Green Technologies for Industrial Waste Remediation (Environmental Science and Engineering) 3031468570, 9783031468575

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Environmental Science and Engineering

Abhilasha Singh Mathuriya Soumya Pandit Neeraj Kumar Singh   Editors

Green Technologies for Industrial Waste Remediation

Environmental Science and Engineering Series Editors Ulrich Förstner, Buchholz, Germany Wim H. Rulkens, Department of Environmental Technology, Wageningen, The Netherlands

The ultimate goal of this series is to contribute to the protection of our environment, which calls for both profound research and the ongoing development of solutions and measurements by experts in the field. Accordingly, the series promotes not only a deeper understanding of environmental processes and the evaluation of management strategies, but also design and technology aimed at improving environmental quality. Books focusing on the former are published in the subseries Environmental Science, those focusing on the latter in the subseries Environmental Engineering.

Abhilasha Singh Mathuriya · Soumya Pandit · Neeraj Kumar Singh Editors

Green Technologies for Industrial Waste Remediation

Editors Abhilasha Singh Mathuriya Ministry of Environment Forest and Climate Change New Delhi, India

Soumya Pandit Department of Life Science, School of Basic Sciences and Research Sharda University Greater Noida, India

Neeraj Kumar Singh Department of Bioscience and Bioengineering Indian Institute of Technology Roorkee Roorkee, Uttarakhand, India

ISSN 1863-5520 ISSN 1863-5539 (electronic) Environmental Science and Engineering ISBN 978-3-031-46857-5 ISBN 978-3-031-46858-2 (eBook) https://doi.org/10.1007/978-3-031-46858-2 © The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 This work is subject to copyright. All rights are solely and exclusively licensed by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors, and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Switzerland AG The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland Paper in this product is recyclable.

Contents

1

Application of Microorganisms in Industrial Waste Treatment . . . . Aparna Gunjal and Dilan Rajapakshe

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An Overview on Fungi and Nanomaterial-Based Technologies for the Treatment of Industrial Effluents . . . . . . . . . . . . . . . . . . . . . . . . Dhirendra Kumar, Sugandha Mishra, Surbhi Kumari, and Amit Kumar Dutta

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Hazardous Effects of Heavy Metals from Industrial Wastewaters and Their Remediation Through Green Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Satish Kumar, Piyal Mondal, and Mihir Kumar Purkait Algal Photo Bioreactors: A Promising Technology for Wastewater Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chitra Devi Venkatachalam, Mothil Sengottian, Sathish Raam Ravichandran, Premkumar Bhuvaneshwaran, and Sarath Sekar Membrane Based Technologies for Industrial Waste Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Janvika Varma, Urjitsinh Zala, Vijay Jagdish Upadhye, Pranay Punj Pankaj, and Anupama Shrivastav

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Valorization of Agro-Industrial Wastes for Biorefinery Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101 Ayushi Singh, Rishi Dikshit, and Neetu Singh

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A Critical Assessment of Processes and Products for Valorization of Agroforestry Industrial Wastes for Biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125 Rocio E. Cardozo, Johana A. Rivaldi, María E. Vallejos, and Nicolás M. Clauser

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Bioaccumulation and Detoxification of Metals Through Genetically Engineered Microorganism . . . . . . . . . . . . . . . . . . . . . . . . . 147 Priya Chauhan, Nitya Panthi, Indrani Mazumdar, and Nazneen Hussain

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Constructed Wetlands for Industrial Wastewater Remediation . . . . 189 Manoj Kumar, Neeraj Kumar Singh, Kalp Bhusan Prajapati, Ruplappara Sharath Kumar, and Rajesh Singh

10 Bioelectrochemical Treatment of Petrochemicals . . . . . . . . . . . . . . . . . 201 Nakul Kumar, Neha Tavker, Pankaj Kumar, and Snigdha Singh 11 Biogenic Nanomaterials: Synthesis, Characterization and Its Potential in Dye Remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221 Manish Kumar, Anshu Mathur, and R. P. Singh 12 Biocatalytic Remediation of Industrial Pollutants . . . . . . . . . . . . . . . . 247 Pratyasha Pallavi, Soumya Koippully Manikandan, and Vaishakh Nair 13 Photocatalytic Treatment of Wastewater . . . . . . . . . . . . . . . . . . . . . . . . 271 Anil Swain and Remya Neelancherry 14 Microbial Biofilm Reactor for Sustainable Wastewater Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285 Adebayo Elijah Adegoke, Oke Morenikeji Abel, Ejafu Michael Ikechukwuka, Ahmed Oke Maryam Opeyemi, and Aguda Opeyemi Nifemi

Chapter 1

Application of Microorganisms in Industrial Waste Treatment Aparna Gunjal and Dilan Rajapakshe

Abstract Various types of wastes, including those from hospital, agroindustry byproducts, household, and industries, pose a serious global issue. Among these, industrial wastes require immediate attention. Utilizing microorganisms for the treatment of industrial offers an economical and environmentally friendly solution. Bacteria, actinobacteria, fungi, yeast, and algae are particularly valuable in this regard. These diverse groups of microorganisms employ various mechanisms, such as direct degradation, conversion into simpler forms, biosorption, anaerobic digestion, and composting, to effectively treat industrial wastes. The chapter focuses on the utilization of different microorganisms and their associated mechanisms for the treatment of industrial wastes. Given the urgency in proper waste management and treatment, this chapter emphasizes the significance of a biological approach for addressing industrial waste challenges. Keywords Actinobacteria · Biosorption · Eco-friendly · Economical

1.1 Introduction The production of highly contaminated water from industrial or municipal sources poses a significant challenge. Therefore, additional advanced methods are necessary to treat the effluent and convert it into a more environmentally friendly, harmless and clean water source. To achieve this goal, various processes are employed in industrial and municipal wastewater treatment plants, utilizing different physical, chemical and biological approaches. In contrast to municipal wastewater, which primarily consists of biodegradable organic matter (Litvinov et al. 2022), the non-biodegradable effluent A. Gunjal (B) Department of Microbiology, Dr. D. Y. Patil, Arts, Commerce & Science College, Pimpri, Pune, Maharashtra 411018, India e-mail: [email protected] D. Rajapakshe Department of Chemistry, University of Kansas, 1567 Irving Hill Road, Lawrence Kansas 66045, USA © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 A. S. Mathuriya et al. (eds.), Green Technologies for Industrial Waste Remediation, Environmental Science and Engineering, https://doi.org/10.1007/978-3-031-46858-2_1

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water generated by farming and agro-related industries, breweries, dairy industry, pulp and paper industry, iron and steel industry, food industry, complex organic chemicals industry, textile industry etc., can be classified as industrial waste (Sophonsiri and Eberhard 2004). Apart from the residues of pesticides and herbicides, farming and agro-related industries produce large quantities of organic and inorganic waste that require further treatment before being sent to a municipal wastewater treatment facility (Rebah et al. 2007). This wastewater can primarily categorized into two types: agricultural residues and agro-related industrial waste. Agricultural residues can be further divided into field residues and process residues. Field residues refer to the leftover materials in the field after harvesting, such as stems, stalks, leaves, and seed pods. Process residues, on the other hand, are the remnants that remain after the crop has undergone processing to create value-added products. Examples of process residues include husks, seeds, roots, bagasse, and molasses. Agro-related industrial waste mainly comprises large quantities of organic waste, including peels and oils generated during post-processing of crops for the production of value-added products (Siddeeg et al. 2019). Breweries generate approximately 3–7 m3 of wastewater per 1 m3 beer production, consisting mainly of leftover yeast, hops, other grains, and sugars from the brewing process (Kanagachandran and Jayaratne 2006). The effluent produced by breweries typically exhibits higher levels of nitrogen and phosphorus due to the specific composition of their waste (Fillaudeau et al. 2006). In the dairy industry, wastewater contains dissolved sugar, proteins, fats, and residues of additives (Sivaprakasam and Balaji 2021). These wastes result from the processes involved in transforming raw milk into value-added products such as consumer milk, cheese, butter, condensed milk, yogurt, ice cream and dried milk (Raghunath et al. 2016). In the pulp and paper industry, the wastewater is heavily contaminated due to bleaching processes applied to lignocellulosic materials. It contains chlorinated organic compounds, including lingosulphonic acids, chlorinated resin acids, chlorinated phenols, chlorinated hydrocarbons, colored compounds, adsorb able organic halogens (AOX), chloroform, catechol’s, chlorate, dioxins, vanillin’s, guaiacols, syringols, furans, and more (Kamali and Khodaparast 2015). These specific organic materials require further treatment before being discharged into a public wastewater treatment facility to avoid significant environmental issues (Sharma et al. 2022). Iron and steel industries produce significant volumes of contaminated water, characterized by a higher proportion of non-biodegradable substances compared to organic waste (Koymatcik et al. 2018). Throughout the production process of iron or steel itself from the iron ores, these industries heavily rely on water (Das et al. 2018). Large blast furnaces, responsible for the initial reduction of iron from ores, require substantial amounts of water for their cooling, resulting in regular contamination with ammonia and cyanide. In the production of coke from coal, an essential raw material in iron and steel industry, considerable quantities of water are utilized for cooling purposes, leading to contamination with gasification byproducts, known as polycyclic aromatic hydrocarbons (PAH) including benzene, anthracene, naphthalene, ammonia, cyanide, phenols, and cresols (Biswas 2013). Secondary processes

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involved in the production of iron or steel, such as the manufacture of sheet, wire or rods generate wastewater containing hydraulic oil, tallow and particulate solids. Moreover, when these iron or steel products undergo additional refining processes like galvanization or painting, highly acidic contaminated water is produced. Prior to galvanizing or painting, the iron or steel products must undergo pickling processes, which often result in acidic effluent containing ferrous chloride or ferrous sulfate. The different types of wastes are presented in Table 1.1. Food processing industries typically generate large quantities of wastewater that is contaminated with surfactants, pesticides, insecticides, and organic animal waste, resulting from washing processes (Cristian 2010). Additionally, these wastewater streams can contain significant levels of growth hormones, antibiotics, feces, and parasites from animals (Roati et al. 2012). Industries involved in the production of complex organic products such as pesticides, paints and dyes, pharmaceuticals, petrochemicals, detergents, plastics, and others, produce highly polluted water containing soluble or particulate forms of product materials, feed-stock materials, by-products, as well as value added products such as plasticizers, washing and cleaning agents, and solvents (Pal 2018). Textile manufacturing industries are recognized as major contributors to industrial wastewater generation worldwide (Mondal et al. 2017). They produce wastewater that contains various toxins, corrosive chemicals, oil and grease, reactive chemicals, and flammable agents. These chemicals are introduced into the effluent during different stages of the textile production processes. Post-conditioning of textiles often leads to the addition of chemical residues, including finishing agents (such as antimicrobial agents, fire-resistant agents, crease-resistant agents, anti-static agents, easy-care finish agents, hydrophilic finish agents, and non-slip finish agents), formaldehyde, silicone, phenols, organo-silver, quaternary ammonium compounds, oxy-ethylated polyamides, silica gel, poly ammonium quaternary salts, chlorinated, brominated and phosphorous-containing flame retardants (Adane et al. 2021). Dyes utilized in the textile industry play a significant role in generating highly contaminated wastewater that cannot be effectively treated using conventional Table 1.1 Different types of wastes No

Types of wastes

Generation of wastes

Reference

1

Kitchen

50 kg per capita per year

United Nations Environment Program’s Waste Index Report (2021)

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Medical

28,747 tons

Chand et al. (2021)

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Industrial

9.2 billion tons

Vignesh et al. (2021)

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Agricultural

500 million tons

United Nations Environment Program’s Waste Index Report (2021)

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Food

222 million tons

Gille (2013)

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Electronic wastes (e-waste)

24.9 million tons

Andeobu et al. (2021)

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biodegradable wastewater treatment methods. The industry exhibits a wide range of dye types, including anthraquinone, azo, xanthene, indigo, phthalocyanine, diphenylmethane and triphenylmethane, nitro sated and nitrated, polymethinic, cationic or basic, reactive, metalliferous, substantive or direct, sulfur, dispersible and vat dyes, as well as pigments. In addition, residual acids such as hydrochloric, sulfuric, phthalic, citric, formic, acetic, nitric, oxalic acid, liquid ammonia, starch and bleaching agents, constitute other major constituents of textile wastewater. Prior treatment is necessary before releasing this wastewater into public wastewater treatment facilities (Topare and Bokil 2021). The composition of wastewater varies depending on the source’s characteristics. Municipal wastewater predominantly consists of biodegradable organic waste and treatment processes commonly applied include screening, aeration, and plain sedimentation, sedimentation with coagulants, filtration, disinfection and softening (Demirbas et al. 2017). In contrast, industrial wastewater treatment facilities require additional treatment steps compared to municipal wastewater treatment plants (Sonune and Ghate 2004). Industrial effluent contains numerous non-biodegradable impurities that necessitate specialized treatment methods (Jern Ng 2006). Therefore, a typical industrial wastewater treatment facility includes processes such as equalization, screening, aeration, neutralization, removal of metal and inorganic material, as well as plain sedimentation, sedimentation with coagulants, filtration, disinfection and softening. In an ideal scenario, the treatment facility should discharge 100% pure water after undergoing the aforementioned processes. The water treatment facility employs various physico-chemical and biological methods, and it is essential to select the most suitable approach for each specific situation. Although it is commonly believed that modern industrial wastewater treatment facilities are responsible for converting industrial waste into cleaner water, biosolids, and industrial sludge, these by-products are not environmentally sustainable, especially the industrial sludge. In solid form, the concentrated industrial sludge collected by many wastewater treatment facilities contains high levels of toxic, hazardous, and environmentally harmful contaminants. Typically, this sludge is either incinerated or disposed of in sanitary waste disposal sites, without consideration for the environmental consequences. These actions can lead to significant and often irreversible environmental problems. While conventional industrial wastewater treatment facilities mainly use biological treatment for organic waste, limited research has been conducted on the biodegradation of other industrial contaminant. In this chapter we will be discussing possible ways to replace existing conventional industrial waste water treatment techniques with advanced biological treatment methods (Dong et al. 2018). Using different types of microbes in waste water treatment has provided a much more efficient and sustainable approach and the resulting biomass is always regarded as an easy-to-manage sludge and a fine commercial raw material (Rani et al. 2019). Based on the fuel that the microorganisms get energy from, a biological waste treatment plant can be contained in any of the following three types (Choi et al. 2006). There can be aerobic microorganisms which involve oxygen to break down organic matter to carbon dioxide, ammonia, and microbial biomass; anaerobic

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which do not involve oxygen to break down organic matter, often forming methane, carbon dioxide, ammonia, and biomass and anoxic which involve other molecules than oxygen for growth, such as for the removal of sulfate, nitrate, nitrite and selenite. The chapter focuses on how microorganisms play important role in treatment of industrial waste which will be economical and eco-friendly way.

1.2 Need for the Treatment of Industrial Waste The industrial wastes contains heavy metals, organic matter which accounts for biochemical oxygen demand (BOD) and chemical oxygen demand (COD), solids such as total (TS), suspended (SS) and volatile solids (VS). The industrial waste due to this composition is complex in nature, hazardous and can cause environmental issues such as water and land pollution. Hence, such industrial waste cannot be disposed directly without any treatment. The BOD and COD of the industrial waste must also be within the limits as per the Central Pollution Control Board (CPCB) or Maharashtra Pollution Control Board (MPCB) before being disposed to the water or land (Litvinov et al. 2022).

1.3 Biological Approaches for Industrial Waste Treatment The chemical approach to treat industrial waste has disadvantages viz., it is costly, time-consuming and also causes environmental pollution. Due to these disadvantages of chemical approach, the use of microorganisms which is termed ‘biological approach’ is the best solution to treat industrial wastes. The biological approach is also sustainable and must be adopted globally to treat various industrial wastes. The microorganisms play a useful and wonderful role to treat industrial wastes (Nagda et al. 2021).

1.3.1 Microorganisms in Industrial Waste Treatment The biological approach for the industrial waste treatment is very eco-friendly, cheap and easy. The biological approach for the industrial waste treatment includes the use of microorganisms (Kushkevych 2021). The group of microorganisms for the industrial waste treatment includes bacteria, fungi, algae and actinobacteria (Fig. 1.1). The bacteria include Pseudomonas, Bacillus, Burkholderia, Serratia, Acinetobacter sp, etc. The fungi include Aspergillus, Penicillium sp., Rhizopus, etc., while the actinobacteria include Streptomyces, Nocardia sp., etc. The algae for the industrial waste treatment includes Spirogyra sp.

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Bacteria

Fungi

Group of microorganisms in industrial waste treatment

Algae

Actinobacteria

Fig. 1.1 Microorganisms in industrial waste treatment

Among these groups of microorganisms, the fungi have the immense ability to fast degrade the complex matter into simple forms and to treat the industrial waste. The various fungi have the ability to form spores also which can remain for a long period. The microorganisms in bioremediation of the pollutants are shown in Table 1.2 (Ayilara and Babalola 2023). About 90% of the pollutants are remediated by these microorganisms. Table 1.2 Microorganisms which help in bioremediation of the pollutants (Avilara and Babalola 2023) Microorganism

Pollutant remediated

Bacteria Pseudomonas aeruginosa and Aeromonas sp.

Chromium, uranium, nickel and copper

Pseudoalteromonas sp. and Agarivorans sp.

Hydrocarbons

Bacillus licheniformis

Dyes

Fungi Aspergillus sp.

n-Hexadecane

Aspergillus and Penicillium sp.

Aliphatic hydrocarbons

Trichoderma, Penicillium, Aspergillus sp.

Cobalt and copper

Algae Chlamydomonas reinhardtii and S. almeriensis

Arsenic

1 Application of Microorganisms in Industrial Waste Treatment Industrial waste

Industrial waste in complex form

Industrial waste in simple form

7 Fungi / actinobacteria/ bacteria/ algae

Degradation

Fig. 1.2 Use of degradation approach by microorganisms to treat industrial waste

1.3.2 Various Methods by Which Microorganisms Can Treat Industrial Waste The methods for industrial waste treatment are filtration, chlorination, sedimentation, chemical approach, etc. The various methods by which microorganisms can treat industrial waste include degradation (Fig. 1.2), biosorption (Fig. 1.3), composting, etc. Degradation is the simplest and easy approach where group of microorganisms specially the fungi can degrade the industrial waste directly and convert the complex into simple form. Biosorption is the use of microbial biomass to treat the industrial waste. In biosorption, the bacterial or fungal biomass can be used directly and see the uptake of waste taken by the microbial biomass. The exact mechanism of biosorption is not yet known, but it said the functional groups such as –OH, –NH2 , –COOH, – CH2 , –SH, –CH3 , –CH, etc. present on the microbial biomass can play a role in this. The industrial waste can be converted into value-added product such as compost by the process of composting. The industrial waste after treatment by the use of microorganisms is converted to humus rich ‘compost’.

1.3.3 Composting Process The composting process is biological process where microorganisms convert the wastes into ‘compost’. This compost is humus like product which can be used for the growth of plants. The composting process makes use of microorganisms such as bacteria, fungi and actinobacteria which degrade the wastes into simple form and convert into compost. The composting process to treat the industrial waste is represented in Fig. 1.4.

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Prepare the media and autoclave

Grow the microorganisms on a rotary shaker with proper temperature and shaking conditions

Centrifuge the broth and use the microbial biomass for treatment of industrial waste by biosorption approach

Fig. 1.3 Biosorption approach by microorganisms to treat industrial waste

Layer of sand Mix properly the content

Layer of gravel Microbial culture Industrial waste to be treated Layer of sand Layer of gravel

Fig. 1.4 Composting process to treat industrial waste

1.4 Trickling Filter for the Treatment of Industrial Waste The trickling filter is also one biological approach to treat industrial waste. It makes use of oxygen (i.e., aerobic) and removes any organic matter present in the industrial waste by the use of different microbes which are attached to the media. The trickling filter makes use of the filtering media. The group of microorganisms (bacteria, fungi, algae and yeasts) works for the treatment of industrial waste (Liang et al. 2021).

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There is a sedimentation tank which is part of the trickling filter. This sedimentation tank removes the biological growth which flows with the effluent from the filtering media.

1.5 Conclusions The biological approach is very significant and best solution to treat various industrial wastes. Also, the use of microorganisms is simple to treat such types of wastes and must be used worldwide. The research in the area on use of microorganisms to treat industrial waste is gaining importance. More research is needed to see the use of microorganisms to treat industrial wastes on a pilot scale. The biological approach for the treatment of industrial wastes will prove to be very cheap and easy. Also, it will be a clean and sustainable approach.

References Adane T, Adugna A, Alemayehu E (2021) Textile industry effluent treatment techniques. J Chem 2021:1–14 Andeobu L, Wibowo S, Grandhi S (2021) A systematic review of e-waste generation and environmental management of Asia Pacific countries. Int J Environ Res Public Health 18:9051. https:// doi.org/10.3390/ijerph18179051 Ayilara M, Babalola O (2023) Bioremediation of environmental wastes: the role microorganisms. Front Agron 2023:1–15 Biswas J (2013) Evaluation of various method and efficiencies for treatment of effluent from iron and steel industry – a review. Int J Mech Eng Robotics Res 2:67–73 Chand S, Shastry C, Hiremath S, Joel J, Krishnabhat C, Mateti U (2021) Updates on biomedical waste management during COVID-19: The Indian scenario. Clinical Epidemiol Global Health 11:100715 Choi IS, Dombrowski EM, Wiesmann U (2006) Fundamentals of biological waste water treatment. John Wiley & Sons Cristian O (2010) Characteristics of the untreated waste water produced by food industry. Analele Universita¸tii Din Oradea, Fascicula: Protec¸tia Mediului 15:709–714 Das P, Mondal G, Singh S, Singh A, Prasad B, Singh K (2018) Effluent treatment technologies in the iron and steel industry – a state of the art review. Water Environ Res 90:395–408 Demirbas A, Edris G, Alalayah W (2017) Sludge production from municipal waste water treatment in sewage treatment plant. Energy Sour Part a: Recovery Utiliz Environ Effects 39:999–1006 Dong Q, Chen Q, Li Z, Zeng S (2018) Application of microbial technology in waste water treatment. Prog Appl Microbiol 1:23–28 Fillaudeau L, Blanpain-Avet P, Daufin G (2006) Water, waste water and waste management in brewing industries. J Cleaner Prod 14:463–471 Gille Z (2013) From risk to waste: global food waste regimes. Soc Rev 60:27–46 Kamali M, Khodaparast Z (2015) Review on recent developments on pulp and paper mill waste water treatment. Ecotoxicol Environ Safety 114:326–342 Kanagachandran K, Jayaratne R (2006) Utilization potential of brewery waste water sludge as an organic fertilizer. J Inst Brewing 112:92–96

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Koymatcik C, Ozkaymak M, Selimli S (2018) Recovery of iron particles from waste water treatment plant of an iron and steel factory. Eng Sci Technol 21:284–288 Kushkevych I (2021) The application of microorganisms in waste water treatment. Processes 9:1914 Liang J, Yuan Y, Zhang Z, You S, Yuan Y (2021) Modeling a three-stage biological trickling filter based on the A2O process for sewage treatment. Water 13:1152 Litvinov V, Gulzhan D, Maksat S, Natalya S (2022) Analysis of the composition of municipal waste water sludge from small settlements in East Kazakhstan. J Ecol Eng 23:105–112 Mondal P, Baksi S, Bose D (2017) Study of environmental issues in textile industries and recent waste water treatment technology. World Scient News 61:98–109 Nagda A, Meena M, Shah M (2021) Bioremediation of industrial effluents: A synergistic approach. J Basic Microbiol 62:395–414 Ng J (2006) Industrial Waste Water Treatment. World Scientific. https://doi.org/10.1142/p405 Pal P (2018) Treatment and disposal of pharmaceutical waste water: Towards the sustainable strategy. Sep Pur Rev 47:179–198 Raghunath V, Punnagaiarasi A, Rajarajan G, Irshad A, Elango A, Kumar G (2016) Impact of dairy effluent on environment - A review. In: Sundaram R (ed) Prashanthi M. Environmental Science and Engineering. Springer Publication, Integrated Waste Management in India, pp 239–249 Rani N, Sangwan P, Joshi M, Sagar A, Bala K (2019) Microbes: a key player in industrial waste water treatment. In: Microbial wastewater treatment. Elsevier Publication, pp 83–102 Rebah F, Ben D, Prevost A, Yezza TR (2007) Agroindustrial waste materials and waste water sludge for Rhizobial inoculant production: a review. Bioresource Technol 98:3535–3546 Roati C, Fiore S, Ruffino B, Marchese F, Novarino D, Zanetti M (2012) Preliminary evaluation of the potential biogas production of food-processing industrial wastes. Am J Environ Sci 8:291–296 Sharma P, Iqbal H, Ramchandra, (2022) Evaluation of pollution parameters and toxic elements in waste water of pulp and paper industries in India: A case study. Case Studies Chem Environ Eng 5:100163 Siddeeg SM, Mohamed T, Faouzi R (2019) Agroindustrial waste materials and waste water as growth media for microbial bioflocculants production: A review. Mat Res Exp 7:012001 Sivaprakasam S, Balaji K (2021) A review of up flow anaerobic sludge fixed film (UASFF) reactor for treatment of dairy waste water. Mat Today: Proceedings 43:1879–1883 Sonune A, Ghate R (2004) Developments in waste water treatment methods. Desalination 167:55–63 Sophonsiri C, Eberhard M (2004) Chemical composition associated with different particle size fractions in municipal, industrial, and agricultural waste waters. Chemosphere 55:691–703 Topare NS, Bokil S (2021) Adsorption of textile industry effluent in a fixed bed column using activated carbon prepared from agro waste materials. Mat Today: Proceedings 43:530–534 United Nations Environment Program’s Waste Index Report (2021) Vignesh K, Rajadesingu S, Arunachalam K (2021) Challenges, issues, and problems with zero waste tools. In: Hussain C (ed) Concepts of advanced zero waste tools. Elsevier, pp 69–90

Chapter 2

An Overview on Fungi and Nanomaterial-Based Technologies for the Treatment of Industrial Effluents Dhirendra Kumar, Sugandha Mishra, Surbhi Kumari, and Amit Kumar Dutta

Abstract Bioremediation refers to remove, degrade, alter, detoxify or immobilize various physical and chemicals wastes from the environment through the action of bacteria, fungi or other living organisms. Certain bioagents, particularly fungi utilize specific biochemical pathways to facilitate the removal of toxic substances from effluents. Fungi and other biofabricated microbes can only thrive in polluted environments when they can metabolize different components present in the effluent. The effectiveness of bioremediation is influenced by the physio-chemical characteristics, concentration, and chemical nature of pollutants, among other factors. Additionally, the microbial load and proper contact with pollutants may also significantly impact the success of the remedial processes. One emerging method for treating pollutants using fungi is known as Mycoremediation. Fungi are well-suited for this role due to their remarkable physio-chemical tolerance capabilities. In recent years, scientists have been captivated by the degradation and treatment of recalcitrant organo-pollutants, such as polychlorinated biphenyls, polycyclic aromatic hydrocarbons and chlorophenols by white rot fungi. Their easy adaptability, high tolerance and symbiotic associations have positioned them as a key player in the realm of effluents treatment. While numerous physical and chemical methods like precipitation, photodegradation, filtration, adsorption, coagulation, and chemical oxidation have been utilized for colour removal from wastewater, many fungi, particularly white rot fungi, have shown promise in the development of biological processes for textile effluent treatment. In the light of these considerations, this chapter provides an overview of waste generation, potential hierarchies„ and the use of fungi and nano bioremediation for managing toxic effluents.

D. Kumar (B) Department of Botany, Ch. Bansi Lal University, Bhiwani, Haryana 127021, India e-mail: [email protected] S. Mishra Department. of Environment Science, Govt. (PG) College for Women, Rohtak, India S. Kumari · A. K. Dutta Amity Institute of Biotechnology, Amity University Jharkhand, Ranchi, India © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 A. S. Mathuriya et al. (eds.), Green Technologies for Industrial Waste Remediation, Environmental Science and Engineering, https://doi.org/10.1007/978-3-031-46858-2_2

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Keywords Bioremediation · Nano-materials · Effluents · Industrial pollutants · Mycoremedies · Waste water

2.1 Waste and Waste Management The items that are no longer useful or desirable to a user are classified as waste or trash. Waste refers to anything that is discarded after serving its purpose or is considered useless or unusable. On the other hand, a collaborative product with little or low economic worth is referred to as a by-product (Amasuomo and Baird 2016). Waste management or waste disposal encompasses the procedures and actions required to handle trash from its creation to its final disposal. This includes monitoring and regulating the waste management process, waste-related legislation, technology, and economic processes, as well as the collection, transportation, treatment, and disposal of waste (van Ewijk and Stegemann 2020). There are various approaches to manage and dispose of different types of waste, including solid, liquid, and gaseous waste. Waste management covers a wide range of waste, such as radioactive, organic, biomedical, domestic, municipal, industrial, and biological wastes (Sohoo et al. 2020; Wandosell et al. 2021). It is well known that waste can pose a threat to different life forms, especially human health. The entire waste management process raises health concerns (Kaur et al. 2018). Apart from directly causing health problems, managing solid waste can indirectly human health by depleting additional water, soil, and food resources (Kong and Ma 2020). Human activities such as processing basic resources, daily activities, and industrial processes like production, manufacturing, and mining generate waste. Waste management is an essential approach to reduce the harmful consequences of waste on the environment, human health, planetary resources, and aesthetics (Shasha and Ibrahim 2022). Municipal solid waste, originating from industrial, commercial, and residential activities, constitutes a significant portion of waste management. There are variations in waste management procedures between developed and developing countries, urban and rural locations, as well as residential and industrial sectors (Krah et al. 2019; Wandosell et al. 2021).

2.1.1 The Waste Hierarchy The concept “3 Rs” stands for Reduce, Reuse, and Recycle. These three principles are categorized in the waste hierarchy based on their effectiveness in minimizing trash. The majority of waste minimization techniques are structured around the waste hierarchy, as illustrated in Fig. 2.1 (Girotto, Alibardi, and Cossu, 2015; Mourad, 2016). The objective is to maximize the value derived from goods while minimizing waste generation throughout the process. The fundamental principle of the waste hierarchy

2 An Overview on Fungi and Nanomaterial-Based Technologies … Fig. 2.1 Types of waste and its management and waste hierarchy

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Recycl e

Mixed waste Ewaste

Industrial waste

Agricultu ral waste

REDUCE

Medic al waste Mixed waste

House hold

waste

Radioact iveWaste

REUSE

is that regulations should prioritize actions aimed at reducing trash production, which is why it is often represented as a pyramid (Roe et al. 2020). The next preferred course of action is to explore alternative uses for the generated waste, promoting reuse. Recycling, including composting and other similar procedures, follows this step. Material recovery and waste-to-energy processes come next. Finally, the last steps involve incineration without energy recovery or disposal in landfills. At this stage, waste that cannot be avoided, redirected, or reclaimed is ultimately disposed of (Lu et al. 2017). According to the waste hierarchy, a product progresses through the successive phases of the waste management pyramid. Each product’s life cycle is depicted in the hierarchy, indicating its final stages (Ang et al. 2021; Salonen 2023).

2.1.2 Global Waste Generation and Handling Practices In most of the developed nations, including Canada, New Zealand, the United States, and much of Europe, curb-side garbage and waste collection sites are established as the primary method of waste Specialized trucks regularly collect the garbage, making it the most popular form of disposal (Azevedo et al. 2021; Barles 2014). In some remote areas, it may be necessary to transport garbage to a transfer station before it is sent to a proper disposal facility. In certain locations, a suction collection system is used, where garbage is transported through small bore tubes by vacuum from residences or businesses. Such systems are common in use in North America and Europe. This process involves separating dry waste from mixed wet garbage with the aim of facilitating the recycling of dry garbage and to composting of wet waste. As a result, significant reductions in the amount of landfill waste occur when separation is practiced, leading to lower air and water contamination (Mishra et al. 2022a). It also emphasizes the importance of considering the type of waste and the most suitable methods of treatment and disposal during the separation process. Additionally, this waste separation makes it easier to apply other waste-management techniques such as

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Fig. 2.2 Various types of available waste

Mixed waste Ewaste

Medical waste

Industri al waste

Agricultural waste

Mixed waste House hold waste

Radioactive Waste

composting, recycling, and burning. Various studies suggest that as a community, we should practice segregation and management based on variety of wastes, as depicted in Fig. 2.2. The community needs to be educated about the process of trash segregation procedure. Segregated waste is often more cost-effective to dispose of compared to mixed garbage, as it requires less physical sorting (Bing et al. 2016). Waste segregation is essential for various reasons, including compliance with regulations, financial savings, and the preservation of the environment and human health. Institutions should facilitate proper waste separation for their employees, which may involve labeling, providing accessible containers, and emphasizing the significance of segregation (Bergeron 2016; Khan et al. 2022). When discussing the types of waste, they can be classified based on their origin, hazardous nature and disposal methods, including household, commercial and industrial, medical, radioactive and electronic and mixed waste. Among these, electronic waste (E-waste) is a prominent concern today, originating from electronic devices and their components like mobile phones, wearable devices, without any intention of re-use (Thakur and Kumar 2022). E-waste is also known as e-scrap in various global regions, and Fig. 2.3 provides a summary of e-waste sources for better understanding. This category encompasses a wide range of products, including household or business items and electrical components powered by batteries or electricity.

2.2 Waste Treatment Methods Bioremediation is a biological process that involves using living organisms such as plants, fungi, microbes and bacteria to clean contamination. It is an amalgamation of waste management techniques (Patwardhan et al. 2022). As global continues to increase, its harmful consequences are becoming evident and pose a significant threat

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Small/Large Household Appliances (Geyser, LED bulbs, Inverter, Refrigerator, Air Conditioner)

Medical devices and accessories

Sources of E-Waste Office electronics goods (laptops, mobile phones, photocopier etc.)

Toys and Sports equipment

Fig. 2.3 Sources of E-waste in a look

to all living being specially humans (Sawant and Thumar 2021). The need for scientific and technological knowledge is also growing rapidly (Kumar and Khan 2021). Scientists actively researching bioremediation as a biologically sustainable, cost effective, environment friendly approach to address the alarming rate of pollution. This method utilizes biological treatments to convert toxic pollutants into environmentally friendly products (Joshi et al. 2022). The capacity of microbes to deal with environmental pollutants is beneficial in detoxifying the environment. For instance, using symbiotic fungi can remediate unfit land for agriculture and make it suitable for agriculture (Muradov et al. 2015). Industrialization in both developed and developing countries, combined with the increasing population, has resulted in the accumulation of the waste containing various contaminants such as polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), heavy metals, textile dyes, persistent organic pollutants, effluents from textile, pesticides, and more. Various fungal enzymes, including laccases, catalases, peroxidases, and cryochrome P-450 monooxygenase, are used to clean contaminated sites. Over time, human beings have developed various technologies to address concurrent problems as needed. The development of modern techniques and solutions has seen significant advancements from past methods (Mishra et al. 2022b).

2.2.1 Physio-Chemical Method Various suitable techniques, as suggested by Riser-Roberts (2020), enable microbes to carry out a range of physical and chemical reactions as part of their metabolism, leading to the degradation and removal of pollutants.

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2.2.2 Phytoremediation Bioremediation is a vast topic that involves the utilization of both plants and microbes. It is further categorized into three main classes: Phytoremediation, microbial remediation, and myco-remediation (He et al. 2017; Kumar and Singh 2022). Phytoremediation, one of the main sub-categories of bioremediation, involves the removal of pollutant and conversion of toxic element into non-toxic or less hazardous forms with the aid of plant entities. These plants employ special mechanisms to alleviate toxic stress from air, soil, groundwater among other sources, using the following methods.

2.2.2.1

Phytoextraction(=Phytoaccumulation)

Phytoextraction involves the use of plants to remove contaminants from soil by accumulating these contaminants in their tissues. It is an effective clean-up technology for soils containing various metals.

2.2.2.2

Rhizofiltration

Rhizofiltration is similar to Phytoextraction, but it focuses on remediating contaminated groundwater rather than polluted soils.

2.2.2.3

Phytostabilization

Phytostabilization refers to the use of specific plants to immobilize soil and water contaminants. The contaminants are either absorbed and accumulated by the plant roots, adsorbed on the roots, or precipitated in the rhizosphere.

2.2.2.4

Phytodegradation (Phytotransformation)

Phytodegradation involves the degradation of organic contaminants from polluted sites through internal and external metabolic processes driven by plants.

2.2.2.5

Rhizodegradation

Also known as enhanced rhizosphere biodegradation, phytostimulation, and plantassisted bioremediation, this process enhances the breakdown of organic contaminants in the soil by soil-dwelling microbes present in the rhizosphere.

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2.2.2.6

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Phytovolatilization

Phytovolatilization is the process in which plants uptake water-soluble contaminants and release them into the atmosphere as they transpire water.

2.3 Natural Attenuation Natural attenuation, also known as biostimulation, involves the use of various fungi as agents of bioremediation. White rot fungi are capable of degrading lignin cellulosic material through the utilization of ligninolytic enzymes such as laccases and peroxidases (Ahmed et al. 2021). Marine fungi including Trichododerma harzianum, Mucor, Aspergillus, Penicillium and Slime moulds, have also shown potential for bioremediation. Extremophilic fungi possess thermotolerance, florescence, and tolerance to harsh conditions (Kumar et al. 2013). For example, Cryptococcus is tolerant to heavy metals, Pestalotiopsis palmarum produce lignin peroxidases, and Lecanicillium muscarium produces chitinases (Ahmed et al. 2021). An exemplary case of symbiotic fungi is the Arbuscular mycorrhizal fungi (AMF), in which fungal partner aids in pollutant removal by providing a higher surface area for absorption through its hyphae and spores, and then mobilizes and binds the pollutants to the root. Ectomycorrhizal fungi, such as Suillusbouinus and Rhizopogonroselus form associations with Pinus Spp. and facilitate the removal of cadmium (Pal and Pandey 2017).

2.3.1 Fungi as a Bioremediation Agent Research are being conducted to determine whether fungi are involved in remediation processes through various methods. The term “fungus” has its origin in Latin, which means mushroom. Fungi are achlorophyllous and heterotrophic thallophytes, and their study fungi is known as mycology (Quintella et al. 2019).Their thallus is composed of hyphae, which collectively form mycelium. Fossil records indicate the presence of fungi in the Devonian and Precambrian periods. Fungi have been used as a source of food since ancient times. Fungi exhibit a wide range of diversity in their form, structure, physiological processes and methods of reproduction, growing in various habitats Genetically modified fungi are utilized in research to better understand their role in remediation. While not all fungi are involved in remediation, many play significant roles in producing commercially useful organic acids, as shown in Table 2.1 (Li et al. 2020). Apart from their remediation potential, each fungus holds unique economic importance in various industries, as food sources, in medicine, enzyme production, agriculture, pathogenesis, spoilage of food items, deterioration of materials, and timber degradations (Jafari et al. 2013).

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Table 2.1 List of some organic acids and concerned fungi used in production S. no.

Organic acid

Name of fungi

Reference

Citric acid

Aspergillus niger and A. wentii

Show et al. (2015)

Lactic, oxalic and succinic acids

Mucor, Rhizopus

Li et al. (2024)

Itaconic acid

Aspergillus itaconicum and A. terreus

Zhao et al. (2018)

Gluconic acid

Aspergillus niger and Penicillium purpurogenum

Ma et al. (2022)

Kojic acid

Aspergillus oryzae

Chen et al. (2022)

Gallic acid

Penicillium glaucum and Aspergillus gallomyces

Feminus et al. (2019)

Fumaric acid

Rhizopus stolonifer

Zaveri (2022)

Researchers have extensively studied white rot fungi, also known as basidiomycetes. Most of these fungi can produce extracellular ligninolytic enzymes such as laccase, manganese peroxidase, versatile peroxidase, lignin peroxidase and dye decolorizing peroxidase, which are responsible for lignin degradation.. Laccases are blue multicopper oxidases that catalyze the monoelectronic oxidation of various substratess, coupled with a full, four-electron reduction of O2 to H2 O, for example, ortho and para-diphenols, polyphenols, aminophenols, and aromatic or aliphatic amines, (Singh et al. 2021a, b). However, issues arise due to their growth in neutral pH, resistance to adverse conditions, and their ability to outcompete autochthonous microorganisms. Recent research has focused on non-white rot fungi, specifically Ascomycetes. In non- ligninolytic fungi, P450s enzymes play an important role in xenobiotic detoxification. Pollutants’ molecular structures traverse cell walls and are further converted by membrane-bound enzymes. Some extracellular oxidation occurs due to Ascomycetes laccases or hydroxyl radial attacks. Certain fungal stain can degrade polychlorinated biphenyls (PCBs) and other contaminants. Trichoderma spp. display high resistance to phenanthrene and benzapyrene in solid media (Petri dishes) and grow at neutral pH, using contaminants as a carbon source. Plastics contamination poses a significant water pollution due to urbanisation (Singh et al. 2020). The Ascomycetes Rhodococus ruber and the fungus Penicillium simplicissium, Fusarium solani and Aureobasidium pullulans produce extracellular enzymes to degrade polyethylene and polyurethane, respectively. Polylactic acid (PLA), a biodegradable polymer, is degraded by Fusarium moniliforme and Penicillium roqueforti. Mercury is remediated by filamentous fungi by through biosorption with an efficiency of 97.50% and 98.73% (V˘acar et al. 2021), while chromium complex is remediated by Aspergillus tamarii in batch and continuous processes (Chang et al. 2020). Trichoderma asperellum degrades Crystal violet dye, and white-rot fungi have been effective in degrading pharmaceutically active compounds under certain conditions, such as enzymes immobilization, fungal reactors. For instance, Aspergillus

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spp. have been found to degrade Triazolo pyrimidine sulphonamide (Chang et al. 2020; Karagoz et al. 2019), Aspergillus versicolor and A. niger to triclosan and endosulfan. Different factors influence the bioremediation rate, including pollutants concentration, nutrients availability for fungal growth, fungal adaptation (acclimatization), accessibility of organic pollutants to fungi, effect of environmental conditions (temperature, pH, oxygen availability).

2.3.2 Limitations of Using Fungi as a Tool of Bioremediation Bioremediation of pesticides is a slower process, and complete removal of contaminants may not always occur. Fungi require more time to adapt to the contaminated environment and effectively remove pollutants (Singh et al. 2021a, b). As a result of partial degradation, there can be an accumulation of the secondary metabolites that may be harmful. Only a limited number of fungal strains capable of mineralizing pesticides (Azubuike et al. 2016).

2.4 Nano-remediation Nano-remediation is an advanced method used to remove contaminants from the environment. It focuses on dealing with pollutant compounds, such as toxic heavy metals, halogenated chemicals, chlorinated solvents and pesticides (Patel et al. 2022). Though it may be slightly costly, it is a highly effective method. Several reports have suggested that nanoparticles exhibit sensitivity, possess a high surface area to mass ratio, and exhibit both electronic properties and catalytic properties (Rado´n et al. 2020). These specific properties of nanoparticles form the basis of the nanoremediation mechanism.

