Advanced Technologies in Wastewater Treatment: Food Processing Industry 0323885101, 9780323885102

Table of contents :
Advanced Technologies in Wastewater Treatment
Preface
List of contributors
Copyright
Contents
1 High-added-value compounds from agro-food industry wastewater
1.1 Introduction
1.2 Food losses and waste: biowaste from the agroindustrial sector
1.3 The problem of environmental contamination and disposal of biowaste
1.3.1 Biowaste as a source of bioactive compounds
1.3.1.1 The case of phenolic compounds
1.4 The emergence and potential of wastewater
1.4.1 Importance of wastewater treatment and applications
1.4.2 Molecules of interest present in wastewaters: properties and benefits
1.5 Conclusions and future trends
Acknowledgments
List of acronyms
References
2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry
2.1 Introduction
2.2 Nature of byproducts obtained from cereals, nuts, and legumes: research evolution
2.3 Nutrient composition
2.3.1 Okara
2.3.2 Rice
2.3.3 Oat
2.3.4 Almond
2.3.5 Tiger nut
2.4 Applications in food industry
2.4.1 Solid wastes or byproducts
2.4.1.1 Antioxidants
2.4.1.2 Fiber supplement and glycemic index reducer
2.4.1.3 Water-holding ingredients
2.4.1.4 Fat replacers
2.4.1.5 Ingredients in gluten-free products
2.4.1.6 Emulsion stabilizers
2.4.2 Liquid wastes
2.4.2.1 Reuse in the same process
2.4.2.2 Biofuel
2.4.2.3 Nutrient extraction
2.4.2.4 Direct use as ingredient
2.5 Conclusions and future trends
List of acronyms
References
3 High-rate anaerobic processes for agro-food wastewater treatment: recent trends and advancements
3.1 Introduction
3.2 Agro-food wastewater characteristics
3.3 Application of high-rate anaerobic systems in agro-food wastewater treatment
3.3.1 The anaerobic filter
3.3.2 Upflow anaerobic sludge blanket reactor
3.3.3 Expanded granular sludge bed reactor
3.3.4 Anaerobic moving bed biofilm reactor
3.3.5 External circulation sludge bed reactor
3.3.6 Anaerobic membrane bioreactor
3.3.7 Anaerobic hybrid reactors
3.3.8 Full-scale application of high-rate anaerobic systems
3.4 Recent trends and future perspectives
3.5 Challenges of wastewater treatment in the agro-food industry
3.6 Conclusions and future trends
List of acronyms
References
4 Food-processing wastewater treatment by membrane-based operations: recovery of biologically active compounds and water reuse
4.1 Introduction
4.2 An overview of pressure-driven membrane processes
4.3 Recovery of biologically active compounds and water from food-processing wastewaters
4.3.1 Olive mill wastewaters
4.3.2 Fish-processing wastewaters
4.3.3 Dairy-processing wastewaters
4.4 Conclusions and future trends
List of acronyms
List of symbols
References
5 Biorefineries to improve water and resource recovery in the seafood-processing industry
5.1 Introduction
5.2 Seafood industry
5.3 Processes to develop biorefinery schemes from seafood wastes
5.3.1 Physical processes
5.3.2 Chemical processes
5.3.3 Thermochemical and thermal processes
5.3.4 Biological processes
5.3.4.1 Aerobic processes
5.3.4.2 Anaerobic processes
5.4 Bioproducts obtained from seafood wastes
5.4.1 Biofertilizers and biostimulants
5.4.2 Biofuels
5.4.3 Biocompounds
5.4.4 Water streams
5.5 Conclusions and future trends
Acknowledgments
List of acronyms
References
6 A valorization approach of food industry wastewater using microwave-assisted extraction
6.1 Introduction
6.2 Wastewater from the food industry
6.2.1 Characterization of wastewater from the olive oil industry
6.2.2 Characterization of wastewater from the sugar industry
6.2.3 Characterization of wastewater from the cheese industry
6.2.4 Characterization of wastewater from the slaughterhouse industry
6.2.5 Characterization of wastewater from the multiproduction food industry
6.2.6 Characterization of wastewater from the seafood industry
6.3 Removal of organic and inorganic compounds in food industry wastewater
6.3.1 Extraction methods of organic and inorganic compounds in food industry wastewater
6.3.1.1 Soxhlet extraction
6.3.1.2 Ultrasound-assisted extraction
6.3.1.3 Supercritical fluid extraction
6.4 What are microwaves?
6.5 Microwave-assisted extraction
6.5.1 Specific applications of microwave-assisted extraction
6.5.2 Kinetic modeling of microwave-assisted extraction
6.6 Conclusion and future trends
List of acronyms
List of symbols
References
7 Supercritical fluid extraction applied to food wastewater processing
7.1 Introduction
7.2 Wastewater and sludge from the food industry: composition and current issues
7.2.1 Dairy
7.2.2 Fruit and vegetable industry
7.2.3 Meat industry
7.2.4 Oil industry
7.2.5 Beverage industry
7.3 Clean extraction technologies for wastewater and sewage sludge treatment: circular economy in high demand
7.4 Supercritical fluid extraction
7.4.1 Fundamentals of supercritical fluid extraction
7.4.2 Supercritical fluid extraction of liquid and semisolid mixtures
7.4.2.1 Supercritical fluid extraction using supercritical water (SFE-H2O)
7.4.2.2 Supercritical fluid extraction using supercritical carbon dioxide (SFE-CO2)
7.4.3 Supercritical fluid extraction applied to wastewater and sludge from the food industry
7.5 Technoeconomic evaluation of supercritical fluid extraction applied to the recovery of value-added molecules
7.6 Conclusions and future trends
Acknowledgments
List of acronyms
List of symbols
References
8 Advances in ultrasound-assisted extraction of bioactive compounds (antioxidant compounds) from agrofood waste
8.1 Introduction
8.2 Main bioactive compounds from waste and byproducts of fruits and vegetables
8.2.1 Pomace
8.2.2 Peels and seeds
8.2.3 Leaves and stems
8.3 Main bioactive compounds from waste and byproducts of animal product processing
8.3.1 Dairy products
8.3.2 Meat products
8.3.3 Marine products
8.4 Emerging technologies for obtaining bioactive compounds
8.5 Fundamentals for ultrasound-assisted extraction
8.6 Variables associated with ultrasound-assisted extraction
8.6.1 Ultrasonic power
8.6.2 Ultrasonic frequency
8.6.3 Solvents
8.6.4 Temperature of ultrasound-assisted extraction
8.6.5 Liquid (solvent) to solid ratio
8.6.6 Time of ultrasound-assisted extraction
8.7 Effect of variables associated with ultrasound-assisted extraction on the extraction of bioactive compounds from byproducts
8.8 Commercial patents: ultrasound and innovative techniques for the extraction of bioactives
8.9 Current trends in the extraction of bioactive compounds
8.10 Conclusions and future trends
List of acronyms
References
9 Integrated advanced technologies for olive mill wastewater treatment: a biorefinery approach
9.1 Introduction
9.2 Chemical composition of olive mill wastewater
9.3 Reuse, applications, and technologies employed
9.3.1 Biofuels
9.3.2 Polysaccharides
9.3.3 Phenolic compounds and other antioxidants
9.3.4 Enzymes
9.3.5 Biosurfactants
9.3.6 Citric acid and lipids
9.3.7 Polyhydroxyalkanoates
9.3.8 Use in agriculture: fertilizers, biopesticides, and irrigation
9.3.9 Food and beverage supplement
9.4 Process integration: biorefinery examples
9.5 Conclusions and future trends
Acknowledgments
List of acronyms
References
10 Advanced strategies for dairy wastewater treatment: a perspective
10.1 Introduction
10.2 Some guidelines for wastewater treatment in the dairy industry
10.3 Dairy wastewater characteristics
10.4 Dairy industry wastewater treatments
10.4.1 Preliminary treatments
10.4.2 Physicochemical treatments
10.4.3 Biological treatments
10.4.4 Complementary treatments
10.5 Recovery and valorization of wastewater components and treatment wastes
10.5.1 Whey: recovering and processing
10.5.1.1 Proteins
10.5.1.2 Lactose
10.5.2 Sludges from primary and secondary treatments
10.5.3 Water reuse
10.6 Conclusions and future trends
List of acronyms
References
11 Winery wastewater treatment for biomolecules recovery and water reuse purposes
11.1 Introduction
11.2 Winemaking process and wastewater generation
11.3 Value-added biomolecules found in winery wastewaters
11.4 Winery wastewater treatment systems
11.4.1 Physical treatments
11.4.2 Physicochemical treatments
11.4.3 Natural biological treatments
11.4.3.1 Anaerobic treatment systems
11.4.3.2 Aerobic treatment systems
11.4.4 Membrane bioreactors
11.4.5 Other bioreactors
11.5 Membrane separation–based processes for biomolecules recovery from winery wastewater
11.6 Wastewater reuse
11.7 Conclusions and future trends
List of acronyms
References
12 Nanomaterials for the removal of organic pollutants from agrofood wastewaters
12.1 Introduction
12.2 Slaughterhouse wastewater
12.3 Dairy wastewater
12.4 Fish processing
12.5 Olive oil manufacturing
12.6 Sugar manufacturing
12.7 Wine making
12.8 Materials for wastewater treatment
12.9 Conclusions and future trends
Acknowledgments
List of acronyms
References
Index

Citation preview

A D VA N C E D TECHNOLOGIES IN W A S T E WAT E R T R E AT M E N T

A D VA N C E D TECHNOLOGIES IN W A S T E WAT E R T R E AT M E N T Food Processing Industry Edited by ANGELO BASILE Hydrogenia and ECO2Energy, and Unit of Chemical-Physics Fund. in Chemical Engineering—Department of Engineering—University Campus Bio-medical, Rome, Italy

ALFREDO CASSANO Institute on Membrane Technology of the Italian National Research Council, ITM-CNR, University of Calbria, Rende, Italy

CARMELA CONIDI Institute on Membrane Technology of the National Research Council of Italy (CNR-ITM), University of Calabria, Rende, Italy

Preface Wastewaters generated from food production and agricultural activities are a remarkable source of environmental pollution, owing to their huge amounts of nutrients, organic carbon, nitrogenous organic and inorganic substances, and suspended and dissolved solids and to their high biochemical and chemical oxygen demands. This book provides an update on the emerging technologies (including oxidative and anaerobic processes, membrane-based operations, ultrasound-assisted extraction (UAE), microwaveassisted extraction (MAE), advanced biological treatment, and nanomaterial-based technologies) that can be used to provide safe and clean water and to recover primary resources from food-processing wastewaters in agreement with biorefinery, process intensification, and circular economy approaches. Innovative and affordable solutions are proposed for the fruit and vegetable, seafood, milk and dairy, wine, and olive oil processing industries. Chapter 1 (Caleja, Pereira, Ferreira, and Barros) considers the high added-value compounds from agro-food industry wastewaters. The food industry is responsible for the annual production of billions of tons of food that are eventually discarded as waste; consequently, it is also responsible for the huge amounts of wastewater that are generated worldwide. These wastes are rich sources of phenolic compounds highlighted by their biological properties, namely, antimicrobials and antioxidants with potential for industrial application. This potential makes the reuse and recovery of waste viable, contributing to the growth of the circular economy and sustainability of the agri-food sector. In Chapter 2 (Lorente, Duarte Serna, Betoret, and Betoret), waste generation by the food industry is shown to be an alarming problem. Consumption of plant-based beverages is increasing considerably, making this sector of the industry more relevant, especially owing to the high residue generation. Increasingly, attempts are being made to reduce it through revaluation and reuse of by-products in different ways. In this chapter a literature review carried out on the by-product nature, composition, properties and possible uses of these wastes shows that these products have both interesting nutritional

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compositions and a wide range of applications in the development of new products, besides the fortification of traditional foods. Meat products, emulsions, gluten-free products, dairy products, and others are just some of the many sectors in which by-products from the vegetable beverage industry play an important role. The results demonstrate the great potential of these by-products in the food industry and encourage further study of their functional and technological properties. Chapter 3 (Bokhary, Leitch, Hong, and Liao) illustrates the recent trends and advancements on the high-rate anaerobic processes for agro-food wastewater (AFWW) treatment. Highrate anaerobic processes appear to be a promising technology for AFWWs treatment in terms of chemical oxygen demand and pollutant removal with a potential for energy savings or even energy-positive scenarios. Various configurations of high-rate anaerobic processes (HRAnPs) for AFWW treatment have been used in laboratory-, pilot-, and commercial-scale applications. In particular, this chapter discusses the performance of prevalent HRAnPs in the treatment of AFWWs. Recent trends and advancements in HRAnPs for the treatment of AFWWs are also considered, and the characteristics of AFWW are highlighted. The performance among reviewed HRAnPs can be comparable, better, or even poorer in some cases. In conclusion, the results of the literature reveal that HRAnPs are effective and viable technologies for the treatment of AFWWs. Chapter 4 (Conidi, Basile, and Cassano) deals with the use of pressure-driven membrane processes in the treatment of foodprocessing wastewaters for the recovery of biologically active compounds and water reuse. Typical applications in the field of olive mill wastewaters (OMWW) and fish- and dairy-processing wastewaters are illustrated and discussed. The results clearly highlight that the combination of membrane operations units in integrated systems can provide a useful approach for redesigning traditional flowcharts in the food-processing industry as well as a fundamental support for the development of sustainable industrial growth in agreement with the process intensification and zero-discharge strategies. Chapter 5 (Gonza´le-Camejo, Andreola, Maceratesi, Toscano, Eusebi, and Fatone) considers biorefineries as a method for improving water and resource recovery in the seafoodprocessing industry. As it is well known that food losses are responsible for noteworthy economic costs and environmental negative impacts, and among all the food-processing activities, the seafood industry is of high importance, especially in coastal regions. Most seafood wastage is currently removed and

Preface

discarded without recovering the valuable materials that it contains. However, seafood waste can be used as raw matter in biorefineries, which are facilities in which different conversion processes are integrated to obtain multiple bioproducts from organic feedstock. Toward this goal, different physical, chemical, thermochemical, and biological processes can be implemented to obtain biofertilizers, biostimulants, biofuels, and other value-added biocompounds. Chapter 5 focuses on the theoretical implementation of biorefineries fed by wastes from the seafood industry. Some processes and technologies are reviewed, as well as some biocompounds that can be obtained from seafood wastes. A valorization approach of food industry wastewater using MAE technique is provided in Chapter 6 (Dertli and Saloglu). Since process water is used in a wide range of manufacturing processes in the food industry, a large amount of wastewater is produced. New, economical, and effective methods have been researched as alternatives to those that are currently being utilized in the treatment of food industry wastewater. In Chapter 6 the treatment of wastewater from the food industry is outlined, and the innovative new MAE method is discussed as an alternative to conventional wastewater treatment methods. Important advantages of MAE are reduced extraction time and solvent amount, increased extraction efficiency, high recovery, ease of use, and low cost. Chapter 7 (Santos, Torres, Campos, Ghiglieno, and Martı´nez) shows how supercritical fluid extraction (SFE) can be applied to food wastewater processing. Considering the composition of food industry wastewater and sludge, which have potential applications in industry and medicine (e.g., pigments, lipids, protein), this chapter discusses the idea of using SFE to recover such compounds. Despite the scarce literature related to this topic, some studies have shown the possibilities of SFE applications mainly using supercritical CO2. In addition, SFE seems to be a promising technique for helping industries adhere to the legislation that applies to food wastewater and sludge disposal. Various advances in UAE of bioactive compounds (antioxidant compounds) from agro-food waste are discussed in Chapter 8 (Martı´nez-Olivo, Dura´n-Castan˜eda, Lo´pez-Ca´rdenas, Rodrı´guez-Romero, Sa´nchez-Burgos, Sa´yago-Ayerdi, and Zamora-Gasga). As has been noted, the food industry generates a significant amount of waste that affects the environment and can be revalued as sources of bioactive compounds. However, conventional extraction is characterized by long periods of time, high energy expenditure, and the use of organic solvents.

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By contrast, eco-green technologies, such as UAE, do not have these limitations. In addition, because UAE is a nonthermal type of extraction, the functionality of the bioactive compounds (BC) is not affected, provided that the process conditions can be evaluated and optimized for each material. Chapter 8 presents general information about agro-food by-products, methods and current trends in the extraction of BC, fundamentals of the UAE method, and its scientific and commercial applications. A biorefinery approach in the integrated advanced technologies for OMWW treatment is used in Chapter 9 (del Mar Contreras, Lo´pez-Linares, and Castro). Olive oil production is an important agro-food industry around the Mediterranean basin. Because the oil content in the olive fruit is around 20%, the olive oil industry generates a huge amount of solid and liquid wastes. The type, composition, and levels of these wastes depend on the olives processed in the mill and the processing conditions. The management of the liquid stream, OMWW, especially from the traditional and three-phase mills, is recognized as one of the main obstacles that the olive oil industry faces. Uncontrolled disposal of OMWW is toxic to the terrestrial and aquatic ecosystems and, in practice, there is not an environment-friendly and economically viable treatment. Therefore many researchers have reported different applications and technologies for OMWW valorization in single processes and in biorefining process sequences to obtain valuable bioproducts. Chapter 9 updates the state-of-the-art concerning the OMWW valorization options. In Chapter 10 (Gomes da Cruz, Lippel Sant’Anna, Colombo Pimentel, and Ribas Vendramel) the treatment of the wastewaters generated by the dairy industry is emphasized. The authors show a perspective on the various advanced strategies for dairy wastewater treatment. Wastewaters from this industrial segment have high organic content, and treatment is necessary to prevent pollution of natural water systems. The treatment techniques that are most suitable for dairy wastewaters are presented and discussed in this chapter. Wastewaters from the dairy industry have chemical substances that can be recovered and reused in industrial products or even constitute new products. Therefore Chapter 10 stresses why “recover, recycle, and reuse” is a concept that is well suited for wastes and wastewaters from the dairy industry. Chapter 11 (Giacobbo, Oliveira, Bernardes, and de Pinho) addresses the treatment of winery wastewaters for biomolecules recovery and water reuse purposes. Winery wastewater has a

Preface

high pollutant load, but it also contains value-added molecules, such as phenolic compounds that can be recovered. The recovery of these biomolecules has aroused great interest, providing benefits such as the valorization of by-products recovered from wastewater; reduction in the pollutant load of winery wastewater, facilitating its treatment and reuse in agriculture; reducing the environmental impacts of wineries; and promotion of the circular economy through the recovery of biomolecules and water reuse. Chapter 11 focuses on the generation of wastewater throughout the winemaking process, indicating the main biomolecules of commercial interest that are present in the wastewater and proposing processes for the recovery of these biomolecules. The main technologies that are used in the treatment of winery wastewater are also reported and discussed, envisaging the reuse of treated wastewater in agriculture. Various aspects of the nanomaterials that are used for the removal of organic pollutants from AFWWs are presented in Chapter 12 (Brazdis, Fierascu, Avramescu, and Fierascu). As has been noted, wastewater treatment is still a challenging subject for researchers, despite all the technologies that have been developed over time. Because of the large volume of discharged effluents, the agro-food industry is one of the major contributors to environmental contamination. The main goal of Chapter 12 is to present the modern nanomaterials-based depollution technologies for wastewater. The editors would like to take this opportunity to express their sincere gratitude to all the contributors of this book, whose excellent support resulted in its successful completion. We would also like to thank the publisher Elsevier; in particular, we give special thanks for their great help to those responsible at Elsevier: Moises Carlo P. Catain, Howell Angelo M. De Ramos, Kavitha Balasundaram, Anita Koch, and Kostas Marinakis.

Angelo Basile Alfredo Cassano Carmela Conidi

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List of contributors C. Andreola Department of Science and Engineering of Materials, Environment and Urban Planning-SIMAU, Universita` Politecnica delle Marche, Ancona, Italy Sorin-Marius Avramescu Research Center for Environmental Protection and Waste Management, University of Bucharest, Bucharest, Romania Lillian Barros Centro de Investigac¸a˜o de Montanha (CIMO), Instituto Polite´cnico de Braganc¸a, Braganc¸a, Portugal; Laborato´rio Associado para a Sustentabilidadee Tecnologia em Regio˜es de Montanha (SusTEC), Instituto Polite´cnico de Braganc¸a, Campus de Santa Apolo´nia, Braganc¸a, Portugal Angelo Basile Hydrogenia and ECO2Energy, and Unit of Chemical-Physics Fund. in Chemical Engineering—Department of Engineering—University Campus Bio-medical, Rome, Italy Andre´a Moura Bernardes Post-Graduation Program in Mining, Metallurgical and Materials Engineering, (PPGE3M), Federal University of Rio Grande do Sul (UFRGS), Porto Alegre, Brazil E. Betoret Institute of Food Engineering for Development, Universitat Polite`cnica de Vale`ncia, Vale`ncia, Spain N. Betoret Institute of Food Engineering for Development, Universitat Polite`cnica de Vale`ncia, Vale`ncia, Spain A. Bokhary Faculty of Natural Resources Lakehead University, Thunder Bay, ON, Canada

Management,

Roxana-Ioana Brazdis Emerging Nanotechnologies Group, National Institute for Research & Development in Chemistry and Petrochemistry—ICECHIM, Bucharest, Romania; Department of Science and Engineering of Oxide Materials and Nanomaterials, University Politehnica of Bucharest, Bucharest, Romania Cristina Caleja Centro de Investigac¸a˜o de Montanha (CIMO), Instituto Polite´cnico de Braganc¸a, Braganc¸a, Portugal; Laborato´rio Associado para a Sustentabilidadee Tecnologia em Regio˜es de Montanha (SusTEC), Instituto Polite´cnico de Braganc¸a, Campus de Santa Apolo´nia, Braganc¸a, Portugal

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List of contributors

Daiane Ferreira Campos Departament of Physics, Federal University of Sa˜o Carlos, Sa˜o Carlos, Sa˜o Paulo, Brazil Alfredo Cassano Institute on Membrane Technology of the National Research Council of Italy (CNR-ITM), University of Calabria, Rende, Italy Eulogio Castro Department of Chemical, Environmental and Materials Engineering, Universidad de Jae´n, Jae´n, Spain; Center for Advanced Studies in Earth Sciences, Energy and Environment (CEACTEMA), Universidad de Jae´n, Jae´n, Spain Carmela Conidi Institute on Membrane Technology of the National Research Council of Italy (CNR-ITM), University of Calabria, Rende, Italy Adriano Gomes da Cruz Federal Institute of Education, Science and Technology of Rio de Janeiro (IFRJ), Department of Food, Rio de Janeiro, Brazil Maria Norberta de Pinho Center of Physics and Engineering of Advanced Materials (CeFEMA), Instituto Superior Te´cnico, University of Lisbon, Lisbon, Portugal; Chemical Engineering Department, Instituto Superior Te´cnico, University of Lisbon, Lisbon, Portugal Marı´a del Mar Contreras Department of Chemical, Environmental and Materials Engineering, Universidad de Jae´n, Jae´n, Spain; Center for Advanced Studies in Earth Sciences, Energy and Environment (CEACTEMA), Universidad de Jae´n, Jae´n, Spain Halil Dertli Department of Chemical Engineering, Faculty of Chemical and Metallurgical Engineering, Istanbul Technical University, Istanbul, Turkey Luana Cristina dos Santos Department of Food Engineering and Technology, School of Food Engineering, University of Campinas, Campinas, Sa˜o Paulo, Brazil S. Duarte Serna Institute of Food Engineering for Development, Universitat Polite`cnica de Vale`ncia, Vale`ncia, Spain ˜ eda National Technological Institute Alba Cecilia Dura´n-Castan of Mexico, Technological Institute of Tepic, Nayarit, Mexico A.L. Eusebi Department of Science and Engineering of Materials, Environment and Urban Planning-SIMAU, Universita` Politecnica delle Marche, Ancona, Italy

List of contributors

F. Fatone Department of Science and Engineering of Materials, Environment and Urban Planning-SIMAU, Universita` Politecnica delle Marche, Ancona, Italy Isabel C.F.R. Ferreira Centro de Investigac¸a˜o de Montanha (CIMO), Instituto Polite´cnico de Braganc¸a, Braganc¸a, Portugal; Laborato´rio Associado para a Sustentabilidadee Tecnologia em Regio˜es de Montanha (SusTEC), Instituto Polite´cnico de Braganc¸a, Campus de Santa Apolo´nia, Braganc¸a, Portugal Irina Fierascu Emerging Nanotechnologies Group, National Institute for Research & Development in Chemistry and Petrochemistry—ICECHIM, Bucharest, Romania; University of Agronomic Sciences and Veterinary Medicine of Bucharest, Bucharest, Romania Radu Claudiu Fierascu Emerging Nanotechnologies Group, National Institute for Research & Development in Chemistry and Petrochemistry—ICECHIM, Bucharest, Romania; Department of Science and Engineering of Oxide Materials and Nanomaterials, University Politehnica of Bucharest, Bucharest, Romania Filippo Giovanni Ghiglieno Departament of Physics, Federal University of Sa˜o Carlos, Sa˜o Carlos, Sa˜o Paulo, Brazil Alexandre Giacobbo Post-Graduation Program in Mining, Metallurgical and Materials Engineering, (PPGE3M), Federal University of Rio Grande do Sul (UFRGS), Porto Alegre, Brazil; Center of Physics and Engineering of Advanced Materials (CeFEMA), Instituto Superior Te´cnico, University of Lisbon, Lisbon, Portugal J. Gonza´lez-Camejo Department of Science and Engineering of Materials, Environment and Urban Planning-SIMAU, Universita` Politecnica delle Marche, Ancona, Italy; CALAGUA—Unidad Mixta UV-UPV, Institut Universitari d’Investigacio´ d’Enginyeria de l’Aigua i Medi Ambient—IIAMA, Universitat Polite`cnica de Vale`ncia, Camı´ de Vera s/n, Valencia, Spain Y. Hong SUEZ Water Technologies & Solutions, Oakville, ON, Canada M. Leitch Faculty of Natural Resources Management, Lakehead University, Thunder Bay, ON, Canada B.Q. Liao Faculty of Natural Resources Management, Lakehead University, Thunder Bay, ON, Canada; Department of Chemical Engineering, Lakehead University, Thunder Bay, ON, Canada

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Francia Guadalupe Lo´pez-Ca´rdenas National Technological Institute of Mexico, Technological Institute of Tepic, Nayarit, Mexico Juan Carlos Lo´pez-Linares Department of Chemical, Environmental and Materials Engineering, Universidad de Jae´n, Jae´n, Spain; Center for Advanced Studies in Earth Sciences, Energy and Environment (CEACTEMA), Universidad de Jae´n, Jae´n, Spain D. Lorente Institute of Food Engineering for Development, Universitat Polite`cnica de Vale`ncia, Vale`ncia, Spain V. Maceratesi Department of Science and Engineering of Materials, Environment and Urban Planning-SIMAU, Universita` Politecnica delle Marche, Ancona, Italy; Department of Agricultural, Food and Environmental Sciences D3A, Universita` Politecnica delle Marche, Ancona, Italy Julian Martı´nez Department of Food Engineering and Technology, School of Food Engineering, University of Campinas, Campinas, Sa˜o Paulo, Brazil Abraham Osiris Martı´nez-Olivo National Technological Institute of Mexico, Technological Institute of Tepic, Nayarit, Mexico Margarida Oliveira ESAS, UIIPS, Instituto Polite´cnico de Santare´m, Santare´m, Portugal; LEAF—Linking Landscape, Environment, Agriculture and Food—Research Center, Associated Laboratory TERRA, Instituto Superior de Agronomia, University of Lisbon, Lisbon, Portugal Eliana Pereira Centro de Investigac¸a˜o de Montanha (CIMO), Instituto Polite´cnico de Braganc¸a, Braganc¸a, Portugal; Laborato´rio Associado para a Sustentabilidadee Tecnologia em Regio˜es de Montanha (SusTEC), Instituto Polite´cnico de Braganc¸a, Campus de Santa Apolo´nia, Braganc¸a, Portugal Tatiana Colombo Pimentel Federal Institute of Education, Science and Technology of Parana´ (IFPR), Department of Food, Parana´, Brazil ´ s Rodrı´guez-Romero National Technological Jose´ de Jesu Institute of Mexico, Technological Institute of Tepic, Nayarit, Mexico

