Recent Advancements In Waste Water Management: Implications and Biological Solutions (Volume 9) (Advances in Chemical Pollution, Environmental Management and Protection, Volume 9) [1 ed.] 0443193886, 9780443193880

Table of contents :
Front Cover
Recent Advancements in Wastewater Management: Implications and Biological Solutions
Copyright
Contents
Contributors
Series editor´s preface
Volume editor´s preface
Chapter One: Antibiotics and hormone residues in wastewater: Occurrence, risks, and its biological, physical and chemical ...
1. Introduction
2. Occurrence and risks
2.1. Antibiotics
2.2. Hormones
3. Treatment of hormones and antibiotics
3.1. Biological
3.2. Physical and chemical treatments
4. Future prospects
References
Chapter Two: Occurrence of pesticides in wastewater: Bioremediation approach for environmental safety and its toxicity
1. Introduction
2. Classification of pesticides
3. Occurrence of pesticides
4. Toxicity
5. Bioremediation of pesticides
5.1. Physicochemical degradation
5.2. Biodegradation
6. Final considerations
References
Chapter Three: Removal of pharmaceutical compounds from water
1. Introduction
1.1. Toxicological effects of pharmaceutical compounds present in water
1.1.1. Effects on humans and agriculture
1.1.2. Effects on aquatic life
1.2. Occurrence of pharmaceutical drugs in surface water
1.3. Occurrence of pharmaceutical drugs in down reservoirs
2. Methods for removal of pharmaceutical compounds
2.1. Removal of pharmaceutical compounds using enzymes
2.1.1. The use of crude enzymes for the removal of pharmaceutical compounds (PC)
2.1.2. Immobilized enzyme for removal of PC
2.2. Enzymatic membrane reactors (EMRs)
2.3. Treatment through fungi
2.3.1. Factors affecting pharmaceutical drug removal performance of fungi
2.4. Adsorption on non-conventional material
2.5. Hybrid technologies for removal of PC
2.6. Treatment of pharmaceutical compounds through microalgae
2.7. Treatment of PC by using organic biomass
2.7.1. Activated sludge process (ASP)
2.7.2. Biofilm reactors and biotic trickling filters
2.7.3. Two phased partitioning bioreactors
2.8. Bio ozone-bio process for treatment of PC
2.9. Pros and cons of different methodologies used for PACs removal
3. Future prospective
4. Conclusion
References
Chapter Four: Biological methods for the removal of microplastics from water
1. Introduction
2. Types of microplastics
3. Sources of microplastics in water
4. Biological solutions for the removal of microplastics from water
4.1. By algae
4.2. By fungi
4.3. By bacteria
4.4. By enzymes
4.5. By using biopolymers
4.6. By marine organisms
5. Microplastic ingestion
6. Control measures for microplastic pollution
7. Microplastic pollution and COVID-19
8. Conclusion
References
Chapter Five: Impact of wastewater irrigation on soil attributes
1. Introduction
2. Sources of wastewater
2.1. Domestic sources
2.2. Industrial sources
2.2.1. Fertilizer industry
2.2.2. Pharmaceutical industry
2.2.3. Animal slaughterhouses
2.2.4. Textile industry
2.2.5. Petrochemical industries
2.2.6. Mining industries
2.2.7. Paper and pulp industry
2.2.8. Leather industry
2.2.9. Sugar industry
3. Impact of wastewater irrigation on soil characteristics
3.1. Effect on physico-chemical characteristics
3.2. Effect on biological characteristics
4. Conclusion and recommendations
References
Chapter Six: Microalgae and advanced oxidative processes as treatment approaches for agro-industrial effluents
1. Introduction
2. Factors that influence the quality of agro-industrial wastewater
3. Microalgae in the treatment of agro-industrial wastewater
4. Advanced oxidative processes
5. Conclusion
References
Chapter Seven: Contamination of soil and food chain through wastewater application
1. Introduction
2. The current scenario of wastewater irrigation
3. Wastewater irrigation in agriculture: A worldwide health challenge
4. The effect of wastewater irrigation on the properties of soil
4.1. Effect of wastewater irrigation on soil microbiome
4.2. The effect of wastewater irrigation on the concentration of toxic elements in the soil
4.3. The effect of wastewater on the concentration of pesticides
4.4. The pharmaceutical and personal care products (PPCPs) in the waste water
5. Impacts of wastewater irrigation on crops
5.1. Persistence of harmful pathogenic microbes in the plant and soil
5.2. Microbial contamination
5.3. Spread of antibiotic resistance
6. The effect of wastewater irrigation on food chain contamination and human health
7. Measures to reduce risks
8. Conclusions
Acknowledgments
References
Chapter Eight: Advanced biomaterials for the removal of pesticides from water
1. Introduction
2. Advanced biomaterials
3. Synthesis of biomaterials for pesticide removal
4. How are biomaterials efficient for water treatment?
5. Removal of pesticides from water
5.1. Role of plant biomaterials in pesticides management
5.2. Effectiveness of bird biomaterial waste in pesticide control in water
5.3. Fungi biomaterials for the remediation of pesticides in water
6. Future perspective
7. Conclusions
References
Chapter Nine: Microalgae mediated wastewater treatment and its production for biofuels and bioproducts
1. Introduction
2. Microalgae
3. Microalgae uses in phycoremediation technology
4. Advantages of phycoremediation
5. Cultivation methods of microalgae
5.1. Hybrid system
5.2. Open cultivation method
5.3. Closed cultivation method
6. Harvesting method
6.1. Biological method of harvesting
6.2. Mechanical harvesting
6.3. Magnetic and electrical harvesting methods
6.4. Chemical methods of harvesting
7. Economic challenges
8. Utilization of wastewater generated microalgal biomass for biofuel production
9. Market trend of microalgae-based wastewater treatment
10. Socio-economic and environmental aspects associated with integrated algae refinery
11. Conclusion
References
Chapter Ten: Beneficial and negative impacts of wastewater for sustainable agricultural irrigation: Current knowledge and ...
1. Introduction
2. Availability and use of wastewater
3. Positive effect of waste water irrigation on physicochemical properties of soil
3.1. Fertization value of waste water
3.2. Soil organic carbon (SOC)
3.3. Soil macronutrients
3.4. Electrical conductivity (EC)
3.5. Exchangeable cations
3.6. Calcium carbonate
3.7. Soil pH
4. Negative effect of long-term sewage irrigation
4.1. Effect of waste water irrigation on total heavy-metal content of soil
4.2. Environmental hazards related to wastewater
5. Effect of waste water irrigation on quality and yield
5.1. Heavy-metal content in plants
5.2. Crop yield
6. Conclusions
Acknowledgment
References
Chapter Eleven: Immobilized enzyme systems for wastewater treatment
1. Introduction
2. Enzyme immobilization for sewage treatment
3. Different methods to immobilize enzymes
3.1. Encapsulation method
3.2. Adsorption method
3.3. Entrapment
3.4. Covalent immobilization
3.5. Cross linking method
4. Applications of immobilized enzymes in wastewater treatment
4.1. Food industry wastewater treatment
4.2. Pharmaceutical wastewater treatment
4.3. Biodegradation of phenol and its derivatives
4.4. Industrial wastewater treatment
5. Future prospective
6. Conclusion
References
Chapter Twelve: Microbial remediation of emerging pollutants from wastewater
1. Introduction
2. Microbial remediation
3. Techniques of microbial remediation
3.1. Bioaugmentation
3.2. Bioventing
3.3. Biostimulation
3.4. Bioreactors
3.5. Biosorption
4. Factors affecting microbial remediation
5. Types of microbial remediation
5.1. Bacterial bioremediation
6. Genetically engineered bacteria (GEB)
6.1. Fungal bioremediation
6.2. Algal bioremediation
7. Microbial fuel cell
8. Role of microorganisms in the removal of some other emerging pollutants
9. Conclusion
References
Chapter Thirteen: Utilization of constructed wetlands for dye removal: A concise review
1. Introduction
2. Dye
3. Phytoremediation of dye-containing wastewater
4. The importance of using CW to treat wastewater containing dye and its advantages over other treatment
5. Removal processes of dye in CW systems
6. Conclusion and future research needs
References
Further reading
Chapter Fourteen: Pathogenic microbes in wastewater: Identification and characterization
1. Introduction
2. Traditional approaches for pathogenic microbial detection in wastewater
2.1. Colony counting and culturing method
2.2. Biosensors
2.2.1. Optical biosensors
2.2.2. Electrochemical biosensors
3. Different molecular methods of wastewater pathogen detection
3.1. Polymerase chain reaction (PCR)
3.1.1. Multiplex PCR (mPCR)
3.1.2. Real-time PCR (rtPCR)
3.2. DNA microarrays
3.3. Lab-on-chip technology
3.4. Fluorescence in-situ hybridization (FISH)
3.5. Dot-blot hybridization
3.6. Next-generation sequencing (NGS)
4. Challenges
5. Future perspectives
6. Conclusion
Acknowledgments
References
Chapter Fifteen: Tidal coastal wetlands for wastewater management
1. Background
2. Wetland definitions
3. Tidal coastal wetlands
3.1. Coastal wetlands
3.1.1. Marshes
3.1.2. Swamps
3.1.3. Bogs
3.1.4. Estuaries
3.1.5. Fen
3.1.6. Coral reefs
4. Significance of coastal wetlands ecosystem services
4.1. Carbon sequestration
4.2. Coastal protection and flood/erosion control
4.3. Wildlife habitat and food
5. Coastal wetlands wastewater management study
5.1. Preamble
5.2. Wastewater treatment and management by coastal wetland
5.3. Case and modelling studies
5.4. Benefits of coastal wetland wastewater treatment system
6. Conclusion
References
Chapter Sixteen: Mechanistic approaches and factors regulating microalgae mediated heavy metal remediation from the aquat ...
1. Introduction
2. Role of microalgae in heavy metal removal
3. Factors affecting remediation of heavy metals
3.1. Biotic factors
3.1.1. Species
3.1.2. Biomass Concentration
3.1.3. Tolerance capacity
4. Abiotic factors influencing metal removal
4.1. Temperature
4.2. pH
4.3. Salinity and hardness
4.4. Metal speciation
5. Recycling of microalgal biomass
6. Algal biomass conversion to produce biofuel
7. Challenges and prospects in heavy metal bioremediation
8. Conclusion
Acknowledgment
References
Chapter Seventeen: Metal organic frameworks-carbon based nanocomposites for environmental sensing and catalytic applications
1. Introduction
2. Synthesis procedures
2.1. In situ synthesis
2.2. Ex situ synthesis
2.3. Other methods
3. Applications
3.1. Sensor
3.1.1. MOF/carbon material composites
3.1.2. CNTs/MOFs
3.1.3. GO/MOFs
3.2. Supercapacitors and batteries
3.3. Absorbents
3.4. Catalysts
4. Outlook and conclusions
References
Back Cover

Citation preview

VOLUME NINE

ADVANCES IN CHEMICAL POLLUTION, ENVIRONMENTAL MANAGEMENT AND PROTECTION Recent Advancements in Wastewater Management: Implications and Biological Solutions

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VOLUME NINE

ADVANCES IN CHEMICAL POLLUTION, ENVIRONMENTAL MANAGEMENT AND PROTECTION Recent Advancements in Wastewater Management: Implications and Biological Solutions Edited by

LUIZ FERNANDO ROMANHOLO FERREIRA Waste and Effluent Treatment Laboratory, Institute of Technology and Research (ITP), Tiradentes University (UNIT), Aracaju, Sergipe, Brazil

AJAY KUMAR Department of Botany, Banaras Hindu University, Varanasi, India

MUHAMMAD BILAL Institute of Chemical Technology and Engineering, Faculty of Chemical Technology, Poznan University of Technology, Poznan, Poland

Academic Press is an imprint of Elsevier 50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States 525 B Street, Suite 1650, San Diego, CA 92101, United States The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom 125 London Wall, London, EC2Y 5AS, United Kingdom First edition 2023 Copyright © 2023 Elsevier Inc. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions. This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary. Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein. ISBN: 978-0-443-19388-0 ISSN: 2468-9289 For information on all Academic Press publications visit our website at https://www.elsevier.com/books-and-journals

Publisher: Zoe Kruze Acquisitions Editor: Jason Mitchell Developmental Editor: Jhon Michael Peñano Production Project Manager: Sudharshini Renganathan Cover Designer: Vicky Pearson Esser Typeset by STRAIVE, India

Contents Contributors Series editor's preface Volume editor's preface

1. Antibiotics and hormone residues in wastewater: Occurrence, risks, and its biological, physical and chemical treatments

xi xv xvii

1

Roberta Anjos de Jesus, Gabriela Pereira Barros, Ram Naresh Bharagava, Jiayang Liu, Sikandar I. Mulla, Lucas Carvalho Basilio Azevedo, and Luiz Fernando Romanholo Ferreira 1. Introduction 2. Occurrence and risks 3. Treatment of hormones and antibiotics 4. Future prospects References

2. Occurrence of pesticides in wastewater: Bioremediation approach for environmental safety and its toxicity

2 3 6 11 11

17

Roberta Anjos de Jesus, Gabriela Pereira Barros, Ram Naresh Bharagava, Jiayang Liu, Sikandar I. Mulla, Lucas Carvalho Basilio Azevedo, and Luiz Fernando Romanholo Ferreira 1. Introduction 2. Classification of pesticides 3. Occurrence of pesticides 4. Toxicity 5. Bioremediation of pesticides 6. Final considerations References

3. Removal of pharmaceutical compounds from water

18 20 22 24 26 29 29

35

Mateen Hedar, Iqra Zaman, Muhammad Imran Din, Nazim Hussain, Azeem Intisar, Adeel Afzal, and Muhammad Amin Abid 1. Introduction 2. Methods for removal of pharmaceutical compounds 3. Future prospective 4. Conclusion References

36 41 56 57 58 v

vi

Contents

4. Biological methods for the removal of microplastics from water

65

Mahnoor Amjad, Azeem Intisar, Adeel Afzal, and Nazim Hussain 1. Introduction 2. Types of microplastics 3. Sources of microplastics in water 4. Biological solutions for the removal of microplastics from water 5. Microplastic ingestion 6. Control measures for microplastic pollution 7. Microplastic pollution and COVID-19 8. Conclusion References

5. Impact of wastewater irrigation on soil attributes

66 66 67 68 72 75 75 75 76

79

Vipin Kumar Singh, Rishikesh Singh, and Ajay Kumar 1. Introduction 2. Sources of wastewater 3. Impact of wastewater irrigation on soil characteristics 4. Conclusion and recommendations References

6. Microalgae and advanced oxidative processes as treatment approaches for agro-industrial effluents

80 81 85 88 90

97

Clara Dourado Fenandes, Gabriela Pereira Barros, Ram Naresh Bharagava, Ajay Kumar, Sikandar I. Mulla, Lucas Carvalho Basilio Azevedo, and Luiz Fernando Romanholo Ferreira 1. Introduction 2. Factors that influence the quality of agro-industrial wastewater 3. Microalgae in the treatment of agro-industrial wastewater 4. Advanced oxidative processes 5. Conclusion References

98 100 101 102 104 105

7. Contamination of soil and food chain through wastewater application

109

Priya Yadav, Rahul Prasad Singh, Rajan Kumar Gupta, Twinkle Pradhan, Amit Raj, Sandeep Kumar Singh, Kaushalendra, Kapil D. Pandey, and Ajay Kumar 1. Introduction 2. The current scenario of wastewater irrigation

110 113

Contents

3. 4. 5. 6.

vii

Wastewater irrigation in agriculture: A worldwide health challenge The effect of wastewater irrigation on the properties of soil Impacts of wastewater irrigation on crops The effect of wastewater irrigation on food chain contamination and human health 7. Measures to reduce risks 8. Conclusions Acknowledgments References

115 116 120

8. Advanced biomaterials for the removal of pesticides from water

133

123 124 124 125 125

Hafiz Adnan Akram, Adeel Afzal, Azeem Intisar, Mateen Hedar, and Nazim Hussain 1. Introduction 2. Advanced biomaterials 3. Synthesis of biomaterials for pesticide removal 4. How are biomaterials efficient for water treatment? 5. Removal of pesticides from water 6. Future perspective 7. Conclusions References

9. Microalgae mediated wastewater treatment and its production for biofuels and bioproducts

134 137 138 139 140 146 146 147

153

Sandeep Kumar Singh, Livleen Shukla, Rahul Prasad Singh, Priya Yadav, and Ajay Kumar 1. 2. 3. 4. 5. 6. 7. 8.

Introduction Microalgae Microalgae uses in phycoremediation technology Advantages of phycoremediation Cultivation methods of microalgae Harvesting method Economic challenges Utilization of wastewater generated microalgal biomass for biofuel production 9. Market trend of microalgae-based wastewater treatment 10. Socio-economic and environmental aspects associated with integrated algae refinery 11. Conclusion References

154 154 155 156 157 158 160 161 162 162 163 163

viii

Contents

10. Beneficial and negative impacts of wastewater for sustainable agricultural irrigation: Current knowledge and future perspectives

167

Priya Yadav, Rahul Prasad Singh, Rajan Kumar Gupta, Sandeep Kumar Singh, Hariom Verma, Prashant Kumar Singh, Kaushalendra, Kapil D. Pandey, and Ajay Kumar 1. Introduction 2. Availability and use of wastewater 3. Positive effect of waste water irrigation on physicochemical properties of soil 4. Negative effect of long-term sewage irrigation 5. Effect of waste water irrigation on quality and yield 6. Conclusions Acknowledgment References

11. Immobilized enzyme systems for wastewater treatment

168 170 170 173 174 176 177 177

183

Mateen Hedar, Azeem Intisar, and Nazim Hussain 1. Introduction 2. Enzyme immobilization for sewage treatment 3. Different methods to immobilize enzymes 4. Applications of immobilized enzymes in wastewater treatment 5. Future prospective 6. Conclusion References

12. Microbial remediation of emerging pollutants from wastewater

184 187 188 196 200 202 202

207

Arooj Ramzan, Vaneeza Aiman, Azeem Intisar, Adeel Afzal, Tajamal Hussain, Muhammad Amin Abid, and Nazim Hussain 1. Introduction 2. Microbial remediation 3. Techniques of microbial remediation 4. Factors affecting microbial remediation 5. Types of microbial remediation 6. Genetically engineered bacteria (GEB) 7. Microbial fuel cell 8. Role of microorganisms in the removal of some other emerging pollutants 9. Conclusion References

208 209 210 212 213 215 219 220 221 222

Contents

13. Utilization of constructed wetlands for dye removal: A concise review

ix

227

Fidelis Odedishemi Ajibade, Oluwaseyi Aderemi Ajala, Hailu Demissie, Kayode Hassan Lasisi, Temitope Fausat Ajibade, Bashir Adelodun, Pankaj Kumar, Nathaniel Azubuike Nwogwu, Adedamola Oluwafemi Ojo, Olawale Olugbenga Olanrewaju, and James Rotimi Adewumi 1. 2. 3. 4.

Introduction Dye Phytoremediation of dye-containing wastewater The importance of using CW to treat wastewater containing dye and its advantages over other treatment 5. Removal processes of dye in CW systems 6. Conclusion and future research needs References Further reading

14. Pathogenic microbes in wastewater: Identification and characterization

228 229 233 235 236 241 241 246

247

Rahul Prasad Singh, Priya Yadav, Rajan Kumar Gupta, Sandeep Kumar Singh, Hariom Verma, Prashant Kumar Singh, Kaushalendra, Kapil D. Pandey, and Ajay Kumar 1. Introduction 2. Traditional approaches for pathogenic microbial detection in wastewater 3. Different molecular methods of wastewater pathogen detection 4. Challenges 5. Future perspectives 6. Conclusion Acknowledgments References

15. Tidal coastal wetlands for wastewater management

248 249 252 256 256 257 257 258

263

Kayode Hassan Lasisi, Fidelis Odedishemi Ajibade, Temitope Ezekiel Idowu, Temitope Fausat Ajibade, Bashir Adelodun, Adedamola Oluwafemi Ojo, Olaolu George Fadugba, Olawale Olugbenga Olanrewaju, and James Rotimi Adewumi 1. Background 2. Wetland definitions 3. Tidal coastal wetlands

264 265 266

x

Contents

4. Significance of coastal wetlands ecosystem services 5. Coastal wetlands wastewater management study 6. Conclusion References

16. Mechanistic approaches and factors regulating microalgae mediated heavy metal remediation from the aquatic ecosystem

271 274 278 279

285

Kapil D. Pandey, Sandeep Kumar Singh, Livleen Shukla, Vineet Kumar Rai, Rahul Prasad Singh, Priya Yadav, Rajan Kumar Gupta, Prashant Kumar Singh, Kaushalendra, and Ajay Kumar 1. Introduction 2. Role of microalgae in heavy metal removal 3. Factors affecting remediation of heavy metals 4. Abiotic factors influencing metal removal 5. Recycling of microalgal biomass 6. Algal biomass conversion to produce biofuel 7. Challenges and prospects in heavy metal bioremediation 8. Conclusion Acknowledgment References

17. Metal organic frameworks-carbon based nanocomposites for environmental sensing and catalytic applications

286 288 290 292 294 294 295 296 296 296

301

Muhammad Tuoqeer Anwar, Muhammad Rehman Asghar, Arslan Ahmed, Shagufta Fareed, Hasan Izhar Khan, and Tahir Rasheed 1. Introduction 2. Synthesis procedures 3. Applications 4. Outlook and conclusions References

302 303 305 316 317

Contributors Muhammad Amin Abid Department of Chemistry, University of Sahiwal, Sahiwal, Pakistan Bashir Adelodun Department of Agricultural and Biosystems Engineering, University of Ilorin, Ilorin, Nigeria; Department of Agricultural Civil Engineering, Kyungpook National University, Daegu, Korea James Rotimi Adewumi Department of Civil and Environmental Engineering, Federal University of Technology, Akure, Nigeria Hafiz Adnan Akram School of Chemistry, University of the Punjab, Lahore, Pakistan Adeel Afzal School of Chemistry, University of the Punjab, Lahore, Pakistan Arslan Ahmed Department of Mechanical Engineering, COMSATS University Islamabad, Sahiwal, Pakistan Vaneeza Aiman School of Chemistry, University of the Punjab, Lahore, Pakistan Oluwaseyi Aderemi Ajala Department of Chemistry, Faculty of Science University of Ibadan, Ibadan, Nigeria; Department of Applied Chemistry, Graduate School of Advanced Science and Engineering, Hiroshima University, Higashihiroshima, Japan Fidelis Odedishemi Ajibade Department of Civil and Environmental Engineering, Federal University of Technology, Akure, Nigeria; University of Chinese Academy of Sciences; CAS Key Lab of Environmental Biotechnology, Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, P.R. China Temitope Fausat Ajibade Department of Civil and Environmental Engineering, Federal University of Technology, Akure, Nigeria; Institute of Urban Environment, Chinese Academy of Sciences, Xiamen; University of Chinese Academy of Sciences, Beijing, P.R. China Mahnoor Amjad School of Chemistry, University of the Punjab, Lahore, Pakistan Muhammad Tuoqeer Anwar Department of Mechanical Engineering, COMSATS University Islamabad, Sahiwal, Pakistan Muhammad Rehman Asghar University of Agriculture, Faisalabad, Pakistan xi

xii

Contributors

Lucas Carvalho Basilio Azevedo Instituto de Ci^encias Agra´rias, Universidade Federal de Uberl^andia, Uberl^andia, MG, Brazil Gabriela Pereira Barros Waste and Effluent Treatment Laboratory, Institute of Technology and Research (ITP), Tiradentes University (UNIT), Aracaju, Sergipe, Brazil Ram Naresh Bharagava Laboratory of Bioremediation and Metagenomics Research (LBMR), Department of Environmental Microbiology (DEM), Babasaheb Bhimrao Ambedkar University (A Central University), Lucknow, UP, India Roberta Anjos de Jesus Waste and Effluent Treatment Laboratory, Institute of Technology and Research (ITP), Tiradentes University (UNIT), Aracaju, Sergipe, Brazil Hailu Demissie University of Chinese Academy of Sciences, Beijing, P.R. China; Department of Chemistry, Arba Minch University 1000, Arba Minch, Ethiopia Muhammad Imran Din School of Chemistry, University of the Punjab, Lahore, Pakistan Olaolu George Fadugba Department of Civil and Environmental Engineering, Federal University of Technology, Akure, Nigeria Shagufta Fareed School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai, China Clara Dourado Fenandes Waste and Effluent Treatment Laboratory, Institute of Technology and Research (ITP), Tiradentes University (UNIT), Aracaju, Sergipe, Brazil Luiz Fernando Romanholo Ferreira Waste and Effluent Treatment Laboratory, Institute of Technology and Research (ITP), Tiradentes University (UNIT), Aracaju, Sergipe, Brazil Rajan Kumar Gupta Laboratory of Algal Research, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India Mateen Hedar School of Chemistry, University of the Punjab, Lahore, Pakistan Nazim Hussain Centre for Applied Molecular Biology, University of the Punjab, Lahore, Pakistan Tajamal Hussain School of Chemistry, University of the Punjab, Lahore, Pakistan Temitope Ezekiel Idowu Center for Applied Coastal Research, University of Delaware, Newark, DE, United States Azeem Intisar School of Chemistry, University of the Punjab, Lahore, Pakistan

Contributors

xiii

Kaushalendra Department of Zoology; Department of Biotechnology, Mizoram University (A Central University), Pachhunga University College Campus, Aizawl, India Hasan Izhar Khan Automotive Engineering Center, University of Engineering and Technology, Lahore, Pakistan Ajay Kumar Department of Botany, Banaras Hindu University, Varanasi, India Pankaj Kumar Agro-ecology and Pollution Research Laboratory, Department of Zoology and Environmental Science, Gurukula Kangri (Deemed to be University), Haridwar, Uttarakhand, India Kayode Hassan Lasisi Department of Civil and Environmental Engineering, Federal University of Technology, Akure, Nigeria; Institute of Urban Environment, Chinese Academy of Sciences, Xiamen; University of Chinese Academy of Sciences, Beijing, P.R. China Jiayang Liu School of Environmental Science and Engineering, Nanjing Tech University, Nanjing, China Sikandar I. Mulla Department of Biochemistry, School of Allied Health Sciences, REVA University, Bangalore, India Nathaniel Azubuike Nwogwu Department of Agricultural and Bioresources Engineering, Federal University of Technology, Owerri, Nigeria Adedamola Oluwafemi Ojo Department of Civil Engineering, Yaba College of Technology, Lagos, Nigeria Olawale Olugbenga Olanrewaju Department of Agricultural and Environmental Engineering, Federal University of Technology, Akure, Nigeria Kapil D. Pandey Laboratory of Algal Research, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India Twinkle Pradhan Laboratory of Algal Research, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India Vineet Kumar Rai Sri Sudrishti Baba Post Graduate College (Affiliated to Jananayak Chandrashekhar University Ballia), Ballia, India Amit Raj Department of Biotechnology, M.AK.A.U.T, Kolkata, West Bengal, India

xiv

Contributors

Arooj Ramzan School of Chemistry, University of the Punjab, Lahore, Pakistan Tahir Rasheed Interdisciplinary Research Center for Advanced Materials, King Fahd University of Petroleum and Minerals (KFUPM), Dhahran, Saudi Arabia Livleen Shukla Division of Microbiology, ICAR-Indian Agricultural Research Institute, Pusa, New Delhi, India Prashant Kumar Singh Department of Biotechnology, Mizoram University (A Central university), Pachhunga University College Campus, Aizawl, India Rahul Prasad Singh Laboratory of Algal Research, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India Rishikesh Singh Department of Botany, Panjab University, Chandigarh, India Sandeep Kumar Singh Division of Microbiology, ICAR-Indian Agricultural Research Institute, Pusa, New Delhi, India Vipin Kumar Singh Department of Botany, K. S. Saket P. G. College, Ayodhya, Uttar Pradesh, India Hariom Verma Department of Botany, B.R.D. Government Degree College Duddhi, Sonbhadra, India Priya Yadav Laboratory of Algal Research, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India Iqra Zaman School of Chemistry, University of the Punjab, Lahore, Pakistan

Series editor’s preface It is a great pleasure for me, as series editor, to introduce this new book titled Recent Advancement in Waste Water Management: Implication and Biological Solutions edited by Luiz Fernando Romanholo Ferreira, Ajay Kumar, and Muhammad Bilal as Volume 9 of the Elsevier Academic Press series titled Advances in Chemical Pollution, Environmental Management and Protection. This volume is an excellent complimentary addition to the two previous books published on wastewater in this series. I am referring to Volumes 5 and 6, edited by Paola Verlicchi, namely, Wastewater Treatment and Reuse—Present and Future Perspectives in Technological Developments and Management Issues and Wastewater Treatment and Reuse—Lessons Learned in Technological Developments and Management Issues, respectively. The thing is that wastewater management remains a key problem to be solved in the coming years. In this respect, I would like to emphasize that watercourses are intensively managed in many areas around the world and face serious problems, such as increasing population in urban areas, i.e., more than 50% of the global population lives in cites. In short, and quoting recently published papers, it is expected that the number of people affected by organic pollution will increase from 1.2 billion in 2000 to 2.5 billion in 2050. Wastewater discharges from cities, especially megacities, and intensive livestock rearing due to increased demand on food supply can be considered the main sources of pollution of our rivers and groundwater. United Nations facts and figures are well known: 3 in 10 people lack access to safely managed drinking water services, 6 in 10 people lack access to safely managed sanitation facilities, and each day, nearly a thousand children die due to water- and sanitation-related diarrheal diseases. The message is crystal clear: more and much more efficient wastewater and drinking water treatment is needed at the global scale. How can we assess the performance of such treatment processes? There is indeed a need to identify appropriate management actions to address the risks due to chemical and microbiological exposure. This book from L.F.R. Ferreira, A. Kumar, and M. Bilal addresses such needs and provides solutions. It reports methods for wastewater characterization of various types of pollutants combined with remediation solutions for better management. In short, this book covers a broad range of removal strategies for a broad range of pollutants, including pharmaceuticals, dyes, pesticides, hormones, metals, and pathogens, present xv

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Series editor’s preface

in wastewaters. Remediation technologies able to reduce the environmental risk posed by the occurrence of these pollutants described in the various chapters of this book are based on microbial degradation, membrane-based hybrid materials, microalgae, immobilized enzymes, and constructed wetlands as well as novel applications of the use of metal-organic framework carbon-based nanomaterials using catalysis. The thing is that we need additional water treatment options to conventional activated sludge procedures for the removal of a comprehensive list of pollutants. An additional advantage of some of these techniques, such as microalgae-based water treatment, is the phytocapture of CO2, reducing greenhouse gases in cities. The book that you now have in your hands contains 17 chapters, discussing different aspects of wastewater management, such as use of low-cost sensors and combining citizen science for better governance of water resources, urban forestry, water accounting methods and simulation models, solutions for mitigation of agricultural drought and sustainable agricultural irrigation, management of coastal wetlands, and remediation and management of polluted wastewaters with pesticides, pharmaceuticals, metals, and pathogens, among others. It is notable that this book contains a lot of information with practical examples or case studies applied to a variety of polluted wastewaters. That being said, this book offers a unique opportunity to better understand and improve wastewater management by providing a comprehensive list of technologies to solve this ubiquitous global problem. The book is multipurpose and can be used as an academic text or as a reference book for those working in the water sector, mainly environmental water authority laboratories and personnel of private water companies involved in wastewater treatment. Finally, I thank all coeditors and all coauthors of this book— well-known experts—for their time and efforts in preparing this excellent and useful book on the recent advancements in wastewater management. DAMIA BARCELO IDAEA-CSIC and ICRA-CERCA, Barcelona and Girona, March 11, 2023

Volume editor’s preface We are delighted to introduce you to this fascinating book, which aims to provide practical information to academics, government policymakers, and various professionals involved in treating environmental contaminants, wastewater treatment technologies, and improving soil productivity as well as those working in the fields of environmental sciences, environmental engineering, and agricultural sciences. The generation of a significant volume of wastewater has been mainly attributed to the remarkable expansion in population and diverse industries worldwide. According to several reports, wastewater is produced by various processes and sectors, including domestic activities, the pharmaceutical and dyeing industries, agrochemical manufacturing, surface runoff from fertilizer-amended agricultural soils, leather cleaning, and water treatment facilities. However, hazardous substances like heavy metals, metalloids, antibiotics, hormones, insecticides, herbicides, pathogenic bacteria, viruses, protozoans, antibiotic-resistant genes, and personal care products are present at unacceptable levels. The generated wastewater, as such, cannot be used for the intended purposes. Therefore, the unacceptable amount of these liabilities limits the application of wastewater. However, given the severe restrictions imposed on water supply by global climate change, the treatment of wastewater using appropriate techniques might be a workable solution to meet the increased demand for irrigation water in agroecosystems. In addition, many beneficial nutrients found in wastewater can be sequestered utilizing cutting-edge separation methods, thus reducing the need for applying artificial fertilizers to agricultural areas to increase crop yield. Therefore, the wise use of wastewater could be essential for developing sustainable agricultural methods. Among these, the characterization, treatment, and application of wastewater are necessary for benefits to be realized in agricultural activities. Characterization is the quantitative measurement of compounds using high-end equipment like HPLC, GC, and ion chromatography. It refers to the analytical evaluation of hazardous wastewater components in terms of physiochemical parameters and detection at low concentration levels. Nowadays, research lays the groundwork for eliminating chemicals that are present over permitted levels. In wastewater treatment facilities, various physicochemical techniques are often used to treat wastewater containing a wide range of contaminants. If wastewater is successfully treated, it will xvii

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provide many opportunities for its use in agricultural activities; nevertheless, comprehensive research on phytotoxicity, ecotoxicology, and toxicology assays and pollutant transmission into the food chain should be carried out to prevent any unfavorable effects of treated wastewater. The purpose of this book is to provide information on the various aspects of wastewater, such as its characterization, treatment, and potential use in sustainable agricultural methods. Characterization would cover pollutants found in wastewater and newly discovered ones, their origins, allowable limits, and the most up-to-date accurate methodologies for contamination identification. Treatment would include any advancements made in the detoxification and decontamination of harmful chemical substances found in wastewater using physical, chemical, and biological methods. This section will also cover significant treatment approach restrictions currently in use and the associated costs for each procedure. The application section will focus on the most recent findings in the use of treated wastewater for agricultural applications, any adverse effects that may result from field application, and critical measures to reduce toxicity, if any. We have present an advanced and up-to-date discussion on the management of wastewater containing hazardous and recalcitrant molecules through microbial remediation, membrane-based hybrid materials, microalgae, immobilized enzymes, constructed wetlands, metal-organic frameworks, and carbon-based nanocomposites as well as its characterization and implications for human life and ecology in general. This book has been designed to concentrate on the advancements made thus far in wastewater characterization, including opportunities in sustainable agricultural practices; newly identified emerging contaminants like pharmaceutics, pesticides, hormones, microplastics, metals, and personal care products; and treatment methodologies developed thus far. Emphasis is also placed on new information related to removing obstacles to the application of treated wastewater. Moreover, all the chapters have been written by active researchers from around the world and are intended to be read by those who are not merely professionals in the field. Moreover, we hope this book will raise awareness of conservation issues by disseminating information about the new technologies used for wastewater management and their characterization in all of their forms, especially among young people and the scientific and business communities. LUIZ FERNANDO ROMANHOLO FERREIRA AJAY KUMAR MUHAMMAD BILAL Editors

CHAPTER ONE

Antibiotics and hormone residues in wastewater: Occurrence, risks, and its biological, physical and chemical treatments Roberta Anjos de Jesusa,*, Gabriela Pereira Barrosa, Ram Naresh Bharagavab, Jiayang Liuc, Sikandar I. Mullad, Lucas Carvalho Basilio Azevedoe, and Luiz Fernando Romanholo Ferreiraa,* a

Waste and Effluent Treatment Laboratory, Institute of Technology and Research (ITP), Tiradentes University (UNIT), Aracaju, Sergipe, Brazil b Laboratory of Bioremediation and Metagenomics Research (LBMR), Department of Environmental Microbiology (DEM), Babasaheb Bhimrao Ambedkar University (A Central University), Lucknow, UP, India c School of Environmental Science and Engineering, Nanjing Tech University, Nanjing, China d Department of Biochemistry, School of Allied Health Sciences, REVA University, Bangalore, India e Instituto de Ci^encias Agra´rias, Universidade Federal de Uberl^andia, Uberl^andia, MG, Brazil ⁎ Corresponding authors: e-mail address: [email protected]; [email protected]

Contents 1. Introduction 2. Occurrence and risks 2.1 Antibiotics 2.2 Hormones 3. Treatment of hormones and antibiotics 3.1 Biological 3.2 Physical and chemical treatments 4. Future prospects References

2 3 4 5 6 6 9 11 11

Abstract This chapter reports on the occurrence, risks, and treatment methods of pollutants (antibiotics and hormones) in wastewater. The misuse of these substances has played a crucial role in environmental contamination and consequently an increase in the prevalence of antibiotic resistant bacteria (ARB) has been observed as well as negative impacts on human and animal health due to the bioaccumulation process. In this context, treatment plants for affluents and effluents, rivers, soil, air, vegetables, among others, have been receiving a significant amount of load containing antibiotics and hormones. However, the current remediation methods of treatment were not designed

Advances in Chemical Pollution, Environmental Management and Protection, Volume 9 Copyright # 2023 Elsevier Inc. ISSN 2468-9289 All rights reserved. https://doi.org/10.1016/bs.apmp.2022.10.001

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to remove these micropollutants which, therefore, remain present in the water resources matrices. Thus, treated wastewater containing antibiotics and hormones, if used for drinking water supply, poses serious risks to human and animal health. The literature reports that combined technology (biological and non-biological) are effective in remediation, that is, alternative technologies emerge as possible solutions to this global problem. Keywords: Antibiotics, Hormones, Occurrence, Risks, Wastewater, Treatment

1. Introduction Antibiotics are essential in disease control and prevention, they can kill and/or inhibit bacterial growth and reproduction based on their mode of action.1 Hormones are responsible for the physiological functional development of many vital organs and processes in the body.2 These pollutants can be obtained via natural organisms or from synthetic materials. The environmental risks arising from the exaggerated production and consumption of these pollutants result in the environmental contamination of water resources and risks to human and animal health.3 According to Van Boeckel et al. in the period between 2010 and 2030 the use of antibiotics could increase by 67% globally.4 These pollutants are one of society’s most important discoveries, which are not only widely used for the treatment of diseases, but also for aquaculture and livestock. However, these pollutants are not well absorbed by humans and animals, approximately 70–90% are excreted in urine or feces as intact bioactive substances or metabolites.5 In addition, animal waste is commonly applied as fertilizer, which leads to diffuse source pollution in the environment.6 Consequently, high concentrations of antibiotics and hormones are detected in various environments, including drinking water, groundwater, wastewater, sediments, among others, where the presence of these pollutants can cause problems to human and environmental health (Fig. 1). Currently, researchers are focusing their efforts on the continuous detection of antibiotics and hormones in aquatic ecosystems from wastewater discharged into the environment. According to Changotra et al. in the pharmaceutical production process, a high volume of clean water is consumed with the generation of large volumes of effluents.7 According to US EPA data, it is estimated that the average daily generation of wastewater by the

Antibiotics and hormone residues in wastewater

3

Fig. 1 Occurrence of antibiotics and hormone residues in wastewater in the environment.

pharmaceutical manufacturing unit is approximately 1.0068
109 L. Thus, due to the huge volume, complex, and hazardous nature of the wastewater generated, industrial pharmaceutical production has been categorized as “red category”.8 Due to the slow growth of these pollutants in the environment, some countries have been adopting remediation procedures, especially in water resources. Environmental control methods can be categorized into physical removal, biodegradation and advanced oxidation processes. However, most wastewater treatment plants today are not designed to remove drugs, as the main focus is on the removal of biodegradables.

2. Occurrence and risks Inefficient treatment of micropolluting contaminated wastewater (antibiotics and hormones) contributes significantly to negative impacts on human and animal health.9 This results from the increased use of prescription drugs and the consequent inefficient treatment of sewage plants that are not designed to remove emerging pollutants from wastewater.

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2.1 Antibiotics Antibiotics have been widely detected in wastewater around the world. This increase is due to the improvement of health services in developing countries, population growth, and agricultural activities (Fig. 2).10 For example, livestock activities contribute significantly to high levels of antibiotics in wastewater, as antibiotics are used in animals in greater amounts (approximately twice as much) compared to humans for disease prevention and growth promotion.11,12 Fekadu et al. confirmed that waste water waste from livestock farming was one of the main reasons for the high concentration of pharmaceuticals in the water resources of African and European continents.13 According to Pereira et al. the most commonly used antibiotics globally were penicillin was used, cephalosporins, macrolides, and fluoroquinolones, respectively.14 The mechanism of action of these drugs is the inhibition of DNA synthesis or RNA transcription.15 The risks associated with the occurrence of antibiotics in the aquatic environment are diverse, including the toxic effects on the microbial structure, growth, respiration, enzymatic activity of aquatic microorganisms, among others.16 Yasser and El-Dahdouh studied the toxicity of amoxicillin, erythromycin, and endosulfan in fish and mosquito larvae. The actors observed the following order of toxicity: amoxicillin > endosulfan > erythromycin. On the other hand, toxicity to mosquitoes: erythromycin > endosulfan > amoxicillin. In addition,

Fig. 2 Occurrence of antibiotics and hormones in the environment and in humans.

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the calculated LC50 values were much lower than the concentration found in different water resources, indicating that the toxicity of the antibiotic mixture results in an antagonistic effect on the species.17 The toxicological risk level of antibiotics can be influenced by various parameters such as concentration, exposure time, aquatic species, and co-occurrence of other antibiotics and/or other contaminants.18 Importantly, there is bioaccumulation of antibiotics in invertebrates and fish muscles after prolonged exposure. Thus, the risks are extrapolated to the human being who consumes aquatic organisms.19 In addition, the reuse of treated wastewater effluents for irrigation is a common practice in many countries. In this context, Wu et al. reported that vegetables (spinach and lettuce) are the ones that most absorb pharmaceuticals and personal care products from the reuse of treated wastewater effluents used in irrigation.20 Prolonged exposure to low subtherapeutic doses of antibiotics in aquatic environments contributes to the development of antimicrobial resistance genes (ARGs) and antibiotic resistant bacteria (ARB).21 The ARB are a serious risk to human and animal health, as they limit the use of antibiotics to treat infectious diseases, especially intractable one. 10 million people could die annually by 2050 if antibiotic-resistant infections are not tackled.22 In 2018 Australian scientists discovered a new superbug resistant to all known antibiotics, Staphylococcus epidermidis.23

2.2 Hormones Hormones pollute waste water resources significantly even at low concentrations can cause biological responses.24 Several studies report that both estrogen hormones and natural and synthetic androgens are prominent in stressing the environment.25 Pollution in the environment can be via point source (effluents and effluent treatment stations) and nonpoint source (agricultural runoff ).26 Hormones act as endocrine disrupting compounds. The main effects of hormones on aquatic life are changes in sexual determination and maturity, among others.22 In addition, there is a growing concern about these steroid pollutants and compounds with similar activities with regard to human health, due to bioaccumulation processes, hormones present in the environment and in the human food chain can have serious adverse effects on human health, since that they are potential for cancerous diseases and minimization in the fertility system.27 Additionally, hormones can cause serious biological effects, such as reduced immune capacity and the biological nervous system.

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Some hormones are naturally produced in the human body being driven by cholesterol, such as the natural estrogens estrone (E1), estradiol (E2), and estriol (E3). E2 is the essential metabolite in pregnant women and has the greatest potential. On the other hand, E3 is the metabolite of E1 and E2.28,29 On average, the amount of estrogen hormones in women’s stool is twice that of men.30 These compounds can reach the sewage treatment plant through human waste. According to Racz and Goel the estrogen hormones E1, E2, E3, and 17α-ethinylestradiol (EE2), respectively in the concentration range between 1 and 500 ng.L1, have been recorded in untreated municipal wastewater. Furthermore, the authors reported that in the effluents of wastewater treatment plants, the elimination of these hormones was insufficient.31

3. Treatment of hormones and antibiotics Conventionally, the treatment of pollutants comprises three stages (preliminary treatment, primary sedimentation and secondary treatment). In the preliminary treatment, entrance screens are normally used. In these, there is biological degradation due to the accumulation of bacterial sludge on the walls. However, at this stage little or no removal of antibiotics or hormones is observed.32 In the primary sedimentation step, the adsorption of the pollutant takes place. The degree of removal depends on several parameters that will be listed in the next topic. Finally, secondary biological treatment is considered the key process for efficient removal of pollutants that occurs through transformation and degradation processes.

3.1 Biological Technological methods for hormone and antibiotic remediation are important due to their toxic effects on the aquatic environment. The literature reports that biological technology is the most used for wastewater treatment (Table 1).43 This stems from its proven robustness, cost, efficiency and low environmental impact.5 There are several biological techniques used, such as photodegradation, volatilization, biosorption, biodegradation, among others (Fig. 3). However, biosorption and biodegradation are the main mechanisms employed. The mechanism of biodegradation may include metabolic and co-metabolic pathways by microorganisms.44 Biological processes that employ microorganisms can produce polysaccharides and proteins that are extracellular polymeric substances.45 These help in the biosorption process,

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Antibiotics and hormone residues in wastewater

Table 1 Different treatments technology used by various researchers in wastewater treatment of antibiotics and hormones. Compound Treatment technology Wastewater Result References

Desogestrel

Supercritical water

Pharmaceutical industry

88.4%

33

E2 and testosterone

Reverse osmosis

Domestic secondary effluent

>95%

34

E1 and E2

Photocatalysis

–

98%

35

E1 and E2

Adsorption and Deactivated and >82% (E1) 36 bacterial degradation activated sludge 78–97% (E2)

Estrogens

Oxidative processes

6 Antibiotics

ARGs

Municipal wastewater treatment

13–79%

37

Anaerobic digestion, Swine anoxic and aerobic wastewater biological treatment treatment

80%

38

Combined treatment Municipal (biological and wastewater non-biological) treatment

>90%

39

Chlorhexidine Photocatalysis digluconate

Pharmaceutical industry

60%

40

24 Antibiotics Biological removal

Wastewater >40% treatment system

41

6 Antibiotics

Wastewater 0.95–1.16 treatment system log

42

Biological removal

Adsorption Photocatalysis Biodegradation Oxidative processes Hybrid processes (biological and non-biological)

Wastewater Antibiotics hormones

ter t wa ste t plan a W en atm tre

Fig. 3 Occurrence and technologies of treatments of hormones and antibiotics.

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due to the presence of several functional groups. According to Fischer and Majewsky antibiotics and hormones in wastewater can be removed mainly by co-metabolic biodegradation, due to their low concentrations, which favors a single source of carbon and nitrogen essential for the growth of microorganisms.46 The literature reports several studies on the removal efficiency of these pollutants that are dependent on the type of bioreactor, pollutant concentrations, and reaction conditions, among others. Shabbir et al. evaluated the biodegradation of two endocrine disrupting compounds, EE2 and bisphenol mediated by periphytic biofilms and the potential additional effect of humic acid. Chromatographic techniques were used to evaluate the biodegradation rate. It was observed that EE2 and BPA (0.2 mg.L1 each) were completely removed (100%) at 36 days of treatment; and biodegradation was significantly increased in the presence of humic acid.47 Yang et al. studied the biodegradation of oxytetracycline, tetracycline, chlortetracycline, amoxicillin, sulfamethazine, sulfamethoxazole, and sulfadimethoxine in slurry. The microorganisms were used under aerobic and anaerobic conditions, being SF1 (Pseudomonas sp.), A12 (Pseudomonas sp.), Bacillus sp., and Clostridium sp.. It was observed that the presence of SF1 and A12 under aerobic conditions and the addition of Bacillus sp. and Clostridium sp. under anaerobic conditions increased the biodegradation of antibiotics in sludge. Additionally, it was verified the stability of biodegradation efficiency that can be maintained for three degradation cycles.48 Biosorption is a physicochemical process that can encompass mechanisms of adsorption, absorption, ion exchange, complexation, and precipitation that occurs between biosorbent and organic and/or inorganic category analytes. Thus, the magnitude of wastewater treatment efficiency depends on some properties such as pollutant load, solubility, hydrophobicity, pH, chemical structures, among others. The degree of hydrophobicity of compounds is proportional to the value of the octanol-water partition coefficients (Kow). Log Kow values less than 2.5, between 2.5 and 4 and greater than 4 are respectively low, medium and high potential for sorption of compounds.22 In general, antibiotics have lower biosorption potentials compared to hormones. Another magnitude parameter for biosorption is the electrostatic interaction. Pollutants can exist in cationic, neutral, and anionic forms according to the pH of the reaction medium.49 In this case, the elucidation of biosorption mechanisms can be complex due to the different chemical and physical compositions of wastewater.50 Proco´pio et al. evaluated the biosorbent from biomass peanut husk (Arachis hypogaea) in EE2 in aqueous matrices. A statistical design was carried out to investigate the adsorptive capacity of peanut shells from the influence

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of agitation rate, pH, and adsorbent mass. The biosorption process removed 90% of EE2 in 24 h with the following experimental conditions (2 g of adsorbent, pH ¼ 6, and agitation at 500 rpm).51 Sunsandee et al. studied Indian almond leaf biomass for dicloxacillin removal from pharmaceutical wastewater. The adsorptive parameters of pH, initial dicloxacillin concentration, biomass dosage, contact time, and temperature were evaluated. Maximum adsorption capacity of 86.93% was observed (pH 6.0, 0.1 g.L1 biomass, dicloxacillin concentration 20 mg.L1, contact time 24 h, temperature 283.15 K). Thus, the authors concluded that considering the cost-benefit ratio, this biomass has potential for removing antibiotics from pharmaceutical wastewater.52

3.2 Physical and chemical treatments The efficiency of biological technology for antibiotics and hormones is only partially successful. In this context, advanced oxidative processes stand out, which are considered promising technologies to completely eliminate emerging pollutants from wastewater (see Table 1).53 Among the oxidizing agents, there are free radicals that are highly reactive, for example, hydroxyls (%OH) that can be used as strong oxidants in the redox process of organic composts in intermediates or in the mineralization process.54 Nguyen et al. investigated the Ni-doped TiO2-based advanced oxidation process of two antibiotics (cephalexin and tetracycline). Cephalexin showed photodegradation of 93.6% and tetracycline of 82.5%. It has been observed that antibiotic removal rates after 5 cycles are greater than 75%.55 Wang et al. investigated a series of antimicrobials frequently detected in municipal wastewater by the ozonation process. Thus, the following were used as a system: synthetic water and a real secondary sewage effluent for the treatment. It was observed that most of the investigated antibiotics (ofloxacin, trimethoprim, norfloxacin, and ciprofloxacin) were degraded in water matrices by direct oxidation of ozone.56 Liz et al. evaluated the photocatalytic activity of TiO2 as a promoter of the degradation of estrogens E1, E2, and EE2 in aqueous solutions and effluent samples. The degradation products of hormones were analyzed by chromatographic techniques and the identification of the degradation product of EE2 by coupling with mass spectrometry. It was observed that TiO2 for 30 min using UVA radiation in the aqueous solution showed degradation rates above 90% for all estrogens. However, in pre-treated sewage samples, immobilized TiO2 was more efficient than free TiO2, allowing ca. 85% removal of E2 and EE2 in 60 min.57

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Vela et al. reported the photodegradation promoted by ZnO in conjunction with Na2S2O8 for six endocrine disruptors in effluents from municipal wastewater treatment plants on a pilot plant scale. The hormones analyzed were bisphenol A, bisphenol B, diamyl phthalate, butyl benzyl phthalate, methyl p-hydroxybenzoate, and ethyl 4-hydroxybenzoate. The influence of operational parameters (catalyst load, electron acceptor effect, and pH) for process optimization was evaluated. It was observed that ZnO together with Na2S2O8 significantly increased the degradation rates compared to the photolytic test. Degradation rates were bisphenols > parabens > phthalates. Furthermore, 83% of the initial dissolved organic carbon was removed and the toxicity decreased to acceptable values (11% inhibition for Vibrio fischeri).58 However, these oxidative processes can consume amounts of energy and chemical reagents.59 Thus, the combination of biological and oxidative techniques constitutes a potential alternative for cost reduction. The synergism of the techniques consists of the pre-treatment step of the biological method causing the reduction of the degradable load resulting in the competitive oxidation with the pollutants. In parallel, the recalcitrant contaminants can be degraded by advanced oxidative post-treatment. The toxicity of organic compounds, especially those from the pharmaceutical industry, prevents the use of biological processes. Thus, more potent treatments are needed, making oxidative processes a valid alternative as a combined technology. Perez et al. compared the remediation of 60 real effluents from a pharmaceutical facility by Fenton oxidation pollution and conductive diamond electro-oxidation. It was observed that in 80% of the samples, conductive-diamond electro-oxidation was more efficient than Fenton oxidation.60 Xu et al. reported hormone degradation by interior micro-electrolysis and Fenton oxidation-coagulation hybrid technology in combination with biological treatments, hydrolysis acidification unit and two-stage biological contact oxidation, in wastewater samples. It was observed that the interior micro-electrolysis showed a chemical oxygen demand (COD) removal efficiency of 31.8%. Fenton oxidation-coagulation reduced COD (30.1%). The biological and non-biological water technology showed concentrations of COD and biochemical oxygen demand in a sulfuric acid solution of 5% (BOD5) in the final effluent of 90 mg/L and 15 mg/L, respectively.61 Changotra et al. reported the remediation of pharmaceutical wastewater of different organic loads through Fenton treatment followed by subsequent biological treatment. Fenton technologies (dark-Fenton, solar-powered photo-Fenton, and electro-Fenton) were used as pre-treatment technologies

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to optimize biodegradability. In the electro-Fenton process, the applied voltage and the hydrogen peroxide dosage were evaluated with parameters in order to make the water biocompatible for further biological degradation. It was observed that Fenton technologies resulted in a significant increase in the BOD/COD ratio, i.e., there was the formation of easily degradable metabolites or secondary products. Thus, COD removal from the combined treatment (Fenton and biological) was approximately 84%.7

4. Future prospects Wastewater quality concerns have reached significant importance globally because the antibiotic and hormone removal technology employed in treatment plants is insufficient. Thus, these pollutants can contaminate surface waters and sometimes groundwater. The development of alternative treatment methods for antibiotics and hormones presents as micro-pollutants of the environment, especially wastewater, is crucial for environmental protection and the safety of human and animal health. It is known that hormones are essential for human development and reproduction, while the application of antibiotics can result in disease control, but their mechanisms of such action are not yet elucidated. Another challenge in this area is the effective removal of these pollutants in order reduce their adverse effects on the environment and health. Most studies focus on biological treatment. Thus, physico-chemical technologies are said to be promising for wastewater remediation. Adsorption processes, removal with nanoparticles and oxidation methods have shown promising results. However, these technologies present the challenge of optimizing the process, aiming at cost reduction and ecological biosecurity, due to their efficiency varying according to the geography of the country and the type of process. This stems from the disagreement and inconsistency in the inspection of the occurrence and destination of these pollutants.

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20. Wu X, Landon Conkle J, Gan J. Multi-residue determination of pharmaceutical and personal care products in vegetables. J Chromatogr A 2012;1254:78–86. https://doi.org/10. 1016/j.chroma.2012.07.041. 21. Haenni M, Dagot C, Chesneau O, Bibbal D, Labanowski J, Vialette M, et al. Environmental contamination in a high-income country (France) by antibiotics, antibiotic-resistant bacteria, and antibiotic resistance genes: status and possible causes. Environ Int 2022;159:107047. https://doi.org/10.1016/j.envint.2021.107047. 22. Cheng D, Ngo HH, Guo W, Chang SW, Nguyen DD, Liu Y, et al. A critical review on antibiotics and hormones in swine wastewater: water pollution problems and control approaches. J Hazard Mater 2020;387:121682. https://doi.org/10.1016/j.jhazmat. 2019.121682. 23. Lee JYH, Monk IR, Gonc¸alves da Silva A, Seemann T, Chua KYL, Kearns A, et al. Global spread of three multidrug-resistant lineages of Staphylococcus epidermidis. Nat Microbiol 2018;3:1175–85. https://doi.org/10.1038/s41564-018-0230-7. 24. Yazdan MMS, Kumar R, Leung SW. The environmental and health impacts of steroids and hormones in wastewater effluent, as well as existing removal technologies: a review. Ecologies 2022;3:206–24. https://doi.org/10.3390/ecologies3020016. 25. Wojnarowski K, Podobi nski P, Cholewi nska P, Smoli nski J, Dorobisz K. Impact of estrogens present in environment on health and welfare of animals. Animals 2021;11:2152. https://doi.org/10.3390/ani11072152. 26. Gonsioroski A, Mourikes VE, Flaws JA. Endocrine disruptors in water and their effects on the reproductive system. Int J Mol Sci 2020;21:1929. https://doi.org/10.3390/ ijms21061929. 27. Adeel M, Song X, Wang Y, Francis D, Yang Y. Environmental impact of estrogens on human, animal and plant life: a critical review. Environ Int 2017;99:107–19. https://doi. org/10.1016/j.envint.2016.12.010. 28. Cui J, Shen Y, Li R. Estrogen synthesis and signaling pathways during aging: from periphery to brain. Trends Mol Med 2013;19:197–209. https://doi.org/10.1016/j. molmed.2012.12.007. 29. Nazari E, Suja F. Effects of 17β-estradiol (E2) on aqueous organisms and its treatment problem: a review. Rev Environ Health 2016;31:465–91. https://doi.org/10.1515/ reveh-2016-0040. 30. Schr€ oder P, Helmreich B, Sˇkrbic B, Carballa M, Papa M, Pastore C, et al. Status of hormones and painkillers in wastewater effluents across several European states—considerations for the EU watch list concerning estradiols and diclofenac. Environ Sci Pollut Res 2016;23:12835–66. https://doi.org/10.1007/s11356-016-6503-x. 31. Racz L, Goel RK. Fate and removal of estrogens in municipal wastewater. J Environ Monit 2010;12:58–70. https://doi.org/10.1039/B917298J. 32. Koh YKK, Chiu TY, Boobis A, Cartmell E, Scrimshaw MD, Lester JN. Treatment and removal strategies for estrogens from wastewater. Environ Technol 2008;29:245–67. https://doi.org/10.1080/09593330802099122. 33. Ribeiro TSS, Moura˜o LC, Souza GBM, Dias IM, Andrade LA, Souza PLM, et al. Treatment of hormones in wastewater from the pharmaceutical industry by continuous flow supercritical water technology. J Environ Chem Eng 2021;9:106095. https://doi.org/ 10.1016/j.jece.2021.106095. 34. Aziz M, Ojumu T. Exclusion of estrogenic and androgenic steroid hormones from municipal membrane bioreactor wastewater using UF/NF/RO membranes for water reuse application. Membranes (Basel) 2020;10:37. https://doi.org/10.3390/ membranes10030037. 35. Lyubimenko R, Gutierrez Cardenas OI, Turshatov A, Richards BS, Sch€afer AI. Photodegradation of steroid-hormone micropollutants in a flow-through membrane reactor coated with Pd(II)-porphyrin. Appl Catal Environ 2021;291:120097. https:// doi.org/10.1016/j.apcatb.2021.120097.

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36. Brasil Bernardelli JK, Liz MV, Belli TJ, Lobo-Recio MA, Lapolli FR. Removal of estrogens by activated sludge under different conditions using batch experiments. Braz J Chem Eng 2015;32:421–32. https://doi.org/10.1590/0104-6632.20150322s00003667. 37. Abusam A, Saeed T, Al-Jandal N. Removal of estrogens in Kuwaiti municipal wastewater treatment plants. J Environ Treat Tech 2020;9:642–6. 38. Wang R, Feng F, Chai Y, Meng X, Sui Q, Chen M, et al. Screening and quantitation of residual antibiotics in two different swine wastewater treatment systems during warm and cold seasons. Sci Total Environ 2019;660:1542–54. https://doi.org/10.1016/j.scitotenv. 2019.01.127. 39. Yang L, Wen Q, Chen Z, Duan R, Yang P. Impacts of advanced treatment processes on elimination of antibiotic resistance genes in a municipal wastewater treatment plant. Front Environ Sci Eng 2019;13:32. https://doi.org/10.1007/s11783-019-1116-5. 40. Sarkar S, Bhattacharjee C. Removal of micro-pollutant using an indigenous photo membrane reactor. J Environ Chem Eng 2020;8:103673. https://doi.org/10.1016/ j.jece.2020.103673. 41. Pu M, Ailijiang N, Mamat A, Chang J, Zhang Q, Liu Y, et al. Occurrence of antibiotics in the different biological treatment processes, reclaimed wastewater treatment plants and effluent-irrigated soils. J Environ Chem Eng 2022;10:107715. https://doi.org/10.1016/ j.jece.2022.107715. 42. Yuan Q-B, Guo M-T, Wei W-J, Yang J. Reductions of bacterial antibiotic resistance through five biological treatment processes treated municipal wastewater. Environ Sci Pollut Res 2016;23:19495–503. https://doi.org/10.1007/s11356-016-7048-8. 43. de Ilurdoz MS, Sadhwani JJ, Reboso JV. Antibiotic removal processes from water & amp; wastewater for the protection of the aquatic environment—a review. J Water Process Eng 2022;45:102474. https://doi.org/10.1016/j.jwpe.2021.102474. 44. Chojnacka K, Skrzypczak D, Izydorczyk G, Mikula K, Szopa D, Moustakas K, et al. Biodegradation of pharmaceuticals in photobioreactors—a systematic literature review. Bioengineered 2022;13:4537–56. https://doi.org/10.1080/21655979.2022.2036906. 45. Costa OYA, Raaijmakers JM, Kuramae EE. Microbial extracellular polymeric substances: ecological function and impact on soil aggregation. Front Microbiol 2018;9:1636. https://doi.org/10.3389/fmicb.2018.01636. 46. Fischer K, Majewsky M. Cometabolic degradation of organic wastewater micropollutants by activated sludge and sludge-inherent microorganisms. Appl Microbiol Biotechnol 2014;98:6583–97. https://doi.org/10.1007/s00253-014-5826-0. 47. Shabbir S, Faheem M, Dar AA, Ali N, Kerr PG, Yu Z-G, et al. Enhanced periphyton biodegradation of endocrine disrupting hormones and microplastic: intrinsic reaction mechanism, influential humic acid and microbial community structure elucidation. Chemosphere 2022;293:133515. https://doi.org/10.1016/j.chemosphere. 2022.133515. 48. Yang C-W, Liu C, Chang B-V. Biodegradation of amoxicillin, Tetracyclines and sulfonamides in wastewater sludge. Water 2020;12:2147. https://doi.org/10.3390/ w12082147. 49. Torres E. Biosorption: a review of the latest advances. Processes 2020;8:1584. https://doi. org/10.3390/pr8121584. 50. Fomina M, Gadd GM. Biosorption: current perspectives on concept, definition and application. Bioresour Technol 2014;160:3–14. https://doi.org/10.1016/j.biortech.2013. 12.102. 51. da Proco´pio AMS, Cais TA, Da Silva WF, Kondo MM, Silva FS, de Andrade SJ. Remotion of the 17α-Ethinylestradiol hormone (EE2) by biosorbent (Arachis hypogaea) in aqueous solutions: validation of analytical methodology and adsorption study. Ci^encia e Nat 2020;42:e11. https://doi.org/10.5902/2179460X42691.

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52. Sunsandee N, Ramakul P, Phatanasri S, Pancharoen U. Biosorption of dicloxacillin from pharmaceutical waste water using tannin from Indian almond leaf: kinetic and equilibrium studies. Biotechnol Rep 2020;27:e00488. https://doi.org/10.1016/j.btre. 2020.e00488. 53. Mahy JG, Wolfs C, Vreuls C, Drot S, Dircks S, Boergers A, et al. Advanced oxidation processes for waste water treatment: from laboratory-scale model water to on-site real waste water. Environ Technol 2021;42:3974–86. https://doi.org/10.1080/09593330. 2020.1797894. 54. Pandis PK, Kalogirou C, Kanellou E, Vaitsis C, Savvidou MG, Sourkouni G, et al. Key points of advanced oxidation processes (AOPs) for wastewater, organic pollutants and pharmaceutical waste treatment: a Mini review. Chem Eng 2022;6:8. https://doi.org/ 10.3390/chemengineering6010008. 55. Nguyen TL, Pham TH, Viet NM, Thang PQ, Rajagopal R, Sathya R, et al. Improved photodegradation of antibiotics pollutants in wastewaters by advanced oxidation process based on Ni-doped TiO2. Chemosphere 2022;302:134837. https://doi.org/10.1016/ j.chemosphere.2022.134837. € 56. Wang H, Mustafa M, Yu G, Ostman M, Cheng Y, Wang Y, et al. Oxidation of emerging biocides and antibiotics in wastewater by ozonation and the electro-peroxone process. Chemosphere 2019;235:575–85. https://doi.org/10.1016/j.chemosphere.2019. 06.205. 57. de Liz M, de Lima R, do Amaral B, Marinho B, Schneider J, Nagata N, et al. Suspended and immobilized TiO2 photocatalytic degradation of estrogens: potential for application in wastewater treatment processes. J Braz Chem Soc 2017;2:380–9. https://doi.org/ 10.21577/0103-5053.20170151. 58. Vela N, Calı´n M, Ya´n˜ez-Gasco´n MJ, Garrido I, Perez-Lucas G, Fenoll J, et al. Photocatalytic oxidation of six endocrine disruptor chemicals in wastewater using ZnO at pilot plant scale under natural sunlight. Environ Sci Pollut Res 2018;25: 34995–5007. https://doi.org/10.1007/s11356-018-1716-9. 59. Lofrano G, Pedrazzani R, Libralato G, Carotenuto M. Advanced oxidation processes for antibiotics removal: a review. Curr Org Chem 2017;21:1054–67. https://doi.org/10. 2174/1385272821666170103162813. 60. Perez JF, Llanos J, Sa´ez C, Lo´pez C, Can˜izares P, Rodrigo MA. Treatment of real effluents from the pharmaceutical industry: a comparison between Fenton oxidation and conductive-diamond electro-oxidation. J Environ Manage 2017;195:216–23. https:// doi.org/10.1016/j.jenvman.2016.08.009. 61. Xu X, Cheng Y, Zhang T, Ji F, Xu X. Treatment of pharmaceutical wastewater using interior micro-electrolysis/Fenton oxidation-coagulation and biological degradation. Chemosphere 2016;152:23–30. https://doi.org/10.1016/j.chemosphere.2016.02.100.

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CHAPTER TWO

Occurrence of pesticides in wastewater: Bioremediation approach for environmental safety and its toxicity Roberta Anjos de Jesusa,*, Gabriela Pereira Barrosa, Ram Naresh Bharagavab, Jiayang Liuc, Sikandar I. Mullad, Lucas Carvalho Basilio Azevedoe, and Luiz Fernando Romanholo Ferreiraa,* a

Waste and Effluent Treatment Laboratory, Institute of Technology and Research (ITP), Tiradentes University (UNIT), Aracaju, Sergipe, Brazil b Laboratory of Bioremediation and Metagenomics Research (LBMR), Department of Environmental Microbiology (DEM), Babasaheb Bhimrao Ambedkar University (A Central University), Lucknow, UP, India c School of Environmental Science and Engineering, Nanjing Tech University, Nanjing, China d Department of Biochemistry, School of Allied Health Sciences, REVA University, Bangalore, India e Instituto de Ci^encias Agra´rias, Universidade Federal de Uberl^andia, Uberl^andia, MG, Brazil *Corresponding authors: e-mail address: [email protected]; [email protected]

Contents 1. 2. 3. 4. 5.

Introduction Classification of pesticides Occurrence of pesticides Toxicity Bioremediation of pesticides 5.1 Physicochemical degradation 5.2 Biodegradation 6. Final considerations References

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Abstract Pesticides are chemical substances used to improve the quality of food products and plant diseases. The occurrence of pesticides in wastewater is receiving attention from the scientific community, since these pollutants have harmful effects and are persistent, undergoing bioaccumulation resulting in risks to human health and environmental damage due to their toxicity. Thus, water safety cannot be guaranteed with the presence of pesticides. The main source of contamination in the water body results from agricultural, urban, and industrial activities. Pesticides when in water bodies come into Advances in Chemical Pollution, Environmental Management and Protection, Volume 9 Copyright # 2023 Elsevier Inc. ISSN 2468-9289 All rights reserved. https://doi.org/10.1016/bs.apmp.2022.10.002

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contact with humans by three ways: (i) ingestion (ingesting contaminated water), (ii) inhalation (vapors in the bath), and (iii) dermal contact (through the bath). Thus, an adequate supply of pesticide-free water remains an environmental challenge. Keywords: Pesticides, Wastewater, Agriculture, Occurrence, Fate, Degradation

1. Introduction During the second half of the 19th century, industrial growth culminated in a global concern in terms of the health impacts of living beings due to environmental pollution by biodegradable and non-biodegradable contaminants. Pesticides are one of the most representative organic pollutants in the environment due to their intensive use in agricultural production that were developed to mimic and therefore replace specific molecules in targeted biological reactions.1 By definition, pesticides are biologically active substances that can be natural or synthetic and, due to the process of bioaccumulation and high toxicity, induce carcinogenic, neurotoxicological, endocrine, reproductive, among others effects on human health.2 In the early 1960s, the first environmental warnings caused by the use of pesticides appeared.3 World production and use of these pollutants has grown strongly over time.4 Currently, approximately 2 million tonnes of pesticides are used worldwide.1 Lindane, dichlorodiphenyltrichloroethane, and malathion are the most commonly used pesticides, accounting for 70% of total use.5 The total consumption of pesticides, 80% is aimed at killing the insects, 15% is herbicide, 1.46% is for fungal plant diseases, while 3% is other forms of pesticides. However, the global consumption of 47.5% of herbicides and 29.5% of insecticides stands out.6 The most pesticide consuming countries are Brazil, Italy, Japan, United States of America, China, Argentina, Canada, India, France, and Thailand.5 An ideal pesticide mechanism should only affect crops and degrade within a period necessary for their effectiveness on non-toxic substances. The pesticide life-cycle assessment in practice after application, these pollutants distribute and accumulate in plant parts, soil, water, biota, and air (Fig. 1A).7,8 The form of use, environmental characteristics and physicochemical properties of the active ingredient are the main variables that affect the fate of pesticides in the environment.2 Water plays a vital role for the survival of living organisms and agricultural productivity in the environment.9 In this scenario, the preservation of environmental quality is one of the main challenges due to the significant

Occurrence of pesticides in wastewater

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Fig. 1 Occurrence of pesticides in the environment (A) and its life-cycle assessment (B).

number of pesticides that are released into the environment, especially in water resources. Arid developing countries have an extensive area under irrigation with wastewater as a result of limited water resources.10 Thus, the literature has considerable attention on remediation due to the growing global demand for water, reuse, and recycling of wastewater. Sources of drinking water for consumption, surface and underground, are regularly monitored for qualitative and quantitative chemical analysis

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of pesticides and their metabolites. The presence of pesticides in aqueous media derives from agricultural runoff and industrial wastewater.11 Thus, it is recommended before releasing the effluent to treat wastewater to remove these pollutants to acceptable levels, especially in dry climatic periods because the dilution of these substances in surface water is reduced. As the removal of pesticides from water is one of the main environmental problems, this work aims to analyze the general panorama of the occurrence of pesticides in wastewater.