2.4.1 Specific Features Responsible for Mechanism of Nano-Remediation The properties of nanoparticles have been extensively studied by researchers, which makes them highly suitable for the remediation process. Additionally, nanoparticles can work in association with enzymes and microorganisms. For a more effective remediation of toxic metals from wastewater, air, and soil, the process is called Biofabrication (Klekotka et al. 2020). Nanoparticles that are formed through the action of microorganisms, plants, fungi, algae etc., fall under the category of Greensynthesized nanoparticles. Biosynthesized nanoparticles are a cost-effective and ecofriendly approach at a large scale that do not produce toxic by-products. Figure 2.4

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shows some specific characteristics of nanoparticles that make them more suitable for the remediation process. These properties include a high surface area and active sites, where the high surface area provides more active sites for better adsorption of toxic metal and pollutants due to the high surface area to mass ratio of nanoparticles. The catalytic properties and chemical reduction capabilities of nanoparticles contribute to faster rate of waste degradation reaction. Nano-structures and materials are highly effective adsorbents that can efficiently remove harmful contaminant from wastewater due to their extremely small sizes (Goswami et al. 2022). These nano-adsorbents have the ability to absorb both organic and inorganic pollutant from wastewater, including carbon-based nanoparticles, metal and metal-oxide based nanoparticles. Carbon nanotubes are currently being used as adsorbent for toxic metal waste of industries. A carbon nanotube is a tube composed of carbon with a small diameter range in nanometres, and they are considered as allotropes of carbon, intermediate between fullerene cages and flat graphene. There are two main types of carbon nanotubes, namely single wall nanotubes (SWNT) and multi-wall nanotubes (MWNT). The MWNT consist of a series of single wall tubes nested within one another (Kaur and Roy 2021). The diameter of SWNT is in the range of 0.7–2.0 nm, while MWNT can have a diameter as great as 30 nm. Both SWNT and MWNT have the capability to adsorb metals from wastewater. For instance, carboxylated multi-wall nanotubes have shown effective adsorption of Arsenic and Manganese. Certain nanoparticles associated with cell membranes, known as membraneassociated nanomaterials, have shown improved membrane permeability and are used in effluent removal. These nanoparticles enhance membrane permeability for pollutant degradation. They adsorb to the surface of cell membrane of microorganism involved in remediation process and are internalized by cells through energyˇ dependent pathways (Cvanˇ carová, Shahgaldian, and Corvini, 2020). The presence of proteins in cell membranes reduces adhesion in these nanomaterials, improving uptake efficiency. Fig. 2.4 Various unique feature of nano-structures and materials

Highly catalytic Higher Surface to volume

High

Absorbent Nanostructures and materials

Diffusability

High Solubility

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2.4.2 Green Synthesize of Nanoparticles The biosynthesized nanoparticles acquire a coating of proteinaceous and bioactive elements on their outer surface, inheriting the properties of specific plant or living source from which they were synthesized. The particular source acts as a strong reducing agent, containing cellular and extracellular components such as protein, alkaloids, phenols, vitamins, fibers, minerals and enzymes. Enzymes being biological catalysts, contribute to faster reaction rates by lowering the activation energy. For instance, biosynthesized iron-oxide nanoparticles from Aspergillus tubingensis (STSP 25) were found to removed more than 90% of heavy metals like Ni, Pb, Cu, and Zn from wastewater through the adsorption method (Mehanty et al., 2020). Bimetallic nanoparticles of Gold chloride and Silver nitrate were used to remediate pharmaceutical effluent, where the nanoparticles acted as biosorbent for heavy metals like Pb, Zn, Cu, and Mn (Adewoye et al., 2021). A novel method involves converting pollutant metals into nanoparticles using culture filtrate of a fungi Fusarium solani YMM20 (Thangavelu and Veeraragavan, 2022). Some nanoparticles are synthesized extracellularly and then removed through centrifugation (Mohammed.Y and Khedr.Y., 2021). Chitosan-based nanoparticles are used for the removal of Co2 +, Cd2 +, Ni2 +, Fe2 +, and Pb2 + as adsorbent, as the cell walls of fungi are composed of chitin.

2.4.3 Nanoparticles Associated with Enzymes In nano-remediation technology, a significant advancement involves the association of nanoparticles with enzymes to enhance their working efficiency. Enzymes have specific optimal conditions, including temperature, pressure and pH, which restrict their use in various environments. However, by immobilizing enzymes on surface of nanoparticles (which have large surface area and active sites), their stability is improved, as immobilization prevents them from unfolding under non-optimal ˇ conditions (Cvanˇ carová et al. 2020; Salehi and Wang 2022). These nanoparticles with associated enzyme can be used in multiple cycles and can be easily separated from the remediated material. Studies have been conducted on the effect of immobilized peroxidase enzyme in wastewater remediation (Darwish et al. 2019). Magnetic nanoparticles have shown to be more efficient in enzyme immobilization, and they can be easily separated easily under the application of external magnetic field (Elbialy et al. 2019; Goswami et al. 2022). The use of magnetic nanoparticles with immobilized enzymes offers a promising approach for efficient and reusable wastewater remediation.

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2.5 Conclusion Bioremediation is a versatile and environment friendly approach. Despite some drawbacks, fungi offer a cost-effective and harmless method of waste management. Bioremediation is a biotechnical process that utilizes living organisms like plants, microbes, fungi and bacteria to clean up contamination. With increasing global pollution and its severe consequences on human and other living beings, effective remediation methods are crucial. Fungi, as bioremediation agents, play a significant role as decomposers, making them essential in the food chain of ecosystems. They play a major role as decomposer thus an essential part of the food chain in an ecosystem. They also have potential applications in phytoremediation when their genes for enzymes like peroxidases, and laccases are effectively expressed in plants. To ensure successful fungal augmentation, a high-quality, high-potential inoculum is required. Phytoremediation can be enhanced by coupling it with arbuscular mycorrhizal fungi, which are used to treat contaminated soils. White-rot fungi (WRF) play a crucial role in degrading various pharmaceutically active compounds under specific degradation conditions, such as enzymes immobilization and fungal reactors. For example, Aspergillus is capable of degrading Triazol-pyrimidine sulphonamide, while Tortula versicolor can degrade drugs like naxopren and carbamazepine (Rodríguez-Rodríguez et al., 2010) and ibuprofen (Marco-Urrea et al., 2009) derived from wastewater. Various reports advocate that drug like diclofenac, ibuprofen and naproxen are rapidly degraded by WRF, reaching 50% degradation levels after 7 days of incubation (Rodarte-Morales et al., 2011). In wastewater treatment plants, the degradation of pharmaceutical compounds (Phc) can be further enhanced by putting fungi in activated sludge during the secondary treatment. Certain fungal strains have the ability to degrade polychlorinated biphenyl (PCB), which are chlorinated hydrocarbons, and Trichoderma spp. Exhibits high resistance to phenanthrene and benzopyrene on solid media in petri dishes. Some non-ligninolytic fungi thrive at neutral pH by utilizing contaminants as a carbon source. Moreover, fungi demonstrate the capability to transform a wide spectrum of pesticides, highlighting their potential as effective bioremediation agents. 3-Phenoxybenzoic acid undergoes hydroxylation to form 3-hydroxy-5-phenoxybenzoic acid, which is further deoxygenated into gallic acid and phenol. Immobilized Tortula versicolor on Sorghum has been found to effectively remove humic substances, while T. versicolor biofilm in K1 carriers demonstrates efficacy in removing diclofenac. Penicillium chrysosporium and Trametes versicolor are capable of degrading monoaromatic hydrocarbons, particularly BTEX (benzene, toluene, ethyl benzene and xylene). In solid waste management, fungi play a crucial role in increasing the efficiency of side products, such as biogas and volatile fatty acids, released during the transformation of complex molecules into simpler ones, known as microbial transformation. Armillaria gemina and Pholiota adipose enhance the saccharification process of willow and rice straw. Recently research has focused on non-white rot fungi, specifically Ascomycetes, where the P450s enzyme plays a vital role in xenobiotic detoxification. Pollutants that pass through cell wall are

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further converted by membrane cell-bound enzymes, leading to extracellular oxidation via Ascomycetes laccases or hydroxyl radial attacks. Moving on to the discussion of nanomaterial-based membrane and nanoparticle-composed membranes, diverse views are available worldwide. Although conventional membranes have dominated the water treatment field, selecting the most suitable membrane for a specific application can be challenging. Each type of membrane is affected by factors such as flow rate, selectivity, stability or high performance constraints. Additionally, current polymer and ceramic membranes are prone to clogging. Despite efforts to modify the membrane surface through chemical means, such as grafting hydrophilic monomers, the effect on reducing membrane fouling needs further improvement. Among the many proposed concepts, the latest advances in nanotechnology show promising potential in membrane technology. These advancements include compact nanoparticles and nanofiber membranes, aligned nanotube membranes, self-assembled twodimensional layer materials and their composites, which hold the potential to address current membrane limitations and enhance water treatment processes. Generally, nanoparticles films can be obtained by isolating nanomembranes on two dimensional interfaces through dry self-assembly processes, filtration and blown film extrusion in the pores. Several single-component nanomaterial films entirely composed of nanoparticles have been developed, such as compact gold nanoparticles monolayer film, functionalized colloidal gold nanoparticles film, polystyrene nanoparticles for auto-assembled thin nanoporous membranes, bonded protein membranes and a new multi-scale porous structure known as the inverted opal (IO) inside the cavity, where individual particles are nested. The tightly packed nanoparticles monolayer itself consists of dodecanethiol-bound gold nanocrystals, which have recently been demonstrated to form mechanically robust self-supporting films. Another report highlighted a new multi-scale porous structure created using large-scale core–shell self-assembly, where individual particles are embedded in the cavities of the opal reverse structure, where individual particles are embedded in the cavities of the opal reverse structure, and selective removal of the colloidal shell creates structured colloidal particles. These nanomaterials have adjustable internal nanochannels with high permeability and size-selective separation capability, enabling successful testing for nanoparticle separation. Nanofiltration membrane aid in separating toxic particles from water resources and can be used to measure water safety levels without requiring ions like Calcium, Magnese magnesium for filtration and toxicity removal, unlike traditional approaches. However, fouling issues arise in nanofiltration membranes after some time, depending upon optimum temperature pressure, pH and other environmental conditions. Nanomembranes may lose stability over time, leading to reduced efficiency and less favorable outcomes. Consequently, changing the nanomembranes becomes necessary to achieve excellent results, but this process can introduce challenges, including high cost and potential impurities. In conclusion, conventional bioremediation coupled with nano-remediation offers promising prospects for restoring the environment in more appropriate state for better living. Nano-remediation shows potential in removing pollutants, dyes and toxic metals from the contaminated sites, particularly in wastewater remediation. However, sustainable development methods for large contaminated sites, especially

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soil-contaminated areas, still require further attention. It is crucial to address all contaminated sites effectively to ensure successful remediation processes.

2.6 Future Concerns The nanoparticles not only exhibit antimicrobial and anti-cancer activities but also offer benefits in in pollutant remediation. In this review, we aim to highlight the role of nanomaterials in pollutant remediation and how nanotechnology provides a great platform for reducing and eradicating environmentally hazardous pollutants, thereby stabilizing the environment. The development of a country encompasses all aspects, including technology, research and development, construction, production, education or industrialization. Nanoparticles have reached their peak usage, being employed in various field. However, the extensive use of nanoparticles raises concerns. While nanoparticles have vast applications and benefits, their accumulation in the environment is a potential issue that needs attention. Little is known about their toxicity, mobility, reactivity, and persistence in air, water and soil. Therefore, their removal from the environment is essential, as the stress of nanoparticle accumulation has not been extensively studied, and this topic has not received sufficient attention. Recent studies have shed light on the risks of mercury sulphide nanoparticles in the environment revealing their presence raising concerns about their increasing risk to both environment and human health. Additionally, there have been efforts to develop a scaffold for measuring the total soil content of engineered nanoparticles, but effective extraction methods of nanoparticles are still lacking. Hence, novel techniques for separating nanoparticles water, air and soil should be invented to complement the nano-remediation process and reduce the stress of nanomaterial accumulation. More research is required to gain a better understanding of this intriguing avenue in science and address the challenges associated with nanoparticle accumulation and their impact on the environment and human health. Acknowledgements The corresponding author (DK) extends special thanks to Prof. (Dr.) Raj Kumar Mittal, the Vice Chancellor, and Prof. R. K. Gupta, Dean-Academic Affairs (DAA), CBLU, Bhiwani, Haryana (India) for their invaluable help, support and guidance throughout this work, as well as for providing research funding (CBLU/DR2023/20/dt.23-01-2023). The authors express their gratitude to the editors for selecting this work and providing opportunity to contribute in such a specialized area. There is no conflict of interest among any of the authors.

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Ang W-Z, Narayanan S, Hong M (2021) Responsible consumption: addressing individual food waste behavior. British Food J 123(9):3245–3263 Azevedo BD, Scavarda LF, Caiado RGG, Fuss M (2021) Improving urban household solid waste management in developing countries based on the German experience. Waste Manage 120:772– 783 Azubuike CC, Chikere CB, Okpokwasili GC (2016) Bioremediation techniques–classification based on site of application: principles, advantages, limitations and prospects. World J Microbiol Biotechnol 32:1–18 Barles S (2014) History of waste management and the social and cultural representations of waste. Basic Environ History 199–226 Bergeron FC (2016) Multi-method assessment of household waste management in Geneva regarding sorting and recycling. Resour Conserv Recycl 115:50–62 Bing X, Bloemhof JM, Ramos TRP, Barbosa-Povoa AP, Wong CY, van der Vorst JG (2016) Research challenges in municipal solid waste logistics management. Waste Manage 48:584–592 Chang J, Shi Y, Si G, Yang Q, Dong J, Chen J (2020) The bioremediation potentials and mercury (II)resistant mechanisms of a novel fungus Penicillium spp. DC-F11 isolated from contaminated soil. J Hazard Mater 396:122638 ˇ Cvanˇ carová M, Shahgaldian P, Corvini PF-X (2020) Enzyme-based nanomaterials in bioremediation. Adv Nano-Bio Technol Water Soil Treat 345–372 Darwish MS, Kim H, Lee H, Ryu C, Lee JY, Yoon J (2019) Synthesis of magnetic ferrite nanoparticles with high hyperthermia performance via a controlled co-precipitation method. Nanomaterials 9(8):1176 Elbialy NS, Fathy MM, Reem A-W, Darwesh R, Abdel-Dayem UA, Aldhahri M, Al-Ghamdi AA (2019) Multifunctional magnetic-gold nanoparticles for efficient combined targeted drug delivery and interstitial photothermal therapy. Int J Pharm 554:256–263 Girotto F, Alibardi L, Cossu R (2015) Food waste generation and industrial uses: a review. Waste Manage 45:32–41 Goswami R, Agrawal K, Shah M, Verma P (2022) Bioremediation of heavy metals from wastewater: a current perspective on microalgae-based future. Lett Appl Microbiol 75(4):701–717 He K, Chen G, Zeng G, Huang Z, Guo Z, Huang T, Hu L (2017) Applications of white rot fungi in bioremediation with nanoparticles and biosynthesis of metallic nanoparticles. Appl Microbiol Biotechnol 101:4853–4862 Jafari M, Danesh YR, Goltapeh EM, Varma A (2013) Bioremediation and genetically modified organisms. Fungi Bioremediators 433–451 Joshi LM, Bharti RK, Singh R (2022) Internet of things and machine learning-based approaches in the urban solid waste management: Trends, challenges, and future directions. Expert Syst 39(5):e12865 Karagoz P, Bill RM, Ozkan M (2019) Lignocellulosic ethanol production: evaluation of new approaches, cell immobilization and reactor configurations. Renew Energy 143:741–752 Kaur R, Kaur K, Kaur R (2018) Menstrual hygiene, management, and waste disposal: practices and challenges faced by girls/women of developing countries. J Environ Public Health Kaur S, Roy A (2021) Bioremediation of heavy metals from wastewater using nanomaterials. Environ Dev Sustain 23:9617–9640 Khan S, Anjum R, Raza ST, Bazai NA, Ihtisham M (2022) Technologies for municipal solid waste management: Current status, challenges, and future perspectives. Chemosphere 288:132403 Klekotka U, Satuła D, Basa A, Kalska-Szostko B (2020) Importance of surfactant quantity and quality on growth regime of iron oxide nanoparticles. Materials 13(7):1747 Kong L, Ma B (2020) Evaluation of environmental impact of construction waste disposal based on fuzzy set analysis. Environ Technol Innov 19:100877 Krah S, Todorovic T, Magnier L (2019) Designing for packaging sustainability. The effects of appearance and a better eco-label on consumers’ evaluations and choice. In: Paper presented at the proceedings of the design society: international conference on engineering design

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Chapter 3

Hazardous Effects of Heavy Metals from Industrial Wastewaters and Their Remediation Through Green Technology Satish Kumar, Piyal Mondal, and Mihir Kumar Purkait

Abstract Over the years, rapid industrialization has led to the emergence of secondary issues, notably heavy metal pollution and wastewater, which require effective remediation strategies to ensure a country’s economic success. Industrial effluents area major source of harmful heavy metals, such as copper, zinc, cadmium, lead, arsenic, chromium, nickel, and mercury, which contaminate both terrestrial and aquatic environments. Thus, it is imperative to address the removal of these hazardous, non-degradable, and persistent heavy metals from industrial effluent in current scenario. Extensive research spanning numerous years has resulted in the development various simple, effective, and affordable methods for eliminating heavy metals, producing efficient outcomes. The commonly used techniques for heavy metal removal include adsorption, ion exchange, flocculation/coagulation, ion floatation, chemical precipitation and electrochemical approaches. However, these techniques come with certain drawbacks, such as high sludge generation requiring additional treatment, limited rejection efficiency, and high energy consumption. Nonetheless, recent times have witnessed the study of more effective, affordable, and inventive green technologies with superior outcomes. Techniques like hydrogels, membrane filtration, photo catalysis, electro-deposition, electrocoagulation, and the utilization of novel adsorbents have been recently developed for enhance efficiency. This chapter presents a comprehensive description of various industrial effluents contaminated with heavy metals and the conventional treatment methods employed over decades. Additionally, it explores green methods and its innovative mechanisms, which have proven to be more effective than conventional techniques for heavy metal removal and recovery of valuable materials from industrial wastewaters.

S. Kumar · P. Mondal (B) · M. K. Purkait Department of Chemical Engineering, Indian Institute of Technology Guwahati, Assam 781039, India e-mail: [email protected] S. Kumar e-mail: [email protected] M. K. Purkait e-mail: [email protected] © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 A. S. Mathuriya et al. (eds.), Green Technologies for Industrial Waste Remediation, Environmental Science and Engineering, https://doi.org/10.1007/978-3-031-46858-2_3

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Keywords Green methods · Heavy metals · Industrial effluents · Conventional techniques

3.1 Introduction As a result of various pollution sources, wastewater has become contaminated with heavy metal ions, stemming from industrial activities such as electroplating, metal smelting, and electrolysis, as well as environmental pollutants. This accumulation of heavy metals in wastewater poses a significant health hazard (Lee et al. 2012). To address this issue and meet the escalating global water demands, effective wastewater treatment is essential for reclaiming freshwater. Ensuring water safety requires thorough treatment to completely remove these pollutants. Table 3.1 provides information on the properties of typical heavy metals found in wastewater, and various effective methods for their removal have been documented (Saleh 2015; Saleh 2015). Traditional processes including chemical precipitation and ion exchange, have been widely used. The chemical precipitation method is favored for its simplicity, while membrane technology, although efficient, incurs high initial costs (Saleh and Abulkibash 2011). However, the ion exchange method has limitations in exchanging anions and cations in concentrated metal solutions, necessitating continuous pH monitoring and control to ensure effectiveness. Industries recognize the potential these processes in recovering valuable metal resources from the effluent streams, Table 3.1 Characteristics of common heavy metals (Saleh 2015) Heavy metals

Human health effect

Common sources

Maximum contaminant level

Arsenic (As)

. Skin damage . Circulatory system issues

. Naturally occurring . Electronics production

0.010 mg L−1 0.010 mg L−1

USEPA

WHO

Cadmium (Cd) . Kidney damage . Carcinogenic

. Naturally-occurring 0.005 mg L−1 0.003 mg L−1 . Steel manufacturing

Copper (Cu)

. Gastrointestinal issues . Liver or kidney damage

. Naturally-occurring . Household plumbing systems

Lead (Pb)

. Kidney damage . Reduced neural development

. Lead-based products 0.0 mg L−1 . Household plumbing systems

Mercury (Hg)

. Kidney damage . Nervous system damage

. Fossil fuel combustion . Electronics industries

1.3 mg L−1

2.0 mg L−1

0.01 mg L−1

0.002 mg L−1 0.006 mg L−1

Values established by the United States Environmental Protection Agency (USEPA). Values established by the World Health Organization (WHO).

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Table 3.2 Evaluation of recently developed technologies for heavy metals removal (Shrestha et al., 2021) Heavy metals removal technologies

Advantages

Disadvantages

Adsorption with recent adsorbents

Low cost, high metal binding Requirement of adsorbent capacities, wide pH range, easy regeneration, low selectivity, operability, flexibility and design excess waste production simplicity

Hydrogels

Easy operability, low cost, more effective, biodegradable, reusable and recyclable

Nanoparticles and nanotechnology

Suitable for sulfate salts and Costly, prone to membrane hardness ions such as Cu(II) and fouling Cd(II), low-pressure requirement

Membrane separation

Suitable for removal of organic and inorganic wastes, small space requirement, high separation selectivity, low pressure

High operational cost, high energy consumption due to membrane fouling, high concentration of sludge production

Biosorption

Simple operation, no additional nutrients requirement, low quantity sludge, low operational cost, high efficiency, bio-sorbent regeneration and low COD

Highly dependent on pH, temperature, type of bio-adsorbent used, reactive site and agitation speed

Electrodialysis

High separation selectivity, rapid Membrane fouling and high process and effectiveness for energy consumption, formation certain metal ions, economic of large particles, high sludge production

Photocatalysis

No sludge production, effective at lab scale, simultaneous removal of metals as well as organic pollutants, less harmful by-product

Highly dependent on pH, temperature, Metal conc. and nature of the material used

Significant amount of O2 requirement, long duration time, limited application

which not only generate revenue from waste but also improves environmental sustainability. Sulfide precipitation offers an economically viable option for recovering even low metals concentration of aluminum, iron, zinc, copper, or nickel. It has advantages over hydroxide precipitation, including greater reactivity of heavy metal ions with sulfides, lower metal sulfides solubility over a wide pH range, denser and more manageable metal sulfide sludges, and higher selectivity with sensitivity to the presence of complexes (Badmus et al. 2021). However, this method also has drawbacks such as high costs, partial efficiency in ion removal, additional operational costs for sludge disposal, and increased membrane-fouling related operating expenses. In recent years, alternative treatments such as photo catalysis, electrochemical processes, flotation, coagulation, and adsorption have gained significant attention for heavy metal removal in industrial wastewaters. This chapter provides an overview of these technologies, their respective mechanisms, and the advancements in their

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application for effectively removing heavy metals from diverse industrial wastewater sources.

3.2 Heavy Metal Sources in Wastewater Due to their diverse chemical properties, heavy metals, serve various purposes, including applications in electronics, machinery, everyday items, and high-end technologies. Consequently, they can enter the food and water consumed by humans and animals from both natural and human-generated sources and human activities, such as mining dumps, landfill leaches, urban wastewater and industrial effluents from metal-finishing, electroplating and electronic industries. As technological activities continue to generate increasing amounts of metal waste, proper waste disposal solutions have become critically important. In certain bodies of water, the concentration of heavy metal exceeds safety limits set to protect the environment. Notably, heavy metal pollutants have a tendency to adhere to sediments and can accumulate in environment, leading to bioaccumulation in the food chain. Historical cases of environmental pollution due to heavy metal utilization, like copper, mercury, and lead, date back to distant times. Lead, in particular, is one of the most frequently detected pollutants in wastewater. The extreme toxicity of lead is a major concern, as it can cause severe damage to the reproductive system, kidneys, and nervous system. Prolonged exposure to lead can cause permanent neurological damage and encephalopathy (US department of Health and Human Services 2007). Cadmium is commonly found in batteries, solders, ceramics, television sets, photography, insecticides, and has various applications in metal finishing industries and electronic compounds production. Rechargeable batteries, which contain nickel cadmium compounds, are a notable source of cadmium exposure (Faroon et al. 2012). However, exposure to cadmium can lead to several health hazard including bone degeneration, renal dysfunction, liver and blood damage, and carcinogenic effects. Higher concentrations of copper, while essential as a trace element for enzyme activation in the photosynthesis process, can cause toxic effects in the human body. Prolonged exposure to copper dust can result in nose, eyes, and mouth irritation, as well as symptoms like nausea, diarrhoea, and potentially, death (Dahiya 2022). Copper is also harmful to aquatic life, even in small amounts, and its environment presence largely stems from mining, metallurgy, and industrial activities (Bengyella et al. 2022). Zinc is an essential nutrient, but excessive ingestion can be hazardous to health, causing issues such as nausea, vomiting, anaemia and cholesterol imbalances (Ismanto et al. 2023). The main sources of zinc are metallurgical and mining processing of zinc ores, as well as its industrial usage. Coal combustion can also release zinc into air, water and soil. Nickel naturally occurs in volcanic rocks and soil, and its salts are widely used in industry for electroplating, automotive parts preparation, cosmetics, batteries, stainless steel and coins. Nickel–cadmium batteries are also manufactured on an industrial scale. However, when nickel salts enter water bodies, they can contaminate and cause health problems such as nausea, vomiting, anaemia, and cholesterol issues.

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Nickel-loaded effluents from paint formulation and enamelling industries further contribute to water contamination. Additionally, the volatile nickel carbonyl form found in cigarette smoke poses health risks (Wong et al. 2000; Organization 2011). Arsenic naturally occurs in the earth’s crust and was first isolated by Albert Magnus in 1250 AD from ores, deriving its name from the Persian word “Zarnikh,” meaning yellow orpiment (Mudhoo et al., 2011). Its toxic nature and contamination in both surface and groundwater are significant concern. Arsenic in commonly found in water as As(V) and As (III), with its mobility influenced by adsorption and solution pH. In certain regions, arsenic concentration exceed permissible limits, posing serious health risks to living beings (Matschullat 2000). Natural rocks weathering and human activities such as pesticide use, smelting, coal combustion and mining contribute to the increase in arsenic levels. The oxides of aluminium, iron and manganese play a vital role in arsenic adsorption in water bodies, and its presence in high concentrations in drinking water can be hazardous to both human and animal health (Berg et al. 2001). Mercury has been recognized as toxic, illustrated by the tragedy of Minamata Bay in Japan, where contaminated fish caused physical deformities and mental disorders in infants born to affected mothers. Mercury can enter the environment from natural sources like volcanic eruptions, rock and soil weathering, as well as human activities such as industrial use, mining, processing, battery manufacturing, and the use of mercury vapour lamps. Methyl mercury represent the most toxic form of mercury. In the industry, there is extensive use of chromium compounds, leading to the release of large amounts of toxic chromium-loaded wastewater into water bodies. This contamination of water bodies with heavy metals can occur through volcanic eruptions and geological weathering of rocks. Additionally, anthropogenic sources like fossil fuel burning, plastic manufacturing, and metal electroplating also contribute to this issue (Mohan, Singh and Singh, 2006). Chromium exists in both hexavalent and trivalent forms, with hexavalent chromium being considered more toxic and hazardous in nature.

3.3 Various Conventional Method for Removal of Heavy Various chemical and physical traditional methods, including adsorption, ion exchange, ion floatation, coagulation/flocculation, chemical precipitation, and electrochemical processes, have been utilized to remove significant amount of heavy metals. Figure 3.1 provides an overview of the numerous techniques developed for metal elimination from the environment, encompassing membrane separation, adsorption, photocatalysis, electrochemical and gravity settling. This chapter delves into recent technological advancements, discussing their associated benefits and drawbacks in effectively removing heavy metals from industrial effluents. Prior to that, a brief overview of the traditional techniques was presented.

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Fig. 3.1 Currently utilized methods for removing heavy metals from industrial effluent (Shrestha et al. 2021)

3.3.1 Adsorption Adsorption is a phenomena in which a specific substance attaches to the surface of a solid through chemical bonds or physical forces. The substance that binds to the solid surface is called the adsorbate (pollutant), while the solid surface itself is referred to as the adsorbent. The adsorption of heavy metals involves three sequential steps: the transportation of heavy metals from bulk solution to the surface of absorbent, the adsorption on the particle surface, and internal movement within the adsorbent particle. Several factors can influence adsorption, including temperature, the type of adsorbent and adsorbate, the presence of additional contaminants, ambient conditions, and experimental circumstances such as pH, pollutant concentration, adsorbent particle size, and contact time. However, the effectiveness of the procedure may decrease in the presence of suspended particles, oils, and greases, necessitating occasional pre-filtration (Ali and Gupta, 2006). Many adsorbents have been extensively researched, including graphene, activated carbon (AC), carbon nanotubes (CNTs), organic wastes such as fruit peels and vegetable peels, zeolite, chitosan and others (Renu et al. 2016; Singh et al., 2018). Activated carbon has been a significant and primary choice for recycling and treating

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industrial and municipal wastewater to produce drinkable grade water due to its excellent adsorption capability, attributed to its tiny particle size, active free valences, and large surface area. However, its widespread use for water treatment is hindered by the high cost of manufacture and regeneration. Studies on coir pith carbon revealed that the highest removal rates for Cu(II), Hg(II), Pb(II), Cd(II), and Ni(II) were 73%, 100%, 100%, and 92%, respectively, at specific pH levels (Kadirvelu et al. 2001). Santhy et al. discovered that metal ion adsorption was ineffective at pH levels below 3 and only efficient at pH levels above 6 (Santhy and Selvapathy 2006). The effectiveness of metal ion adsorption (Cu(II), Cd(II), and Zn(II)) on porous carbon was studied in batch mode operation, and it was found that pH, contact time, carbon dosage, and initial concentrations of metal-ion all increased with prolonged contact time. The presence of common anions like chloride and sulfate did not affect the elimination of metal ions up to 3000 mg/L. Nickel demonstrated the highest removal rate of 90% by AC, but the removal rate decreased as the heavy metal concentration increased (Karnib et al. 2014).

3.3.2 Ion-Exchange The ion exchange method, which involves utilizing dissolved pollutants in the form of ions, is another effective approach for water treatment. This method relies on temporarily retaining ions and facilitating the removal of impurities from the solution. Ion exchange is used to disinfect, soften, deionize, or de-alkalescent water. It can be tailored and utilized for various purposes, including the selective removal of different pollutants, and bed polishing. For water filtration, zeolites, montmorillonite, artificial organic resin, polymeric resin, and humus organic dark soil can serve as exchange media. These ion exchangers may consist of anion, cation, or amphoteric species. Various optimization goals can be explored for ion exchange. For instance, improving the contact duration can lead to smaller equipment size while using less resin to achieve higher removal rates. Anionic resins are often employed when there are fewer contaminants present, whereas cationic resins, including weak acidic resins with the (-COOH) group and acidic resins with the (-SO3 H) group, are more frequently used (Fu and Wang, 2011; Zhao et al., 2016)., as depicted in the following equations: ) ( n M − S O3 H + M n+ → R − S O3− n M + n H + ) ( n M − C O O H + M n+ → R − C O O − n M + n H + (M = Metal).

(3.1)

(3.2)

However, ion exchange has certain drawbacks, such as the necessity for a pretreatment procedure, due to the need for chemical reagents to recover the resins Additionally, the presence of grease or oil necessitates their removal, leading to potential secondary pollution. The selectivity of ion exchange resins for heavy metal removal

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further exacerbates these limitations, making this technique less effective in the presence of other contaminants.

3.3.3 Flocculation/coagulation Coagulation and flocculation have long been utilized to eliminate dissolved pollutants and suspended particles from water. These processes are highly cost-effective and effective compared to other water treatment technologies However, removing clumps of particles in suspension can be challenging due to the repelling electrostatic force caused by the negative charge on suspended particles. The coagulation technique is employed to address this issue, where coagulants are introduced to enhance particle collisions and reduce adverse forces. This results in the formation of substantial amounts of flocs and agglomerates, which can be eliminated using appropriate filtration or sedimentation techniques. Temperature-controlled chemical additions are employed to regulate the coagulation process. Three types of coagulants are used: inorganic polymers, organic polymers, and electrolytes. Inorganic polymers include various compounds of iron and aluminium, such as ferrous sulphate, aluminium chloride, ferric chloride, and aluminium sulphate. Organic polymers, also known as synthetic polyelectrolytes, contain cations and anions functional groups in their backbones as coagulants. In the flocculation process, particles are precipitated out of the water and then physically removed. High molecular weight polymers are added to the mixture to clump the particles together, transforming them into microflocs that are easier to remove. Coagulation-flocculation can be used in combination with other traditional methods to effectively remove metal effluents from water waste. Figure 3.2 illustrates the comprehensive representation of heavy metal removal through coagulation-flocculation process. Soares et al. investigated the most suitable procedures for the removal of Cr3+ , 2+ Zn , Cd2+ , Ni2+ , and Cu2+ , from industrial effluents, namely bioremediationflocculation and sedimentation (Soares et al. 2002). Additionally, other studies discuss purifying water on an industrial scale through well-established methods like electrocoagulation and flocculation.

3.3.4 Precipitation The concept behind this method is to chemically bond undesirable particles with another substance. In this approach, wastewater is treated by introducing a different chemical component, leading to a chemical reaction that entraps particles and converts them into solids, which can then be separated later. In water, various heavy metals from different chemical processes can be present as byproducts. To address this, caustic soda and limestone are added to the wastewater containing heavy metals. Under alkaline pH conditions, these metals form metal hydroxide or carbonates. The

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Fig. 3.2 Coagulation and flocculation method for heavy metal removal representation (Shrestha et al. 2021)

addition of these chemicals increases the pH of wastewater, causing the conversion of metals into hydroxide and carbonate molecules. These hydroxides, sulphides, and carbonates can be easily separated as they are insoluble in water. This characteristic of metals is utilized in water treatment. Chemical precipitation offers several advantages, including low cost, a straightforward process, and non-metal selectivity (Ismanto et al. 2023). However, it produces a significant amount of sludge that poses challenges in proper disposal. Disposing of the sludge left over after the treatment requires considerable effort. Additionally, this method is less effective when the water contains extremely low amounts of metals. A similar process can be used for the precipitation of sulphides, with sodium and hydrogen sulphides being the two most commonly utilized options within the same pH range. Chen et al. (2018)investigated a typical chemical precipitation procedure for the removal of heavy metals such as Zn (II), Pb (II), and Cu (II) from aqueous solutions (Chen et al. 2018).

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3.3.5 Electrochemical Treatment Since 1889, electricity has been utilized water purification, with this technology first developed in the United Kingdom. It is considered one of the most effective approaches globally due to its sludge-free nature and autonomous handling system, making it a preferred among many technologists. However, this method is highly costly as it requires a constant source of electricity. Consequently, several countries, due to the high cost of electricity, have opted for more traditional water purification methods instead. Among the traditional electrochemical treatment techniques are electrocoagulation, electrodeposition, electrodisinfection, electroxidation, and electroflotations. In electrocoagulation, impurities can float when electrocoagulated using hydrogen gas generated at the cathode, andcoagulants are formed on the anode through electrolytic oxidation of the anode materials. Targeted metals can be extracted from the medium when they interact with the ion of opposing charge and/ or metallic hydroxide floc generated among the impurities. The electrode arrangements in typical electrocoagulation setups can be either monopolar or bi-polar. For instance, the use of monopolar configuration of iron electrodes at basic pH can efficiently remove metals like Cu, Zn, Mn, and Ni (Al Aji, Yavuz and Koparal, 2012). In certain scenarios, electrocoagulation with adsorption/complexation can be oxidize As(III) to produce As(V). Efforts have been made to reduce the cost associated with electrochemical water treatment. Additionally, using platinum plate and stainless steel AISL904Lplates are used to removal of Cu(II) from industrial contaminants rather than three-dimensional electrodes. The use of foam with a larger surface area has shown effective treatment of effluents, although it can increase the process cost. The effectiveness of advanced oxidation and electrochemical processes, along with their models, labs, and applications, were described by Oke et al. (2020). Studies utilizing a monopolar configuration demonstrated that COD and colour removal from various industrial wastewater were more efficient with electrochemical oxidation compared to a bipolar setup (Nidheesh et al., 2020). It was found that treating industrial water with a tin dioxide anode can reduce water and electrolyte usage by up to 70% (Orts et al. 2020). An evaluation of the effectiveness of the electrochemical advanced oxidation technique in treating industrial wastewater was published in 2018 (Garcia-Segura et al. 2018).

3.4 Green Method for Removal and Recovery of Heavy Metals from Industrial Effluent Coagulation/flocculation and chemical precipitation are known to be the simplest and least expensive of the conventional technologies. It has been found that highly acidic effluents are not efficiently treated by these technologies. Toxic sludge is produced in large quantities, which is further treated chemically for stabilization and then disposed of properly. Studies with adsorbents have shown tremendous results with

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high removal efficiency of heavy metals; however, they require high energy, removal rates are low, limiting capacity is high, and reduction rate is slower. Ion-exchange is both economical and effective, but has several drawbacks including fouling of the ion exchange media by the metallic, oil, clay, grease, and organic materials (Le and Nunes 2016). Metal recovery is generally difficult to achieve after cleaning. The maintenance cost of the process generally increases due to the cleaning program. In addition, the presence of free acids reduces the treatment efficiency. It has been observed that increasing ionic strength leads to a decrease in removal efficiency, and ion floatation technology is highly dependent on pH and temperature (Vel˙i and Pekey 2004). Removal efficiency is affected by temperature, in addition to surfactant concentration. To better address the problem posed by the high cost of sacrificial electrodes, and for the need for rapid and efficient operation, a number of novel methods and technologies have been developed, which are summarized below.

3.4.1 Membrane Filtration Process In the membrane separation process, a semi-permeable membrane is used to force feed water is forced under high pressure, to remove the pollutants from solution. Membrane separation process can be classified based on pore diameter into microfiltration (MF), ultrafiltration (UF), nano-filtration (NF), and reverse osmosis (RO). The permeability of the membrane, pressure, temperature, and molar concentration influence the molecular diffusion rate across the membrane. The separation of materials through membrane is based on three principles: adsorption, sieving, and electrostatic phenomena. Adsorption occurs when hydrophobic interactions exist between the membrane and the solute. The separation efficiency of materials is also determined by the membrane pore size and solute diameter. Consequently, membrane pore size and the solute diameter. various membrane processes with distinct separation methods have been developed (Nqombolo et al. 2018). The increasing popularity of polymeric membranes today is due to their high mechanical strength, flexibility, and ease of fabrication. Water-soluble polymers are widely utilized in polymer enhanced ultrafiltration processes (PEUF) for rapid adsorption of metallic ions present in wastewater. The solution pH plays a vital role as the interaction of the metallic cations with acidic functional groups depends on it. The sorption capacities follow the order: SO3 H > P(O)(OH)2 > COOH, whereas opposite trend is obtained for selectivity: COOH > P(O)(OH)2 > SO3 H (Beaugeard et al. 2020). Evaluating g the cost-effectiveness of materials is a crucial step when considering their use. Polymers can also act as super adsorbent, offering an alternative solution for efficient wastewater treatment. Polyacrylonitrile (PAN) and Arabic gum (AG) were graft co-polymerized using redox activator such as KMnO4 /HNO3 in aqueous solution (Dutta and De 2017). The grafted copolymer was chemically modified by reacting with hydrazine hydrochloride„ followed by hydrolysis in a a basic medium. The synthesized grafted polymer was then used for treating wastewater to extract Cu2+ , Pb2+ and Cd2+ . The highest adsorption capacities were found to be

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1017 mg/g for Pb2+ , whereas for Cu2+ and Cd2+ and approximately 413 and 396 mg/ g for Cu2+ and Cd2+ respectively. Recently, a wide range of materials have been investigated for constructing membranes and absorbents to identify optimal removal efficiency. Aromatic conjugated polymers (ACPs) like polyaniline and polypyrrole exhibited superior metal elimination efficiency due to their high surface area, and charge density, allowing them to capture metal ions effectively. The efficiency of polymeric membranes for aqueous metal separation largely depends on membrane porosity (Jasiewicz and Pietrzak 2013).

3.4.2 Photo Catalysis Photo catalysis is an oxidation process widely used in wastewater treatment and considered a highly promising technique that surpasses other methods. It was developed for environmental purposes, including hydrogen evolution, inspired by research on photosynthesis. Semiconductors such as TiO2 , ZnO, CeO2 , CdS, ZnS, etc. are utilized in photocatalytic processes due to their well-known photocatalytic properties (Daghrir et al. 2013). Photo catalysis exhibits a potent oxidizing ability, enabling it to break down heavy metal complexes and separate them from the metal ions. Simultaneously, it can oxidize and decompose organic complexes (Alansi et al. 2021). Figure 1 illustrates the basic mechanism of photo catalysis. When semiconductors are illuminated, electron–hole pairs are created in the conduction and valence bands, respectively. These charge carriers move and have a redox potential, leading to the splitting of H2 O molecule, generating OH radicals, while adsorbed oxygen captures the electrons (Buzzetti et al. 2019). The fundamental mechanism of photo catalysis involves three main stages. Firstly, charge carriers are generated when high energy light or light with energy equal to the bandgap of the semiconductor is applied. Secondly, the electron–hole pair created moves to the surface of the semiconductor, where electrons move from the valence band (vb) to the conduction band (cb) of the photocatalyst. Finally, the generated holes oxidize the H2 O molecule, producing ·OH, while O2 molecules are reduced to form superoxide radical anion (O2− ) by the electrons present in the conduction band, as shown below Eq. (3.4)–(3.6) (De Lasa, Serrano and Salaices, 2005). − + M O + hv → ecb h vb

(3.3)

( −) M O ecb → oO 2−

(3.4)

+ M O(h + vb ) → H + oO H

(3.5)

Pollutant + R O S → Co2 + H2 O + Degradation Pr oduct

(3.6)

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Photocatalytic materials, primarily, metal oxides such as ZnO, TiO2 , CdS, and CuO have been extensively utilized for treating wastewater to remove various pollutants, both organic and inorganic in nature. TiO2 based photocatalytic reduction of arsenate (As) is shown in the following Eq. (3.7)–(3.11), carried out in the presence of hydroxylmethyl radical, known for its strong reducing properties (De Lasa et al. 2005). − T i O2 + hv → ecb + h+ vb

(3.7)

+ H2 O + hvvb → H + + oO H

(3.8)

C H3 O H + oO H → oC H2 O H + H2 O

(3.9)

oC H2 O H + As(V ) → C H2 O + As(I V ) + H +

(3.10)

− − As(I V ) + ecb /etrap (oC H2 O H ) → C H2 O + As(I I I ) + H +

(3.11)

In 2019, Chen et al. (2019) provided an overview of the methods and challenges involved in enhancing polarization to promote activation of molecular oxygen and charge separation induced by photo- and piezoelectric effect (Chen et al., 2019). Additionally, Dhandole et al. (2020) synthesized a composite of TiO2 nano-rod doped with rhodium/antimony and titanate nanotube (RS-TONR/TNT) tor study the removal efficiency of organic pollutants and heavy metals from wastewater (Dhandole et al., 2020). Zhao et al. (2012)conducted a study on the optical, electronic, and structural properties of BiOX (X = Cl, Br, I) based on Density Functional Theory (DFT) (Zhao et al., 2012). In this study, conduction bands minimum (CBM), valence band maximum (VBM), absorption coefficients, state densities, and atomic charge population of the material were computed (Zhao et al., 2012). They established that BiOX crystals have promising potential as photocatalytic semiconductors. In their review article, Yang et al. (2018) showcased how the photocatalytic activity of BiOX can be enhanced and provided a holistic approach for designing nanomaterials based on BiOX for photocatalysis (Yang et al. 2018). They elaborated on the multiple crystal facets of BiOX, the specific internal electric field (IEF) of BiOX, and the potential of BiOX nanomaterials for hydrogen production through photocatalytic water splitting. Al-Sherbini et al. (2019)presented the production of Chitosan thin films doped with Ag nanoparticles, which were employed for various applications, such as the photo-oxidation of organic pollutants, the removal of heavy metals, and the display of antibacterial properties. The outcomes demonstrated that the CS/Ag bio-nanocomposites exhibited a favorable photodegradation rate, efficient removal of heavy metals, and significant antimicrobial activity (Al-Sherbini et al. 2019).

