and sewage sludge are being used (IEA GHG 1999). Globally, biomass is not a significant source of fuel in manufacturing industries in large scale. But certain countries like Brazil and Scandinavia acknowledged that biomass can be significant (Möllersten et al. 2003). Reduction of CO2 not associated with combustion is released from a variety of production from various industries which transform materials biologically, physically and chemically. The process includes: • Usage of C as a reducing agent in the metal production (commercially) from ores (IPCC 2001; IEA GHG 2000). • Thermal decomposition/calcination of dolomite and limestone in lime or cement production (IPCC 2001; IEA GHG 1999). • Fermentation of biomass. For example, converting sugar to alcohol. Use of fuels as feedstocks in petrochemical processes (Christensen and Primdahl 1994; Chauvel and Lefebvre 1989). Storage and assessment of carbon dioxide require extensive depiction of carbon dioxide sources. Source of carbon dioxide for capture basically depends on partial pressure, volume, aspects of integrated systems, suitable reservoir proximity, and its concentration (IPCC 2005). Carbon dioxide emission occurs from different sources where fossil fuel is the main source in industries, power plant generation, transport, and domestic sectors. Industrial and power generation sector produces huge emission volumes that make them acquiescent to incorporate carbon capture technology. It is less acquiescent for small point sources and mobile sources like transport and other sectors to capture carbon at present. However, many advancements in technologies in production of fuels have allowed the carbon capture from energy used in these sectors. More than one metric tons of carbon dioxide from over seventy-five hundred large carbon dioxide sources has been identified which are geographically distributed around the world (IEA 2019). Indian sub-continent (Southern Asia), eastern coast (South East Asia), North West Europe, and North America particularly Midwest and free board of USA are four clusters among the global carbon emission. According to International energy agency report 2019, it has been projected that emission sources from South East and Southern Asia are likely to increase, whereas emission from regions like Europe may slightly decrease by 2050. It appears that there is an efficient link between opportunities and sources if compared with geographical dispersal of emission from sources with geological storage opportunity. But a detailed study is required to confirm the suitability of such geographical sites for carbon storage. Research suggests that in ocean storage, only a small percentage of large source emission has the ocean storage potential, because maximum proportion of emission source has carbon dioxide concentration less than fifteen percent with a very little proportion which is less than two percent has concentration more than ninety five percent (IEA 2019). This means more proportion of carbon emission from sources is more suitable for carbon dioxide capture as compared with less carbon emission source which are less suitable. This in turn has the cost effectiveness on various

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carbon capture techniques. Similarly, high content carbon source has a chance of low capture cost as compare to low content carbon source because only compression and dehydration are required for high content carbon source, whereas low content carbon source largely depends on rate of instigation of biofuels, hydrogen liquefaction, and gasification of fossil fuels for future development in carbon capture plant size. At present, technologies have been changed which allow carbon capture from low emission sources. This include centralized manufacture of gaseous and liquid energy carriers like ethanol or hydrogen, methanol, etc., from fossil fuels, also production of energy carriers or electricity from biomass. This advancement in technologies allows carbon capture and storage.

3.1.3 Impacts of Changing Global Carbon Cycle After water vapor, carbon dioxide and methane are the second and third most important greenhouse gases. Radiative properties of the atmosphere are strongly influenced by these greenhouse gases resulting in an increase of CO2 and CH4 concentrations. There is a serious concern about the imbalance in the carbon cycle and its implications. This is due to a large increase in atmospheric CO2 over a short time relative to historical variations and likely to continue for foreseeable future, and therefore, it is a growing concern that this increase in atmospheric CO2 and CH4 concentrations can cause significant global warming and other changes in the global climate by altering the water and heat a balance of earth’s atmosphere and surface. As water vapor precipitates and condenses from the atmosphere, it is not considered the most important climate relevant greenhouse gas in the earth’s atmosphere, but CO2 and CH4 . Many physical evidences have shown this as well. Formation of (UNFCCC) United Nations Framework Convention on Climate Change in 1992 is a consequence of link between climate change and CO2 emission. It is an international recognition that deals with the vulnerability of global climate to human actions. Intergovernmental Panel on Climate Change (IPCC) established by the United Nations acts as a tool for synthesizing scientific information which has released five comprehensive assessments on scientific basis of climate change. International Council for Science Unions (ICSU) has also proposed several projects which are devoted to global carbon budget. It is a matter of concern which has become a challenge for controlling the increase in the CO2 concentration in the atmosphere that has attracted many international as well as national attentions. The overall objective of research in global carbon cycle has been taken into account for complete mass balance of the CO2 production which is caused by anthropogenic activities which include its processes and sources that remove it from the atmosphere (sink) and reservoirs where carbon is stored.

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3.2 Global Carbon Budget The global carbon budget is important for understanding the global carbon cycle in a better way. It gives the precise assessment of anthropogenic CO2 emissions and their redistribution among the terrestrial biosphere, oceans, atmosphere, land use change drivers, and permissible emission of a given climate stabilization target that is important in support of different development of climate projects and future climate-change policies. A very important initiative in this is the “Global Carbon Project.” It is an international research project within the Future Earth research initiative on global sustainability. It is also a research partner of the World Climate Research Program. The main aim of the project is to develop a complete picture of the global carbon cycle, including both human and biophysical dimensions with the interactions and feedbacks between them. The latest update of global carbon budget was published in the year 2019 which was the 14th edition of the annual update which started in the year 2006. Key points of global carbon budget are based on the data published by Friedlingstein et al. (2019). • Slow growth in fossil carbon dioxide emissions is projected for 2019, at +0.6% (range: −0.2 to +1.5%). The 2019 growth is slower than over the past two years, with +1.5% in 2017 and +2.1% in 2018. • CO2 emissions from oil use are expected to grow at +0.9% in 2019 (range: +0.3 to +1.6%), driven by growth in China (+6.9%), but with weaker growth in India (+1.5%), EU28 (+0.5%), and a decline in the US (−0.5%). The last decade saw CO2 emissions from oil grow steadily at +1.4%. • Coal is still the main source of CO2 emissions, but its emissions are expected to decline—0.9% in 2019 (range: −2.0 to +0.2%). This global decline in coal is due to big drops in the USA (−10.5%) and EU28 (−10%) and weak growth in China (0.8%) and India (2%). The last decade (2009–2018) saw CO2 emissions from coal grow at only +0.6%. • Climate and energy policies are emerging but are still insufficient to reverse trends in global. CO2 emissions need to decrease to net zero globally to stop further warming of the planet. Deforestation fires also drive CO2 emissions up in 2019. • Land and ocean carbon sinks continue to increase in line with emissions, absorbing about 55% of the total anthropogenic emissions. There is no sign of either land or ocean carbon sinks reaching saturation. • Atmospheric CO2 concentration continues to grow by more than 2 ppm per year and is projected to reach 410 ppm averaged over the year in 2019. • Natural gas continues to grow strongly in 2019, with natural gas being the fastest growing source of emissions and projected to grow +2.6% in 2019 (range: +1.3 to +3.9%), driven by growth in all regions, including the USA (+3.5%), EU28 (+3.0%), China(+9.1%), and India (+2.5%). The last decade saw CO2 emissions from natural gas grow steadily at +2.3%. Natural gas was the biggest contributor to the growth in fossil emissions in recent years.

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• In 2019, there were more fires in deforestation zones than most recent years. Preliminary estimate of fire emissions in deforestation areas indicate that emissions from the Amazon will be higher in 2019 than in recent years, but lower than in the 1990s and early 2000s. The atmospheric CO2 concentration and the land and ocean carbon sinks continue to grow.

3.3 Capture and Storage of Carbon Dioxide The capture and storage of carbon dioxide is mostly relevant for centralized large carbon sources like large industries and power plants. The main purpose of carbon capture is to generate stream which can readily fetch to a carbon storage site. Energy required for operating the carbon capture systems decreases the comprehensive efficiency of power generation and other processes. This leads to increase in environment impact, fuel requirement, and solid wastes which is similar to the base plant without carbon capture. Although more structured plants are available that can replaces the in efficiency ones. Net impact of these structured plants is congruent with clean and safe emission fuels with low carbon for transportation and also for small-scale applications. For future development in carbon capture techniques, energy minimization is required in order to improve the efficiency of energy conservation process which is highest in priority for future technology. This will minimize the overall cost and environment impacts. Presently, industrial plants such as ammonia production facilities and natural gas processing are separating carbon dioxide routinely. But these plants are removing carbon in order to meet the demands but not for storage. Various small power plants has also been applied for carbon capture, but power plants at larger scale which produces hundreds megawatts of electricity which are major source of carbon dioxide emission have shown no application.

3.3.1 Importance of Carbon Sequestration Processes • Carbon dioxide capture and sequestration can play a crucial role in reducing GHG emission into the atmosphere. • It enables low-carbon electricity generation from power plants. • As reported in Indian Network on Climate Change Assessment (INCCA) report, Indian agriculture has a prospect of removing 85.5 metric tons of CO2 per year out of which 80% is delivered by cost-effective options (Sapkota et al. 2019). • An emission in India is done from electric power generation. This carbon share can be reduced by using carbon sequestration technologies. • Carbon sequestration technologies can dramatically reduce CO2 emissions by 80–90% from power plants that burn fossil fuels.

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3.3.2 Carbon Sequestration The process of removal of carbon from the atmosphere and depositing it in the reservoir is called as carbon sequestration, or it is the process of capturing and then storing of atmospheric carbon dioxide to mitigate the climate change and global warming. Carbon pool is the term used for carbon storage. It refers to a mechanism that has the capacity to release or accumulate. This can be human or natural induced, e.g., atmosphere, soils, wood products, forest biomass, etc. There is a complex mixture of dead and live organic minerals and matter in a forest carbon pool. Carbon dioxide stored in geological pool falls under human induced carbon pools. CO2 from industrial sources can be captured at the source and re-injected into spent oil fields to enhance recovery or be injected into geologically stable formations for sequestration. If not captured at the source, CO2 can be partially removed from the atmosphere by terrestrial sequestration (vegetation regrowth). Carbon sequestration also refers to the long-term carbon dioxide storage to reduce its emissions in the atmosphere which should implement the following principles that are the environmental impact should be minimal, storage must be verifiable, safe, and indefinite (Lackner and Brennan 2009).

3.3.2.1

CO2 Capture Systems

For 80 years, C has been captured from industrial process streams (Kohl and Nielsen 1997). Most of carbon dioxide captured is emitted into the atmosphere because earlier there was no incentive to store it. Presently, carbon dioxide captures from process streams are natural gas purification and synthesis gas production which has hydrogen in it. The gas is used for production of alcohols, synthetic liquid fuel, and ammonia. Also presently, there are four basic systems for capturing CO2 from use of fossil fuels and/or biomass: • • • • •

Capture from industrial process streams, Post-combustion capture, Oxy-fuel combustion capture, Pre-combustion capture (Fig. 3.1). Pre-combustion: As the name suggests, this process is performed before the combustion process is completed. This is the process where fossil fuel is obtained without carbon. In this technique firstly, the coal is oxidized in steam. It is then combined with air. The mixture prepared then forms synthesis gas at very high temperature which is referred to as syngas. Syngas basically is a mixture of CO (carbon monoxide), CO2 (carbon dioxide), H (hydrogen), and a small amount of CH4 (methane). The entire process is known as gasification. Next step in his process is shift reaction where CO (carbon monoxide) and H2 O (water) are converted to H2 (hydrogen) and CO2 (carbon dioxide). Here, the range of carbon dioxide is 15–50%. Carbon dioxide is then captured, transferred, and sequestered.

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Fig. 3.1 Schematic diagram of carbon sequestration process. Reproduced after GIEC (2005)

This process is also used to remove dilute carbon dioxide at a low pressure because rich carbon dioxide is removed at a high pressure even before hydrogen is combusted on water gas shift reaction. This technique is very efficient as it provides availability of concentrated carbon dioxide but is also highly expensive for base gasification process. • Post-combustion: Carbon dioxide removal from the flue gases is done in this process. This technique uses the chemical absorption processes with solvents of monoethanolamine (MEA), and the process is termed as amine separation process. MEA solution is added in an absorber. This solution is basically used to obtain the carbon dioxide by selectively absorbing from the overall carbon dioxide (Pant et al. 2017). The selected carbon dioxide is then sent to the stripper. Pure carbon dioxide is prepared by heating the carbon-dioxide-rich monoethanolamine solution in the stripper, and then, generated carbon dioxide incline with monethanolamine solution comes out of the stripper. The obtained gas is again then sent to the absorber for recycling. Steam is generated in the power generation system where coal is burnt with the help of air in the boiler. Prepared stem is then used to operate the turbine which generates electricity. N2 and CO2 are present in the exhaust from the flue gases. This technology is basically used to scour the solvents with the help of amine. Scrubbing depends upon the reaction of chemicals with CO2 to produce high temperature of carbon dioxide that is appropriate for the compression and storage of gas. Scrubbing plants can be used to reduce the amount of acid gasses such as NO2 and SO2 (Giri and Pant 2018). In this technique, main benefit of amine scrubbing in this technique is that it can be added with the existing power plants and industries in a befitted location.

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Commercially, it is used in the small-scale industries. Carbon dioxide separation from the flue gas is a challenging task. Carbon dioxide with high volume, dilute concentrations and low pressure separation is treated. Corrosion occurs with the impurities of flue gases that degrade the solvents. Also, carbon dioxide capture through solvent scrubbing has a limited experience so far for the large-scale operations. • Oxy-fuel combustion: Here, in this technique, fuel present in air is removed with oxygen. The maximum percentage of gas in the atmosphere is nitrogen (78.08%), oxygen (20.95%). and the remaining percentage of inert gases. In oxy-fuel combustion, fuel is appended with the existing atmospheric air for combustion. There is incomplete combustion as gases in the atmosphere do not react with inert gases. But a high temperature is obtained by using oxygen instead of air, overcoming incomplete combustion. Thus, we can say that this method is burning of fuel with pure oxygen. The technique acts in the air as primary oxidant air. Other than above techniques which were already discussed, there were distinct techniques which are based on the geology which are as follows: 3.3.2.2

Ocean Sequestration

Oceans are one of the most favorable places to sequester carbon. Oceans take up almost a third of carbon emitted by anthropogenic activities. Ocean sequestration involves storage of C in oceans through direct injection. In this, liquefied carbon dioxide is directly injected into a thousand meters deep, either directly from tankers or from shore stations through long pipes at sea. At this depth, carbon dioxide is denser than sea water which might be possible to store on the bottom as liquid or deposits of icy hydrates.

3.3.2.3

Geologic Sequestration

Here, natural pore spaces in geologic formations serve as reservoirs for long-term CO2 storage. In this, carbon dioxide is usually pressurized till CO2 becomes liquefied. It then is injected into geological basins and porous rock formations. Geological sequestration sometimes is also called as tertiary recovery or enhanced oil recovery because later it can be used later in producing oil wells. In enhanced oil recovery, liquid carbon dioxide injected into oil-bearing geological formation to reduce the viscosity of oil allows the oil to flow more easily into the oil well.

3.3.2.4

Terrestrial/Biological Sequestration

In this, a generous amount of C is stored in natural carbon sinks like vegetation and soils. In natural sinks, usage of photosynthesis for increasing the C fixation, changing

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land use practices, and reducing the decomposition of organic matter can enhance carbon uptake. It also refers to storage of atmospheric C in soils, aquatic environment, woody plants, and vegetation. Growing plants, particularly larger plants like trees can enhance the potential of biologic sequestration. For near-term application, geologic sequestration is thought to have the largest potential. Similar to natural weathering, there are processes that convert CO2 to solid inorganic carbonates using chemical reactions, and also the process offers an opportunity of safe and permanent storage of carbon dioxide during a long period (Allen and Brent 2010). But the main disadvantage in this process is its high cost. The largest storage of CO2 is the ocean. It consists of carbon dioxide, injected deep down the oceanic surface where it forms hydrates or dissolved plumes that are heavier than water which sinks at the bottom of the ocean. Natural estimated rate through the process that accelerates the transfer of carbon dioxide into the ocean is 2 Gton/year (Khoo and Tan 2006). Other various techniques were also tested to perform the transfer of carbon dioxide into the ocean, e.g., inclined pipe, pipe towed by dry ice and ship, and vertical injection. With the advantage increase of CO2 concentration in the ocean through various processes, there can be a serious consequences in marine ecosystem as well as this shall affect the growth of corals and also increase ocean acidification. Thus, the geological sequestration of C is considered the most viable one (Yang et al. 2010). Unlikeable coal seams, enhanced gas or oil recovery (EGR or EOR), depleted oil and gas fields, and deep saline formations are the most used sites for geological storage of carbon that are based on the economic point of view (Solomon et al. 2008), and adequate storage capacity, porosity, and permeability are required for geologic storage. A stable geological environment and a satisfactory sealing cap rocks are also required. With all its merits, the main concern of carbon storage is its leakage into the atmosphere that can render this process as ineffective in global warming reduction. The study of these aspects was reported by Mathias et al. (2008). There are several consequences of carbon dioxide leakage, i.e., death of small and low-lying animals living in enclosed low level areas where the accumulation of carbon dioxide is maximum as it is heavier than air. Asphyxiation is another consequence where carbon dioxide is harmful for health of the human beings when the concentration is greater than 0.5–1.5% compared with atmospheric concentration which is 0.038% (Allen and Brent 2010). Also, the acidification of portable ground water presented nearby is a consequence of injection of carbon dioxide in geological formations. Hydrodynamic trapping and a combination of two is the most effective method of CO2 storage in the subsurface of the earth. Several other improved technologies are being developed for C sequestration to overcome the challenges being made by the older techniques. But it is important to choose one or a combination of several other technologies for formulating the energy policies at global and national level for future economic growth. Following options can be grouped into two broad categories, i.e., abiotic and biotic sequestration.

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3.3.3 Abiotic Sequestration This strategy of C sequestration has received a considerable attention; it has a larger sink capacity than biotic sequestration in theoretical terms. Abiotic sequestration involves engineered techniques as well as chemical and physical reactions without the involvement of living organisms. The technique involves: in the oceanic injection method, a pure carbon dioxide stream and a liquefied carbon dioxide that is separated from the industrial sources are injected deep into the ocean. The technique involves: 1. 2. 3. 4. 5.

Formation of CO2 lake by pumping it into a depression at the bottom of the ocean floor. Injection of CO2 below 1000 m through a multitudinous at the ocean floor. It then rises to 1000 m approx. depth forming a droplet plume as it is being lighter than the water. Sink of mixture in the deep ocean as it is injected as a denser sea water–carbon dioxide mixture at approximately 500–1000 m. Discharge of carbon dioxide through a large pipe that is towed behind a ship. However, injection of carbon dioxide can also possess many adverse effects on the biota of deep sea ocean (Seibel and Walsh 2001).

The other abiotic method is geological injection; in this technique, carbon dioxide is injected into oil wells that are old so as to increase the yield, coal seams, saline aquifers, and stable rock strata (Baines and Worden 2004). This technique also involves injection, liquefaction, capture, and transport of industrial carbon dioxide into deeper geological strata. Carbon dioxide from the industries can be injected into aquifers where it reacts with various other dissolved salts that form carbonates, and also there is hydrodynamic sequestration. In its supercritical state, CO2 has a much lower viscosity and density than the liquid brine. At this state, carbon dioxide is injected into the geological strata. A multiphase environment occurs in situ where there is formation of gas like phase, and also it dissolves in aqueous phase. There could be an economic strategy of enhanced oil recovery (EOR) where carbon dioxide is injected into the reservoirs where it displaces gas/oil. It has raised production from oil and gas fields which has been a decline through carbon-dioxide-enhanced recovery. Carbon dioxide can be injected into unminable coal seams where methane is observed, and further, it absorbs on the coal twice as much as methane. This process has enhanced the gas recovery of coalbed methane (CBM). However, principal concerns about geological sequestration, similar to that of the oceanic, are (Kintisch 2007), i.e., reliability of storage of vast quantities of CO2 in geological strata and the cost, which need to be resolved.

3.3.3.1

Scrubbing and Mineral Carbonation

The technique involves the conversion of industrial emitted carbon dioxide into calcium carbonate (CaCO3) , magnesium carbonate (MgCO3 ), and other mineral

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carbonates that are thermodynamically and geologically stable. Mimicry of natural inorganic chemical conversion of carbon dioxide is used to achieve mineral carbonation (Fan and Park 2004; Giri et al. 2018). In scrubbing, a carbonate solvent or amine is used to chemically absorb the carbon dioxide. This is the most widely used method of C capture. Solvents like lithium silicate (Li2 SiO3 ), potassium carbonate (K2 CO3 ), nickel, and ceramic-based compounds are used to purify carbon dioxide by passing it through an absorption column that contains the solvents. By heating the carbon-dioxide-rich amine and then re-precipitated through mineral carbonation, pure carbon dioxide gas can be recovered. Stable rocks are thus formed as carbonated where carbon dioxide is sequestered perpetually.

3.3.4 Biotic Sequestration In this technique, higher plants and micro-organisms remove carbon dioxide from the atmosphere. The process differs from management options that lower the offset emission. It further involves:

3.3.4.1

Oceanic Biotic Sequestration

This involves various biological processes that lead to carbon sequestration via photosynthesis. Photosynthesis by phytoplankton is one of the method that fixes approx. 45 Pg C yr−1 (Falkowski et al. 2000). Phytoplankton deposited on the floor of the ocean forms some particulate organic matter that helps in sequestration. Iron (Fe) is one of the limiting factors for the growth of phytoplankton in the ocean; thus, it is an important fertilization on biotic carbon dioxide sequestration in the oceanic ecosystem (Boyd et al. 2004), but ocean fertilization can also hamper the ocean ecology, and currently, with the state of knowledge, ocean fertilization is still a debatable issue (Johnson and Karl 2002).

3.3.4.2

Terrestrial Biotic Sequestration

It consists of a major carbon sink due to photosynthesis and carbon dioxide storage in living and dead organic matter. Terrestrial sequestration is also transfer of atmospheric carbon dioxide into pedologic and biotic carbon pools. It is also considered as no-regret strategy as it owes to many auxiliary advantages like improved water quality and soil quality, increased crop yield and degraded ecosystems restoration (Lal et al. 2003). Also there are multiple benefits associated with it even without threat to climate change globally. Three principle components are there for terrestrial carbon

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sequestration, i.e., soils, wetlands, and forests. Carbon is stored as resistant polymeric carbon compounds and as lignin by the forest ecosystem. Carbon sequestered in forests then can be harvested through woody debris, woody plants and products, and timber. Net primary productivity of forest ecosystem is not saturated on a present carbon dioxide concentration which may rise with rise in the concentration of atmospheric carbon dioxide through the effect of carbon fertilization. One of the viable options for carbon sequestration in terrestrial ecosystem is afforestation, and also refurbishment of debased tropical forest is another useful option (Lamb et al. 2005). By improving the management of regrowth of degraded tropical landscapes, the potential for carbon sequestration can be enhanced.

3.4 Barriers to Implement CCS There are many barriers associated with the carbon sequestration process, which are: technical barrier, institutional barrier, financial barrier, and other barriers. Technical barrier includes commercial demonstration of high point sources of carbon dioxide which is used for capturing technologies but is not standard for high point source. Also it has some stability issues as many parts of India are seismically active. Cost and potential of depleted oil and gas are determined using technical barriers. However, institutional barriers do not meet overall development goals as it does not contribute to the sustainable development. High energy penalty and high capital are involved in financial barrier. Other barriers involve regulatory, acceptance, and storage. Presently, carbon capture and storage (CCS) is in demonstration phase that is gaining a single degree of technology confidence via the large-scale development. In India, it has a major barrier in CCS establishment. CCS lacks capture of geological storage side data and technology that can be installed in power plants whose sources are location, capacity, and permeability. The implementation of this technique has some another issues like increasing the cost of power output and electricity. The major barrier which has come so far in CCS in India is the deficit of electricity and electrification in India. However, in other developed nations, the C storage uses enhance oil recovery which is one of the best and most effective options for this technique.

3.5 Recent Developments on Carbon Capture and Storage It is very important to differentiate between a mobile source and stationary source. Mobile source includes automobiles, airplanes, etc., whereas stationary sources include factories, power plants, etc. (Wilcox 2012). Capturing carbon dioxide directly from the mobile source is not possible at present, and thus, work is more focused on capturing carbon dioxide from the stationary sources. Intergovernmental Panel on Climate Change (IPCC) assumes increase in average global temperature association

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with the warming of the climate system from increasing anthropogenic greenhouse gases concentrations in the atmosphere. About 80% of the contribution is from fossil fuels with 10% from renewable energy (International Energy Agency (IEA) 2013). Basically, this is because of the over dependency on non-renewable energy resources as renewable energy resources are able to keep up with the increasing energy demand associated with a growing world population. Thus, carbon dioxide utilization next to storage can be an integral component of carbon management.

3.5.1 Coal Fires Power Plants It is an old technology from which gases emitted from stationary sources. Natural gases are used as it contains more carbon dioxide which is placed inside the pipelines. Amine scrubbing process is used by gas companies for this task. The process was discovered by Bottoms in 1930 which was used to separate out carbon dioxide from methane. Similar kind of process can also be used for removal of carbon dioxide from flu gas. But the disadvantage with this process is that subsequent compression of carbon dioxide with regeneration of amine solution for geological storage and transport requires extensive amount of energy. Thus, a carbon capture power plant becomes more expensive with reduction in efficiency as high as thirty five percent (Herzog and Golomb 2004). Although nowadays various research is focussed on finding alternative for coal fires plant pant, like, membrane or solid absorption that can increase the efficiency of absorption process. Another alternative to it is adding carbon capture at the very beginning, so that it can give more possibilities to optimize the efficiency of carbon capture and combined power generation. Oxy-combustion is one such example. In this, coal is burned with pure oxygen, and carbon dioxide is capture by condensing the water. In this process, oxygen should be separated from air which is also an energyintense process. For this, alternative can be IGCC, i.e., integrated gasification combined cycle, chemical looping where coal is being converted into syngas and CO2 capture process involves separation from H2 . Carbon dioxide is considered as a waste product in context with flu gas. But there are many applications where it can be considered as an essential and valuable commodity.

3.5.2 Dilute Source Carbon Dioxide Capture Recent advances in separation material include carbon selective absorbents, solvents, and membranes. These are used for post-combustion CO2 capture. The membranes are based on supported amine material, polymeric membrane, mixed matrix

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membranes, amine materials, metal organic framework material, etc. The most relevant one for post-combustion carbon capture is aqueous amine absorption process. Although research on membrane materials, solvents and adsorbents has not been sufficiently considered the long-term stability of these materials in the presence of flu gas particulates like SOx , NOx , H2 O, O2 , Hg and particulates for carbon capture (Jones and Maginn 2010).

3.5.3 Enhances Oil Recovery Figure 3.2 represents the various methods of EOR which is mainly categorized into four groups. Chemical methods are constructed on injecting different chemical reagents or their mixtures with water through projection wells or injections in the reservoir so as to clean the wellbore perforation zone such as matrix acidization or to enhance sweep effectiveness of displace in fluids (Abramova et al. 2014). In thermal EOR, there is change in chemical and physical parameters oil. In this method, crude oil is heated in situ so as to decrease the viscosity and thus mobility ratio. This method changes the properties of oil instead of the reservoir such as in hydraulic fracturing which is creating or increasing artificial permeability (Santos et al. 2014). Thermal EOR can cover about 30–58% of oil (Abramova et al. 2014). Different thermal EORs vary in terms of recovery factor of oil which depends upon heterogeneity and type of formation. Recovery from SAGD and stream flooding is around 40–60%, whereas from cyclic steam injection is 10–30% (Alvarez and Han 2013; Jiang et al. 2010). The most common EOR method used at present is miscible flooding or gas injection. In this method, miscible gas is introduced into the reservoir for reducing the

Adapted and modified after Patel et al., 2018 Fig. 3.2 Conventional EOR classification and its type Adapted and modified after Patel et al. (2018)

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interfacial tension among water and oil. This improves the oil displacement (Fath and Pouranfard 2014). Carbon dioxide and nitrogen are released is produced in this method. Gas method has the capability to increase the oil production around 5–19% which is more if compared to ordinary flooding method during secondary recovery (Davarpanah 2016). Polymers and surfactants change the surface and interfacial tensions, reduce the viscosity, and increase the mobility of oil in respect of water which increases the recovery rate. Chemical EOR method can recover about 35% of reserves (Raffa et al. 2016). In physical EOR method, geophysical fields are used to affect the reservoir instead of matter which is chemicals, gas, streams, etc. This method is developing over past few years and is still low as compared to other methods. The fields used in this method vary from electromagnetic to acoustical (Abramova et al. 2014). This is comparatively less expensive as these are non-invasive, but still there is lack of information available for this method, and satisfactory results are yet to obtain from this method. CO2 is considered as a valuable commodity for enhanced oil recovery. One of the best options for carbon storage is depleted oil fields. There is a huge market for carbon dioxide where it can become an important stimulus for developing more efficient carbon capture technique, for example, man-made carbon dioxide can compete with carbon from natural reservoirs (ARI, advance resource international 2010).

3.5.4 Carbon Dioxide to Chemicals and Fuels Presently, chemical industries are utilizing around 7% of all oil as feed stock for carbon. This can range from plastic industry to soap industry. But there is longterm challenge for various chemical industries to replace oil by a renewable feed stock. Practicality of carbon dioxide usage as a chemical feedstock can substantially be improved if the cost of C is adequately high, so that oil can be replaced by CO2 . But carbon-free resources like wind and solar are still expensive for such carbon utilization schemes. Upgrading carbon dioxide to fuel is a challenge as it requires energy. Fossil fuel as an alternative makes no sense; here, it can be used as energy source. Only advantage of fossil fuels is their high energy density, whereas for renewable energies like solar and wind, energy storage at a large scale is required so as to ensure production of electrical power at times when there is no wind or sun.