2. Classification of pesticides Pesticides have different physical and chemical properties. Therefore, they are classified according to their mode of action, spectrum of activity, chemical nature, and level of toxicity.12 Based on the mode of action to produce the desired effect, pesticides can be classified as: (i) non-systemic and (ii) systemic. The systemic ones penetrate plant tissues and are transported within the plant vascular system. On the other hand, non-systemic ones are said to be those that do not penetrate plant tissues (plant vascular system).12,13 In the spectrum of action, pesticides can be broad or selective spectrum.14,15 These are designed to kill specific pests, however the broadspectrum ones are designed to kill a wide range of pests and other non-target organisms. Classification based on target can be: insecticides (insects), herbicides (weeds), bactericides (bacteria), fungicides (fungi), acaricides (mites and ticks), molluscicides (slugs and snails), nematicides (nematodes), preservatives of wood (wood-destroying organisms), and rodenticides (rodents).16 The classification in terms of toxicity to human health is defined by the World Health Organization (WHO), being coded by classes: Ia (extremely dangerous), Ib (highly dangerous), II (moderately dangerous), III (slightly dangerous), and IV (no acute risks).17,18 Pesticides are generally divided into seven types with regard to their chemical nature, including organochlorines, organophosphates, carbamates, pyrethroids, amides, anilines, and heterocyclic nitrogen compounds.12 Table 1 presents the main components of the common groups of pesticides.19 Organochlorines have an organic chain made up of five or more Cl atoms. Due to their stable chemical structure, they often accumulate and are persistent in the environment. Thus, most were banned in world agriculture for causing severe endocrine disruption.20

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Table 1 Components of pesticide classes.19 Group Chemical composition

Organochlorine

Characteristics

Non-polar and Lipid soluble, toxic to lipophilic atoms variety of animals and including C, Cl, and H long-term persistence

Example

Lindane

Organophosphate Aliphatic, cyclic and heterocyclic possess central P atom in molecule

Soluble in organic solvent Malathion as well as water Less persistence than chlorinated hydrocarbons

Carbamates

Chemical structure based on alkaloid of a plant species

Relatively low persistence Carbaryl

Pyrethroids

Alkaloid obtained from Less persistent than other Pyrethrins petals of plant species pesticides, therefore safest to be used as household insecticides

Biological

Microorganism, viruses Applied against forest Affect and their metabolic pests (butterflies) and crop other products caterpillars

Organophosphates contain a phosphate group in their structure and present irreversible acute toxicities, such as the inhibition of the enzyme acetylcholinesterase, responsible for the hydrolysis of acetylcholine in the nervous system of living beings.21 Carbamates are compounds that are derived from carbamic acid and act by reversibly inactivating the enzyme acetylcholinesterase.12 Pyrethroids are synthetic analogues of natural pyrethrins that show high efficacy, easy biodegradation, and low toxicity to mammals.22 For this reason, there has been an increase in the commercialization of pyrethroids in the last 30 years. However, this class of pesticides is highly toxic to aquatic organisms.23 Amide pesticides are widely used in recent years, however, some are persistent and mutagenic such as butachlor and metolachlor.24 Another type of pesticides is aniline and dinitroaniline, which are highly toxic to aquatic organisms and can harm the thyroid gland and liver, such as trifluralin and pendimethalin, so these compounds have been banned in many European countries. Heterocyclic compounds containing nitrogen, such as imidazole and triazole, have become alternative and promising compounds for the development of new pesticides. They currently represent 70% of all newly developed synthetic pesticides.25

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3. Occurrence of pesticides

Pesticides

Starting in the 1940s, the production and use of pesticides increased rapidly. For example, there are approximately 750 different glyphosate based pesticide formulations around the world are being used in the environment, and agriculture accounts for the largest share of the use.2,26 Pesticides contaminate water resources via point and non-point sources. The point mode originates from a fixed location through a direct movement of pesticides due to their improper disposal. Urban use of insecticide is considered as a point source pesticide in wastewater.19 On the other hand, non-point contamination refers to the movement of the pollutant to large areas along watersheds that originate from agricultural activities due to the leaching process.19,27 Wastewater is contaminated by persistent chemicals from pesticides that are commonly released by agricultural crops, industries, urban use, and pesticide production plants. Water generated in pesticide production requires excessive treatment before being mixed with domestic wastewater.11 In addition, significant amounts of insecticide are used for the treatment of raw materials in the wood industry. This is the type of pesticide with the highest detection in urban areas.19,28 The circulation of pesticides in the biosphere is dependent on destination, form of transport, adsorption capacity, and solubility, among others. Thus, there are various fates in the environment after being applied on Earth. In general (see Fig. 2), after application, the pesticide that is not absorbed by the treated plants will be retained in the soil through surface runoff or undergo biotic or abiotic degradation.14

No transformation

Chemical structure unchanged

Abiotic degradation

Chemical or physical transformation

Adsorb by soil

Co-metabolism

Metabolites

Mineralization

Nutrients to soil

Biotic degradation

Fig. 2 Fate pesticides.

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In the biotic process, biological degradation occurs, which is mediated by microorganisms which results in the mineralization process in which the pesticide decomposes or by co-metabolization where the microbial reaction transforms pesticides into other chemicals.29 On the other hand, the abiotic process can occur through physical or chemical transformation. In physical transformations via photochemical reactions, pesticides decompose in the presence of ultraviolet radiation. However, in chemical transformations via redox reactions of pesticides, electron transfer and hydrolysis with air, water and other existing compounds occur. According to the National Water-Quality Assessment, pesticides are found more often in surface water than groundwater. According to the report published in 1990 by the Environmental Protection Agency, 50% of water pollution in rivers and streams is due to the release and mixing of chemicals used in agricultural soils.6 Thus, according to the European Union (EU) enacted standard, pesticides are classified into priority levels when detected in drinking water (see Table 2).9,30 The risks associated with the use of pesticides are greater when users are less qualified and unaware of adequate protection strategies. To date, there is no global legislation for the management of these pollutants. The government of each country is expected to take appropriate measures to minimize the health and safety risks to farmers and consumers after use. Some forms of management include training, guidance, and monitoring of farmers Table 2 Risk classification of pesticides.30 Class Criteria

High priority Pesticides or relevant metabolites present in produced drinking water Priority

Pesticides or relevant metabolites present in drinking water sources >0.1 mg.L 1 (for 90th % of all data > LOQ) Non-relevant metabolites present in drinking water sources >1 mg. L 1 (for 90th % of all data > LOQ)

Potential priority

Pesticides or relevant metabolites present drinking water sources >0.1 < 0.1 mg.L 1 (for 90th % of all data > LOQ) Non-relevant metabolites present in drinking water sources >0.1 < 1 mg.L 1 (for 90th % of all data > LOQ)

Low priority

Not detected pesticides and or relevant metabolites and pesticides or relevant metabolites present drinking water sources do not exceed 0.01 mg.L 1

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regarding the risk of storage, use, and disposal of pesticides, for example, in the process of labeling hazardous substances in which the active ingredient must be indicated.31–33

4. Toxicity Despite the enormous contribution of pesticides to increasing agricultural yields through pest control and also in the control of diseases transmitted by insects to humans (e.g., malaria, dengue, encephalitis, filariasis, and others),26,34 these pollutants, for example, have been proven to be toxic to humans and the environment35 since during the transformation of these pollutants there is production of metabolites and secondary inorganic products that may have varying levels of toxicity than the substrate.36 Pesticide contamination is more alarming in developed countries than in developing countries.6 Exposure to pesticides in water resources can occur in three ways: (i) ingestion (drinking contaminated water), (ii) inhalation (vapors in the bath), and (iii) dermal contact (through bathing). The lethality of the pesticide is greatest when humans are exposed through oral exposure. Thus, humans when exposed to these contaminants triggers acute and chronic health problems (see Fig. 3). These encompass neurological diseases (onset of Parkinson’s disease), memory disorders, birth defects, cancer, reduced vision, headaches, nausea, coma, death, among others.37–39 Therefore, improving research on biological markers would be useful to assess the health risk of pesticide exposure. While a greater amount of pesticide can harm people compared to target pests, minimal dosages are needed to destroy humans in many ways. Some diseases caused by pesticides are discussed.

Fig. 3 Toxicological effects of pesticides.

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Cancers are mainly linked to age, however, prolonged exposure to pesticides is one of the main causes of the disease. Pesticides enhance the spread of tumor growth through DNA alteration via mutagenesis and/or inappropriate mitogenesis.40 Studies have shown that out of a total of 20.646 pesticide applicators, 2.907 individuals developed cancer.41 It is reported in the literature that the ingestion of phenoxyacid-based herbicides increases the risk of non-Hodgkin’s lymphoma by six times.42 Color cancer is the second leading cause of death and this increase may be related to the use of pesticides, especially those containing heterocyclic aromatic amines.43 The pesticide imazethapyr is commonly used in agriculture increasing the risk of bladder cancer by 137% and colon cancer by 78%.6 Exposure to organochlorine pesticides is important in the etiology of breast cancer. In southeastern Iran, there was evidence of an increased risk of breast cancer in women due to exposure to organochlorines.44 Pesticides are significant contributors to a global diabetes pandemic, especially organochlorines and metabolites.45 Juntarawijit and Juntarawijit reported that the prevalence of diabetes is associated with exposure to all types of pesticides (insecticides, herbicides, fungicides, rodenticides, among others), especially organochlorine (endosulfan), organophosphate (mevinphos), carbamate (carbaryl/Sevin), and fungicide (benlate).46 The disease of Parkinson’s it is caused by the early death of dopaminecontaining neurons in the substantia nigra of the brain neural cells.6 This is the second most common neurodegenerative disease after Alzheimer’s disease.47 Although Parkinson’s disease has no proven cause due to exposure to pesticides, these can cause neurotoxic processes via oxidative stress. According to a meta-analysis, prolonged exposure to pesticides was associated with an increased risk of disease of Parkinson’s of up to 11%.39 Oxidative stress plays a crucial role in the manifestation of neurodegenerative diseases.48 Some herbicides are factors for a higher risk of developing this disease because they interrupt the bioenergy and redox activity of metabolism, example rotenone and paraquat.47,49 Toxicity and persistence make the elimination of pesticides in wastewater a crucial factor. There are several guidance values for pesticides in water as a measure to protect public health defined by the WHO, United States, Australia, EU, and Japan,19 however, the values are dependent on socioeconomic conditions dietary, geographic, and industrial for each country.50 Therefore, the impact of these pollutants is difficult to judge, as physicians may not identify symptomatic indications due to intoxication and poor legislation.6,51

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5. Bioremediation of pesticides The use of pesticides causes many serious risks to human health and the environment. The degradation of pesticides is the result of biological, chemical and physical processes; however, some methods have lower responses, specificities and sensitivities. In this context, bioremediation is an emerging and promising technology for the decontamination of places polluted with pesticides.

5.1 Physicochemical degradation Chemical degradation processes can be quite expensive depending on the treatment. Generally, contaminated substances must be pre-treated and chemically processed to obtain potentially less toxic and harmful intermediate compounds. Despite the efficiency of chemical methods, there is often the production of more persistent and harmful metabolites than the parent compounds.52 Thus, chemical degradation and physical degradation are hyphenated for best results. Reactions where a chemical bond is broken in the presence of water is known as hydrolysis. This is one of the possible ways of transforming pesticides in the soil and in living organisms. The main chemical degradation parameters that influence the hydrolysis rate are the control of pH, temperature, the presence of metal ions and dissolved organic matter.53 Thus, polar pesticides show higher degradation rates compared to non-polar pesticides, due to their higher water solubility. In aquatic inputs that have a pH in the range between 5 and 8, most pesticides are stable. On the other hand, higher degradation rates are observed in alkaline and acidic conditions, respectively.54 The main mechanism of physical degradation is photolysis, in which light and temperature are the most important parameters. Techniques such as lowering freezing temperatures are used to aid in pesticide degradation.55 Another common physical degradation process is incineration, in which it completely destroys pollutants.56 Photodegradation is a physicochemical process that occurs in the atmosphere, water and the top layer of the soil under radiation exposure and is classified into four groups (direct, indirect, photosensitized, and photocatalytic).54 Direct photodegradation is based on the absorption of photons by molecules to higher energy states via homolysis, heterolysis

Occurrence of pesticides in wastewater

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or photolysis.57 Indirect photodegradation is the reaction with photooxidizing agents (hydroxyl radicals, O3 or NO3), which occur naturally in the atmosphere. Briefly, the molecule absorbs the photon resulting in chemical bond dissociation, then very reactive radical forms are generated.58,59 Photosensitization is based on the absorption of photons by the molecule, where the energy of its excited state is transferred to the pesticide via homolysis, heterolysis and photolysis. In addition, there may be oxidation and reduction processes, for example, the photo-Fenton reaction.60 Photocatalytic is a light-induced catalytic process.61,62 The literature reports numerous semiconductors for this process. Various metal oxides (TiO2, ZnO, WO3, Fe2O3, AgI/C3N4, TbFeO2 among others) used for photocatalysis. Most of the literature reports degradation of persistent and toxic pesticides with TiO2 and ZnO nanomaterials.63,64 Sangami and Manu synthesized Fe nanoparticles from eucalyptus leaf extracts. The characterization results confirmed that the nanoparticles had a surface area of 36.62 m2.g 1 and a size in the range between 20 and 70 nm of spherical particles. Thus, the nanoparticles were used as Fentontype catalysts for the degradation of ametryn in aqueous media. The optimal values found were 2.125, 6, 3.5, and 135 min for H2O2/COD, H2O2/Fe, pH, and reaction time, respectively.65 Abramovic et al. evaluated the photochemical degradation of thiacloprid under a variety of solution conditions, varying initial H2O2 concentrations and pH. It was observed that UV radiation, or H2O2 alone, did not produce significant degradation of thiacloprid. Thus, using the hyphenated methods (UV/H2O2) it was possible to observe that 97% of the thiacloprid was removed in about 120 min. It is known that the degradation of thiacloprid is accompanied by the formation of various ionic by-products (Cl , acetate, formate, sulfate, and ammonium) and organic intermediates, so after 35 h of irradiation, 17% of the organic carbon remained undegraded.66

5.2 Biodegradation The microbial community of a given area plays an important role in maintaining the quality of the environment.67 Biodegradation occurs through microorganisms, which act as enzymatic catalysts. The degradation of organic pollutants by microorganisms is a natural process in the environment, in which organic matter is broken down into CO2 and H2O.68

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Thus, for microbial activity to occur, it is necessary that: (i) the microorganism is present in the environment containing the pesticide, (ii) the pesticide is accessible to the microorganism and (iii) the microorganism biomass allows its proliferation.54,69 In aqueous media, the biodegradation process depends on the existence of particulate matter, salinity, nutrients, temperature, oxygen concentration, redox potential, bioavailability, and microbial adaptation.70 Chauhan and Jan evaluated the biodegradation of organophosphate pesticides mediated by the laccase enzyme produced from Pseudomonas sp. using agro residues (potato peel). The temperature and pH for maximum enzymatic activity were 80 °C and 9.0 °C, respectively. It was observed that the ions Na+, K+, Pb+2, Ca+2, Cu+2, and Co+2 increased the enzymatic activity. Laccase showed biodegradation rate for dichlorophos, chlorpyrifos, monocrotophos, and profenovos in 45.99%, 80.56%, 75.45%, and 81.846%, respectively, in the absence of any mediator.71 Zhen et al. investigated the biodegradation of the herbicide isoproturon using laccase from Trametes versicolor. The herbicide showed low degradation only with laccase, due to the presence of the electron-withdrawing group in the chemical structure of isoproturon. Thus, the influence of laccase mediating systems was investigated. It was observed that within 24 h, isoproturon was completely degraded in the presence of laccase and 1-hydroxybenzotriazole (HBT). Biodegradation took place at acidic pH at 50 °C. The presence of metallic ions Cu2+, Zn2+, and Cd2+ positively improved the degradation of isoproturon with the laccase-HBT system. The transformation products showed much lower ecotoxicity to green algae than the original isoproturon.72 Anjos et al. evaluated a bacterial consortium isolated from the Brazilian Cerrado (Lysinibacillus xylanilyticus CBMAI2085, Bacillus cereus CBMAI2067, Lysinibacillus sp. CBMAI2051, and Bacillus sp. CBMAI2052) for biodegradation of the pyrethroid esfenvalerate in liquid culture medium. It was observed that in 12 days, 90% of the pesticide was degraded producing 3-phenoxybenzoic acid and 2-(4-chlorophenyl)-3-methylbutanoic acid.73 Hu et al. reported for the first time the white rot fungus Trametes versicolor for the biodegradation of medium to high polarity pesticides (malathion, neonicotinoids acetamiprid, and imidacloprid). It was observed that the fungus degraded 100% of malathion after 48 h, acetamiprid and imidacloprid degraded 20% and 64.7%, respectively, after 7 days. The authors found that the cytochrome P450 system, rather than the extracellular enzyme laccase, was responsible for the degradation of acetamiprid and imidacloprid. In addition, the transformation products were less toxic than the investigated pesticides.74

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6. Final considerations Although pesticides are beneficial in pest management and control of some diseases. These have potential deleterious effects on human health and the environment that must be taken into account for a sustainable approach. The magnitude of these effects is related to the physicochemical properties of pesticides (solubility, half-life, adsorption capacity, biodegradability, among others), so pesticides have different environmental fates. In this scenario, pesticides are routinely detected in water resources around the world. Wastewater treatment aims at water management to increase the availability of potable water, increase the environmental nexus and growth of the economy. Thus, remediation techniques must be appropriate to the environmental needs of each country.

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30. Sjerps RMA, Kooij PJF, van Loon A, Van Wezel AP. Occurrence of pesticides in Dutch drinking water sources. Chemosphere 2019;235:510–8. https://doi.org/ 10.1016/j.chemosphere.2019.06.207. 31. Amare C, Golibe E. Risks associated with the use of insecticides in cowpea conservation. Int J Pap Adv Sci Rev 2022;3:11–7. https://doi.org/10.47667/ijpasr.v3i1.139. 32. Andersson E, Isgren E. Gambling in the garden: pesticide use and risk exposure in Ugandan smallholder farming. J Rural Stud 2021;82:76–86. https://doi.org/10.1016/j. jrurstud.2021.01.013. 33. Sharafi K, Pirsaheb M, Maleki S, Arfaeinia H, Karimyan K, Moradi M, et al. Knowledge, attitude and practices of farmers about pesticide use, risks, and wastes; a cross-sectional study (Kermanshah, Iran). Sci Total Environ 2018;645:509–17. https://doi.org/10.1016/ j.scitotenv.2018.07.132. 34. Rekha SN, Naik R. Prasad, pesticide residue in organic and conventional food-risk analysis. J Chem Heal Saf 2006;13:12–9. https://doi.org/10.1016/j.chs.2005.01.012. 35. Rasheed T, Bilal M, Nabeel F, Adeel M, Iqbal HMN. Environmentally-related contaminants of high concern: potential sources and analytical modalities for detection, quantification, and treatment. Environ Int 2019;122:52–66. https://doi.org/10.1016/j.envint. 2018.11.038. 36. Bose S, Kumar PS, Vo D-VN, Rajamohan N, Saravanan R. Microbial degradation of recalcitrant pesticides: a review. Environ Chem Lett 2021;19:3209–28. https://doi. org/10.1007/s10311-021-01236-5. 37. Upadhayay J, Rana M, Juyal V, Bisht SS, Joshi R. Impact of pesticide exposure and associated health effects. In: Pesticides in crop production. Wiley; 2020. p. 69–88. https://doi. org/10.1002/9781119432241.ch5. 38. Sabarwal A, Kumar K, Singh RP. Hazardous effects of chemical pesticides on human health–Cancer and other associated disorders. Environ Toxicol Pharmacol 2018;63:103–14. https://doi.org/10.1016/j.etap.2018.08.018. 39. Yan D, Zhang Y, Liu L, Shi N, Yan H. Pesticide exposure and risk of Parkinson’s disease: dose-response meta-analysis of observational studies. Regul Toxicol Pharmacol 2018;96:57–63. https://doi.org/10.1016/j.yrtph.2018.05.005. 40. Gallagher RP, MacArthur AC, Lee TK, Weber J-P, Leblanc A, Mark Elwood J, et al. Plasma levels of polychlorinated biphenyls and risk of cutaneous malignant melanoma: a preliminary study. Int J Cancer 2011;128:1872–80. https://doi.org/ 10.1002/ijc.25503. 41. Asghar U, Malik MF. Pesticide exposure and human health: a review. J Ecosyst Ecography 2016;01:1–4. https://doi.org/10.4172/2157-7625.S5-005. 42. Singh NS, Sharma R, Parween T, Patanjali PK. Pesticide contamination and human health risk factor. In: Modern age environmental problems and their remediation. Cham: Springer International Publishing; 2018. p. 49–68. https://doi.org/10.1007/978-3319-64501-8_3. 43. Martin FL, Martinez EZ, Stopper H, Garcia SB, Uyemura SA, Kannen V. Increased exposure to pesticides and colon cancer: early evidence in Brazil. Chemosphere 2018;209:623–31. https://doi.org/10.1016/j.chemosphere.2018.06.118. 44. Paydar P, Asadikaram G, Fallah H, Zeynali Nejad H, Akbari H, Abolhassani M, et al. Serum levels of organochlorine pesticides and breast Cancer risk in Iranian women. Arch Environ Contam Toxicol 2019;77:480–9. https://doi.org/10.1007/s00244-01900648-3. 45. Tang M, Chen K, Yang F, Liu W. Exposure to organochlorine pollutants and type 2 diabetes: a systematic review and Meta-analysis. PLoS One 2014;9:e85556. https:// doi.org/10.1371/journal.pone.0085556. 46. Juntarawijit C, Juntarawijit Y. Association between diabetes and pesticides: a case-control study among Thai farmers. Environ Health Prev Med 2018;23:3. https:// doi.org/10.1186/s12199-018-0692-5.

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CHAPTER THREE

Removal of pharmaceutical compounds from water Mateen Hedara, Iqra Zamana, Muhammad Imran Dina, Nazim Hussainb, Azeem Intisara,*, Adeel Afzala,*, and Muhammad Amin Abidc a

School of Chemistry, University of the Punjab, Lahore, Pakistan Centre for Applied Molecular Biology, University of the Punjab, Lahore, Pakistan Department of Chemistry, University of Sahiwal, Sahiwal, Pakistan *Corresponding authors: e-mail address: [email protected]; [email protected] b c

Contents 1. Introduction 1.1 Toxicological effects of pharmaceutical compounds present in water 1.2 Occurrence of pharmaceutical drugs in surface water 1.3 Occurrence of pharmaceutical drugs in down reservoirs 2. Methods for removal of pharmaceutical compounds 2.1 Removal of pharmaceutical compounds using enzymes 2.2 Enzymatic membrane reactors (EMRs) 2.3 Treatment through fungi 2.4 Adsorption on non-conventional material 2.5 Hybrid technologies for removal of PC 2.6 Treatment of pharmaceutical compounds through microalgae 2.7 Treatment of PC by using organic biomass 2.8 Bio ozone-bio process for treatment of PC 2.9 Pros and cons of different methodologies used for PACs removal 3. Future prospective 4. Conclusion References

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Abstract Increasing concentration of pharmaceutical compounds in aquatic bodies and reservoirs is becoming a serious global concern. They show significant bioactive properties and their long-term persistence in the environment causes an irreparable damage to living and non-living systems. Hence, there is a great need to tackle this issue on global level. This chapter sums up the latest literature on the mitigation of pharmaceutical drugs from water using biological means such as enzymes (crude and immobilized enzymes), fungi, algae, organic biomass and microorganism, etc. Moreover, some explanation of the ancient biological schemes mainly the trickling reactors, activated sludge

Advances in Chemical Pollution, Environmental Management and Protection, Volume 9 Copyright # 2023 Elsevier Inc. ISSN 2468-9289 All rights reserved. https://doi.org/10.1016/bs.apmp.2022.12.001

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process, advanced biological processes, commonly moving bed reactors based on biofilms and two-phased partitioning bioreactors are also included. These innovative management methods are proficient to stand against high toxin loads and can bear a wide range of contaminants that are not soluble in water. Effective removal efficiencies are demonstrated by quantitative data from the literature that highlights these biological processes as the most favorable and viable track for the biodegradation and biotransformation of numerous drugs. Keywords: Pharmaceutical drugs, Water contamination, Mitigation, Organic biomass, Algae, Fungi, Bioreactors

1. Introduction The maximum allowable quantities of new environmental contaminants are not systematically regulated, and it is questionable whether these contaminants will have any short-, intermediate-, or long-term consequences on human health. Even though some of these newly discovered impurities were in water for years, now it seems that they are being found and acknowledged as potentially deadly pollutants.1 The European Union Water Framework Directive (EUWFD) modifies the listing of primary concern compounds every 4 years in accordance with the environmental protection principle.2 Pharmacological and personal care products (PPCPs), or chemicals found in skincare and beauty products household goods, and, particularly, novel medical drugs created to have huge impacts and characteristics and to combat contagious diseases, have recently been added to the list.3 Pharmaceutical products and their derivatives have raised the most concerns among all these new organic pollutants.4 This is primarily attributable to the wide range of these chemicals and their heavy recent usage. There are reported to be 6 million PPCPs available commercially worldwide, and the weight of medicinal compounds consumption has been growing by 3–4% year.5 Because of this situation, large levels of these metabolites that have an approximated 50 μg/L antibiotic content have been disposed in urban wastewaters. Due to their permanence in water, overuse of antibiotics and drugs and their resistance to degradation affects not only those who misuse these items but also the entire populace. The most of these medications, such as penicillin, nitroimidazoles, and sulfamethoxazole, exhibit genotoxic and carcinogenic qualities in addition to having limited biodegradability and potential toxicity.6 Pharma companies, pharmacies, livestock manure, investigations using therapeutic compounds, and the release of outdated medication into the ecosystem are the primary contributors of pharmacological contaminants in ecosystem.

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Pharmaceutical pollutants, sometimes known as emerging contaminants (ECs), have drawn increasing attention because of their extremely toxic and possible risk to environments and people. These pollutants are consumed in large quantities across the globe and are unintentionally or intentionally introduced into the water supply. These pollutants cannot be successfully eliminated by the biological processes-based traditional treatment procedures. Therefore, it is crucial to create effective and long-lasting removal techniques for these new pollutants. Numerous studies have been undertaken on the elimination of medicinal residues. Conventional activated sludge treatment (CAS), membrane bioreactors (MBR), built wetlands, algae photo bioreactors, and biological treatment are the main biological removal techniques for these chemicals from water system.7–11 Various methods used for the removal of pharmacological components from water bodies have been elaborated in Fig. 1. MBR is regarded as a cutting-edge sewage treatment process which has grown significantly in popularity and may be able to successfully remove such organic micro-pollutants. However, there is presently a dearth of information on the effectiveness of MBR and other systems in terms of pharmacological pollutants removal. This chapter gives a general overview of

Fig. 1 A summary of the different biological techniques involving removal of pharmaceuticals.

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how different methodologies and processes are used to remove pharmacological chemicals from the environment. The pros and cons of different processes and their effectiveness for the removal of pharmaceutical components are also highlighted.

1.1 Toxicological effects of pharmaceutical compounds present in water The improvement and provision of improved human health and a safer way of life as a result of biomedical scientific research advancements and discoveries has resulted in a high requirement for the manufacturing of pharmaceutical substances and a corresponding rise in population. These pharmacological (bioactive molecules) substances were expelled in wastewater because the body was unable to completely digest them. The outflow of treated wastewater introduces this micro-pollutant into the receiving water bodies. Because of their risk of eco-toxicity, pharmaceutical chemicals permanence across both groundwater and surface waters is becoming a serious issue. The water quality is lowered by pharmaceuticals drugs which also have a harmful influence on living things. So many studies have been done over the past 20 years on the presence, effects, and removal of pharmaceutical residues from the environment. This article gives a general overview of how biological treatment processes are used to remove pharmaceutical chemicals from the environment.12 The presence of pharmacologically active chemicals (PACs) in ecological system like lakes and rivers has gained attention over the past 10 years because they have the potential negative impacts on aquatic life as well as human health. Discharge of unprocessed or inefficiently processed sewage is thought to be a key source of PACs occurrence in environment since a large fraction of them mess up in wastewater through human excretion and careless disposing of unintended medications. Due to the requirement for efficient PACs removal, a number of advanced wastewater treatment methods, including MBR and advanced oxidation processes, have developed. Pharmacological substance carbamazepine (CBZ), which persists in traditional treatment systems and is commonly found in watercourses, has been suggested as a biomarker to evaluate effluent quality.13 Sulfonamides have lethal effect on the embryo of zebrafish. Similarly, other hazardous medical waste cause many problems including contagious diseases, mental impairments and many carcinogenic agents present in them cause serious ailments.14,15

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1.1.1 Effects on humans and agriculture Municipal drinking water, private and commercially available bottled water containing harmful contaminants are exposed to our streams and rivers, from there pharmaceutical compounds leach into our agriculture system and cause major contamination to our food chain.16,17 The extent of any contaminant causes adverse effects on the environment can be estimated in an environmental risk assessment (ERA).18,19 Both of the contact paths pose entirely altered magnitudes and entirely diverse trials concerning to their degradation. The former method is accidental, startling that may occur by means of intake of liquid and diets polluted by medicinal deposits that partook into the location as a consequence of their planned practice, i.e., through secretion or rinsing as well as upon dumping, which then gets “recycled.” The second exposure path includes equally both involuntary and resolute human exposure to waste, unemployed medications got deposit as trashes which cause eventually a high percentage of disposals. This disposal causes critical, complex exposures, largely to solo toxin bodies at a specific period, and stands for accountable noteworthy living sickness and deaths.20 Different types of drugs and their hazardous impacts and enlisted in Table 1.21 The most susceptible people are infant children, disease suffering victims or elderly population.22 Table 1 Pharmaceutical drugs and their hazardous effects. Drug type Harmful effects

Antibacterials or antimicrobials

Itchy skin hardness of throat, wheezing, coughing, clammy skin

Antidepressants

Agitation, anxiousness, feeling sickness, stomach ache and indigestion

Antihistamines

Drowsiness, dryness of mouth, vomiting, blurred vision and restlessness

Inhaled corticosteroids

Hoarse voice, mood swings, hair loss, forgetfulness, diabetes, bruising, acquiring high blood pressure

Diabetic medications

Gas, bloating, diarrhea, Vitamin B12 deficiency, and an upset stomach

Angiotensin converting enzyme (ACE) inhibitors

Erection problems, high potassium levels in blood leading to problem of heart rhythm Fluid buildup causes swelling of the skin

Proton pump inhibitors (PPIs)

Allergic reaction or food sensitivity

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1.1.2 Effects on aquatic life These compounds can result poison to living organisms existing in our atmosphere. Some evidences were provided by the Scandinavian society of cell toxicology,23 i.e., The presence of these drugs in aquatic reservoirs can change the equilibrium of living classifications inside water as certain compounds are aimed at moderating the endocrinal functions and disturb natural immunity24 thus causing severe toxicity, mutations in human behaviors and hereditary modifications in aquatic animals, cold-blooded vertebrates, arthropods and eukaryotes. One more adverse effect of a drug in a living system is that one drug may increase the susceptibility of other drugs in the body as well. Studies revealed that verelan PM (an angiotensinconverting enzyme inhibitor control level of Ca metal) possibly will upturn the vulnerability of organisms to further toxins25,26

1.2 Occurrence of pharmaceutical drugs in surface water The widespread presence of harmful drugs in ecosystems is a result of the overuse of pharmaceuticals. These products have been found in sludge, soil, detritus, groundwater, subsurface water, sandy loam, upstream running water, marine and terrestrial animals, and vegetation, according to numerous investigations. This section provides a thorough assessment of current understanding regarding the detrimental consequences of antibiotic traces in the water habitats, specifically in groundwater, aquifer, and marine waters.27 In 2005 to 2010, according to US Geological survey studies, it was concluded that drug industrialization plants are surely a major birthplace of their exposure to our surroundings. Discharge from any pharmaceutical manufacturing plant is supposed to have 10–1000 times more concentration of contaminants than discharge from wastewater treatment plants (WWTPs).28The presence of pharmaceutical compounds in the environment was demonstrated more than 30 years ago by researchers.29,30 Different means of exposure of pharmaceuticals into the environment include humanoid or Animalia flows, drain water sewage, tempered bio-solids, industrialized left-over, homeopathic left-over by healthcare and animal medications, dump degradation and other types of sludge. However, at surface of aquatic origins, pharmaceuticals frequently exist in traces. A report estimated about further 50 drugs inside 140 rivers through 31 regions in the America.31 Livestock and human beings may be exposed to drugs in unsanitary conditions. For instance, residues of enrofloxacin in drinking water may impair

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the pharmacokinetics of doxycycline, and studies have revealed that sick broiler chickens had larger concentrations of the drug deposited in their liver. There have been traces of erythromycin, macrolides, clarithromycin, ciprofloxacin, norfloxacin and other drugs found in tap water, according to a study done in Madrid, Macao, and Guangzhou in China.32

1.3 Occurrence of pharmaceutical drugs in down reservoirs Urban aquifers are frequently contaminated with antibiotics because of human activities. Although one of the excellent natural purifiers for keeping contaminated substances out of groundwater sources is soil. However, a number of factors highly affect the soil such as the composition of pollutants, their quantity, and behavior. Once polluted, subsurface water is difficult to reverse.33 Introduction of these compounds into the environment is done chiefly through wastewater seepages from municipal treatment plants31 hospital sewages6 and from livestock activities.34 In a recent review,35 the presence of numerous pharmaceuticals was testified in reservoirs from Germany, England, Italy, Canada and America. One of most repeatedly occurring compounds was clofibric acid, that is a lipid regulator.36 In further research37 carbamazepine and clofibric acid were recognized in few tests found in the Netherlands and presence of antibiotics such as sulphamethoxazole was also reported. Mostly concentrations in drinking water did not exceed more than 100 ng/L.

2. Methods for removal of pharmaceutical compounds Residual medicines (antimicrobial agents, antipsychotics, anxiolytics, and metabolic processes) have started to be regarded as developing and emerging pollutants in recent years due to their ongoing input and persistence in aquatic ecosystems even at low quantities. As a result, in recent decades, more attention has been paid to the design of comprehensive, reliable, and economical materials and procedures for the treatment of sewage. Owing to their anticipated or confirmed detrimental effects on human health and the aquatic resources, medicinal chemicals have arisen as new category of contaminants in water.38,39 The concern of environmental exposure to pharmaceuticals has been discussed by a plethora of international entities and panels, who have set rules, laws, and policies to control and restrict the presence of

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pharmaceuticals in the environmental media. For example, the European Commission (EC) now requires an environmental impact assessment of medications for use in humans and animals to support the authorization of all new medications for market approval.38 Various methods are designed to remove these drugs from the water which are discussed in this review. Because of their ongoing discharge into aquatic ecosystems and likelihood for harmful health impacts, medicinal drugs considered as emergent trace organic compounds have been under more and more scrutiny in recent years. The rising amount of information about the prevalence, fate, and consequences of these chemicals in the environment and during wastewater treatment has been greatly aided by the continual advancement of analytics. An essential part of managing and enhancing wastewater treatment approaches is tracking the ecological effects of medicines and their potential toxic effects.40

2.1 Removal of pharmaceutical compounds using enzymes Biochemical reactions can be facilitated to occur at a rapid rate by biologically made catalysts which are called enzymes and through cleaner methods these enzymes are able to serve a vital part for checking contamination.41 Today enzymes are being employed for alteration of pollutants into less destructive compounds in Lab scale reactors.41 Wastewater treatment facilities frequently fail to completely remove trace organic substances like medicines, which cause a continuous runoff into the aquatic system. Bioremediation techniques have grown significantly in significance recently as a means of resolving this problem since they may have a reduced carbon footprint than conventional chemical or physical remediation techniques. Since they may target individual molecules, enzyme-based technologies are a promising alternative in this situation. In order to comprehend the fundamental transformation mechanism and determine the applicability of various enzymes exhibiting diverse specific characteristics for bioremediation objectives, varied monitoring of enzymatic reactions is crucial for this aim.42 Degradation of various compounds which are carcinogenic in nature are feasible as a consequence of the reaction of oxidase or dehydrogenase enzymes that work extracellularly, such as diaryl propane oxygenase, Mn-dependent(NADH-oxidizing) peroxidase, reactive-black-5-hydrogen-peroxide oxidoreductase and laccase.43 Rodrı´guez-Rodrı´guez and their co workers studied the decomposition of two pharmaceutical compounds, namely, naproxen and carbamazepine

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using the enzyme laccase extracted from a fungus. They observed the growth rate and activity of Trametes versicolor on sewage sludge. Studies on the decomposition of naproxene (NAP, an analgesic) and carbamazepine (CBZ, an antiepileptic) in 25%—bioslurry cultures revealed elimination of about 47% and 57% within 24 h, respectively. In sludge solid cultures with 38% bulking material, entire degradation of NAP and roughly 48% for CBZ were accomplished in less than 72 h. Given that CBZ is so persistent in sewerage systems, its breakdown is particularly surprising. The findings suggested that T. versicolor might be a promising biocontrol agent for the removal of new contaminants in sewage sludge.44 The pharmacological drug-removal from water using different strategies with the aid of enzymes is provided in Table 2. Enzymes show some preference over synthetic catalysts with regard to the production of enantiomerically pure intermediates and other commercial purposes. This preference is due to some factors that they pose, i.e., base (on which organism will grow) being specific, functioning above gentle settings, efficiency input and causing no poisonous.60 A potential biocatalyst, laccase has a wide range of potential uses, including phytoremediation, biological treatment, bio bleaching of cellulose fibers, biomedical applications, fabric finishing, and alcohol stabilization.61Each subunit of laccase has three kinds of Cu atoms, making for the catalytic site. The type 1 atom (T1) involves the oxidation of the compound and gives the biocatalyst its color. The given electron is then internally transmitted from T1 to other copper sites, where the oxygen is reduced to water. A radical is produced by the one-electron oxidative reaction at site T1, and two water molecules are produced by the four-electron reducing at points T2 and T3. The first radical is somewhat reactive and can be converted to a quinone either spontaneously or through an additional enzyme-catalyzed process. Additionally, non-biocatalytic radical processes for polyphenol compounds, including humic acids, are also feasible and may lead to their incomplete breakdown.62 Due to its higher redox potential, lignin peroxidase (LiP) can oxidize substances that some other biocatalysts are unable to degrade. Both phenol and non-phenolic molecules can be targeted by it, which can then result in vigorous reaction, carbon-carbon dissociation, polyphenol degradation, methylation, and heterocyclic ring fission.63 The catalytic process of LiP is a well-known peroxidase reaction in which the original enzyme is oxidized by hydrogen peroxide to produce LiP-I, which has two electron deficits. The target molecule is oxidized by LiP-I, which then transforms into one electron less LiP-II. LiP-II transforms back into the original LiP

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Table 2 Different enzymes used for the removal of pharmaceutical drugs from waste water. Pharmaceutical Enzyme used for the removal Removal drug of drug efficiency References

Tylenol

Laccase

26%

45

Napropamide

Amidases

90%

46

Erythromycin

Lysates

96%

47

Atenolol

Tyrosinase

90%

48

Diazepam

Laccase

68%

48

Ketoprofen

Cytochrome P450


90%

49

Carbamazepine

Laccase

66%

50

Chlortetracycline

Laccase

58.3%

51

Bisphenol A

Laccase

100%

52

Fenofibrate

Laccase

37%

45

Mefenamic acid

Laccase

99%

53

Triclosan

Laccase

65%

52

Pentachlorophenol

Laccase extract

80%

54

Naproxen

Laccase

95%

55

Paracetamol

Horseradish peroxidase(HRP)

98%

56

Genistein

Manganese Peroxidase (MnP)

93%

57

Sulfadiazine

Laccase

100%

58

Sulfamethoxazole

p-Diphenol oxidases

53%

59

when it oxidizes a different target component. Poor molecular weight redox mediators play a significant function due to low mobility and the availability of active sites of biocatalyst for target molecules.64 2.1.1 The use of crude enzymes for the removal of pharmaceutical compounds (PC) Pollutant elimination from liquid or fluids by using extricated or crude enzymes instead of using living cultures have more advantageous. Crude enzymes are extracted from microorganisms and can approach a great response kinesis even at slight heat as well as acidity or alkalinity range.

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Furthermore, they never require the constant inclusion of nutritive or else strive through Microbes. In a 2-day operation, Naproxen was reported to be 90% being impassive taking a preliminary volume of 10 mg/L, by using crude enzymes. While the removal efficiency was found to be only 68% by performing reaction in whole-cell cultivation for the same period of time.65 Different enzymes are used for the degradation of medical drugs residue present in water. Diclofenac (DFC) and carbamazepine (CBZ) were predominantly found in water sources. Zhang and Sven studied the in vitro decomposition of these two compounds in water using the crude extract of LiP. The affecting factors, such as pH, and temperature were investigated. It was discovered that LiP totally metabolized DFC at pH 3.0–4.5, but CBZ degradation efficiency was often 99

82

Gemfibrozil

Trametes versicolor

95

78

Ibuprofen

Phanerochaete chrysosporium

75–90

82

Ketoprofen

Trametes versicolor

100

77

Metronidazole

Trametes versicolor

85

79

Numerous pharmaceutical drugs are removed from water using different species of fungi, some of examples are described in Table 3. Lucas et al. studied the importance of sorption process for the elimination of medical drugs from waste water. In batch studies, the adsorption of four Pharmaceutical compounds (carbamazepine, diclofenac, and iopromide) by six distinct fungi was first assessed. PACs quantities from the fungi treatment were assessed in both liquid and solid (biomass) samples. Between 3% and 13% of the overall amount of contaminants removed were attributable to the sorption process. In a perpetual bioreactor that treated sewage from an animal hospital over the course of 26 days, the sorption of 47 PACs in fungus was also assessed. PACs levels found in the mycelial extract were comparable to those seen in the effluent from traditional sewage treatment plants. This may imply that managing fungal biomass as trash in a similar way to how sludge from sewage treatment is treated is necessary.83

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2.3.1 Factors affecting pharmaceutical drug removal performance of fungi Toxin configuration, class to which fungi belongs, enzymatic arrangement, growth channel, acidic and basic nature of channel, heat and inflating means being the agents whose interaction or implementation influence the elimination efficacy of a white rot fungi.84 Since the process takes place in the occurrence of a freely compostable specie, thus removal of any toxin aided by white fungi occurs by the metabolic effect of some other species as well. Trametes versicolor (a WRF) was analyzed to remove up to 90% of the antibacterials ciproxin, ciloxan, cetraxal and fluoroquinolones at 2 mg/L within a week of maturation period inside liquor intermediate.85 Some valuables of white-rot fungi that mark these striking for exclusion of Pharmaceuticals are described as: (1)enzymes generated from these fungi are nonspecific which make them enable for the humiliation of a varied series of micro pollutants; (2) their hyphal development is capable of producing a steady colonization of fungi which aids WRF toward exchanging toxins; (3) manufacturing as well as enzyme excretion to damage composites that are not much soluble in water; and (4) A steady capability toward reduction of compounds inside a media that lacks nutrients over a varied range of pH mostly 3–9. The pictorial illustration of degradation of PACs is given in Fig. 2.

Fig. 2 Graphical representation of decomposition of PACs using WRF. Reprinted from Naghdi, M., et al., Removal of pharmaceutical compounds in water and wastewater using fungal oxidoreductase enzymes. Environ Pollut, 2018. 234: p. 190–213, with the permissions of Elsevier.

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2.4 Adsorption on non-conventional material In contrast to many other tertiary treatments, adsorption offers benefits including reduced energy usage and easier operating conditions, making it standing out as a potential treatment option. Despite receiving substantial research as a medicinal adsorbent, commercially available activated carbon’s large-scale applicability is constrained by its significant expense. As a result, numerous research for pharmaceuticals absorption from water and wastewater have focused on adsorbent materials built on clays, charcoal, chitin, agricultural and commercial residues, and metal-organic scaffolds. These quasi low-cost substances have also been examined in more detail for treatment of sewage.86 In order to lower the dangers involved with waste disposal, much focus has been dedicated to the useful usage of sewage sludge. In addition to being used in other ways, sludge has also been used to make biochar, which has been used to remove various contaminants from water. Several therapeutics waste chemicals from the aqueous environment have shown incredible potential to be adsorbed by sludge-based Biochar.87 The efficient and environmentally friendly bio polymers class of chitosan-based materials (hybrid) exhibits significant potential for the successful adsorption of these chemicals. The usage of functionalized Chitosan adsorbents was significant for the efficient removal of certain drugs. For example norfloxacin can adsorb on chitosan beads and effectively remove from effluent at pH range from 2 to 8.88

2.5 Hybrid technologies for removal of PC Due to their resistive character, wastewater treatment plants (WWTP) are regarded as sites for pharmacological contaminants. Whereas most residues flow through the sewage treatment plant operations, some drugs may be destroyed or eliminated via the biochemical or chemical treatment pathways. Pharmaceutical effluent remediation is investigated using a wide range of treatment techniques, such as adsorption, bioremediation, membranerelated processes, improved oxidizing mechanisms, etc. Several studies have published information on the elimination of PC from municipal sewerage systems, whereas others have concentrated on specific techniques such membrane bioreactors. Some of these hybrid techniques are illustrated in Fig. 3. Medicinal products cannot be removed from effluents by standard sewage treatment plant techniques. The WWTP uses the standard sewage treatment procedure, which includes primary treatment (activated sludge),

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Fig. 3 Different hybrid techniques for the removal of PC. Reprinted from Eniola, J.O., et al., A review on conventional and advanced hybrid technologies for pharmaceutical wastewater treatment. J Clean Prod, 2022: p. 131826, with the permission of Elsevier.

biological treatment (biodegradation), and chemical treatment (dechlorination). The chemical compositions of the medicinal components, the operating circumstances of the recovery process, and other factors all affect the removal effectiveness of PC.89

2.6 Treatment of pharmaceutical compounds through microalgae The removal of pharmaceuticals through microalgae is classified in the following levels: (1) swift sorption because of physical and chemical exchanges concerning plasma membrane and the contaminants, (2) relatively gentle path transmitting fragments through the plasma membrane, and lastly (3) probably by winding-up equally by means of bio aggregation, bio removal, or both.90 The procedure involved for degradation of PACs through algal species. Bioadsorption of a pollutant is vastly influenced by its configuration, chromophoric nature, the existence of a functional group, and microalgal species as well. 50–71% removal of tetracycline was observed using species of a green algae (Chlorella vulgaris) inside (HRAP)by way of bioadsorption pathway in a period of 44 h. The removal based on tetracycline increased with increasing in column size91 Bioaccumulation may be slower than adsorption but serve as a vigorous procedure ingesting power. Several algal species are able to store up impurities even in contradiction of volume variance concerning the protoplasm and outer situation, like(Spirogyra) was reported to accrue about 850 whiles more radioactive phosphorus (like p-32) as opposed to water.92 it was investigated that an algal specie (Nannochloropsis limmetica) was able

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to accumulate primsol (10%), TMP/SMX(12%), and tegretol XR(13.5%) underneath shadowy settings above 13 day period, whereas 27% of triclosan over a 6 day period. Cessation of drugs yielded through enzymatic catalyzation is a metabolic process called Biodegradation. Usually, unicellular algal species pivot multi-faceted parental complexes into elementary mixes. The Mechanism proceeds through quite a few hydrolytic procedures (e.g., isomerization, De-isomerization, hydration, dihydroxylation, carbonylation, decarbonylation, oxidative rusting, reductive reaction, ring splitting, demetallized reactions, then phosphorylation) Unicellular algal biodegradation of drugs, chemicals and pesticides is done through a series of enzymes in three phases.93 Primary stage is decontamination of drugs catalyzed through an enzyme CYP450 and include oxidative, reductive and acylation courses. Following stage also involves conversion of lipotropic, diamine composites into aqua phobic complexes done by fusing their aryl substituents. Second phase secures cell from oxidative damage. The electro permeabilized sets like oxirane and carboxylic group by forming a conjugation by GSH.94 Third phase involves a number of enzymes and involves biotransformation of the drug species in some elementary as well as reclaimed structures95 Photo-biodegradation includes mainly two kinds of photo dissociation responsible for decay of Pollutants inside deteriorating aqua bodies: straight and Uninterrupted and secondary type photo dissociation. In the course of directed photo dissociation, there is no involvement of microalgae, the absorbed toxin particles containing conjugated pi linkage, cyclic aromatic hydrocarbons, as well as their main moieties are able to straight captivate Ultraviolet light radiations, thus as a result get disintegrated.96 During indirect photolysis, a minor part of free or solo chlorophyll (1 Chl) in the microalgae will go through an intersection mechanism even inside the system to arrange a ternary chlorophyll molecule (3 Chl)), some active classes of oxygen (%OOH, 1 O2, Hydroxide radical, O2%,) are produced reacting with oxygen (3 O2) in unexcited form. Algal cells release carboxylic acid, which produces an alternative active oxygen type: RO (peroxy radical).92 Greater would be the generation of free radicals by a high concentration of microalgae.97 Volatilization, also known as dematerialization is a process that varies with drug or composite specificity. Though, this provides extra feasibility in an exposed lake or water reservoirs despite of closed light dependent biosensor.98

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2.7 Treatment of PC by using organic biomass Many advanced technologies and procedures have been investigated for the elimination of pharmaceutical drugs from aquatic environment, underground water, commercial and clinical wastewaters, in addition to drinking-water treatment facilities. The main drawbacks of these approaches are their high costs, their difficulty in practical implementation, and, occasionally, their requirement for the employment of additional, frequently dangerous chemical reagents, which results in less environmentally friendly operations. Physisorption remediation techniques using biomass, on the other hand, are more in accordance with environmental friendly development and environmentally benign concepts. Adsorption techniques are also thought to be efficient, adaptable, and practical from an economic standpoint. Numerous spongy polymers, including activated charcoal resin, silicone clay, carbon nanofibers, kaolin, graphite, chitosan and xanthan, have been investigated to increase the adsorption capability of medicines onto adsorbents. Due to its superior adsorption performance when compared to the others, Biochar has grabbed the most consideration among them. The exceptional physical and chemical characteristics of biomass-derived carbonaceous materials (Biochar), notably their large specific area, high porosity volume, clearly defined porous morphology, and changeable surface composition, have garnered a lot of interest.99,100 Yangshuo et al. reported the elimination of various medical drugs from water using a novel adsorbent made up of biomass. He used magnetic genipin-crosslinked chitosan/graphene oxide-SO3H (GC/MGO—SO3H) composite as an adsorbent. Batch experimentation was used to examine the adsorption capacity of different drugs. As the temperature rises from 298 to 313 K, the maximum adsorption capacity of tetracycline and ibuprofen increase from 473.25 to 556.28 mg/g and 113.27 to 138.16 mg/g.101 2.7.1 Activated sludge process (ASP) Activated sludge process (ASP) is a conventional practice. Advantage of using this technique is its partition into compartments that enable the method to be efficient as by the way of main setup container bio-solids can be again introduced to the anoxic section through the use of an aquatic vivarium pump. Ventilation and intercourse of bio-solids thus can be reached. While traditional wastewater treatment methods are effective for a wide variety of substances, numerous persistent organic contaminants

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are particularly resilient, and residues of these pollutants can still be discovered at the sewage treatment facilities’ output.98,102 Activated sludge (AS) systems are the most widely employed of the several implementing innovative techniques used in current wastewater treatment procedures. It is centered on the oxygenation and agitation of sewage, which has a very large population of microbial biomass. Some strain conglomerates can degrade traditional macro pollutants (C, N, and P), but other conglomerates may adapt to various pollutants, like compounds, enabling their decomposition.103 2.7.2 Biofilm reactors and biotic trickling filters This procedure is broadly cast-off aiming at the treatment of pharmaceuticals. Immobilization of biomass over a support material in a biological trickling filter is the main method. But primarily for the omission of biochemical oxygen demand (BOD) as well as chemical oxygen demand (COD) this method is practiced broadly at waste water treatment plants.104,105 Basile reported a review about removal of endocrine-disrupting chemicals (EDC). ASP and trickling filter method was reported to eliminate EDC from sewage under same ambient condition. For all pollutants under investigation, trickling filters had removal performance >70%, whereas the equivalent activated sludge system had higher removal rates >85%. Although such a strategy has a lot of potential, fundamental understanding is still insufficient.106 2.7.3 Two phased partitioning bioreactors Two-phase partitioning bioreactors (TPPBs) are categorized because of its bi discrete parts, in which one part is non-mixable and compatible for biotic pollutant (target substrate) therefore also known as organic phase. While the other part containing microbes is the aqueous phase.107 In an experiment styrene got almost up to 90% degraded in a test using a TPPB system worked as a bio trickling filter108

2.8 Bio ozone-bio process for treatment of PC The use of pharmaceuticals by humans has grown in recent years and is predicted to continue growing due to the expanding global population and rising average age. Due to its characteristics, such as significant fluctuations in water quality and volume, complicated composition, high

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pollutant content, and poor biodegradability, pharmaceutical wastewater (PW) has always been challenging to treat in order to meet the effluent water quality standard. If individual treatment processes like biological treatment or ozonation is carried out directly, the toxic substances in pharmaceutical wastewater may affect the biological system, thus affecting the treatment effect. Also individual process has limitations for removal of pharmaceuticals from secondary clarified effluents with a high organic matter concentration. Combining two processes will enable cost-effective removal of pharmaceutical. In order to remove increased pharmaceuticals from wastewater effluent, a biological-ozone-biological treatment procedure (BO3B) based on three steps was developed. The first biological treatment stage removes organic materials, decreasing the ozone dose necessary for the following ozone treatment of bio recalcitrant pharmaceuticals. The second biological treatment aims to remove possibly hazardous byproducts of ozonation. The examined key-parameters for adjusting process performance are the applied ozone dosage and the hydraulic retention time (HRT) of the bioreactors. The goal of this study is to see how the applied ozone dosage and HRT affect the performance of BO3B. Its efficiency is evaluated using both chemical and toxicological characteristics.109 A cost-effective BO3B to mitigate pharmaceuticals and hence the toxicity they inflict, is believed to be established from an appropriate combination of biological and ozone treatments.110,111

2.9 Pros and cons of different methodologies used for PACs removal Biotic control using appropriate microbes (bacteria, algae, fungi) is of the latest interest. Several microbes are being used. However, categorizing them under the most efficient methods bears some disapproval because of the restricted life of the enzymes. However, membrane enzymatic treatments provide advantages like membrane provides a second line of contaminant removal.112 By pilot plant–3-stage moving bed biofilm reactors (MBBRs) using bacterial consortia (biomass), Ibuprofen was removed more than 90%. 2: Through sponge-based MBBR, activated sludge, the same drug was removed up to 93.7%  3.3%. Immobilization of enzymes can cause censorious polysaccharide, sugars and proteins to be conjoined thus enzyme gets sealed in a negative symmetry, therefore, enzyme disability in the course of restriction is an actual trial in this practice.113 While there are

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disadvantages of conventional processes like they cannot achieve discharge limit, reactor blockage lengthy setup period and choice of bacterial groups and are particular as well. Bi phased partitioning bioreactors provide an extraordinary exclusion for aqua phobic composites, phenols and polycyclic aromatic hydrocarbons which are poisonous organic composites, volatile organic compounds114 and salvage of biomass confrontation to poisonous substances, i.e., 3: MBR with submerged hollow-fiber ultra-filtration membrane removal efficiency of Diclofenac was up to 80%. Moving bed biofilm reactor provides compact, uncomplicated and full-bodied design, minor vessel capacity, amplified mass maintenance period for steady-nourishing bio-organisms, chances of attaining growth of both aerobic and anaerobic bio-organisms even in the same reactor and fall of pneumatic head damage. Owing to its great effectiveness and reasonable charge, the MBBR scheme seems to be the utmost favorable cure. This specially designed bio-support material provides larger surface area for biofilm formation. Today the objective of planning these corresponding developed schemes is varied-directional, primarily, to increase the dispensability of pharmaceuticals for its enriched bio accessibility as maximum of these composites are soluble in water to a very lesser extent. In order to establish biological removal approaches these methods seem to be promising115 as MBBR was reported to remove diclofenac and naproxen with a removal efficiency of 72.8% and 82.3%, respectively.

3. Future prospective These contaminants exist in trace amounts; therefore, there are still many concerns about how they will degrade biologically. Effective decomposition of a particular medication cannot be ensured in the absence of information about bioremediation mechanisms, deterioration systems, and the ability to examine byproducts. Further study should be done on the bacterial diversity that are deteriorating, since knowing whether certain microbes are responsible for the procedure or whether different populations collaborate symbiotically to degrade drugs will help us better understand it and perhaps even maximize drug degradation throughout sewage treatment. Conventional methods for the removal of pharmaceutical compounds from water are slow and less efficient. MBR technology is now regarded as an intriguing option for improving existing sewage systems in addition to supplying isolated communities with better quality treated wastewater set ups, particularly when wastewater reclamation is taken into consideration.

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MBRs combine relatively lengthy sludge retention times with higher biomass contents, which are typically considered to be advantageous for the microbial degradation of recalcitrant chemicals, the situation with a large number medical drug contaminant found in wastewater. However, these advanced methods are complexed and costly. In order to acquire a better understanding of the decomposition potential of medicines in bioremediation of wastewater, it is clear that much more research is still needed. The majority of studies conducted on the utilization of enzymes and other methodologies for the treatment of PC to date have been very carefully managed, but there remains a significant gap between laboratory and industrial scale research, and even between academic and commercial applications. The employment of enzymes for the treatment of a complicated mixture of numerous medications in wastewater treatment is currently far from becoming applied, despite their extraordinarily promising prospects. Biocatalysts are nevertheless possible to claim that enzymes are at least appropriate for the direct treatment of well specified waste streams, such as hospital or certain industrial effluent. Improvements in the adaptability and application of enzymes under actual treatment conditions ought to be the goal of future research and innovation.

4. Conclusion Some major causes of introduction or runoff of pharmaceutical drugs into the water bodies are the remains of waste water treatment plants, aquatic waste from agricultural and veterinary activities, supping of dumping grounds and a constant and unending revelation of these toxins to human water reservoirs and our cultivation. Biological treatments seem to be environmental friendly means of their degradation by the usage of enzymes, organic molecules and plant biomasses and bacterial and fungal cultures, etc. These methods got efficient results even 90% removal of the major adverse compounds like ibuprofen, diclofenac, paracetamol and naproxen, etc. However, using some microorganisms in pure form do not give effective handling as some micro-organisms are not commonly available, being costly, restricted life of the enzymes and conversion of enzymes to negative confirmations during the immobilization process. However, using some hybrid means, i.e., the settlement of biomass on trickling reactors, moving bed biofilms reactors, membrane bioreactors and two phase portioning bioreactor provide better biodegradation. Advance biological treatments (MBBR system and two-phase partitioning bioreactor) are the best and

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promising techniques concluded due to their compact, simple strategy, enlarged mass maintenance period for steady-nourishing bio organisms, chances of attaining growth of both aerobic and anaerobic organisms even in the similar reactor and evident quantitative data from literature.

References 1. Richardson SD. Water analysis: emerging contaminants and current issues. Anal Chem 2009;81(12):4645–77. 2. White I, Howe J. POLICY AND PRACTICE: planning and the European union water framework directive. J Environ Plan Manag 2003;46(4):621–31. 3. Halling-Sørensen B, et al. Occurrence, fate and effects of pharmaceutical substances in the environment—A review. Chemosphere 1998;36(2):357–93. 4. Tijani JO, et al. Pharmaceuticals, endocrine disruptors, personal care products, nanomaterials and perfluorinated pollutants: a review. Environ Chem Lett 2016;14 (1):27–49. 5. Daughton CG. Non-regulated water contaminants: emerging research. Environ Impact Assess Rev 2004;24(7–8):711–32. 6. K€ ummerer K. Drugs in the environment: emission of drugs, diagnostic aids and disinfectants into wastewater by hospitals in relation to other sources–a review. Chemosphere 2001;45(6–7):957–69. 7. Sipma J, et al. Comparison of removal of pharmaceuticals in MBR and activated sludge systems. Desalination 2010;250(2):653–9. 8. Rivera-Utrilla J, et al. Pharmaceuticals as emerging contaminants and their removal from water. A review. Chemosphere 2013;93(7):1268–87. 9. Badia-Fabregat M, et al. Identification of some factors affecting pharmaceutical active compounds (PhACs) removal in real wastewater. Case study of fungal treatment of reverse osmosis concentrate. J Hazard Mater 2015;283:663–71. 10. Tambosi JL, et al. Removal of pharmaceutical compounds in membrane bioreactors (MBR) applying submerged membranes. Desalination 2010;261(1–2):148–56. 11. Zdarta J, et al. Free and immobilized biocatalysts for removing micropollutants from water and wastewater: recent progress and challenges. Bioresour Technol 2022;344:126201. 12. Tiwari B, et al. Review on fate and mechanism of removal of pharmaceutical pollutants from wastewater using biological approach. Bioresour Technol 2017;224:1–12. 13. Hai FI, et al. Carbamazepine as a possible anthropogenic marker in water: occurrences, toxicological effects, regulations and removal by wastewater treatment technologies. Water 2018;10(2):107. 14. Lin T, Chen Y, Chen W. Impact of toxicological properties of sulfonamides on the growth of zebrafish embryos in the water. Environ Toxicol Pharmacol 2013; 36(3):1068–76. 15. Perez-Alvarez I, et al. Determination of metals and pharmaceutical compounds released in hospital wastewater from Toluca, Mexico, and evaluation of their toxic impact. Environ Pollut 2018;240:330–41. 16. Qin Q. The fate and impact of pharmaceuticals and personal care products in agricultural soils irrigated with reclaimed water. Crit Rev Environ Sci Tech 2015; 45(13):1379–408. 17. Hammad HM, et al. Uptake and toxicological effects of pharmaceutical active compounds on maize. Agr Ecosyst Environ 2018;258:143–8.

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18. Carlsson C, et al. Are pharmaceuticals potent environmental pollutants? Part I: Environmental risk assessments of selected active pharmaceutical ingredients. Sci Total Environ 2006;364(1–3):67–87. 19. Jones O, Voulvoulis N, Lester J. Aquatic environmental assessment of the top 25 English prescription pharmaceuticals. Water Res 2002;36(20):5013–22. 20. Daughton C. Pharmaceuticals as environmental pollutants: the ramifications for human exposure. Int Encycl Public Health 2008;5:66–102. 21. https://www.nhs.uk/ & https://www.ijpbs.net. 22. Smith RG, Burtner AP. Oral side-effects of the most frequently prescribed drugs. Spec Care Dentist 1994;14(3):96–102. 23. Narvaez JF, Jimenez C. Pharmaceutical products in the environment: sources, effects and risks. Vitae 2012;19(1):93–108. 24. Epel D. Use of multidrug transporters as first lines of defense against toxins in aquatic organisms. Comp Biochem Physiol A Mol Integr Physiol 1998;120(1):23–8. 25. Wright GD. Bacterial resistance to antibiotics: enzymatic degradation and modification. Adv Drug Deliv Rev 2005;57(10):1451–70. 26. Prisant LM, Black HR, Messerli FH, Weber MA. P-71: results of a community-based trial of a chronotherapeutic verapamil formulation. Am J Hypertension 2002;15(S3):58A. 27. Bilal M, et al. Antibiotics traces in the aquatic environment: persistence and adverse environmental impact. Curr Opin Environ Sci Health 2020;13:68–74. 28. Phillips PJ, et al. Pharmaceutical formulation facilities as sources of opioids and other pharmaceuticals to wastewater treatment plant effluents. Environ Sci Technol 2010;44 (13):4910–6. 29. Kim SD, et al. Occurrence and removal of pharmaceuticals and endocrine disruptors in south Korean surface, drinking, and waste waters. Water Res 2007;41(5):1013–21. 30. Organization, W.H. Pharmaceuticals in drinking-water; 2012. 31. Kolpin DW, et al. Pharmaceuticals, hormones, and other organic wastewater contaminants in US streams, 1999–2000: A national reconnaissance. Environ Sci Technol 2002;36(6):1202–11. 32. Dafouz R, et al. Does the presence of caffeine in the marine environment represent an environmental risk? A regional and global study. Sci Total Environ 2018;615:632–42. 33. Lu T, et al. Evaluation of the taxonomic and functional variation of freshwater plankton communities induced by trace amounts of the antibiotic ciprofloxacin. Environ Int 2019;126:268–78. 34. Shore LS, Shemesh M. Naturally produced steroid hormones and their release into the environment. Pure Appl Chem 2003;75(1112):1859–71. 35. Zwiener C. Occurrence and analysis of pharmaceuticals and their transformation products in drinking water treatment. Anal Bioanal Chem 2007;387(4):1159–62. 36. Richardson SD. Environmental mass spectrometry: emerging contaminants and current issues. Anal Chem 2008;80(12):4373–402. 37. Stolker AA, et al. Liquid chromatography with triple-quadrupole or quadrupole-time of flight mass spectrometry for screening and confirmation of residues of pharmaceuticals in water. Anal Bioanal Chem 2004;378(4):955–63. 38. Khasawneh OFS, Palaniandy P. Occurrence and removal of pharmaceuticals in wastewater treatment plants. Process Saf Environ Prot 2021;150:532–56. 39. Gros M, et al. Removal of pharmaceuticals during wastewater treatment and environmental risk assessment using hazard indexes. Environ Int 2010;36(1):15–26. 40. Aus der Beek T, et al. Pharmaceuticals in the environment—global occurrences and perspectives. Environ Toxicol Chem 2016;35(4):823–35. 41. Singh Arora D, Kumar Sharma R. Ligninolytic fungal laccases and their biotechnological applications. Appl Biochem Biotechnol 2010;160(6):1760–88.

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42. Stadlmair LF, et al. Enzymes in removal of pharmaceuticals from wastewater: a critical review of challenges, applications and screening methods for their selection. Chemosphere 2018;205:649–61. 43. Garcı´a-Gala´n MJ, et al. Biodegradation of sulfamethazine by Trametes versicolor: removal from sewage sludge and identification of intermediate products by UPLC–QqTOF-MS. Sci Total Environ 2011;409(24):5505–12. 44. Rodrı´guez-Rodrı´guez CE, Marco-Urrea E, Caminal G. Degradation of naproxen and carbamazepine in spiked sludge by slurry and solid-phase Trametes versicolor systems. Bioresour Technol 2010;101(7):2259–66. 45. Arca-Ramos A, et al. Recyclable cross-linked laccase aggregates coupled to magnetic silica microbeads for elimination of pharmaceuticals from municipal wastewater. Environ Sci Pollut Res 2016;23(9):8929–39. 46. Helbling DE, et al. Structure-based interpretation of biotransformation pathways of amide-containing compounds in sludge-seeded bioreactors. Environ Sci Technol 2010;44(17):6628–35. 47. Krah D, et al. Micropollutant degradation via extracted native enzymes from activated sludge. Water Res 2016;95:348–60. 48. Kumar VV, Cabana H. Towards high potential magnetic biocatalysts for on-demand elimination of pharmaceuticals. Bioresour Technol 2016;200:81–9. 49. Arca-Ramos A, et al. Assessing the use of nanoimmobilized laccases to remove micropollutants from wastewater. Environ Sci Pollut Res 2016;23(4):3217–28. 50. Naghdi M, et al. Immobilized laccase on oxygen functionalized nanobiochars through mineral acids treatment for removal of carbamazepine. Sci Total Environ 2017;584:393–401. 51. Taheran M, et al. Degradation of chlortetracycline using immobilized laccase on Polyacrylonitrile-biochar composite nanofibrous membrane. Sci Total Environ 2017;605:315–21. 52. Xu R, et al. Triclosan removal by laccase immobilized on mesoporous nanofibers: strong adsorption and efficient degradation. Chem Eng J 2014;255:63–70. 53. Kosjek T, et al. Fate of carbamazepine during water treatment. Environ Sci Technol 2009;43(16):6256–61. 54. Tamagawa Y, et al. Removal of estrogenic activity of 4-tert-octylphenol by ligninolytic enzymes from white rot fungi. Environ Toxicol 2007;22(3):281–6. 55. Marco-Urrea E, et al. Biodegradation of the analgesic naproxen by Trametes versicolor and identification of intermediates using HPLC-DAD-MS and NMR. Bioresour Technol 2010;101(7):2159–66. 56. Xu R, et al. Enzymatic removal of paracetamol from aqueous phase: horseradish peroxidase immobilized on nanofibrous membranes. Environ Sci Pollut Res 2015;22 (5):3838–46. 57. Tamagawa Y, et al. Removal of estrogenic activity of endocrine-disrupting genistein by ligninolytic enzymes from white rot fungi. FEMS Microbiol Lett 2005;244(1):93–8. 58. Sathishkumar P, et al. Laccase mediated diclofenac transformation and cytotoxicity assessment on mouse fibroblast 3T3-L1 preadipocytes. RSC Adv 2014;4(23):11689–97. 59. Rahmani K, et al. Elimination and detoxification of sulfathiazole and sulfamethoxazole assisted by laccase immobilized on porous silica beads. Int Biodeter Biodegr 2015;97:107–14. 60. Chatterjee A, et al. The role of the mammalian DNA end-processing enzyme polynucleotide kinase 30 -phosphatase in spinocerebellar ataxia type 3 pathogenesis. PLoS Genet 2015;11(1):e1004749. 61. Fernandez-Fernandez M, Sanroma´n MA´, Moldes D. Recent developments and applications of immobilized laccase. Biotechnol Adv 2013;31(8):1808–25.

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62. Strong P, Claus H. Laccase: a review of its past and its future in bioremediation. Crit Rev Environ Sci Technol 2011;41(4):373–434. 63. Naghdi M, et al. Removal of pharmaceutical compounds in water and wastewater using fungal oxidoreductase enzymes. Environ Pollut 2018;234:190–213. 64. Gold MH, Wariishi H, Valli K. Extracellular peroxidases involved in lignin degradation by the white rot basidiomycete Phanerochaete chrysosporium. ACS Publications; 1989. 65. Li X, et al. Removal of carbamazepine and naproxen by immobilized Phanerochaete chrysosporium under non-sterile condition. N Biotechnol 2015;32(2):282–9. 66. Zhang Y, Geißen S-U. In vitro degradation of carbamazepine and diclofenac by crude lignin peroxidase. J Hazard Mater 2010;176(1–3):1089–92. 67. Tatsumi K, Wada S, Ichikawa H. Removal of chlorophenols from wastewater by immobilized horseradish peroxidase. Biotechnol Bioeng 1996;51(1):126–30. 68. Meiczinger M, et al. Stability improvement of laccase for micropollutant removal of pharmaceutical origins from municipal wastewater. Clean Technol Environ Policy 2022;1–11. 69. Guardado ALP, et al. A novel process for the covalent immobilization of laccases on silica gel and its application for the elimination of pharmaceutical micropollutants. Environ Sci Pollut Res 2021;28(20):25579–93. 70. Zdarta J, et al. Removal of tetracycline in enzymatic membrane reactor: enzymatic conversion as the predominant mechanism over adsorption and membrane rejection. J Environ Chem Eng 2022;10(1):106973. 71. Zdarta J, et al. Multi-faceted strategy based on enzyme immobilization with reactant adsorption and membrane technology for biocatalytic removal of pollutants: a critical review. Biotechnol Adv 2019;37(7):107401. 72. Rios G, et al. Progress in enzymatic membrane reactors–a review. J Membr Sci 2004;242 (1–2):189–96. 73. Meng F, et al. Recent advances in membrane bioreactors (MBRs): membrane fouling and membrane material. Water Res 2009;43(6):1489–512. 74. Shao S, Wu X. Microbial degradation of tetracycline in the aquatic environment: a review. Crit Rev Biotechnol 2020;40(7):1010–8. 75. Guo D, et al. Silicate-enhanced heterogeneous flow-through electro-Fenton system using iron oxides under nanoconfinement. Environ Sci Technol 2021;55 (6):4045–53. 76. Hata T, et al. Elimination of carbamazepine by repeated treatment with laccase in the presence of 1-hydroxybenzotriazole. J Hazard Mater 2010;181(1–3):1175–8. 77. Cruz-Morato´ C, et al. Degradation of pharmaceuticals in non-sterile urban wastewater by Trametes versicolor in a fluidized bed bioreactor. Water Res 2013;47(14):5200–10. 78. Nguyen LN, et al. Removal of trace organic contaminants by an MBR comprising a mixed culture of bacteria and white-rot fungi. Bioresour Technol 2013;148:234–41. 79. Cruz-Morato´ C, et al. Hospital wastewater treatment by fungal bioreactor: removal efficiency for pharmaceuticals and endocrine disruptor compounds. Sci Total Environ 2014;493:365–76. 80. Rodarte-Morales A, et al. Operation of stirred tank reactors (STRs) and fixed-bed reactors (FBRs) with free and immobilized Phanerochaete chrysosporium for the continuous removal of pharmaceutical compounds. Biochem Eng J 2012;66:38–45. 81. Lucas D, Barcelo´ D, Rodriguez-Mozaz S. Removal of pharmaceuticals from wastewater by fungal treatment and reduction of hazard quotients. Sci Total Environ 2016;571:909–15. 82. Rodarte-Morales A, et al. Biotransformation of three pharmaceutical active compounds by the fungus Phanerochaete chrysosporium in a fed batch stirred reactor under air and oxygen supply. Biodegradation 2012;23(1):145–56.