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3.4.3 Electrocoagulation Electrocoagulation involves using electrodes as anode and cathode, leading to oxidation and reduction, along with various physicochemical processes like coagulation, adsorption, and reduction. This technique is cost-effective and easily manageable for large-scale removal of heavy metals from industrial wastewater (Arroyo et al., 2009). Electrocoagulation has been successfully employed to treat wastewater containing dyes, heavy metals, nitrates, fluorides, and phenolic compounds. Recent studies have focused on its application for removing heavy metals from wastewater (Kongsricharoern and Polprasert, 1995). One such study by Golder et al. (2007a, b) examined the efficacy of electrocoagulation for eliminating Cr3+ from aqueous solutions (Golder et al. 2007b) using iron electrodes. They observed that both coagulation and adsorption mechanisms played crucial roles in removing Cr3+ during electrocoagulation. The highest removal of Cr3+ from aqueous solutions was achieved at higher current densities using a multi-electrode electrocoagulation system with both bipolar and monopolar configurations (Golder et al. 2007a). However, the high cost of the resin used in this technique makes it expensive for large-scale industrial applications, despite its ability to treat pollutants down to parts per billion (ppb) levels. To remove Cr6+ from aqueous solutions, Gao et al. (2005) employed a combination of electrocoagulation and electro-flotation systems (Gao et al., 2005). Heidmann and Calmano (2008) conducted a systematic study on the efficiency of electrocoagulation system utilizing aluminum electrodes for removing heavy metal ions in a laboratory setting (Heidmann and Calmano 2008). Akbal and Camcı (2011) also studied heavy metal removal from wastewater through electrocoagulation process utilizing iron and aluminum electrodes in monopolar configurations (Akbal and Camcı 2011). They investigated how electrode material, current density, wastewater pH, and conductivity affected removal efficiency. Their findings showed that using an electrocoagulation system with Fe-Al electrodes was effective, achieving 100% removal of Cu, Cr, and Ni observed within 20 min at a current density of 10 mA cm−2 and pH of 3.0. Furthermore, Adhoum et al. (2004) conducted research on the effectiveness of electrocoagulation with an aluminum sacrificial anode for treating wastewater contaminated with metal ions (Adhoum et al. 2004). Their findings demonstrated successful removal of Cu, Zn, and Cr, with the technique proving highly efficient and relatively speedy when compared to conventional methods. Additionally, direct electrochemical reduction of Cr6+ can be achieved at the cathode (CENKIN and BELEVTSEV 1985), where hydroxyl ions generated facilitate the co-precipitation of Cu, Zn, and Cr.

3.4.4 Ozonation Wet oxidation is a type of chemical oxidation that is particularly effective for removing organic contaminants rather than inorganic ones like heavy metals. This

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method employs air or oxygen as an oxidizing agent, although other forms of oxidation, such as chlorine, ozone, and hydrogen peroxide, require an electrical current to induce a redox reaction. While nanomaterials can be utilized in this process, they also come with some drawbacks. Chlorine, even in small amounts is a hazardous gas and can produce hazardous contaminants that need to be addressed after remediation. Moreover, ozone has toxic effects in small concentrations and generates hazardous by-products, demanding significant energy. The production of hydrogen peroxide also necessitates substantial energy due to the high temperature and pressure involved in wet oxidation (Martínez-Huitle and Ferro 2006). In Hu and Xia’s (2018) study, ozone MBs were employed to remediate TCE from groundwater (Hu and Xia 2018). Zhang (2020) also demonstrated the effectiveness of PS with BCnZVI for the remediation of TPHs from soil, involving both chemical degradation and biodegradation (Zhang et al. 2020). Ozonation is an attractive method for effluent treatment due to its ability to degrade toxic organic compounds, thus enhancing biodegradability of the effluent. Ozone serves as an effective oxidizing agent, selectively oxidize double bonds and aromatic structures (Maddila et al. 2013). It operates through two mechanisms when attacking organic compounds: direct ozonation with ozone molecules and indirect free radical mechanism involving highly oxidative hydroxyl radicals. While ozone molecules can readily break down aromatic organic pollutants by disrupting the aromatic ring and forming intermediary compounds such as small chain carboxylic acids, aldehydes, and ketones (Ikhlaq, Brown and Kasprzyk-Hordern, 2015), these intermediates are not easily susceptible to ozone attack and therefore accumulate in the solution. This renders direct ozonation less efficient in achieving a high rate of degradation rate. In contrast, indirect free mechanisms, such as the transformation of ozone molecules into hydroxyl radicals, exhibit greater oxidation capability than ozone molecules, making them more effective at achieving a high degradation rate. Hydroxyl radicals are non-selective in nature, capable of breaking down all types of organic and inorganic compounds (von Gunten 2003). Despite its numerous advantages, ozonation is constrained by the short half-life of ozone, necessitating a continuous ozone generation, leading to increased energy consumption and higher operating costs (Tang et al. 2016). To improve the cost-effectiveness of t the effluent treatment process, it is crucial to optimize ozone generation and usage. Combining ozonation with hydrogen peroxide, UV light, biological treatment, or catalysts can enhance the hydroxyl radicals production, thereby increasing degradation efficiency and reducing operational time and cost (Gómez-Pacheco et al. 2011). A more recent approach, catalytic ozonation, has been shown to effectively remove all types of organic matter from the effluent (Wang et al. 2016).

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3.4.5 Biological Treatment of Organic and Heavy Metals-Laden Water Ahmad et al. (2017) emphasized the significance of using bacteria and microorganisms as a primary approach for addressing environmental pollution (Ahmad et al. 2017). Numerous studies have reported their effectiveness in degrading heavy metals and organic pollutants. However, there are certain limitations associated with their usage. For instance, not all microorganisms can degrade all types of pollutants. Moreover, the presence of growth-inhibiting factors such as electron acceptors or donors (sulphate, oxygen and nitrate) can hinder their activity and growth (Edwards and Kjellerup 2013). Biosorption offers several advantages over other methods, particularly in its potential to recover pollutants, especially heavy metals, and it is a cost-effectiveness, allowing for the regeneration of the microorganisms used (Ajao et al. 2020). Various studies have addressed the challenges associated with this method, and simultaneous removal of both organic and heavy metal pollutants has been demonstrated. In a study by Wang et al. (2007), expired milk that had undergone fermentation and bactofugate were separately used to biodegrade organic matter in leachates containing iron (II) and chromium (III). Both heavy metals and organic matter were efficiently removed, with expired milk showing higher removal efficiency than bactofugate (Wang et al. 2007). The removal of organic matter was assessed by measuring the chemical oxygen demand (COD), while detailed kinetic investigations showed that reductive elimination was responsible for removing 90% of the heavy metal ions from the leachate (Wang et al. 2007). Biofilms have been employed to explore the possibility of degrading multiple organic pollutants and heavy metal ions simultaneously. Due to their structural holes, biofilms possess water channels, exchange genetic material, and can withstand predators, pH changes, and toxic chemicals, making them ideal for this important task (Edwards and Kjellerup 2013). Kılıç et al. (2007) isolated three different bacteria from textile and tanning wastewater using ribosomal RNA analysis, namely Pseudomonas aeruginosa, Salmonella enterica, and Ochrobactrium sp (Kılıç et al. 2007). This bacterial consortium effectively treated hexavalent chromium and dye pollutants simultaneously and performed better than the supplemented sludge from which they were isolated. Similarly, Chirwa and Wang (2000) reported that a consortium of anaerobic bacteria augmented with Escherichia coli ATCC 33,456, an organism capable of reducing reducing chromium(VI), jointly eliminated phenol and chromium(VI) (Chirwa and Wang 2000). An increase in the amount of degraded phenol was observed to increase the amount of reduced chromium(VI), demonstrating the synergistic effect for their simultaneous removal.

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3.5 Advancement in Green Technologies and Future Prospective 3.5.1 Hybrid Methods In recent years, several novel and hybrid treatment methods have been extensively researched to address the ineffectiveness of traditional treatment methods in successfully removing various types of heavy metals. The integrated or hybrid approach leverages the advantages of existing treatments to overcome limitations and constraints. These hybrid systems significantly reduce the exposure of heavy metals in wastewater treatment plant (WWTP) effluents. Typically, the physical and/ or chemical remedies are incorporated into hybrid systems following the biological treatment technologies. The following subsections offer a detailed explanation of numerous combinations that can be used in such hybrid systems for the effective removal of heavy metals.

3.5.1.1

Adsorption- Membrane Filtration Method

Due to the non-biodegradability of the majority of heavy metals, such as lead and cadmium, their presence in water and wastewater poses a serious threat to human health (Senguttuvan et al. 2021). In a hybrid system utilizing an adsorbentultrafiltration membrane, cadmium and lead were successfully removed using a polyethersulfone ultrafiltration membrane (MWCO = 20,000 Da) with Aceh natural zeolite as a adsorbent (adsorbent dose = 10–100 mg L−1 ) (Mulyati and Syawaliah 2018). The adsorption process in the initial 20 min exhibited rapid adsorption, followed by a gradual increase in the amount of adsorbed metal until equilibrium was reached after 80 min. This phenomenon was attributed to a reduction in the active sites of the adsorbent or the available contact surface area. Moreover, the amount of metal ions moving from the bulk liquid phase to the adsorbent’s active site determined the adsorption capacity (Jiang et al. 2010). The solution pH played a significant role in the chemical equilibrium between adsorbate and adsorbent, as well as the surface charge of the adsorbent. Cadmium and lead adsorption increased rapidly as the pH increased in the range of 2 to 9, with the peak adsorption occurring at pH 7. However, the post treated water samples did not meet the drinking water quality criteria (10 and 5 g L−1 for Pb and Cd, respectively). The maximum reductions achieved by zeolite adsorption for cadmium were 86% and 89%, respectively. Moreover, after membrane removal, the permeation values of Pb and Cd were 242 and 210 g L−1 , respectively. Integrating adsorption and UF membrane removal techniques in a hybrid approach may be effective in reducing the levels of Pb and Cd in water (Mulyati and Syawaliah 2018). Strong acidity and high concentrations of inorganics, organics, and particulate matter are common characteristics of the wastewater from metal-plating industry. In a study, actual samples of hazardous metal-plating industrial effluent (TSS = 102 mg

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L−1 , pH 2, COD = 463 mg L−1 , Cu = 51 mg L−1 , Zn = 4.2 mg L−1 , Cr = 332 mg L−1 , and Ni = 186 mg L−1 ) were treated using a submerged Al2 O3 ceramic microfiltration (MF) membrane with pore size of 0.1 μm in combination with fluidized AC granules as the adsorbent (Chang et al. 2020). When the untreated wastewater was neutralized, it caused colloid formation and aggregation of particle (At pH 7, the average aggregate size expanded from 10.1 μm at pH 2 to 28.7 μm), leading to fouling at the membrane surface and a significant reduction in membrane flow. The point of zero charge of the aluminium oxide ceramic membrane was determined to be 5.4 (Gulicovski et al. 2008), and at a pH of 2 for the raw wastewater, the membrane became negatively charged, resulting in the rejection of heavy metal cations However, at pH 7, charge neutralization increased the concentration of suspended solids from 100 to 450 mg L−1 due to colloid precipitation and particle aggregation. Although the membrane exhibited high rejection rates for Zn, Cu, Cr, and Ni (98%, 48%, 59%, and 81%, respectively), the membrane pressure increased rapidly at pH 7. The ceramic MF membrane with fluidized adsorbent system failed to remove any heavy metals when the pH level was 2. The production of many metal–organic particle complexes, which the membrane can easily remove, was thought to be the cause of the increased effectiveness of heavy metal rejection at alkaline pH levels solution (N˛edzarek et al. 2015). Furthermore, the cake layer formed by the total suspended particles in raw wastewater on the membrane surface could also function as a secondary membrane, enhancing the membrane’s capacity to remove heavy metal ions. In the removal of Cd, Co, Hg, Pb, and Ni from highly polluted river water, a novel hybrid system of adsorption-membrane was used. Functionalized MWCNTs served as the adsorbent, while a highly non-hydrophobic ceramic membrane with pore dimension of 0.2 m showed minimal membrane fouling (Ainscough et al. 2017). Initially, the membrane had a high permeation rate approx. 1400 L m−2 h−1 bar−1 for clean water. However, when exposed to a severely polluted feed water sample containing used motor oil reduced to about 100 L m−2 h−1 bar−1 and remained constant over time (10 days). Due to the easy rejection of microorganisms, MF membranes with small pore sizes are expected to have high removal capability. The adsorbent demonstrated extremely high removal efficiencies (99.3% and 99.5%, respectively) for hydrocarbons and selective heavy metals. In addition, the adsorbent was easy to regenerate using a 50% w/v aqueous acetic acid solution, and the regenerated adsorbent exhibited nearly identical removal rates to the fresh adsorbent (Ainscough et al. 2017). In a separate investigation focused on Ni removal, a hybrid PAC-MF membrane system with surfactant enhancement was utilized. The surfactant created an additional membrane layer on the surface and within the membrane pores, resulting in greater steric effects and an increase in the system’s removal capacity when the concentration exceeded the critical micells concentration (CMC) (Aydiner et al. 2006). However, it was observed that the steady-state flow of the system significantly decreased, which was a significant drawback, even though the membrane flux varied greatly with the pore size, type of surfactant, membrane material, and concentration.

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Hybrid Systems Using Advanced Oxidation Processes

Emerging experimental researches has shown that advanced oxidation processes (AOPs) are highly effective in treating various types of heavy metals (Rosman et al. 2018). Hybrid systems have been developed to enhance the effectiveness of the various physical and biological treatment processes by incorporating the unique characteristics of AOPs, such as ozonation, ultrasonic radiations, gamma radiations, and others. Nguyen et al. (2013) investigated the removal of emerging contaminents (ECs) using UV oxidation in combination with the MBR treatment. While UV oxidation can breakdown persistent and hydrophilic molecules, the presence of bulky organic materials reduces its effectiveness (Nguyen et al. 2013). To address this, applying UV oxidation as a polishing stage in conjunction with the MBR permeate significantly improved the overall removal efficiency of the entire system (Chong et al. 2010). The combined MBR and UV oxidation procedures demonstrated good removal of all of the targeted ECs. Most ECs were eliminated by more than 95% except for fenoprop (94%), ketoprofen (93%), salicylic acid (92%), carbamazepine (90%) and metronidazole (85%). Some ECs, such as E1, naproxen, and ibuprofen, were totally eliminated. Given that it was marginally removed by MBR (32.17%) and UV oxidation (30.7%) when used separately, carbamazepine is regarded as a biologically resistant molecule. Nevertheless, when these two processes were used in combination, carbamazepine was removed with a removal efficiency of 90%. The MBR-UV oxidation system is the promising hybrid system for the elimination of different types of contaminants, according to the study’s overall findings.

3.5.2 Nano Remediation Numerous environmental applications of nanotechnology exist, including monitoring, cleanup, and pollution detection and prevention. Land, water, and air pollution poses a significant risks to our environment today. Various techniques, such as adsorption, chemical reactions, filtering, and photo-catalysis, can be used to remove a wide range of pollutants, including agricultural effluents, toxins, heavy metals, trash, herbicides, oil spills, and fertilizers. Nanomaterials have unique properties that make them suitable for removing harmful toxins from the environment. This emerging technology is affordable, safe, and environmentally friendly. Consequently, making it a potential alternative to traditional remediation techniques like solidification, soil vapour extraction, soil thermal desorption, and groundwater pump and treatment systems. Nanomaterials offer greater reactivity and productivity than traditional materials due to their larger surface area. They can be designed and synthesised with functional groups that enable selective and effective pollutant remediation through special surface chemistry. Moreover, their physical characteristics, such as porosity, can be modified to enhance their capabilities further. Biodegradable nanomaterials are

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particularly effective for cleanup, as they leave no trash or contaminants behind after the process is completed. The continued presence of Cu As, and Pb in aquatic environment at levels exceeding permissible limits has detrimental effects on human health. Scientists have synthesized numerous functionalized nanomaterials with reactive surface groups that effective adsorption of hazardous metals. For instance, ultrafine magnesium ferrite (Mg0.27 Fe2.50 O4 ) nanocrystallites have recently been reported to exhibit effective removal capabilities for both As(IV) and As(III) (Tang et al., 2013). The nanocrystallites exhibit supermagnetic characteristics, a large surface area (482 m2 /g), and adsorption efficiency of 83.4 mg/g and 127.4 mg/g, for As(III) and As(V) respectively. Similarly, a core–shell form of Fe-Ti bimetallic oxide on magnetic Fe3 O4 has been utilized as a nanoadsorbent for the neutralization of fluoride from drinking water and wastewater. Magnetic bio adsorbent with core–shell have outstanding adsorption and regeneration ability in multiple cycles (Aiswarya et al., 2022; Aiswarya and Das, 2023). This nanoadsorbent demonstrates excellent adsorption capacity and super magnetic behaviour with fluoride removal adsorption efficiency of 57.22 mg/g. In both cases, magnetic techniques can be used to separate the adsorbents, allowing for their reuse in removing contaminants. Moreover, the elimination of Cu(II) was accomplished by cyclodextrin-modified Fe3 O4 attributable to the significant adsorption capabilities of hydroxyl and carboxyl moieties on the carboxymethyl-bcyclodextrin (Badruddoza et al., 2011). The adsorption mechanism was temperature and pH-dependent and followed second-order kinetics. The Langmuir model fits the adsorption capacity for Cu(II) removal was found to be 47.3 mg/g. Furthermore, the nanoadsorbents exhibit a high recycling rate, with a 96.2% desorption ability, making them suitable for repeated use.

3.5.3 Other Emerging Simultaneous Removal Strategies Researchers continue to explore effective methods for simultaneous removal of organic and heavy metal contaminants from water, seeking environmentally friendly approaches (Altenburger et al., 2018). Yuan and coworkers investigated the use of sulphide and oxygen to break down hazardous chromium (VI) in an environmental sample, leading to the formation of oxysulfur and hydroxyl radicals, which further oxidized organic contaminants like azo dyes, aniline, bisphenol A, and phenol. Simultaneously, chromium (VI) was reduced to chromium (III) by the sulphide ion acting as a reducing agent, with low pH favoured this process (Yuan et al., 2016, 2019). In another approach, L-methionine and L-serine, two amino acids, were used to create two distinct metalloligands using oxamide as a base to develop a stable organicmetal structure in water. In order to effectively remove both organic and heavy metal contaminants (like Tl+ , Pb2+ , and Hg2+ ) at the same time, the functional side chains of the reactant amino acids (–CH2 CH2 SCH3 and –CH2 OH) work in concert (Mon et al. 2019). Feng et al. reported that this organic-metal structure successfully removed multiple pollutants simultaneously (Feng et al. 2018).

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A jar test experiment was conducted in the third effort, employing coagulation and iron (III) chloride for the simultaneous elimination of cyanide, chromium, and phenol. The presence of cyanide negatively impacted removal of chromium, necessitating increased ultrafiltration. Nevertheless, the contaminants were efficiently removed with high synchronous removal efficiency after coagulant treatment (Golbaz et al. 2014). The fourth approach involves functionalizing GO sheets with both biguanide and polyethersulfone to create a composite. This composite demonstrated its capacity to retain dyes, remove copper, act as an antifouling, reject salt, and have flux permeability for clean water. The hydrophillic nature and surface roughness of membrane facilitated the simultaneous removal of dyes and copper. It has also been explored if PAHs and heavy metals (Cu, Ni, Pb, Zn, Cd, and Cr) can be removed from synthetic storm water using a filter bed of microporous biochar. When compared to the effectiveness obtained with the usage of benzo(a) pyrene, higher removal of phenanthrene was seen among the series of PAHs employed for this experiment. The average percentage of PAHs removed overall was about 68% (Reddy et al. 2014). Composting has been explored as a practical and cost-effective alternative for mitigating hazardous contaminants in soils. Huang et al. achieved the simultaneous removal of copper and EDTA by employing ozonation in an acidic environment (Huang et al. 2016). Further investigations into ozonation were conducted, focusing on the concurrent removal of copper, Cu-EDTA complex and TOC, resulting in excellent removal performance (Huang et al. 2016). Additionally, there has been research into self-propelling micromotors. Maturi and Reddy’s micromotor not only enhanced the transfer of reactive species but also improved micro mixing, leading to a high rate of water decontamination (Maturi and Reddy 2006). The primary drawback of this approach lies in its high manufacturing cost, which has hindered its practical implementation. Current efforts are focused on developing scalable and cost-effective microjets. In one instance, a combination of MnO2 , SiO2 , and Fe2 O3 were utilized to create tubular micromotors. Furthermore, a microjet was employed in conjunction with photocatalysis under UV light and adsorption to achieve the simultaneous removal of divalent lead, divalent cadmium, tetracycline, and rhodamine B (Maturi and Reddy 2006). The accumulation of heavy metals poses a significant risk to human health and contributes to environmental degradation, rendering heavy-metal pollution a critical concern. A rapid, accurate, and efficient approach is urgently needed for detecting cations of heavy metals in the environment.

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3.6 Conclusion The discharge of heavy metals from industrial effluents poses a serious threat to both human health and the environment. These metals posses highly toxic and can lead to severe complications when they accumulate within the body over time. Encouragingly, green technology offers a viable solution to address this concern. The utilization of diverse eco-friendly approaches, including phytoremediation, bioremediation, and nanotechnology holds the potential to effectively mitigate elevated levels of heavy metals in the soil and water systems. It is important for industries to embrace sustainable and ethical practices that prioritize the safeguarding of the environment and human health. By embracing green technologies, we can ensure that industrial growth and development occur in a manner that is both safe and sustainable for future generations. There is a significant future scope of study in the field of adverse impacts of heavy metals stemming from industrial effluents and its remediation through green technology. Further investigation can be conducted to develop more effective, efficient and sustainable green technologies capable of extracting heavy metals from contaminated soil and wastewater. Furthermore, exploring the viability of using natural and locally available materials for heavy metal removal is essential. Researchers could explore the viability of synergistic effects achieved by combining different green technologies. Additionally, studies can be undertaken to understand the social and economic factors that influence the adoption and implementation of green technology in industries. Future research can also focus on developing policies and regulations that promote environmentally responsible practices in the industrial sector. On the whole, a substantial scope for future research exists in this domain, capable of contributing to sustainable industrial advancement while safeguarding the environment and public health.

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Chapter 4

Algal Photo Bioreactors: A Promising Technology for Wastewater Treatment Chitra Devi Venkatachalam, Mothil Sengottian, Sathish Raam Ravichandran, Premkumar Bhuvaneshwaran, and Sarath Sekar

Abstract Many species of microalgae have the capability to uptake the nutrients from the wastewater even in the presence of nitrogen, phosphorus, inorganic and organic toxins and pathogens. Algae grow in light or dark environments and also by the uptake of carbon dioxide or any other inorganic and organic carbon source. The bacteria already present in the wastewater breaks the complex organic matter, while algae consume them and provide the oxygen necessary to treat the water by compensating the Biological Oxygen Demand. Algal photo bioreactors are a promising technology in treating the wastewater and also carbon sequestration. There are various configurations of algal photobioreactors namely: vertical plastic bag, tubular, column, panel, and membrane photo bioreactor. This book chapter explains these configurations and also the parameters such as nutrient concentration, mixing and agitation, pH, light, and temperature that influence the growth of algae in the photo bioreactor. It also explains the need for different components in the photo bioreactor to vary or control the process parameters and also provides solutions for the challenges involved during use of photo bioreactor for wastewater treatment. Keywords Microalgae · Wastewater · Photo bioreactor · Biological oxygen demand

C. D. Venkatachalam (B) · P. Bhuvaneshwaran · S. Sekar Department of Food Technology, Kongu Engineering College, Perundurai, Tamil Nadu 638060, India e-mail: [email protected] M. Sengottian · S. R. Ravichandran Department of Chemical Engineering, Kongu Engineering College, Perundurai, Tamil Nadu 638060, India © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 A. S. Mathuriya et al. (eds.), Green Technologies for Industrial Waste Remediation, Environmental Science and Engineering, https://doi.org/10.1007/978-3-031-46858-2_4

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4.1 Introduction Algae can range from single-celled organisms, such as Chlamydomonas, to complex multicellular forms, such as seaweed. In single-celled algae, the cell wall provides structure and protection, while in multicellular forms, the cells are organized into tissues and organs, such as leaves and stems. Many algae also have chloroplasts, the site of photosynthesis, which are surrounded by a double membrane and contain chlorophyll and other pigments (Umen 2014). The life cycle of algae can vary greatly depending on the species. Some algae have a simple life cycle that involves only a single stage, while others have complex life cycles that involve multiple stages, including different forms of sexual and asexual reproduction (Heesch et al. 2021). For example, Chlamydomonas has a simple life cycle, in which cells divide and grow under favorable conditions, and produce spores or zoospores when conditions become unfavorable. Seaweed, on the other hand, have more complex life cycles, in which they produce spores or spores that develop into new individuals, or they can undergo sexual reproduction, producing gametes that fuse to form a new individual (Liu et al. 2017). Algae bioreactors are extensively used in the cultivation of both micro and macro algae. Some of the applications of these bioreactors are biomass production for nutraceuticals (Udayan et al. 2022), biofuel (Ummalyma et al. 2022), wastewater treatment (Al-Jabri et al. 2020), carbon-di-oxide fixation (Daneshvar et al. 2022), algae scrubber to filter water (Allesina et al. 2016), etc. When this reactor is exposed to sunlight or any other source of light for the algae to consume the nutrients and grow it is called an algal photobioreactor. The photobioreactor provides optimal light and growth conditions for the algae, and can control factors such as temperature, pH, and nutrient levels. Algal photobioreactors can be operated either as open or closed systems, and can use a variety of light sources, including natural light or artificial lamps. The use of algal photobioreactors has the potential to provide sustainable and environmentally friendly solutions for many industries. Algae can break down complex organic chemicals through a process known as degradation or mineralization. In this process, microorganisms, such as bacteria, fungi, and algae, decompose organic matter into simpler substances, such as carbon dioxide, water, and mineral nutrients (Joutey et al. 2013). This process is important in the cycling of nutrients in the environment, as it helps to return organic matter and nutrients to the soil, where they can be taken up by plants and other organisms. Algae can also play a role in breaking down pollutants, such as oil spills and toxic chemicals, by using them as a source of energy for growth and degradation. The degradation of complex organic chemicals in algae is facilitated by enzymes, which are proteins that catalyse chemical reactions. These enzymes are produced by the algae or associated microorganisms, and they help to break down the complex organic compounds into simpler substances.

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4.2 Wastewater a Rich Source of Nutrients Wastewater is a rich source of nutrients mainly nitrogen and phosphorous, where nitrogen helps in increasing the light capturing ability of the cells, metabolism and improving plant growth, while phosphorous helps exchanging energy between the algal cells and in maintaining the quality i.e. protein content present in it etc. The other trace elements also support the growth of certain species of algae. They are capable of absorbing and breaking down a range of organic compounds and heavy metals. By using wastewater as a growth medium for algae, it is possible to simultaneously clean the wastewater and produce biomass for various applications, such as biofuels, feed, or fertilizer. However, it is important to note that the quality of wastewater can vary greatly and may require pre-treatment or supplementation with additional nutrients to support optimal algal growth. Algae can grow in a variety of wastewater types, including: Domestic wastewater (from households), Industrial wastewater (from manufacturing processes), Agricultural wastewater (from livestock farming and irrigation), and Municipal wastewater (from cities and towns). The type of algae that grows in these wastewaters can vary based on the conditions and the presence of nutrients (Bhatt et al. 2022). Domestic household wastewater contains a variety of nutrients that can support the growth of algae, including: Nitrogen: found in human waste, food waste, and cleaning products, Phosphorus: found in detergents, cleaning products, and human waste, Carbon: found in food waste, paper products, and organic matter, Potassium: found in food waste and cleaning products. Other elements and minerals, such as sulphur, magnesium, calcium, and iron, may also be present in smaller amounts and can support algal growth. The exact composition of household wastewater can vary based on the local water supply and the types of products used by households (Tjandraatmadja et al. 2020; Rout et al. 2021). Industrial wastewater can contain a variety of nutrients that can support the growth of algae, including: Nitrogen: found in industrial chemicals, such as ammonia and nitrates, Phosphorus: found in detergents, cleaning products, and industrial chemicals, Carbon: found in organic waste, such as solvents, sugars, and organic acids, Potassium: found in some industrial chemicals and process water. The exact composition of industrial wastewater can vary greatly depending on the type of industry and the processes used. For example, wastewater from food processing plants may contain higher levels of organic matter, while wastewater from metal finishing operations may contain heavy metals and other pollutants (Acién Fernández et al. 2018). Agricultural wastewater or the wash water from fields contain nitrogen, phosphorous and potassium which are mainly from animal waste, fertilizers, and soil (Pandit et al. 2021). For example: dairy farming operations may produce high levels of nitrogen and phosphorus, while irrigation runoff may contain high levels of salts and minerals that are helpful for the growth of algae.

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Municipal wastewater consists of human waste, food waste, and cleaning products and they typically undergo treatment before discharge to reduce the levels of pollutants and pathogens, but some nutrients may still be present in the treated effluent (Sisman-Aydin and Simsek 2022).

4.3 Algae Cultivation Techniques 4.3.1 Based on Culturing Conditions 4.3.1.1

Photoautotrophic

Photoautotrophic algae are algae that produce their own food through photosynthesis, using light energy to convert carbon dioxide into organic compounds. These algae are primary producers and play an important role in the ecosystem, as they form the base of the food chain for many aquatic and terrestrial organisms. Some common examples of photoautotrophic algae include diatoms, green algae, and cyanobacteria. The maximum biomass concentration (1.25 g L−1 ) and lipid content (32.2%) was achieved by Chlorella under blue light in starch wastewater (Ren et al. 2022). Chlorella fusca var. vacuolata and Anabaena variabilis showed that they can survive in hazardous environments and degrade upto 90% of 2,4-dinitrophenol of concentration 5 to 40 µM (Hirooka et al. 2003).

4.3.1.2

Mixotrophic

Mixotrophic algae are algae that can obtain energy and nutrients through both photosynthesis and heterotrophic means, such as consuming organic matter. This ability to switch between energy sources makes mixotrophic algae highly adaptable and able to thrive in environments where light and nutrients are limited. Some mixotrophic algae are also capable of shifting between different modes of nutrition depending on the availability of resources in their environment. Examples of mixotrophic algae include dinoflagellates, Euglena, and chlorophytes. Galdieria sulphuraria (pH = 1 to 4; temperature = 25 to 56 °C) showed a removal rate of BOD5 (16.5 ± 3.6 mg L−1 d−1 ) and ammoniacal nitrogen (6.09 ± 0.92 mg L−1 d−1 ) in this mixotrophic system of 700 mL compared to that in a photoautotrophic high rate algal ponds system (Nirmalakhandan et al. 2019).

4.3.1.3

Heterotrophic

Heterotrophic algae are algae that obtain their energy and nutrients by consuming other organic matter, rather than through photosynthesis. They are unable to produce

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their own food and must rely on a source of organic carbon, such as dead plant material or other microorganisms, to survive. Heterotrophic algae are typically smaller and less complex than photoautotrophic algae and play a less significant role in the ecosystem. Some examples of heterotrophic algae include heterokonts, haptophytes, and labyrinthulomycetes. Chlorella protothecoides and Ettlia sp. a system of microalgae and bacteria degraded thiocyanate from wastewater and yielded an increased lipid productivity of 28.7 folds and 17.3 folds under photoheterotrophic photoautotrophic conditions respectively (Ryu et al. 2014).

4.3.2 Based on Design of Reactors 4.3.2.1

Open System

In open pond systems, algae are grown in large, shallow ponds, typically outdoors, and are exposed to sunlight for photosynthesis. The ponds are usually fed with a nutrient-rich water source to promote growth, and the algae are typically harvested using physical or chemical methods (Costa et al. 2019).

4.3.2.2

Closed System

In closed photobioreactors, algae are grown in controlled environments, such as closed tanks or tubes. The photobioreactors are designed to optimize light penetration, temperature, and nutrient levels for the specific type of algae being cultivated (Narala et al. 2016). Artificial light sources, such as LED lamps, can be used to supplement or replace natural sunlight. Regardless of the cultivation method, the algae are typically grown in a monoculture, or a single species culture, to simplify the cultivation process and improve yields. The algae are usually grown in suspended culture or attached to a support medium. In a suspended culture, the algae are constantly suspended in the liquid and can freely move and grow. This method allows for efficient mixing of the algae and the growth medium, ensuring that the algae are exposed to an optimal environment for growth. In an algal culture over support, the algae are able to grow in a defined area, and their growth can be more easily controlled and monitored compared to a suspended culture. The support also provides a physical structure that helps prevent contamination by other microorganisms and enables the efficient removal of waste products from the culture (Lin-Lan et al. 2018).

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4.4 Photo Bioreactors and Different Configurations 4.4.1 Vertical Plastic Bags The photobioreactor consists of a clear plastic bag that is filled with a growth medium and algae and suspended vertically in a well-lit location. The plastic bag allows light to penetrate and provides a suitable environment for the algae to grow, while also preventing contamination from external sources. The use of plastic bags allows for a compact and simple design, making it a cost-effective solution for large-scale algae cultivation. Vertical plastic bag photobioreactors have become popular in recent years due to their ease of use, low maintenance requirements, and high efficiency. Turbidostat (1 L) and sunlit modules (5–25 L) bags for small scale and NOVAgreen ( 1000 mg/L) remain relatively high. To meet reclamation requirements, MBR can be applied for treating such effluent. (Kosseva and Webb 2020) achieved the conversion of distillery effluent from a mesophilic to a thermophilic state using a flat stainless steel membrane module in a heated aerobic MBR. A pilot-scale study conducted by (Sharma et al. 2021) revealed that a hybrid N.F. and R.O. process could effectively remove color and contaminants from distillery spent wash while achieving a high water recovery rate. Remarkable rejections of 99.80% for TDS, 99.90% for COD, and 99.99% for potassium were achieved through the R.O. process, while N.F. effectively removed color. Additionally, this process maintains a considerable flux level compared to pure water flux. Notably, (Sharma et al. 2021). found that membrane fouling did not significantly impact the efficacy of wastewater treatment, and the pollutant levels in the permeates were well below the maximum contaminant levels defined by the World Health Organization standards.

5.3.3 Food Processing Industry Wastewater from the manufacture of starch, fish and meat, slaughterhouses, salad dressings and margarine, canned foods, processed vegetables, etc. are included in the food processing wastewater effluent. Pollutant concentration in the wastewater effluent from the food sector can vary significantly due to changes in product composition and season, depending on time and location. The wastewater stream generated during food preparation carries a foul odour, has a dark colour, and is highly contaminated with organic materials, suspended solids, and fine particles. Due to their high organic content, these streams cannot be directly discharged into the municipal sewage system (beyond the legally permitted limits). Wastewater generated during food processing poses a significant due to its varied contaminants, which can significantly affect the efficiency of a conventional sewage treatment facilities. The activated sludge method is commonly used to treat wastewater from agricultural processing (Shrivastavaet al. 2022). Advanced operational methods are necessary to manage bulking issues, which often cause lower quality effluent. Membrane technology allows for wastewater from food processing to be treated beyond the levels required by municipalities. Additionally, the concentrated by product can often be put to good use. PTFE membranes are commonly used in dairy and food processes to concentrate liquor. The use of hollow-fibre M.F. membranes in the activated sludge

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process for solid–liquid separation offer several benefits, such as ease of maintenance, reduced reactor volume, no sludge escape during bulking, and no need for a sedimentation tank (Garnier et al. 2023).

5.3.4 Metal Processing Industry Numerous industries, including those involved in the production of batteries, electrical cables, electronic microchips, and metal finishing, generate wastewater containing heavy metals. Due to their substantial toxicity, heavy metals are recognized as among the most hazardous environmental pollutants. Environmental regulations mandate that industries treat heavy metal-laden wastewater to reduce their concentrations to permissible levels. In addition to wastewater purification, methods methods capable of metal recovery are intriguing because the price of noble materials like heavy metals is constantly rising. Various studies suggest that membrane processes can effectively eliminate or recover heavy metals like Cu2+ and Cd2+ from wastewater sources. Heavy metals-containing industrial wastewater can be reused after being treated by R.O. and N.F., these methods can contribute to alleviating the pressure on conventional water resources. In the presence of EDTA as a chelating agent, (Arana Juve et al. 2022) demonstrated the feasibility of removing Zn2+ and Cu2+ from wastewater using a low-pressure R.O. method. For instance, during the production of electronic microchips, a micro-filtration device and the R.O. process were employed to eliminate cadmium from wastewater, achieving concentrations below detection (i.e., 0.01 mg/l) (Masood et al. 2023). (Das et al., 2019) study showcased the effective removal of trivalent chromium from tanning wastewater using R.O. technology.

5.3.5 Dye and Textile Industry The textile industry is characterized by the extensive use of various chemicals and large quantities of water. Detergents and caustics are employed to eliminate grit, wax, oils, and debris. Bleaching enhances brightness and purity, while dyes, fixing agents, and numerous inorganic agents are used to achieve the desired array of colors. Sizing chemicals are added to improve weaving, while oils aid knitting and spinning. Latex and adhesive serve as binders, and a variety. Many different types of specialized chemicals, including softeners, stain-release agents, and wetting agents, are employed. In some ways, the growth of the chemical industry was driven by the demands of the textile industry. Many of these chemicals find their way into the final product, often unnecessarily, leading to their elimination from the fabric. To address the environmental impact of the textile sector, state authorities and local municipalities have begun to focus on the treatment of wastewater from textile mills. Regulatory bodies are examining

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factors such as high salt content, persistent presence of BOD, irreversible COD, heavy metals, and effluent colour for their toxic effects. As mill seek new discharge permits, the challenge of discharged effluent potentially jeopardizing permit renewal arises. To address these challenges, the development of membrane separation processes has emerged as a solution for textile mills. Membranes offer solutions for color removal BOD reduction, salt reduction and reuse, PVA recovery, and latex recovery among other issues. What sets membrane technology apart is its potential to provide return on investment through pollution reduction. Due to the increased commodity status of membranes and the possibility of using a point source approach, capital investment is now competitive with traditional end-of-pipe treatment. In many instances, priceless goods can be recovered and used again, lowering overall costs. Membrane processes have the capacity to concentrate, isolate, and remove dyes from effluent (Fig. 5.4) (Shah 2023). Due to their capacity to significantly reduce pollutant concentrations, membrane technologies prove highly effective in treating effluents from textile manufacturing for water reuse (Ahmad and Alshammari 2023). Moreover, membranes have unique qualities like resistance to microbial assault, a harsh chemical environment, and temperature. Among various studies, it is widely established that N.F. (Nanofiltration) membranes offer optimal performance for treating textile wastewater. This preference stems from the advantages that N.F. membrane has benefits over other membranes hold over other types, including, lower osmotic pressure difference, higher permeate flux, better retention of multivalent salts and molecules with a molecular weight of over 300 daltons, and comparatively reduced investment and operating costs (Shah 2023).

Fig. 5.4 Membrane method for recycling textile wastewater

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N.F. processes also exhibit proficiency in handling high concentrations, separating low molecular weight organic molecules, and distinguishing divalent ions from monovalent salts.

5.4 Restriction Numerous industrial wastewater undergo reuse via a series of membrane filtration processes. To effectively operate membrane processes, proper control of membrane flux and feed conditions is essential encompassing pressure, temperature and turbulence. Over continuous long-term operation, the decline in permeate flux, induced by factors like particle blocking, concentration polarization, and fouling, along with the resulting rise in costs, pose significant challenges to membrane process utilization. Fouling can arise from various physio-chemical and biological processes, all leading to increased deposition of solid material on the membrane surface (blinding) and within the membrane structure (pore restriction or pore plugging/occlusion). An additional constraint is their limited resistance to extreme pH conditions and specific organic solvents. However, membrane flux can be maintained at a constant level by effectively mitigating fouling, selecting appropriate membranes, and preventing concentration polarization. One way to address fouling by per-treating the wastewater before subjecting it to the membrane process. Cross-flow processes, compared to dead-end filtration, are considered more effective in maintaining steady-state conditions that minimize fouling. The prevention of concentration polarization is crucial for optimal operation. Strategies to alleviate this include reducing pressure, lowering feed concentration, increasing turbulence, back-washing or back flushing, introducing pulsing feed flow, or repositioning the membrane. The selection of an appropriate membrane device is a critical consideration for managing industrial wastewater. Higher driving pressure can lead to membrane compression, diminishing flux, and elevated temperatures may exacerbate this effect. Compacted membranes are typically irreversible, except in rare cases where gradual compaction restoration might be possible. Moreover, improper membrane selection can lead to molecular alterations.

5.5 Future Perspectives The exploration of novel membrane materials that exhibit enhanced permeability and resistance to chemical, thermal, and biological challenges is imperative. The pivotal advancement in reducing membrane fouling resistance involves designing membranes with a low affinity for well-known foulants present in the feed-stock. Many contaminants, such as humic acids, phenol, carboxylic groups, and natural organic materials (NOM), can be repelled by highly negatively charged membranes, enabling operation at elevated flux levels.

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Currently, significant emphasis is placed on the development of highly negatively charged membranes, like blends of sulphonated poly ether ether ketone (SPEEK) or sulphonated poly ether sulphone (SPEES) with polysulphone or polyethersulphone. These membranes are poised to be available in the market soon. The forthcoming generation of membranes will be crafted through advanced membrane technologies for industrial wastewater treatment research, yielding heightened efficiency, reduced energy consumption, and minimized environmental impact. The progress of membrane research and development can further our fundamental understanding of how membrane materials interact with liquids and solids, at microscopic and atomic scales. The subsequent phase involves characterizing and constructing predictive computational models of separation, fouling, and transport processes intrinsic to inorganic and organic membranes employed in industrial effluent treatment. These models will integrate existing data to foster collaboration and innovation in membrane separation systems or operational strategies, resulting in novel advancements in membrane technology and the establishment of affordable, highly efficient industrial wastewater recovery systems.