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3.5.5 CO2 Incorporation into Building Material and Construction Cement industries are the second-largest emitter of CO2 that produces around 7% of carbon dioxide (International Energy Agency Greenhouse Gas R&D Program (IEAGHG 2002). Around 1.6 Gigatons per year of CO2 emission can be reduced if 10% of building materials can be replaced with carbonate minerals (Agarwal et al. 2016). However, to reduce issues related to mechanical strength of materials, the correct composition of carbonate mineral is important.

3.6 Carbon Capture and Storage Structure in India In India, around 53.7% of electricity are being produced by coal which directly emits carbon into the atmosphere (Sood and Vyas 2017). About 40% emission is from power generation, and transportation and industries emission is 32 and 15%, respectively. 11% of carbon emission is from commercial and residential sectors (Sood and Vyas 2017). All the percentage of carbon emission is not viable for carbon sequestration. The techniques for carbon capture and storage is mostly applicable in power plants, stationary sources, and large industries because of high capital and economic costs. But the advancements in CCS technologies due to storage and transportation of carbon dioxide will help in controlling the evaded cost of carbon capture. In India during 2007 and 2008, a certain care was taken to capture carbon or for carbon sequestration. Nearly 30 projects were sponsored by researchers across the country during the financial year which depends upon carbon storage (Viebahn et al. 2014). India’s action on research and development approach is very low due to not having any particular policy on carbon capture and storage. Absence of carbon capture and sequestration will cause the increase in cost around 70% by 2050 due to the emission of carbon (Rao and Kumar 2014). CCS in India is at an initial stage only. Four initiating key points are followed in India which are: Capture of pure CO2 streams in industry. This process is easy to generate pure stream of CO2 . Examples are gas industries and fertilizers. Enhanced oil recovery (EOR) offshore and onshore. Indian government has already initiated a plan from the offshore sour gas at Hazira in Gujarat. The recovery from this technique is done almost 70 km away from the onshore, and almost 1200 tons of received carbon dioxide is transported to the oil field each day (Sood and Vyas 2017). This reduces oil viscosity and maintains the pressure. New power plant designs in India are there like UMPPs (unimpaired performance and less upfront costs). This new technique starts with technology generation such as

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advanced supercritical steam conditions. It also exports carbon dioxide for foreign EOR activities. The UMPP project is mainly formed by shipping terminals, and it is design for imported coal such as Mundra. The Department of Science and Technology (DST) started the Indian CO2 sequestration Applied Research (ICOSAR) for carbon capture and storage. The CCS projects are always carried out in three steps which are absorbing, pre-combustion, and post-combustion.

3.7 Conclusion Carbon sequestration is important for maintaining the natural carbon cycle which is most affected by human activities. Thus, there is a need to imply these technologies effectively. Also there is a need to conserve existing forests with a great requirement of reforestation. This can be achieved by adopting natural sequestration first and then installing various improved CCS technologies that can manage carbon emission and its corresponding effects at its point source. Then, only carbon emission and potential harmful impacts can be reduced. Natural ocean and terrestrial sinks are presently absorbing approximately 60% of the 8.6 Pg C per year (Lal 2008). But the capacity of natural sinks is not enough to take in all the carbon dioxide induced by human activities until the carbon neutral energy sources take effect. Carbon management and sequestration presents an opportunity for us to address climate change concerns while still enjoying the benefits of fossil fuels. Basically, C sequestration should be seen as a part of an overall scheme that involves non-carbon sources and improved efficiency. Presently, we need many mitigation options which are cost effective to address the climate-change issues. A progressive approach in C storage and utilization research will enhance and improve our understanding of the long-term effects of large-scale injection of carbon dioxide in various geological formations. This further will empower us to evolve substitutes for geological storage like carbon mineralization and will enhance the development of the innovative chemistry to convert carbon dioxide into synthetic chemicals and fuels.

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Chapter 4

Soil Carbon Sequestration for Soil Quality Improvement and Climate Change Mitigation Ruma Das, Avijit Ghosh, Shrila Das, Nirmalendu Basak, Renu Singh, Priyanka, and Ashim Datta

4.1 Introduction The word ‘climate change’ is a very important and burning issue for recent time. According to National Geographic Society (2019), climate change is the long-term alteration of temperature and typical weather patterns in a particular location or the planet as a whole. Thus, the weather pattern becomes less predictable which can make it difficult to maintain and grow crops in regions that depend on farming. The most important effect of climate change is global warming which is due to the increase in greenhouse gas emissions. The atmospheric carbon dioxide (CO2 ) level has been increasing day by day, and within last ten years it has increased to 413 ppm on 2020 from 388 ppm on 2010 (Global climate change NASA 2020). The increasing level of CO2 is the major contributor of temperature rise on earth surface (Ekwurzel et al. 2017). After ocean and geological C (C) pool, terrestrial ecosystems are the largest C pool which is approximately 3170 Pg(Pg; petagram = 1015 g) (Ahirwal and Maiti 2018; Ontl and Schulte 2012), and soil is the biggest terrestrial C sink, which stores R. Das (B) · S. Das Division of Soil Science and Agricultural Chemistry, ICAR-Indian Agricultural Research Institute, New Delhi, India A. Ghosh ICAR-Indian Grassland and Fodder Research Institute, Jhansi, Uttar Pradesh, India N. Basak · Priyanka · A. Datta Division of Soil and Crop Management, ICAR-Central Soil Salinity Research Institute, Karnal, Haryana, India R. Singh Centre for Environment Science and Climate Resilient Agriculture , ICAR-Indian Agricultural Research Institute, New Delhi, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2021 D. Pant et al. (eds.), Advances in Carbon Capture and Utilization, Energy, Environment, and Sustainability, https://doi.org/10.1007/978-981-16-0638-0_4

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nearly 2157–2293 pg of C to 1 m depth (Batjes 2014). According to Lal (2008), approximately 80% of the terrestrial C pool is stored into the soil. Therefore, any change in soil C level significantly influences the CO2 concentration in atmosphere (Ontl and Schulte 2012). With the changing climate, people nowadays realized the importance of sustainability. Here lies the importance of the term soil quality as it is considered as a conceptual translation of the sustainability concept towards the soil. Soil organic C (SOC) is a key indicator of soil quality. Because, in soil, C is mainly present in organic form and contributed 58% of soil organic matter (SOM) which affects the physical, chemical and biological properties of soil, and different soil processes are affected by soil microorganisms and eventually maintain the soil quality (Vasu et al. 2020; Ontl and Schulte 2012). Karlen et al. (2003) stated that though soil quality includes both inherent and dynamic properties of soil, but it mostly focusses on the dynamic properties that can be modified by different management practices and is mainly monitored in the soil surface (0–20 or 30 cm depth). According to the United States Department of Agriculture Natural Resources Conservation Service (USDANRCS), ‘Soil quality is the capacity of a specific kind of soil to function, within natural or managed ecosystem boundaries, to sustain plant and animal productivity, maintain or enhance water and air quality, and support human health and habitation’ (Karlen et al. 1997). Therefore, maintaining soil quality is very important for sustainable agriculture (Bünemann et al. 2018). The climate change and soil quality are strongly interdependent to each other, thus are greatly affected by soil C sequestration. The C sequestration is the process by which atmospheric C is removed and locked into soil for a longer period of time (Lal 2008). As, SOC is considered as an important part of global C cycle, therefore, any soil and climatic factors which affect the C cycle subsequently affect the C sequestration in soil and vice versa. Therefore, we start our discussion by explaining the C cycle in soil–plant–atmosphere continuum, understanding different mechanisms of C sequestration in soil along with dynamics and pools of SOC. We critically discuss various factors affecting the soil C sequestration especially the interaction of SOC with clay minerals and how it varies with the clay type, management practices, changes in land use system especially in salt-affected soil, organic matter quality and abundance of soil microorganisms. We then discuss how the C sequestration is related to soil quality and climate change. Lastly, we conclude by briefly discussing the important findings for better understanding the relations among C sequestration, climate change and soil quality.

4.2 C Cycle in Soil–Plant–Atmosphere Continuum Soil should be considered as a four-dimensional body (length, width, depth and time) when studying C cycle as progressive environmental process may alter SOC concentration. Theoretically, SOC should increase over time, and it would attain maxima after certain period of time. We may define SOC status as

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 SOC concentration =

(parent material, soil properties,

climate, landscape position and slope aspect) However, globally soils contain ~1500 Pg to 1 m depth (Batjes 1996) and 2344 Pg to 2 m depth (Jobbágy and Jackson 2000) of organic C, while soil inorganic C (SIC) stock is ~720 Pg and 950 Pg up to 1 and 2 m depths, respectively (Batjes 1996). However, presently CO2 concentration in the atmosphere is mounting from an average 1.5 ppm per year, i.e. 3.3 Pg C per year during the decade of 1990s (Batjes 1996) to 2.3 ppm during the last decade (Lindsey 2020). Researchers forecasted that CO2 concentration may increase from 800 to 1000 ppm by the end of twenty-first century, unless immediate management options are adopted. Globally, crop land covers ~20% of the earth surface and thus farming practices have a major influence on C exchange between soil and atmosphere. The rate of SOC accumulation depends on the size and capacity of the soil reservoir. The positive impact of SOC in crop land is far beyond the soil quality and fertility and extended to the protection of pollution of surface and ground water, minimization of greenhouse gases (GHGs) emission from terrestrial ecosystems (Swarup et al. 2000; Manna et al. 2018). Thus, stabilization mechanism, of C, SOC dynamics and total C stocks, has been discussed here.

4.2.1 Mechanism of C Stabilization in Soil Stabilization of C is mainly mediated by three mechanisms, i.e. chemical, physical and biochemical processes. (a) Chemical stabilization by organo-mineral complex formation through chemical or physiochemical bindings with minerals is present in silt and clays. Chemical stabilization protects SOC from microbial disintegration through physico-chemical association between SOM and soil matrix (e.g. soil clay and silt particles). Clay and silt in soil may facilitate formation of micro- and macroaggregates and safeguard SOM. But cultivation would tend to break this down and release C as CO2 . In addition to the clay content, clay types (e.g. 2:1 versus 1:1 versus allophonic clay minerals) influence the stabilization of organic matter. (b) Physical stabilization protects SOM from microbial decomposition by occluding within macro- and/or microaggregates and adsorption onto minerals (Tisdall and Oades 1982). The occlusion would result in accessibility of SOM to microbes through organo-minerals and organo-metal interaction (Ghosh et al. 2019a; Ghosh et al. 2016). Organo-minerals and organo-metal interaction involve various phenomena such as adsorption on mineral surfaces, complexation and precipitation. These complex phenomena promote SOM stabilization primarily (Ghosh et al. 2016). However, tillage breaks up soil aggregates, thereby increasing the availability of

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organic C for soil microorganisms (Modak et al. 2019). (c) Biochemical stabilization of SOM involves complex chemical transformation reaction of organic matter to recalcitrant compounds to prevent microbial attack resulting in stability (Ghosh et al. 2019b).

4.2.2 Soil Organic Carbon Pools and Dynamics As the global soil C pool is greater than the atmospheric and biotic pool combined, therefore, the atmospheric CO2 concentration will be affected by the changes in SOM content. It is imperative to comprehend SOC dynamics which is essential for mitigating the harmful effects of climate change as there are evidences about the significant potential of salt-affected soils for C sequestration (Lal 2004a, b; Setia et al. 2013).The SOC consists of several pools, namely active, slow and passive, with differential turnover rate ranging from months to over several hundred to thousands years. The transformational relationships among these pools have been depicted in Fig. 4.1. (a) (b)

(c) (d)

Structural litter fraction: This consists of straw, wood, stems and related plant parts. The C:N ratio varies around 150:1. These are high in lignin. Metabolic pool fraction: It comprises plant leaves, bark, flower, fruits and animal manure. The C: N ratio ranges from 10 to 25. This fraction contributes mineral nitrogen when it is decomposed. Active SOC pool: It is a labile form of C, comprising fresh plant and animal residues. This pool is linked to soil biological processes. Slow SOC pool: It is the intermediate phase between active and passive C pool, comprising detritus. This is associated with soil physical process and chemical activity.

Passive SOC pool: This pool comprises humus or non-labile form of C and is not biologically active. It is related to C sequestration and climate change.

4.2.3 Potential of C Sequestration The amount of C present in the soil is the function of land use change, soil type, climate (rainfall and temperature) and management practices. As (a) soil factors govern physically protected, i.e. potential C, (b) climate determines the net primary productivity, i.e. attainable C and c) management practices fix actual C (Fig. 4.2). These three terminologies are used in soil C sequestration study. They are SOCpotential , SOCattainable and SOCactual . SOCpotential is the SOC level that could be achieved if there were no limitations on the system except soil type. The value of SOCattainable is the realistically best case scenario for any production system. To achieve SOCattainable , no constraints to productivity (e.g. low nutrient availability, weed growth, disease,

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Fig. 4.1 Soil organic pool and dynamics in century model. Modified from Parton et al. (1987)

subsoil constraints, etc.) must be present. Decreased productivity, induced by the reducing factors, leads to lower returns of organic C to soil and lower actual organic C contents (SOCactual ) (Ingram and Fernandes 2001). The potential of SOC sequestration is enormous. World’s degraded soils (1216 Mha) and agricultural soils (4961 Mha) are capable of sequestering C (Lal 2004a, b). As high as 66–90 pg, C can be sequestered over 25–50 years in these soils (Lal 2004a, b). There is also a large potential of grassland for soil C sequestration.

4.3 Factors Affecting C Sequestration in Soil Soil C per se soil C sequestration is the fundamental of sustainability as well as soil quality. The C sequestration in soil depends on various factors like soil clay

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Fig. 4.2 Relationship between C sequestration situation and soil organic C (SOC) level. Modified from Ingram and Fernandes (2001)

content and its mineralogy, different management practices such as fertilizer and tillage, nature of organic matter in soil, changes in land use system especially in salt-affected soil and abundance of soil microorganisms. Moreover, the SOC content of top soil is mainly affected by climate and cultivation, whereas at deeper horizons by pedological traits such as clay content and mineralogical make up of soil (Rao et al. 2019).

4.3.1 Content and Type of Clay Minerals Clay minerals are the diverse group of hydrous layer alumino silicates, and most active soil particle due to their small size (90%) in feed gases (typically >90%) (IEA 2001). The high amount of energy requirement to provide the refrigeration is a major disadvantage of cryogenic separation of CO2 particularly for dilute gas streams (Burt et al. 2010). An additional disadvantage is that to avoid the blockages, water removal is must before the gas stream is cooled. It has certain advantage of straight making of liquid form of CO2 . Cryogenic separation is usually considered for high pressure, high concentration gases as obtained in pre-combustion capture or oxygen combustion (Figueroa et al. 2008).

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Soluble Carbonate-Based Systems

In this system, an aqueous carbonate is reacted with carbon dioxide to form bicarbonate and then releases CO2 after heating at certain temperature which further back to a carbonate (Arshad 2009). It has significantly lower energy requirement for regeneration as compared to amine-based absorption. Rochelle et al. (2006) investigated K2 CO3 /piperazine (PZ) (5:2.5 mol basis) having carbon dioxide absorption rate 10–30% enhanced as compared to 30% aqueous MEA solution. An approximately 5% lower energy was needed when compared 40 versus 30% for MEA. Further, structured packing shows an added 5% energy savings and also additional 5–15% reduction in energy was obtained by multi pressure stripping (Rochelle et al. 2006).

8.3.2.4

Ammonia-Based Systems

The operation of ammonia-based system is like operation of amine-based system. In this system, ammonia and its derivatives are used and reacted with CO2 by means of various mechanisms (Arshad 2009). Ammonium carbonate reacted with carbon dioxide and water to form ammonium bicarbonate. In this system, heat of reaction is considerably lower than amine-based absorption which resulted in saving of energy (Resnik et al. 2004, 2006). Ammonia-based system has a numerous advantages as compared to amine systems such as: high absorption capacity, no degradation during complete processing, low cost, tolerance to oxygen in the flue gas, and regeneration at pressure of 20 bar. Ammonia losses during regeneration due to higher volatility relative to MEA are the major concern (Yeh et al. 2005).

8.3.2.5

Membrane Systems

In membrane system, the best features of membranes and solvent are used to develop the solvent supported membrane system for carbon dioxide capture (Arshad 2009) where the flue gas passed through a bundle of membrane tubes, and an amine solution flowed through the shell side of the bundle by a physical or chemical interaction (Scholes et al. 2008). CO2 passed from side to side to the membrane and amine absorbed the CO2 . At the same time, impurities are blocked from the amine which further decreases the loss of amine (Falk Pederson et al. 2000). The variety of membranes is used for the gas separation such as: zeolites, polymeric, and porous inorganic membranes (Scholes et al. 2008). Typically, a single unit of membranes may not be obtained the desired separation; hence multiple stages are needed necessary which may lead to increase in complexity of system, high energy consumption, and high costs. Hence, much development is required in this area for carbon dioxide capture in power plants (Figueroa et al. 2008).

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Enzyme-Based Systems

Generally, biologically methods involve the biological reaction occurring naturally for CO2 with living organisms which may also employ for capture of CO2 . An enzymatic system achieves CO2 capture and liberate by imitating the mechanism of the mammalian respiratory arrangements (Figueroa et al. 2008). A laboratory scale demonstration was performed using carbonic anhydrase (CA) in a hollow fiber membrane module and observed 90% capture of CO2 . In comparison to MEA process, enzyme-based system has a significant technical improvement (Arshad 2009).

8.3.2.7

Adsorption

Adsorption may be performed as a temperature swing (TSA) or pressure swing adsorption (PSA). In PSA, the gas mixture passed through an adsorbent bed at elevated pressure to reach the equilibrium. When the bed is fully saturated with CO2 , the bed is regenerated by reduced pressure (Chaffee et al. 2007; Arshad 2009). In TSA, the adsorbent bed is regenerated by increasing bed temperature. The working with solids is difficult as compared to liquids, and also solids have low capacity and selectivity; hence, it has been not commercialized (IEA 2001). Highly porous adsorbents have been used for CO2 capture by physical adsorption. The number of materials has been employed for CO2 capture: silica, zeolites, metal-organic frameworks, covalent organic frameworks, carbonaceous materials, etc. Hedin et al. (2013) presented critical review of different adsorbents for CO2 capture.

8.3.2.8

Metal Organic Frameworks (MOFs)

Metal organic frameworks (MOF) are a novel hybrid material fabricated from metal ions with well-defined coordination geometry and organic bridging ligands (Arshad 2009). The high storage ability and the low recovery of heat are observed in MOF. The highest absorption capacity was obtained with MOF-177 having the highest surface areas (Willis et al. 2006).

8.3.2.9

Supported Solid Material

Nelson et al. (2006a, b) experimented sodium carbonate (Na2 CO3 ), a supported sorbent. This supported sorbent is less expensive and regenerable and formed sodium bicarbonate (NaHCO3 ) by reaction with water and CO2 . The sorbent is regenerated by temperature swing process with release of water and CO2 . Over 90% CO2 was observed at pilot plant with lower capital costs and energy requirements as compared to MEA system (Nelson et al. 2006a, b).

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8.3.3 Need of ILs Relative to Amine A variety of solvents have been employed for chemical absorption of CO2 (Rochelle 2009). Because of high reactivity, high thermal stability, high capacity, and high selectivity, most of the amines are extensively used carbon dioxide absorption (Riemer and Ormerod 1995; Kothandaraman 2010). Absorption by MEA to capture postcombustion carbon dioxide is still considered the most efficient and the least expensive among available technologies (Jamal et al. 2006; Oyenekan and Rochelle 2006; Henni et al. 2008). In addition to earlier mentioned, the amine technologies have numerous drawbacks of solvent degradation, toxic by product release, operational instability, and frequent equipment maintenance due to certain reasons (Arshad 2009; Zhang et al. 2013; Liu et al. 1999; Yu et al. 2012; Torralba-Calleja et al. 2013). Hence, it is extremely required to exploit new solvents to perform significantly better than conventional amines for the thermal stability, energy requirement, chemical degradation, corrosivity, and volatility (Ramdin et al. 2012), In the past few decades, ionic liquids (ILs) have been emerging as a potential option to the amines due to their extraordinary properties such as: negligible volatility, high chemical/thermal stability, and most important tunability (Ramdin et al. 2012; Aghaie et al. 2018; Rochelle 2009; Yu et al. 2012; Anthony et al. 2002). Extensive work has been presented in the literature for capture of CO2 using various ILs (Aghaie et al. 2018). Torralba-Calleja et al. (2013) listed few benefits of ILs as compared to the amine for absorption of CO2 . These benefits are included as: less energy requirement for regeneration of ILs, almost no chance for reaction with impurities and hence no corrosion with high chemical and thermal stability (>300 °C) of ILs, due to negligible vapor pressure, no loss in the gas stream in regeneration, and high potentials to make tuneable ILs for specific application by adjusting cations and anions.

8.4 Ionic Liquids Ionic liquids (ILs) are liquids consist of cations and anions (Arshad 2009). Ionic liquids are different than ionic solutions. Ionic solution is a salt solution in molecular solvent with 100 °C or below melting point (Arshad 2009). A liquid is formed when sodium chloride (NaCl, mp 801 °C, a common salt, is heated to high temperature which consists completely ions, a molten salt and not IL. ILs are liquid at room temperature. In literature, room temperature molten salts, fused salts, ionic melts, organic ionic liquids, liquid organic salts, non-aqueous ionic liquids, molten salts, and ionic fluids are found as few alternative labels for ILs (Welton 1999; Stark and Seddon 2008). ILs have unique properties which attracted them in many applications. The ILs have negligible vapor pressure at the ambient conditions due to strong ion–ion interactions relative to other intermolecular forces (London forces and ion-dipole interactions) in organic solvents (Henni et al. 2013; Aghaie et al. 2018). In other properties,

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ILs are superior to conventional organic solvents, such properties are: large electrochemical window, high thermal stability, and capacity to dissolve various polarities compounds (Zhang et al. 2004). In addition, physical and chemical properties of ionic liquids can be tuned by designing suitable anion and cation for specific applications (Wasserscheid and Welton 2008). Often, ILs are referred as “green solvents” due to negligible vapor pressure which eliminate release of solvent (Arshad 2009; Anthony et al. 2004). In view of environmental concern, ILs are characteristics of: low vapor pressure, non-volatile, high chemical stability, inflammable, high thermal stability, large electrochemical window, tuneable and designer character, tunable polarity, wide liquid temperature ranges, high ionic conductivity, high loading capacity, easy recyclability and diversiform structure/property modulation, excellent solvent properties, and recyclable which make them environmentally friendly compared to other chemicals such as amines (Yang et al. 2011; Ghandi 2014; Welton 1999; TorralbaCalleja et al. 2013). The tuneability of cation and anion of ILs is important feature which can be obtained by varying the structures of ions and hence their properties such as Lewis acidity, density, hydrogen-bonding capability, viscosity, gas solubility, hydrophobicity, and conductivity (Plechkova and Seddon 2008; Rogers et al. 2000). Ionic liquids (ILs) (composed of cations and anions) with a low melting point ( [C6 mim][Tf2 N] which interpreted as, the solubility increases as the numbers of fluorine in the alkyl side (Anderson et al. 2007; Muldoon et al. 2007). Anion has significant control on solubility of CO2 and the bis(trifluoromethylsulfonyl)-imide anion ([Tf2 N]) has the maximum affinity for CO2 . The solubility order is observed for anion as [NO3 ] < [DCA] < [BF4 ] < [PF6 ] < [CF3 SO3 ] < [Tf2 N] < [methide] (Aki et al. 2004). The strong coulombic interactions due to more fluorine atoms are responsible for higher solubility of CO2 (Zhao et al. 2012). Besides CO2 other gases such as CH4 , C2 H4 , C2 H6 , CO, NO, O2 , H2 , N2 , etc. are also the constituents of flue gas from a power plant, syngas, and natural gas. ILs have highest solubility and selectivity relative to other gases (Zhao et al. 2011). The anion plays a key role in the absorption of CO2 , whereas the cation is supposed to have a secondary role (Aki et al. 2004). Kanakubo et al. (2005) studied the effect of the anions with [bmim] cation at 333 K and solubility of CO2 decreasing in order of the anions: [C7 F15 CO2 ] > [Methide] > [Tf2 N] > [PF6 ] > [DCA] > [BF4 ] > [MeSO4 ] > [SCN] > [NO3 ]. Anthony et al. (2002) performed the experimental study to investigate the solubility of CO2 and other gases (nitrogen, ethane, argon, ethylene, hydrogen, oxygen,

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carbon monoxide, and methane) in 1-n-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF6 ]. The significant difference in solubility for CO2 relative to other gases was observed. The solubility of the various gases in [hmpy][Tf2 N] at 298 K is observed as SO2 > CO2 > C2 H4 > C2 H6 > CH4 > O2 > N2 (Anderson et al. 2007). Similar trend was observed for solubility in [bmim][Tf2 N], [bmim][PF6 ], and [hmim][Tf2 N] (Anthony et al. 2002, 2005; Anderson et al. 2007). Jacquemin et al. (2006a, b) investigated the solubility of various gases in [bmim][PF6 ] and [bmim][BF4 ] which was observed in the decreases way as: CO2 > H2 > CO > N2 > O2 > Ar > CH4 > C2 H6 . The absorption mechanism for carbon dioxide capture in conventional ILs is mainly by physical absorption. The anions of ILs have a significant control on the CO2 solubility than the cations of ILs of ionic liquids. Conventional imidazolium-based ILs are used for CO2 capture having less corrosion of the absorption column and other equipments. Also, the heat capacity of these ILs is almost 1/3rd of those aqueous systems, which further reduces the investment and operating cost (Perissi et al. 2006; Soosaiprakasam and Veawab 2008). Conventional ILs can be easily regenerated using heat treatment, nitrogen bubbling, pressure sweep with vacuum (Li et al. 2008a, b; Sanchez et al. 2007). The major drawback of conventional ILs for the CO2 absorption is lower capacity than traditional alkanomine process (Zhao et al. 2012). The capture of CO2 using pure conventional ILs from the flue gas of power plants (coal or natural gas-based) is not an encouraging option since conventional ILs have lower absorption capacity for CO2 with lower pressure (Zhang et al. 2012). Hence, ionic liquids with functionalized and other activated using another molecule with chemical sorption or both physical and chemical sorption must be obtained to trounce these shortfalls.

8.5.2 Functionalized ILs The use of conventional ILs, for carbon dioxide capture from flue gas is mired due to the low capacity and solubility ( phosphonium >

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imidazolium and anions in the order of BF4 > PF6 > Tf2 N.of PILs (Zhao et al. 2012). Furthermore, the sorption/desorption rates of the PILs are quite fast as compared to other ILs. These polymers are very prospective as sorbent and membrane materials for CO2 separation (Zhang et al. 2013).

8.5.5.2

Novel Polymerized ILs

The innovative PILs are polytriazoliums (PTA), deep eutectic monomer (DEM) and polyurethane (PU)-based ILs. Triazolium has two isomers depend on nitrogen position within ring as 1,2,3-, and 1,2,4-triazoliums. Deep eutectic solvents are non-toxic, cheap, and alternatives to ILs (Abbott et al. 2004). Deep eutectic monomers (DEMs) are molecular complexes formed by mixing hydrogen bond donor and acceptor which are undergone photopolymerization or polycondensation to make PILs based on DEM (Isik et al. 2016a, b). ILs can be incorporated into polyurethanes to make new PILs. Many PILs have been synthesized based on cationic polyurethanes using imidazolium or phosphonium and various diisocyanates, cations and anions (Williams et al. 2008; Morozova et al. 2017).

8.5.5.3

Biomaterial-Based PILs

Chitin and chitosan are the natural biomaterial which can be a considered as a substitutes for amino-functionalized synthetic polymers dissolving in the 1-butyl-3methylimidazolium chloride ([BMIm]Cl). These polymeric ILs can be used for CO2 capture as it has a strong ability to disrupt hydrogen bonds (Xie et al. 2006). Chitosan is an N-deacetylated product of chitin (natural polymer) having similar structure of cellulose (Foster and Webber 1960). Neat [BMIm]Cl and chitosan powder has almost no ability for absorption of carbon dioxide (Yang et al. 2011). But with 10 wt% chitosan/IL and chitin/IL solutions demonstrated approximately 8.1% and 3.8% CO2 fixing efficiency, respectively, at equilibrium. Chitosan has amino groups and chitin has no amino groups. The sorption reached to 98% for chitosan/IL solution in 180 min (Xie et al. 2006). A mixed IL 1-butyl-3-methylimidazolium chloride ([C4 mim][Cl]) with chitin or chitosan is used by Xie et al. (2006). For the chitosan/IL mixture, the measured absorption capacity exceeds the theoretical capacity due to the physical absorption of CO2 in these liquids. Physical absorption is also observed for the chitin/IL mixture (Zhao et al. 2012).

8.5.5.4

Performance of PILs

Cation and anion play significant role in features and characteristics of PILs. The capacities of PILs for different cations and anions are observed as: ammonium > pyridinium > phosphonium > imidazolium and BF4− > PF6− > (CF3 SO2 )2 N−

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[95,96]. Backbone polymers in PILs have the CO2 capacity performance in the order of polystyrene > polymethylmethacrylate > polyethylene glycol (Tang et al. 2005b, c, d). The PILs based on acid-containing poly-DEMs have the sequence for CO2 capture as: citric acid > oxalic acid > malonic acid (Isik et al. 2016b). Morozova et al. (2017) studied PILs based on 4,4 -methylene bis(cyclohexyl isocyanate) and diquinuclidinium as cationic backbone along with thirteen various anions and order is observed as: BF4 > Ac > PF6 > B(CN)4 > CH3 CH(OH)COO > NO3 > (CF3 CF2 SO2 )2 N > (CF3 SO2 )2 N > FeCl3 Br > CF3 SO2 -N-CN > N(CN)2 > ZnCl2 Br > CuCl2 Br. The PILs are very viscous at room temperature and easy to be applied as membrane materials. Hence, the combination of PILs and SILMs may provide higher CO2 absorption capacity (Zhao et al. 2012).