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83. Lucas D, et al. The role of sorption processes in the removal of pharmaceuticals by fungal treatment of wastewater. Sci Total Environ 2018;610:1147–53. 84. Rodarte-Morales A, et al. Degradation of selected pharmaceutical and personal care products (PPCPs) by white-rot fungi. World J Microbiol Biotechnol 2011;27(8):1839–46. 85. Prieto A, et al. Degradation of the antibiotics norfloxacin and ciprofloxacin by a white-rot fungus and identification of degradation products. Bioresour Technol 2011;102(23):10987–95. 86. de Andrade JR, et al. Adsorption of pharmaceuticals from water and wastewater using nonconventional low-cost materials: a review. Ind Eng Chem Res 2018;57(9):3103–27. 87. Ihsanullah I, et al. Removal of pharmaceuticals from water using sewage sludge-derived biochar: a review. Chemosphere 2022;289:133196. 88. Karimi-Maleh H, et al. Recent advances in using of chitosan-based adsorbents for removal of pharmaceutical contaminants: a review. J Clean Prod 2021;291:125880. 89. Eniola JO, et al. A review on conventional and advanced hybrid technologies for pharmaceutical wastewater treatment. J Clean Prod 2022; 131826. 90. Yu Y, et al. Investigation of the removal mechanism of antibiotic ceftazidime by green algae and subsequent microbic impact assessment. Sci Rep 2017;7(1):1–11. 91. de Godos I, Mun˜oz R, Guieysse B. Tetracycline removal during wastewater treatment in high-rate algal ponds. J Hazard Mater 2012;229:446–9. 92. Azma M, et al. Improved protocol for the preparation of axenic culture and adaptation to heterotrophic cultivation. Open Biotechnol J 2010;4(1). 93. Peng F-Q, et al. Biotransformation of progesterone and norgestrel by two freshwater microalgae (Scenedesmus obliquus and Chlorella pyrenoidosa): transformation kinetics and products identification. Chemosphere 2014;95:581–8. 94. Nakajima N, et al. Glycosylation of bisphenol A by freshwater microalgae. Chemosphere 2007;69(6):934–41. 95. Petroutsos D, et al. Detoxification of 2, 4-dichlorophenol by the marine microalga Tetraselmis marina. Phytochemistry 2008;69(3):707–14. 96. Challis JK, et al. A critical assessment of the photodegradation of pharmaceuticals in aquatic environments: defining our current understanding and identifying knowledge gaps. Environ Sci: Processes Impacts 2014;16(4):672–96. 97. Liu X, Wu F, Deng N. Photoproduction of hydroxyl radicals in aqueous solution with algae under high-pressure mercury lamp. Environ Sci Technol 2004;38(1):296–9. 98. Suarez S, Lema JM, Omil F. Removal of pharmaceutical and personal care products (PPCPs) under nitrifying and denitrifying conditions. Water Res 2010;44(10):3214–24. 99. Xiang Y, et al. Carbon-based materials as adsorbent for antibiotics removal: mechanisms and influencing factors. J Environ Manage 2019;237:128–38. 100. Lessa EF, Nunes ML, Fajardo AR. Chitosan/waste coffee-grounds composite: an efficient and eco-friendly adsorbent for removal of pharmaceutical contaminants from water. Carbohydr Polym 2018;189:257–66. 101. Liu Y, Liu R, Li M, Yu F, He C. Removal of pharmaceuticals by novel magnetic genipin-crosslinked chitosan/graphene oxide-SO3H composite. Carbohydr Polym 2019;220:141–8. 102. Eckenfelder WW, Cleary JG. Activated Sludge Technologies for Treating Industrial Wastewaters. DEStech Publications, Inc; 2013. 103. De Cazes M, et al. Membrane bioprocesses for pharmaceutical micropollutant removal from waters. Membranes 2014;4(4):692–729. 104. Naz I, et al. Assessment of biological trickling filter systems with various packing materials for improved wastewater treatment. Environ Technol 2015;36(4):424–34. 105. Kasprzyk-Hordern B, Dinsdale RM, Guwy AJ. The removal of pharmaceuticals, personal care products, endocrine disruptors and illicit drugs during wastewater treatment and its impact on the quality of receiving waters. Water Res 2009;43(2):363–80.

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CHAPTER FOUR

Biological methods for the removal of microplastics from water Mahnoor Amjada, Azeem Intisara,*, Adeel Afzala, and Nazim Hussainb a

School of Chemistry, University of the Punjab, Lahore, Pakistan Centre for Applied Molecular Biology, University of the Punjab, Lahore, Pakistan *Corresponding author: e-mail address: [email protected] b

Contents 1. 2. 3. 4.

Introduction Types of microplastics Sources of microplastics in water Biological solutions for the removal of microplastics from water 4.1 By algae 4.2 By fungi 4.3 By bacteria 4.4 By enzymes 4.5 By using biopolymers 4.6 By marine organisms 5. Microplastic ingestion 6. Control measures for microplastic pollution 7. Microplastic pollution and COVID-19 8. Conclusion References

66 66 67 68 68 69 69 70 70 71 72 75 75 75 76

Abstract Excessive use of plastic without its proper disposal in recent years has made plasticpollution a seriously growing global concern. Low disintegration rates of microplastics make their removal inevitable. Particularly in water, it needs immediate considerations and measures due to its adverse effects on humans and marine biota. This chapter encompasses an overview of various biological methods for removing microplastics from water. These methods include biodegradation of microplastic contaminants by algae, fungi, bacteria, enzymes, zooplankton, sea clams, corals and marine microorganisms like archaeans and eukaryotes. Moreover, bio-polymers like lignin, cellulose, chitin and starch are also used for their elimination by the formation of larger flocs which are later removed. Among all, adsorption by sea weed microalgae, Fucus vesiculosus, the modified starch biopolymers, ingestion by marine organisms like Red Sea giant clams and marine fungus, Zalerion maritimum were found to be highly effective for Advances in Chemical Pollution, Environmental Management and Protection, Volume 9 Copyright # 2023 Elsevier Inc. ISSN 2468-9289 All rights reserved. https://doi.org/10.1016/bs.apmp.2022.10.003

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plastic degradation. Thus, apart from chemical methods, novel biological approaches need to be adopted to lessen these lethal environmental effects of plastic pollution. Keywords: Microplastic pollution, Water, Algae, Fungi, Bacteria, Marine organisms, Biopolymers, Enzymes

1. Introduction The invention of plastic revolutionized the course of the world, however, due to improper discarding of the plastic products with their over use, the harms caused by plastic to mother nature as well as to mankind have reached an alarming level. The plastic wastes dumped into the oceans had reached over a total of 13 million tons by 2018. Besides, they are expected to rise exponentially to about 250 million tons by 2025.1 Water is inevitable for human survival, thus, microplastics pollution in drinking water can cause potent harms to humans.2 Microplastic pollution, particularly in the water, needs serious considerations and frequent measures as statistics indicate varying concentration in drinking water ranging from a few to up to 1000 particles per liter in various regions.2 There has been a steady accumulation of microplastics in aquatic ecosystems. Studies show almost 0–3146 microplastic particles per kg were found in the dry weight of sediments. It calls for quick remediation and techniques for their removal for a less-polluted and clean environment.3 The properties of plastics such as flexibility, durability, low cost, easy handling (due to being lightweight) and corrosion resistance make them widely acceptable compounds. Plastic is a non-conductor of heat and electricity. Therefore, it has immense importance in industrial and commercial usage.4

2. Types of microplastics On the basis of their sizes, plastic wastes can be divided into four groups: Microplastics are plastic particles which are less than 5 mm in size.5 Microplastics are grouped into primary micro and secondary microplastics depending upon their origin.6 Primary MPs are primarily synthetic polymers. They come from packaging and manufacturing of various items. These micro-sized plastics are also formed as exfoliates of different processes. A further grouping of primary plastics is microbeads. They constitute polystyrene, polyethylene and polypropylene beads and are vastly utilized in cosmetic and personal care products.7 The secondary MPs are created by fragmentation of

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larger plastic debris owing to different environmental, chemical or mechanical processes. Thus wind, light and water exposure can cause photo-degradation, thermal degradation and hydrolysis eventually converting these microplastic contaminants into secondary MPS.8 The plastic debris is classified into three more groups as nano-plastics (smaller than 1 μm), meso-plastics (5–20 mm) and macro-plastics (larger than 20 mm).9

3. Sources of microplastics in water Microplastic pollutants enter the water through various pathways. They can pollute the water due to erosion of different plastic products.10 When waste water having microplastic debris is discharged into surface water, these particles accumulate in aquatic environments.11,12 Besides, decay of plastic wastes present in the environment can also lead to microplastic deposition in water.13 Another prime source of majority of microplastics are the wastewater treatment plants.14,15 Most of these treatment plants are made near water bodies thus they constitute a major source of microplastic accumulation. Over 1873 treatment plants in China are located near aquatic environments in coastal areas where their effluents are released.16 In waste water treatment units, bigger plastic debris are removed while smaller microplastic particles are passed from these plants and are moved and deposited to aquatic ecosystems.17 Various biological methods for the removal of microplastics from waste water are provided in Fig. 1. Biological methods for the removal of microplastics from waste water

Removal by bacteria

By Bacillus gottheilii and Bacillus cereus strains

Removal by fungi

By Zalerion maritimum fungus

Microplastic ingestion

By Zoplankton, Scleractinian corals, Red Sea Giant clam Tridacna maxima

Adsorption on algae

By Fucus vesiculosus and Pseudokirchne riella subcapitata

Removal by biopolymers

By cellulose, lignin, chitin and starch

Removal by marine organisms

By Souda consortium, Agios consortium and Euphausia superba

Bio-filtration

By passing effluents of WWTPs through 4 zoned pilotscale biofilter

Fig. 1 Various biological methods for the removal of microplastics from waste water.

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4. Biological solutions for the removal of microplastics from water 4.1 By algae Microplastics accumulation in marine environments is much more alarming compared to other pollutants. The reason is toxic and long-lasting effects of bioaccumulation of microplastics on aquatic life including reptiles, fishes and marine mammals.18 Waterborne microplastics have high capabilities to adsorb on algal surfaces.19 The adherence characteristics of these pollutants on seaweed microalgae, i.e., Fucus vesiculosus was reported by Sundbæk et al.20 These fluorescent polystyrene microplastics showed large sorption rates of about 94.5%. The sorbent algal cells had thin micro-channels in order to stop the movement of these plastic particles inside algal tissues while these contaminants had approximately 20 μm diameter. High sorption rates were observed mostly around the cut surfaces of these edible microalgae as alginate substances are released from the algal cell walls present in the cut surfaces which in turn increased the sorption and adherence of these particles on the micro algae. Alignate is released due to the gelatinous nature of the anionic polysaccharides present in this sea weed. The surface charge of microplastics and chemical nature of algae play a key role in determining their adsorption by algae.21,22 Nano plastics (nano polystyrene) and microplastics were observed to decrease algae growth and chlorophyll a production that eventually contributed to lower the photosynthesis rates, especially by green microalgae— Scenedesmus obliquus. This reduced algal growth was exhibited by plastic concentrations in the range of 0.22–103 mg polystyrene per liter.23 It is explained by decrease of carbon dioxide levels possibly due to absorption of plastics by different algal species (Scenedesmus and Chlorella) besides adverse effects on chlorophyll-a concentrations by nano plastics. These plastic particles blocked air and light that affected algal photosynthesis.21 This adsorption highly impacted biodiversity by making drastic changes in sedimentary systems.24 Analysis of Pseudokirchneriella subcapitata (a unicellular algae) indicated adsorption of polystyrene particles on it. These particles were 20–500 nm in size. Microplastics sorption on algae was greatly affected by charge on particle’s surface as positively-charged polystyrene particles were observed to be firmly adsorbed on algae compared to the negative ones. The reason lies in

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the chemical structure of algae as it is composed of anionic polysaccharides which adsorb positively charged microplastic contaminants much more effectively.22

4.2 By fungi Zalerion maritimum, a marine fungus, was reported to exhibit very effective biodegradation of microplastics, particularly polyethylene micro particles.25 It was examined in a reactor where these pollutant concentrations were measured at different time spans. On exposure of these plastic particles with this fungus for 14 days, polyethylene exhibited removal efficiency of over 43% (with weight variation of 56.7%  2.9%). Based on size and mass changes, the removal reaction rates of polyethylene plastics differed.26 But this Z. maritimum fungus was found to consume microplastic debris as a source of its nutrients. It was concluded by examination of the biological compounds like protein decrease with the passage of time.27 The optical and electron microscopy analysis showed that the biological contents were found on the microplastic surfaces, which exhibits the capabilities of the fungi to deteriorate the microplastic contaminants. Rapid increase in intensity of new bands, after their interaction with fungi, were determined by FTIR analysis at 3700–3000 cm 1 and 1700–1500 cm 1. These regions represent hydro peroxide with hydroxyl groups. Hence, this analysis confirms the polyethylene particle’s oxidative removal.25 Similar changes were reported in another study involving photocatalytic degradation of polyethylene microplastic wastes from the wastewater. These low-density particles were removed under the action of visible light. Removal of these polyethylene particles was observed after their exposure with visible light for 175 h.28

4.3 By bacteria Two bacterial strains, i.e., Bacillus gottheilii and Bacillus cereus were used to observe their removal potential of various microplastic particles, i.e., polystyrene, polyethylene and polyethylene terephthalate. Both these Bacillus strains were taken from mangrove surface sediments. Microplastic mass loss was measured to examine and compare their degradation rates which showed that lowest disintegration of half-life, i.e., 363 days along with the swiftest mass loss, i.e., 0.0019 per day were observed when polystyrene microplastics were removed by using Bacillus cereus. While B. gottheilii showed a bit less efficiency with polyethylene particles with half-life of

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431.2 days and mass loss of 0.0016 per day. B. gottheilii exhibited removal potential of 3%, 5.8% and 6.2% (for PET, PS and PE removal respectively). FTIR analysis and electron microscopy techniques were used to examine the biodegradation results showing morphological changes including cleavage of bonds, and structural variations.29 Many analytical techniques including Raman spectroscopy, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy were used for assessing the degradation of various microplastics through which many holes and cracks were seen. Removal of polystyrene and nylon 6 (PA6) microplastics was reported with their respective weight losses of about 22% and 25.6%.30

4.4 By enzymes Bacterium Idonella sakaiensis was found to be involved in polyethylene terephthalate hydrolysis. This bacterium produces enzymes, i.e., lipases, cutinases and esterases. On reaction of these enzymes with the microplastic polymer resin, i.e., polyethylene terephthalate (PET), these microplastics were converted into less harmful monomers, i.e., ethylene-glycol and terephthalic acid. Thus the enzymes lipases, cutinases and esterases found in Idonella sakaiensis bacterial strains are responsible for PET hydrolysis—along with the hydrolysis of this reaction intermediate [mono(2-hydroxyethyl) terephthalic acid]—when these bacterial strains are grown on PET.31 Utter biodegradation of the PET film was observed after a span of 6 weeks at temperature of about 30°C. Barth et al. reported that enzymes can be associated with membrane bioreactor technique (which is used in commercial waste water treatment plants). Thus enzymatic membrane reactors can be used for microplastic degradation especially for PET removal.32

4.5 By using biopolymers Lesser biological methods for microplastics treatment have been reported till now, primarily due to poor charge density alongside lesser water solubility of such biological systems.33 These characteristics lead to lower efficiency of these bio-based solutions. In order to overcome this problem, various bio-based flocculants can be used to interact with microplastic debris. It results in the formation of larger flocs which are then removed. Thus biopolymers like cellulose and lignin can be used after insertion of charged groups in them. It is done to enhance their water solubilities which in turn leads to stronger interactions with the microplastics. Glycidyl trimethyl-ammonium chloride (GTMAC) was used

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for cationization of biopolymer, i.e., lignin for 1 h at 70 °C (with GTMAC/ lignin molar ratio of 2:1). This method proved quite effective as it enhanced the charge density of the cationic lignin to approximately 1.10 mEq per gram.34 A study reported use of chitin as a bio-based flocculant which showed quite promising results.35 Cationic charges were introduced in polysaccharide chitin (by using 3-chloro-2-hydroxypropyl trimethylammonium chloride). The new polymer thus generated was then observed to exhibit potential to be used in water treatment as a flocculant.36 Starch was used to form cationized flocculating agents to be used in water treatment. The cationic parts of some molecules like glycidyl tetradecyl, dodecyl and octyl dimethylammonium chloride [(GTDAC), (GDDAC) and (GODAC)] were introduced in polysaccharide polymer starch. Flocculating abilities of these modified polymers were observed in supernatant liquid samples. Flocculation (in terms of transmittance) of the GTDAC modified starch polymer came out to be about 93.9% more compared to the other two bio polymers. While for GDDAC, the transmittance of liquid samples by using microwave irradiation technique was reported to be about 92%.36,37 The formation of cationic starch derivatives is shown in Fig. 2. This technique can be used as a future bio-based solution for water treatment as the cationic starch derivatives showed significant results, even better than commercial flocculants. This study suggested the key role of hydrophobicity of flocculating agents in contaminants removal.37

4.6 By marine organisms The abilities of different marine microorganisms (i.e., archaeans, eukaryotes and some bacterial strains) to biologically disintegrate the synthetic microplastic pollutants found in aquatic environments and coastal sediments were discussed by Harrison et al.38 Thus the strong relationship between marine organisms and microplastics was found.

Fig. 2 Formation of cationic starch derivatives. Reprinted from Wei Y, Cheng F, Zheng H. Synthesis and flocculating properties of cationic starch derivatives. Carbohydr Polym 2008;74(3):673–679, with the permission of Elsevier.

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Polyethylene particles are of immense importance as approximately 80% of microplastics are polyethylene. They are subjected to weathering in marine ecosystems.39 Hence their disintegration by marine microorganisms needs to be adopted. Marine organisms are reported to show encouraging results for polyethylene removal, with 7.5% mass reduction of low-density polyethylene particles (LDPE).40 A study on Souda consortium and Agios consortium exhibited their removal capabilities of polyethylene microplastics (secondary MPs) out of which Souda consortium marine community showed promising results with higher removal potential, i.e., 18% compared to Agios community that exhibited 8% removal efficiency—of the initial polyethylene weight, after 2 months.41 Analysis of their masses was done again after 1 month and their weight loss suggested that these polyethylene particles were a carbon source for these marine organisms. It led to the attachment of these microbes to these plastic particles which eventually resulted in their degradation.27

5. Microplastic ingestion A study suggested that polystyrene micro-pollutant particles imparted significant negative impacts on zooplankton’s health and activities.42 It was observed that attachment of microplastic debris to zooplankton’s upper shell affected its feeding habits, which in turn influenced its growth.43 The above study suggested a biological removal way to lessen the hazardous environmental effects of plastic pollution. Thus zooplankton showed high effectiveness in removal of 1.7–30 μm polystyrene micro particles. It happens through ingestion and capture in its body. Zooplankton’s intestine can hold these particles for over 7 days. Tridacna maxima, also referred as the Red Sea giant clam, was also reported to exhibit plastic removal abilities from water. This Sea clam can capture about 53–500 μm of polyethylene microplastic contaminants.44 The clam’s shells are significantly involved in the plastic uptake. About 66.03% of polyethylene microplastics were observed to be removed from the wastewater which were sorbed on the shell’s surfaces. Thus this marine clam can be used for microplastics biodegradation in the waste water containing lesser plastics amounts.45 The body size of clam, initial concentration of microplastics and their retention inside clam bodies highly influenced the removal efficiency of plastic debris. Thus larger clams can hold and adsorb larger concentrations of MPs in them compared to the smaller clams and they tend to remain inside the digestive tracts of various clams where they are ingested.

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Scleractinian corals also showed ingestion and uptake of micro-sized plastic wastes mainly polypropylene particles. These particles remained in the mesenterial tissues inside their guts for a time span of almost 24 h. Scleractinian corals exhibited an ingestion rate of approximately 50 μg plastic cm 2 per hour as water treatment plants release their discharges in the seas. These effluents have large concentrations of microplastic pollutants that can be ingested by coral reefs present in the marine ecosystem.46 Briefly, marine biota including a few bacteria, zooplankton, corals, marine fungi and algae can be used for biological degradation of microplastics— present in in aquatic ecosystems—in low concentrations. Microplastics can sometimes also act as a source of nutrients for a few organisms, thus, these microplastic ingestion techniques can work for lesser amounts of plastic debris to lessen the hazardous environmental impacts of microplastic pollution. A comparison of various biological solutions for the removal of microplastics is provided in Table 1. Table 1 Comparison of various techniques for microplastics removal. Techniques Materials and quantities used Removal efficiencies

References

Adsorption on Polystyrene particles (having 94.5% algae 20 μm diameter) were adsorbed on seaweed microalgae, i.e., Fucus vesiculosus

20

Removal by fungi

Polyethylene particles were 43% removed by marine fungus Zalerion maritimum (with weight variations of 56.7%  2.9%) after their exposure for 14 days

25

Bio-filtration

The effluents of waste water treatment plants (containing 24.8 μg/m3 concentration) were passed through 4-zoned biofilter

89% removal potential 47 in terms of microplastic initial mass concentration

Removal by marine organisms

Polyethylene particles were exposed to Souda consortium and Agios consortium for 2 months span

18% removal potential 41 of polyethylene particles exhibited by Souda consortium and 8% by Agios consortium Continued

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Table 1 Comparison of various techniques for microplastics removal.—cont’d Techniques Materials and quantities used Removal efficiencies References

Removal by biopolymers

GTDAC and GDDAC modified starch polymers were used on supernatant wastewater samples to form cationized flocculating agents

37 93.9% removal efficiency of GTDAC and 92% for GDDAC modified starch polymer

Ingestion

Polyethylene microplastics About 66.03% (having size ranges in removal capability between 53 and 500 μm) were ingested by 24 Red Sea giant clams (Tridacna maxima)

44

Removal by bacteria

Bacillus gottheilii strains taken from mangrove surface sediments were reacted to polystyrene, polyethylene and polyethylene terephthalate particles

5.8%, 6.2% and 3% efficiency for PS, PE and PET removal using Bacillus gottheilii

29

Removal by enzymes

PET film was exposed to bacterium Idonella sakaiensis for 6 weeks

Lipases, cutinases and esterases enzymes hydrolyzed PET and converted them into less harmful monomers, i.e., ethylene-glycol and terephthalic acid at 30 °C

31

Activated sludge

47.4 n/L influent 16.6% removal concentration of efficiency microplastics from water treated through activated sludge, with 34 n/L effluents concentration

Biodegradation Polystyrene microplastics 7% removal potential from sludge water were in lab and 43.7% on treated for 56 days at 70 °C in site lab and for 45 days on site, using hyper-thermophilic composting technique

48

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6. Control measures for microplastic pollution A study showed over 4.8–12 million metric tons of plastic wastes were found in the oceans and these plastic debris are expected to rise to an alarming level in the coming years.1 A loss of 13 billion$/year was calculated for the entire marine ecosystem due to the plastic pollution. Therefore, an immediate formulation of rules against its usage is necessary, else all organisms would exceedingly suffer due to the contaminated environment in the coming years.8 Strict rules and policies are recently being made in various countries to overcome this plastic usage like action and fine on its use and strict ban on plastic bottles and bags. Besides, research on the high threats of plastics should be increased too.

7. Microplastic pollution and COVID-19 Since the outbreak of the lethal pandemic COVID-19, plasticcontaining PPEs (personal protection equipment) have largely been used worldwide in order to combat the virus, especially after the World Health Organization reported it as a fatal global pandemic in March 2020.50 Thus excessive use of protective masks as precautionary measures against the virus has led to a gradual increase in plastic wastes.51 Almost 11 g of polypropylene along with other plastic derivatives are found in a single N95 mask. Thus long-lasting effects of COVID-19 as PPE pollution are gradually becoming a great threat to mother nature as the PPE litter will remain in the surrounding atmosphere for years and years without proper disposal, leading to their degradation into microplastics depending upon various factors as exposure to UV rays, pH and temperature change.52 N95 and surgical masks are composed of polyester, polyethylene and polypropylene like polymers along with an inner layer made of fibers.53 In the pandemic, the excessive use of PPEs will aggravate the plastic pollution in the rivers and seas in near future.54 Eventually, this water pollution can pose serious threats to marine life.

8. Conclusion Chemical methods have significant potential for removing microplastic contaminants and are thus widely used in waste water treatment plants, however, biological methods are environment-friendly and don’t

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involve the use of chemicals. Sea weed microalgae, Fucus vesiculosus is experimentally proven to be quite efficient for adsorption of polystyrene particles. The modified starch biopolymer showed highly significant results as a flocculating agent for microplastics removal in the water treatment. Similarly, Red Sea giant clam and marine fungus, Zalerion maritimum also showed great potential for biodegradation of polyethylene microplastics. With the rapid increase in plastic pollution globally, there is a dire need for further studies on the effectiveness and limitations of bio-based solutions so that new biological techniques can be adopted for waste water treatment on commercial scale.

References 1. Jambeck JR, Geyer R, Wilcox C, Siegler TR, Perryman M, Andrady A, et al. Plastic waste inputs from land into the ocean. Science 2015;347(6223):768–71. 2. Pivokonsky M, Cermakova L, Novotna K, Peer P, Cajthaml T, Janda V. Occurrence of microplastics in raw and treated drinking water. Sci Total Environ 2018;643:1644–51. 3. Maes T, Van der Meulen MD, Devriese LI, Leslie HA, Huvet A, Fre`re L, et al. Microplastics baseline surveys at the water surface and in sediments of the North-East Atlantic. Front Mar Sci 2017;4:135. 4. Thompson RC, Moore CJ, Vom Saal FS, Swan SH. Plastics, the environment and human health: current consensus and future trends. Philos Trans R Soc B 2009;364:2153–66. 5. Sighicelli M, Pietrelli L, Lecce F, Iannilli V, Falconieri M, Coscia L, et al. Microplastic pollution in the surface waters of Italian Subalpine Lakes. Environ Pollut 2018;236: 645–51. 6. Avio CG, Gorbi S, Regoli F. Plastics and microplastics in the oceans: from emerging pollutants to emerged threat. Mar Environ Res 2017;128:2–11. 7. Coppock RL, Cole M, Lindeque PK, Queiro´s AM, Galloway TS. A small-scale, portable method for extracting microplastics from marine sediments. Environ Pollut 2017;230:829–37. 8. Chatterjee S, Sharma S. Microplastics in our oceans and marine health. Field Actions Sci Rep J Field Actions 2019;Special Issue 19:54–61. 9. Napper IE, Thompson RC. Plastic debris in the marine environment: history and future challenges. Global Chall 2020;4(6):1900081. 10. Duis K, Coors A. Microplastics in the aquatic and terrestrial environment: sources (with a specific focus on personal care products), fate and effects. Environ Sci Eur 2016;28(1):1–25. 11. Chang M. Reducing microplastics from facial exfoliating cleansers in wastewater through treatment versus consumer product decisions. Mar Pollut Bull 2015;101 (1):330–3. 12. Hartline NL, Bruce NJ, Karba SN, Ruff EO, Sonar SU, Holden PA. Microfiber masses recovered from conventional machine washing of new or aged garments. Environ Sci Technol 2016;50(21):11532–8. 13. Lambert S, Scherer C, Wagner M. Ecotoxicity testing of microplastics: considering the heterogeneity of physicochemical properties. Integr Environ Assess Manag 2017;13 (3):470–5. 14. Browne MA, Crump P, Niven SJ, Teuten E, Tonkin A, Galloway T, et al. Accumulation of microplastic on shorelines woldwide: sources and sinks. Environ Sci Technol 2011;45(21):9175–9.

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15. Long Z, Pan Z, Wang W, Ren J, Yu X, Lin L, et al. Microplastic abundance, characteristics, and removal in wastewater treatment plants in a coastal city of China. Water Res 2019;155:255–65. 16. Jin L, Zhang G, Tian H. Current state of sewage treatment in China. Water Res 2014;66:85–98. 17. Murphy E, King EA. Smartphone-based noise mapping: Integrating sound level meter app data into the strategic noise mapping process. Sci Total Environ 2016;562:852–9. 18. Cole M, Lindeque P, Halsband C, Galloway TS. Microplastics as contaminants in the marine environment: a review. Mar Pollut Bull 2011;62(12):2588–97. 19. Rios LM, Moore C, Jones PR. Persistent organic pollutants carried by synthetic polymers in the ocean environment. Mar Pollut Bull 2007;54(8):1230–7. 20. Sundbæk KB, Koch IDW, Villaro CG, Rasmussen NS, Holdt SL, Hartmann NB. Sorption of fluorescent polystyrene microplastic particles to edible seaweed Fucus vesiculosus. J Appl Phycol 2018;30(5):2923–7. 21. Bhattacharya P, Lin S, Turner JP, Ke PC. Physical adsorption of charged plastic nanoparticles affects algal photosynthesis. J Phys Chem C 2010;114(39):16556–61. 22. Nolte TM, Hartmann NB, Kleijn JM, Garnæs J, Van De Meent D, Hendriks AJ, et al. The toxicity of plastic nanoparticles to green algae as influenced by surface modification, medium hardness and cellular adsorption. Aquat Toxicol 2017;183:11–20. 23. Besseling E, Wang B, L€ urling M, Koelmans AA. Nanoplastic affects growth of S. obliquus and reproduction of D. magna. Environ Sci Technol 2014;48(20):12336–43. 24. Green DS, Boots B, O’Connor NE, Thompson R. Microplastics affect the ecological functioning of an important biogenic habitat. Environ Sci Technol 2017;51(1):68–77. 25. Pac¸o A, Duarte K, da Costa JP, Santos PS, Pereira R, Pereira M, et al. Biodegradation of polyethylene microplastics by the marine fungus Zalerion maritimum. Sci Total Environ 2017;586:10–5. 26. Boudart M, Djega-Mariadassou G. Kinetics of heterogeneous catalytic reactions. Princeton University Press; 2014. 27. Sivan A. New perspectives in plastic biodegradation. Curr Opin Biotechnol 2011;22 (3):422–6. 28. Tofa TS, Kunjali KL, Paul S, Dutta J. Visible light photocatalytic degradation of microplastic residues with zinc oxide nanorods. Environ Chem Lett 2019;17(3):1341–6. 29. Auta H, Emenike C, Fauziah S. Screening of Bacillus strains isolated from mangrove ecosystems in Peninsular Malaysia for microplastic degradation. Environ Pollut 2017;231:1552–9. 30. Liu B, Jiang Q, Qiu Z, Liu L, Wei R, Zhang X, et al. Process analysis of microplastic degradation using activated PMS and Fenton reagents. Chemosphere 2022;298:134220. 31. Yoshida S, Hiraga K, Takehana T, Taniguchi I, Yamaji H, Maeda Y, et al. A bacterium that degrades and assimilates poly (ethylene terephthalate). Science 2016;351 (6278):1196–9. 32. Barth M, Wei R, Oeser T, Then J, Schmidt J, Wohlgemuth F, et al. Enzymatic hydrolysis of polyethylene terephthalate films in an ultrafiltration membrane reactor. J Membr Sci 2015;494:182–7. 33. Laszlo J. Solubility and dye-binding properties of quaternized and peroxidasepolymerized kraft lignin. Environ Technol 1999;20(6):607–15. 34. Kong F, Parhiala K, Wang S, Fatehi P. Preparation of cationic softwood kraft lignin and its application in dye removal. Eur Polym J 2015;67:335–45. 35. Salehizadeh H, Yan N, Farnood R. Recent advances in polysaccharide bio-based flocculants. Biotechnol Adv 2018;36(1):92–119. 36. Chen Q, Wu Y, Pu Y, Zheng Z, Shi C, Huang X. Synthesis and characterization of quaternized β-chitin. Carbohydr Res 2010;345(11):1609–12.

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37. Wei Y, Cheng F, Zheng H. Synthesis and flocculating properties of cationic starch derivatives. Carbohydr Polym 2008;74(3):673–9. 38. Harrison JP, Sapp M, Schratzberger M, Osborn AM. Interactions between microorganisms and marine microplastics: a call for research. Mar Technol Soc J 2011;45(2):12–20. 39. Corcoran PL, Biesinger MC, Grifi M. Plastics and beaches: a degrading relationship. Mar Pollut Bull 2009;58(1):80–4. 40. Restrepo-Flo´rez J-M, Bassi A, Thompson MR. Microbial degradation and deterioration of polyethylene–a review. Int Biodeterior Biodegradation 2014;88:83–90. 41. Tsiota P, Karkanorachaki K, Syranidou E, Franchini M, Kalogerakis N. Microbial degradation of HDPE secondary microplastics: preliminary results. In: Paper presented at the Proceedings of the international conference on microplastic pollution in the Mediterranean Sea; 2018. 42. Cole M, Lindeque PK, Fileman E, Clark J, Lewis C, Halsband C, et al. Microplastics alter the properties and sinking rates of zooplankton faecal pellets. Environ Sci Technol 2016;50 (6):3239–46. 43. Collignon A, Hecq J-H, Galgani F, Collard F, Goffart A. Annual variation in neustonic micro-and meso-plastic particles and zooplankton in the Bay of Calvi (Mediterranean– Corsica). Mar Pollut Bull 2014;79(1–2):293–8. 44. Arossa S, Martin C, Rossbach S, Duarte CM. Microplastic removal by Red Sea giant clam (Tridacna maxima). Environ Pollut 2019;252:1257–66. 45. Martı´ E, Martin C, Co´zar A, Duarte CM. Low abundance of plastic fragments in the surface waters of the Red Sea. Front Mar Sci 2017;4:333. 46. Hall N, Berry K, Rintoul L, Hoogenboom M. Microplastic ingestion by scleractinian corals. Mar Biol 2015;162(3):725–32. 47. Liu F, Nord NB, Bester K, Vollertsen J. Microplastics removal from treated wastewater by a biofilter. Water 2020;12(4):1085. 48. Liu M, Lu S, Song Y, Lei L, Hu J, Lv W, et al. Microplastic and mesoplastic pollution in farmland soils in suburbs of Shanghai, China. Environ Pollut 2018;242:855–62. 49. Chen Z, Zhao W, Xing R, Xie S, Yang X, Cui P, et al. Enhanced in situ biodegradation of microplastics in sewage sludge using hyperthermophilic composting technology. J Hazard Mater 2020;384:121271. 50. Shah SGS, Farrow A. A commentary on “World Health Organization declares global emergency: a review of the 2019 novel Coronavirus (COVID-19)”. Int J Surg 2020;76:128. 51. Adyel TM. Accumulation of plastic waste during COVID-19. Science 2020;369 (6509):1314–5. 52. Abbasi SA, Khalil AB, Arslan M. Extensive use of face masks during COVID-19 pandemic:(micro-) plastic pollution and potential health concerns in the Arabian Peninsula. Saudi J Biol Sci 2020;27(12):3181–6. 53. Aragaw TA. Surgical face masks as a potential source for microplastic pollution in the COVID-19 scenario. Mar Pollut Bull 2020;159:111517. 54. De-la-Torre GE, Aragaw TA. What we need to know about PPE associated with the COVID-19 pandemic in the marine environment. Mar Pollut Bull 2021;163:111879.

CHAPTER FIVE

Impact of wastewater irrigation on soil attributes Vipin Kumar Singha,*, Rishikesh Singhb, and Ajay Kumarc a

Department of Botany, K. S. Saket P. G. College, Ayodhya, Uttar Pradesh, India Department of Botany, Panjab University, Chandigarh, India Department of Botany, Banaras Hindu University, Varanasi, India ⁎ Corresponding author: e-mail address: [email protected] b c

Contents 1. Introduction 2. Sources of wastewater 2.1 Domestic sources 2.2 Industrial sources 3. Impact of wastewater irrigation on soil characteristics 3.1 Effect on physico-chemical characteristics 3.2 Effect on biological characteristics 4. Conclusion and recommendations References

80 81 81 82 85 85 87 88 90

Abstract Changing climatic conditions, continuously increasing human population, and industrialization have led to rising demand of water for different purposes including domestic and industrial ones. The water used in different processes ultimately becomes unfit for direct human consumption purposes. However, large amount of wastewater generated can be utilized for irrigation in agricultural activities to accomplish the need of fresh water. Irrigation with wastewater has considerable potential to improve the crop productivity in an order to achieve the goal of global food security. Although, the presence of useful micronutrients and macronutrients in wastewater may enhance the soil productivity, nevertheless, the availability of hazardous metals, pathogenic microbes, and the genes conferring resistance to antibiotics and pesticides may put the agroecosystem at environmental risk by modulating microbial community characteristics and food chain contamination. Furthermore, continuous irrigation with wastewater may result in substantial changes in soil physical, chemical, and biological characteristics. Such environmental risks can be minimized to a greater extent by employing suitable wastewater treatment techniques. The present chapter deals with different sources of wastewater generation, physico-chemical characteristics, and finally the impact of wastewater on different soil characteristics.

Advances in Chemical Pollution, Environmental Management and Protection, Volume 9 Copyright # 2023 Elsevier Inc. ISSN 2468-9289 All rights reserved. https://doi.org/10.1016/bs.apmp.2022.10.004

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Keywords: Agroecosystem, Bioaccumulation, Metal contamination, Nutrient cycling, Soil microbes

1. Introduction Freshwater resources around the globe are not equally distributed. The demand for freshwater is far high than the current availability of water in very large population of the world.1 Restricted availability of freshwater is supposed to substantially compromise the human life activities and development prospects.2 As per literature report, around 60% of the global population is expected to experience the physical unavailability of freshwater by the year 2025.3,4 Out of nearly 70% freshwater employed for irrigation, agriculture sector consumes the biggest proportion. However, some of the countries utilize greater than 95% of the generated water.5 Strikingly, the competition for share of freshwater in municipal, industrial, and agriculture activities is already high in water stressed region of the globe causing the production of large amount of wastewater. The continuous depletion of freshwater resources, therefore, calls for the application of alternative water sources including wastewater generated from different paths in agriculture, particularly in developing countries.6,7 For instance, large numbers of small scale farmers belonging to water stressed area are relied on wastewater for crop irrigation.8,9 Large amount of wastewater generated globally is either produced by domestic or industrial activities. Domestic wastewater, generally enriched with carbon, nitrogen, and phosphorus, is originated from different appliances including wash basins, washing machines, kitchen sinks, shower, and bath, apart from human originated excretory products.10,11 For convenience, the domestic wastewater can be divided into black water and gray water types depending upon source and level of contamination.12 The organic material and nutrient content is relatively high in black water as compared to gray water.13 Considerably huge amount of industrial wastewater is generated after utilization in diverse industries for intended purposes. Generally, the industrial wastewater is categorized in two major types, i.e., inorganic and organic. Inorganic industrial wastewater is originated mainly from metallic and non metallic operations, whereas industrial wastewater of organic type is released during chemical synthesizing processes requiring organic counterparts. Important wastewater sources of industrial

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origin comprise of fertilizer, pharmaceuticals, slaughterhouses, mining, petrochemical, paper and pulp, leather, and textile based industries.14–19 The inadequacy and uneven distribution of fresh water has directed the application of wastewater derived from different sources for agricultural irrigation. Crop irrigation with wastewater to fulfill the rising water shortage is reported by different researchers.20–22 However, irrigation with wastewater holds multiple advantages and challenges due to possible modulation in soil natural characteristics. The investigations of Libutti et al.23 have showed higher concentration of soil chemicals after irrigation with wastewater in comparison to freshwater irrigation, suggesting proper treatment prior to field application. A study on the impact of irrigation with treated wastewater presented insignificant effect on soil characteristics, except increased electrical conductivity and sodium absorption ratio.24 Thus, the irrigation with treated wastewater may impose negative influences not only on the physico-chemical attributes but also on biological characteristics of soil.21 Further, different kinds of inorganic and organic contaminant may be introduced in soil even after irrigation with treated wastewater.25,26 On the other hand, advantageous impact of treated wastewater irrigation on soil and plant characteristics is also described.27,28 The contrasting effect of wastewater irrigation on soil and plant attributes, therefore, suggests the application of suitable treatment technology along with the introduction of state of art analytical technology to eliminate the negative consequences, if any. The present chapter is an attempt to shed light on different sources of wastewater, characteristic feature, and influences on soil characteristics.

2. Sources of wastewater 2.1 Domestic sources Because of continuously rising human population, considerably increased quantity of domestic wastewater is released, especially in developed cities.29 Residential settings are considered to release around 75% of domestic wastewater, whereas remaining is generated from official settlements, public workplaces, and commercial places.30 Domestic wastewater falling in the category of gray water and black water is released during washing activity from sources like hand wash basins, kitchen, body washing, washing machines, and toilets. Gray water accounts for 50–80% of domestic wastewater and contains nitrogen, phosphorus, potassium, and organic matter ranging from 9 to 14%, 20–32%, 18–22%, and 29–62%, respectively.31–33

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Typically, gray water possesses reduced amount of suspended solids and have lowered turbidity, suggesting the presence of dissolved contaminants to a greater extent. The quantity of gray water is nearly one to sevenfolds higher in comparison to black water.34 The quality of gray water generated from different sources differs with reference to geography, characteristics of human population, and distribution pattern.35

2.2 Industrial sources Industrial development is regarded as backbone to global economy. Industries are important contributors to excessive generation of wastewater after use of freshwater for different processes. Industries account for approximately 28% of wastewater out of 80% of global wastewater production.36 As per an estimate of United Nations, the need of water for industries would raise upto 19% of worldwide water requirement in the year 2020.37 A number of industries including pharmaceuticals, textile, mining, sugar, and leather are well documented for enormous production of wastewater. The composition of industrial wastewater from different sources varies significantly according to the nature of substrate utilized. 2.2.1 Fertilizer industry Fertilizer industries are known to contribute a massive volume of wastewater with diverse chemical characteristics. The wastewater effluents possess varying concentrations of alcoholic contaminants, nitrogenous substances like ammonia and nitrate, acids, salts, phosphorus, and hazardous heavy metals including copper, zinc, aluminum posing undesirable threat to natural environment.38–40 Chemical characterization of effluents from various sources by authors presented chemical oxygen demand (COD) ranging from 50 to 1.4  105 mg/L and NH3-N between 6.0 and 1700 mg/L. Moreover, varying levels of inorganic contaminants like fluoride, sulfate, sodium, potassium, calcium, and magnesium have also been reported in fertilizer industry wastewater. 2.2.2 Pharmaceutical industry Pharmaceutical industries directed toward the synthesis of useful drugs for the management of health disorders are known to use excessive volumes of freshwater, eventually releasing wastewater. Pharmaceutical industries are estimated to consume nearly 22% of the entire industrial freshwater utilization. Pharmaceutical wastewater may contain varying concentration of antibiotics, hormones, anti-inflammatory drugs of steroidal and nonsteroidal nature, beta blockers, antidepressants, and antihistamines.41–45

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2.2.3 Animal slaughterhouses On a global scale, nearly 30% of total freshwater is utilized in industries concerned with meat processing.46,47 Interestingly, 62 Mm3 of water is consumed annually in meat processing industries.48 The worldwide production of meat based on beef, poultry, and pork industries has raised twofolds in preceding 10 years and is estimated to rise continuously by 2050. Therefore, expanding meat production is supposed to increase the production of wastewater from slaughterhouses49 flourishing exceedingly in countries oriented toward meat as major diet. The wastewater originated from slaughterhouses differs substantially with respect to COD, BOD, phosphorus, total nitrogen content, organic carbon, and solids.50–52 2.2.4 Textile industry Global annual production of dyes is estimated as 7  107 and 104 tons of synthesized dyes are consumed by textile industries.53 Textile industries employ various types of chemically synthesized dyes and release heavy amount of colored wastewater containing different kinds of contaminants with persistent nature,54,55 because of substantially reduced binding of colors to fabrics. The colored wastewater negatively influences photosynthetic activity and human health.56 Further, the reduced penetration of light to lower water depth and compromised availability of oxygen affects the vital processes of aquatic flora and fauna. The problem may be exacerbated multifolds due to presence of certain heavy metals and chlorine used as the ingredients of synthetic dyes.57 2.2.5 Petrochemical industries Petrochemical industries are ranked top among exceedingly rising sector essential for raising the economic output.58 The presence of six oil and petroleum based industries among 10 large industries, signifies the global importance. Petrochemical industry wastewater enriched with multifarious organic material is reported to have high chemical oxygen demand (COD) and biological oxygen demand (BOD), therefore exert hazardous effects on environment and human health.59–61 The COD of petrochemical wastewater may reach as high as 11,500 mg/L. The organic components of petrochemical wastewater like toluene and xylene are of slow degradation nature and can influence the environmental complexes for longer durations.62 Further, the wastewater from petroleum industries contains increased concentrations of phenols, benzene, solubilized minerals, volatile organic compounds, and polycyclic aromatic hydrocarbons.63–65

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2.2.6 Mining industries Mining processes including ore smelting generate wastewater containing increased concentrations of different heavy metals including cadmium, zinc, lead, arsenic, and copper.66–70 Coal mining areas are another source of wastewater, differing in composition according to geographical locations, mineral characteristics, and hydrological attributes.71 Generally, mine wastewater is of acidic nature enriched with varied concentrations of heavy metals.72 Discharge of large volumes of mine wastewater disturbs the ecological balance responsible for environmental degradation. 2.2.7 Paper and pulp industry As the need of paper based products has risen with the time, establishment of newer industries are expected. Paper and pulp industry is recognized as one of the most water and energy demanding sector around the globe. Paper and pulp industry consumes high volumes of water leading to generation of wastewater in larger quantities. In this context, developing countries are considered to generate comparatively higher volumes of wastewater because of lessened reuse of wastewater and inefficient wastewater treatment technology. In general, one ton of paper production requires 5–100 m3 of water and varies according to nature of substrate, quantity of paper formed, and potential of water reusability.73 Paper and pulp industry is identified as one of the sixth largest contributor to environmental pollution. The toxic effluents of complex chemical nature generated from paper and pulp based industry contain various inorganic and organic contaminants exerting unwanted effect on environment and human health.74 Wastewater generated during bleaching process is registered to have high COD and suspended solids contributed by plant fibrous substances. The volume of wastewater produced after bleaching, generally contains chemical residues and constitutes approximately 25–35% of total wastewater effluent.75 The paper and pulp industry wastewater include persistent chemical contaminants such as furan, resin, tannins, chlorophenols, and organic halogens.76,77 2.2.8 Leather industry Leather industry has important role in generating revenue, particularly in India.78 The leather purification process consumes enormous quantity of water leading to generation of wastewater effluents reaching to 150 tons per day. In general, the processing of one ton of raw skin material generates 20,000–80,000 L of wastewater with undesirable odor and suspended

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materials.79 Leather industry wastewater is characterized to have increased COD, BOD, reduced form of chromium, NaCl, calcium, magnesium, sulfide compounds, and other hazardous contaminants including oils, tannins, and biocides, posing detrimental effects on environment and humans.80–82 2.2.9 Sugar industry Wastewater produced from sugar industry has greater potential to contaminate the environment. In India, an estimated 1000 L of wastewater is produced after industrial crushing of one ton sugar cane. Moreover, the production of one ton sugar is accompanied with the generation of 70 cubic meters wastewater enriched with organic substances.83 The characteristic type of organic constituents and nature of sugar industry wastewater largely depend on the operating conditions and utilized raw substrates. The COD and BOD values of wastewater reaching as high as 4850 and 1950 mg/L, respectively is registered.84 Additionally, the wastewater had high load of suspended solids, dissolved solids, and organic carbon. As the direct discharge of untreated sugarcane wastewater exerts negative effect on both terrestrial and aquatic environment,85 proper treatment before final discharge is suggested.

3. Impact of wastewater irrigation on soil characteristics Wastewater has important opportunities not only in fulfilling the shortage of huge amount of water required in agricultural irrigation, but also in supplementing necessary nutrients. The introduction of wastewater as source of water for soil irrigation is widely reported and is much commonly practiced in developing countries because of high wastewater treatment cost.86,87 Therefore, wastewater irrigation may be considered as an effective strategy to reduce soil degradation and vital nutrient depletion after continuous cropping.25 Wastewater released from different sources ultimately reaches to aquatic and terrestrial ecosystems causing ill effects. The presence of various soluble and insoluble substances, heavy metals, pesticides, pharmaceuticals, dyes, and volatile substances in wastewater are expected to modulate the soil physical, chemical, and biological characteristics after irrigation.88–90 The studies on effect of wastewater on different soil physico-chemical attributes are described in following sections.

3.1 Effect on physico-chemical characteristics Investigation of Angin et al.25 has reported rise in salinity and reduction in soil pH after wastewater irrigation. In addition, there was substantial rise in

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organic matter, nitrogen content, positively charged ions, and heavy metal content of selected soil samples. The raised concentration of soil’s heavy metals content suggested the treatment of wastewater before application for irrigation. Undesirable effects of treated fish processing wastewater on electrical conductivity and sodium adsorption ratio (SAR) are presented by Vallejos et al.87 Rise in SAR value was observed after soil irrigation with wastewater causing transformation of non-saline soil to saline ones. The increased salinization in due course may alter soil structure and influence permeability, thereby inducing detrimental effects on organic matter synthesis by green plants.91 Although, there was insignificant change in total soil carbon, significant reduction in organic carbon content was registered after wastewater irrigation. The irrigation was also noticed to induce reduction in carbon/nitrogen value of soil microcosm. Impact of urine and coffee processing wastewater (1:2 ratio) irrigation on soil properties is demonstrated by Alemayehu et al.92 Considerable increase in soil organic carbon (SOC) and available phosphorus was observed after wastewater irrigation. Further, the irrigation led to significant enhancement in soil salinity. The soil analysis showed changes in pH and total nitrogen by 0.16 and 0.07 units, respectively. However, no significant differences were recorded in micronutrient and cation exchange characteristics, except few cations. Supplementation of brewing wastewater on soil attributes including % sand, % silt, % clay, bulk density, organic matter, pH, cations, and SAR is presented by Gorfie et al.93 Wastewater irrigation reduced the bulk density of soil rendered by addition of organic matter. Organic matter and organic carbon was found to be highest in soil irrigated with wastewater in comparison to control. Significant rise in sodium, potassium, calcium, magnesium, chloride, nitrate nitrogen, and phosphorus content of soil was also registered after wastewater irrigation. Research has documented increment in soil organic matter, nitrogen, phosphorus, and potassium ranging from 34.9–64.9%, 40.7–57.2%, 67.6–390.0%, and 35.4–240.9%, respectively upon irrigation with swine wastewater at 0–20cm depth.94 Similarly, rise in soil salinity posing negative effect on soil characteristics was also described. Wastewater irrigation caused the accumulation of heavy metals including chromium, copper, zinc, lead, and cadmium ranging from 0.75% to 222.6%. Furthermore, long duration (5 years) supplementation of wastewater introduced the greater amount of tetracycline group of antibiotics in comparison to those soil irrigated for 3 years. The occurrence of heavy metals and antibiotics at depth greater than 100 cm implied downward migration and plausible contamination of

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groundwater. Experimental investigations conducted by Aman et al.95 suggested the enhancement in cation exchange potential, electrical conductivity, and SAR after irrigation with industrial wastewater.

3.2 Effect on biological characteristics The presence of myriads of inorganic and organic contaminants in wastewater originated from different locations after introduction in soil has the potential to modulate the soil biological attributes. Changes in microbial activity and community structure may directly or indirectly influence and govern the cycling of nutrients important for optimum biological functioning of soil. The increase in soil microbial biomass and enzymes such as beta glucosidase and alkaline phosphatase following introduction of treated municipal wastewater has been marked by Adrover et al.96 The modification in soil biological activity was mainly ascribed to addition of organic matter. Appraisal of the impact of treated wastewater irrigation on rhizospheric microbial community is recently documented.97 Changes in microbial community structure were the resultant of modification in soil moisture and organic material content brought about by wastewater irrigation. Soil irrigation with wastewater imposed negative effect on abundance of actinobacteria members belonging to orders solirubrobacterales and gaiellales was probably linked with decline in microfauna population. Two folds rise in soil microbial biomass subsequent to field irrigation with tannery wastewater is endorsed by Alvarez-Bernal et al.98 Nevertheless, organic carbon content and the enzymatic activities of proteases and hydrolases were found to be uninfluenced by wastewater irrigation. Analysis of the impact of wastewater irrigation on biological attributes suggested significant enhancement in basal respiration of soil,28 rendered by increment in microbiological activity. In comparison to control, the enhancement was observed to fall in the range of 95–130% for different soil samples irrigated with treated wastewater. Congruent report on considerable rise in microbial processes after irrigation with treated wastewater is recently presented.99 Application of reclaimed wastewater for irrigation was noticed to restrict the alteration in mycobiota characteristics of soil. The improved soil microbiological activities were supported by the introduction of organic matter, essential nutrients, and diverse microbes present in treated wastewater used for irrigation purposes. Furthermore, improved plant productivity and rhizodeposition directed by wastewater irrigation was also important factor responsible for raised microbial community activity.

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Contrasting effects of irrigation with wastewater on microbial activity is presented by different researchers. Some of the investigations have indicated the reduction in biomass and activity of soil bacteria upon amendment of reclaimed wastewater.100,101 On the other hand, augmentation in microbial activity102 apart from insignificant impacts of wastewater irrigation on microbial quantity has also been demonstrated.103,104 The impact of treated wastewater irrigation on soil microbial characteristics is not consistent. The experimental investigation conducted by Xu et al.105 has documented reductions in number of soil actinomycetes, fungi, nitrite oxidizing bacteria, nitrate bacteria, and those bacteria performing denitrification in contrast to rise in number of ammonia oxidizing bacteria and cellulose degrading bacteria as determined by most probable number after 20 years of irrigation with reclaimed wastewater. The contrasting effects of wastewater on soil biological features mainly result from considerable variation in chemical characteristics, suggesting the introduction of raw/treated wastewater to compatible agricultural sites in order to avoid soil degradation.

4. Conclusion and recommendations Wastewater emanating from different industries may be considered as an important alternative to continuously depleting freshwater resources under the influence of rising human population, industrialization, and climate change. The reclaimed wastewater has immense potential to be employed in agricultural irrigation. The presence of varied inorganic and organic materials in wastewater holds the possibility to modify the soil characteristics. Short term and long term irrigation are described to exert varying effects on soil attributes. The irrigation with wastewater directly and after treatment possesses the ability to modify the physico-chemical features like pH, bulk density, electrical conductivity, field capacity, sodium adsorption ratio, ion exchange capacity, organic matter content, and macro/micronutrient composition. The continuous irrigation has the risks of adding unwanted contaminants like heavy metals, dyes, oils, persistent organic pollutants, and pharmaceuticals to a level responsible for soil degradation and eventually reduced soil productivity. Moreover, continued irrigation may contaminate the groundwater resources with hazardous contaminants. The presence of sufficient organic and inorganic nutrients in wastewater is suggested to modulate the microbial community after introduction in soil. Alteration in microbial community characteristics induced by substantial changes in soil characteristics, therefore would affect the microbially assisted

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nutrient cycling. Investigations have shown both advantageous and negative contrasting effects on soil properties depending on the composition of wastewater. However, in the context of depleting soil nutrients and freshwater reserves, wastewater irrigation has multiple opportunities in managing soil and crop productivity. Based on literature review, following recommendations can be made. Ø A single kind of wastewater may not be suitable for all types of soil for irrigation purposes and vice versa. Ø Wastewater should be introduced in soils after pretreatment. The level of contaminants of either organic or inorganic nature should be within the recommended limits. Ø The impact of wastewater irrigation on soil properties should be monitored regularly in order to alleviate the hazardous impacts of contaminants. Ø The transfer of noxious contaminants like heavy metals and antibiotics from soil to growing plants should be examined to prevent food chain contamination. Ø The wastewater either treated or diluted should be preferred more for non-food plants such as ornamental plants rather than food crops. Ø Study on long term effect of wastewater treatment on soil microbiological parameters is recommended for maintaining microbial activity, and nutrient cycling. Ø Effect of wastewater irrigation on soil fauna is very less studied. Study of wastewater irrigation on key annelids and arthropods is necessary for conserving soil productivity. Ø The contaminants of wastewater like heavy metals and antibiotics may be accumulated in soil higher than the recommended limits and may be transferred to food chain at an unacceptable level. Ø The long term effect of wastewater irrigation on soil salinization and sodicity is warranted to conserve the natural soil productivity. Ø High throughput analytical techniques should be developed to detect even the trace level of traditional as well as emerging contaminants in order to minimize the detrimental effects on human health and environment. Ø Less expensive techniques for extracting the contaminants present in wastewater needs to be developed. Ø Fate and transport of wastewater contaminants need extensive investigation to protect the soil from degradation. Ø The assessment of transport of wastewater contaminants to lower soil depth and groundwater are inevitably required to restrict the contamination of soil and groundwater resources.

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97. Kargol AK, Cao C, James CA, Gough HL. Wastewater reuse for tree irrigation: influence on rhizosphere microbial communities. Resour Environ Sustain 2022;9:100063. 98. Alvarez-Bernal D, Contreras-Ramos SM, Trujillo-Tapia N, Olalde-Portugal V, Frı´asHerna´ndez JT, Dendooven L. Effects of tanneries wastewater on chemical and biological soil characteristics. Appl Soil Ecol 2006;33(3):269–77. 99. Guedes P, Martins C, Couto N, Silva J, Mateus EP, Ribeiro AB, et al. Irrigation of soil with reclaimed wastewater acts as a buffer of microbial taxonomic and functional biodiversity. Sci Total Environ 2022;802:149671. 100. Bastida F, Torres IF, Romero-Trigueros C, Baldrian P, Veˇtrovsky´ T, Bayona JM, et al. Combined effects of reduced irrigation and water quality on the soil microbial community of a citrus orchard under semi-arid conditions. Soil Biol Biochem 2017;104:226–37. 101. Kayikcioglu HH. Short-term effects of irrigation with treated domestic wastewater on microbiological activity of a Vertic xerofluvent soil under Mediterranean conditions. J Environ Manage 2012;102:108–14. 102. Bastida F, Torres IF, Abadı´a J, Romero-Trigueros C, Ruiz-Navarro A, Alarco´n JJ, et al. Comparing the impacts of drip irrigation by freshwater and reclaimed wastewater on the soil microbial community of two citrus species. Agric Water Manag 2018;203:53–62. 103. Ibekwe AM, Gonzalez-Rubio A, Suarez DL. Impact of treated wastewater for irrigation on soil microbial communities. Sci Total Environ 2018;622:1603–10. 104. Li B, Cao Y, Guan X, Li Y, Hao Z, Hu W, et al. Microbial assessments of soil with a 40-year history of reclaimed wastewater irrigation. Sci Total Environ 2019;651:696–705. 105. Xu DL, Zhang CY, Qu SM, Ma X, Gao MX. Characterization of microorganisms in the soils with sewage irrigations. Afr J Microbiol Res 2012;6(44):7168–75.

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CHAPTER SIX

Microalgae and advanced oxidative processes as treatment approaches for agro-industrial effluents Clara Dourado Fenandesa, Gabriela Pereira Barrosa, Ram Naresh Bharagavab, Ajay Kumarc, Sikandar I. Mullad, Lucas Carvalho Basilio Azevedoe, and Luiz Fernando Romanholo Ferreiraa,* a

Waste and Effluent Treatment Laboratory, Institute of Technology and Research (ITP), Tiradentes University (UNIT), Aracaju, Sergipe, Brazil b Laboratory of Bioremediation and Metagenomics Research (LBMR), Department of Environmental Microbiology (DEM), Babasaheb Bhimrao Ambedkar University (A Central University), Lucknow, UP, India c Department of Botany, Banaras Hindu University, Varanasi, India d Department of Biochemistry, School of Allied Health Sciences, REVA University, Bangalore, India e Instituto de Ci^encias Agra´rias, Universidade Federal de Uberl^andia, Uberl^andia, MG, Brazil *Corresponding author: e-mail address: [email protected]

Contents 1. Introduction 2. Factors that influence the quality of agro-industrial wastewater 3. Microalgae in the treatment of agro-industrial wastewater 4. Advanced oxidative processes 5. Conclusion References

98 100 101 102 104 105

Abstract With population growth and the expansion of environmental regulations on the permanence of water quality, questions are being asked about the challenges faced by wastewater treatment plants from agro-industrial effluents. The generation of industrial effluents is a matter of global concern, as the containment and release of pollutants pose a risk to the health of ecosystems. The main factor that influences the development of processes for the treatment of wastewater is the origin of the effluent, since the composition and concentration of waste will determine the appropriate treatment. The agro-industrial effluents from dairy products, legumes or sugar-energy, have high organic loads that influence the rates of COD, BOD, in addition to being wastewater with a high concentration of suspended solids, nutrients (phosphorus and nitrogen) Advances in Chemical Pollution, Environmental Management and Protection, Volume 9 Copyright # 2023 Elsevier Inc. ISSN 2468-9289 All rights reserved. https://doi.org/10.1016/bs.apmp.2022.10.005

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and pesticide residues, which fit them as unsuitable for direct disposal into the receiving water body. These pollutants require careful processes to avoid overloading water bodies. To remove or reduce these pollutants from wastewater, several strategies have been proposed, including physical-chemical and biotechnological ones that aim to reduce the concentration of these pollutants through environmental legislation. When analyzing that the main factor that influences the efficiency of the treatment processes is the origin of the effluent, strategies were highlighted as promising for the technological advance that contributes to the improvement of the performance in the treatments and the quality of removal of several pollutants. Keywords: Microalgae, Advanced oxidative processes, Effluents, Pollutants

1. Introduction The biggest challenge today is the supply of drinking water, due to the scarcity faced by climate change.1 Thus, improper disposal of wastewater from industrial processes is a practice that goes against water protection and ecosystem health, causing an emerging concern that must be addressed by the scientific community. In parallel with this scenario, the intensification of agro-industrial activities seeks to accompany population growth to meet the demand for food and sugar-energy. However, food production and processing is listed as an important water-consuming agricultural activity, which is also reflected in wastewater that becomes a significant environmental problem.2 The effluents released from these industries are considered to be of high resistance. For distillery wastewater such as grapes and sugar cane the COD value is generally found in the range of 70,000–1,00,000 mg L
1, while legume processing wastewater contains chemical oxygen demand (COD) in the range of 3500–10,000 mg L
1 and industrial wastewater from dairy products contain COD in the range of 2000–5000 mg L
1.3–6 Therefore, wastewater from agro-industry has a high organic load that causes danger to the environment and requires adequate and comprehensive management.7 Consequently, investigating the factors that influence the treatment of agro-industrial effluents should be an important focus to achieve environmental safety and economic efficiency.2 For the treatment of these effluents, biological approaches and aerobic and anaerobic methods are already applied.8 However, despite biological treatment processes being considered an environmentally sound option, some problems such as toxicity, low biodegradability and seasonal

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production affect treatment efficiency.1 Furthermore, with these treatments it is not possible to reach the legal release limits for this type of effluents, in addition to having a high energy consumption. Thus, an important factor to be evaluated is the implementation of process polishing optimization to reduce the concentration of pollutants and reduce energy consumption, especially with regard to anaerobic processes that are responsible for 45–75% of the total cost of the stations wastewater treatment.9,10 When taking into account the low efficiency, high cost and operational space that conventional treatments require, it is essential to investigate new alternatives that can be adaptable to the demands of each agro-industry wastewater. In this scenario, advanced oxidative processes (AOPs) prove to be an interesting alternative for effluent polishing7,11 as shown in Fig. 1. Thus, by coupling biological processes to advanced chemical processes (AOPs), which can be operated close to ambient temperatures and pressures, in addition to rapid oxidation, it is an innovative alternative for the degradation of pollutants1,12 Therefore, this work aims to address the main solutions that are being implemented to mitigate the factors that influence the wastewater treatment processes in different sectors of the agro-industry, shining a light on future works.

Fig. 1 Wastewater production regime and perspective of biological treatment and advanced oxidative processes.

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2. Factors that influence the quality of agro-industrial wastewater The main effluents generated by the agro-industry come from distilleries, the dairy and food industry. Alcohol distilleries generate wastewater called vinasse, and its composition may vary according to the origin of the raw material such as sugar cane, corn, lignocellulosic materials, or fruits such as grapes.13 Regardless of origin, effluents from the distillery industry have high COD (85,000–110,000 mg L
1), BOD (25,000–35,000 mg L
1), ammoniacal nitrogen (800–1100 mg L
1), acidic pH (4.0–4.5) in addition to a high load of biodegradable and non-biodegradable organic matter, being therefore considered one of the most polluting in the world.10 Agro-industrial effluents are rich in organic compounds that are also responsible for the characteristic dark color, due to the presence of furfural (caused in acid hydrolysis), humic and tannic (phenolic) acids, caramels (generated in the heating processes of sugars), and melanoidins (Maillard reaction caused mainly in the sterilization process at low pressures and high temperatures between sugars and proteins).4 The dark color caused by chemical and biochemical reactions in industrial processes, generate residual water that prevents the permeation of light, preventing the production of dissolved oxygen and aquatic life in the system. Likewise, the disposal of distillery wastewater in the soil cannot always be considered an option, due to the low pH that alters the alkalinity of the soil, influencing the availability of manganese that inhibits seed germination.14 Another aspect that also contributes to the generation of large amounts of agro-industrial effluent is the food industry. Tons of wastewater are used in cleaning, salting, fermentation or starch processing processes.3,15–17 Soy processing, for example, generates about 10 tons of effluent with COD: 13,215 mg L
1, TN: 267.1 mg L
1 and TP: 56.3 mg L
1.16 Likewise, the effluent generated in the potato processing industries, which is a basic input for the world’s food, has high COD (37,000 mg L
1), in addition to high concentrations of soluble phosphorus (560 mg L
1) and soluble nitrogen (620 mg L
1), generating approximately 17 L per kg of processed input.18 Dairy products are also of concern, since for every 1 L of processed milk, about 10 L of effluent rich in fats, lactose, detergents and sanitizing agents are generated, which contribute to a COD of 2593.3 mg L
1, TN: 283 mg L
1 and PT: 115.9 mg L
1.19

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Despite the different characteristics and compositions of agro-industrial effluents, anaerobic treatment is implemented for effluents from dairy products to the distillery industry mainly due to the advantage of obtaining biogas. However, after anaerobic digestion, distillery effluents still show high concentrations of COD, BOD (around 40,000 mg L
1 and 10,000 mg L
1 respectively), ammonia nitrogen (1000–1100 mg L
1) and melanoidin content (2%), responsible for the dark color with a complex structure and difficult to degrade.4 Concurrently, effluents from the food processing industry that undergo anaerobic digestion still have a high concentration of total nitrogen (TN: 178–307.64 mg L
1) and total phosphorus (TP: 22.7–37.57 mg L
1).10 Therefore, when analyzing the main factors that influence the quality of the effluent such as COD, TN and TP, it is not plausible to assume that the primary processing is sufficient for the treatment of wastewater from the agro-industry. Given this scenario, polishing alternatives have been investigated in the literature, aiming at the effective reduction of contaminants, nutrients and organic load that overload the environment.

3. Microalgae in the treatment of agro-industrial wastewater Normally, agro-industrial effluent treatment processes are determined in stages where the first moments of treatment are not suspended, which can occur by autoclave, flocculation, centrifugation and subsequent anaerobic treatment. After the initial step, the effluent still has other dissolved contaminants that need to be removed, therefore, a polishing process is necessary. Microalgae can be implemented at this stage due to their ability to metabolize organic matter and nutrients present in agro-industrial effluents. Among the various microalgae present in the ecosystem, studies indicate that species that have heterotrophic metabolism (which use organic carbon in the absence of light)20,21 or mixotrophic cultivation (that have the ability to use organic and inorganic carbon simultaneously in the presence of light)22 present the necessary skills to be implemented in the treatment of wastewater from the agro-industry. However, it is worth mentioning that each species will respond differently according to the C:N:P nutrient conformation, organic matter composition, pH, and COD of each effluent. Mattos and Bastos,17 For example, he used Desmodesmus heterotrophic microalgae species in a stirred batch reactor for the treatment of raw

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sugarcane vinasse, obtaining a COD (36.2%) and nitrogen (52.1%) removal. Likewise, Santana et al.23 using a robust microalgae strain Micractinium sp. EmbrapajLBA32 in a flat PBR air transport plate (15 L) achieved a removal of nitrate (46.7%) and ammoniacal nitrogen (39%) and smaller extensions of removal of total organic carbon (TOC–7.2%), from a clarified sugarcane vinasse (nitrate: 39.41 mg L
1 and TOC: 25660 mg L
1). As it is a biological treatment, other factors besides the composition of the effluent are considered limiting for the process. One of the main bottlenecks is the presence of total solids and the high turbidity of the effluents, which can affect the growth of microalgae by hindering the penetration of light, and the formation of flakes that lead to the settlement of the culture.24 The other problem is the presence of bacteria, zooplankton, protozoa and other microorganisms that hinder the growth of microalgae by competing for nutrients present in the agro-industry effluent.25,26 Therefore, microalgae cultivation is not a substitute for conventional treatments, and should be considered as a secondary polishing treatment. Despite being a promising treatment for large-scale application, microalgae grown in agro-industry effluents are still reported in the literature as tests under controlled indoor conditions.16,27–31 Factors such as light intensity, temperature, reactor setup (which can be a closed photobioreactor (PBR) for critical light or open lagoon conditions), robust microalgae strain, microalgae biomass harvest control, nutrients, and the variation of wastewater that can affect the removal of organic and inorganic nutrients, as well as microalgae growth and accumulation of carbohydrates and lipids for bioethanol and biodiesel production32–34 are parameters that must be evaluated for industrial prospecting of this technology.