5.6 Summary Membrane processes hold considerable potential for treating diverse industrial effluents. To effectively employ membrane technology, it is imperative to select the most suitable membrane for the specific industrial effluent in question. Enhancing the applicability of N.F., U.F., M.F., R.O., and E.D can be achieved by combining these aforementioned membrane processes while considering the desired effluent quality and economic considerations. Options such as combining membrane processes with conventional treatment and/or Pre-treatment, as well as employing two-stage membrane applications, offer diverse choices for addressing various industrial wastewater scenarios. Critical to the widespread adoption of membrane technologies are the economic feasibility of such systems and the growing need for stringent environmental regulations. Extensive pilot and bench-scale investigations have consistently demonstrated the technical feasibility of membrane processes. In the near future, one can anticipate the emergence of full-scale applications and a substantial expansion in the number and scale of installations. The ongoing research and development in this field will continue to enhance our understanding of how to effectively harness membrane technology.

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Chapter 6

Valorization of Agro-Industrial Wastes for Biorefinery Products Ayushi Singh, Rishi Dikshit, and Neetu Singh

Abstract In the present scenario, with the increase in population, the food and agro-industrial sector has rapidly gone through a revolutionary phase to meet the demands. As a result, the waste generation also increasing. If left untreated, it causes harmful effects on the environment. Valorization is a relatively new approach in the management of these residues from the agro-industrial sector. The objective of valorization for agro-waste management includes the conversion of waste into decomposable substrates which can be further converted into valuable products by microbial and chemical action. In terms of environmental sustainability, the use of agro-industrial wastes in biorefinery processes has received much attention. The waste biorefinery process uses agro-industrial wastes to effectively manage waste streams. This chapter provides a comprehensive exploration of agro-waste management, from its generation and challenges to its transformation into valuable resources. It offers insights into cutting-edge techniques and processes, highlighting the potential benefits for various industries and the broader environment. This knowledge will empower readers/people to make informed decisions and contribute to a more sustainable and efficient approach to agro-waste utilization. Keywords Agro-industrial waste · Environmental sustainability · Valorization · Biorefinery products

A. Singh (B) · N. Singh Department of Food and Nutrition, Babasaheb Bhimrao Ambedkar University, Uttar Pradesh, Lucknow 226025, India e-mail: [email protected] R. Dikshit Department of Human Development and Family Studies, Babasaheb Bhimrao Ambedkar University, Uttar Pradesh, Lucknow 226025, India © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 A. S. Mathuriya et al. (eds.), Green Technologies for Industrial Waste Remediation, Environmental Science and Engineering, https://doi.org/10.1007/978-3-031-46858-2_6

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6.1 Introduction In the current scenario, driven by the expanding global population, there is an increasing demand for diverse food and energy sources to fuel and accelerate growth. Consequently, the adoption of industrialization and modern technologies is being embraced worldwide for flexibility in production and enhancing product quantity and quality of products. The development and utilization of these technologies have led to a substantial rise in agro-industrial food waste generation. Unfortunately, a significant proportion of this garbage is indiscriminately deposited in landfills as a result of the exorbitant expenses linked to the necessary treatment techniques aimed at diminishing the organic burden emanating from both commercial enterprises and residential dwellings. Global food waste production has reached an alarming 1.3–1.4 billion tonnes, and it is expected to reach 2.6 billion tonnes by 2025. According to the United Nations Environment Programme (UNEP), fruit and vegetable waste resulted in a loss of 400 billion US dollars in revenue (Kumar et al. 2022). The Food and Agricultural Organization (FAO) estimates that between 40 and 50% of all food produced globally goes to waste, particularly among roots, tubers, fruits, and vegetables (Freitas et al. 2021). The continuous rise in the quantities of organic waste, which are experiencing a daily increase, has detrimental effects on the well-being of ecosystems and, eventually, the overall health of the people. The 12th Sustainable Development Goal (SDG) places a strong emphasis on the responsibility of consumption and production. The objective of this goal includes reducing food waste and managing all waste in an environment-friendly manner through reduction, recycling, and reuse to check wastage and maintain food security. Agro wastes encompass materials such as coffee grounds, sugarcane wood pallets, fruit seeds and peels, legumes husk, cellulose, and more. These substances serve as sources for organic acids, enzymes, biofuel, biopolymers, and other valuable compounds. The effective management of these organic wastes involves a series of steps aimed at ensuring sustainability while minimizing environmental impact given the heterogeneous composition of agro-wastes containing organic matter, a variety of products can be derived through biological, chemical, mechanical, and thermal treatments. This chapter explores the pressing issue of agro-industrial waste management in the context of a growing global population’s demand for food and energy. With billions of tons of waste generated annually, the challenge of reducing food waste while promoting sustainable consumption and production is highlighted. The chapter delves into innovative trends in agro-waste management, emphasizing the transformation of waste into valuable resources through biorefineries and resource recovery processes. Notably, it introduces novel techniques like microwave and ultrasound treatments, as well as advanced fermentation methods for producing biofuels, enzymes, antibiotics, phytochemicals, biomaterials, and biofertilizers. By presenting solutions to extract value from agro-waste, the chapter aims to provide readers with insights into sustainable practices that can contribute to a more efficient and environmentally friendly approach to waste utilization.

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6.2 Trends Followed in the Management of Agro-Waste The utilization of agro-industrial wastes for introducing innovative products has experienced notable growth. For instance, agricultural and industrial wastes were once considered a significant challenge within the food production chain, primarily due to the high cost of evacuation and the natural effect of disposing of them (Cattaneo et al. 2020). Traditionally, agricultural and industrial wastes were perceived as having neither a financial burden nor a positive outcome, as their primary utilization was for soil amendment or the production of fodder (Nazzaro et al. 2018). However, this perspective is evolving due to the emergence of various novel technologies aimed at recycling these agricultural and industrial wastes, thereby creating value from them. The exploration of resource recovery has been a prominent focus within the food business sector. This process entails the retrieval of valuable resources from agricultural and industrial waste materials with the purpose of producing food additives. Additionally, these byproducts are utilized as inputs in order to facilitate the development of novel goods (Udugama et al. 2020). Significant attention has been dedicated to the synergist conversion of biomass into alkyl glucosides, polysaccharides, polyols, and aromatic compounds (Rosero-Chasoy et al. 2020). The adoption of a fresh approach to processes has been spurred by the integrated process model that connects the transformation sequence for manufacturing fuels, diesel, and other products, such as plastics, similar to the oil industry. This new approach mirrors phases akin to those comprehensively linked in the oil refining sector, yet it has been repurposed to harness renewable biomass. As implied by the prefix “bio”, the term biorefinery alludes to a powerful methodology of a few cycles coordinated in chains and mechanical courses equipped for changing over natural matter (or waste) into esteem-added items, for example, biofuels, synthetic data sources, intensity, power, and explicit synthetic compounds with significant pharmaceutical potential (Ahmad et al. 2020). Biorefineries have become a tangible reality in several countries worldwide, particularly in agriculturally advantageous nations. It is essential to mention that the efficiency aspects of agro-energetic agribusiness have exhibited differentiation, mostly due to the advancement of horticulture yields in relation to optimal growth circumstances, regional expansion, and a focus on research and development (Fonseca et al. 2020). A few yields like Cotton, wheat, bananas, espresso, potatoes, sugar sticks, eucalyptus, corn, and different harvests have filled fundamentally in this situation, as has the age of related lignocellulosic squander. Subsequently, a few businesses have proactively applied the biorefinery model to modern cycles to profit from vegetable fiber organization and possibly other important items from sequential innovations (Longati et al. 2020). Biorefineries can be used in different industrial cycles, and they can be integrated into already consolidated industries or they can be autonomous, operating independently of a specific industry (Freitas et al. 2021). We have associated advantages and disadvantages in each case, so the best proposition should be evaluated concerning working circumstances and monetary advantages. However, it is worth noting that

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there are three key supporting aspects that strengthen the credibility of a contemporary interaction centered on a biorefinery. The process of treatment involves the breakdown of a certain component into biomass, which is then transformed into value-added commodities (Pachon et al. 2020). Although the idea of biorefineries is currently seen as crucial to executing a reasonable bio-based economy (Dragone et al. 2020). In biorefineries, the utilization of food waste like feedstock is still in its beginning phases of improvement, with few examinations assessing its monetary reasonability for an enormous scope the exploration (Cristobal et al. 2018). Scientists as of late distributed a concentrate in which agro-modern waste is utilized as another financially savvy adsorbent in wastewater filtration. The expulsion pace of copper particles from fluid arrangements and boring wastewater utilizing an unmodified lemon strip as an agro-modern waste (Meseldzija et al. 2019). Biomass can likewise be utilized to supplant traditional materials in the blend of materials utilized in common development, bringing energy costs and contributing down to the viable administration of agro-modern waste (Jannat et al. 2020). The ongoing situation of agro-modern waste use is inseparably connected to the improvement of new advances, especially those equipped for separating high-added-esteem parts for use as food enhancements and medications.

6.3 Types and Sources of Agro-Industrial Waste In contemporary times, a limited array of diverse agro-waste variants can be readily observed.

6.3.1 Fruit and Vegetable Processing Wastes (FVW) The fruit and vegetable industry generates a lot of waste. Planned overproduction and noncompliance with retailer quality standards are the primary causes of fruit and vegetable waste before it reaches consumers in developed nations [16]. Fruit and vegetable processing wastes present ecological issues because of their extreme biodegradability, addressing a critical biomass shortage and finance as well to the organizations. The system of reuse and reduce is developed to handle Fruit and vegetable processing wastes has been proposed (Plazzottaet al. 2017). Anaerobic change of foods grown from ground waste to biofertilizer diminishes ecological contamination while likewise further developing soil nourishment (Chakravarty and Mandavganr 2021). As a high carbon-to-nitrogen ratio prevented soil microorganisms from introducing nutrients to crops and obstructed soil insurance, the primary challenge in bioprocessing 500 g of fruit and vegetable processing wastes is it’s high carbon and low nitrogen content. To resolve this issue, FVW (Fruits and vegetable Waste) was co-processed with another eco-squander, in particular slaughterhouse wastewater (SWW). The absorption interaction is partitioned

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into two stages. The initial step is anaerobic processing, trailed by a second step of oxygen-consuming assimilation utilizing Trichoderma reesei under enhanced conditions. After the subsequent step, a worthy added biofertilizer with a diminished C: N proportion of 12–10.8 is framed, bringing about a reduction in FVW. Grape-primarily produced FVW which can be used as a biosorbent for metals for waste management (Gupta et al. 2019). The discoveries plainly showed the utility of fruit and vegetable processing wastes on the board at both the family and modern levels.

6.3.2 Edible Oil Waste The unusable cooking oil, which is disposed of as a loss by families and eateries subsequent to searing, can be utilized to make latrine (shower) cleansers. Utilizing waste cooking oil, a greener and more secure farming item for bugs the executives were created. The emulsifiable concentrate (EC) of neem is comprised of 8–10% emulsifying specialists and 60–70% natural solvents that go about as inactive fixings. The EC definition was produced using oil-based unstable natural solvents (VOCs), which profoundly entered plant tissues and hurt different physiological ways of behaving. To balance these adverse consequences, WCO containing linolenic corrosive (3%) (20–60 g) can be utilized as an elective dissolvable in this plan, consequently in a roundabout way lessening waste administration and expanding safe nuisance the board by 90% (Iqbal et al. 2021). WCO-based definitions explain the harmful effects like dermal harmfulness, inward breath risks, combustibility, and plant poisonousness issues like phytotoxicity, and have further developed detailing solidness. Polylactic acid (PLA) is a biopolymer that is eco-friendly, biodegradable, straightforward, and thermalplastic.

6.3.3 Coffee Processing Waste (CW) CW is a carbon–nitrogen source from coffee bean cultivation worldwide. Additionally, it is economical and friendly to the environment. After carbonizing the NaCrO2 powder and the nitrogen-doped carbon in CW, a composite terminal material was produced (Awasthi et al. 2020).

6.3.4 Kitchen Waste Kitchen waste is the major source of agricultural waste in daily life. This waste undergoes the vermicomposting process for 45 days at 20–25 0C with 60% moisture. This process increases phosphorous (31.38–55.89%) and potassium (33.40–63.15%) production. Earthworm development was helped by kitchen squandering; however,

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the overabundance of squanders hampered their development (Zhi-Wei et al. 2019). Tea powder is a kitchen waste that is high in carbon content due to sugar and milk proteins. This was used by researchers to create fluorescent carbon specks (Compact discs) (Gunjal et al. 2019).

6.3.5 Brewery Processing Waste After the brewing process, the byproduct sludge residue is formed. It is the source of silicon oxide (SiO2) and a small amount of aluminum oxide (Al2 O3 ) and iron oxide (FeO). By combining antacid fluids (NaOH and Na2 SiO2 ) with BSA, ashbased geopolymer concrete (BSAGC) was produced (Okeyinka et al. 2019). In the case of the BSAGC, the blending extents of considerable grade consist of 1:2:4 proportions of cover, fine aggregate, and coarse total. Ferulic corrosive (FA) is an anti-oxidant against microbial, mitigating, hostile to apoplexy, and against malignant growth properties (Anjali et al. 2022). Utilizing helpful bacterial strains, for example, Cupriavidus necator, brewery handling waste can be aged to deliver sugars (Corchado-Lopo et al. 2021).

6.4 Biorefinery Concept and Management The ongoing populace size has brought about the best utilization of accessible assets for creating economical agrarian practices to lead domesticated animal waste, agroindustrial waste, crop deposits, and foods grown from ground waste (Cusenza et al. 2021). Farmers all over the world benefit from livestock production and crop cultivation. Animal compost is used as an energy source, and in multiple locales, it is utilized basically as biogas production or essentially handling for consumption (Khoshnevisan et al. 2021). Human and government associations are basic to the progress of a bio-treatment facility in light of energy, food, and substance creation. The product’s composition is determined by the biomass used in the manufacturing process (Fang et al. 2021). Table 6.1 portrays biorefinery products that originate from agro-industrial biomass by utilizing different transformation innovations. A deep-rooted bio-processing plant is available in different locales, which adds to the maintainability of the environment, individuals, creature life, and land. Plants produce energy as biomass, which is synthetically put away. The biorefinery’s ultimate goal is to use stored energy to support life (Rajendran et al. 2021). With a socioeconomic approach, the principal worry in biorefinery the board is guaranteeing self-viability in the fields of energy, fertilizer creation, and food. This wide information on biomass openness and accessibility, soil type and ripeness, populace extension, land accessibility, horticultural results, etc. is required (Shahid et al.

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Table 6.1 Some Agro-industrial biomass biorefinery products are produced using various conversion technologies (Yaashikaa et al. 2022) Agro-industrial wastes

Conversion techniques

Corn fiber

Enzymatic hydrolysis & biodetoxification

Grape pomace

Solid state fermentation

Maize stover

Hydrolysis of complex sugar and Solid state fermentation

Succinic acid (C4 H6 O4 )

Cotton shoot

Solid state fermentation

Lactic acid (C3 H6 O3)

Wheat bran

Fermentation

2,3-butanediol ((CH3 CHOH)2 )

Maize cob molasses

Fed-batch fermentation

Palm oil empty fruit Bunches

Fermentation

Product Bioethanol (C2 H5 OH)

Structure

2021). Individuals from the bio-treatment facility and the board hierarchical panel might be expert individuals and counsels from various administrative organizations, neighborhood networks, and financial specialists.

6.5 Methodologies for Valorization of Agro-Industrial Waste Majorly the residue generated by agro-industries goes through three basic steps for conversion into a valorized product. The first one is the pretreatment method which allows the rigid non-decomposable raw material to into fermentable sugars, on the second step the fermentable sugar is treated to convert into bio-materials, and the last purification is done to remove impurities via distillation.

6.5.1 Pretreatment Methods of Agro Wastes For the fermentation refineries, agro-food wastes are used as feedstock to recover sugars. As a result, simple carbohydrates are the most important intermediate substance for converting organic waste into cost-effective products (Tuly et al. 2022). The lignocellulosic biomass’s crystalline structure is the primary obstacle to sugar

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retrieval. The crystalline cellulose is insoluble and indestructible due to the protective layer of hemicellulose and lignin that surrounds it. The pretreatment process is required for the structural change before the main treatment which improves treatment efficiency. In comparison to hydrolysis, the pretreatment process increases the yield from 20 to 90% (Yaashikaa et al. 2022). There are several pretreatment methods mentioned below for sugar retrieval.

6.5.1.1

Microwave Treatment

This is the latest technique which is highly efficient due to less energy consumption and a great potential for the transformation of agrogenic wastes into fermentable substrates. When compared to conventional methods, it has several advantages, including extraction selectivity, lower installation costs, ease of maintenance, shorter extraction times, shorter preparation times, and lower electrical energy consumption. Microwaves can be used in combination with different thermal or chemical treatments for the extraction of protein, pyrolysis oil, butyric acid, bio-oil, bio-butanol, and so on (Kumar et al. 2022; Freitas et al. 2021).

6.5.1.2

Ultrasound Treatment

Ultrasound is a non-conventional method that is feasible on the Industrial level. The ultrasound waves disrupt the cell wall and penetrate easily and deeply into the matrix. It causes the extraction of thermo-sensitive compounds. It also reduces extraction time and temperature Tables 6.1 and 6.2. Table 6.2 The table below is presenting the ultrasonic pretreated food wastes and the product extracted (Kumar et al. 2022) Agro waste

Ultrasonic pretreatment

Product after pretreatment

Orange peel

Ultrasound with hydrolysis in an acidic medium

Pectin, Cellulose, and essential oils

Watermelon rind biomass

Deep Eutectic solvent method followed by ultrasound treatment

Bioenergy

Waste potatoes

Acid and ultrasonic treatment

Ethanol

walnut processing waste

Ultrasound treatment

High methylated pectin

Tomato processing waste

Ultrasound treatment

Pectin

Custard apple seed

Ultrasonic extraction

seed oil

Ragi straw

Alkaline treatment with ultrasound

polyhydroxy butyrate

Carrot pomace

Heating with ultrasound treatment Pectin

Rice straw

ultrasound treatment

Cellulose fiber

Citrus peel method

Pressure assisted ultrasound

Pectin

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Steam Explosion

Acetic acid is produced during the chemical and physical process of steam explosion to assist in the hydrolysis of hemicellulose. The utilisation of biomass in various processes has several advantages, including cost-effectiveness, environmental sustainability, and reduced chemical usage. However, it is important to consider potential limitations such as partial biomass disruption and the generation of inhibitory compounds, as these factors can potentially impede microbial activity in future processes. The overall yield of sugar is also reduced by the water wash during this process. In a study, steam was used to treat birch biomass for enzymatic reactions, and higher temperatures produced the highest efficiency (Kumar et al. 2022).

6.5.1.4

Ammonia Fibre Explosion

This is a physicochemical pretreatment technique in which liquid ammonia and lignocellulosic waste are mixed in equal amounts for short periods at high temperatures (Zhao et al. 2020) The liquid ammonia in this process is 1–2 kg of ammonia per kilogram of dry waste, kept for 30 min at 90 °C. As a result, in the next process of enzymatic hydrolysis requirement of enzymes is less and the hydrolysis improved. The advantage of this method is that the output contains the minimum amount of inhibitors. In this case, ammonia gets recycled which conserves not only money but environment also (Kumar et al. 2022).

6.5.1.5

Enzymatic Hydrolysis

Hydrolysis is carried out by several enzymes, including amylase, protease, cellulase, lipase, and pectinases. By breaking down starch, these enzymes create sugars that can be turned into ethanol. Anaerobes need rigorous anaerobic conditions to grow, whereas cellulases produced by other bacteria break down lignocellulosic biomass. Treatment with fungi is becoming more and more popular, and cellulase-producing Trichoderma is the subject of extensive research. For FW’s ultra-rapid hydrolysis, a fungal mash produced in situ and rich in various hydrolytic enzymes was utilized. The production of various enzymes has been extensively investigated using solidstate fermentation (SSF). However, attention must be paid to the enzyme’s price and economic viability (Kumar et al. 2022).

6.5.1.6

Pyrolysis

Pyrolysis produces biochar in solid, bio-oil in liquid and vapor condensate, and syngas in a gaseous state by decomposing cellulose at extremely high temperatures between 300 and 800 °C in the anaerobic condition or the presence of inert gas. Pyrolysis is more beneficial than combustion because it happens at low temperatures

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and the emission of pollutants is comparatively low. The time and temperature on which the substrate is kept for pyrolysis are the essential functional conditions for the product composition produced by the process (Kumar et al. 2022).

6.5.2 Treatment Methods of Agro Wastes 6.5.2.1

Fermentation

In the fermentation process, microorganisms convert starch, cellulose, hemicelluloses, or sugars into renewable biomaterials. The biomass is decomposed into fermentable sugar with the help of enzymes the sugar is further converted into bioethanol by yeast fermentation. The impurities are removed by the distillation process. The byproducts generated during the gasification process can be utilized in the production of animal feed, while sugarcane bagasse serves as a fuel source for boilers (Yaashikaa et al. 2022). Using the fermentation method, agro residues can be transformed into multiple products with added value. The various bio-products that are produced through fermentation from food waste are described below.

6.5.2.2

Acetic Acid

The production of acetic acid is controlled by acetogenic fermentation. Several metabolic pathways, including protein fermentation, can result in the production of acetic acid. Researchers have found that mixed fermentation yields the most acetic acid at pH 8.2 and 20 °C (Feng et al. 2020). Additionally, an anaerobic environment is required for the production of acetic acid to prevent the production of propionic and butyric acids (Arras et al. 2019).

6.5.2.3

Butyric Acid

The beverage, chemical, cosmetic, textile, plastic, pharmaceutical, and food industries all make extensive use of butyric acid. Through butyric acid fermentation, waste food is transformed into butyric and acetic acids. Through the EMP pathway, glucose is transformed into pyruvate during fermentation, which is further transformed into butyric acid and acetic acid. The highest yield of butyric acid was obtained at 65 °C and a pH of 5.0–6.0 (Wang et al. 2020).

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Bioethanol

Bioethanol is an excellent clean energy source made from ethanol produced from biological sources. The process of food waste fermentation leads to the synthesis of ethanol, largely accomplished through a series of three distinct stages, first hydrolysis (Complex carbohydrates to monosaccharides), second glycolysis (glucose into pyruvate and then acetaldehyde via hydrogenase enzyme), and third dehydrogenation (acetaldehyde into ethanol). The distillation process is used to separate ethanol from other by-products in the final step. In this process, the major microorganism is Zymomonas mobilis [36]. The efficiency of ethanol production is strongly affected by the hydrolysis stage. The optimal conditions for fermentation involve maintaining a pH range of 4.5–5.5 and a temperature range of 20−35 °C (Yuan et al. 2022).

6.5.2.5

Volatile Fatty Acid

During the acidogenesis phase, the process of mixed fermentation gives rise to the formation of volatile fatty acids (VFAs), which serve as a significant intermediary compound. For bioelectricity, biodiesel, and biogas, VFAs are excellent carbon sources. VFAs can also be used to make bio-surfactants, bio-flocculants, and polyhydroxyalkanoate. The nature of food waste substrates considerably influences the rate of volatile fatty acid (VFA) generation during acidogenesis. It depends on when the glucose ratio: peptone: Under anaerobic conditions, glycerol yields the maximum VFA when maintained at 38:32:31 (Velvizhi et al. 2020). The optimal pH for VFA production is between 5.5 and 11.0, but this can vary depending on the type of substrate (Wainaina et al. 2019). The yield of VFA has been reported to increase with hydrothermal treatment (25–55 °C) of the substrate (Yin et al. 2014).

6.5.2.6

Lactic Acid

Lactic acid is widely employed in the chemical, medicine, cosmetic, and food sectors due to its role as a flavor enhancer, acidulant, and preservative. Microbial fermentation is said to be the source of 90% of the industrially produced lactic acid whereas chemical methods produce only ten percent (Chenebault et al. 2022). Lactic acid bacteria, or LAB, need a pH of 3.9–5.0 and a temperature of 20–45 °C to produce lactic acid (Nagarajan et al. 2022). The process of glucose conversion into pyruvate, and subsequently into lactate or lactic acid, is facilitated by the enzyme lactate dehydrogenase, as directed by the Lactic Acid Bacteria (LAB) (Singhvi et al. 2019). Homolactic acid fermentation yields lactic acid alone, whereas heterolactic acid fermentation yields ethanol and carbon dioxide as byproducts. Through the Bifidus pathway, Bifidobacteria produce both lactic acid and acetic acid.

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Gasification

The process of gasification involves transforming biomass into a gaseous mixture that includes methane (CH4 ), nitrogen (N2 ), carbon monoxide (CO), and other elements using gasifiers ranging in power from 20 to 500 kW. The process makes use of gaseous media like steam, oxygen (O2 ), and heat. The application of steam and the kinds of gasification agents used to determine the choice of biomass gasification method (Fang et al. 2021). The various stages of the gasification process may have an impact on the amount of heat required for drying. At temperatures between 200 and 650 °C, the pyrolysis interaction undergoes thermal degradation of the dried biomass, and the char is gasified to produce syngas at temperatures between 700 and 1000 °C .

6.5.2.8

Combustion

The biomass’s chemical energy undergoes conversion into heat energy, mechanical power, or electricity. Geomaterials are produced as debris by purposefully and technically valorizing the agroindustrial waste materials through direct combustion. Turbines, boilers, or electric furnaces are used to carry out the combustion process (Yuan et al. 2022). When biomass is burned to generate high-pressure vapor for a turbine connected to a generator, boilers can generate energy more easily. The conversion efficiency for biomass combustion was found from 20 to 40% when the system exceeded 100 MWe. It was discovered that these conversion techniques performed better on biomass with high moisture content.

6.5.2.9

Trans-Esterification

Trans-esterification is the chemical reaction by which an alcohol group reacts with fat or oil to produce ester and glycerol. Biodiesel “vehicle fuel” is made from biomass combined with methanol or ethanol and a catalyst like sodium or potassium hydroxide via an esterification process (Encinar et al. 2021). Glycerol can be utilized in pharmaceuticals, cosmetics, and other industries as a byproduct.

6.6 Agro-Industrial Waste and Valorized Products 6.6.1 Agro-Industrial Waste- Means of Biofuel The use of biofuels in place of fossil fuels has the potential to bring about many advantages. Several studies have utilized agro-industrial waste, such as potato, rice straw, sweet potato waste, sugar beet waste, sugarcane bagasse, and so on, as a

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raw substance for the production of biofuels (Yogalakshmi et al. 2022). Because harvesting agro residues takes less time, they can be used as a substitute for forest residues. It contributes to forest conservation and is a significant environmentally friendly method for reducing deforestation. Numerous researchers have proposed the production of bioethanol from lignocellulosic materials and other agricultural residues as a potential biofuel (Saini et al. 2015). It can replace fossil fuels like petroleum, diesel, gasoline, etc. which is not only cost-effective but also environmental friendly. Another study demonstrated that various agricultural weeds and residues can be used to produce biogas (Paepatung et al. 2009). The need for lowcost energy sources is growing as a result of widespread industrialization and population growth. For the production of biofuels, an enormous amount of waste materials are available. By fermenting vegetables (peels from carrots, onions, and potato waste) with Saccharomyces cerevisiae, bioethanol was produced (Mushimiyimana and Tallapragada 2016). To get the most out of agricultural residues, bioethanol production is the only option that can be used. The utilization of the banana pseudostem, a frequently seen and easily accessible waste material, has been found to be a viable approach for the manufacture of bioethanol. This process involves the pretreatment of the pseudostem with Aspergillus species, which has been shown to be effective in enhancing bioethanol production. (Ingale et al. 2014). Clostridium species were also utilized in the production of butanol from agricultural residue (Maiti et al. 2016). As the result concluded agro-industrial wastes are the best means of biofuel production which is lucrative and eco-friendly.

6.6.2 Agro-Industrial Waste—As Substrate for SSF Agro-industrial wastes are packed with nutrients and minerals. The majority of agroindustrial residues contain antioxidants, enzymes, natural dyes, and pigments. These food ingredients have a high nutritive value and can be used to make new food products for industrial production, making them a better solution for the environment and the economy (Bellemare et al. 2017). The lignocellulosic components are present in it, which is difficult to break down, but it’s a better substrate for mushroom cultivation (Kamthan and Tiwari 2017). Hydrogen is the upcoming energy source for future generations. The study demonstrated that the agro wastes of obstinate nature are decomposed by vermin-humusassociated micro-organisms to produce hydrogen (Oceguera-Contreras et al. 2019).

6.6.3 Agro-Industrial Waste Enzyme Production The diverse composition of industrial and agricultural waste provides favorable conditions for the cultivation of microorganisms involved in the production of enzymes in the course of fermentation (Viveka et al. 2021). Enzymes made from

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agro-industrial waste are shown in Table 6.3. These raw materials help microbes to grow at a faster rate. Fungal strains are used to produce cellulolytic enzymes (β-glucosidase and endoglucanase) (Kalogeris et al. 2003). Another study demonstrated that SSF can be used to produce phenolics from corn cob (Topakas et al. 2004). Oil cakes, fruit and vegetable peels, field residues, and other food industry raw materials produce glucoamylase and amylase enzymes via bacterial activity. Four enzymes amylase, protease, pectinase, and cellulase are produced by Bacillus species using agricultural leftovers such as cereal brans, sunflower olive oil cake, and oatmeal. For maximum production, chemical pretreatment was used. Amylase was made from four different types of agricultural waste, including soybean meal, sugarcane bagasse, wheat flour, and wheat bran. This study utilized Rhizopus microspores due to their abundance of carbon sources (Salim et al. 2017). Wheat bran was the material that produced the most of these materials. The application of agro-industrial by-products such as cane bagasse, maize cob, and coconut husks for the production of ellagitannins (Buenrostro-Figueroa et al. 2014). Corn cob was found to produce the most enzyme than sugarcane bagasse and husk of coconut. When producing lipase enzymes, oil cakes were used, and particularly palm kernel oil cakes produced the most lipase (De Oliveira et al. 2017) Table 6.3. Table 6.3 Utilization of agro–industrial waste as a source of enzyme (Kapoor et al. 2016) Agro waste

Enzymes produced

Babassu cake

α-amylase, lipase

Corn cob

cellulase and cellobiose

Coffee pulp/pod husk

Pectinase, tannase, laccase

Grapes pomace

Pectinase

Apple pomace

Cellulase, xylanase, pectinase

Orange pomace

Tannace,

Sugar bagasse

Lipase, laccase, pectinase

Wheat bran

α-amylase, pectinase, Xylanase, cellulose, cellobiase, protease, endo-mannanase, chitinase,

Wheat straw

Cellulase, Xylanase

Tomato pomace

Laccase

Lentil husk

Protease, α-amylase

Olive, canola, mill waste

Lipase, laccase, β-glucosidase

Rice straw

Cellulase, xylanase,

β-glucanase

Oatmeal

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6.6.4 Agro-Industrial Waste- Antibiotic Production Microorganisms can be selectively killed or inhibited from growing by antibiotics. Antibiotics are generally bioactive compounds that were in greater demand as a result of human development, industrialization, and population growth. Bioactive compounds are abundant in agricultural wastes like corn cobs, rice hulls, and peanut shells. Thus agro-waste is also used in the industrial production of antibiotics and other products with additional value (Kashif and Shahid 2022). Through SSF, the oxytetracycline antibiotic was made from groundnut shells as a raw material. This production procedure made use of Streptomyces rimosus (Kasapidou et al. 2015). Agro-waste can be used to make antibiotics at a low cost by using the appropriate fermentation methods. Neomycin, oxytetracycline, and rifamycin were found to be produced through solid-state fermentation (SSF) (Kashif and Shahid 2022).

6.6.5 Agro-Industrial Waste- Phytochemical Production Agro residues could become essential substrates for the production of photochemical due to their abundance of biologically active compounds. Beneficial phytochemicals with health benefits like antiradical, antibiotic, immunomodulatory, anticarcinogenic, and cardiovascular protective properties can be found in by-products of fruit and vegetable processing (Kasapidou et al. 2015). Numerous studies showed how these agro-residues and their bioactive compounds could be used to make functional foods and cosmetics (Casas-Godoy et al. 2022). The subsequent table presents data regarding phytochemicals derived from agro-industrial waste, elucidating their associated health advantages and applications within various industries (Oleszek et al. 2023) Table 6.4.

6.6.6 Agro-Industrial Waste- Biomaterial Production Lignocellulosic raw materials are matrices that are natural, renewable, biodegradable, and good for the environment. They are inexpensive, available in large quantities, and have characteristics that make them efficient for multiple industrial applications. These matrices have the following advantages over synthetic inputs: a wide range of loads that can be extracted from agro-industrial and forest sources; low density and lower consumption of energy; specific modulus and strength; reactive surfaces that are simple to change and use for different groups; high potential for use in nanoparticle systems and recycling. The majority of lignocellulosic biomass consists, on average, of lignin (10–25% by weight), hemicellulose (20–30%), and cellulose (40–50% by weight). Through biofilms and bionanocomposites synthesis,

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Table 6.4 Agro-industrial waste as the source of phytochemicals Agro-industrial residue

Phytochemicals

Health benefits

Industrial application

Sugar bagasse

Gallic, coumaric, caffeic, chlorogenic, and cinnamic acids, isoflavones, quercetin

Antioxidant, antimicrobial, antihyperglycemic activity

Reducing reagent

Corn husk, cobs, tassel, pollen, silk, fiber, stigma

Phenolic acids, flavonols, anthocyanin

Antioxidant, antimicrobial, antidiabetic, anticarcinogenic, activity

Natural preservatives, stabilizers, emulsifiers, and colorings

Soybean leaves, pod, pericarp, twigs, and okara

Phenolic acids, isoflavones, lecithin, flavonols, flavones, catechin, saponins

Antioxidant, Food antimicrobial, anticancer, supplements cardiovascular activity, anti-estrogenic

Potato peels

Phenolic acids, Antioxidant, flavonols, anthocyanins, hepatoprotective, glycoalkaloids anti-inflammatory, anti-obesity properties

Precursors for hormone

Olives pomace, leaves, Phenolic acids, olive mill wastewater secoiridoids, flavonoids

Antioxidant, antitumor, Nutraceutical antiradical, antimicrobial additives activity

Citrus peels

Organic acids, phenolic acids, rutin, catechin, volatile compounds

Antidiabetic, antioxidant, Natural food antimicrobial, nticancer preserver, for metabolic syndrome

Grapes pomace including seeds, pulp, skins, stems, and leaves

Phenolic acids, Savona’s, catechins, anthocyanins, resveratrol, fatty acids

Antioxidant, anti-inflammatory, anti-proliferative activity

Food additive, colorant, antioxidant

Apple pomace, peels, skin, flesh, seeds, and stem

Phenolic acids (chlorogenic, ferulic), flavonols (quercetin glycosides), dihydrochalcones (phloridzin), catechins

Antioxidant, antitumor, anti-inflammatory, antimicrobial, antidiabetes, antiobesity activity

Food Ingredient, yellow Pigment corrosion inhibitor

Banana peels, rotting fruit, leaves, stems, flowers, pseudo parts

Phenolic acids (ellagic, ferulic), flavanols, flavanones, catechins

Antioxidant, antimicrobial, platelet aggregation inhibitory, anti-hyperglycemic activity

Biofungicide, corrosion inhibitors, colorant

Antioxidant activity

Food additives, natural colorant

Tomato peel, seeds, Phenolic stems, leaves, and pulp acids,flavonole, flavanones, isoflavones,resveratrol, carotenoids

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the lignocellulosic content of biomass can be utilized in the formation of multipurpose biomaterials, applied in the fields of food, medicine, engineering, and pharma industries. Biosensing, controlled drug delivery, and tissue engineering scaffolds can all benefit from these nanocellulosic biomaterials (Fortunati and Balestra 2019). Biofilms Using chitosan and silver nanoparticles, a biofilm of sugar bagasse’s lignocellulosic components was created (Aradmehr and Javanbakht 2020). The product with high lignin concentrations had excellent flexibility and swelling properties. Antioxidant and antimicrobial properties can be found in the produced hydrogel. A nanocellulosebased nano-biofilm was derived from plant biomass (Hassan et al. 2019). Corn leaves after agro-industrial processing were used without chemical treatment. Cellulose content, firmness, mineral composition, odor, pH, shape, tensile strength, and water absorption were all examined. Once it is biodegradable, the elaborate product can take the place of petroleum-based plastic. Bionanocomposits The continuous casting technique is employed to fabricate bionanocomposite films including gelatin and nanocrystals derived from eucalyptus cellulose (Leite et al. 2020). The UV barrier’s transparency, adaptability, and thermal properties made the produced products satisfactory and used in biodegradable food packaging. Ultrasound was used to create bengkoang/cellulose nanofiber-starch biocomposites from pineapple residues (Mahardika et al. 2019). The tensile strength increased in developed materials than fiber-free alternatives, suggesting that they could be used in food-safe systems based on renewable matrices. Rice straw cellulose nanocrystals were utilized in the production of biocomposites containing chitosan (Xu et al. 2018). Ultrasonic acid hydrolysis was used to create the materials. Biosensing, controlled drug delivery, and food packaging systems are all potential uses for newly developed products.

6.7 Agro-Industrial Waste–Biofertilizer Production Some nutrients like nitrogen (N), potassium (K), and phosphorous (P) are essential for the growth of plants which is present in the soil. After harvesting the amount level declines so the soil becomes less fertile. To improve its quality and compensate for the nutrients some natural or chemical fertilizers are added. In recent years, the use of synthetic fertilizers for controlling pests to increase agricultural production has increased. However, the majority of chemical fertilizers harm both plants and soil microbes. The microbes can break down the organic compounds when organic fertilizers are applied, which improves the soil’s physical, chemical, and biological properties (Varjani and Upasani 2021). Biofertilizers can be made by using microorganisms to break down food and residues from agriculture. These wastes can be used by the microbes as a source of nutrition and they produce compost which is used

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as a biofertilizer (Zhang et al. 2016). Composting not only reduces the amount of waste in the solid state but also turns it into a useful biofertilizer. The most acceptable substrates for microbes to produce compost are waste from oil mills and wine factories. Fungi are important for biodegradation, the composting process is initiated by bacteria (Cerda et al. 2018). Utilizing agricultural waste as a biofertilizer can boost food production. The biofertilizers group generally contains microbes based on function, inexpensive, and abundance. Arbuscular mycorrhiza, Azolla, Azospirillum, Cyanobacteria, Phosphate solubilizing bacteria (PSB), and Rhizobium fungi are the primary members of this group (Bhattacharjee et al. 2014). When compared to chemical fertilizers, these bio-fertilizers are extremely beneficial and do not pose any environmental risks. Utilizing earthworms is yet another method by which agricultural waste can be used to make biofertilizers. Vermicomposting is the process of turning agricultural waste into high-quality compost primarily composed of worm castings and decaying organic matter. Phosphorus (P), nitrogen (N), potassium (K), and soil microbes, particularly PSB and nitrogen-fixing bacterias, are abundant in vermicompost (Devi and Prakash 2015). The composition of this substance primarily consists of agricultural wastes, such as cow dung, dry leaves and grass, rotting fruits and vegetables, rice straw, and similar organic materials. It is a great growth stimulant. Vermicompost-produced biofertilizer outperforms NPK chemical fertilizers in terms of macro and micronutrient content. By enriching the soil with the necessary nutrients, the vermicompost-rich biofertilizer can increase crop plant growth rates (Singh et al. 2022) (Fig. 6.1).

6.8 Future Perspectives of Valorized Agro-Industrial Waste Natural sources of several nutrients are present in agricultural wastes. If it is disposed of improperly, it can pose major risks to the environment and disrupt the ecological cycle. A potential option in terms of economics, social implications, environmental effects, and overall sustainability, is to valorize food residues and wastes into valuable resources. They are beneficial because of less cost and easy availability. Lignocellulosic biomass present in agro residues can be converted into fuel, enzymes, and other bioresources. But the product formed needs purification to separate impurities which is more costly and may be considered as an alternate solution. The selection of the right methods and technologies, and the right strains of microbes are necessary to scale up the quality and quantity of desired products. The utilization of agroindustrial waste has the potential to serve as a forerunner for reducing manufacturing costs, promoting waste management through recycling, and generating environmentally sustainable organic fertilizers that enhance soil quality and augment crop productivity. The implementation of suitable pre-treatment methodologies can enhance both the quality and quantity of valorized waste materials. For example, the utilization of microbial treatment for the conversion of lignocellulosic materials into biofuel has

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Fig. 6.1 Transformation of agro waste in Biofertilizers by microorganisms

notable advantages over chemical treatment methods. The efficiency and environmental friendliness of the system are notably enhanced. The value of agro waste as valuable products has increased significantly. Further research is needed to figure out how to increase the production of bioactive chemicals, biofuels, enzymes, and other products by using inexpensive residues.

6.9 Conclusions The foundation of a sustainable nation is laid by the sustainable environment and the sustainable environment can be formed not only by reducing pollution but also by transforming waste into valuable outputs. The agro-industrial wastes are increasing the pollution load. The agro residues are biomass rich in organic matter, especially nutrients like minerals, fibers, oils, and so on. The conversion of this waste into resources is a big challenge. Several non-conventional technologies are developed which are highly efficient and require less money, fewer resources, and less time to produce the valorized product. The biomass is heterogeneous and mainly treated by thermal, chemical, and microbial methods. The products obtained from waste

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are biofuel, biofertilizers, biomaterial, enzymes, phytochemicals, antioxidants, and so on. These are the renewable resources more feasible and environment friendly. The modern technologies developed are more significant except for the purification techniques, it is laborious and expensive. The agro-industries must adopt the process of managing industrial waste on a wide scale because as the population increases waste management is also considered without raising prices. Future research in this area will primarily focus on the incorporation of new advanced technologies, genetic modification of the productive strains, enhancement of fermentation layout, and checking for downstream processing techniques that are environmentally beneficial.