8.5.6 Supported Ionic Liquids Membranes (SILMs) For better performance of ILs in terms of absorption capacity, efficiency, and rate, ILs are used as a solvent and employed in SILs (supported liquid membranes). The supported liquid membrane, generally, has a supporting membrane which may be porous or non-porous and a solvent phase (be located in the pores or between two non-porous membrane sheets) (Ramdin et al. 2012). The solute molecules are transported by diffusion/dissolution makes possible a separation or reaction or both in liquid phase and then desorbs at the other face of the membrane (Kumelan et al. 2006). During the evaporation of liquid phase, solvent loss is the major disadvantages of conventional supported liquid membranes (Kumelan et al. 2010) which can be eluded by using ILs as a solvent because of exceptional properties which includes: low volatility, high thermal stability, and high chemical stability (Jacquemin et al. 2006a, b). Few excellent reviews are available on supported IL membranes, which can be referred for further details (Bara et al. 2007a, b; Jalili et al. 2010). The supported ionic liquids membranes (SILM) are explored for CO2 absorption which is prepared by using IL as liquid phase of membrane (Zhao et al. 2012). SILM has higher surface area for contact between gas and ILs. The viscosity and nonvolatility are the unique properties of IL which can prevent the membrane solvent flowing away from porous membrane, which greatly extends the life of SILM without losing the separation ability and selectivity for CO2 (Zhao et al. 2012). SILM is suitable for CO2 from flue gases at high temperature due to their non-flammability and high thermal stability.

8.5.6.1

Supported Conventional IL Membranes

Scovazzo et al. (2004) investigated conventional ILs supported on the porous hydrophilic polyethersulfone (PES) with four water stable anions: trifluoromethanesulfone [CF3 SO3 ], dicyanamide [DCA], chloride [Cl], and bis(trifluoromethanesulfonyl) amide [Tf2 N]− . The obtained selectivities (4–61) and

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permeabilities (2.6 × 10−8 to 7.5 × 10−8 cm3 cm/cm2 s kPa) are relatively higher than polymer ILs (Zhao et al. 2012). A better absorption capacity of carbon dioxide was achieved by supported [C4 min][Tf2 N] to porous Al2 O3 (Baltus et al. 2005), [C4 mim][PF6 ] to a porous (ceramic or zeolite) material (Moriya et al. 2007), and [C4 min][BF4 ] on the PVDF (poly-vinylidene fluorolide) (Park et al. 2009). The structure of the support has a huge impact on stability of membrane, and the sponge structure has higher stability than a finger structure observed for supported [C2 mim][Tf2 N] on the polymeric hollow fiber (Kim et al. 2011).

8.5.6.2

Supported-Functionalized and Other IL Membranes

The separation of CO2 and CH4 gas has been investigated using supported 1butyl-3-methylimidazoliumbis (trifluoromethylsulfonyl)-imide ([C4 mim][Tf2 N]), N-aminopropyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C3 NH2 mim][Tf2 N]) and N-aminopropyl-3-methylimidazolium trifluoromethanesulfone ([C3 NH2 mim][CF3 SO3 ]) on the porous hydrophilic polytetrafluoroethylene (PTFE) membrane (Hanioka et al. 2008; Shishatskiy et al. 2010). A higher permeability for CO2 is observed in amine-functionalized SILM as compared to other SILM as there is simple solution-diffusion mechanism in conventional SILM while CO2 permeated by chemical reaction mechanism. These functionalized SILMs have high stability and no detectable loss (for 260 days). The high temperature prohibited the separation and reaction of CO2 and amine moiety, hence the permeability of CO2 decreased with increase in temperature (Zhao et al. 2012; Jindaratsamee et al. 2011). Ilconich et al. (2007) prepared by insertion of cross linked nylon supports and depositing [H2 NC3 H6 mim][Tf2 N] on the membrane for separation of carbon dioxide from hydrogen. The higher temperature reduces the permeability and it may be due to the impact of high temperature on stability of carbonate, which allow to dominate the diffusion phenomenon (Hanioka et al. 2008).

8.5.6.3

Comparison and Performance of SILM

The hydrophobic supported SILMs are more stable than hydrophilic support, and these SILMs have a high attraction for CO2 over other (Zhao et al. 2012; Neves et al. 2010). The presence of water vapor in gas stream increases the permeability but decreased selectivity considerable. The decrease in selectivity may be due to the formation of water clusters inside the membrane; it is more significant for the less hydrophobic conventional IL (Zhao et al. 2012; Neves et al. 2010). As the operating temperature increases, enlargement of free volumes inside the polymer membranes occurred, and hence, the permeability increases but the selectivity decreases. It occurs as the permeability is more dependent on the structure of membrane than interaction of gas molecules (Zhao et al. 2012).

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The new SILMs (supported on polymeric hollow fiber) confirmed that the selectivity increases with increase in pressure and maintain mechanical stability (Kim et al. 2011). The support with dense polymer chains having a torturous structure has stronger resistance to pressure as compared to a cylindrical void structure (Zhao et al. 2012). However, the supported conventional ILs membranes are unsuitable at high pressures due to decrease in gas solubility with increase in pressure. The properties of ILs can be improved sufficiently by the insertion of an organic salt with amine group functionality (Iarikov et al. 2011). The combination of supported IL membranes with functionalized IL may be superior option for capture of carbon dioxide at higher pressures and temperatures (Scovazzo et al. 2009). The SILM has numerous disadvantages including thick membrane (≥150 μm) (Scovazzo et al. 2004; Ilconich et al. 2007; Bara et al. 2009), not applicable for high temperature flue gases for CO2 capture. Further, to develop more economical and efficient SILMs, in-depth investigation on the role of anion and cation of ILs and membrane structure has been needed to produce more stable, more permeable, and thinner membranes (Scovazzo 2009).

8.5.7 Supported IL Phase (SILP) Materials The material for CO2 capture should be cheaper, easier to handle, resistant to degradation and endure at higher temperatures and pressure (Kolding et al. 2012). A lot of attentions have been received to employ the solid support to impregnate ILs (Shahrom et al. 2018). The supported ionic liquid phase (SILP) materials have been exploring the advantages of the ILs and its support to overcome limitations of intrinsic mass transfer by improving surface area (Kolding et al. 2012). Yu et al. (2012) reviewed many solid supports and observed that amine impregnated solid support has high CO2 adsorption capacity. Romanos et al. (2014) studied an inverse SILPs, a novel supported ionic liquid phase systems. SILP was prepared by insertion of ILs into the nanoporous materials (e.g., silica nanoparticles) which demonstrated sufficiently high CO2 absorption capacity with fast kinetics (Shahrom et al. 2018). The CO2 sorption capacity of 1.5–3.3 mmol of carbon dioxide/g of IL and the CO2 /N2 selectivity of >200 was found which make it eligible as a promising material to capture CO2 at industrial scale. The SIPL, tetrahexylammonium prolinate [N6666 ][Pro] IL (40%w/w loading of IL) with silica support and also other anions L-Isoleucinate [Ile], Glycinate [Gly], LAsparaginate [Asn], and L-Tyrosinate [Tyr] have been investigated for CO2 capture (Kolding et al. 2012). The good temperature stability and high absorption capacity for CO2 were found for these SILP materials. The absorption of carbon dioxide was confirmed as reversible using prolinate SILP material which was stable at 80 °C for desorption for 24 h and it is appropriate for reversible CO2 capture in industrial applications using a temperature swing process (Kolding et al. 2012).

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Polesso et al. (2019) investigated silica and alumina impregnated with imidazolium ILs having [Br] and [Tf2 N] anions by physical wet method for CO2 absorption. It has improved CO2 capture and higher selective capacity (CO2 /N2 ) (~6.1). The support of commercial alumina with 20 wt% of mbmim[Tf2 N] obtained higher CO2 /N2 selectivity (~9.5). Also, fast sorption kinetics was observed using this material relative to pure ILs. Shahrom et al. (2018) synthesized activated carbon impregnated with 10 wt% of 1-hexyl-3-methyl imidazolium bis (trifluoro methyls ulfonyl) imide [hmim][NTf2 ], (vinylbenzyl) trimethylammonium glycine [vbtma][gly], and poly[vbtma][gly] to investigate the capture of CO2 . The activated carbon impregnated with [vbtma][gly] gives higher capacity with 19.91 mmol CO2 /g at 20 bar. Further, a series of activated carbon impregnated with 10, 20 and 30 wt% of [vbtma][gly] were synthesized to study the optimum composition of [vbtma][gly] for capture of CO2 and obtained at 20 wt% of poly[vbtma][gly]. Zhang et al. (2009) observed the almost equimolar absorption within 80 min using dual amino-functionalized phosphonium ILs, (3aminopropyl) tributylphosphonium AA salts ([aP4443 ][AA]) supported on SiO2 . Zhai and Rubin (2017) experimented PVDF hollow fiber membrane contactors with 1-ethyl-3-methylimidazolium ethyl sulfate [emim][EtSO4] and 1-ethyl3-methylimidazolium acetate [emim][Ac] which are showing physical and chemical absorption, respectively. The fibers with the ILs immobilized D + [emim][EtSO4] would be promising for capture of CO2 due to enhanced CO2 permeance (43% increase) as compared to neat membrane. Carbon dioxide capture has been investigated by Zhang et al. (2006a, b) using functionalized ILs [P(C4 )4 ][AA] having a series of amino acids as an anion with phosphonium ILs supported on porous silica gel. These have been synthesized by reaction of tetrabutylphosphonium hydroxide [P(C4 )4 ][OH] with amino acids, including glycine, l-alanine, l-b-alanine,l-serine, and l-lysine. These ILs, [P(C4 )4 ][b-Ala]-SiO2 , [P(C4 )4 ][Gly]-SiO2 and [P(C4)4 ][Ala]-SiO2 reached to CO2 absorption in 60% biodegradability (Gathergood et al. 2006). A large number of ester/ether group imidazolium-based ILs experimented and ester-functionalized ILs found higher degradation and other have not any significant effect (Morrissey et al. 2009). Morrissey et al. (2009) and Farrell et al. (2009) found that the [octylsulphate] anion has significant role in high biodegradation of ILs. Biochemical oxygen demand (BOD5) was evaluated for the biodegradation of pyridinium, ammonium, phosphonium, and imidazolium-based ILs and no degradation was observed (Wells and Coombe 2006). Similarly, no biodegradation of [bmim][PF6 ] was observed as per OECD 301D by Gathergood et al. (2004). Docherty et al. (2007) investigated [ompy], [hmpy], [bmpy], [omim], [hmim], and [bmim] cations with [Br] anion for biodegradability. The pyridinium ILs obtained the higher biodegradability compared to the imidazolium ILs. Esterfunctionalized pyridinium ILs having anions (octylsulphate, PF6 , Br, iodide, and bis(trifluoromethylsulfonyl)imide) were investigated for biodegradability by Harjani et al. (2009). The effect of the anion of ILs on the biodegradability was not significant (Zhang et al. 2010a, b; Harjani et al. 2009). Pyridinium ILs with an carbamate, acetal, or ether functionality have considerably lower biodegradation (Ford et al.

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2010). The lactate or napthenic acid anions of 2-hydroxyethylammonium-based ILs were found to be very biodegradable (Yu et al. 2006, 2008, 2012; Pavlovica et al. 2011). Atefi et al. (2009) functionalized phosphonium cation with an ether, alkane, alcohol, or ester moiety and paired with octylsulphate, triflimide, or halide anions. The ILs having octylsulphate anion observed an increased biodegradation and [PF6 ] > [BF4 ] > [Cl] > [DCA] > [Br]. Overall the toxicity of ILs is increased with length and number of alkyl chain of the cation. In future, more unified and efficient methods should be used to assess the toxicity of ILs (Ramdin et al. 2012).

8.7 Conclusion and Discussion The present CO2 capture methods, specifically amine system, usually experience the high capital and operating costs, degradation of solvent, high loss of solvent, solvent corrosiveness, solvent toxicity, high volume of absorption column, and high regeneration energy (Aghaie et al. 2018). The capture of carbon dioxide using ILs is an emerging technology which is interesting and promising alternative due to the exceptional properties of ILs including thermal stability, negligible volatility, high absorption capacity, tunable structure and hence its properties (Zhang et al. 2012). New and novel ILs can be designed based on relation among structure, properties, and absorption mechanism which plays grave function for development of technology. ILs must have three essential characteristics: high absorption/separation/capture capacity, low viscosity for better fluid flow behavior, cost effectiveness, low energy for regeneration of the ILs (Yang et al. 2011). In general, the solubility of CO2 in ILs increases with increase in molar volume, molecular weight, and free volume of ILs (Ramdin, et al. 2012). Carvalho and Coutinho (2010) reported that the solubility of CO2 in ILs is dominated by entropic effects rather than solute–solvent interactions. The solubility of CO2 in ILs should be

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investigated in per volume solvent (molarity) or on a molality basis and it should not be in mole fraction basis due to the strong molecular weight (molar volume) effect (Karadas et al. 2010). The capture of CO2 in conventional ILs is mainly a physical absorption mechanism and solubility is very low at conditions of post-combustion capture as compared to the amine process. The absorption capacity of ILs for CO2 can be has been effectively enhanced by functionalization of conventional ILs with an amine and other active moiety. In this manner, functionalized ILs allow carbon dioxide to react with the amine chemically and achieved the better than (1:1) reaction stoichiometry relative to conventional amine systems (Ramdin et al. 2012). Even though, task specific or the functionalized ILs are more appropriate for capture of carbon dioxide, these are additionally 2–4 times costlier as compared to conventional ILs. Apart from solubility, selectivity is also significant in industrial separation. Generally, carbon dioxide is far soluble than other (e.g., H2 , N2 , O2 ) and hence higher selectivity for CO2 except SO2 and H2 S which better soluble than CO2 in ILs (Ramdin et al. 2012). Based on regular solution theory, CO2 /CH4 and CO2 /N2 selectivity can be enhanced using ILs having a low molar volume. The main conclusions based on the available data and study can be obtained as: anions have significant role for CO2 solubility in ILs; fluorination increases solubility with little effect of cations and significant effect of anions; long chains of alkyl or ether-functionalized cations improve CO2 solubility (Ramdin et al. 2012; Lei et al. 2014; Makino et al. 2014; Anderson et al. 2007). The competent capture of carbon dioxide as a green house gas from flue gases is extremely difficult in view of technological status and economic performance (Ramdin et al. 2012). In general, available technologies comprises extremely high energy penalty, consequently, the cost of capture of CO2 for various gases which makes these technologies less attractive for large-scale commercial applications. Number of alternative options are under consideration as process and material. In specific, ILs are the promising material for the capture of CO2 due to their distinctive properties. The evaluation of energy and economic performance of ILs-based technologies are key steps for industrial application and its commercialization. Carbon dioxide capture by ILs have been getting much attention among various emerging technologies (Zhang et al. 2012). Because of negligible vapor pressure of ILs, less energy consumption for absorption/desorption, no contamination, and no significant losses of ILs are observed. The energy losses using [bmim][Ac] are reduced by 16%, investment by 11%, and equipment footprint by 12% as compared to monoethanolamine (MEA) process (Shiflett et al. 2010). The energy savings of 12–16% is reported as compare to MEA process. Thus, ILs offers a potential mode for cost and energy efficient carbon dioxide capture from flue gases of various industries specially power plants (Zhang et al. 2012). Zhai and Rubin (2017) performed the feasibility and costing of 1-hexyl-3methylimidazolium bis(trifluoromethylsulfonyl)imide for capture of carbon dioxide from pre-combustion pathway. The energy consequences are mainly due to compressors and solvent pumps; and the compressors and absorbers have major cost share in

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capital cost. Using the Integrated Environmental Control Model (IECM) for power plant assessments, $62/t CO2 is the cost avoided by the IL-based CO2 capture system. The preliminary study on the performance and cost for IL-based and Selexol-based CO2 capture systems show that an IL-based carbon dioxide capture system may be possible feasible option to amine system. Commercial availability of ILs are essential for its industrial application, but still many of the ILs are at laboratory scale. Hence, focus must be given on the low cost production of these ILs and make it available for commercialization and industrial applications through pilot plant studies (Zhang et al. 2012). Based on the available data on biodegradability and toxicity of ILs, it can be depicted that many commonly ILs used for CO2 capture are non-biodegradable and highly toxic. Based on the critical review and discussion in literature on ILs (Joglekar et al. 2007), Ramdin et al. (2012) presented few barriers for commercialization of ILs. The glimpses of these barriers are stated as: need of physicochemical and thermodynamic data (only for few ILs are available; still more data on viscosity, density, diffusion coefficients, surface tension, specific heat, heat of fusion, chemical/thermal stability, corrosivity, water solubility, etc. is needed); need of lifetime and recyclability studies; as such no scale-up studies are available; need of engineering investigations (process and manufacturing costs, systematic process engineering, scale up); need of health, safety, and environmental performance studies, i.e., toxicity and biodegradability; and finally the high cost of ILs. In nutshell, the flexibility with intrinsic advantages of ILs for capture of CO2 are providing augment to a promising and expansive field. The few ILs are highly attractive for absorption of CO2 although capture rate is almost comparable to aqueous amine technologies. The main challenges affecting ILs for capture of CO2 are cost, availability, compatibility, and purity (Torralba-Calleja et al. 2013). The major criteria for perfect capture of CO2 are high solubility of CO2 , less energy requirement for regeneration, relatively lower cost compare to amine and other systems, life of ILs for reusability, and eco-friendly. Additionally, apart from process and engineering design features of capture of carbon dioxide processes using ILs, their low solubilities, high viscosity, price of ILs and processing, purity, compatibility, and availability, are the key challenges to develop suitable methods to carbon dioxide capture by using ionic liquids at commercial and an industrial scale (Aghaie et al. 2018). Still there is a lot of scope to have a systematic study on the development of suitable material to overcome all barriers in present ILs to have appropriate system of CO2 capture.

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Chapter 9

The Climate Smart Agriculture for Carbon Capture and Carbon Sequestration: The Challenges and Opportunities S. Senjam Jinus, Tracila Meinam, Koijam Melanglen, Minerva Potsangbam, Akoijam Ranjita Devi, Lucy Nongthombam, Thoudam Bhaigyabati, Helena D. Shephrou, Kangjam Tilotama, and Dhanaraj Singh Thokchom

S. Senjam Jinus (B) · H. D. Shephrou College of Horticulture and Agri-Biotechnology, FEEDS Group of Institutions, Hengbung, Kangpokpi, Manipur 795129, India T. Meinam · K. Melanglen Department of Horticulture, School of Agriculture, School of Horticulture, Pandit Deen Dayal, Upadhyay Institute of Agricultural Sciences, Utlou, Manipur 795134, India M. Potsangbam Department of Horticulture, North Eastern Hill University, Tura Campus, Chasingre, West Garo Hills, Meghalaya 794002, India A. R. Devi Faculty of Agricultural Sciences, SRM Institute of Science and Technology, SRM Nagar, Kattankulathur, Tamil Nadu 603203, India L. Nongthombam Biswanath College of Agriculture, Assam Agricultural University, Biswanath Chariali, Assam 78176, India T. Bhaigyabati Institutional Advanced Level Biotech Hub, Imphal College, Imphal, Manipur, India K. Tilotama Foundation for Environment and Economic Development Services, Henbung, Kangpokpi, Manipur 795129, India D. S. Thokchom Ethno-Medicinal Research Centre, FEEDS Campus, Hengbung, Kangpokpi, Manipur 795129, India © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2021 D. Pant et al. (eds.), Advances in Carbon Capture and Utilization, Energy, Environment, and Sustainability, https://doi.org/10.1007/978-981-16-0638-0_9

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9.1 Introduction Acute agriculture practice that increases production livable, improves adaptation, diminishes or removes greenhouse gases is the hallmarks of climate smart agriculture. In this context, the key objective of climate smart agriculture in capturing carbon can be defined as food protection and growth, in which the three interlinked pillars efficiency, adaptation, and mitigation (Fig. 9.1) are required to achieve this objective (FAO 2013; Lipper et al. 2014). To date, due to climate crises in the atmosphere resulting from an increase in the concentration of carbon dioxide, great interest has been drawn in the possibility of increasing the rate of carbon capture through climate smart agricultural (Fig. 9.2) practices which are described below in this chapter, as well as through genetic engineering to capture carbon and storage. However, in the present climate change sense, little exposure is given to the concepts of carbon capture in agricultural points of view, which is meant to be an effective, smart way to mitigate potential pollution impacts on ambient greenhouse gas concentrations. Possible approaches and climate smart agriculture that affect the increased pace of carbon dioxide reduction from the environment through up-to-date farming practices to boost gigantic activities, preserving carbon by habitats such as plant waste, decomposing detritus, and organic soil are illustrated in the form of various literatures insights in this paper. Throughout this episode, soils of agricultural land that are extremely active habitats may become microbial scrubbers and carbon capture by trapping CO2 from the atmosphere. In consonance with Schahczenski and Hill (2009), creative agricultural methods such as tillage reduction, advanced sustainable farming programs, soil regeneration, soil use reform, and irrigation and water management are need of the hour in which farmers, city folks, hills dweller, urban gardener, and whole agrarian community can combat climate change. By doing such clever management practices, it will provide many opportunities in all three pillars Fig. 9.1 Climate smart agriculture and its three pillars. Image by Dr Senjam Jinus S.

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Fig. 9.2 Precision agriculture (PA)

of climate smart agriculture (Fig. 9.1) to increase productivity, boost farm energy production and enhance air and soil quality.

9.2 Climate Smart Agriculture and Carbon Sequestration In this chapter, we provide a bird’s eye view on climate smart agricultural practices which include intercropping, crop rotation, mulching, agroforestry, increased harvesting, protection of land, sustainable field production, conservative farming,

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increased water management, and phytosequestration. As a part of these resource management practices, soil carbon emissions can be minimized by minimizing degradation of soil organic material, lowering deforestation and supplying material inputs.

9.2.1 Agroforestry Annually, the current global net biome productivity is around 3 gigatonnes (Gt) and at measurable amounts, CO2 is captured by plants in all biomes (Jansson et al. 2010). From this biome biological sequestration would mainly come from prevented deforestation in tropical land (Tavoni et al. 2007). The majority of this is believed to be contained in forests in the Northern Hemisphere (Jansson et al. 2010). When agricultural waste lands are vegetated, carbon is captured and can accumulate SOM into the soil (Montagnini and Nair 2004). When these lands are converted into perennial vegetation, today’s climate change accumulation reverses carbon losses from soils (Post and Kwon 2000). Agroforestry program which is one of the climate change strategies can be used to raise overland and soil carbon supplies and minimize soil depletion, as well as to reduce greenhouse gas emissions (Albrecht and Kandji 2003; Mutuo et al. 2005). At the same time, it will help farmer and agrarian communities to tackle several other problems affecting these properties, such as economic diversification, sustainability, and water safety (Schoeneberger 2008). At the community level, long rotation systems such as agroforestry, home gardens, and boundary plantings can sequester significant quantities of carbon in plant biomass and in long-lasting wood products (Albrecht and Kandji 2003; Mutuo et al. 2005). It is estimated that tropical agroforestry system’s carbon sequestration (CS) potential is between 12 and 228 megagram (Mg) ha−1 . Post and Kwon (2000), deciphered that during the early stage of perennial trees, optimum amount of CS is 100 g Cm−2 yr−1 while average rates are like forests and grasslands, that is, 33.8 and 33.2 g Cm−2 y−1 , respectively. The ability of tree-based agroforestry systems to sequester carbon in the humid top carbon sequestration throughout plants can be more than 70 Mg C ha−1 and up to 25 megagram (Mg) ha−1 in the top 20 cm of soil. In overall, the capacity for carbon sequestration by agroforestry is forecasted at 9, 21, 50, and 63 Mg C ha−1 in semiarid, sub-humid, tropical and temperate regions, respectively (Montagnini and Nair 2004). Some report says that in the depleted soils of sub-humid top carbon sequestration, over continuous maize cultivation with increased fallow agroforestry activities have been shown to raise top soil carbon stocks up to 1.6 Mg C ha−1 y−1 . For small land resources, the capacity for carbon sequestration varies from 1.5 to 3.5 Mg C ha−1 year−1 (Montagnini and Nair 2004). It is around 0.9 ± 0.3 Pg C year−1 globally for carbon sequestration (CS) through agroforestry and conservation agriculture and offsetting 25–75% of the annual carbon (C) emissions (Lal 2005; Silver et al. 2000). In addition, based on the Earth’s total suitable area for crop production, which is 585–1215 × 106 ha, a minimum of 1.1–2.2 petagram (Pg) of carbon could be stored in agricultural ecosystems over the next 50 years . Mutuo et al. (2005) also

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suggested that this promising smart practice can be used to increase above ground and soil C stocks and reduce soil degradation, as well as to mitigate greenhouse gas emissions. Thus, such a genuinely win-win opportunity can restore degraded soils, enhance biomass production, purify surface and ground waters, and reduce C from the atmospheric (Lal 2005; Silver et al. 2000).

9.3 Mulching Mulching management has been used in many places all over the world to improve agricultural sustainability (Gu et al. 2016). Mulch covering the field protects energy by reducing surface evaporation (Patil et al. 2013) which significant link to nutrient supply, playing a key role in the C and N cycle and the sink of carbon (Duiker and Lal 1999). To check the effects of different mulches, straw mulch, plastic mulch, and no mulch, it is reported highest corn yields in the plastic mulch (21–25%) and soil organic carbon found highest in the straw mulch plots (Scopel et al. 2005). In Xiaofuling watershed of Danjiangkou reservoir in China, group of scientists found that straw mulching had a significant effect on soil, increasing soil organic carbon (SOC) content and stock in slopping arable land, and that live grass mulching was more effective than rice straw mulching (Gu et al. 2016). Under no-tillage mulchbased (NTM) cropping systems, the SOC stocks in the 0–30 cm topsoil layer of the fields varied between 4.2 and 6.7 kg C m−2 and increased on average with 0.19 kg C m−2 yr−1 (Neto et al. 2010). Impact of mulch over a 5-year period research observed increased soil carbon levels by 23–29% (Scopel et al. 2005). Another reports on under no-till, ridge till, and plow till increased total C% from 1.26 to 1.50, 1.20 to 1.47, and 0.95 to 1.10, respectively, with increase in mulch rate from 0 to 16 Mg ha−1 , when a study conducted by Kahlon et al. 2013. The CS rate will be inclined as more as application of mulches and period of mulching extended. Even, the fluctuation in mulch rates variation attributed the amount of CS. For example, say different application about 4 and 11 years of mulching impacted 41% CS and 52% CS, respectively (Duiker and Lal 1999). In addition, mulching can significantly increase soil organic matter (SOM) from 1.26 to 1.50% (Kahlon et al. 2013, Chandra et al. 2019) and carbon sequestration (CS) in the topsoil layer of 0–5 cm (Duiker and Lal 1999). It also improved the soil’s physical and chemical properties and agricultural soils can be nourished with CS up to 8–16 Mg ha−1 yr−1 (Kahlon et al. 2013; Chandra et al. 2019). Concurrent enhancements of soil aggregation, by the mulching, help to increase soil organic carbon (SOC) concentration but the initiation of SOC concentration inclines only in macroaggregates. The prime attribution to SOC concentration can be brought only if the 32–58% variation in the soil water stable aggregates (SWSA) is maintained. This feature helps to sequester more carbon in the soil which ultimately contributes toward soil organic carbon storage, carbon sequestration, and climate change mitigation (Chandra et al. 2019). In conclusion, carbon-rich soils are desirable (American Society of Agronomy 2018) and awareness of changes in the

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concentration of carbon (C) and the physical, mechanical and hydrological properties of mulching is required to determine the viability of implementing conservation practices to preserve production and enhance productivity and mitigation of the climate crises by removing greenhouse gases (Kahlon et al. 2013). Crop residues The crop residues are the remains of the agricultural crops (Novelli et al. 2017) and it has huge potential to produce carbon-neutral energy (Marie 2010). This crop residue can be used as source of CS and maintain the good quality of soil, and thus it helps in nutrient management and conservation (Lal 1997). If we want to increase the crop residue production significantly, intensive agriculture system can do the better gigantic tasks which leads to increase the SOM (Nakajima et al. 2016) and soil aggregation and hence carbon storage (Novelli et al. 2017). In the course of time, within the systems of this soil biome, soil microorganisms play a crucial role in the carbon sequestration process by transforming crops residues into smaller carbon molecules that are more likely to be protected and sequestered (Six et al. 2006). However, every year large amount of crop residue is required for erosion protection, and considerably more is needed to retain soil carbon (Marie 2010). Lehtinen et al. (2014) conducted a meta-analysis and found that soils with clay content of >35% have more SOC levels which was tended to increase with residue retention with increasing response from duration of retention. So, if we want to increase SOC deeper in the soil profile, incorporation of crops residues into soil has been shown useful (Alcántara et al. 2016). However, to provide that protective level of crops biomass, only high residue crop systems (e.g., 8164.66 kg/ac corn-soybean) can be benefited (Marie 2010). In USA, it is reported that a total of 367 × 106 Mg yr−1 crop residues from 9 cereal crops, 450 × 106 Mg yr−1 for 14 cereals and legumes, and 488 × 106 Mg yr−1 for 21 crops is produced (Lal 1997). In the Mekong Delta of Vietnam, rough rice (Oryza sativa L.) of about 21 Mt and an estimated rice straw of about 24 Mt. produces annually. So, the prevalent of crop residues in this Mekong Delta can increase SOM and sequester as CS significantly and therefore, reducing GHG emissions (Arai et al. 2015). Globally, the total crop residue production from cereal crops is 2802 × 106 Mg yr−1 and from 27 food crops is 3758 × 106 Mg yr−1 . From by incorporation of such crops residues in the field, 40–60% of total agricultural C emissions can turn into an useful carbon capture and sequester (Lal 1997).