4. Advanced oxidative processes Although agro-industrial effluents present a large fraction of biodegradable organic compounds, their biorecalcitrant characteristic (due to the toxic contribution of pesticides carried), as well as the inadequate proportion of C:N:P, hinders the efficiency of the biological treatment process.35–37 In addition, fermentation effluents, such as sugarcane and orange grape residues, become richer in alcohols and phenols as the effluents accumulate, which reduces their biodegradability in aerobic treatments.38

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Therefore, the variability in the flow and composition of agro-industrial effluents, during the processing time, is a challenge for the development of treatments.37,38 To improve the degradability of raw wastewater from agro-industry to be used for biological cultivation, pre-physico-chemical methods can be used. The application of advanced oxidative processes (AOP) is presented as a good alternative. In particular, Fenton processes and Advanced Oxidation Processes based on sulfate radicals (S-AOPs) have gained relevance in recent studies as they can be considered an effective way to reduce the nutrient load and color of wastewater.7 These processes can cleave the carbon double bond and convert refractory effluent molecules into a simpler form that can be easily assimilated by microalgae. S-AOP is considered a recent process for the treatment of agroindustrial effluents and can be applied to degrade or remove recalcitrant pollutants such as resistant bacteria and antibiotics, as well as pesticides and non-biodegradable organic matter.39 Although S-AOP acts on the mineralization of organic materials through sulfide radicals (SO4%
) which provides greater stability, and brings advantages compared to the Fentos process, its rate of degradation of organic matter is slower than that observed between OH% and organic compounds.1,40,41 However, other advantages of S-AOP cited by Genc¸ et al.,42 such as: performance in a wide pH range, radicals with greater solubility, and selectivity make it a relevant alternative process in recent years. Table 1 shows the comparison of the efficiency between the processes for the treatment of wastewater from different agro-industries. Although advanced oxidative processes have promising applicability, their sizing and operation must be performed with caution, as they can produce by-products with greater global toxicity than the original matrix. To avoid such problems, other treatment processes can be coupled or combined, such as membrane technologies,46 activated carbon or posttreatment anaerobic processes.7,40 Despite the disadvantages regarding energy costs and caution in the generation of by-products, S-AOP are advantageous when you want to obtain a smaller treatment time and area.47 Furthermore, for effluents that have recalcitrant components, biological treatment may not provide a positive response, while the high oxidative potential of SR-AOP and AOP degrades toxic components. On the other hand, by-products must be monitored to validate the treatment of each effluent and its ecotoxicity.47,48

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Table 1 Application of S-AOP and Fenton process to treat wastewaters from agroindustry. Wastewaters Process Efficiency Reference

Palm oil mills

Winery

Olive mil

Dairy

Electro—S-AOP

77.7% COD removal 98% color removal 99.7% SS removal

11

Electro Fenton after biological treatment

99.6% COD removal

12

Application of sulfate radical based advanced oxidation process-Metal-heat or UV activated PS

For metal activated PS: 1 55% COD removal 40% TOC removal For UV activated PS: 96% COD removal 71% TOC removal

Solar Fenton after biological treatment

71% COD removal 71% phenolic compounds removal 50% color removal

43

S-AOP Homogeneous process (synthetic OMW)

39% COD removal 63% Tph removal 37% TOC removal

7

Fenton

76% COD removal

44

Sono-activated PS

74.5% COD removal

7

Fenton-like (precipitation with 100% COD removal 45 Ca(OH)2 + aerobic degradation) 100% H2O2

5. Conclusion Considering the published studies, it is clear that there is great interest in combining advanced oxidative processes with biological treatments, for the economic benefits, effectiveness of inactivating antibiotic-resistant bacteria and effective removal of COD and TOC and residual color. Assuming the complete degradation of recalcitrant compounds in chemical oxidation processes is not economically viable. However, oxidizing radicals are able to convert recalcitrant compounds into more biodegradable compounds capable of being treated in biological processes. Therefore, combinations can be made, considering the characteristics and origin of the agro-industrial effluent, where three steps (biological process + AOP + biological process) can be a viable option as long as ecotoxicity is monitored.

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47. Van DP, Fujiwara T, Tho BL, Toan PPS, Minh GH. A review of anaerobic digestion systems for biodegradable waste: configurations, operating parameters, and current trends. Environ Eng Res 2020;25:1–17. https://doi.org/10.4491/EER.2018.334. 48. Rastogi A, Al-Abed SR, Dionysiou DD. Sulfate radical-based ferrous–peroxymonosulfate oxidative system for PCBs degradation in aqueous and sediment systems. Appl Catal Environ 2009;85:171–9. https://doi.org/10.1016/J.APCATB.2008.07.010.

CHAPTER SEVEN

Contamination of soil and food chain through wastewater application Priya Yadava, Rahul Prasad Singha, Rajan Kumar Guptaa, Twinkle Pradhana, Amit Rajb,*, Sandeep Kumar Singhc, Kaushalendrad, Kapil D. Pandeya, and Ajay Kumare a

Laboratory of Algal Research, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India b Department of Biotechnology, M.AK.A.U.T, Kolkata, West Bengal, India c Division of Microbiology, ICAR-Indian Agricultural Research Institute, Pusa, New Delhi, India d Department of Zoology, Mizoram University (A Central University), Pachhunga University College Campus, Aizawl, India e Department of Botany, Banaras Hindu University, Varanasi, India ⁎ Corresponding author: e-mail address: [email protected]

Contents 1. 2. 3. 4.

Introduction The current scenario of wastewater irrigation Wastewater irrigation in agriculture: A worldwide health challenge The effect of wastewater irrigation on the properties of soil 4.1 Effect of wastewater irrigation on soil microbiome 4.2 The effect of wastewater irrigation on the concentration of toxic elements in the soil 4.3 The effect of wastewater on the concentration of pesticides 4.4 The pharmaceutical and personal care products (PPCPs) in the waste water 5. Impacts of wastewater irrigation on crops 5.1 Persistence of harmful pathogenic microbes in the plant and soil 5.2 Microbial contamination 5.3 Spread of antibiotic resistance 6. The effect of wastewater irrigation on food chain contamination and human health 7. Measures to reduce risks 8. Conclusions Acknowledgments References

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Abstract Current time, wastewater irrigation is becoming more prominent as a response to the decline in freshwater resources triggered by climate change. Globally, population density and freshwater resources are not distributed equitably. Wastewater irrigation has been identified as a severe environmental concern in many nations due to pesticides, heavy metal, etc. accumulation in food crops and soils, as well as potential health hazards to those who consume these foods. In terms of agricultural use, as well as environmental contamination and toxicological, this approach has both beneficial and negative consequences. However, wastewater is a significant necessary source of plant nutrients, the presence of harmful pollutants and bacteria in wastewater poses a number of environmental, sanitary, and health hazards after long-term agricultural irrigation. As wastewater irrigation becomes more common, human health risks become more important since the advantages to food security and livelihoods must be evaluated against exposure to various contaminants. This chapter discussed the impact of wastewater irrigation on the biological, chemical, and physical attributes of soil including pH, anions and cations, organic matter, and microbial activities. We described how potentially toxic elements (PTEs) accumulate in soil body and how they are transferred to flora and fauna. Keywords: Wastewater, Irrigation, Toxicity, Heavy metals, Soil contamination, Health risk

1. Introduction By 2050, there will be 9.5 billion people on the planet, which will require a 60% increase in the food production for the feeding.1 Water is one of the most precious resource, required for the normal functioning of living organism. But currently most of the leading cities of world facing scarcity of water and it has been estimated by 2025, 60% of the world’s population will be facing a freshwater scarcity.2 Nowadays, wastewater is widely utilized for crop plant irrigation in locations where fresh water is limited. Despite the fact that it is illegal in most countries, utilized untreated wastewater for agricultural irrigation.3,4 Various human endeavors, including commercial industrial, and residential activities, produce wastewater. Municipal wastewater is sometimes divided into three categories: rural, urban, and agricultural sources. The amount of wastewater produced is expanding in lockstep with the fast growth of the population, cities, industries, and home water supplies.5 The amount of wastewater generated by regular activities of humans is determined by the amount of water available in the residence, the cultural type, water cost, and economic situations.6 The most prevalent application of untreated wastewater is agriculture. The use of wastewater to irrigate the agricultural land has increased during the last few years. Reusing wastewater is becoming more prevalent as a way to fulfill

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the increasing demand for water. This resource generally includes high quantities of both healthy nutrients and harmful contaminants, posing both opportunities and challenges for agriculture.7 It has been reported that application of wastewater supplies adequate levels of macronutrient (Nitrogen, Potassium, and Phosphorus) to land and plants.8 Poor farmers are enticed to use wastewater to irrigate crops because it can reduce the cost of crop production by 10–20%.9 Aside from these advantages, there are a number of disadvantages to using wastewater for crop irrigation.8,10,11 The potentially toxic elements (PTEs) including zinc, copper, chromium, cadmium, nickel, mercury, lead, and parasitic worms are found in waste water, all of which represent significant risks to human health and the environment.12,13 Untreated wastewaters can usage as crop irrigation results in soil hardening and shallow groundwater contamination. The existence of potentially hazardous substances is the main issue with wastewater crop irrigation14,15 (Fig. 1). The accumulation of PTEs in land and crops caused by irrigation of wastewater causes soil pollution, which has an impact on food safety.10,16,17 Due to the presence of hazardous substances that have long-term negative effects on the environment and human health, the contamination of agricultural soils by wastewater application causes health issues.18,19 The main route of toxic elements exposure to humans is through intake of food crop, this could cause a number of health issues for people if the toxic elements content surpassed the safe limit.20,21 Continual usage of toxic elements contaminated vegetables can result in an accumulation of hazardous metals in human kidneys and livers, disrupting physic-biochemical processes.22 In developed countries, studies on the potential health risks with eating toxic elements contaminated foods and vegetables are being conducted. In less developed countries, however, there is very little research.21,22 However, there is a considerable variation in how low- and high-income countries collect, clean, and reuse wastewater irrigation for crop.8 This disparity between the two groups could be due to a variety of factors, including consideration of the accessibility of fresh water for agriculture irrigation, wastewater treatment resources, farmers awareness of the effects of wastewater agricultural irrigation on the environment and human health, and the adoption of regulations for wastewater usage in agriculture.8,14 There are other social, economic, and business factors that affect wastewater treatment and reuse for irrigation of crops in both high- and low-income countries. On a national and global scale, there is a wealth of information about wastewater generation, its usage to irrigate crops, and the accompanying health and the environment problems. Researchers, scientists, and politicians can benefit

Fig. 1 The possible food chain contamination by wastewater crop irrigation.

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greatly from a comprehensive assessment that highlights all of these features on a national and international scale. As a result, we highlight and assess the current picture of wastewater generation and usage to irrigate crops, as well as the accompanying environmental and health hazards, on a national and worldwide scale in this review. Furthermore, the paper examines the wastewater history irrigation for crops and provides some future views and management measures to reduce the dangers associated with wastewater irrigation for crops.

2. The current scenario of wastewater irrigation Today, especially in several semi-arid and dry countries, it is almost compulsory for farmers to utilize any source of water when freshwater is scarce.11 As a result of the absence of viable alternatives, agricultural irrigation with wastewater becomes a viable choice.8 The agricultural sector consumes up to 70% of total water consumption,23 accounting for a large share of total municipal water reuse.24 Partially treated or untreated municipal and industrial wastewater has been estimated to be employed to irrigate over 20 million ha of crop worldwide.4 The utilization of wastewater for agriculture irrigation is gaining popularity these days. The usage of treated wastewater has expanded in industrialized nations due to the rapid development, advancement, and acceptance of wastewater.25,26 In United States, China and Europe, the utilization wastewater for irrigation has increased by 10–29% per year, and in Australia 41%.25 Global wastewater release exceeds 400 billion m3/year, contaminating around 5500 billion m3 of water every year.4 The type and quality of wastewater utilized varies between and within countries. Approximately 44 countries utilizing 15 million m3/day of water for agricultural purposes.27 The utilization of treated wastewater and freshwater is given in (Table 1). Food produced by wastewater irrigation is expected to be consumed by 10% of the global population.28 In low-income countries, reuse of wastewater for agriculture is not proper regulated, and the environmental and economic challenges are little recognized.8,11 Although it is forbidden but several poor countries utilize direct sewage water for irrigation.29 Several developing and less developed countries of Asia, Africa and America directly utilized waste water for irrigation.5,30 On the other hand, wastewater is used after treatment in middle-income countries.31 China is the world’s most populous country, as well as the most wastewater-producing country and from industrial and

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Table 1 Treated wastewater and Freshwater utilization status in different developed and developing countries. Water utilizing sectors and their Status of water reuse and their Country percentage percentage

Europe 44% in Agriculture, 40% in Industry 20% Landscape irrigation, 2.2% and energy production, 16% in Groundwater Recharge, 6.8% public water supply Recreational, 8.3% Non-potable urban uses, 2.3% Indirect potable uses, 32% Agriculture irrigation, 19.3% Industrial, 8% Environmental Enhancement, 1.5% Other Greece 83% in Irrigation, 1.3 in Animal 58.38% Agricultural irrigation, husbandry, 2.2% in Industry, 13% in 17.7% Irrigation of forested land public use (potable), 1.2% Other and firefighting, 23.92% Landscape irrigation India

87% in Agriculture, 7% in Industrial, 4% in Domestic, 2% in Energy

78% Agricultural irrigation, 12% Industrial use, 4% Thermal power plant, 6% Groundwater recharge and artificial lakes

South Africa

60% in Agriculture, 27% in 9% Landscape and sports field Domestic, 3% in Industrial, 4% in irrigation, 48% Industry, 43% Power, 3% in Mining, 3% in Other Agriculture

USA

41% in Freshwater thermoelectric plants, 37% in Agricultural irrigation, 6% in Industries, 14% in Domestic, 3% in Livestock and aquaculture

37% Agricultural irrigation, 2% Geothermal energy, 7% Golf course irrigation, 17% Landscape irrigation, 12% Groundwater recharge, 7% Seawater intrusion barrier, 4% Recreational impoundment, 4% Wetlands wildlife habitat, 8% Industrial and commercial, 2% Other

Modified form of Kesari KK, Soni R, Jamal QMS, Tripathi P, Lal JA, Jha NK, Siddiqui MH, Kumar P, Tripathi V Ruokolainen J. Wastewater treatment and reuse: a review of its applications and health implications. Wat Air and Soil Poll, 2021;232(5):1–28.

urban sources approx. 68.5 billion tons of wastewater discharged, which is coequal to annual flow volume of Yellow River’s.32 It has been claimed that China’s wastewater is used to irrigate an area of roughly 1.33106 ha each year.33 In India, metropolitan cities discharge around 38,354 million liters/day of wastewater, while treatment capacity is only 11,786 million liters/day and remaining untreated wastewater is used for crop irrigation.34

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According to the Development Finance Corporation,35 roughly 73% of urban wastewater generated in India goes untreated. In Mexico, processed wastewater irrigates around 70,000 ha, while untreated wastewater irrigates roughly 260,000 ha.36 In Ghana, informal irrigation uses wastewater diluted from streams and rivers to irrigate an area of 11,500 ha, which is larger than the formal irrigation area.37

3. Wastewater irrigation in agriculture: A worldwide health challenge Wastewater is utilized for irrigation in both untreated and treated forms, depending on the economic and geographic environment of the nations.9 Due to the scarcity of treatment facilities in many nations, waste is frequently dumped into waterbodies with no or little treatment.11 Around 11% croplands of peri-urban or urban agriculture are irrigated by untreated or partially treated wastewater.38 Untreated wastewater contains variety of toxins originating from domestic, hospitals, industrial and agricultural sources. Animals and human communities those living near wastewater irrigation field are at risk from hazardous compounds originating from these sources skin irritation and infection from several diseases.39 Protozoan, fungal, bacterial, and Viral diseases viz. amoebiasis, giardiasis, salmonellosis, cholera, shigellosis, viral enteritis, hepatitis A and other disorders have been directly associated to wastewater exposure.28 Agricultural workers can get dermatitis and rashes from coming into touch with untreated wastewater on a regular basis. Heavy metal exposure from inhalation and intake of contaminated food has been directly related to several chronic health problems. Cadmium accumulation, for example, causes kidney damage and osteoporosis. In Japan, this is known as itai-itai illness, and it was first connected to rice paddies being irrigated with severely Cd loaded water.40 mechanism of uptake of personal care products and polycyclic aromatic hydrocarbons in food chain in not very expose yet41,42 (Fig. 1). Because of these globally spread health dangers, WHO have set recommendations to ensure that pollutant levels in water do not exceed levels that are detrimental to human health.28 Because it provides a regular source of water in fluctuating or drought conditions, wastewater is also developing as a type of climate change adaptation.43 Many factors that influence wastewater use, efforts to reduce health concerns should be balanced against the need for better food nutrition, livelihoods and security.44 The actual amount of exposure to wastewater toxins has to be investigated in the context of

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these health concerns. However, there is a significant variation in how lowand high-income nations collect, clean, and reuse wastewater for crop irrigation.8 This disparity between the two groups could be due to a variety of factors, including the availability of fresh water for crop irrigation, wastewater treatment resources, farmer awareness of environmental and human health issues related to wastewater crop irrigation, and the implementation of wastewater use laws in the agriculture sector.8,14 There are other social, economic, and business factors that affect wastewater treatment and reuse for crop irrigation in low- and high-income nations. On a national and global scale, there is a wealth of information about wastewater generation, its use for crop irrigation, and the accompanying environmental and health problems. Researchers, scientists, and politicians can benefit greatly from a comprehensive assessment that highlights all of these features on a national and international scale. As a result, we highlight and assess the current picture of wastewater generation and use for crop irrigation, as well as the accompanying environmental and health hazards, on a national and worldwide scale in this review. Furthermore, the paper examines the history of wastewater irrigation for crops and provides some future views and management measures to reduce the dangers associated with wastewater irrigation for crops.

4. The effect of wastewater irrigation on the properties of soil The application of waste water significantly affects the physicochemical properties of the irrigated soil. Several earlier research have shown that wastewater application alters the soil’s physical, chemical, and biological properties,45 which can affect metal and other nutrient biogeochemical behavior (mobility and bioavailability). As a result, changes in soil parameters results adversely impact on the productivity and texture of plant and soil and also creates a health issues for human beings (Fig. 2).

4.1 Effect of wastewater irrigation on soil microbiome Soil is the natural hot spot of microbial communities including bacteria, fungi, actinomycete. These microbial species play significant role in soil mineralization, antibiotic production, synthesis and decomposition of toxic compounds, etc.46–48 However, the impact of wastewater on soil microbial activity might be direct or indirect, depending on the physicochemical features of the soil.49 In a study, Saadi et al.50 reported shift in microbial diversity from bacterial to fungal in the metal communicated soil.

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Fig. 2 Exposure pathway representing serious health concerns from wastewaterirrigated crops.

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Similarly long-term application of municipal wastewater application significantly lowers the arbuscular mycorrhizal fungi variety.51 Mechri et al.52 reported olive mill effluent, significantly affect the microbial community structure. However contrary to this, irrigation with wastewater could be a source of beneficial microorganisms for soils as reported by Covarrubias et al.53 For an example, ammonia-oxidizing bacterial community in soil was transformed by wastewater irrigation, and the Nitrosomonas and Nitrosospira species became dominant.52 The soil irrigated with waste water sometimes increases the enzymatic activity such as hydrolytic enzymes, dehydrogenase, etc. in the soils.54,55 However, the increased activity of dehydrogenase results oxidation of organic molecules, which impact the availability of organic carbon.55 The provision of nutrients and organic matter from wastewater irrigation is intended to boost several metabolic processes and organisms.46,47 In several studies it has been found that irrigation with wastewater effluent boosts the soil’s nutritional content, creating a favorable environment for bacterial growth.56 Bacteria from wastewater effluent build in soil and, because to the quantity of nutrients provided by long-term irrigation, can persist for lengthy periods of time.

4.2 The effect of wastewater irrigation on the concentration of toxic elements in the soil The application of waste water for agricultural irrigation results deposition and accumulation of heavy metals or toxic elements in the soil. Although heavy metals are required in the small quantity for the normal functioning and physiology of plants, but the presence of excess amount adversely affect the texture or productivity of plant and soil and also health concern.57–59 The presence of toxic elements such as Cd, Cr, Cu, Ni, Pb, and Zn, are well known the waste water or the sewage water, which have severe effect on the soil after long-term application. The non-degradable nature, of these toxic elements have a long environmental persistence and can easily accumulated in the soil.11,16,60 However, the accumulation of toxic elements in higher quantity in the top soil is reported by various authors.61,62 The concentration or amount of the toxic elements presence in the waste water depends upon various factors such source, area and volume of the waste water. In the previous study, various authors reported the deposition of toxic elements or heavy metals in the soil after long-term application of waste water for agricultural irrigation.63–65 In a study, Khan et al.16 reported accumulation of found a Pb and other toxic elements in wastewater-irrigated

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soils in compare to normal water irrigated soil. Shahid et al.21 reported accumulation and adverse effect of Cd deposition in the soil after waste water utilization. Generally, the toxic elements or heavy metals deposited in the top soil and their mobility toward downward is comparatively more than the parent minerals salt. The physic-chemical properties of the soil, electrical conductivity presence of organic matters, generally influence the mobility and bioavailability of the heavy metals and toxic elements.66,67

4.3 The effect of wastewater on the concentration of pesticides In the recent past, huge amount of pesticides have been frequently used to control the pest growth and enhance the agricultural production. However, the regular use of chemical pesticides led to resistance pest, environmental pollution and health concern of consumers/human beings.68,69 Pesticides are one of the compounds present in the soil after long-term utilization, who’s persistent in the soil and environment is very high.70 However, some of the pesticides are banned in the various parts of the countries but due to prompt response and easy in availability still made popular for the pest control.71 Persistent organic pollutants (OCPs) include various chemical including organochlorine. Organophosphate, etc. In the environment, OCPs are renowned for their severe high persistence, bioaccumulation and high magnification power.72

4.4 The pharmaceutical and personal care products (PPCPs) in the waste water PPCPs is a broad term used for the daily using products of humans such as pharmaceuticals waste, hospital waste, soap, toothpaste skincare, etc.73,74 As the impact of PPCPS on the environments and on the human beings are very less known, so, these are commonly referred as pollutants of emerging concern.75,76 The emerging pollutants can be released into the aquatic and soil habitats as waste from animal farms and sewage treatment plants.77 The use of treated wastewater or contaminated river water for irrigation is another source of PPCPs in the soil.78 However, the PPCPs with low hydrophobicity are also frequently found in the soils. Through organic material interactions, these can be collected from the soil.79 In a study in Spain of 166 emerging pollutants and heavy metals (such as Cd, Ni, Pb, and Hg), 38 pharmaceuticals have been reported from tertiary treated wastewater, albeit in low concentrations.80

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5. Impacts of wastewater irrigation on crops The utilization of waste water for agricultural irrigation is a common practice in most of the countries especially in low-income countries. However, in most of the part these waste water has been used without any treatment, which have both positive and negative impact on the agricultural products or the crop quality.11,14 The presence of harmful pathogenic bacteria and the toxic elements also severally affect the health of consumers and environment as well.3,81 In addition, the presence of enhanced level of salt concentration in the waste water get accumulated in the root zone of the plant which results improper water movement and physiology. The regular use of salt rich water or the sodium rich water degrades the texture and productivity of soil.14,82 Potential toxic elements (PTE) contamination of plants occurs directly through root uptake in the soil. Toxic element accumulates in high amounts in vegetables and crops watered with wastewater, posing a health concern for consumers. Several studies have shown that wastewater-irrigated plants can absorb and accumulate toxic element at levels over the maximum permitted limits (MPLs), posing substantial public health risks.83,84 In the previous published report, it has been stated that utilization of waste water in the agricultural irrigation can result in the accumulation of toxic heavy metals in the edible parts.85 For example, Chopra et al.86 reported accumulation of different heavy metals such as Pb, Cu, Zn, Ni, Cd, and Cr in the various crops such as Beta vulgaris, Phaseolus vulgaris, Spinacea oleracea, and Brassica oleracea. Similarly, Lu et al.87 reported accumulation of different heavy metals such as Cr, Pb, Ni, and Zn in the maize. Jamali et al.88 also reported such type of accumulation in the vegetables. Sharma et al.89 reported accumulation of Ni and Pb in the Beta vulgaris and also reported enhanced level of Cu, Fe, Mn, Zn, Pb, Cd, and Ni in the red cabbage and cauliflower after waste water irrigation. Similarly, Balkhair and Ashraf90 also reported higher level of Cr, Pb, Ni, and Cd in the edible part of okra after irrigation with waste water. However, the accumulation of toxic elements in the plants or plant organs including the edible parts depends upon the various factors such as nature and types of heavy metals, soil physic-chemical properties, the waste water related variables. As the metals present in the soil varies with their present free charges, ions, which form a complex structure with the organic and inorganic compounds present in the soil.91–93 Thus, the chemical speciation

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of toxic elements plays a significant role in the transmission of toxic compounds and heavy metals. It has been observed that the deposition of toxic metals led by waste water generally deposited on the top soil, and their mobility toward downwards are faster than the metals deposited from the parent materials.94,95 However, it is well known that the ability of accumulation of heavy metals from the soil to the plants are species specific.96,97 Some of the plant species accumulates higher amount of toxic metal generally termed as hyperaccumulators.98,99 The hyper accumulator plants can accumulate more than 100 times, toxic elements than the normal plants.92,96 The accumulation of the toxic elements in the plants varies within the organ. The most higher c concentration of accumulation occurs in the root portion (>90%). However, very less amount is transported or reached to the stem portion and one of the most probable reasons for this are the presence of negative charge on the pectin of roots endodermis causes element sequentialization in the plant roots.66 Although the accumulation of heavy metals in the different parts of plants severally determined their health and physiology.20,100,101 The presence of enhanced level of metals in the plants different portion can be beneficial and harmful and it depends upon the edible portion of the plants. For an example, the accumulation of heavy metals in the roots is beneficial for the leafy vegetables, while translocation of heavy metals to the shoot portion is beneficial for the tuber’s food. Similarly, the plants having edible portion below the ground have higher risk of contamination, whereas lower risk have been observed to plants, whose edible parts present above the ground.102,103 The optimum concentration of heavy metals required in the plants for the normal functioning. However, their presence in excess concentration adversely affects the physiology and metabolism of plants. The presence of heavy metals in higher amount alters the nitrogen metabolism, water uptake, reduced photosynthesis, etc.104 In addition, also induced root browning, necrosis, chlorosis, and leaf rolling.105

5.1 Persistence of harmful pathogenic microbes in the plant and soil It is well known that some of the pathogen such as causal pathogen of gastro-intestinal infections multiply only inside the digestive tract. They resist die-off to varied degrees depending on their habitat, which has an impact on disease causation and transmission.106 Helminth eggs, which can live for several years in the soil, are the most environmentally resistant

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diseases. Pathogen survival times in the soils and plants are the severe concern for pathogenicity and their transmission. The impact of temperature on pathogen survival has received a lot of attention. Low temperatures improve the survivability of E. coli in the soils.107

5.2 Microbial contamination The presence of pollutants in the untreated wastewater has been considered as a serious health hazard.108 Some of the microbial strains such as Pseudomonas aeruginosa, Salmonella typhimurium, Vibrio cholerae, E. coli, Shigella sonnei, are the common water borne disease that causes acute human diseases or infections after consumptions.109,110 This water borne diseases can be released in to the environment with the waste water, hospital waste, sewage water, etc.

5.3 Spread of antibiotic resistance Antibiotics are currently widely utilized to treat human diseases; nevertheless, they are also widely used in poultry, animal husbandry, biochemical industries, and agriculture. Antibiotic overuse and/or misuse has resulted in multi-resistant microorganisms carrying several resistance genes.111,112 In the previous study, authors reported various types of antibiotic pathogens in the waste water such as methicillin-resistant Staphylococcus aureus and vancomycin-resistant enterococci present in the wastewater even after treatment.113,114 However, the use of treated wastewater for irrigation promotes the growth and persistence of total and fecal coliform bacteria.115 In addition, in several studies Clostridium, Salmonella, Streptococci, Viruses, Protozoa, and Helminths reported in the crops irrigated with treated wastewater.116 In a study, Goldstein117 observed survivability of antibiotic resistance bacteria (ARBs) in the secondary treated wastewater and found health concerns to consumers, who drink reclaimed water.117 The Centers for Disease Control and Prevention (CDC) in the United States and the World Health Organization (WHO) have already deemed ARBs to be a serious health risk. Some off the pathogens such as Enterococcus faecium, S. aureus, Klebsiella pneumoniae, Acinetobacter baumannii, Pseudomonas aeruginosa, and Enterobacter species have been designated as “priority status” pathogens in the WHO list. Because their occurrence in the food chain is considered a potential and major threat to human health.118 In addition, these pathogens showed multidrug resistance against various antibiotics like oxazolidinones, lipopeptides, macrolides, fluoroquinolones, tetracyclines, β-lactams,

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β-lactam–β-lactamase inhibitor combinations. Even these antibiotics are considered as the last line of defense.119,120

6. The effect of wastewater irrigation on food chain contamination and human health The residual of toxic compounds in the food crop is a global concern because of their adverse impact on the human health. The utilization of waste water for the agricultural irrigation is one of the prime reasons of the food chain contamination.14 Recently, in the less developed countries use of untreated water for the agricultural irrigation is most frequently practiced.8,121 However, the utilization of untreated waste water and sanitation increased the illness at an alarming rate throughout the world. According to a published report, in the year 2012, approx. 842,000 deaths have been occurred in the developing countries due to sanitation services, drinking of contaminated water and improper hand washing.122–124 The discharge of untreated waste water including the urban discharge or industrial effluents into the oceans harm around 245,000 km2 of marine ecosystems and the food chains.125 Clinical research has demonstrated that excessive dietary toxic elements buildup can lead to major systemic health problems, which have been associated to the etiology of various human disorders and diseases such as nervous or digestive disorders126,127. The consumption of the waste water can lead to the depletion of nutrients in the human bodies resulting variety of issues such as growth retardation, malnutrition-related disorders, reduced psychosocial capacities, gastrointestinal cancer, etc. However, the toxic elements such as Pb and Cd can act as carcinogens and mutagenesis.40 Furthermore, Pb has been linked to inappropriate hemoglobin synthesis, kidney and tumor infection, raised blood pressure, and reproductive system dysfunction.66,128 Due to the lack of effective defensive systems to attenuate the harmful effects of these metals and eliminate them from the body, toxic elements are even capable of generating toxic effects in living animals, including humans, at extremely low levels. As a result, food safety and risk assessment receive a lot of attention around the world. Children and newborns are more vulnerable to wastewater toxins than adults,129 and their exposure to these chemicals has been mentioned in various papers.130 The use of wastewater for crop irrigation and the attendant health problems were first addressed in legislation in the early 1800s. During that time, the

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use of wastewater for crop irrigation in peri-urban regions resulted in devastating epidemics of a variety of waterborne diseases.131,132 Therefore, there is need to understand and aware the people especially of less developing countries, regarding the health concern and side effect of the toxic elements present in the waste water.126,133 Several studies, particularly in low-income countries, back up this claim.134 To minimize potential health concerns and make prompt decisions/policies, a systematic risk assessment is required to explore the hidden truth of the toxic compounds exposure.135

7. Measures to reduce risks Treatment of waste water is the greatest option. However, the prices of engineering-based technologies on a large scale are generally unaffordable for the low-income countries. The WHO (World Health Organization),28 on the other hand, supports simple farm-based initiatives, low-cost treatment alternatives, and so-called “nontreatment” choices, all of which can greatly lower the risk. In the event that this is not practicable, the impacted regions may have to be shut down.

8. Conclusions In the irrigated agriculture, the use of (untreated) wastewater is a most common measures, which results several adverse effects on the crop and soil quality. However, the extent of contamination depends upon various factors such as source, nature and amount of contaminants. Peri-urban farmers in many underdeveloped nations have little options other than to use surface water. In terms of the scope and complexity of the corrective steps that must be taken, soil salinization is one of the most difficult problems to solve. Crop diversification may be a way to mitigate this issue while also providing economic and on-farm benefits to farmers. Heavy metal pollution and specific ion toxicities pose a new form of concern, particularly where industrial effluent is used. Industrial wastewater, on the other hand, is frequently localized and hence much easier to clean or keep out of farming. The majority of wastewater irrigation research has focused on microbiological pollutants and risk assessment but still there is need to investigate the new method of pathogen identifications, control the transmission channel and also to control disease outbreak.

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Acknowledgments The authors are thankful to the, Center of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi for providing the lab facilities and University Grant Commission, New Delhi for financial assistance in the form of fellowship as JRF/SRF.

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CHAPTER EIGHT

Advanced biomaterials for the removal of pesticides from water Hafiz Adnan Akrama, Adeel Afzala, Azeem Intisara,*, Mateen Hedara, and Nazim Hussainb a

School of Chemistry, University of the Punjab, Lahore, Pakistan Centre for Applied Molecular Biology, University of the Punjab, Lahore, Pakistan *Corresponding author: e-mail address: [email protected] b

Contents 1. 2. 3. 4. 5.

Introduction Advanced biomaterials Synthesis of biomaterials for pesticide removal How are biomaterials efficient for water treatment? Removal of pesticides from water 5.1 Role of plant biomaterials in pesticides management 5.2 Effectiveness of bird biomaterial waste in pesticide control in water 5.3 Fungi biomaterials for the remediation of pesticides in water 6. Future perspective 7. Conclusions References

134 137 138 139 140 142 144 145 146 146 147

Abstract The present scientific development has a significant effect on the agricultural sector. The use of pesticides is a widespread practice to increase the crop yield to meet the increasing demand of the growing population. Unfortunately, the excessive use of pesticides has posed serious health threats because of their release in an uncontrolled and unmonitored way in water bodies. The consumption of such water contaminated with pesticides affects not only humans but also aquatic life and ultimately the whole ecosystem. Biotransformation and bioremediation are economical as well as environmentfriendly approaches to treat the water polluted with pesticides. They utilize biomaterials such as fungi/plants or their related products. Herein, these two processes and associated biomaterials are discussed along with a focus on the plant and fungal enzymatic mechanism which is the core of the bioremediation process. Keywords: Pesticides, Biomaterials, Water contamination, Bioremediation

Advances in Chemical Pollution, Environmental Management and Protection, Volume 9 Copyright # 2023 Elsevier Inc. 133 ISSN 2468-9289 All rights reserved. https://doi.org/10.1016/bs.apmp.2022.10.006

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1. Introduction Changes occur in physical, chemical, and biological properties of water due to the addition of toxic organic, inorganic and radiological substances. These sources of pollution can be industrial waste, pesticide waste, domestic waste, and agriculture waste.1 Water is the most essential resource for human life as it is used for drinking, irrigation, cleaning, and food production.2 The industrial sector releases about 300–400 tons of waste in water bodies globally containing heavy metals, sludge, and toxic contents which ultimately pose huge threats to human beings.3 Industrial and municipal wastewater contains a large amount of mixed organic pollutants including polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and bischlorophenyl-trichloroethane are released into open water without being treated and ultimately causing highly toxic water pollution.4 A similar study on water pollution reported metals and metalloids cause health risks present in vegetables and consumable water.5 Water contamination is a major world issue, and it is a need of the hour to revisit and reassess policies regarding water resources being implemented worldwide. As water is a basic human right, however, recent studies reported waste or contaminated water as the main cause of diseases and deaths worldwide.6 Beyond environmental issues, these heavy metals exposures cause different diseases including liver problems, gastrointestinal issues, nervous system issues, kidneys, and renal problems last but not least these act as prohibitive agents in the formation of enzymes that are responsible for the formation of heme in bone marrow ultimately leading to blood disease.7,8 Removal of these heavy metals-related contaminants is necessary for better health conditions worldwide. Several methods have been developed for the removal of these metals which include adsorption, ion exchange, electro-dialysis, liquid extraction, chemical precipitation, and membrane filtration.9–12 The use of biomaterials in wastewater treatment is a modern phenomenon involving living and non-living biomaterials. Many of these biomaterials employ the process of biosorption in the removal of waste materials which is considered efficient, economical, and eco-friendly.13 Biomaterials obtained from algae, fungi, bacteria, and agricultural by-products have been the prime focus of study for biosorption of wastewater materials as reported in studies.14,15 Chemical compounds employed to control/kill/repel pests such as rodents, insects, weeds, and fungi in the agriculture sector are named

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pesticides. The uncontrolled flourishing of these pesticides might be destructive or will harm the crops in farming terrains. Thus, pesticides are employed to dispose of or to control pests in agricultural land areas, this step improves crop productivity by reducing the harms of pests, increasing production uplift the living standard of the population worldwide. Approximately 2 million tons of pesticides are used every year to manage weeds, pests, and insects.16 Excessive and unnecessary use of pesticides is the primary reason for the increase in toxicity levels of these substances in water bodies. Nonpersistent pesticides, which break easily on light exposure, are less harmful and are favorably used in food.17 Various synthetically prepared halogenated chemicals are used as pesticides globally in the form of fungicides, insecticides, biocides, and herbicides where only a small amount of these pesticides is actively utilized and remaining is released into the environment.18–20 Several studies suggested that agricultural waste and industrial effluents are the prime reason behind the contamination of water bodies ultimately changing neutral water into alkaline water.21,22 Bioaccumulation of the food chain is caused by the same reasons.23 Due to the genotoxic, neurotoxic, and mutagenic effects of the recalcitrant residues, these substances pose serious health hazards for mammals19 and they initiate an inflammatory response by altering the production of chemokines and cytokines.24 These compounds are difficult to degrade due to high molecular mass, low polarity, and lipophilic nature and that’s why they have longer half-life which causes their accumulation in nature.25 Biomaterials are naturally occurring or synthetic materials which include polymeric, ceramic, or metallic materials, and composites. They are compatible with living tissue and they are incorporated into human beings for a variety of purposes.26 Cellulose is a versatile biomaterial with potential application in the treatment of industrial and municipal wastewater. Cellulose has been used in wastewater filtration membranes employing the phenomenon of microfiltration and osmotic filtration. Cellulose and its derivatives are used extensively for the removal of pesticide and its residues from water. Some of the examples are described in Fig. 1. Cellulose obtained from spinifex is an excellent adsorbent for different heavy metals including the highly toxic element mercury in the form of Hg+ which is potentially harmful to fishes and human beings. Biomaterials neutralize charged particles in waste waters which results in flocculation of metals released from pesticides, in the entire process they decontaminate wastewater. Coagulation is a process in which suspended

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Fig. 1 Cellulose and its derivative for the removal of pesticides from water.

particulate matter is aggregated, proving to be a potential coagulant in the wastewater treatment process. One of the easily available biomaterials is cellulose, nano cellulose has a significant contribution to the treatment of municipal and industrial wastewater treatment. Sensor-based on the piezoelectric feature of nanocellulose are being developed and used for the pesticides removal process.27 Being an agricultural country there is excessive use of pesticides for crop protection and enhancement of food protection in Pakistan. Excessive and unmonitored use of these pesticides results in the release of these pesticides containing heavy metals and other toxic elements in the environment and it is essential to degrade them to protect human beings in particular, and the environment as a whole in general. Several studies are reporting the employment of microorganisms or biomaterials derived from them. Bacteria species such as Chromobacterium spp., Bacillus spp., Klebsiella spp., and Lysinibacillus spp., have been reported in the degradation of chlorinated pesticides which make water undrinkable for living organisms.28–31 Fungal species such as Penicillium spp., Phanerocheate spp., Candida spp. and Ganoderma spp. have been used in the degradation of such chemicals, which are harmful to living organisms.32–35 The presence of mycelia, a tool for deeper penetration and a large area for adsorption, in fungi makes it a better option for degradation

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than bacteria, and fungi produce and release extracellular enzymes such as peroxidases, laccases, esterases possessing broad selectivity for a variety of substrates. These extracellular enzymes facilitate the oxidation of phenolic compounds and ultimately play a significant part in their degradation.36–39 These additional qualities which make fungi potential agents for degradation and detoxification are absent in bacteria. Macrophytes employ an excellent mechanism of inorganic contaminant uptake through membrane transport and organic contaminant uptake through diffusion.32 Plant species are excellent agents for phytoremediation of a wide variety of pesticides such as Juncus effusus remediate tebuconazole in hydrophobic medium, riverine macrophyte Acorus calamus remediate chlorpyrifos and Cyperus rotundus remediate triazophos pesticides.33–35

2. Advanced biomaterials Due to their elevated levels of toxicity and limited biodegradability, specific organic pollutants (SOPs) which include certain phenolic content, polycyclic aromatic hydrocarbons, insecticides, and herbicides, pose risks to human health and the environment. For the removal of SOPs from water, low-cost biosorbents are thought to be a tempting replacement for traditional adsorbents. Higher adsorption capabilities, excellent modifiability and recyclability, vulnerability to harmful compounds, and ease of use in the treatment strategies are only a few benefits of these substances.36 Different methods have been developed to decompose emerging pollutants using a variety of integrated approaches through advanced biomaterials. It is beginning to receive critical attention to produce new composite biomaterials for cleaning the contaminated environment by utilizing the biophysical characteristics of the materials and the digestion of microbes.37 The most commonly used biomaterials for the removal of pesticides in water are cellulose,38 chitin,39 chitosan,40 lignocelluloses,41 and biomasses of animals and birds.42 Microbes are also utilized to obtain biomaterials to find their applications in waste management for the degradation of pesticides. Fungi and bacteria are the more effective source to get biomaterial for the treatment of water because their life cycle is short and they can produce a bulk of biomaterials for use at a commercial scale to bioremediate pesticides and other contaminants present in water.43,44 Moreover, different functional groups present in biomaterial react with pesticide to trap or adsorb it on their surface to remove them from waterbodies. For example, it has been reported

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that functional groups present in lignocellulose remove the pesticide from water.45 Dehaghi et al. removed permethrin pesticide from contaminated water. They utilized an adsorbent made up of chitosan and ZnO nanoparticles. This adsorbent composite proved to be very effective for the removal of pesticides from water.46 Lignin which is an important component of humic substances and plant material has a significant impact on how organic pollutants are transported through the ecosystem because of its exceptional affinity for pesticides.47 Boudesocque et al. studied the effect of lignocellulosic substrate (LS) on the adsorption of pesticides and their subsequent removal from water. LS was obtained from agro-industries where it was a byproduct. The retention capacity of adsorbents made up of lignocellulosic material was observed for four distinct kinds of pesticides. The batch and column methods were employed to check its capacity. The process was conducted to check the condition of pH and concentration gradient of insecticide at the lab and commercial levels. The pesticides were examined at concentrations ranging from 2
107 to 3
104 mol/L. The retention of insecticide in the vicinity of copper(II) and an emulsifier was studied to evaluate the impact of inorganic and organic contaminants. These experiments suggested that LS had no effect on other contaminants and was an effective agent for the herbicides under investigation. These retention capabilities demonstrate that LS potentially offers a quick, efficient, and affordable way to remove insecticides from industrial wastewaters. This biopolymer could therefore help purify contaminated water.48

3. Synthesis of biomaterials for pesticide removal Biomaterials can be synthesized artificially, or they can be extracted from microorganisms and plants. Sarvanthi et al. reported synthesis of zerovalent iron nanoparticles extract of Calotropis gigantea flowers having excellent potential for decontamination of water. They cut the flower into fine pieces, ground it, and boiled it for five minutes. Boiled material was filtered using Whatman filter paper no. 1 to remove unwanted substances. Extract of the flower was mixed with ferric nitrate nonahydrate with a ratio of 1:1, change in color from pink to black indicated the formation of zerovalent iron nanoparticles. The product was washed with ethanol and water and then dried at 60 °C. They proved that these particles are effective in the decontamination of water by decolorization of methylene blue and aniline removal.49

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Phosphorus is the main component of pesticides and its presence in a normal range is good but exceeding phosphorus from 2 μM is the cause of eutrophication in water bodies. For effective removal of phosphorus from water bodies, Chen et al. synthesized ceramic biomaterials from scallop shell. They mixed scallop shells, montmorillonite, and starch and homogenized them. Then they added distilled water to the mixture and initiated the granulation process artificially. The product was in grey and spherical shape. They experimented with its potential to remove phosphate from water by using it on sodium phosphate and an excellent result was obtained.50 Naphthalene due to its characteristic odor is used as a fumigant insecticide and it is released into water bodies due to excessive use. Biosynthesis of gold and copper nanoparticles from different plant extracts has been presented as an efficient technique to decontaminate water containing naphthalene. Abbas et al. used Aloe barbedensis and Azadirachta indica extract as a precursor to synthesize gold and copper nanoparticles.51 Carbofuran is used to control insects and protect crops from them similarly iprodione is an excellent fungicide to control different crop diseases. Due to excessive use, leaching, and runoff from applied fields, these two chemicals are being reported in groundwater and other water bodies causing harmful effects for human beings in particular and the environment in general.52,53 Recently, Toledo-jaldin et al. employed magnetic composites developed from sugarcane bagasse and peanut shells to remove carbofuran and iprodione from ground and surface water to make it less harmful to living organisms. They coprecipitated sugarcane bagasse and peanut shells with ferric chloride and ferrous chloride in a nitrogen atmosphere. Drops of sodium hydroxide were added to the coprecipitated substance and the formation of the product was indicated by a color change from orange to black, and the product was stored until use for adsorption of carbofuran and iprodione from the surface and groundwater.54

4. How are biomaterials efficient for water treatment? There are a lot of conventional methods for the treatment of pesticides contaminated water which include reverse osmosis, chemical precipitation, ion exchange, activated carbon adsorption, coagulation and flocculation, flotation, and membrane filtration. These all methods have their shortcomings such as in reverse osmosis membrane is clogged and is costly,55 in chemical precipitation large volume of sludge is produced and toxic compounds are released,56 and employment of activated carbon adsorption is corrosive

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and abrasive,57 application of ion exchange process is costly and only certain ions can be removed,55 while we use flocculant and coagulants large volumes of sludge is produced and a large number of chemicals are consumed58 and membrane filtration is a low-speed process with poor selectivity and highly expensive.59 Considering the shortcomings of conventional methods, there is urgent need of development of biomaterial-based methods to overcome problem of pesticides presence in water bodies. In previous parts, we explained beneficial perspectives of biomaterials in water bioremediation and removal of pesticides. They are eco-friendly, cost-effective, less toxic, easy to handle and employ, high selectivity, and long-term useable.

5. Removal of pesticides from water Numerous hydrophilic chemicals that can pollute water can also effectively contaminate topsoil and form strong bonds with the various soil constituents. Groundwater contains a variety of pesticides, herbicides, and soil fertilizers. In theory, a different class of pesticides with a label as possible groundwater pollutants may enter groundwater if their aqueous solubility was greater than 3 mg/L.60 Using biomaterials like cellulose or chitosan that may decrease, complicate, and/or sequester harmful chemicals, biomonitoring techniques may be capable of removing water contaminated by highly soluble organic compounds. Innumerable fungi possess natural carbohydrates in their cell walls, including chitin or cellulose. The texture of polysaccharides plays an important role in biosorption, and physiological changes to these surfaces may improve their ability to combine both metallic ions and organic molecules.61 Saiano, Filippo, and Maurizio Ciofalo studied the degradation of pesticides from an aqueous solution. They used the biomass obtained by boiling the mycelium of ascomycetes fungi using NaOH to remove the pesticide from water. Oxadixyl was used as a model of aqueous organic contamination that can get dissolved in water in the range of 3400 mg/L. It was shown that the new, inexpensive material could retrieve approximately 6 mg of oxadixyl per gram of sorbents. The results of the experiment and the Langmuir adsorption isotherm model exhibited a remarkable correlation.61 Moringa oleifera, whose seeds have indeed been employed as coagulants and adsorbents for contaminants in water pollution management, is one of the many interesting cost-effective materials that can be utilized to create a biosorbent. Because new methods are required to remove insecticides from the aquatic systems, Bezerra et al. examined the M. oleifera seed hulls

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(h-MO) at ambient temperature and varying solute contents to adsorb diuron from polluted water. Biochemical, morphological, and textural investigations were employed to characterize the bio-adsorbent that was used in this study. The procedure of this experiment is illustrated in Fig. 2. By comparing the weight of the adsorbent material and the pH solution, the ideal experimental setting to bio-adsorb the pesticide was identified. The sorption of the h-MO was discovered to be significantly higher than the capacities of other biological adsorbents when it was tried compared to other sorbent materials that had previously been used to remove diuron from polluted water.62 Atrazine herbicides like trizine are employed for weed suppression because of their effective eradicating properties and affordable price. Because of its stable composition, challenging decomposition, prolonged environmental residence, and toxic effects on both organisms and people, the investigation of atrazine elimination from the ecosystem is important.

Fig. 2 The use of h-MO for the removal of Diuron from wastewater. @Reprinted from Bezerra CDO et al. Assessment of the use of Moringa oleifera seed husks for removal of pesticide diuron from contaminated water. Environ Technol 2020;41(2):191–201.

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As a result, many processing technologies, including sorption, photocatalytic analysis, bioremediation, and others, have been discovered and are frequently used for atrazine disposal.63,64 To eliminate atrazine, Zhao et al. studied the pyrolysis process of corn stem into biochar. They discovered that this activated carbon had a strong capability for atrazine adsorption and that its adsorption efficiency was improved after being treated with ammonium dihydrogen phosphate.65

5.1 Role of plant biomaterials in pesticides management Plants employ a wide variety of techniques in the phytoremediation of heavy metals from pesticides which include rhizo-filtration, phytoextraction, phytostabilization, phytovolatilization, and phytotransformation. In rhizofiltration, aquatic plants absorb heavy metals through roots,66 in phytoextraction metals are stored in plant tissues and then plants are removed,67 in phytostabilization metals are stabilized by roots resulting in less availability,49 in phytovolatilization, volatile metals (Hg, Se) are evaporated from leaves surface68 and phytotransformation absorbed organic materials are degraded through enzymes in plant body.69 Plants uptake metal through roots and then transport them into various parts of the body. These metals move in the form of ions in the plant body. These heavy metals sourced from pesticides can be stored in shoots for a long time. Some contaminants are volatilized by different reactions, and they are evaporated from the surface of leaves. Plants detoxify contaminants by transforming them into plant tissues using enzymes, contaminants are detoxified and these tissues can be leaves or any other tissues.32 Lv et al. developed a method in which they used the plant to remove tebuconazole in a water solution. They planted these species in pots with a mixture of sand and commercial potting substance for a few days. Then they incubated these plants in hydroponic solution for almost 10 days. A sample of tebuconazole was prepared using a syringe of 20 mL for injection in solution. At the start, pH was 8.5 and on the 24th day, pH was reduced to 4.2, showing a change in hydrogen ion concentration of the solution. This was 24 days experiment in which effusus removed tebuconazole from water with 41% efficiency. This is a comparably good result touching the threshold of statistical significance. Chemical was absorbed through roots and translocated through shoots as its concentration in roots and shoots indicated. Tebuconazole was present in the planted system, with 14–26% of that sample being fed to plants through roots which means the whole concentration

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of chemicals was not being absorbed. The translocation factor of tebuconazole was about 2.2 which means it moved slowly through shoots and take time to reach the whole plant while in roots, the concentration factor was the excellent value of 58 which indicate the effectiveness of root of effusus in absorbing tebuconazole and presenting itself as an excellent decontamination agent. The reported accumulation capacity of the plant for tebuconazole is 720 μg g1 which is an excellent indicator in a study where enantioselectivity is also being evaluated. The lower value of the translocation factor indicates that this plant not only absorbs this chemical but also metabolizes it. Removal of pesticides from water using wetland plants has produced comparable results as provided in Table 1 and more research in this field needs to be carried out.33 Table 1 Summary of plant species used in phytoremediation of pesticides with their accumulation capacity. Plants Active chemicals of pesticide Capacity Reference

Hydrilla verticillata

Chlordane

1060.95 μg L1 70

Pistia stratiotes

Chlorpyrifos

0.036 mg g1

Typha latifolia

Dieldrin

Ceratophyllum submersum Aldrin

Lemna minor

Plantago major

0.60 ng g 0.38 ng g

1

72

1

72

1

Endosulfan

0.73 ng g

Flazasulfuron

27 μg g1

73

1

Dimethomorph

33 μg g

Chlorpyrifos

0.23 g1

Cyanophos

76.91 μg g1

Imidacloprid

37.21 μg g

1 1

Azoxystrobin

20.62 mg kg

Carbosulfan

9.47 mg kg1

Chlorpyrifos

71

36.86 μg g

1

1

74 75 76 77 78

Rumex dentatus

Carbosulfan

9.5 mg kg

Helianthus annus

Azoxystrobin

18.29 mg kg1 76

Glycine max

Azoxystrobin

25.32 mg kg1 76

Eleocharis mutala

Imidacloprid

13.51 μg g1

Jancus effusus

Tebuconazole

720 μg g

1

77

79 33

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In most developed methods for the removal of contaminants from water such as pesticides and industrial waste, the adsorption technique is being used.80–82 In adsorption of carbofuran and iprodione, sugarcane bagasse and peanut shell magnetic composite has been used. These two materials are easily available, cheap and have no toxicity. Composite was added in pesticide solution at room temperature and pH was kept almost neutral during the whole experiment. Reaction achieved equilibrium in 8–12 h and after that reaction was continuous and absorption was at a steady rate. By Langmuir isotherm, it was calculated that removal capacities of the composite containing sugarcane bagasse and peanut shell for carbofuran and iprodione were 47.4–95.5 and 2.16–25.5 mg/g respectively, and these indicate an excellent capacity to absorb with a commercial feature. The surface was made up of two materials therefore it was heterogenous and it produced a steady rate of removal of mentioned chemicals present in pesticides.41

5.2 Effectiveness of bird biomaterial waste in pesticide control in water Eggshells are discarded as waste material since they are a type of food that is consumed in enormous amounts by households, cafes, and food manufacturers. Since they are natural and have the potential to enhance the economy, solid wastes are now valued by all.83 Eggshell is a naturally occurring substance that comprises more than 95% calcium carbonate (CaCO3).84 Because of its high porosity, eggshell has recently been the topic of a variety of fascinating research. Many years ago, there had been a significant amount of interest in the utilization of biodegradable material, such as eggshells, to shield the ecosystem from contaminants.85,86 Insecticides particularly contribute substantially to environmental degradation in agribusiness, which is a global issue. Kınayt€ urk and some other researchers studied the sorption ability of the eggshell surface to remove the pesticide from wastewater. They used the eggshell of five different birds to remove the three most commonly used insecticides from water and the environment. They used UV/FTIR, Atomic force spectroscopy (AFM), and some other techniques to estimate the amount of pesticide which was removed by eggshell. AFM pictures were used to analyze the interactive effects of pesticides on eggshell surfaces, and it was discovered that the eggshells’ semi-circular surface structures had become squashed upon sorption. The impact of adsorption was determined as well as morphological examination using FTIR spectroscopy. Both adsorption and desorption processes were also evaluated using UV–vis spectroscopy. The interface of perforated media made of several kinds of eggshells and an aqueous pesticide solution was due to electronegativity interactive surface, making it the perfect

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adsorbent due to the hydroxyl groups. Eggshell is a readily available waste product. This study demonstrated the potential of discarded eggshells as an eco-friendly adsorbent.87 Eggshell is an effective adsorbent because of the membrane’s permeability and surface composition, which enable it to eliminate lethal metals, phenolic content, dyes, and herbicides from effluent. Pettinato et al. utilized the eggshell waste material to remove pesticide and heavy metals from water. They observed that the use of these materials to adsorb contaminants from sewage by adjusting the additional settler of membrane enhances the efficacy of membrane biological reactor (MBR). Wastewater purification process became 100% effective using eggshell waste as adsorbent.88 The different approaches used for the utilization of eggshell biomaterial as adsorbent for the removal of pesticides and heavy metals are illustrated in Fig. 3.

5.3 Fungi biomaterials for the remediation of pesticides in water Chitin is present in fungi in the range of 2–42% and it is used to produce biopolymer chitosan. Its percentage yield varies with species, environment, and pan of culture.89 2,4-Dichlorophenoxyacetic acid (2,4-D) is an excellent herbicide that kills broadleaf weeds, but its excessive use causes its runoff into nearby water bodies or ground water resulting in pollution of water. Chitosan has been used to remove this herbicide chemical from water through biosorption. Nunes et al. prepared an aqueous solution of 2,4-D

Fig. 3 Graphical representation of different methods for the removal of pesticides from water by using egg shell waste biomaterial.87,88

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and they suspended 50 mg chitosan in that aqueous solution of 2,4-D at varying concertation from zero to 1
105 at 1.0
104 mol L1. They measured adsorbed herbicide by a difference in the amount of herbicide in chitosan and that in water solution using a UV/vis spectrometer. Results showed adsorption of 2,4-D as a function of pH and maximum adsorption occurs at pH ¼ 1.8, and at this pH, the surface of chitosan is highly protonated which enhances the interaction of adsorbent and adsorbate. Results support the assumption of an acidic environment favors adsorption of 2,4-D ion chitosan is correct.80

6. Future perspective The remediation of pesticides by the new biomaterials exhibits outstanding performance and excellent tolerability and represents a new area of investigation in the field of pesticide management in water. But it has flaws in itself. For instance, the biomaterial’s preparation procedure may harm the microbial performance and the immobilized medium is readily destroyed, which causes the destruction of materials and bacteria and several other issues. Future directions for the technology include addressing these problems, creating moderate processing conditions, choosing the best trapping media, and creating new biomaterials that have a minimal environmental impact and are recyclable. The excellent adsorption capabilities, effectiveness, simplicity of reconfiguration, and affordability of biomaterial showed that low-cost bio sorbents made from biomass obtained from different biological resources have a high capacity to remove organic pesticide residues, and herbicides from water. The type of contaminants, their characterization, and the procedures used to make the adsorbents all affect the adsorption processes and capabilities to remove the pesticide from water. Selectivity of appropriate biomaterial and modifying approaches are therefore essential and require additional consideration. Additionally, this research aids in making recommendations for future studies in the area of reducing organic pollutants in aquatic environments.

7. Conclusions Pesticides are a commonly used class of agrochemicals that are widely employed to incapacitate crop-harming pests. Moreover, they are important for agribusiness as well as to cope with the increasing demand for food due to

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the increase in population. Unfortunately, alongside the productive outcomes of pesticides, they are of grave concern due to their health hazards, especially in water bodies. The use of eco-friendly and low-cost methods is highly in demand therefore biotransformation and bioremediation are of prime importance. This chapter is a thorough study of recent biomaterials utilized for the effective removal of pesticides from water bodies including their synthesis, mechanism, and good selectivity. As discussed, aquatic plants and fungal-based materials are among the excellent choices as biomaterials. Moreover, plant and fungal enzymatic systems have been discussed to understand their potential to remove pesticides effectively from water bodies.

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18. Intisar A, et al. Occurrence, toxic effects, and mitigation of pesticides as emerging environmental pollutants using robust nanomaterials—a review. Chemosphere 2022;293:133538. 19. Jayaraj R, Megha P, Sreedev P, Article R. Organochlorine pesticides, their toxic effects on living organisms and their fate in the environment. Interdiscip Toxicol 2016;9 (3–4):90–100. 20. Jit S, et al. Evaluation of hexachlorocyclohexane contamination from the last lindane production plant operating in India. Environ Sci Pollut Res 2011;18(4):586–97. 21. Remucal CK. The role of indirect photochemical degradation in the environmental fate of pesticides: a review. Environ Sci Process Impacts 2014;16(4):628–53. 22. Rajmohan K, Chandrasekaran R, Varjani S. A review on occurrence of pesticides in environment and current technologies for their remediation and management. Indian J Microbiol 2020;60(2):125–38. 23. Wu L, et al. Isotope fractionation approach to characterize the reactive transport processes governing the fate of hexachlorocyclohexanes at a contaminated site in India. Environ Int 2019;132:105036. 24. Limaye A, et al. Modulation of signal transduction pathways in lymphocytes due to sub-lethal toxicity of chlorinated phenol. Toxicol Lett 2008;179(1):23–8. 25. Yilmaz B, et al. Endocrine disrupting chemicals: exposure, effects on human health, mechanism of action, models for testing and strategies for prevention. Rev Endocr Metab Disord 2020;21(1):127–47. 26. Biswal T, BadJena SK, Pradhan D. Sustainable biomaterials and their applications: a short review. Mater Today Proc 2020;30:274–82. 27. Ray SS, Iroegbu AOC. Nanocellulosics: benign, sustainable, and ubiquitous biomaterials for water remediation. ACS Omega 2021;6(7):4511–26. 28. Bajaj A, et al. Isolation and characterization of a novel Gram-negative bacterium Chromobacterium alkanivorans sp. nov., strain IITR-71T degrading halogenated alkanes. Int J Syst Evol Microbiol 2016;66(12):5228–35. 29. Manickam N, et al. Bacillus mesophilum sp. nov., strain IITR-54T, a novel 4-chlorobiphenyl dechlorinating bacterium. Arch Microbiol 2014;196(7):517–23. 30. Kwon G-S, et al. Biodegradation of the organochlorine insecticide, endosulfan, and the toxic metabolite, endosulfan sulfate, by Klebsiella oxytoca KE-8. Appl Microbiol Biotechnol 2005;67(6):845–50. 31. Gaur VK, et al. Rhamnolipid from a Lysinibacillus sphaericus strain IITR51 and its potential application for dissolution of hydrophobic pesticides. Bioresour Technol 2019;272:19–25. 32. Anand S, et al. Phytoremediation of heavy metals and pesticides present in water using aquatic macrophytes. Phyto and Rhizo Remediation 2019;89–119. 33. Lv T, et al. Phytoremediation of imazalil and tebuconazole by four emergent wetland plant species in hydroponic medium. Chemosphere 2016;148:459–66. 34. Wang Q, et al. Phytoremediation of chlorpyrifos in aqueous system by riverine macrophyte, Acorus calamus: toxicity and removal rate. Environ Sci Pollut Res 2016;23 (16):16241–8. 35. Li Z, et al. A comparison on the phytoremediation ability of triazophos by different macrophytes. J Environ Sci 2014;26(2):315–22. 36. Ngo HH, et al. Typical low cost biosorbents for adsorptive removal of specific organic pollutants from water. Bioresour Technol 2015;182:353–63. 37. Gao Q, Wong YS, Tam N. Removal and biodegradation of nonylphenol by immobilized Chlorella vulgaris. Bioresour Technol 2011;102(22):10230–8. 38. Rana AK, et al. Sustainable materials in the removal of pesticides from contaminated water: perspective on macro to nanoscale cellulose. Sci Total Environ 2021;797, 149129. 39. Rissouli L, et al. Decontamination of water polluted with pesticide using biopolymers: adsorption of glyphosate by chitin and chitosan. J Mater Environ Sci 2017;8:4544–9.

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40. Saifuddin N, et al. Chitosan-silver nanoparticles composite as point-of-use drinking water filtration system for household to remove pesticides in water. Asian J Biochem 2011;6(2):142–59. 41. Mohammad SG, et al. Porous activated carbon from lignocellulosic agricultural waste for the removal of acetampirid pesticide from aqueous solutions. Molecules 2020;25 (10):2339. 42. Kochi LY, et al. Aquatic macrophytes in constructed wetlands: a fight against water pollution. Sustain For 2020;12(21):9202. 43. Hai FI, et al. Pesticide removal by a mixed culture of bacteria and white-rot fungi. J Taiwan Inst Chem Eng 2012;43(3):459–62. 44. Khan AG. Role of soil microbes in the rhizospheres of plants growing on trace metal contaminated soils in phytoremediation. J Trace Elem Med Biol 2005;18(4):355–64. 45. Mohammad SG. Biosorption of pesticide onto a low cost carbon produced from apricot stone (Prunus armeniaca): equilibrium, kinetic and thermodynamic studies. J Appl Sci Res 2013;9(13):6459–69. 46. Dehaghi SM, et al. Removal of permethrin pesticide from water by chitosan–zinc oxide nanoparticles composite as an adsorbent. J Saudi Chem Soc 2014;18(4):348–55. 47. Beulke S, et al. Evaluation of simplifying assumptions on pesticide degradation in soil. J Environ Qual 2005;34(6):1933–43. 48. Boudesocque S, et al. Use of a low-cost biosorbent to remove pesticides from wastewater. J Environ Qual 2008;37(2):631–8. 49. Sravanthi K, Ayodhya D, Yadgiri Swamy P. Green synthesis, characterization of biomaterial-supported zero-valent iron nanoparticles for contaminated water treatment. J Anal Sci Technol 2018;9(1):1–11. 50. Chen N, et al. Removal of phosphorus from water using scallop shell synthesized ceramic biomaterials. Environ Earth Sci 2014;71(5):2133–42. 51. Abbas S, et al. Synhesis of silver and copper nanoparticles from plants and application as adsorbents for naphthalene decontamination. Saudi J Biol Sci 2020;27(4):1016–23. 52. Roudani A, et al. Removal of carbofuran pesticide from aqueous solution by adsorption onto animal bone meal as new low cost adsorbent. Chem Process Eng Res 2014;28:2014. 53. Garbin JR, et al. Influence of humic substances on the photolysis of aqueous pesticide residues. Chemosphere 2007;66(9):1692–8. 54. Toledo-Jaldin HP, et al. Low-cost sugarcane bagasse and peanut shell magneticcomposites applied in the removal of carbofuran and iprodione pesticides. Environ Sci Pollut Res 2020;27(8):7872–85. 55. Singh A, Kumar CS, Agarwal A. Phytotoxicity of cadmium and lead in Hydrilla verticillata (lf ) royle. J Phytology 2011;3(8). 56. Aziz HA, Adlan MN, Ariffin KS. Heavy metals (Cd, Pb, Zn, Ni, Cu and Cr (III)) removal from water in Malaysia: post treatment by high quality limestone. Bioresour Technol 2008;99(6):1578–83. 57. Sivakumar V, Asaithambi M, Sivakumar P. Physico-chemical and adsorption studies of activated carbon from agricultural wastes. Adv Appl Sci Res 2012;3(1):219–26. 58. Fu F, Wang Q. Removal of heavy metal ions from wastewaters: a review. J Environ Manag 2011;92(3):407–18. 59. Qin J-J, Oo MH, Kekre KA. Nanofiltration for recovering wastewater from a specific dyeing facility. Sep Purif Technol 2007;56(2):199–203. 60. Barbash JE, Resek EA. Pesticides in ground water: distribution, trends, and governing factors. Ann Arbor Press; 1996. 61. Russell AJ, et al. Biomaterials for mediation of chemical and biological warfare agents. Annu Rev Biomed Eng 2003;5(1):1–27. 62. Bezerra CDO, et al. Assessment of the use of Moringa oleifera seed husks for removal of pesticide diuron from contaminated water. Environ Technol 2020;41(2):191–201.

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63. Graymore M, Stagnitti F, Allinson G. Impacts of atrazine in aquatic ecosystems. Environ Int 2001;26(7–8):483–95. 64. Fan X, Song F. Bioremediation of atrazine: recent advances and promises. J Soils Sediments 2014;14(10):1727–37. 65. Zhao X, et al. Properties comparison of biochars from corn straw with different pretreatment and sorption behaviour of atrazine. Bioresour Technol 2013;147:338–44. 66. Rawat K, Fulekar M, Pathak B. Rhizofiltration: a green technology for remediation of heavy metals. Intl J Inno Biosci 2012;2(4):193–9. 67. Thakur S, et al. Plant-driven removal of heavy metals from soil: uptake, translocation, tolerance mechanism, challenges, and future perspectives. Environ Monit Assess 2016;188 (4):1–11. 68. Sharma S, Singh B, Manchanda V. Phytoremediation: role of terrestrial plants and aquatic macrophytes in the remediation of radionuclides and heavy metal contaminated soil and water. Environ Sci Pollut Res 2015;22(2):946–62. 69. Cac¸ador I, Duarte B. Chromium phyto-transformation in salt marshes: the role of halophytes. In: Phytoremediation. Springer; 2015. p. 211–7. 70. Chaudhry Q, et al. Prospects and limitations of phytoremediation for the removal of persistent pesticides in the environment. Environ Sci Pollut Res 2002;9(1):4–17. 71. Prasertsup P, Ariyakanon N. Removal of chlorpyrifos by water lettuce (Pistia stratiotes L.) and duckweed (Lemna minor L.). Int J Phytoremediation 2011;13(4):383–95. 72. Guo W, Zhang H, Huo S. Organochlorine pesticides in aquatic hydrophyte tissues and surrounding sediments in Baiyangdian wetland, China. Ecol Eng 2014;67:150–5. 73. Rachel D, Michel C, Philippe E. Phytoremediation of fungicides by aquatic macrophytes: toxicity and removal ratio. Ecotoxicol Environ Saf 2009;72(8):2096–101. 74. Romeh AA. Phytoremediation of cyanophos insecticide by Plantago major L. in water. J Environ Health Sci Eng 2014;12(1):1–8. 75. Romeh A. Phytoremediation of water and soil contaminated with imidacloprid pesticide by Plantago major L. Int J Phytoremediation 2009;12(2):188–99. 76. Romeh A. Evaluation of the phytoremediation potential of three plant species for azoxystrobin-contaminated soil. Int J Environ Sci Technol 2015;12(11):3509–18. 77. Romeh AA. Efficiency of Rumex dentatus L. leaves extract for enhancing phytoremediation of Plantago major L. in soil contaminated by carbosulfan. Soil Sediment Contam Int J 2016;25(8):941–56. 78. Romeh AA, Hendawi MY. Chlorpyrifos insecticide uptake by plantain from polluted water and soil. Environ Chem Lett 2013;11(2):163–70. 79. Mahabali S, Spanoghe P. Mitigation of two insecticides by wetland plants: feasibility study for the treatment of agricultural runoff in Suriname (South America). Water Air Soil Pollut 2014;225(1):1–12. 80. Nunes AR, Arau´jo KR, Moura AO. 2,4-Dichlorophenoxyactic acid herbicide removal from water using chitosan. Res Chem Intermed 2019;45(2):315–32. 81. Zhang L, Zeng Y, Cheng Z. Removal of heavy metal ions using chitosan and modified chitosan: a review. J Mol Liq 2016;214:175–91. 82. Qamar SA, et al. Chitosan-based hybrid materials as adsorbents for textile dyes—a review. Case Stud Chem Environ Eng 2020;2, 100021. 83. Carvalho J, Arau´jo J, Castro F. Alternative low-cost adsorbent for water and wastewater decontamination derived from eggshell waste: an overview. Waste Biomass Valorization 2011;2(2):157–67. 84. Owuamanam S, Cree D. Progress of bio-calcium carbonate waste eggshell and seashell fillers in polymer composites: a review. J Compos Sci 2020;4(2):70. 85. Onwubu SC, et al. An in situ evaluation of the protective effect of nano eggshell/ titanium dioxide against erosive acids. Int J Dent 2018;2018.

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86. Chen J, et al. Synthesis of hydroxyapatite nanorods from abalone shells via hydrothermal solid-state conversion. Mater Des 2015;87:445–9. 87. Kınayt€ urk NK, Tunalı B, T€ urk€ oz Altug D. Eggshell as a biomaterial can have a sorption capability on its surface: a spectroscopic research. R Soc Open Sci 2021;8(6):210100. 88. Pettinato, M., Chakraborty, S., Arafat, H. A., & Calabro, V., Eggshell: a green adsorbent for heavy metal removal in an MBR system. Ecotoxicol Environ Saf, 2015 121, 57–62 Ecotoxicol Environ Saf 2015;121:57–62. 89. Abo Elsoud MM, El Kady E. Current trends in fungal biosynthesis of chitin and chitosan. Bull Natl Res Centre 2019;43(1):1–12.

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CHAPTER NINE

Microalgae mediated wastewater treatment and its production for biofuels and bioproducts Sandeep Kumar Singha,* , Livleen Shuklaa, Rahul Prasad Singhb, Priya Yadavb, and Ajay Kumarc a

Division of Microbiology, ICAR-Indian Agricultural Research Institute, Pusa, New Delhi, India Laboratory of Algal Research, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India c Department of Botany, Banaras Hindu University, Varanasi, India *Corresponding author: e-mail address: [email protected] b

Contents 1. 2. 3. 4. 5.