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Chapter 7

A Critical Assessment of Processes and Products for Valorization of Agroforestry Industrial Wastes for Biorefinery Rocio E. Cardozo, Johana A. Rivaldi, María E. Vallejos, and Nicolás M. Clauser

Abstract The technical and economic assessment of biorefinery processes is complex, mainly due to the uncertainties related to the cost and type of lignocellulosic biomass, energy consumption, production costs, market price of final products, required investment, and utilized processes and technologies. The design of biorefinery is based on the principles of conventional chemical process design. Within this design and process assessment, several uncertainties are involved. In process design, the primary uncertain factors are linked to the proposed conversion pathways and their estimations (including chemical and physical properties, transfer coefficients, and others), the involved processes (such as mass and energy flow rates and variations, integration strategies, and others), external factors (like availability of raw materials, product demands, prices, and environmental conditions), and technological factors (equipment availability, process maturity, others). Among the challenges encountered in assessing product and process selection, the following can be mentioned: (i) understanding aspects related to the product, such as the relationship between the product profits and manufacturing cost; (ii) accounting for evolving technologies, demands, and competition with new products over time; and (iii) comprehending the economic aspects to obtain maximum benefit. This chapter delves into the critical assessment of processes and products for the valorization of agroforestry industrial wastes for biorefinery contexts. Keywords Agroforestry wastes · Biorefinery design · Uncertainty · Product selection

R. E. Cardozo · J. A. Rivaldi · M. E. Vallejos (B) · N. M. Clauser FCEQYN, Programa de Celulosa y Papel (PROCyP), Félix de Azara, IMAM, CONICET, UNaM, 1552 (3300) Posadas, Argentina e-mail: [email protected] © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 A. S. Mathuriya et al. (eds.), Green Technologies for Industrial Waste Remediation, Environmental Science and Engineering, https://doi.org/10.1007/978-3-031-46858-2_7

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7.1 Introduction In the current global economic system, concepts such as circular economy (CE), bioeconomy (BE), and circular bioeconomy (CBE) have emerged as response to the growing demand of society to improve the use of natural resources and reach sustainable development for a sustainable future (Clauser et al. 2022). The “green economy” paradigm encompasses diverse industrial sectors, including forestry, agriculture, food, pharmaceutical, pulp and paper, energy, and others (Ubando et al. 2020; Clauser et al. 2021). On a global scale, it is estimated that up to 90% of fossil-derived products could potentially be substituted by renewable raw materials (Clauser et al. 2021). Over recent years, numerous governments around the world have been working to develop policies to reduce waste from industry, and replace fossil-based products to achieve CBE (Clauser et al. 2021). In the year 2018, the European Union contribution to the biobased industries amounted to 780 billion EUR (Bioplastics 2021), while the biobased products sector in the United States generated a total revenue of approximately 470 billion USD in 2017 (de Guzmán 2022). The biorefinery concept stands out as one of the most promising approaches for attaining the objective of sustainable development, which mainly aims to use renewable feedstocks to produce value-added products. Implementing new processes with a focus on the bioeconomy should start in the first step of the process implementation, which means the design of the process. In this sense, integrating sustainability in process design contributes to minimizing uncertainties and risks associated with process implementation (Gargalo et al. 2016; Clauser et al. 2022). Figure 7.1 presents a simplified scheme of achievements allowed by the biorefinery concept.

Fig. 7.1 Achievements allowed by biorefinery platforms

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Developing new biorefinery processes requires a comprehensive evaluation of the designated process, encompassing available biomass, desired products, and the chosen procedure (Clauser et al. 2021).

7.2 Agro and Forestry Industrial Byproducts Biorefinery Status and Outlook At present, approximately 1,300 biorefineries are operational globally, with half of them in the United States. Around thirty percent are concentrated in France, China, Finland, Germany, The Netherlands, and Sweden, while the remaining facilities are distributed across other nations (IEA-Bioenergy 2022). However, there is a lack of data on feedstock, processes, and platforms used in many of these reported biorefineries. Primary biomass (starch, oil, sugar crops, and lignocellulosic biomass from wood and grass) is the main feedstock. Secondary biomass, including organic residues and agroforest wastes, alongside multi-feedstock options, and others, are employed to a lesser degree. Therefore, it is advisable to devise an integrated biomass supply to reduce feedstock expenses. Furthermore, the development of diverse pretreatment and valorization procedures becomes imperative to surmount technical hurdles primarily linked to the complex chemical composition of biomass (Clauser et al. 2022). Residual lignocellulosic biomass from the agroforest industry holds pivotal significance as a feedstock for energy, fuels, bioproducts, and materials. However, developing conversion and application processes require significant investments. The platform most used is biochemical conversion, whereas fermentation is the typical process. The chemical platform ranks second, predominating the catalytic conversion, esterification, and hydrogenation processes. Comparatively, the employment of mechanical and thermo-chemical platforms is less used, while the extraction, separation, gasification, and pyrolysis processes are predominant. The progression of conversion processes, covering pretreatment, fractionation, purification, conversion, recovery, and byproduct reuse, is not yet optimized in many cases or is still in an early development stage. Consequently, production costs remain high, and process yields are limited. In biorefineries centered on biofuels, the esterification and fermentation processes are predominant in biodiesel and bioethanol production (IEA-Bioenergy 2022). The biorefineries can be categorized based on their end products, namely energydriven biorefineries for energy and product-driven biorefineries for high-value products (Fig. 7.2) (Cardona Alzate et al. 2020). Currently, biorefineries produce mainly biofuels (60%), chemicals (building blocks, pharmaceuticals, and nutraceuticals), and polymers and fibers (25% and 10%, respectively). Animal feed and food are produced less (IEA-Bioenergy 2022). In scenarios involving high-added value products, the loss of functionalities or properties of the valuable compounds during the processing is a technical barrier that could be avoided by improving the separation

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Fig. 7.2 Illustration of the approach to the potential of biorefineries of the residual lignocellulosic biomass from agroforest industries

and extraction processes by optimizing the operational conditions in pretreatment and conversion processes. Conversely, enhancing the competitive edge of biobased products against certain conventional products can be accomplished by refining their properties, diversifying their applications across various markets, establishing certifications and standards, and/or disseminating awareness regarding their environmental advantages. Commercialization and Highlight of Bioproducts Biofuels, such as bioethanol and biodiesel, predominantly derive from conventional biomass. Currently, bioethanol is primarily produced from maize (60%), sugarcane (25%), as well as other sources like molasses, wheat, cassava, or sugar beets, whereas that biodiesel is produced from vegetable oils (75% rapeseed, soybean, and palm) or used cooking oils (20%). Bioethanol from lignocellulosic feedstock makes up a small segment of total biofuel production. The biofuel market depends on national policies that regulate bioethanol-gasoline blends (E10, 10%), provide support to farmers, reduce greenhouse gas emissions, and/or increase energy independence (OECD-FAO 2022). The United States leads global bioethanol production (47%) mainly from maize, followed by Brazil (26%) from sugarcane and maize. Technologies based on lignocellulosic feedstock represent only a small fraction of total production. In 2031, world production could reach around 140 billion liters. The price of bioethanol ranged from 0.4 to 0.6 USD/L in 2019–2022 (OECD-FAO 2022). The risks and uncertainties in the market are related to (i) the policy environment: changes in directive levels, implementation mechanisms, investment in alternative feedstocks, tax exemptions, subsidies, and technological development; (ii) feedstock: competition with food use

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Fig. 7.3 Potential value-added chemicals from lignocellulosic biorefinery, current manufacturers, and prices (Usmani et al. 2021; Singh et al. 2022)

and land use, and blending regulations; and (iii) prices: Russia’s war against Ukraine impacted the market and competitiveness (OECD-FAO 2022). Figure 7.3 presents the potential value-added chemicals attainable through lignocellulosic biorefinery, detailing current manufacturers and associated prices (Usmani et al. 2021; Singh et al. 2022). Bioorganic acids such as lactic acid, levulinic acid, succinic acid, propionic acid, glutamic acid, and acetic acid can be obtained from C5 and C6 sugars. These acids have many applications in the pharmaceutical, chemical, and food industries. For example, acetic acid is used in the production of chemicals, plastics, and polymers, and the food and beverage, ink, and paint industries. It also produces various chemicals for industries such as construction, textiles, rubber, and coatings. China is the leading producer of acetic acid, followed by the United States, and both countries, along with the rest of Asia and Western Europe, account for the largest market share of acetic acid (90% of world capacity) (Shah 2014). The primary industrial use of acetic acid includes producing vinyl acetate, terephthalic acid, acetic anhydride, acetate esters, chloroacetic acid, and ethanol. Vinyl acetate is used in the manufacture of polymers for adhesives and coatings. Terephthalic acid is primarily used to manufacture polyethylene terephthalate resins, fibers, and films (packaging). Acetic anhydride is used to produce cellulose acetates, while ethyl and sec-butyl acetates are used as solvents for inks, paints, and coatings (Wakatsuki 2012). Acetic acid sourced through biomass fermentation is used as an acidity regulator in the food industry (designated as E 260). Its function includes preventing microbial growth in food products such as ketchup, mayonnaise, other sauces, marinades, and dressings, and within the meat industry. Other applications of acetic acid include natural cleaning agents, biological pesticides, feed ingredients, and cosmetic products. The biological production of acetic acid accounts for only 10% of world production (Vidra and Németh 2017). The escalating demand for packaging, food, beverage, and textile industries in China, India, Thailand, and Korea means that

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the bio-acetic acid market continues to grow rapidly (Mordor-Intelligence 2023). Currently, biobased acetic acid is produced by oxidation of ethanol by acetic acid bacteria, with companies like Sekab (Sweden, 24,000 t/year, from 1 and 2G ethanol); Jubilant Life Science (India, from 1G ethanol, sugarcane molasses); Songyuan Ji’an Biochemical Co., Ltd (China, 150,000 t/year 1G ethanol) Ltd.; and ZeaChem (US, from cellulosic sugars by a bio-catalytic process) leading the way. The latter approach could also be extended to the cellulosic ethanol industry to obtain acetic acid from lignocellulosic biomass hydrolysates (Calderon and Arantes 2019). Lactic acid is commercially produced from carbohydrates (mainly sugars from starches) by bacteria or fungi, although it could also be produced from C5 and C6 sugars of the cheaper lignocellulosic feedstocks. The world production of lactic acid is 1.4 million t/year, mainly used to produce food and beverage (47%), polylactic acid (PLA) (38%), chemical (10%), and solvent in pharmaceuticals and personal care products (6%) (Indufor 2018; Statista 2023). The United States and China account for approximately 90% of the global production capacity. Lactic acid is a key compound for a broad range of chemicals, some of which are currently derived from petroleum, and biodegradable plastic production (polylactic acid (PLA), accounting for around 40% of the global market). Lactic acid can also be used to produce propylene oxide, an essential compound in the production of polyurethanes. The primary manufacturing companies include Nature Works LLC (US), Corbion Purac (The Netherlands), Chongqing Bofei Biochemical Products (China), among others (Juodeikiene et al. 2020). Global levulinic acid production is estimated at around 3,000 t/year, representing only 20% of the global production capacity. However, its commercial production has not occurred due to various technological challenges, such as downstream integration (Covinich et al. 2020). China and the United States are the leading producers, including GF Biochemicals; Zibo Shuangyu Chemicals Ltd, Biofine International, among others. GF Biochemicals has demonstration plants in Italy and the United States. Additionally, Biofine has operated a demonstration plant in the United States using different types of biomass. Levulinic acid can be used as a pharmaceutical additive in anti-inflammatory drugs and anti-allergen agents, a precursor of fuel additives (methyl tetrahydrofuran), solvents applicable to fine chemicals (levulinic esters, gamma-valerolactone), herbicides and pesticides, plasticizers, among others (Indufor 2018). Furfural is produced by the acid-catalyzed conversion of C5 sugars from lignocellulosic biomass. The world market for furfural is estimated to be around 200,000 400,000 t/year. China and the Dominican Republic are the key producers of furfural in the world, mainly from corn cob and sugarcane bagasse (21). China is the world’s leading producer (Teiling; Nutrafur Furfural Espanol; TransFuran, others), but only two major furfural producers are outside of China: Central Romana (Dominican Republic) and Illova Sugar (South Africa) (Singh et al. 2022). The primary use of furfural is furfuryl alcohol production (almost 90%), followed by applications as a solvent in lubricating oils and butadiene extraction (4%), while the rest is used in other applications, such as chemicals, pharmaceuticals, and flavoring intermediates (Indufor 2018).

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The global xylitol market was estimated to be around 200,000 tons in 2020, and it had been growing in recent years. Currently, xylitol is produced by the catalytic conversion of C5 sugars from the hemicellulosic fraction of lignocellulosic biomass. Xylitol is an alternative sweetener and an anticariogenic agent, especially suitable for people with diabetes since their metabolism is independent of insulin (Indufor 2018; IEA-Bioenergy 2020). Xylitol production is concentrated in China, using corn cobs or sugarcane bagasse (60 to 70% of global production capacity). The major producing countries of xylitol are China and the US, using corn cob (agro-industrial waste) and hardwood (birch, a byproduct of the paper and pulp industry), respectively. The major producing companies are Dupont Danisco (US); Xylitol Canada, Inc. (Canada); DFI Corporation (US); Zuchem Inc. (US); Shandong Futaste Co., Ltd. (China); Roquette Freres Hunan JK; International Trade Corporation (China), Jinjiang Weijia (China), among others (IEA-Bioenergy 2020). Lignin is a byproduct of cellulosic pulp production that generates more than 50 million tons of lignin, mainly burned to produce energy and recovery reagents. Lignosulfonates are the leading product, with an annual production of approximately 1.3 million t/year from the residual liquor from sulfite pulping, or post-sulfonation of kraft lignin. Currently, various companies are developing other lignin markets and applications (kraft, organosolv, hydrolysis, and alkaline lignin); however, they have not yet decided which markets and applications to target. Lignin is commercially available for various applications ranging from composite materials and surfaces active agents to a wide range of resins. However, lignin markets that have not yet been established are currently limited at present and actual markets (Wenger et al. 2020). Vanillin can be obtained by softwood lignin treatment; however, only 20% of vanillin is commercially produced from lignin, and around 80% is produced from crude oil. The current demand for vanillin is estimated to be about 20,000–22,000 t/year (Khwanjaisakun et al. 2020). The value of vanillin depends on the source; the natural vanillin produced from Madagascar vanilla is the most expensive (USD 600/ kg), whereas vanillin from lignin and crude oil have similar prices (USD 15–40/kg) ˇ (Ludmila et al. 2015).

7.3 Strategies of Process Design in Biorefinery Processes Biorefinery designs are based on classical chemical engineering process design; but due to uncertainties in each stage of the design, different strategies are necessary to make optimal decisions. A process flow diagram is a useful tool as the initial approach to organizing the process schematically. It provides an overview of the units, main input, and output streams, and facilitates design adjustments until a fully integrated process is achieved. Pretreatment Pretreatment is typically the first stage of the biorefinery design and depends on factors such as the type of lignocellulosic feedstock and the recovered fractions

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(cellulose, hemicelluloses, and lignin). The pretreatment function is to fractionate the byproduct to release sugars; some methods applied on agroforestry feedstock are shown in Table 7.1. Nevertheless, numerous papers have studied combined pretreatments, for example, (i) autohydrolysis followed by delignification in pine sawdust and sugarcane bagasse; (ii) steam explosion followed by acid treatment in pine sawdust; (iii) combined acid and alkaline pretreatments; (iv) organosolv pretreatment then by acid pretreatment; and (v) alkaline pretreatment followed by organosolv in pine sawdust, among others (Clauser 2019; Rezania et al. 2020; Imlauer Vedoya et al. 2022). Liquid–Solid Ratio (LSR) In different stages of the process, specific considerations are associated with different types of ratios and yields. For example, in pretreatment, using the appropriate liquid– solid ratio (LSR) to efficiently fractionate the raw material components and determine the appropriate volume to be heated to the required temperature is essential. In the pretreatment, two main streams are generated, (i) the residual solid (pretreated material or cellulosic fibers) continues to the main process, and (ii) the spent liquor carries on the secondary process. Finally, both streams are driven to intermediate recovery, conversion, and purification stages to produce multi-products. Concentration is also a critical factor in processes such as fermentation, catalysis, and hydrolysis. The solids concentration is commonly related to the final conversion yield, and economic parameters like operational costs, energy, and cooling water (Clauser et al. 2020, 2021). Conversion Processes The definition of the product(s) should contribute to the design of the main process and potential secondary products. Current strategies in biorefinery design focus on valorizing all biomass fractions and producing multiple products; however, this approach directly affects equipment costs and their connections due to additional installations on integration strategies, in addition to the high investment of the main process. Furthermore, utility demand also increases, and the number of operators often increases (Clauser et al. 2021). Plant Scale Biorefinery design involves implementing the models, starting with the lab scale and continuing with the pilot scale to validate the results. Biorefineries are commonly classified into small, medium, and large scale according to the production capacity. In this regard, some important features are analyzed. On the industrial scale, the feedstock cost is commonly higher than the utilities, which is a common feature of industries that directly impacts capital expenditure (CAPEX) and operating expenditures (OPEX). Moreover, due to the amount of heat generated in the streams, it is possible to take advantage of heat exchange networks that lead to lower costs of utilities. However, for small scales, due to the lower capacities, integration of mass and energy is more difficult; therefore, they must be externally provided (Cardona Alzate et al. 2020) (Fig. 7.4).

• Fiber swelling and lignin extraction from lignin-carbohydrate complex and partial hydrolysis of lignin. (Clauser 2019) • Alkali reactive like NaOH, Na2 CO3 , NaOH and H2 O2 Ca(OH)2

• Concentrated acid hydrolysis dissolves cellulose and hemicelluloses at low temperatures. It is energetically more favorable than dilute acid hydrolysis at high temperatures. High amounts of neutralization residues are corrosive and difficult to recycle. Higher degradation of sugars. (Rezania et al. 2020) • Diluted acid hydrolysis dissolves mainly hemicelluloses. Lower degradation of sugars

• High temperatures and long times, it does not use chemical reagents • Acetic acid is generated from hemicelluloses, which act as a catalyst for hydrolysis • Degradation products are formed, and it is not recommended for raw materials with high lignin content

Pretreatment

Table 7.1 Fractionation treatment types applied to lignocellulosic biomass Fraction extracted

Rice husk Corn stover, miscanthus, and switchgrass

Eucalyptus globulus sisal fiber

Extractives, hemicelluloses, lignin

Hemicelluloses

Pine sawdust Hemicelluloses sugarcane bagasse

Feedstock

(continued)

Arismendy Pabón et al. (2020), Mirmohamadsadeghi et al. (2016)

Vargas and Vecchietti (2018), Xavier et al. (2018)

Clauser (2019)

Ref.

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High-pressure steam and

• Catalysts hydrolysis the internal bonds between lignin and hemicelluloses • Solvent favors lignin extraction. It is recovered by distillation (Chen et al. 2017)

temperature (20–50 bar, 210-290ºC) during a short time, followed by quick depressurization (explosion) • Destructuring of the material, depolymerization, and breaking of lignin-carbohydrate bonds. (Clauser et al. 2018)

•

Pretreatment

Table 7.1 (continued) Fraction extracted

Pine sawdust Mixture of sawmill waste of softwood

Hemicelluloses, lignin

Pine sawdust Hemicelluloses sugarcane bagasse and trash. Brown leaves

Feedstock

(continued)

Clauser (2019), Abdou Alio et al. (2021)

Clauser et al. (2018), Farzad et al. (2017)

Ref.

134 R. E. Cardozo et al.

• Thermochemical pretreatment using volatile ammonia as the catalyst • A dry-to-dry process that does not cause significant changes in biomass composition and does not require any washing step

• Based on the use of solvent composed of large organic cations and small inorganic anions with a low vapor pressure that typically melts below 100 °C • Lignin and carbohydrates can be dissolved simultaneously (Elgharbawy et al. 2016; Chen et al. 2017)

Pretreatment

Table 7.1 (continued)

Cellulose, hemicelluloses, lignin

Hemicelluloses, lignin

Agricultural and forestry biomass

Pennisetum sinese (P. sinese), salix chips, and pine chips

Fraction extracted

Feedstock

Hu et al. (2022)

Elgharbawy et al. (2016)

Ref.

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Fig. 7.4 Issues about building a biorefinery process

From the above, most of the factors involve uncertainties related to technical, economic, and environmental performance. Mainly, techno-economic studies provide valuable insights into factor impacts and potential opportunities. Therefore, it is evident that a sensitivity analysis should be included in the design of biorefineries.

7.4 Technical and Economic Assessment and Its Uncertainties The technical and economic analysis of biorefinery is critical to developing the process from the laboratory scale to the pilot scale and industrial scale. These assessments involve significant sources of uncertainty, demonstrating the need to carefully develop both aspects to determine the factors that influence biorefinery profitability (Clauser et al. 2021). Economic assessment has a set of considerations that can be explained as follows. Equipment The comprehensive design of the process makes it easier to identify which equipment to use at each stage, the capacity, requirements, and units needed. Regarding the cost estimation, an installation factor is applied to each piece of equipment depending on the equipment type and its operation. Studies commonly adopt equipment costs using databases and are updated then to the present with the plant index reported year to year at Chemical Plant Cost Index (CEPCI) (Clauser 2019; Clauser et al. 2021).

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Feedstock and Supplies Quantify the volume of feedstock, reagents, electricity, steam, and water required. At this stage, the development of the mass balance should be useful to consider possible recoveries that could impact the costs. Mass and Energy Balances The literature has shown that solvents and reagents recovery is necessary to achieve a profitable process. For example, ethanol used in organosolv delignification and NaOH in alkaline treatment can be almost entirely recovered or recovered at a high percentage. Similarly, this occurs with energy through the integration that must be mandatorily applied in the processes of biorefineries to save energy consumption and steam (Cardona Alzate et al. 2020). Streams Recoveries and Energy Integration As mentioned previously, biorefinery processes generate secondary streams with a fraction of the input reagents that can be recovered and returned to the process. Moreover, the product of the secondary streams can generate high revenues, for example, in certain processes that occur with lignin-rich spent liquor. On the other hand, the output streams can contain heat that can be integrated into other processes, called cold and hot streams. Pinch analysis is a methodology to optimize energy recovery through integration, minimizing capital investment. Several studies were reported with considerable improvements. (Clauser et al. 2021). Also, mass integration could improve the overall process economy (Clauser et al. 2020, 2021). Industries Lifetime The biorefinery analysis should also consider the projected scale and lifetime (depending on the context of each country). The scale of the process depends on the availability of the feedstock. Updated feedstock sources available and their location is essential to know evaluate and determine the location of the biorefinery facility (Cardona Alzate et al. 2019). Similarly, the availability of reagents needed for the process, the utilities (electricity, steam, and water), and the availability of labor are critical. The development of the cash flow allows for determining the economic parameters, such as the payback indicator used in companies to calculate the period of return on investment in a project, the internal rate of return, and the net present value. In addition, the lifetime of biorefineries is a cash flow requirement that influences the indicators, which are mainly reported from 10 to 30 years. The lifetime of a plant also depends on the uncertainties of factors like the economic context of the region and the maturity of the technologies necessary for the development of the industry. Table 7.2 presents recent studies with different lifetimes and scales adopted in the techno-economic analysis.

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Table 7.2 Lifetime used in recent biorefinery studies Country-region

Feedstock

Lifetime

Capacity

Ref.

United Kingdom

Forestry residues

20

20 td /d

Rojas Michaga et al. (2022)

United States

Blended pine residues and switch grass

30

275, 500, and 785 ODMT/d

Lan et al. (2021)

Argentina

Lignocellulosic biomass

10

156,000 t/y

Clauser et al. (2020)

Germany

Beech wood

30

400,000 td /y

Nitzsche et al. (2016)

Argentina

Pine sawdust

10

128,800 t/y

Clauser et al. (2018)

Brazil and Sweden

Eucalyptus, pine, spruce, corn, rice husks and straw, barley straw, wheat straw, others

15

500 td /d

(Tanzer et al. 2019)

United Kingdom

Corn stover

20

600 td /d

(Thaore et al. 2018)

MT Metric Tons–ODMT oven-dry metric ton–BDMT bone dry metric ton–td /d ton dry per day

Price Variations Many techno-economic and sensitivity analysis studies agree that price and cost fluctuations significantly affect the economic performance of biorefineries. Therefore, sales prices and costs require further analysis. Different scenarios of external and internal aspects must be considered within a project feasibility study to develop effective response strategies and control financial risks. Critical Factors, Distribution, and Simulation The uncertainty involved in multiple aspects of the biorefinery design makes it necessary to identify the variables most influence the process and assess their effects on the system and its behavior. The variations in sales prices, raw material costs, and required inputs represent a large number of variables that affect the biorefinery model. These variables are included in the risk and sensitivity analysis. A few examples include raw material costs, chemicals, energy costs, water, enzymes, and product selling prices. Technical factors include variables such as LSR, yields, steam economy, and optimum wash ratio (Clauser 2019). One common approach is to adjust each evaluated variable to different probability distributions. In this sense, the triangular distribution is used when data availability is limited, and a minimum value, a probable value, and a maximum value are adopted based on previous information and trends. The uniform distribution represents variables in which all minimum and maximum values have the same probability of occurrence. In contrast, the normal distribution represents a data set in which most of the

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values are grouped in the center of the range and, the rest decreases symmetrically towards either end. Some authors choose to use log-normal and log–log distributions when they have a better understanding of the data (Mandegari et al. 2018). Risk and Sensitivity Analysis Simulation software is an effective tool to save resources and time in studying the potential biorefinery location and the plants in operation. The simulation of the set of variables that make up a process facilitates evaluating and analyzing existing and emerging processes to find the optimal process configuration. Uncertainty represents the existence of multiple values and the absence of information. Process modeling and computer-assisted simulation are growing strongly due to the successful results obtained in industrial development for designing, analyzing, and optimizing industrial processes. Using the simulation software at different stages of the process could reduce the uncertainties, both for technical development and economic evaluation and even to assess sensitivity. The simulation software commonly used are @Risk, Crystal Ball, Aspen Plus, GAMS, ChemCAD, UniSim Design, SuperPro Designer, Promax, ProSimPlus, and others.

7.5 Biorefinery Product Selection and Its Uncertainties In the product design process, factors like product structure, composition, customer requirements, quality, and final disposal are considered, which gives each product its specific characteristics. In a biorefinery context, the selection of products is a complex process because it requires an integrated approach that considers technical, economic, environmental, and market concerns (Cardona Alzate et al. 2019). To evaluate the most promising products is necessary to consider most of the factors related to the product, its integration with a specific production process, and the external facility context, including market, environment, consumers, and technologies. The standard design of the chemical process and its products is based on fundamental steps: (i) preliminary design, (ii) conceptual design, (iii) detail engineering, and (iv) setting up. (Stuart and El-Halwagi 2014). The configuration of the developed process must consider the specific conditions of the area to be established, such as raw material available, climatic conditions, technologies, and economy. For this reason, applying heuristic selection methods could help evaluate the overall system involved in product design (Stuart and El-Halwagi 2014). Conceptual and Informational Design In the design of biorefinery processes, it is critical to determine the promissory products that could be produced from each biomass source, because the number of products to obtain has been increasing during the last few years. Therefore, the

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first step consists of selecting products from elaborated lists of products from literature, also identified as building blocks. The National Renewable Energy Laboratory (NREL) and several authors have produced interesting reports about that (Clauser et al. 2021). A multi-criteria decision-making tool involving techno-economic, market, and environmental factors could identify a preliminary list of products based on their potential (Cardona Alzate et al. 2019). This process is known as hierarchical, and it is a critical stage that requires a strategic data selection design that can characterize the best products based on different factors. The hierarchical process is based on heuristic methods of multi-criteria decision-making, and fundamental factors of biorefinery product design are integrated. (Gómez and Cabrera 2008). The main factors to consider in the product selection are the raw material, technical and economic factors, environment, and markets. Raw Material It is commonly the starting point of the process because the fractionation process depends on the characteristics of the feedstock. As mentioned, lignocellulosic biomass comprises three main fractions: hemicelluloses, cellulose, and lignin. Therefore, the products selected must be defined based on these fractions. Technical Factors It involves the technology selected and steps involved (reactors, evaporators, distillation columns, crystallizers, others), number of operators, energy consumption, integration strategies, and supplies (acids, solvents, microorganisms, others). Another aspect to consider are regional adaptability, which refers to the characteristics of existing industries in the region in which the new products are to be developed and evaluating the capacity of current value chains to allow the establishment of new value chains (qualified labor, know-how, biomass handling, others) (Cardona Alzate et al. 2019). Market Factors It is necessary to consider customers’ preferences and requirements and incorporate them into successful market models, supply chain strategies, and product delivery (Chambost et al. 2011). Besides, emerging product trends should be considered, like environmentally friendly products, biobased products, and recycled products (Amoah et al. 2019). Other factors to consider are trend analysis, market volume, and commercial value of the products. Environmental Factors Sustainability is one of the most important concepts related to biorefineries. Therefore, the impact factors of these new processes must be considered, such as wastes generated, life cycle assessment, and carbon footprint (IEA-Bioenergy 2009).

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7.6 Commercial Technologies North American countries and the European Union have developed technologies that have enabled the production of several biobased products on a commercial scale. Most of these facilities are integrated with pulp and paper mills (Area et al. 2019). In Europe, Metsä Group has transformed from the conventional production of cellulosic pulp into a high-efficiency integrated biorefinery in which kraft pulp is produced as the main line and integrates the cogeneration of multiple products such as oil, turpentine, biogas, sulfuric acid, among others (Niklas von Weymarn 2020). On the other hand, the Borregaard Company has managed to incorporate the production of high-value biobased chemical products derived from the different fractions of biomass on a commercial scale, such as ethers, acetate, nitrocellulose, vanillin, micro fibrillated cellulose, and others (Borregaard 2019). In the United States, the development and investment in the production of biofuels and renewable hydrocarbons can make substantial progress in the future development of biorefinery processes (Energy 2023). Some chemical products that are currently commercialized on a small scale include nanocellulose, microfibrillated cellulose, and succinic acid. Additionally, the American Process Company has patented several efficient fractionation technologies for lignocellulosic biomass (Area et al. 2019). In Latin America, the Suzano company in Brazil is the first company that has adapted the configuration of its pulp and paper production line to a new configuration with lignin cogeneration on a commercial scale and nanocellulose on a pilot scale. Table 7.3 shows some of the biobased products that have been produced on a commercial scale.

7.7 Conclusions The valorization of agroforestry industrial waste for biorefinery requires critical process and product assessment to overcome the limitations that delay their implementation on a commercial scale. Currently, around 1,300 biorefineries worldwide produce 1G bioethanol and biodiesel from rapeseed, soybean, or palm. Residual lignocellulosic biomass from the agroforest industry is a critical feedstock for energy, fuels, bioproducts, and materials due to low cost and high availability. However, the development processes for the lignocellulosic biomass fractionation and conversion require significant investments. The most commonly used platforms are biochemical and chemical conversion. These conversion processes are not yet optimized in many cases or are still in an early development stage, so production costs are high, and process yields are low. Esterification and fermentation processes are predominant in biodiesel and bioethanol production.

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Table 7.3 Biobased products at commercial scale Country

Company

Biobased product

Scale

Finland

Metsä group

Oil, turpentine, biogas, sulfuric acid

Commercial Niklas von Weymarn (2020)

Norway

Borregaard

Ethers, acetate, Commercial Borregaard (2019) nitrocellulose, vanillin, micro fibrillated cellulose

Finland

Fortum

Bio-oil

Commercial Area et al. (2019)

Germany

Tecnaro

Bioplastics and biocomposites

Commercial Nägele and Pfitzer (2023)

Sweden

Aditya birla group’s Dissolving cellulose, lignin, ethanol

Commercial Area et al. (2019)

France

GFBiochemicals

Levulinic acid

Commercial Granata and Flamini (2023)

Finland

UPM

Bio-diesel and bio-naphtha

Commercial UPM BioVerno (2023)

United States Myriant

Succinic Acid

Commercial Area et al. (2019)

United States FiberLean

Microfibrillated cellulose

Commercial FiberLean (2023)

Brazil

Suzano

Ref.

Lignin

Commercial Area et al. (2019)

Nanocellulose

Pilot

Canada

West Fraser

Lignin

Commercial Area et al. (2019)

Canada

RYAM

Carboxylated Cellulose Nanocrystals (CNC)

Commercial RYAM (2023)

In the case of high-added value products, the loss of functionalities or properties of the valuable compounds during processing is a technical barrier that could be avoided by improving the separation and extraction processes by optimizing the operational conditions in pretreatment and conversion processes. On the other hand, the competitiveness of biobased products with some conventional products could be achieved by improving their properties, broadening their uses to other markets, setting their certification and standardization, and/or spreading their environmental benefits. A techno-economic analysis of biorefinery can be carried out based on estimations of the investment required and economic indicators. Besides, risk and sensitivity analysis is required to assess the effects of uncertainties on the overall feasibility. The most significant parameters and variables that impact the feasibility of biorefinery are commonly related to factors like technical, economic, environmental, and market (potential products, production rate, raw material and product prices, sales

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price, fixed cost, capital investment, and others). Besides, variables like scale, lifetime, and integration strategies, involve uncertainties and they must be determined and evaluated. The selected variables could be adjusted by statistical distribution to understand their influence better. Product selection is critical in the overall process design and must be evaluated considering an integrated approach of economic, technical, environmental, and market factors. In this sense, one promising strategy is applying hierarchical methods, in which regional data like feedstock, technologies, market, and environmental concerns are critical to select the most promising products correctly. Several technologies are currently implemented at a commercial scale. Besides biofuels, new biobased products are emerging in the bioeconomy sector. The advances in the last years in biorefinery process design and assessment have been improved considerable, and several assessment strategies could be applied to evaluate all steps to the development of biorefinery processes at a commercial scale.

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Chapter 8

Bioaccumulation and Detoxification of Metals Through Genetically Engineered Microorganism Priya Chauhan, Nitya Panthi, Indrani Mazumdar, and Nazneen Hussain

Abstract Rapid pace of industrialization and unimpeded growth of the human population have resulted in increased discharge of hazardous metals possessing both harmful and carcinogenic properties. These metals serve as a significant catalyst for pervasive environmental pollution due to their high toxicity, wide prevalence, and resistance to degradation. One of the most serious environmental challenges with metals is its non-degradable nature; for which these contaminants tend to accumulate in the food chain, even at low concentration and thus contribute to interruptions in the survival equilibrium. Conventional remediation methodologies are well established; however, the technology is inadequate for pollution mitigating applications owing to its considerable drawbacks: expensive, generation of sludge waste via chemical precipitation, secondary disposal problem. Microbial bioremediation of heavy metals has received significant global attention for it plays a significant role in the fate, transport, mobility, and distribution of the contaminants in a more viable and sustainable manner. Moreover, the recent advancements in molecular biology and genetic engineering have led to the exploration and construction of genetically engineered microbes (GEMs) for abatement of metal pollution. The study elucidates that the metal binding proteins and sequestration of metal ions remains in the forefront for bioaccumulation and transportation of toxic metal by GEMs. Recombinant expression of unique import-storage systems in GEMs contributes to enhanced uptake and sequestration via stabilization of charges on biomolecules, production of metabolites, P. Chauhan · N. Panthi · I. Mazumdar · N. Hussain (B) Department of Biosciences, School of Life Science, Assam Don Bosco University, Kamarkuchi, Assam 782402, India e-mail: [email protected]; [email protected] P. Chauhan Advanced Level Institutional Biotech Hub, Handique Girls’ College, Guwahati, Assam 781001, India N. Panthi National Forensic Sciences University, Guwahati, Assam 781125, India I. Mazumdar District Level Laboratory (DLL), Public Health and Engineering Department (PHED), Govt of Assam, Guwahati 782105, India © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 A. S. Mathuriya et al. (eds.), Green Technologies for Industrial Waste Remediation, Environmental Science and Engineering, https://doi.org/10.1007/978-3-031-46858-2_8

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signalling molecules, and enzyme catalysis. This study also consolidates the challenges on environmental concerns and regulatory constraints. Research on these gaps of GEMs could foster potential avenues and commercialization of the technology. Keywords Metals · Environmental pollutants · Genetically engineered microorganisms · Detoxification · Sustainable

8.1 Introduction Exposure to pollutants from heavy metals (HMs) is a pervasive issue affecting various forms of life, often breaching their safety barriers, and rendering them susceptible and vulnerable to the harmful effects of it (Sharma et al. 2021b). With the increase in the discharge of HM in industrial and anthropogenic waste, the concern of HM accumulation has increased worldwide. Pollution load of heavy metals has been considered as one of the most severe threats to the ecosystem health for its abundance, persistence, and toxic properties. In addition to anthropogenic activities, natural geogenic activities such as volcanic eruption, atmospheric deposition, geological weathering, and pedogenesis of metal containing minerals also contributes to the release of toxic heavy metals. Other most common natural sources of HM are the igneous and sedimentary rocks (Alengebawy et al. 2021). Fortunately, these inherent processes result in gradual release of the contaminants. However, activities such as extensive mining, agricultural waste disposal, and fossil fuel combustion are recognized as substantial sources of toxic heavy metals like Hg, Pb, U, Cd, Zn, Cr, Ni, Co, Cu and metalloids like As, industrial effluents being the major contributors (Sharma and Kumar et al. 2021). Remarkably, the binding behaviour of heavy metals is largely affected by a suite of physicochemical and biological processes (Sharma et al. 2021b). Consequently, the control of heavy metal pollution has become the keystone for enhancing the protection of food chain. Conventional approaches like pyrolysis, land filling etc. are considered non-efficient as it is reported to produce a huge amount of toxic end products (Pande et al. 2020). The leachate generated via traditional methodologies often end up contaminating the soils and the ground water (Sharma and Kumar et al. 2021). However, bioremediation is considered a cost-effective and environmentfriendly technology with great potential to degrade and detoxify organic and inorganic compounds from contaminated sites safeguarding the environment (Jayaram et al 2022). This integrated microbial technology relies on enhanced detoxification and breakdown of harmful contaminants, either by intracellular accumulation or by enzymatic transformation to less- or non-toxic molecules and contributes to the restoration of the natural ecosystem (Singh et al. 2008a; Pande et al. 2020). This technique is intervened via three step processes that includes biotransformation, biodegradation, and mineralization (Iravani and Varma 2020). Figure 8.1 illustrates the various methods of bioremediation. Bioremediation operates on redox processes that rely on the alteration of chemical structure via oxidation and reduction driven by the microbial communities for

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Fig. 8.1 Mechanisms of bioremediation

degradation of the pollutants (Sharma et al. 2021c). The microbial process enhances the degradation by transforming hazardous metals and metalloids into neutral, less mobile, and less toxic compounds (Sharma et al. 2021a). The primary fact to understand about degradation of heavy metals is that these compounds can never be lost; they are either transformed or converted to less stable form. During the process, physiological changes in the fundamental properties of heavy metals like alteration in the pH, mineralization of metals contributes widely in the transformation of hazardous pollutants (Pande et al. 2020). The effectiveness of a bioremediation process is arbitrated by primary parameters including selected microbial types, microbial characteristics, pollutants properties, pollutant concentrations at the contaminated site, and prevailing physico-chemical environmental conditions (Zhang et al. 2020). Many microorganisms have the capacity to naturally degrade, convert, or chelate different harmful substances. The relatively slow rates, though, put a limit on these natural processes (Singh et al. 2008a). In comparison, genetic modifications strengthen the metabolic capabilities of indigenous microorganisms, enhancing the biodegradation of the target metals (Saxena et al. 2020). Genetic changes or metabolic engineering can amplify catabolic metabolism rates and the ability of microbial cells to interact with heavy metals (Mosa et al. 2016; Chen et al. 1999). Over the past decade, proteomic studies have efficiently provided physiological profiles of bacteria in protein levels, complementing the construction of modified microorganisms (Zhang et al. 2019a).

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8.2 Heavy Metals Heavy metals, characterized by high atomic weight and a density greater than 5 g/cm3 (Zhang et al 2019c), also serve as sources of free radicals and causes oxidative stress, thereby significantly impacting biological molecules (Wu et al. 2016). Within the environment, they frequently coexist with various organic and inorganic pollutants, such as benzene, toluene, polychlorinated biphenyls (PCBs), Polyaromatic hydrocarbons (PAHs), dioxins, dyes, polymers, pesticides hydrocarbons, explosives, chlorinated organics, nitro-aromatics and pharmaceuticals are non-biodegradable and persistent (Saxena et al. 2020; Yin et al 2020). The degradation of these pollutants, once released into the environment, poses a considerable challenge. In addition to the industrial effluents and other anthropogenic activities, the prolonged use of inorganic and organic fertilizers in agriculture stands as a primary contributor to the release of heavy metals into the environment (Alengebawy et al. 2021). Some of the highly toxic heavy metals are mercury (Hg), cadmium (Cd), vanadium (V). Cadmium is one of the most studied heavy metals. V(V) is the most toxic of four oxidation states (Zhang et al. 2019b). Conventional remediation of heavy metals often leads to secondary contamination, disrupting the microenvironment and rendering the soil and water bodies unsuitable for supporting growth (Mosa et al. 2016). HMs tends to accumulate in the agricultural soil and thereby gets absorbed by the plants. The accumulation of HMs can be described as an assemblage of metals and its various forms in the ecosystem (Alengebawy et al. 2021).

8.2.1 Effect of Heavy Metals on the Ecosystem Heavy metals often lack relevance in the biochemical functions of living organisms; instead, they pose harmful threats to their health, growth, and development (Sharma and Kumar 2021). Certain HMs are indeed required by organisms in minimal concentrations for several cellular functions. However, an increase in the metal concentration beyond permissible limit renders acute toxicity in the environment (Alengebawy et al. 2021). The World Health Organization (WHO) has established standard maximum residue limits (MRL) or permissible thresholds for various compound and elements. The guideline limits set by WHO for HMs in drinking water are listed in Table 8.1. These pollutants cast a menacing shadow over the entire ecosystem, profoundly disrupting both its structure and function. An alarming combination of heavy metals includingcadmium, lead, copper, and zinc lead to a hazardous blend of environmental and health concerns (Zhang et al 2019c). Metal toxicity manifests in cellular organisms at both cellular and molecular levels (Priyadarshini et al 2021). Apart from the biotic components of the ecosystem, waterbodies and soil are the two major abiotic components of the ecosystem that gets contaminated by the immense release of HMs in the environment. Due to the high

8 Bioaccumulation and Detoxification of Metals Through Genetically … Table 8.1 Permissible limits of heavy metals in drinking water

Metals

Guideline value (mg/L)

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References

As

0.01 mg/L

WHO (2022)

Cd

0.003 mg/L

WHO (2022)

Cr

0.05 mg/L

WHO (2022)

Cu

2 mg/L

WHO (2022)

Hg

0.01 mg/L

WHO (2022)

Ni

0.07 mg/L

WHO (2022)

Pb

0.009 mg/L

WHO (2022)

Mn

0.08 mg/L

WHO (2022)

levels of these HMs in the environment, they infiltrate the food chain, which causes their bioaccumulation in organisms’ cells and increases the potential for serious illnesses like cancer and cardiovascular disorders. In the presence of heavy metals, physiologically significant cations are altered and replaced by toxic metal ions, thus rendering the enzymes non-functional (Zhang et al. 2020). The robust interaction between metal ions and sulfhydryl groups of the enzymes is the most common cause of metal toxicity in microbial cells. However, many organisms have developed tolerance mechanisms to specific metal ions (Mosa et al. 2016; Sharma et al 2021a, b, c). Some of the toxic effects of HMs on humans and plants are listed in Table 8.2.