9.3.1 Soil Biota Management Within the soil environment, accomplishment of biological sequestration by microbial activities helps to improve the physical, chemical, and biological properties of soil (Six et al. 2006). In due course of carbon sequestration, major soil microbes like fungi maximize the amount of carbon allocated to the soil and producing compounds that improve aggregate stability (Govindarajulu et al. 2005). If the vital soil biota of microbes like fungi and soil bacteria are rich, carbon sequestration can higher up to

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49.9 g C kg−1 in soils (Bailey et al. 2002). Carbon and nitrogen also can reach at 1.32– 1.82 where microbial communities are higher (Six et al. 2006). Mesovores are the soil-dwelling living organism like insects, worms, and nematodes which can help to refine the larger pieces of plant residues into smaller forms. These residues are again metabolized by smaller organisms such as fungi and bacteria. Then, different types and differing size of carbon and complex chemical composition are synthesized which are associated with silt and clay particles or incorporated into soil aggregates (Six et al. 2006; Grandy and Neff 2008; Grandy and Wickings 2010). By the reciprocal sharing of arbuscular mychorrizal fungi (AMF) and plant roots, such mutual activities provide the soil with rich nutrients and organic carbon (Govindarajulu et al. 2005). The biomass of the plant increases effectively as it nourishes the AMF thereby enhancing the process of photosynthesis and eventually increases the amount of carbon into the soil (Rillig et al. 2001). During the process, AMF releases sticky substances called glomalin protein which helps to bind soil aggregates together and leading to protect soil carbon (Rillig 2004). Wilson et al. (2009) found that this organism AMF was strongly positively associated to soil aggregation and carbon sequester. Retrieval of soil biota and its ecological processes breaks down soil organic matter into active soil organic fractions and resistant or stable organic mineral complexes also referred to as humus (Srinivasarao 2017). Such soil biota helps to enrich soil fertility and efficiency, thus encouraging the soil carbon (Lal et al. 2007). In soils, both organic and inorganic sources of carbon are present, so agricultural land use management usually has a stronger effect on soil organic carbon composition (Srinivasarao et al. 2014). In conclusion, for soil organic carbon capture and sequestration, worldwide capability is projected at 0.6–1.2 Gt C year−1 , consisting of 0.4–0.8 Gt C year−1 through the endorsement of recommended cropland smart soil management practices, and through improved rangelands and grasslands for irrigated soils is 0.01–0.03 Gt C year−1 (Lal et al. 2007).

9.3.2 Improved Grazing and Livestock Management Globally, 40% of the land is made up of grassland (Wang and Fang 2009) and to date, grazing, the most intensive utilization of grassland is likely to have a sizeable effect on over a 5th of the global soil carbon storage potentials (Scurlock and Hall 1998). Decomposition of soil organic matter is affected by grazing scheme and strength by impacting the biomass and abundance of microbes, leading to organic matter stabilization (Jastrow et al. 2007) and therefore regulate the turnover of soil energy (Bardgett et al. 2003). In a site where the organic material fettered with carbon sequestration capacity could become the fungal–bacterial supremacy. In such sites, greater fungal domination is organically active and bound with richness in soil carbon (Jastrow et al. 2007). Higher Grazing rate is possible if we grow huge acreage of C4 food crop production and grasses in controlled grassland area which can help to increase organic matter content (Frank et al. 1995). Growing more productive grass species and which can nourish sufficient moisture and nutrients, also contribute

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to boost productivity and carbon capture potential (Conant et al. 2001). Worldwide practicing of smart agriculture and sustainable forestry farming together has a significant scope for capturing carbon through smart grassland management or preserving depleted pastures (FAO 2010). One research report says that soil organic carbon stocks were reduced less than those in cropland area, and biomass rose in certain regions owing to the reduction of deforestation and eventually forest encroachment (Ogle et al. 2004). In contrary to the forest, such biomass is a limited seasonal carbon reservoir and is mainly herbaceous in the grassland systems and thus furnish soils, the foremost carbon reserve (Ogle et al. 2004). In light of climate change and agricultural farming context, activities that sequester carbon in grasslands often improve tolerance and thus enhance long-term pliable to evolving climates crises (FAO 2010). Nonetheless, to reduce the detrimental consequences of pasturing or restoration of deteriorated fields; efficient maintenance of grasslands with sowing better plants, drainage, fertilizing will all contribute to carbon sequestration (Conant and Paustian 2002; Follett et al. 2001; Conant et al. 2001; Ogle et al. 2004). Many studies have shown that efficient grassland management can also minimize net vegetation emissions of carbon, in particular in dry environments (Allard et al. 2007), and promote soil carbon storage (Wilsey et al. 2002). It is reported that productive grassing maintenance contributed to a soil carbon stock inclined by an average of 0.35 Mg C ha−1 year−1 (Conant et al. 2001). However, such environments can be efficient habitats but restricted seasonal expansion, sequestration and grazing changes may minimize carbon absorption in contrast with the other habitats, in terms of species diversity or development (Ogle et al. 2004). Activities such as getting rid of significant quantities of aboveground biomass, strong stockpilings, and other inadequate farming activities are essential regulated factors that affect the development of farming areas and have contributed to soil carbon stocks being lessen (Conant and Paustian 2002; Ojima et al. 1993).

9.3.3 Animal Manure Animal manure can be used as source of carbon and the addition of animal manure to different crop fields has impacts on soil carbon contents (Stewart et al. 2007). Different researchers conducted the experiments in Germany to check the soil’s C levels. The experiment showed that the annual application rate of 200 Mg ha−1 yr−1 of manure to the crop field shows a high level of SOM with respect to adjacent fields (Blair et al. 2006). Powlson et al. 2011 reported that the mean annual SOC sequestration rates of three long-term (>49) years of manure applications ranged from 10 to 22 kg C ha−1 yr−1 t−1 of dry solids, while SOC sequestration rates with shorter-term experiments (8–25 years of farmyard manure, cattle slurry and boiler litter) were from 30 to 200 kg C ha−1 yr−1 t−1 of dry solids (Rahman et al. 2016; Cheng et al. 2016). In another study, the farm yard manure was applied to the rice–wheat cropping system with NPK fertilizers and results showed significantly an increase in

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C sequestration in farm yard manure-applied plots than NPK-applied plots (Naresh et al. 2017). In the rice–rice cropping system poultry manure is found to be more efficient in increasing C and other nutrients in soils and microbial activities which contribute to CS (Rahman et al. 2016; Cheng et al. 2016).

9.3.4 Pastures and Pasture Leys in Crop Rotations Undercomparable pedoclimatic zones, in undisturbed natural systems, managed grassland and pasture systems can support higher levels of soil organic matters than intensively managed cropping soils. Conversion from cropping to pasture or use of a pasture phase in a cropping patterns can increase soil organic carbon content. Notillage under pasture and enhanced soil aggregation leads to increased protection of soil organic carbon (Six et al. 2004). Generally, there is an also higher level of biomass return in pasture systems via plant deposition and return of animal excreta, with less export of biomass. In a meta-analysis of the impact of land-use change on SOC concentrations, Guo and Gifford (2002) found that the SOC stocks increased by on average 19% after the transition from crop to pasture, with the length of time since conversion having no clear effect on the amount of C accumulated. The rate of SOC accumulation under pasture depends largely on soil type and climate, as compared with other management factors (Conyers et al. 2015; Rabbi et al. 2015; Sanderman et al. 2010). Nonetheless under long-term pastures, SOM sequestration is increased particularly with the inclusion of nitrogen fixing legumes and with fertilization that increase net primary production (Haynes and Williams 1992; Orgill et al. 2017). Conversely, pasture management can have limited or no impact on SOC sequestration in cases where the growth potential of the pasture is limited by inadequate soil nutrition or where the composition of the pasture as cover grass has low legume content (Badgery et al. 2014).

9.3.5 Land Use The soil organic carbon is highly sensitive to changes and management practices. Land-use change is widely recognized as a net source of green house at global level. Land-use options for enhanced C sequestration at the landscape and regional scales include protection and selective management of native ecosystems and use of appropriate and smart management practices in manipulated ecosystems (Metting et al. 2001). Among the different land-use systems, total C stock was highest in forest soils followed by fodder system, paddy, maize, cotton, red gram, intercrop, chilli, permanent fallow and lowest in castor system. The soil organic carbon dynamics under tropical garden land systems and the results revealed that organic carbon status of

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the soil increased with balanced application of NPK fertilizers combined with organic manure. Underconservation agriculture, 0.5–1.0 t C ha−1 yr−1 , can be sequestered in humid temperate conditions, 0.2–0.5 in humid tropics and 0.1–0.2 in semiarid zones. Post and Kwon (2000) estimated the maximum rate of carbon accumulation during the early aggrading stage of perennial vegetation growth, while substantial, are usually much less than 100 C m−1 yr−1 . Average rate of accumulations is similar for forest or grassland establishment 33.8 g C m−2 yr−1 and 33.2 g C m−2 yr−1 , respectively. In conclusion, as we know that carbon is held in the form of soil organic carbon and this organic carbon is highly sensitive to land use or changes in land use system as mentioned above (Post and Kwon 2000). Smart management practices such as tillage, cropping systems, and mulching lead to changes of soil organic carbon status (Purakayastha et al. 2008). In addition, adoption of best land-use systems such as conservation tillage, mulching, and cropping system in a long run could enhance the organic soil carbon sequestration and mitigation of green house gases.

9.3.6 Tillage Tillage is the mechanical cultivation of soil by devices and machinery for seed germination, planting and plant production (Zia et al. 2018). Several co-workers revealed that carbon sequestration and deposition in the soil profile have been greatly influenced by tillage activities such as conservation tillage, no-tillage, and traditional tillage (Deen and Kataki 2003; Sheehy et al. 2015) and found higher in conservation tillage soils in comparison to traditional tillage (Deen and Kataki 2003; Sheehy et al. 2015). In this light, it has also been established that sustainable laying activities improve renewable soil and carbon sequestration relative to conventional tillage (Deen and Kataki 2003; Sheehy et al. 2015). Grandy and Robertson (2006) found that tilling a previously untilled soil quickly reversed nearly all the previously recorded gains by disrupting aggregates and exposing carbon molecules to microbial attack. If we look the matter globally, carbon sequestration capacity by cultivation and tillage is about 0.9 ± 0.3 Pg C year−1 for the annual carbon emissions reduced by 25–75% (Lal 2005; Silver et al. 2000). By doing such clever practices, it can be a well-balanced approach that recovers depleted soil, increases the production of crops, purifies ground and surface water and decreases atmospheric carbon (Lal 2005; Silver et al. 2000).

9.3.7 Zero Tillage It is a kind of conservation agriculture which comprises of minimum soil disturbance along with crop residues, cover crops, and their diversification and improving SOM and leading to mitigate carbon emissions through carbon sequestration (CS) up to

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0.16–0.49 Mg C ha−1 yr−1 (Zia et al. 2018). Since soils in these systems remain undisturbed, soil aggregates remain intact and increases and thus protecting carbon physically (Cambardella and Elliott 1992; Six et al. 2000). So, in order to maintain gains in soil carbon, it is important to continuously manage soils with no-till (Powlson et al. 2016). In another studies support that (no-tillage) NT sequesters more soil organic carbon (SOC) compared with conservation tillage (CT) (Syswerda et al. 2011; Varvel and Wilhelm 2011). In Brazil, they target to increase the agricultural area under zero tillage from 32 to 40 million ha by 2020 to mitigate C emissions. It was calculated that average annual CS is 1.61–1.48 Mg C ha−1 yr−1 in Brazil for the 8 years from 2003 to 2011. So, converting 8 million ha of cropland to zero tillage can sequester an estimated soil C storage of about 8 Tg C yr−1 in 10–15 years (Corbeels et al. 2016). Meanwhile, in our country, Haryana, reports showed that by adopting zero tillage nearly USD 97.5 ha−1 can be earned extra and can reduces the tillage implement costs, labor and fuel costs by spending USD 76 ha−1 and 97.5 USD earnings show that shifting from conventional to zero tillage reduces cost and additionally, sequester C emission by 1.5 Mg C ha−1 season−1 (Agarwal 2008) From these evidences, what we could learn is zero tillage generates considerable benefits up to US D 97 ha−1 ; it also increases the crop yield by 5–7%, saving costs up to USD 52 ha−1 (Erenstein 2007; Erenstein et al. 2008; Landers et al. 2003). Perhaps, many studies have deciphered that no-till can increase soil carbon rapidly, especially at the soil surface (West and Post 2002). Baker et al. (2007) that examined carbon changes to soil depths greater than 30 cm and resulted no-till tends to show increased carbon at shallow depths where crop residues are found, but at greater depths plowed soils typically sequester more carbon. In support of this finding, Blanco-Canqui and Lal (2008) mentioned carbon sequestration are greater at soil depths of 30 cm. Ironically, in soil depth of (35 of 51 cm), no significant difference in carbon sequestration between plowing and no-till was found (Baker et al. 2007; Blanco-Canqui and Lal 2008). This finding is supported in a study, in Quebec, Canada, over a period of three years also found that the amount of sequestered carbon did not differ between no-till and plowing. The findings also reported higher carbon accumulation from no-till only where the top several centimeters of soil were measured. When the measurements included the entire soil profile, the higher carbon accumulation in plowed fields at lower depths compensated for the lower amount of carbon near the soil surface. So, different fertilization rates did not alter these results (Poirier et al. 2009). In fact, on average, the no-till systems may have lost some carbon over the period of the experiment (Baker et al. 2007).

9.3.8 Conservation Tillage The soil organic carbon concentration increase from conservation farming induces improved physical and chemical qualities of soil which ultimately lead to increase biodiversity and the mitigation of climate change by carbon sequestration (Powlson et al. 2016). Several studies have demonstrated that CT also can increase soil carbon

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by increasing soil aggregation and physically protecting carbon, but sequestration generally occurs at rates lower than no-till (West and Post 2002; Halvorson et al. 2002). Further raising carbon sequestration is affected by agricultural practices, such as conservation tillage (West and Marland 2002). As in a study involving different tillage practices like CT, ZT, NT, and CoT, it showed that CS throughout the profile was significantly affected by tillage practices. A variety of studies agreed that notillage (NT), in contrast with conservation tillage (CT), sequesters more organic carbon in the soil (Syswerda et al. 2011, Varvel and Wilhelm 2011). Changes in the SOC are greatly influenced by long-term tillage practices. For example, soil from 0 to 60 cm after 25 years of CT showed 5% higher soil bulk density for conservation tillage as compared to conventional tillage practices. Analysis also showed that CS and storage was significantly higher in CT soil than conventional tillage (Deen and Kataki 2003). By embracing conservation tillage, carbon sequestration may be improved by 3.15 ± 2.42 t ha−1 (Deen and Kataki 2003; Sheehy et al. 2015; Luo et al. 2010). So, it can be concluded that conservative tillage practices, viz. conservation, zero tillage, and no-tillage, showed that there is the greatest potential of carbon sequestration while applying zero tillage, no-tillage, and conventional tillage increased SOM and CS as compared to CoT (Deen and Kataki 2003; Sheehy et al. 2015).

9.3.9 Cropping System and Intensity Carbon sequestration optimization in agriculture can be done by cropping systems, such as crop rotation, intercropping, and cover cropping which help to influence more yield and economic benefits (Drinkwater et al. 1998), total increased C sequestered with biomass, and stabilized the soil organic matters (Wang et al. 2010). Cropping intensity and rotations have the potential to sequester 14–29 MMTC yr−1 (Follett 2001). Moreover, it can also be attained by improved soil fertility, extensive cropping systems with shifting cultivation cropped fallows and cover crops (Hutchinson et al. 2007). By doing continuous and intense cropping system leads to accumulate 10–17% more SOM and N (Sherrod et al. 2003). The potential of tillage, land cover, nutrients, and cropping system management in CS is up to 30–105 million metric tons of C (MMTC) yr−1 (Follett 2001). Finding over a period of 12 years cropping systems on organic management system that employed increased rotational diversity and extensive use of winter cover crops led to a significant increase in soil carbon, despite extensive tillage for weed control (Syswerda et al. 2011). In crop based rice–wheat cropping system even without any fertilization contributed toward carbon sequestration (1.94 Mg C/ha) with soil organic carbon pools and carbon sequestration rate of 7.84 Mg C/ha and 0.22 Mg C/ha/yr, respectively. Soil quality indices such as particulate organic carbon (POC) were influenced by cropping system: with CS < CC < CCOA where (CC) (Zea mays L.); corn–soybean [Glycine max (L.) Merr.] (CS); corn–corn–oat–alfalfa (oat, Avena sativa L.; alfalfa, Medicago sativa L.) (CCOA), and corn–oat–alfalfa–alfalfa (COAA). CS [continuous

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grain sorghum {Sorghum bicolour (L.) Merr.] cropping system exhibited isotopes (δ13C) value ranging from −15 to −20%, suggesting most SOC was derived from this C4 species. Increase in SOM can be seen under long-term maize–wheat–cowpea cropping system up to 1.83 Tg C yr−1 (Purakayastha et al. 2008). It is estimated that across 10 cropping systems, annual soil CS rates range up to 0.56 Mg C ha−1 yr−1 (Kong et al. 2005). In contrast, intense cropping systems always cause depletion of SOM but applying crop residues, balanced fertilization with NPK and use of organic amendments can increase CS levels to 5–10 Mg ha−1 yr−1 . As these amendments also contain 10.7–18% C in them, they also help in CS (Mandal et al. 2007). Thus, by adopting these strategies, biomass production is increased and so, the C usage in the plants is increased and more C is sequestered in the plant and soil. If nutrient inputs combined the above strategies, this CS amount can be doubled (Follett 2001).

9.3.10 Cover Crops Planting cover crops is a promising option to sequester carbon in cropping systems by the implementation of smart agricultural management practices (Vicente-Vicente et al. 2016). Cover crops can sequester carbon with the help of their roots and shoots which feeds on bacteria, fungi, earthworm, and other soil organisms, which increases soil carbon level over time (McVay et al. 1989; Kuo et al. 1997; Sainju et al. 2003). A cover crop may raise the soil organic matter in two ways: (i) raise carbon biomass inputs and (ii) hold soil driest with the plants water intake and hence minimize carbon mineralization in the summer with enough precipitation in the normal fallow season (Godde et al. 2016). Cover cropping provides additional residue that not only reduces soil erosion but also improves soil productivity by increasing soil organic carbon (SOC) (McVay et al. 1989; Kuo et al. 1997; Sainju et al. 2003). Soil CS rates in cover cropping are much higher than that of fields with low or no cover cropping which suggests that the adoption of cover cropping is a sustainable and efficient measure to mitigate climate crises (CC) (Vicente-Vicente et al. 2016). However, in semiarid climates, cover crops to a larger extent are not likely to have these SOC benefits because of a lack of water for crop growth during the fallow (Godde et al. 2016). A review from Poeplau and Don (2015) found that soils under cover crops had significantly higher SOC stocks than associated reference crops, with a mean annual change of 0.32 Mg ha−1 yr−1 to a soil depth of at least 20 cm. In the olive orchards, vineyards, and almond plants, the maximum carbon sequestration amount is found to be up to 5.3 t C ha−1 year−1 . In the first years after transition of management, soil carbon sequestration continues to be the maximum, slowly hitting equilibrium (Vicente-Vicente et al. 2016). In southern Illinois, Olson et al. (2010) conducted 8year study on impact of no-till (NT), non-legume (NL), low nitrogen supply legume (LNL), and high nitrogen supply legume (HNL) cover crops and increased SOC content by 0.17, 0.41 and 0.43 Mg C ha−1 yr−1 and −0.01, +0.01 and +0.02 Mg N

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ha−1 yr−1 (Mazzoncini et al. 2011). Another experiment conducted by Novara et al. 2019, the vineyard soil which was managed with Vicia faba cover crop, was found to have highest SOC content with an average value of 9.52 ± 0.34 g kg−1 the slope area and 10.47 ± 0.2 g kg−1 in the flat vineyard. Also, the SOC at 0 to 30 cm increased more in cover crops with 120–130 kg N ha−1 yr−1 than in weeds with 0 kg N ha−1 yr−1 , regardless of tillage (Sainju et al. 2006). In a meta-analysis of different sites trial, the cover crops treatments had a significantly higher SOC stock than the reference crop land with a total mean SOC stock accumulation of 16.7 ± 1.5 Mg ha−1 for a soil depth of 22 cm (Poeplau and Don 2014). Winter cover crops use soil residual N that may leach into groundwater after crop harvest in the fall and, depending on species, can sequester atmospheric C and/or N, thereby reducing the amount of N fertilizer required for summer crops Meisinger et al. 1991; Kuo et al. 1997). Thus, soil organic carbon and nitrogen concentration can be conserved or maintained by reducing their loss through mineralization and erosion, and by sequestering atmospheric CO2 and N2 in the soil using no-till with cover crops and N fertilization (Sainju et al. 2002).

9.3.11 Composting Composting is the systematic and controlled breakdown of different types of organic matter including animal manure, woody material, and other organic waste (Farina et al. 2018). The benefits of compost applications, by reducing all the negative impacts produced by them, using chemical fertilizers, reduced use of pesticides, improved tilth and workability say reducing consumption of fuels tends to obscure the potentially important effect of composting, in which biogenic carbon is held in soils for a period of time before the carbon is released (Favoino and Hogg 2008). In the event of composting, some amount of carbon in manure loses and converted into more stable carbon types, which makes the remaining carbon less decomposable when added to the soil (Biala 2011). If we apply the compost in different plots, the soil organic C stock will increase significantly when compared with the initial stock (Farina et al. 2018). Various finding shown that soil containing composted manure has retained about three times as much carbon as soil with added raw manure (Biala 2011). Across a number of rangeland sites in California, compost amendments have led to a noticeable rise in surface soil C stocks over a single growing season. Moreover, overall climate gain of compost adjustment peaked 15 years after application (Silver et al. 2018). In north western Italy, a study in Corn (Zea mays L.) and Vetch (Vicia villosa Roth.) field having calcareous silt loam soil says that when fertilized with a municipal solid waste compost and they found that, when N2 O and CO2 fluxes were combined, compost reduced by 49% and the CO2 equivalent emitted following urea application while Vetch did not show such an effect (Alluvione et al. 2010). In another experiment to monitor the influence of organic and inorganic fertilizers on the SOC stock in a soil depth of 0–60 cm under an intensive wheat–maize cropping system in the North China Plain, which involves 7 treatments, viz. CM, compost; HCM, half compost nitrogen (N) plus half fertilizer N; NPK, fertilizer N, phosphorus

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(P), and potassium (K); NP, fertilizer N and P; NK, fertilizer N and K; PK, fertilizer P and K; and CK, control without fertilization, they found that the stabilization rate of exogenous organic carbon (C) into SOC was only 1.5% in NPK-treated soil but amounted to 8.7–14.1% in compost-amended soils (CM and HCM) (Fan et al. 2014). The application of rice straw compost at 2 tonnes/ha along with inorganic fertilizers increases C and N concentration significantly on a sandy loam soil (Sodhi et al. 2009). Measurements of POM-C (particulate organic matter) in the soil were 45% higher and SOC was 16% greater where compost was applied in place of N fertilizer (Fortunaa et al. 2003). In an investigation done by (Fabrizio et al. 2009), compost C accumulated in the soil after 150 days of application was 4.24 Mg ha−1 and 6.82 Mg C ha−1 for 50 and 85 Mg ha−1 compost rate, respectively. This slight increase in the fraction of carbon retained with the increase in compost application rate could be due to the highly stable state of the compost prior to application. So, it is a well-balanced condition to increase C storage in the soil as well as plant growth and yield by chemical fertilization. The compost application at the rate of 10 Mg ha−1 yr−1 results in higher CS. This clear cut indicates that composting not only increases the net primary production but also the C content of the soil (Baldi et al. 2018).

9.3.12 Biochar and Bagasse Carbon is captured in plant products as biomass and such biomass can contribute to C sequestration through deliberate addition of biochar to soil, wood burial, or the use of durable plant products (Jansson et al. 2010). Biochar is usually obtained by the breakdown of crop biomass, bagasse sugarcane fibrous residues, and wood chips, at a low temperature range (350–600 °C) in the atmosphere having very little or no oxygen (Laird 2008). When these biomass and crop residues are pyrolyzed, it produces syngas, bio-oils, and charcoal (Joseph et al. 2007). During the process of charcoal formation, biogas released from it can be captured and used as a fuel source, typically for heating (Marie 2010). When this biochar is applied to soils, research has shown that it can increase soil health, crop yields, reduce leaching of organic and inorganic fertilizers, and some evidence exists that it can reduce soil emissions of N2 O and CH4 (Joseph et al. 2007). If the condition remained optimum during the process of biochar formation including temperature and oxygen, then almost >50% of the C is retained by the biochar with respect to original biomass (Laird 2008). Controlled charcoal production may permit sequestration of more carbon for longer periods (Marie 2010). Application of oak biochar and bamboo biochar @ 0.5% each can ameliorate the soil through increasing the content of organic carbon and improving the soil aggregation. Each biochar has less lability but more accumulation of organic C which could contribute to sequestration of carbon in the soil (Demisie et al. 2014). Windeatt et al. 2014 studied the characteristics of biochar produced from crop residues, the result shows that biochar carbon sequestration potential was 21.3% to 32.5%. In an experiment, bagasse ash (BA), rice husk ash (RHA), and RHA mixed with fly ash (FA) were applied to wheat to evaluate soil organic carbon (SOC) and

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microbial activity in a loamy sand soil after four years of wheat-rice cropping. BA application resulted in C accrual at 525 kg ha−1 y−1 in soil, whereas RHA and FA did not have a significant effect (Benbi et al. 2017). Creamer et al. 2014 investigated on the adsorption of CO2 by using biochar produced from sugarcane bagasse (SBG) and hichory wood (HW). They concluded that the bagasse biochar produced at 600 °C showed the most adsorption of CO2 (73.55 mg g−1 at 25 °C). However, even when the feedstock was exposed to only 300 °C pyrolysis, the biochar was still able to capture more than 35 mg g−1 CO2 at 25 °C (Kameyama et al. 2010). Biochar addition to soil has also been reported to alter soil microbial community structure, and to both stimulate and retard the decomposition of native soil organic matter (SOM) (Farrell et al. 2013). In Japan, biochar has been used for decades as a soil fertility amendment (Marie 2010). In conclusion, biochar is resistive to microbial attack and hence when applied to the soil will remain stable for thousands of years and thus reduce the release of terrestrial C to the atmosphere in the form of CO2 (Lehmann 2007). The application of bagasse as a biomass in the field showed that bagasse has the potential to sequester C at about 1200–1800 t C yr−1 (Kameyama et al. 2010). It is reported that, biochar could remove up to 5.2 Pg C per year in 2050 and lower atmospheric CO2 in 2050 by 25 ppm.

9.3.13 Crop Rotation The incorporation of different plants in a cycle often brings in a larger diversity and the tolerance of certain carbon compounds to decomposition into the soil (West and Marland 2002). Crop rotational variability has substantial impacts on the climate change accumulation of soil carbon by enhancing the capacity of soil microbial communities to rapidly absorb and preserve plant residues in aggregates (Tiemann et al. (2015). Researchers found that more diverse crop rotations consistently have higher soil carbon and soil microbial biomass than less diverse systems, especially when cover crops were included in the rotation (McDaniel et al. 2014). In a study conducted by (West and Post 2002) to quantify potential soil C sequestration rates for different crops in response to decreasing production tillage intensity or enhancing rotation complexity, and to estimate the duration of time over which sequestration may occur, they concluded that enhancing rotation complexity can sequester an average 20 ± 12 g C m−1 1 yr−1 . McConkeya et al. (2003) investigated to determine carbon sequestration for different tillage systems in semiarid to sub-humid climates and coarse to fine-soil texture in Saskatchewan, Canada. They found that crops rotations without bare fallow have greater potential for sequestering soil organic carbon in the humid than in the drier climate and cropped rotations can sequester 27–430 kg C ha−1 per year more than crop rotation without bare fallow annually. A short-term effect of tillage and crop rotations on carbon sequestration and aggregate stability under sprinkler-irrigated crop production resulted that crop rotation with maize–oats maize enhance soil organic carbon relative to the maize–wheat–maize and maize– fallow–maize crop rotation and therefore cover crops, especially oats, have greater

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influence on SOC accumulation and aggregate stability than tillage, irrespective of soil type (Njaimwe et al. 2016). An experiment conducted by Witt et al. 2000, to study the effects of soil aeration, N fertilizer, and crop residue management on crop performance, soil N supply, organic carbon (C) and nitrogen (N) content where two annual double-crop systems were evaluated for two year period, i.e., maize–rice (M– R) rotation where maize (Zea mays L.) was grown in aerated soil in the dry season (DS) followed by rice (Oriza sativa L.) grown in flooded soil in the wet season (WS). They found that there was 11–12% more C sequestration and 5–12% more N accumulation in soils continuously cropped with rice than in the maize–rice rotation. A study conducted by a group of scientists on a cropping system for 10 years by comparing no-till and stubble mulch management on four dryland cropping systems: continuous wheat (CW) (Triticum aestivum L.); continuous grain sorghum (CS) (Sorghum bicolor [L.] Moench.); wheat/fallow/sorghum/fallow (WSF); and wheat/fallow (WF) resulted that total SOC content in the surface 20 cm was increased 5.6 t C ha−1 in the continuous wheat no-till treatment and 2.8 t C ha−1 in the continuous grain Sorghum no-till treatment compared with the stubble mulch treatment (Potter et al. 1997). Gobin et al. 2013 constructed a crop rotation geo-database covering 10 years of crop rotation in Flanders using the parcel registration (Integrated Administration and Control System) to elicit the most common crop rotation on major soil types in Flanders including crops like winter wheat, winter barley, sugar beet, potato, grain maize, silage maize, and winter rapeseed; the catch crops (yellow mustard and Italian ryegrass). They opined that a very large percentage of carbon sequestration is influenced by crops cover dynamics and also stated that the total carbon sequestered is largely contributed by crop residues of grain maize and winter wheat followed by catch crops. From the various finding mentioned above, we conclude that the addition of a plant range are easiest means that can incorporate number of carbon compounds in the soil, thus enhancing the sequestration capacity of soil energy (West and Marland 2002).