Introduction Microalgae Microalgae uses in phycoremediation technology Advantages of phycoremediation Cultivation methods of microalgae 5.1 Hybrid system 5.2 Open cultivation method 5.3 Closed cultivation method 6. Harvesting method 6.1 Biological method of harvesting 6.2 Mechanical harvesting 6.3 Magnetic and electrical harvesting methods 6.4 Chemical methods of harvesting 7. Economic challenges 8. Utilization of wastewater generated microalgal biomass for biofuel production 9. Market trend of microalgae-based wastewater treatment 10. Socio-economic and environmental aspects associated with integrated algae refinery 11. Conclusion References

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Abstract Depletion of fossil has shifted focus of researchers toward biofuels. Crops and vegetable oils have not been able to meet the demand of rising population but microalgae have proved to be major producer of biofuel.1 Microalgae are photolithoautotroph comprising of prokaryotic cyanobacteria and eukaryotic green algae, due to their eco-friendly Advances in Chemical Pollution, Environmental Management and Protection, Volume 9 Copyright # 2023 Elsevier Inc. 153 ISSN 2468-9289 All rights reserved. https://doi.org/10.1016/bs.apmp.2022.10.007

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nature, easily grown on arable land which make them suitable to produce biofuel.2,3 Due to generation of biomass they are also subjected to anaerobic digestion to produce biogas. Microalgal biomass is also suited to produce different bio based products, e.g., fertilizers, biomethanol, biochar etc. Keywords: Microalgae, Biofuels, Phycoremediation, Cultivation, Harvesting

1. Introduction Depletion of fossil has shifted focus of researchers toward biofuels. Crops and vegetable oils have not been able to meet the demand of rising population but microalgae have proved to be major producer of biofuel.1 Microalgae are photolithoautotroph comprising of prokaryotic cyanobacteria and eukaryotic green algae, due to their eco-friendly nature, easily grown on arable land which make them suitable to produce biofuel.2,3 Due to generation of biomass they are also subjected to anaerobic digestion to produce biogas. Microalgal biomass is also suited to produce different bio based products, e.g., fertilizers, biomethanol, biochar etc. Major demerit which affects production of high value product is the harvesting cost, hence suitable cultivation and harvestation method is required to generate high biomass.4,5 Wastewater generation is another global concern which leads to eutrophication due to excessive liberation of nutrients in fresh water, which significantly affects flora and fauna of aquatic ecosystem.6 There are various physical and chemical methods are applied to treat wastewater but they have proved to be costly, labor intensive etc. Due to inefficiency of both aforesaid methods microalgae outclass both the methods as they are cost effective, eco-friendly, non-toxic etc., which further helps in nutrient recovery from wastewater which help them to produce biomass which can processed to produce different products, i.e., fertilizers, bioenergy, biochar etc.

2. Microalgae It has been discovered that algae, which are photosynthetic organisms and may be further subdivided into microalgae, cyanobacteria, and macroalgae, are a rich source for the manufacture of biofuels and a variety of other chemicals. They are able to cultivate in several types of water, including freshwater, seawater, brackish water, and even wastewater. In their natural state, microalgae are autotrophic, which means that they are able to produce

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their own nutrition by assembling simple inorganic chemicals. It is believed that there are between 200,000,800,000 different types of algae. Up to 50,000 different species of algae have been discovered up to this point for a variety of applications, including the generation of biofuels and the treatment of wastewater.7 It has been discovered that microalgae are very useful in the process of sequestration of Carbon dioxide from the atmosphere. Microalgae are frequently referred to produce variety of biofuels, pharmaceutically and industrially important products. During the cultivation process, they are able to thrive in a broad variety of environmental circumstances, such as pH, salinities, temperatures, and varying amounts of light intensity. They are capable of growing on their own or in a mutually beneficial relationship with other microbes like bacteria and fungus. Microalgae are photolithoautotrophs which are similar to plants but lack cellular structure as terrestrial plants. These organisms may be found in both freshwater and saltwater environments. In the presence of light, whether natural or artificial, they undergo a process of photosynthesis that is extremely similar to that of plants. They can generate substantial amount of different industrially important biomolecules. The physiology of algae, the rate at which they develop, as well as the elements that make up their cells are all affected by environmental conditions such as temperature, light (intensity, time, and color), salinity, pH, concentration of nutrients, and concentration of oxygen and carbon dioxide.

3. Microalgae uses in phycoremediation technology The process of phytoremediation is dependent on the characteristics of microalgae, which include their photosynthetic nature and their capacity to extract both carbon and energy from the sun. The fundamental presumption behind phycoremediation status as a safe biotechnology is that microalgae will convert a small number of components into harmless chemicals, hence enabling wastewater to be cleaned, reused, or disposed of in a secure manner.8 These microalgae are also referred to as harmful algal blooms and cause a variety of issues in the environment in which aquaculture takes place.9 As a result, the microalgal strains that are utilized in the process of phycoremediation need to not cause any diseases. Other aspects, such as the wastewater nutrient content, competition between external organisms and the organisms that are native to the area, need to be taken into consideration before using microorganisms, including microalgae, in the treatment of

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wastewater. Many microalgae, including cyanobacteria, diatoms, and prymnesiophytes, cause issues in the aquaculture industry and should not be employed in phycoremediation technology. Microalgae have the ability to adjust their growth to accommodate a wide range of environmental circumstances, and they may survive for a longer time. It’s because of their potential to produce cysts, which, when exposed to unfavorable conditions, can remain in a dormant state for an extended period of time. It is necessary for their growth that a supply of nitrogen and trace elements be available. Since wastewaters include a high concentration of contaminants, the utilization of microalgae for remediation to treat wastewater which is used to reduce pollutants and production of biomass that is generated. Furthermore, algae species appear to be the perfect organisms for remediation investigations since they are simple to grow, adapt, and manipulate in a laboratory context. Chlorella sp. has recently seen a rise in popularity as a bioremediation and pollution control agent due to the fact that it has a rapid growth rate and is capable of removing a large quantity of both organic and inorganic components.10,11

4. Advantages of phycoremediation The capacity of microalgae to reproduce and grow in wastewater is the primary benefit of adopting technology based on microalgae. This ability increases the remediation efficiency in respect to other traditional methods. Process of phycoremediation may begin with the addition of a starter inoculum of microalgae. These microalgae thrive in wastewater because the water contains the nutrients necessary for their further development. Chemical treatment, on the other hand, utilizes chemical compounds which solubilizes various substances present in. One of the benefits of phycoremediation technology efficient utilization of metabolic machinery of microalgae to reduce toxicity of pollutants and transform various compounds of wastewater to high value products.10 Theoretically, the best way to treat wastewater would be to use a natural process that doesn’t create toxic byproducts or add chemicals, and it would also have to be able to get rid of a wide range of difficult contaminants at the same time.12 The above aforesaid potential of microalgae holds merit over conventional methods to treat wastewater. In addition, the process of photosynthesis, which requires microalgae to consume CO2 from the atmosphere, is a significant contributor to the phenomenon of global warming.10,13

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5. Cultivation methods of microalgae As they can grow in less ideal conditions and thrive without the use of fertilizers, pesticides, or other chemical inputs, microalgae are quickly replacing traditional agricultural plants. There are variety of microalgae culture techniques available, and they may be easily grown in a variety of wastewater sources.

5.1 Hybrid system It is a combination of many distinct growing systems for the purpose of recovering resources from wastewater. Here, a photo bioreactor is combined to algal turf scrubber or open pond. This method not only serves to minimize the price tag associated with creating microalgae biomass, but it also maximizes the advantages of the integrated system. In the research carried out by Narala et al.14 a comparative analysis of various biomass cultivation methods was carried out. The researchers came to the conclusion that hybrid systems produced the greatest amount of biomass in comparison to photo bioreactors, open raceways, and algal turf scrubbers. By co-culturing Scenedesmus simris, Chlorella sorokiniana, Chlorella vulgaris, in a hybrid anaerobic baffled reactor and photo bioreactor, Khalekuzzaman et al.15 were able to successfully remove organic solids. Additionally, they were able to produce a significant amount of lipids by increasing the amount of lipids produced by 44%.

5.2 Open cultivation method When it comes to the mass cultivation of microalgae, this method is considered to be one of the more traditional and efficient approaches. Because it is simple to construct and cultivate while requiring a lower amount of energy, this type of cultivation system is generally favored for use on commercial grounds. This system is well equipped with paddles which helps in mixing of nutrients, provide sufficient CO2 and doesn’t allow microalgae to settle down. There is a considerable risk of microbial contamination during open culture, which most of the times doesn’t allow microalgae to grow. Another problems that are linked with open cultivation include evaporation and the preservation of temperature. Despite this, strategy is still favored since it has a cheap cost of production when it comes to the cultivation of microalgae.

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5.3 Closed cultivation method Microalgae are supplemented with nutrients as well as the desired growing conditions, such as autotrophy, heterotrophy, or mixotrophy, in photo bioreactors. Photo bioreactors provide ideal optimum growth condition, hence are used for closed cultivation system. Additionally, photo bioreactors can be designed according to need and installed in less space. In addition, the main advantage of photo bioreactors is that there is a low risk of contamination; nevertheless, the primary problem connected with them is the high expense of maintenance and cleaning, among other things. They are further broken down into categories based on the configurations that they use, such as bubble columns, airlifts, tubular reactors, and so on. At the industrial level, the most common types of bioreactors that are employed are airlift and bubble column reactors. Even so, they are constructed through materials such as glass, plastic, or acrylic, and furthermore, they are put to use in the manufacturing of high-value compounds that have important commercial applications. According to the findings of a study that was carried out and completed by Nugroho and Zhu,16 the high maintenance costs of photo bioreactors may be reduced by making use of low-cost materials for resource recovery, such as wastewater and energy saving pumps. Additionally, light penetrance is an issue that is linked with photo bioreactors. As a result, in order to alleviate this problem and other operational concerns, photo bioreactors should be constructed in such a manner that there is no obstruction in the generation of microalgal biomass. The scraping approach was used to extract the Chlorella vulgaris that grew in an algal biofilm bioreactor that they constructed. The bioreactor used wastewater from hog dung as its feedstock. Another problem that was caused by photo bioreactors was light penetration in relation to anaerobic digested wastewater. Chen et al.17 were able to tackle this problem by employing hollow fiber membranes, which prevented the entry of pollutants and led to the rupture of algal biofilm.

6. Harvesting method For commercial purposes, the microalgal biomass that has been formed during the treatment of wastewater has to be collected. There are a variety of ways, both conventional and modern, for harvesting microalgal biomass and some of them will be addressed below:

6.1 Biological method of harvesting It is accomplished through the secretion of an extracellular substance, which ultimately results in the harvesting of microalgae through wastewater.

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Studies have also supported biological method to harvest; for instance, poly-glutamic acid (PGA), which is secreted from Bacillus licheniformis to harvest Desmodesmus having flocculation efficiency of than 98%. Another study was also described, in which low molecular weight exopolysaccharide from Scenedesmus acuminatus was employed to collect the microalgae’s biomass. This reduces the cost of microalgae harvesting per metric tonne.18 In addition, Jiang et al.19 stated that bacteria and fungus are used as bioflocculants to harvest microalgae. In addition, it has been discovered that biopolymers are efficient bio-flocculants that may be obtained at a low cost.

6.2 Mechanical harvesting The most common techniques for harvesting microalgal biomass include auto-sedimentation, centrifugation, filtration, and others in which the biomass is allowed to settle to the bottom while clear liquid is retained at the top. This method has been around for a long time and has proven to be effective. Studies on auto-sedimentation have shown that it is difficult to harvest motile algae such as Euglena, but it is simple to harvest Scenedesmus and Spirulina.20 Floatation is another approach that may be used, and it is more successful than auto-sedimentation. In auto-sedimentation, aeration generates air bubbles, which leads to the transportation and separation of algal cells. Flotation can be accomplished in a number of ways, including the following: electrolytic flotation; ozonation-dispersed flotation (ODF), Foam flotation technique effectively utilized for efficient harvestation of microalgae with low consumption of energy, as described by Zhang and Zhang.21 Filtration is an additional ideal approach that takes use of the pressure differential that is delivered on both sides of the membrane. This method is used on an industrial scale without the risk of contamination, and many authors have stated that its utilization is prevalent in the industrial setting. Scenedesmus was discovered to be readily collected by employing polyvinylidene fluoride membrane with a pore size of 3 μm. Using a vacuum membrane with pores of 0.45 μm, Molino et al.22 conducted another trial that was similarly effective in harvesting Scenedesmus almeriensis. Even nanofibers are employed to gather microalgae biomass; however, this technique has limitations due to the fact that the nanofibers might be mechanically destroyed. The industrial sector is primarily dependent on centrifugation in order to extract high-value energy products. Although centrifugation is a technology for harvesting biomass that is both extremely successful and quick, it is not without drawbacks. It is both an expensive and an energy-intensive process.23

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6.3 Magnetic and electrical harvesting methods Both of these techniques of harvesting microalgae biomass are sophisticated approaches. In the electrical way of harvesting, the microalgae biomass clumps together as the negative charge carried by their surfaces migrates to the anode.24 Kim et al.25 provided further confirmation that an aluminum anode with regard to an Al-platinum electrode was successful in collecting microalgal biomass from Nannochloropsis, proving the validity of the previous investigation. In addition, the efficiency of harvesting can be further improved by optimizing the timing of polarity exchanges. In addition, it was shown that iron and aluminum electrodes are effective in the collection of Nannochloropsis biomass without having a major influence on the production of lipids.26

6.4 Chemical methods of harvesting This method uses different type of chemical flocculants and coagulants, and it is regarded as an extremely cost-effective approach.27 Due to the fact that the growing medium has same density as well as negative charge on the surface as that of microalgae, the microalgae will always be found in a scattered state. Caetano et al.28 concluded utilization of chitosan and calcium chloride doesn’t affect cell structure and they are also reliable to collect microalgae.

7. Economic challenges In spite of these benefits, the use of micro-algae for the treatment of wastewater is still hindered by a number of practical and economic problems, which would need to be overcome for the technology to achieve industrial use. The amount of energy that must be used throughout the cultivation process is one such obstacle. Microalgae cultivation, like traditional wastewater treatment operations, frequently employs aeration and pumping systems to produce turbulent flow that improves the exchange of O2 and CO2. A techno-economic study of the adoption of microalgal technology in the Arabian Gulf based on combined flu gas biofixation and wastewater treatment indicated a positive financial advantage for emerging economies that are not focused on the mining or production of mineral oil. It was stated that the break-even selling price (BESP) of the produced biocrude (usually the selling price of the product) was $0.544 per kg of biomass, which corresponds to $0.9 L 1 for the extracted biocrude. This price covers the operational expenditures (OPEX). In areas with an adequate amount of solar

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radiation, high rated algae ponds, also known as HRAPs, have been demonstrated to offer a significant amount of potential for the treatment of municipal wastewater. Energy generation from harvested algal biomass was reported at 800–1400 GJ/ha/year by another study that looked at the feasibility of using HRAP for wastewater treatment to create cheap biofuel.

8. Utilization of wastewater generated microalgal biomass for biofuel production Microalgae have attracted a lot of attention from scientists because of its potential use in wastewater treatment due to their exceptional nutrient removal properties. Numerous scholars have examined and recorded the topic, related to biochemical composition of wastewater, advent of microalgal technologies for wastewater treatment, different variables which is used to utilize microalgae to remediate wastewater. The growth rates and yields of photoautotrophic microalgae are lower than those of their heterotrophic counterparts. One of the biggest hurdles for a microalgal biorefinery is maximizing the photosynthetic growth of microalgae for industrial scale algal farming. The other two are product extraction from collected biomass and the growth of new algae strains. The process of “dewatering,” refers dehydrating algal cells, which is crucial for extracting high value products from microalgae as they significantly utilize different types of nutrients from wastewater to grow and produce biomass. Nitrogen, phosphorus, and other organic pollutants may cause severe and irreparable damage to natural water bodies and aquatic wildlife if they are not adequately treated before being discharged into water bodies. In aquatic environments, eutrophication, which is the most common type of environmental change, reduces the amount of oxygen in the water. It can either cause other living creatures to die or slow their rate of growth significantly.29 performed a study to see whether or not it would be possible to generate huge quantities of biofuels and energy by cultivating algae on wastewater, and they came to the conclusion that it would generate huge quantity. Microalgae are able to effectively take nutrients from wastewater, which satisfies the nutritional requirements necessary for the growth and development of the microalgae. They further adds advantage to bring down biological oxygen demand, chemical oxygen demand also other nutrients in wastewater. The use of wastewater as a nutritional medium in open ponds and other types of growth systems may be accomplished by a number of different species of microalgae, which have been identified. Ramachandra et al.30 investigated the potential

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for lipid production in three species of isolated algae grown in urban wastewater, Euglena sp., Spirogyra sp., and Phormidium sp. Mahapatra et al.31 explored whether or not sewage water could be used for the mass growth of the algae Euglena sp. In wastewater, it was found that Chlorococcum sp. grew at the greatest rate (1.3360.072 g/L), produced the maximum amount of biomass (0.90 mg L 1 day 1), and had the highest lipid productivity (30.55% w/w).

9. Market trend of microalgae-based wastewater treatment Developed countries have successfully incorporated the microalgae based technologies to treat wastewater and produce biomass which could produce high value compounds. North America has planted nearly 130 companies whose aim is to produce microalgal biomass to produce biofuel and also bears advanced system to produce 100 L biodiesel from 1 tonne of microalgae.32,33 In Victoria, Australia they have utilized fish waste for production of 1 Kt wet microalgal biomass. European Union funded projects have used different microalgae to produce omega-3 which helps in feeding fish culture. To enhance the number of companies to use microalgae mediated wastewater treatment, the companies still need to have work at ground level investigation.

10. Socio-economic and environmental aspects associated with integrated algae refinery Microalgae bears the advantage to be cultivated on the non-arable land and due to photosynthetic efficiency they can fix carbon dioxide which they can remediate wastewater in rural and urban areas.34,35 Hence, microalgae helps small-scale industry to start the business. Microalgae cultivation provides tremendous opportunity in the field of agriculture as a source of biofertilizers, aquaculture which help in development of rural sector.36 Other than this microalgae are known to produce diverse array of compounds which sustains human population. Biorefinary approach has helped production of variety of high value products from microalgae which helps in maintaining green environment which supports socio-economic development. Microalgae biorefinary approach offers several advantage: (i) wastewater and carbon dioxide helps in cultivation of microalgae, which reduces the cultivation cost and even aids in removing organic pollutants from

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environment. (ii) utilization of bioflocculants also helps in reducing the cultivation cost (iii) selection of higher algal biomass productivity to produce high energy compounds (iv) economic sustainability of microalgae is assessed by screening of microalgae (v) combination of different techniques help in utilizing microalgal biomass in a better way.

11. Conclusion Industrialization and urbanization has resulted into extensive generation of wastewater and depletion of fossil fuels which has resulted to rise in global and economic challenges. In respect to mitigate these challenges there urgent of advent of technology which could simultaneously treat wastewater also generate different types of high value products causing no zero harm to ecosystem. In which microalgae outclass all the other microorganism and other classical methods as they are known to reduce significant amount of pollutants in wastewater also produces nutritionally enriched biomass which produces different valuable commodities and are found to alternate of fossil fuels.

References 1. Chisti Y. Biodiesel from microalgae. Biotechnol Adv 2007;25(3):294–306. 2. Sheehan J, Dunahay T, Benemann J, Roessler P. A look back at the US Department of Energy’s aquatic species program: biodiesel from algae. vol. 328. National Renewable Energy Laboratory; 1998. p. 1–294. 3. Acreman J. Algae and cyanobacteria: isolation, culture and long-term maintenance. J Ind Microbiol Biotechnol 1994;13(3):193–4. 4. Hoffmann JP. Wastewater treatment with suspended and nonsuspended algae. J Phycol 1998;34(5):757–63. 5. Oswald WJ. My sixty years in applied algology. J Appl Phycol 2003;15(2):99–106. 6. Correll DL. The role of phosphorus in the eutrophication of receiving waters: a review. J Environ Qual 1998;27(2):261–6. 7. Kiran MG, Pakshirajan K, Das G. An overview of sulfidogenic biological reactors for the simultaneous treatment of sulfate and heavy metal rich wastewater. Chem Eng Sci 2017;158:606–20. 8. Oswald WJ. Micro-algae and wastewater treatment. J Microbial Biotechnol 1988;305–28. 9. Kalwani M, Devi A, Patil K, Kumari A, Dalvi V, Malik A, et al. Microalgae-mediated wastewater treatment and enrichment of wastewater-cultivated biomass for biofuel production. In: Expanding horizon of cyanobacterial biology. Academic Press; 2022. p. 259–81. 10. Azarpira H, Dhumal K, Pondhe G. Application of phycoremediation technology in the treatment of sewage water to reduce pollution load. Adv Environ Biol 2014;2419–24. 11. Rao POLUR, Kumar RR, Raghavan BG, Subramanian VV, Sivasubramanian V. Application of phycoremediation technology in the treatment of wastewater from a leather-processing chemical manufacturing facility. Water SA 2011;37(1).

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12. Lim PE, Ong SA, Seng CE. Simultaneous adsorption and biodegradation processes in sequencing batch reactor (SBR) for treating copper and cadmium-containing wastewater. Water Res 2002;36(3):667–75. 13. Rawat I, Kumar RR, Mutanda T, Bux F. Dual role of microalgae: phycoremediation of domestic wastewater and biomass production for sustainable biofuels production. Appl Energy 2011;88(10):3411–24. 14. Narala RR, Garg S, Sharma KK, Thomas-Hall SR, Deme M, Li Y, et al. Comparison of microalgae cultivation in photobioreactor, open raceway pond, and a two-stage hybrid system. Front Energy Res 2016;4:29. 15. Khalekuzzaman M, Alamgir M, Islam MB, Hasan M. A simplistic approach of algal biofuels production from wastewater using a hybrid anaerobic baffled reactor and photobioreactor (HABR-PBR) system. PLoS One 2019;14(12): e0225458. 16. Nugroho YK, Zhu L. Platforms planning and process optimization for biofuels supply chain. Renew Energy 2019;140:563–79. 17. Chen X, Li Z, He N, Zheng Y, Li H, Wang H, et al. Nitrogen and phosphorus removal from anaerobically digested wastewater by microalgae cultured in a novel membrane photobioreactor. Biotechnol Biofuels 2018;11(1):1–11. 18. Yang L, Zhang H, Cheng S, Zhang W, Zhang X. Enhanced microalgal harvesting using microalgae-derived extracellular polymeric substance as flocculation aid. ACS Sustain Chem Eng 2020;8(10):4069–75. 19. Jiang X, Gao G, Zhang L, Tang X, Shao K, Hu Y, et al. Role of algal accumulations on the partitioning between N2 production and dissimilatory nitrate reduction to ammonium in eutrophic lakes. Water Res 2020;183: 116075. 20. Mathimani T, Mallick N. A comprehensive review on harvesting of microalgae for biodiesel–key challenges and future directions. Renew Sustain Energy Rev 2018; 91:1103–20. 21. Zhang H, Zhang X. Microalgal harvesting using foam flotation: a critical review. Biomass Bioenergy 2019;120:176–88. 22. Molino A, Mehariya S, Karatza D, Chianese S, Iovine A, Casella P, et al. Bench-scale cultivation of microalgae Scenedesmus almeriensis for CO2 capture and lutein production. Energies 2019;12(14):2806. 23. Tan JS, Lee SY, Chew KW, Lam MK, Lim JW, Ho SH, et al. A review on microalgae cultivation and harvesting, and their biomass extraction processing using ionic liquids. Bioengineered 2020;11(1):116–29. 24. Mubarak M, Shaija A, Suchithra TV. Flocculation: an effective way to harvest microalgae for biodiesel production. J Environ Chem Eng 2019;7(4): 103221. 25. Kim J, Ryu BG, Kim K, Kim BK, Han JI, Yang JW. Continuous microalgae recovery using electrolysis: effect of different electrode pairs and timing of polarity exchange. Bioresour Technol 2012;123:164–70. 26. Fayad N, Yehya T, Audonnet F, Vial C. Harvesting of microalgae Chlorella vulgaris using electro-coagulation-flocculation in the batch mode. Algal Res 2017;25:1–11. 27. Udaiyappan M, Hasan HA, Takriff MS, Abdullah SRS. A review of the potentials, challenges and current status of microalgae biomass applications in industrial wastewater treatment. J Water Process Eng 2017;20:8–21. 28. Caetano NS, Martins AA, Gorgich M, Gutierrez DM, Ribeiro TJ, Mata TM. Flocculation of Arthrospira maxima for improved harvesting. Energy Rep 2020;6:423–8. 29. Batten D, Beer T, Freischmidt G, Grant T, Liffman K, Paterson D, et al. Using wastewater and high-rate algal ponds for nutrient removal and the production of bioenergy and biofuels. Water Sci Technol 2013;67(4):915–24. 30. Ramachandra TV, Madhab MD, Shilpi S, Joshi NV. Algal biofuel from urban wastewater in India: scope and challenges. Renew Sustain Energy Rev 2013;21:767–77.

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31. Mahapatra DM, Chanakya HN, Ramachandra TV. Euglena sp. as a suitable source of lipids for potential use as biofuel and sustainable wastewater treatment. J Appl Phycol 2013;25(3):855–65. 32. European Union, BLUE BIOECONOMY. WWW.EUMOFA.EU Situation report and perspectives, 2018; 2018. https://doi.org/10.2771/053734. 33. Salama ES, Kurade MB, Abou-Shanab RA, El-Dalatony MM, Yang IS, Min B, et al. Recent progress in microalgal biomass production coupled with wastewater treatment for biofuel generation. Renew Sustain Energy Rev 2017;79:1189–211. 34. Hamed I. The evolution and versatility of microalgal biotechnology: a review. Compr Rev Food Sci Food Saf 2016;15(2016):1104–23 [1541-4337.12227]. 35. Wen Z, Johnson MB. Microalgae as a feedstock for biofuel production; 2009. 36. Ronga D, Biazzi E, Parati K, Carminati D, Carminati E, Tava A. Microalgal biostimulants and biofertilisers in crop productions. Agronomy 2019;9(4):192.

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CHAPTER TEN

Beneficial and negative impacts of wastewater for sustainable agricultural irrigation: Current knowledge and future perspectives Priya Yadava, Rahul Prasad Singha, Rajan Kumar Guptaa, Sandeep Kumar Singhb, Hariom Vermac,*, Prashant Kumar Singhd, Kaushalendrae, Kapil D. Pandeya, and Ajay Kumarf a

Laboratory of Algal Research, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India b Division of Microbiology, ICAR-Indian Agricultural Research Institute, Pusa, New Delhi, India c Department of Botany, B.R.D. Government Degree College Duddhi, Sonbhadra, India d Department of Biotechnology, Mizoram University (A Central university), Pachhunga University College Campus, Aizawl, India e Department of Zoology, Mizoram University (A Central university), Pachhunga University College Campus, Aizawl, India f Department of Botany, Banaras Hindu University, Varanasi, India *Corresponding author: e-mail address: [email protected]

Contents 1. Introduction 2. Availability and use of wastewater 3. Positive effect of waste water irrigation on physicochemical properties of soil 3.1 Fertization value of waste water 3.2 Soil organic carbon (SOC) 3.3 Soil macronutrients 3.4 Electrical conductivity (EC) 3.5 Exchangeable cations 3.6 Calcium carbonate 3.7 Soil pH 4. Negative effect of long-term sewage irrigation 4.1 Effect of waste water irrigation on total heavy-metal content of soil 4.2 Environmental hazards related to wastewater 5. Effect of waste water irrigation on quality and yield 5.1 Heavy-metal content in plants 5.2 Crop yield

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6. Conclusions Acknowledgment References

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Abstract Currently world faces the high risk of water crisis and the rising human population and changing climatic conditions accelerate this challenge. Therefore there is urgent need of water management for the human beings and all the living organisms. Agriculture is currently the world’s largest water consumer. Furthermore, it has been anticipated that by 2050, the amount of water available for agricultural irrigation will have to increased by 70% to meet the demand of food for the rising global population. In this scenario, wastewater may be a viable option as a source of water for the agricultural irrigation. Although the waste water contains various trace elements and fertilizers contents and these can be used to enhance the agricultural production. However the presence of heavy load of some toxic compounds/metals in the waste water negatively affect the quality of plant, soil as well as environment and human health. Therefore in this chapter we have discussed briefly the merit and demerits of waste water utilization for agricultural irrigation. Keywords: Heavy metals, Waste water, Nutrient yields, Sustainable agriculture, Ground water

1. Introduction For the living organism, water is one of the most essential thing for the survival but their limitation and decreasing content can cease the lives of living organisms. In addition, water is also an important resource for the social and economic development.1,2 However the natural resources of water are continuously depleting and it creates a panic situations for the human kind. Recently the crisis of water in some leading cities of various countries, such as South Africa, UK, India are the critical examples of shortage and mismanagement of water resource. The global rising population, global warming, changing climatic conditions and rising industrialization continuously accelerate the problem of water shortage.3,4 As per report after the 1980, each years the need of water has been increased with 1% globally5,6 and it has been estimated that it can reach up to 20–30% up to 2050 from the current level.7 However it has been estimated that currently approximately more than two-third of ground water resources are used in the agricultural irrigation process.

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Waste water is the residual, low quality water that is produced after anthropogenic behaviors or after industrial use. The rising industrialization continuously released huge amount of waste water in the environment, rivers or open land, that not only affect the human health but also contaminate the natural resources of water.8,9 According to a published report approximately 30 million tons of waste water released each year globally, 70% out of which, used in the agricultural process as a source of irrigation.10 The huge percentage of water resource are used in the agriculture, it has been estimated that approximately 60–90% of the total water used in the agriculture for irrigation process. It can be varied depending upon the climatic conditions or the area.5,6,11 However to feed the rising global population the agricultural productivity shall have to enhanced by 70% from the current level at 2050,12 which needs an extra 53% of water from the current level.13 Agricultural activities accounted for more than 70% water withdrawals in 2005 worldwide.14 However the increasement in the water needs will create a severe threat for the survival of living organism, because the natural resources of the water are continuously diminishing. Therefore uses of waste water for the agricultural irrigation is gaining momentum now a days. The presence of heavy metals or fertilizers content in the waste water, can be a suitable alternative of chemical fertilizers.15 But the heavy load of chemical effluents, toxic metals, heavy metals have severe threat after utilization in the agricultural irrigation due to adversely affecting texture and productivity of soil and crop as well as the health of human beings.16,17 But in the various part of the world the utilization of waste water has been considered as an alternative of chemical fertilizers.18 For an example, in the early 1990s, around 73,000 hectares lands in India were irrigated using waste water, and later increasing each year.19 The treatment of waste water is an urgent need before utilization in agricultural irrigation that will be ahead of sustainable crop production. Although whether the waste water is treated or not, it contains higher load of nutrients.20 The direct use or flow of waste water in the agricultural land can contaminate the soil, water and environment, which ultimately affect the health of human beings.21 Currently more than 80% of the waste water have been used in the agriculture without any treatment,22 which significantly affect the environment, and socioeconomic development.23 Therefore there is need to discuss both positive and negative impact of waste water on the plant-crop water system during agricultural irrigation.

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2. Availability and use of wastewater In last few years over extraction has resulted in a significant drop in groundwater levels (up to 200 m in some places). The Central Ground Water Board (CGWB) research also stated that in the majority of Indian areas, the water table is lowering at a rate of 1 m per year. It will be a difficult task for researchers and policymakers to slow the rate of decrease in the coming years. Humans have used tainted water for a variety of purposes. As a result of fierce competition have been observed in the agriculture for groundwater and surface water supplies with industries, which results, near the cities or the urban land, most of the farmers utilized the municipal or industrial effluents waste water for the agricultural irrigation.24 The use of waste water is not a choice, but rather a constraint or pressure to use it for agricultural purposes. Due to the lack of natural streams and groundwater, people have been forced to consume water of low quality. The continuous increasing needs of water for the daily consumption equally increased the generation of waste water. According to previous report it has been estimated that 70–80% of the home supply water, accountable for waste water generation. According to the Central Public Health and Environmental Engineering Organization (CPHEEO), total waste water generation accounts for 70–80% of home water supply.25 However according to a World Bank report on waste water generation and treatment, stabilization ponds are the best waste water treatment solution in most developing nations, because land is often accessible at a low cost of opportunity, and experienced labor and sophisticated equipment are in short supply.26

3. Positive effect of waste water irrigation on physicochemical properties of soil 3.1 Fertization value of waste water Organic matter, plant nutrients, inorganic matter, toxic compounds, and pathogens make up the real composition of waste water, whose composition and contents vary and depends upon the source and origin. The presence of higher content of nutrients such as nitrogen, potassium and phosphorous in waste water also termed them low cost fertilizers.27 The presence of higher concentrations of nutrients makes the waste water utilization rate more than 70% in the agricultural sector.28

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3.2 Soil organic carbon (SOC) The optimum or increased soil organic carbon content is considered as an indicator of improved soil health and quality at the certain extent. As a reservoir of plant-available nutrients, it has been the sole indicator of soil quality.29 The long-term usage of waste water for crop irrigation results in much higher SOC than GW-irrigated soils.30 A 38–79% rise in SOC content has been found in subtropical Indian soils after long-term irrigation of waste water in compared to the ground water.29 Similarly the application of distillery effluent to Nepalese soils resulted 7.8-fold enhancement in the soil organic matter.31 Yadav et al.32 reported 1.24–1.73% enhancements in the soils of Kurukshetra, Haryana, India after 25 years. However the continuous use of waste water for the irrigation process can lead to the deposition of heavy metals and toxic compounds, which adversely affect the crop nutrients quality and also deposited toxic residue in the grain.33

3.3 Soil macronutrients Soil fertility improvement with waste water irrigation has been well documented over time.18,32 In the previous study, various author reported significant enhancement in the soil fertility after utilization of waste water as agricultural irrigation.34,35 Gupta and Mitra36 reported near to two time content of total nitrogen, phosphorous and potassium after waste water irrigation in compared to ground water irrigated soil. Similarly Hayes et al.37 reported 5.3-fold enhancement in available phosphorous, 2.55-fold increment in the NH4 N and 4.4 times enhancement in total nitrogen after utilization of waste water as a source of irrigation.

3.4 Electrical conductivity (EC) Sewage irrigation has a significant impact on the chemical parameters such as pH and electrical conductivity (EC) of the soil. The continuous use of waste water raised the pH and salt content of the soils, which results degradation of soil quality. In a study Ramesh30 reported enhanced EC and higher pH in the waste water irrigated soil in compare to normal water irrigation. Similar type of results were published by Rusan et al.18 after 10 years treatment with the waste water. Tiwari et al.38 also reported similar types relatively higher pH and EC of observation after sewage water treatment as compared to tube well water. Yaseen and Ishtiaque39 not found significant changes in the EC, pH, soils present under the canal water. However, soil Ca2+, Mg2+ concentrations were 0.5 mmol L 1 higher in soils watered with industrial effluent

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than in areas irrigated with potable water. In a study Bhise et al.40 also reported the adverse effect of waste water treatment on the soil physicochemical properties like EC, ratios of soluble cations (Na/K and Na/Mg) and the heavy-metal content. However, a study with a short-term (2 years) application of sewage waste water to Spain’s calcareous soils found a modest increase in EC and Na+ content in soils compared to lands watered with ground water.41 The increasing salt content of soil that receives waste water on a regular basis has been compared to the TDS of waste water at its original level.42

3.5 Exchangeable cations Continuous irrigation with sewage water significantly enhances exchangeable cations. In a study Priyanie et al.43 reported enhanced concentration of N, P, K after direct and lift irrigation with sewage water. Similar type of observation the enhanced N, P, K content were also reported in the sewage-irrigated soils.44 Cao et al.45 also reported enhanced content of N, P, K in the waste water treated soil in compared to without waste water treatment soil. Kiziloglu et al.46 reported that waste water treatment affect the physicochemical properties of the soil up to the 0–30 cm depth after 1 year of irrigation.

3.6 Calcium carbonate The treatment of waste water significantly reduced the content of CaCO3 in the soil. In a study McClean et al.47 observed significant reduction in calcium carbonate in the waste water is due to the decreased soil pH and presence of organic acids in the soil, which are the results of waste water treatment. The anaerobic decomposition of the organic matter results in the production of CaCO3 solubilization and subsequent leaching in the root zone.48 However contradictory report also available, regarding increase or decrease of calcium carbonate (CaCO3) concentration after utilization of waste water. El-Hady49 reported significant enhancement of CaCO3 in the waste water irrigated soil, while El-Arby and Elbordiny50 reported 1.42% decreased in the waste water irrigated soil in compare to ground water irrigated soil.

3.7 Soil pH Different perspectives exist on the impact of long-term waste water treatment on soil pH. In previous study author have reported that irrigation with

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waste water results enhancement in the soil pH.18,41 Saravanamoorthy and Kumari51 reported 0.4 unit rise in the soil pH after long-term use of textile industry effluents in compare to the ground water irrigated soil. Similarly 0.5 unit increment in the soil pH after long-term application of sewage waste water.36 A significant enhancement of 0.5 units in soil pH was observed in soil after irrigation with mixture of domestic and industrial effluents.49 The enhancement in the soil pH after waste water treatment is may be due to the presence and accumulation of large number of cations like Na+, Ca2+, and Mg2+ in the soil surface.52 In a study Osaigbovo and Orhue53 reported the presence of higher amount of Ca2+ and Mg2+ in the pharmaceutical effluents, raised the soil pH. However in another study Yadav et al.32 reported significant reduction in the soil pH after waste water irrigation. Similar types of observation, reduction in soil pH were reported by various authors like distillery effluents,31 industrial effluents,54 and steel industry effluents.55 The probable reason for the drop of pH is due to anaerobic decomposition of organic acid present in the waste water.48

4. Negative effect of long-term sewage irrigation 4.1 Effect of waste water irrigation on total heavy-metal content of soil The heavy metals present in the environment are required in small quantity for the normal functioning of plant or soil. As it the immobile, nonbiodegradable and persistent in environment. The accumulation and concentration of heavy metals present are generally higher in the surface soil and gradually decreases from top to bottom.56,57 However the irrigation with waste water significantly accumulate the heavy metals in surface soil. For example, Yadav et al.32 reported accumulation of heavy metals after long-term irrigation of waste water. Similarly Muchuweti et al.58 reported enhanced level of DTPA-extractable Cd, Co, and Ni after long-term irrigation with untreated with municipal waste water. In an another study Kharche et al.44 reported enhanced level of Fe, Mn, Zn, Cu, Cd, Cr, and Ni in the sewage-irrigated soils in compare to the normal soil.44 Lin et al.59 reported accumulation of Cr and Ni in the soil profile after long-term effluent recharge. The distribution of heavy metals in the soil depends upon various factors including the elements and the soil texture.57 However the accumulation of heavy metals in the soil in the excessive concentration not only contaminated the soil but also affect the texture and nutrients quality of the crops.58

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In a study Ambika and Ambika60 reported utilization of sewage results enhanced nutrient load, like dissolved nitrates, besides these also contained high concentration of pesticides, heavy metals, and other toxic materials.

4.2 Environmental hazards related to wastewater Waste water plays an essential role in the sustainable agricultural practices, by meeting the requirement of water for agricultural irrigation. This not only benefitted the crops but also save the fresh water for drinking purposes. The presence of large amount of nutrients and fertilizers enhance the agricultural production and food grain quality and also reduce the burden of fertilizers.61 Although the higher contents of organic carbon in the waste water improved the physical and biological quality of soil.62 However the use of waste water not only enriches the agricultural field but also supplies the field with trace toxic metals. In the previous study various authors reported their observation after utilization of waste water during the agricultural irrigation. The long-term use of waste water causes deposition of Cd, Cr, Pb, As, Ni, Cu, and Zn in the soil and also negatively impacted the soil quality.63 In a study Dotaniya et al.64,65 reported 25–30 times enhancement in the Cr content in the soil after long-term use of tannery effluent. T€ urkdogan et al.66 also reported more than 3.4 times higher accumulation of heavy metals in the waste water treated soil in compared to the normal ground water treated soil. Although the presence of enhanced concentration of heavy metals not only adversely affect the soil quality but also affect the presence of native microflora.67 The presence of native microflora helps in the mineralization of nutrients, nutrient availability to the plants. The disturbance of microbial structures can imbalance the nutrients cycle.68

5. Effect of waste water irrigation on quality and yield 5.1 Heavy-metal content in plants Plant species differed greatly in terms of heavy-metal and micronutrient bioaccumulation. The content of heavy metals and micronutrients in economic plant parts has been found to be higher during the irrigation with waste water and their concentration varies among the different plant species.69 For an example, Dheri et al.21 reported spinach has been found to accumulate more Pb, Cr, and Cd than Trifolium alexandrinum L. Further Hundal and Arora70 reported higher concentration of pollutants in the leafy vegetables in

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compare to root crops such as potato and carrot. Further in a study El-Arby and Elbordiny50 reported comparative study of accumulation of heavy metals after irrigation with waste water in the order of jojoba > khaya > axodium > Italian cypress. However, Maize and Tsunga grown in Zimbabwe irrigated with sewage waste water have higher concentration of Cd, Cu, Pb, and Zn.58 Further in a study Sharma et al.71 reported the effect of seasons on the accumulation of heavy metals. In the season of summer they reported higher Cd content in the Beta vulgaris, while in the summer and winter observed higher content of Pb and Ni in the suburban area of Varanasi, India. Similarly Singh and Kumar72 also recorded higher levels of Zn, Pb, Cd level in the okra and Spinach after irrigation with industrial effluents in the Delhi, India. Amiri et al.73 recorded Pb, Cr, and Ni concentrations in the roots of yellow sweet clover have also found in the enhanced level after treatment with waste water. Heavy-metal accumulation and absorption by plants grown in contaminated environments, on the other hand, generally followed the order of magnitude of greater availability in the surrounding medium.74,75 However a direct significant relationships have been found between soil heavy-metal content and heavy-metal uptake by the plants and heavy-metal concentration in the plants and heavy-metal concentration in waste water effluents.21 Even different plant parts of the same species have differed significantly in their ability to absorb, translocate, and accumulate heavy metals and micronutrients.76,77 In a study Nawaz et al.54 reported rice grown after irrigation with industrial waste water retain higher content of Cu from the soils primarily in the straw and translocate trace amount to the grains. Similar type of observation were reported by Brar and Arora77 in the curds, of Cauliflower which have higher tendency to accumulate Zn, Cu, Fe, Mn, Pb, and Ni than the leaves after irrigated with sewage waste water. Further in a study Brar et al.57 reported higher contents of heavy metals in the leaves in compared to tubers of potato.

5.2 Crop yield The waste water irrigation have also a significant impact on the crop yield. As the waste water contains a huge amount of nutrients, that act as an stimulant for the crop growth and hence enhanced the agricultural productions.78 In the generalized view, the waste water irrigation have positive significant effect on the leafy vegetables such as cauliflower, cabbage, spinach, a growth.79 However some contradictory reports are also available, like

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radish, which is sensitive to waste water.80 In the previous published reports various authored reported the enhanced crop production after irrigation with waste water. For instance a significant increase in dry matter yield of Trifolium sp. was reported by Singh et al.81 after irrigation with waste water. Similarly Udayasoorian et al.82 reported enhanced yield of maize, sunflower, groundnut, and soybean after irrigation with waste water. Similarly, a significant increase in the barley biomass has been reported after utilization with municipal waste water.18 In a study Sharma and Kansal83 reported enhanced grain yields of wheat, rice, and cotton after utilization of sewage waste water for irrigation. Saravanamoorthy and Kumari51 reported enhanced yield of peanut pod after the use of textile industry effluents. However in a study Ale et al.31 reported reduced growth of rice and wheat after irrigation with distillery effluents. In the study mixed types of observation in the crop yields have been observed after irrigation with waste water. However in most cases enhanced agricultural production and crop yields have been reported.

6. Conclusions Currently huge amount of ground water have been used for the agricultural irrigation but the limited resource of ground water and their decreasing content is a severe threat of human survivality. In this regard, search of an alternative way of agricultural irrigation is an immediate need. The uses of waste water which are generated from the households and industries for the agricultural irrigation is an immediate need. In the various countries huge amount of agricultural lands have been irrigated with waste water. Which have both positive and negative impact on the texture and quality of soil and crops. However on the basis of the literature reviewed, it is possible to conclude that certain industrial effluents have potential to use for irrigation because of their positive effect on the soil quality and enhanced crop yields. The high concentration of heavy metals and toxic compounds presence in the waste water needs treatment to reduce their toxic effect on crop and soil quality. Because crop genotypes and even crop cultivars within genotypes respond differently to waste water irrigation, crop selection becomes more important in these circumstances. More importantly, carbon sequestration via waste water irrigation has the potential to sustain long-term soil fertility. However, for safe and long-term waste water use, periodic monitoring of the chemical composition of waste water, soil, and crop produce is recommended for sustainable agriculture.

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Acknowledgment This study was supported by a SERB-Start Up Research Grant (SRG) to P.K.S. is thankful to the Science and Engineering Research Board (SERB), New Delhi, for financial support in the project (File No. SRG/2022/0005111).

References 1. Davies EG, Simonovic SP. Global water resources modeling with an integrated model of the social–economic–environmental system. Adv Water Resour 2011;34(6):684–700. 2. FAO of the United Nations. Coping with water scarcity—an action framework for agriculture and food security. Rome, Italy: Land and Water Division; 2012. Available online: http:// waste. waterw.fao.org/3/a-i3015e.pdf. [accessed on 9 March 2020]. 3. Kihila JM. Indigenous coping and adaptation strategies to climate change of local communities in Tanzania: a review. Clim Dev 2018;10(5):406–16. 4. Liu J, Wang Y, Yu Z, Cao X, Tian L, Sun S, et al. A comprehensive analysis of blue water scarcity from the production, consumption, and water transfer perspectives. Ecol Indic 2017;72:870–80. 5. Velasco-Mun˜oz JF, Aznar-Sa´nchez JA, Batlles-delaFuente A, Fidelibus MD. Sustainable irrigation in agriculture: an analysis of global research. Water 2019;11(9):1758. 6. Velasco-Mun˜oz JF, Aznar-Sa´nchez JA, Belmonte-Uren˜a LJ, Lo´pez-Serrano MJ. Advances in water use efficiency in agriculture: a bibliometric analysis. Water 2018;10 (4):377. 7. Bouwer H. Integrated water management for the 21st century: problems and solutions. In: Perspectives in civil engineering: commemorating the 150th anniversary of the American Society of Civil Engineers; 2003. p. 79–88. 8. Benavides L, Avella´n T, Caucci S, Hahn A, Kirschke S, M€ uller A. Assessing sustainability of wastewater management systems in a multi-scalar, transdisciplinary manner in Latin America. Water 2019;11(2):249. 9. Zhang Y, Zhang Y, Shi K, Yao X. Research development, current hotspots, and future directions of water research based on MODIS images: a critical review with a bibliometric analysis. Environ Sci Pollut Res 2017;24(18):15226–39. 10. Cheraghi M, Lorestani B, Yousefi N. Effect of waste water on heavy metal accumulation in Hamedan Province vegetables. Int J Bot 2009;5(2):109–93. 11. Velasco-Mun˜oz JF, Aznar-Sa´nchez JA, Belmonte-Uren˜a LJ, Roma´n-Sa´nchez IM. Sustainable water use in agriculture: a review of worldwide research. Sustainability 2018;10(4):1084. 12. Fischer G, Tubiello FN, Van Velthuizen H, Wiberg DA. Climate change impacts on irrigation water requirements: effects of mitigation, 1990–2080. Technol Forecast Soc Change 2007;74(7):1083–107. 13. De Fraiture C, Wichelns D. Satisfying future water demands for agriculture. Agric Water Manag 2010;97(4):502–11. 14. FAO. FAO’s information system on water and agriculture (AQUASTAT): water agricultural and other water uses; 2016. 15. Oteng-Peprah M, De Vries NK, Acheampong MA. Greywater characterization and generation rates in a peri urban municipality of a developing country. J Environ Manage 2018;206:498–506. 16. Reznik A, Dinar A, Herna´ndez-Sancho F. Treated wastewater reuse: an efficient and sustainable solution for water resource scarcity. Environ Resour Econ 2019;74(4):1647–85. 17. Singh KP, Mohan D, Sinha S, Dalwani R. Impact assessment of treated/untreated wastewater toxicants discharged by sewage treatment plants on health, agricultural, and environmental quality in the wastewater disposal area. Chemosphere 2004;55(2):227–55.

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18. Rusan MJM, Hinnawi S, Rousan L. Long term effect of wastewater irrigation of forage crops on soil and plant quality parameters. Desalination 2007;215(1–3):143–52. 19. Strauss M, Blumenthal UJ. Use of human wastes in agriculture and aquaculture: utilization practices and health perspectives; 1990. 20. Fonseca AFD, Herpin U, Paula AMD, Victo´ria RL, Melfi AJ. Agricultural use of treated sewage effluents: agronomic and environmental implications and perspectives for Brazil. Sci Agric 2007;64:194–209. 21. Dheri GS, Brar MS, Malhi SS. Heavy-metal concentration of sewage-contaminated water and its impact on underground water, soil, and crop plants in alluvial soils of northwestern India. Commun Soil Sci Plant Anal 2007;38(9–10):1353–70. 22. Herna´ndez-Sancho F, Molinos-Senante M, Sala-Garrido R. Economic valuation of environmental benefits from wastewater treatment processes: an empirical approach for Spain. Sci Total Environ 2010;408:953–7. 23. Ansari FA, Ravindran B, Gupta SK, Nasr M, Rawat I, Bux F. Techno-economic estimation of wastewater phycoremediation and environmental benefits using Scenedesmus obliquus microalgae. J Environ Manage 2019;240:293–302. 24. Ghimire SK. Evaluation of industrial effluents toxicity in seed germination and seedling growth of some vegetables. Doctoral dissertation, M. Sc. dissertation, Kirtipur, Kathmandu, Nepal: Central Department of Botany, Tribhuvan University; 1994. 25. Wankhade K. Urban sanitation in India: key shifts in the national policy frame. Environ Urban 2015;27(2):555–72. 26. Shuval HI, Adin A, Fattal B, Rawitz E, Yekutiel P. Wastewater irrigation in developing countries: health effects and technical solutions. Technical Paper No. 51, Washington, DC: World Bank; 1986. 27. Chaw R, Reves AS. Effect of wastewater on Mentha piperita and Spinacia oleracea. J Environ Biol 2001;51:131–45. 28. Minhas PS, Samra JS. Wastewater use in peri-urban agriculture: impacts and opportunities; 2004. 29. Rattan RK, Datta SP, Chhonkar PK, Suribabu K, Singh AK. Long-term impact of irrigation with sewage effluents on heavy metal content in soils, crops and groundwater—a case study. Agric Ecosyst Environ 2005;109(3–4):310–22. 30. Ramesh G. Soil and water resource characteristics in relation to land disposal of sewage effluents and suitability of sewage water for irrigation. Doctoral dissertation, Hyderabad: Acharya N.G. Ranga Agricultural University; 2003. 31. Ale R, Jha PK, Belbase N. Effect of distillery effluent on some agricultural crops, a case of environmental injustice to local farmers in Khajura VDC, Banke. Sci World 2008;6(6):68–75. 32. Yadav RK, Goyal B, Sharma RK, Dubey SK, Minhas PS. Post-irrigation impact of domestic sewage effluent on composition of soils, crops and ground water—a case study. Environ Int 2002;28(6):481–6. 33. Manzoor J, Sharma M, Wani KA. Heavy metals in vegetables and their impact on the nutrient quality of vegetables: a review. J Plant Nutr 2018;41(13):1744–63. 34. Campbell CA, Davidson HR. Effect of temperature, nitrogen fertilization and moisture stress use by Manitou spring wheat. Can J Plant Sci 1983;59:603–26. 35. Chhabra R. Sewage water, utilization through forestry. New Delhi, India: National Printers; 1989. p. 1–9. 36. Gupta SK, Mitra A. Advances in Land Resource Management for 21st Century. New Delhi, India: Soil Conservation Society of India; 2002. p. 446–60. 37. Hayes AR, Mancino CF, Pepper IL. Irrigation of turfgrass with secondary sewage effluent: I. Soil and leachate water quality. Agron J 1990;82(5):939–43. 38. Tiwari RC, Kumar A, Mishra AK. Influence of treated sewage and tubewell water irrigation with different fertilizer levels on rice and soil properties. J Indian Soc Soil Sci 1996;44(3):547–9.

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39. Yaseen SM, Ishtiaque M. Effect of marginal quality groundwater on crop yields and soil. J Drain Water Manag 2002;6:49. 40. Bhise PM, Challa O, Venungopalan MV. Effect of waste water irrigation on soil properties under different land use systems. J Indian Soc Soil Sci 2007;55(3):254–8. 41. Morugan A, Garcı´a-Orenes F, Mataix-Solera J, Go´mez I, Arcenegui V, Navarro MA, et al. Short-term effects of treated waste water irrigation on soil. Two years of a study monitoring a Mediterranean calcareous soil. In: EGU general assembly conference abstracts; 2009. p. 12483. 42. Mohammad MJ, Mazahreh N. Changes in soil fertility parameters in response to irrigation of forage crops with secondary treated wastewater. Commun Soil Sci Plant Anal 2003;34(9–10):1281–94. 43. Priyanie A, Philipp W, Robert S, Sreedhar A, Axel D. An atlas of water quality, health and agronomic risks and benefits associated with wastewater irrigated agriculture—a study from the banks of the Musi river, India; 2008. 44. Kharche VK, Desai VN, Pharande AL. Effect of sewage irrigation on soil properties, essential nutrient and pollutant element status of soils and plants in a vegetable growing area around Ahmednagar city in Maharashtra. J Indian Soc Soil Sci 2011;59(2):177–84. 45. Cao VP, Nguyen BP, Tran KH, Bell RW. Irrigating rice crops with waste water to reduce environmental pollution from catfish production in the Mekong Delta. In: Technical report CARD project VIE/06/023; 2010. 46. Kiziloglu FM, Turan M, Sahin U, Angin I, Anapall O, Okuroglu M. Effect of waste water irrigation on soil and cabbage plant (Brassica olerecea var. capitate cv Yalova-1) chemical properties. J Plant Nutr Soil Sci 2007;170:166–72. 47. McClean CJ, Cresser MS, Smart RP, Aydinalp C, Katkat AV. Unsustainable irrigation practices in the bursa plain, Turkey. In: Diffuse pollution conference, Dublin; 2003. p. 60–5. 48. Wang TS, Cheng SY, Tung H. Dynamics of soil organic acids. Soil Sci 1967;104 (2):138–44. 49. El-Hady BAA. Compare the effect of polluted and river Nile irrigation water on contents of heavy-metals of some soils and plants. Res J Agric Biol 2007;3:287–94. 50. El-Arby AM, Elbordiny MM. Impact of reused wastewater for irrigation on availability of heavy metals in sandy soils and their uptake by plants. J Appl Sci Res 2006;2(2):106–11. 51. Saravanamoorthy MD, Kumari BR. Effect of textile waste water on morphophysiology and yield on two varieties of peanut (Arachis hypogaea L.). J Agric Technol 2007;3(2):335–43. 52. Schipper LA, Williamson JC, Kettles HA, Speir TW. Impact of land-applied tertiary-treated effluent on soil biochemical properties. J Environ Qual 1996;25(5): 1073–7. American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. 53. Osaigbovo AE, Orhue ER. Influence of pharmaceutical effluent on some soil chemical properties and early growth of maize (Zea mays L). Afr J Biotechnol 2006;5(18). 54. Nawaz ALLAH, Khurshid KASHIF, Arif MS, Ranjha AM. Accumulation of heavy metals in soil and rice plant (Oryza sativa L.) irrigated with industrial effluents. Int J Agric Biol 2006;8(3):391–3. 55. Kansal BD, Dhaliwal GS. Effects of domestic and industrial effluents on agricultural productivity. In: Management of agricultural pollution in India. New Delhi, India: Commonwealth Publishing Co; 1994. 56. Aghabarati A, Hosseini SM, Maralian H. Heavy metal contamination of soil and olive trees (Olea europaea L.) in suburban areas of Tehran, Iran. Res J Environ Sci 2008;2:323–9. 57. Brar MS, Khurana MPS, Kansal BD. Effect of irrigation by untreated sewage effluents on the micro and potentially toxic elements in soils and plants. In: 17th World congress of soil science, Bangkok (Thailand), 14–21 Aug 2002; 2002. 58. Muchuweti M, Birkett JW, Chinyanga E, Zvauya R, Scrimshaw MD, Lester JN. Heavy metal content of vegetables irrigated with mixtures of wastewater and sewage sludge in Zimbabwe: implications for human health. Agric Ecosyst Environ 2006;112(1):41–8.

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59. Lin C, Negev I, Eshel G, Banin A. In situ accumulation of copper, chromium, nickel, and zinc in soils used for long-term waste water reclamation. J Environ Qual 2008;37 (4):1477–87. 60. Ambika SR, Ambika PK. Crop growth and soil properties affected by sewage water irrigation—a review. Agric Rev 2010;31(3):203–9. 61. Alam MGM, Snow ET, Tanaka A. Arsenic and heavy metal contamination of vegetables grown in Samta village, Bangladesh. Sci Total Environ 2003;308(1–3):83–96. 62. Hussain I, Raschid L, Hanjra MA, Marikar F, Van Der Hoek W. Wastewater use in agriculture: review of impacts and methodological issues in valuing impacts; 2002. 63. Rattan RK, Shukla LM. Critical limits of deficiency and toxicity of zinc in paddy in a Typic Ustipsamment. Commun Soil Sci Plant Anal 1984;15(9):1041–50. 64. Dotaniya ML, Das H, Meena VD. Assessment of chromium efficacy on germination, root elongation, and coleoptile growth of wheat (Triticum aestivum L.) at different growth periods. Environ Monit Assess 2014;186(5):2957–63. 65. Dotaniya ML, Saha JK, Meena VD, Rajendiran S, Coumar MV, Kundu S, et al. Impact of tannery effluent irrigation on heavy metal build up in soil and ground water in Kanpur. Agrotechnology 2014;2(4):77. 66. T€ urkdogan MK, Kilicel F, Kara K, Tuncer I, Uygan I. Heavy metals in soil, vegetables and fruits in the endemic upper gastrointestinal cancer region of Turkey. Environ Toxicol Pharmacol 2003;13(3):175–9. 67. Bansal RL, Nayyar VK, Takkar PN. Accumulation and bioavailability of Zn, Cu, Mn and Fe in soils polluted with industrial waste water. J Indian Soc Soil Sci 1992;40(4):796–9. 68. Wang Y, Shi J, Wang H, Lin Q, Chen X, Chen Y. The influence of soil heavy metals pollution on soil microbial biomass, enzyme activity, and community composition near a copper smelter. Ecotoxicol Environ Saf 2007;67(1):75–81. 69. Adhikari S, Mitra A, Gupta SK, Banerjee SK. Pollutant metal contents of vegetables irrigated with sewage water. J Indian Soc Soil Sci 1998;46(1):153–5. 70. Hundal HS, Arora CL. Studies on toxic trace elements in vegetables and corresponding soils. Indian J Hortic 1993;50(3):273–8. 71. Sharma RK, Agrawal M, Marshall F. Heavy metal contamination of soil and vegetables in suburban areas of Varanasi, India. Ecotoxicol Environ Saf 2007;66(2):258–66. 72. Singh S, Kumar M. Heavy metal load of soil, water and vegetables in peri-urban Delhi. Environ Monit Assess 2006;120(1):79–91. 73. Amiri SS, Maralian H, Aghabarati A. Heavy metal accumulation in Melilotus officinalis under crown Olea europaea L forest irrigated with wastewater. Afr J Biotechnol 2008;7 (21):3912. 74. Alloway BJ, Jackson AP, Morgan H. The accumulation of cadmium by vegetables grown on soils contaminated from a variety of sources. Sci Total Environ 1990;91:223–36. 75. Kim IS, Kang KH, Johnson-Green P, Lee EJ. Investigation of heavy metal accumulation in Polygonum thunbergii for phytoextraction. Environ Pollut 2003;126(2):235–43. 76. Barman SC, Kisku GC, Salve PR, Misra D, Sahu RK, Ramteke PW, et al. Assessment of industrial effluent and its impact on soil and plants. J Environ Biol 2001;22(4):251–6. 77. Brar MS, Arora CL. Concentration of micro-elements and pollutant elements in cauliflower (Brassica oleracea convar botrytis var botrytis). Indian J Agric Sci 1997;67 (4):141–3. 78. Zalawadia NM, Patil RG, Raman S. Effect of distillery waste water with fertilizer on onion and soil properties. J Indian Soc Soil Sci 1996;44(4):802–4. 79. Murtaza G, Ghafoor A, Qadir M, Rashid MK. Accumulation and bioavailability of Cd, Co and Mn in soils and vegetables irrigated with city effluent. Pak J Agric Sci 2003;40 (1–2):18–24. 80. Bakhsh K, Ashfaq M, Alam MW. Effects of poor quality of ground water on carrot production: a comparative study. J Agric Soc Sci 2005;8(11):15–78.

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81. Singh RR, Singh V, Shukla AK. Yield and heavy metal contents of berseem as influenced by sewage water and refinery effluent. J Indian Soc Soil Sci 1991;39(2):402–4. 82. Udayasoorian C, Devagi P, Ramaswami PP. Case study on the utilization of paper and pulp mill effluent irrigation for field crops. In: Proceedings of workshop on ‘bioremediation of polluted habitats’; 1999. p. 71–3. 83. Sharma VK, Kansal BD. Effect of nitrogen, farm yard manure, town refuse and sewage water on the yield and nitrogen content of maize fodder and spinach. Indian J Ecol 1984;11:77–81.

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CHAPTER ELEVEN

Immobilized enzyme systems for wastewater treatment Mateen Hedara, Azeem Intisara,⁎, and Nazim Hussainb,⁎ a

School of Chemistry, University of the Punjab, Lahore, Pakistan Centre for Applied Molecular Biology, University of the Punjab, Lahore, Pakistan Corresponding authors: e-mail address: [email protected]; [email protected]

b ⁎

Contents 1. Introduction 2. Enzyme immobilization for sewage treatment 3. Different methods to immobilize enzymes 3.1 Encapsulation method 3.2 Adsorption method 3.3 Entrapment 3.4 Covalent immobilization 3.5 Cross linking method 4. Applications of immobilized enzymes in wastewater treatment 4.1 Food industry wastewater treatment 4.2 Pharmaceutical wastewater treatment 4.3 Biodegradation of phenol and its derivatives 4.4 Industrial wastewater treatment 5. Future prospective 6. Conclusion References

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Abstract The release of wastewater discharges can have a ubiquitous and detrimental effect on the ecosystem. The administration of numerous chemicals such as organic dyes, medicines, and commercial reagents, has led to soil and water pollution, directly attributed to rapid industrialization and economic development. For the protection of the environment, it is essential to remove these compounds before effluent-release. The degradation of components present in wastewater is usually catalyzed by the enzymes. The potential and advancement of green technology in various realms of applicability are expanding dramatically in this era of sustainable practices. It is well known that enzymes function under moderate conditions, catalyze reactions with maximum efficiency, and are biodegradable. Enzyme immobilization is frequently utilized because enzymes have

Advances in Chemical Pollution, Environmental Management and Protection, Volume 9 Copyright # 2023 Elsevier Inc. 183 ISSN 2468-9289 All rights reserved. https://doi.org/10.1016/bs.apmp.2022.10.009

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limitations, such as their susceptibility to environmental factors. Immobilized enzymes are used extensively in waste water treatment because they are less expensive, more ecofriendly, and simpler to use. In this chapter, applicability of immobilized enzyme systems for the treatment of various chemical compounds present in wastewater has been discussed. Moreover, the use of different supports and methodologies for the immobilization of biocatalysts has also been elaborated. Furthermore, the commercial use of immobilized enzymes to treat water contaminants along with their pros and cons have also been included. Keywords: Wastewater treatment, Enzyme, Immobilization, Biodegradation

1. Introduction Diverse contaminants are released into aquatic habitats at disturbingly high amounts. Conventional activated sludge treatment which is the much more popular wastewater treatment technique, can efficiently remove the majority of contaminants, but it is challenging to remove pollutants including oil, grease, medicines, insecticides, and plastics. Oil, grease, and organic contaminants make up the majority of these pollutants.1 Dairies, oil mills, abattoirs, and food waste sites are typically the sources of wastewater that contains oil and grease.2 The speed at which substrates, products, and oxygen are transferred will be compromised by oil and grease that settle on bodies of water. The floatable grease and oil could lead to bloom of spread of germs, poor deposition, and reduced sludge volume due to the activated sludge’s poor performance.3 In addition to being characterized as micro pollutants, other contaminants such as medications, insecticides, plastics, and personal care items are also referred to as emerging contaminants or evolving concern pollutants. Due to their exposure levels, which range from nanograms to micrograms per liter, these substances are typically difficult to detect or manage. They pose a serious hazard to the environment and all living things because they are generally poisonous, easy to bio accumulate, and difficult to natural microbial degradation.4 People are becoming more concerned globally due to the growing environmental contamination, which is primarily brought on by manmade activities. Different kinds of organic contaminants in our water systems and wastewater, such as phenols, medicines, insecticides, dyes, estrogens, and personal care products are progressively being detected.5–7 Their presence in unidentified and unregulated dosages adversely affects water quality and poses a major risk to people and aquatic life.8 Due to their potential for being mutagenic and carcinogenic,9 the majority of the aforementioned

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compounds are also recognized as emerging contaminants (ECs) and are categorized as group 1 carcinogens by the World Health Organization.7 The lack of effective solutions for the appropriate disposal, management, and recycling of debris necessarily cause this problem to intensify. Regrettably, the majority of these chemicals are resistant to conventional treatment methods and are not effectively eliminated by today’s wastewater treatment facilities.10 Most previously used EC removal techniques suffer from low efficiency and the production of several byproducts and wastes. For instance, hazardous solvents are utilized and toxic byproducts are produced by following the degradation process.11 Two of the most often used processes in wastewater treatment plants are ozonation12 and photo catalysis.13 For instance, a specific compound can hardly be degraded by ozonation or photolysis alone, and the treated water may be more vulnerable as a consequence of ozonation. The employment of combined photo catalysis and ozonation becomes more appealing because the effectiveness of these treatments is upgraded by generating hydroxyl radicals, a potent oxidant that may totally oxidize the organic material existing in the aquatic media.14 Environmental researchers are now obliged to develop more sophisticated treatment procedures for treating wastewater that contains trace amounts of persistent organic substances, such as organo-halogens, organic insecticides, detergents, and organic dyes. In comparison to individual treatment, a mixture of many treatments generally results in high removal efficiencies. A combination of several treatment methods, such as ozonation, vacuum ultraviolet, and ultraviolet hydrogen peroxide treatments improves the removal of pollutants from the wastewater.15 However, attributed to the formation of ozone and the use of high-energy consumable UV lamps, these approaches require a large amount of energy and are therefore quite expensive.16 Other approaches, such filtration, coagulation, or chemical coalescence, lead to secondary disposal issues.17–19 The Development and optimization of effective alternative method that is affordable, smart, greener, and ecologically sustainable has therefore become important. The employment of microbes and enzymes in biological methods of pollutant removal appears to be of special importance in this respect.20 The necessity for the development of better waste treatment procedures has arisen as a result of the introduction of increasingly strict criteria for the release of pollutants into the environment. The development of enzymatic treatment technologies for solid, liquid, and toxic waste has been the subject of extensive research. Numerous enzymes from various plants and microbes have been identified to be significant in a wide range of applications for waste treatment. Specific recalcitrant

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contaminants can be removed by precipitation or transformation into other products by the action of enzymes. They can also alter waste qualities to make it more treatable or help to turn debris into products with value-added features.21 Enzymes are biological catalysts created by living organisms are mandatory for the numerous metabolic functions of the cells and are essential for maintenance of cell and body and for the proper functioning of life. Enzymes are quite particular in the substrates they operate on, and frequently a variety of enzymes are needed to carry out the series of metabolic processes carried out by living cells.22 Various microbes produce a substantial percentage of metabolic, oxidative, reductive, and hydrolytic enzymes.23,24 The crucial functions that microbial enzymes play as metabolic catalysts have led to a variety of industrial uses for these enzymes. Industrial enzymes have a very broad range of applications in both industrial and commercial settings. Different enzymes are used in waste water treatment for the removal of contaminants. Facchin et al. studied the secretion of enzyme and their applications for the treatment of wastewater. They isolated lipase and other hydrolytic biocatalysts yielding microbes to check their functionality for the decomposition of fatty and oily material present in wastewater.25 Enzymes are biological catalysts that catalyze different biochemical reactions, and they are extensively distributed in plants, animals, and microorganisms. Enhanced catalytic activity, specificity, sensitivity, and renewability are all benefits of these catalysts. They can also function under conditions of low pH, temperature, and pressure.1,2 After the initial run, though, enzyme cannot be retrieved and utilized again, rendering the process unprofitable.3 However, enzymes are very useful for treatment of waste but they find some limitations. Immobilized enzymes seem to be more durable and resistant to environmental changes than pure enzymes. Immobilized enzymes can also be removed from the reaction mixture and employed in subsequent cycles due to their improved stability. These benefits encourage their use in a variety of industries.26 The discovery of immobilized enzyme dates back to 1916. The researchers who conducted this research found that the physically adsorbed invertase on charcoal properly maintained its catalytic efficiency.27 Immobilization enables quick enzymatic recoveries, efficient enzyme assay termination, and repeatable enzymatic analysis, all of which lower assay costs. Additionally, the chemical stability, pH, and temperature survivability are typically enhanced after immobilization. Depending on these benefits, immobilized enzymes have found widespread use in a variety of industries, including the pharmaceutical, food,28 wastewater management,29 and textile industries.30

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Enzymes that have been immobilized can be used in multitude of disciplines. For the immobilization of enzymes, several novel techniques have recently been developed that are more effective and widely applicable. This domain has rapidly developed into an interdisciplinary field over the past 20 years. The present study is a thorough analysis of a wide range of publications on various enzymes that have been immobilized on diverse supporting materials and are used for waste water treatment.

2. Enzyme immobilization for sewage treatment Enzymes that have been immobilized are frequently used in numerous processes. The technique of immobilization and the support material can be chosen depending on the kind of application. In addition to being able to be removed from the reaction medium and utilized again, immobilized enzymes also shield the enzyme from adverse environmental factors such as high temperatures, solvents, oxidizing agents, etc. The immobilized enzymes are also extensively employed in the foodstuff, medicinal, bioremediation, disinfectant, and textile industries, and many others. The enhanced enzyme loading that results in regulated diffusion from enzymes also helps in optimizing stability. Utilizing immobilization techniques lowers the expense of wastewater treatment.31 The whole process for waste water treatment using immobilized enzymes is elaborated in Fig. 1. Biocatalysts are now utilized to break down the dye components. Peroxidases, laccase,

Fig. 1 Schematic diagram of enzyme immobilization and its use for waste water treatment.

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and azo reductases are the enzymes utilized in sewage treatment. These enzymes may reduce their activity when exposed to high temperatures, low or elevated pH levels, and high ionic concentrations; immobilized enzymes are utilized to address this issue. Wastewater can be treated using immobilized enzymes, especially if the water has been contaminated by one or more pollutants that can be precisely altered or removed enzymatically. It is notable in this context that an intriguing approach for the elimination of nitrate and nitrite in water utilizing immobilized enzymes has recently been discovered.32 Nitrates, a frequent and dangerous groundwater recharge pollutant, is currently eliminated either through physical and chemical processes that do not decompose it or through microbial degradation, which requires a lengthy and slow process. Mellor et al. reported a quick and effective method of removing nitrate that makes use of enzymes that have been immobilized. The electrical current drives the breakdown, which completely converts the nitrates to Nitrogen gas without leaving any other dangerous byproducts. Co immobilization of Nitrate reductase and crude nitrate reductase along with N2O reductase was carried out to construct electro-bioreactor Enzymes were obtained from corn and a nitrogen fixing bacteria Rhodo pseudomonas. These biocatalysts incorporated electron-carrying pigments in some polymer matrices, and they were then applied to the cathode’s surface in different thicknesses. When a low voltage is applied, nitrate-containing water is driven past the anode and onto the activated material on the cathode, leading in two-step nitrate reduction to Nitrogen gas via nitrite intermediate route. In comparison to free solution, the co-immobilized state of the enzyme exhibits greater activity.33

3. Different methods to immobilize enzymes Different techniques are used to immobilize enzymes for the waste water treatment. Mainly, Physical and chemical methods are used to immobilize enzyme. Physical methods include entrapment and adsorption of enzyme on support while chemical methods consist of covalent immobilization and cross linking between enzyme and solid support. Various method used for enzyme immobilization are shown in Fig. 2. Adsorption method is most demanding because it is very easy to regenerate enzyme using this method. Covalent immobilization causes conformational changes in enzyme which affects its enzymatic activity.34

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Fig. 2 Different methodologies for immobilization of enzymes.