List of contributors

Didem Saloglu Department of Disaster and Emergency Management, Disaster Management Institute, Istanbul Technical University, Istanbul, Turkey Jorge Alberto Sa´nchez-Burgos National Technological Institute of Mexico, Technological Institute of Tepic, Nayarit, Mexico Geraldo Lippel Sant’Anna Junior Federal University of Rio de Janeiro (UFRJ), Alberto Luiz Coimbra Institute of Graduate Studies and Research in Engineering (COPPE), Rio de Janeiro, Brazil Sonia Guadalupe Sa´yago-Ayerdi National Technological Institute of Mexico, Technological Institute of Tepic, Nayarit, Mexico Talyta Mayara Silva Torres Department of Chemical and Food Engineering, Federal University of Santa Catarina, Floriano´polis, Santa Catarina, Brazil G. Toscano Department of Agricultural, Food and Environmental Sciences D3A, Universita` Politecnica delle Marche, Ancona, Italy Simone Maria Ribas Vendramel Federal Institute of Education, Science and Technology of Rio de Janeiro (IFRJ), Department of Food, Rio de Janeiro, Brazil Victor Manuel Zamora-Gasga National Technological Institute of Mexico, Technological Institute of Tepic, Nayarit, Mexico

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Contents List of contributors .....................................................................................xiii Preface ........................................................................................................xix

1 High-added-value compounds from agro-food industry wastewater ............................................................................................................1 Cristina Caleja, Eliana Pereira, Isabel C.F.R. Ferreira and Lillian Barros 1.1 Introduction .......................................................................................... 1 1.2 Food losses and waste: biowaste from the agroindustrial sector..................................................................................................... 2 1.3 The problem of environmental contamination and disposal of biowaste ............................................................................ 6 1.3.1 Biowaste as a source of bioactive compounds.........................8 1.4 The emergence and potential of wastewater................................... 11 1.4.1 Importance of wastewater treatment and applications..........13 1.4.2 Molecules of interest present in wastewaters: properties and benefits .............................................................16 1.5 Conclusions and future trends .......................................................... 17 Acknowledgments .................................................................................... 18 List of acronyms ....................................................................................... 18 References ................................................................................................. 18

2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry...........................................................25 D. Lorente, S. Duarte Serna, E. Betoret and N. Betoret 2.1 Introduction ........................................................................................ 25 2.2 Nature of byproducts obtained from cereals, nuts, and legumes: research evolution ............................................................. 28 2.3 Nutrient composition ......................................................................... 33 2.3.1 Okara ..........................................................................................37 2.3.2 Rice .............................................................................................38 2.3.3 Oat ..............................................................................................39 2.3.4 Almond ......................................................................................39 2.3.5 Tiger nut.....................................................................................41 v

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2.4 Applications in food industry ............................................................ 42 2.4.1 Solid wastes or byproducts ...................................................... 42 2.4.2 Liquid wastes............................................................................. 52 2.5 Conclusions and future trends .......................................................... 57 List of acronyms ....................................................................................... 58 References ................................................................................................. 58

3 High-rate anaerobic processes for agro-food wastewater treatment: recent trends and advancements...............................................67 A. Bokhary, M. Leitch, Y. Hong and B.Q. Liao 3.1 Introduction ........................................................................................ 67 3.2 Agro-food wastewater characteristics .............................................. 70 3.3 Application of high-rate anaerobic systems in agro-food wastewater treatment ........................................................................ 71 3.3.1 The anaerobic filter ................................................................... 71 3.3.2 Upflow anaerobic sludge blanket reactor ...............................72 3.3.3 Expanded granular sludge bed reactor ...................................76 3.3.4 Anaerobic moving bed biofilm reactor.................................... 78 3.3.5 External circulation sludge bed reactor...................................79 3.3.6 Anaerobic membrane bioreactor ............................................. 81 3.3.7 Anaerobic hybrid reactors ........................................................ 87 3.3.8 Full-scale application of high-rate anaerobic systems ...........88 3.4 Recent trends and future perspectives ............................................. 89 3.5 Challenges of wastewater treatment in the agro-food industry ............................................................................................... 90 3.6 Conclusions and future trends .......................................................... 91 List of acronyms ....................................................................................... 92 References ................................................................................................. 92

4 Food-processing wastewater treatment by membrane-based operations: recovery of biologically active compounds and water reuse........................................................................................................101 Carmela Conidi, Angelo Basile and Alfredo Cassano 4.1 Introduction ...................................................................................... 101 4.2 An overview of pressure-driven membrane processes................. 104 4.3 Recovery of biologically active compounds and water from food-processing wastewaters ......................................................... 107 4.3.1 Olive mill wastewaters............................................................ 108

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4.3.2 Fish-processing wastewaters .................................................113 4.3.3 Dairy-processing wastewaters ............................................... 116 4.4 Conclusions and future trends ........................................................ 120 List of acronyms ..................................................................................... 121 List of symbols........................................................................................ 121 References ............................................................................................... 121

5 Biorefineries to improve water and resource recovery in the seafood-processing industry .........................................................................127 J. Gonza´lez-Camejo, C. Andreola, V. Maceratesi, G. Toscano, A.L. Eusebi and F. Fatone 5.1 Introduction ...................................................................................... 127 5.2 Seafood industry .............................................................................. 131 5.3 Processes to develop biorefinery schemes from seafood wastes ............................................................................................... 131 5.3.1 Physical processes .................................................................. 132 5.3.2 Chemical processes.................................................................133 5.3.3 Thermochemical and thermal processes ..............................135 5.3.4 Biological processes ............................................................... 137 5.4 Bioproducts obtained from seafood wastes .................................. 139 5.4.1 Biofertilizers and biostimulants..............................................140 5.4.2 Biofuels .................................................................................... 142 5.4.3 Biocompounds ........................................................................ 142 5.4.4 Water streams ......................................................................... 144 5.5 Conclusions and future trends ........................................................ 145 Acknowledgments .................................................................................. 146 List of acronyms ..................................................................................... 146 References ............................................................................................... 146

6 A valorization approach of food industry wastewater using microwave-assisted extraction ....................................................................155 Halil Dertli and Didem Saloglu 6.1 Introduction ...................................................................................... 155 6.2 Wastewater from the food industry................................................ 157 6.2.1 Characterization of wastewater from the olive oil industry ............................................................................... 158

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6.2.2 Characterization of wastewater from the sugar industry .................................................................................... 158 6.2.3 Characterization of wastewater from the cheese industry .................................................................................... 158 6.2.4 Characterization of wastewater from the slaughterhouse industry ......................................................... 159 6.2.5 Characterization of wastewater from the multiproduction food industry ............................................... 159 6.2.6 Characterization of wastewater from the seafood industry .................................................................................... 159 6.3 Removal of organic and inorganic compounds in food industry wastewater......................................................................... 160 6.3.1 Extraction methods of organic and inorganic compounds in food industry wastewater..............................162 6.4 What are microwaves?..................................................................... 167 6.5 Microwave-assisted extraction........................................................ 170 6.5.1 Specific applications of microwave-assisted extraction....... 172 6.5.2 Kinetic modeling of microwave-assisted extraction............. 173 6.6 Conclusion and future trends.......................................................... 175 List of acronyms ..................................................................................... 176 List of symbols........................................................................................ 176 References ............................................................................................... 176

7 Supercritical fluid extraction applied to food wastewater processing ..........................................................................................................179 Luana Cristina dos Santos, Talyta Mayara Silva Torres, Daiane Ferreira Campos, Filippo Giovanni Ghiglieno and Julian Martı´nez 7.1 Introduction ...................................................................................... 179 7.2 Wastewater and sludge from the food industry: composition and current issues ...................................................... 181 7.2.1 Dairy ......................................................................................... 182 7.2.2 Fruit and vegetable industry................................................... 184 7.2.3 Meat industry........................................................................... 184 7.2.4 Oil industry .............................................................................. 186 7.2.5 Beverage industry ................................................................... 188 7.3 Clean extraction technologies for wastewater and sewage sludge treatment: circular economy in high demand ................... 189

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7.4 Supercritical fluid extraction ........................................................... 192 7.4.1 Fundamentals of supercritical fluid extraction...................... 193 7.4.2 Supercritical fluid extraction of liquid and semisolid mixtures ................................................................................... 197 7.4.3 Supercritical fluid extraction applied to wastewater and sludge from the food industry ........................................ 199 7.5 Technoeconomic evaluation of supercritical fluid extraction applied to the recovery of value-added molecules ....................... 202 7.6 Conclusions and future trends ........................................................ 206 Acknowledgments .................................................................................. 206 List of acronyms ..................................................................................... 207 List of symbols........................................................................................ 207 References ............................................................................................... 207

8 Advances in ultrasound-assisted extraction of bioactive compounds (antioxidant compounds) from agrofood waste .................217 Abraham Osiris Martı´nez-Olivo, Alba Cecilia Dura´n-Castan˜eda, Francia Guadalupe Lo´pez-Ca´rdenas, Jose´ de Jesu´s Rodrı´guez-Romero, Jorge Alberto Sa´nchez-Burgos, Sonia Guadalupe Sa´yago-Ayerdi and Victor Manuel Zamora-Gasga 8.1 Introduction .................................................................................... 217 8.2 Main bioactive compounds from waste and byproducts of fruits and vegetables ................................................................. 219 8.2.1 Pomace................................................................................... 220 8.2.2 Peels and seeds ..................................................................... 220 8.2.3 Leaves and stems.................................................................. 221 8.3 Main bioactive compounds from waste and byproducts of animal product processing ....................................................... 222 8.3.1 Dairy products ....................................................................... 222 8.3.2 Meat products........................................................................ 222 8.3.3 Marine products .................................................................... 224 8.4 Emerging technologies for obtaining bioactive compounds ..................................................................................... 224 8.5 Fundamentals for ultrasound-assisted extraction ....................... 228 8.6 Variables associated with ultrasound-assisted extraction .......... 229 8.6.1 Ultrasonic power ................................................................... 230 8.6.2 Ultrasonic frequency ............................................................. 230

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8.6.3 Solvents ................................................................................. 231 8.6.4 Temperature of ultrasound-assisted extraction .................. 231 8.6.5 Liquid (solvent) to solid ratio ............................................... 232 8.6.6 Time of ultrasound-assisted extraction ............................... 232 8.7 Effect of variables associated with ultrasound-assisted extraction on the extraction of bioactive compounds from byproducts ...................................................................................... 233 8.8 Commercial patents: ultrasound and innovative techniques for the extraction of bioactives .................................. 233 8.9 Current trends in the extraction of bioactive compounds .......... 236 8.10 Conclusions and future trends ...................................................... 238 List of acronyms ..................................................................................... 238 References ............................................................................................... 239

9 Integrated advanced technologies for olive mill wastewater treatment: a biorefinery approach ...............................................................247 Marı´a del Mar Contreras, Juan Carlos Lo´pez-Linares and Eulogio Castro 9.1 Introduction ...................................................................................... 247 9.2 Chemical composition of olive mill wastewater............................ 252 9.3 Reuse, applications, and technologies employed ......................... 254 9.3.1 Biofuels .................................................................................... 254 9.3.2 Polysaccharides ....................................................................... 257 9.3.3 Phenolic compounds and other antioxidants ....................... 258 9.3.4 Enzymes ................................................................................... 259 9.3.5 Biosurfactants .......................................................................... 259 9.3.6 Citric acid and lipids................................................................ 260 9.3.7 Polyhydroxyalkanoates ........................................................... 260 9.3.8 Use in agriculture: fertilizers, biopesticides, and irrigation................................................................................... 261 9.3.9 Food and beverage supplement ............................................ 262 9.4 Process integration: biorefinery examples..................................... 263 9.5 Conclusions and future trends ........................................................ 267 Acknowledgments .................................................................................. 267 List of acronyms ..................................................................................... 267 References ............................................................................................... 268

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10 Advanced strategies for dairy wastewater treatment: a perspective ...................................................................................................275 Adriano Gomes da Cruz, Tatiana Colombo Pimentel, Geraldo Lippel Sant’Anna Junior and Simone Maria Ribas Vendramel 10.1 Introduction ...................................................................................275 10.2 Some guidelines for wastewater treatment in the dairy industry.................................................................................276 10.3 Dairy wastewater characteristics..................................................278 10.4 Dairy industry wastewater treatments.........................................280 10.4.1 Preliminary treatments ..................................................... 280 10.4.2 Physicochemical treatments............................................. 281 10.4.3 Biological treatments ........................................................ 284 10.4.4 Complementary treatments.............................................. 290 10.5 Recovery and valorization of wastewater components and treatment wastes .............................................292 10.5.1 Whey: recovering and processing ................................... 293 10.5.2 Sludges from primary and secondary treatments.......... 298 10.5.3 Water reuse........................................................................ 300 10.6 Conclusions and future trends .....................................................302 List of acronyms ..................................................................................... 304 References ............................................................................................... 304

11 Winery wastewater treatment for biomolecules recovery and water reuse purposes .........................................................311 Alexandre Giacobbo, Margarida Oliveira, Andre´a Moura Bernardes and Maria Norberta de Pinho 11.1 Introduction ...................................................................................311 11.2 Winemaking process and wastewater generation......................313 11.3 Value-added biomolecules found in winery wastewaters ............. 316 11.4 Winery wastewater treatment systems .......................................319 11.4.1 Physical treatments ........................................................... 319 11.4.2 Physicochemical treatments............................................. 321 11.4.3 Natural biological treatments........................................... 324 11.4.4 Membrane bioreactors...................................................... 331 11.4.5 Other bioreactors............................................................... 332

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11.5 Membrane separation based processes for biomolecules recovery from winery wastewater........................332 11.6 Wastewater reuse..........................................................................336 11.7 Conclusions and future trends .....................................................340 List of acronyms ..................................................................................... 341 References ............................................................................................... 342

12 Nanomaterials for the removal of organic pollutants from agrofood wastewaters ........................................................................355 Roxana-Ioana Brazdis, Radu Claudiu Fierascu, Sorin-Marius Avramescu and Irina Fierascu 12.1 Introduction ...................................................................................355 12.2 Slaughterhouse wastewater .........................................................357 12.3 Dairy wastewater...........................................................................357 12.4 Fish processing..............................................................................359 12.5 Olive oil manufacturing ................................................................361 12.6 Sugar manufacturing ....................................................................363 12.7 Wine making..................................................................................364 12.8 Materials for wastewater treatment.............................................366 12.9 Conclusions and future trends .....................................................375 Acknowledgments .................................................................................. 375 List of acronyms ..................................................................................... 375 References ............................................................................................... 376 Index........................................................................................................... 383

1 High-added-value compounds from agro-food industry wastewater Cristina Caleja1,2, Eliana Pereira1,2, Isabel C.F.R. Ferreira1,2 and Lillian Barros1,2 1

Centro de Investigac¸a˜o de Montanha (CIMO), Instituto Polite´cnico de Braganc¸a, Braganc¸a, Portugal 2Laborato´rio Associado para a Sustentabilidade e Tecnologia em Regio˜es de Montanha (SusTEC), Instituto Polite´cnico de Braganc¸a, Campus de Santa Apolo´nia, Braganc¸a, Portugal

1.1

Introduction

Considering the annual waste in the food sector reflected throughout the value chain, it is important to establish strategic actions to reduce this waste, creating opportunities for its reuse and valorization. As a result of the high food production, huge amounts of wastewater also arise from this sector. Thus waste disposal has become a significant cost factor and an important aspect in the manufacturing units (Hanchang, 2009). The reuse of agroindustrial waste, including wastewater, translates into an advantageous opportunity in the development of byproducts, as well as the addition of lost value, through the sustainable use of this waste (Egea, Torrente, & Aguilar, 2018). In most cases, these residues contain bioactive compounds that may generate several positive effects on human health, owing to their biological activity in the organism (Kumar & Naraian, 2019). Among the bioactive molecules is the phenolic compounds class, with beneficial properties that are attributed to their ingestion (Montenegro et al., 2021). This chapter emphasizes the problem of food losses and the reuse of biowaste from the agroindustrial sector, addressing their properties, the harm caused by the environmental impact, the emergence of wastewater from the agro-food industry, the importance of their treatment, and the possible applications. With this theme, is proposed to solve a problem that affects the whole world, to define strategies for the reuse of these effluents, Advanced Technologies in Wastewater Treatment. DOI: https://doi.org/10.1016/B978-0-323-88510-2.00010-5 Copyright © 2023 Elsevier Inc. All rights reserved.

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Chapter 1 High-added-value compounds from agro-food industry wastewater

and in this way to increase the development of the economy, society, the industrial innovation and contribute to the preservation of the planet, including flora, fauna, and ecosystems.

1.2

Food losses and waste: biowaste from the agroindustrial sector

Food production leads people to adopt a lifestyle with intensive needs and desires for natural resources, which leads to a negative environmental impact (Aschemann-Witzel, Varela, & Peschel, 2019). Ecological disturbances have become more numerous, widespread, and intense, causing problems on a global scale and making humankind and our practices the main threat to the environment (Caldeira, De Laurentiis, Corrado, Holsteijn, & Sala, 2019). In this way, the great demand for food combined with consumerism and the competitiveness of the global market has led to an increase of food production and processing and, consequently, to the massive production of waste from this sector (De Jesus, 2018). The definition of waste is “any substance or object that the holder discards or intends or is obliged to discard” (Directive, 2008/98/EC). More specifically, biowaste is waste resulting from living organisms or of organic origin (e.g., sewage, agricultural or forestry residues, manure, sawdust, and food scraps) mainly constituted by organic matter. According the European Waste Framework Directive (EWFD) (2008/98/EC), biowaste is defined as “biodegradable garden and park waste, food and kitchen waste from households, restaurants, caterers and retail premises and comparable waste from food processing plants.” In its Article 22, the EWFD prescribes that member states shall take measures to encourage: “(1) the separate collection of biowaste with a view to the composting and digestion of biowaste; (2) the treatment of biowaste in a way that fulfils a high level of environmental protection; (3) the use of environmentally safe materials produced from biowaste.” Postharvest food losses have been analyzed by the Food and Agriculture Organization of the United Nations (FAO). In its latest report, the FAO (2019a) divulges that 14% of food is wasted worldwide and that the Central and South Asia together account for the highest rate with values of 21% of food losses, followed by North America and Europe with values of 16%; Australia and New Zealand account for the lowest food residues with a value of 6% (Fig. 1.1). The available literature reports that 56% of the world’s total food residues is produced by Europe, North

Chapter 1 High-added-value compounds from agro-food industry wastewater

Figure 1.1 Percentage of food loss in the world. Adapted from FAO. (2019a). The State of Food and Agriculture 2019. Moving forward on food loss and waste reduction. Rome. Licence: CC BY-NC-SA 3.0 IGO. ISBN 978-92-5-131789-1.

America, and countries such as China, Japan and South Korea (Lipinski, Kitinoja, Searchinger, & Hanson, 2013). Annually, in the European Union, the total production of biological residues is estimated to be 76.5 102 million tons of food and garden waste, including mixed municipal solid waste, and up to 37 million tons of waste from the food and beverage industry (Table 1.1). Although biomass also includes materials of animal origin, in the field of extracting valuable substances and compounds from biowaste, much more attention has been paid to materials of vegetal origin (FAOSTAT, 2017). Animal wastes include blood from slaughterhouses and skin, bones, excrement, and visceral parts from the meat and fish production industries. This global annual production is 263 million tons in the meat sector and 128 million tons in the fish sector ˇ ˇ (Jablonsky´, Skulcov, Malvis, & Sima, 2018). Agroindustrial residues are produced in the processing of food, leather, fibers, and wood and the production of sugar and alcohol, among other sources. The production of these residues is normally

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Chapter 1 High-added-value compounds from agro-food industry wastewater

Table 1.1 Food waste in the European Union estimated in 2011. Industry

Byproducts

Approximate total (metric tons)

Meat Fish Dairy Eggs Cereals Fruit Vegetables Potatoes Sugar beets Oil crops

Blood, guts, bones, intestines, skin, fats, hair, and feathers 14.2 Heads, viscera, tails, skin, spines, and shells 4.2 Milk whey 6.8 Shells 1.8 Leaves and seeds 15.6 Leaves, seeds, skins, stems, and pulp 28.1 Leaves, seeds, skins, stems, and pulp 31.3 Peels 9.4 Pulp, molasses, and yeast 5.1 Leaves, marc, gum, and soaps 12.7

Source: Based on Caldeira, C., De Laurentiis, V., Corrado, S., Holsteijn, F., & Sala, S. (2019). Quantification of food waste per product group along the food supply chain in the European Union: a mass flow analysis. Resources, Conservation and Recycling, 149, 479 488.

seasonal and conditioned by the maturity of the culture or supply of the raw material (Costa Filho et al., 2017). These residues can be classified as either organic or inorganic waste. Organic residues are generated by the agriculture and livestock sectors and are crop residues (e.g., coffee, cocoa, bananas, soybeans, corn), waste generated in animal husbandry, and effluents and residues produced in agroindustry, such as slaughterhouses and dairies. Inorganic solid waste includes packaging produced in the segments of pesticides, fertilizers, and veterinary pharmaceutical inputs, among others (Alencar, Batista, Nascimento, da Cunha, & Leite, 2020). Considering organic waste on a global scale, namely, waste from food production, about one third of the food that is produced (1.3 billion tons/year) for human consumption is discarded annually (Fig. 1.2). The FAO estimates that Latin America and the Caribbean have 6% of the world’s food losses. Moreover, the region loses and/or wastes approximately 15% of available food annually. These large amounts of effluents are due to the continuous evolution of the agroindustrial sector, and are generated in the processes of transformation of raw materials (Chen et al., 2019). According to FAO data, the highest rate of loss occurs among roots, tubers, and oilseeds (25%), followed by fruits and vegetables (21%) (Fig. 1.3). Cereals and pulses lose only up to 8%. The loss of meat and animal products is 12% and occurs predominantly as a result of inadequate packaging, storage, and transport and nonconsumption before the expiration date and disposal of markets after the expiration date (FAO, 2019a).

Chapter 1 High-added-value compounds from agro-food industry wastewater

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Figure 1.2 Global food losses per year. Based on http://www.fao.org.

Figure 1.3 Percentage of food losses. Aadapted from FAO. (2019a). The State of Food and Agriculture 2019. Moving forward on food loss and waste reduction. Rome. Licence: CC BY-NC-SA 3.0 IGO. ISBN 978-92-5-131789-1.

The data of Fig. 1.3 refers to the physical quantity lost for different commodities divided by the amount produced. An economic weight is used to aggregate percentages at regional or commodity group levels, so that higher-value commodities carry more weight in loss estimation than lower-value ones. Household waste is mostly composed by food waste and, in developed countries, 40% of food loss occurs at the consumer level (Arun et al., 2020).

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Chapter 1 High-added-value compounds from agro-food industry wastewater

Losses in developed countries are as high as those in developing countries. However, in poor countries, more than 40% of food losses are generated in the postharvest and processing phases, whereas in the developed countries, more than 40% of food losses are generated in the retail and consumption phases. Food waste by the consumer in developed countries is estimated to be around 222 million tons, and is practically as high as the total net food production that occur in sub-Saharan Africa, which is around 230 million tons (Pap, Pongra´cz, Myllykoski, & Keiski, 2014). Wastewater also emerges as a biowaste from the agro-food industry, resulting from washing, scalding, cooking, pasteurization, and cooling and washing of processing equipment and facilities (Alencar et al., 2020). The inadequate disposal of these waters, predominantly into the soil, is also harmful to the environment, making it vital to know its characteristics and identify its potential, not only to resolve the environmental problems caused by the inadequate disposal, but additionally to derive economic value from these wastes (Toop et al., 2017; Woiciechowski et al., 2013). In addition to all the environmental harm (most of which is classified as high magnitude), food waste involves the waste of other resources that are used in the food industry, namely water, energy, and land for agricultural production (Chen et al., 2019; Wunderlich & Martinez, 2018). All of these losses are unsustainable, and they lead to serious and worrying social and economic impacts. The reuse of these discarded products will allow greater sustainability in the industrial sector, adding value to this type of biowaste and consequently reducing environmental destruction (Wunderlich & Martinez, 2018).

1.3

The problem of environmental contamination and disposal of biowaste

In recent decades, concerns about environmental conservation have increased due to the awareness that environmental quality is the basis for preserving the lives of future generations. In this way, the environment has ceased to be a consumer good of the productive sector and has become a heritage of humanity (Lanna, 2002). Every year, from primary production to final consumption, huge amounts of waste are discarded into the environment. These residues, which come from the agroindustrial sector and

Chapter 1 High-added-value compounds from agro-food industry wastewater

from domestic use, are usually dumped in sanitary landfills or incinerated. However, this type of disposal causes serious environmental problems (Arun et al., 2020). This problem has become a growing concern in several sectors, mainly food and environmental (Toop et al., 2017; Woiciechowski et al., 2013). The environmental impact resulting from the production of waste translates into the emission of greenhouse gases. Global food waste generates significant amounts of methane gas (CH4) and carbon dioxide (about 4.4 gigatons of CO2). These gases are highly harmful to the environment, as they contribute significantly to global warming. (Al-Obadi, 2021). In accounting for aggregated greenhouse gases emissions, uneaten food is estimated to emit 3.6 gigatons of CO2 eq/year with an additional 0.8 gigaton of CO2 eq/year resulting from associated land use, land use change, and forestry activities (FAO, 2017a). Therefore the release of atmospheric pollutants makes it urgent to find alternatives to the disposal of these biowastes in landfills and incineration (Ageˆncia Portuguesa do Ambiente, 2019; Ministe´rio do Ambiente e da Ac¸a˜o Clima´tica, 2020). Among the agroindustrial activities with the greatest polluting potential are the production of cattle and swine, coffee production, pulp and paper production, beer, milk and derivatives, and biodiesel (generation of residual glycerol) (Silva and Pogacnik, 2020). The adverse ecological impacts that are caused by severe environmental problems can be classified according to several characteristics: reduction of biodiversity and replacement of dominant species, increased water toxicity, and increased turbidity of water and decreased lifespan of lakes (Cai, Stephen, Park, & Li, 2013). In the European Union, environmental legislation has been very important, contributing significantly to the introduction of sustainable waste management practices. The primary aim of waste legislation is the prevention of waste generation. The Waste Framework Directive/98/EC (2008) defines waste prevention as “measures taken before a substance, material or product has become waste, that reduces the quantity of waste, including reuse or extension of life-span, the adverse impacts of the generated waste and the content of harmful substances in materials and products. Once waste is formed, it should be recycled or recovered for better environmental and economic performance” (Lazarevic, Buclet, & Brandt, 2010). Furthermore, the environmental impacts of the food chain would have been meaningless if the produced goods became waste. Therefore waste minimization and utilization are a

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Chapter 1 High-added-value compounds from agro-food industry wastewater

desirable strategy because the waste streams from the food industry are a good source of organic content, which s usually rich in valuable compounds, such as oils and sugars (Pap et al., 2014).