9.3.14 Intercropping Intercropping is an important technique that can be pursued in the evolving environment conditions with favorable outcomes (Layek et al. 2018). The intercropping systems involve row intercropping, strip intercropping, mixed cleaning, and relay intercropping that mainly rely on spatial distribution and cropping objectives with characteristic carbon sequestration of different crops (Wang et al. 2010). To optimize the efficiency of C sequestration in agriculture, cropping systems, such as crop rotation, intercropping, cover cropping, etc., play a critical role by influencing optimal yield, total increased C sequestered with biomass, and that remained in the soil (Wang et al. 2010). Soil C sequestration potential of strip intercropping is similar in magnitude to that of currently recommended management practises to conserve organic matter in soil (Cong et al. 2014). With the increased leaf cover in the intercropping system, transpiration cools up the microclimate, reducing the soil temperature (Miao

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et al. 2016). Observed that the ability of soil carbon sequestration for strip crosscropping is close in magnitude to the management practices currently recommended for soil conservation in the field. Intercropping can contribute by increasing yield, improving soil quality and soil sequestration to multiple agroecosystem services. Intercropping increases aboveground and belowground crop productivity suggesting potential for carbon sequestration (Cong et al. 2015). Intercropping system with minimum soil tillage is effective in maintaining and sometimes increasing the levels and stocks of soil organic carbon and some soil organic matter fractions such as microbial C and humic substances and therefore, these systems can be alternative form of sustainable soil management (Maia et al. 2019). Soil organic C content in the top 20 cm is 4 ± 1% greater in intercrops than in sole crops, indicating a difference in C sequestration rate between intercrop and sole crop systems of 184 ± 86 kg C ha−1 yr−1 (Cong et al. 2014). In wheat–maize intercropping system, carbon emission of 2400 kg C/ha during the growing season, about 7% less than monoculture maize, of 2580 kg C/ha was reported (Hu et al. 2015). Therefore, intercropping can contribute to multiple agroecosystem services by increased yield, better soil quality, and soil C sequestration (Cong et al. 2014).

9.3.15 Bamboo Plantation Bamboo plantation having a potential growth period of between 120 and 150 days completed can do a better job of carbon sequestration (Nath et al. 2015). Such nature of vigorous growth producing high biomass (Nath et al. 2015) has made bamboo a particularly attractive carbon sequestration plant and one hectare of bamboo plantation could sequester 60 tons of CO2 /year (Anonymous 2014a). This biomass can again generate chips and pellets and as the alternative of fuel; as a result, it can sequester approximately 1.78 kg of C (Patel et al. 2017). An average of carbon storage and sequestration rate in woody bamboos ranges from 30–121 Mg ha−1 and 6– 13 Mg ha−1 yr−1 , respectively (Nath et al. 2015). In India, Choudhury (2015) revealed that with the increase in CO2 concentration from 380 ppm to 750 ppm the seedling growth and other qualitative parameters showed better results in Bambusa tulda, B. nutans, B. balcooa, and Dendrocalamus hamiltonii. In Central Japan (Latitude 35 ° N), the aboveground net primary productivity (ANPP) including leaf turnover for Phyllostachys bambusoides was recorded at 24.6 ton/ha/year in a 6-year-old bamboo plantation (Isagi et al. 1993). Homegarden bamboos were important sinks of atmospheric carbon due to their rapid growth and high productivity (Nath et al. 2008). According to a study conducted by Tariyal et al. (2013), where the total carbon stock and carbon sequestration capacity of the four main bamboo species of Uttarakhand (Bambusa balcooa, Bambusa nutans, Bambusa vulgaris and Dendrocalamus strictus) were analyzed, it was concluded that the highest total carbon stock was in Dendrocalamus strictus (381.50 t ha−1 ) while the lowest stock was shown by Bambusa vulgaris (160.11 t ha−1 ). Contrary to this, the maximum carbon sequestration potential was seen Bambusa balcooa (99.81 t ha−1 yr−1 ) whereas minimum was observed

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in Bambusa vulgaris (57.77 t ha−1 yr−1 ). Contrarily to this, the overall capacity for carbon sequestration was seen as Bambusa balcoa (99.81 t ha−1 yr−1 ) while Bambusa vulgaris was the minimum (57.77 t ha−1 yr−1 ). Bamboo has also been shown to have high carbon sequestration ability and to be an ideal substrate for carbon sequestration. Bamboo sequestered carbon in continuously growing rhizome mats and phytoliths, but in order to optimize total carbon sequestration, bamboo must be processed and produced into durable products such as construction materials and buildings (Anonymous 2014a). The species Dendrocalamus hamiltonii sequestered the highest total carbon (118.72 ton/ha) in India (Choudhury 2015). In conclusion, bamboo plantation has a high carbon sequestration potential due to its rapid accumulation of biomass and its efficient fixation of CO2 (Nath et al. 2015).

9.3.16 Topography Topography influences soil nitrogen and carbon through erosion and redistribution of soil materials through leaching, infiltration and runoff potentials (Senthilkumar et al. 2009; Creed et al. 2002). However, the effects of topography on soil carbon are likely to vary in magnitude under agricultural systems with different management practices (Senthilkumar et al. 2009) and soil depth. Soil depth controls soil nitrogen and carbon dynamics by bioturbation, placement of plant and animal residues on the surface of the soil and/or incorporation of organic materials within the epipedon and endopedon of soil. A report says that organic carbon and total nitrogen contents of the soils were significantly affected by depth and slope position. In depth of 0–30 cm had significantly increase in organic carbon and total nitrogen than the other soil depths. At the valley sites, the average carbon sequestered at different topographic sites ranged from 123.4 g Cm2 at the mid-slope to 569.84 g Cm2 . Soil carbon and nitrogen sequestration reduced significantly with depth, at the summit and valley position. However, at the mid-slope, the 0–30 and 90–120 cm depth sequestered significantly increased carbon (Fissore et al. 2017; Garcia-Ruiz 2010; Lasanta et al. 2001; Kazi et al. 2018). Generally, from the reports, slope steepness shows to be a productive tool to decipher patterns in soil carbon storage.

9.3.17 Semi-arid Lands Planting trees in semiarid regions, precipitated in the unsaturated zone (USZ), has the potential for increasing sequestration of atmospheric carbon dioxide, inorganic carbon storage (carbonate salts), by ~1 billion tons of atmospheric CO2 yr−1 (1 Pg CO2 yr−1 ) (Moinester et al. 2016). Meena et al. (2019) selected two forest sites, i.e., north ridge (NRF) and central ridge (CRF) to study the assessment of carbon pools in a semiarid forest ecosystem of Delhi, India, at 0–10 cm and 10–20 cm depth and resulted 90.51 Mg ha−1 biomass and 63.49 Mg C ha−1 carbon and they

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suggested that the potential pools of carbon storage in these forests are plant biomass and soils of semiarid forest. Mureva et al. (2018) stated that negative correlation between changes in soil organic C stocks in the 0–100 cm soil layer and mean annual precipitation (MAP) was seen. The most humid site (1500 mm MAP) had less C in shrub-encroached sites while the drier sites (300–350 mm MAP) had more C than their paired open grasslands. Hence, they suggested that soil organic C gains in low precipitation areas, i.e., semiarid areas, with a threshold value between 750 and 900 mm. Tiessen et al. (1998) reviewed on the data of carbon and biomass budgets under different land use in tropical savannas and some dry forest. For semiarid tropic the global data showed a wide ranges of biomass carbon stocks (20–150 Mg C/ha), net primary production (2–15 Mg C ha−1 yr−1 ), and litter production (2– 10 Mg C ha−1 yr−1 ). Dabasso et al. (2014) studied on carbon stock on semiarid pastoral ecosystems of Northern Kenya. Considering the heterogeneity of semiarid pastoral ecosystem of Northern Kenya, the samples were collected during wet and dry season and from various landscape types. Across the landscape types and season, they found an average carbon stock of 93.01 ± 15.72 tonnes/ha and they stated that this measured amount of stored carbon is sufficient to have an important contribution in controlling the atmospheric concentration of greenhouse gases. By these different findings, growing plants on semiarid lands has been suggested as a way to increase carbon storage in soils (http://www.esa.org.).

9.3.18 Nutrient Management Agricultural practices such as no or reduced tillage, increased crop intensity, crop rotation (Christopher and Lal 2007), crops residue inputs, and N fertilization management directly influenced organic matter and N in the soil tending to CS (Dolan et al. 2006). Nutrients management (especially N) to promote C sequestration from agricultural residues (Christopher and Lal 2007) is an important practice as suggested by many scientists (Van et al. 2006; Poeplau et al. 2017). Smart management practice of nitrogen in soil increases formation of SOM or humus and biomass yield which is limited by the availability of nitrogen (N) nutrient (Christopher and Lal 2007). Intensive use of N fertilizers is vital to employ to achieve higher economic value of high grain yields and is generally perceived to bring about CS and by increasing the inputs of crop residues (Khan et al. 2007). In one experiment conducted under controlled laboratory incubations, direct application of nutrients to crop residues is effective in enhancing the formation of stable SOC through increased humification efficiency (Moran et al. 2005; Kirkby et al. 2013). Report says that stocks of SOC is increased across the 5 year period by 5.5 Mg C/ha over 0–160 cm in the soil profile where supplementary nutrients were added, as compared with a decrease of 3.2 Mg/ha where wheat straw only was incorporated, with 90% of this loss (relative to initial levels) being in the 0–10 cm layer (Kirkby et al. 2016). If we compared with conventional technique, NT would greater organic C, N, and SOM at depths of 0–2.5, 2.5–7.5, 7.5–15, and 15–30 cm. Thus, increases in SOM were directly related to the

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tillage practice and nutrients management (Havlin et al. 2005). It is also suggested that application of fertilizer in leguminous phase in a crop rotation is not recommended to increase SOC, as the leguminous phase can lead to less incorporated biomass C into the soil organic matter pool than other crops, reducing subsequent SOC. It can also contribute to higher soil N which promotes C mineralization and consequently SOC loss. So, instead, the leguminous phase without fertilizer can increased crop yields and SOC because of fixed N added to the soil (Godde et al. 2016). However, this findings are contrary as reported by Hoyle et al. 2011), who described the inclusion of green manure in fertilizers resulted positive impact on SOC. Apart from this different reports, the most effective use of nitrogenic fertilizers is precision agriculture which improving fertilizer efficiency through using GPS tracking to reduce nitrous oxide emissions and to find the possible ways to capture carbon (www.attra. ncat.org/farm_energy/nitrogen.html).

9.3.19 Precision Farming Precision agriculture is commonly characterized as a method of farm management centered on knowledge and technology, which defines, evaluates, and manages spatial and temporal variation in areas for optimum productive output and rentability, sustainability, and land resource security through the minimization of production’s costs. In wider view, weather heterogeneity, land charts, aerial photographs, field camera location photographs and grid charts describing production, weather restrictions, and the background of pest have been used widely to classify land-like areas with equal productivity. As finding by previous researcher which mentioned above, conservation tillage techniques can decrease carbon emissions related to farming operations, while precision agriculture technologies led to an optimization of the exhaustible sources such as fossil fuels and fertilizers (Cillis et al. 2018). Eory and Moran (2017) considered four mitigation measures connected with precision agriculture (improved timing of mineral nitrogen (N) application, improved timing of organic N application, full allowance of manure N supply and avoiding N excess). All of them showed considerable GHG abatement potential with “Improved timing of mineral N application” reaching 0.3 tCO2 -eq/ha. In this, GPS tracking can be used to reduce nitrous oxide emissions thereby improving fertilizer efficiency. Such precise farming can eliminate the risk for NO3 pollution in soil and surface waters. In agronomical point of view, fuel consumption can also be reduced (and the respective GHGs) in the case of mechanical precision weeding, along with through the production of the avoided pesticides, because the tractor pulling the weeding implement will confront lower draught forces coming from soil tilling when the angle of the harrow tines will be less aggressive than with the conventional tillers (Peteinatos et al. 2015). For certain situations, the application of these quantitative details decreases the consumption of resources and pesticides and thereby increases the movement

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of resources and emissions of greenhouse gases. Such activities also encourage the sequestration of soil organic matter. In addition, the total plant/seed quantity used in the field can be lower (less GHG emissions coming from the production of the plant or the seed) or the same as in conventional seeding is possible when applying variable rate planting/seedling (VRP/VRS). Nevertheless, an effect of VRP/VRS on GHG emissions can be expected through the increased yield (Hörbe et al. 2013). Balafoutis et al. (2017) studied on the potential of precision agriculture technologies (PATs) to mitigate greenhouse emissions by providing a short description of the technology and the impacts that have been reported in literature on greenhouse gases reduction and the associated impacts on farm productivity and economics. They concluded that PA has several positive impacts on agricultural systems translated to increased farm productivity and income and recently there is significant interest on the possible GHG emission mitigation using PATs. All categories of PATs (guidance, recording, and reacting) contribute to the reduction of GHG emissions due to their interconnections and it is difficult to separate them according to importance. The synergy between conservation tillage systems, especially NT, and PA strategies represents a useful tool in terms of carbon emissions mitigation with a reduction of 56% of total CO2 as compared to CT (Cillis et al. 2018). By PA, irrigation system enables in less fertile fields which can be transformed into agricultural croplands and improves the ability of soil organic matter extracted by enhanced biomass growth. Another perceptive of utilization of state of the art in understanding the processes leading to SOC sequestration can be made using modern innovations such as nanoenhanced products (e.g., nanofertilizers and nanopesticides) with a nano-based smart delivery system (use of halloysite) to provide nutrients at the desired site, time and rate to enhance productivity. Hydrogels and zeolites, the nanoporous materials, can store water in the soil during the rainfall season and release it slowly during the dry season, thus minimizing the adverse effects of environmental stress (Lal 2004). Zhang et al. (2017) separated soil nanoparticles from acid red soil (Ferralic Cambisol) including long term (26 years). They reported that the content of allophane which is a natural nanoparticles under raw pig manure treatment (0.64 g kg−1 ) was much higher than under unfertilized control (CK), chemical nitrogen, and phosphorus and potassium fertilizers (NPK) treatments. This study may indicate long-term organic manure amendment initializes positive feedback loop for further SOC sequestration. Thus, precision agriculture (PA) is a special instrument for balancing agricultural development and environmental needs. In conclusion, adopting various technologies of precision agriculture like efficient use of crop residue, conservation agriculture, integrated nutrient management, agroforestry, cover crop, use of organic and other biosolids, etc., along with soil C will have marked influence on sustainable crop production and impart climate resilience Qureshi et al. (2018). Hence, such smart practice addresses both the economic and environmental problems affecting today’s farming.

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9.3.20 Watershed Management Watershed security may be one of the key policy steps to mitigate danger of global warming (Bernoux et al. 2011). The expected rise in average earth temperature by 1.50–5.80 °C (IP Climate Change 2001) in the future would raise hydrological shortage and volatility to ensure the crops production (Bernoux et al. 2011). To cope this malady, watershed management helps to combine land and water policy, to define and to prepare for contact with water, vegetation, animals, and human land use within a watershed’s physical borders within the sense of climate change (Rdrwa.ca. 2020). According to Bernoux et al. (2011) soil carbon sequestration if integrated to watershed management may serve as a bridge in addressing the global issues of climate change. They have also added that in order to tackle development challenges successfully in the context of climate change, it is crucial to properly consider the linkages among land-use change such as deforestation and conversion among forest, grasslands and croplands; land resources management is soil, water, vegetation and biodiversity management, and the vulnerability or resilience of local livelihoods. It has proven effective to reduce deforestation on sloping fields, stabilize habitats, provide clean water, maintain and somehow boost small-to-mediumscale agricultural production systems (Menon 2007). Lashanizand and Siahmansour (2016) conducted a research on determining the effects and potential of biological operations of watershed management in carbon sequestration to modify climatic changes at Iran. The results for the selected sited showed that with watershed management biological operations enjoyed accurate and controlled management system and have favorable carbon sequestration conditions (2025 kg per ha land area) than the areas that lack any type of management (122 kg per ha land area). Such carbon trading creates an opportunity for the regeneration of degraded lands and watersheds through a variety of practices. Tree planting on degraded land that cannot sustain crop production will contribute to carbon sequestration. It validates the synergistic relationship of watershed, land and water management that should be deliberately promoted in climate change and carbon market negotiations and cooperation (Bernoux et al. 2011). The control of sub-surface water contributes which offers a basis for systematic decision: evaluation of watershed quality and status; determining watershed challenges; establishing and re-short- and long-priorities and initiatives and targets (Rdrwa.ca. 2020). The downward cycle can be disrupted by sustainable cultivation and management with a decrease in climate risk and an improvement in people’s willingness to become adaptive and also contribute to climate change mitigation with increased carbon sequestration and decreased greenhouse gas emissions. (Bernoux et al. 2011). Lashanizand et al. (2012) reported that the Romeshgan flood distribution area with carbon sequestration as weigh as 78.4 tons per ha was a successful project in terms of carbon sequestration with the efficient management as well as biological and mechanical watershed operation. Such all few finding predicted that watershed conservation and effective use of the soil and water are critical fields of growth that pose several improvements in the cooperation capacity of food health, climate change, and climate mitigation (Bernoux et al. 2011).

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9.3.21 Organic Agriculture Organic farming (OF) is believed to improve soil fertility by enhancing soil organic matter (SOM) contents. An important co-benefit would be sequestration of carbon from atmospheric CO2 showed that the positive organic farming effects on soil respiration, soil organic carbon stocks, and soil organic carbon sequestration rates were significant even in organic farms with low manure application rates. Higher organic matter contents in soil can also boost soil microbial activities, which will benefit soil conservation and plant growth found that soils under OF had significantly higher C stocks, concentrations, and rates of C increase than those under conventional farming (CF) and attributed these differences to the intrinsically higher C inputs in OF. In their analysis OF receive, on average, much higher external (manure, slurry, compost) C inputs (1.20 Mg C ha−1 y−1 ) than CF (0.29 Mg C ha−1 y−1 ). The global average sequestration potential of organic croplands to be 0.9–2.4 Gt CO2 per year, which is equivalent to an average sequestration potential of about 200–400 kg C per hectare and year for all croplands. In addition to the soil carbon pool, organic agriculture encourages agroforestry as well as the integration of landscape elements, leading to a further carbon sequestration in plant biomass.

9.3.22 Zero Budget Natural Farming Clean cultivation, together with zero expenditure, is part of the global agroecology trend. When we compared the expenditure of zero budget natural farming with the traditional high-cost farm chemical production method, it is a win-win solution. Particularly, this is effective in addressing climate change risks. This type of Indian farming focuses on regenerative measures. This natural ways uses the photosynthesis forces in plants to lock the carbon cycle enhance soil quality, nutrient density, and crop intensity. Thus, it is a comprehensive method of farming. In this type of farming, we can cultivate natural resources and restore habitats for food, health, and healthy livelihoods to remain regenerative. Hence, the costs will be lessened as the foreign inputs will be removed and on-site tools are used to restore the soils biome. Moreover, the farmer’s income will increase, restore ecological health, and tolerance of climate is seen from using a diverse variety of multilayered crop systems. The farming primarily focuses on soil microbiota, soil aeration, improved development of soil and humus, and percolation. Also, the water is preserved and healthy yields can be obtained in even severely affected areas of environment. It also eradicates chemical fertilizers and pesticides, and further helps in reducing the ocean acidification and also the marine pollution from land-based activities. There will be landscape restoration and biodiversity loss prevention. The microbial content and water retention capacity

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will be improved and the chemical fertilizers runoff into rivers and wetlands will be reduced which result in ensuring water quality and availability at the time of extreme weather conditions. It is also reported that carbon dioxide emitted is reduced from the agriculture sector as the land having more than 202,500 ha and most of the 500,000 farmers are converting their lands to natural farming.

9.3.23 Biosequestration and Microalgae Biological sequestration involves use of CO2 sequester; microalgae, because they use carbon dioxide for synthesis of energy in the process called photosynthesis and subsequently, reduce CO2 emission efficiently. In the service of carbon fixation, this organism saves a lot of energy and also have high photosynthetic efficiency, algae have active bicarbonate pumps and can concentrate bicarbonate in the cells. In the process, the bicarbonate is dehydrated, either naturally or by carbonic anhydrase, and the resulting CO2 is absorbed by Calvin cycle action, eventually in the form of algal biomass. For every gram of algal biomass produced, between 1.6 and 2 grams of CO2 can be captured. Biomass of this organism contains approximately 50% of carbon by cell dry mass, therefore it is used for CO2 sequestration process. It is reported that efficiency of microalgae using solar energy to fix carbon dioxide is 10– 50 times higher than that of other terrestrial plants. The efficiency of algae capture of CO2 can differ depending on the state of algae physiology, pond chemistry, and temperature. Carbon dioxide fixation efficiencies as high as 80–99% are attainable under optimum conditions and with gas residence times as short as two seconds. And also, CO2 fixation accompanied by microalgae photosynthesis results in production of bioproducts such as pigments, sustainable biofuels, food, animal and aquaculture feed products, and other value-added items such as cosmetics, nutraceuticals, pharmaceuticals, biofertilizers, bioactive substances which are added benefit from the microalgae mediated CO2 sequestration process (Yadav et al. 2017. Another big service of microalgae is it can be fed with infamous waste gasses such as CO2 and nitrogen oxides and sulfur oxides from flue gas, inorganic and organic carbon, N, P and other pollutants from agricultural lands, industrial and wastewater sources, so as to give us the ability to turn them into bioenergy, useful goods and types that are least harmful to the environment. To illustrate few findings, CO2 fixation potential of microalgae at various CO2 partial pressures generated by CO2 generating buffer (KHCO3 /K2 CO3 ). In their reports, Chlorella sp. can sequester CO2 at 28 ± 1.2%, while the specific growth rate and carbon fixation rate were observed at 0.064 h−1 and 68.9 ± 1.91 mg L−1

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h−1 , respectively S. obliquus SA1, strain tolerance to 13.8 ± 1.5% CO2 concentration and 40 °C temperature and it was found to be significantly lowered the inlet CO2 concentration from 13.8 ± 1.5% to 0.5%. Chlorella vulgaris is fully effective in extracting nitrates and phosphates from the waste water medium. The rate of CO2 fixation (RCO2 ) by Chlorella vulgaris P12 cultivated photoautotrophically in bubble column photobioreactors under different CO2 concentrations (ranging from 2 to 10%) and aeration rates (ranging from 0.1 to 0.7 vvm) showed that the maximum RCO2 (2.22 g/L/d) was obtained by using 6.5% CO2 and 0.5 vvm after 7 days of cultivation at 30 °C. Analysis of sequestrate CO2 by Spirulina platensis and Chlorella vulgaris under various levels of salinity and CO2 revealed that the fastest growth rate reached during the first 4 days and the higher concentration of biomass at CO2 from 0.03 to 10%, respectively. The final CO2 sequestration rate for Spirulina platensis and Chlorella vulgaris was 0.49 and 0.152 g/L/d in natural water, respectively, while 0.419 and 0.097 g/L/d in artificial seawater were registered at 10% CO2 concentrations, respectively. From the above few finding, we can assume that CO2 biomitigation through these microalgae is considered as an eco-friendly and promising alternative to the existing carbon sequestration methods.

9.3.24 Phytosequestration and Impact of Plant Genetic Engineering on Phytosequestration The photosynthetic uptake of atmospheric carbon dioxide (CO2 ) by land plant has important role in global carbon (C) cycling (Tuskan and Walsh 2001; Lal 2004, 2008; Houghton 2007; Graber et al. 2008; Jansson et al. 2010). The enhancing terrestrial C biosequestration includes improving photosynthetic incorporation of atmospheric CO2 into plant biomass; increasing C shunting into cellular C pools with low turnover, such as cell walls; and enhancing the allocation of C as recalcitrant organic matter to deep roots for transfer to the SOC pool. The feasibility of improving photosynthetic capacity by the genetic manipulation of the Calvin cycle in the typical green microalgae Chlorella vulgaris and suggested a possible role for aldolase over expression in promoting the regeneration of ribulose 1, 5-bisphosphate in the Calvin cycle and energy transfer in photosystems. In relevant to plant model organism, using genetic methodologies in tobacco (Nicotinia gene), researchers have modified photosynthesis and shown that genetically modified tobacco plants have increased their growth by more than 40% and have gained about 25% more plant biomass than unmodified plants. Some trials have succeeded; for example, Kromdijk et al. (2016) optimized photoprotection recovery in tobacco leaves and increased dry matter production by 15%. Carbon lost through photorespiration may be reduced by the introduction of C4 photosynthetic pathway in C3 plant (Wang et al. 2017). C3 crops engineered with reduced photorespiration could theoretically increase the photosynthetic rate by 10–30% (Metting et al. 2001), resulting in a 6% yield increase (Sinclair et al. 2004). Increased photosynthesis could lead to a 50% increase in

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productivity (Long et al. 2006). Transgenic perennial cereals in agriculture could increase the transfer of C to root biomass. Switchgrass was five times more efficient in sequestering C in root biomass (at a rate of 1.1 Mg per ha per year) than corn (0.2 Mg per ha per year; Lemus and Lal 2005). According to Lemus and Lal (2005), the potential for soil C sequestration in bioenergy plantations alone is 1.6 GT per year which can be increased to 2–3 GT with plantations of engineered trees endowed with enhanced photosynthesis. If bioenergy crops are cultivated in 375 million ha of land by 2050, sequestration may equal 0.8 GT per year. This amount could double in genetically improved perennial grasses and SRWC with increased C partitioning to roots. This reallocation of resources should be coupled with enhanced photosynthesis in order to avoid lowering in biomass yield for energy purposes, as it may be utilized for respiration, flowering, and seed set (Jansson et al. 2010). Cultivation of transgenic plants having drought and salinity tolerance will raise net primary production and bioenergy crops will offset fossil fuel emission. The combined effects may enhance C sequestration in arid and semiarid ecosystems correspond to 2–3 Gigatonne of carbon per year (Jansson et al. 2010). Apart from holistic services of plants kingdom, diverse metabolic capabilities, superior growth rates, and ability to store or secrete energy-rich hydrocarbons are the relatively high photosynthetic conversion efficiencies of algae communities. In order to reduce the unit cost of algal biomass, significant advances in the development of genetic manipulation tools have recently been achieved with microalgal model systems with higher photosynthetic capacity and genetic engineering are being used to manipulate central carbon metabolism in these organisms. Having found little achievement presented here, the application of genetic engineering to improve energy production phenotypes in eukaryotic microalgae is still in its infancy and such technology will provide an insight into targeted genetic engineering toward algal trait improvement for CO2 biomitigation uses.

9.4 Challenges, Way Forward and Conclusion In terrestrial systems, the total C stock (i.e., organic and inorganic C) is estimated to be around 3170 gigatons; in the soil is 2500 GT and 560 GT and 110 GT in plant and microbial biomass, respectively, while in the oceans is 38,000 GT (Tuskan and Walsh 2001; Lal 2004, 2008; Houghton 2007; Graber et al. 2008). The soil C pool, which is 3.3 times the size of the atmospheric C pool of 760 GT, includes about 1550 GT of soil organic carbon (SOC) and 950 GT of soil inorganic carbon (SIC) (Lal 2004, 2008). Although carbon sequestration and reductions in greenhouse gas emissions can occur through a variety of smart agricultural practices, perhaps, there are numerous challenges while making these three pillars of climate smart agriculture

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into reality. Durability is among the greatest liabilities of combating climate crises through regenerative agriculture. While soil carbon sequestration can be permanent in theory, however, it often is not. The reason being the carbon could be released back to the atmosphere as easily as it is gained as a result of decomposition or mineralization. Meanwhile, it is for this reason sequestered carbon is considered a short-term alternative for carbon removal from the atmosphere. The losses of terrestrial carbons are due to the disturbances, such as fire, wind-throw, drought or pests, and through human activities like deforestation and changes in unplanned agricultural practices leading to land degradation. According to many studies, the overall terrestrial C sink is expected to weaken with global warming as the CO2 fertilizing effect loses out to increased plant and soil respiration (Bonan 2008; Sokolov et al. 2008) but the extent by which the C pools will decrease is unclear (Canadell et al. 2007). So, the annual fluxes of C between the atmosphere and land is 123 GT, which represents the photosynthetic C uptake of the global terrestrial system or the gross primary productivity. 60 GT of GPP captured by plants returned immediately to atmosphere through plant respiration (Jansson et al. 2010). The carbon benefits of no-till farming, for instance, mostly evaporate when the farmer decides to till again, which happens on an estimated 30% of no-till farms. In agroforestry systems which are effective carbon sinks, however intensively controlled agroforestry operations in conjunction with annual crops are like conventional agriculture, which does not lead to carbon sequestration (Montagnini and Nair 2004). In semiarid climates, cover crops to a larger extent may not likely to have these SOC benefits because of a lack of sufficient water for crop growth during the fallow (Godde et al. 2016). So, growing plants on such semiarid lands has been suggested as a way to increase carbon storage in soils. But the drawback is that the fossil fuel costs of irrigating these lands may exceed any net gain in carbon sequestration. Additionally, in many semiarid regions surface and groundwater contain high concentrations of dissolved calcium, and bicarbonate ions which increase release of CO2 into the atmosphere (http://www.esa.org.). It is also suggested that application of fertilizer in legume plants in a crop rotation phase is not a smart way to increase SOC, as the leguminous phase can lead to less incorporated biomass C into the soil organic matter pool than other crops, reducing subsequent SOC. It can also contribute to higher soil nitrogen which promotes C mineralization and consequently SOC loss. So, instead, the leguminous phase without fertilizer can increased crop yields and SOC because of fixed nitrogen added to the soil (Godde et al. 2016). In addition to its challenges, the agricultural activities which are undertaken to mitigate or offset GHG emissions can also intensify emissions and cause leakage. Moreover, some of these agricultural practices can lessen crop yields leading to the expansion of farmland elsewhere and converts valuable wildlife habitat to farmland and generates emissions, potentially nullifying the original carbon sequestration benefits. In another instance, in order to increase soil carbon, sometimes cultivated crop land is converted to permanent pasture lands. However, pasture is generally used to feed livestock, which emit methane. If the pasture is retained and grazed, leakage occurs more rapidly than ongoing sequestration. If the pasture is retained and not grazed, the income generated from cropping is likely to surpass the benefits

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of sequestration. Also, it is known that agricultural soil carbon sequestration has a serious measurement issue. Despite having the technologies capable of measuring soil carbon in specific sites, the measurement can be difficult, laborious and expensive which hinders the farmers to participate in carbon sequestration programs. Also, changes within the range of 10% are very difficult to detect because of sampling errors, small-scale variability, and uncertainties with measures and analysis. Even if little gains or losses in soil carbon at various scales are detected, it is not simple to link such changes to management or land-use practice in a given context. The capacity of the soil to sequester and retain carbon is also limited as it reaches the saturation point. Besides, it is not easy to separate the portion of carbon sequestered in the soil as result of management activities or land use from that of which occurred naturally. All policies, grants or investments that fund or incentivize some action completely determine that the action would not have taken place in the absence of policy implementation. The difficulty is compounded in terrestrial carbon sequestration projects because the direct, human-induced changes in carbon stocks must be differentiated from changes in carbon stocks driven by natural processes (e.g., biomass carbon stock recovery after a fire) and indirectly by human actions (e.g., enhanced biomass carbon stocks driven by CO2 fertilization or N deposition; increased soil carbon stocks driven by shifts in species composition). Moreover, the necessity of addressing the challenge of climate change does not allow us to follow the traditional and sequential research, development, and demonstration (RD&D) path, which might take as much as thirty years for carbon capture and sequestration to become commercial. Thus, having seen the challenges, risks and potential for perverse outcomes and high transaction costs, it is wise not to either uncritically support soil carbon sequestration nor turn our backs on the massive potential that soil carbon sequestering management practices might have on carbon levels in the atmosphere. Although there have been advances in tackling most of these challenges, deliberate actions especially by practitioners and policymakers alike are much needed to enhance carbon capture and sequestration in the soil ecosystem. It should also be recalled that, once the policy has been implemented, poor policy can be difficult to remove as it establishes a group of beneficiaries with an incentive to continue and if the sequestration is employed as a direct substitute for preventing or reducing emissions, soil carbon sequestration may not be an efficient strategy to mitigate the climate change. In addition, demonstration projects are required in large scale for testing and understanding the cost and performance of carbon capture technologies and storage reservoirs and demonstration to the public ensuring that carbon capture and sequestration is an effective and safe carbon mitigation approach.