Peroxidases find their potential applications in waste water treatments.35 Entrapment method is mainly used to immobilize horseradish peroxidase (HRP) enzyme for the removal of effluents in waste water. For example, Singh et al. studied the entrapment of HRP and its potential usage for wastewater treatment. HRP was entrapped in polyacrylamide gel in the presence and absence of proline. In both cases, 8% yield of immobilized biocatalyst was obtained with 8% polyacrylamide beads. The activities and stabilities of both enzymes were compared and it was seen that the enzyme immobilized in the presence of Proline showed enhanced activity and stability. After eight times of its reuse, enzyme immobilized in the presence of proline lose 60% of its activity while the other one lose 90% activity. It was suggested that enzyme immobilized in the presence of proline is a promising method to increase activity of HRP.36 One of the essential aspects that can impact an enzyme’s performance is the approach used to immobilize the enzyme. Enzyme immobilization can be accomplished using a range of methodologies, each of which has advantages and disadvantages.

3.1 Encapsulation method Enzymes are enclosed in membranes that are selectively permeable, like cellulose nitrate or nylon, as part of the encapsulation process. Application of the encapsulation approach is common in the pharmaceutical, food, textile,

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and sewage treatment sectors.37 Encapsulation is typically a straightforward and inexpensive immobilization technique that can increase the enzymatic activity because of the large contact area between both the biocatalyst and substrate.38 It has taken a lot of past research and work to figure out how to use various peroxidases to decolorize colored aqueous solutions. HRP is a promising biocatalyst to remove effluents present in wastewater released from textile, leather and paper industries. It is immobilized using encapsulation method to enhance its activity and reusability. Immobilization of HRP enzyme and its potential applications were studied by Alemzadeh, I., and S. Nejati. Enzyme was immobilized on porous alginate beads. 1% Na-alginate along with 5% Ca-alginate was utilized to encapsulate enzyme. When HRP is immobilized, its pH profile changes, showing larger values in basic and acidic solutions. The percent conversion falls as the initial phenol content rises. The amount of phenol that converts the most is 2 mM Immobilized enzyme had a reduced effectiveness compared to free enzyme at the same dose, according to research on the chosen period of phenol elimination. However, the capsules could be reused up to four times without even any variations to their retention effectiveness. Phenol elimination increases gradually as enzyme concentration rises from 0.15 to 0.8 units/g alginate. It has been discovered that the starting phenol content influences the ratio of hydrogen peroxide/phenol at which the maximum phenol removal is attained; in the solutions of 2 and 8 mM phenol, this ratio was 1.15 and 0.94, respectively. The prospect of uninterrupted phenol elimination was demonstrated to be viable based on the findings of the current study.39 Gholami-Borujeni et al. immobilized HRP enzyme on Ca-alginate beads by using encapsulation method and studied its uses to remove, degrade and detoxify azo dyes from wastewater. For the profitable and effective decolonization of textile effluent discharge, immobilized horseradish peroxidase (HRP) on calcium alginate gel beads have been developed and applied. It was possible to determine the ideal circumstance for the immobilization of HRP on calcium alginate gel beads, which results in a specific activity of 15 U/g calcium alginate. Following immobilization, the optimal gelation condition was determined to be 2% w/v of Na-alginate solution and 2% w/v of CaCl2
6H2O. This was done by taking into account biocatalyst encapsulation efficacy, retention activity, and enzyme permeability of the capsules. When an enzyme is immobilized, its pH profile changes, showing larger values in basic and acidic solutions. The effectiveness of the capsules diminished after 10 cycles of use.40

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Advantages can be found in the entrapment and encapsulating enzymes, such as a significant larger surface for the interaction of biocatalyst with reactant involves the utilization of relatively small volume. The shortcomings of this method include the need for a high enzyme concentration and the infrequent deactivation of the enzyme upon encapsulation. In order to keep the enzyme inside the capsule, the pore size of the membrane also needs to be extremely tiny.41 Azo dyes are regarded as being resistant, non-recyclable, and unrelenting among the classes of compounds of dyes. The management of effluents containing dyes is regarded to be one of the most difficult challenges in the process of sustainable development. Dyes, which are intricate aromatic hydrocarbons, are typically used to color a variety of substrates, including suede, fabrics, papers, etc. Owing to their poisonous and inhibiting nature, they are occasionally amalgamated with toxic metals on the structural interfaces and are thought to have somewhat negative effects on the environment.42–44 HRP enzyme degrade different azo dyes.45 Degradation of azo dyes were studied using immobilized HRP and free enzymes. Compared to the free enzyme, HRP that was confined in calcium alginate gel only partially decolored the azo dye straight yellow (52%) while free enzyme decolorized it up to 69%. The azo dye was decreased by enzyme immobilization using gel or alginate. The same dye was removed using the immobilized enzyme beads two or three more times, although with lower efficacy.46 However, dealing with the issue of enzyme spillage is one of this technique’s shortcomings. Additionally, it needs a lot of substrate because the membrane’s pore size restrictions may make it difficult for a massive substance to pass through.31 To reduce enzyme activity loss and maximize reusability, immobilization processes must be tuned. The continuous treatment of enormous amounts of effluent has a lot of potential using this form of enzyme delivery.47

3.2 Adsorption method One of the most straightforward reversible immobilization techniques that can be employed is physical adsorption, which can be carried out in mild environments. Weak forces including hydrogen bonding, ionic contact, and van der Waals attraction are used to directly adsorb or adhere the enzyme to the carrier material. Because of its low cost, simplicity of setup, and lack of mass transfer constraints, the adsorption method is widely employed.48

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Degradation of chlorophenol from the waste water was studied by Tatsumi et al. HRP enzyme was immobilized and its functionality for degradation of chlorophenol was studied. Enzyme was physically adsorbed on magnetite support. Physical adsorption method was more preferable as compared to cross linkage. It was discovered that the enzyme was immobilized with 100% of its maintained activity. Horseradish peroxidase was also found to be preferentially adsorbed on magnetite, and the immobilization produced a 20-fold upsurge in the rate of crude biocatalyst refinement. Each chlorophenol was nearly completely removed when immobilized peroxidase was used to treat a solution containing different chlorophenol, Additionally, the elimination of total organic carbon and absorbable organic halogen was upto 90%. Anyhow, Whole elimination of each chlorophenol could not be achieved using soluble peroxidase, and elimination of 2,4,5-trichlorophenol specifically had the lowest removal rate which was only 36%.49 A search has been performed for a less expensive, more convenient, and straightforward substitute for the immobilization of biocatalysts and their subsequent widespread applications in the fabric waste treatment process. For the first time, industrial laccase was physically immobilized to green coconut fiber, a commercial byproduct from the food industry using the method of adsorption. It was discovered how the immobilization circumstances affected the physical characteristics of enzyme. The characterization of the immobilized enzyme was then carried out, and kinetics parameters of immobilization were determined. Its feasibility for continuous applications was demonstrated by improved thermal and mechanical stabilities compared to standard industrial laccase. Last but not least, the effectiveness of immobilized laccase for the ongoing oxidative decomposition of different destructive synthetic dyes as well as a combination of them in batch mode was assessed. Decolorization of the solutions as a result of adsorption process on the supporting material and as a result of biocatalyst action were both seen as phenomena. The immobilized industrial laccase is ideal for incessant dye decolorization from industrial sewage as evidenced by the extraordinary percentage of decolorization of nearly all dyes in the initial two cycles and also an effective dye removal from the dye mixture.50 Nevertheless, this approach has a drawback in that the adsorbed enzymes have low operational stability. Due to the poor interaction between the biocatalyst and support, this could lead to the denaturation of enzymes in rigorous operating conditions.48 Due to variable adsorption kinetics, differences in the level of unwinding, and competitive binding interactions, immobilization of enzyme through adsorption from a mixture is challenging to manage.51

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3.3 Entrapment Entrapment is a permanent immobilization technique in which the enzymes are physically held in place inside of the permeable matrix scaffold that lets products and substrates pass through but holds the enzymes in place.52 Gelatin, polymers, and carbohydrates are a few examples of the biological supports that are frequently employed as entrapment purposes.53 This approach can produce high resilient to catalytic inactivation because of the large improvement in heat and storage stabilities.54 This is due to the immobilized enzymes’ resistance to enzymatic denaturation in adverse circumstances. Furthermore, numerous investigations demonstrated that entrapped peroxidases can support enzymatic reuse and maintain the catalytic decolonization effectiveness after usage up to a number of repetitions.55,56 But besides these benefits, entrapment techniques are currently not frequently used for industrial scale applications.57 For the purpose of degrading textile dyes, horseradish peroxidase (HRP) was immobilized onto chitosan beads using the entrapment method. The purification of HRP, its immobilization on chitosan and characterization are illustrated in Fig. 3. The highest immobilization yield was demonstrated by stable and firm quality chitosan beads made with a chitosan content of 2.5%. The entrapped enzymes showed an increase in optimum pH toward basic area. The free enzymes have their optimal activity at 7 pH. The thermal Stability of immobilized enzyme was increased and it showed it optimum

Fig. 3 Immobilization of HRP on chitosan support for the breakdown of dyes in textile wastewater. Reprinted from Bilal M, et al. Enhanced bio-catalytic performance and dye degradation potential of chitosan-encapsulated horseradish peroxidase in a packed bed reactor system. Sci Total Environ 2017;575:1352–1360 with the permission of Elsevier.

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activity at 70 °C. The decolorization of four distinct textile dyes, including Remazol Brilliant Blue R (RBBR), Reactive Black 5 (RB5), Congo Red (CR), and Crystal Violet, was also carried out using this entrapped-HRP enzyme. In six successive batch procedures, the decolorization effectiveness of the immobilized was quite high. According to the findings, immobilized HRP is a desirable option for application as an industrial biocatalyst in more wide-ranging bioremediation of fabric dyes and seepages.58 Like numerous other biocatalysts, laccases can be utilized constantly in the immobilized form. It has potential for bioremediation of waste water. Chhabra, Mishra, and Sreekrishnan studied the immobilization of laccase and its uses for the biodegradation of dyes. Laccase enzyme was isolated from Cyathus bulleri. Its immobilization was carried out by using the process of entrapment. Polyvinyl Alcohol was utilized to entrap enzyme and nitrate or boric acid was used for its cross linking. Using a fixed bed column, immobilized laccase was employed to perform dye degradation in both sequential and continuous modes. By conducting an LC MS/MS study, the byproducts of the dye Acid Red 27 were detected. The technique provided quite efficient laccase immobilization and stability which was greater than 70% after 5 months of preservation at 4 °C. The generated dye effluent underwent batch decolorization and resulted in 90–95% decolorization for up to 10–20 cycles. For a maximum of 5 days, continuous decolorization in a bioreactor with packed beds resulted in decolorization rates of approximately 90%. In the vicinity of a mediator, the immobilized laccase was also effective at decolorizing and breaking down Acid Red 27.59 As the enzymes are entrapped in porous material, variation in the pore size cause leakage of enzymes and there is also restriction in mass transfer of reactants to convert into products. So this method is not feasible as compared to other methods used for immobilization.60

3.4 Covalent immobilization The greatest potential link between the supporting material and the biocatalyst is typically achieved through covalent immobilization, which also reduces leakage problems. Additionally, covalent bonding permits the greatest improvement in operational robustness specifically with respect to heat, pH, chemical agents, and also regarding preservation, and it typically does not interact with the mass transport of chemicals or products. These are essential components for any commercial process to be feasible.61,62

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Vineh et al. studied the immobilization of HRP enzyme on graphene support. Covalent immobilization approach was used and cross linking of immobilized biocatalyst was carried out through glutaraldehyde. Immobilized biocatalyst was used to biodegrade the phenolic content present in wastewater. The catalytic efficacy of HRP was enhanced upto 8.5 times after immobilization. Immobilization increased the enzyme capacity for reuse, and after 10 times of reuse, 70% of the original activity was still present. The immobilized HRP was less vulnerable to pH fluctuations than the unbound HRP as a consequence of the buffering action. For significant phenol content (2500 mg/L), the immobilized and free enzyme had degradation efficiencies of 100% and 55%, respectively.63 Although covalent immobilization of enzyme for the waste water treatment is advantageous however it finds its some limitations. After covalent immobilization, there is a chance that enzyme will modify sterically and its activity will be reduced. Moreover, covalent bonding is irreversible. Therefore, supports used for immobilization cannot be reused because of the irreversible bonding between enzyme and support. However, in some circumstances enzyme release under benign circumstances is feasible, enabling support recovery. For covalent immobilization, the support often needs to be both functionalized and activated. To prevent all of the aforementioned drawbacks and to provide the greatest gain in enzyme immovability and activity, all of these processes must be carefully planned. Actually, a poorly planned immobilization technique can have the opposite consequence.64–66

3.5 Cross linking method Another way of permanent enzyme immobilization without the use of a composite material or scaffold is cross-linkage, widely recognized as copolymerization. This procedure often entails the use of multifunctional chemicals to create intermolecular cross-links between the biocatalyst molecules. The two most often utilized functional chemicals are diazonium salt and C5H8O2. For instance, Sun et al. investigated the use of C10H18O5 to immobilize HRP cross-linked on nanofiber framework. Additionally, the compound showed increased stability, renewability, and excellent resistance to microbiological assaults. It also had better catalytic activity. However, because to its costly preparation and challenging reaction control, this technique’s practical application is constrained. Another disadvantage is the potential for catalytic capabilities to be lost as a result of denaturing the biocatalyst during immobilization.67

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Bilal, Muhammad, et al. immobilized manganese peroxidase (MnP) biocatalyst. Chitosan beads were used as support which was activated by the aid of glutaraldehyde and cross linking method of immobilization was employed. This immobilized enzyme was used to degrade and detoxify textile dyes effluents present in wastewater. The efficacy of the immobilize biocatalyst was accessed in terms of decolorization, enhanced purity of water, and decreased toxic effects. 97.31% of dye colors were removed using these immobilized biocatalysts. The biological treatment of fabric wastewater by the immobilized MnP shown excellent efficiency and can be applied to the biodegradation of hazardous compounds in sewage. It is recommended to monitor treated wastewater using biocontrol agents to assess the bio-efficacy of the waste management procedure for secure discharge of effluents into rivers and lakes.68

4. Applications of immobilized enzymes in wastewater treatment One of the top candidates to effectively and cheaply remove the majority of the contaminant from sewage is the use of immobilized enzymes in treating wastewater. Immobilized enzymes find their numerous applications in biodegradation of various types of effluents like pesticides, medicinal residues, dyes and phenolic compounds present in water.69–71 Some of these application is illustrated in Fig. 4.

Fig. 4 Potential applications of immobilized enzymes for waste water treatment.

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4.1 Food industry wastewater treatment The enzyme lipase may hydrolyze fats and oils into long-chain fatty acids and glycerol. For the degradation of lipids and oils to remediate the sewage from the food sector, immobilized lipase is of great interest. Slow degradation rate is a shortcoming of traditional treatment procedures; as a result, oil and fats are absorbed onto the surface of the sludge. Oil and grease (O&G) are present in high concentrations in the wastewater produced by the pet food industry, making it challenging to treat using traditional biological treatment methods. Researchers has assessed the hydrolysis of O&G found in animal food industry wastewater. Lipase enzyme was extracted by Candida rugosa and its immobilization was done on Ca-alginate material. The hydrolysis of O&G was carried out using this enzyme. The results demonstrated that the biocatalytic activity which hydrolyze about 50% of the O&G. A noteworthy increase in chemical oxygen demand and volatile fatty acid was also detected. p-nitro phenyl palmitate was used to confirm the activity of enzyme. This experiment was carried out for 3 days. 65% of alginate beads were recovered after the reaction. Enzymes retained 70% of its activity. This study highlights the possibility of using immobilized lipase as a first step in the bioremediation of animal feeds waste.72 Because of the existence of compounds needed to protect milk prior to inspection, such as chloramphenicol, the effluent released by milk quality assurance laboratories is more complicated than that of dairy companies. This type of sewage has undergone industrial-scale microbial filtration system containing reactor treatment.73 Additionally, lactose present in dairy products enhances the biological oxygen demand of water when its higher percentage is found in dairy discharges which contributes to environmental contamination.74 A commercially accessible form of β-galactosidase which is extracted from Kluyveromyces fragilis is called Lactozym™. Roy, Ipsita, and Munishwar N. Gupta. Studied the hydrolysis of lactose by immobilizing Lactozym™ on cellulose beads. The reusability of immobilized enzyme was enhanced upto three times after immobilization. Immobilized biocatalyst can be applied to create a method for lactose hydrolysis that will enable the usages of whey in addition to the creation of lower lactose dairy products and in treating dairy wastewater for degradation of lactose.75

4.2 Pharmaceutical wastewater treatment The issue of pharmacological wastes polluting water is serious when you consider the rapid expansion of the pharmaceutical market, the use of both human and animal medications, and the growing amount of medicines,

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antidepressants, and stimulants. Drugs are not completely metabolized by living things and wind up in sewage before being treated in a plant that treats sewage. Due to the fact that the techniques of pollution remediation presently in employ do not completely decompose trace levels of hormones or medications, new means of eradication of these components are being investigated, that may also include the use of immobilized biocatalysts.76 A potential environmentally friendly method for removing medicinal chemicals that are discharge into the ecosystem by sewage effluent is enzyme-based decomposition using ligninolytic biocatalysts, such as laccase. Prior to commercial applications, nevertheless, the drawbacks of employing the enzyme in its free states, such as recyclability and durability, should be kept in mind. Taheran et al. immobilized laccase enzyme on nanofiber and studied its functionality for the removal of medicinal residues in water. Biochar fused nanofiber membrane was taken as support to immobilize laccase on it. Immobilized biocatalyst was used to degrade three medicinal compound in batch. These three compounds belong to three different classes of pharmaceutical compounds. Enhanced Thermal, pH storage stability was observed for immobilized biocatalyst. This biocatalyst was reused upto 10 times with retention of 17% original activity.77 Garcia et al. extracted laccase from Pycnoporus sanguineus. The enzyme extract was immobilized on Ca and Cu alginate and chitosan support and it was applied for the biodegradation of 17α-ethinylestradiol (EE2). The immobilized biocatalyst on Ca-beads in a medium devoid of buffer produced the best degradation results. In addition, the immobilized enzyme reusability was enhanced upto five times to remove EE2.78

4.3 Biodegradation of phenol and its derivatives phenol and its derivatives are known to be devastating environmental pollutants that pose a harm to aquatic life, terrestrial life, and mankind. This hazardous is based on comparatively significant toxicity of these compounds, even at low doses. The International Programme on Chemical Safety states that organic molecules from various industries have the potential to kill living things by harming their nerves and muscles, hearts, kidney and other organs.54 The wastewater from a variety of industrial processes, including coal transformation, metal plating, medicinal production, pulp, garment, and thermoplastic manufacturing, as well as petroleum refineries, contains these harmful compounds. The International Program on Chemical Safety states that the toxic effects of phenolic content, at even low doses,

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makes their disposal without adequate treatment a serious danger to both animals, and aquatic life. Long term exposure to all these aromatic chemicals can have adverse health effects on people, including nausea, malnutrition, migraines, diarrhea, and skin rashes.79 Therefore, it is essential to create a more affordable, environmentally friendly, and long-lasting technology for the treatment of industrial wastewater. Immobilized enzyme was reportedly employed for treating wastewater, according to a variety of sources. Arslan effectively utilized PET fibers, popularly recognized as polyethylene terephthalate, to immobilize HRP for azo dye decolorization. Due to their strong endurance to various pH and temperature extremes and their enormous particular surface area, PET fibers have lately received a great deal of attention as scaffolds for immobilized enzyme. According to the investigation, glyceryl methacrylate was used to modify PET fibers, and benzoyl peroxide served as the trigger. The results of the dynamic tests showed that immobilized HRP has a greater affinity and catalytic performance than free HRP. At pH 7 and 40 °C, immobilized HRP had a highest dye decolorization efficacy of 98% in 45 min.80 Taghizadeh et al. synthesize Zeolite Y and after preparation delaminated and desilicated it for its modification. Laccase enzymes was immobilized on three different form of zeolite Y. These immobilized enzymes were used to biodegrade bisphenol A (BPA). It was observed that enzymatic efficacy was enhanced in delaminated support material.81 Li et al. used iron oxide polyacrylnitrile (PAN) magnetic nanofibers (MNFs) to immobilize HRP enzyme and performed further studies on it to check its capability to biodegrade phenolic compounds present in waste water. The immobilized HRP displayed greater enzymatic activity but exhibited no variation in optimal pH when compared to the unmodified HRP. 40% immobilized enzymes were used to treat phenolic wastewater, and it was successful in removing phenol with an efficacy of 85% after the initial use as well as 52% after five further reuses. It was anticipated that the immobilized enzymes would find use in wastewater treatment, particularly for the elimination of phenol.82

4.4 Industrial wastewater treatment The fabric industry has significantly damaged ecosystem and caused serious environmental problems. The primary component of the fabric industry’s wastewater is dye, of which 20% is discarded or eliminated as a result of insufficient retention on the garment. The significance of immobilized biocatalysts as possible bio-remediating agents has expanded.83

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Dye pollution is currently ranked among the most dangerous categories of environmental contaminants. This reality is brought about by an increase in the usage of fabrics and other basic goods which are colored mostly with anthracenedione, azo dyes. These substances are easily disposed of in residential sewage as laundry wastes, although the majority of dyes are discharged directly from the textile industry as wastes during dying procedures. Dye migration into different water bodies, including seas, rivers, and even aquifers, is a result of inadequate sewage treatment. Because of their inherent toxicity and cancer-causing qualities, dyes can quickly accumulate all across the food system and disrupt the physiological mechanisms of an environment that has been contaminated.75,84,85 Zamora et al. immobilized HRP enzyme on different supports and checked their capability to biodegrade waste chemicals and dyes discharged from paper, textile and other industries. It was observed that Amberlite IRA-400 support which is actually an ion exchange resin showed the maximum immobilization yield and its efficacy of biocatalyst after immobilization on this resin enhanced and decolorization of dyes were achieved after 4 h of reaction. The combination of photo-enzymatic decolorization process therefore seems to be a highly effective remediation technique with significant potential for treating industrial wastewater.86 A promising biocatalyst, laccase has the potential to be used in a variety of processes, such as treatment of sewage, green synthesis, bio decolorizing of pulp production, biosensors, fabric finishing, and alcohol stabilization. Enzyme applications can benefit from a number of improvements owing to the immobilization process because both the preservation and functional stabilities are usually improved. Furthermore, immobilized enzymes have the benefit of being reusable over free enzymes.87 Minussi et al. obtained laccase enzyme from Trametes versicolor and immobilized it in the presence of 1-hydroxybenzotriazole and applied it for the degradation of dyes and phenolic content present in waste water of olive mill.88

5. Future prospective Wastewater treatment has a lot of potential for biocatalytic processes. Enzymatic processes heavily depend on the kinds and sources of enzymes. Therefore, more research is required to examine how well enzymes operate on particular types of wastewater. The elimination of recalcitrant contaminants has demonstrated the viability of enzyme-based wastewater treatment. However, a lot of the research were carried out in experimental or laboratory settings, and the wastewater was synthetic, which makes them

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unsuitable for real-world use. Therefore, there is a pressing demand for more investigation on actual wastewater treatment at larger-scale. Enzymes are unable to breakdown some resistant contaminants, such as plastics and medicines, at all. Although mediators are a practical technique to improve enzymatic function, their toxicity must be taken into consideration. It is preferable to utilize fewer mediators, even though some studies are dedicated to discovering natural mediators that could reduce the undesirable results. Enhancing the enzymes’ capacity to act as catalysts, which promotes the breakdown of these resistant pollutants, is a practical application of genetic engineering. Another viable option is to discover additional novel enzymes to catalyze the destruction of resistant contaminants. Regardless of the benefits of biocatalytic wastewater treatment, the primary barrier to using biocatalyst is their prohibitive budget. Enzyme wastewater treatment on a wide scale is simply not commercially viable. Nonetheless, the operating cost can really be significantly reduced if the highest immobilized enzyme reusability is attained through the adoption of standardized immobilization techniques. A future multidisciplinary approach to sewage treatment is the outcome of the fusion of nanomaterials and enzymatic technologies. These innovative biocatalytic applications may assist these biocatalysts to be used to their highest possible extent. To offset the high start-up and operating costs, future studies in this field should focus on improving the reusability of immobilized enzymes and optimizing the activity of crude enzyme synthesis. Enzyme activity loss to a certain extent accompanies the immobilization processes, therefore immobilized biocatalysts have a limited shelf life. Finding suitable immobilization supports and techniques for enzyme immobilization is therefore essential to decrease enzymatic activity loss and increase enzyme recyclability. The research of advanced scaffolds, support surface functionalization, and chemical modification are currently the methods used to identify appropriate carriers. Enzyme immobilization procedures can be improved by a deeper comprehension of enzyme properties such as morphology and reaction mechanisms. Since most studies only include the elimination of one or two types of pollutants from activated sludge by a particular enzyme, selectivity is both an advantage and a disadvantage of enzyme-based wastewater treatment. The real wastewater, however, is complicated, and one biocatalyst could not breakdown it. Consequently, it’s crucial to create immobilization methods that allow several enzymes to work together. Because enzymes can only break down a single substrate into smaller chemicals, this approach cannot entirely eliminate contaminants on its own.

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6. Conclusion In many different industries, including the food industry, the drug industry, biological treatment, surfactants industry, textile manufacturing, etc., enzyme immobilization is a commonly used approach. Due of its technological and financial advantages, this method is adopted. Biocatalysts have been immobilized in enormous quantities and employed in numerous large-scale systems. The expenditure of the enzymes can be reduced with this stabilization technique. Enzymes are given operational stability through immobilization. Enzymes are important in the breakdown of pollutants, and enzymatic management and engineering have proven to be significant in the treatment of wastewater. Immobilized biocatalysts can be used in sewage treatment to provide ecologically friendly rehabilitation strategies that are significantly less destructive than traditional methods. They have a benefit over the traditional physical and chemical treatment methods due to their adaptability and effectiveness, even in moderate reaction circumstances. The enzymes are obtained from natural source and are biodegradable which can lessen their negative environmental effects, making enzymatic treatment of wastewater an environmentally sound method. In the degradation process of recalcitrant pollutants such fats, oil, medications, care products, insecticides, and industrial chemicals, enzymatic reactions are proved to be promising. Nevertheless, as enzymes only break down complex molecules into simpler ones, this approach can only serve as a pretreatment method and must be used in conjunction with other techniques to obtain complete treatment. The use of this technology now faces several challenges, necessitating research into actual wastewater applications, larger-scale applications, biocatalytic activity and stability enhancement and the development of different enzyme systems. Additional research should be done to improve the analysis procedure and assess the biological treatment options.

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51. Hirsh S, et al. A comparison of covalent immobilization and physical adsorption of a cellulase enzyme mixture. Langmuir 2010;26(17):14380–8. 52. Sheldon RA. Enzyme immobilization: the quest for optimum performance. Adv Synth Catal 2007;349(8–9):1289–307. 53. Datta S, Christena LR, Rajaram YRS. Enzyme immobilization: an overview on techniques and support materials. 3 Biotech 2013;3(1):1–9. 54. Jun LY, et al. An overview of immobilized enzyme technologies for dye and phenolic removal from wastewater. J Environ Chem Eng 2019;7(2), 102961. 55. Asgher M, et al. Recent trends and valorization of immobilization strategies and ligninolytic enzymes by industrial biotechnology. J Mol Catal B: Enzym 2014;101:56–66. 56. Bilal M, et al. Horseradish peroxidase-assisted approach to decolorize and detoxify dye pollutants in a packed bed bioreactor. J Environ Manage 2016;183:836–42. 57. Dwevedi A. Basics of enzyme immobilization. In: Enzyme immobilization. Springer; 2016. p. 21–44. 58. Bilal M, et al. Enhanced bio-catalytic performance and dye degradation potential of chitosan-encapsulated horseradish peroxidase in a packed bed reactor system. Sci Total Environ 2017;575:1352–60. 59. Chhabra M, Mishra S, Sreekrishnan TR. Immobilized laccase mediated dye decolorization and transformation pathway of azo dye acid red 27. J Environ Health Sci Eng 2015;13 (1):1–9. 60. Go´recka E, Jastrzębska M. Immobilization techniques and biopolymer carriers. Biotechnol Food Sci 2011;75(1):65–86. 61. Zucca P, Sanjust E. Inorganic materials as supports for covalent enzyme immobilization: methods and mechanisms. Molecules 2014;19(9):14139–94. 62. Wu JCY, et al. Enhanced enzyme stability through site-directed covalent immobilization. J Biotechnol 2015;193:83–90. 63. Vineh MB, et al. Stability and activity improvement of horseradish peroxidase by covalent immobilization on functionalized reduced graphene oxide and biodegradation of high phenol concentration. Int J Biol Macromol 2018;106:1314–22. 64. Barbosa O, et al. Heterofunctional supports in enzyme immobilization: from traditional immobilization protocols to opportunities in tuning enzyme properties. Biomacromolecules 2013;14(8):2433–62. 65. Sollai F, et al. Irreversible affinity immobilization of lentil seedling amine oxidase with activity retention. Environ Eng Manag J 2007;6(1):31–5. 66. Wu H, et al. Catechol modification and covalent immobilization of catalase on titania submicrospheres. J Mol Catal B: Enzym 2013;92:44–50. 67. Sun H, et al. Improved biodegradation of synthetic azo dye by horseradish peroxidase cross-linked on nano-composite support. Int J Biol Macromol 2017;95:1049–55. 68. Bilal M, et al. Chitosan beads immobilized manganese peroxidase catalytic potential for detoxification and decolorization of textile effluent. Int J Biol Macromol 2016;89:181–9. 69. Guzik U, Hupert-Kocurek K, Wojcieszy nska D. Immobilization as a strategy for improving enzyme properties-application to oxidoreductases. Molecules 2014;19 (7):8995–9018. 70. Ba S, et al. Laccase immobilization and insolubilization: from fundamentals to applications for the elimination of emerging contaminants in wastewater treatment. Crit Rev Biotechnol 2013;33(4):404–18. 71. Wong JKH, et al. Potential and challenges of enzyme incorporated nanotechnology in dye wastewater treatment: a review. J Environ Chem Eng 2019;7(4), 103261. 72. Jeganathan J, Bassi A, Nakhla G. Pre-treatment of high oil and grease pet food industrial wastewaters using immobilized lipase hydrolyzation. J Hazard Mater 2006;137(1):121–8.

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73. Omil F, et al. Anaerobic filter reactor performance for the treatment of complex dairy wastewater at industrial scale. Water Res 2003;37(17):4099–108. 74. Bashir N, Sood M, Bandral JD. Enzyme immobilization and its applications in food processing: a review. Int J Chem Stud 2020;8:254–61. 75. Roy I, Gupta MN. Lactose hydrolysis by Lactozym™ immobilized on cellulose beads in batch and fluidized bed modes. Process Biochem 2003;39(3):325–32. 76. Nhung NTT, et al. Short-term association between ambient air pollution and pneumonia in children: a systematic review and meta-analysis of time-series and case-crossover studies. Environ Pollut 2017;230:1000–8. 77. Taheran M, et al. Covalent immobilization of laccase onto nanofibrous membrane for degradation of pharmaceutical residues in water. ACS Sustain Chem Eng 2017;5 (11):10430–8. 78. Garcia LF, et al. Optimization of laccase–alginate–chitosan-based matrix toward 17 α-ethinylestradiol removal. Prep Biochem Biotechnol 2019;49(4):375–83. 79. World Health Organization. Phenol: health and safety guide. WHO; 1994. 80. Arslan M. Immobilization horseradish peroxidase on amine-functionalized glycidyl methacrylate-g-poly (ethylene terephthalate) fibers for use in azo dye decolorization. Polym Bull 2011;66(7):865–79. 81. Taghizadeh T, et al. Biodegradation of bisphenol A by the immobilized laccase on some synthesized and modified forms of zeolite Y. J Hazard Mater 2020;386, 121950. 82. Li J, et al. Immobilization of horseradish peroxidase on electrospun magnetic nanofibers for phenol removal. Ecotoxicol Environ Saf 2019;170:716–21. 83. Mouni L, et al. Removal of methylene blue from aqueous solutions by adsorption on Kaolin: Kinetic and equilibrium studies. Appl Clay Sci 2018;153:38–45. 84. Parra-Arroyo L, et al. Laccase-assisted cues: state-of-the-art analytical modalities for detection, quantification, and redefining “removal” of environmentally related contaminants of high concern. In: Laccases in bioremediation and waste valorisation. Springer; 2020. p. 173–90. 85. Berradi M, et al. Textile finishing dyes and their impact on aquatic environs. Heliyon 2019;5(11), e02711. 86. Peralta-Zamora P, et al. Effluent treatment of pulp and paper, and textile industries using immobilised horseradish peroxidase. Environ Technol 1998;19(1):55–63. 87. Fernandez-Fernandez M, Sanroma´n MA´, Moldes D. Recent developments and applications of immobilized laccase. Biotechnol Adv 2013;31(8):1808–25. 88. Minussi RC, et al. Purification, characterization and application of laccase from Trametes versicolor for colour and phenolic removal of olive mill wastewater in the presence of 1-hydroxybenzotriazole. Afr J Biotechnol 2007;6(10).

CHAPTER TWELVE

Microbial remediation of emerging pollutants from wastewater Arooj Ramzana, Vaneeza Aimana, Azeem Intisara,*, Adeel Afzala, Tajamal Hussaina,*, Muhammad Amin Abidb, and Nazim Hussainc a

School of Chemistry, University of the Punjab, Lahore, Pakistan Department of Chemistry, University of Sahiwal, Sahiwal, Pakistan Centre for Applied Molecular Biology, University of the Punjab, Lahore, Pakistan ⁎ Corresponding authors: e-mail address: [email protected]; [email protected] b c

Contents 1. Introduction 2. Microbial remediation 3. Techniques of microbial remediation 3.1 Bioaugmentation 3.2 Bioventing 3.3 Biostimulation 3.4 Bioreactors 3.5 Biosorption 4. Factors affecting microbial remediation 5. Types of microbial remediation 5.1 Bacterial bioremediation 6. Genetically engineered bacteria (GEB) 6.1 Fungal bioremediation 6.2 Algal bioremediation 7. Microbial fuel cell 8. Role of microorganisms in the removal of some other emerging pollutants 9. Conclusion References

208 209 210 211 211 211 212 212 212 213 213 215 215 216 219 220 221 222

Abstract A volume of 326 million cubic miles of water is present on earth, out of which only 3% is fresh, and a significant portion is locked up in glaciers. Water pollution is increasing daily, so the competition for water resources is intense all over the world. Rapid urbanization,

Advances in Chemical Pollution, Environmental Management and Protection, Volume 9 Copyright # 2023 Elsevier Inc. 207 ISSN 2468-9289 All rights reserved. https://doi.org/10.1016/bs.apmp.2022.11.003

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poor sanitation, and industrialization adversely affected natural water resources, thus creating severe problems for human health. The contamination rate is so high that water treatment needs special attention. Microbial bioremediation has the potential to solve this problem by maintaining environmental (pH, temperature, nutrient content, etc.) and biological factors which ensure their stability and growth in contaminated water bodies. This type of remediation involves the use of various techniques to ensure the complete degradation of multiple pollutants. Bacterial, fungal, and algal remediations have different mechanisms of work in mitigating these pollutants. This chapter mainly emphasizes the microbial bioremediation of toxic heavy metals (cadmium, chromium, lead, copper, arsenic, mercury, etc.) from water, however, bioremediation of some other significant pollutants viz. nitrogen, phosphorous, and dyes have also been elaborated. Keywords: Bioremediation, Microorganisms, Genetically engineered bacteria, Heavy metals, Dyes, Nitrogen and phosphorous

1. Introduction Water is the second most crucial component after air for survival. Despite its importance for all living organisms, the availability of fresh water is deficient and unevenly distributed worldwide.1 The increase in population has not only increased consumption, but the modification of our lifestyle has also disturbed the natural balance. Rapid industrialization, urbanization, and improper sanitary systems cause water pollution.2 About 80% of untreated wastewater is discharged into water bodies, including those utilized for household purposes. This is causing water stress worldwide as freshwater resources become scarce. Research predicts that nearly 60% of the worldwide population will face water problems by 2025.3 Heavy metals are regarded as the most hazardous of the different water contaminants. The presence of heavy metals in wastewater results from a variety of natural processes and human activities. Multiple industries, such as textiles, electroplating, dyes, automobiles, batteries, and many more, discharge heavy metals into the surroundings.4 These industries discharge contaminants into the air, soil, and waterways.5 Heavy metals including Hg, As, Ni, Ti, Cd, Cr, Co, Pb, Cu, Zn, Ag, B, etc., enter the food chain and accumulate in the human body, causing deleterious health effects.6 In addition to damaging human health, these pollutants adversely affect plants and animals.7 This environmental deterioration increased the need for remedial approaches.

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The aim is to mitigate harmful contaminants from wastage. Several techniques have been developed to treat wastewater including chemical, physical and biological methods. For the elimination of toxic pollutants from wastewater, both conventional and innovative methods are used. Traditional procedures, such as electrochemical treatment, ion exchange, evaporation, precipitation, and osmosis, demand high energy input, rendering them very costly. Moreover, many of these techniques limit the sustainable eradication of metals and other contaminants from the environment.8,9 Modern approaches such as biological technologies, which are more cost-effective and sustainable, are widely used to remove impurities, notably heavy metals, from wastewater4 because these methods use microorganisms (bacteria, fungi, algae) for the deterioration of contaminants or conversion of pollutants to less toxic form without using any hazardous chemical and do not pollute the environment.10,11

2. Microbial remediation Bioremediation is the biological degradation of pollutants found in soil, sediments, and groundwater into nontoxic compounds. It comprises three essential components; microorganisms, food, and nutrition, collectively termed the bioremediation triangle. Microorganisms have a vital function because they convert chemicals into H2O, CO2, CH4, and biomass.12 It’s a natural process involving microorganisms that lower the concentration of pollutants. As microorganisms adapt to fast environmental change, they play a significant role in sustaining the ecosystem’s sustainability. They are ubiquitous and have an influence on the whole ecosystem; they have the ability to grow during their lifespan.13 Cells of microbes are responsible for several activities, such as carbon fixation, nitrogen fixation, sulfur metabolism, and methane metabolism, which govern biogeochemical cycles. These organisms manufacture metabolic enzymes that aid in safely disposing of numerous pollutants by reducing complicated harmful compounds into less toxic substances.14 This method is preferred over physio-chemical processes due to its versatility, efficiency, economical and eco-friendly nature.15 The schematics of wastewater treatment for various emerging pollutants through microbial remediation is provided in Fig. 1.

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Fig. 1 Removal of pollutants by microbial remediation.

3. Techniques of microbial remediation Various bioremediation strategies are used based on the saturation and aeration levels of a specific area. In-situ procedures cause minimum disruption to the groundwater and soil at the site.16 This method is often favored since it needs less material movement and is inexpensive. In-situ bioremediation is often divided into intrinsic bioremediation and engineered in-situ bioremediation but the main types are bioventing, biostimulation, biosparging, and bioaugmentation.17 Ex-situ methods are those that are used on water and soil that has been eradicated from an area by pumping or excavation.16 Technologies for ex-situ bioremediation are classified as solid phase or slurry phase. Composting, land farming, biopiles, and bioreactors are among the most crucial techniques.17 When selecting a bioremediation method, many factors are considered, including the sort of environment, the nature of the pollutant, the level of contamination, the area, and the cost. In addition to these factors, the effectiveness of bioremediation is determined by pH, nutrients, temperature, and oxygen levels.12 Quantitative evaluation of in-situ bioremediation of pollutants and heavy metals from the Bohai sea of China showed bioremediation efficiencies of n-alkanes and polyaromatic hydrocarbons (PAHs) in sediments are 32.84  50.42% after 70 days of bioremediation. The concentration of heavy metal is decreased by 72.06% in the Bohai sea China.18 Ex-situ bioremediation describes a process in which contaminated water is pumped to the site of bioremediation.19 The removal of fuel oil (TPHC10-C28) and diesel oil (TPHC10-C40) from contaminated water done by ex-situ had showed degradation of about 63% and 70% after 28 days of bioremediation.20 The detail of some of the techniques of microbial bioremediation is given below.

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3.1 Bioaugmentation In the process of bioaugmentation, there are specific sites where the removal of pollutants demands the use of microorganisms. They may also outcompete the native microorganisms, which implies that they can quickly clear up the site. It has been shown that the use of bioaugmentation in ecosystems including soil and water may result in the elimination of harmful substances. Nonetheless, a variety of cautions and restrictions have also been recorded. There are locations in bioaugmentation where microorganisms are necessary to remove pollutants. They are also capable of outcompeting native microbes, allowing them to swiftly clean the place. Bioaugmentation has been observed to remove hazardous substances from habitats such as soil and water. Nonetheless, certain restrictions have been found. For example, it has been discovered that abiotic and biotic stress factors reduce the number of foreign microbes following their addition to a contaminated site. Inadequate growth nutrients, like substrates, temperature variations, and pH, as well as competition between exogenous and indigenous microbes cause them.21,22

3.2 Bioventing Bioventing is the most prevalent in-situ technique for stimulating microorganisms by supplying contaminated areas with air and nutrients. To release contaminants into the environment via biodegradation, restricted airflow as well as low oxygen levels are required. Bioventing is capable of simulating the in-situ microbial degradation of simple hydrocarbons in the soil. It is restricted by the inability to provide oxygen to contaminated soil and the inadequacy of shallow contamination aeration.17

3.3 Biostimulation It involves the addition of rate-limiting nutrients like oxygen, nitrogen, phosphorus, and electron donors to heavily polluted sites to stimulate microorganisms to degrade hazardous and toxic contaminants. It is regarded as the most effective technique for hydrocarbon remediation among all bioremediation strategies.23 Non-ionic surfactants and inorganic fertilizers are used for the bioremediation of water contaminated with engine oil treated through ex-situ technique. The objective of the treatment was to reduce the total petroleum hydrocarbons (TPH) where 67.20% reduction in TPH concentration was observed after 42 days. The optimum values for achieving maximum degradation were 4.22 g and 10.69 μg/g for NPK and non-ionic surfactant, respectively. Organic nutrients are potentially useful as stimulating nutrients for biostimulation.24

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3.4 Bioreactors It is a vessel in which a succession of biological processes transforms raw materials into particular product(s). There are several modes of operation for bioreactors, including batch, sequencing batch, fed-batch, multistage, and continuous. The ideal growth parameters for bioremediation are provided by the bioreactor. The bioreactor-based remediation of contaminated soil offers several benefits relative to ex-situ remediation techniques. A bioreactor-based bioremediation approach with superior control of temperature, pH, aeration and agitation, concentrations of substrate and inoculum, decreases bioremediation time effectively. The adaptability of bioreactor designs permits maximal biodegradation with minimal abiotic losses.25

3.5 Biosorption In this process, microbes act as biosorbent but few factors must be considered before the microbe is selected. These are regeneration, kinetics of sorption, recovery of bounded metals, maximum sorption capacity, reusable, less expensive, and the kinetics of metals should be fast. Three broad categories of biosorbents are used: dead biomass, living cultures, and exopolysaccharides. Dead cells absorb metals better as compared to living cells. Filamentous fungi such as Aspergillus, Mucor, Actinomycetes, Penicillium, and Streptomycetes proved to be the best biosorbents for metal uptake and have shown the maximum capacity.26

4. Factors affecting microbial remediation Both the abiotic or environmental and biotic or biological factors affect the process of bioremediation. The reduction of organic molecules via microbes with inadequate carbon sources, and competitive interactions between microorganisms and bacteriophages is aided by biotic or biological factors. In many instances, the rate of pollutant degradation varies depending on the amount of the pollutant and the quantity of catalyst present in the biochemical process. The activity of the enzyme, interactions, development for biomass production, composition, and population size are among the most essential biological parameters.27 The interaction among microorganisms and pollutants is also dependent on abiotic or environmental conditions. pH, soil structure, temperature, moisture, water solubility, content of oxygen and redox potential, nutrients,

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chemical structure, solubility, and toxicity of contaminants all affect the growth and activity of microorganisms. The pH range of 6.5–8.5 is regarded as optimal for biodegradation in most of the terrestrial and aquatic systems. Moisture regulates contaminant metabolism by influencing the type and amount of soluble elements, as well as the pH and osmotic pressure of aquatic and terrestrial ecosystems.28

5. Types of microbial remediation 5.1 Bacterial bioremediation Bacterial bioremediation is the most vital technique for treating harmful contaminants that are not biodegradable, such as heavy metals. Metal remediation by bacteria has gotten a lot of interest since it is a safe, productive, and practical approach for treating heavy metal-containing wastewater. These metal-tolerant bacteria may attach cationic poisonous heavy metals to negatively charged bacterial components as well as living or dead biomass parts. This bacterial biomass effectively operates as biosorbent for bioremediation of metals under multi-metal environments because of their high surface area to volume ratio.29 The species of bacteria separated from metalcontaminated settings are much more resistant to heavy metal toxicity than those obtained from non-contaminated settings. For chromium bioremediation, both Gram-positive and Gram-negative bacteria isolated from water, soil, and another chromate-contaminated environment, particularly effluents from tanneries and electroplating firms, have been used. In contrast to Gram-negative bacteria, Gram-positive bacteria demonstrated a substantially higher resistance to hazardous Cr(VI) at relatively high concentrations.30 Numerous bacteria, such as Bacillus, Pseudomonas, Ochrobactrum, and Acinetobacter, were found to be efficient in reducing Cr(VI) to Cr(III), in which Cr(VI) could partially enter the cell by sulphate transport channels and partially be excreted by intracellular, extracellular, or membrane reduction. Most bioremediation research has concentrated on pure bacteria, which show a significant decrease in effectiveness at high Cr(VI) concentrations. The sterile conditions necessary for pure cultures (to avoid external bacterial contamination) may lead to high operating costs, hence limiting their use. In contrast, mixed bacterial consortiums are easier to run, more stable, cost-effective, and more likely to survive, making them preferable for the functional use of naturally Cr(VI)-contaminated water with low

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Cr(VI) concentrations. More significantly, owing to the catabolic flexibility of various microorganisms that may complement each other, total elimination of contaminants may be achieved by employing mixed bacterial culture.31 The mechanism to remove Cr(IV) through mixed bacteria consortium is shown in Fig. 2. Cesium removal from wastewater using P. aeruginosa PAO1 was studied, where it exhibited an excellent efficiency of 76.1% from the contaminated water.32 Lead and cadmium are considered to be highly toxic metals. Bacterial strain-specific removal of these metals was found where the most efficient metal removers were Bifidobacterium lactis Bb12, Lactobacillus fermentum ME3, and Bifidobacterium longum 46. The high removal efficiency of lead and cadmium were 175.7 mg/g and 54.7 mg/g dry biomass, respectively with B. longum 46.33 As(III) is oxidized by microorganisms over a broad pH range, depending on the species. Thiomonas arsenivorans strain b6 is one such bacterium that can oxidize As(III) at low pH (4).34 Moreover, the majority of known As(III)-oxidizing species exhibit optimal oxidation at a pH range close to neutral. Also reported is the optimal pH of 7 for As(III) oxidation by Alcaligenes faecalis strain O1201.35

Fig. 2 Mechanism of chromium bioremediation by mixed bacterial consortium. Reprinted from Ma L, et al. Microbial reduction fate of chromium (Cr) in aqueous solution by mixed bacterial consortium. Ecotoxicol Environ Saf 2019;170:763–770 with permission of Elsevier.

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6. Genetically engineered bacteria (GEB) Genetically engineered bacteria (GEB) are microbes whose genetic material has been modified using recombinant DNA technology to develop a strain with increased degrading characteristics against a broad variety of chemical pollutants for water, soil, and activated sludge bioremediation.36 GEM relates to organisms (e.g., fungi, yeast, and bacteria) that have been engineered by humans through in vitro molecular biology procedures to accomplish a specific task.37 It provides the benefit of generating microbial strains that can tolerate unfavorable stress conditions and can be deployed as bioremediators in a variety of challenging environmental settings.36 The usage of GEB-based remediation of multiple heavy metal contaminants is at the frontline because it is environmentally friendly and poses fewer health risks than physio-chemical techniques, which are less eco-sustainable and harmful to human health. Microbiological and ecological understanding, and biochemical processes would be required for effective in situ bioremediation of heavy metal-contaminated areas by GEB.38 GEB have a greater potential for degradation and are proven to be effective in decomposing a wide range of contaminants under controlled settings. Different strains of Mycobacterium marinum, Escherichia coli, Bacillus idriensis, Pseudomonas putida, and Ralstonia eutropha, etc., have genes incorporated into their genomes, allowing them to carry out bioremediation of hazardous metallic ions in polluted environments.38 The different GEB for the mitigation of heavy metals are provided in Table 1.

6.1 Fungal bioremediation The use of fungi for the degradation of contaminants or the conversion of contaminants to less toxic ones due to its strong enzymatic mechanism, exclusion by permeability barriers, intracellular precipitation, and chelation of metal ions is called mycoremediation.45 Due to their rapid growth and remarkable binding characteristics, fungi are a superior option for the bioremediation of heavy metals. As a result of their rapid rate of multiplication and the ease with which they may undergo morphological and genetic alteration, they can be cultured in large numbers in a simple and cost-effective manner.46 In general, a fungus uses two procedures to order to detoxify metals. The first method, known as biosorption, includes the binding of metal to the surface of the fungus, and the second method, known as bioaccumulation, consists of the intracellular absorption of metals through

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Table 1 Different genetically engineered bacteria for the removal of heavy metals. Heavy Modified gene GEB metal expression Results Ref.

Escherichia coli

Arsenic

Metalloregulatory protein (ArsR)

100% removal efficiency

39

Escherichia coli JM109

Mercury

Hg2+ transporter

96% removal

40

Pseudomonas putida

Chromium Chromate reductase (ChrR)

–

41

Escherichia coli

Cadmium

PCS gene expression

–

42

Pseudomonas fluorescens 4F39

Nickel

Phytochelatin synthase 80% removal

Pseudomonas K-62

Mercury

Organomercurial lyase

–

43 44

cellular metabolism.47 These are extensively utilized as biosorbents to remove hazardous metals due to their exceptional metal absorption and recovery capabilities.48 The effectiveness of Aspergillus sp. in removing chromium from tanning wastewater has been reported. A bioreactor system removed 80% of the total Cr from the synthetic medium at pH 6, compared to 65% from the tannery wastewater. This may be due to the availability of organic contaminants that inhibit the organism’s reproduction.49 The tendency of Coprinopsis atramentaria to bioaccumulate Pb2+ and Cd2+ at a concentration 800 mg/L and 1 mg/L, respectively, is being investigated. That’s why it has been reported as an efficient heavy metal ion absorbent for bioremediation.50 Aspergillus niger, Saccharomyces cerevisiae, Penicillium chrysogenum, and Rhizopus oryzae might be employed to transform hazardous Cr(VI) to less toxic or harmless Cr(III).51 Candida spp. absorb substantial amounts of Ni and Cu, between 57% and 71% and 52% to 68%, respectively. However, the process is influenced by the initial concentration of metal ions and pH.52 The bioremediation mechanism for the removal of copper by fungi53 is provided in Fig. 3.

6.2 Algal bioremediation Bioremediation by algae, or phycoremediation, has evolved as a feasible technique for eliminating contaminants from wastewater.54,55 Since algae

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Cu++ ions

Cu–Transporter

Efflux Pump

Cell Wall

Cytoplasm

Diffused or Transported Cu++ inside the cell

Accumulated Cu++ inside the vacuole of the cell

Metabolic process

R

Vacuole

Surface Functional group

C O

Outside of the cell

Electrostatic attraction

O

Fig. 3 Bioremediation mechanism for the removal of copper by fungi. Reprinted from Kumar V, Dwivedi S. Bioremediation mechanism and potential of copper by actively growing fungus Trichoderma lixii CR700 isolated from electroplating wastewater. J Environ Manage 2021;277:111370 with permission of Elsevier.

are abundant, affordable, have a great capacity for metal removal, environment-friendly, and provide significant products, hence, this is a viable technology for the removal of heavy metals. In general, algae are divided into two categories: macroalgae and microalgae55 Macroalgae are multicellular microorganisms with a maximum size of several meters,56 whereas, microalgae are unicellular species with a maximum size of 0.2 to 100 μm57 and are primarily categorized into four primary categories, namely diatoms, green, golden, and blue-green algae.55 The majority of the contaminants are eliminated by the biosorption, bioaccumulation, and detoxifying mechanisms demonstrated by algae during the process of algal bioremediation. In the process of biosorption, the sorption of heavy metals onto the surface of the biomass happens regardless of whether or not the biomass is active.58 During the process of bioaccumulation, heavy metal ions are transported within the cells of the algae. In detoxification, algae generate several phyco-chelators that assist in the conversion of hazardous heavy metal to a substance that is not hazardous.59 A diversity of non-pathogenic algae, notably Chlorella sp., Spirulina sp., Chlamydomonas sp., Nostoc sp., Oscillatoria sp., and Scenedesmus sp., are used for wastewater treatment.60

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Microalgae are recognized as exceptional bio-remediators due to their high tolerant capacity, high binding affinity, ease of growth, large surface area, environmental sustainability, reusability, and the fact that dead biomass can be efficiently utilized for bioremediation i.e., no nutrients or other dimensions are needed.61 The mitigation of various hazardous heavy metals by algal bioremediation is provided in Table 2. In comparison to fungus and bacteria, algae can remediate around 15.3% to 84.6% of heavy metals, according to statistical analysis.68 This method has many benefits over other bioremediation techniques since algae have a higher potential for heavy metal absorption and can be reproduced. Moreover, algal biomass may be reused all year, does not release any hazardous byproducts, and is cost-effective. Algae reduce heavy metals in two steps. Initially, it adsorbs metals from the cell surface (biosorption). These ions are absorbed by the cell wall due to the presence of functional groups (like thioether, sulfhydryl, hydroxyl, carboxylic, amide, and imidazole). Positively charged ions are attracted to negatively charged ions on the cell wall, lowering the concentration of heavy metals. The second step involves the slow transport of metal ions into the cell (bioaccumulation), followed by further detoxification, efflux, or compartmentalization.6 The mechanism of heavy metals removal by microalgae is provided in Fig. 4.68,69 Table 2 Algal bioremediation of various toxic heavy metals. Removal Pollutants Algal strain efficiency (%)

Remediation time

Ref.

Cadmium

Chlorococcum humicola

17

6 days

62

Arsenic

Scenedesmus almeriensis

40.7

3h

63

Lead

Gelidium amansii

100

2–24 h

64

Chromium

Pseudochlorella pringsheimii and Chlorella vulgaris

80

1 day

65

Mercury

Ulva lactuca

98

12 h

66

Copper

Chlorophyceae spp.

88

10 min

63

Cobalt

Chlorococcum humicola

44

–

62

Nickel

Oedogonium westi

59–89

7 days

67

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Fig. 4 Mechanism of heavy metals removal by microalgae.

7. Microbial fuel cell Microbial fuel cell (MFC) is a method in which microorganisms transform chemical energy derived from the oxidation of organic or inorganic molecules into ATP via successive processes in which electrons are transported to a terminal electron acceptor to produce an electrical current.70 The utilization of MFC as an alternative energy source is regarded as a dependable, clean, and efficient process that use renewable energy sources and does not produce hazardous byproducts.71 It is considered an effective method that successfully generates energy from wastewater.72 Single-chambered and dual-chambered MFCs are the two primary types of MFCs based on their construction. Dual-chambered MFCs have distinct cathodic and anodic chambers, while single-chambered MFCs have both anode and cathode in a single chamber.72 The accumulation of selenium in biological organisms may be caused by the release of significant quantities of selenium into the environment as a result of industrial and agricultural activities. Selenium is essential for the metabolism of humans and animals, but only in trace levels. Two of the most important forms of inorganic selenium are selenite (SeO3)2 and selenate (SeO4)2 . When compared

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to selenate, selenite has a higher toxicity level,66 and aquatic plants absorb it more rapidly. Therefore, wastewater dominated by selenite is more potent in bioaccumulating selenium in food chain compared to those that are polluted with selenate.73 The removal of selenium in a single-chamber MFC using acetate and glucose as the carbon sources was studied. Up to 125 mg/L of selenite had no effect on power production when glucose was the substrate. At 150 mg Se/L, the coulombic efficiencies of MFC containing glucose improved from 25% to 38%. The MFC fed with acetate and glucose removed almost 99% of 50 mg Se/L and 200 mg Se/L selenite in 48 and 72 h, respectively, suggesting the possibility of adopting this method for the remediation of selenium.73

8. Role of microorganisms in the removal of some other emerging pollutants The textile industry is a significant user of water and a major source of polluted water, including dyes. For the treatment of textile wastewater, microbiological techniques offer the advantages of being cost-effective, ecologically acceptable, and generating less sludge. Microorganisms isolated from dye-contaminated areas or wastewater treatment plant sludge hold the utmost potential for application in water treatment because of their ability to thrive in harsh environments. Adsorption, enzymatic breakdown, or a combination of the two is the route of microbial decolorization. Reductases and oxidases are responsible for the process of microbial degradation. The purpose of microbial remediation is to decolorize and purify effluents polluted with dyes.74 Staphylococcus and Bacillus species have the ability to decolorize Mordant Black 11 dye. In the absence and presence of carbon source for 72 h, both strains decolorized the dye by more than 50%. Bacillus subtilis MB378 was the most efficient and effective strain, decolorizing 75.23% of Mordant Black 11 dye in 48 h at 37 °C in glucose-supplemented media. The bacterial strain was also able to survive dye concentrations of up to 150 mg/L of Mordant Black 11.75 A fungus, Thermomucorindicae seudaticae was effectively employed to adsorb azo anthraquinone dye mixtures. The optimal temperature and pH for adsorption were determined to be 55 °C and 7.0, respectively.76 Numerous species of fungi are reportedly capable of decomposing dye compounds into simple molecules.77 Spirogyra sp., a common green algae, was recommended as an efficient biomaterial for removing azo dye reactive yellow 22.78 A microalga known as Cosmarium sp. is suitable to treat water containing Triphenylmethane and Malachite Green dyes.79

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Table 3 Various microorganisms and their efficiency in the removal of different pollutants. Contaminants Microorganisms Results Ref.

Nitrogen

Photosynthetic bacteria 90% nitrogen removal efficiencies were obtained under suitable condition

84

Phosphorous

Chlorella sp. (algae)

83.2%–90.6% removal of phosphorus

85

Nitrogen and Phosphorous

Nannachloropsis oculata (algae)

95% N removal and 98% P removal was observed

86

Azo dye

Funalia trogli

–

87

Congo red

Bacteria consortium SKB II

90% removal

88

Coracryl violet

P. chrysosporium

100% removal

89

Coracryl black

P. sanguineus

67% removal

89

Blue BCC

Bacteria consortium SKB I

74% removal

88

The efficiency of algae to remove dye may be increased by accelerating algal growth. For example, the dye-removing properties of Synechocystis sp. along with Phormidium sp. were enhanced by the addition of tricontanol hormone, a growth regulator for plants.80 According to reports, Oscillatoria sp. decolorize 23% of Nigrosin dyes, 91% of Malachite Green, and 75% of Congo Red at a concentration of 0.05%.81 Because nitrogen and phosphorus contribute to eutrophication in natural water, the removal of these elements from wastewater has also emerged as a crucial global concern.82 Microorganisms such as microalgae have the potential to transform the nutrients (phosphorus and nitrogen) into biomass and bio-products, which assists in enhancing the treatment of wastewater in a more sustainable way.83 The list of microorganism for the removal of different pollutants is presented in Table 3.

9. Conclusion The uneven accumulation of heavy metals in the atmosphere is because of increasing human interference. Heavy metal distribution is substantially influenced by microbes. Although physical and chemical

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treatments are used, they have several drawbacks, including high treatment costs and the formation of toxic, complicated sludge. In this regard, microbial bioremediation appears to be superior because it is an ecologically friendly, effective, and inexpensive method. It has the ability to degrade contaminants present in different wastewater bodies without producing any hazardous by-products. But it is relatively a slow process and the impact of biotic and abiotic factors has a great influence on its working efficiency. Compared to ex-situ, in situ showed a higher rate of bioremediation. Among all techniques, GEB has shown the best result and increased the remediation rate, as it showed a 96% increase in the uptake of pollutants. Instead of using a pure culture of microorganisms, a group of fungi, algae, and bacteria should be used that will provide metabolic diversity and will enhance the rate of bioremediation. Despite its advantages, bioremediation has several disadvantages related to its slowness and time consumption; also, the products of biodegradation are often more harmful than the original substance. There is currently no accepted endpoint for the bioremediation process, which makes it difficult to evaluate its efficacy. Additional research is required to develop technologies for bioremediation to identify biological solutions for the bioremediation of pollutants from a variety of environmental systems.

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CHAPTER THIRTEEN

Utilization of constructed wetlands for dye removal: A concise review Fidelis Odedishemi Ajibadea,b,c,*, Oluwaseyi Aderemi Ajalad,e, Hailu Demissiec,f, Kayode Hassan Lasisia,c,g, Temitope Fausat Ajibadea,c,g, Bashir Adelodunh,i, Pankaj Kumarj, Nathaniel Azubuike Nwogwuk, Adedamola Oluwafemi Ojol, Olawale Olugbenga Olanrewajum, and James Rotimi Adewumia a

Department of Civil and Environmental Engineering, Federal University of Technology, Akure, Nigeria CAS Key lab of Environmental Biotechnology, Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, P.R. China c University of Chinese Academy of Sciences, Beijing, P.R. China d Department of Chemistry, Faculty of Science University of Ibadan, Ibadan, Nigeria e Department of Applied Chemistry, Graduate School of Advanced Science and Engineering, Hiroshima University, Higashihiroshima, Japan f Department of Chemistry, Arba Minch University 1000, Arba Minch, Ethiopia g Institute of Urban Environment, Chinese Academy of Sciences, Xiamen, P.R. China h Department of Agricultural and Biosystems Engineering, University of Ilorin, Ilorin, Nigeria i Department of Agricultural Civil Engineering, Kyungpook National University, Daegu, Korea j Agro-ecology and Pollution Research Laboratory, Department of Zoology and Environmental Science, Gurukula Kangri (Deemed to be University), Haridwar, Uttarakhand, India k Department of Agricultural and Bioresources Engineering, Federal University of Technology, Owerri, Nigeria l Department of Civil Engineering, Yaba College of Technology, Lagos, Nigeria m Department of Agricultural and Environmental Engineering, Federal University of Technology, Akure, Nigeria ⁎ Corresponding author: e-mail address: [email protected] b

Contents 1. 2. 3. 4.

Introduction Dye Phytoremediation of dye-containing wastewater The importance of using CW to treat wastewater containing dye and its advantages over other treatment 5. Removal processes of dye in CW systems 6. Conclusion and future research needs References Further reading

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Advances in Chemical Pollution, Environmental Management and Protection, Volume 9 Copyright # 2023 Elsevier Inc. 227 ISSN 2468-9289 All rights reserved. https://doi.org/10.1016/bs.apmp.2022.11.004

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Abstract Water discharges from the textile industry are the main environmental concern and the chemicals it carries. Industrial fields such as textile, rubber, paint, leather, paper, cosmetics and dyeing systematically use toxic dyes, causing severe pollution of water and environmental problems, which in turn threaten human health, aquatic life and the environment. Constructed wetlands (CWs) are low-energy, environmentally friendly, and natural treatment systems. CWs are well known for their ability to remove suspended solids, nutrients, and biological oxygen demand from domestic wastewater. It has been demonstrated that CWs can remove dye from textile wastewater. CWs harbour a great variety of microbial communities that enhance the efficacy of removing contaminants from wastewater. This chapter reviewed the classification of dye and the role of phytoremediation in the decontamination of dye-containing wastewater. Overall, this chapter essentially presents an overview of the concepts of different kinds of CW for dye removal. Keywords: Constructed wetland, Dye, Phytoremediation, Textile industry, Wastewater

1. Introduction Industrial development and swift population growth have heightened the need for textile materials, resulting in the dramatic upsurge of textile industries and indiscriminate disposal of their effluents. Textile dyeing processes are the most environmentally unfriendly waste-producing industries because they generate colored wastewaters that are severely polluted with several dyes, textile auxiliaries, and chemicals.1,2 In the textile industry, the effluents contain high concentrations of total suspended solids (TSS), color, chemical oxygen demand (COD), total dissolved solids (TDS), total suspended solids (TSS), and biological oxygen demand (BOD), which are capable of negatively impacting the water quality, causing odours, and threatening economic activities.3,4 The properties of textile effluent are determined by the manufacturing process, technology, and chemicals used. Most textile wastewater consists of dye wastes, which are toxic to the biosphere and block sunlight, causing serious ecological problems.5,6 These textile dye wastewaters directly threaten living creatures because of their highly toxic, mutagenic, and carcinogenic contents.4,7,8 Moreover, due to their complex structure and synthetic origin, these dyes are designed to withstand degradation over time, exposure to sunshine, soap, water, and oxidizing

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agents. Traditional wastewater treatment techniques cannot easily remove them.9 This situation necessitates the development of simple, cheap, and viable technology for the treatment of textile dye wastewater. In recent years, dye-containing wastewater has been treated with a variety of methods, including membrane filtration, precipitation, ultrasonication, adsorption, photocatalysis, chemical oxidation, bioremediation, and constructed wetland (CW).10–19 CW has been greatly preferred for dye contaminants degradation in wastewaters due to its pollutant removal efficiency, high reusability, ease of operation, low energy, and cost requirements without any adverse environmental effects. The chapter is structured to provide an outline of CW in dye removal. Firstly, the description, characteristics, applications, and examples of different dye classes were enumerated. Also, the phytoremediation efficiency of various macrophytes for dye removal was explained. Moreover, the advantages of CW systems were expounded. More importantly, the removal processes of dye in CW systems were expounded. Lastly, future research needs were put forward.

2. Dye Dyes are colored compounds that can be fixed to fabrics, usually in solution. They are also referred to as substances containing chromophore and auxochrome groups. Due to their saturation, the chromophore group determines the dye color, while the auxochrome group controls the dye fiber reaction. Dyes are classified as natural dyes (extracted from natural or plant sources, e.g., carmine, orcein, haematoxyline etc.) and synthetic dyes (derived from organic or inorganic compounds, e.g., direct, basic, acid, mordant, reactive, metal complex, disperse, vat, sulfur, etc.). In a broader sense, dye classifications depend on some factors based on source (natural and synthetic), chromophoric groups (triarylmethane, azo, nitro and nitroso, anthraquinone, indigo), and ionic nature as illustrated in Fig. 1. The chemical structure of dyes is complex and dyes are used for many industrial purposes. Dyestuffs, especially synthetic dyes, have stable structures due to the presence of complex aromatic structures and the resonance and to the π conjugated bond characteristic; also, they are deliberately intended to be recalcitrant with poor biodegradability.20

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Natural

Source Synthetic

Triarylmethane

Dye

Chromophoric

Classification

group

Azo Indigo Nitro and Nitroso Anthraquinone Anionic dye

Ionic nature

Cationic dye Non-ionic dye

Fig. 1 The significant classifications of dye.

Though colored products provide joy to the eye, indiscriminate disposal of dye effluent in receiving water bodies poses a considerable risk, even with low concentrations, since it interferes with solar penetration, consumes dissolved oxygen and hinders breathing, thereby disrupting photosynthetic and biological activities in waters.8,21 As a result of long-term exposure to dye contaminants, including cationic, reactive, and direct dyes, aquatic and terrestrial organisms, including humans, can develop carcinogens and mutagens and exhibit high toxicity.22,23 The toxicological and environmental impacts of textile dyes are increasingly being considered, mainly because of their increased use in the current era. Fig. 2 illustrates the chemical structure of important dyes, and Table 1 discusses the description of different types of dyes.

Utilization of constructed wetlands for dye removal

Fig. 2 The chemical structures of selected dyes.

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Table 1 The description, characteristics, application and examples of different classes of dyes. Classes of dye Characteristics Application

Acid dye As a result of the presence of sulfonic acid groups, acid dyes are extremely soluble in water. They are used both in acidic and neutral conditions. They are also known as anionic ( ve) dyes. They possess molecular structures with large aromatic rings and sulfonyl and amino groups.

They are utilized in the coloring of nylon, wool, and silk, except for cotton. E.g., Nigrosine, eosin, India ink, and picric acid.

Basic dye Basic dyes are positively charged (cationic) dyes with functional groups such as (–NH2) or (–NR2) groups. They are soluble in alcohol and methylated spirit. However, they are insoluble in water. They react with negative sites and are attached to fabrics used under acidic conditions.

Besides being used for dyeing and printing jute, they are also used in wool and acrylic fiber processing. E.g., Malachite green and crystal violet.

Direct dye

Direct dyes are soluble in water. They are anionic and can be used both in neutral and alkaline solutions. They are colorful, but; they fade with washing. They are applied as pH indicators and as biological stains.

Coloring applications in cotton, rayon, nylon, wool paper, leather, and silk.

Disperse dye

Non-ionic and no ionizing groups are They are used for dyeing present. They are organic synthetic dyes nylon, polyester, and suitable for dyeing hydrophobic fibers. They polyacrylonitrile. are less soluble in water.

Reactive Reactive dyes develop covalent bonds dye between dyes molecules and end sites (–NH2, –OH, –SH and –Cl) of substrates such as fiber. They are anionic, soluble in water, and can be used in neutral and alkaline media. They are available in several kinds, such as liquid, print paste, and powder. They have an excellent wash, light fastness and are relatively cheap. Vat dye

They are used for coloring cotton, rayon, flax, cellulose, polyamide, and wool fibers.

Vat dyes are sourced naturally from They are used for vegetables and animals. They are insoluble in coloring cellulosic fiber, water. Under alkaline conditions, they give such as cotton. excellent and stable colors to fibers. They have poor robbing characteristics. They are expensive and cause skin diseases in contact with human skin.

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Table 1 The description, characteristics, application and examples of different classes of dyes.—cont’d Classes of dye Characteristics Application

Solvent dye

Solvent dyes are highly soluble in nonpolar organic solvents. Used in textile coloring processes, they are insoluble in water. They found applications as color lubricants in cutting operations in the automotive and industrial sectors.

Acrylics, PVC, polyester, PMMA, PETP, acetates, nylon, polystyrene, and styrene monomers are used for coloring materials, as well as identifying cell structural components in medical studies and research.

Mordant Mordant dyes have the unique capability to dye form insoluble color lakes when bound to metals. They may be of natural and synthetic nature. They are also known as chrome dyes, thus commonly applied as inorganic chromium. Cold water is the preferred solvent, and they have good color durability.

A variety of fibers are made using them, including modacrylic fibers, protein fibers, and nylon.