1.3.1

Biowaste as a source of bioactive compounds

In recent years, owing to the greater concern of science and society for the environment, there has been an increase in the number of researches works aimed at the use of agroindustrial residues as a way of using them to generate products with high added value (Beltra´n-Ramı´rez et al., 2019). Given the worrying amounts resulting from the disposal of these wastes, and their consequences at an economic and environmental level, their use translates into a way to minimize the impacts caused by incorrect disposal of these wastes on the environment, namely, water contamination. In addition, these residues have been highlighted because they present in their composition molecules of high value with potential for application and recovery (Alencar et al., 2020). Most of the biowastes that are produced in the fruit and vegetable sector include the skin and seeds of fruits and/or vegetables, peels, stalks, or products that have physical or chemical damage. These biowastes are commonly underutilized, and their potential value is often lost. However, they have significant value, considering that these residues contain important levels of nutrients and bioactive compounds. The traditional ways of using this type of biowaste are in animal feed, incineration, and composting, although they do not always demonstrate efficiency and entail costs that are many times higher than those estimated by the companies themselves (Valente, 2015). Rather than using them conventionally, an alternative valorization of these materials is to create higher value-added products. Depending on the raw material and processing that originated them, biowastes may contain varying levels of basic nutrients, such as protein, lipids, minerals, and carbohydrates (sugars and fibers), and may also include functional compounds of high differentiated value, such as vitamins, carotenoids, polyphenols, and peptides (Pintado & Teixeira, 2015). Some researchers have obtained various ingredients from byproducts. Some examples are obtaining fibers, hemicelluloses, beta-glucans and prebiotic oligosaccharides from cereal

Chapter 1 High-added-value compounds from agro-food industry wastewater

Table 1.2 Molecules of interest obtained from biowaste discarded by the food industry. Molecule of interest

Biowaste

Extraction method References

Vitamin C

Saffron tepals

Carotenoid

Papaya

Polyphenols, mangiferin, and pectin

Mango peel

Ultrasound-assisted extraction Ultrasound-assisted extraction Soxhlet and pressurized solvent extraction Sequential extractions using different solvents Microwave- and ultrasound-assisted extraction

Polysaccharides

Mango and passion fruit peel, cashew bagasse, green coconut husk and sugarcane bagasse Essential oils, polyphenols, Orange peel and pectin

Flavonoids

Orange citrus pulp

Liquid-solid extraction and precipitation

byproducts (e.g., rice bran, spent grain); obtaining polyphenols and organic acids from roots and tubers (e.g., sugarcane residues, cassava); obtaining phytosterols, polyphenols, and pectins from oilseed crops (e.g., soy, olive pomace); and obtaining pectins, fibers, carotenoids, and polyphenols from fruits and vegetables (e.g., skins of various fruits, tomato pomace) (Galanakis, 2012; Pintado & Teixeira, 2015). Several researchers have evaluated and determined the nutritional profile and bioactive potential of several raw materials discarded by the food industry, showing satisfactory results in terms of obtaining high-value compounds and producing relevant metabolites. Some studies are represented in Table 1.2. Many studies that have proven the biological action of these residues, with interest for the industrial sector, aiming at their use as a functional and bioactive ingredients (Barreto, Zancan, & de Menezes, 2015). This alternative has attracted great interest by researchers and the industrial sector in the last few decades (Sawasdee & Stathopoulos, 2017).

1.3.1.1

The case of phenolic compounds

Phenolic compounds or polyphenols (Fig. 1.4) are secondary metabolites that are produced naturally by plants under normal

Stelluti, Caser, Demasi, and Scariot (2021) Li et al. (2015) Cavalcante (2018)

Vidal (2020)

Boukroufa, Boutekedjiret, Petigny, Rakotomanomana, and Chemat (2015) Cypriano, da Silva, and Tasic (2018)

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Chapter 1 High-added-value compounds from agro-food industry wastewater

Phenolic compounds

Anoxidant

Free radical capture

Anmicrobial

Inhibion of enzyme oxidaon

Aninflammatory Antumor

Inducon of endogenous anoxidant enzymes Impact on the cell cycle

Anviral

Figure 1.4 Bioactive action inherent in the polyphenols that are present in plant matter (Miyamae et al., 2011; Kasala et al., 2016). Based on Miyamae, Y. M., Kurisu, M. K., Han, J. H., Isoda, H. I., & Higemori, H. S. (2011). Structure— activity relationship of caffeoylquinic acids on the accelerating activity on ATP production. Chemical and Pharmaceutical Bulletin, 59, 502 507; Kasala, E. R., Narendra, L., Barua, C. C., Gogoi, R. (2016). Antioxidant and antitumor efficacy of Luteolin, a dietary flavone on benzo (a) pyrene-induced experimental lung carcinogenesis. Biomedicine et Pharmacotherapy, 82, 568 577.

and stressed conditions. In plants, these compounds have important biological functions, namely, growth regulation and protection against viruses, bacteria, insects, predators, oxidative stress and ultraviolet radiation as well as interfering with the attraction of pollinators and animals for seed dispersal. In foods, these compounds contribute to sensory characteristics such as color, aroma, flavor, and astringency (Farha et al., 2020; Kumar & Naraian, 2019; Rodrı´guez-Pe´rez, Segura-Carretero, ´ jo, Contreras, & del, 2019; Wen, Alseekh, & Fernie, 2020; Arau Farias, Neri-Numa, & Pastore, 2021). These compounds are made up of at least one hydroxylated aromatic ring; can be in the simple form or linked with sugars, organic acids, and other molecules; and can be soluble or insoluble in water (Rodrı´guez-Pe´rez et al., 2019). The literature divides phenolic compounds in two principal groups: flavonoids and phenolic acids (Arau´jo et al., 2021). Phenolic compounds are among the most described phytochemicals for their bioactive potential (Fig. 1.4) in preventing the onset of chronic noncommunicable diseases such as cancers, diabetes, and cardiovascular diseases, owing to their antioxidant effects, minimizing oxidative stress and its consequences. The antioxidant action of these compounds occurs in different ways, according to the chemical structure, but it is mainly due to their oxidation-reduction properties, playing an important role in the absorption and neutralization of free radicals (Zardo, 2019). The bioactive properties of phenolic compounds have been related to their antiinflammatory (Maleki, Crespo, & Cabanillas, 2019; Margin˘a et al., 2020), antiviral (Levy, Delvin, Marcil, & Spahis, 2020), antitumor (Carvalho et al., 2020; Zabaleta et al., 2020), antioxidant (Silva & Pogacnik, 2020), and antimicrobial potentials (Olszewska, Ge˛das, & Simo˜es, 2020) and their immunoregulatory (Carvalho et al., 2020) and prebiotic effects, favoring the composition and abundance of the intestinal microbiota

Chapter 1 High-added-value compounds from agro-food industry wastewater

and the production of metabolites that are significant to health, with the potential for decreasing intestinal inflammation (Alves-Santos, Sugizaki, Lima, & Naves, 2020; Pei, Liu, & Bolling, 2020). In addition, they influence the prevention of metabolic disorders such as obesity, insulin resistance, type 2 diabetes, and cardiovascular disease (Neri-Numa et al., 2020); therapeutic properties of neurodegenerative diseases (Silva & Pogacnik, 2020) and celiac disease (Dias, Pereira, Pe´rez-Gregorio, Mateus, & Freitas, 2021); atherosclerosis mitigation (Cullen, Centner, Deitado, Fernandez, & Salazar, 2020). The potential for combating SARS-CoV-2 infection has also been proven (Levy et al., 2020).

1.4

The emergence and potential of wastewater

Water is a crucial element for human survival, because is connected to all daily activities in all countries around the world. In 2018 the United Nations estimated that 2 billion people live in countries that are experiencing high water stress, which is likely to worsen as population and demand for water increase (Owodunni & Ismail, 2021). Water, raw materials, and energy are key resources used in the food-processing industry. In particular, water is used for numerous activities and purposes, such as product washing, scalding, cooking, pasteurization, cooling, cleaning, and conveying of raw materials and to sanitize plant machinery and areas. This water is discarded and termed as industrial wastewater (Galanakis, 2018). Wastewater “is a combination of used water from one or more sources including domestic households, farms, institutions, and/or commercial and industrial establishments, containing toilet water (black water), kitchen or bathroom water (gray water) as well as storm water. The exact composition of such polluted water sources varies widely, depending on the distance to the city, the sources of pollution (households, industry, agriculture) and how much the wastewater is diluted by other sources of water” (FAO, 2019b). Currently, it is estimated that approximately 2250 km/year of effluent is discharged into the environment, 330 km3/year as urban wastewater, 660 km3/year as industrial wastewater (including cooling water), and 1260 km3/year as agricultural drainage (FAO, 2021). Considering the high amount of wastewater produced, this type of discarded solution is a hazard to the environment, requiring appropriate management approaches

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Chapter 1 High-added-value compounds from agro-food industry wastewater

(Alencar, Batista, Nascimento, da Cunha, & Leite, 2020; Cassano, Rastogi, & Basile, 2015). Untreated wastewater may contain pathogens, such as bacteria, viruses, protozoa, and parasitic worms; organic particles, such as feces, hair, food, paper fibers, and plant material; inorganic particles, such as suspended solids, nutrients, sand, or heavy metals; and pesticides, grease, microplastics, and other organic compounds or toxins (FAO, 2019b). This wastewater causes severe pollution problems, and owing to a high organic load and nutrient content in the food industry wastewater, reflects a chemical oxygen demand reaching tens of thousands of milligrams per liter (Chen et al., 2019). According to UNESCO data, more than 80% of the wastewater that is generated globally is probably discharged into the environment without appropriate treatment. This uncontrolled discharge of industrial wastewater has increased the turbidity and pH of water, destroying its quality. All of this may lead to both surface and groundwater contamination, which translates into the emergence of several hazards to human health (Owodunni & Ismail, 2021). Considering the basis of plant or animal origin, the wastewaters that are generated by different branches of the agro-food industry can be divided into two classes and seven subclasses. The wastewater from vegetable origins can be divided into four subclasses: from cereals, root and tubers, oil crop and pulses, and fruit and vegetables (Cassano et al., 2015). These wastewaters contain macropollutants and micropollutants. The macropollutants can contain chemical oxygen demand, biochemical oxygen demand, total suspended solids, fats, oils, and nutrients (nitrogen and phosphorous). The micropollutants are usually hormones, surfactants, antibiotics, and pesticides. However, the composition of food waste is not always the same because of the nature of food processing, the seasonality of crops, and postharvesting processing (Galanakis, 2012). Considering the environmental consequences of these wastewaters, several technological innovations, including those in clean technologies and processes are being introduced in the manufacturing units and aim to introduce into food processing some advanced wastewater treatment practices for recycling spent process waters onsite and reducing the amount of wastewater discharged into municipal sewage treatment plants. Another measure that is being taken to solve this problem is to reduce the amounts of water and wastewater from the manufacturing process (closedloop/zero emission systems) and the reuse of treated waters in the food-processing industry (Bolzonella & Cecchi, 2007).

Chapter 1 High-added-value compounds from agro-food industry wastewater

The reuse of these tributaries comes as a result of food waste contains high-added-value compounds (i.e., phenols, carotenoids, pectin, hemicelluloses, oligopeptides, lactose, proteins) that can be recovered and recycled inside the food chain as functional additives in different products. Nevertheless, for this, conventional and emerging technologies that offer interesting perspectives are applied, considering the huge quantities of food-related materials that are discharged worldwide (Cassano et al., 2015).

1.4.1

Importance of wastewater treatment and applications

In recent years, the valorization of residues has gained importance as an alternative option to discarding waste. This can involve any industrial process that involves the reuse, generating useful products or energy (Kabongo, 2013). The circular economy concept (Fig. 1.5) proposes that waste can become a raw material in another process or be transformed into a new product (Lett, 2014). The term “circular economy” is a powerful connecting concept to foster the fundamental links among resource use, waste, and emissions and to contribute to integrating environmental (output-related) and economic (input-related) policies (Mayer et al., 2019).

Figure 1.5 Schematic representation of the circular economy system. From https://eco.nomia.pt/pt/economia-circular/estrategias.

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Chapter 1 High-added-value compounds from agro-food industry wastewater

In this sense, wastewater treatment emerges as an asset to the productive sector, contributing to the increase of the circular economy and, consequently, to the sustainability of this sector (FAO, 2017b). The control and management of wastewater are very important. This management through treatment has two major objectives: to protect the environment by reducing the pollution of fresh water resources, hence reducing the health risks, and to mobilize this available water resource for mitigating water scarcity and improving food production (Bazza, 2002). In the case of wastewaters, the high concentrations of ammonia, suspended solids, chroma, and turbidity do not allow these waters to be reused, in many cases. This is one of the reasons why a pretreatment stage should be performed (PachaHerrera, Nagy, & Magyar, 2021). Population growth and industrialization have led to an increase in water consumption and consequently to an increase in the amounts of effluents discharged into the sewage system. Thus it has become significantly important to increase water availability and conserve water resources in order to ensure the reuse and recycling of wastewater (Tekile, Kim, & Lee, 2017). Wastewater treatment arose from the need to reduce concentrations of specific pollutants to safe levels for reuse of effluents or release into the environment (Peirce, Weiner, & Vesilind, 1998). Effluent treatment strategies include a combination of biological and physicochemical processes, and the choice of treatment method depends mainly on operational costs, the source and quality of the wastewater, and the intended reuse of the effluent (Egbuikwem, Mierzwa, & Saroj, 2020). Several conventional methods are used for the treatment of wastewater that, despite being considered effective, have several limitations, namely, the fact that they are ineffective in reducing the levels of heavy metals, toxic compounds, phosphorus and nitrogen; they generally require more than one step to treat most compounds; and they are considered unprofitable (Rajasulochana & Preethy, 2016). The methods that have been applied in wastewater treatment include adsorption, coagulation, biological treatments, and advanced oxidative processes. The latter processes have gained great prominence, as they demonstrate great potential in converting a large part of organic pollutants into smaller compounds or even CO2 (Bagal & Gogate, 2014; Collivignarelli et al., 2020). In these processes activated sludge processes can be combined to form membrane bioreactors to improve the capability of removing pollutants in biological treatment processes (Stephenson, Brindle, Judd, & Jefferson, 2000). In addition,

Chapter 1 High-added-value compounds from agro-food industry wastewater

pressure-driven membrane operations such as microfiltration, ultrafiltration, nanofiltration, and reverse osmosis can be used to treat high-strength wastewaters or at the end of conventional treatment systems to produce purified water for recycling or reuse and to recover valuable compounds (Cassano et al., 2015). In the specific case of biowastes from the agri-food sector, there are two distinct categories: the biological effluents and the solid wastes. The biological effluents (considered the liquid wastes) result from production processes and must be treated according to their concentration of organic matter. These bioresidues are the result of washing floors and transport boxes, among others. Each of these waste categories requires a different type of treatment and specialized professional labor, since they have highly polluting substances that can harm the environment (Caldeira et al., 2019). The use of treated wastewater can be an advantage because it reduces the risks posed by drought and environmental pollution by increasing the volume of water available for productive activities and landscape restoration (Carey & Migliaccio, 2009). In addition, a very important advantage is the reduction of the quantity of untreated wastewater that is released into the environment. Another advantage is that new technologies for treating wastewater for fertigation (the application of fertilizer via irrigation) have demonstrated the capacity to accelerate the restoration of carbon and nutrients in degraded soils, increase soil fertility, and improve productivity (FAO, 2017b). In the context of the use of byproducts from the agri-food sector, the objective of sustainable agriculture is to make the most of agricultural ecosystems. The purpose of this exploitation is to maintain its biological diversity, productivity, regenerative capacity, vitality, and ability to function in a way that can satisfy significant ecological, economic, and social functions at the local, national, and global levels without threatening other ecosystems (FAO, 2021). Thus more attention has been given to the benefits of water recycling and reuse as well as the importance of developing cost-effective treatment technologies with a low environmental impact (Jiang et al., 2021). A variety of types of wastewater have been successfully used as substrates for the primary production of some raw materials, for example, for the production of microalgae. In recent years, the cultivation of microalgae using wastewater as a source of nutrients has been proposed as a feasible strategy for wastewater treatment and the production of renewable resources. According to studies carried out by Liu, Ge, Cheng, Wu, and Tian (2013) and Luo et al. (2016), the growth of microalgae in some kinds of wastewater was even faster than

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Chapter 1 High-added-value compounds from agro-food industry wastewater

that in special microalgae culture media. Other studies have suggested the removal of excess nutrients from these waters; however according to Lv, Feng, Liu, and Xie (2017) and Alsarayreh, Almomani, Khraisheh, Nasser, and Soliman (2022), at present, most studies on microalgae cultivation in industrial wastewater emphasize the removal of toxic pollutants such as metal ions and toxic organic compounds rather than nutrient removal and algal biomass production. Also, according a study published by Muylaert et al. (2015), the use of anaerobic digestion to convert organic waste streams into methane is growing worldwide and generates a nutrientrich effluent that could be processed with microalgae. In some cases, farmers use wastewater for irrigation, although they may not be aware of the pollution level of the water they use. This agricultural practice appears to be a solution to allow farmers to grow crops throughout the year. In this case, this practice also translates into a productive advantage because these wastewaters also contain nutrients that can improve the successfully crop growth (FAO, 2019b).

1.4.2

Molecules of interest present in wastewaters: properties and benefits

Wastewater from the agro-food sector comes in large part from food processing. This means that they have compounds with high value in their composition, owing to the migration of the compounds present in food to the water (Oliveira & Franca, 2008). Food waste and, consequently, wastewaters contain highadded-value compounds (e.g., phenols, carotenoids, pectin, hemicelluloses, oligopeptides, lactose, proteins) that can be recovered and recycled inside the food chain as functional additives in different industrial foodstuffs. For this purpose, conventional and emerging technologies offer interesting perspectives, considering the huge amounts of food-related materials discharged worldwide (Cassano et al., 2015). Most industries and human actions generate wastewater, and as a consequence, there are different kinds of wastewaters, each with a singular chemical composition and volumetric production over time. The nitrogen and phosphorus amounts that result from the anaerobic digestion of food waste are around 1600 1900 and 300 mg L21, respectively (Henze & Comeau, 2008; Muylaert et al., 2015). Wastewater has a relatively low nutrient content, with usually less than 1% nitrogen and less than 0.5% phosphorus.

Chapter 1 High-added-value compounds from agro-food industry wastewater

Considering this low nutrient content, it is not cost-effective to transport wastewater over long distances. However, application at short distances is viable, becoming a way of valuing this natural resource (Muylaert et al., 2015). Nevertheless, there is a big gap regarding the chemical composition of wastewaters obtained in the agroindustrial sector, since the research work that has been carried out to determine its composition in molecules of high value is still very scarce. The continuity of studies will enable confirmation of the presence of bioactive compounds that are potentially beneficial to health in this type of tributary and valuing them in order to explore their potential in the formulation of novel products and, consequently, for the increment of the global economy. Thus the use of wastewater could become a great alternative for obtaining promising sources of bioactive compounds.

1.5

Conclusions and future trends

Faced with the problem resulting from the disposal of biowaste from the agro-food sector and, consequently, contamination of soil and water, it is important to define strategies and establish measures that allow the reduction of both and contribute to the environmental and economic balance. In this way, the use of resources in a more correct and efficient way, the reduction of waste, the modification of production residues in order to obtain the maximum use within the production chain, and the best consumption and management of residues are crucial factors to take into account in reducing negative impacts. The correct management of all these factors will result in a marked contribution to the circular economy through the reduction of waste generated and ensuring economic benefits. This global concern regarding the generation of waste, which is categorized into industrial, agricultural, sanitary, and urban solids, drives the so-called sustainable biotechnology, which encourages zero waste. This intervention, in addition to helping to combat environmental pollution, will allow to the restoration of organic soil and will positively contribute to efforts to minimize global warming. Consequently, it will also contribute to the economy, encouraging the use of these residues for the production of high-value items. Thus one of the major current challenges is centered on the processing of agroindustrial byproducts for the recovery of high-value compounds and production of relevant bioactive metabolites through chemical and biotechnological processes. Additionally, better management of these biowaste will

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Chapter 1 High-added-value compounds from agro-food industry wastewater

contribute to the reduction of wastewater and facilitate its treatment to remove unwanted organic and inorganic matter that is harmful to the environment and health. Considering that wastewaters from the agroindustrial sector are also sources of nutrients, it further studies on their use for promising applications in the same sector become important and necessary. In view of the data that have been obtained by the entities that are responsible for monitoring agroindustrial and environmental activity, it can be seen that food waste is a complex problem in society and that occurs throughout the food chain, so it becomes central to raise awareness and provide more knowledge to all stakeholders (producers, traders, and consumers) to ensure the planet’s sustainability. It is necessary and urgent to seek solutions and actions focused on integrated planning, increasing the collective social awareness and a sense of the community protection. In the future, the scientific community should further study the chemical and nutritional composition of wastewater and test its biological activity in order to define strategies for its reuse with the aim of considerably reducing the effluents generated from the agro-food industry and stimulating the circular economy as well as the sustainability of this sector. These technological advances and adequate environmental management would enhance the minimization of environmental impacts.

Acknowledgments The authors are grateful to the Foundation for Science and Technology (FCT, Portugal) for financial support through national funds FCT/MCTES (PIDDAC) to CIMO (UIDB/00690/2020 and UIDP/00690/2020) and SusTEC (LA/P/0007/2021); national funding by F.C.T. and P.I., through the institutional and individual scientific employment program-contract for L. Barros and E. Pereira (2021.03908. CEECIND) contracts, respectively. C. Caleja is thankful for her contract through the project Healthy-PETFOOD (POCI-01-0247-FEDER-047073).

List of acronyms EWFD FAO UNESCO

European Waste Framework Directive Food and Agriculture Organization of the United Nations United Nations Educational, Scientific and Cultural Organization

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Chapter 1 High-added-value compounds from agro-food industry wastewater

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Lett, Lina (2014). Global threats, waste recycling and the circular economy concept. Argentine Journal of Microbiology, 46, 1 2. Levy, E., Delvin, E., Marcil, V., & Spahis, S. (2020). Can phytotherapy with polyphenols serve as a powerful approach for the prevention and therapy tool of novel coronavirus disease 2019 (COVID-19)? American Journal of Physiology-Endocrinology and Metabolism, 319, E689 E708. Li, A. N., Li, S., Xu, D. P., Xu, X. R., Chen, Y. M., Ling, W. H., . . . Li, H. B. (2015). Optimization of ultrasound-assisted extraction of lycopene from papaya processing waste by response surface methodology. Food Analytical Methods, 8, 1207 1214. Available from https://doi.org/10.1007/s12161-014-9955-y. Lipinski, B., Kitinoja, L., Searchinger T., & Hanson C. (2013). Reducing food loss and waste. Working Paper, Instalment 2 of Creating a Sustainable Food Future. Washington, DC: World Resources Institute, Lisa. Liu, J., Ge, Y., Cheng, H., Wu, L., & Tian, G. (2013). Aerated swine lagoon wastewater: A promising alternative medium for Botryococcus braunii cultivation in open system. Bioresource Technology, 139, 190 194. Available from https://doi.org/10.1016/j.biortech.2013.04.036. Luo, L., He, H., Yang, C., Wen, S., Zeng, G., Wu, M., . . . Lou, W. (2016). Nutrient removal and lipid production by Coelastrella sp. in anaerobically and aerobically treated swine wastewater. Bioresource Technology, 216, 135 141. Available from https://doi.org/10.1016/j.biortech.2016.05.059. Lv, J., Feng, J., Liu, Q., & Xie, S. (2017). Microalgal cultivation in secondary effluent: Recent developments and future work. International Journal of Molecular Sciences, 18(1), 79. Available from https://doi.org/10.3390/ ijms18010079. Maleki, S. J., Crespo, J. F., & Cabanillas, B. (2019). Anti-inflammatory effects of flavonoids. Food Chemistry, 299, 125124. Margin˘a, D., Ungurianu, A., Purdel, C., Ni¸tulescu, G. M., Tsoukalas, D., Sarandi, E., & Tsatsakis, A. M. (2020). Analysis of the intricate effects of polyunsaturated fatty acids and polyphenols on inflammatory pathways in health and disease. Food and Chemical Toxicology, 143, 111558. Mayer, A., Haas, W., Wiedenhofer, D., Krausmann, F., Nuss, P., & Blengini, G. A. (2019). Measuring progress towards a circular economy: A monitoring framework for economy-wide material loop closing in the EU28. Journal of Industrial Ecology, 23, 62 76. Ministe´rio do Ambiente e da ac¸a˜o clima´tica. (2020). Biorresı´duos: Contas certas nos resı´duos. ,https://eco.nomia.pt/contents/documentacao/2020orientacoes-biorresiduos-v1.pdf.. Miyamae, Y. M., Kurisu, M. K., Han, J. H., Isoda, H. I., & Higemori, H. S. (2011). Structure—Activity relationship of caffeoylquinic acids on the accelerating activity on ATP production. Chemical and Pharmaceutical Bulletin, 59, 502 507. Montenegro, J., dos Santos, L. S., de Souza, R. G. G., Lima, L. G. B., Mattos, D. S., Viana, B. P. P. B., . . . Teodoro, A. J. (2021). Bioactive compounds, antioxidant activity and antiproliferative effects in prostate cancer cells of green and roasted coffee extracts obtained by microwave-assisted extraction (MAE). Food Research International, 140, 110014. Muylaert, K., Beuckels, A., Depraetere, O., Foubert, I., Markou, G., & Vandamme, D. (2015). Wastewater as a source of nutrients for microalgae biomass production. Biomass and biofuels from microalgae (pp. 75 94). Cham: Springer. Neri-Numa, I. A., Cazarin, C. B. B., Ruiz, A. L. T. G., Paulino, B. N., Molina, G., & Pastore, G. M. (2020). Targeting flavonoids on modulation of metabolic syndrome. Journal of Functional Foods, 73, 104132.

Chapter 1 High-added-value compounds from agro-food industry wastewater

Oliveira, L. S., & Franca, A. S. (2008). Low-cost adsorbents from agri-food wastes. Food science and technology: New research, 171 209. Olszewska, M. A., Ge˛das, A., & Simo˜es, M. (2020). Antimicrobial polyphenol-rich extracts: Applications and limitations in the food industry. Food Research International, 134, 109214. Owodunni, A. A., & Ismail, S. (2021). Revolutionary technique for sustainable plant-based green coagulants in industrial wastewater treatment—A review. Journal of Water Process Engineering, 42, 102096. Pacha-Herrera, D., Nagy, P. T., & Magyar, T. (2021). Microalgae cultivation integrated into agro-industrial wastewater treatment. Ecocycles, 7, 35 45. Available from https://doi.org/10.19040/ecocycles.v7i2.210. Pap, N., Pongra´cz, E., Myllykoski, L., & Keiski, R.L. (2014). Waste minimization and utilization in the food industry: Valorization of food industry wastes and byproducts. Pei, R., Liu, X., & Bolling, B. (2020). Flavonoids and gut health. Current Opinion in Biotechnology, 61, 153 159. Peirce, J.J., Weiner, P.R.F., & Vesilind, A. (1998). Chapter 8, Wastewater treatment. In Environmental pollution and control (4th ed.). ´ stria Pintado, M. E., & Teixeira, J. A. (2015). Valorizac¸a˜o dos subprodutos da indu alimentar: Obtenc¸a˜o De Ingredientes De Valor Acrescentado. Boletim de Biotecnologia, 10 12. Available from http://repositorium.sdum.uminho.pt/ bitstream/1822/35328/1/document_21039_1.pdf. Rajasulochana, P., & Preethy, V. (2016). Comparison on efficiency of various techniques in treatment of waste and sewage water—A comprehensive review. Resources Technology, 2, 175 184. Rodrı´guez-Pe´rez, C., Segura-Carretero, A., Contreras, M., & del, M. (2019). Phenolic compounds as natural and multifunctional anti-obesity agents: A review. Critical Reviews in Food Science and Nutrition, 59, 1212 1229. Sawasdee, S.C., & Stathopoulos, C.E. (2017). Extraction, isolation and utilization of bioactive compounds from fruit juice industry waste. ,https://rke.abertay. ac.uk/ws/portalfiles/portal/14655600/Stathopoulos_Extraction_ IsolationAndUtilizationOfBioactiveCompounds_Author_2018.pdf.. Silva, R. F. M., & Pogacnik, L. (2020). Polyphenols from food and natural products: Neuroprotection and safety. Antioxidants, 9(61). Stelluti, S., Caser, M., Demasi, S., & Scariot, V. (2021). Sustainable processing of floral bio-residues of saffron (Crocus sativus L.) for valuable biorefinery products. Plants, 10, 1 15. Available from https://doi.org/10.3390/ plants10030523. Stephenson, T., Brindle, K., Judd, S., & Jefferson, B. (2000). Membrane bioreactors for wastewater treatments. London: IWA Publishing. Tekile, A., Kim, I., & Lee, J.-Y. (2017). Applications of ozone micro- and nanobubble technologies in water and wastewater treatment: Review. Journal of Korean Society of Water and Wastewater, 31(6), 481 490. Toop, T. A., Ward, S., Oldfield, T., Hull, M., Kirby, M. E., & Theodorou, M. K. (2017). AgroCycle—developing a circular economy in agriculture. Energy Procedia, 123, 76 78. In J. K. Sahu (Ed.), Advances in food process engineering (pp. 595 629). USA: Taylor and Francis Group. Valente, J.M. L.D. (2015). Subprodutos alimentares: Novas alternativas e possiveis aplicac¸o˜es farmaceˆuticas. Unpublished Master’s thesis, Universidade Fernando Pessoa. ,https://bdigital.ufp.pt/bitstream/10284/5312/1/PPG_23519.pdf.. Vidal, C.S. (2020). Desenvolvimento de uma metodologia modelo para obtenc¸a˜o de plissacarı´deos de de parede celular de resı´duos agroindustriais. ,https:// www.alice.cnptia.embrapa.br/bitstream/doc/1130975/1/TS2020.026.pdf..