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Sokolov AP, Kicklighter DW, Melillo JM, Felzer BS, Schlosser CA, Cronin TW (2008) Consequences of considering carbon-nitrogen interactions on the feedbacks between climate and the terrestrial carbon cycle. J Clim 21:3776–3796 Srinivasarao C (2017) Carbon sequestration and climate smart agriculture under climate change: threats. Strat Policies 1:91 Srinivasarao C, Lal R, Kundu S, Babu MP, Venkateswarlu B, Singh AK (2014) Soil carbon sequestration in rainfed production systems in the semiarid tropics of India. Sci Total Environ 487:587–603 Stewart CE, Paustian K, Conant RT, Plante AF, Six J (2007) Soil C sequestration: concept, evidence and evaluation. Biogeochemistry 86:19–31 Syswerda SP, Corbin AT, Mokma DL (2011) Agricultural management and soil carbon storage in surface vs. deep layers. Soil Sci Soc Am J 75:92–101 Tariyal K, Upadhyay A, Tewari S, Melkania U (2013) Plant and soil carbon stock and carbon sequestration potential in four major bamboo species of North India. J Adv Lab Res Biol 4(3):90– 98 Tavoni M, Sohngen B, Bosetti V (2007) Forestry and the carbon market response to stabilize climate. Energy Policy 35(11):5346–5353 Tiemann LK, Grandy AS, Atkinson EE, Marin-Spiotta E, McDaniel MD (2015) Crop rotational diversity enhances belowground communities and functions in an agroecosystem. Ecol Lett 18(8):761–771 Tiessen H, Feller C, Sampaio EVSB, Garin P (1998) Carbon sequestration and turnover in semi-arid Savanna and Dry forest. Clim Change 40:105–117 Tuskan GA, Walsh ME (2001) Short-rotation woody crop systems, atmospheric carbon dioxide and carbon management: A US case study. For Chronicle 77:259–264 Van GKJ, Six J, Hungate BA (2006) Element interactions limit soil carbon storage. Proc Natl Acad Sci 103:6571–6574 Varvel GE, Wilhelm WW (2011) No-tillage increases soil profile carbon and nitrogen under longterm rainfed cropping systems. Soil Tillage Res 114:28–36 Vicente-Vicente JL, García-Ruiz R, Francaviglia R, Aguilera E, Smith P (2016) Soil carbon sequestration rates under Mediterranean woody crops using recommended management practices: a meta-analysis. Agr Ecosyst Environ 235:204–214 Wang W, Fang J (2009) Soil respiration and human effects on global grassland. Glob Planet Change 67(1):20–28 Wang Q, Li Y, Alva A (2010) Cropping systems to improve carbon sequestration for mitigation of climate change. J Environ Prot 1:207–215 Wang S, Tholen D, Zhu XG (2017) C4 photosynthesis in C3 rice: a theoretical analysis of biochemical and anatomical factors. Plant, Cell Environ 40:80–94. https://doi.org/10.1111/pce. 12834 West TO, Marland GA (2002) Synthesis of carbon sequestration, carbon emissions, and net carbon flux in agriculture: Comparing tillage practices in the United States. Agr Ecosyst Environ 91:217– 232 West TO, Post WM (2002) Soil organic carbon sequestration rates by tillage and crop rotation: a global data analysis. Soil Sci Soc Am J 66(6):1930–1946 Wilsey B, Parent G, Roulet N, Moore T, Potvin C (2002) Tropical pasture carbon cycling: Relationships between C source/sink strength, aboveground biomass, and grazing. Ecol Lett 5(3):367–376 Wilson GWT, Rice CW, Rillig MC, Springer A, Hartnett DC (2009) Soil aggregation and carbon sequestration are tightly correlated with the abundance of arbuscular mycorrhizal fungi: results from long-term field experiments. Ecol Lett 12(5):452–461 Windeatt JH, Ross AB, Williams PT, Forster PM, Nahil MA, Singh S (2014) Characteristics of biochar from crop residue: Potential for carbon sequestration and soil amendment. J Environ Manage 146:189–197

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Witt C, Cassman KG, Olk DC, Biker U, Liboon SP, Samson MI, Ottow JC (2000) Crop rotation and residue management effects on carbon sequestration, nitrogen cycling and productivity of irrigated rice systems. Plant Soil 225(1):263–278 Yadav GS, Lal R, Meena RS, Babu S, Das A, Bhowmik SN, Datta M, Layak J, Saha P (2017) Conservation tillage and nutrient management e ects on productivity and soil carbon sequestration under double cropping of rice in north eastern region of India. Ecol Ind. https://doi.org/10.1016/ j.ecolind.2017.08.071 Zhang J, Xiao J, Li S, Ran W (2017) Manure amendment increases the content of nanomineral allophane in an acid arable soil. Sci Rep 7(1):1–8 Zia URF, Muhammad S, Nukshab Z, Khurram N, Muhammad MH (2018) Enhancing carbon sequestration using organic amendments and agricultural practices. In: Carbon capture, utilization and sequestration. http://dx.doi.org/10.5772/intechopen.79336

Chapter 10

Quantification of the Soil Organic Carbon and Major Nutrients Using Geostatistical Approach for Lahaul Valley, Cold Arid Region of Trans-Himalaya Praveen Kumar, Pardeep Kumar, Munish Sharma, Nagender Pal Butail, and Arvind Kumar Shukla

10.1 Introduction The quantification of soil organic carbon (SOC) is very important to understand the processes of mineralization, erosion, and soil carbon sequestration under different terrestrial ecosystems. The soil organic carbon is the property of soil aggregates which comprises the “plant, animal tissues, and microbial biomass at various stages of decomposition” (Lal 2018). However, the total content may vary with climatic factors, addition of biomass, land use practices and erosion rate (Meersmans et al. 2010). In late 1850s, the measurement of SOC was primarily seen only as an indicator for the soil fertility, but now, the focus of the scientific community has shifted with a wide perspective to facilitate the soil and environmental decisions for sustainable agriculture. The soil is the largest sink or source for atmospheric carbon having long mean residence time (MRT) that can mitigate the effect of global warming (Olson et al. 2014; Lal 2018). The sustainable land use practices and site-specific soil management can bring a positive C-budget to partially mitigate the rise in atmospheric carbon (Lal and Bruce 1999). The various studies demonstrate the role of soil organic carbon in mitigating climate change and providing healthy food for attaining food security (Lal 2004a; Zhang et al. 2017; Chen et al. 2019; Nayak et al. 2019). So, there are many perspectives for studying soil organic carbon and its fraction in different terrestrial P. Kumar · P. Kumar (B) · M. Sharma · N. P. Butail Department of Soil Science, CSKHPKV, Palampur 176062, Himachal Pradesh, India A. K. Shukla ICAR-Indian Institute of Soil Science, Nabibagh, Berasia Road, Bhopal, Madhya Pradesh 462038, India © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2021 D. Pant et al. (eds.), Advances in Carbon Capture and Utilization, Energy, Environment, and Sustainability, https://doi.org/10.1007/978-981-16-0638-0_10

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ecosystem. In this context, several international treaties (i.e., Kyoto protocol) also strengthen the requirement of soil organic carbon status for maintaining healthy carbon budgeting. The organic carbon present in the soil provides a major input for calculating the organic carbon stock as well as net carbon flux (West and Marland 2002; Schrumpf et al. 2011; Mohamad et al. 2016). So, the mapping of soil organic carbon in various terrestrial ecosystems is important to generate the baseline of carbon pools for analyzing the balance of agro-ecosystems in the global carbon cycling. The agricultural practices including change in land use, agricultural activities, i.e., pruning, harvesting, fertilization, tillage, etc., and soil management practices can significantly alter the organic matter in soil. Beside, some statistical uncertainties in the agricultural practices, change in land use pattern, and land cover contribute approximately 20 percent of the global carbon emissions (IPCC 2001; Mohamad et al. 2016). The organic carbon content in soil is also controlled by several other factors; including climate, hydrology, parent rock, vegetation association, and anthropogenic activities viz. biomass burning, changes in land use pattern, deforestation, and level of pollution. So there are many factors; including natural as well anthropogenic, which can influence the organic carbon content in the soil. The previous studies in different regions of the world also mark the considerable changes of SOC content with depth, land use, nutrient reserve, mineralogy, and landscape (Lorenz and Lal 2005; Barre et al. 2017; Yang et al. 2018). A wide physiographical variation was noticed in the soil organic carbon content of the Indian soils under different land use system (Gupta and Rao 1994; Bhattacharyya et al. 2000; Paul et al. 2018). The soil organic carbon is considered as an indicator of soil degradation, health, and productivity (Fageria 2012; Obalum et al. 2017). However, this is not a sole indicator for all the soil types, as it requires a wide range of validation in different agro-ecological contexts (Biancalani et al. 2012). The carbon sequestration in agriculture provides a simple, cost-effective measure to capture carbon and an opportunity to gain economic sustainability from diversifying incomes. As a consequence, the scientific community has an increased interest in the evaluation of soil organic carbon to delineate carbon pool sizes and fluxes for limiting the emissions of greenhouse gases. The cold arid region is ecologically fragile, facing threats from natural as well human interventions due to change in land use pattern and soil degradation. The study area is endowed with complex geobotanical landscapes, the arable land is mainly filled with the sediments derived from the complex geological environment (Kumar et al. 2018), and this may bring varied degree of carbon sequestration capability and nutrient availability in the soil. The marginal farmers residing in the area require site specific farming inputs for the sustained intensification in hill agriculture. However, the background information on SOC content and availability of the major nutrients is sparsely distributed along the extreme regions of Trans-Himalaya, India. There are few studies which provide the status of the soil variables in the cold desert Himalaya (Sharma et al. 2006; Charan et al. 2013). Moreover, the status of soil nutrients needs to be evaluated temporally for suggesting site-specific recommendations to increase/sustain the crop yields. So, the present study was planned to delineate SOC content and availability of the major nutrients in different agro-ecosystem of

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the Lahaul valley to provide insight for eco-environmental protection and sustainable agriculture.

10.2 Materials and Methods 10.2.1 Study Area The study area is the part of temperate region of Lahaul valley, Trans-Himalaya, India. The area is characterized by xeric environment with sparse vegetation due cold arid climatic conditions, scanty rainfall, and massive snowfall. This extreme region is approachable through Rohtang Pass, Baralacha Pass, and Kunzum Pass, while it remains cut off from the rest of the world during heavy snowfall (November to March). A very few indigenous tree species, i.e., Salix spp., Juniperus spp., Betula utilis, Hippophae salicifolia, Crataegus songarica, and Robinia pseudoacacia, are dominant, which make the area ecologically vulnerable (Kumar et al. 2018). The Lahaul valley is characterized by high hills, steep slopes, narrow valley subregions, alpine rangelands, and rocky outcrops. The major rock type comprises greenish shale, limestone, and quartzite (Gupta and Kumar 1975). The study area is located in the complex geological environment, and our focus was confined to the evaluation of soil organic carbon and major nutrients from the arable land of the Lahaul valley.

10.2.2 Soil Sampling and Analysis The soil sampling was carried out in the month of October, 2019, before the start of the snowfall in the valley subregion. At each sampling location, some preliminary steps were followed, which includes gentle removal of plants and litter and other unwanted materials from the surface. The soil samples were collected from the surface (0– 15 cm) and subsurface (15–30 cm) to delineate variations in SOC content and major nutrients in the soil. The soil sampling was carried out by using the methodology described in detail by Ohlinger (1996) and Barre et al. (2017). A clean handheld auger was used for the soil sampling in the agricultural field, and a total of five soil sub-samples were collected (one from the center and other from the four cardinal directions). The collected samples were mixed together to make a composite sample for surface as well as subsurface for the respective site. These samples were kept in the airtight polythene bag for further processing and analysis. In the laboratory, these samples were spread on the clean plastic tray, air dried for a few days depending upon the moisture condition, and sieved through a 2 mm sieve. Further, these samples were oven dried at 60 °C and packed in a clean plastic bottle for analysis. A rapid titration method was used to measure the soil organic carbon (SOC)

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Fig. 10.1 Location of the sampling sites on the basemap adapted from Google Earth with respect to India

content (Walkley and Black 1934). The available nitrogen was analyzed using alkaline permanganate (Subbiah and Asija 1956), phosphorus with bicarbonate extraction method (Olsen 1954), and potassium with neutral normal ammonium acetate extraction methods (Black 1965) (Fig. 10.1).

10.2.3 Geostatistical Analysis The geostatistical approach was applied along with descriptive statistics. The geostatistical analysis deals with spatial data to estimate the value of the unsampled location from the sampled one (Goovaerts 1997; Liu et al. 2008). There are a number of interpolation techniques to estimate the quantities that vary in space and represent the outcomes of spatial analysis (Robinson and Metternicht 2006; Reza et al. 2015). The ordinary Kriging (OK) technique is most common that provides reliable estimates to calculate the weighted sums of the neighboring samples to check the spatial dependence among the data point. The OK interpolation technique predicts the value of the unsampled location (x0 ) by considering the Z (x0 ) as the line sum of the parameter from measured sites (Wang 1999; Shit et al. 2016). Z (x0 ) =

n 

λi˙ z(xi )

(10.1)

i=1

where Z (x0 ) represent the predicted value and Z (xi ) is the sample value of the position x0 and xi , respectively. During interpolation, sites (n) were searched within the neighborhood with weighting coefficient λi˙ .

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The normality and skewness were checked with the guidelines as described in detail by Krig (1981). The semivariogram was generated to check the range of spatial dependence in the dataset. The semivariogram analysis has also been used by many researchers to check the degree of spatial dependence in soil variables as given in Eq. 10.2 (Goovaerts 1997; Lark 2000; Behera et al. 2016). m(h) 1  γ (h) = [Z (X i + h) − Z (X i )]2 2m(h) i=1

(10.2)

where (h) describes the magnitude of lag distance with number of observation pair m(h) separated by Z(Xi), Z(Xi + h) is the sample values at two points (Xi) and (Xi + h), respectively. A suitable model is fitted for the experimental variogram using hit and trial approach and the variogram parameters (i.e., range, nugget and sill) for the Kriging procedure. The various stationary models, i.e., exponential (Eq. 10.3), Gaussian (Eq. 10.4), and spherical (Eq. 10.5) models were tested for the best fitted with the experimental semivariogram using the equations (Burgess and Webster 1980; Tesfahunegn et al. 2011):    h y(h) = c0 + c1 1 − exp − a   2  h y(h) = c0 + c1 1 − exp − 2 a   3h h3 y(h) = c0 + c1 − 3 when h ≤ a 2a 2a = c0 + c1 when h ≥ a

(10.3)

(10.4)

(10.5)

In these equations, the C 0 represents the nugget, C 1 stand for the partial sill, and ‘a’ is the range. The nugget-to-sill ratio {i.e., C 0 /(C 0 + C 1 )} was used to describe the spatial structure of the measured soil variables in the study area.

10.3 Results and Discussion The descriptive statistics was applied to analyze the soil samples for different parameters. The value of the mean and the median are close representing non-appearance of the outliers while calculating the central tendency. The surface samples showed the soil organic carbon (SOC) varied from 6.15 to 23.7 g/kg with the mean value 15.26 g/kg (Table 10.1). In subsurface soil, the SOC content ranged between 5.7 and 30.9 g/kg with the mean value 13.58 g/kg. In general, the SOC content decreased with depth for most of the subsurface soil samples. This may be due to erosional processes, while the range toward the higherside (i.e., 30.9 g/kg) can be correlated

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Table 10.1 Descriptive statistics of the studied soil variables from the Lahaul valley Property

Mean

Minimum Maximum Standard deviation CV(%) Skewness Kurtosis

Surface (0–15 cm) OC (g/kg) N (kg/ha) P (kg/ha) K (kg/ha)

15.26

6.15

−1.11

23.7

4.84

31.70

0.09

342.58

28.80

10.56

1.01

0.42

8.04

45.85

9.47

45.76

0.81

−0.12

221.63 109.37

348.30

67.55

30.48

0.21

−1.11

30.9

5.53

40.75

1.08

1.15

293.34

35.65

16.41

0.23

1.07

40.20

8.27

45.26

1.15

1.21

68.28

35.08

0.59

0.31

272.80 243.8 20.69

Subsurface (15–30 cm) OC (g/kg) N (kg/ha)

13.58

5.7

217.21 140.68

P (kg/ha)

18.26

K (kg/ha)

194.65

5.22 81

393

with higher biomass in the deeper strata that may be due to addition of biomass or the residual from the past forest cover in agroforestry system. The major nutrients viz. nitrogen (N), phosphorus (P), and potassium (K) showed a range from 243.8 to 342.58 kg/ha, 8.04 to 45.85 kg/ha, and 109.37 to 348.30 kg/ha, respectively, in the surface soil layer (Table 10.1). The normality of the acquired data was tested with the Kolmogorov–Smirnov (K–S) method and quantile-quantile (Q–Q) plot (Fig. 10.2a). The scatter plot for the observed and predicted value is shown in Fig. 10.2b for the validation of the results by semivariogram model (Fig. 10.3). The exponential was the best-fitted model for the soil organic carbon determined from the coefficient of determination (R2 ). The nugget-to-sill ratio 0.75 was related to strong, moderate, and weak correlation of the estimated value. The weak-to-moderate spatial dependency can be correlated with the stochastic

Fig. 10.2 a Q–Q plot and b semivariogram model of soil organic carbon for the surface soil samples with the observed and predicted values

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Fig. 10.3 Semivariogram and the fitted model of soil organic carbon for the surface soil samples

factors viz. fertilization, cropping system, and human intervention, while the strong spatial dependency can be correlated with intrinsic factors, i.e., parent material and soil formation factors as discussed by many researchers (Cambardella et al. 1994; Liu et al. 2008; Vasu et al. 2017; Bhunia et al. 2018). The nugget-to-sill ratio (0.551) was calculated, which shows the moderate spatial dependence from the semivariogram analysis. Many researchers used the best fit criterion to sort out the appropriate model from the interpolation techniques (Santra et al. 2008; Reza et al. 2015). The similar approach was used to select appropriate interpolation technique from the geostatistical analyst tool in GIS platform. Figure 10.4 shows the spatial distribution map of SOC content prepared using OK interpolation technique for the samples collected from the arable land of the Lahaul valley. The map depicts that the SOC content varies significantly with the parent rock. The higher concentration was noticed toward the Trans-Himalaya region and the western part of the study area. However, the south-eastern part of the valley represents the lowest concentration of the SOC content in soil. This variation may arise due to different agricultural practices that influence the overall organic carbon content in soil. Many researchers pointed out the positive influence of elevation gradient for increasing SOC content due to higher vegetation and plant litter (Martin et al. 2014; Bian et al. 2020); however, in the present study, the results are contradictory as the highest concentration of SOC content in green color (>18.4 g/kg) does not correspond to the highest altitude of the study area (Fig. 10.4). This was possibly due to influence of precipitation and temperature and ‘hump shaped’ plant diversity pattern in mountainous region (Lal 2004b; Martin et al. 2014; Kumar et al. 2018). The soil samples collected from the study area might have passed through similar climatic oscillations, but the variation of parent rocks and sediment thicknesses might had caused a significant variation in the calculated soil properties. The soil physiochemical properties and their variation with geological setup and parent rock have already been discussed by many researchers for different regions of the world (Guo and Gifford 2002; Heckman et al. 2009; Barre et al. 2017). This has also been noticed from the present study which shows linkage of the soil organic carbon with the parent rock material, geological setup, and land use.

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Fig. 10.4 Spatial distribution map of soil organic carbon content in the Lahaul valley

The similar modeling approach was also tested with the major nutrients, where the Inverse Distance Weighting (IDW) interpolation technique provides the better representation of the spatial data. Figure 10.5 shows the spatial distribution map from surface and subsurface soil samples for available nitrogen (N), phosphorus (P), and potassium (K) in the study area. The mean value of the N showed the low concentration, while considering the value of nitrogen Silvipasture > Agrisilviculture > Agrihorticulture

Total carbon sequestration was found in the decreasing order: Ulmus Villosa > Albizia procera > Quercus, > Pinus roxburghii > Alnus nitida > Acacia catechu > Acacia mollissina > Eucalyptus tereticornis

Biomass accumulation followed the trend: Forest > silvipasture > agrohorticulture > horticulture > agriculture and the rate of C-sequestration was maximum in the agrohorticulture

Main results

Table 12.2 Recent studies conducted in western Himalaya to understand the carbon sequestration potential of different land uses

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References

Singh et al. (2019)

Krishan et al. (2017)

Verma and Garkoti (2019)

Ajit et al. (2017)

S. No.

6

7

8

9

Table 12.2 (continued)

District—Kupwara, Jammu and Kashmir

Kumaun region, Uttarakhand

Garhwal region, Uttarakhand

Districts-Kangra, Hamirpur, Una, Bilaspur, Solan and Sirmaur Himachal Pradesh

Study location

Agroforestry

Quercus leucotrichophora Forest

Six forest types: Pinus wallichiana, Quercus leucotrichophora, Quercus floribunda, Quercus semecarpifolia, Cedrus deodara, Abies spectabilis

Agriculture, horticulture, agrisilvicultural, silvopastoral, agrihorticulture, agrihortisilviculture, forest, grassland

Land uses

Existing agroforestry systems at farmers’ field in Kupwara district were estimated to offset completely the GHG emissions from agriculture/irrigation sector on account of electricity consumption throughout the state of J&K

Carbon stock of banj oak was found maximum in 10–20 cm dbh size class followed by 20–30 cm dbh

Belowground carbon stocks in Abies pindrow forests had maximum carbon assimilatory capacity, whereas Cedrus deodara forest has minimum BGC stocks

Forest land use system had higher carbon stock (vegetation + litter + soil) among all land use systems, but agrihortisilviculture system had higher carbon stock than agriculture and all other agroforestry systems

Main results

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to decrease greenhouse gas emission from agriculture. The average soil carbon stock in the soils of agricultural lands was 2.03 kg m–2 which was less as compared to closed canopy forests, open forests and disturbed forests with average soil carbon stock 3.39, 2.06 and 2.86 kg m–2 , respectively (Shaheen et al. 2017). The plowing, overgrazing and soil degradation in agricultural soil may be attributed to the least carbon content values representing negative impacts of these practices on soil carbon

a

b

Plate 12.1 Traditional land use systems in western Himalaya. a Dense coniferous forest in the temperate zone. b A silvipasture system. c Traditional agroforestry land use. d Terrence farming in the hills. e Cultivation of kiwi in horticulture farms. f Apple orchard at flowering stage in mid Himalaya

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c

d

Plate 12.1 (continued)

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e

f

Plate 12.1 (continued)

sequestration under cultivated areas in comparison to the forests. These issues indicate toward a need to develop sustainable and economically profitable agriculture setup including forest trees, i.e., agroforestry system according to climate and altitudinal gradient in order to fulfill the food demand of the growing population along with improved carbon sequestration in the land use. The existing agroforestry land use systems in western Himalayan region assist to convene the diverse needs of food, fodder, fuel wood and timber along with producing significant biomass. These agroforestry systems also contribute for a significant contribution toward C stock by atmospheric CO2 sequestration. Due to the government imposed ban on felling green/live trees in the entire Himalayan

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region of India, agroforestry systems may prove to be a good source of earning significant C credit to the farmers. Thus, sequestering C through agroforestry is now thought out as a striking economic opportunity for mitigating global climate change and C trading along with providing multiple products in the mountainous region of western Himalayan states. Nair et al. (2009) suggested that the Kyoto Protocol allowed developed countries with a GHG reduction commitment to invest in mitigation projects in the developing countries under the Clean Development Mechanism (CDM), and there is an attractive opportunity for main practitioners of agroforestry, especially the resource poor farmers in the Himalayan region where small land holdings are merely sufficient for subsistence farming. IPCC (2007) also pointed out in its special report that the conversion of wasteland and grassland to agroforestry has the best potential to store atmospheric CO2 other than direct benefits. Kumar et al. (2012) studied six traditional agroforestry systems in the villages of Pauri Garhwal district of Uttarakhand to estimate structure and carbon sequestration potential of traditional agroforestry systems. They inferred that the average total carbon stock of trees in traditional agroforestry system was 32.56 t /ha and soil organic carbon was 56.74 t/ha. In hill’s agroforestry systems, farmers usually fulfill their fodder and fuel wood needs by lopping the trees. The requirements of small timber are also met by harvesting occasionally a few trees at rotation of 30–40 years, and commercial felling is generally not practiced. Therefore, criteria of no leakage under CDM projects are met intrinsically in these agroforestry practices. Apart from using organic manures and conservation agriculture practices in crop-based agriculture farming systems to improve soil carbon stock, the carbon sequestration in traditional agroforestry system can be improved by reducing the overexploitation of the resources from the trees by lopping of branches frequently and its proper management. The overexploitation of resources from traditional agroforestry trees lessens the input of biomass and litter in the agroforestry system.

12.5 Carbon Sequestration in Horticulture/Agrihorticulture System Horticulture is comparatively a much recent land use change which has succeeded in the western Himalayan states. A transformation from conventional food crop cultivation to agrihorticultural land uses did well largely because of economic inducements and monetary benefits to the farmers which were ensured with the help of subsidy provided by government and increasing demands in the market. The perennial fruit crops are different from seasonal crops in their nutritional requirement due to their plant size, density, root spread, growth pattern, phenomenon of bud differentiation and their relationship with the yield during the bearing and offseason (Savita et al. 2016a, b; 2015). Agrihorticulture systems are the common land use systems, which are persistent in Himalaya (Yadav et al. 2016). These systems are the amalgamation of agriculture crops grown in the interspaces of fruit trees. The fruit-based system

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consists of three main components, viz. main crop, filler crop and inter-crops which occupy three different tiers in space of the production system (Patil and Kumar 2017). In the present scenario, these systems are the backbone of food, nutritional and livelihood security in hilly terrain of western Himalayan states. Although local farmers do not follow standard spacing and orientation patterns for planting fruit trees but randomly grown fruit trees in between the agricultural land serve the purpose to obtain diversified outputs, these systems improved farm income and reduced risk. Along with these benefits, studies in agrihorticulture systems in the western Himalayan ecosystem revealed that combination of fruit trees with conventional crop has also a substantial potential of C-sequestration as compared to the agricultural land use (Table 12.2). Rajput and Bhardwaj (2016), observed the influence of five different altitudes and existing agro-ecosystems on biomass and carbon sequestration potential in Kullu district of Himachal Pradesh. Five prevailing land uses, viz. agriculture, agrohorticulture, horticulture, silvipasture and forest at four elevations representing about 1 ° C temperature change, were taken for this study. It revealed that maximum C-sequestration potential was displayed by agrohorticulture land use system situated at the altitudinal range of 2000–2300 m asl and minimum by agriculture land use system at the altitudinal range of 1100–1400 m asl. The rate of C-sequestration potential in fruit-based agrohorticulture land use was superior to all combinations of forests, silvipasture systems. Agriculture crops are generally subjected to intensive management practices which results into higher biomass production in the agriculture land use, but the produce is harvested and removed from the fields annually leading to the lower C-sequestration potential. On the other hand in fruit-based agrihorticulture/agroforestry systems, which are similarly subjected to rigorous management practices, the biomass keeps on accumulating year after year in fruit trees for a longer time, and only small amount of biomass, i.e., pruned wood and fruits, is removed annually which results into their higher C-sequestration potential. The fruit-based systems that are a common land use in many parts of the temperate ecosystem of western Himalaya generally include the Malus domestica, Prunus armeniaca, Citrus sinensis, Prunus domestica, Pyrus communis, Prunus persica, Juglans regia, etc. The fruiting and flowering tendency of trees increases extraction of carbon from atmosphere and stores significant amount of carbon as cellulose inside the plants (Patil and Kumar 2017). Thus, considering the expansion of agriculture for sustainability of growing population and shrinking forest area, the orchards may affirmatively contribute to holistic development under climate change scenario in the temperate environment of western Himalaya. Unlike forest tree species, the potential of horticulture tree species for carbon sequestration has not been explored, and the research studies quantifying carbon sequestration potential of various fruit trees in western region are still meager. Keeping in view the extensive contribution of horticulture in the economy of western Himalayan region of India, viz. Himachal Pradesh, Jammu and Kashmir, Leh and Uttarakhand, there is need to identify and extend appropriate propagation methods, management systems and suitable species to make the most of carbon storage with better fruit productivity. More research investigations are required to quantify CO2 sequestration capacity in different fruit trees of this area including indigenous and less exploited beneficial wild fruit tree species.