8.2.1.1

Animals

The discharge of heavy metals not only pollutes the environment but also disrupts the ecological balance and biological metabolism of living organisms resulting in hazardous and deleterious effects on their health, some being carcinogenic and able to induce mutagenic effects (Saxena et al. 2020). Both animals and humans encounter heavy metals through inhalation or ingestion (Wang et al. 2020). Moreover, toxic metals can infiltrate organism via dermal absorption. Heavy metals are absorbed in animals through the food chain which thereafter accumulate and localize in tissues and cells in high concentrations and cause increased metal toxicity. The intake of toxic components by the living organisms and their accumulation in different organs of the body damages the various body systems including the nervous, skeletal, endocrine, immune and circulatory systems (Lamas et al. 2016). These metals often interfere in the adsorption of elements in the living body which further induce toxic effects on the cells. Heavy metals have been found to have degradative effects on cellular organelles and cell components of the living including lysozymes, cell membranes, enzymes, nucleic acids and nuclear proteins and mitochondria to name a few (Sharma and Kumar 2021). Increased Cu concentrations cause DNA damage, oxidative stress, and reduced cell growth (Avenant-Oldewage and Marx 2000). Ingestion of Vanadium leads to serious respiratory conditions including pulmonary tumors. Additionally, it

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Table 8.2 Harmful effects of heavy metals on human and plants Heavy metals

Humans

Plants

Reference

Cu

Liver & kidney damage, dizziness, Affect the root growth headaches, nausea; vomiting, stomach cramps

Kodama et al.(2012)

Co

Effect on eye, pulmonary functions Reduced the amino acids sugar, starch, and protein content

Leyssens et al. (2017)

Cr

Hyperaemia, cancers, acute renal failure, acute tubular necrosis, necrosis, lymphocytic and histiocytic infiltration

Damage the nutritional status

Abdel-Gadir et al. (2016); Lim et al. (2017)

Hg

Behavioural disorders and neurological such as memory loss, tremors, insomnia germination, plant height

Chlorosis, reduced the seed

Rice et al. (2014); Andreoli and Sprovieri (2017); Engwa et al. (2019)

Cd

Damage the kidney and bones

Affect the germination rate

Nordberg (2004)

Mn

Parkinsonian syndromes affect the mortality rate

Reduction in the concentration of chlorophyll

Meeker et al. (2010)

As

Cancer, damage the pregnancy, and Reduced the leaf, and skin problems plant health

Nizam et al. (2013); Heck et al. (2014)

Ni

Reduced lung function, Adult Respiratory Distress Syndrome, and cancer of the nasal sinus and lung

Decreased enzyme activity which affected Calvin cycle and CO2 fixation

Zdrojewicz et al. (2016)

Pb

Affects central nervous system, anemia etc

–

Mahurpawar (2015)

Sn

Affects central nervous system, visual defects

–

Mahurpawar (2015)

also causes allergic reactions such as asthma, conjunctivitis, rhinitis etc. (Zhang et al. 2019b). Exposure to Cd2+ results in health ailments including renal diseases, high blood pressure and even bone fractures (Hrynkiewicz et al. 2015). Additionally, Cd exposure triggers mitochondrial dysfunction, osteoporosis, pediatric cancer and results in stunted growth in children (Schoeters et al. 2006; Sherief et al. 2015). Children are particularly susceptible to Pb toxicity and it results in neurological conditions affecting the learning ability and behaviour which are irreversible. Pb exposure increases dullness, irritability in the CNS subsequently resulting in epilepsy, coma, headache and even death (Pfadenhauer et al. 2014). Zn toxicity results in poor appetite, diarrhea, nausea, headache, vomiting (Alengebawy et al. 2021). Cd is reported to interfere with calcium metabolism which thereby results in renal disorders, neurodegenerative diseases, diabetes even lung, breast and prostate cancers

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(Avenant-Oldewage and Marx, 2000). Scientific reports have also reported the association of Cd toxicity with reproductive fertility and musculoskeletal diseases such as rheumatoid arthritis, osteoporosis, and osteoarthritis (Reyes-Hinojosa et al. 2019; Kumar and Sharma 2019). Pb is carcinogenic to animals and is lethal at higher concentrations. Common symptoms of Pd toxicity include renal dysfunction, hypertension, and abdominal issues (Ogwuegbu and Ijioma 2003). Cu accumulation is primarily reported in the brain, liver and kidneys and gastrointestinal disorders are observed. Moreover, acute Cu toxicity is linked to neurological complications, heart issues, and renal failure (Alengebawy et al. 2021).

8.2.1.2

Plants

Plants require essential nutrients, minerals, and vital elements such as Zn, Co, Cu, Mg, Mn, Iron and Ni, in trace amounts to facilitate proper growth and development (Singh et al. 2011). However, exposure to higher concentrations of such elements result in the decline of metabolic activities of plants. In the presence of higher concentrations of heavy metals varied physiological and biochemical deficiencies are observed (Shahid et al. 2011). Aquatic plants are more exposed to the heavy metals in the water bodies. Uptake of heavy metals by terrestrial plants mainly occurs through the roots in the soil (Goyal et al. 2020). Plants can absorb heavy metals from the soil and the atmosphere either directly or indirectly (Angelova et al. 2004). The soil effectively stores heavy metals and transports them to plant via vascular system (Alengebawy et al. 2021). The xylem parenchyma plays an important role in the transport and translocation of heavy metals into the plant and their conducting tissues (Seregin and Kozhevnikova 2008). The heavy metal uptake by plants is facilitated by transport proteins, chelating agents and pH changes (Tangahu et al. 2011). HM aerosols dispersed into the atmosphere settle onto the foliar surfaces of the leaves and some gradually penetrates the plant body (Gaur et al. 2014). Notably, heavy metals like Zn, Cu and Cd can partially penetrate leaf surface, while Pb tends to remain on the surface as precipitate. Heavy metals have also been reported to enter the plants through the stomata, lenticels and wounds etc. (Angelova et al., 2004). Metal toxicity in plants results in loss of fertility, crop yield, destruction of chlorophyll (Pichhode and Nikhil 2016). Furthermore, plants are primary producers and therefore are involved in the biomagnifications of the heavy metals at the successive trophic levels of the food chain (Goyal et al. 2020). Toxic concentrations of heavy metals induces the formation of reactive oxygen species and free radical which damages nucleic acids, lipids, proteins, membrane structure and alters the membrane permeability (Phaniendra et al. 2015). Due to the oxidative stress triggered by metal toxicity, the plant suffers from numerous physiological conditions which may often lead to the death of the plant (Wu et al. 2016). Cd is reported to alter and damage the physiological and biochemical properties of plants along with the loss of vital minerals (Nazar et al. 2012). Reports indicate that Cd toxicity inhibits the iron transport systems, reduces chlorophyll content, hampers seed germination, photosynthesis and other metabolic processes (Hayat et al. 2019). Heavy metal pollution also diminishes the quality and yield of crops. Studies have

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revealed that mill effluents have adverse effects on seed germination and growth of rice, mustard and pea. It also has been observed that an effluent concentration exceeding 50% was found inhibitory for plant growth parameters (Kumar et al 2020). Another study confirmed that the concentration of Cd and Zn were higher in leaves as compared to the seeds (Angelova et al. 2004). Even at lower concentrations, Pb obstructs healthy plant growth, reduces crop yield and productivity and nutrient uptake, while also affecting cell membrane permeability (Alengebawy et al. 2021). A study on the effect of Cu on maize plants revealed that excessive Cu concentration in soil results in shortened height plants (Barbosa et al. 2013). Higher concentration of Cu inhibited the production of root hairs and seedlings in Betula papyrifera and Lonicera tatarica respectively (Patterson and Olson 1983). Moreover, accumulation of higher concentrations of Zn in plants causes instability in the physiological processes in plants followed by plant death. Zn amd Cu poisoning in plants has also been linked to reports of chlorosis in plant leaves (Ebbs and Kochian 1997). Toxic concentrations of Zn promote senescence and results in chromosomal aberration in plants (Sharma and Talukdar 1987).

8.2.1.3

Soil

The contamination of soil and water bodies by heavy metals is a pressing concern in the contemporary world (Mosa et al. 2016). Heavy metals in the soil affect the growth of the plant either directly or indirectly. The physicochemical properties of the soils have an influence on the magnitude of the effect of heavy metals. It alters the soil microbial communities which affects the enzyme activities in the soil (Hoornweg and Bhada-Tata 2012). Soil enzyme activity serves as an indicator of soil biological activity. Cd exhibits a more toxic effect on the enzymes as it is readily mobile and has a lower affinity for soil colloids. It has been observed that high concentration of Cu inhibits b-glucosidase activity (Singh and Kalamdhad 2011). Elevated concentrations of heavy metals in soil disrupt its buffering capacity and consequently restrict the habitat for plants, disrupting their nutritional, ecological, and evolutionary interactions (Gupta et al. 2019). Furthermore, HMs moves slowly in soil as compared to its movement in water-bodies; thus, making them unavailable to the microorganisms (Sharma and Kumar 2021). Additionally, Cd readily binds to the soil organic compounds and thus becomes immobile and are absorbed by the plant which eventually enters the food chain (Karaca et al. 2010). High concentration of HM deteriorates the quality of soil, fertility and also confers damage to soil microbiome (Borah et al. 2020). Furthermore, inadequate nutrient and organic content, poor soil water retention, and poor ion cation exchange capacity are all correlated with heavy metals (Singh and Kalamdhad 2011). Bakshi et al. (2018) confirmed that heavy metal cations lead to significant changes in ion concentration, thereby lowering of the pH of the soil solution.

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Agroecosystems are primarily polluted by the biotic and abiotic byproducts of farming practices. Prolonged and unregulated use ofboth organic and inorganic fertilizers, contributes to the accumulation of heavy metals in agricultural soil over time, leading to a decline in soil fertility (Alengebawy et al. 2021). Cadmium, due to its high mobility and toxicity, raises serious concerns when it comes to its accumulation in soil. The presence of HMs leads to changes in soil pH and organic matter content. Under lower pH conditions, the bioavailability of Cd increases, therefore pH acts as an indicator of the soil quality. Cd also absorbs the organic matter in the soil which affects the physicochemical properties of the soil (An 2004). The accumulation of vanadium in the ecosystem significantly alters microbial communities, resulting in reduced richness and diversity in soil (Zhang et al. 2019a). Pd reportedly decreases soil nutrients, microbial diversity, and soil fertility. The biosorption capacity and humic acid content is also reported to be affected by Pb toxicity. Additionally, higher concentrations of Cu and Zn is reported to disrupt soil homeostasis (Alengebawy et al. 2021). Liao et al (2005) reported significant inhibition in microbial activity and their metabolic processes under cadmium contaminated paddy soil. A synergistic combination of Cd and salinity resulted in reduced microbial respiration and the content of microbial biomass in cell. A combination of Pb and Cd substantially damages soil microbial populations. Cu toxicity induces cell wall destruction and protein denaturation in microbes. Even at lower concentrations, Cu causes a substantial reduction in oxidation potential within microbial cells and brings about changes in microbial community composition (Alengebawy et al. 2021).

8.3 Microbial Bioremediation of Heavy Metals Microbial bioremediation presents a sustainable and environmentally friendly approach, leveraging microbial metabolic processes and products to remove, reduce, and transform toxic organic and inorganic substances, including HMs (Kumar and Bharadvaja 2020). The fate of hazardous heavy metal ions in the soil ecosystem is largely dependent on the interactions of these ions with different organic components. One such potent organic substance which can be exploited in heavy metal remediation is the microbial communities. Microbes have been documented to catalyse redox reactions leading to changes in metal mobility in soil and propensity for uptake. Microorganisms have adapted to extreme conditions given their adaptation mechanisms, which allow them to be able to thrive in environmental conditions comprising of high concentrations of heavy metal (Mosier et al. 2013; Issazadeh et al. 2013). This might be because microorganisms have a high surface area-to-volume ratio and thus carries a high capability for sorbing metals. They play an important role in the biological cycling of heavy metals bringing about bioremediation of those metals (Issazadeh et al. 2013). Although, it is difficult to understand the natural adaptive behaviour of microorganisms in a community; as most of the studies have been

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conducted under laboratory conditions for which accurate observation and data are scarce; it has transformed the field of environmental remediation (Mosier et al. 2013). Metabolomic studies have played a significant role in studying the microbial isolates in the natural setting (Mosier et al. 2013). Compared to the common biotreatment processes, bioremediation carried out by microorganisms are reported to be safe, eco-friendly, and a cost-effective method for decontamination of ecosystems (Yin et al. 2020). These organisms possess extensive catabolic potential and unique resistance mechanisms that facilitate heavy metal utilization through various biotransformation processes that includes mobilization of metals and cell surface mechanisms (Sharma et al. 2021c). The detoxification of HM pollutants includes extracellular barrier exclusion (prevent metal from entering cell), extracellular (metal-binding to extracellular polymeric substances) and intracellular (metal trapped within the cytoplasm) sequestration, active transport efflux system (export metal away from intracellular environment using efflux system), and enzymatic detoxification (transform metal from a high toxic form to a less harmful form by enzymes) mechanisms. Some of the innate processes also complement the process of bioremediation which include chemotaxis, biosurfactant and biofilm formation. Chemotaxis is a well-known behavioural adaptation exhibited by microorganisms. In bioremediation, this ability allows microbes to sense and migrate toward the pollutants increasing their availability at the contamination site and enhancing the bioremediation process. Biosurfactants have reportedly enhanced the process of biodegradation of several organic and inorganic pollutants. Biosurfactants provide bacteria access to hydrophobic organic pollutants while improving chemotaxis between the bacteria and the contaminant. Biofilms are formed by the combined action of diverse groups of microorganisms (Pande et al. 2020). Microbial mechanisms for bioremediation include precipitation, biosorption, bioaccumulation, enzymatic transformation etc. Microbial degradation of heavy metals generally progresses through several processes such as biosorption, bioleaching, biomineralization, biotransformation and bioaccumulation. Over time, microbes have developed pathways such as adsorbent, accumulation, methylation, oxidation and reduction to resist heavy metal toxicity including specific pathways novel for metallic reduction. Metabolic secretions from microbial cells also aid in heavy metal degradation (Sharma et al. 2021a). Of all microbial communities, fungi and algae serve as better remedial organisms suited for bioremediation (Hansda et al. 2016). The reason for the preference of use of fungi in bioremediation over other microorganisms is due their successful gene editing and transport (Sharma et al. 2021a). Fungal species primarily enhance tertiary treatment and residual organic compound removal, while microalgae display a great potential for inorganic nutrient uptake (Akhtar et al. 2013). Sahoo et al. (1992) investigated the bioaccumulation ability of Bacillus circulans against Cu, Cd, Zn, Ni and Co and found significant removal of Cu (80%) and Cd (44%) by the bacteria (Sahoo et al. 1992). The GYP1 strain of B. cepacia exhibited high resistance to high concentrations of cadmium (Zhang et al. 2019b). Bioaccumulation carried out by mixed cultures have also been found beneficial and have been observed to accumulate higher concentration of metal ions (Mishra and Malik 2013). It also enables them to be stable and

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survive better (Igiri et al. 2018). Some of the microbial genus involved in bioremediation include Mycobacterium, Acinetobacter, Flavobacterium, Actinobacteria, Alcaligenes, Beijerinckia, Arthrobacter, Methylosinus, Bacillus, Micrococcus, Serratia, Nitrosomonas, Rhizoctonia, Pseudomonas, Nocardia, Phanerochaete, Penicillium, Xanthobacter, and Trametes (Saxena et al. 2020). The microbial tolerance towards heavy metal ions is evaluated through the determination of the lowest concentration of the metal which exhibits inhibitory action on the microbial cells or minimum inhibitory concentration (MIC) (Mishra and Malik 2013). The availability of the metal ions in a medium varies depending on its type and state which often affects the MIC of the metals under study (Mishra and Malik 2013). Another factor responsible for variation in MICs of a microbial strain is the nature of the metal being tested (Mishra and Malik 2013). Most of the studies conducted till date, are conducted under laboratory conditions and the data is devoid of the exact MIC values of the metals in natural conditions. However, it should be noted that microbial strains isolated from highly contaminated sites display higher MIC as well as demonstrate higher metal uptake capabilities (Mishra and Malik 2013). The type of cellular respiration exhibited by the microorganism, their adaptability and survival in a habitat also affects the remediation processes (Kumar and Bharadvaja 2020). Endophytic microorganisms’ association with phytoremediation has been observed, where they enhance phytoremediation efficacy. Endophytes aid in breaking down complex molecules into simpler forms, mobilizing metal ions and facilitating uptake by the plant. Heavy metals have limited movement in soil, making direct adsorption by plant roots challenging. The interaction between plant roots and soil microorganisms can enhance metal adsorption in the root system leading to heavy metal accumulation in the plant roots. Plants and microbes together play an important part in a host’s ability to adapt to environmental alterations. (Sharma and Kumar 2021). The use of microorganisms in bioremediation has been studied for more than decades, and now several microbial species are found to aid in the process of bioremediation, yet the mechanisms and metabolism involved are not very clear and a vast area still remains unexplored (Yin et al. 2020). Therefore, further research and studies needed to be conducted to shed some light on them.

8.4 Genetically Engineered Microorganisms (GEMs) for Enhanced Bioremediation Microorganisms adapted to thrive in high heavy metal concentration are ideal candidates for bioremediation (Mishra and Malik 2013). However, the bioremediation process carried out by the indigenous group of microorganisms is often reported to be impotent for its inability to work efficiently under large scale conditions. Therefore, there is an urgent need to improve and widen the application of microbial

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bioremediation by exploiting the recent advances in the field of genetic engineering (Igiri et al. 2018). Genetically engineered microorganisms (GEMs) are created by the introduction of a gene of interest into a microbe thereby enhancing its desirable trait (Saxena et al. 2020). The designing an appropriate GEM for heavy metal restoration encompasses unique aspects of optimization which includes understanding on the metabolic routes, pathway improvisation of the substrate flux to avoid the accumulation of toxic and inhibiting intermediates, enhance the process-relevant properties of microorganisms, and biochemical-structural–functional relationship of the component enzymes (Timmis and Pieper 1999). Additionally, altering the genetic makeup and cellular chemistry leads to changes in cellular components, improved desirable characteristics, and enhanced adsorption capacity (Igiri et al. 2018). Genetic engineering and recombinant DNA technologies offer the advantage of constructing single strain with multiple desired traits that enhance bioremediation properties, such as heavy metal stress tolerance, over-expression of metal chelating agents, and metal bioaccumulation (Iravani and Varma 2020; Liu et al. 2018). Moreover, expression of specific transport genes can also be embellished by constructing engineered bacteria with augmented abilities of heavy metal remediation. For instance, high Hg toxicity in the ecosystem has led to remarkable evolution in the virulence factors of bacteria. Usage of Hg reductase along with Hg resistance gene (mer) cluster in an operon participates to detoxify Hg2+ to volatile Hg (Singh et al. 2011). The operon consists of genes like merA and merB, mer, merP, merR and merD, mere, and merH for each playing a role in Hg detoxification (Ruiz and Daniell 2009). Correspondingly, Bae et al. (2000) designed synthetic genes encoding for protein analogs of phytochelatins and studied the ability to bind Cd. It was reported that the Cd2+ binding stoichiometry of the constructed phytochelatin was higher than the values reported for metallothioneins. Scientific reports also revealed that GEMs have better genetic makeup and thereby known for its an exceptional candidate for eliminating complex and persistent pollutants to tackle heavy metals (Pande et al. 2020; Jayaram et al. 2022). The demonstrated ability of numerous microorganisms to degrade and convert mercury, a highly hazardous heavy metal that can be released into the environment, is noteworthy. The utilization of GE Escherichia coli strain JM109, capable of removing mercury from contaminated water, soil, or sediment has been reported (Azad et al. 2014).With the help of recombinant DNA technology, degradative pathways and catabolic pathways can be improved. These processes serve as potential routes for partial or complete degradation of toxic xenobiotic pollutants (Leungsakul et al. 2005; Timmis et al. 1994). Dioxygenases and monooxygenases are two common enzymes that have evolved using the DNA techniques and have been applied to bioremediation (Leungsakul et al. 2005). For microbial communities, the environmental transcriptomic approach may be a promising technique. Furthermore, RNA technology has been developed for bioremediation procedures such sulphate oxidation, chemical assimilation, and nitrogen acquisition (Poretsky et al. 2005). Another technology for the development of GEMs encompasses the exploitation of “Protein engineering” for improvement in the stability of enzymes to widen the

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substrate specificity and kinetic properties involved in degradation process (Dua et al. 2002). Likewise, construction of novel metabolic routes based on partial metabolic sequences coupled with enzymes efficient in channeling of intermediates is also another central pathway undertaken in microbial remediation technologies (Rojo et al. 1987). Numerous gene families encode proteins and a diverse community of genes encoding proteins crucial for detoxification are also expressed in cellular transport systems (Kozminska et al. 2018). Several studies have demonstrated the use of channels to improve As3+ and Hg absorption during the bioaccumulation process. One such demonstration is the accumulation of As3+ using E. coli homotetramer glycerol facilitators (GlpF) (Singh et al. 2010). Furthermore, metal buildup was observed using Streptomyces coelicolor, Corynebacterium diptheriae, as well as Saccharomyces cerevisiae homolog Fps1 (Villadangos et al. 2014). MerT/P transporter, from Serratia marcescens, Pseudomonas K-62, and Pseudomonas K-12, responsible for Hg resistance and transport of Hg(II) to the cell cytoplasm for reduction, were evaluated (Deng and Jia 2011; Boyd and Barkay 2012). MerC, MerE, and MerF are additional potential Hg importers; it is hypothesised that these importers share a common mechanism of absorption. The various mer operon systems are included in Table 8.3. The ability of E. coli to bioremediate heavy metals was also genetically altered by combining a reporter gene, from a strain of Staphylococcus aureus that is resistant to arsenate, and DNA shuffling mechanisms to purify arsenate. In a different application, it was shown that genetically modified E. coli with the sequence encoding the Shigella flexnerii MerR proteins Hg (II) metal-binding domain (MBD) reduced mercury levels (Qin et al. 2006). In comparison to nonMBD cell lines, the recombinant cells produced a significant amount of MBD on the cell surface, which were able to bind 6.1-fold more Hg (II), and showed greater resistance to Hg (II). The recombinant cells frequently preferentially binds Hg when other heavy metals, such as Zn(II) and Cd, are present (II). The distinct growth rate of recombinant plasmid GEMs is a key element in their survival and development in the environment. However, plasmid-free cells usually outgrow plasmid-bearing cells due to the increased metabolic burden brought on by the presence of plasmid cells. Geographic variation in the environment of imported GEMs is significant because it aids in determining the interactions and relationship between GEMs and indigenous microbial groups and other ecosystem variables (Dua et al. 2002). Thus, this section has described specific proteins and genes expressed during the stress condition of microbes that are very important for providing strength to microorganisms. A variety of GEMs have been developed by using the strains of Bacillus idriensis, Ralstonia eutropha, Sphingomonas desiccabilis, Pseudomonas putida, Escherichia coli, Mycobacterium marinum etc. (Valls et al. 2000; Parnell et al. 2006; Schué et al. 2009). A list of GEMS involved in heavy metal bioremediation is presented in Table 8.4. Interestingly, recent advancements have led to the development of a technology called ‘Effective Microorganisms’. The technique is developed by Dr. Teruo Higa, wherein a liquid composition of non-pathogenic, aerobic and anaerobic beneficial microorganisms are investigated and explored for wide applications in the field of bioremediation (Jayaram et al. 2022). Microalgae play a crucial role in phytoremediation, a process that involves the incorporation of metal cations from

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Table 8.3 Bacteria with mer operon systems. (Source Jan et al., 2009) Bacteria

Type of mer operon system

Achromobacter sp AO22

Tn5051

Morganella morgani M567

Tn5074

Pseudomonas aeruginosa GD86

transposon Tn501

Shigella Flexneri

transposon Tn21

Xanthomonas sp W17

Tn5053

Klebsiella pneumoniae M426

Tn5073

Serratia marcescens J53

pDU1358

Acinetobacter calcoaceticus JM83

pKHL2

P. fluorescens

pMER419

Pseudomonas sp K-62

pMR26

Staphylococcus aureus

p1258

Mycobacterium marinum

pMM23

P. stutzeri

pPB

the environment to remove metals from contaminated streams and sediments (Diep et al. 2018). Some genetically modified algae with high potential for bioremediation are Chlamydomonas reinhardtii and Chlorella ellipsoidea. The Glutamate-Cysteine Ligase (GCL) genes most likely originated in cyanobacteria and were transferred to eukaryotes by horizontal gene transfer. Eukaryotic GCLs, in contrast to cyanobacterial GCLs, have two extra cysteine residues that join to form a disulfide link, which assists in maintenance of oxidative stress. While group III GCLs are prevalent in microalgae and plants and feature a highly conserved ALXAXSPFXXGK motif, group II GCLs proteins are primarily found in heterotrophic eukaryotes (Musgrave et al. 2013). The microalgal species most frequently utilized in genetic engineering is Chlorophyta C. reinhardtii. MT genes from Festuca rubra have been cloned in the plastidial genome of C. reinhardtii, resulting in a mutant able to grow to 80 M in the presence of cadmium concentrations (Han et al. 2008). The effectiveness of gene editing, transport, and scaling-up make fungi the preferred species in bioremediation. Recent advancements in enzymology, molecular biology, and biotechnology are the driving factors for the creation of engineerimproved fungi and mycoremediation (Diep et al. 2018). Exploration on recombinant and engineering technologies with respect to the construction of genetically modified fungal strains includes nuclease mediated genome editing and TAL effector nucleases (TALEN) for the construction of peptides such as phytochelatins (Sharma et al. 2021b). Many of the current genetic modification approaches have proven useful in modifying metabolic pathways or enzymes to provide the necessary characteristics. Myco-transformation genes from fungi are well-known to be involved in the bioremediation process. Therefore, it is possible to construct fungal mutants that oversecrete

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Table 8.4 Genetically engineered bacteria involved in remediation of heavy metals Bacteria

Modified gene expression

Heavy metals

References

Ralstonia eutropha CH34

Metallothionein (MT)

Cd

Valls et al. (2000)

Deinococcus radiodurans strains

Hg (II) resistance gene (merA)

Hg

Brim et al. (2000)

Escherichia coli and Moraxella sp.

Expressing EC20 (with 20 cysteines)

Cd and Hg

Bae et al.(2001), (2003)

P. fluorescens 4F39

Ni transport system

Ni

Deng et al. (2005)

E. coli strain

Organomurcurial lyase gene expression

Hg

Murtaza et al. (2002)

P. putida strain

Chromate reductase (ChrR)

Cr

Ackerley et al. (2004)

E. coli SE5000

Ni transport system and MT

Ni

Deng et al. (2005)

P. putida 06,909

Expression of a metal-binding peptide (EC20)

Cd

Wu et al. (2006)

E. coli JM109

Hg2 + transporter and MT

Hg

Zhao et al. (2005)

Pseudomonas K-62

Express Hg transport system and organomercurial lyase

Hg

Kiyono and Pan-Hou (2006)

E. coli JM109

Cd transport system and Cd MT

Deng et al. (2007)

Acidithiobacillus ferrooxidans strain

Hg ion transporter gene expression

Hg

Sasaki et al. (2005)

Pseudomonas strain K-62

MerE protein encoded by transposon, Tn21

Hg

Ng et al. (2009)

Achromobacter sp AO22

Hg reductase expressing Hg mer gene

Ng et al. (2009)

B. subtilis BR151

Luminescent Cd sensors Cd

Wu et al. (2006)

E. coli strain

AsIII S-adenosylmethionine methyltransferase gene

As

Yuan et al. (2008)

Pseudomonas putida 06,909

Expression of metal binding peptide (EC20)

Cd

Wu et al. (2006)

Meshorhizobium huakuii subsp. rengei strain B3

PCSAT

Cd

Sriprang et al. (2003)

Ensifer medicae MA11-copAB

copAB

Cu

Hsieh et al., (2009)

Meshorhizobium huakuii subsp. rengei strain B3

MTL4 and ATPCS

Cd

Ike et al., (2007)

Pseudomonas putida KT2440

Phytochelatin synthase (PCS)

Cd, Hg, Ag

Yong et al., (2014) (continued)

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Table 8.4 (continued) Bacteria

Modified gene expression

Heavy metals

References

Methylococcus capsulatus

CrR genes for Cr(VI) reductase activity

Cr

Al Hasin et al., (2010)

Bacillus megaterium strain Mercuric ion binding MB1 protein

Hg

Hsieh et al., (2009)

B. subtilis BR151

Luminescent Cd sensors Cd

Murtaza et al. (2002)

necessary enzymes and to use these mutants to design different wastewater treatment options. It has been reported that filamentous fungus has great resistance and restoration capacity for the bioremediation of heavy metals as Cd, Cu, and Ni (up to 1500 mg L) from contaminated soil and wastewater (Akhtar et al. 2013). Reduction of Cr 6+ to Cr3+ by A. flavus and A. niger were reported (Priyadarshini et al. 2021). Different models of recombinant Pleurotus eryngii ERY4 laccase gene expressed in host S. cerevisiae are biologically inactive. Gene alterations in 4NC3 results in the expression of chimerical iso-form enzymes with high-temperature activity, pH, and multiple substrate affinity. The genome sequence has established a solid base for work in agriculture, technology, industry, pharmacy, and restoration fields.

8.4.1 Factors Affecting the Capacity of Microbial Bioremediation The capability of microbial bioremediation can be influenced by a varied number of biotic and abiotic factors which includes physical and chemical properties of metal ions, characteristics of the microbial strains used in the degradation process, and environmental conditions (Zhang et al. 2020). A change in pH tends to bring variations in the enzyme activity, solution chemistry, metal speciation as well as the cell surface chemistry (Oves et al. 2017). Lower pH values cause the dissolution–precipitation equilibrium between the metal ions to break. This enhances the ion exchange capacity between metal ions and H+ on the soil surface and thereby increases the metal bioavailability in soil solution (Sheoran et al 2016). Sahoo et al. (1991) reported that a higher pH favoured the process of adsorption. Additionally, the ideal pH range varies among different microbes. For instance, some microbial decomposition is inhibited at extremely high pH levels (Liu et al. 2017). At lower pH, the adsorbent surface is more positively charged which reduces the attraction between adsorbent and the metal cations thus increasing its toxicity (Igiri et al. 2018). Temperature is another significant factor that affects microbial growth at unfavorable extremities (Mishra & Malik 2013). High temperature increases the solubility of heavy metal ions thereby enhancing the bioremediation process (Igiri et al. 2018). This might be because the temperature directly affects the strength and capacity of metal adsorption

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on microbial cell surfaces. Other factors affecting the bioremediation process include the type of biomass, presence of competing ions, ionic strength, chemical forms of the metals, redox potential, contact time, presence of other pollutants, nutrient concentration, initial metal ion concentration, salt concentration, chemical composition of heavy metals, moisture etc. (Igiri et al. 2018; Hansda et al. 2016). Salt concentration is directly proportional to ionic strength of the aqueous solution. Bioaccumulation could also be hampered by improper soil moisture. As per reports, increased soil moisture clogs the pores, thus reducing soil aeration. Additionally, low soil moisture restricts growth and metabolism of microorganisms (Dibble and Bartha 1979). The density of clay soil, in contrast to loam and sand, harbours low amounts of metals, indicating that the texture of the oil impacts the bioavailability of metals in the soil (Leahy and Colwell 1990). Multiple redox forms of metal ions prevail in the soil which influences the type of microbial community inhibiting the area. Each microbial type has their specific redox potential (Sheoran et al. 2016). The presence of heavy metals itself causes degradative effects on the organisms directly. Additionally, coexistence of heavy metals with other contaminants affects the bioremediation process, rarely exhibiting a positive effect on the microbial growth (Lu et al. 2014). It should be noted that low concentrations of the metals such as Ca, Mn, Mg, Zn stimulate biological activities (Sandrin and Hoffman 2007). The coexisting organic and inorganic pollutants reportedly compete with heavy metals for adsorption on soil surface thus reducing their bioavailability in the soil (Zhang et al. 2020). Studies have shown that Co(II) interferes with the biosorption and transport of Mg(II) (Mishra and Malik 2013). Nutrient supply stimulates the growth of soil microbiome, making them rich and diverse. As metal rich effluents are unable to supply the adequate quantity of required nutrients for microbial growth, in order to achieve ample degree of metal removal nutrients need to be supplemented (Zhang et al. 2019b). The efficiency of heavy metal removal is also linked to the media used, which vary with different microbes. Studies have shown that for several microbial strains, the maximum bioaccumulation capacity was accomplished when glucose or sucrose were used as the carbon source (Mishra and Malik 2013). Therefore, to achieve an enhanced level of metal remediation, environmental factors and nutritional status of the strains are the primary factors that counts the remediation efficiency (Mishra and Malik 2013).

8.4.2 Mechanism In contrast to the traditional remediation methods, microbial bioremediation utilizes several biochemical mechanisms for the removal and detoxification of HMs. Bacterial cells excrete special proteins that react with the metals ions in the cell segregating them into insoluble metal compounds. These bacterial specialized proteins restricts the metal ions from interfering with the normal metabolic processes (Hansda et al. 2016). Microbes have developed various mechanisms for heavy metal detoxification including intracellular and extracellular sequestration, active efflux systems, and biotransformation (Hrynkiewicz et al. 2015).

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Bioaccumulation

Microorganisms exhibit potential metal ion absorptions. Bioaccumulation is an energy dependent uptake process carried out by living cells. During the process, heavy metals ions transit across the cell membrane and cytoplasm (Ayangbenro and Babalola 2017). Microbes bind to heavy metals through receptors that concentrate the metals and pollutants from the environment (Mosa et al. 2016). The cellular structures of the microbes play an important role in the active uptake of the metal ions. Microorganisms have negatively charged cell walls; thus, they possess anionic structures on their cell surface which readily promotes to binding of specific metal ions (Igiri et al. 2018). The primary sites for metal binding in the cell wall of fungi can withstand and detoxify heavy metal ions consisting of chitin, inorganic ions, lipids, nitrogen-containing polysaccharides, polyphosphates, and proteins (Ayangbenro and Babalola 2017). Fungal cells further secrete organic acids and proteins to facilitate the immobilization of heavy metal ions (Mishra and Malik 2013). Bacterial cell walls are rich in metal-binding ligand components. The carboxylic groups in teichoic acid are associated with the peptidoglycan layer of gram-positive bacteria. These molecules are involved in proton uptake and later are served as the chemisorption sites for metal binding (Issazadeh et al. 2013; Mishra and Malik 2013; Igiri et al. 2018, Jayaram et al. 2022). The presence of the phosphate groups within the lipopolysaccharides and phospholipids serves as major metal binding sites in gram negative bacteria (Hansda et. al., 2016, Hrynkiewicz et al. 2015). Additionally, the outer membrane of the bacterial cells is rich in polygalacturonic acid, to which metals like copper, zinc and cadmium form complexes thus promoting biosorption (Hansda et al. 2016; Jayaram et al. 2022). Studies have suggested that bioaccumulation and biosorption may often occur simultaneously and biosorption is often followed by bioaccumulation. A metabolically inert or passive metabolic process promotes the accumulation of heavy metal ions on the surface of microorganisms. This includes processes like ion exchange, complexation, precipitation and physical adsorption. Physical adsorption enables metal ions to bind to the functional groups of the cell membrane through van der Waals forces. Since this process is independent of cellular metabolism, it can be carried out by either dead or living cells. The other way is a metabolism-dependent bioaccumulation process, carried out via an ATP-driven active transport and/or via bioprecipitation often associated with biotransformation (Hansda et al. 2016; Mishra and Malik 2013; Priyadarshini et al 2021). Owing to its dependence on cellular metabolism, it takes place only in living cells (Priyadarshini et al 2021). A saturation level is maintained for accumulation of heavy metals occurring outside of the cell via adsorption. Intracellular accumulation is regulated via the mechanism of metal efflux (Diaz-Ramirez et al. 2008). Metabolism-dependent metal ion uptake process is comparatively slower than biosorption. However, it should be noted that biosorption plays a limited role in the bioaccumulation process. The transport of the metal ions across the cell membrane is highly dependent on the metabolism of the cell associated with the active defence system of the microorganisms. It should

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Fig. 8.2 Overview of bacterial bioaccumulation and bio-sorption

be noted that microorganisms use the same mechanism of cell membrane transport as used for the metabolically important ions for heavy metal ion transportations (Hansda et al. 2016). An overview of the process of bioaccumulation and biosorption is depicted in Fig. 8.2. Reports of bioaccumulation of cadmium by P. putida 62BN, B. cereus, Citrobacter sp., of uranium by P. aeruginosa and S. cerevisiae, mercury by Rhizopus arrhizus have been documented (Issazadeh et al. 2013; Oves et. al., 2017). Multiple farmlands that were affected with metals revealed Burkholderia cepacia GYP1 isolates to have high capacity for cadmium bioaccumulation. It has also been hypothesized that at lower Cd concentrations intracellular accumulation is dominant in B. cereus RC-1 (Zhang et al. 2019a). Additionally, B. cepacia GYP1 was observed to response well under Cd stress (Zhang et al. 2019a, b, c). It was reported that under poor nutrient conditions the bioaccumulation of Cd in GYP1 occurred in three steps. The adsorption of Cd ions to the organic functional group on the outer membrane initiated the process. This was followed by the transportation and sequestration of Cd in the cytoplasm. However, upon the increase in intracellular Cd concentrations, an energy dependent efflux system was observed to release the excessive Cd ion to help shield themselves from Cd toxicity. Simultaneously, the secretion of EPS also contributes in entrapment of effluxed cadmium (Zhang et al. 2019a). Following bioaccumulation, the metal ions are precipitated and stored in specific organelles, a process termed as compartmentalization (Hansda et al. 2016, Priyadarshini et al 2021). The microbial cell wall is the first to interact with the extracellular metal ions. The cell wall interacts with the metal ions passively with the help of the functional groups of the cell wall (Hrynkiewicz et al. 2015). A metal homeostasis system regulates the concentration of internalized metals wherein the ligands and proteins form complexes to avoid the reaction of

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metal ions with biomolecules (Hansda et al. 2016). Several visualization and analytical techniques such as analytical electron microscopy (AEM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray and diffraction analysis (XRD), X-ray photoelectron spectroscopy (XPS), imaging and micro-X-ray fluorescence (µXRF) etc. allows the researchers to assess and locate the site of heavy metal accumulation in microbial cells (Mishra and Malik 2013). It has been reported that Ni is accumulated in cells as nickel oxalate dihydrate crystals (Magyarosy et al. 2002). The involvement of the CadA pump in the removal of intracellular Cd has been established and described for Staphylococcus aureus (Nucifora et al. 1989). Most microbial cells accumulate Cd2+ in the cell envelope and within the cytoplasm. In contrast, Pseudomonas strains sequestered Cd2+ in and around the cell periphery than within the cytoplasm (Hrynkiewicz et al. 2015).

8.4.2.2

Biosorption

Microorganisms perform biosorption of heavy metals by using adenosine triphosphate (ATP) or spontaneous physicochemical absorption pathways (Sharma et al. 2021a, b, c). The number of pollutants that are adsorbed depends on the chemical makeup and k inetic equilibrium of the sorbent’s cellular surface (Mosa et al. 2016). Shewanella spp. and Geobacter spp. have been reported to couple intracellular oxidation of organic matter (Lovley et al. 1993) in the cytoplasm and later to extracellular reduction of oxidized metal ions. These two genus of gram negative bacteria have evolved the mechanism of electron transfer by the process of extracellular electron transfer (Jiang et al. 2019). Scientific reports also suggests that these two microbial species facilitate the reduction of Fe(II); which is later coupled to the oxidation of organic matter (Shi et al. 2016; White et al. 2016). They are also involved in the transfer of metal ions such as uranium and chromium (Jiang et al. 2020). The biosorption capacities of some microorganism are listed in Table 8.5. Instances have been observed where bioaccumulation displays higher heavy metal removal potential than biosorption mechanisms (Mishra and Malik 2013). However, biosorption turns out to be a better option for heavy metal remediation as compared to bioaccumulation due to the fact that the intoxication of the heavy metals occurs outside the cell which allows regeneration and reuse of the adsorbed metals (Hansda et. al., 2016; Mishra and Malik 2013). Microbes are also found to deploy compounds in the extracellular medium which facilitates complex formation of metal ions outside the cell (Hansda et al. 2016). Biosorption gives another benefit of reuse of metal through desorption of adsorbed metals using dilute eluents and cyclic use of regenerated biomass (Mishra and Malik 2013). Metal Reducing (MTR) Pathway Metal reducing pathways are commonly observed in the dissimilatory metal-reducing microorganisms (DMRM) as well as for extracellular electron transfer (Jiang et al. 2020). One of the best characterized metal-reducing metabolic pathways for the

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Table 8.5 Some microorganisms and their biosorption capacities Metals

Microorganisms

Biosorption (mg/g)

References

Cd

Bacillus cereus

31.95

Huang et al. (2013)

Cr

Bacillus megaterium

30.7

Srinath et al. (2002)

Cr

Bacillus coagulans

39.9

Srinath et al. (2002)

Pb

Pseudomonas aeruginosa

123

Gabr et al.(2008)

Cr(VI)

Bacillus sphaericus

44.5

Velásquez and Dussan (2009)

Ni

P. aeruginosa

113

Gabr et al. (2008)

Cr(VI)

B. sphaericus

45

Velásquez and Dussan (2009)

Zn

Streptomyces ciscaucasicus

54

Li et al. (2010)

Pb

Pseudomonas putida

270.4

Uslu and Tanyol (2006)

Zn

Bacillus firmus

418

Salehizadeh and Shojaosadati (2003)

Cr(IV)

Aeromonas caviae

284.4

Loukidouet al. (2004)

Pd

Desulfovibrio desulfuricans

128.2

de Vargas et al.(2004)

Cd

Aeromonas caviae

155.3

Loukidou et al. (2004)

transfer of electrons from quinol in the cytoplasmic membrane to the extracellular Fe(III) hydroxides is observed in Shewanella oneidensis MR-1 (Jiang et al. 2019). Investigations have revealed the presence of multiheme c-type cytochromes CymA, STC, MtrA and Omca and the trans-outer-membrane porin-like protein MtrB. CymA, a quinol dehydrogenase in the cytoplasmic membrane oxidizes quinol and facilitate the transfer of released electrons to the periplasmic STC (small tetraheme cytochrome) and Fcc3 (flavocytochrome), which further facilitates the transfer of electrons across the periplasm to the MtrA of the trans-outer-membrane protein complex. MtrB and MtrC complexes with MtrA, thus forming the MtrABC complex which transfers the electron from the periplasm to the bacterial surface. MtrC uses its solvent-exposed heme on the bacterial surface to transmit electrons to Fe (III) directly. Additionally, MtrC interacts with OmcA and facilitates the transfer of electrons to Fe(III) hydroxides (Jiang et al. 2019; Shi et al. 2016; White et al. 2016). Geobacter species are known to use porin-cytochrome (Pcc) pathways. These pathways consist of multi-heme c-cyt and outer membrane porin-like proteins. It has been demonstrated that multi-heme c-Cyts CbcL, ExtA, ExtD, ImcH, PpcA, PpcD, OmaB, OmaC, OmaC, OmcB and porin-like protein ExtC, OmbB and OmbC are involved in bacterial extracellular electron transfer (Liu et al. 2018; White et al. 2016; Shi et al. 2016). The movement of electron across the cell membrane in Mtr-pathway by Shewanella oneidensis MR-1 is illustrated in Fig. 8.3.