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2 Opportunities for the valorization of waste generated by the plantbased milk substitutes industry D. Lorente, S. Duarte Serna, E. Betoret and N. Betoret Institute of Food Engineering for Development, Universitat Polite`cnica de Vale`ncia, Vale`ncia, Spain

2.1

Introduction

Health concerns are increasingly present in today’s society. That is why consumers are demanding more and more the presence of healthy products on the market; therefore the development of new products is a priority for companies in order to satisfy the consumers’ demand (Butnariu & Sarac, 2019). Some of the many products that are part of this healthy trend are vegetable drinks, also called plant-based beverages (Sethi, Tyagi, & Anurag, 2016). Plant-based beverages are drinks made from a vegetable raw material, mainly cereals but also nuts and legumes. Although their appearance is very reminiscent of milk, their composition and nutritive value are very diverse, and in some countries they cannot legally be named vegetable milks because the term “milk” can refer only to secretions from the mammary gland of food-producing animals. It is therefore not a milk substitute even though the consumption pattern is very similar to that of milk and a large number of consumers turn to this type of beverage to replace milk to some extent, either because they are lactose intolerant, they are allergic to cow’s milk, or for ideological reasons. It is worth mentioning that vegans, people who do not consume any animal products, including meat, milk, eggs, honey, and other products in the same category, represent a significant portion of the consumers of plant-based drinks. Vegans usually turn to this type of product to replace milk. Worldwide, 11% of people claim to be vegetarians and 3% say they are vegans, which represents an increase of 52% and 153%, respectively, since 2016 (Silva, Silva, & Ribeiro, 2020). Plant-based Advanced Technologies in Wastewater Treatment. DOI: https://doi.org/10.1016/B978-0-323-88510-2.00004-X Copyright© 2023 Elsevier Inc. All rights reserved.

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Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

beverages are also of great interest to people who want to prevent hypercholesterolemia, owing to the absence of cholesterol in these beverages. More and more plant-based drinks are becoming available in supermarkets, whereas a few years ago they was rarer products. The market for plant-based drinks is continuously growing. For instance, in North America, milk consumption per capita has declined over the last decade, while there has been a substantial growth in the plant-based milk alternative beverage industry over the last few decades (Chalupa-Krebzdak, Long, & Bohrer, 2018). In Spain the consumption of vegetable drinks was 226,104.33 L in 2017, and it increased to 228,565.57 L in 2019, evidence of the growth of this trend (MAPAMA, 2019). Soy drinks were among the first to become popular, owing to its nutritional composition, but nowadays, beverages based on cereals, nuts, and oilseed are trending, owing to their functional properties. Some of the raw materials include rice, oats, spelt, quinoa, walnuts, almonds, hazelnuts, canary seed, sesame, coconut, tiger nut, and so on. Simultaneously, soybean beverages are losing popularity because they have a lower consumer sensory acceptability (Sethi et al., 2016). While there is no official classification for plant-based beverages, Sethi et al. (2016) suggest the following five categories as the main groups: • Cereal-based beverages, including oat, rice, corn, and spelt wheat drinks • Pseudo-cereal-based beverages, including quinoa, and amaranth drinks • Nut-based beverages, including almond, coconut, hazelnut, pistachio, and walnut drinks • Legume-based beverages, including soy, peanut, lupine, and bean drinks • Seed-based beverages, including sesame, linseed, sunflower seed, and hemp drinks Plant-based beverages are rich in antioxidant compounds and help to prevent diseases, as mentioned before. Moreover, they are a cheaper product compared to conventional milks. However, plantbased beverages have low bioavailability of minerals and vitamins, owing to some antinutrients and a lack of protein (Aydar, Tutuncu, & Ozcelik, 2020). Only legume-based beverages have a high protein content (Vanga & Raghavan, 2018). Many of the plant-based drinks on the market are enriched with some components, such as calcium or vitamins, to make up for deficiencies in these nutrients. Another solution to compensate for the lack of nutrients is to mix two or more kind of beverages, for example, rice and coconut (Vanga & Raghavan, 2018).

Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

The manufacturing process for all these beverages is very similar. The raw material is soaked in water and then milled. After that, the liquid phase is separated from the solid one and subjected to homogenization and pasteurization operations to stabilize and commercialize the final product (Rincon, Braz Assunc¸a˜o Botelho, & de Alencar, 2020). The solid material that is left is usually called press cake, and it is usually discarded or used as animal feed or fertilizer (Bartkiene et al., 2020). Although most of the waste that is generated in the vegetable beverage industry is solid, there is also some liquid waste. Liquid wastes are typically generated in previous stages, such as milling or washing. For instance, in the rice industry, wastewater is generated during rice milling. This byproduct is commonly called rice mill wastewater. Nowadays, one of the biggest problems in the food industry is the massive generation of waste and byproducts. It is estimated that one-third of the food that is produced is lost during the production process (Comunian, Silva, & Souza, 2021). Governments and other authorities strive to reduce the negative impact of food losses and waste. The European Union is working to implement the goals of the United Nations 2030 Agenda, which include sustainable development. “Action on sustainable food systems and preventing food waste (SDG 12) will be taken through the EU Platform on Food Losses and Food Waste, to support the UN target of halving per capita global food waste by 2030. Targeted action is planned to facilitate food donation and the safe use of food not suited for human consumption for production of animal feed as well as more effective date marking on food” (EUR-Lex—52016DC0739—EN—EUR-Lex, n.d.). At the same time, food companies are working to reduce food waste and to contribute to the circular economy; an economic model in which the value of products, materials, and resources remains in the economy for as long as possible, thus reducing waste generation. The current economic model based on the sequence extract, produce, consume, throw away is no longer sustainable, owing to the volume of waste that is generated (EEA, 2016). To contribute to zero waste, research is needed into the potential uses of all food waste, including that produced by vegetable beverages. Solid byproducts or wastes generated in the plant-based beverage industry contain a considerable amount of nutritional compounds that may be useful for the development of functional foods (Bartkiene et al., 2020). Bioactive compounds such as vitamins, phenolic compounds, carotenoids, pigments, and polyunsaturated fatty acid make these byproducts very valuable for the industry, even though the bioactive compounds are

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Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

unstable in some industrial processes (Comunian et al., 2021). Moreover, other byproducts are generated during the industrial process, especially in the first stages, such as the remove of bran layers of cereals or blanching nut skins. These kinds of byproducts, which usually are discharged, have a good nutritional profile and therefore have the potential for valuable applications in the food industry (Comunian et al., 2021). Depending on their nutritional composition and properties, they will be better for one use or application than another. Finally, as a last resort, if the byproduct cannot be used directly for the development of a product, the components of interest can be extracted in order not to waste this source of nutrients. In this context, the aim of this chapter is to overview the nature, composition, and properties of byproducts and wastes from the plant-based beverage industry and to explore valorization opportunities in the food industry.

2.2

Nature of byproducts obtained from cereals, nuts, and legumes: research evolution

There is very little liquid waste from the plant-based beverages industry, since the liquid that is extracted is the intended for sale and consumption. Liquid wastes are those generated in previous stages, such as milling or washing. The cleaning water can be usually be reused with minimum or no treatment, as the water condition is relatively pure with the low level of impurities. Contact water, such as soaking and cooking water, is characterized by a high chemical oxygen demand and biochemical oxygen demand due to protein, polypeptide, oligosaccharide, and other organic components. Although most plant-based beverages are derived from cereals and nuts, soybeans have been crucial in the development of this industry. This legume was the first used to produce a plant-based beverage. It was first consumed in China. During the second half of the 20th century its consumption spread all over the world (Mordor Intelligence, 2017). The main solid residue from soybean industrialization is okara. Okara is the byproduct that is obtained from the production of soy milk and tofu. It is the insoluble part of soybeans and looks like an off-white pulp (Harthan & Cherney, 2017). About 1.1 kilogram of fresh okara is produced from each kilogram of soybean processed into soy milk or tofu (Li et al., 2013;

Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

Lu, Liu, & Li, 2013). This byproduct is also known as soybean curd residue or soybean residue (Jose´ Villanueva-Sua´rez, Luisa Pe´rez-Co´zar, & Redondo-Cuenca, 2013). Most of the okara is dumped; on only some occasions, it is destined for animal feeding. Owing to the increasing popularity of soybean products during the last decade, okara is the byproduct for which more information is available compared to other wastes from plantbased beverage industry. It is considered a very interesting byproduct whose nutritional composition and potential uses will be detailed in the following sections. Rice (Oryza sativa) is a monocotyledon crop belonging to the Poaceae family. Worldwide, the annual production of this grain is around 480 million metric tons. It grows in more than 100 countries, China and India being the main producers (Amagliani, O’Regan, Kelly, & O’Mahony, 2017). Rice is considered one of the cheapest cereals in terms of production. Therefore it is predictable that from this amount of rice, a very large quantity of waste will be generated per year. During the process of rice industrialization a fraction of the rice grains are usually separated because they are broken. Broken rice makes up 15% of the total processed rice. It is sold at 30% 50% of the rice value and is usually used for beverages or animal feed (da Silva et al., 2020). Besides broken rice, a considerable amount of the grain’s outer layers is removed during rice processing, increasing the concentration of nutrients in the bran and rendering it an important source of nutrients that seems relevant for the food industry and therefore for human consumption (Faria, Bassinello, & Penteado, 2012). Moreover, during rice milling three kinds of byproducts are generated: rice mill wastewater, rice husks, and rice bran. The husks and bran are equivalent to 20% 25% and 10% of the unpeeled grain weight, respectively (Rodrı´guez-Restrepo, Ferreira-Santos, Orrego, Teixeira, & Rocha, 2020). Rice bran is the major byproduct ˜os, Va´zquez, & that is obtained in rice processing (Saman, Fucin Pandiella, 2019). Bran constitutes approximately 8% 10% (w/w) of the whole rice kernel (Sohail, Rakha, Butt, Iqbal, & Rashid, 2017). It includes pericarp, seed coat, nucellus, aleurone, pulverized embryo, and some starchy endosperm and hull fragments (Amagliani et al., 2017). The rice husk is the outer layer of the whole grain, and it is not as useful in the food industry as bran. This is mainly because rice husks are not edible, and although they do have nutrients of interest, such as antioxidative phenolic compounds, they are difficult to extract. Therefore rice husks have been less investigated than rice bran (Wanyo, Meeso, & Siriamornpun, 2014). Recently, the valorization of rice bran has been gaining in importance.

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Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

Oat (Avena sativa) is a cereal belonging to the Poaceae family. It is an annual crop that is used for both animal and human nutrition. As with rice, the main byproduct of oat is bran. Oat bran is a very common byproduct that is generated during milling and constitutes about 50% of the whole grain (based on dry matter content). Specifically, oat bran contains β-glucans, which are proven to have cholesterol-lowering effects (Whitehead, Beck, Tosh, & Wolever, 2014). For example, it has been added to meat products to reduce the adverse effects of cholesterol (Talukder & Sharma, 2010). Furthermore, some studies have indicated that consumption of oat- and barley-rich foods may reduce the risk of some chronic diseases such as coronary heart disease, type 2 diabetes, and cancer (Gangopadhyay, Hossain, Rai, & Brunton, 2015). Apart from bran, there exist other byproducts related to oat. Starch is the major component of oat kernels and may account up to 60% of the dry weight. As a byproduct of oat processing and fractionation, the starch can also be utilized for food and nonfood applications (Zhu, 2017). The oat hull is the outer layer of the entire oat grain, being 20% 30% of the total weight of oat. Hulls can be processed to obtain oat hull fiber, which contains 90% insoluble fiber (Daou & Zhang, 2012). It is not as widely used in the food industry as oat bran. Almond (Prunus dulcis) is the nut of the almond tree. A brown skin covers the kernel or edible part, the skin is covered by a shell (hardened endocarp), and the outermost layer is the hull (flesh but thin mesocarp, green shell cover). During almond processing, these layers are removed, reducing the edible part of the almond to 40%. The main industrial processes that affect the skin are blanching or roasting, and during blanching, two other byproducts are generated: blanched skin (the layer next to the kernel) and blanch water. Almond hulls are the most discarded byproduct annually, with a total of 6 million tons (Prgomet, Goncalves, Domı´nguez-Perles, Pascual-Seva, & Barros, 2017). Almond shells are an underutilized agriculture byproduct (Gong, Holtman, Franqui-Espiet, Orts, & Zhao, 2011). Around 0.8 1.7 M tons of almond shells are discarded annually (Prgomet et al., 2017). Although they are not edible, almond shells have numerous applications in the food industry. The main use is the extraction of compounds such as xylitol or xylooligosaccharides (Gong et al., 2011). Another valuable residue is almond press cake. It is the byproduct resulting from the pressing of almonds to obtain oil (de Souza, Dias, Koblitz, & de Moura Bell, 2020). Almond cake, like almond shells, is used for extraction of valuable components such as oil or proteins.

Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

There are many published research works that analyze the effect of extraction methods on the quality and quantity of extracted compounds. However, scientific literature about composition and uses of press cake from almond milk is scarce. There is no term for describing the solid that remains after obtaining an almond beverage. The term “almond pulp” is sometimes used in homemade recipes; however, it is not mentioned in any scientific article. This demonstrates that this byproduct has not yet been studied and could be very interesting to research. The last residue that we consider in this review comes from tiger nuts. Tiger nut (Cyperus esculentus), or chufa, is a weed plant from tropical and Mediterranean regions. These tubers are used mainly to prepare a milk-like beverage known as horchata de chufa, a very popular beverage in the Valencian community (Sa´nchez-Zapata et al., 2012). 50 million liters of this drink are consumed every year, generating an estimated value of 60 million euros. During its production there result different byproducts, which can represent up to 60% of the raw material (Rosello´-Soto et al., 2019). Horchata is obtained by the mechanical pressing of tubers, followed by the extraction of the liquid fraction (Codina-Torrella, Guamis, Ferragut, & Trujillo, 2017). After the mechanical extraction the byproduct that is obtained can be pressed again to separate it into solid and liquid components. The liquid extraction is called horchata drained water; the solid extraction is known as solid tiger nut byproduct. The drained water is therefore a liquid that is not very abundant but still contains nutrients. Sa´nchez-Zapata et al. (2012) state that compounds present in this byproduct are beneficial from technological and health-related points of view. They also state that if horchata drained water is treated, it could be reused to reduce water consumption. The solid byproduct is an excellent source of insoluble fiber, which is normally destined to organic mass for combustion, compost, and feed pro´ , Barat, Alava, & Grau, 2017). Solid tiger nut duction (Verdu byproduct can be used in the development of new products, thus potentially responding to society’s demand for functional foods. Additionally, these byproducts could be a valuable source of oils and other compounds, such as macronutrients and micronutrients or even bioactive compounds (Rosello´-Soto et al., 2018). Fig. 2.1 shows the evolution in the number of published scientific works related to byproducts from the plant-based beverages industry and the main areas of research interest. The key words “raw material press cake” resulted in published works

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Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

related to byproducts from plant-based beverages industry. The addition of the terms “functional food” or “bioactive compounds” allows us to discriminate the interest and the application of the byproduct being considered. To numerically quantify the evolution in the number of published scientific works, the relative increase (in percent) has been calculated, considering the difference in the number of items between the two periods 2011 2015 and 2016 2020, referred to as the number of items in the period 2011 2015. Additionally, searches for soybean have been merged with okara to consider the most relevant information about this byproduct. It can be noted in Fig. 2.1 that the main byproducts considered on scientific research are those from rice and soy, followed by almond and oat. There are more published works in relation to functional foods than in relation to bioactive components. Although the content of bioactive components is one of the most relevant characteristics that determines the use of these byproducts, many studies consider its use as a technological ingredient that is capable of improving both the nutritional and

Figure 2.1 Number of scientific published works related to byproducts from the plant-based beverages industry and functional food area. The relative increase was calculated as the difference in the number of articles published between the periods 2016 2020 and 2011 2015, divided by the number of articles published in the period 2011 2015, expressed as a percentage. The title of each graphic corresponds to the keywords used in the search.

Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

the technological properties of the final foods. Regarding the relative increase observed in the last 5 years compared to the previous 5-year period, it is high in all byproducts and greater in relation to bioactive compounds. In addition, the number of research works with okara, almonds and oats has increased more than with the rest of byproducts. Although there has been a considerable increase in research in this area, there is still much to investigate. While some wastes have very clear uses, others remain an uncertainty in the food industry.

2.3

Nutrient composition

It is essential to know the composition of considered byproducts to define the possible uses and to establish the most important valorization opportunities. Byproducts composition will determine their nutritional and technological properties. The type and amount of fiber, the lipid profile and the kind and percentage of proteins will determine the nutritive and dietary value, water, and oil interaction properties, foaming capacity, and other relevant properties for food industry applications. Table 2.1 shows published data of macronutrient in the byproducts considered in this review. In addition, it is necessary to consider antinutritional factors, which are the compounds that affect the nutritional value of some foods, especially seeds, by interfering with or inhibiting the assimilation of nutrients. Some of these byproducts have antinutritional factors in their composition. For instance, rice bran and oat bran contain polyphenols, oxalates, phytate, and trypsin inhibitors. Soybeans contain saponins, tannins, trypsin inhibitors, oxalate, and phytate (Nikmaram et al., 2017). Therefore the use of some of these byproducts is limited to animal feed (Vong & Liu, 2016). The presence of several antinutrients in soy compared to other raw materials makes consumers reject soy drinks and choose other alternatives. The proper treatment of these compounds can remove the antinutritional factors and increase the value of the byproducts. Fermentation is one of the best solutions to overcome the presence of antinutrients in plant-based beverages. Adeyemo and Onilude (2013) used Lactobacillus plantarum and the enzymes produced by this microorganism to reduce the antinutritional factors from soybean. Other methods to improve the nutritional quality of legumes and cereals are thermal treatment, enzyme application, soaking, sprouting, and irradiation (Nikmaram et al., 2017).

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Table 2.1 Macronutrient composition of different byproducts. Byproduct

Protein

Fat

Dietary fiber

Fiber Fiber Carbohydrate Units soluble insoluble

References

Byproduct from tofu Byproduct from tofu Byproduct okara

15.31 6 0.33 28.52

5.90 6 0.01 9.84

58.60 6 0.20 55.48

1.91 6 0.06 4.71

55.63 6 0.07 50.77

Lu et al. (2013)

Okara (fresh matter)

33.4 6 0.3 7.91 6 0.25

8.5 6 0.3 6.22 6 0.45

54.3 6 2.3 13.83 6 0.49

4.2 6 1.8 3.25 6 0.09

50.1 6 2.9 10.58 6 0.40

Okara

15.2 33.4 8.3 10.9 42.4 58.1 4.2 14.6 40.2 50.8 3.8 5.3

Enzymatic hydrolyzed okara Okara

33.4 6 1.2

9.6 6 0.1

39.1 6 0.5 25.5

16 6 2 12.0

12.2

32.6

12.32 6 0.24 21.91 6 0.43 11.77 6 0.0 12.32 6 0.2 15.00 6 0.4 12.9 6 0.1 12.8 6 0.3

20.31 6 0.92 4.31 6 0.43 12.27 6 0.7 20.31 6 0.9 22.40 6 0.3 16.53 6 0.8 13.9 6 0.2

28.60 6 0.32 53.25 6 0.79

17.92 6 0.26

g/100 g dry Castellanos Fuentes et al. (2020) matter g/100 g dry Jose´ Villanueva-Sua´rez et al. (2013) matter g/100 g Gul et al. (2015)

1.38 6 0.18

g/100 g

Gul et al. (2015)

71.04 6 0.2

% dry matter % dry matter % dry matter % dry matter % dry matter

Huang and Lai (2016)

Okara Rice bran Bran fiber rice Rice bran (Thailand) Rice bran (Korea) Rice bran (Iran) Rice bran (Portugal) Rice bran (Colombia)

46.4 6 2.9

10.7 6 3.3

2.56 3.9 6 0.2 2.44 6 1.29

35.7 6 1.3 31 6 5

62.07 6 0.2 56.2 6 3.5

% dry matter % dry matter g/100 g dry matter g/100 g fresh matter g/100 g dry matter g/100 g dry matter

Redondo-Cuenca et al. (2008) Mateos-Aparicio et al. (2010a); Mateos-Aparicio et al. (2010b); Mateos-Aparicio et al. (2010c) Guimara˜es et al. (2018)

Vong and Liu (2016) Jose´ Villanueva-Sua´rez et al. (2013)

Choi et al. (2011) Rafe et al. (2017) Rodrı´guez-Restrepo et al. (2020) Rodrı´guez-Restrepo et al. (2020) (Continued )

Table 2.1 (Continued) Byproduct

Protein

Fat

Dietary fiber

Rice bran

14.7 6 0.03 10.90 6 0.09 10.73 6 0.06 11.73 6 0.07 10.01 6 0.6 17.5

20.9 6 0.20 12.45 6 0.23 11.62 6 0.64 11.04 6 0.14 10.80 6 0.08 13.1

6.66 6 0.05 13.51 6 2.08 10.97 6 0.07 11.95 6 0.15 10.16 6 0.19 23.34

2.17

21.17

52.33

19.25

17.2

14.90

1.80

13.10

48.55

Whole rice bran 16.61

17.87

24.15

1.48

22.67

33.24

Treated rice bran Roasted rice bran Oat bran

19.38

20.05

25.38

0.74

24.64

28.21

18.93

18.34

20.45

0.11

20.34

33.76

Rice bran (Thailand) Rice bran (Thailand) Black rice bran (Thailand) Red rice bran (Thailand) Stabilized rice bran Probiotic rice bran

Oat bran extract Oat bran Oat bran Oat hull

17.93 6 6.84 6 0.15 0.02 13.1 6 0.4 ,1.7

15.55 6 1.05 1.1

17.0 16.6 6 0.56

17 16.5 6 0.84

7.5 7.5 6 0.65

Fiber Fiber Carbohydrate Units soluble insoluble 52.3 6 0.26

% w/w

Amagliani et al. (2017)

45.31 6 1.00

% dry matter % dry matter % dry matter % dry matter g/100 g fresh matter g/100 g fresh matter Dry weight basis Dry weight basis Dry weight basis g/100 g dry matter % fresh matter g/100 g % fresh matter

Moongngarm et al. (2012)

47.56 6 0.82 47.86 6 1.12 49.96 6 1.34

11.47 6 0.92 39.45 46 7.9 6 0.49

References

8.5 6 0.38 90

Moongngarm et al. (2012) Moongngarm et al. (2012) Moongngarm et al. (2012) Bhosale and Vijayalakshmi (2015)

Bhosale and Vijayalakshmi (2015)

Faria et al. (2012) Faria et al. (2012) Faria et al. (2012) Nedeljkovi´c et al. (2017) Ralla et al. (2018) Herranen et al. (2010) Talukder and Sharma (2010) Daou and Zhang (2012) (Continued )

Table 2.1 (Continued) Byproduct

Protein

Fat

Dietary fiber

Fiber Fiber Carbohydrate Units soluble insoluble

Press cake almond Wheat flour Baru flour (almond) Almond press cake Tiger nut (Egypt) Solid byproduct tiger nut

7.34 6 0.01 9.8 29.46 6 1.04 37.20 6 0.72 4.33

3.63 6 0.09 1.4 11.84 6 0.69 16.25 6 0.79 22.14

63.68 6 0.01 2.3 38.80 6 3.74

78.97 6 0.27

1.75 6 0.12

8.85 6 1.11

59.71 6 0.03

Horchata drained water

16.90 6 0.05

8.27 6 0.03

Tiger nut milk

1.1

3.9

2.35

1.83

Tiger nut milk byproduct Tiger nut flour

5.5

16.0

30.55

39.6

5.1

28.4

19.25

38.0

5.07 6 1.31

33.73 6 2.43

75.1 11.57

15.47 0.11

59.61 6 0.08 67.44 6 0.13

% fresh matter g/ kg fresh matter g/100 g g/100 g % fresh matter % dry matter g/100 g fresh weight g/100 g fresh weight % flour weight % flour weight % flour weight

References

Aydos et al. (2019) Pineli et al. (2015) Pineli et al. (2015) Souza et al. (2019)

Sa´nchez-Zapata et al. (2009)

Sa´nchez-Zapata et al. (2012)

Aguilar et al. (2015) Aguilar et al. (2015) Aguilar et al. (2015)

Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

2.3.1

Okara

A variety of raw materials, geographical locations, and processing factors are some of the reasons why nutritional values differ among raw materials. Soybeans usually have variations in their chemical composition depending on the variety, cultural practices, solar incidence, and other environmental factors. Therefore during the water-soluble soybean extraction process the product characteristics can vary depending on the feedstock that is used (Guimara˜es et al., 2018). In relation to its chemical composition, okara has a high moisture content, which results in short durability and difficulty in conservation and commercialization (Guimara˜es et al., 2018). This high moisture content, which is around 70% 80%, makes it susceptible to spoilage, and most of it is dumped and burned as waste (Yang, Fu, & Yang, 2020). This is the main disadvantage related to the utilization of this byproduct. Some solutions proposed by different authors will be discussed later in this chapter. The main carbohydrate in okara is cellulose, which is a very rich source of dietary fiber. The insoluble dietary fiber (IDF) accounts for more than 90% of the total dietary fiber and has the potential to be used in the food industry as a functional ingredient (Wang et al., 2020). IDF increases fecal bulk and reduces gastrointestinal transit time. Moreover, it seems to have a positive effect on diarrhea and constipation and as a treatment for irritable bowel (Mateos-Aparicio et al., 2010a, 2010b, 2010c). Other compounds of okara dietary fiber are arabinose, galactose, xylose, and galacturonic acid (Lu et al., 2013). In addition, okara has a considerable amount of high-quality proteins and, especially, essential amino acids. Soybean curd residue contains about 27% protein (dry basis) with good nutritional quality and a superior protein efficiency ratio, which shows potential as a good source of vegetable protein for human consumption (Jose´ Villanueva-Sua´rez et al., 2013). Moreover, its technological properties, such as emulsification, water- and fat-binding, and foaming properties, make it suitable for extraction and isolation. The most predominant amino acids in okara are glutamic acid, aspartic acid, and tyrosine plus phenylalanine (Li et al., 2013). Okara contains other components of importance, such as isoflavones. About 12% 30% of the isoflavones in soybeans remain in okara during soy milk production. These isoflavones are mainly glucosides (28.9%), but there are also aglycones (15.4%) and a smaller quantity of acetyl genistin (0.89%) (Vong

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Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

& Liu, 2016). Research suggests that soybean isoflavone affects resistance to cancer, prevents osteoporosis, diminishes antibacterial inflammation, and controls cardiovascular disease (Jose´ Villanueva-Sua´rez et al., 2013). Finally, minerals are not as relevant as the previous components, but they also bring benefits to the byproduct, such as antioxidant capacity. The main microelement in okara is potassium, but it also contains iron, manganese and zinc, among others.