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12.6 Soil Carbon Sequestration Under Different Land Uses The IPCC recognized the creation and strengthening of carbon sinks in the soil as an apparent option for increasing removal of CO2 from the atmosphere and has established the soil organic carbon pool as one of the five major ones for the land use, land use change in forestry sector. Soil has long been considered as the major organic carbon sink of terrestrial systems of the earth (Post et al. 1982), and soil organic carbon is considered as an important characteristic of soil fertility as well as the environment because of great carbon sequestration potential of soils. Lal (2004) reported that the total soil carbon pool of 2300 Pg is three times the atmospheric pool (770 Pg) and 3.8 times to that of vegetation pool (610 Pg). A reduction in soil organic carbon pool by 1 Pg is equal to an atmospheric improvement of CO2 by 0.47 ppm. Soil can also be a source (CO2 , CH4 and N2 O) or sink (CO2 and CH4 ) of greenhouse gases depending on land use and the adapted managements (Lal 1999). Growing anthropogenic disturbances of the Himalayan areas have proved to be a major cause of soil degradation and depletion of carbon stocks. However, the assessment of soil organic carbon is not the only criteria for evaluating C stock in soil. Different soil organic carbon pools are important in influencing the CO2 loading into the atmosphere. Labile carbon is the fraction of soil organic carbon with most speedy turnover times, and its oxidation makes the flux of CO2 between soils and atmosphere. The labile organic matter fractions (active pool) generally include microbial biomass C, particulate organic matter, readily mineralizable C, easily extractable C and carbohydrates (Haynes 2005), whereas the non-labile pool (passive pool) is more stable and recalcitrant fraction of soil organic carbon forming organic-mineral complexes with soil mineral and gets decomposed gradually by microbial activity (Wiesenberger et al. 2010). Thus, the labile soil organic carbon pools are better indicators of soil quality (Vieira et al. 2007), while the non-labile soil organic carbon pools add to the indication of total organic carbon stocks which will remain in the soil for a longer time (Chan et al. 2001). The variation in soil organic matter fractions as a function of land use alterations has been used for approximation organic matter dynamics and to quantify carbon stocks (Galdos et al. 2009). The impact of land use change in soil C dynamics is interpreted by carbon management index (CMI) which integrates carbon pool index (CPI) and the lability index (LI) (Assis et al. 2010). The lability index is further the ratio of the labile carbon to the non-labile carbon. This quantification of soil organic carbon stocks helps for finding suitable soil management so as to improve the productivity of all the land use systems. Verma and Sharma (2007) conducted a study in the field experiments, 6– 32 years long which were located in the wet-temperate zone of northwest Himalayas under different cropping systems, viz. maize–wheat, rice–wheat, soybean–wheat, Guinea grass and Setaria grass. Based on CMI ≥ 100 as the criterion of system sustainability (Blair et al. 1995), only the grass system was found to be sustainable. The modification of soil properties due to land use changes more often depends on vegetation types, microclimate, litter and root biomass and substrate availability; and consequently contribute to soil organic carbon storage apart from other factors such

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as soil pH and other nutrients which also influence CO2 production and emission from soil (Rawat et al. 2016). Similarly the altitude, aspect and vegetation cover and land use have noteworthy impact on soil organic carbon dynamics through organic carbon inputs, decomposition and stabilization in the hilly terrains. The plant or tree type has a significant effect on the vertical distribution of soil organic carbon (Jobbagy and Jackson 2000). Various studies conducted in the western Himalayan region (Table 12.3) for assessing the carbon storage potential of soil under different land uses revealed that the vegetation cover in these areas not only determines the amount and type of organic carbon inputs but also their location of accumulation, as either aboveground litter set down on the soil surface or in the subsoil layer. The high-altitude ecosystems are reported to have in general higher root: shoot ratios than other ecosystems (Yang et al. 2009). Because of these intricate environmental interrelationships, soil organic carbon is extremely heterogeneous in mountainous areas owing to the localscale variability in soil environment and microclimate (Sidari et al. 2009). Rajput et al. (2016) reported that forest land use system displayed the maximum value of soil organic carbon stock followed by agrihorticulture, horticulture, agrisilviculture, grassland and silvipasture land use system in Shimla district of Himachal Pradesh. However, the slope aspect controls the microclimatic factors such as soil temperature, moisture, vegetation and microorganisms by affecting the solar radiation and evapotranspiration, and this also suggests a strong association of slope aspect with soil organic carbon. While many studies have reported higher soil organic carbon content (Sharma et al. 2010) on the north-facing slopes of the western Himalayas, Sidari et al. (2008) reported lower soil organic carbon content on the northern aspect direction. On the other hand, Han et al. (2010) did not find any significant difference in soil organic carbon content between the north-facing and south-facing slopes. Along with the available studies in relation to the influence of land uses on soil organic carbon buildup under different climatic state of affairs on western Himalaya to abet public policy decisions about land uses and their management for optimization of organic carbon stock build up, the effect of plant/tree phenological stages, rainfall patterns or seasonal variations on the short-term fluctuations in soil labile and recalcitrant carbon fractions should also be given considerable attention to understand the short-range gains and losses in significant components of soil organic carbon stock, i.e., labile and non-labile pools of soil organic carbon to understand the detailed dynamics of carbon flux in different land use systems.

12.7 Conclusion and Discussion It can be concluded that the carbon studies in western region of Himalayan ecosystem are fairly challenging owing to varying topography and difficulties in accessibilities. Precise assessment of CO2 emissions or C storage capacity as a result of land use changes and other anthropogenic activities are a few challenging issues for making policies for better carbon sequestration. However, the widespread varying forest

References

Wani et al. (2014)

Chisanga et al. (2018)

Dar and Sundarapandian (2015)

Singh et al. (2011)

S. No.

1

2

3

4

Uttarakhand

District Pahalgam & Anantnag, Jammu & Kashmir

District—Kullu, Himachal Pradesh

South region of Kashmir

Study location

Maximum carbon density in 0–100 cm soil layer was recorded in agrihorticulture system and minimum in the barren land

Soil organic carbon CO2 mitigation density as t ha−1 was highest in Abies pindrow-Picea smithiana (closed) and lowest in Cedrus deodara (open)

Main results

Forest, grassland, horticulture, agriculture land use systems in four climatic conditions (subtropical, altitude: 500–1200 m; temperate 1200–2000 m; lower alpine 2000–3000 m; upper alpine, 3000–3500 m)

(continued)

SOC stocks were greater in natural ecosystems like forests and pastures than agriculture. Pattern of SOC stock build up across the altitude was: temperate > loweralpine > upper alpine > subtropical

Two forest types—Pinus wallichiana Greater SOC stock was recorded in and Abies pindrow the Pinus wallichiana forest type compared to Abies pindrow forest type

Agriculture, horticulture, agrihorticulture, agrihortisilviculture, silvipasture and barren land

Six forest strata: Cedrus deodara (closed), Cedrus deodara (open), Abies pindrow-Picea smithiana (closed), Abies pindrow-Picea smithiana (open), Pinus wallichiana (closed) and Pinus wallichiana (open)

Land uses

Table 12.3 Recent studies conducted in western Himalaya to understand the carbon sequestration potential of soil in different land uses

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Kalambukattu et al. (2013)

Gosain et al. (2015)

S. No.

5

6

7

Table 12.3 (continued)

District—Almora, Uttarakhand

Kumaun region, Uttarakhand

Foothill Himalaya of Jammu & Kashmir

Study location

Forest: Oak (Quercus leucotrichophora (Banj Oak), Pinus roxburghii (Chir Pine)

Four agriculture land uses: Organic farming, soybean, wheat, fodder crops, barren land and undisturbed oak (Quercus incana) forest

Agriculture, forest, horticulture and degraded lands

Land uses

Oak forests resulted in significantly greater C stock (vegetation + litter + soil pool) than the pine forests. In the oak forests, the soil holds almost double C stock as compared to that contained in above-ground vegetation

Carbon management index CMI followed the trend: Forest > Organic farming > Soya bean > Wheat ≈ Fodder > Barren land Labile carbon values under different systems Followed the trend: forest > organic farming > fodder ≈ soybean > wheat > barren land

Agricultural and degraded lands had up to 25% lower SOC stocks than forest soils, indicating that deforestation or conversion of forest land to agricultural uses are contributing to losses of up to 12.4 Mg ha− 1 SOC over time from the top half a meter layer of soil

Main results

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types play a vital role in carbon flux and act as carbon sink by storing large quantities of carbon for a long period of time in the Himalayan zone. This storage of organic matter in biomass offers a lag for complete carbon emission on account of respiration. While increased sequestration of atmospheric carbon in the soil, as stable soil organic matter pool, provides a long-term way out than standing biomass. In case of other land uses, the combination of fruit trees or other multipurpose tree species has shown the potential to store carbon and came out as feasible choice for mitigating carbon dioxide along with sustaining the livelihood of marginal farmers of the area. Overall, it can be said that tree-based systems should be promoted on agricultural lands for mitigating climate change and earning income through various products and obtained carbon credits. Acknowledgements The authors are grateful to Dr. J.P Mehta, Assistant Professor—Botany, HNB Garhwal University, Srinagar, Uttarakhand (India), for providing the photographs of different land uses in western Himalaya with consent for using in this chapter.

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Part V

Value Addition Techniques

Chapter 13

Progresses in Bioenergy Generation from CO2 : Mitigating the Climate Change Tanvi Sharma, Reva Bhardwaj, Rupali Bhardwaj, Anand Giri, Deepak Pant, and Ashok Kumar Nadda

13.1 Introduction These days, the interest in the clean energy generation has been quickly expanded as a direct result of the monetary development around the world. To fulfill this developing need, a bounteous measure of non-renewable energy sources is required (Giri et al. 2020; Leung et al. 2014). The depletion of non-renewable energy sources is frequently considered as one of the dangers to nature in context of the carbon dioxide (CO2 ) discharge. CO2 is primary green house gas (GHG), present on the land surface, sea, and environment where animals, plants, and microorganisms, assimilates and produces it every day (Kapoor et al. 2020; Spigarelli and Kawatra 2013). Notwithstanding, the pattern of discharging and expending CO2 must be adjusted essentially. To diminish the GHGs, CO2 sequestration and conversion capacity has increased to a great extent. In any case, we must develop the techniques and measures for capturing the CO2 as a feedstock. In this way, using CO2 and converting it into synthetic substances, will be useful to mitigate the CO2 emission (Peters et al. 2009). During the recent years, the transformation of CO2 into value-added synthetic compounds utilizing various methods are getting an incredible consideration from the researchers as it results in reducing the harmful GHGs (Kumar et al. 2019; Sharma Tanvi Sharma, Reva Bhardwaj and Rupali Bhardwaj have equal contribution to this manuscript. T. Sharma · R. Bhardwaj · R. Bhardwaj · A. K. Nadda (B) Department of Biotechnology and Bioinformatics, Jaypee University of Information Technology, Waknaghat, Solan 173234, India A. Giri Department of Environmental Sciences, Central University of Himachal Pradesh, Kangra 176206, Himachal Pradesh, India D. Pant School of Earth and Environmental Sciences, Central University of Himachal Pradesh, Dharamshala, Himachal Pradesh 176215 , India © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2021 D. Pant et al. (eds.), Advances in Carbon Capture and Utilization, Energy, Environment, and Sustainability, https://doi.org/10.1007/978-981-16-0638-0_13

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et al. 2020a, b). So, we need to find alternatives that uses the CO2 present in the atmosphere and converts it into valuable products (Sharma and Kumar 2021). Methanol is one of the important product that can be made from CO2 . Methanol does not emit extra CO2 into the atmosphere, and it has high volumetric and gravimetric energy density and is a very important fuel that is replacing the use of fossil fuels (Patterson et al. 2019). Its prime benefit is to reduce greenhouse gas emissions from vehicles. It has the highest hydrogen to carbon ratio in comparison with any liquid fuel and can be readily degraded in both aerobic and anaerobic environments. Methanol has the potential to reduce carbon emissions by 65–95%. It is highly versatile in making everyday products, and it is efficiently combustible, easily distributed, and widely available, making it affordable to use. Out of the total energy consumption of the world, 49% of it is met by fuels like gasoline, diesel, jetoils, etc. (Lewis and Nocera 2006). As compared to conventional fuels, its benefits are high as compared to gasoline and diesel. Recently, indeed, the various industries across the globe are using methanol as a crude material for making various items. Methanol is utilized in the production of solvents such as the acids. It can also be utilized in direct methanol powered devices which are utilized for the transformation reactions in the industries (Fig. 13.1). Methanol is viewed as the significant natural feedstocks that are utilized in businesses with a yearly production of 65 million tons around the world (Dalena et al. 2018). Various aspects of conversion of carbon dioxide to bioenergy based

Fig. 13.1 Description of the anthropogenic carbon cycle for the production of methanol

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products such as methanol and fixation of CO2 using microbes and other biological entities have been discussed in this chapter.

13.2 Conversion of CO2 into Methanol by Chemical Methods The methanol production from direct hydrogenation of CO2 is an attractive strategy, as this process has several advantages such as it requires less energy for product purification and fewer by-products formation. CO2 can be valorized through hydrogenation, focusing on reverse water–gas shift reaction (RWGS), methanation, and methanol production (Gutterød et al. 2020). In literature, various metal organic frameworks have been reported for the CO2 capture, and they have great potential to convert the atmospheric CO2 in heterogeneous catalytic system. The methanol synthesis from CO2 hydrogenation and RWGS is a thermodynamically limited reaction, and equilibrium conversion of CO2 decreases with increasing reaction temperature; therefore, it needs a catalytic system (Kaisar and Sreedevi 2018). Methanol is also prepared by the hydrogenation of carbon dioxide by reverse water–gas shift reaction. The catalyst used is Ni/Al12 O19, and this process is largely used in an industrial scale (Samimi and Rahimpour 2019). Lately, it has been observed that indium oxide is a highly selective catalyst in the thermal hydrogenation of CO2 to methanol, and hydrogenation of CO2 to methanol is being carried out commercially using heterogeneous CuZnO supported on Al2 O3 (Chun 2020). Methanol formed by carbon dioxide via catalytic CO2 hydrogenation is efficient for storing energy and CO2 capture. Methanol thus formed has a neutral carbon footprint and is a clean source of energy. In the European Union, a pilot plant was built by the MefCO2 project that produces 500 tons of methanol per year (Bowker 2019). In Iceland, CRI has a commercial plant that has 4000 metric tons per year of methanol production capacity. They utilize this renewable methanol for bio-diesel production, automobiles, and the production of synthetic material (Olah 2013). Nonetheless, the heterogeneous catalyst has numerous focal points regarding partition, strength, taking care of, cost, and reusing of the catalyst.

13.2.1 Heterogeneous Catalytic Method Heterogeneous catalysts for conversion of CO2 to methanol are widely used for the industrial purposes. It generally involves the rapid separation of fluid from the solid catalyst, and the catalyst that is used can be again produced (Table 13.1). Among heterogeneous catalysts, Cu/ZnO/ZrO2 have been mostly studied due to their high selectivity and conversion rate. In this catalyst, ZnO increases the Cu dispersion and

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Table 13.1 Various methods for conversion of CO2 into methanol S. No.

Methods

Catalysts/Photocatalysts/Electrode Comments

References

1

Heterogenous

Cu ZnO ZrO2

High selectivity and conversion rate

Zhong et al. (2020)

2

Homogenous

Ru3 (CO) 12 MO(CO)6 Rh(CO)12 CO2 (CO)8

Involves rapid separation of methanol and recycling of catalyst.

Kothandaraman et al. (2016)

3

Electrochemical Cu Fe Mo Pt Hg

Cu is Albo et al. considered (2015) as a more promising electrode, utilized in conversion of CO2 into methanol and other value-added products

4

Photochemical

Reduction Gondal et al. of CO2 into (2013) methanol using visible light

CdS/TiO2 Bi2 S3 /TiO2

both ZnO and ZrO2 improve the stability and CO2 absorption capacity. The incorporation of metal oxides such as Ga2 O3 , Al2 O3 , MgO, SiO2 , and La2 O3 enhances the activity and modifies the redox properties (Zhong et al. 2020). Various companies such as Sinetix, HaldorTopsoe, and Mitsubishi Gas Chemical are producing a highly stable catalyst for the production of methanol (Al-Saydeh and Zaidi 2018).

13.2.2 Homogenous Catalytic Method Different types of homogeneous catalysts are also being used for the conversion of CO2 into valuable compounds (Table 13.1). The catalysts for CO2 conversion are available in the form of metal complexes, organic solvents, and ionic solvents (Zarandi et al. 2019). Referring to different studies, it has been observed that some basic heterocyclic organic compounds like pyrimidine elevate the CO2 reduction

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reaction and its conversion as compared to other heterogeneous catalysts. Recently, it is observed that basic heterocyclic organic compounds like pyrimidine increase the reduction reaction of CO2 conversion as compared to other homogeneous catalysts (Albo et al. 2015). A distinctive heterogeneous catalyst was tried for immediate CO2 conversion into methanol. In a previous study, Ru3 (CO)12 catalyst in the presence of potassium iodide was studied for the hydrogenation of CO2 to CH3 , CH4 , and methanol (Tominaga et al. 1993). Furthermore, it was reported that Ru3 (CO)12 KI was better for CO2 conversion than another metal carbonyl including Fe2 (CO)9 , Mo(Co)6 , Rh4 (CO)12 , W(CO)6 and Co2 (CO)8 (Huff and Sanford 2011; Tominaga et al. 1993). Kothandaraman et al. (2016) firstly captured CO2 directly from the air and converted it into methanol. In this process, Ru-based catalyst and polyamine were used for methanol production. After CO2 conversion, methanol was separated and the catalyst was recycled to produce more methanol.

13.2.3 Electrochemical Reduction of CO2 to Methanol The electrochemical reduction method attracted the interest of the researcher which is eco-friendly and has economic benefits. This process is simple and can be used under ambient conditions (Zarandi et al. 2019). The electrochemical strategy is utilized for CO2 conversion to important synthetic compounds, for example, methanol by utilizing electricity as the energy source. In this method, electric energy is applied to create a potential between two electrodes to transform CO2 into reduced form (Yaashikaa et al. 2019). Reduced chemical species are obtained after the electrocatalytic CO2 reduction reaction (Fig. 13.2). The electrolytes used in these reactions affect the reduction of CO2 . Solvents used also play a key role in maintaining pH, conductivity, and toxicity. Various experiments have been reported for CO2 conversion on the terminals of metal (Kuhl et al. 2014). Various metal electrodes such as copper, ruthenium, molybdenum, titanium, iron, mercury, and platinum have been studied for electrochemical reduction of CO2 , but among them, copper (Cu) is one of the most promising electrodes (Albo et al. 2015). The hydrogen evolution reaction (HER) is significant in the CO2 electrocatalyst reduction in which water presents as an electrolyte. Consequently, the reported metals that have been utilized as electrocatalyst in CO2 reduction should have moderately greater HER (Goeppert et al. 2014). In a previous study, it was found that methanol production rate was 1.2 × 10−4 molm−2 s−1 on electrodeposited cuprous thinfilm electrodes in potassium carbonate solution (Le et al. 2011). Moreover, MoS2 rods/TiO2 nanotubes electrodes were reported for electrochemical CO2 reduction and found that CH3 OH yield reached 202.2 mgL−1 at 6 h (Li et al. 2014). Qu et al. (2005) reported the RuO2 /TiO2 nanotubes and nanoparticles for the methanol production and showed 60.5% CO2 conversion efficiency. Wu et al. (2019) revealed that when a cobalt phthalocyanine was dispersed on carbon nanotubes, it has high selectivity and catalytic activity for the electrochemical CO2 reduction to methanol. Modification is done in electrocatalysts to increase the reduction efficiency and increase

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Fig. 13.2 Schematic representation of electrochemical system for the conversion of CO2 into methanol

the faradaic efficiency. Recently, the catalysts are being modified and designed to control the dimensions of nanoparticles showing a mono-dispersive configuration (Zarandi et al. 2019). In most recent years, electrochemical CO2 transformation is broadly utilized in a research field; however, it has not been effectively utilized in mechanical procedures.

13.2.4 Photochemical Reduction of CO2 to Methanol Normally, this CO2 transformation technique is utilized to convert captured CO2 to methanol and other value-added products by utilizing sunlight, (Fan et al. 2013) (Table 13.1). Nowadays, this technique has attracted the interest of people and is being considered as one of the most appealing strategies for the utilization of CO2 . The photocatalytic CO2 transformation process is a blend of photochemical and photophysical procedures together (Gondal et al. 2013). Although this strategy has a few resemblances with electrolytic CO2 reduction in both these methods, molecular catalyst is used. Various experiments have shown the ability of metal oxides and semiconductors such as titanium dioxide, silicon carbide, zinc oxide, and tungsten trioxide, for the conversion of CO2 to methanol (Zhang et al. 2019). Li et al. (2012) proved that CdS/TiO2 and Bi2 S3 /TiO2 are promising photocatalysts to reduce CO2 into methanol using visible light. The methanol production efficiency of TNTs-Bi2 S3 and TNTs-Bi2 S3 was 224.6 μmol/L and 159.5 μmol/L, respectively. In another study, the ability of Nd/TiO2 synthesized by the sol–gel method was studied, and they found

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that the maximum methanol production yield was 184.8 μmol/g for 8 h (Luo et al. 2009). The main drawback of CO2 reduction to methanol using the photochemical method is that the reaction is reversible. Thus, to alleviate the methanol oxidation, it is important to find new methods so it can be applied to the industrial level too.

13.2.5 MOF for CO2 Reduction Various classes of a porous material including zeolites, porous organic polymers, porous carbons, covalent organic frameworks (COFs), and metal–organic frameworks (MOFs) have been reported for CO2 capture (Ding et al. 2019). Recently, MOFs are emerging out as a new class of crystalline materials due to their unique features such as large surface area, crystalline nature, handy pore structure, and chemical tunability (Fig. 13.3) (Maina et al. 2017). Debatin et al. (2010) synthesized zinc-imidazolate-4-amide-5-imidate framework, and CO2 uptake capacity of these MOF was found to be 2.1 mmol g1 at 1 bar and 298 K. Furthermore, MOFs incorporated with nanoparticles, metal oxides, and other catalytically active species have also been studied for CO2 conversion. As an example, Ag NPs were impregnated into the cavities of MIL-101 by a liquid impregnation–reduction method. The resultant Ag@MIL-101 materials had excellent catalytic activity (96.5%) and stability

Fig. 13.3 Metal organic framework (MOF) for the CO2 capture and conversion

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at 50 °C (Liu et al. 2015 Sharma et al. 2018). Gutterød et al. (2020) studied the role of the platinum nanoparticles impregnated in ZR-based UiO-67 MOF in the hydrogenation of CO2 into methanol using a kinetic analysis. In the resultant MOF, methanol was formed at the interface of platinum nanoparticles and linker-deficient Zr6 O8 nodes.

13.3 Use of Biological Systems for CO2 Capture and Utilization Various photosynthetic microbes such as algae and bacteria can assimilate CO2 (Table 13.2). Moreover, some of the autotrophic bacteria were also studied for utilizing CO2 . The most important advantage of microbial CO2 conversion is the natural ability of microbes to take up CO2 through their metabolic pathways. The CO2 fixing routes have been developed through enzymatic processing of CO2 by formulating C–H, C–O, and C–C bonds cleavage (Ramsey et al. 2009). The most commonly used pathways for CO2 reduction are pentose phosphate, citric acid cycle (Peters et al. 2011). Furthermore, various microbial enzymes have been utilized for the conversion of CO2 . The direct use of microbes is affected by environmental factors, low product yield, and growth. In this context, protein engineering and synthetic biology are ideal methods for engineering the microbes, and thus making the process economically viable. Table 13.2 Biological agents involved in conversion of CO2 Class

Species

Comments

References

Algae

Nannachlorissp Chlorella vulgaris Chlamydomonas reinhardtti Scendesmusquadricauda

High photosynthesis rate Rapid reproduction rate

Pavlik et al. (2017); Sharma et al. (2020a, b)

Bacteria

Clostridumaceticum Clostridium kluyveri Clostridium ljungdahli Acetobacteriumkloodii

Clostridiumis considered best for CO2 fixation and having numerous biotechnological applications Assorted pathway for creation of metabolites Resistance to poisonous metabolites and substrates

Jajesniak et al. 2014

Yeast

Saccharomyces cerevisiae

Involved in CO2 fixation

Zelle et al. 2008

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13.3.1 Algae for CO2 Fixation Algae are present throughout the world and one of the most commonly researched organisms for CO2 fixation. Algae can be found in freshwater–water or marine ecosystems individually or in a form of chains. They lack stems, leaves, or roots and have a vast range of sizes. CO2 is utilized as a carbon source by them for photoautotrophic growth and produces over half of the atmospheric oxygen (Shi and Theg 2013). As algae use the CO2 by the Calvin–Benson pathway and convert the inorganic carbon to organic compounds. One molecule of phosphoglycerate is diverted to focal on pathways of metabolic activity, while the other is used in the continuation of the cycle. The key enzyme for carboxylation of CO2 is RuBisCO, and it has a high affinity for CO2 and O2 . So, it creates a problem in an environment because of the high O2 affinity and low fixations present in the atmosphere. Algae possess three significant constituents of CCM including dynamic bicarbonate take-up transporters, a set of carbonic anhydrases (CAs), and a subcellular small-scale compartment inside which most of RuBisCO is found. Furthermore, micro and macroalgae can fix inorganic carbon effectively. Various algal species, such as Nannochlorissp., Scenedesmus quadricauda, Chlorella vulgaris, Nannochloropsis sp., and Chlamydomonas reinhardtii, have been studied to CO2 fixation (Pavlik et al. 2017). Microalgae have a high photosynthesis rate due to their small size, rapid reproduction rate, and synthesis of oil, pigment, etc., because of its complex metabolic reactions. Hence, making microalgae is highly efficient for converting carbon dioxide (Yen et al. 2013). Chlamydomonas reinhardtii and Volvox carteri have been genetically engineered for increasing the CO2 fixation efficiency (Beer et al. 2009; Walker et al. 2005). To improve the CO2 fixation efficiency of algae species, screening and domestication would be major promising strategies.

13.3.2 Bacteria for CO2 Fixation Various carbon-capturing bacteria are Acetobacterium woodii, Clostridium aceticum, Clostridium kluyveri, Clostridium ljungdahlii, Rhodopseudomonas palustris, Rhodococcus erythropolis, Ralstonia eutropha, Synecococcus elongatus, Rhodobacter sphaeroides, etc. (Jajesniak et al. 2014). Among various bacteria reported for CO2 fixation, Clostridium fixes CO2 using the Wood–Ljungdahl pathway. They are anaerobic and gram-positive microbes, but their cultivation is difficult and expensive because of its obligate nature (Tracy et al. 2012). Numerous strains in the Clostridium class can fix CO2 , as a carbon source. Clostridia shows numerous attractive attributes for biotechnological applications such as the capacity to use a wide range of carbon substrates, assorted pathways for the creation of helpful metabolites, and resistance to poisonous metabolites and substrates (Durre and Eikmanns 2015). Typical environmental condition is normally deadly to most of its species.

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Early work with Clostridium concentrated mostly on the creation of acidic corrosive and related items. In any case, the collection of hereditary material relevant to Clostridia has altogether extended after the improvement of plasmid DNA innovations and chromosomal control advances. The utilization of the portable gathering II introns for focused quality disturbance (Targetron or ClosTron) is well known for the hereditary building of Clostridium. The utilization of ClosTron was shown by designing Clostridium acetobutylicum for butanol–ethanol formation (Cooksley et al. 2012). Moreover, in the cyanobacterium Synochococcus elongates the carbon assimilation mechanism was studied, and it produces 2,3-butanediol from CO2 and glucose in dark (Kanno et al. 2017). Furthermore, the various microbial enzymes has been used for the conversion of CO2 . Formate dehydrogenase enzyme is a good biological catalyst known for its reversible reduction of CO2 (Ruiz-Valencia et al. 2020). Another enzyme used for the conversion of CO2 is carbonic anhydrase. It is present in various organisms like eubacteria, vertebrates, algae, archaea, plants, and animals (Moroney and Ynalvez 2007; Sharma and Kumar 2020). This enzyme is efficient in capturing CO2 in a cost-effective and eco-friendly manner as raw materials such as metal oxide ores, industrial waste, and marble mines are easily available (Bhagat et al. 2018). In recent study, carbonic anhydrase immobilized onto electrospun nanofiber is used for the conversion of CO2 into bicarbonates, and the bicarbonate solution formed was utilized for microalgae growth (Jun et al. 2020). Moreover, an organic procedure for CH4 formation from CO2 is named as biogenic methane. Nitrogenase is an ATP-dependent enzyme that carries out the multi-electron reduction of an inert molecule. Fixen et al. (2016) expressed nitrogenase enzyme in an anoxygenic phototroph of Rhodopseudomonas palustris and found that it is capable of CO2 reduction to methane in the presence of light under in vivo condition. In another study, Zhang et al. (2013) expressed phosphoribulokinase (PRK) with ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO) in E. coli and converted CO2 into a fermentation product. Microbes can be used as biocatalysts for converting CO2 into useful products. They can be used in microbial electrochemical technologies using these biocatalysts in electrochemical cells to supply or gain electrons from various biochemical reactions that utilize CO2 as a carbon source for the production of fuels and other products. Worldwide attempts are being made to convert methane into methanol using CO2 as a source; due to the increase in production of methanol, its price is also decreasing and has got equal to the price of glucose (Antoniewicz 2019).