3. Phytoremediation of dye-containing wastewater As a green and reliable technology, phytoremediation has been credited for its low design and maintenance costs, independent solar power, and aesthetic appeal. In addition, it has a longer-standing potential and is, therefore, better suited for use on contaminated terrain than other costly treatment options.24,25 Phytoremediating plant roots can be colonized by soil-borne bacteria, which can enhance plant growth and be utilized for bioremediation.26–28 Some wild plants have previously been used to treat textile effluents such as Phragmites australis, Blumea malcolmii, Rumex hydrolapathum, Typhonium flagelliforme, and Rheum rabarbarum.29–33 Furthermore, macrophytes can act as dye decolorizers and detoxicators in dye-containing wastewater. Studies at a microcosmic scale and in situ degradation of dyes have been conducted with these aquatic plants.34,35 Plants in hydroponic systems and the phytoremediation performances they exhibit are presented in Table 2, including initial dye concentrations, removal efficiency, and treatment time. Constructed wetlands are designed and fabricated to depurate pollutants employing natural mechanisms such as vegetation (macrophytes), soil, and microbial communities.52–54 Among the major components of

Table 2 Phytoremediation performances of different wild/indigenous plants for textile dyes and effluents. Concentration Decolorization % S/N Macrophyte Dye (mg/L) time (h) Decolorization Reference

1

Alternanthera philoxeroides Remazol Red

70

72

100

Rane et al.34

2

Pogonatherum crinitum

Effluent

NA

288

74

Watharkar et al.36

3

Nasturtium officinale

Acid Blue 92

20

96

78

Torbati et al.37

4

Ipomoea hederifolia

Scarlet RR

50

60

96

Rane et al.38

5

Typha angustifolia

Reactive Blue 19

75

144

70

Mahmood et al.39

6

Bouteloua dactyloides

Effluent

NA

24

92

Vijayalakshmidevi and Muthukumar40

7

Petunia grandiflora

Brillaint Blue G

20

36

86

41,42

8

Azolla filiculoide

Acid Blue 92 and Basic Red 46

20

168 and 144

80 and 90

Vafaei et al.,43 Khataee et al.44

9

Lemna minor

Acid Blue 92 and Methylene Blue

2.5 and 10

144

77 and 98

Reema et al.,45 Khataee et al.46

10 Portulaca grandiflora

Reactive Blue 172

20

40

98

Khandare et al.47

11 Glandularia pulchella

Remazol Orange 3R and Green HE4B

20

96 and 48

100 and 92

48,49

12 Aster amellus

Remazol Orange 3R Remazol Red

20

72 and 60

100 and 96

,4950

13 Typhonium flagelliforme

Brilliant Blue R

20

96

65

Kagalkar et al.32

14 Blumea malcolmii

Direct Red 5B, Methyl orange, Malachite 20 green, Red HE4B, and Reactive Red 2

72

80, 76, 96, 88 Kagalkar et al.31

15 Phragmites australis

Acid Orange 7

Eight times a 68 and 98 day and 144 h

75 and 100

Davies et al.,51 Ong et al.33

NA: Not available. Source: Khandare R, Govindwar S. Phytoremediation of textile dyes and effluents: current scenario and future prospects. Biotechnol Adv 2015;33:1697–714.

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constructed wetlands are aquatic macrophytes which absorb contaminants through their plant parts, along with enzymes that could act as catalysts for efficient pollutants degradation. Also, a variety of rhizosphere bacteria within their root zone area facilitate the removal of contaminants more effectively.55 Specifically, aquatic macrophytes have recently been used in various artificial wetlands to decolorize and degrade colors from textile wastewater, such as Typha angustifolia, Typha domingenesis, Phragmites australis, Ipomoea aquatic, Ammannia baccifera, Alternenthera philoxeroides, Fimbristylis dichotoma, Salvinia molesta, and Paspalum scrobiculatum.56–58

4. The importance of using CW to treat wastewater containing dye and its advantages over other treatment Conventional technologies such as biological and physicochemical (coagulation, flocculation, sedimentation, membrane filtration, and advanced oxidation) treatments have been applied to remove dye from dye-rich wastewater. However, these methods have numerous disadvantages, such as high investment and maintenance costs, low efficiency, and the formation of sludge and toxic by-products. CWs are a promising eco-friendly and more sustainable treatment technology that is energy-efficient, simple to design, and economically and environmentally friendly, with their optimal biophysicochemical treatment conditions. These have been proven from global experiences. CWs are an excellent alternative from both an economic and environmental standpoint, and they are less expensive and have low maintenance costs (up to 90% lower) than conventional technologies. CWs have a more aesthetic appearance than conventional treatment methods. CW does not produce any by-products in practice. Biomass from plants is the only by-product that can be considered in CWs. The biomass can be further exploited as a biofuel for energy production or used as compost. In addition, CWs do not require the addition of chemical additives. Locally available resources can be sourced for the construction of CWs. In CWs, energy and water requirements in very low. CWs and physicochemical methods are compared in Table 3. CWs are often designed to take advantage of many processes in natural wetlands, with more controlled environments. Hence, the reduction or removal of contaminants such as dyes is accomplished by diverse treatment mechanisms, including adsorption, filtration, sedimentation, chemical precipitation, microbial interactions, and macrophyte uptake or transformation.

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Fidelis Odedishemi Ajibade et al.

Table 3 The main comparison between constructed wetlands (CWs) and physicochemical methods. Constructed Wetlands (CWs) Physicochemical methods

Performance Wholly effective and efficient in Possess low dye removal removing and mineralizing efficiency. These methods don’t different types of dyes involve the complete elimination or removal of dyes Sustainability The use of plants, microbial Produces sludges and greenhouse microorganisms, enzymes and the gases production of non-toxic end products make it eco-friendly. Energy Less consumption

High

Water Less consumption

Less

Use of chemicals

Always required

Not required

By-products No sludge as a by-product

Produces large volumes of sludge

Cost investment

Economically unviable because large mechanical parts and‘equipment is needed.

Low operating and maintenance costs

5. Removal processes of dye in CW systems The removal of dye from wastewater in CWs involves several mechanisms. The main mechanisms are physicochemical and biological processes occurring in the rhizosphere under aerobic, anaerobic, or anoxic conditions. These processes are induced by the interaction of the dye with plants, microorganisms, and the soil. Physiochemically, under anaerobic treatment, the cleavage of the N]N in Azo dyes occurs, producing an aromatic amine that cannot be further reduced under the same anaerobic conditions. However, aromatic amines can be reduced aerobically, while azo dyes can be reduced anaerobically, anoxically, or aerobically. Biologically, microbes break the azo bond and reduce the dye into aromatic amines by secreting enzymes such as laccase, azo reductase, peroxidase, and hydrogenase. Further mineralizing these dye metabolites results in simpler non-toxic compounds that are used as a source of energy. Anaerobic and aerobic conditions are

Utilization of constructed wetlands for dye removal

237

necessary to degrade and mineralize azo dyes since they are not biodegradable under aerobic conditions. Various environmental and microbial factors have been reported to influence textile azo dyes’ degradation. These factors include hydrogen ion concentration, oxygen, temperature, pH, inoculum size, carbon and nitrogen supplementation, concentration, structure, and toxicity. Plant-associated microorganisms are potent enough to degrade and detoxify synthetic dyes and also completely mineralize them under certain environmental conditions. Shehzadi et al.58 established the potential of 41 culturable bacterial endophytes isolated from wetlands, including Typha domingensis, Pistia stratiotes, and Eichhornia crassipes to degrade textile effluent and promote plant growth. Patil et al.59 degraded Navy Blue HE2R (NB-HE2R) textile dye using adventitious roots of Ipomea hederifolia endophytically colonized by Cladosporium cladosporioides. Similarly, it has been reported that Klebsiella aerogenes S27 from Suaeda salsa is entirely able to degrade malachite green.60 In the United States, the color removal efficiency was reported for the removal of acid blue and reactive blue from textile wastewater at 98%.61 In Portugal, acid orange was removed from dye solution at 74% removal efficiency.30 Similarly, in Tanzania, Slovenia and Turkey, the color removal efficiency was reported for various dyes in real wastewater at 77%,62 reactive black, disperse yellow, and vat yellow at 90% removal efficiency from dye solutions,63 and acid yellow at 95% removal efficiency in 90 days from textile wastewater64 respectively. Noonpui and Thiravetyyan65 investigated Azo dye removal in CW, showing 97% dye removal; however, the removal efficiency of each dye molecule influenced the removal efficiency. It has been proven that using a microbial fuel cell (MFC) in combination with CWs can be an affordable treatment for textile dye wastewater. Several recent studies have shown that CW-MFC systems are more efficient at treating textile dye wastewater than conventional CWs.66–68 According to a study by Xu et al.,69 the anodic microbial community plays a key role in the performance of a CW-MFC system due to its importance in understanding the microbial community structure. MFCs can be coupled with CWs because of the redox gradients in CWs, which enable anaerobic anodes and aerobic cathodes, which are essential for MFCs to operate.69 A compilation of previous related works on the removal of dye or mixture from CWs is presented in Table 4.

Table 4 Previous studies on dye removal by constructed wetlands. Design CWs system characteristics

Initial dye Country of concentration operation Plant used Dye/Wastewater (mg. L-1) pH

VF

Gravel-sand

USA

P. australis AB113, *RB171

100

7.6–7.8 70

98% color

960

61

VF

Gravel-sandy clay soil

Portugal

P. australis AO7

40

5

77

64% COD, 71% TOC and 74% color

NA

Davies et al.30

127

5

48

93% COD, TOC, and 99% color

NA

Davies et al.70

84

72% COD, 59% sulfate, and 77% color

29.04

Mbuligwe62

Duration (days) Removal efficiency

HRT (h) Reference

HF

Gravel-sand

Tanzania

Typha and Various dyes in NA cocoyam real wastewater

NA

VF

Gravel-sandzeolite-peat

Slovenia

Without plant

12–7.6 90

60% EC, 70% dye, 88% COD NA and TOC

VF-HF

Gravel-sand-tuff Slovenia

P. australis **RB5, 30 DY211, VY46

7.6–7.8 60

84% COD, 93% TSS, 52% TN, 88% sulfate, 87% Norganic—331% NH4-N, 90% color, 80% anion surfactant and 93% TSS

NA

Bulc and Ojstrsˇek63

VF

Gravel-sand

Thailand

Typha

20

7.8

NA

60% COD, 86% TDS, and 49% color

360

Nilratnisakorn et al.72

UF

Gravel-glass beads

Japan

P. australis AO7

50, 100

7.7

365a

98% dye, 90% COD, 67% TN, 72 and Ong et al.33 28% TP, 98% NH4-N, 100% 144 NO3-N

RR22, VR13, NA **RB5

RR141

Ojstrsˇek et al.71

95% COD and 86% NH4-N, 48 94% color

Ong et al.73

6.0–7.5 –

98% COD, 97% color

96

Cumnan and Yimrattanabovorn74

2000

6.1–4.0 NA

80% color

96

Yadav et al.75

Mixture dyes into different metabolites

NA.

NA

0.042

0% COD, 74% TOC, 70% BOD

NA

Kabra et al.48,49

Portulaca grandiflora

Mixture dyes into different metabolites

NA

NA

0.05

37% TOC, 41% turbidity, 59% NA COD, 38% BOD, 71% TDS, 60% TSS

Khandare et al.76

Ipomoea aquatica

ABRX3

150

NA

NA

91.24% color

72

Fang et al.77

Various dyes in NA real wastewater

NA

3

79% COD, 77% BOD, 59% TDS, 27% TSS

NA

Shehzadi et al.58

VF

Gravel-sludge

N/A

P. australis AO7

50

NA

FWS-SSF

Shale

Thailand

P. australis Azo Dye

NA

BF-MFC

Copper India electrodes-sludge

C. indica

MB

VF.

Coconut shavings-soil with bacteria

India

Gaillardia pulchella

VF.

India Coconut shavings-sandgravel-soil with bacteria

CVU-MFC Gravel-GCA electrode

China

27

VF.

Pakistan Coconut shavings-gravels and soil

Typha

VF

Gravel-sandzeolite

Canna and AY 2G E107 Typha

250

8

90

94% PO4-P, 77% NH4-N, 95% color, 64% COD

90

Yalcuk and Dogdu64

HSF

Rice husk-gravel Malaysia

Typha latifolia

AO7

300

NA

NA

100% color

120

Tee et al.78

MO

450

NA

NA

87.6% color

72

Fang et al.79

CVU-MFC Gravel-GAC

Turkey

China

Continued

Table 4 Previous studies on dye removal by constructed wetlands.—cont’d Design CWs system characteristics

Initial dye concentration Country of operation Plant used Dye/Wastewater (mg. L-1) pH

SSF

Malaysia

Scirpus grossus

Paper mill effluent

NA

China

Ipomoea aquatica

ABRX3

Phragmite australis

AM

Gravel-sand

CVU-MFC Gravel-GAC AB

Gravel-activated Malaysia sludge

Duration (days) Removal efficiency

HRT (h) Reference

NA

95 days

66.1% COD, 55.8% color, 87.2% suspended solid (SS.)

120

Mojiri et al.80

300

NA

NA

92.7% color

72

Fang et al.81

26

NA.

NA

98–91% COD, 100% color

24

Lehl et al.82

CVU-MFC Gravels-glass beads

Malaysia

T. Latifolia AR18

500

NA

463

91% color

24

Oon et al.83

CW-MFC NA

India

Fimbristylis ADMI dichotoma

NA

NA

NA

82.2% color, 70% COD

72

Rathour et al.67

RHF

Fine gravel

Tunisia

Typha AM domingensis

10-25

7–7.7

NA

92% color, 56% COD

3.1

Haddaji et al.14

FTWs

NA

Pakistan

Phragmites Textile dye australis wastewater

NA

NA

730

92–91% BOD, 86% color

NA

Tara et al.84

Malaysia

Typha latifolia

200

CVU-MFC Gravels-carbon felt electrode

HSSF-MFC A dual-chamber India MFC-stainless steel electrode

AR18, AO7, CR

Fimbristylis ADMI dichotoma

NA

120

96% AR18, 67% Acid Orange 24 7 (AO7), 60% C.R.

Oon et al.83

62% COD, 90% color

Patel et al.66

96

AB: Acid blue; *RB: Reactive blue; VF: Vertical-flow; AO: Acid orange; COD: Chemical oxygen demand; TOC: Total organic carbon; HF: Horizontal flow, **RB: Reactive black; DY: Disperse yellow; VY: Vat yellow; TSS: Total suspended solid; TN: Total nitrogen; N: Nitrogen; NH4-N: Ammonium nitrogen; RR: Reactive red; VR: Vat red; AM: Amaranth dye; HRT: Hydraulic retention time; EC: Electrical conductivity; UF: Upper flow; NO3-N: Nitrate nitrogen; TDS: Total dissolved solids; FWS: Free water surface; SSF: Subsurface flow; BOD: Biochemical oxygen demand; AY: Acid yellow; PO4-P: Ortho-phosphatephosphorus; NA: Not applicable; HSF: Horizontal subsurface-flow; SSF: Subsurface flow; AB: Aerobic-anaerobic baffled; RHFA: Re-circulating horizontal flow; BF-MFC: Batch flow-microbial fuel cell; CVU-MFC: Continuous vertical upflow-microbial fuel cell; ABRX3: Reactive Brilliant Red X-3B; MO: Methyl Orange; GAC: Granular activated carbon; AR18: Acid Red 18; CR: Congo Red, HSCW-MFC: Horizontal sub-surface flow—microbial fuel cells; ADMI: American Dye Manufacturer’s Institute, FTWs: Floating treatment wetlands.

Utilization of constructed wetlands for dye removal

241

6. Conclusion and future research needs CWs are an environmentally friendly, cheap, simple-to-use, and effective technology widely accepted for treating a variety of municipal sewage, stormwater runoff, agricultural runoff, and industrial wastewater. This chapter reported that the high removal efficiency of dye, COD, and other contaminants was due to the interplay between plants, water, soil, and microorganisms in CW. Using this technology, wastewater of different origins can easily be treated in a natural and low-cost manner, especially dye-containing wastewater. Biodegradation of textile dyes in CW needs to be extensively studied from a simple and applied perspective and studies should emphasize case studies that are more similar to real-world situations. This biodegradation process should focus on environmental factors, degradation rate, degradation mechanisms and degradation pathways that influence pollutant removal. Finally, it is crucial to ensure that the intermediate products from dye degradation have no toxic effects on aquatic environments.

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42. Watharkar A, Rane N, Patil S, Khandare R, Jadhav J. Enhanced phytotransformation of Navy-Blue RX dye by Petunia grandiflora Juss. with augmentation of rhizospheric Bacillus pumilus strain PgJ and subsequent toxicity analysis. Bioresour Technol 2013;142:246–54. 43. Vafaei F, Khataee A, Movafeghi A, Salehi L, Zarei M. Bioremoval of an azo dye by Azolla filiculoides: study of growth, photosynthetic pigments and antioxidant enzymes status. Int Biodeterior Biodegrad 2012;75:194–200. 44. Khataee A, Dehghan G, Zarei M, Fallah S, Niaei G, Atazadeh I, et al. Degradation of an azo dye using the green macroalga Enteromorpha sp. Chem Ecol 2013;29:37–41. 45. Reema R, Saravanan P, Kumar M, Renganathan S. Accumulation of Methylene Blue dye by growing Lemna minor. Sep Sci Technol 2011;46:1052–8. 46. Khataee A, Movafeghi A, Torbati S, Salehi Lisar SY, Zarei M. Phytoremediation potential of duckweed (Lemna minor L.) in degradation of CI Acid Blue 92: artificial neural network modeling. Ecotoxicol Environ Saf 2012;80:291–8. 47. Khandare R, Kabra A, Kurade M, Govindwar S. Phytoremediation potential of Portulaca grandiflora Hook. (Moss-Rose) in degrading a sulfonated diazo reactive dye Navy Blue HE2R (Reactive Blue 172). Bioresour Technol 2011;102:6774–7. 48. Kabra A, Khandare R, Kurade M, Govindwar S. Phytoremediation of a sulphonated azo dye Green HE4B by Glandularia pulchella (Sweet) Tronc. (Moss Verbena). Environ Sci Pollut Res 2011;18:1360–73. 49. Kabra A, Khandare R, Waghmode T, Govindwar S. Differential fate of metabolism of a sulfonated azo dye Remazol Orange 3R by plants Aster amellus Linn., Glandularia pulchella (Sweet) Tronc. and their consortium. J Hazard Mater 2011;190:424–31. 50. Khandare R, Kabra A, Tamboli D, Govindwar S. The role of Aster amellus Linn. In the degradation of a sulfonated azo dye Remazol Red: a phytoremediation strategy. Chemosphere 2011;82:1147–54. 51. Davies L, Ferreira R, Carias C, Novais J. Integrated study of the role of Phragmites australis in azo-dye treatment in a constructed wetland: from pilot to molecular scale. Ecol Eng 2009;5:961–70. 52. Ajibade FO, Nwogwu NA, Lasisi KH, Ajibade TF, Adelodun B, Guadie A, et al. Removal of nitrogen oxyanion (nitrate) in constructed wetlands. In: Oladoja NA, Unuabonah IE, editors. Progress and prospects in the management of oxoanion polluted aqua systems. The Netherlands: Springer Nature, The Netherlands; 2021. https://doi.org/ 10.1007/978-3-030-70757-6_12. 53. Ajibade FO, Wang H, Guadie AA, Ajibade TF, Fang Y, Sharif HMA, et al. Total nitrogen removal in biochar amended non-aerated vertical flow constructed wetlands for secondary wastewater effluent with low C/N ratio: microbial community structure and dissolved organic carbon release conditions. Bioresour Technol 2021;124430. https://doi.org/10.1016/j.biortech.2020.124430. 54. Ajibade FO, Adewumi JR. Performance evaluation of aquatic macrophytes in a constructed wetland for municipal wastewater treatment. FUTA J Eng Eng Technol 2017;11(1):1–11. 55. Hadad HR, Maine MA, Bonetto CA. Macrophyte growth in a pilot-scale constructed wetland for industrial wastewater treatment. Chemosphere 2006;63:1744–53. 56. Chandanshive V, Rane N, Gholave A, Patil S, Jeon B, Govindwar S. Efficient decolorization and detoxification of textile industry effluent by Salvinia molesta in lagoon treatment. Environ Res 2016;150:88–96. 57. Kadam SK, Chandanshive VV, Rane NR, Patil SM, Gholave AR, Khandare RV, et al. Phytobeds with Fimbristylis dichotoma and Ammannia baccifera for treatment of real textile effluent: an insitu treatment, anatomical studies and toxicity evaluation. Environ Res 2018;160:1–11.

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58. Shehzadi M, Afzal M, Khan M, Islam E, Mobin A, Anwar S, et al. Enhanced degradation of textile effluent in constructed wetland system using Typha domingensis and textile effluent-degrading endophytic bacteria. Water Res 2014;58:152–9. https://doi.org/10. 1016/j.watres.2014.03.064. 59. Patil SM, Chandanshive VV, Rane NR, Khandare RV, Watharkar AD, Govindwar SP. Bioreactor with Ipomoea hederifolia adventitious roots and its endophyte Cladosporium cladosporioides for textile dye degradation. Environ Res 2016;146:340–9. 60. Shang N, Ding M, Dai M, Si H, Li S, Zhao G. Biodegradation of malachite green by an endophytic bacterium Klebsiella aerogenes S27 involving a novel oxidoreductase. Appl Microbiol Biotechnol 2019;103(5):2141–53. 61. Pervez A, Headley AD, Terzis E. The treatment of azo dyes using reed bed treatment systems. In: Means JL, Hinchee RE, editors. Wetlands and remediation. Columbus: Battelle Press; 2000. p. 187–94. 62. Mbuligwe SE. Comparative treatment of dye-rich wastewater in engineered wetland systems (EWSs) vegetated with different plants. Water Res 2005;39(2):271–80. 63. Bulc TG, Ojstrsˇek A. The use of constructed wetland for dye-rich textile wastewater treatment. J Hazard Mater 2008;155(1-2):76–82. 64. Yalcuk A, Dogdu G. Treatment of azo dye Acid Yellow 2G by using lab-scale vertical-flow intermittent feeding constructed wetlands. Selcuk Univ Nat Appl Sci 2014;3:355–68. 65. Noonpui S, Thiravetyan P. Treatment of reactive azo dye from textile wastewater by burhead (Echinodorus cordifolius L.) in constructed wetland: effect of molecular size. J Environ Sci Health A 2011;46:37–41. 66. Patel D, Bapodra SL, Madamwar D, Desai C. Electroactive bacterial community augmentation enhances the performance of a pilot scale constructed wetland microbial fuel cell for treatment of textile dye wastewater. Bioresour Technol 2021;332:125088. https:// doi.org/10.1016/j.biortech.2021.125088. 67. Rathour R, Patel D, Shaikh S, Desai C. Eco-electrogenic treatment of dyestuff wastewater using constructed wetland-microbial fuel cell system with an evaluation of electrode-enriched microbial community structures. Bioresour Technol 2019;285: 121349. https://doi.org/10.1016/j.biortech.2019.121349. 68. Saba B, Khan M, Christy AD, Kjellerup BV. Microbial phyto-power systems—a sustainable integration of phytoremediation and microbial fuel cells. Bioelectrochemistry 2019;127:1–11. https://doi.org/10.1016/j.bioelechem.2018.12.005. 69. Xu F, Cao FQ, Kong Q, Zhou LL, Yuan Q, Zhu YJ, et al. Electricity production and evolution of microbial community in the constructed wetland-microbial fuel cell. Chem Eng J 2018;339:479–86. https://doi.org/10.1016/j.cej.2018.02.003. 70. Davies LC, Pedro IS, Novais JM, Martins-Dias S. Aerobic degradation of acid orange 7 in a vertical-flow constructed wetland. Water Res 2006;40(10):2055–63. 71. Ojstrsˇek A, Fakin D, Vrhovsˇek D. Residual dyebath purification using a system of constructed wetland. Dyes Pigments 2007;74(3):503–7. 72. Nilratnisakorn S, Thiravetyan P, Nakbanpote W. A constructed wetland model for synthetic reactive dye wastewater treatment by narrow-leaved cattails (Typha angustifolia Linn.). Water Sci Technol 2009;60(6):1565–74. 73. Ong S, Ho L, Wong Y, Dani Leonard D, Hafizah S. Semi-batch operated constructed wetlands planted with Phragmites australis for treatment of dying wastewater. Eng Sci Technol Taylor’s Univ 2011;6(5):623–31. 74. Cumnan S, Yimrattanabovorn J. The use of constructed wetland for azo dye textile wastewater. Int J Civ Eng Build Mat 2012;2(4):150–8. 75. Yadav AK, Dash P, Mohanty A, Abbassi R, Mishra BK. Performance assessment of innovative constructed wetland-microbial fuel cell for electricity production and dye removal. Ecol Eng 2012;47:126–31. https://doi.org/10.1016/j.ecoleng.2012.06.029.

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76. Khandare R, Kabra A, Kadam A, Govindwar S. Treatment of dye containing wastewaters by a developed lab scale phytoreactor and enhancement of its efficacy by bacterial augmentation. Int Biodeterior Biodegrad 2013;78:89–97. https://doi.org/10.1016/j. ibiod.2013.01.003. 77. Fang Z, Song H, Cang N, Li X. Performance of microbial fuel cell coupled constructed wetland system for decolorization of azo dye and bioelectricity generation. Bioresour Technol 2013;144:165–71. 78. Tee HC, Lim PE, Seng CE, Mohd Nawi MA, Adnan R. Enhancement of azo dye Acid Orange 7 removal in newly developed horizontal subsurface-flow constructed wetland. J Environ Manag 2015;147:349–55. https://doi.org/10.1016/j.jenvman.2014.09.025. 79. Fang Z, Song H, Yu R, Li X. A microbial fuel cell-coupled constructed wetland promotes degradation of azo dye decolorization products. Ecol Eng 2016;94:455–63. https:// doi.org/10.1016/j.ecoleng.2016.06.020. 80. Mojiri A, Ziyang L, Tajuddin RM, Farraji H, Alifar N. Co-treatment of landfill leachate and municipal wastewater using the ZELIAC/zeolite constructed wetland system. J Environ Manag 2016;166:124–30. https://doi.org/10.1016/j.jenvman.2015.10.020. 81. Fang Z, Cheng S, Wang H, Cao X, Li X. Feasibility study of simultaneous azo dye decolorization and bioelectricity generation by microbial fuel cell-coupled constructed wetland: substrate effects. RSC Adv 2017;7:16542–52. https://doi.org/10.1039/C7RA01255A. 82. Lehl HK, Ong SA, Ho LN, Wong YS, Saad FNM, Oon YL, et al. Decolorization and mineralization of Amaranth dye using multiple zoned aerobic and anaerobic baffled constructed wetland. Int J Phytoremed 2017;19(8):725–31. https://doi.org/10.1080/ 15226514.2017.1284748. 83. Oon YL, Ong SA, Ho LN, Wong YS, Dahalan FA, Oon YS, et al. Constructed wetland–microbial fuel cell for azo dyes degradation and energy recovery: influence of molecular structure, kinetics, mechanisms and degradation pathways. Sci Total Environ 2020;137370. https://doi.org/10.1016/j.scitotenv.2020.137370. 84. Tara N, Arslan M, Hussain Z, Iqbal M, Khan QM, Afzal M. On-site performance of floating treatment wetland macrocosms augmented with dye-degrading bacteria for the remediation of textile industry wastewater. J Clean Prod 2019;217:541–8.

Further reading 85. Al-Isawi R, Scholz M, Al-Tharwani I, Al-Mansori N, Hassan AA. Experimental vertical-flow constructed wetlands treating domestic wastewater contaminated by diesel spill. In: 2018 11th international conference on Developments in eSystems Engineering (DeSE). IEEE; 2018. p. 340–4. 86. Lehl HK, Ong SA, Ho LN, Wong YS, Naemah F, Oon YL, et al. Decolourization and mineralization of Acid Red 27 metabolites by using multiple zoned aerobic and anaerobic constructed wetland reactor. Desalin Water Treat 2019;160:81–93. 87. Ong SA, Ho LN, Wong YS, Chen SF. Artificial aeration to enhance the mineralization of mono azo (methyl orange)-containing wastewater using recirculated up-flow constructed wetland. Environ Eng Manag J (EEMJ) 2014;13(1):37–42. https://doi.org/10. 30638/eemj.2014.006. 88. Wesenberg D, Kyriakides I, Agathos S. White-rot fungi and their enzymes for the treatment of industrial dye effluents. Biotechnol Adv 2003;22:161–87.

CHAPTER FOURTEEN

Pathogenic microbes in wastewater: Identification and characterization Rahul Prasad Singha, Priya Yadava, Rajan Kumar Guptaa, Sandeep Kumar Singhb, Hariom Vermac,*, Prashant Kumar Singhd, Kaushalendrad, Kapil D. Pandeya, and Ajay Kumare a

Laboratory of Algal Research, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India b Division of Microbiology, ICAR-Indian Agricultural Research Institute, Pusa, New Delhi, India c Department of Botany, B.R.D. Government Degree College Duddhi, Sonbhadra, India d Department of Biotechnology, Mizoram University (A Central University), Pachhunga University College Campus, Aizawl, India e Department of Botany, Banaras Hindu University, Varanasi, India *Corresponding author: e-mail address: [email protected]

Contents 1. Introduction 2. Traditional approaches for pathogenic microbial detection in wastewater 2.1 Colony counting and culturing method 2.2 Biosensors 3. Different molecular methods of wastewater pathogen detection 3.1 Polymerase chain reaction (PCR) 3.2 DNA microarrays 3.3 Lab-on-chip technology 3.4 Fluorescence in-situ hybridization (FISH) 3.5 Dot-blot hybridization 3.6 Next-generation sequencing (NGS) 4. Challenges 5. Future perspectives 6. Conclusion Acknowledgments References

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Abstract The rapid global industrialization and rising word human populations produced every year billions tons of wastewater and it has been estimated that more than 75% of these wastewater discharged into the open land without any treatment. However, these waste water contains huge amount of chemicals, pathogenic microorganism, heavy

Advances in Chemical Pollution, Environmental Management and Protection, Volume 9 Copyright # 2023 Elsevier Inc. 247 ISSN 2468-9289 All rights reserved. https://doi.org/10.1016/bs.apmp.2022.10.010

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metals and toxic substances etc. The pathogenic wastewater microbe’s identification and characterization has become one of the most challenging aspects, Molecular approaches have provided the means to examine and classify harmful microbial diversity and characterize specific organisms without the necessity for cultivation throughout the previous decade. Despite the need for quick molecular results, conventional wastewater microbial detection assays can take several days to produce a result. This timeframe is no longer acceptable, given the emergence of new molecular-based technologies. This chapter discusses current latest techniques which are used to characterize and identify the pathogenic microbes in the waste water. Keywords: Wastewater, Pathogens, Molecular techniques, Biosensor, Microarray, NGS

1. Introduction The rapid global industrialization and rising human populations produced every year, billions tons of wastewater and it has been estimated that more than 75% of these wastewater discharged into the open land without any treatment. However these waste water contains huge amount of chemicals, pathogenic microorganism, heavy metals or also toxic compounds etc.1–3 Some of the pathogenic microbes are known to cause diseases and have disastrous consequences for humans.4 Waterborne infections wreak havoc on health-care systems and global economy, impeding socioeconomic progress. As a result, identifying and characterizing pathogenic microbial communities in wastewater systems is critical. The routinely utilized sampling strategies are insufficient to sustain infection control in this scenario. Furthermore, present technologies do not equip us with adequate reaction mechanisms in such situations. The field of harmful microbe identification is not a new, and microorganisms have been a part of life on Earth since the dawn of time. Indeed, a current resurgence in microbial influence has provided researchers with new insights into the functioning mechanisms of microbe-human life symbiosis. Microbial culture technique is the most common method for detecting harmful microorganisms present in the waste water.3 Traditional culture-based approaches are low-cost, simple to apply, and well standardized, therefore widely utilized to study the harmful microorganisms.5 Furthermore, culture-based approaches sometimes underestimate the number of microorganisms when used in quantitative research. This has an impact on target quantification accuracy and understates pathogen prevalence in the human population. As a result, molecular techniques have swiftly become the standard for detecting harmful wastewater bacteria as a fast analytical tool with high

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accuracy and specificity than traditional approaches. These traditional approaches are prone to long experimental turnaround times and missing the correct sample interval. Because of the wrong sample duration, organisms and their growth responses may be misinterpreted.6 Molecular approaches can be classified into two classes based on the biological markers used: nucleic acid targeting methods and protein/antigen targeting methods.7 Fluorescence amplification-based methods includes polymerase chain reaction (PCR), DNA microarray, fluorescence in situ hybridization (FISH), and molecular chip, as well as sequencing-based methods like pyro, Illumina, and nanopore sequencing, are the common nucleic acid targeting methods.8,9 Although the microorganism present in the wastewater concentrations are typically lower than indicator microorganisms, necessitating a very sensitive detection approach. Because of the presence of different inhibitors in the wastewater matrix, false-negative results are common. Furthermore, sample processing processes fluctuate depending on the downstream analytical methodology. As a result, using molecular detection technologies to detect harmful bacteria in wastewater reliably and quantitatively is becoming more common. However, there have been few researches to explore and identify the harmful microbial flora in wastewater, and characterization studies are lacking.

2. Traditional approaches for pathogenic microbial detection in wastewater The presence of even small number of pathogenic microorganism can cause a severe threat to the living organism. The detection and identification of pathogenic microorganism is an important aspect to avoid the contamination of environment, air, soil, water or the human beings. However the traditional methods to detect and quantify harmful microorganisms in water samples involve time-consuming pre-concentration processes before detection. The most prevalent methods for detecting microorganisms are based on a variety of microbial culturing techniques, such as agar plate cultures and other liquid cultivation techniques, as well as biosensors.10,11 These classic detection methods have a considerable impact and help detect pathogenic bacteria from contaminated water. Nonetheless, they have several drawbacks, the most significant of which is the length of the study, which can range from a few hours to a few days.

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2.1 Colony counting and culturing method Until recently, in vitro methods were widely used to detect and identify the microbial strains and is the most widely used approach for the identification, and it involves growing and plating the organisms directly. The cultivation of microbial strains has opened up a world of microscopic life detection, with Koch’s postulates serving as the first set of rules.12 Koch’s postulates are a set of guidelines that establish whether or not a certain pathogen can cause disease. However, for industrial applications that require quick findings, such as the food and water sectors, culturing-based tests are frequently inconvenient.13 According to researchers, traditional culture methods help only in the cultivation and partial identification of microorganism.14 Although these traditional methods of counting is simple to follow, but to avoid the contamination aseptic conditions must be followed. In most of the cases, the cultured based techniques is the first choice and used for the detection of microbial strains In addition the traditional pathogen detection procedures necessitate a significant quantity of laboratory equipment, and time consumables. Unfortunately, laboratory employees must frequently be educated to produce and interpret results, making widespread use by non-specialists challenging. Although culturing techniques are still the preferred method but it is clear that more quick, reliable, and user-friendly solutions are required for wastewater pathogen detection.

2.2 Biosensors Biosensors for the detection of harmful bacteria have gotten a lot of attention in recent years. Such sensors are extremely useful for detecting even the tiniest amount of bacteria in wastewater. Biosensors are miniature devices that allow for the creation of portable sensors that can monitor wastewater on-site.15 Detecting microorganisms in water and wastewater using biosensor-based techniques has been a popular research topic16,17 and broadly reported as bio-recognition molecules and transduction mechanisms for the detection of aquatic infections, with oligonucleotide probes and antibodies being the most frequent. Biosensors have allowed for real-time detection of microbial contamination. For pathogenic wastewater borne microorganisms identification, biosensor technology may be essentially classified into two types: optical and electrochemical biosensors. 2.2.1 Optical biosensors As the optical biosensors are highly sensitive and accessible, now a days frequently applied to detect the pathogenic microorganism in the waste water.18,19

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There are various types of optical approaches have been used to detect the microbes, in which surface plasmon resonance (SPR)20 and resonant mirror21 are the frequently used. However in a study, it has been reported that molecular probes using surface-enhanced Raman spectroscopy can be able to detect E. coli and Listeria in a very specific binding manner with a reasonably quick detection period of bacterial specific antigens.22 The hybridization with the complementary DNA probes, mounted on the surface of an optical electrode fiber could be used to count the quantity of free aptamers. The lower level of E. coli in the tested samples could explain the greater fluorescence signal. For on-site wastewater testing, the designed system is low-cost, quick, sensitive, and portable. In a study Wu et al.,23 identify E. coli and S. typhimurium, using a sensitive and simple aptasensor based on the colorimetric test. In this method the aptamers have higher affinity for the target microorganisms and adsorbed on the AuNPs surface and the targeted bacteria changes the conformation of aptamers resulting changes in the color. Although this method is quick, and specific, and it can quantify the entire bacterium without the use of specialized equipment or pretreatment. 2.2.2 Electrochemical biosensors Many portable instruments have been recently developed to amperometrically detect the microorganism present in the waste water via electrooxidation or electro reduction.24 Despite its low sensitivity, this method could be applied to water and wastewater analysis to detect the pathogenic microorganism.25–27 Despite the fact that potentiometric approach is not widely used for detecting bacterial contamination, its success in assessing E. coli, DH5a in water using a potentiometric alternating biosensor that is very sensitive, quick, inexpensive, and small.28 Now a days electrochemical dual apt sensor have been used for the detection of Staphylococcus aureus in the aquatic samples.29 During analysis main aptamer was used in the detection method, which was mounted on magnetic beads using a particular biotin-streptavidin reaction. Because the impedance biosensor is made up of two real and imaginary portions, its projection requires a complex mathematical procedure. Despite label-free recognition and simpler sensor fabrication, only a few studies on microbe detection using impedance biosensors have been reported. Muhammad-Tahir and Alocilja,30 reported a single-use impedimetric system for the detection of E. Coli. During the study, Anti-E. coli antibody was used on a self-assembled monolayer of gold electrode to create an impedance immunosensor to detect presence of E. coli in the river water samples, which might be used for wastewater monitoring. The increase in electro-transfer

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resistance caused by E. coli specific binding to the electrode was directly proportional to the bacterial concentration.31 Magnetic nanoparticles and AgNPs are used in an electrochemical dual aptasensor for the detection of S. aureus.29

3. Different molecular methods of wastewater pathogen detection Polymerase chain reaction (PCR) is one of the oldest and most promising detection technique of microbes using the small quantity of microbial DNA and the specific primers. Now a days various types of PCR such as real time PCR, mPCR, RT-PCR have been available, which significantly amplify and quantify the microbial DNA present in the sample. Some of the PCR such as mPCR have the ability to detect the various microbes simultaneously which is time saving. However the another Real-time PCR precisely quantify the microbial population present in a sample and also eliminates the dependency of gel electrophoresis. FISH is a potent yet old technology that was originally designed for cytogenetic investigations and is now employed in oncology and microbiology. In the waste water samples, the presence of pathogenic microbes can be identifying using fluorescently tagged DNA/RNA probes in FISH. Fluorescent microscopes are used for detection. Another reliable technology is DNA microarray, which can detect hundreds of genes in a single test. DNA microarrays require advanced technology and are nevertheless expensive to perform. DNA microarrays have been successfully utilized to detect harmful bacteria in water, wastewater, and sludge samples, despite their primary usage in gene expression analysis. Immunological approaches based solely on antibody specificity, whether polyclonal or monoclonal. The fluorescent tagging of antibodies, either before or after their incubation in the sample, is used to detect them. Finally, next-generation sequencing (NGS) has been used to detect pathogen microorganisms in environmental samples by extracting DNA and sequencing it, followed by bioinformatics analysis of the data to determine the presence of pathogen microorganisms in the sample. Each of the strategies used to monitor waterborne pathogens has proven to be effective. The next section briefly discusses molecular approaches for wastewater microbe detection.

3.1 Polymerase chain reaction (PCR) PCR is one of the most widely used technique used for the identification of microbial strains present in the sample.32 The PCR is a three-step cyclic

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method which involves denaturation, annealing, and extension in order to exponentially amplify the target DNA sequence.33 PCR cycling improves the specificity of the target DNA identification in low quantities of microorganisms in the environmental sample.34–36 After staining with ethidium bromide, the amplified products are identified by agarose gel electrophoresis.34 It is possible to identify very little amounts of target DNA using PCR. For pathogen identification in wastewater, two forms of PCR are commonly used. 3.1.1 Multiplex PCR (mPCR) By employing coding of various pathogens specialized primers in the same sample, mPCR allows simultaneous diagnosis of numerous target species. In comparison to traditional PCR, mPCR enables detect several genes simultaneously. However the designing of primer during the study is the most important step, so that detect various distinct DNA sequences. The use of mPCR assay simply differentiate the pathogenic and commensally E. coli present in the clinical and ambient water sources.37 In a study, Fan et al.38 detected various pathogenic microorganisms. 3.1.2 Real-time PCR (rtPCR) In contrast to conventional PCR, which needs agarose gel electrophoresis to detect PCR product synthesis, rt PCR allows evaluates the DNA samples by measuring the fluorescence signals of samples even present in very precise quantity.36 During quantification the fluorescence intensity is directly proportional to the amount of PCR product. SYBR Green dyes, TaqMan probes, and molecular beacons are examples of fluorescent systems used in this method. Molecular beacons and TaqMan probes are FRET-based fluorescence detecting methods incorporated into primers that only create signal if DNA complementary to the primers is accessible.39,40 This approach provides great sensitivity, uniqueness, and speedy identification reduces the risk of cross-contagion, and there is no need for a post-PCR evaluation.41 Real-time PCR has several advantages over traditional end-point PCR techniques, including increased sensitivity, specificity, and detection speed. It also eliminates the need for post-PCR analysis, reducing the risk of contaminant carryover. For pathogen identification, dual-labeled fluorescent probes such as TaqMan probes and the fluorescent dye SYBR Green are commonly utilized.42 At concentrations as low as one target molecule per reaction, these rtPCR devices can correctly detect and calculate pathogens. In the case of Giardia lamblia and Giardia ardeae diagnosis in wastewater

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samples, rtPCR is sensitive up to 0.45 cysts per result.43 Real-time PCR was used to detect L. monocytogenes in biofilms, with a number of L. monocytogenes developing in a biofilm of 6102 CFUcm-2.44 For the detection of pathogenic strains of L. pneumophila, molecular methods based on rtPCR have been described.45 Quantitative reverse transcriptase rtPCR was used to detect RNA viruses in water, providing a numeric approximation of pathogens present.46 This method is useful for distinguishing live cells using messenger RNA (mRNA) detection. This method, however, cannot discriminate between damaged genomes.47

3.2 DNA microarrays Microarrays are a type of genomic technology commonly used to investigate gene expression and the benefit of this technology is the simultaneously detection of multiple genes in a single test.16,48,49 Currently a variety of microarray having high specificity and sensitivity have been used to detect the pathogenic microbes present in the waste water.7 In a study Wilson et al.50 reported various pathogenic microorganism using the microarray similarly Inoue et al.51 reported 941 pathogenic bacteria from the ground water.

3.3 Lab-on-chip technology To establish a microfluidic network, a lab-on-chip (LOC) technology has been used which contains a microchip with wells and channels, where samples and reagents are stored and delivered to the reaction chambers. However the chip is associated with a computer, through which data will be analyzed and also with a control and identification device.52,53 During the analysis mixture can be analyzed within a fraction of time using chip-based capillary electrophoresis. In a study Blaskovic and Barak,54 reported an oligonucleotide-based assay to detect the pathogenic bacteria. Similarly Stratis-Cullum et al.55 used the combination of biochip with the enzyme linked immunosorbent assay to detect Bacillus globigii spores. Microchips outperform classic capillary or gel-based technologies in terms of speed, reagent usage, and integration. Lagally et al.56 used E. coli and S. aureus cells to demonstrate the efficacy of their approach by detecting pathogens and genotype. Zheng et al.57 reported in a study, how the microfluidic device used for the quick deconstruct and reassemble of DNA. Although the significance of this study in the microbiological detection and identification system has yet to be realized. Because of the very

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complicated nature of the samples to be evaluated, sample pretreatment for fluidics remains a difficulty with the downsizing of full systems.58

3.4 Fluorescence in-situ hybridization (FISH) This technique have been used to determine the population of different microbial communities in a sample. In another words, this technique, enable to evaluate the specific microbial cell present in the waste water, activated sludge, etc.47,59,60 By using the FISH techniques various authors detected pathogenic bacteria present in the different environment,61 By using this techniques various authors identified the pathogenic microorganism such as Salmonella spp. in wastewater,62 and Helicobacter pylori in surface water and wastewater.63 The FISH has been also used to analyze survival process during the contamination identification and enumeration of pathogenic microorganism present in the sample.36,47,59

3.5 Dot-blot hybridization The most important features of this technique the prompt response and evaluation from the various samples. The designing and specificity of the probe is the most crucial step during the dot-blot hybridization.64,65 However, some drawbacks are also present in this technology like time consummation and the probe designing, which influence the rate of morphological characterization of the microorganism.66 In the previous study various author reported the presence of bacterial communities in the sludge, nitrifying and methanogenic bioreactors.67,68 However in the previous study, the detection of microorganisms using dot-blot hybridization showed 40% of filamentous bacteria belongs to the phyla bacteroidetes and approx. 14% of belongs to nitrite-oxidizing bacteria present in a biofilm samples.69

3.6 Next-generation sequencing (NGS) Next generation sequencing is a latest techniques broadly utilized to quantify the metagenomic DNA of a sample.70 However the sequencing output is slightly complex but it provide a broad picture of any analyzed samples. The Illumina based sequencing, Pyrosequencing are the some latest approach of NGS (.36,71 Through this approach millions of nucleotides base pair analyzed in a single run with high accuracy.36,72 In the previous study various author have used the NGS to quantify the microbial structure of any sample. In a study **Cai and Zhang73 reported various human pathogens from then waste water treatment plants using high-throughput shotgun

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sequencing technique. Similarly Ye and Zhang74 reported various bacterial genera from the waste water treatment plants using 454 pyrosequencing method. Guo et al.75 used metagenomic sequencing based on NGS sequencing to evaluate microbial composition of sludge. Similarly Dunkel et al.76 used Illumina sequencing to identify common bulking and foaming bacteria present in the wastewater

4. Challenges It is critical to emphasize and comprehend that the detection of pathogenic microorganisms present in water, wastewater, and sludge is a required prerogative. Infectious agents must be identified (e.g., bacteria, fungi, protozoa, and viruses). Finding quick and inexpensive ways to check water quality has become a regular source of concern for authorities and a hot topic among researchers. It has been established that the vast majority of microbes are non-pathogenic, with only a small number, less than 0.1% causing disease. These techniques must be founded on methods of identification and characterization that are robust, smart, fast, sensitive, selective, and dependable. Because the field is so fascinating and evolving, new molecular approaches are continuously emerging to overcome these restrictions. These are also innovative, with the majority combining immunological assays with various sensors and semiconductors. Many research efforts have gone into developing automatic, integrated, and downsized techniques; yet, practical applications still face hurdles. Electrochemical biosensors, despite being very promising sensing technologies, suffer a few obstacles that must be solved. One such issue is that most current sensors are only capable of detecting a single bacterium type. The detection of multiple organism simultaneously required for the detections of harmful microbes for their possible applications.

5. Future perspectives Other measures (such as turbidity and dissolved organic matter) are still used in industrial domains (water treatment plants and wastewater disinfection) to screen for microbiological water quality. The development of quick and effective pathogen detection methods could help to improve real-time monitoring of pathogenic bacteria load in wastewater. In several

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scientific domains, artificial intelligence and machine learning have opened up new possibilities. The prediction of multiple conventional and molecular approaches is used to monitor E. coli concentration in wastewater in real time. Rapid testing instruments should also meet the criteria, which include the following features: affordability, sensitivity, specificity, user friendliness, speed and robustness, equipment-free functionality, and end-user deliverability. These criteria are especially relevant when on-site testing is required in remote and resource-constrained locations. In the not-too-distant future, methods for rapidly and accurately detecting the presence and concentration of bacteria will be available to collect data from water sources and combine it with machine learning algorithms to make better and faster decisions about wastewater pathogenic microbial characterization.

6. Conclusion Waterborne infections are a major global health concern, particularly in developing nations. Methods for detecting such viruses quickly are critical for improving the general health of the target population living in potentially contaminated locations. Despite the abundance of research on culture-based and molecular biology-based wastewater techniques, further research and combinational methodologies are still required. Pure culture is required for traditional culture-based microbial identification methods, which is arduous and time-consuming. To assess the microbial community structure in wastewater, the most up-to-date molecular biology-based approaches are required. Molecular biology techniques are quick, inexpensive, extremely sensitive, provide precise phylogeny information, and allow for speedy sample profiling. As a result of molecular biology approaches, scientists and process engineers may investigate the structure and function of microbial communities, which aids in the identification and characterization of pathogenic bacteria from wastewater. However, because no single strategy meets all, if not most, of the developing criteria for quick, effective, repeatable, and sensitive findings, there is still a significant knowledge vacuum in this area.

Acknowledgments The authors are thankful to the Department of Botany Centre of Advanced Study, Institute of Science, Banaras Hindu University, Varanasi for the lab facilities. University Grant Commission, New Delhi, for providing financial assistance in the form of JRF/SRF.

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CHAPTER FIFTEEN

Tidal coastal wetlands for wastewater management Kayode Hassan Lasisia,b,c, Fidelis Odedishemi Ajibadea,c,d,*, Temitope Ezekiel Idowue, Temitope Fausat Ajibadea,b,c, Bashir Adelodunf,g, Adedamola Oluwafemi Ojoh, Olaolu George Fadugbaa, Olawale Olugbenga Olanrewajui, and James Rotimi Adewumia a

Department of Civil and Environmental Engineering, Federal University of Technology, Akure, Nigeria Institute of Urban Environment, Chinese Academy of Sciences, Xiamen, P.R. China University of Chinese Academy of Sciences, Beijing, P.R. China d CAS Key Lab of Environmental Biotechnology, Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, P.R. China e Center for Applied Coastal Research, University of Delaware, Newark, DE, United States f Department of Agricultural and Biosystems Engineering, University of Ilorin, Ilorin, Nigeria g Department of Agricultural Civil Engineering, Kyungpook National University, Daegu, Korea h Department of Civil Engineering, Yaba College of Technology, Lagos, Nigeria i Department of Agricultural and Environmental Engineering, Federal University of Technology, Akure, Nigeria ⁎ Corresponding author: e-mail address: [email protected] b c

Contents 1. Background 2. Wetland definitions 3. Tidal coastal wetlands 3.1 Coastal wetlands 4. Significance of coastal wetlands ecosystem services 4.1 Carbon sequestration 4.2 Coastal protection and flood/erosion control 4.3 Wildlife habitat and food 5. Coastal wetlands wastewater management study 5.1 Preamble 5.2 Wastewater treatment and management by coastal wetland 5.3 Case and modelling studies 5.4 Benefits of coastal wetland wastewater treatment system 6. Conclusion References

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Abstract Tackling the global water scarcity problem and inadequate clean water supply, caused majorly by various upsurging anthropogenic factors, must be addressed decisively by establishing a sustainable framework for effective wastewater treatment and Advances in Chemical Pollution, Environmental Management and Protection, Volume 9 Copyright # 2023 Elsevier Inc. 263 ISSN 2468-9289 All rights reserved. https://doi.org/10.1016/bs.apmp.2022.11.002

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management. The tidal coastal wetland is a cost-effective and sustainable treatment ecosystem that is valuable in managing secondary treated effluents, as documented. It also ensures the delivery of safe water into the environment compared to conventional treatment methods. They have been labelled as one of the most productive ecosystems with high economic importance. However, factors such as climate change, sea-level rise, nutrient inputs and sediment delivery have impacted negatively on this wetland hence resulting in continuous degradation and loss. Therefore, this chapter first provides an overview of the various forms of tidal coastal wetlands and their economic importance. Next, case and modelling studies supported some key information on the essence of tidal coastal wetlands in the effective wastewater management process. Keywords: Tidal coastal wetland, Ecosystem services, Wastewater treatment, Wastewater management

1. Background Approximately 4% of the earth’s land area is made up of coastal zones. These zones are important because they serve as a habitat for more than one-third of the global population and 95% of marine fisheries catch.1 One of the most interesting features of coastal areas is the coastal wetlands. Some of the most economically important ecosystems have benefitted humanity with a range of ecosystem goods and services.2–4 In addition, they act as a buffer between terrestrial and aquatic ecosystems by preventing eutrophication in inland and coastal waters.5 Unfortunately, they are constantly being threatened by various factors such as a change in land use, rising sea levels, changes in global climatic conditions, increasing nutrient availability, overfishing, and many more.6–9 In addition, they undergo many environmental fluctuations over different periods because of their sensitive nature, making them more vulnerable, hence undermining potential benefits.2 Changes in land use or alteration in hydrology caused by climate change or other anthropogenic factors are constantly having a devastating effect on these wetlands. Furthermore, coastal pollution caused by sewage and wastewater runoff has been described as a major hazard threatening human health and contributing to the cryptic degradation of coastal ecosystems.10,11 Meanwhile, tidal coastal wetlands (or other naturally occurring wetlands) can help reduce this sewage and wastewater pollution via sediment filtering and trapping, nutrient absorption, and reduction. Therefore, these ecologically sensitive ecosystems must be protected, particularly by implementing appropriate methods for sustainable management, especially in wastewater management.

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Here in this chapter, an overview is first provided on some generally accepted definitions of wetlands and what tidal coastal wetlands represent. Different coastal wetlands were briefly discussed, such as marshes, swamps, bogs, estuaries, fen, and coral reefs. Some economic importance of this productive ecosystem: carbon sequestration, coastal protection, flood control, wildlife habitat, and food and water quality improvement were highlighted. A specific focus was then set on wastewater treatment and management fundamentals and how coastal wetlands can be helpful to wastewater management systems. This includes the review of some case and modelling scenarios. Some benefits of the wetland system as an effective wastewater management option were provided.

2. Wetland definitions To start with, too many definitions have been used to describe what wetland means; some are even confusing, while others are contradictory. One of these confusions is caused by the nature of the environment, which is seasonally or permanently affected by water availability. Another source of confusion that seems more important is the specific requirements of the people engaging in the study and management of these wetlands. Although these contentions are not within this chapter’s context, some definitions must be given to understand and manage the system properly. In subsequent sections, this will facilitate a better understanding of our discussion on tidal coastal wetlands. The conservation and sustainable use of wetlands was made public by the Ramsar Convention during the Convention on Wetlands of International Importance, especially as Waterfowl Habitat, 1971. The convention unanimously defines wetlands as “Wetlands are areas of marsh, fen, peatland, or water, whether natural or artificial, permanent or temporary, with water that is static or flowing, fresh, brackish, or salt, including areas of marine water, the depth of which at low tide does not exceed 6 m.”.12 Wetlands are also defined concisely by Smith13 as “a halfway world between terrestrial and aquatic ecosystems and exhibit some of the characteristics of each.” This definition is relevant for regions where wetlands may only become “wet” for a short time during a year, with a perfect example being the tropics marked by wet and dry seasons. Additionally, the Army Corps of Engineers of the U.S., in an effort to establish a uniform set of criteria, developed a three-criteria methodology hinged on vegetation, soils, and hydrology and later adopted it as national

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standard. They defined wetlands as “areas that are inundated or saturated by surface or groundwater at a frequency and duration sufficient to support, and that under normal circumstances do support, a prevalence of vegetation typically adapted for life in saturated soil conditions”.14 All the stated definitions show that wetlands largely encompass a wide range of hydrological and ecological factors. Whichever definition is adopted, it is essential to take cognizance of the presence of water, vegetation, and soil condition with respect to the prospective study to be undertaken.

3. Tidal coastal wetlands Tidal coastal wetlands are in coastal areas usually influenced by alternating floods and ebbs of tides.15 They are generally identified as tidal salt marshes, tidal freshwater wetlands (marshes and forests), and mangrove swamps (Fig. 1). Mitsch and Gosselink16 reported that about 270,000 km2 of coastal wetlands are available worldwide, representing almost 4% of all the wetlands in the world. More than half of this stated area of coastal wetlands are mangroves with tidal marshes.17 For example, the total reported extent of wetlands considered as coastal or estuarine wetlands in the U.S. is approximately 32,000 km2 with salt marsh, tidal freshwater marshes, and mangrove swamps claiming 19,000km2, 8,000 km2 and 5,000 km2, respectively.16,18 Like other wetlands, tidal wetlands benefit humans by providing some goods and services

Fig. 1 Tidal coastal (freshwater) wetland. Barendregt A. Tidal freshwater wetlands, the fresh dimension of the estuary. In: Finlayson C, Milton G, Prentice R, Davidson N, editors. The wetland book. Dordrecht: Springer; 2016. doi:10.1007/978-94-007-6173-5_103-2.

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(These goods and services are discussed later in the section). Unfortunately, they are constantly at risk of degradation or loss as a consequence of global change19,20 as rising surface temperatures drive accelerating rates of sea-level rise and also alter the intensity and frequency of tropical storms.21,22 To understand and match the common nomenclature given in literature, tidal coastal wetlands will be referred to as “coastal wetlands” in subsequent sections.

3.1 Coastal wetlands As initially described in the introduction section, wetlands are highly productive ecosystems that can be seen in almost all places globally. They can either be natural or artificial (man-made). Coastal wetlands are transient zones between terrestrial and marine ecosystems,16 and depending on prevailing climatic and hydrological conditions; they can be grouped into several categories. We shall limit our discussion of the various form of these natural wetlands in this section. They include fens, estuaries, swamps, bogs, marshes, deltas, mires, lakes, coral reefs, lagoons, and floodplains. Below is a brief discussion of some of these wetlands as outlined by the Federal Geographic Data Committee.23 3.1.1 Marshes These wetlands have their soil constantly saturated with water and are mainly occupied with soft-stem vegetation. They act as protection by reducing the current flow of flood, storing excess water hence recharging the groundwater (Fig. 2). The slow migration of water in marshes helps the settlement of nutrients at the base form of high biodiversity, which the plants and microorganisms can utilize presents in marshes for their growth and development. Marshes are largely discovered or formed at the banks of rivers, particularly in regions where extensive deltas have been constructed. 3.1.2 Swamps These wetland types are defined as flooded woodlands occurring in low-lying areas where the soil is supersaturated, especially during the growing season (Fig. 3). Swamps can be subdivided into forests, shrubs, and mangroves. Forest swamps occur at the coast region of water storage or reservoirs and are recipients of water from lakes and rivers. The nature of the tree growing in swamps are dry and deciduous. Meanwhile, mangrove swamps are characterized by halophytic (salt-tolerant) trees and plants. They are found chiefly in tropical and subtropical regions of vegetation.

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Fig. 2 Tidal marshes. Keddy. Freshwater marshes. In: Encyclopedia of ecology. 2008. p. 1690–1697. https://doi.org/10.1016/B978-008045405-4.00338-4.

Fig. 3 Swamps. Burton TM. Swamps: wooded wetlands. In: Likens GE, editor. Encyclopedia of inland waters. Amsterdam, The Netherlands/Boston, MA, USA: Elsevier; 2009. p. 549–557. doi:10.1016/B978-012370626-3.00063-6.

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3.1.3 Bogs Bogs are characterized by peat soil/peat-deposited freshwater wetlands, having poor nutrients and weak acidic soil conditions (Fig. 4). They are created when organic materials such as leaves, litter, and other organic materials naturally decompose over time due to active microbial processes. The central parts of the bog are supplied by rainwater and are predominant in glaciated areas of the Northern United States of America. 3.1.4 Estuaries These wetland types develop where freshwater from the river meets saltwater, thus creating habitats rich in nutrients and sediment from the land and sea, connecting the two for the growth of microorganisms and plants (Fig. 5). They are regarded as a habitat of high conservation value because of the varieties of conditions favorable for the living welfare of wildlife. However, they can be affected by climate change, inappropriate catchment development, increased algal bloom, degree of tides, and nutrient input. Some measures to tackle these problems include improving catchment areas, restricting fishing, and native vegetation, reducing pollution and sedimentation, and so on. Types of estuaries include deltas, salt marshes, tidal mud flats, and channels.

Fig. 4 Bogs. Butt MA, Zafar M, Ahmed M, Shaheen S, Sultana S. Types of wetland and wetland plants. In: Wetland plants. Cham: Springer; 2021. doi:10.1007/978-3-030-69258-2_3.

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Fig. 5 Estuary. Balasuriya A. Coastal area management: biodiversity and ecological sustainability in Sri Lankan perspective. Biodivers Clim Change Adapt Trop Islands 2018;701–724. doi:10.1016/B978-0-12-813064-3.00025-9.

Fig. 6 Carpha alpina fen. Hope GS. Nature of Alpine ecosystems in the tropical mountains of Asia. In: Encyclopedia of the World’s biomes; 2020, p. 300–310. doi:10.1016/B978-0-12409548-9.11980-3.

3.1.5 Fen These wetland types are characterized by low shrubs, sedges, and abundant grasses. Just like bogs, there is peat soil although alkaline in nature (Fig. 6). Their water table is usually close to the surface, and their surface often has a

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Fig. 7 Coral reefs. Burkepile DE, Hay ME. Coral reefs. In: Encyclopedia of ecology. 2nd ed. 2008; vol. 2, p. 426–438. doi:10.1016/B978-0-444-63768-0.00323-1.

micro-relief of hummocks, hollows, and pools. The nature of the fen largely depends on the geologic settings and the proportions of lateral inflow from surroundings water and not necessarily from precipitation. Like the estuaries, they are productive habitats having nutrient-rich condition that provides a diversity of plant life, which in turn supports several animal species that thrive in them. 3.1.6 Coral reefs These are among the most productive and diverse existing ecosystems covering approximately 0.1–0.5% of the ocean floor (Fig. 7). Coral polyps (the animal responsible for building reefs) can take several forms. The reefs are known as the “rainforests of the sea” due to the diversity of life in the corals’ habitats. Many marine fishes depend on healthy coral reefs for their shelter, food, reproduction, and even raising their young.

4. Significance of coastal wetlands ecosystem services Although tidal coastal wetlands have not been given the deserved attention and care, they have been beneficial in no small measure, especially in human well-being and economic development in the past Century .24–26 Many of them depend totally or partly on groundwater for their hydrological balance. Generally, some of the important services provided by the tidal

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coastal wetland’s ecosystem include carbon sequestration, flood protection, sediment accumulation for land accretion, habitation for wildlife, tourism resorts, water/wastewater quality improvement, management, etc. However, these services were better categorized into four classes by the Millennium Ecosystem Assessment,27 as given in Table 1. Three of these critical ecosystem services are briefly described below with the exception of water and wastewater quality improvement and management. This will be covered in more detail in Section 5.

4.1 Carbon sequestration Coastal wetlands have been one of the most critical and cost-effective ecosystems used for atmospheric carbon(iv)oxide (CO2) sequestration.28–31 This concept has been an excellent option for combating the climate change impacts in the world, and this has been achieved at no or limited costs.30,32 The process of sequestering CO2 in natural or artificial sinks is generally referred to as carbon sequestration (C.S.), and this is achieved in such a way that it can be maintained within the sink for an extended period with minimal chances of returning into the atmosphere.33,34 This is the exact role of coastal wetlands. They help the reduction of atmospheric CO2, and it is either sequestered as organic material in the soil or in plant and animal Table 1 Tidal coastal wetland ecosystem services categories. Ecosystem services categories Structures and functions

Provisioning

This aspect of services deals with products such as food, fiber, timber, water, genetic resources, and other raw materials

Regulating

This aspect of services deals with flood protection, carbon sequestration, sediment stabilization, erosion control, coastal protection from storms, water purification and supply, pollution uptake, disease regulation, pollination, climate regulation, air quality regulation, and natural hazard regulation

Cultural

This service addresses the unique and aesthetic landscape of cultural heritage, spiritual enrichment, ecotourism, recreation, formal and informal education, and research

Supporting

This service includes nutrient cycling, reproductive habitat and nursery for fish, standardizing living space for diverse flora and fauna, and gaming

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biomass. This usually results in massive organic carbon accumulation in wetland sediment.35 The average long-term carbon sequestration rates in soils or sediments for swamps, marshes and mangroves are almost 20 greater than in the forest.36 Although one of the sources of greenhouse gas emissions is the coastal wetlands, they are produced in small quantities owing to the sulfate-reducing bacteria in the saline water. These will subdue the methanogens bacteria by outshining them for energy sources.37,38 Several global-scale estimates of carbon sequestration and storage in coastal wetlands have been reported (Refs. 39–44).

4.2 Coastal protection and flood/erosion control Dwellers of coastal regions are at greater risk of flooding because of continuous developmental activities resulting in intensifying storms and sea level rise. Up to 5% of the global population will be directly affected annually by coastal flooding.45–47 Seawalls’ defense structures have been built to manage flood risks. However, it is more beneficial to adopt nature-based coastal protection, such as wave- and surge-absorbing coastal wetlands.48 Coastal wetlands offer a natural protection against coastal flooding and storm surges mainly by dissipating wave energy. They represent buffers between the winds and waves of storms and the areas beyond. The salt marshes are the most effective natural coastal habitats for reducing wave heights, along with coral reefs, which represent areas drained by tides and coastal wetlands flood.49,50 In addition, wetland plants and trees can reduce flood water speed, thus helping to guard nearby property against flood damage. Coastal wetlands also reduce coastal erosion by strengthening the shore sediments and riverbanks of the region, and this is achieved by binding soil with their roots. This action helps dampen wave action and absorb tidal forces.51 When located between rivers and high ground, they aid in buffering shorelines against erosion.

4.3 Wildlife habitat and food Another great potential and resourcefulness of the coastal wetland ecosystem are its high plant productivity rates in which the sun’s energy is converted into plant materials. Thus, this represents a unique food web for wildlife species within and outside the wetland. In addition to being a source of food, these wetlands (especially the areas of dense vegetation) are the place of home and shelter for wildlife.25 These abodes even represent a place of security for this wildlife to hide from predators. The nature of the water in these

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coastal wetlands determines the kinds of plants and animals that survive and live there, which could be salty or fresh. Some of these wetlands remain wet, while some dry out after some seasons. Some plants that cannot tolerate salt wither and die when it is salty and moist, while salt-tolerant plants such as Pickleweed thrive. Tides sometimes migrate seawater from the ocean, and during this movement, tiny particles of plants and animal decay called detritus are transported alongside. Some animals, such as shrimp, bent-nose clams, and innkeeper worms, thrive on this detritus. Wetland is the primary habitat of some species like muskrats, bullfrogs, Canadian geese, wood ducks, great blue herons, beaver, snapping turtles, etc. In contrast, other species such as wood frogs, black bear, moose, deer, and marsh hawks do not primarily dwell in these wetlands but serves as an essential habitat for a part of their life cycle or during specific periods of the year.

5. Coastal wetlands wastewater management study 5.1 Preamble Man’s daily activities are filled with water-dependent situations that often lead to water pollution, making them available and limited useable water highly polluted. When water’s chemical, biological or physical state or properties change due to the introduction of contaminants and pollutants to the degree that they render the water unsafe for use, it is termed wastewater.52 This polluted water must be treated and effectively managed to meet water demand and shield the environment.53 Due to the various degree and types of contaminants present in wastewater, it is often difficult to identify and quantify them. Therefore, some universal parameters to assess the quality of water include pH, temperature, conductivity, total suspended solids (TSS), total Kjeldahl nitrogen (TKN), ammonium (NH4+dN), nitrate (NO3 dN), total phosphorus (T.P.), biological oxygen demand (BOD) and chemical oxygen demand (COD).53,54 One of the undisputable roles of wetlands is the overall water quality improvement, which can be achieved through the treatment and management of wastewater.55,56 Generally, wetlands are good water filters. They act as media for water storage and are highly relevant in improving the quality of water stored in them or water runoff coming into them from other sources.57 They clean the water, replenish groundwater, and regulate the runoff in urban areas. Numerous plants that grow in wetlands serve as filters by purifying the water that will eventually be discharged downstream.58,59 Historically, the use of wetlands to treat, remediate and manage wastewater is dated back to the Indus valley civilization as far back as 2500 BCE before the industrial

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revolution. Still, the inception of the industrial revolution enhanced technological advancement. At this period, the primary criteria for treating wastewater had been established.52,60 The self-cleaning ability of water via wetlands to naturally remove contaminants was explored, and this has been focused on for several decades as more systems were put in place to improve water quality.61 It is one of the most preferred systems for improving water quality emanating from different water pollution sources up to date because of their economic benefits. Although, the use of constructed or artificial wetlands for treating and managing wastewater could incur grave costs depending on some other factors (Refs. 55,62,63). Under wastewater management, coastal wetlands can either serve as a single treatment entity or may be incorporated as a part of an integrated wastewater treatment system. Meanwhile, their long-term stability in performing this management role effectively depends on the interaction between sea level rise, sediment deposition, vegetation growth, and human factors.64–66

5.2 Wastewater treatment and management by coastal wetland Coastal wetland renders many vital ecosystem services and functions, as highlighted in Section 4. Another such function is water and wastewater treatment and quality improvement. For an extended period, natural wetlands, including coastal types, have been a perfect substitute for conventional wastewater treatment systems, especially at the tertiary treatment level67 after undergoing secondary treatment. This has been predominantly employed in the U.S. and Europe. In modern wastewater treatment evolution, it is required that wastewater can only be discharged into the environment after undergoing a three-level stage of treatment processes, namely primary treatment (which deals with the removal of heavier solids by gravity sedimentation),53 secondary treatment (which entail using oxidation and microbial decomposition)52 and tertiary treatment (which involves the removal of nitrogen and phosphorus using wetlands system or alum/ chlorination).68 This is done to reduce the potential risk that discharged wastewater limited only to secondary-level treatment could pose on aquatic systems.69 Economic treatment of wastewater at the tertiary level is thus made possible by wetlands.68

5.3 Case and modelling studies The scientific study of wetlands in treating wastewater commenced comprehensively a few decades ago, although they have been used to treat

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wastewater for centuries. At inception natural wetlands were predominantly used for this purpose before the invention of constructed wetlands,70 although the latter is mainly used today. Several natural wetlands have been reported as effective processors of wastewater effluent and wastewater assimilators, and they ascertain that they can physically, chemically, and biologically eliminate pollutants, sediments, and nutrients from wastewater flowing through or discharged in them.69–73 And for coastal regions like Louisiana in the U.S., often characterized by degraded water quality caused partly by inadequate sewage treatment, these wetland functions are paramount in addressing the issue.70,74 Although, only in a few cases have scientists (especially in the U.S.) conducted research in coastal wastewater facilities in states like Louisiana,70 North Carolina,75–77 and South Carolina78 and focused on the wastewater management aspect in the practical term. In this regard, most of the works in the U.S. and other countries are computational. Researchers adopt modeling studies as a form of best water quality management practice, and this has largely been used to address non-point source pollution control problems.79 By this, a mathematical model can be developed and employed to simulate hydrodynamics, water quality, and the ecosystem. This can then be verified with the field data and, when in agreement, can be applied to predict the various conditions of hydrological and waste input related to the ecosystem dynamics. Some hydrodynamic modeling of the water column in the wetland system has been studied.80–82 Furthermore, water quality and ecosystem models have been used to model fate and transport phenomena for contaminant and water quality management in wetlands ecosystems.15 A one-dimensional simulation model of wetland hydrology and nutrient-driven interactions between wastewater and the wetland ecosystem was developed by Kadlec and Hammer.83 The hydrology model predicted the overflow patterns, and mass balance calculations were engaged for the phosphorus, nitrogen, and chloride fluctuations. Their investigation also included environmental phenomena like plant biomass growth patterns. Also, Mitsch and Reeder84 developed a wetland nutrient model in which hydrology, productivity, and phosphorus were calibrated using field data from a freshwater coastal wetland of Lake Erie, one of the North American Laurentian Great Lakes. The model was used to supplement field data to quantify the overall contribution of ecosystem metabolism, sedimentation, resuspension, and lake hydrodynamics to the cycling and retention of phosphorus in the wetland. Lung and Light85 developed a numerical model and used it to simulate the fate and transport of copper in the Old Woman Creek wetland ecosystem in Northern Ohio, USA. Using Nielsen’s nutrient

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uptake equation, they calculated the relative contributions of sedimentation, macrophyte uptake in the removal of copper from wastewater, and copper speciation in the water column and sediment. Their findings demonstrated that sedimentation and macrophyte absorption promote copper elimination. Mitsch and Wise86 estimated the phosphorus retention of existing and restored coastal wetlands in a tributary watershed (Quanicassee River basin) of the Laurentian Great Lakes in Michigan, USA. They discovered that a straightforward Vollenweider-type model could serve as a rational tool to give better information on how and what can be expected in terms of phosphorus reduction under various wetland restoration scenarios. The model also showed how important inflows, wetland depth, previous soil conditions, and restoration efforts were in relation to one another. Yang et al.15 developed a water quality and ecosystem model to simulate nutrients, heavy metals, and aquatic plants in the Erh-Chung Flood Way wetland in Taiwan. A sediment system was also incorporated into the model. RMA2 and WASP/EUTRO5 models were used to calibrate four water quality variables: macrophyte biomass, suspended solids, heavy metals in macrophytes, and heavy metals in the water column and sediment. Collecting site-specific water quality data supported the model calibration and verification analyses.15 Other works using mathematical models to simulate hydrodynamics, water quality, and ecosystem parameters in natural wetlands have been documented.86–88 Meanwhile, most of the modelling studies recently being carried out are geared toward constructed wetlands.89–92

5.4 Benefits of coastal wetland wastewater treatment system Some benefits accrue from using coastal wetland systems for water treatment and management aside from the low operating cost compared to man-made or constructed wetlands and conventional treatment methods. These benefits are briefly discussed as follows: (i) Reduced cost of treatment Proper wastewater treatment and management processes could be capital demanding as they require the initial installation capital cost and the continuous operating and maintenance cost. During wastewater treatment operations, specific treatment levels of water quality parameters such as pH, BOD, COD, and so on are set to ascertain the safe quality of the discharged effluents, and this is mostly associated with conventional treatment processes (including physical, chemical, and biological processes) which are considerably expensive. However, some of these treatments can be

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undertaken at reduced rates if coastal wetlands are used as an initial approach to filter off and absorb nutrients and contaminants present in the wastewater. (ii) Higher level of treatment For continuous sustainability of natural wetlands (both coastal and inland), there is a need for a constant influx of nutrients for biomass growth. Wetlands’ natural growth and decay may not be sufficient to maintain high-quality vegetation. Although the place of macrophytes in water purification and treatment is not direct, they remain a valuable structural medium.93–96 The primary removal of phosphorus and heavy metals is accomplished by chemical processes such as adsorption, chelation, and precipitation, which are facilitated by macrophyte vegetation’s attenuation of water flow and sedimentation of particulate matter.11,97 They also stabilize the wetland soil surface while the soils themselves act as absorption mediums for pollutants.11 Therefore, when vegetation quality is improved with respect to volume and health, the wastewater treatment ability is greatly increased, even to higher levels compared to conventional treatment methods.55 For instance, wetlands often treat up to tertiary standards, while most traditional methods are stopped at the secondary treatment level. In addition, wildlife habitat and other visual characteristics are also enhanced. (iii) Improvement in water quality The water quality of existing receiving water bodies such as lakes, ponds, and so on may be improved when polluted water is rechanneled into wetlands before discharging into the surface or groundwater sources. This is more appropriate when the discharge made into the existing receiving waters meets the discharge standards. However, the economic value of this water quality improvement may be difficult to assess.55

6. Conclusion The wastewater management process, which essentially encompasses wastewater treatment, is not a choice but an obligation to ensure sustainable environmental protection. The use of wetlands (both natural and artificial) for effective treatment and management of wastewater has been established over the last Century. Coastal wetlands belong to the natural category of treatment which is effective in treating tertiary effluents of various categories. They have a cost advantage compared to constructed (or artificial) wetlands and other conventional treatments. In this chapter, an overview was provided on coastal wetlands as productive ecosystem services which are

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beneficial to humans, wildlife, and the economic development of a nation. Although reports have been released on the continuous global loss of these natural wetlands, they have negatively impacted these productive ecosystems. In this light, some useful information was provided on the essentiality of wastewater treatment and management using coastal wetlands as a reminder. Some previous studies done in this respect were briefly highlighted, and the benefits of using this wetland system for water treatment and management before discharge are also explained. As limited studies have reported the use of coastal wetlands for water management, this chapter thus supplements the relevance of coastal wetlands in water treatment and management.