2.3.2

Rice

Carbohydrates represent the major constituents of cereals, including rice. Around 34% 62% of carbohydrates are reported to be available in bran (Amagliani et al., 2017). Starch is the most abundant carbohydrate in rice; however, it is more prevalent in the grain than in the bran. The carbohydrates that are present in rice bran include arabinoxylans, glucans, and hemicellulose (Gul et al., 2015). Rice fiber is concentrated mainly in the outer layers of the rice caryopsis (Amagliani et al., 2017). A few articles detail the percentage of insoluble and soluble dietary fiber (SDF), but according to Table 2.1, insoluble fiber is much more abundant in bran than soluble fiber (i.e., 16.1 times more abundant). The proteins that are present in rice bran are glutelin (22% 45%), globulin (13% 36%), albumin (12.5% 43%), and a few portions of prolamin (1% 5%) (Rodrı´guez-Restrepo et al., 2020). Nutritional quality of rice proteins is estimated to be equivalent or higher than other cereals but considerably lower than proteins derived from animal sources, legumes, and oilseed crops. There are studies on different methods of extraction in order to use rice proteins as value-added ingredients in nutritional products, including sport nutrition supplements and infant formulas (Amagliani et al., 2017). Minerals are generally more concentrated in the outer layers of rice grain, being mainly distributed between rice bran (around 72%) and rice endosperm or white rice (around 28%). As it is well known, mineral content is strongly influenced by cultivation conditions, including soil structure condition and fertilization, as well as by rice processing (Faria et al., 2012). Utilization of rice bran is limited due to enzymatic activity after rice dehulling. This byproduct is rich in lipids and an intense lipase activity in the presence of endogenous lipoxygenase causes rapid deterioration of these lipids by rancidification. Because of lipid susceptibility, the commercial use of rice bran

Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

requires enzymatic inactivation immediately after bran separation to avoid fatty acid liberation, extend its shelf life and allow its commercialization for human consumption (Faria et al., 2012). Therefore the method of stabilization results to be very important because it modifies bran composition. Rice husk is less popular than bran. It contains an antioxidant defense system to protect the rice seed from oxidative stress. The major phenolic compounds that are present in rice husk are ferulic acid and p-coumaric acid along with isovitexin, a potent antioxidant (Singh, 2018).

2.3.3

Oat

Carbohydrates are the major constituent of oat bran, especially starch but also arabinoxylan and oligosaccharides. Besides carbohydrates, oat contains proteins, such as globulins and α- and β-polypeptides, which account for around 80% of the total protein content, as well as albumins, prolamins, and glutelins. Ralla et al. (2018) demonstrated that oat bran extract containing surface-active saponins and proteins might be used as a natural emulsifier. One very valuable component in oat is β-glucan. Oat β-glucan is a linear polysaccharide (1-3), (1-4)-β-D-glucan, which is a soluble oat fiber being able to attenuate blood postprandial glycemic and insulinemic responses, as well as to lower blood total cholesterol and low-density lipoprotein cholesterol. In addition, it can improve high-density lipoprotein cholesterol and blood lipid profiles and to maintain body weight (Daou & Zhang, 2012). The high fiber content of the oat bran is followed by a good source of B complex vitamins, fat, minerals, tocopherols, and phenolic compounds (Patel, 2015).

2.3.4

Almond

Few information about composition of almond byproducts is available. The main contribution about macronutrients highlights its fiber as insoluble and an outstanding content compared to other nuts. The main insoluble fiber-forming compounds in the almond shell are cellulose, ranging from 30% to 50%, hemicellulose in 19% 29% and lignin in 20% 50% (Prgomet et al., 2017). Most of the published research works seek to determine phenolic compounds profile and antioxidant properties.

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Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

Phenolic compounds are aromatic secondary metabolites in plants, which are found largely in fruits, vegetables, cereals, and beverages, and constitute a main part of the human diet. Some of the most popular phenolic compounds are resveratrol in wine and isoflavones, which are abundant in soya. Almonds are important sources of phenolic compounds; almond hulls, almond skins, almond shells, and almond fruits contain those compounds (Barreira, Ferreira, Oliveira, & Pereira, 2010). Naringenin is the most abundant identified compound in almonds, followed by kaempferol-3-O-rutinoside, kaempferol-3O-glucoside, and kaempferol and eriodictyol-7-O-glucoside. Blanched almond skin was found to be the richest in all the classes of compounds analyzed and the highest in scavenging and cytoprotective activity (Smeriglio et al., 2016). In particular, it is estimated that around 60% 80% of the almond phenolic compounds are found in the skin. However, during the blanching process, some of these compounds can be lost because of the exposure of the almond to high temperatures. Even though almond skin is exposed to lower temperatures compared to roasting (2 minutes at a temperature of almost 100 C is the time and temperature used in the industry for blanching), polyphenols are easily lost by hot water blanching (Prgomet et al., 2017). Almond shell contains trace amounts of phenolic compounds, such as caffeic acid, ferulic acid, quercetin, sinapinic acid, kaempferol, isorhamnetin, and p-coumaric acid. These phenolic compounds have antioxidant activity due to their redox properties. Some of the antioxidant compounds that are present in almond hull are chlorogenic acid, cryptochlorogenic acid, and neochlorogenic acid (Meshkini, 2016). Phenolic compounds are also found in blanched skins and blanching water. Smeriglio et al. (2016) characterized the phenolic content and antioxidant activity of blanched skin and blanch water within the natural almond skin. The results showed that the total phenolic content expressed in milligrams gallic acid equivalent (GAE) per 100 g of fresh weight was 703.0 6 15.9 for natural skin, 313.8 6 2.3 for blanched skin, and 73.9 6 0.5 for blanch water. Water solubility of these compounds determines their presence or absence. The presence of antioxidant compounds with high added value highlights the potential use of blanch water in the nutraceutical industry (Prgomet et al., 2017). In particular, blanch water precipitate contains compounds such as nonpolar aglycones (isorhamnetin and kaempferol), partially insoluble glycosides (quercetin glycoside, kaempferol glycoside, rutinoside, isorhamnetin glycoside, rutinoside, and

Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

naringenin glucoside), and even more water-soluble catechins. This demonstrates that all these compounds permeate the skin in blanch water, dissolve to their limit of solubility, and then precipitate out (Prgomet et al., 2017).

2.3.5

Tiger nut

Available data reveal the tiger nut to be rich in essential dietary constituents, such as proteins (3.28% 8.45%), fats (22.14% 44.92%), fibers (8.26% 15.47%), and ash (1.60% 2.60%). The industrially relevant recoverable compounds are starch, soluble carbohydrates (mainly in the form of horchata), lipids, and fibers (Rosello´-Soto et al., 2018). The solid byproduct from horchata has an outstanding amount of dietary fiber, being the main component of interest in this kind of product; 99.8% of this dietary fiber is insoluble. However, it is generally accepted that fiber sources suitable to be used as food ingredients should have a ratio SDF to IDF close to 1/3. Tiger nut byproduct, adequately complemented with other ingredients could be used in dietetic-physiological products. The intake of IDF is related to the feeling of satiety, as fiber absorbs water, takes up space in the stomach, and reduces the need to consume more food (Sa´nchez-Zapata, Dı´az-Vela, Pe´rez-Chabela, Pe´rez-Alvarez, & Ferna´ndez-Lo´pez, 2013). This tuber is also notable for its high fat content, which is the reason why the tiger nut is often a good raw material for oil extraction. In particular, the lipid profile of the tiger nut includes a high percentage of monounsaturated fatty acids, oleic acid being the most abundant of all the monounsaturated fatty acids. In smaller proportions there are polyunsaturated acids, such as linoleic acid (Rosello´-Soto et al., 2019). Some research work has been done to evaluate the impact of different techniques of oil extraction from tiger nut byproducts. For example, Rosello´-Soto et al. (2019) studied the effect of supercritical carbon dioxide extraction at different pressures for oil recovery, and the results were positive. The content of α-tocopherol was higher than that obtained with conventional methods of oil extraction. Additionally, it increased the presence of phenolic compounds and showed lower levels of oxidation, avoiding the use of toxic organic solvents that are usually used in conventional extractions. Generally, in the extraction processes, the method that is used determines the quality and nutritional value of the final product. Cold press extraction using organic solvents is considered the

41

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Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

conventional extraction mode, which is used for industrial production of tiger nut oil (Rosello´-Soto et al., 2019). Horchata drained water is a valuable source of antioxidants, owing to the presence of phenols and their reducing power and lipid peroxidation inhibition. In particular, Sa´nchez-Zapata et al. (2012) determined that the total phenolic content in horchata drained water was 169.8 6 10.5 mg GAE/L. These compounds come from the tiger nut cell wall and from food processing, such as organic or inorganic cleaning agents (Sa´nchez-Zapata et al., 2012). Some of the phenolic compounds that are present in tiger nuts are p-hydroxybenzoic acid, vanillic acid, p-hydroxybenzaldehyde, vanillin, p-trans-coumaric acid, trans-ferulic acid, p-cis-coumaric acid, and cis-ferulic acid. They all contribute to improving the antioxidant capacity. Tiger nuts also contain tocopherols, which are described as the most remarkable natural group of antioxidants present in vegetable oils (Gasparre, Pan, da Silva Alves, Rosell, & de J. Berrios, 2020).

2.4

Applications in food industry

To establish applications at industrial level, it is crucial to know the main technological properties of solid waste and the pretreatments that can be used to reduce the biological oxygen demand in wastewater. The following subsections explore these issues in more detail.

2.4.1

Solid wastes or byproducts

The composition and properties of the different byproducts are essential to determine their potential uses. The way in which different compounds interact in a food is also conditioned by their chemical structure and the food structure. Interactions among components (micro and macronutrients including water), the length and branching of polysaccharide chains, the solubility of proteins, and the level of unsaturation of fats are examples of some of the characteristics that will determine functionality of byproducts and the most appropriate applications in each case (Fig. 2.2). Table 2.2 summarizes the main applications of byproducts from plant-based beverages industry considered in the published research works from 2011 to 2020. The most common applications derive from their fiber and antioxidant content and include their use as antioxidants, fiber supplements, fat replacers, gluten replacers, emulsion stabilizers, and water-holding ingredients.

Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

43

Figure 2.2 Main solid waste origin and applications.

Table 2.2 Potential uses of the different byproducts. Byproduct

Featured property

Potential use

References

Okara

Rich in dietary fiber

Castellanos Fuentes et al. (2020)

Fermented okara

Antiosteoporotic effects

Fermented okara

Good water- and oil-holding capacity and swelling capacity index Higher water absorption capacity and emulsifying properties High fiber content

Substrate for preparing food ingredients containing L. casei ATCC 393 Products with high antiosteoporotic effects Technological ingredient in food industry Functional and healthy food products

Hu et al. (2019)

Formulation of enriched vegetal paste Additive for different food systems

Guimara˜es et al. (2018) Wouters, Rombouts, Fierens, Brijs, & Delcour, (2016) Albuquerque et al. (2016) Jose´ VillanuevaSua´rez et al. (2013)

Fermented okara

Okara Okara protein isolate

Low solubility

Okara powder

Rich in nutritional and functional compounds Water and oil retention capacity, swelling capacity.

Enzymatically hydrolyzed okara byproduct Okara powder

Low glycemic index

Substrate to folate production by starter and probiotic cultures Extraction of polysaccharides, functional ingredients, substrate in in vitro fermentability. Flour replacer to make noodles and bread for diabetics

Yang et al. (2020) Wang et al. (2020)

Lu et al. (2013) (Continued )

44

Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

Table 2.2 (Continued) Byproduct

Featured property

Potential use

References

Soybean curd residue

Swelling and water retention capacity

Texturing additive

Okara treated with high hydrostatic pressure. Fermented rice bran and fermented rice flour Water-soluble extract of rice byproduct Rice flour with konjac flour Rice flour Rice bran and broken rice Rice flour, starch, and protein Rice flour with transglutaminase Stabilized rice bran or its components Rice flour

Higher oil retention capacity

Extraction of soluble dietary fiber

Antioxidant properties

Gluten-free cookies

Mateos-Aparicio et al. (2010a, 2010b, 2010c) Mateos-Aparicio et al. (2010a, 2010b, 2010c) Christ-Ribeiro et al. (2021)

Increased viscosity, breakdown, Gluten-free bakery products and hot paste viscosity Hardness and chewiness Gluten-free rice bread Lactose-free drinks

Xu, Zhang, Wang, and Li (2020) Wu et al. (2019) Costa et al. (2017)

Dough consistency, high hydration capacity Water and oil absorption capacity Water and fat absorption, emulsifying and foaming capacity High viscosity

Mancebo et al. (2016). Altindag et al. (2015)

Rice bran oil

Fat stabilizer

Oat bran

Gelling capacity

Oat bran

Gelling capacity

Oat protein

Faster onset of gel formation

Oat bran

Emulsifying properties

Oat bran

Gelling capacity

Oat starch

Swelling capacity

Lactose-free ice cream

Gluten-free cookies Gluten-free cookies

Da Silva et al. (2020)

Supplements in various food Gul et al. (2015) matrices (e.g., bread, pizza, tuna oil, milk powder) Gluten-free rice bread Alvarez-Jubete et al. (2009) Production of fried snacks, beef Lerma-Garcı´a et al. patties, etc. (2009) To maintain firmness and avoid Lima Ribeiro et al. syneresis in petit suisse cheese (2021) Partial fat replacer in cookies Mili´cevi´c et al. (2020) Reduction of syneresis in yogurt Bru¨ckner-Gu¨hmann et al. (2019) To stabilize emulsions, prevent Huc-Mathis et al. coalescence (2019) Partial fat replacer Nedeljkovi´c et al. (2017) Fat replacer Zhu (2017) (Continued )

Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

45

Table 2.2 (Continued) Byproduct

Featured property

Oat bran Oat bran

Lowering glycemic impact Water-holding capacity and emulsion stability Oat starch and Foaming capacity and protein emulsifying activity Almond press cake Foaming capacity from oil extraction Partially delipidified almond flour Blanched almond Water binding capacity skins Almond hulls High antioxidant capacity Flour (byproduct from oil extraction) Almond cake Almond husk Tiger nut flour

Tiger nut flour Tiger nut fiber Unsaturated fatty acids of tiger nut fiber Tiger nut liquid byproducts Tiger nut wet fibrous flour Tiger nut flour Solid tiger nut byproduct

Antioxidant capacity

Potential use

References

Fiber-enriched extruded snacks Fiber enricher in chicken patties

Brennan et al. (2012) Talukder and Sharma (2010) Mirmoghtadaie et al. (2009) de Souza et al. (2020) Barreira et al. (2019)

To improve cake properties Substrate for production of protein and lipids Cookies elaboration

Composite dough with wheat flour

Pasqualone et al. (2018) Protection against oxidative damage Meshkini (2016) and membrane protein degradation Cookie elaboration Pineli et al. (2015)

Antioxidant capacity Lipid peroxidation inhibition Limits starch degradation during extrusion and increases antioxidant activity High emulsifying ability

Natural antioxidant Natural antioxidant Gluten-free snacks

Sarkis et al. (2014) Barreira et al. (2010) Gasparre et al. (2020)

Gluten-free baking

Extraordinary water and oil holding capacities Beneficial fatty acid profile

Healthier fiber-rich meat products

Rosello´-Soto et al. (2018) Rosello´-Soto et al. (2018) Rosello´-Soto et al. (2018)

Antioxidant capacity Low wettability and diffusion of water and oil Emulsifying and shortening capacity

To improve nutritional quality of Longaniza de Pascua sausage

Rosello´-Soto et al. (2018) To produce bread, cakes, and snacks Verdu´ et al. (2017)

Water replacer on meat

Gluten free baking

Aguilar et al. (2015)

Gluten free baking

Aguilar et al. (2015) (Continued )

46

Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

Table 2.2 (Continued) Byproduct

Featured property

Potential use

References

Horchata drained water Horchata drained water Dietary fiber powder

Natural antioxidant

Substitute of water addition to foods Inhibition of lipid peroxidation

Sa´nchez-Zapata et al. (2012) Sa´nchez-Zapata et al. (2012) Sa´nchez-Zapata et al. (2009)

Dietary fiber powder Solid tiger nut byproduct Solid tiger nut byproduct

Important antioxidant properties Low water absorption and adsorption, high emulsifying activity and stability High water-holding capacity

High oil-holding capacity

Fiber enricher in food products

Products requiring hydration, viscosity development, and freshness preservation Cooked meat products

High emulsifying activity and great emulsion stability

Sa´nchez-Zapata et al. (2009) Sa´nchez-Zapata et al. (2009) Sa´nchez-Zapata et al. (2009)

The use of byproducts as a substrate for the growth of some microorganisms is a very useful application. However, there is not much information on this. Albuquerque, de, Bedani, Vieira, LeBlanc, and Saad (2016) supplemented starter and probiotic strains, adding okara in the growth media to increase the folate production, achieving positive results. Castellanos Fuentes et al. (2020) also proved that okara is an adequate substrate for the production of functional ingredients containing probiotic microorganisms. Therefore it is a relevant application.

2.4.1.1 Antioxidants Antioxidants are substances found in certain foods that protect the body from the action of free radicals, which cause aging processes and some diseases. The human body cannot neutralize free radicals, so it is through the diet that it obtains antioxidants (also named antiradicals) with the capacity to neutralize them. When antioxidants are not available, oxidative damage such as lipid peroxidation, DNA degradation, protein modification, and inflammation occur, worsening human health. Epidemiological studies have demonstrated that eating a diet rich in antioxidants prevents oxidative stress associated diseases by inhibiting oxidation of macromolecules (Meshkini, 2016). The best-known antioxidant substances are vitamins C and E and carotenoids. However, there are other compounds with this

Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

feature, such as polyphenols, including flavonoids (flavones, isoflavones, flavonones, anthocyanins, and catechins), that are strong antioxidants and contribute significantly to the total antioxidant capacity. Plant products are the main source of antioxidants in diet. Moreover, compounds with antioxidant capacity are usually concentrated in the byproducts generated after plant products processing, even more than in the edible part. Concerning cereals, nuts, and pulses used to obtain vegetable beverages, different studies provide the total antioxidant capacity as well as the identification of specific components in the byproducts. The most relevant ones are highlighted as follows. Processed foods that are rich in fats need the addition of antioxidants to prevent fat oxidation. Byproducts from almond or the drain water from horchata can perform this function efficiently. For instance, Sa´nchez-Zapata et al. (2012) demonstrates how the level of inhibition of lipid oxidation is directly proportional to the concentration of horchata drained water, making it a very profitable natural antioxidant for the industry. Almond husks, almond cake, and blanched almond skin also showed good antioxidant capacities, according to various authors, as they have a high content of phenolic compounds, making them suitable for the elaboration of functional foods (Barreira et al., 2010; Sarkis et al., 2014; Pasqualone et al., 2018). Rice bran is an excellent source of antioxidant compounds, including polyphenols such as gallic acid, protocathecoic acid, coumaric acid, tocopherols, tocotrienols, and gamma-oryzanol, which can prevent the oxidation reaction of cells that cause tissue and DNA damage (Christ-Ribeiro et al., 2021).

2.4.1.2

Fiber supplement and glycemic index reducer

The glycemic index (GI) indicates the time it takes for a food to raise the blood glucose level. A high GI means a food releases glucose very quickly when eaten. Using glucose as the reference (GI 5 100), a GI # 55 is considered low, a GI between 56 69 is considered medium, and a GI $ 70 is considered high. Dietary fiber lowers the GI by delaying the release of glucose into the blood. There are several mechanisms by which glucose absorption in intestine is slowed down by fiber, such as viscosity increase of intestinal juice, which impedes the glucose diffusion, or the glucose binding which decreases the available glucose concentration in the intestine (Lu et al., 2013). Another mechanism is the retard of α-amylase action through capsuling starch granules, delaying its degradation and therefore glucose

47

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Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

release (Brennan et al., 2012). IDF and SDF have different effects on blood glucose lowering. SDF can delay gastric emptying and form membranes in gastric and intestine, thereby slowing the digestion and absorption of food. IDF absorbs glucose to retard its absorption by intestine (Lu et al., 2013). Another well-studied effect of fiber is its ability to lower the level of cholesterol in blood through different mechanisms, but all of them based on avoiding the absorption of cholesterol. Some of the dietary fiber substances are pectins, cellulose, β-glucans, or hydrocolloids (Mudgil & Barak, 2013). From a dietary point of view, it is desirable that the ratio of soluble fiber to insoluble fiber in a food should be around 2/1 (Bas-Bellver, Andre´s, Seguı´, Barrera, & Jime´nez-Herna´ndez, 2020). This should be considered when using any of the byproducts as an ingredient to increase the fiber content. As was mentioned before, almost all of the dietary fiber from okara is insoluble; therefore its incorporation into functional foods can lower the GI. For instance, Lu et al. (2013) incorporated okara powder into bread, noodles, and steamed bread; the glucose levels after consumption were lower than those after consumption of control foods (the same products but made only with conventional ingredients and no okara). These products are very suitable for the diabetic population. The inclusion of oat bran in snack products prolongs the glucose release period and has demonstrated potential to boost satiety. Oat bran can contribute to lowering the glycemic impact of foods through the effect by which β-glucans contained in oat bran alter the rheological nature of food that is being digested. The mechanism of glycemic response delay is the starch encapsulation (Brennan et al., 2012). Beta-glucans have also a cholesterollowering ability that is due to their capacity to form a gel-like network modifying the regular gastrointestinal viscosity and impeding the absorption of cholesterol (Mudgil & Barak, 2013). High fiber content in rice bran can also slow down the absorption of glucose, being very suitable for the treatment of type 2 diabetes mellitus. Supplementation of rice bran has been successfully done in various foods, such as bread, cakes, noodles, pasta, and ice cream, without significantly affecting the functional and textural properties. Therefore the addition of rice bran can contribute to the development of functional foods, which are highly demanded nowadays (Gul et al., 2015).

2.4.1.3 Water-holding ingredients Water-holding capacity (WHC) is defined as the amount of water that is retained by a certain quantity of dry fibers under

Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

specific conditions (Mudgil & Barak, 2013). In meat products, this is a very relevant value, since a high WHC avoids exudation phenomena and determines the visual acceptability, weight loss, and cook yield as well as sensory traits on consumption (Warner, 2017). WHC is determined mainly by dietary fiber. Talukder and Sharma (2010) added oat bran to chicken meat patties to increase the fiber content. They showed that the more oat bran is added, the higher is the WHC. WHC also depends on the way in which the fiber is processed and on its chemical and physical structure. Tiger nut solid byproduct has a high WHC because of its high proportion of hemicellulose and lignin and the structure of fiber, so it is suitable for addition to products that need hydration or viscosity development, such as baked foods or cooked meat products (Sa´nchez-Zapata et al., 2009).

2.4.1.4

Fat replacers

Fat replacers are either fat substitutes (lipid-like substances) or mimetics (protein or carbohydrate substances). The largest group of fat replacers are carbohydrate-based ingredients, which function by imitating the functional and sensory properties of real fats. In addition to the ability to mimic fat, some replacers possess functional constituents, such as fibers. This can improve the functional profile of the final products. Cereal milling fractions are used to replace fat, in particular corn bran fiber in muffins, rye or rice bran in meatballs, or wheat and oat bran fibers in dry fermented sausages. They are byproducts with confirmed fat replacing abilities (Mili´cevi´c et al., 2020). A significant decline in cholesterol content was observed from the addition of wheat and oat bran to patties (Talukder & Sharma, 2010). Mili´cevi´c et al. (2020) revealed that fat replacement using bran gels at the level of 30% resulted in the fatreduced added-value cookies in terms of dietary fiber, minerals, and phenolics.

2.4.1.5

Ingredients in gluten-free products

Gluten is a set of proteins that are present in cereals such as wheat, barley or spelt. It is composed of glutenin and gliadin, and they are responsible for the elasticity of flour dough and the consistency and sponginess of breads and baked doughs. There are disorders related to gluten intake, celiac disease being the best known of them. The prevalence of celiac disease among the general population is estimated to be 1% in Western nations, and there is growing evidence for underdiagnosis of

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the disease, especially in non-Western nations (Green, Lebwohl, & Greywoode, 2015). Interest in developing gluten-free products has been growing over the last decade or so. The development of these kind of products is challenging because gluten confers unique viscoelastic properties to dough, making it difficult to develop gluten-free bread formulations with high quality and a competitive price (Aguilar et al., 2015). Most rice byproducts, such as rice bran, rice husk, or broken rice, are milled into flour. In fact, rice flour is the most used gluten-free flour for bakery products, and it is often formulated with flours, starches, and proteins from cereals, pulses, pseudocereals, and other plant materials to achieve optimal batter or dough properties and bakery product quality (Xu et al., 2020). Different milling methods have been reported to affect the properties of rice flour significantly, especially the particle size of the rice flour, the content of damaged starch, and the state of the starch granules (Wu et al., 2019). Rice flour is commonly used for gluten-free bread, owing to its rheological properties, but it can also be used in cookies or other bakery products, depending on the formulation. Additionally, baru (Brazilian almond) flour from oil extraction has been used as a replacer of wheat flour for cookie production, having a positive influence on the nutritional and antioxidant characteristics of cookies besides the impact on acceptance (Pineli et al., 2015). Unlike cereals, almonds are not starchy, so their flours do not have the functional properties of those polysaccharides in dough. Starch in grain flours fills the gluten network and absorbs water during cooking; the main structural effect can be observed in a tenderization of dough and setting of structure during baking. Together with water, starch makes up more than half the volume of dough. The hydrolysis of starch also contributes to the availability of fermentable sugars, influencing the production of gas and aeration of dough. However, the reduction in carbohydrates caused by the use of partially defatted baru flour can contribute to a reduction in glycemic loads, which are typically high in baked goods. The high fiber content also contributes to this reduction (Pineli et al., 2015). Several researchers have studied the benefits and properties of using tiger nut flour in gluten-free baking. Tiger nut milk byproduct impaired bread quality (darkest color and hardest crumb), owing to its fiber size and content. Consequently, it is preferable to combine tiger nut flour with other flours. For example, the use of tiger nut flour together with chickpea flour could substitute shortening and emulsifier agents without

Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

negatively affecting crumb softness (Aguilar et al., 2015). Gasparre et al. (2020) incorporated 10% tiger nut flour into a rice-based formulation, showing that it was suitable for making gluten-free snacks with acceptable physical properties and an increase in ash, protein, and total phenol content. Aguilar et al. (2015) formulated a gluten-free dough with corn starch and tiger nut milk byproduct and analyzed their properties. The batter showed a solid elastic behavior and a low bake loss, owing to the high WHC of the solid by-product.