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Fig. 8.3 MR-1 metal reducing pathway in Shewanella oneidensis. Electrons are exported to an extracellular acceptor from the CymA quinol dehydrogenase located in cytoplasmic membrane. The released electrons are facilitated to the periplasmic STC (small tetraheme cytochrome) and Fcc3 (flavocytochrome) which further facilitates electrons across MtrA, MtrB, MtrC; thus, forming complex which transfer electron from periplasmic to bacterial surface

8.4.2.3

Biotransformation

Biotransformation affects the toxicity and mobility of metal ions. Metals are transformed either by redox or alkylation reactions where microorganisms act as a catalyst (Hansda et al., 2016, Jayaram et al. 2022). Detoxification of heavy metals by microorganisms is carried out by metal binding which involves chelators such as metallothionein, phytochelatins, metal binding peptides, vacuole compartmentalization and volatilization (which involves turning metal ions into volatile state), valence transformation mechanisms, putative entrapment in EPS, and extracellular chemical precipitation (Ayangbenro and Babalola 2017; Mishra & Malik 2013; Igiri et al. 2018). Chelators are reported to bind heavy metals and facilitate microbial adsorption and transportation of metal ions (Ayangbenro and Babalola 2017). Organomercurial lyase converts methyl mercury to its lesser toxic component Hg(II), which is further reduced by an enzyme named mercuric reductase encoded by merA gene of metal resistant bacteria, to the volatile form of Hg(0) (Ayangbenro and Babalola 2017; Hansda et al. 2016). Chromate reductase is observed to reduce Cr(IV) to its lower toxic state Cr(III) (Mishra and Malik 2013). Cupriavidus metallidurans CH34 have been observed to volatilize Hg through a series of reactions (Jayaram et al., 2022). Another microbe Pseudomonas stutzeri is found to reduce Cr (IV) anaerobically (Jayaram et. al., 2022). A strain of Enterobacter sp. was identified to have the ability to produce ACC deaminase, indole acetic acid, solubilize phosphate as

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well fix nitrogen. Atomic absorption spectrometry revealed that the strain exhibited high Cd removal efficacy whilst conferring Cd tolerance to the plants. SEM analysis revealed no distortion of surface morphology of the strain even when grown in high Cd concentration (Mitra et al. 2018). Polti et al. (2014) demonstrated the reduction of Cr(VI) and removal of Cr by Actinobacteria and Streptomyces respectively. Reduction of heavy metals have also been observed by Flavobacter and Acinetobacter (Kumar et al. 2011).

8.4.2.4

Sequestration

Metal sequestration can occur through either intracellular or extracellular. Intracellular sequestration metal ions form complexes with various compounds in the cell cytoplasm. Cysteine-rich peptides and glutathiones play an important role in intracellular sequestration. Among all the metal-binding ligands present in the cellular components of a microbe amine (–NH2 ) binds to the anionic and cationic metal species more actively via electrostatic interaction and surface complexation respectively (Igiri et al. 2018; Higham et al. 1986). Extracellular sequestration facilitates the accumulation of the metal ions by cellular components in the periplasm (Cha and Cooksey 1991). Bacteria also possess the ability to expel absorbed metal ions from the cytoplasm to be sequestered in the periplasm. Metal precipitation and complexation are both extracellular sequestration (Thelwell et al. 1998). In the presence of heavy metals, cysteine-rich peptides such as glutathione, phytochelatins and metallothioneins are rapidly produced. These peptides bind with metal ions, sequestering them into biologically inactive and less toxic forms. Phytochelatins have higher metal binding capacity and can incorporate high levels of inorganic sulfide as compared to metallothioneins. Metallothioneins are cysteine precursor proteins, rich in thiol groups, which are ideal for the binding of nonessential metals. Synthesis of metallothionein supports the bioaccumulation process and they are responsible for bioprecipitation, and intracellular chelation (Igiri et al. 2018; Mishra and Malik 2013; Bae et al., 2000).

8.4.3 Heavy Metal Resistance by Microorganism The effectiveness of microbe assisted bioremediation is crucially dependent on the resistance of microorganisms against heavy metals (Mosa et al. 2016). Microorganisms have evolved several mechanisms to resist and defend themselves from heavy metals. This includes various mechanical mechanisms such as via metal oxidation, methylation, demethylation, metal–ligand degradation, metal efflux pumps, extracellular barrier, extracellular and intracellular sequestration, reduction of the metal ions and production of metal chelators (Igiri et al. 2018). Biosorption is often the primary strategy applied to resist metal stress (Priyadarshini et al. 2021). With the recent

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advances in genomics and proteomics a wide array of genes has been discovered that are responsible for heavy metal bioaccumulation and are involved in the mechanism of metal resistance (Mishra and Malik 2013). Table 8.6 lists microorganism reported with high tolerance to heavy metals. Natural resistant pathways for heavy metals are reported in many microorganisms and are regulated by specific metalloregulatory proteins. These metalloregulatory proteins are highly selective in nature and exhibit selective affinity to heavy metals mercury and arsenic. These proteins are exploited to design a MerR domain with high mercury binding affinity (Singh et al. 2008a). Transgenes such as mer operon genes which consist of functionally distinct genes for reduction and resistance to mercury including mercuric ion transporter gene merC in Acidithiobacillus ferrooxidans. Mercuric ion transporter genes merR and merD, merE and merH also facilitates the detoxification of Hg2+ to volatile Hg by mercury reductase that occurs in three sequential steps. A genetically modified mercury resistant strain of Escherichia coli, contains both regulatory transporter genes (merT-merP) and metallothionine genes. It was observed to successfully extract and remove Hg2+ from electrolytic wastewater. Another genetically engineered radiation resistant bacterium, Deinococcus radiodurans, facilitated the bioremediation of radioactive waste containing mercury ions (Saxena et al 2020; Sharma et al. 2021a). Accumulation of Cd2+ by Mezorhizobium huakuii was enhanced upon the incorporation of a phytochelatin coding transgene from Arabidopsis thaliana (Sriprang et al. 2003). Genetically engineered strains of E. coli have also been reported to increase bioaccumulation of Cd while strains Table 8.6 List of potential microorganisms reported for the high tolerance of heavy metals Heavy metals

Microbes

Reference

Cu

Kocuria sp. CRB15

Hansda and Kumar (2017)

Fe, Ni, Cr, Zn

Bacillus sp. PS-6

Sharma et al. (2021c)

Cd

Klebsiella pneumoniae

Pramanik et al. (2017)

Cd

Enterobacter, Leifsonia, Klebsiella, Bacillus

Ahmad et al. (2016)

Cd

Rhodococcus sp., Flavobacterium sp.

Belimov et al. (2015)

Cr, Co, Mn, Pb Bacillus cereus, Pseudomonas moraviensis

Hassan et al. (2017)

Cd, Pb

Azospirillum

Arora et al. (2016)

Pb

Bacillus sp. MN3-4

Shin et al. (2012)

Cd

Leifsonia, Klebsiella, Enterobacter

Ahmad et al. (2016)

Cd, As

Mesorhizobium huakuii

Ike et al. (2008)

Zn, Cd

Chryseobacterium humi, Ralstonia eutropha

Marques et al. (2013)

Cd

Klebsiella pneumoniae

Pramanik et al. (2017)

Hg, Cd, Ag

Pseudomonas putida

Yong et al. (2014)

Pb, Cu, As

Curtobacterium sp. NM1R1, Microbacterium sp. Roman-Ponce et al. (2017) CE3R2

Cu

Kocuria sp. CRB15

Hansda and Kumar (2017)

Ni

Bacillus licheniformis

Jamil et al. (2014)

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of rhizobacterium expressing metal-binding peptide (MBP)—EC20, Pseudomonas putida 06,909 alleviate Cd toxicity (Kotrba et al. 1999; Chellaiah 2018). Another recombinant strain, Caulobacter cresentus JS4022/p723-6H showed an increased bioaccumulation potential due to its ability to produce RsaA-6His fusion protein (Patel et al. 2010). Arsenic removal from contaminated sites by microorganisms has also been reported. This is due to their ability to induce the expression of ars genes. Chen et al. (2019) has reported that metal resistance genes in microbes were found to coexist with antimicrobial resistant genes. The gene arsC and ereC were reported to be abundantly exploited in bioremediation. Other heavy metal genes identified in the study were arsB, pbrT, czcA, czcC, czcD, copA, copB, pcoA, copA and pcoA were involved in the oxidization of Cu+ to Cu2+ . A positive correlation was also observed between arsenic and ars genes and between Cd and genes pbrT, chrB, arsB and arsC. Network analysis revealed that the phenomenon of metal resistant coexisting antimicrobial resistant genes depicted positive correlation on the mobility of the metal ion (Chen et al. 2019). However, it has been observed that the catabolic genes responsible for PAHs degradation by sphingomonads are not distributed in clusters (Yin et al. 2020). A transposon named Tn6048 reported increased proliferation under a Pb contaminated environment and conferred increased Pb and Zn resistance to microorganisms (Chen et al. 2019). A recombinant, E. coli constructed with the incorporation of arsM gene from Rhodopseudomonas palustris, reportedly transformed highly toxic inorganic As into less toxic volatile trimethylarsine. Additionally, a metalloregulatory protein ArsR in E. coli has been documented to eliminate high concentration of arsenic (Sharma et al 2021b). It should be also noted that the metal resistance genes were found to be abundant in sites with higher diversity of bacteria (Chen et al. 2019). Membrane transport protein encoded by nixA gene facilitates the transport of Ni2+ across a membrane. In fact, a recombinant strain of E. coli, named SE5000, containing nixA gene accumulated Ni2+ from aqueous solution. Over-expression of membrane transport proteins increase bioaccumulation of Ni2+ by significant volumes (Saxena et al 2020; Sharma et al. 2021a). Another recombinant strain of E. coli transformed by the introduction of serine acetyltransferase gene from Ni hyperaccumulating plant, Thlaspi goesingense showed enhanced resistance to Nickel (Freeman et al 2005).

8.4.4 Pathway Construction and Alteration of the Intrinsic Genes Since standard bioremediation procedures are ineffective and have financial limitations, a novel strategy called pathway engineering or pathway construction has been under investigation for decades now (Tripathi et al. 2021). Gene editing, pathway construction and modification of intrinsic genes aid in modifying the rate limiting steps of the microbial metabolic processes involved in metal remediation (Jayaram et al. 2022). Bioremediation uses diverse transforming enzymes for biosorption

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of different heavy metals (Sharma and Kumar 2021). Hydrolases, dehalogenases, transferases, and oxidoreductases are few of the many classes of enzymes that are commonly involved in bioremediation processes of heavy metals and pollutants, of which microorganisms are excellent sources (Hansda et al. 2016). The presence of heavy metals induce stress in the microbial cells which affect the expression level of proteins; of which most of them are being upregulated (Mishra and Malik 2013). Enhanced enzyme activity and substrate capabilities can be achieved by the expression of hybrid gene clusters recombinantly. However, hybrid gene cluster modifications are limited only to certain species of microorganisms (Saxena et al 2020). The increasing information and database on enzymes and pathways involved in biodegradation offer the opportunity to reconstruct the pathways and express improved enzymes using genetic engineering and recombinant technologies (Chen et al. 1999). In response to heavy metal interactions, microorganisms predominantly produce metal-binding proteins and peptides including phytochelatins (PCs) and metallothionein (MTs). These thiol-rich peptides, in their biologically inactive forms, have the capacity to bind to a variety of heavy metals and reduce them through sequestration (Chen et al. 1999; Hussain et al. 2020). These thiol peptides produced by microbes at different subcellular locations are found to be responsible for the enhancement of heavy metal bioaccumulation. Scientific reports suggest that MTs and PCs bind to heavy metals non-specifically; and thus, specialised heavy metal transporters are used to improvise the accumulation of specific target heavy metals. Expression of MTs in E.coli have resulted in improved biosorption of heavy metals. However, the removal of metal by intracellular MTs has been noted to be insufficient due to limited uptake of heavy metals by soil. One solution to this problem is the expression of MTs on the cell surface. Metal-binding peptides are an alternative to MTs that may have greater affinity and selectivity for heavy metals. Peptides with an abundance of cysteine residues bind to Cd2+ and Hg2+ with a very high affinity (Hussain et al. 2018). Site-directed mutagenesis, which is frequently guided by computer-assisted modelling of the 3-D protein structures, can tailor control mechanisms and enzyme characteristics. With the help of pathway engineering, it is possible to customise an enzyme’s active site volume and topology according to the substrate. This aids the technology with increased substrate specificity, enzyme specificity, substrate binding efficiency, and rate of biodegradation (Tiwari et al. 2013). Efforts have been made to incorporate genes obtained from plants, responsible for the synthesis of PCs. One such attempt led to a 20-fold increase in the accumulation of heavy metals when the enzyme phytochelatin synthase (AtPCS) from the plant Arabidopsis thaliana was overexpressed in E. coli (Sauge-Merle et al. 2003). Heavy metal remediation was accomplished with the help of other similar initiatives as well. As much as PCs potentially accumulates heavy metals, the insufficient supply of its precursor glutathione (GSH) limits the production of PC thereby decreasing heavy metal accumulation. This can be avoided by creating strains that can co-express the GSH-producing enzymes. GSH play a significant role in Cd binding peptides synthesis. These Cd binding peptides inactivate and sequester Cd ions by forming intracellular stable cadmium complexes (Zhang et al. 2019a). The production of PC

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synthase in S. cerevisiae, is noted to maintain an adequate supply of GSH; thus has been demonstrated as a potential construction (Singh et al. 2008b). Additionally, it has also been observed that detoxification of heavy metals can be achieved by the incorporation of sulfide into PC-metal complexes in yeasts and aerobic production of H2 S (Ortiz et al. 1995). Another example of co-expression of an enzyme is GlpF, a particular arsenic transporter in E. coli, and fMT, acquired from the marine algae, Fucus vesiculosus, is reported for increased arsenic accumulation (Singh et al. 2008c). The accumulation of Cd has also been linked to the insertion of the mntA gene, which expresses a Cd uptake transporter (Kang et al. 2007). Mercuric reductase (merA), an enzyme involved in the resistant pathway, and often used in combination with polyphosphate for removal of inorganic and organic mercury (Kiyono et al. 2003). Another concerning source of heavy metal contaminants are the radionuclides from nuclear plant leak or nuclear weapons. These types of radioactive contaminants are best dealt by radiation resistant bacteria (Singh et al. 2008a). The first reported use of radiation resistant bacterium is the Deinococcis geothermalis, a thermophilic bacteria that uses the mer operon coding for Hg2+ reduction (Brim et al. 2003). The bacterium, Deinococcus radiodurans is reported to withstand acute exposure to ionising radiation of 15,000 Gy without lethality (Chen et al 1999). GEMs constructed to deal with mixed radioactive contaminants are capable of reducing metals like Hg, Fe(III), U(VI) and Cr(VI) at high temperature and ionizing radiation. Use of polyphosphates as metal phosphates in P. aeruginosa for radionuclide precipitation by the overexpression of polyphosphate kinase and exopolyphosphatase has been demonstrated (Renninger et al. 2004). Studies have shown that the improved versions of enzymes produced through pathway engineering constructions enhance the accumulation of heavy metals along with the precipitation efficacy of radionuclide contaminants (Singh et al. 2008a).

8.4.5 Role of Extracellular Polymeric Substances (EPS) Microbial cells encounter various environmental stresses including actions by antibiotics, temperature and pH fluctuations into the extremities, desiccation, and high salinity conditions (Mahapatra et al. 2020). EPS are produced by bacteria as a self defense mechanism to safeguard themselves from adverse environmental conditions (Pal and Paul 2008). Under natural conditions, EPS are involved in cellular adhesion, and aggregation and floc formations (Sutherland 2001). Microbial extracellular polysaccharides are complex mixtures of high molecular weight, water soluble biopolymers, possessing on their surface, functional groups such as carboxyl and phenolic groups and other low molecular weight non-polymeric constituents (Mahapatra et al. 2020; Pal and Paul 2008). The functional groups thus present facilitate the immobilization and reduction of heavy metal ions in the polluted environment (Mahapatra et al. 2020; Pal and Paul 2008). They are reported to be poly-ionic and acidic in nature owing to the presence of uronic acids, pyruvate and inorganic residues

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such as sulfate and phosphates (De Philippis et al. 2007). The main constituents of EPS vary among different microorganisms and include polysaccharides, proteins, lipids, uronic acids, humic substances etc. Cell lysates and cell surface material shedings also contribute to the EPS composition (Pal and Paul 2008). EPS can be present either in secreted form or the bacteria may be embedded in the EPS. The secreted form act as surface active agents and possess higher heavy metal removal potential than the EPS secreting biomass (De Philippis et al. 2011). These substances are bioavailable and non-living biosorbent; thus diminishing the pathogenicity issues associated with live organisms for bioremediation processes. They serve as a template for metal cation adsorption and works as a heavy metal exclusion response mechanism (Mahapatra et al. 2020; Tourney and Ngwenya 2014). Extracellular polymeric substances (EPS) play an important role in biofilm-mediated bioremediation (Igiri et al. 2018). An overview of EPS-mediated bioremediation is illustrated in Fig. 8.4. Biofilms are composed of 97% water and are aggregates of microbial cell in EPS (Sutherland 2001). They have a relatively higher tolerance even to lethal concentrations of inorganic elements. By adhering to the metal ions and limiting their entry into the biofilm, EPS around the biofilms shields the cells from the damaging effects of heavy metals (Jang et al. 2001). Although microbial exopolymers are remarked to be nonspecific in heavy metal tolerance but it has also been observed that microbial exopolymers and pigments possess high affinity to bind heavy metals (Mishra and Malik 2013). Positively charged ions and negatively charged EPS interact to achieve EPS-mediated sorption. Amino acids like aspartic and glutamic acids contribute to the anionic properties of nucleic acids in the EPS mixture (Sutherland 2001). Stimulated EPS production by Rhodopseudomonas acidophila and Pseudomonas putida in the presence of heavy metals and other toxic compounds (Sheng et al. 2005; Priester et al. 2006). Metal ion sequestration is favoured by the structural and chemical makeup of EPS. Furthermore, EPS also prevents the cellular penetration of metal ions. Ion exchange, chelation, and precipitation are few examples of mechanisms that lead to the biosorption and immobilisation of heavy metal by EPS. The actions of the EPS are limited to the bacterial cell surface and the surrounding and are devoid of any bacterial metabolisms (Ayangbenro and Babalola 2017). The immobilization occurs within the exopolymeric matrix. The enzymatic activity in EPS aid in the biotransformation of heavy metals and the subsequent precipitation of those metals. The binding of metal to the EPS through the functional groups is influenced by the surrounding pH, metal concentration, presence of organic matter and biomass (Pal and Paul 2008). The ability and function of EPS is affected by the nature of biomass preparation and the availability of specific polymers, the microbial species involved, growth phases, nutrient availability, environmental conditions, and regulation of the metabolic pathway of EPS production (Pal and Paul 2008). Electrostatic interactions between the metal ligands and the negatively charged functional groups of the biopolymers, such as uronic acids, phosphoryl groups, carboxylic groups, etc., bind to create stable complexes of EPS with metals, cationic bindings are also reported (Santamaria et al., 2003). Chemotaxis also braces biofilm formation by attracting the microorganisms to the site of contamination (Pande et al. 2020). Melanin, a component of the fungal cell wall, consists of various groups with high affinity to metal ions

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which spare them from the toxic effects of heavy metals (Mishra and Malik 2013). Analyzing the biological activities and composition of EPS in the biofilm matrix combined with visualization techniques TEM and EDX, it was reported that Cr(III) accumulated in the exopolymeric matrix, outside of the bacterial cell. Pd(II), on the other hand, was reported in both extracellular and intracellular spaces (Vilchez et al. 2011). The mechanism of bioaccumulation and biotransformation may also vary among species depending on their ability to produce extracellular polymeric substances (Mishra and Malik 2013). Potential entrapment of Cd by cellular EPS secretions have also been reported from the extracellular adsorption of Cd on the cell surface (Zhang et al. 2019a). Additionally, Malik (2004) observed that in the presence of Pb, the strain of Pseudomonas marginalis exhibited maximal resistance against the Pb (Malik 2004). Bacterial EPS are comparatively more stable than EPS produced by other eukaryotic microorganisms (Sheng et al. 2005). EPS isolated from both living as well as non-living biomass functions as biosorption agents (Liu et al. 2018). Additionally, EPS produced by cyanobacteria are widely studied and are reported to possess metal chelating abilities (Freire-Nordi et al. 2005). Hyphomonas MHS-3, Methylobacterium organophilum NCIB 11,278 KC1, Thiobacillus ferrooxidans R1, Pseudomonas sp. NCIMB 2021, Rhodovulum sp. PS88, Pseudomonas putida, Pseudoalteromonas CAM 025, Acinetobacter sp. 12S, Enterobacter cloacae, Serratia marcecens are some of EPS producers (Pal and Paul 2008). A strain of Paenibacillus polymyxa (P13), isolated from fermented sausages, reportedly produced EPS under osmotic stress which possessed the ability to potentially bind to Cu(II) ions (Prado Acosta et al. 2005). Interaction and complexation of Ni(II), Cr(VI) and Mo(IV) with isolates of sulphate reducing was reported by EPS secretions in liquid media (Beech and Cheung 1995). Shewanella oneidensis MR-1 have also been reported to demonstrate EPS production and reduce metals in association with specific c lipoproteins that include the c-type cytochrome (Dohnalkova et al. 2005). Many microbial groups are responsible for EPS production of diverse and varied characteristics under different environmental conditions. EPS produced under stressful environmental conditions has been reported to potentially enhance the processes of bioremediation, especially the process of biosorption (Pal and Paul 2008). The specificity and metal binding capacity of EPS is limited to a small number of potential cation binding functional groups. However, the ease of application and role in biofilm and biogranules production exhibit their ability to be used as an efficient bioremediation approach (Liu et al. 2018).

8.4.6 Microbes as Nano-Factories of Metal It has been well observed that microorganisms have the capacity to reduce and precipitate metals in their metallic forms to nano-crystals of varying size, morphology and properties. These contribute to their bioaccumulation and detoxification (Iravani and Varma 2020). Following sorption on the cell surface with the help of metal binding proteins; the metal ions undergo a change in their oxidation states and deposit the

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Fig. 8.4 Overview of EPS involvement in bioremediation

oxides of the metal and zero valent metals on or into their cells. This, further, leads to the production of metal nanoparticles by the cell, which later allows the recovery of these metals for further reuse. Nanoparticles owing to their small size, high specific surface area and uniform size distribution assist in microbial remediation. The particle size and deposition site of the nanoparticle are crucial parameters and can be altered in certain cases by altering the initial metal concentration (Mishra and Malik 2013; Iravani and Varma 2020). Au(0) nanoparticles are known to be deposited intracellularly (Corte et al. 2011). Ag(I) reduction by bacterias can be enzymatic or nonenzymatic. In an non enzymatic, an increase in pH and temperature is reported to accelerate the silver recovery (Fu et al. 2006). Some of the microbial species play a significant role in biogenic metal reduction and recovery. These includes Klebsiella pneumonia, Pseudomonas stutzeri AG259, Lactobacillus A09, Corynebacterium sp. SH09, Aeromonas SH10, Lactobacillus spp., Enterococcus faecium, Lactococcus garvieae, Pediococcus pentosaceus, Staphylococcus aureus, P. aeruginosa and E. coli for silver reduction and recovery (Shahverdi et al. 2007; Fu et al. 2006). Zhang et al. (2006) examined the bioaccumulation of Cd into carp in the presence of TiO2 nanoparticles. It was also observed that TiO2 nanoparticles had a high adsorption and affinity for Cd ions. TiO2 nanoparticles exist in 3 different forms naturally. The biosynthesis of TiO2 nanoparticles have been reported in Saccharomyces cerevisiae and Lactobacillus species as well as Fusarium oxysporum, a pathogenic fungus. TiO2 nanoparticles have multiple applications among those they are reported to play an important role in the removal of toxic compounds (Waghmode et al. 2019). Fungal cells of Verticillium reportedly produce silver nanoparticles intracellularly; whilst Fusarium oxysporum and Aspergillus niger have been observed to produce silver nanoparticles extracellularly (Duran et al. 2005; Sadowski et al. 2008). Nanoparticle

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biosynthesis minimizes the use of hazardous materials for nanoparticle preparation. However, nanoparticle synthesis takes a longer period of time (Mishra and Malik 2013).

8.5 Conclusion Heavy metals are naturally occurring but have seen a significant increase due to heightened industrial and human activities, resulting in rapid accumulation within the ecosystems and subsequent environmental concerns. Elevated levels of HMs in the environment have adverse effects on both biotic and abiotic elements such as plants, animals, and soil. Consequently, the effective removal of these HMs becomes paramount. While various physical and chemical conventional techniques are available, their have prompted researchers to explore alternative methods, such as bioremediation, which employs biological organisms to efficiently degrade and detoxify the HMs. Microorganisms offer a promising avenue for processes. Numerous microbial communities have shown effectiveness in degrading and converting HMs into less toxic forms. These processes are affordable, environmentally friendly, and nontoxic. However, a toxic concentration of HMs in the surrounding limits the efficacy of the removal. This review highlights the potential of GEMs to address these challenges and enhance the efficiency of bioremediation. Genetic modification can target genes responsible for heavy metal absorption, translocation, sequestration, and tolerance in both plants and microorganisms, thereby enhancing heavy metal accumulation or tolerance capacities. The use of GEMs for bioremediation of heavy metal is cost effective, sustainable, non-toxic. Nevertheless, there are limitations to the application of GEMs, primarily stemming from concerns about horizontal gene transfer between GEMs and native microbial communities. The use of biogenic nanoparticles for bioremediation is another advancing field. However, many interesting and potential metals remain unexplored. while the potential for biotechnological applications is promising, a deeper understanding of microbial genetic makeup and natural transformation abilities is essential for designing ecologically safe GEMs with desired characteristics, ultimately improving the bioremediation process.

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Chapter 9

Constructed Wetlands for Industrial Wastewater Remediation Manoj Kumar, Neeraj Kumar Singh, Kalp Bhusan Prajapati, Ruplappara Sharath Kumar, and Rajesh Singh

Abstract Industrial wastewater is being discharged into nearby bodies of water, putting a strain on the environment’s ability to sustain itself. Unfortunately, the threats to human health arising from this practice are not being adequately addressed. Therefore, the treatment of such effluent is essential but challenging due to its complex composition. In the field of industrial wastewater treatment, a combination of various biological and physicochemical approaches is typically employed. Notably, the latter technologies are preferred for their energy efficiency and lower operating expenses. Constructed wetlands (CWs) offer affordable and long-lasting methods for treating wastewater. Traditionally used for domestic and urban wastewater treatment, CWs have undergone significant advancements in technology and expanded field research over the last few decades. As a result, CWs are now being applied to treat wide range of wastewater types, including those from the petrochemical and refinery industries, the food industry (encompassing fruit, dairy, meat, and vegetable preparation sectors, as well as abattoirs), the paper and pulp, textile, steel, aquaculture, wine, distillery, the paper and pulp, textile, and mixed industrial effluents industries. In this chapter, the authors present the main types of CWs, describing their primary applications for industrial wastewater treatment. Special attention is given to the removal of organic matter and nutrients, along with a detailed explanation of their operational processes and expected performances. M. Kumar (B) Department of Hydro and Renewable Energy, Indian Institute of Technology Roorkee, Roorkee, Uttrakhand 247667, India e-mail: [email protected] N. K. Singh · R. S. Kumar Department of Biosciences and Bioengineering, Indian Institute of Technology Roorkee, Roorkee, Uttrakhand 247667, India K. B. Prajapati Department of Environmental Sciences, Central University of Haryana, Mahendragarh, Haryana 123031, India R. Singh School of Environment and Sustainable Development, Central University of Gujarat, Gandhinagar, Gujrat 382030, India © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 A. S. Mathuriya et al. (eds.), Green Technologies for Industrial Waste Remediation, Environmental Science and Engineering, https://doi.org/10.1007/978-3-031-46858-2_9

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Keywords Constructed wetlands · Industrial wastewater · Remediation · Sustainability · Performance · Applications

9.1 Introduction One of the significant environmental concerns related to water contamination is industrial discharge. In the last century, unregulated release of industrial effluent flow into rivers, lakes, and coastal areas has caused harm to both biotic and abiotic components of the environment (Kumar et al. 2021). The discharge of various lifestyle chemicals from municipal wastewater is also a considerable problem, directly impacting human health and damaging aquatic ecosystems and drinking water resources (Kumar and Singh 2017). Industrial wastewaters contain a range of pollutants specific to the manufacturing process, such as alkalis, sulfides, tannins, BOD, COD, solids, colors, nutrients, salts, phenols, toxic metals, grease, and oil (Hai et al. 2015; Lofrano et al. 2013; Saeed and Sun 2017; Tan et al. 2017; Vymazal 2014). CWs offer an effective natural treatment method for industrial and municipal wastewater due to their lower maintenance and operational costs (Kumar and Singh 2019; Wang et al. 2017). Vertical flow CWs with a variety of substrate beds are commonly employed as an environmentally responsible approach for pollutant removal (Kumar and Singh 2021). Achieving higher removal rates in wetland systems depends on input loadings and wastewater biodegradability (Saeed and Sun 2017). Lower wastewater biodegradation rates can be attributed to the lack of biodegradable organics in wastewater, which hinders nitrogen removal pathways and microbial activities (Kadlec and Wallace 2009). On the other hand, higher loadings often exceed the disposal capacity of these natural systems (Dan et al. 2011; Mitchell and McNevin 2001; Trang et al. 2010). Constructed wetlands, also known as natural biological reactors, are considered a practical choice for wastewater treatment due to their straightforward operational mechanism (Khan et al. 2009). These systems consist of a complex network of plant roots, medium, and associated biofilms that facilitate wastewater treatment through various physical, biological, and chemical pathways (Kadlec and Wallace 2009; Langergraber et al. 2009). In wetland environments, the biodegradability of industrial wastewater can be unfavorable, significantly affecting microbial growth and related removal processes (Saeed et al. 2018; Yang et al. 2018a, b). To overcome carbon deficiency in such environments, certain media with specific physical and chemical characteristics are used to stimulate biofilm formation. For example, carbon leaching from sugarcane materials or adsorption by construction materials or organic coco peat in VF-CWs has shown promising results (Saeed et al. 2018; Saeed et al. 2012; Saeed and Sun 2013). Notably, the efficiency of pollutant removal in wetland systems is impacted by the integration of CWs. Hybrid wetland systems such as VF arranged by HF systems, have proven to be more effective at treating wastewater compared to multistage wetlands of the same kind, thanks to an appropriate catalyst enhancing microbial reaction (Bulc and Ojstrsek 2008; Calheiros et al. 2009; Soroko 2007). Industries often experience rapid

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changes in water usage and wastewater production due to fluctuations in production and demand. These variations can influence how well-constructed wetlands remove pollutants, asa significant increase in wastewater volume may reduce retention times and removal rates (Saeed and Sun 2012). The primary objective of utilizing CWs for industrial wastewater remediation is to effectively treat and remediate the wastewater to meet regulatory standards and minimize environmental impacts. CWs offer a flexible and adaptable approach to industrial wastewater treatment, aiming to achieve effective remediation while considering environmental sustainability. This chapter provides a comprehensive review of a CWs, including their classification, plants, substrates, pollutants removal, Conclusions, and future outlook.

9.2 Constructed Wetlands (CWs) CWs are engineered structures designed to mimic the functions of natural wetlands in treating wastewater or Domestic and municipal wastewater, sewage from wastewater treatment plants, urban runoff, livestock wastewater, stormwater, and landfill leachate are other major sources of pollution to the aquatic environments. CWs find various applications, including domestic wastewater treatment, industrial wastewater remediation, stormwater management, and water reuse (Retta et al. 2023). They combine physical, biological, and chemical processes to effectively remove pollutants and improve water quality (Zhang et al. 2014). The key components of a CW include a water source or influent, a substrate or bed material, wetland vegetation, and water flow and distribution system. These components work together to achieve efficient pollutant removal (Almeida et al. 2017). CWs offer several advantages, including low operational costs, energy efficiency, aesthetic value, and potential to create habitat for wildlife. They can capable of effectively removing pollutants containing nutrients, heavy metals, organic substances, suspended solids, and some organic compounds. The treated water from CWs can often be safely discharged or reused for various non-potable purposes, such as irrigation or industrial processes (Kamilya et al. 2022). However, it is essential to customize the design, sizing, and operation of CWs to suit specific site conditions, treatment goals, and characteristics of the treated wastewater. Regular monitoring and maintenance are crucial to ensuring optimal performance and longevity of the CW system (Vymazal 2010).

9.3 Constructed Wetland Types Engineered systems known as CWs are employed to treat various types of water including wastewater, and stormwater, by emulating natural wetland processes (Retta et al. 2023). Several types of CWs, each with its own unique structure and function. Here are some common types:

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. Free Water Surface (FWS) Wetlands: FWS wetlands are the most commonly used for wastewater treatment. They have shallow water depths and feature emergent vegetation, such as reeds or cattails, growing on the water’s surface. The wastewater flows through the wetland in a controlled manner, allowing for pollutant removal through physical, biological, and chemical methods (Wu et al. 2014). . Subsurface Flow (SSF) Wetlands: SSF wetlands involve the movement of wastewater from below the wetland’s surface through a gravel or sand bed. Vegetation is often planted on the surface, and the wastewater passes through the root zone, where microbial and plant processes help in pollutant removal (Nivala et al. 2013). . Vertical Flow (VF) Wetlands: VF wetlands are similar to SSF wetlands, but the wastewater flows vertically from top to bottom through a layered media system. The media layers typically include coarse-grained material at the top and finegrained material at the bottom. Plants are commonly grown on the surface, and the wastewater percolates through the media, providing treatment (Vymazal 2017). . Horizontal Flow Constructed Wetlands (HFCW): HFCW are engineered wetland structures designed for treating wastewater and stormwater. In HFCW, water flows horizontally through the wetland, following a shallow gradient, before being discharged or collected for further treatment. HFCW utilize physical, biological, and chemical processes to improve the quality of the water and remove impurities (Vymazal 2014). . Hybrid Constructed Wetlands: Hybrid systems integrate CWs with other treatment technologies, such as activated sludge processes, biofilters, or chemical dosing units. By leveraging the strengths of both wetlands and other treatment methods, hybrid systems can achieve higher treatment efficiency (Vymazal 2013a, b). . Floating Treatment Wetlands (FTW): FTWs consist of floating mats or rafts that support wetland vegetation. They are useful in ponds, lakes, or lagoons to enhance water quality by absorbing nutrients and contaminants. FTWs are particularly beneficial for stormwater treatment or in places where land availability is limited. It is crucial to recognize that the design and performance of CWs can vary based on specific requirements, local conditions, and the targeted pollutants for removal (Colares et al. 2020). Therefore, the selection of wetland type should be based on the particular goals.

9.3.1 Free Water Surface (FWS) Constructed Wetlands FWS are the most commonly used forms used for stormwater management and wastewater treatment (Fig. 9.1). These wetlands mimic natural wetland systems where water flows freely across the wetland’s surface. They employ physical, biological, and chemical processes to remove contaminants and improve water

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Fig. 9.1 Free water surface (FWS) constructed wetlands

quality. FWS wetlands effectively remove many pollutants, including organic waste, suspended particulates, nutrients (such as nitrogen and phosphate), heavy metals, and specific pathogens. They provide habitat for wildlife, enhance biodiversity, and offer aesthetic and recreational benefits. FWS wetlands can be used in various applications, including wastewater treatment plants, urban stormwater management, agricultural runoff control, and industrial wastewater treatment (Wu et al. 2014).

9.3.2 Vertical Flow (VF) Constructed Wetlands CWs with Vertical Flow (VF) are engineered wetland systems designed to improve water quality and treat wastewater (Fig. 9.2). In VF-CWs, water flows vertically through a media bed, which is usually composed of a layered arrangement of coarse and fine-grained materials. This unique design allows for effective treatment of pollutants by combining physical, biological, and chemical processes. VF CWs have proven to be effective in treating a diverse range of pollutants, including contaminants, nutrients (such as phosphate and nitrogen), suspended solids, and organic matter. These wetlands are commonly employed for decentralized wastewater treatment, small-scale applications, and retrofitting existing treatment systems. VF wetlands are versatile and can be adaptable to different climates (Vymazal 2017).

9.3.3 Horizontal Flow (HF) Constructed Wetlands CWs with Horizontal Flow (HF) are engineered wetland systems designed to treat wastewater and stormwater (Fig. 9.3). In HF-CWs, water flows horizontally through the wetland following a shallow gradient before being discharged or collected for further treatment. HF wetlands employ physical, biological, and chemical processes to effectively remove pollutants and enhance water quality. HF wetlands effectively remove various contaminants, including organic material, suspended particles, nutrients (such as phosphate and nitrogen), heavy metals, and particular pathogens. They provide habitat for wildlife, enhance biodiversity, and offer aesthetic and recreational

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Fig. 9.2 Vertical flow (VF) constructed wetlands

Fig. 9.3 Horizontal flow (HF) constructed wetlands

benefits. HF wetlands are utilized in various applications, including wastewater treatment plants, urban stormwater management, agricultural runoff control, and industrial wastewater treatment. They are particularly suitable for areas with gentle topography and a feasible horizontal flow path (Vymazal 2014).

9.3.4 Hybrid Constructed Wetlands (HCWs) Hybrid constructed wetlands (Hybrid CWs) are engineered wetland systems that combine constructed wetlands with other treatment technologies to improve water treatment and pollutant removal (Fig. 9.4). HCWs leverage the strengths of wetland processes and other treatment methods to optimize treatment performance and

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Fig. 9.4 Hybrid constructed wetlands

address specific water quality challenges. HCWs offer a versatile and efficient approach to water treatment and pollutant removal. By combining CWs with other treatment technologies, HCWs can achieve higher treatment efficiencies, target a broader range of pollutants, and provide more versatile solutions for water quality management. HCWs contribute to sustainable water management by providing effective treatment, reducing environmental impact, and promoting the reuse of treated water (Vymazal 2013a, b).

9.3.5 Floating Treatment Wetlands (FTW) Floating Treatment Wetlands (FTWs) are a type of CWs system that comprises floating mats or rafts planted with wetland vegetation. Unlike traditional wetlands rooted in submerged or saturated soils, FTWs float on the water surface, providing a unique approach to water treatment and ecological restoration in natural and engineered water bodies. FTWs offer an innovative and eco-friendly approach to water treatment and ecological restoration. They can effectively remove nutrients, sediment, and specific contaminants from water bodies, improving water quality and promoting the overall health of aquatic ecosystems. FTWs also provide a visually appealing and sustainable solution for urban water management, stormwater treatment, and habitat creation (Colares et al. 2020).

9.4 Contructed Wetland Substrate Selection and Role The design and performance of artificial wetlands depend heavily on the choice of substrate (media or bed material) and wetland plants. Substrates play an important support role in biological treatment process. It provides physical support and carrier for the plants and microorganism in CWs (Yang et al. 2018a, b). On the other hand, selecting wetland plants affects the effectiveness of treatment and the wetland system’s ecological functioning (Yang et al. 2022). This Table 9.1 provides

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Table 9.1 Substrate selection for constructed wetlands Substrate material Particle size distribution Hydraulic conductivity Treatment applications Gravel

2–20 mm

High

Solids removal, initial sedimentation, nitrification

Crushed stone

5–20 mm

Moderate to high

Solids removal, nitrification, denitrification

Sand

0.05–2 mm

Moderate

Fine solids removal, organic matter decomposition

Soil

Varies

Low to moderate

Nutrient uptake, organic matter decomposition, plant growth

general information, and the selection of substrate material should be based on sitespecific conditions, treatment goals, and the type of pollutants being targeted. The hydraulic conductivity and particle size distribution can vary depending on the project requirements.

9.5 Contructed Wetland Plant Selection and Role Vegetation plays an important role in wastewater treatment wetlands (Brix 2003). Constructed wetland vegetation that emerges from the water’s surface. Plants like reeds, cattails, and bulrushes are frequently employed in constructed wetlands. These plants have extensive root systems that provide additional surface area for microbial attachment, promote oxygen transfer to the substrate, and help absorb and remove minerals and organic substances. Many types of plants are used for constructed wetlands (Vymazal 2013b; Arliyani et al. 2021). The variety of constructed wetlands plants is essential for removing nutrients since they take up and assimilate nitrogen, phosphorus, and other nutrients from the water column, thereby reducing their availability for algal growth (Wu et al. 2015). This Table 9.2 provides general information, the local conditions that should be considered while selecting wetland plant species, treatment goals, and the targeted pollutants.

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Table 9.2 Wetland plant selection for constructed wetlands Wetland plant species

Growth form

Nutrient uptake

Organic matter decomposition

Habitat value

Typha spp.

Emergent

High

High

High

Phragmites australis

Emergent

High

High

High

Carex spp.

Emergent

Moderate

Moderate

Moderate

Juncus spp.

Emergent

Moderate

Moderate

Moderate

Lemna spp.

Floating

High

Low

Low

Nymphaea spp.

Floating

Moderate

Low

High

Ceratophyllum spp.

Submerged

High

Low

Moderate

9.6 Constructed Wetland Technology for Industrial Wastewater Treatment The discharge of industrial wastewater into the aquatic environment has been one of the main threats to the ecosystem. CWs, particularly in emerging nations, have been projected to offer a low-cost and low maintenance treatment another for industrial effluent (Hadad et al. 2006). Several scholars treated textile wastewater by CWs through different conditions, such as; hydraulic loading rates (Yalcuk and Dogdu 2014), dye concentration (Yadav et al. 2012; Hussein and Scholz 2017), hydraulic retention time (Chandanshive et al. 2018), type of plant (Fang et al. 2015), type of media (Jayalakshmi et al. 2023). The many benefits and uses of constructed wetlands have come to be more understood over the past ten years, which are more frequently utilized to clean different types of wastewater (Kadlec and Reddy 2001). The remediation of industrial wastewater may be successfully and sustainably accomplished using constructed wetlands. Constructed wetlands can reduce pollution and enhance water quality by utilizing natural processes and the interactions between the vegetation, substrate, and microbial communities in wetlands. Furthermore, using artificial wetlands is widely acknowledged as an eco-technology, which is beneficial for small groups or organizations that cannot afford expensive conventional treatment systems (Karim et al. 2004). Because the wetland system solely uses natural energy to decrease pollution, it is energetically sustainable. It has lower construction and operating costs than conventional wastewater treatment systems (Ran et al. 2004). Thousands of CWs worldwide receive and treat numerous municipal, urban, and industrial runoff wastewater (Solano et al. 2004). Total suspended solids (TSS), metals, phosphorus, nitrogen, and BOD/COD are all effectively treated by CWs (Kadlec and Knight 1986). The CW is the most effective method for removing micropollutants and pharmaceuticals from wastewater (Matamoros and Boyona 2006). For the remediation of textile effluent, HF-CWs growing in Leptochloa fusca showed promise (76% for BOD, 80% for COD, 76% for color, and 29% for TSS) (Hussain et al. 2018).