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51. Wondie A. Improving management of shoreline and riparian wetland ecosystems: the case of Lake Tana catchment. Ecohydrol Hydrobiol 2010;10:123–31. 52. Lofrano G, Brown J. Wastewater management through the ages: a history of mankind. Sci Total Environ 2010;408:5254–64. https://doi.org/10.1016/j.scitotenv.2010.07.062. 53. Metcalf E. Wastewater engineering: treatment and reuse. Mc Graw Hill; 2008. 54. Stefanakis AI, Bardiau M, Trajano D, Couceiro F, Williams JB, Taylor H. Presence of bacteria and bacteriophages in full-scale trickling filters and an aerated constructed wetland. Sci Total Environ 2019;659:1135–45. 55. Breaux A, Farber S, Day J. Using natural coastal wetlands systems for wastewater treatment: an economic benefit analysis. J Environ Manage 1995;44:285–91. https://doi.org/ 10.1006/jema.1995.0046. 56. Hunter RG, Day JW, Wiegman AR, Lane RR. Municipal wastewater treatment costs with an emphasis on assimilation wetlands in the Louisiana coastal zone. Ecol Eng 2019;137:21–5. https://doi.org/10.1016/j.ecoleng.2018.09.020. 57. de Groot D, Brander L, Max Finlayson C. Wetland ecosystem services. Wetl B I Struct Funct Manag Methods 2018;323–33. https://doi.org/10.1007/978-90-481-9659-3_66. 58. Engelhardt KAM, Ritchie ME. The effect of aquatic plant species richness on wetland ecosystem processes. Ecology 2002;83:2911–24. Available at http://www04.sub.su.se: 2079/stable/pdfplus/3072026.pdf. 59. Suhani I, Monika Vaish B, Singh P, Singh RP. Restoration, construction, and conservation of degrading wetlands: a step toward sustainable management practices. Restor Wetl Ecosyst A Trajectory Towar A Sustain Environ 2020;1–16. https://doi.org/10. 1007/978-981-13-7665-8_1. 60. Vuorinen HS, Juuti PS, Katko TS. History of water and health from ancient civilizations to modern times. Water Sci Technol Water Supply 2007;7:49–57. https://doi.org/10. 2166/ws.2007.006. 61. Thorslund J, Jarsjo J, Jaramillo F, Jawitz JW, Manzoni S, Basu NB, et al. Wetlands as large-scale nature-based solutions: status and challenges for research, engineering and management. Ecol Eng 2017;108:489–97. https://doi.org/10.1016/j.ecoleng. 2017.07.012. 62. Vymazal J. Constructed wetlands for wastewater treatment. 2nd ed. Elsevier Inc.; 2018. https://doi.org/10.1016/B978-0-12-409548-9.11238-2. 63. Omondi, D.O. and Navalia, A.C., Constructed Wetlands in Wastewater Treatment and Challenges of Emerging Resistant Genes Filtration and Reloading. https://doi.org/10. 5772/intechopen.93293. 64. Ge ZM, Cao HB, Cui LF, Zhao B, Zhang LQ. Future vegetation patterns and primary production in the coastal wetlands of East China under sea level rise, sediment reduction, and saltwater intrusion. J Geophys Res Biogeosci 2015;120:1923–40. https://doi.org/10. 1002/2015JG003014. 65. Kirwan ML, Megonigal JP. Tidal wetland stability in the face of human impacts and sea-level rise. Nature 2013;504:53–60. https://doi.org/10.1038/nature12856. 66. Mudd SM, Howell SM, Morris JT. Impact of dynamic feedbacks between sedimentation, sea-level rise, and biomass production on near-surface marsh stratigraphy and carbon accumulation. Estuar Coast Shelf Sci 2009;82:377–89. https://doi.org/10.1016/ j.ecss.2009.01.028. 67. Richardson CJ, Davis JA. Natural and artificial wetland ecosystems: Ecological opportunities and limitations. In: Reddy KR, Smith WH, editors. Aquatic plants for water treatment and resource recovery. Orlando, FL: Magnolia Publishing; 1987. p. 819–54. 68. Ahmed S, Popov V, Trevedi RC. Constructed wetland as tertiary treatment for municipal wastewater. Proc Inst Civ Eng Waste Resourc Manag 2008;161:77–84. 69. Sloey TM, Roberts BJ, Flaska SR, Nelson JA. Critical research gaps for understanding environmental impacts of discharging treated municipal wastewater into assimilation wetlands. Wetlands 2021;41. https://doi.org/10.1007/s13157-021-01396-8.

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70. Day Jr JW, Ko J, Rybczyk J, Sabins D, Bean R, Berthelot G, et al. The use of wetlands in the Mississippi Delta for wastewater assimilation: a review. Ocean Coast Manage 2004;47:671–91. 71. Nagabhatla N, Metcalfe CD. Multifunctional wetlands: pollution abatement and other ecological services from natural and constructed wetlands. Cham: Springer International Publishing; 2018. 72. Rybczyk JM, Day Jr JW, Conner WH. The impact of wastewater effluent of accretion and decomposition in a subsiding forested wetland. Wetlands 2002;22:18–32. 73. Zhang X, Feagley SE, Day JW, Conner WH, Hesse ID, Rybczyk JM, et al. A water chemistry assessment of wastewater remediation in a natural swamp. J Environ Qual 2000;29:1960–8. 74. Brantley CG, Day JW, Lane RR, Hyfield E, Day JN, Ko JY. Primary production, nutrient dynamics, and accretion of a coastal freshwater forested wetland assimilation system in Louisiana. Ecol Eng 2008;34:7–22. https://doi.org/10.1016/j.ecoleng.2008.05.004. 75. Birch AL, Emanuel RE, James AL, Nichols EG. Hydrologic impacts of municipal wastewater irrigation to a temperate forest watershed. J Environ Qual 2016;45 (4):1303–12. https://doi.org/10.2134/jeq2015.11.0577. 76. Nielsen L, Hazel DW, Frederick DJ, Nichols EG. Using municipal waste sites for cellulosic biomass production in North Carolina. NC Woody Biomass 2011. Retrieved from https://content.ces.ncsu.edu/using-municipal-waste-sites-for-cellulosicbiomassproduction-in-north-carolina. 77. Shifflett SD, Hazel DW, Frederick DJ, Nichols EG. Species trials of short rotation woody crops on two wastewater application sites in North Carolina, USA. BioEnergy Res 2014;7(1):157–73. https://doi.org/10.1007/s12155-013-9351-2. 78. Knight RL, Clarke RA, Keller CH, Knight SL, Petry C. Great swamp natural effluent management system–a summary of thirteen years of operations. Ecol Eng 2014;73:353–66. https://doi.org/10.1016/j.ecoleng.2014.09.018. 79. Kuo JT, Lai JS, Lung WS, Yang CP. A simplified water quality model for wetlands. Int J Sediment Res 2004;19(2):96–105. 80. Hsu MH, Kuo AY, Kuo JT, Liu WC. Modeling estuarine hydrodynamics and salinity for wetland restoration. J Environ Sci Health Part A: Toxic/Hazard Subst Environ Eng A 1998;33(5):891–921. 81. Liu WC, Hsu MH, Wang CF. Modeling of flow resistance in mangrove swamp at mouth of tidal Keeling River, Taiwan. J Waterway, Port, Coastal Ocean Eng 2003;129(2):86–92. 82. Somes NLG, Bishop WA, Wong THF. Numerical simulation of wetland hydrodynamics. Eur Earthquake Eng 1998;25(6/7):773–9. 83. Kadlec RH, Hammer DE. Modeling nutrient behavior in wetlands. Ecol Modell 1988;40:37–66. 84. Mitsch WJ, Reeder BC. Modelling nutrient retention of a freshwater coastal wetland: Estimating the roles of primary productivity, sedimentation, resuspension and hydrology. Ecol Modell 1991;54:151–87. 85. Lung WS, Light RN. Modelling copper removal in wetland ecosystem. Ecol Modell 1996;93:89–100. 86. Mitsch WJ, Wise KM. Water quality, fate of metals, and predictive model validation of a constructed wetland treating acid mine drainage. Water Res 1998;32:1888–900. 87. Subrahmanyam S, Adams A, Raman A, Hodgkins D, Heffernan M. Ecological modelling of a wetland for phytoremediating Cu, Zn and Mn in a gold–copper mine Site using typha domingensis (Poales: Typhaceae) near Orange, NSW, Australia. Eur J Ecol 2017;3:77–91. https://doi.org/10.1515/eje-2017-0016. 88. Villar MP, Domı´nguez ER, Tack F, Ruiz JH, Morales RS, Arteaga LE. Vertical subsurface wetlands for wastewater purification. Proc Eng 2012;42:1960–8. 89. Almuktar SAAAN, Abed SN, Scholz M. Recycling of domestic wastewater treated by vertical-flow wetlands for irrigation of two consecutive Capsicum annuum generations. Ecol Eng 2017;107:82–98. https://doi.org/10.1016/j.ecoleng.2017.07.002.

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90. Greenway M, Simpson JS. Artificial wetlands for wastewater treatment, water reuse and wildlife in Queensland, Australia. Wat Sci Technol 1996;33:221–9. 91. Mustafa A. Constructed wetland for wastewater treatment and reuse: a case study of developing country. Int J Environ Sci Dev 2013;4:20–4. 92. Rousseau DP, Vanrolleghem PA, De Pauw N. Model-based design of horizontal subsurface flow constructed treatment wetlands: a review. Wat Res 2004;38:1484–93. 93. Ajibade FO, Nwogwu NA, Lasisi KH, Ajibade TF, Adelodun B, Guadie A, et al. Removal of nitrogen oxyanion (nitrate) in constructed wetlands. In: Oladoja NA, Unuabonah IE, editors. Progress and prospects in the management of oxoanion polluted aqua systems. Netherlands: Springer Nature; 2021. https://doi.org/10.1007/978-3-03070757-6_12. 94. Ajibade FO, Wang H, Guadie AA, Ajibade TF, Fang Y, Sharif HMA, et al. Total nitrogen removal in biochar amended non-aerated vertical flow constructed wetlands for secondary wastewater effluent with low C/N ratio: microbial community structure and dissolved organic carbon release conditions. Biores Technol 2021;124430. https://doi. org/10.1016/j.biortech.2020.124430. 95. Ajibade FO, Adewumi JR. Performance evaluation of aquatic macrophytes in a constructed wetland for municipal wastewater treatment. FUTA J Eng Eng Technol 2017;11(1):1–11. 96. Ajibade FO, Adeniran KA, Egbuna CK. Phytoremediation efficiencies of water hyacinth in removing heavy metals in domestic sewage (A Case Study of University of Ilorin, Nigeria). Int J Eng Sci 2013;2(12):16–27. 97. Kivaisi AK. The potential for constructed wetlands for wastewater treatment and reuse in developing countries: a review. Ecol Eng 2001;16:545–60. https://doi.org/10.1016/ S0925-8574(00)00113-0.

CHAPTER SIXTEEN

Mechanistic approaches and factors regulating microalgae mediated heavy metal remediation from the aquatic ecosystem Kapil D. Pandeya, Sandeep Kumar Singhb, Livleen Shuklab, Vineet Kumar Raic, Rahul Prasad Singha, Priya Yadava, Rajan Kumar Guptaa, Prashant Kumar Singhd, Kaushalendrae, and Ajay Kumarf,* a

Laboratory of Algal Research, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India Division of Microbiology, ICAR-Indian Agricultural Research Institute, Pusa, New Delhi, India c Sri Sudrishti Baba Post Graduate College (Affiliated to Jananayak Chandrashekhar University Ballia), Ballia, India d Department of Biotechnology, Mizoram University (A Central university), Pachhunga University College Campus, Aizawl, India e Department of Zoology, Mizoram University (A Central University), Pachhunga University College Campus, Aizawl, India f Department of Botany, Banaras Hindu University, Varanasi, India *Corresponding author: e-mail address: [email protected] b

Contents 1. Introduction 2. Role of microalgae in heavy metal removal 3. Factors affecting remediation of heavy metals 3.1 Biotic factors 4. Abiotic factors influencing metal removal 4.1 Temperature 4.2 pH 4.3 Salinity and hardness 4.4 Metal speciation 5. Recycling of microalgal biomass 6. Algal biomass conversion to produce biofuel 7. Challenges and prospects in heavy metal bioremediation 8. Conclusion Acknowledgment References

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Abstract Heavy metal is considered to be most lethal and toxic when entered in food chain along with terrestrial aquatic system. The waste water is an important source of deposition of heavy metals or toxic elements in the aquatic ecosystem, Hence remediation becomes very important for the survivality of living organisms present in the aquatic ecosystem. Microalga technology plays vital role in heavy metal remediation from the aquatic ecosystem as microalgae dominates over other biological organism and other traditional method to detoxify heavy metals in an eco-friendly manner. The remediated heavy metals are taken up by the microalgae as a nutrient source, which helps in producing biomass which is valorize into different forms of energy as world is facing immense energy crises, so microalgae is considered to be alternative form of fossil fuel which helps in overcoming energy crisis by producing different type of biofuel. Keywords: Waste water, Aquatic ecosystem, Heavy metals, Bioremediation

1. Introduction The term “algae” refers to a vast group of diverse microscopic species that are capable of adapting and growing in every environment due to their high photosynthetic efficiency.1,2 For growth and photosynthesis, they mostly require sunlight, carbon dioxide, nitrogen, and phosphorus, as well as some trace elements. The most numerous class of primary producers are algae, which are responsible for around 32% of the total photosynthesis globally.3 According to Olguı´n and Sa´nchez-Galva´n,4 remediation can be achieved from various species of algae and cyanobacteria which is referred to as phycoremediation. This can include removal, degradation, assimilation, and other processes. Heavy metal contamination is one of the major environmental challenges that the modern world must deal with, and it is the primary cause for concern.5 Elements having properties of metal and also bear atomic number more than twenty are referred to as heavy metals also atomic density more than 20 g/cm3 which is 5 folds higher than water.6,7 Heavy metals are designated as toxic metals include Ni, As, Cd, Cr, Zn, Hg, and Pb, among other precious metals include Ag, Pt, Pb, Au and radionuclides include U, Ra, and Th. Because of their extremely long biological half-lives, the fact that they are non-biodegradable, bioaccumulate, and heavy metal pollution is a major cause for concern.8 The presence of heavy metals in aquatic habitats poses a potential risk to the aquatic animals and ecosystems. After entering the human food chain through consumable aquatic plants,9,10 vegetables,5 and aquaculture products,11–13 heavy metals have the potential to cause severe side effects in humans. Previous research

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has revealed that the majority of heavy metals are lethal to human beings when it comes in contact or is ingested. This can lead to malfunction in a variety of essential systems such as the cardiovascular system, the kidneys, the bones, and so on.14 Heavy metals are produced from rapid urbanization and industrialization, as well as agricultural practices and other anthropogenic activities. These heavy metals, when released into water bodies without first being cleaned contaminate those water bodies. Numerous industrial sectors such as pharmaceutical industry, textile industry, automobile, paper and pulp industry are major sources of heavy metal release into environment which causes aquatic and terrestrial pollution. At the moment, a significant proportion of the world’s population lives in metropolitan areas, which results in an enormous amount of wastewater being produced. In the current situation, recycling and reusing wastewater is being evaluated as a feasible solution to cope with the developing water problem. This is because recycling and reusing wastewater can reduce the amount of water that is wasted. As a result of advances in technology, as well as the necessity to satisfy the requirements of both the economy and society as part of sustainable development, the focus has changed away from efforts to reduce pollution and toward those that seek to recycle and reuse wastewater. The treatment of industrial wastewater that contains heavy metals prior to its discharge into aquatic ecosystems is very necessary in order to wipe off toxicity produced by heavy metals toward environment and associated food chain which is linked with it. If the concentration of the metal is less than 100 mg/L, numerous physicochemical processes, including precipitation, adsorption, filtration, coagulation, floatation, photocatalytic degradation etc., are utilized.15 However, the majority of these technologies require a lot of energy and are therefore quite costly. Oswald,16 concluded, phycoremediation an eco-friendly approach which can be used to remove heavy metals from polluted water and soil.17 The removal of xenobiotic pollutants from water and wastewater can also be accomplished with the use of biosorbents made from either living or dead algal biomass. In addition to this, microalgae are photolithoautotrophs which uses carbon dioxide to disintegrate toxic compounds in wastewater18,19). Microalgae do not require any special media or cultivable land for growth as they can easily grow on different types of wastewater. In addition, due to the naturally high productivity of most freshwater and marine algae species, these organisms along with biomass production perform bioremediation activities too.20 Conventional wastewater treatment technologies accomplish the same goal; however, they do so through a series of steps

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that require significant amounts of energy and, as a result, are very costly. Microalgae plays an crucial role in wastewater phycoremediation and also in bioenergy production which aids in socioeconomic development and improves global economy. Increase urbanization and industrialization are reasons for worldwide scarcity of water and energy resources. The restricted amount of energy sources has redirected the attention of people all over the world toward several alternative possibilities and the development of environmentally friendly technology for the generation of alternative fuels.21 Utilization of carbon-free, renewable biofuels and their production are currently the only viable choices for ensuring the long-term health of both the economic and the environment. The conclusion has now been reached after extensive research that biofuels have been identified as potentially useful renewable alternatives to other types of energy sources. In spite of this, the viability of first-generation biofuels was called into doubt because they were produced using food crops as the primary source of raw materials. The combination of the generation of biofuels using biomass derived from microalgae with the treatment of wastewater appears to be an efficient in respect of other energy sources.22 The production of algal biofuels from wastewater has the potential to assist in the development of a sustainable economy and has the additional potential to assist in the reduction of fresh water demands for biofuels. Therefore, it is of utmost importance to ensure that wastewater is treated by phycoremediation in order to achieve both remediation and the generation of biomass, which may be put to use in the manufacture of products with added value as well as biofuels.23 The purpose of this chapter is to provide an overview of the algae technologies that are used for the removal of heavy metals from wastewater and the possibility for these technologies to also be used in the production of energy.

2. Role of microalgae in heavy metal removal Microalgae are a type of photosynthetic organism that can be found in both marine and freshwater habitats. Their mode of photosynthesis is quite similar to that of terrestrial plants. They form the largest group of primary producers on the planet, as measured by biomass, and contributes toward 32% photosynthesis across globe.3 Researchers from all around the world have recently focused a lot of attention on the many benefits of employing microalgae in metal biosorption and reducing them to a minimum level.24 Heavy metal refers to a metal component that has a medium density and a

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low concentration and is either hazardous or poisonous. According to ecological standards, a heavy metal is any substance that either causes or is incapable of causing naturally harmful or significantly damaging effects on the environment. According to Herrera-Estrella and Guevara-Garcia,25 heavy metals such as copper, nickel, manganese, cobalt, and zinc each have a potentially hazardous biological function, but they are also essential micronutrients for the development of plants. Heavy metals are often classified as radionuclides (U, Ra), precious metals (Pd, Au) and toxic metals (Cu, As, Pb).26 In the context of urbanization, population increase, and industrialization, a growing worldwide interest in the reduction of heavy metal contamination in a variety of biological systems is emerging. Reports have clearly stated disposal of untreated wastewater and heavy metals had resulted into global issues. During the 1950s, research on algae was conducted across the state of California which showed positive result in increasing dissolved oxygen content further in cleansing wastewater. In the process of photosynthesis, these algae produce carbon dioxide (CO2) as well as other components that are essential for the formation of microalgae and the extraction of nutrients cycle.27 It was originally thought that algae ponds may be used to mitigate generation of effluents prior to the release of water in order to reduce eutrophication.28 In the same way that traditional processing systems do, algae are able to remove nutrients from the water treatment process, i.e., potassium and nitrogen. In conjunction with the treatment of wastewater, the production of algal biofuel might be considered economically equal. When compared with photoautotrophic growth rates, the improvements in lipid and biomass capacity produced by heterotrophic microalgae result from their consumption of organic effluent.29,30 The phenomenon of microalgae mediated heavy metal treatment can be broken down into two distinct categories: (1) bioaccumulation by live cells, and (2) biosorption. Microalgae require minimum nutrients and optimum growth conditions to grow also possess capability to remove heavy metals.31 Rajamani et al.31 explain in greater detail how microalgae are able to effectively sequester heavy metals. They also discuss the transgenic approaches that have been utilized to improve the heavy metal binding efficiency of microalgae. One of the transgenic approaches is the utilization of fluorescent HM biosensors that have been developed using transgenic Chlamydomonas, Chlorella and Scenedesmus, most commonly used microalgae for removing metals from wastewater, have been shown to have affinity for polyvalent metals. However, the significance of marine micro- and macro-algal species as biosorbents for metal uptake has been

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elaborated by32 (Zn, As, Cd, Mo, Pb, Se, Al, Mg, V, Ca, Fe, Co, Sr, Cu, Ni, Mn, K). The following microalgae are specifically mentioned which includes Chlorella miniata, Lyngbya taylorii, Spirogyra sp., Chlamydomonas reinhardtii, Phaeodactylum tricornutum, Spirulina platensis, Chlorella salina, Cyclotella cryptica, Stigeoclonium tenue, Scenedesmus subspicatus, Porphyridium purpureum, Stichococcus bacillaris.32 Chlorella, Scenedesmus, and P. tricornutum were all listed by Perales-Vela et al.33 as having the ability to remove Cd, U, and Cu. C. reinhardtii, Spirulina platensis, Chlorella sp., Scenedesmus sp. and Tetraselmis sp. are among other microalgae species which have largely contributed toward lowering of cadmium level toward the safe limit. In a study by Sbihi et al.34 which concluded Planothidium lanceolatum have the efficiency to take up 275 mg g 1 of cadmium. In the context of pH ranging from 4 to 7.5, research on cobalt remediation has shown that Oscillatoria angustissima and Spirogyra have reported to reduce 15.22 mg g-l and 12.82 mg g 1 of cobalt from wastewater. Out of the three forms of chromium (i.e., Cr3+, Cr+O72 , and Cr6+) that have been researched, Spirulina sp. and Chlorella sp. are found out to be potential contenders to remove the hexavalent form of chromium (Cr6+) under pH range spanning from 2 to 8.2 investigated. Most copper removal research focus on Cu2+, have done by using Chlorella vulgaris showing pH range 4–7. Doshi et al.35 reported that Spirulina sp. was found to be an effective copper remover (389 mg g 1). Spirulina sp. (1378 mg g 1) and P. lanceolatum (118.66 mg g 1) are two potential organisms that may remediate Ni and Zn, respectively.34,35 Another study on C. reinhardtii immobilized microalgae is reported to remove lead (380.7 mg g 1) from the environment.36

3. Factors affecting remediation of heavy metals There are various factors which regulate removal of heavy metals by microalgae these factors are divided into biotic factors as well as abiotic factors which have been discussed in below section.

3.1 Biotic factors 3.1.1 Species There are different class of microalgae which act specifically to a metal, most of the studies reported have concluded different members of same genus respond differently to a specific metal. Some chlorophycean members like Scenedesmus obliquus respond to cadmium toxicity at 0.58 mg L 1 whereas Desmodesmus pleiomorphus respond at 1.92 mg L 1.

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3.1.2 Biomass Concentration Increase metal removal is directly linked to an increase in biomass concentration. Biomass levels can reduce metal binding by a certain amount per unit mass in specific instances.37 On the other hand, when biomass concentrations are extremely high, a decrease in metal removal has been seen in some instances. A decrease in the average distance between available adsorption sites and biomass partial agglomeration (which limits the effective surface area available for sorption) could both account for this. A screen effect could also develop in situations when biomass concentrations are higher. Metal ions are prevented from attaching to the binding sites, resulting in a decrease in removal of metal from per unit of biomass.38 When the biosorbent concentration is raised in dead Spirogyra species, copper uptake reduces by (40.5 g L 1). According to the study, Spirulina maxima’s Pb2+ absorption decreased from 121 mg g 1 to 21 mg g 1 when the biomass content grew from 0.1 to 20 g L 1. This means that only a limited amount of biomass can be increased in order to improve metal uptake. However, metal binding per unit cell mass may decrease if the biomass concentration exceeds a particular threshold. 3.1.3 Tolerance capacity Microalgae have different antioxidant enzymes i.e. superoxide dismutase, ascorbate peroxidase etc. are regulated in them when metals disrupt the oxidative balance. As a result, the level of oxidized proteins and lipids in algal cells can be used to determine stress intensity. An important defense mechanism that an organism employs in response to a hostile environment is called tolerance. Wong and Beaver,39 reported that Chlorella fusca was able to thrive well in lake consisting of high metal concentration than Ankistrodesmus bibraianum. Tolerance of microalgae to heavy metal depends on the defensive response against oxidative damages; several strategies is being postulated to lower significant impact of heavy metal on living organism. These mechanisms include formation of proteins, i.e., phytochelatin, glutathione which binds to toxic heavy metals which regulates in microalgal cell through transportors present on microalgae. Algal tolerance to HM depends on defences against generation of radical oxidative scavenger, chemical exudates chelation, also efflux of metal ion through ATPase pumps. According to a study reported where production of peptides by microalgae preferentially produce peptides that bind HMs.3 It is possible to manage the cytoplasmic concentration of these organometallic complexes by partitioning them into vacuoles, which prevents or neutralises their potential harmful effects. Phytoplanktons that

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have become acclimated to low concentrations of pollutants may be able to tolerate concentrations up to hundreds of times greater if exposed repeatedly to high concentrations.40 Even C. vulgaris shows resistance toward copper toxicity as a consequence of prolonged contact to the element, demonstrating as a result an improved capacity to resist copper enrichment.41

4. Abiotic factors influencing metal removal 4.1 Temperature The biosorption of metal ions is influenced by a number of variables, including temperature. Among these the metal ion species stability, ligands, ligand complex and the metal ions solubility. Aksu,42 found that an increase in temperature resulted in an increase in the amount of Ni2+ that was absorbed by the dry biomass of C. vulgaris. Earlier study by Aksu42 found that a rise in temperature (from 20 to 50 °C) reduced biosorption capacity of Cd by 85.3–51.2 mg g 1. According to Lau et al.43 there is some evidence that temperature has an impact on metal biosorption, but it is less significant than pH.

4.2 pH pH of the water is possibly the most critical factor in determining how well microalgal biomass can adsorb metals.44,45 It has an effect on metal speciation in solution and algal tolerance because it affects both metal binding sites on the cell surface and water chemistry. In a report on algae, Peterson et al.46 found that metal toxicity was pH dependent. Microalgal cell surface have functional groups which possess acid-base characteristics. In the presence of low pH, ligands attached at cell surface could bind to hydronium ions H3O+, thus preventing metal cations from approaching. Functional groups are attached to H+ ions at low pH, which makes it difficult for positively charged metal ions to bind to the substance because of repulsive forces.24 There are reports that as pH drop, cell surfaces become positively charged due to lowering in metal ion attraction and biomass. This, in turn, makes it easier for them in attaching to cations to large extent. At low pH, cell surfaces become positively charged by lowering biomass and metal ion attraction. Therefore, a higher pH facilitates uptake of metal as due to negatively charged microalgal surface. In the process of binding through ionic attraction, these events are of great significance. For instance, it is observed that

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the biosorption capacity of Spirogyra biomass toward copper enhanced from 31 to 86% when the pH was adjusted from 1 to 7.38 In addition, it has been found that the HM (copper, cadmium, and zinc) binding capability of the blue-green alga Chroococcus paris increased when the pH increased from 4 to 7.47 Because the precipitation of most metals is more likely to take place at higher pH levels, and this generally results in a reduction in removal of metal, hence become important to determine pH level which is best for algae–metal interactions. For instance, it was shown that the alga Phormidium sp. exhibited increased toxicity toward Zn at higher pH than optimal pH range of 3.5–4.0.48 According to research done by Stary´ et al.,49 the absorption of zinc and cadmium by the algae S. obliquus was found to be a linear function of pH in the range of 5–9, whereas the uptake of mercury was found to be pH independent.

4.3 Salinity and hardness The uptake of HM is influenced by salinity, with the ideal salinity value varying depending on the metal being taken up. For instance, in the case of the algae S. bacillaris, the optimal salinity for cadmium was 2.5%, whereas the optimal salinity for copper was 20%; in essence, excessive concentration of salt can significantly constrain the binding of metal.50 When the NaCl concentrations were between 0.5 and 1.0 M D. salina large amount of cadmium uptake was reported; however, when the NaCl concentrations were 41.0 M cadmium uptake was found out to be minimum.51 In a study which concluded level of toxicity of metals (Cd, Cu, Ni, Sn and Zn) decreased when the concentration of chloride or salinity increased.40 In addition, Wang40 found that a decrease in the amount of high alkalinity and hardness in the water induced a reduction in the hazardous effect of metals i.e. copper, mercury, cadmium etc.

4.4 Metal speciation Metal ion species, pH, and the variety of complexing agents found in natural waterways can influence the harmful effects of trace metals on aquatic animals.52 Whereas, pH regulates metal cations binding to microalgae.24 In addition, Pagnanelli et al.53 reported a number of impacts of metal speciation on the sorption of HM by Sphaerotilus natans. According to RodeaPalomares et al.,54 free zinc and cadmium ions in solution were hazardous to cyanobacterial species. On the other hand, there is a shortage of data that brings together measures of metal speciation and the consequences that it

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has on microbes. As a result, a concrete concept regarding the impact of metal speciation under field conditions on algae continues to elude researchers.55

5. Recycling of microalgal biomass The use of the flocculating agent chitosan, which is one of the best approach used for algal recovery and it is more widely recognized for numerous microalgal species than the use of any other technique. In the process of harvesting microalgae, flocculating agents typically eliminate the need for time-consuming and costly centrifugation. The ion binding method is another option, in which it does not poses any health risks, less effective and depends on the pH and ionic strength of the media that is around it. It is also suggested to use natural polysaccharides (such as carrageenan or alginate, agar) or synthetic polymers (such as polyacrylamide, photo cross-linkable resin, or silica gel) for gel entrapment. Because of their lower biomass toxicity, natural polysaccharides such as alginate would be preferred over synthetic ones.24

6. Algal biomass conversion to produce biofuel Combustion of aviation fuel releases a variety of pollutants into the atmosphere, including nitrogen oxides, carbon monoxide, partially burned hydrocarbons, trace chemicals, and particulates. The demand for transportation causes the fuel industry to go through 5 million barrels of oil every single day. It is necessary for the aviation industry to lower its carbon footprint by switching to alternative fuels in order to have an effect on the composition of the atmosphere, which is what causes ozone depletion and climate change. The rich oil structure of algae, which is directly linked to the process of photosynthesis, is one of the factors contributing to the increasing sustainability of algae biofuels produced from algal feedstock. The enormous amount of oil that algae produce can be cut down due to the separation of their cell structures. In exchange, algae take in carbon dioxide and release oxygen.56 Biofuels derived from algae may convert any and all sources of energy into biofuels with added value. Oil extracted from microalgae used to produce jet fuel, which was then combined with an industrial fuel that was either bio-derived synthetic paraffin kerosene (Bio-SPK), or hydro-treated renewable jet fuel (HRJ), hydro-treated vegetable oil (HVO). The use of hydrotherapy has been given the ASTM

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Standard D7566 accreditation. In order to set the stage for Bio-SPK/HEF, the oil is first cleansed by utilizing the conventional cleaning methods. The extraction of olefins can be made more efficient via the use of thermal and oxidative stabilization, and the strength of combustion can be made more robust through the reduction of oxygen. During the second step, the isomerized diesel fuel separates paraffin from the jet collection. This produces a fuel that contains the same kind of atoms that are often found in regular oil. The Fischer–Tropsch method is a further method that can be used for the processing of high-quality fuels such as natural gas, wood and coal used in rocket propulsion. Through the process of gasification, liquid fuels were derived from the biomass of algae.57 Due to the numerous safety concerns associated with aviation fuel, there are currently a large number of research studies being conducted on the creation of microalgal biofuel.

7. Challenges and prospects in heavy metal bioremediation Microalgae have found out to be eco-friendly and show high affinity toward tolerating various kinds of pollutants including heavy metal and efficiently remediating them, and uptake of heavy metal results in production of biomass which is engulfed to produce various kinds of biofuels to have positive impact on economy. On the other hand the application of microalgae also possess various challenges which affects removal of heavy metals from wastewater.58 Although the removal of heavy metals (HMs) by microalgae is a promising and effective alternative to traditional methods, it is necessary to isolate robust microalgal strains and combine them with the appropriate pretreatment steps or other technologies in order to further improve the efficiency of HM remediation and reduce the operating cost. Because of the potential that they have for use in industry, several technologies, such as granulation, whole-cell immobilization, and microalgae biofilm, have drawn a lot of attention over the course of their development. The efficiency of HM removal can also be improved through the surface and chemical modification of microalgal biomass, as well as through the integration of microalgae biomass with other technologies for HM removal. 1. Microalgae mediated removal of heavy metals is one of the widely known and classical method. But there are various issues arising due to presence of heavy metals or selection of potential microalgae which could effectively remove heavy metals. Some solutions, such as the use of microalgae produced in a specific environment or the pre-treatment of wastewater

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according to the growing parameters of microalgae, may thus be used to tackle these issues. 2. To develop effective equilibrium and kinetic model, there needs to sufficient knowledge related to biosorption and bioaccumulation of heavy metals. The majority of HMs have a discernible impact on the expansion of microalgae as well as the accumulation of lipids and several other by-products. An important role can be played by certain heavy metal ions (HMs), such as Cu and Fe, which can influence the accumulation of microalgae lipids, as well as algae color change and hormone levels. For the production of biodiesel with the desired performance and quality, microalgae can be altered using HMs. 3. In order to implement the bioremediation of HMs on a wide scale using microalgae, additional research on both upstream cultivation and downstream purification is required.

8. Conclusion Heavy metal is considered to be most lethal and toxic when entered in food chain along with terrestrial aquatic system. Hence it remediation becomes very important. Microalga technology plays vital role in heavy metal remediation as microalgae dominates over other biological organism and other traditional method to detoxify heavy metals in an eco-friendly manner. The remediated heavy metals are taken up by the microalgae as a nutrient source which helps in producing biomass which is valorize into different forms of energy as world is facing immense energy crises, so microalgae is considered to be alternative form of fossil fuel which helps in overcoming energy crisis by producing different type of biofuel.

Acknowledgment This study was supported by an ICMR grant to Dr. Prashant Kumar Singh (PKS) is thankful for the Indian Council of Medical Research (ICMR), New Delhi, for financial support in the project (File No. 5/7/1770/Adhoc/NER/RBMCH-2021).

References 1. Latiffi NAA, Mohamed RMSR, Apandi NM, Kassim AHM. Application of phycoremediation using microalgae Scenedesmus sp. as wastewater treatment in removal of heavy metals from food stall wastewater. Appl Mech Mater 2015;773:1168–72. 2. Rawat I, Kumar RR, Mutanda T, Bux F. Dual role of microalgae: phycoremediation of domestic wastewater and biomass production for sustainable biofuels production. Appl Energy 2011;88(10):3411–24.

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43. Lau PS, Lee HY, Tsang CCK, Tam NFY, Wong YS. Effect of metal interference, pH and temperature on Cu and Ni biosorption by Chlorella vulgaris and Chlorella miniata. Environ Technol 1999;20:953–61. 44. Indhumathi P, Syed Shabudeen PS, Shoba US, Saraswathy CP. The removal of chromium from aqueous solution by using green micro algae. J Chem Pharm Res 2014; 6(6):799–808. 45. Jeba Kumar ST, Balavigneswaran CK, Arun Vijay M, Srinivasa Kumar KP. Biosorption of lead(II) and chromium(VI) by immobilized cells of microalga Isochrysis galbana. J Algal Biomass Util 2013;4(4):42–50. 46. Peterson HG, Healey FP, Wagemann R. Metal toxicity to algae: a highly pH dependent phenomenon. Can J Fish Aquat Sci 1984;41(6):974–9. 47. Les A, Walker RW. Toxicity and binding of copper, zinc, and cadmium by the blue-green alga, Chroococcus paris. Water Air Soil Pollut 1984;23:129–39. 48. Hargraves JW, Whitton BA. Effect of pH on tolerance of Hormidium rivulare to zinc and copper. Oecologia 1976;26:235–43. 49. Stary´ J, Havlik B, Kratzer K, Pra´ˇsilova´ J, Hanusˇova´ J. Cumulation of zinc, cadmium and mercury on the alga Scenedesmus obliquus. Acta Hydrochim Hydrobiol 1983;11(4):401–9. 50. Wilde WE, Benemann JR. Bioremoval of heavy metals by the use of microalgae. Biotechnol Adv 1993;11(4):781–812. 51. Rebhun S, Ben-Amotz A. Effect of NaCl concentration on cadmium uptake by the halophilic alga Dunaliella salina. Mar Ecol Prog Ser 1986;30:215–9. 52. Crist RH, Oberholser K, Shank N, Nguyen M. Nature of bonding between metallic ions and algal cell walls. Environ Sci Technol 1981;15:1212–7. 53. Pagnanelli F, Esposito A, Toro L, Veglio` F. Metal speciation and pH effect on Pb, Cu, Zn and Cd biosorption onto Sphaerotilus natans: Langmuir-type empirical model. Water Res 2003;37:627–33. 54. Rodea-Palomares I, Gonza´lez-Garcı´a C, Leganes F, Ferna´ndez-Pin˜as F. Effect of pH, EDTA, and anions on heavy metal toxicity toward a bioluminescent cyanobacterial bioreporter. Arch Environ Contam Toxicol 2009;57:477–87. 55. Meylan S, Behra R, Sigg L. Accumulation of copper and zinc in periphyton in response to dynamic variations of metal speciation in freshwater. Environ Sci Technol 2003;37 (22):5204–12. 56. Suganya T, Varman M, Masjuki H, Renganathan S. Macroalgae and microalgae as a potential source for commercial applications along with biofuels production: a biorefinery approach. Renew Sust Energ Rev 2016;55:909–41. https://doi.org/10.1016/ j.rser.2015.11.026. 57. Trivedi J, Aila M, Bangwal D, Kaul S, Garg M. Algae based biorefinery—how to make sense? Renew Sust Energ Rev 2015;47:295–307. https://doi.org/10.1016/j.rser. 2015.03.052. 58. Kaloudas D, Pavlova N, Penchovsky R. Phycoremediation of wastewater by microalgae: a review. Environ Chem Lett 2021;19:2905–20.

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CHAPTER SEVENTEEN

Metal organic frameworks-carbon based nanocomposites for environmental sensing and catalytic applications Muhammad Tuoqeer Anwara,*, Muhammad Rehman Asgharb, Arslan Ahmeda, Shagufta Fareedc, Hasan Izhar Khand, and Tahir Rasheede a

Department of Mechanical Engineering, COMSATS University Islamabad, Sahiwal, Pakistan University of Agriculture, Faisalabad, Pakistan School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai, China d Automotive Engineering Center, University of Engineering and Technology, Lahore, Pakistan e Interdisciplinary Research Center for Advanced Materials, King Fahd University of Petroleum and Minerals (KFUPM), Dhahran, Saudi Arabia *Corresponding author: e-mail address: [email protected] b c

Contents 1. Introduction 2. Synthesis procedures 2.1 In situ synthesis 2.2 Ex situ synthesis 2.3 Other methods 3. Applications 3.1 Sensor 3.2 Supercapacitors and batteries 3.3 Absorbents 3.4 Catalysts 4. Outlook and conclusions References

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Abstract MOFs are the state-of-the-art crystalline materials which are synthesized through the combination of organic linkers and metal ions clusters. Unique features such as artificial tailorability, excellent porosity and facile synthesis make them suitable candidate in a variety of applications. However, their applicability is being hindered due to insufficient electro-activity and electrical conductivity. In addition to that, they are less stable in some media. To overcome aforementioned issues, MOFs can be combined with carbon-based materials such as graphene, CNTs, and carbon blacks to achieve sufficient

Advances in Chemical Pollution, Environmental Management and Protection, Volume 9 Copyright # 2023 Elsevier Inc. 301 ISSN 2468-9289 All rights reserved. https://doi.org/10.1016/bs.apmp.2022.12.002

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electrical conductivity along with mechanical strength and other new functionalities. The area of application thus widens beyond single phase MOFs. This chapter mainly focuses on the grouping of reports related to MOF-carbon composites in the recent times. The synthesis procedures accompanied with application are also discussed. Keywords: Metal organic frameworks, Synthesis, Sensor, MOF-based composites, Absorbents, Catalysts

1. Introduction Metal organic frameworks are assembled using metal ions and organic linkers and found to exhibit porous structure. In comparison with other porous materials, tunability of pores and introduction of functionalities make them useful for specific tasks. Additionally, ease of synthesis leads to widespread application areas including catalysis, gas storage, sensors, and drug delivery, etc.1,2 In the meanwhile, MOF exhibit some intrinsic issues as well, such as low electronic conductivity and instability in harsh environments, which is usually required in different applications.3 Moreover, most of the MOFs are obtained in powder form which leads to reduced mechanical strength. When MOFs are employed as absorbents and molecules are absorbed, mass transfer gets affected.4 Though the diffusion coefficient is usually quite higher, but it may cause adverse effect on adsorption capacity, which means that the porosity cannot be fully utilized.5 Different strategies have been adopted to overcome challenges faced by MOFs. These include opting for different ligands and modifying them through functionalization, doping different metal ions, interchanging ligands/metal ions and making nanocomposites using MOFs.6 Among these, the latter has attracted attention of scientists and researchers due to ease of handling and synthesis and mitigation of the drawbacks of the individual components and thus creating synergistic effects. Nanocomposites have been successfully synthesized using metal nanoparticles, polymers, carbon, silica and polyoxometalates.7–10 Among these composites, MOFs’ combination with carbon-based materials is eye-catching with former being state of the art and the latter being classical. Different forms of carbon including allotropes, textures, and structures with variable degree of graphitization offer variety of applications in today’s world due to the excellent properties of high mechanical strength, low cost, high surface area, mesoporosity, chemical robustness, and less harmfulness.11,12 So, MOFs-carbon based composites offer excellent stabilities, improved functionalities, and adequate

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electronic conductivities. In this chapter, more emphasis is laid on MOFs composites with CNTs, graphene, carbon fiber and porous carbon which have been reported in the recent times. The synthesis procedures accompanied with application will also be discussed.

2. Synthesis procedures In simple words, a composite can be defined as a material consisting of at least two individual ingredients which are combined to achieve synergistic effect while maintaining their individual identity simultaneously. Usually, these two components are regarded as matrix and functional species. MOFs in combination with other functional materials can also be synthesized using different methods, namely in situ methods and multistep methods. Nanoparticle based MOFs can be synthesized by combining the precursor of the both (in situ methods), whereas functionalized materialbased MOFs can be prepared by mixing MOF and functional materials (multistep methods). Additionally, improved electrocatalytic properties can be achieved by modification of post-synthesis procedures. Overall enhanced electrochemical properties of MOF composites can be attributed to the intrinsic electroactivity of MOFs accompanied with stability of the functional material. In addition to that, synthesis of such composites is thought to be achieved at relatively lower temperatures and without the need of special (e.g., inert) environments. Thence, it is possible to synthesize MOFs’ composites using carbon-based nanostructures, metal oxide nanoparticles and metal nanoparticles with improved surface area along with porosity, followed by tailored electrocatalytic activities. In case of MOFs-carbon based nanocomposites, MOFs can be grown on carbon-based template or mixed with carbon matrices/materials.

2.1 In situ synthesis It can be further divided into single pot and multistep synthesis processes. In single pot synthesis, all the reactants are provided in single reactor, thus avoiding lengthy procedures and washing of intermediates. The usual procedure consists of adding carbon-based material into MOF which is already dissolved into solvent followed by hydrothermal process at the same conditions and environments. This procedure is employed for almost every MOF-carbon based nanocomposite. Nanocomposites thus prepared when exposed to different gases, showed that defects and functionalities of carbon-based materials acted as nucleation sites for MOFs crystals and led

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Fig. 1 Schematic for the preparation of Ni-MOF@CNT heterostructures. Adapted with permission from Elsevier. Xu C, Liu L, Wu C, Wu K. Unique 3D heterostructures assembled by quasi-2D Ni-MOF and CNTs for ultrasensitive electrochemical sensing of bisphenol A. Sensors Actuators B Chem 2020;310:127885.

to adsorption properties.13 Another nanocomposite was reported in which CNTs were pretreated with H2O2 to enhance their solubility in different solvents and to the form surface hydroxyl groups, which acted as anchoring sites for metal nodes.14 Similarly, Ni-MOF and CNTs-based nanocomposite was reported, and it was synthesized at room temperature using in situ process and employed as electrochemical sensor (Fig. 1). In comparison with pristine CNTs, the surface area enhanced due to the introduction of Ni-MOF. The synergistic effects between the constituent materials led to excellent electrochemical activity toward the detection of a very toxic compound BPA. Interestingly, the same technique was successfully used for the sensing of BPA in water buckets, receipts, and movie tickets and the results were in line with chromatographic analysis.15 Some other nanocomposites were also synthesized using single pot methods.16,17 Sometimes multistep synthesis is employed instead of single pot synthesis. For instance, the preparation of MOF-carbon based membranes, which are dense, and defect free require multistep synthesis. Furthermore, heterogenous crystallization which is realized through the presence of surface functional groups, cannot be achieved through single pot synthesis. So, other favorable approaches are utilized. Secondary growth is usually used to synthesize MOF-carbon membranes. The method produces robust and defect free membranes by depositing MOF crystals on the seeds which further act as nucleation site. Seeding can be achieved using spin coating, dip coating and wiping.18 Another way to synthesize MOF-carbon composite is with the help of metal oxides and other carbon-based materials. For example, ZIF-8/MWCNT composite can be synthesized using precursors of MWCNTs and zinc oxide. The process consisted of adsorption of zinc oxide on MWCNTs trailed by addition of ligands to produce MOF.19 It is important to note that organic linkers not only help in conversion of metal

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oxides to metal ions but also act as organic linkers. Another method is liquid phase epitaxy which is an excellent way to tailor coating thickness, homogeneity, and structure penetration by controlling growth cycles. This approach is usually applied to synthesize MOF-CF composites.20

2.2 Ex situ synthesis In situ methods offer their own benefits but uncontrolled carbon-based materials may cause coordinative reactions thus ruining or destroying MOFcarbon structure. So, ex situ approaches are used which involve integration of pre-synthesized MOFs and carbon-based materials. One of the methods is direct mixing which is employed to produce carbon paste electrodes or electrodes of supercapacitors. For example, a composite of HKUST-1 MOF and rGO was synthesized and employed as electrode material of supercapacitor. The MOF lacked sufficient electrical conductivity which was enhanced by combining with rGO leading to remarkable electrochemical properties. Specific capacitance, energy and power was found to be superior as compared to individual materials.21 Another approach is self-assembly method which is carried out using direct mixing and undergoes π-π stacking, electrostatic interactions and hydrogen bond, etc. Basically, the individual components attract each other to form MOF-carbon composite.

2.3 Other methods Pickering-emulsion method is another way to provide substantial interfacial area which leads to product growth. It has been observed that GO can act as stabilizer for the synthesis of different composites and remarkably change the porosity and morphology of the composite accompanied with increased water resistance.22

3. Applications 3.1 Sensor For designing a new sensor in electrochemistry, required attributes can be achieved by modifying the surface of the electrode with the help of materials such as graphene, gold, and newly developed carbon substrates. The applications of such sensors included monitoring of pollutants using environmental and biosensing systems. As MOFs exhibit excellent properties, functionalized MOFs (using graphene, CNTs, metal oxide nanoparticles, enzymes) are being developed for electrochemical sensing. Sensing method

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sensitivity depends on the decrease in overpotential through electrochemical reduction or oxidation and it is achieved by tailoring pore volume, porosity, and surface area. These novel materials can be utilized in a variety of applications favorably for electrochemical sensing. 3.1.1 MOF/carbon material composites MOFs have been extensively used for a variety of applications, but in electrochemical sensing applications, they pose a number of challenges such as low electroactivity, inadequate electronic conductivity and instability in aqueous media. To counter such challenges, MOFs have been used in combination with more conductive materials such as CNTs, GO, rGO which results in excellent electrical conductivity and improved mechanical strength of MOFs. In addition to the aforesaid carbon materials, other materials have also been utilized such as Vulcan XC-72 and macroporous carbon. In the following section, their design, construction, and electrochemical properties are discussed. 3.1.2 CNTs/MOFs Though MOFs exhibit excellent properties such as sufficient surface area, ordered crystalline structure, adjustable pore size and thermal stability, yet are limited due to insufficient electronic conductivity and electrocatalytic activity. The aforesaid issue is countered by using conductive materials such as CNTs. CNTs are preferable due to excellent aspect ratios, high specific surface areas and other electrical/mechanical properties. MOF in combination with SWCNT was synthesized and found to be an affective electrochemical sensor for organophosphate pesticides. The functionalization of SWCNTs was carried out using benzoic acid which helped in achieving porous structure of organic-inorganic architecture. Excellent surface area (1210 m2 g 1) was reported for the aforesaid composite. It was observed that zinc ions interlinked with SWCNTs’ benzene moieties. Resultant composite showed excellent electrocatalytic reduction. The LOD calculations revealed that it was far less (2.3 ng) than the ones obtained from CPE and hanging mercury drop electrode. Relative standard deviation was also sufficient (4.04%) to reproduce the results.23 Another MOF-MWCNT based sensor was reported for H2O2. The MOF was prepared and immobilized on the conductive part. In phosphate buffer solution, two major peaks were observed for redox process of copper in MOF. Additionally, the prepared sensor showed excellent electrocatalytic activity for H2O2 reduction. It was used for H2O2 monitoring of water samples obtained from different sources and recovery rate was quite higher

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(99%).24 Another combination of MOF and SWCNT was synthesized to detect CT and HQ. The synthesis process included the deposition of SWCNTs on glassy carbon electrode trailed by addition of Cu-MOF-199 through electrodeposition. The prepared composite exhibited excellent electrocatalytic activity due to synergetic effect of Cu-MOF-199 and SWCNTs. In addition to that, it demonstrated anti-interference behavior and excellent reproducibility. Amperometry was further employed to analyze the interference of ions at the electrode. It was also noted that the modified electrode had selectivity toward CT and HQ. Interestingly, recovery rates were found to be quite higher for CT (96.5–104%) and HQ (96.4–102%).25 Another composite consisting of metal and CNTs was synthesized using hydrothermal method. GCE was modified and then employed for the redox reaction of H2O2. The mechanism for electrocatalytic reaction comprised oxidation of Mn II to Mn IV followed by reduction to Mn II by H2O2. In order to avoid decrease in selectivity, the parameter was fixed to 0.4 V which led to the absence of too negative or too positive potentials. Similarly, MOF-CNT and Prussian blue were combined together, and this novel composite was employed for sensing 17β-estradiol. The composite had high surface area and excellent electrical conductivity, whereas, the addition of PB ensured amplified signals along with fast electron transmission. It was found that the prepared sensor had outstanding sensitivity and excellent selectivity as shown in the Fig. 2.26

Fig. 2 (A) DPV of MIP-PB-MIL-CNTs/GCE using different amounts of E2 PBS solution in a solution with 5 mM Fe(CN)6 3 /4 and 0.1 M KCl (a–f: 10 14–10 9 mol L 1). (B) Relationship of peak values of MIP-PB-MIL/CNTs-GCE (a) and NIP-PB-MIL-CNTs/GCE (b) with varying amounts of E2 (10 14–10 9 mol L 1). Adapted with permission from Elsevier. Duan D, Si X, Ding Y, Li L, Ma G, Zhang L, Jian B. A novel molecularly imprinted electrochemical sensor based on double sensitization by MOF/CNTs and Prussian blue for detection of 17β-estradiol. Bioelectrochemistry 2019;129:211–217.

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MWCNTs and benzenedicarboxylic acid-based MOF were combined together with the help of solvothermal method to form a new unique composite. It was employed for H2O2 monitoring. During the synthesis process, MOF NPs were found to be uniformly distributed over the CNTs making sure their strong connection with the latter. It was also noted that the conductivity values for nickel-based MOF were superior to that of simple MOF. The sensitivity was also found to be better than the bare GCE and its combination with Ni-MOF and MWCNTs. Metformin was electrochemically determined using GCE modified with the help of prepared composite. MOF could be prepared with two methods which led to different crystallite sizes. Interestingly, the overall error for the determination of metformin in pharmaceutical samples was found to be less than 4%.27 Urea was detected using Ni-MOF and MWCNTs modified ITO electrode. It was observed that the prepared sensor had great selectivity for urea even in the presence of different compounds such as glucose, AA, UA, and creatinine. This sensor was also employed in practical scenario for the determination of urea in samples of urine.28 Benzimidazole based MOF and MWCNTs were employed to modify glassy carbon electrode to determine the presence of glucose. Interestingly the prepared hybrid demonstrated excellent electrocatalytic behavior as compared to their individual components. This was ascribed to the high electrical conductivity of MWCNTs and presence of plenty of active sites at MOF. LOD was found to be ppb and linear range was 1–4000.29 In addition to the CNTs, graphene has also been exploited for the formation of MOF-graphene composites for electrochemical sensing as graphene offers unique attributes such as excellent carrier mobility and sufficient surface area. The core advantage of such composite is better conductivity, higher electron transfer rates, and stability due to the nano-graphitic impurities.

3.1.3 GO/MOFs Graphene is considered as analogous of CNTs as it offers excellent electrical conductivity along with other unique properties. Graphene has further been modified to other forms such as graphene oxide, graphene nanoribbons, reduced graphene oxide, etc., to take advantage of different functionalities such as oxygen, epoxy, hydroxyl, and carboxylic groups. It has also been studied that agile electron transfer occurs at the edge plane instead of basal plane. A short description of graphene and MOF based composites for electrochemical sensing application is given below.

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A nanocomposite comprising MOF-525 and GNR has been reported to monitor the nitrate through electrocatalytic oxidation. Thin films of nanocomposite were synthesized using ITO glass substrates. It was interesting to note that a fast charge transfer was observed for the prepared composite as compared to pristine MOF-525. A more pronounced electrocatalytic oxidation of nitrate was noticed and its rate was tailored by redox reaction of MOF-525. As a result, overall rate of electrocatalytic process accelerated.30 Another composite consisting of Cu-based MOF and reduced graphene oxide was synthesized and employed for determining HQ, catechol, and resorcinol. Strong voltammetry signals were observed due to the high electrical conductivity of ERGO and porosity of MOF. Quantum chemical computations further elaborated specificity of prepared composite toward dihydroxy benzene isomers. DBIs were sensed in wastewater, tap water, and rainwater accompanied with recovery rates around 100%.31 Similarly, MOF was used in combination with ERGO/GCE for determination of DA and AOCP. Composite was synthesized by sonicating individually made GO and MOF in distilled water. Electrochemical reduction was further employed to produce Cu(tpa)-ERGO/GC. The redox peaks for the prepared catalyst were found to be superior to simple ERGO/GCE. The prepared cathode also exhibited better anti-interference effects for DA and AOCP. Surprisingly, recovery rates were found to be 101% and 98% for spiked urine serum samples, respectively.32 Shortly, the presence of graphene can lead to better performance in terms of selectivity and sensitivity. It has been noted that the peak potentials go down when nanocomposites are used instead of pristine MOFs. This is due to the fact that graphene possesses excellent electrical conductivity. It is also worth mentioning that electrical conductivity of graphene significantly affects the conductivity of nanocomposite. In the meanwhile, vulnerability of graphene-based materials in oxidative environments may pose limitations for their use in electrocatalysts.

3.2 Supercapacitors and batteries Energy density and high power are two important parameters for energy storage devices. In comparison with batteries, supercapacitors (also known as electrochemical capacitors) have high power density and improved cycle stability. Supercapacitors are classified into two groups based on their charge storage capacity and materials employed. One stores electrical energy with the help of electrochemical double-layer capacitor by using electrostatic forces.

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This type uses carbon-based materials with high surface areas such as graphene, carbon nanotubes, porous carbon and so on.33–35 The other type which is known as pseudo capacitors, employs conductive polymers and transition metal oxides for reversible and fast redox reactions on surface. Efforts are being made to improve power density by the introduction of new materials and additives. Core characteristics of supercapacitor materials include adequate electrical conductivity, tunable pore size, and sufficient surface area. Being emerging porous materials, MOFs are good candidate for such requirements and have been reported as electrode material.36 Additionally, if MOFs are combined with conductive materials such as carbon-based ones, improved life cycles, energy and power densities are realized due to synergistic effect of interaction between the two materials. In order to achieve optimized energy and power combination, both faradic and no-faradic processes are utilized in supercapacitors. Additionally, the shuttle effect is restricted by introducing sulfur species into large pores of carbon-based material and MOF. So, composite electrodes have been synthesized with an aim to ensure chemical and physical charge storage mechanisms. Carbon-based material is believed to be beneficial in such applications as it can improves the capacitance through electrostatic effects and its large surface area can increase contact between different materials. Whereas MOF can serve as pseudocapacitive material facilitating faradic reactions and fast ion diffusion through porous skeleton.37 In the recent times, nanocomposites of graphene and MOFs have been reported. Among these, Zr-MOF exhibited excellent capacitance in 1 M tetraethylammonium tetrafluoroborate. Another nanocomposite comprising doped MOF and rGO was studied for energy storage applications. The doping stabilized the MOF and assisted reversible redox reactions. Interestingly, a higher value of capacitance (758 F g 1) was observed for the prepared composite in comparison with pristine MOF and physically mixed composite. High energy density (37.8 Wh kg 1) was also observed for the prepared composite.38,39 Recently, transition metal MOFs in combination with CNTs have also been area of research for applications in supercapacitors. For example, Cu-MOF@CNT composite was synthesized by simple ultrasonication and employed in supercapacitors. The presence of CNTs ensured enhanced electrochemical storage capacity accompanied with improved accessibility of electrolyte. It is worth mentioning that the nanocomposite showed remarkable specific capacitance along with high-rate performance (Fig. 3).40 In the last decade, MOFs-carbon based nanocomposites have been extensively reported. The porous structure of MOF is helpful to produce

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Fig. 3 (a) Specific capacitance vs current densities, (b) IITI-1/CNT/GCE cycling stability test, inset exhibits first 25 cycles (Electrolyte used: 1 M Na2SO4). Adapted with permission from John Wiley and Sons. Ansari SN, Saraf M, Gupta AK, Mobin SM. Functionalized Cu-MOF@CNT hybrid: synthesis, crystal structure and applicability in supercapacitors. Chem Asian J 2019;14(20):3566–3571.

void spaces, which in turn, limits the volume expansion during electrochemical cycling. Their combination with carbon material leads to the creation of triple-phase boundary which is essential for enhanced electrochemical performance. In case of Li-S batteries, MOF-carbon can restrict polysulfide entry thus enhancing the cycle performance and specific capacity. For example, a layer of graphene nanosheets over MIL-101 (Cr)/S formed an excellent conductive network. The capacity was found to be 512 mAh g 1 (300 cycles), which was way better than simple MIL-101 (Cr)/S.41 Likewise, MnCC@S was reported with a hollow cubic structure. Electrochemical performance was observed to be excellent owing to chemisorption and capture of polysulfides.42 Another excellent composite MIL-53-on-rGO was synthesized and proved to be an ideal substrate for applications in Li-S. Interestingly, a capacity of 601 mAh g 1 was observed for S-in-MIL-53-on-rGO after 400 cycles due to combined effects of higher conductivity of rGO and intrinsic porosity of MOF.43 It is evident that CNTs and graphene have 2D and 1D structure with outstanding thermal and electrical properties, which makes them suitable candidate for Li-ion batteries, but there is some distinction between the two which affects the battery performance. When GO is employed as a conductive agent, it can establish large conductive sites thus reducing the contact resistance for electrode material and improving overall conductivity. Carbon nanotubes are onedimensional tubular structures which offer conjugate effect. When trace amount of CNTs is added, conductive network is formed, which in turn,

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is favorable for enhanced stability and capacity of the batteries. But presence of van der Waal forces leads to dispersion issues, consequently deteriorating conductive properties. Poor cycle performance has also been reported when CNTs are used as electrode material. In the contrast, GO can serve as buffer during volume change due to porous structure and efficiently reduces crushing of active materials and enhances cycle stability.44 Shortly, nanocomposites can be used as separators, electrolyte, and electrode material in batteries. When MOFs are used in combination with some conductive materials, electrical conductivity problem is overcome, thus improving the electrochemical performance.

3.3 Absorbents A number of noble and transition metals can be employed to synthesize MOF structures with a provision of active sites for adsorption. For instance, MOF-5/GO synthesized using hydrothermal process, was employed for adsorption of ammonia. It was interesting to note that the prepared composite showed enhanced absorption capacity as compared to the individual components due to the formation of additional pores between them.45 Similarly, another composite consisting of Cu, Zn, MOF, and graphite oxide has been reported. Surprisingly, the composite delivered better performance in terms of surface area, porosity, and crystalline structure. Additionally, GrO-MIL-101 was synthesized through solvothermal method and it showed reduced crystal size, adequate pore volume and surface area in comparison with MIL-101. Adsorption capacity of acetone was measured to be 20.10 mmol g 1 which was substantially higher than the MIL-101.46 Cu-BDC@CNT and Cu-BDC@GrO were synthesized through one pot eco-friendly solvothermal method and employed for removal of Bisphenol A from water to protect aquatic and human life. The prepared nanocomposites showed outstanding adsorption capacities toward BPA absorption, which were multiple times higher (164.1 and 182.2 mg/g) than the Cu-BDC-MOF (60.2 mg/g). Moreover, it was found that maximum amount of BPA could be absorbed from water in half an hour. The adsorption process was believed to be accomplished through π-π interactions between BPA and nanocomposites.47 The superparamagnetic materials such as Fe3O4 along with MOF@CNT and MOF@GO have been reported as a novel materials for recovery and magnetic separation of absorbents. The nanocomposites were synthesized using eco-friendly facile process and employed for absorption of MB, a novel pollutant. It is worth noting that the use of carbon-based substrates resulted in

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Fig. 4 Removal of MB through (i) GO based and (ii) CNT-based hybrid nanocomposites. Adapted with permission from Elsevier. Jabbari V, Veleta JM, Zarei-Chaleshtori M, Gardea-Torresdey J, Villagrán D. Green synthesis of magnetic MOF@GO and MOF@CNT hybrid nanocomposites with high adsorption capacity towards organic pollutants. Chem Eng J 2016;304:774–783.

reduced aggregation and enhanced dispersiveness within MOF. Also, small pores were observed between MOF and substrates. The adsorption capacity was found to be higher for prepared nanocomposites in comparison with parent materials (Fig. 4) and was ascribed to the covalent bonding and peculiar structure of MOF.48

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3.4 Catalysts Carbon-based MOF composites demonstrate attractive features that can be used for electrocatalytic processes including stability, high surface area and strong metal/metal oxide interactions. In addition to their use in batteries, supercapacitors and as a sensor, they can be further used as heterocatalysts and electrocatalysts. It is well established that MOF-carbon composite can act as electrocatalysts due to availability of active metal sites and enhanced electrical conductivity. (CoP)n/CNT was employed for the oxidation of water.49 Additionally, it has been reported that graphene can significantly improve OER/HER performance during water-splitting due to the interactions between graphene and catalysts which facilitates dispersion of the loaded catalyst and produces more active sites. Moreover, combination of graphene with transition metal catalysts leads to charge transfer from TMCs to graphene and consequently producing positively charged metal centers and assisting electrocatalytic process. Graphene also provides conductive network and helps in charge transfer kinetics, which is pivotal to OER/HER. It is found to be chemically stable under harsh environments and restricts sintering, bleaching and aggregation. So, it has proved to be an excellent electrocatalyst for water splitting. Several studies have been conducted to explore the potential of graphene and its hybrids as electrocatalysts for OER and HER and as a bifunctional catalyst. An electrocatalyst was synthesized using GO and POMOFs and employed for HER. The prepared catalyst showed comparable performance with commercially available catalysts.50 Similarly, Cu2(BDC)2(dabco)/rGO was synthesized and employed for HER, ORR and OER.51 In another study, Ni-based MOF was combined with GO to form an electrocatalyst. The resultant catalyst possessed small particle size accompanied with large surface area and led to outstanding electrocatalytic performance (small Tafel plot, OER overpotential 260 mV, HER overpotential 142 mV @ 10 mV cm 2).52 Likewise, low-cost MOF@GO was synthesized through in situ deposition of bi-metallic ZIF on nanosheets of graphene oxide and employed as electrocatalyst in Zn-Air batteries. Interestingly, the electrocatalyst showed better performance in terms of OER and ORR using alkaline media as compared to ZnCo-ZIF. This excellent performance was attributable to close interactions between the constituent materials, structural porosity and improved ion conductivity. When used as Zn-Air battery’s cathode, excellent electrochemical performance in terms of cyclic stability, energy density and charge discharge capability was observed (Fig. 5) and it paved the path for applications in energy storage and conversion devices.53

Fig. 5 (A) Zn–air battery schematic (ZAB) employing ZnCo-ZIF@GO as air cathode, Zn foil as anode. (B) OCV of ZAB. (C) Charge/discharge polarization plots of ZnCo-ZIF@GO and Pt/C + RuO2. (D) Discharge polarization plots and related power density of ZnCo-ZIF@GO and Pt/C + RuO2. (E and F) Cycling performance of ZnCo-ZIF@GO and Pt/C + RuO2 @ 10 mA cm 2, 30 min/cycle. Adapted with permission from RSC. Xiao Y, Guo B, Zhang J, Hu C, Ma R, Wang D, Wang J. A bimetallic MOF@graphene oxide composite as an efficient bifunctional oxygen electrocatalyst for rechargeable Zn–air batteries. Dalton Trans 2020;49(17):5730–5735.

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Though MOF-graphene based electrocatalysts show comparable electrocatalytic performance, yet they are still unable to match the potential of PGM catalysts. There are a number of challenges which need to be addressed before commercialization of such electrocatalysts. In the recent times, organic pollutants are being removed using photocatalytic degradation. During such reaction, free reactive species (h+, %OH, %O2 ) get entangled on semiconductors. MOFs have been reported as new class of photocatalysts, however, there are still some avenues, such as fast recombination rate between charge carriers, which need to be addressed. Researchers have provided a solution by combining MOFs with carbon-based materials, thus mitigating the aforesaid issue. For instance, a hybrid consisting of coordination polymer nanobelt material and functional carbon fiber was synthesized and it demonstrated tremendous photocatalytic performance for the degradation of rhodamine B. The degradation efficiency was found to be higher (88.48%) in visible light region as compared to parent coordination polymer (57.52%). The better performance was attributed to the impeded rate of recombination of electrons and holes.54 Similarly, MOFs-carbon composites can be used in different organic reactions. Basically, the introduction of carbon-based materials leads to hydrophobic environment thus restricting vulnerability of coordination bonds for water molecules and increasing likelihood of active sites toward the reactant. So, the catalytic performance and thermal stability considerably increased. ZIF-8/Pt-rGO was synthesized via. solvothermal method in which 2-methylimidazole was used as stabilizing and caping agent and it showed excellent conversion efficiencies (4.8% for cis-cyclooctene, 21% for n-hexene). The selective performance was attributed to the selective permeability of MOF coating.55 Additionally, MOFs-carbon based composites have been used as precursors for the synthesis of different catalysts mainly through annealing.

4. Outlook and conclusions MOFs have been used for a decade or so, but their intrinsic issues hinder practical applications. Therefore, MOF composites have been introduced to tackle these issues. MOF-carbon based composites offer unique properties which arise from well-studied chemistry and decades of practical experience. A few of such properties are introduction of novel functionalities, stable and tunable structures, template assisted synthesis, etc. Synthesis procedures are of prime importance as they decide final properties which

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will be ultimately related to the possible practical applications. Function based synthesis is strongly recommended but it’s in initial stage for MOF composites. Different methods have been developed to perform specific tasks which is meaningful but there is still room for improvement. There is still need to analyze the relationship between synthesis procedure, product structure and probable applications so that rules can be decided to opt for a particular procedure in advance. Application areas of MOF-carbon composites are vast as they can be applied to areas other than catalysis, gas storage and separation. These areas include electrochemical sensing and batteries/supercapacitors which is realized through enhanced electrical conductivity. These composites can be further applied to other areas such as drug delivery and biomedical imaging due to stable, porous and hierarchical structures. In addition to that, vulnerable MOFs can be further investigated to expand the application areas. In short, although there are some avenues which need to be addressed, yet MOFcarbon composites offer a bright perspective for large application areas of MOFs. So, subsequent efforts may lead to exploitation of these MOFs in a more fruitful way.

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