2.4.1.6

Emulsion stabilizers

An emulsion is a homogeneous mixture of two immiscible liquids, where one is the continuous phase, and the other is dispersed in it. There are emulsions consisting of an oil phase in an aqueous phase, known as oil-in-water emulsions, such as milk. There are also water-in-oil emulsions, such as butter. Huc-Mathis et al. (2019) studied the emulsifying properties of oat bran. Oat bran samples were dried and micronized to obtain an oat bran powder. They evaluated if oat bran powder could stabilize oil in water emulsions. The mechanisms of stabilization of the oil droplets were given by insoluble and soluble components. Insoluble fibers maintained the stability through pickering mechanism. Pickering emulsion uses single solid particles as stabilizers, which accumulate at the interface between two immiscible liquids and stabilize the droplets against coalescence (Yang et al., 2017). Furthermore, soluble components such as proteins or pectins stabilize the smallest droplets. Emulsifying properties of oat protein isolate can decrease with succinylation (Mirmoghtadaie et al., 2009). As was mentioned before, tiger nut flour can maintain baking characteristics of bread when it is combined with chickpea flour, replacing emulsifier compounds (Aguilar et al., 2015). Sa´nchez-Zapata et al. (2009) compared the emulsifying activity and emulsion stability of tiger nut solid byproduct with other fiber sources such as chia, passion fruit, or lima bean. The emulsifying activity of the tiger nut solid byproduct was 70.33 mL/100 mL, and its emulsion stability was 100 mL/ 100 mL, making it the most efficient compared with the other fiber sources. Fermented okara with Kluyveromyces marxianus shows a wide range of emulsification activity index and emulsification stability, enabling its use as a raw material. Moreover, the fermentation improved the mobility of free water and prevented oil droplet polymerization (Hu et al., 2019).

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2.4.2

Liquid wastes

The protection of the planet has introduced the need for increased sustainability at an industrial level. This challenge requires the treatment and reuse of wastewater generated by the vegetable beverage industry. Industries need to reach the zerowaste level, for which they require the implementation of innovative technological solutions based on recycling and reuse. These are the guidelines set by a circular economy, which replaces the concept of lifecycle and promotes reduction, alternative reuse, recycling, and recovery of materials in the production/distribution and consumption processes (Gurreri, Cipollina, Tamburini, & Micale, 2020a; Gurreri, Cipollina, Tamburini, & Micale, 2020b). Liquid wastes generated by the plant based beverage industry can be used for different purposes. The most studied applications are to reuse in the same process, to produce biohydrogen, for nutrients or bioactive compounds extraction, and to use as ingredients (Fig. 2.3). The main aspects concerning them are explained below. In all cases, it is necessary to carry out pretreatments or alternative treatments, some of which are summarized in Table 2.3.

2.4.2.1 Reuse in the same process The plant-based food industry generates large volumes of wastewater containing high concentrations of suspended solids, chemical oxygen demand, conductivity, turbidity, or color among others. Food wastewater cannot be discharged directly, and it could be reused in the process following treatment; that will result in large productive and financial advantages. Traditional physicochemical and biological treatments applied

Figure 2.3 Main wastewater treatments and applications.

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Table 2.3 Some examples of applications and required treatments for wastewater from plantbased beverage industry. Applications

Required treatments

Raw materials

References

Wastewater with the best quality

Ultrafiltration

Cassini et al. (2010)

Wastewater with the best quality Wastewater with the best quality Biohydrogen production Biohydrogen production

Electrocoagulation

Wastewater from isolated soy protein production Wastewater from almond industry Wastewater from almond industry Rice mill wastewater

Biohydrogen production Biohydrogen production

Electrodialysis

Dark fermentation and mixotrophic microalgae cultivation Fermentation by Enterobacter aerogenes and Rice mill wastewater Citrobacter ferundii assisted enzymatic hydrolysis Fermentation by Enterobacter aerogenes and Rice mill wastewater Citrobacter ferundii assisted enzymatic hydrolysis Fermentation by Enterobacter aerogenes Rice mill wastewater

Biohydrogen production Recovery of proteins

Fermentation by Enterobacter and Clostridium species Ultrafiltration

Soy wastewater

Recovery of proteins

Ultrafiltration

Soybean wastewater

Recovery of proteins Recovery of proteins

Dried by using a Mini B-290 lab spray dryer Ultrafiltration

Extraction from polyhydroxyalkanoate Recovery of β-glucan

Spray-dried to produce a powder and used from a recombinant strain of Pseudomonas Ultrafiltration

Soy whey wastewater Rice starch wastewater Soybean wastewater

Protein, oligosaccharide, and isoflavone isolation Water substitute in different foods Use in liver pate formulation

Rice mill wastewater

Oat mill waste Soy wastewater

Valero et al. (2011) Valero et al. (2015) Liu et al. (2013) Hassan et al. (2021) Ramprakash and Muthukumar (2014) Ramprakash and Muthukumar (2014) Ramu et al. (2021) Cassini et al. (2010) Chen et al. (2019) Li et al. (2014) Doan and Lai (2021) Hokamura et al. (2017) Patsioura et al. (2011) Wang and Serventi (2019)

Horchata drained Sa´nchez-Zapata water et al. (2012) Wastewater from tiger Sa´nchez-Zapata nut et al. (2013)

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Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

to food liquid wastes demand significant physical space, owing to the great volumes of unit operations that are involved and implies great chemical product utilization. Thus alternative treatments have been explored to improve the space economy and significantly reduce the use of chemical product utilization. In this context, membrane technologies have attracted a great deal of research interest and relevant advances have been made. Membrane technologies can be an economically and technologically viable technique for water and wastewater treatment due to high selectivity, high levels of product recovery and avoided use of chemicals (Gurreri et al., 2020b). In the treatment of liquid waste of plant origin, two membrane techniques should be highlighted: electrodialysis and ultrafiltration. Electrodialysis is an electromembrane process that separates ion by the transport through selective membranes under an applied electric field, thus producing two streams at different concentration (Gurreri et al., 2020a; Gurreri et al., 2020b). In the almond industry, electrodialysis has proved to be a suitable technique for decreasing the conductivity of wastewater that had previously been treated by electrocoagulation and electrooxidation (Valero et al., 2015). A study of the reuse of the concentrate solution was done, and the results showed that it can be concentrated 10 times. The treatment was successfully scaled up to a preindustrial electrodialysis system (Valero et al., 2015). Ultrafiltration is a membrane process that promotes the separation of molecules in solution based on size, where a pressure gradient is the driving force of the process (Cassini et al., 2010). Common compounds retained by ultrafiltration membranes include colloidal particles, biomolecules, polymers, and some sugars. The production of proteins from some legumes generates wastewater with a very high organic load, composed mainly of soluble proteins and carbohydrates and that have a high chemical oxygen demand. Cassini et al. (2010) studied the use of ultrafiltration to reduce organic load and protein content. They evaluated the performance of three ultrafiltration membranes (5, 20, and 50 kDa) in the treatment of wastewater from isolated soy protein production. The 5kDa membrane showed the best results: the lowest permeate flux reduction, the most elevated retention percentages (34% chemical oxygen demand, 52% of protein, 21% total solids, and 86% total suspended solids), and the wastewater with the best final quality.

2.4.2.2 Biofuel Hydrogen is considered a biofuel because it uses water to produce electricity and is considered a clean form of energy

Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

(Liu et al., 2013). Biohydrogen is seen as one of the most viable energy substitutes, owing to its higher energy content and environmentally friendly nature (Hassan et al., 2021). Biological production, that is, production involving fermentation processes, is one of the most efficient methods, as it consumes less energy and can be carried out at atmospheric pressure (Kotay & Das, 2008). It uses agricultural industrial waste that is rich in starch and cellulosic materials, which are first hydrolyzed to produce fermentable sugars (Ramprakash & Muthukumar, 2014). Biological species that are used for hydrogen production include cyanobacteria, photosynthetic bacteria, and bacterial species, such as facultative anaerobes (Enterobacter sp. and Citrobacter sp.) and strict anaerobes (Clostridium sp. and rumen bacteria) (Das & Vezirog
lu, 2001; Kotay & Das, 2008). Some industrial wastewaters, such as dairy process wastewater, rice winery wastewater, distillery and molasses wastewater, cassava wastewater, and rice mill wastewater, have been used successfully for biohydrogen production (Ramprakash & Muthukumar, 2014; Ramu et al., 2021). Among the pretreatments that are used are acid, enzymatic, and microbial hydrolysis (Ramprakash & Muthukumar, 2014); others, such as heat, ultrasonication, and alkali, have been also used (Ramprakash & Muthukumar, 2014).

2.4.2.3

Nutrient extraction

The recovery of nutrients from cereal and legume wastewater is drawing high interest from researchers. It contributes to the circular economy by valorizing wastes and reducing the environmental impact. Some applications of proteins or bioactive compounds that are recovered include use as food ingredients, algae culture, animal feed, and active packaging design (Chen et al., 2019). Membrane separation processes are a sustainable alternative for this recovery, as they greatly reduce energy consumption and the use of chemical agents. Ultrafiltration is a common technique that is used to recover colloidal particles, biomolecules, or polymers, although sometimes the high viscosity of the wastewater will cause serious membrane fouling and inefficient separations. For this reason, it is necessary to investigate each specific application and find solutions that provide higher yields. Proteins from rice are of great interest, owing to their colorlessness and bland taste. They are highly digestible proteins of high biological value, rich in amino acids such as cysteine, methionine, tryptophan, and phenylalanine (Doan and Lai,

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2021). Thus the wastewater that is discharged from rice starch production contains a significant amount of valuable proteins. Ultrafiltration, used by other authors for the recovery of protein from other wastewaters (Herna´ndez, Muro, Ortega, Vela´zquez, & Riera, 2019; Sriniworn, Youravong, & Khongnakorn, 2016) proved to be an effective method to recover rice protein from wastewater in rice starch production. Soy protein isolates are a group of macromolecules with different structures and molecular weights, identified as globulins. They have been attributed functional properties, such as cholesterol reduction and prevention of cardiovascular diseases, which have increased their interest for the food industry. Wastewater from soy protein isolate production is rich in soluble proteins, found in small molecules that were not removed during the production process. Cassini et al. (2010) demonstrated that the use of ultrafiltration membranes in the pretreatment of soy protein isolate wastewater was very promising for organic load reduction and protein content recuperation. Isoflavones are also present in soy protein isolate wastewater. Although research on the recovery of soy isoflavones is scarce, Xu et al. (2005) demonstrated the efficiency of reverse osmosis to obtain concentrates of these components from wastewater resulting from the production of soy milk. Oats are among the cereals that have high amounts of watersoluble fiber, protein, and β-glucan. The acceptance of β-glucan from cereals as a functional ingredient has increased interest in its incorporation in food formulation. Patsioura et al. (2011) carries out an optimization of ultrafiltration for the recovery of β-glucan from solid and liquid waste from oat mills, using three types of membranes. Although the results were satisfactory, good separation yields between β-glucan and proteins were not obtained.

2.4.2.4 Direct use as ingredient When the wastewater does not come from cleaning but from pretreatments applied to the raw material or from posttreatments of the solid waste, it can be interesting to use the water directly as an ingredient in other food processes. Processing of tiger nuts to obtain horchata generates a second extraction, namely, horchata drained water. Sa´nchezZapata et al. (2012) studied the properties of this wastewater and found that its properties make it a valuable source of natural antioxidants and fiber. The same authors studied the effect on the physicochemical and sensory properties of cooked pork

Chapter 2 Opportunities for the valorization of waste generated by the plant-based milk substitutes industry

liver pate when 50% of the water required was replaced by drained horchata water. The results showed no significant changes in the physicochemical properties and revealed better overall acceptance by a panel of inexperienced tasters.

2.5

Conclusions and future trends

An exhaustive review of scientific published works related to the byproducts that are generated in the production of plantbased beverages and other products has shown that the most investigated byproducts are not those that are derived directly from the production of the vegetable beverages but those that originate in previous stages (e.g., hulls, skin). Regarding press cakes, there is still not enough information, but some studies have shown that they have a high potential, both for the extraction of compounds of interest such as oils, dietary fiber, and antioxidants for the elaboration of functional foods, owing to their beneficial properties. For wastewater, a large amount of research work focuses on the application of pretreatments for the reduction of the organic load. An improvement in the efficiency of these steps would enable different applications, such as the production of biofuels or the recovery of nutrients. The use of this type of byproducts contributes to the circular economy and economically benefits the companies. The plantbased beverage sector is growing, so knowing the best uses for each type of byproduct that is generated in this area is crucial. In fact, the significant growth in the number of scientific articles that are being published on these byproducts shows that their properties are beginning to be studied. Throughout the chapter, it has been shown that byproducts from the plant-based beverages industry have both an interesting nutritional composition and a wide range of applications in the development of new products besides the fortification of traditional foods. Meat products, emulsions, gluten-free products, dairy products, and others are just some of the many sectors in which these byproducts play an important role. This is therefore an area for further research in order to optimize food production processes. Future research in this field is very important, owing to the need to increase the sustainability of the agro-food system by adding value to potentially highly versatile byproducts. The development of extraction techniques and the application of innovative technologies as pretreatment will allow the recovery of many components of interest with multiple applications.

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List of acronyms GAE GI IDF SDF WHC

Gallic acid equivalents Glycemic index Insoluble dietary fiber Soluble dietary fiber Water-holding capacity

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Vong, W. C., & Liu, S. Q. (2016). Biovalorisation of okara (soybean residue) for food and nutrition. Trends in Food Science and Technology, 52, 139 147. Available from https://doi.org/10.1016/j.tifs.2016.04.011. Wang, X., Zhang, Y., Li, Y., Yu, H., Wang, Y., & Piao, C. (2020). Insoluble dietary fibre from okara (soybean residue) modified by yeast Kluyveromyces marxianus. LWT, 134, 110252. Available from https://doi.org/10.1016/j. lwt.2020.110252. Wang, Y., & Serventi, L. (2019). Sustainability of dairy and soy processing: A review on wastewater recycling. Journal of Cleaner Production, 237, 117821. Wanyo, P., Meeso, N., & Siriamornpun, S. (2014). Effects of different treatments on the antioxidant properties and phenolic compounds of rice bran and rice husk. Food Chemistry, 157, 457 463. Available from https://doi.org/10.1016/j. foodchem.2014.02.061. Warner, R. D. (2017). The eating quality of meat-IV water-holding capacity and juiciness. Lawrie’s meat science: Eighth edition (pp. 419 459). Elsevier. Available from https://doi.org/10.1016/B978-0-08-100694-8.00014-5. Whitehead, A., Beck, E. J., Tosh, S., & Wolever, T. M. S. (2014). Cholesterollowering effects of oat β-glucan: A meta-analysis of randomized controlled trials1. American Journal of Clinical Nutrition, 100(6), 1413 1421. Available from https://doi.org/10.3945/ajcn.114.086108. Wouters, A. G., Rombouts, I., Fierens, E., Brijs, K., & Delcour, J. A. (2016). Relevance of the functional properties of enzymatic plant protein hydrolysates in food systems. Comprehensive. reviews in food science and food safety, 15, 786 800. Available from https://doi.org/10.1111/15414337.12209. Wu, T., Wang, L., Li, Y., Qian, H., Liu, L., Tong, L., . . . Zhou, S. (2019). Effect of milling methods on the properties of rice flour and gluten-free rice bread. LWT, 108, 137 144. Available from https://doi.org/10.1016/j.lwt.2019.03.050. Xu, P., Drewes, J., Bellona, C., Amy, G., Kim, T., Adam, M., & Heberer, T. (2005). Rejection of emerging organic micropollutants in nanofiltration reverse osmosis membrane applications. Water environment Research: A Research Publication of the Water Environment Federation. 77, 40 48. Available from https://doi.org/10.2175/106143005X41609. Xu, J., Zhang, Y., Wang, W., & Li, Y. (2020). Advanced properties of gluten-free cookies, cakes, and crackers: A review. Trends in Food Science and Technology, 103, 200 213. Available from https://doi.org/10.1016/j.tifs.2020.07.017. Yang, L. C., Fu, T. J., & Yang, F. C. (2020). Biovalorization of soybean residue (okara) via fermentation with Ganoderma lucidum and Lentinus edodes to attain products with high anti-osteoporotic effects. Journal of Bioscience and Bioengineering, 129(4), 514 518. Available from https://doi.org/10.1016/j. jbiosc.2019.10.003. Yang, Y., Fang, Z., Chen, X., Zhang, W., Xie, Y., Chen, Y., . . . Yuan, W. (2017). An overview of pickering emulsions: Solid-particle materials, classification, morphology, and applications. Frontiers in Pharmacology, 8, 287. Available from https://doi.org/10.3389/fphar.2017.00287. Zhu, F. (2017). Structures, properties, modifications, and uses of oat starch. Food Chemistry, 229, 329 340. Available from https://doi.org/10.1016/j. foodchem.2017.02.064.

3 High-rate anaerobic processes for agro-food wastewater treatment: recent trends and advancements A. Bokhary1, M. Leitch1, Y. Hong3 and B.Q. Liao1,2 1

Faculty of Natural Resources Management, Lakehead University, Thunder Bay, ON, Canada 2Department of Chemical Engineering, Lakehead University, Thunder Bay, ON, Canada 3SUEZ Water Technologies & Solutions, Oakville, ON, Canada

3.1

Introduction

The fast growth of the world’s population requires increased food-manufacturing processes to meet the demand. However, during food production and processing, large quantities of potable water will be used. It is estimated that about 70% of the freshwater is used in food production with about 20% being used in the production and processing streams (Steduto et al., 2012). For example, production of ready-to-eat foods constitutes one of the largest water users among the agro-food companies because of the large amounts of water (about 40 m3 ton21 of raw food) that are needed in the processing steps (NahimGranados et al., 2020). Water consumption is expected to increase as a result of the growing demand for food of the rapid global population growth (around 83 million annually). This may result in the generation of large amounts of wastewater coupled with potentially harmful byproducts. The usual fate of wastewater is to be discharged into a wastewater management facility. On the one hand, most of the constituents of agro-food wastewaters (AFWWs) are biodegradable with chemical oxygen demand (COD) strength suitable for anaerobic digestion and convertible to biogas. On the other hand, their discharge may cause adverse consequences ranging from eutrophication in receiving water bodies to the formation of a dead zone that needs a further solution (Tauseef et al., 2013). Wastewater has Advanced Technologies in Wastewater Treatment. DOI: https://doi.org/10.1016/B978-0-323-88510-2.00009-9 Copyright © 2023 Elsevier Inc. All rights reserved.

67

68

Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

been reported to contribute up to 6% of all anthropogenic CH4 emissions, or about 450 million metric tons of carbon dioxide equivalent (Tauseef et al., 2013). Besides the environmental impacts, wastewater discharge presents a missed opportunity to capture methane as a relatively clean energy source. AFWWs are widely diverse in their strength and characteristics. They contain both organic and inorganic compounds as well as nutrients due to their varied sources for example dairy, snacks, fruits, vegetables, sweets, beverages, and distillery (Aderibigbe et al., 2017). Table 3.1 presents the characteristics of some AFWWs. In general, AFWWs contain high concentrations of biochemical oxygen demand (BOD), total suspended solids (TSS), and COD as well as total phosphorus (TP) and nitrogen (Aderibigbe et al., 2017). Thus these wastewaters should be treated in an environmentally acceptable manner to reduce their potential ecological impacts while alleviating to some extent the global water scarcity. Several processing techniques have been employed to treat AFWWs, including coagulation, flocculation, membrane filtration, adsorption, and oxidation (Leifeld et al., 2018). However, these methods use costly reagents and generate solid waste, which needs further treatment. Aerobic digestion and combined anaerobic/aerobic treatment were also used. However, aerobic digestion is an energy sink because of aeration demand combined with high maintenance and monitoring requirements. Thus the use of reliable and cost-effective technologies is needed for the treatment of AFWWs. High-rate anaerobic processes (HRAnPs) have emerged as capable alternative techniques to effectively handle the highstrength AFWWs of the fast-growing food industry. HRAnSs are gaining attention as a result of their higher loading capacity and biogas production, which offset the energy cost of the facility in some cases. The use of HRAnPs would overcome the shortcomings of above-mentioned systems, owing to no aeration required, high loading capacity compared with low-rate anaerobic digesters, and reduced carbon footprint (Rajagopal et al., 2013). Various HRAnPs were developed, including the anaerobic filter (AF), upflow anaerobic sludge blanket (UASB) reactor, expanded granular sludge bed reactor, static granular bed reactor, anaerobic moving bed biofilm reactor (AMBBR), external circulation sludge bed reactor, anaerobic membrane bioreactor (AnMBR), and anaerobic hybrid reactors. This chapter focuses on the work that has been done recently on AFWWs treatment using the most common high-rate anaerobic treatment digesters and discusses their current trend and advancements.

Table 3.1 Properties of some agro-food wastewaters (Katayon et al., 2004; Erden et al., 2010; Latif et al., 2011; Mota et al., 2013; Basset et al., 2016; Malollari et al., 2019; Aderibigbe et al., 2017; Valta et al., 2017). Wastewater source

COD (mg L21)

BOD5 (mg L21)

Total P (mg L21)

Total N (mg L21)

pH

Total solid (mg L21)

TSS (mg L21)

Meat processing Dairy Fruits Vegetables Sugar vinasse Slaughterhouse Alcohol-distillery Ice cream Cheese Palm oil mill effluent Cheese whey Nestle factory Pet food

250 5160 400 15,200 1500 430 1500 15,496 17,677 3160 31,600 5090 22,600 200 12,000 23,000 40,000 30,000 85,000

50 170 6250 500 250 500 42,200 2000 5500 6000 16,000 2.5 520 2.5 27 10,000 30,000

5 101 15 45

77 10 90

6 9 4.5 6.5 8 6.5 9.5 4 4.4

2 2028 250 2750

50 1640 300 400 450 900 2800 2900

60,000 86,000 880 20,300

30,000 60,000 680 9710

47 64 50 105 16.8 172.8 130 1163.2 5.55 4.31 700 37 100 21

300 700 75

38 124

900 1760

210

1130

N, nitrogen; P, phosphorus; TSS, total suspended solids; VFA, volatile fatty acids.

3.5 5.2 3.8 3.5

7.6 6.5 4.9 4.7

3.8 6.0 3.9

11,110 15,420 2 15.5 2913 4.0 665 1600 3900 30,000 70,000 3000 65,000 2480

417 3 265

VFA (mg L21)

199 2160 52 1282 928 2176 260 280

9000 40,000 1350 22,000 1670 4540

70

Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

3.2

Agro-food wastewater characteristics

Wastewater source

The properties of the feedstock govern the rate of organic loading, the addition of nutrients or not, and potential toxicity/ process stability. Some substrates, such as those with high lipid content, may cause foam formation (Mainardis et al., 2020). Also, the components of the effluents and their sizes determine whether or not a pretreatment step is required. Based on its strength, wastewater is generally categorized into low-strength wastewater (,2000 mg L21 COD) and medium to high strength wastewater ( . 2000 mg L21 COD) (Table 3.1). Table 3.1 shows the characteristics of some selected AFWWs. The composition of AFWWs varies extensively, depending on its sources and processing conditions, but the most reported substances include starches, oil, fatty acids, fats, proteins, and cellulose. Most foodprocessing facilities generate high-strength organic wastewater. For example, the dairy products wastewater (cheese, cheese whey, and milk permeate) has a total COD strength in the range of 400 86,000 mg L21, while the COD of slaughterhouse wastewater is fluctuating between 3160 and 31,600 mg L21. The reported COD value for ice cream wastewater ranged between 200 and 12,000 mg L21. Beverage and cheese effluents appear to contain a much higher concentration of COD than other effluents. Depending on the diverse strengths of the wastewater, the biogas production potentials varied, as shown in Fig. 3.1. AFWWs are generally characterized by high concentrations of phosphorus, nitrogen, and micronutrients that are required for microbial growth (Latif et al., 2011).

Palm oil mill effluent Coffee wastewater Sugarcane vinasse wastewater Alcohol distillery wastewater Starch wastewater Whey wastewater Milk permeate Brewery wastewater Slaughterhouse wastewater Cheese wastewater

100 191 222 236 299 299 309 327 331 336 0

50

100 150 200 250 300 Biogas yield (m3CH4/ton COD)

350

Figure 3.1 Biogas potential of various AFWWs sources under varied operating conditions and reactor configurations.

400

Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

3.3

71

Application of high-rate anaerobic systems in agro-food wastewater treatment

Owing to the high treatment capacity, various configurations of HRAnPs have been used to treat AFWWs. In the subsequent section the most predominant HRAnPs were thoroughly discussed. Fig. 3.2 shows the schematics of some high-rate anaerobic reactors.

3.3.1

The anaerobic filter

AF performance has been examined in a variety of AFWWs (Di Berardino et al., 2000; Yu et al., 2002; Omil et al., 2003). Both upflow and downflow operating modes have been used, but ¨ ceer (2017) treated downflow is less common. Kalat and Yu

Figure 3.2 Schematics of high-rate anaerobic reactor (A) anaerobic filter (AF), (B) upflow anaerobic sludge blanket (UASB), (C) expanded granular sludge bed (EGSB), (D) external circulation sludge bed (ECSB), and (E, F) anaerobic membrane bioreactors (AnMBR).

72

Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

vegetable oil refining wastewater by upflow AF under varied organic loading rate (OLR) (0.98 9.96 kg COD m23
d) and hydraulic retention time (HRT) of 24 hours. The system achieved 97% COD removal, while the methane yield was 353.8 m3 CH4 ton21 COD removed. The methane production was similar under different temperature ranges [mesophilic (35 C) and thermophilic (55 C)]. Rajakumar et al. (2011) reported a 78% COD removal efficiency under an OLR of 10.05 kg m23
d, 12 hours HRT, and a mesophilic temperature (29 C 35 C) for poultry slaughterhouse wastewater using AF at an upflow velocity as low as 1.38 m d21; the methane yield was 217.7 m3 CH4 kg21 COD removed. Rajinikanth et al. (2009) assessed the performance of four upflow AF packed with lowdensity polyethylene support and operated under high OLR (12 27 kg COD m23
d) to treat wastewater from different small-scale agro-food industries. The author reported that 80% of COD was removed for the winery wastewater, and it was believed that the support medium used was good at retaining biomass in the system, which could be up to 70% of the reactor volume. The packing media is one of the factors affecting AF performance as the microbial film grows on it. Thus its selection needs to be accorded close attention. Rajakumar and Meenambal (2008) studied the performance of hybrid UASB and AF reactors. The hybrid UASB showed higher COD removal efficiency (80% total COD and 86% soluble COD) compared to the AF system (70% total COD and 79% soluble COD). This result may indicate the superiority of UASB over the AF system. Despite the simplicity, reduced operating costs, and good stability of AF, it has some limitations such as solid buildup in the packing material, causing blockage of the reactor, and biofilm deterioration due to the buildup of nondegradable solids (Karadag et al., 2015). Therefore pretreatment of wastewater is required to remove solids that may clog the filter. Table 3.2 shows the results of an AF reactor that processes different AFWWs.