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9.7 Conclusions and Future Outlook CWs are a practical and sustainable solution for the sewage treatment. They offer numerous advantages, including cost-effectiveness, low energy requirements, and the potential for water reuse. Through natural processes and the synergistic interactions between wetland vegetation, substrate, and microbial communities, constructed wetlands can effectively remove numerous pollutants from industrial wastewater, including organic matter, heavy metals, nutrients, and certain recalcitrant compounds. Using constructed wetlands for industrial wastewater remediation has shown promising results, with studies reporting significant reductions in pollutant concentrations and improved water quality. The specific design and configuration of constructed wetlands should be tailored to the characteristics of the industrial wastewater and treatment goals. Factors such as choice of wetland plant species, substrate selection, hydraulic flow, and system monitoring are critical in achieving optimal treatment performance. In conclusion, constructed wetlands offer a promising approach for wastewater remediation, providing cost-effective and environmentally friendly treatment solutions. Ongoing research and technological advancements will further optimize their performance, expand their applications, and contribute to sustainable industrial wastewater management in the future.

References Almeida CMR, Santos F, Ferreira ACF, Lourinha I, Basto MCP, Mucha AP (2017) Can veterinary antibiotics affect constructed wetlands performance during treatment of livestock wastewater? Ecol Eng 102:583–588 Arliyani I, Tangahu BV, Mangkoedihardjo S (2021) Plant diversity in a constructed wetland for pollutant parameter processing on leachate: a review. J Ecol Eng 22(4) Brix H (2003) Plants used in constructed wetlands and their functions. In: Dias V, Vymazal J (eds) 1st International seminar on the use of aquatic macrophytes for wastewater treatment in constructed wetlands. Lisbon Portugal, pp 81–109 Bulc TG, Ojstrsek A (2008) The use of constructed wetland for dye-rich textile wastewater treatment. J Hazard Mater 155(1–2):76–82 Calheiros CS, Rangel AO, Castro PM (2009) Treatment of industrial wastewater with two-stage constructed wetlands planted with Typha latifolia and Phragmites australis. Bioresour Technol 100(13):3205–3213 Chandanshive VV, Kadam SK, Khandare RV, Kurade MB, Jeon BH, Jadhav JP, Govindwar SP (2018) In situ phytoremediation of dyes from textile wastewater using garden ornamental plants, effect on soil quality and plant growth. Chemosphere 210:968–976 Colares GS, Dell’Osbel N, Wiesel PG, Oliveira GA, Lemos PHZ, da Silva FP, Lutterbeck CA, Kist LT, Machado ÊL (2020) Floating treatment wetlands: a review and bibliometric analysis. Sci Total Environ 714:136776 Dan TH, Chiem NH, Brix H (2011) Treatment of high-strength wastewater in tropical constructed wetlands planted with Sesbania sesban: horizontal subsurface flow versus vertical downflow. Ecol Eng 37(5):711–720

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Fang Z, Song HL, Cang N, Li XN (2015) Electricity production from Azo dye wastewater using a microbial fuel cell coupled constructed wetland operating under different operating conditions. Biosens Bioelectron 68:135–141 Hadad HR, Maine MA, Bonetto CA (2006) Macrophyte growth in a pilot-scale constructed wetland for industrial wastewater treatment. Chemosphere 63(10):1744–1753 Hai R, He Y, Wang X, Li Y (2015) Simultaneous removal of nitrogen and phosphorus from swine wastewater in a sequencing batch biofilm reactor. Chin J Chem Eng 23(1):303–308 Hussain Z, Arslan M, Malik MH, Mohsin M, Iqbal S, Afzal M (2018) Integrated perspectives on the use of bacterial endophytes in horizontal flow constructed wetlands for the treatment of liquid textile effluent: phytoremediation advances in the field. J Environ Econ Manage 224:387–395 Hussein A, Scholz M (2017) Dye wastewater treatment by vertical-flow constructed wetlands. Ecol Eng 101:28–38 Jayalakshmi R, Soundaranayaki K, Kannan MS (2023) Removal of Methylene Blue dye from textile wastewater using vertical flow constructed wetland. Mater Today Proc 77:365–370 Kadlec RH, Knight RL (1986) Treatment wetlands. Lewis Publishers, New York Kadlec RH, Wallace SD (2009) Treatment wetlands, 2nd edn. CRC Press, Boca Raton FL 334872742 USA Kamilya T, Majumder A, Yadav MK, Ayoob S, Tripathy S, Gupta AK (2022) Nutrient pollution and its remediation using constructed wetlands: insights into removal and recovery mechanisms, modifications and sustainable aspects. J Environ Chem Eng 10(3):107444 Karim MR, Manshadi FD, Karpiscak MM, Gerba CP (2004) The persistence and removal of enteric pathogens in constructed wetlands. Water Res 38(7):1831–1837 Khan S, Ahmad I, Shah MT, Rehman S, Khaliq A (2009) Use of constructed wetland for the removal of heavy metals from industrial wastewater. J Environ Manage 90(11):3451–3457 Kumar M, Singh NK, Singh R (2021) Application of constructed wetlands in degradation and detoxification of industrial effluents: challenges and prospects. Bioremediat Environ Sustain 43–82 Kumar M, Singh R (2017) Performance evaluation of semi continuous vertical flow constructed wetlands (SC-VF-CWs) for municipal wastewater treatment. Bioresour Technol 232:321–330 Kumar M, Singh R (2019) Assessment of pollutant removal processes and kinetic modelling in vertical flow constructed wetlands at elevated pollutant loading. Environ Sci Pollut Res 26:18421–18433 Kumar M, Singh R (2021) Area-based speciation kinetic analysis of multipollutant removal in constructed wetlands to enhance the treatment efficiency. Environ Sci Water Res Technol 7(6):1090–1102 Langergraber G, Giraldi D, Mena J, Meyer D, Peña M, Toscano A, Brovelli A, Korkusuz EA (2009) Recent developments in numerical modelling of subsurface flow constructed wetlands. Sci Total Environ 407(13):3931–3943 Lofrano G, Meriç S, Zengin GE, Orhon D (2013) Chemical and biological treatment technologies for leather tannery chemicals and wastewaters: a review. Sci Total Environ 461:265–281 Matamoros V, Boyona JM (2006) Elimination of pharmaceuticals and personal care products in subsurface flow constructed wetlands. Environ Sci Technol 40(18):5811–5816 Mitchell C, McNevin D (2001) Alternative analysis of BOD removal in subsurface flow constructed wetlands employing Monod kinetics. Water Res 35(5):1295–1303 Nivala J, Wallace S, Headley T, Kassa K, Brix H, van Afferden M, Müller R (2013) Oxygen transfer and consumption in subsurface flow treatment wetlands. Ecol Eng 61:544–554 Ran N, Agami M, Oron G (2004) A pilot study of constructed wetlands using duckweed (Lemna gibba L.) for treatment of domestic primary effluent in Israel. Water Res 38(9):2241–2248 Retta B, Coppola E, Ciniglia C, Grilli E (2023) Constructed wetlands for the wastewater treatment: a review of Italian case studies. Appl Sci 13(10):6211 Saeed T, Sun G (2012) A review on nitrogen and organics removal mechanisms in subsurface flow constructed wetlands: dependency on environmental parameters, operating conditions and supporting media. J Environ Manage 112:429–448

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Chapter 10

Bioelectrochemical Treatment of Petrochemicals Nakul Kumar, Neha Tavker, Pankaj Kumar, and Snigdha Singh

Abstract The petroleum-based sector generates substantial effluents, posing a potential risk to water sources and air quality. Within petrochemical industries, notable quantities of organic and inorganic pollutants, oil complexes, surfactants, and polymers are present. The waste and wastewater originating from petrochemical activities encompass aliphatic and aromatic hydrocarbons, cancer-causing agents, and industrial refuse, which substantially impact the environment, human health, and the well-being of animals and plants. Petroleum corporations consume considerable water throughout their industrial operations and discharge wastewater. This wastewater, originating from the petrochemical sector, contains recalcitrant pollutants such as sulfur compounds, dissolved solids, and potent, concentrated hydrocarbons, all of which could harm the environment. Bioelectrochemical systems (BESs) emerge as a viable solution for treating a variety of petrochemicals, encompassing olefins, hydrocarbons, and wastewater produced during petroleum refinement. Importantly, BESs exhibit the capacity to generate bioelectricity and value-added chemicals. This chapter delves into the feasibility of employing bioelectrochemical methods and other technological avenues for treating wastewater derived from petroleum and related industries. The chapter also scrutinizes bioelectrochemical systems’ challenges in treating petroleum-based waste and wastewater, proposing potential remedies. Keywords Bioelectrochemical systems · Petrochemicals · Wastewater

N. Kumar (B) Gandhinagar Institute of Sciences, Gandhinagar University, Katraj, Gandhinagar, Gujarat, India e-mail: [email protected] N. Tavker National Innovation Foundation, Gandhinagar, Gujarat, India P. Kumar · S. Singh Department of Environmental Science, Parul Institute of Applied Sciences, Parul University, Vadodara, Gujarat, India e-mail: [email protected] © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 A. S. Mathuriya et al. (eds.), Green Technologies for Industrial Waste Remediation, Environmental Science and Engineering, https://doi.org/10.1007/978-3-031-46858-2_10

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10.1 Introduction The escalating global population and concurrent industrialization, which gives rise to substantial wastewater production, drive an increasing demand for fossil fuels. Current research explores alternative and renewable energy sources to cater to the surging energy requirements (Armstrong 2022). A bio-electrochemical device known as a microbial fuel cell (MFC) holds the potential to effectively address the current issues with wastewater management and the energy crisis by using microbes as biocatalysts. The reality of an autonomous wastewater treatment plant is still attainable, even though the dream of massive MFC power generation has long since faded. Microbes can directly turn chemical energy into electricity by metabolizing the organic components within the substrate. Diverse types of intricate petrochemicals, including farming, household insecticides, agricultural petrochemicals, etc., have already been studied in MFCs (Sarmin et al. 2020). These studies have shown their potential applicability within MFCs, facilitating effective treatment alongside simultaneous power generation. However, due to their inherent challenges in biodegradability, petrochemical wastewater (PCW) from the petroleum sector has only occasionally been employed in MFC (Yeruva et al. 2015). Only a few studies have demonstrated PCW usage, including phenolic compounds, besides other aromatic and aliphatic hydrocarbons. Still, the results were unsatisfactory because of the complicated interactions between the substrates and the microorganisms. Furthermore, various conventional methods such as adsorption, coagulation, biofiltration, and flocculation have previously been employed to cleanse PCW of pollutants. However, these techniques necessitate substantial energy and do not fully comply with stringent environmental regulations. None of the researchers have utilized PCW from an acrylic acid factory in a double chamber MFC. Therefore, the primary aim of the present study is to investigate whether MFC technology can treat PCW from an acrylic acid facility utilizing anaerobic bacteria. Anaerobic sludge (AS) was selected due to its ready availability and potential to support a variety of microorganisms (Koul et al. 2022). The environmentally advantageous principle of “green chemistry” has been used in the biosynthesis of nanoparticles to create eco-friendly nanoparticles involving bacteria, fungi, plants, and actinomycetes, a process called the “green approach”. Forming nanoparticles with innovative properties through biosynthesis employing the organisms is a sustainable alternative (Kumar and Sinha 2022). Both single-celled and multicellular microbes partake in these syntheses. The study examined the performance of an AS-fueled MFC fed with PCW, assessing power generation, colonic efficacy, and Chemical Oxygen Demand (COD) removal efficiency. Moreover, electrochemical impedance spectroscopy was employed to analyze the interactions at the electrode/biofilm/electrolyte interface. At the same time, cyclic voltammetry (CV) elucidated the electron transport process (Tabish et al. 2023).

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Industrial wastewaters often contain substantial amounts of organic and inorganic contaminants, with organic showing significant concentrations and an extensive range of molecular structural variety. More precisely, effluent from petrochemical companies is typically less biodegradable and contains a variety of contaminants with high carbon and salt concentrations (Sathya et al. 2022). Diverse structural compounds found in petrochemical wastewater (PCW), such as polycyclic aromatic and aliphatic hydrocarbons, cyanides, octanols, formaldehyde, phenols, organic acids, and sulphides, among others, call for treatment before disposal. PCW can be treated using various techniques, including physical, biological, chemical, etc. Advanced membrane bioreactors (MBRs) can be used to treat PCW physically. However, the procedure has some limitations because of the high operational and investment expenses. Similar issues plague biological treatment approaches, such as the microorganisms’ inability to easily access hydrocarbons due to their complicated structures and water-insoluble nature, especially when saline levels in wastewater are higher (Balapure et al. 2015). Therefore, extra conversion processes are needed to increase the efficiency of conventional wastewater treatment methods to overcome these limits. Bioelectrical treatment was introduced as the revolutionary concept of employing bioelectrochemical systems to address the environmental challenges the petrochemical industry poses. This innovative approach leverages the intricate interplay between microorganisms and electrodes to initiate and facilitate biochemical processes capable of mitigating the detrimental byproducts and pollutants stemming from petrochemical processes. By harnessing the potential of these bioelectrochemical interactions, this treatment method offers a sustainable and environmentallyconscious strategy for remediating contaminated air, water, and soil. The study underscores the potential of bioelectrical treatment to reshape conventional waste management techniques in the petrochemical sector, offering a financially viable and energy-efficient alternative that aligns with the growing global push for ecologically sound industrial practices.

10.1.1 Principle of Bio Electrochemical System (BES) Bioelectrochemical treatment has emerged as a promising and innovative approach for the remediation of petrochemical-contaminated environments (Debnath and Dutta 2023). Petrochemicals, such as benzene, toluene, xylene, ethylbenzene, and polyaromatic hydrocarbons (PAHs), pose significant environmental risks due to their toxic and persistent nature. Conventional remediation methods often suffer drawbacks, such as high energy consumption, production of secondary pollutants, and limited effectiveness against recalcitrant compounds. In contrast, bioelectrochemical treatment harnesses the power of microbial activity and electrochemical reactions to efficiently degrade and remove petrochemical contaminants while generating useful energy or valuable byproducts. This environmentally friendly and sustainable approach has garnered increasing interest as researchers and practitioners seek

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alternative, more effective strategies to tackle petrochemical pollution and its associated challenges. With ongoing research and advancements, bioelectrochemical treatment holds the potential to play a vital role in the quest for cleaner and healthier environments (Varjani and Upasani, 2017; Mohammadi et al. 2020). BESs are categorized into five different types. BES can be operated similarly to MFC or microbial electrolysis cells (MECs), where electric power is recovered to improve the reaction kinetics. However, the energy gain is significantly lower, and system losses result in a substantial increase in essential energy beyond the calculated value. The term “activation overpotential losses” refers to some losses caused by faulty catalysis, whereas “ohmic loss” is caused by resistance in the electrolyte and electrode. Substrate dispersion to the cathode oxygen at the anode causes certain concentration losses (Dwivedi et al. 2022). The biochemical energy of organic waste, such as low-strength wastewater and lignocellulosic biomass, can be converted by BESs into electricity, hydrogen/ chemical products in MECs created at the cathode by an electrochemical reduction process (Pant et al. 2012). BESs under milder conditions, utilizing a variety of organic substrates, and typically eschew the use of metals as catalysts. The scope for these systems has been substantially enlarged by the newly revealed usage of BES for product synthesis through microbial electrosynthesis. BESs are up-and-coming technologies thanks to newer application concepts, improved electrode, separator, and catalyst substitute materials, and unique designs (Rozendal et al. 2009). This article delves into the recent advancements in BESs, primarily focusing on their diverse applications beyond power generation, subsequent performances, and current limitations (Fig. 10.1). Fig. 10.1 Illustration of a fuel cell (Tavker and Kumar 2023)

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10.2 Types of BES BESs may be categorized as MFCs and enzymatic fuel cells depending on the biocatalyst (EFCs) and classified into MFCs, microbial electrolysis cells (MEC), microbial desalination cells (MDCs), and microbial solar cells depending on their mode of use (MSC). In-depth explanations of the MSC concept have been provided (Aiyer 2021). Recently, the idea of utilizing BESs as a technique of simultaneous desalination and energy retrieval in MDC was presented. Afterwards, investigators went on to better describe it. Recently, stacked MDCs with concentration chambers and desalination chambers separated by compartmental anion exchange membranes (AEMs) and cation exchange membranes were reported (CEMs) (Nishio et al. 2013). A twodesalination-chambered SMDC with an external resistance of 10 achieved the highest total desalination rate (TDR), 1.4 times faster than a single-desalination-chambered MDC (Jacobson et al. 2011). The acronym MXC—the X for the various types and applications—was recently coined for these systems. The microbial electrochemical snorkel (MES), a condensed design of a “short-circuited” MFC, has been developed to treat urban wastewater. An MES, unlike MFCs, ensures optimal efficiency for oxidizing organic materials without diverting energy to produce electricity. A MES thereby improves the effectiveness of treatment rather than providing current. Several operational peculiarities can distinguish these different BES kinds, further addressed in depth (Tavker and Kumar 2023).

10.2.1 Microbial Fuel Cell (MFC) MFC is an innovative bio-electrochemical system that utilizes microorganisms to convert organic matter into electricity. The MFC operates based on the metabolic activities of certain bacteria that oxidize organic substrates, releasing electrons in the process. These electrons are then transferred to an electrode, creating an electrical current to be harvested as usable energy (Vishwanathan 2021). The technology holds significant promise in renewable energy generation and wastewater treatment, offering a sustainable and environmentally friendly alternative to traditional methods. MFCs have the potential to play a vital role in addressing energy security and environmental concerns, making them a promising avenue for a greener and more sustainable future. MFC is a cutting-edge bio-electrochemical device that employs the metabolic activity of microorganisms to convert organic matter into electrical energy. The principle behind MFCs involves the transfer of electrons produced during the microbial degradation of organic substrates to an electrode, creating an electric current. The process occurs in two chambers separated by a proton exchange membrane, with microorganisms residing in the anode chamber. As these microorganisms consume organic compounds, they release electrons, which are conducted through an external circuit to the cathode chamber (Zheng et al. 2020). At the cathode, electrons combine

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with protons and oxygen to produce water. MFCs have shown great promise as a sustainable energy source, with applications ranging from renewable energy generation to wastewater treatment and potential use in remote or off-grid locations. As research and development in MFC technology continue to advance, it holds the potential to revolutionize how we produce clean energy and address environmental challenges (Mittal and Kumar 2022). A multianode system has been devised to enhance the effectiveness of microbial fuel cells (MFCs) in removing pHs. The soil/sediment microbial fuel cell (SMFC) developed by Li et al. (2014) incorporates three anode layers arranged in parallel, with an activated carbon (AC) air–cathode positioned at the bottom. The researchers noted that the multianode microbial fuel cell (MFC) exhibited a greater efficacy in removing pollutants known as persistent hydrocarbons (PHs) compared to a single-anode MFC system (Table 10.1). Table 10.1 Removal of hydrocarbon using MFC and MES Sr. no

Technology

Approach

Results and contribution

References

1

MFC

Utilized an MFC with mixed microbial consortia

Effective removal of Li et al. (2018) hydrocarbon compounds from petrochemical effluent, showcasing high degradation efficiency. The MFC generated electricity while simultaneously treating the effluent, demonstrating the potential for energy-neutral treatment processes

2

MES

Employed a MES system with specialized electrodes

Demonstrated enhanced Kong et al. (2020) methane production through electrochemical reduction of carbon dioxide, using petrochemical effluent as the substrate. This approach not only treated the effluent but also converted it into a valuable resource, showcasing the potential of MES in coupling wastewater treatment with energy recovery and resource production

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10.2.2 Microbial Electrolysis Cell (MEC) MEC device uses microorganisms to produce hydrogen gas from organic matter or wastewater. The MEC is similar to an MFC, but instead of producing electricity, it has hydrogen gas. In an MEC, bacteria at the anode oxidize organic matter and produce electrons and protons. The electrons are transferred to the cathode through an external circuit. At the same time, the protons are transmitted through a membrane to the cathode (Rousseau et al. 2020). At the cathode, the electrons and protons react to produce hydrogen gas. MECs can use various organic matter sources, including wastewater, agricultural, and food waste. They have several advantages over traditional hydrogen production methods, including lower energy requirements and the ability to use low-grade organic matter as a feedstock. MECs have potential applications in renewable energy production, wastewater treatment, and carbon capture and utilization. They can produce hydrogen fuel for vehicles or as a renewable energy source for power generation. They can also treat wastewater while producing hydrogen gas as a byproduct. In addition, MECs can capture and utilize carbon dioxide emissions by using them as feedstock for organic matter production (Kadier et al. 2016). MECs are a comparatively modern technique for electro-hydrogenation from acetate and fermentation byproducts. Bacteria, known as exoelectrogens, oxidize a substrate and release electrons to the anode in MEC. Since the cathode in an MFC produces current by reducing oxygen when oxygen is present, but the cathode in MEC is anaerobic, no impulsive current generation is possible when no oxygen is present (Amar Dubrovin et al. 2022). A small external voltage is applied to the circuit to enable hydrogen production at the cathode through proton reduction. In practice, hydrogen evolution on acetate requires a voltage of >0.2 V, significantly lower than the 1.8–2.0 V needed in low-temperature electrolysis for hydrogen production via water electrolysis. Therefore, the cathodic reaction occurs without oxygen. In contrast, the anodic reaction is the same as in microbial electricity generation in MFC. The term “bio-electrochemically assisted microbial reactors” was also used to describe these systems (BEAMR). This technology’s idea, operational principles, and state-of-the-art have already been detailed. The MEC has a more excellent hydrogen recovery and a more considerable substrate diversity than the fermentative reactor that produces hydrogen from waste (Gautam et al. 2023; Tang et al. 2022). Zhang et al. (2020) demonstrated effluent from a hydrogen-producing darkfermentation reactor as a microbial electrolysis cell (MEC) substrate for additional hydrogen production. The effluent contained ethanol and other organic compounds that could be oxidized at the anode of the MEC to produce hydrogen gas. The two-stage process involved producing hydrogen gas through dark fermentation and using the effluent from the dark fermentation reactor as a substrate in the MEC for additional hydrogen production. The researchers found that this two-stage process was more efficient than dark fermentation alone and required only 1.12 kWh/m3 H2 of electrical energy, significantly less than the amount required for water electrolysis. This study highlights the potential of MECs as a complementary technology to

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other hydrogen production methods, such as dark fermentation, to increase overall hydrogen production efficiency. It also demonstrates the ability of MECs to use complex organic substrates, such as the effluent from a dark fermentation reactor, for hydrogen production, which could have important implications for waste treatment and renewable energy production. Although further research is needed to reduce methane generation, improve the efficiency of converting organic matter into electricity, and increase the recovery of the hydrogen gas generated at the cathode, MECs are an effective technology for extracting hydrogen from swine wastewater. Based on COD reduction, these authors described treatment efficacies in MEC tests with swine wastewater ranging from 19 to 72% (Mishra et al. 2023). Additionally, the CE was low, showing that a significant portion of electrons failed to convert into current. Glycerol has been tested as a substrate in MECs for hydrogen production and methane reduction. Glycerol is a byproduct of biodiesel production. It is produced in large quantities, making it an attractive potential substrate for bioenergy production. However, studies have shown that glycerol requires a higher applied voltage (0.9 V) for constant electrolysis operation and methane reduction compared to acetate, which typically requires an applied voltage of 0.5 V. This is because the oxidation of glycerol at the anode of the MEC requires a higher energy input due to its complex molecular structure compared to simpler substrates such as acetate (Yuan et al. 2023). Despite the higher energy input required, glycerol remains an attractive substrate for MECs due to its abundance as a byproduct of biodiesel production. Additionally, converting glycerol to hydrogen through MECs can provide an additional revenue stream for biodiesel producers and reduce the environmental impact of glycerol waste disposal. Using complex substrates such as glycerol in MECs can increase the diversity of feedstocks for renewable energy production and reduce waste in industrial processes. However, further research is needed to optimize the performance of MECs using complex substrates and improve energy efficiency (Chilakamarry et al. 2021).

10.2.3 Enzymatic Biofuel Cell (EFC) Enzymatic Biofuel Cell (EFC) is an innovative and environmentally friendly bioelectrochemical device that utilizes enzymes as biocatalysts to convert biochemical energy into electrical energy. Like MFCs, EFCs operate based on the principle of electrogenic reactions but differ in their use of enzymes instead of microorganisms. In an EFC, the anode houses specific enzymes that facilitate the oxidation of organic compounds, breaking them down into electrons and protons. These electrons then flow through an external circuit to the cathode, reacting with oxygen and protons producing water (Xiao 2022). The critical advantage of EFCs lies in their high specificity and efficiency, allowing for precise control over the biocatalytic reactions. This specificity enables EFCs to utilize various fuel sources, including sugars, alcohol, and other biodegradable substances, making them versatile for multiple applications.

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Enzymatic Biofuel Cells hold tremendous potential in biomedical devices, wearable electronics, and portable energy sources, offering a sustainable, clean energy alternative with minimal environmental impact. Ongoing research aims to enhance the performance and stability of EFCs, making them a promising technology for the future of bio-electrochemical systems (Wiltschi et al. 2020).

10.3 Need and Functioning of Bio Electrochemical System Bio-electrochemical systems (BES) have gained significant attention due to their unique ability to integrate biology with electrochemistry to address various environmental and energy challenges. The need for bio-electrochemical systems arises from the growing demand for sustainable and eco-friendly solutions in the face of energy shortages and environmental degradation. The functioning of BES relies on the interaction between microorganisms, enzymes, and electrodes to catalyze bioelectrochemical reactions, enabling the conversion of organic matter into electrical energy or the removal of pollutants from wastewater (Zheng et al. 2020).

10.4 Oil Field and Petrochemical Wastewater Treatment Oil fields and petrochemical facilities generate vast amounts of wastewater containing various contaminants, making wastewater treatment a critical aspect of their operations. The wastewater produced in these industries typically contains hydrocarbons, heavy metals, toxic compounds, and high salinity, posing severe environmental risks if not adequately treated. Advanced treatment technologies are employed to remove these pollutants and ensure compliance with environmental regulations before discharge or reuse. The treatment process may involve several stages, such as primary separation to extract oil and solids, biological treatment to degrade organic compounds, chemical treatment for specific contaminants, and advanced treatment processes like membrane filtration or activated carbon adsorption to achieve stringent water quality standards (Medeiros et al. 2022). The successful treatment of oil fields and petrochemical wastewater protects the environment and facilitates water reuse, reducing the demand for fresh water and promoting sustainable practices within the industry. These technologies can potentially contribute to more sustainable and efficient use of oil and petroleum resources while reducing their environmental impact (Yu et al. 2017). Eliminating contaminants from oily waste is a significant challenge faced by oil refinery companies due to the complex nature of the waste. Oily waste contains a variety of organic and inorganic pollutants, as well as heavy oil complexes, surfactants, and polymers, which can have a significant impact on the environment and human health. Aliphatic and aromatic hydrocarbons are some of the most common pollutants found in oily waste, and their presence can harm the environment, including plants and animals. It is essential to manage this waste before

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it is disposed of into water or other streams and to coordinate with relevant agencies to ensure that the management is done in a way that is mindful of the local ecology. Various treatments are used for effluent from oil refineries, such as filtration, coagulation, reverse osmosis, flocculation, and adsorption. These treatments can help remove contaminants and pollutants from the waste, making it safer for disposal or reuse. However, it is essential to note that these treatments can also generate secondary waste streams, which must be managed appropriately to prevent further environmental damage (Ji et al. 2002). One of the primary goals of these processes is to reduce the chemical oxygen demand (COD) of oily waste. COD measures the amount of oxygen required to oxidize the organic matter in the waste, and it is an essential parameter for assessing the pollution level in water bodies (Demırcı et al. 1998). The standard treatment methods used to handle oil field effluents and petrochemical effluents are shown in Fig. 10.2. Most oil and refinery industries release the most harmful waste, oily effluents. Different removal techniques are used for these contaminants depending on the needs and effectiveness of each sector. Precipitation, -redox reaction, and membrane filtering are the standard pretreatment procedures. The micro-flocculation, which uses ceramsite as a filter media and polyaluminum chloride as a coagulant, is a promising method for filtering out minute suspended particles. Due to its highly poisonous character, petroleum effluent is more evident against the direct introduction into water streams (Abuhasel et al. 2021). Traditional therapies come in various

Fig. 10.2 Conventional treatment practices for petrochemical wastes (Sevda et al. 2020)

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forms and have drawbacks, ranging from sensitivity to efficacy. Therefore, the treatment methods have significantly changed over the past many years due to integrating the two procedures for effective contaminant removal. The combined coagulation and adsorption techniques eliminate organic materials and other hazardous substances, lowering COD. The organic matter is oxidized into CO2 and H2 O during the wet oxidation, a straightforward conventional treatment (Wang et al. 2017). Due to the occurrence of active molecule binding sites, the biological results have demonstrated an effective influence. Due to the lipophilic contact, the electrondonating or electron-withdrawing binding sites primarily interact with biological molecule structures and, as a result, have prospective applications in the biomedical fields. These functionalized compounds are synthetic spirocyclic agents that could be investigated about various antimicrobial/microbial species. To produce specific applications, such spirocyclic’s structural and physicochemical characteristics could be altered by swapping the active sites with required functional elements (Kumar et al. 2022). Due to 163 heavy pollutants from the petrochemical sectors in wastewater management in BES, some effluents have a very high chemical oxygen demand. Microwaveassisted catalytic moist air oxidation treatment is an advanced technique that can remove non-degradable compounds at optimal temperature and pressure since traditional methods cannot eliminate heavy pollutants. With typical temperature and pressure conditions, the supercritical water-oxidation treatment uses oxygen as H2 O2 as an oxidant to remove organic debris from oil effluent (Ma et al. 2009). The traditional activated sludge treatment significantly reduces COD and other pollutants like phenol, aldehyde, and organic acids in refinery effluent.

10.5 Removal of Toxic Elements Under anaerobic conditions, sulphate is one of the least promising electron acceptors. Sulfates only display a 6% metabolic activity rate compared to oxygen as the terminal electron acceptor. According to this theory, sulfate-rich wastewaters are thermodynamically unfavourable (He and Angenent 2006; Gupta et al. 2022). However, biocathodes supplemented with sulfate-reducing bacteria do better in reducing sulphate. An upsurge in applied potential enhanced sulfate removal in the current investigation. At 400 mV, the inlet sulphate concentration of 260 mg/L was reduced to an outlet sulphate concentration of 207 mg/L, resulting in the removal of 53 mg/L (sulphate removal, 20%). Removal efficiencies were recorded at 29% (76 mg/L) and 35% (90 mg/L) for 600 mV and 800 mV, respectively. The highest sulfate removal rate (76 mg/L, 47%) was recorded at 1000 mV (Hamelers et al. 2009). Sulfates may undergo oxidation in BESs in addition to reduction, creating elemental Sulphur in the anodic microenvironment. Sulfate may not immediately receive electrons from the cathode electrode during biocathodic sulphate reduction processes. Sulfate concentration may have decreased in the current instance due to both cathodic and anodic processes.

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Sulfate removal efficiency is substantially lower when compared to COD removal efficiency, which explains why unfavourable circumstances are prevalent in the current system. One of the primary pollutants in PRW, along with sulphate, is nitrate. Nitrate concentration in the recent PRW sample was kept to a maximum of 28 mg/ L. Nitrate has a high metabolic activity rate compared to sulphate, which was 93% (with oxygen). With all the studied applied potentials, the current system’s nitrate removal effectiveness was around 95% (Jain et al. 2017). Its high metabolic rate and the not noticeably high concentration of sulphate in the inlet PRW may be the causes of the most excellent efficiency shown for nitrate removal.

10.6 Microbial Electrochemical Technologies (MET) for Petrochemicals Researchers’ interest in METs’ strategies for energy recovery and PW therapy has increased significantly in recent years. METs can cleanse wastewater and produce value-added gaseous fuels like CH4 and H2 . In this regard, the next part describes the precise process, the recovered treasures, the application, and the viability of various kinds of METs for treating petrochemical waste. Also outlined are the advantages, drawbacks, and chances for MET scaling up in the future (Jadhav et al. 2022). The METs are an innovative and environmentally friendly technology that combines electrochemical and biological wastewater treatment processes with simultaneous energy recovery to produce power and value-added products like H2 , H2 O2 , and CH4 (Priyadarshini et al. 2022). The electroactive microbes, also recognized as green biocatalysts, can decompose organic materials in wastewater and create protons and electrons from the foundation of METs. METs are categorized as (a) MFCs, which generate electrical power from organics; (b) MDCs, which generate power while also desalinating brackish water; and (c) MECs, which generate energy while also treating wastewater and recovering value-added products (Ramírez-Vargas et al. 2018). Exoelectrogenic microbes found in the anodic chamber of MEC, an altered arrangement of MFC, oxidize wastewater’s organic content to produce CO2 , protons, and electrons. The protons are subsequently moved from the anodic to the cathodic chambers through PEM, where they are reduced to form H2 at the cathode. However, because the cathode’s reduction potential is lower than the anode’s, reducing protons to H2 does not result in the spontaneous flow of electrons across the external circuit. Therefore, for the reaction to start, MEC needs an external voltage source of 0.2 V (Jothinathan et al. 2021). In addition, CH4 is frequently found in MEC when H2 is produced due to the development of hydrogenotrophic methanogens or when electro-methanogenic bacteria directly take electrons from the cathode when the system is run under biotic cathodic conditions (Table 10.2). The effectiveness of these bioelectrochemical treatments can vary depending on the specific conditions, petrochemical concentrations, and system design.

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Table 10.2 Summarizing the bioelectrochemical treatment of petrochemicals Petrochemical Bioelectrochemical Process overview treatment

Advantages

Challenges

Benzene

Microbial fuel cells Microorganisms (MFCs) oxidize benzene at the anode, generating electrons and protons. Electrons flow through an external circuit, generating electricity. Protons migrate through a proton exchange membrane to the cathode, which reacts with oxygen, forming water

Efficient removal of benzene. Simultaneous electricity generation. Low operating cost and energy consumption

Long startup time to develop microbial communities. Contamination and inhibition of microorganisms by other pollutants Limited scalability for large-scale applications

Toluene

Microbial electrolysis cells (MECs)

Toluene is oxidized at the anode, releasing electrons and protons. Electrons travel through an external circuit, and protons move to the cathode through a proton exchange membrane. Hydrogen gas is produced at the cathode by reducing protons

High removal efficiency of toluene. Hydrogen production is a valuable byproduct. Reduced energy consumption compared to traditional treatments

Catalyst poisoning due to impurities in petrochemicals System instability due to changes in feed composition High capital cost for large-scale implementation

Xylene

Bioelectrochemical Xylene is systems (BES) biodegraded at the anode, producing electrons and protons. Electrons flow through the external circuit, while protons migrate to the cathode through a proton exchange membrane. Oxygen reduction occurs at the cathode

Effective degradation of xylene. Electricity generation from the treatment process. Environmentally friendly approach

Sensitivity to environmental conditions (pH, temperature, etc.). Slower treatment rates for higher xylene concentrations Anode fouling and maintenance issues (continued)

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Table 10.2 (continued) Petrochemical Bioelectrochemical Process overview treatment

Advantages

Challenges

Ethylbenzene

Microbial fuel cells Microorganisms (MFCs) oxidize ethylbenzene at the anode, generating electricity. Electrons flow through an external circuit, while protons migrate to the cathode to react with oxygen, forming water

Direct conversion of ethylbenzene to electricity. Low energy consumption. Sustainable and eco-friendly process

Limited degradation efficiency at high ethylbenzene concentrations Anode and cathode material stability issues Challenges in maintaining stable microbial communities

Polyaromatic hydrocarbons (PAHs)

Bioelectrochemical PAHs undergo remediation microbial degradation at the anode, generating electrons and protons. Electrons are transferred through the external circuit, and protons move to the cathode, where they reduce oxygen to water

Effective removal of PAHs. Electricity generation during the remediation process. Potential for in-situ and ex-situ applications

Limited efficiency for complex and recalcitrant PAHs Long-term stability of microbial communities. Optimization is required for specific PAH mixtures

Researchers are continuously working to optimize and improve these technologies to address the challenges and enhance their application potential (Table 10.3).

10.7 Conclusion In conclusion, bioelectrochemical treatment of petrochemical wastewater offers a promising and sustainable solution to the environmental challenges posed by the petrochemical industry. By leveraging the unique abilities of microorganisms and enzymes, bioelectrochemical systems can effectively degrade organic pollutants, remove heavy metals, and detoxify wastewater. Integrating biology with electrochemistry ensures efficient treatment and opens up opportunities for clean energy generation through microbial fuel cells or enzymatic biofuel cells. The specificity of enzymatic reactions allows for the utilization of a diverse range of biodegradable fuels, enhancing the versatility of these treatment systems. As the world strives for a more environmentally friendly and resource-efficient future, the continued research

Dualphase

Column

11.46

–

83 ± 3

–

–

–

TPHs

TPHs

TPHs

PAHs

TPHs

n-alkanes

Two columns

Tubular

U-tube

Column

Column

12.25

TPHs

BESs type

Initial contamination level (g kg−1 )

Targeted pollutants Maximum power/ current output

–

Comamonas testosteroni, Pseudomonas putida, and Ochrobactrum anthropi

Desulfobulbuss, Geobacteraceae, and uncultured Archaea

Carbon cloth-activated carbon air-cathodes

Graphite felt anode, active carbon felt cathode

Carbon cloth or biochar anode-activated carbon cloth with catalyst layers cathode

2 11.1 ± 1.4% versus 7.3 ± 0.5% 15.2 ± 0.6% 78.7%

125 ± 7 C, 0.85 ± 0.05 mW m−2 86 ± 0.1 mA

31% versus 26%

29.8 mW m−2 132 ± 17 mW m−2

79% versus 43%

70.4 ± 0.2 mA m−2 (8.8 ± 0.3 mW m−2 )

Duration (days)

120

64

25

182

45

64

82–90% versus 68% 120

Maximum removal efficiency (%) versus control

73–86 mA m−2

Graphite granule or biochar anode, 70.4 mA m−2 stainless

Electrode materials

Table 10.3 Removal efficiencies of bioelectrochemical remediation based on the earlier studies

Lu et al. (2014a)

Lu et al. (2014b)

Wang et al. (2012)

Huang et al. (2011)

Yu et al. (2019)

Lu et al. (2014b)

Lu et al. (2014a)

References

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and development in bioelectrochemical treatment hold significant potential for transforming the petrochemical industry into a more sustainable and responsible sector. By adopting these innovative technologies, we can protect water resources, minimize environmental impacts, and pave the way for a greener and more sustainable future. Acknowledgements The authors are thankful to Gandhinagar University and Parul University for providing the necessary facilities.

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Chapter 11

Biogenic Nanomaterials: Synthesis, Characterization and Its Potential in Dye Remediation Manish Kumar, Anshu Mathur, and R. P. Singh

Abstract In the present era, the nanotechnology industry is producing a wide variety of products used in many areas such as medical, pharmaceutical, environmental, and daily life. The use of nanomaterials (NMs) to combat one of the persistent environmental pollutants, like dyes, have been extensively explored. However, several drawbacks, such as high energy costs and hazardous chemicals, are associated with the NMs production process, which can be addressed by the application of ecofriendly biogenic nanomaterials (BNMs). In the current scenario, the translation of conventional NM-based dye degradation approaches is needed. In this regard, BNMs have shown enormous potential to become novel agents for dye remediation. The intriguing properties, such as reasonable energy demands and scope for tailored activities of BNMs, make them a superior candidate for dye remediation over counter partners. This chapter reviews the state-of-the-art synthesis, characterization, and potential of BNMs for dye remediation and their future research directions. Keywords Biogenic nanomaterials · Dye degradation · Enzyme-linked composite · Photocatalysis · Photocatalyst

11.1 Introduction The rise in global population and continuous industrial and agricultural development has contaminated water sources. Currently, commercial dyes are widely applied in the cosmetics, paint, paper, plastics, tannery, and textile industries (Shah 2014). Annually, these industrial activities lead to the discharge of over 50,000 tons of dyes into water bodies (Patil et al. 2022). Chromophores and auxochromes make up the majority of dye molecules. Chromophores are responsible for color production, while auxochromes boost solubility and increase affinity for fibers (Saad et al. M. Kumar (B) · A. Mathur · R. P. Singh Department of Biosciences and Bioengineering, Indian Institute of Technology Roorkee, Roorkee 247667, India e-mail: [email protected]; [email protected] © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 A. S. Mathuriya et al. (eds.), Green Technologies for Industrial Waste Remediation, Environmental Science and Engineering, https://doi.org/10.1007/978-3-031-46858-2_11

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2023). There are different dyes, viz. acidic, anthraquinone-based, azo, basic, diazo, and metal complex dyes (El Harfi and El Harfi 2017). Dyes in the aquatic system affect aesthetic merit, water-gas solubility, and transparency. This results in decreased light penetration through water, leading to low photosynthetic activity. This further generates oxygen deficiency and de-regulation of biological cycles in the aquatic biota (Hassaan et al. 2017). Most dyes are highly toxic, and mutagens have acute to chronic effects, depending on organisms, exposure concentration, and time. Researchers have applied several approaches: adsorption, biodegradation, chemical oxidation, coagulation-flocculation, membrane separation, and photocatalysis to remove azo dyes from wastewater (Piaskowski et al. 2018; Bal and Thakur 2022). However, it has been found that combining different approaches is much more efficient than individual approaches. In the current era, scientists have focused on combining biological approaches with other remediation methods, such as biophysical, biochemical, and Nano-based, because they are more effective than traditional methods (Adetunji et al. 2021; Boregowda et al. 2021). Among all the approaches, the recent development in the field of nanotechnology results in the focus of the research community on the employment of NMs to remove dyes from dyes contaminated waterbodies. NMs are materials with one or more than one external dimensions dimension between 1 and 100 nm. The small size of NMs imparts their extraordinary properties, viz. electron conduction properties, large surface area, more surface-active sites, and quantum effect. These unique properties of MNs positively affect their performance as adsorbents, catalysts, sensors, or other applications (Asha and Narain 2020). Primarily, NMs are synthesized by physical or chemical means. But this synthesis frequently approaches outcome by generating a mix of NMs with deprived morphology and properties Moreover, the synthesis it requires elevated temperatures for the synthesis process and proves toxic to the environment (Abid et al. 2021; Saleh 2021; Uribe-López et al. 2021). Thus, substituting these chemical synthesis processes involving hazardous chemicals has attracted the consideration of the scientific and academic fraternity. Hence, the idea of environmental stewardship and the worry for sustainable production has strengthened the researchers to explore greener and ecologically feasible ways to synthesize highly efficient NMs for removing dyes form dyes contaminated water bodies (Cai et al. 2017; David and Moldovan 2020). Recently, several BNMs, for example, carbon nanotubes (Sargin et al. 2020), graphene (Sun et al. 2023), TiO2 -NPs (Lu et al. 2023), and ZnO-NPs (Mashentseva et al. 2022), had used to synthesize unique materials to remove dyes. Therefore, this work aims to review the latest investigation of biogenic synthesis of NMs, their characterization, and their application in dye removal with the possible mechanism.

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11.2 Biogenic Nanomaterials The materials with dimensions