13.3.3 Yeast for CO2 Fixation As compared to E. coli, Saccharomyces cerevisiae has pulled in less consideration as a potential answer for anthropogenic CO2 emanation (Guadalupe-Medina et al. 2013). To acquire a critical number of useful RuBisCO units, co-articulation of E. coli protein collapsing chaperones GroEL and GroES was essential. The created framework was described by a 90% decrease in the side effect glycerol development

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and a 10% expansion in ethanol production, for a sugar-constrained culture (Natesh et al. 2018). Another pertinent model is the improved creation of malic corrosive in S. cerevisiae by building a CO2 focusing pathway that returns through the carboxylation of pyruvate (Zelle et al. 2008).

13.4 Bio-based Products from CO2 13.4.1 Bioplastics Many bacteria are capable of converting CO2 into eco-friendly plastic, i.e, polyhydroxybutyrate (PHB) using sunlight. PHB is a biodegradable as well as biocompatible, thermoplastic as comparable to petrochemically inferred polypropylene (Markl et al. 2018). Cupriavidusnecator is a gram-negative facultative hydrogen oxidizing bacterium; it produces single cell proteins and polyhydroxybutyrate (PHB) depending on the supply of nutrients. It can be converted into valuable products like crotonic acid and other fuels (Yu 2018). This bacterium was cultured on a mixture of gases like hydrogen, oxygen, and carbon dioxide. C. necator fixes CO2 under aerobic conditions using the Calvin–Benson–Bassham cycle and has more CO2 fixing capacity as compared to green algae. It grows on glucose and glycerol under aerobic conditions (Shimizu et al. 2015). There are certain pathways for converting inorganic CO2 into its organic form. This has instigated an impressive enthusiasm for the business creation of this polymer. PHB is appropriate for use as nourishment bundling material taking into account its protection from water and UV radiation and its impermeability to O2 . Additionally, it is being applied in careful stitches. Significantly, PHB can be prepared to utilize previous advances and in blend with other manufactured polymers (Mozumder et al. 2015).

13.4.2 Bio-alcohol The use of CO2 to synthesize bio-alcohols have concentrated on ethanol using microbial genera such as Rhodobacter spp. The utilization of ethanol as a substitution for ordinary gas is tested by the fact that ethanol has short half life, low vitality, and is destructive to current motor and fuel foundation (Costa et al. 2015). Further, it promptly assimilates the water and weakening in the capacity tank. The natural synthesis of isopropanol is possible using microbial systems. Similarly, it can be used to esterify fat and oil for bio-diesel production, which diminishes its propensity to take the shape at decreasing temperatures.

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13.4.3 Bio-diesel Because of their high lipid contents and simplicity of development, the bio-diesel is used as non-inexhaustible oil-based fuel. Lipids, as triacylglycerides (TAGs), commonly provide the energy to the living cells. Once removed, the lipid can be changed into unsaturated fatty acid methyl esters (FAME) or bio-diesel through transesterification (Sharma et al. 2012; Sharma et al. 2019). The physical attributes of FAME are like those of fossil fuels. Critically, it is non-poisonous and also biodegradable. The utilization of bio-diesel as a low-mix part in the vehicle fuel does not require any progressions in the framework.

13.5 Conclusion Carbon dioxide transformation is introducing both a chance and a test widely for the supportability of conditions. The fundamental systems of CO2 mitigation should concentrate on the use of CO2 , reusing CO2 with the sustainable methods. In this way, the change of CO2 into synthetic products for example, methanol will expend an enormous conversion of captured CO2 where the market size of methanol is possibly broad. Moreover, the synthesized methanol can be utilized rather than the non-renewable energy source, accordingly lessening the reliance on petroleum based derivative and contributing to the market development of CO2 use. Thus, the various strategies for CO2 transformation into methanol have been accounted in this chapter. This incorporates homogeneous/heterogeneous catalysts, electrochemical, and photochemical based methods. In any case, the superior in the CO2 transformation procedure can be accomplished by utilizing a successful impetus. The poor item selectivity and the low/high response temperatures are viewed as the primary boundaries in the heterogeneous CO2 conversion process. The above findings showed that among different strategies proposed for CO2 transformation to methanol or to other value added products, the electrochemical cells are ideal over various other techniques. Also, photochemical procedures offer an appealing way to convert CO2 to methanol utilizing sun-based energy. In future, more techniques should be discovered which use the principles of green chemistry and convert more CO2 into methanol rather than emitting other hazardous by-products. The techniques should be cost effective and should be implanted on large scale in an environment friendly manner. Acknowledgements The financial support from the Jaypee University of Information Technology, Waknaghat, to undertake this study is thankfully acknowledged. Further, the authors have no conflict of interest either among themselves or with the parent institution.

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Chapter 14

Recent Advances in Enzymatic Conversion of Carbon Dioxide into Value-Added Product Anand Giri, Suman Chauhan, Tanvi Sharma, Ashok Nadda, and Deepak Pant

14.1 Introduction Nowadays, climate change and global warming are major environmental issue due to continuous increase to atmospheric carbon dioxide concentration and vast growth in industrialization (Yaashikaa et al. 2019). Due to extensive deforestation, agriculture, population growth, rapid industrialization, the current overall concentration of atmospheric CO2 is 400 ppm as compared to preindustrial level 280 ppm (Giri and Pant 2018) so requires to minimizing of atmospheric CO2 . Carbon dioxide (CO2 ) capture, sequestration, and utilization process has been widely recognized effective techniques for reducing CO2 concentration from the atmosphere. IPCC estimated in 2001 the global average annual mean surface air temperature which is increased between 1.4 and 5.8 °C till 2100. This rise in temperature has been causing global warming, and other climatic changes like in 2006 Australia faced extreme drought of in 1000 years (https://www.theguardian.com/world/2006/nov/08/australia.drought), deadly dust storms in India in May, 2018 (Sarkar et al. 2019), deadliest hurricanes in U.S. (Great Galveston hurricane in 1900, Okeechobee hurricane in 1928, hurricane Katrina in 2005) , forest fire, sea level rise, tsunami, etc., are the main consequences of global climate change (Pant et al. 2017). Currently, different technologies have been used for CO2 capture and storage (CCS) by carbon capture, transportation, and storage which are main three steps (Huntley and Redalje 2007). The rise in CO2 A. Giri (B) · S. Chauhan Department of Environmental Sciences, Central University of Himachal Pradesh, Kangra, India T. Sharma · A. Nadda Department of Biotechnology and Bioinformatics, Jaypee University of Information Technology, Waknaghat, Solan 173234, India D. Pant School of Earth and Environmental Science, Central University of Himachal Pradesh, Dharamshala, Himachal Pradesh 176215, India © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2021 D. Pant et al. (eds.), Advances in Carbon Capture and Utilization, Energy, Environment, and Sustainability, https://doi.org/10.1007/978-981-16-0638-0_14

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levels in the atmosphere could also minimize by transformation of carbon dioxide into value-added products by different physical, chemical, electrochemical, photochemical, and biological or enzymatic methods. The biological or enzymatic method provides an environmentally friendly and promising way for effective CO2 conversion or fixation due to high stereo-specificity and chemo-selectivity of enzyme (Shi et al. 2015; Giri et al. 2020; Sharma et al. 2020), while all methods mentioned above have some major drawbacks of these include: large investment and high energy input, high transportation cost, reusability, and environmental toxicity (Irfan et al. 2019). Strategies for CO2 conversion or fixation by enzymatic method to value-added products not only offer promising new technologies for carbon dioxide reduction but also for an efficient production of value-added products. Enzymes catalyze the biotransformation CO2 at moderate reaction conditions (temperature, pressure, less require energy) and provide high yield than other transformation methods. This enzymatic transformation of CO2 has attracted increasing international interest for its industrial applications and its capability to turning this greenhouse gas into added value products (Long et al. 2017). The molecule of carbon dioxide shows chemically inert and thermodynamically stable, and some external energy requires an energy input for CO2 transformation; thus, it would be reasonable to think about suitable enzymatic catalyst as energy sources for CO2 conversion. The biotransformation of carbon dioxide by enzymatic method is currently under investigation worldwide in various aspects like fuel production of biofuels along with different value-added products and chemicals (methane, organic acids, bicarbonate, glucose, alcohols, etc.) (Yaashikaa et al. 2019).In short, today, it is an urgent need to reduce the rising atmospheric carbon dioxide from the environment and emphasis on green and renewable energy to decrease dependency on conventional fossil fuels. In regards to industrial application, an enzyme system for CO2 biotransformation simply chooses a potential for carbon dioxide conversion into useful chemicals and fuels for sustainable and clean environment. Finally, the present book chapter mainly focused on enzymatic transformation of CO2 , as well as the future perspectives.

14.2 Enzymatic Transformation of CO2 Enzymatic CO2 transformation can be categorized into two types: direct and indirect transformation of carbon dioxide. They are addressed further in the following in more detail.

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14.2.1 Indirect Transformation of CO2 Indirect transformations of CO2 involve indirectly utilization of carbon dioxide to produce useful chemicals are discussed below. Photosynthesis is one of indirect transformation of CO2 through microbial transformation or through plant bio-fixation.

14.2.1.1

Natural Transformation of CO2 in Cells

In natural, CO2 fixation/ transformation into organic materials are important for biological evolution and essential factor for regulating atmospheric CO2 concentrations (Fuchs 2011; Shi et al. 2015). The carbon dioxide (CO2 ) assimilation into organic matter is facilitated by major six CO2 -fixing pathways including the reductive pentose phosphate cycle (Benson–Calvin cycle), the reductive citric acid and acetylCoA pathway, 3-hydroxypropinate cycle, 3-hydroxypropinate/4-hydroxypropinate pathway, and the dicarboxylate/4-hydroxybutyrate cycle and converts atmospheric CO2 to organic compounds (Wolosiuk et al. 1993; Shi et al. 2015). The reductive pentose phosphate cycle or Calvin cycle is one of the most important pathways for photosynthetic organism to incorporate CO2 into the cell carbon cycle with 7 × 106 g carbon consumption rate on the annual basis (Berg 2011). The key enzymes in Calvin cycle are ribulose-1,5-bisphosphatecarboxylase/oxygenase (RubisCO) and phosphoribulokinase (PRK) which are potential to photosynthetic carbon reduction cycle. Ribulose-1,5-bisphosphatecarboxylase/oxygenase (RubisCO) catalyze the electrophilic addition of carbon dioxide to ribulose-1,5-bisphosphate (5C) compound (Fast and Papoutsakis 2012) and transform to several intermediate products like 3phosphoglycerate, 1,3-diphosphoglycerate, and 3-phosphate glyceraldehyde, and in the final stage, 3-phosphate glyceraldehyde transform into 5-phosphate ribulose. Furthermore, 3-phosphate glyceraldehyde can be converted into amino acids, sugar, and fatty acids (Shi et al. 2015). The reductive citric acid cycle or tricarboxylic acid cycle (TCA) converts carbon dioxide and water into carbon compounds. The main following enzymes 2-oxoglutarate ferredoxinoxido reductase, ATP citrate lyase, isocitrate dehydrogenase, pyruvate ferredoxinoxido reductase are involved in the reductive tricarboxylic acid cycle or CO2 fixation pathways (Hügler et al. 2005). The reductive citric acid cycle involves four steps of carboxylation reactions, in which, succinyl-CoA is reductively carboxylated with carbon dioxide into α-ketoglutarate/2-oxoglutarate in presence of a-ketoglutarate synthase/2-oxoglutarate synthase. Further, α-ketoglutarate/2oxoglutarate and CO2 are transformed into verity of compounds like isocitrate, citrate, pyruvate, etc. The pyruvate is then converted into phospho-enolpyruvate (PEP) in presence of pyruvate kinase, and then, oxaloacetate is formed. Finally, oxaloacetate is converted into succinyl-CoA in presence of series of key enzyme (Thauer 2007; Fuchs 2011).

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The reductive acetyl-CoA pathway is a major CO2 fixation mechanism in anaerobic environments to turn CO or CO2 into carbon cells (Roberts et al. 1994) and mainly found in acetogenic, methanogenic bacteria and Eubacteria. In the reductive acetyl-CoA pathway, CO2 is converted into formate and carbon monoxide by formate dehydrogenase and CO dehydrogenase (CODH), respectively (Roberts et al. 1994; Berg 2011). Similarly, 3-hydroxypropionate, 3-hydroxypropionate/4hydroxybutyrate, and dicarboxylate/4-hydroxybutyrate all above six major pathways catalyze the conversion CO2 or bicarbonate in cells.

14.2.2 Direct Transformation of CO2 In the direct transformation process, carbon dioxide is converted directly using biocatalysts into useful chemicals. In this method, carbon dioxide is used as substrate and source of hydrogen, and biocatalysts are the additional requirements for conversion. The role of enzyme and products in direct transformation of carbon dioxide is discussed in this section briefly.

14.2.2.1

Transformation of CO2 to Formate

Demand of future and sustainable energy needs alternatives to current energy technologies mainly based on fossil fuels. Hydrogen has been considered a promising alternative energy feedstock, but hydrogen storage and transportation is a major complexity for its optimum utilization (Schlapbach and Züttel 2011). Schuchmann and Müller (2013) discovered hydrogen-dependent CO2 reductase from Acetobacteriumwoodii bacteria which directly uses dihydrogen and catalyze the hydrogenation of carbon dioxide to formate or formic acid (FA) which is a promising and intermediate reservoir for hydrogen storage and distribution. Formate/formic acid (FA) also used for various chemical intermediates, silage preservation, animal feed additives, and most promising candidate for low-temperature fuel cell (Rees and Compton 2011). NAD-dependent formate dehydrogenase (FDH) from Candida boidinii is also used for various CO2 reductions into formate (Kim et al. 2014) and showed very less CO2 reducing activity. The formate dehydrogenase (FDH) from Thiobacillus sp. (TsFDH) exhibits the high CO2 -reducing activity and showed 5.8 time higher formate production rate as compared to formate dehydrogenase (FDH) from Candida boidinii (CbFDH) (Choe et al. 2014).

14.2.2.2

Transformation of CO2 to Carbon Monoxide

Carbon monoxide dehydrogenase (CODH) is a type of dehydrogenese enzyme that can convert carbon dioxide into carbon monoxide in the presence of the required electron donor like NADH, NADPH, MV+2 , etc. by following equation (Sultana

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et al. 2016). The reduction of carbon dioxide into carbon monoxide possesses fuel value that offers a feasible new alternative energy sources (Olah 2005). CO2 + 2H+ + 2e− ←→ CO + H2 O The reduction of carbon dioxide into carbon monoxide is primarily catalyzed by Ni and Fe containing CO dehydrogenases ([NiFe] CODH) through reversible redox reaction and the synthesis of acetyl-COA (Jeoung and Dobbek 2007). The active site of ([NiFe] CODH) contains Ni and Fe centers bridged bound to three sulfur ligands (3Fe-4S) which is coordinated with His, Cys amino acid residue, sulfido, and a H2O/OH-ligand. In the catalyzing reaction of CO2 reduction, two-electron process occurs during the reduction process and form reduce Ni center followed by carbon dioxide is bound to the Ni center with Ni-C bound and stabilized by Fe center. Simultaneously, the hydrogen bond is formed between carboxylate oxygen atoms (O2 ) and protonated histidine residue (His93). The Fe1 loss water molecule and formed a CO2 complex, and another oxygen molecule (O1 ) of CO2 complex is bound to Fe1 and formed hydrogen bound with a protonated lysine residue (Shi et al. 2015). First time in 2003 (Shin et al. 2003) implement the reduction of CO2 to CO in vitro by utilizing ([NiFe] CODH) from Moorella thermoacetica which showed efficient combination of enzyme conversion of CO2 to CO. The expression of Fe proteins (vnfH- and nifH)-encoded of Mo- and V-nitrogenases in Azotobacter vinelandii strains commonly the reduction of nitrogen (N2 ) to ammonia (NH3 ) also capable to catalyze CO2 to CO in vitro and vivo (Seefeldt et al. 1995; Rebelein et al. 2016).

14.2.2.3

Transformation of CO2 to Methanol

The enzymatic conversion of carbon dioxide into methanol is a promising new recycling technique not only for green house management but also for efficient fuel production (Obert and Dave 1999). The use of enzyme for transformation of CO2 to methanol provides a facile low-temperature route and higher energy capacity for direct fuel generation from carbon dioxide. In 1994, Kuwabata et al. used two-enzyme system for conversion of carbon dioxide into methanol using FateDH and methanol dehydrogenase (MDH) as catalyst and pyrroloquinolinequinone (PQQ) as an electron mediator. The enzyme FateDH reduces CO2 to formate, and the enzyme, methanol dehydrogenase (MDH), reduces formate into formaldehyde and then methanol. The conversion of CO2 to methanol is catalyzed by three oxido-reductases: formate dehydrogenase (FateDH), formaldehyde dehydrogenase (FaldDH), and alcohol (ADH) dehydrogenases like methanol dehydrogenase (MDH) which are dependent on the reduced form of cofactor β-Nicotinamide adenine dinucleotide (NADH) (Amado 2013). The following enzymes are able to catalyze the sequential reduction of CO2 to value added products like formate, formaldehyde, and methanol, presented in Fig. 14.1.

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CO 2 FateDH

Fig. 14.1 Enzymatic transformation of CO2 to methanol promoted by FateDH, FaldDH, and ADH

NADH

NAD+

Formate FaldDH

NADH

NAD+

Formaldehyde

NADH

ADH

NAD+

Methanol However, this method still has several problems like deleterious of enzyme by cosolvents and catalyst in sol–gel process needs some modification in process to improve the stability the biological activity (Xu et al. 2006). The immobilization of enzyme and hybrid enzymetic/photocatalytic approach for high enzymatic activity improved stability for efficient CO2 transformation into methanol which was recently proposed in many studies (Aresta et al. 2014; Luo et al. 2015). The photocatalytic/enzymatic integrated approach combining by heterogeneous photocatalysts in the process of NADH regeneration from NAD+ represents an important step toward the potential application in hybrid CO2 reduction technology to methanol.

14.2.2.4

Transformation CO2 to Methane

Recently, researchers found remodeled nitrogenase of Rhodopseudomonas palustris is able to take CO2 from the air and turn it into methane. Purified remodeled nitrogenases of Rhodopseudomonas palustris containing two amino acids substitutions (α-195 by Gln and α-70 by Ala) near the site of its FeMo cofactor are able to CO2 transformation into methane (Shi et al. 2015; Fixen et al. 2016). The bacterial Mo-dependent nitrogenase enzyme catalyzes the dinitrogen (N2 ) to two ammonia molecule and evolution of H2 by following equation. N2 + 8H+ + 16ATP + 8e− −→ 2NH3 + H2 + 16ADP + 16Pi Remodeled nitrogenases reduce CO2 to methane by eight electrons and make it unique among all known catalyzed enzyme reactions. Furthermore, the reduced CO2

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is also able to react with acetylene to form propylene by following reactions (Omae 2012; Yang et al. 2012). CO2 + 8H+ + 8e− −→ CH4 + 2H2 O CO2 + HC = CH + 8H+ + 8e− −→ H2 C = CH − CH3 + 2H2 O

14.2.3 Transformation of CO2 to Bicarbonate Another strategy of enzymatic CO2 conversion into value product is CO2 mineralization in bicarbonate by enzyme carbonic anhydrase (CA) with high turnover rate. Recently, CA mediated conversion of CO2 has attracted much attention toward green house management. Carbonic anhydrase is zinc containing metalloenzyme comprises three histidine residues, and a hydroxide ion or water molecule catalyzes the carbon dioxide by following equation (Giri and Pant 2019a). + CO2 + H2 O −→ HCO− 3 + H

The CO2 sequestrating by carbonic anhydrase for precipitating carbonate minerals are being actively investigated (Prabhu et al. 2011; Giri et al. 2018; Giri and Pant 2019a). CA can categorized into five distinct classes of α, β, γ, δ, ζ with few structural similarities, but all CAs similar active site of a divalent zinc ion or associated metal ion. The proposed mechanism of CO2 hydration and CO2 mineralization by CA could be summaries as follows: Nucleophilic attack on C atoms of CO2 by zinc (Zn2+ ) bound –OH to yield bicarbonate then displaced by molecule of water (Giri and Pant 2019a) (Fig. 14.2). Fig. 14.2 Schematic representation of CA reaction mechanism to accelerate CO2 uptake to facilitate carbonate precipitation

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The first CA was discovered in 1933 by Meldrum and Roughton from erythrocytes in the role of transition of the bicarbonate anions (Meldrum and Roughton 1933) and in 1940 Neish identified the first plant originated CA and its different characteristics from previously known erythrocytes CA (Neish 1940). The prokaryotic CA was discovered by Veitch and Blankenship in 1963 and extracted from Neisseria Sicca in 1972. The active center of α CA contained by Zn atom and tetrahedral coordinated with three histidine residues and single water molecule, predominate in mammals (Domsic and McKenna 2010; Giri and Pant 2019a). However, the β CA shows oligomeric quaternary structure and Zn atom tetrahedral coordinated with two molecule of cysteines, and single molecules of histidine and aspartate. In the γ class of CA, the Zn atom is coordinated in a penta mode to three molecules of histidines and two water molecules (Alber and Ferry 1994). The β CA predominate in eukaryotes and γ CA were mostly present in Archaea. The δ class of CA found in Thalassiosira weissflogii showed a different amino acid sequence, compared to other α, β, and γ CAs (Tripp et al. 2001). Several research group purified carbonic anhydrase from organisms that thrive in extreme environments utilize to formation of calcium carbonate (Capasso et al. 2012). The converting CO2 into bicarbonate by using enzyme CA in biomimetic approaches is thermodynamically favorable compared to other CO2 mitigation techniques and carbonate minerals further used for building and industrial applications (Giri et al. 2018; Sharma and Kumar 2020). The urease is also a metalloenzyme containing nickel belonging to the group of hydrolases that play an important role in nitrogen requirement in plants and microorganism. The function of urease is to catalyze hydrolysis of urea into ammonia and carbamate. The carbamate further hydrolyzed into the additional mole of ammonium and carbonic acid. The shifting of bicarbonate toward carbonate ion increases the influx of calcium ions and obligates the bacterial export of calcium ion outside the bacterial cell. The availability of calcium and dissolve inorganic carbon in the microenvironment precipitated calcium carbonate outside the cell by following equation (Castro et al. 2016) (Fig. 14.3; Table 14.1). CO(NH2 ) + H2 −→ NH2 COOH + NH3 NH2 COOH + H2 O −→ NH3 + H2 CO3 + H2 CO3 −→ HCO− 3 +H − 2NH3 + 2H2 O −→ 2NH+ 4 + 2OH + 2− + + − HCO− 3 + H + 2NH4 + 2OH −→ CO3 + 2NH4 + 2H2 O

Ca2+ + Cell −→ Cell − Ca2+

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Fig. 14.3 Schematic diagram of carbonate formation by urease activity NH2CONH2 (Urea)

Urease

Ca2+ CaCO3

CO3 + NH3

- - - -- - - - - - -

CO32- + NH4+ + OH-

Table 14.1 Bacterial carbonic anhydrase and role in bicarbonate precipitation CA source

Isolation site

Calcite precipitation

References

Bacillus sp.CR2

Mine tailing soil

2.32 mg/cell mass (mg) Achal and Pan (2011)

Lysinibacillus sp. strain LHXY2

Karst cave

980 mg/100 ml

Lü et al. (2019)

B. pasteurii NCIM 2477

Culture

–

Sarada et al. (2009)

Bacillus and Virgibacillus

Desalination plant

–

Silva-Castro et al. (2015)

B.megateriumSS3

Calcareous soil

187 mg/100 ml

Dhami et al. (2013)

B.turiniensis

Calcareous soil

167 mg/100 ml

Dhami et al. (2013)

Bacillus sp. strain (5C-1)

Karst cave

–

Wang et al. (2010)

Citrobacter freundii

Himalayan rocks

230 mg CaCO3/mg of purified CA

Giri et al. (2018)

Pseudomonas spp.

Himalayan rocks

–

Giri and Pant (2019b)

Cell − Ca2+ + CO2− 3 −→ Cell CaCO3 In general, enzyme carbonic anhydrase and urease play an important role in production in carbonate by biomineralization. Biocementation and biodeposition are also new emerging technologies which offer a cost effective, environmentally sound, and appropriate alternative on the conventional construction industry. Furthermore, the use of these technologies promises to reduce CO2 emissions and mitigate the effects of climate change.

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Conversion of CO2 to Other Chemicals

Beside CA, there are several other types of carboxylases in cells and have also been explored to catalyze the carboxylation of raw materials and have potential to other biocatalytic applications including: carboxylation of epoxide, aromatic compounds, hetro-arometic compounds, and aliphatic substrate (Glueck et al. 2010). The enzymatic carboxylation reactions derived mainly from catabolic pathways with potential for biocatalytic applications given. The reactions are categorized into four classes, by according to substrate type:

Biocarboxylation of Epoxides A novel enzymatic reaction has been investigated involving the metabolism of aliphatic epoxides by Xanthobacter strain Py2 (Allen and Ensign 1996). The pathways of epoxy degradation seem to be regulated by the presence or absence of CO2 . In the absence of CO2 , propene-grown Xanthobacter Py2 catalyze the isomerization of aliphatic epoxides. On the other hand in the presence of CO2 , the carboxylation reaction of epoxide formed acetoacetate and beta-hydroxybutyrate (Glueck et al. 2010; Shi et al. 2015). Both CO2 dependent and no-dependent pathways were reported to be dependent on NAD+ . A novel type NADPH-dependent pyridine nucleotidedisulfide oxidoreductase is very essential protein for epoxide degradation (Swaving et al. 1996).

Biocarboxylation of Aromatic (Phenolic) Compounds The second route of carboxylation reaction is also called aromatic carboxylation. Initially, partially purified phenylphosphate enzymes from Thauera aromatic were used in the carboxylation of phenol in presence of CO2 to synthesize phydroxybenzoic acid under ambient conditions (Aresta Dibenedetto 2002). The metabolism of aromatic (phenolic) compounds in aerobic bacteria is commonly proceeding via oxidation using molecular oxygen as a co-substrate. The anaerobic carboxylation in Thauera aromatic proceeds via involving two enzyme system (i) phenylphosphate synthase (ATP-dependent activation of phenol to phenylphosphate) and (ii) regioselective (para-)carboxylation of the activated intermediate to p-hydroxybenzoic acid by metal (Mg2+ , Mn2+ and K+ )-dependent phenylphosphate carboxylase. The divalent metal ion in enzyme acts as a Lewis acid by increasing the electrophilic nature of CO2 . Acetyl-CoA is the final product of aromatic (phenolic) degradation by oxygen-sensitive phenylphosphate synthase (Glueck et al. 2010). The first example of biotechnological application of a carboxylase was phenol to p-hydroxybenzoic acid at ambient temperature and pressure (Aresta et al. 1998). 4-hydroxybenzoate decarboxylases purified from Enterobacte spp., Clostridium hydroxybenzoicum, and Chlamydophila pneumonia can also catalyze phenol in the presence of CO2 to yield 4-hydroxybenzoate. Similarly, 3,4-dihydroxybenzoate

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decarboxylase from Clostridium hydroxybenzoicum can catalyze phenol and catechol in the presence of bicarbonate into 3,4-dihydroxybenzoate (Miyazaki et al. 2001).

Biocarboxylation of Hetero-aromatic Compounds Pyrrole-2-carboxylate decarboxylase is an important enzyme for hetero-aromatic compounds synthesis. The Pyrrole-2-carboxylate decarboxylase from Bacillus megaterium PYR2910 can be used for formation of Pyrrole-2-carboxylate, which is a potential herbicide used in agricultural purposes (Omura et al.1998).

14.2.3.2

Biocarboxylation of Aliphatic Substrates

Pyruvate decarboxylase can be used for enzymatic synthesis of pyruvic acid from acetaldehyde and CO2, which again converted into lactic acids by using multi-enzyme systems. Lactic acids can also be formed from ethanol and CO2 which can be used in food, cosmetic, pharmaceutical, and chemical industry (Miyazaki et al. 2001; Tong et al. 2011).

14.3 Future Perspectives and Conclusion Biocatalysts are generally expensive, stability issue, activity, and reusability, which restrict their optimum use in industrial purposes. Several enzymatic engineering such as chemical modification, genetic engineering, and immobilization need further optimum use of enzyme with economic viable, improving enzymatic activity and stability and reusability (Giri and Pant 2019b). Biocatalysts are needed faster CO2 transformation for industrial and environmental purposes. Thus, considerable research is required toward the CO2 management into valuable products by discovery of novel enzyme system as well as enzyme engineering system. Although, a considerable research should also been focus in novel enzymatic and multi enzymatic technologies for CO2 conversion into different products. Scientific and technical advances are still needed for link between fundamental and industrial research in CO2 transformation and mitigation. Acknowledgements The financial support from the CSIR, Govt. of India, to undertake this study is thankfully acknowledged.

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