3.3.2

Upflow anaerobic sludge blanket reactor

The concept of the UASB reactor dates back to the 1970s, and at present, most installed full-scale digesters are based on this concept (Mainardis et al., 2020; Chen et al., 2020). In AFWWs processing, UASB digesters were successfully employed to treat slaughter wastewater (Dendooven and Escamilla-Silva, 2005), dairy wastewater (Tawfik et al., 2008), soybeanprocessing wastewater (Dong et al., 2010), sugar industry

Table 3.2 Synopsis of performance of anaerobic filter reactor for treatment of various agro-food wastewaters. Wastewater source

Scale Reactor Feed tCOD volume (mg L21) (L)

HRT (h) OLR (kg Temperature tCOD Biogas Methane References COD m23
d) (˚C) removal production content (%)

Food industry wastewater Soybean wastewater Dairy wastewater

Lab

10

530 2620

31 133

0.41 1.23

35

81.7 92.5 0.20 0.55a

Lab

10.5

7520 11,450

35 25

8.16 13.5

35

92

3 7.5b

78

Full

12,000

8671 12,487

44.4 168 2.8 5.9

35 37

66.8 93

3.79b

67 71

Poultry slaughterhouse wastewater

Bench

5.4

3000 4800

36 8

0.77 3.43

29 35

70

0.74b

56 75

Agro-food wastewater Poultry slaughterhouse wastewater Vegetable oil refining wastewater

Lab

10

1900 30,000

4

12 27

33

80

—

—

Lab

5.4

3000 4800

12

10.05

29 35

78

0.24c

46 56

Lab

1.2

17,688 24,787 24

0.98 9.96

35/55

97

0.26 0.39c

91

m3 biogas kg21 COD removed. m3 biogas m23 reactor
d. c 3 m CH4 kg21 COD removed. a b

84.3 89.9

Di Berardino et al. (2000) Yu et al. (2002) Omil et al. (2003) Rajakumar and Meenambal (2008) Rajinikanth et al. (2009) Rajakumar et al. (2011) Kalat and Yu¨ceer (2017)

74

Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

wastewater (Hampannavar and Shivayogimath, 2010), rice mill wastewater (Saini et al., 2016), starch wastewater (Lu et al., 2016), and palm oil mill effluent (Krishnan et al., 2017). The UASB reactor has many positive characteristics such as low capital cost, high OLR capacity, short HRT, less excess sludge generation, and low power demand (Latif et al., 2011; Lu et al., 2016). However, reactor startup and granulation are two important aspects of UASB reactor operation, and they need special attention for better performance. In AFWWs, both single- and two-stage UASB digesters have been used, and a broad range of operating conditions was examined. The investigated range of OLR was 0.42 60 kg COD m23
d, while the applied HRT was in the range of 2 60 hours. Increased OLR was found to decrease removal efficiency, which in turn depends on the wastewater source. While it is not recommended to run the UASB system under HRT less than 2 hours, owing to the washing of the granules induced by the high flow rate of the effluent (Wu et al., 2021). It has been reported that operating a UASB reactor under an OLR of 1.75 5 kg COD m23
d and mesophilic temperature are highly effective for the treatment of slaughterhouse wastewater (Musa et al., 2019). Rodrigues et al. (2021) reported an OLR of 3.91 kg COD m23
d and an HRT of 24 were optimal for anaerobic treatment of diluted soybean molasses, but it was found that higher OLR (6.98 kg COD m23
d) reduces methane production. Conversely, the reported optimal OLR for a three-stage UASB system for cassava wastewater treatment was 15 kg m23
d (Jiraprasertwong et al., 2019). The reported result indicates that the performance of the three-stage UASB system is better than that of single- and two-stage anaerobic processes in terms of increased OLR and energy production. Various temperature ranges (psychrophilic (,20 C), ambient, mesophilic (35 37 C), and thermophilic 50 C 60 C) were tested. Among the operating temperatures that were used, the mesophilic was the most used temperature range (Table 3.3). This could be due to the stable performance of anaerobic microorganisms and lower energy demand. The applied upflow velocities of the fluid ranged between 0.5 and 1.0 m h21. The COD removal efficiencies ranged between 39% and 99.3%; the TSS, phosphorus, and volatile suspended solid decomposition efficiencies ranged from 66% to 98%, 60% to 90%, and 72% to 75%, respectively. Ammonia removal efficiency by UASB can reach 96% (Fard et al., 2020). In some cases, posttreatment or pretreatment has been required to enhance the efficacy of COD and nutrient removal. Biogas

Table 3.3 The reported UASB reactor results of selected studies between 2019 and 2021. Wastewater source

Scale Reactor Feed tCOD volume (L) (mg L21)

HRT (h)

OLR (kg Temperature tCOD COD m23
d) (˚C) removal (%)

Biogas yield

References

Chocolate-processing wastewater Pistachio wastewater

Lab

6200

6

2 6

15 30

39 94

0.3 1.9c

49,800

5.4

1 4.56

35

89.77

0.332a 0.16a

Esparza-Soto et al. (2019) Gu¨r and Demirer (2019) Liang et al. (2019) Musa et al. (2019) Vidal et al. (2019)

2.8

Lab

Synthetic wastewater of guar gum Slaughterhouse wastewater Synthetic slaughterhouse wastewater Sugar refinery wastewater Chocolate-processing wastewater Sulfate-rich sugarcane vinasse Glutamate-rich wastewater Slaughterhouse wastewater Dairy wastewater Synthetic wastewater

Lab

4.7

1100

10

0.42 2.84

37

70 84

Lab

12

32,000

24

1.75 32

35

. 90

Lab

1.2

1700

10

3.94 8.15

37

70

0.35b

Lab

11

20,000

8

54

35

69.2 92

Pilot

244

7372.5

6.2

10.3/7.9

17 19

59.5/71.4

Lab

3.5

52,480

30

3 10

35

78

Lab

6

2000

4.5 6 8.3 10.8

35

95.5 96.5

3360

26

2,800,000 5.5

1300 2800 5000

40 48 12 24 3 20

23 27 35

98 92.9 99.3

12

500 4000

12 48 0.28 6.98

25

70 83

0.615 0.766d Zhang et al. (2019) 0.49 3.42c Alcaraz-Ibarra et al. (2020) 0.92 4.12c Barrera et al. (2020) 0.31a Chen et al. (2020) Fard et al. (2020) Ji et al. (2020) Chen et al. (2021) 0.023 0.356a Rodrigues et al. (2021)

Full Lab

Soybean molasses

Lab

Lab

m3 CH4 kg21 COD. m3 CH4 m23 reactor
d. c 3 m -biogas m23 reactor
d. d 3 m CH4 kg21 volatile suspended solid
d. a b

2.67 3.66

62.2 98.6

76

Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

productivity varied with wastewater sources. For example, the reported methane yield was 0.11 m3 CH4 kg21 COD for palm oil mill effluent (Krishnan et al., 2017), 0.33 m3 CH4 kg21COD removed for starch wastewater (Lu et al., 2016), and 0.32 m3 CH4 kg21 COD removed for slaughterhouse wastewater (Rajakumar et al., 2012). Table 3.3 summarizes the recently reported UASB reactor results. The UASB reactor has been shown to successfully treat various sources of agricultural food wastewater under very long solids retention time (SRT) and short HRT. But research is still needed to advance the applications of UASB technology in agricultural food wastewater in terms of energy yield and effluent quality.

3.3.3

Expanded granular sludge bed reactor

EGSB, a high-rate reactor that utilizes retained granular biomass, is used to process a broad range of wastewaters (low and high strength) (Connelly et al., 2017). The sludge bed of EGSB is expanded to improve the contact between treated waste and biomass. This design coupled with high mixing intensity facilitates the treatment of high-strength wastewaters under low HRT. It can operate at a higher loading rate of up to 30 kg COD m23
d with increased liquid upward flow velocities without biomass washout compared to UASB (6 10 m h21 versus 0.5 2 m h21) (Lim and Kim, 2014; Yi Fan et al., 2017). Also, the influent dilution provided by effluent recirculation allows the processing of toxic and recalcitrant compounds (Cruz-Salomo´n et al., 2019). EGSB reactor mainly consists of an extended bed and a three-phase separator and in its simple form is a variant of UASB (Connelly et al., 2017). The higher upflow velocity of EGSB can be achieved either by using longer reactors or by recycling effluents (or both). Table 3.4 summarizes the performance of EGSB reactors in AFWWs treatment. EGSB is used for the treatment of various AFWWs, and COD concentration in the range of 4000 30,000 mg L21 was treated. A high COD removal efficiency (80% 98%) was obtained (Table 3.4). However, most of the studies have focused on reactor performance rather than design optimization. HRTs ranging from 4 hours to 20 days were examined and were dependent on treated wastewater. The longer the HRT, the higher is the strength of the wastewater and vice versa. The effect of HRT on the processability of wastewater was examined more intensively compared to SRT. Sheldon and Erdogan (2016) examined a wide range of HRT (12 60) and upflow velocities (Vup: 0.59 1.1 m h21) and

Table 3.4 The performance of EGSB reactors treating agro-food wastewaters. Wastewater Scale Reactor source volume (L)

Feed tCOD (mg L21)

Feed TS (g L21)

HRT (h)

OLR (kg pH COD m23
d)

Biogas Temperature tCOD (˚C) removal production (L d21) (%)

Starch WW

Lab

3.4

4000 18,000

2 16

4 24

0.125/0.5/1.0

4.4

30

31.1

Palm oil mill effluent Palm oil mill effluent Simulated dairy wastewater Sugarcane vinasse Distillery wastewater Palm oil mill effluent Beet sugar industrial wastewater Soft drink industry wastewater Whiskey distillery wastewater Sugarcane vinasse

Lab

21.56

4331 35,000

67.2

48

1.45 17.5

7

35

89 96

70

Lab

1.3

97,000

67.3

10/5d

1.3 10.4

6

55

90

51 73

Lab

3.6

4000

24 48 167/88/111a

37 15

80

60

Lab

12.5

6000

15

4.8

7

35

73.4

Pilot

45/60

5000 30,000

20d

3 9

5.5 7.5 35

Pilot

423.9 m3

71,179 12,341

Lab

6.5

Lab

9

2242 11,717

12 60 11

Lab

20

4710

16

9.4

Batch

3.3

70,470

49.75

7d

Sugarcane juice Lab

1.96

205,300

5 15

Sugarcane molasses Acid brewery spent

Lab

1.5

844,700

Lab

2.27

a

Fixed OLR. kg sucrose m23d21. Conversion percentage.

b c

0.06

9.8d

35

48 12 0.8 3.2

6.9

98

Methane References content

259

71 76

94.89

36

35 37

93

17

70

6.2

37

91/88

3.01

72.8 74.5

5.1

7.2

26

75

4.2

76

24 1

182.9b

4 5

30

93c

52.40

6.2

24 1

180 360b

5.5

30

15

36 12 15 46

5.9

37

83

Guo et al. (2008) Zhang et al. (2008) Fang et al. (2011) Bialek et al. (2012) Qinglin et al. (2012) Ghorbanian et al. (2014) Wang et al. (2015) Ambuchi et al. (2016) Sheldon and Erdogan (2016) Connelly et al. (2017) RamosVaquerizo et al. (2018) de Menezes and Silva (2019) Freitas et al. (2020) CastillaArchilla et al. (2021)

78

Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

achieved up to 93% COD removal at HRT of 12 hours, Vup of 0.85 m h21, and OLR of 11 kg COD m23
d. A wide range of OLRs (0.125 46 kg COD m23
d) was tested. However, an OLR above 40 kg COD m23
d has been found to cause inhibition of microbial metabolic activity, owing to increased production of volatile fatty acids (VFA) (Cruz-Salomo´n et al., 2019). Most of the studies were performed at the mesophilic conditions (Table 3.4). However, examination of the three temperature ranges (psychrophilic, mesophilic, and thermophilic) would be of interest, since the temperature of AFWWs varies (could be warmer or colder than the mesophilic range). Also, treating wastewater at its original temperature can be more reliable in terms of resource conservation and reactor feasibility. Biogas and biohydrogen yield were promising. Biohydrogen as high as 0.11 L hydrogen g21 COD was reported for starch wastewater (Guo et al., 2008), and a biogas yield of 244.64 mL CH4 g21 COD was obtained from sugarcane vinasse (Ramos-Vaquerizo et al., 2018). de Menezes and Silva (2019) reported a sucrose conversion value above 93.0%. However, when HRT was decreased from 4 hours to 1 hour, sucrose conversion decreased to 73%. A BOD5/COD greater than 0.3, a concentration of suspended solids (TSS) less than 8%, and a C/N ratio of 30/1 to 15/1 have been recommended for better EGSB reactor performance (Cruz-Salomo´n et al., 2019). Despite the superiority of EGSB over the UASB reactor, the EGSB system is still in its infancy, and fewer publications have addressed AFWWs treatment.

3.3.4

Anaerobic moving bed biofilm reactor

Owing to the high volumetric OLR and low sludge generation, the anaerobic moving bed biofilm reactor is considered a very reliable process for high-strength wastewater treatment (di Biase et al., 2018). Biomass grows in the AMBBR on a protected surface inside the reactor. Thus the biomass is retained in the system, and high organic loading can be treated (di Biase et al., 2018). AMBBR is used to treat various AFWWs sources such as breweries, wineries, vinasses, and milk wastewaters (Sheli and Moletta, 2007; Wang et al., 2009a; di Biase et al., 2016). di Biase et al. (2018) treated brewery wastewater by AMBBR and achieved COD removal efficiency of 88% and methane yield 0.34 m3 CH4 kg21-sCOD under HRT of 18 hours and OLR of 4.0 kg-sCOD m23
d. Using AMBBR, Chai et al. (2014) treated winery wastewater and reported 80% COD removal under OLR of 29.59 kg COD m23
d and HRT of 1.55 days. Sheli and Moletta

Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

(2007) reported soluble COD removal efficiency in the range of 81.3% 89.2% at an OLR of 29.6 kg sCOD m23
d for vinasse wastewater. Wang et al. (2009a) achieved 86.3% 73.2% total COD removal for milk permeate. In another study, Wang et al. (2009b) found that OLRs of 5.5 and 9.5 kg tCOD m23
d were more suitable for the treatment of milk permeate. Rodgers et al. (2004) treated whey wastewater by AMBBR at mesophilic conditions and reported the highest (89%) COD removal at HRT of 1 d and OLR of 11.6 kg COD m23
d. Table 3.5 summarizes the performances of AMBBR treating various AFWWs. A wide range of wastewaters was treated, and AMBBR was able to treat elevated organic loading up to 30 kg COD m23
d with stable treatment efficiency. A high COD removal efficiency (70% 97%) and promising methane yield (0.30 0.36 m3 CH4 kg21 COD) were obtained (Table 3.5). These results indicate the ability of AMBBR to treat high-strength AFWWs at different organic loading ranging from 1 kg COD m23
d to 30 kg COD m23
d. However, most of the studies were performed at mesophilic or submesophilic conditions; therefore considering various temperature ranges would be of interest.

3.3.5

External circulation sludge bed reactor

ECSB, the third generation of EGSB systems, was developed by Hydro Thane STP to treat different types of wastewaters at typical loading rates in the range of 15 35 kg COD m23
d. EGSB differs from ECSB in that there are two gas-solid-liquid separators in the reactor, which are used to facilitate biomass retention under a high OLR and enhance process stability (Connelly et al., 2017). Several large-scale ECSB facilities are currently in operation around the world. For example, Dazong Biology in Tengzhou has installed an ECSB reactor to treat 3400 m3 d21 of cornstarch wastewater. Also, Oland Brewery in Canada has installed an ECSB with a capacity of 620 m3 d21 for wastewater treatment with the goal of producing 1200 m3 of biogas per day. Diamantis and Aivasidis (2018) have evaluated the performance of a large-scale ECSB reactor (1000 m3 working volume) for processing cheese and other dairy product wastewaters under OLR of 5 18 kg COD m23
d and have reported total COD removal efficiencies in the range of 75% 82% and biogas production in the range of 0.41 0.48 m3 kg21 COD, while soluble COD removal was greater than 96%. Lin et al. (2019) reported COD removal of 95% and a biogas production rate of 729 3466 m3 d21 for whiskey distillery wastewater using

79

Table 3.5 Summary of anaerobic moving bed biofilm reactor performance treating various agro-food wastewaters. Wastewater source

Scale Reactor volume (L)

HRT (d)

OLR (kg PH COD m23
d)

Whey wastewater Wine distillery wastewater Milk permeate

Lab

20 0.5

1 21

Milk permeate Brewery wastewater Brewery wastewater

Temperature tCOD (˚C) removal (%)

7.0 7.8 35

70 97 81.3 89.2

Lab

32.9

6.33 1.55 1.6 29.6

7.0

Lab

30

2 27.6

2 28

7.0

Bench Bench Lab

30 30 4

116 9.7 41.5 4.9 1

0.5 6.5 1.5 11 5 20

Lab

4

0.25 1

4.0

35

Biogas production (m3 CH4 kg21 COD)

References

0.33

Rodgers et al. (2004) Sheli and Moletta (2007) Wang et al. (2009a) Wang et al. (2009b) di Biase et al. (2016) di Biase et al. (2018)

86.3 73.2

0.341

7.0 20 25 7.0 35 40 6.9 7.7 35

82 92 84 96 80 90

0.301 0.313 0.36

7.1

88

0.34

35

Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

a full-scale ECSB reactor (490 m3). Table 3.6 shows the performance of three full-scale ECSB facilities that treat AFWWs.

3.3.6

Anaerobic membrane bioreactor

AnMBR has gained considerable concern recently as a promising solution for wastewater treatment, owing to short HRTs, high biomass concentration, low sludge production, highquality effluent for reuse, and bioenergy generation (Liu et al., 2012, Bokhary et al., 2021). By incorporating the membrane filtration, the HRT and SRT can be decoupled in AnMBRs, achieving a substantial reduction in bioreactor volumes, thus reducing capital expenditures (Bokhary et al., 2021). Several types of AFWWs are treated by AnMBR. Table 3.7 summarizes the applications of AnMBRs in AFWWs treatment. Treated wastewater has a COD strength of 880 to more than 35,000 mg L21, SRT ranges from 8 days to several months, OLR fluctuates from 0.88 to 30 kg COD m23
d, and HRT spans from 10 hours to several days. Using AnMBRs, COD removal above 90% can be accomplished, while biogas production in the range of 0.136 m3 kg21 COD—0.38 m3 kg21 COD can be obtained. Effects of various factors on the performance of AnMBR have been studied including mixed liquor suspended solids (MLSS) concentrations, the ratio of food-to-microorganism (F/M), HRT, SRT, pH, and temperature. Lower MLSS has been associated with better treatment efficiency (e.g., higher COD, color, and suspended solids removal) and increased membrane flux. Katayon et al. (2004) reported a 2 times higher flux (5.03 L m22
h) for low MLSS concentrations (4340 5390 mg L21) than that (2.27 L m22
h) for higher MLSS concentrations (6330 10,780 mg L21). It has been reported that too high or too low F/M ratios can be detrimental to microbial growth, methane yield, and sludge deflocculation (Liu et al., 2012). A high F/M ratio can also lead to an upsurge in the extracellular polymeric substances (EPS) concentration due to the higher use of food by microorganisms, which in turn leads to increased membrane fouling (Mutamim et al., 2013). Thus the F/M ratio needs to be optimized for better treatment efficiency. Reportedly, food wastewaters can be successfully treated by AnMBR with a positive energy balance. For instance, Galib et al. (2016) treated meat-processing wastewater by AnMBR under OLRs ranged from 0.4 to 3.2 kg COD m23
d, and the energy analysis showed that the process could produce a net energy profit of 16 1.83 kWh m23 at OLRs of 1.3 and 3.2 kg COD m23
d. The researchers believe in the likelihood of energy-positive food wastewaters treatment with AnMBRs. On

81

Table 3.6 Performance of full-scale ECSB reactors treating agro-food-related wastewaters. Wastewater source

Scale Reactor volume (m3)

Temperature tCOD Feed tCOD HRT OLR (kg (h) COD m23
d) (˚C) removal (mg L21) (%)

Biogas Methane References production Content

Alcohol distillery wastewater Cheese wastewater Whiskey distillery wastewater

Full

425

6530

16

9.9

37

70.7

2.5a

70

Connelly et al. (2017)

Full

1000

3000 8000

12

5 18

29 6 1

75 82

0.37b

77

Full

490

53,000

349 d 18.4

30 40

95

729 3466c

75

Diamantis and Aivasidis (2018) Lin et al. (2019)

m3biogas m23 reactor
d. Nm3 biogas kg21 COD removed. c 3 21 m d . a b

Table 3.7 Results of selected AnMBR studies of agro-food wastewaters treatment. Wastewater source

Brewery wastewater Alcohol distillery wastewater Food industry wastewater Food wastewater Sugarcane vinasse Coffee wastewater Potatoprocessing wastewater Brewery wastewater Molasses

Scale Reactor volume (L)

Feed tCOD (mg L21)

Feed TSS (g L21)

HRT (h)

120

80,000 90,000 100 150 60 100

Lab

4

22,600

417

360

Lab

20

880

2.110

18

400

2000 15,000

60

Lab

61

15,496 17,677 2.8 2.9

53 86

Lab

7

16,000

430

3000

12

Pilot

SRT (d)

PH OLR (kg COD m23
d)

78 103

28.5 1.5

50

45/30

Temperature (˚C)

Reactor MLSS (g L21)

tCOD removal (%)

Biogas production (m3 CH4 kg21 COD)

Methane content

References

6.9 7.2 35 37

51

99

0.28

65 80

7.5 8.5 53 55

1 8

97

0.26

55

Anderson et al. (1996) Choo and Lee (1996)

4.34 10.78

99.2

6 8

81 94

0.88 4.8

7

37

0.5 2.5

7.0 7.5 23

96.9

1.96 11.8

7

55 57

67

6

7

38

11

95

2 10

6.8 7.3 35

11

99

0.136 60 70 0.21

60

0.38

54

Lab

15

17,000

2.8

30

Lab

10

8300 110,900

8.4 17.1 60 2400

81.8 1535 1.1 2.8

7.4 7.6 34

Slaughterhouse

Pilot

200

3160 31,600

48 168

50

3 3.5

7

37

17 25

78 90

0.365

70

Winery wastewater Meatprocessing wastewater Food wastewater

Lab

50

6752

55.2

560

1.75

7

35

4.78

96.7

0.57

87

Lab

5

4398

1640

5/2/1

0.4 3.2

7

24

1.920 2.630 88 95

0.13 0.18

Lab

24

2115

183.3

13

2.95

30 35

10.7 14

0.21

94.4

98.3

57 68

Katayon et al. (2004) He et al. (2005) Mota et al. (2013) Qiao et al. (2013) Dagnew et al. (2014) Chen et al. (2014) De Vrieze et al. (2014) Jensen et al. (2015) Basset et al. (2016) Galib et al. (2016) Jeong et al. (2017)

(Continued )

Table 3.7 (Continued) Wastewater source

Scale Reactor volume (L)

Feed tCOD (mg L21)

Feed TSS (g L21)

HRT (h)

SRT (d)

OLR (kg PH COD m23
d)

Temperature (˚C)

Food waste slurry Synthetic wastewater Food-recycling wastewater Food wastewater Synthetic food wastewater Synthetic food waste

Pilot

1300

444

0.248

20

40/70

0.794 0.458

28

Lab

94

Lab

24

52,100

140.9

18.5 22.7 70

2.17 3.08

Lab

1.57

15,000

1050

110

2.3 3.6

Lab

10

8240

5.09

480 24

Lab

15

73,900

1128

120 720

tCOD removal (%)

Biogas production (m3 CH4 kg21 COD)

85 97

0142 0.612

. 98

0.29

15 35

98

0.24

37

98.2

35

.97

37

1000

30 60

3 8.65

7

6

7.2 7.5

Reactor MLSS (g L21)

22

23.63

Methane content

0.139

70

0.48 0.57

60

References

Mon˜ino et al. (2017) Berkessa et al. (2018) Cho et al. (2018) Zhu et al. (2017) Ariunbaatar et al. (2020) Cheng et al. (2020)

Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

the other hand, Kubota’s submerged AnMBR process has been effectively operated in several large-scale food and beverage industries for effluents treatment. Using the Kubota process, Kanai et al. (2010) reported approximately 12 GJ d21 recovered energy from distillery wastewater treatment, which is four times the energy required (4 GJ d21) as electricity and heat for the submerged AnMBR process. AnMBR has been applied to efficiently remove pollutants such as COD, total nitrogen (TN), ammonia, and TP in wastewater. Zhu et al. (2017) treated food waste fermentation wastewater by MBR, and the average removal efficacies of COD, TN, ammonia, and TP by the system were 98.2, 81.5, 99.8, and 77.8%, respectively. The high pollutant removal by AnMBR has been attributed to its rich microbial community. However, Ariunbaatar et al. (2020) reported lower overall removal efficiencies for total ammoniacal nitrogen (17.3%), TP (40.39%), and TN (61.5%). The lower removal efficiency was explained by the release of nitrogen by seed sludge and treated feed in the digester. Membranes such as microfiltration (MF) and ultrafiltration (UF) were used to retain the biomass and maintain a high microbial concentration in the reactor (Table 3.8). Maintaining a high microbial concentration in AnMBR allows the system to handle wastewater with high COD strength. Among the employed membranes, MF was the most utilized membrane, this could be due to the associated cost. Both hollow-fiber and flat-sheet membrane configurations have been used in the treatment of AFWWs. Membrane separation is carried out with the use of either sidestream or submerged configurations of the MBR. The external configuration is used to simplify the module maintenance and monitoring, but this configuration increases the operational costs because of the recirculation loop requirement (Mutamim et al., 2013). Both MF and UF membranes were used with long-term sustainable membrane fluxes varying from 2 to 18.9 L m22
h and transmembrane pressure (TMP) in the range of 1 200 kPa (Table 3.8). The membrane can be constructed from either a polymeric or ceramic material, but the polymeric membrane [e.g., polyvinylidene difluoride (PVDF), polyethersulfone, and polyethylene] is most used in AFWWs treatment. Among the polymeric membranes, PVDF is the most widely employed membrane material and is used in both flat-sheet and hollow-fiber configurations (Table 3.8). The employed membrane pore sizes ranged between 0.02 and 0.4 µm. The wide use of polymeric membrane can be explained by its ease of manufacture, low cost, and possibility of modification with coating materials. The ceramic membrane has been reported to have good filtration

85

Table 3.8 Membranes used with AnMBR and their materials, pore sizes, and fluxes. Wastewater Type

Brewery wastewater Alcohol distillery wastewater Food industry wastewater Food wastewater Beverage/vegetable oil wastewater Supermarket wastewater Snack food wastewater Synthetic wastewater Sugarcane vinasse Coffee wastewater Potato-processing wastewater Brewery wastewater Food wastewater Molasses Slaughterhouse wastewater Winery wastewater Food wastewater Food waste recycling wastewater Food wastewater Synthetic food wastewater

Scale Material

Pore size (µm)

FP

Full Pilot Lab Lab Lab Pilot

UF UF MF UF

0.4

0.00162 0.32 0.93

Submerged, HF ExternalFS SubmergedHF

0.20

0.175

0.1 0.45 0.2

1 0.045 0.116 12.8

UF MF MF MF MF UF

SubmergedFS SubmergedHF SubmergedHF SubmergedHF SubmergedFS ExternalHF

0.4 PES

PVDF PVDF PVDF PEI ChlorinatedPE

Membrane module

0.024 0.0336

Lab Lab Full Pilot

Surface Membrane area type (m2)

TMP (kPa)

References

3 26

Anderson et al. (1996) Choo and Lee (1996)

23 200 55

2.27 5.03 13.1 18.9 5.43

Katayon et al. (2004) He et al. (2005) Jakopovi´c et al. (2008)

15 60 1 35 50 3 9 10

7.9 18.0 6.5 8.0 2 5 4.8 5.1 7.6 10

Zhu et al. (2011) Diez et al. (2012) Liu et al. (2012) Mota et al. (2013) Qiao et al. (2013) Dagnew et al. (2014)

8 4 12 0.020 0.99 1.6 7 20.2 1.17/3.13/6.4 9.2

Chen et al. (2014) Ramos et al. (2014) De Vrieze et al. (2014) Jensen et al. (2015) Basset et al. (2016) Galib et al. (2016) Jeong et al. (2017)

7.18 14.21

Zhu et al. (2017) Ariunbaatar et al. (2020)

External, FS

Lab Pilot Lab Pilot Lab Lab Bench

PVDF 0.4 ChlorinatedPE 0.4 PVDF 0.2 PVDF 0.04 Ceramic 0.1

0.047 2 0.12 0.93 0.01 0.046 0.05

UF MF UF UF MF UF UF

SubmergedHF SubmergedHF SubmergedFS SubmergedHF External SubmergedHF SubmergedFS

2 4 1 2 30 2 30

Lab Lab

PVDF PVDF

0.066

UF

HF Tubular

18 32

0.02 0.03

Flux (L m22
h)

17.5 56 10 40

FP, Fluoropolymer; FS, flat-sheet membrane; HF, hollow-fiber membrane; PE, polyethylene; PEI, polyetherimide; PES, polyethersulfone; PVDF, polyvinylidene fluoride.

Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

performance and is easier to clean than the polymeric membrane, owing to its high chemical durability, but it is associated with a high manufacturing cost (Mutamim et al., 2013). The foremost limitation of the AnMBR process for industrial applications lies in membrane fouling. Membrane fouling increases TMP and reduces membrane flux. Influent properties, operating conditions, soluble microbial products, EPS, and inorganic compounds were found to play a significant role in membrane fouling (Zhu et al., 2011; Liu et al., 2012). Several fouling mitigation strategies were developed, such as the operation of the AMBR under the critical flux, modification of the membrane properties, backflushing of the membrane, sparging of the membrane by the generated biogas to create turbulence over the membrane surface, membrane relaxation, and/or chemical cleaning (Bokhary et al., 2020). The best-known MBR manufacturers are Kubota, SUEZ Water Technologies & Solutions ZeeWeed, and Mitsubishi. Kubota dominated the installation, while SUEZ installed more capacity water treatment through its membrane. Kubota’s submerged AnMBR has been used effectively in many large-scale AFWW treatments (Kanai et al., 2010). SUEZ has installed different pilots (e.g., Oregon, Deschutes, Brewery with a capacity of 1500 gallons per day and influent COD between 5000 and 30,000 mg L21) and full-scale (e.g., Delaware Brewery with 200,000 gallons d21 and influent COD of 18,000 mg L21). AnMBRs for a variety of food wastewaters (SUEZ, 2022). SUEZ’s ZeeWeed hollow-fiber AnMBR has also been used on the pilot level for the treatment of meat and potato processing wastewater, and the system was evaluated at high OLR (10 20 kg COD m23
d) and achieved remarkable COD (99%) removal efficiency (Dagnew et al., 2014). Furthermore, several pilot-scale AnMBR demonstration plants were installed for food and beverage wastewater treatment using SUEZ AnMBR technologies in recent years (SUEZ, 2022). Moreover, one full-scale AnMBR plant (a municipal wastewater treatment plant receiving blended industrial wastewater with a treatment capacity of 400,000 gallons per day in Grand Rapids, Michigan, USA) was expected to be commissioned in 2022 (SUEZ Water Technologies and Solutions).

3.3.7

Anaerobic hybrid reactors

Hybrid reactors, which were developed to overcome the shortcomings of an individual system by combining the positive features of two combined systems, have also been used in the treatment of AFWWs. Rajagopal et al. (2010) used a hybrid

87

88

Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

configuration of the UASB-AF reactor with different packing volume ratios to process wine distillery vinasse wastewaters with the aim of reducing biomass washout and minimizing reactor clogging. The hybrid system achieved 85% COD removal under OLR of 18 kg COD m23
d and HRT for 24 hours without blockage in the reactor, and biomass washing was reduced. Burman and Sinha (2020) used a hybrid upflow-membrane bioreactor system to treat high-strength simulated wastewater. The hybrid system improved both the membrane performance and the COD removal efficiency. As high as 97% COD removal was accomplished under HRT of 3.5 d. McHugh et al. (2006) treated whey wastewater by EGSB-AF hybrid reactor and reported a COD removal efficiency of 90%, at OLR of 13.3 kg COD m23
d and psychrophilic temperature. Najafpour et al. (2006) used a hybrid system of upflow fixed film (UFF) and UASB for palm oil mill wastewater treatment, and a COD removal of 97% was reported in 3-day HRT. The hybrid system (UFF-UASB) is characterized by rapid granulation of sludge (20 days). Combined systems were also employed for the treatment of AFWWs. Meyo et al. (2021) digested poultry slaughterhouse effluent by combining a pretreatment step with EGSB -BR. This system achieved a COD removal of 97%, while the removal of fats, oil, and grease was about 97.5%. Sheldon and Erdogan (2016) used a combined EGSB/MBR process for soft drink industry effluent processing and found COD removal of up to 95%.

3.3.8

Full-scale application of high-rate anaerobic systems

Full-scale configurations of various high rate anaerobic digesters were used to treat AFWWs. Omil et al. (2003) treated dairy wastewater with a total COD concentration of 10.5 g L21 by a full-scale AF (12 m3) under an OLR of 5 6 kg COD m23
d and a mesophilic temperature (35 37 C). The system was operated for 634 days, and 90% COD removal was achieved, while the biogas production was 3.7 L biogas L21 reactor
d. Treating similar wastewater, Ji et al. (2020) used a combined process of the anaerobic baffled reactor and UASB (2800 m3). The UASB system operated under HRT ranging from 40 48 days, ambient temperature, and 1.6 g L21 COD. The process showed stable performance over 18 months of operation with 96% COD removal. The UASB reactor showed a 6.6% increase in COD removal compared to the AF reactor, but despite the treatment

Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

of the same influent (dairy wastewater), the total COD of the wastewater was different. The reported COD removal of cheese whey wastewater using a full-scale ECSB reactor under OLR in the range of 4 18 kg m23
d was equal to that reported for the UASB dairy wastewater treatment system (Diamantis and Aivasidis, 2018). Connelly et al. (2017) operated a full-scale EGSB bioreactor (425 m3) for 6 months to treat alcohol distillation spent water under OLR of 9 kg COD m23
d, HRT of 16 hours, 6.5 g L21 COD, and mesophilic (37 C) conditions. The reported COD removal was only about 70.7%, which is lower by about 20% compared to ECSB and UASB reactors. The differences in COD removal between these systems can be elucidated by the diverse sources and properties of the treated wastewater and bioreactor operating conditions. Using a full-scale AnMBR, Christian et al. (2011) stated a COD removal of more than 99% for Kubota submerged AnMBR treating salad dressing and barbeque sauce wastewater from Ken’s Foods in the United States under mesophilic (33 C) conditions and 33.5 g L21 influent COD. Using SUEZ’s full-scale AnMBR (200,000 gal d21 capacity and influent COD of 18,000 mg L21) for brewery wastewater treatment, the system is anticipated to save 55 million gallons per year of water and to generate $700,000 year21 of renewable energy (SUEZ, 2022). AnMBR exhibited better COD removal efficiency and higher biogas productivity compared to its counterparts. These merits are coupled with a high-quality effluent and food waste reduction.

3.4

Recent trends and future perspectives

Several HRAnPs and their hybrids have been used in the treatment of AFWWs and have shown high capacity in terms of COD removal and energy yield. The applications of HRAnPs in the treatment of AFWWs are expected to increase in the future, owing to the increased food demand, which will increase the generation of wastewater that should be effectively treated. The applications of HRAnPs are likely to extend to the production of other forms of bioenergy, such as hydrogen production or other value-added biomaterials, such as VFAs, which represent a new route for biochemical production. VFAs can be exploited as feedstock for various biopolymers production (Kim et al., 2018). For VFAs to be produced in large quantities, they certainly entail the adoption of such HRAnPs. Recently, the UASB reactor has been used intensively and proved its success in various commercial installations due

89

90

Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

to its compactness and reduced operational costs. In the same context, the use of AnMBR is expanding in this field, as is evidenced by the number of studies discussed in this chapter. AnMBR can outperform its counterparts through its treatment efficiency and short HRT due to the decoupling of the SRT from the HRT. Advances in membrane design and fouling reduction procedures could also make AnMBR a practical solution for future AFWWs processing.

3.5

Challenges of wastewater treatment in the agro-food industry

Two types of challenges may arise during the treatment of AFWWs: wastewater-related challenges and digesters-related challenges. Concerning the wastewater, agro-food industry wastewater is diverse, and each source has unique properties that need to be considered during treatment. HRAnPs are sensitive to the high concentration of various ions and toxicant substances, such as phenol-rich and sulfate-rich influents. Also, wastewater associated with the agriculture and food industries can sometimes be contaminated with pesticides (Campos-Man˜as et al., 2019), and it has been reported that acetoclastic methanogenesis can be significantly inhibited by pesticides (Garcı´a-Mancha et al., 2017). In addition, there are no clear design guidelines for most of the high-rate systems; in general, each system has its own designed OLR. Besides this issue, the strength of the wastewater varies greatly between sources. Therefore each wastewater source must have its design parameters for the reactor. HRAnPs are subject to changes in operating conditions due to shock loading and temperature and pH fluctuations, and any disruption in the system is likely to be associated with a long recovery time. As for general systems, anaerobic digestion is ineffective to remove nutrients and must be followed by a method that deals with nitrogen and phosphorus removal (Manas et al., 2012). Therefore most HRAnPs require posttreatment, as their effluents may contain pathogens and nutrients that need further processing. AnMBR can satisfy effluent discharge standards of nutrients, but membrane cost and fouling may hamper its wide application. In HRAnSs, a significant portion of the generated methane can be dissolved in the permeate or attached to the granules and needs to be recovered (Daud et al., 2018). Anaerobic digestion produces excess sludge that requires

Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

further treatment and/or appropriate discharge. Also, there is a possibility of emitting foul odors from the systems during wastewater treatment. On the other hand, each reactor configuration has its own challenges, ranging from blockage of the AF reactor to fouling of AnMBR. For example, among the challenges for UASB applications are granule washout and deterioration (Wu et al., 2021). The proper granulation and granulation time are the key to the successful operation of the UASB digester. Granulation that is not well established may result in sludge washout and poor effluent quality. In terms of the AMBBR, scaling on the biofilm carrier causes undesirable impacts on the AMBBR’s performance, and maintaining biofilms in optimal condition is a challenge. In AnMBR, although several fouling mitigation measures have been developed, membrane fouling still contributes significantly to the total energy requirements of AnMBR, hampering its widespread adoption. Overall, the scaling-up of laboratory findings to design and operation on a commercial scale is limited and therefore not well understood, owing to the lack of operational knowledge and experiences on full-scale design (Connelly et al., 2017).

3.6

Conclusions and future trends

HRAnPs are promising technologies for AFWWs treatment. Performance between HRAnPs can be comparable, better, or poorer in some cases. Among the HRAnPs that were reviewed in this chapter, the UASB system was the most popular configuration in food-processing wastewater treatment. However, AnMBR has shown improved performance in terms of biomass biodegradation, a small footprint, and higher-quality effluent. However, the energy consumption and operating cost of highrate systems need to be further addressed via technoeconomic studies. Also, their complex dynamics need further elucidation for improved and stable performance. In the future, the adoption of HRAnPs in processing AFWWs, especially UASB and AnMBR, is likely to increase, owing to increased food demand. The implementation of AnMBR in AFWWs treatment could surpass its counterpart (UASB) if membrane costs were reduced, which accounts for a significant portion of the capital and operating expenditures. Moreover, the effectiveness and simplicity of membrane-fouling control strategies need further development.

91

92

Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

List of acronyms AF AFWWs AMBBR AnMBR BOD COD ECSB EPS F/M FP FS HF HRAnPs HRT MBR MF MLSS OLR PE PEI PES PVDF SGBR SRT TMP TSS UASB UF VFAs

Anaerobic filter Agro-food wastewater. Anaerobic moving bed biofilm reactor Anaerobic membrane bioreactor Biochemical oxygen demand Chemical oxygen demand External circulation sludge bed Extracellular polymeric substances Food-to-microorganism Fluoropolymer Flat-sheet Hollow-fiber membrane High-rate anaerobic processes Hydraulic retention time Membrane bioreactor Microfiltration Mixed liquor suspended solids Organic loading rate Polyethylene Polyetherimide Polyethersulfone Polyvinylidene difluoride Static granular bed reactor Solids retention time Transmembrane pressure Total suspended solids Upflow anaerobic sludge blanket Ultrafiltration Volatile fatty acids

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Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

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Chapter 3 High-rate anaerobic processes for agro-food wastewater treatment

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4 Food-processing wastewater treatment by membrane-based operations: recovery of biologically active compounds and water reuse Carmela Conidi1, Angelo Basile2 and Alfredo Cassano1 1

Institute on Membrane Technology of the National Research Council of Italy (CNR-ITM), University of Calabria, Rende, Italy 2Hydrogenia and ECO2Energy, and Unit of Chemical-Physics Fund. in Chemical Engineering—Department of Engineering—University Campus Bio-medical, Rome, Italy

4.1

Introduction

Over the last decade, the food-processing industry has experienced tremendous growth and is one of the fastest-growing sectors throughout the world. At the same time, it has been recognized as one of the largest consumers of water (i.e., as an ingredient in production processes and products, for cleaning of equipment/plants and food products, and in sanitation and disinfection) (Sekoulov, 2002; Shrivastava, Ali, Marjub, Rene, & Soto, 2022). This results in the production of significant amounts of unwanted wastewaters. The characteristics and the volume of food-processing wastewaters depend on the type of product and operations involved in the process. Specifically, they contain high suspended solids, high biochemical (BOD), and chemical oxygen demand (COD), carbohydrates, proteins, lipids, hormones, antibiotics, pesticides, and nutrients (nitrogen and phosphorus). However, it is frequently difficult to predict the composition of these wastewaters, owing to handling processes and seasonal variations (Roma´n-Sa´nchez, Molina Ruiz, Casas Lo´pez, & Sa´nchez Pe´rez, 2011). Typical characteristics of agro-food industry wastewaters are presented in Table 4.1. The management of these effluents has become a major challenge for food-processing industries due to its potential impact on the environment. However, agro-food wastewaters Advanced Technologies in Wastewater Treatment. DOI: https://doi.org/10.1016/B978-0-323-88510-2.00011-7 Copyright © 2023 Elsevier Inc. All rights reserved.

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Table 4.1 Typical characteristics of agro-food industry wastewaters (Pervez et al., 2021). Typical parameters

Standard volume (mg L21)

Total suspended solids Biochemical oxygen demand Chemical oxygen demand Total phosphorus Total nitrogen pH

50 50 250 2 10 5.5
9.0

can be also considered available sources of biologically active compounds (i.e., polyphenols, proteins, oligopeptides, carotenoids, hemicellulose, pectin, lactose) that can be recovered for interesting applications in the cosmetics, pharmaceuticals, and food industries, offering a new approach for their recycling and providing at the same time economic resources (Foti et al., 2021). In addition, with the growing scarcity of potable water, the possibility of water reuse from agro-food wastewater is an important challenge for sustainable industrial processes (Garnier, Guiga, Lameloise, & Degrand, 2020). Among different techniques that have been proposed for the management of food-processing wastewaters, membrane processes represent a cost-effective solution. These processes offer many advantages over traditional separation processes (e.g., flocculation, evaporation, solvent extraction, centrifugation, adsorption), owing to their mild operation conditions of temperature and pressure, thereby preserving the functional property of bioactive compounds contained in food wastewaters, high separation efficiency toward target solutes, nonuse of additives and consequently reduced risk of contamination, easy scaling-up, and low energy consumption (Castro-Mun˜oz, Cassano, & Conidi, 2018; Nazir et al., 2019) (Fig. 4.1). Particularly, pressure-driven membrane operations, such microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), and reverse osmosis (RO) represent useful tools for the purification, fractionation, concentration, and recovery of bioactive compounds on the basis of their specific molecular weight cutoff (MWCO) and using pressure as driving force (Cassano, ˜ oz, Conidi, Ruby-Figueroa, & Castro-Mun˜oz, 2018; Castro-Mun ˜ ez-Ferna´ndez, & Fı´la, 2016; Conidi, Drioli, & Cassano, Ya´n 2018). These processes, combined in a sequential form or integrated with other separation technologies, have been largely

Chapter 4 Food-rocessing wastewater treatment by membraneased operations

Figure 4.1 Advantages of membrane processes in the treatment of agro-food industry wastewaters.

investigated in the logic of producing enriched fractions of bioactive compounds and water with high degree of purity (Ahmad, Ang, Teow, Mohammad, & Hilal, 2022; Cassano, Conidi, & Drioli, 2021). At this purpose, MF and UF are typically employed as pretreatment steps for removing undesired substances (e.g., suspended solids, microorganisms, macromolecules) from food-processing wastewaters, while NF and RO can be used to fractionate and concentrate bioactive compounds and to produce clear water as permeate stream. The aim of this chapter is to provide an overview of pressure-driven membrane processes in the separation, concentration, and purification of biologically active compounds and in water reuse from food-processing wastewaters. Fundamentals of pressure-driven membrane processes are discussed first. Then selected applications of these processes, also in integrated systems, are analyzed and discussed, highlighting the key advantages over traditional separation technologies.

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4.2

An overview of pressure-driven membrane processes

Pressure-driven membrane processes are based on the use of permselective membranes that are capable of transporting solvent fluids and solutes under a hydrostatic pressure difference. As a result, the feed stream is split into a purified fraction (permeate) that contains all components passing through the membrane and a concentrated fraction (retentate) that contains all rejected components (Fig. 4.2). Pressure-driven membrane processes include four categories: MF, UF, NF, and RO in decreasing order of pore size and increased rejection capacity (Ahmad, Ang, Leo, Mohammad, & Hilal, 2021). They are typically classified according to the pressure applied through the membrane, pore size, and separation mechanism (Van der Bruggen, Vandecasteele, Van Gestel, Doyen, & Leysen, 2003). MF membranes have a symmetric or asymmetric structure with pore size of the order of 0.05
10 μm, which is suitable to separate colloids, suspended solids (typically particles responsible for turbidity), and bacteria from other, smaller solutes. Low operating pressures (from 0.5 to 2 bar) associated with high tangential velocity (5 m s21 at an applied pressure of 0.5 bar) are typically applied. UF membranes present an asymmetric structure with a dense active layer having a pore size in the range of 10
100 nm. Usually, colloidal particles, polymers, micelles, proteins, and emulsions as well as other molecules not larger than 0.1 μm in diameter are retained. UF membranes are typically characterized by the MWCO, defined as the equivalent molecular weight of the smallest species that exhibits 90% rejection. This value for UF membranes is between 103 and 106 Da. Hydrostatic pressures are generally between 1 and 5 bar (Cheryan, 1998). The main separation mechanism in MF and UF processes is based on the sieving effect, and solutes are separated according to their dimensions although other factors, such as charge, molecular shape, and interactions between the membrane and solutes being filtered, are also involved.

Figure 4.2 Schematic of cross-flow filtration system.

Chapter 4 Food-rocessing wastewater treatment by membraneased operations

NF membranes are characterized by separation capabilities between those of UF and RO membranes. They operate at lower pressures (usually in the range of 3
40 bar) than RO membranes. These membranes have pore sizes in the range of 0.5
3 nm and MWCO of 200
1000 Da with typical salt rejection rates of 80%
100% for divalent salts, such as Na2SO4, and low rejection rates (10%
30%) for monovalent salts (i.e. NaCl) allowing the separation of uncharged organic molecules with low molecular weights and multivalent ions from water. Polymeric NF membranes contain ionizable groups such as sulfonic or carboxylic acid groups, able to produce a surface charge in the presence of a feed solution. Therefore the separation mechanism is based other than on size exclusion and steric hindrance also on Donnan exclusion effects (Nath, Dave, & Patel, 2018). RO membranes are able to separate solutes with a molecular weight higher than 300 Da from a solvent, usually water. These membranes have a dense structure with no detectable pores, and separation occurs by means of a solution diffusion mechanism (Goh, Wong, & Ismail, 2022). The particle size range for RO applications is of 0.1
1 nm, and hydrostatic pressures of 10
100 bar are applied to obtain significant transmembrane fluxes. The separation capabilities of pressure-driven membrane processes are shown in Fig. 4.3.

Figure 4.3 Separation capabilities of pressure-driven membrane processes.

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Pressure-driven membrane processes are generally operated according to a cross-flow configuration (Fig. 4.2) in which the feed stream is filtered tangentially to the membrane surface at a certain velocity to prevent membrane fouling and cake formation on the membrane surface. This configuration is preferred at large scale because it guarantees a self-cleaning mechanism of the membrane and longer operating times in comparison with the traditional dead-end filtration, in which the feed stream flows perpendicularly to the filter media, producing a cake layer of retained particles on the membrane surface whose thickness strongly affects the permeation rate. The membrane performance in pressure-driven separation process is evaluated mainly in terms of recovery factor and separation capability. The latter is usually expressed as retention or rejection (R) as follows:   Cp R5 12 ð4:1Þ Cf where Cp and Cf are the concentration of a specific component in the permeate and feed solutions, respectively. Rejection values are between 0% (for components that completely permeate through the membrane) and 100% (for components that are completely rejected by the membrane). The recovery factor (Δ) is given by Δ5

Vp Vf

ð4:2Þ

where Vp and Vf are the volumes of the permeate and feed solution, respectively. The recovery rate values are between 0 and 1. Sometimes it is also expressed as the volume concentration ratio (VCR): VCR 5

V0 Vr

ð4:3Þ

where Vr is the retentate volume and V0 is the initial feed volume. For application at industrial scale, membranes are packed in small, compact units or modules to fulfill important requirements, such as high membrane packing density and mechanical resistance. Different types of module design are available, and all are based on two types of membrane configuration: flat and tubular. Spiral-wound and plate-and-frame modules are manufactured with flat-sheet membranes, whereas hollow-fiber, capillary, and tubular modules are based on a tubular geometry.

Chapter 4 Food-rocessing wastewater treatment by membraneased operations

They are quite different in their design, production cost, mode of operation, and energy requirement for pumping the feed solution through the module. The selection of suitable configurations for a specific application depends on different parameters, such as energy consumption, production cost, packing density, and mainly the control of membrane fouling and concentration polarization phenomena. In general, membrane fouling occurs by the deposition and accumulation of retained particles (macromolecules, suspended solids, colloids, etc.) onto the membrane surface or in the membrane pores, leading to a reduction in membrane permeability. In addition, the degree of membrane fouling negatively influences the quality of filtrate, the lifetime of the membrane, the frequency of cleaning, and, consequently, the operating costs (Scha¨fer, Fane, & Waite, 2000). Different approaches have been studied to mitigate the onset of membrane fouling. The most common procedures involve appropriate pretreatment of the feed solution including sedimentation, coagulation, precipitation, prefiltration, pH adjustment. Another strategy is the modification of membrane surface. It is well known that high hydrophilicity and low surface roughness can reduce fouling formation. To achieve these properties, different strategies for the surface modifications of membranes have been investigated, including the introduction of hydrophilic groups (such as
OH and
NH2 groups) or nanoparticles directly in the polymer structure, surface grafting, and coating (Diez & Rosal, 2020; Razmjou, Mansouri, & Chen, 2011).

4.3

Recovery of biologically active compounds and water from foodprocessing wastewaters

Pressure-driven membrane operations represent a useful approach to separate macromolecules and micromolecules from agro-food wastewaters (Cassano, Conidi, Galanakis, & ˜ oz, 2016). Their combination in hybrid systems or Castro-Mun with conventional unit processes offers new opportunities to convert these residues into value-added sources, contributing to the circular economy approach, environmental protection, and economic growth (Tapia-Quiro´s et al., 2022). Specific applications in the field of olive oil production and the fish and dairy industries have been reported.

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4.3.1

Olive mill wastewaters

Olive oil production generates large quantities of aqueous wastes, known as olive mill wastewaters (OMWWs). They constitute a dark-brown liquid with acid reaction (pH between 3 and 6) characterized by high concentrations of organic compounds, including sugars, tannins, organic acids, pectins, polyalcohols, and polyphenols. The high content of organic matter makes OMWWs phytotoxic and resistant to biological degradation, creating severe environmental and economic problems for their disposal. Different procedures, such as biological, physical, and chemical treatments, including aerobic and anaerobic digestion, flocculation, evaporation, sedimentation, advanced oxidation processes, electrocoagulation, or combined technologies, have been proposed to reduce the toxicity and organic load of OMWWs (Ammary, 2005; Angelidaki, Ahring, Deng, & Schmidt, 2002; Benamar et al., 2020; Deˇ germenci, Cengiz, Yildiz, & Nuhoglu, 2016; Lafi, Shannak, Al-Shannag, Al-Anber, & AlHasan, 2009). Recently, in relation to the greater interest in natural compounds with biological activity, research has been oriented toward the recovery of polyphenols as compounds with high added-value, transforming OMWWs from effluents into raw material with high potential economic value. Indeed, polyphenols are well known for their excellent biological properties, such as antiinflammatory, anticancer, antioxidant, hypoglycemic, and cardioprotective properties (Obied et al., 2005; Sajadimajd et al., 2020). Membrane separation processes such as MF, UF, NF, and RO represent promising technologies for separating, purifying and concentrating polyphenols from OMWWs. In particular, integrated membrane processes, based on a sequential combination of these processes, have been studied in terms of the logic of producing specific fractions enriched in polyphenols and freshwater to be reused in the olive oil process, for irrigation or for its safe discharge into sewage (Gebreyohannes, Mazzei, & Giorno, 2016). A membrane-based process for the total recovery of polyphenols, organic substances, and water from OMWWs was investigated by Russo (2007). It was based on a preliminary MF of the pretreated OMWW, followed by two UF steps operated with 6-kDa and 1-kDa membranes, respectively, and a final RO treatment of the UF permeate. Experimental results indicated the MF process as a critical step for the selective fractionation of phenolic compounds due to severe fouling phenomena and

Chapter 4 Food-rocessing wastewater treatment by membraneased operations

difficulties in the cleaning procedures. The 6-kDa polymeric membrane allowed the purification of polyphenols contained in the MF permeate, reducing total nitrogen (TN) of 68%, minerals of 33%, glucose of 37%, and dried residue of 38%. No differences in the selectivity of hydroxytyrosol were detected in comparison with 1-kDa ceramic membranes. The RO process allowed concentration of these substances (with rejection values ranging between 96% and 99%) with the production of a retentate fraction enriched in purified low-molecular-weight polyphenols for application in pharmaceutical, food or cosmetic industries and ultrapure water (RO permeate) suitable for beverage formulations. In another study, Paraskeva, Papadakis, Tsarouchi, Kanellopoulou, and Koutsoukos (2007) evaluated the performance of a combination of UF, NF, and RO membranes to fractionate OMWWs. Raw wastewaters were previously prefiltered with a polypropylene (PP) screen (80 μm) and then ultrafiltered with a multichannel ceramic membrane (pore size of 100 nm). The UF permeate was processed with spiral-wound NF (MWCO 200 Da) or RO (MWCO 100 Da) membranes. The UF process allowed the separation of high-molecular-weight constituents, including lipids, fats, and suspended solid particles from the prefiltered wastewater, while the NF process allowed the production of a concentrated fraction containing more than 95% of phenolic substances of the initial value from the UF permeate. An improved efficiency of the OMWWs treatment was achieved by applying RO after UF. Permeate fractions coming from NF and RO processes showed quality characteristics to be used for irrigation or discharged in aquatic systems according to national or EU regulations. An integrated process based on the use of UF and NF membranes for the recovery of bioactive compounds and water from OMWWs was investigated by Cassano et al. (Cassano, Conidi, Giorno, & Drioli, 2013). OMWWs were previously ultrafiltered with hollow-fiber membranes in polyvinylidene fluoride with a pore size of 0.02 μm to remove suspended solids. The clarified stream was submitted to a second UF step by using a composite fluoropolymer membrane with a MWCO of 1000 Da. The obtained permeate was concentrated through a NF spiralwound polyamide (PA) membrane having a MWCO of 180 Da. The UF membranes showed rejection rates of about 26% and 31% toward polyphenols allowing their recovery in the permeate stream, while the observed rejection of the NF membrane was of about 93%. This membrane retained all the analyzed low-molecular-weight polyphenols, producing a retentate

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fraction with high total antioxidant activity and therefore of interest for food, pharmaceutical, or cosmetic applications; on the other hand, the permeate stream depleted in phenolic compounds was suggested as suitable solution for membrane cleaning or other aims (irrigation, process water, washing solution, etc.). UF retentate fractions, mainly composed of organic substances at high molecular weight, could be submitted to an anaerobic digestion treatment for the production of biogas. A schematic representation of the investigated process is depicted in Fig. 4.4. A sequential design for the fractionation of OMWWs, based on the use of MF and NF membranes, was investigated by Di Lecce et al. (2014). OMWWs were pretreated by MF to obtain a

Figure 4.4 Integrated membrane process for the recovery of biologically active compounds and water from OMWWs. Adapted from Cassano, A., Conidi, C., Giorno, L., & Drioli, E. (2013). Fractionation of olive mill wastewaters by membrane separation techniques. Journal of Hazardous Materials, 248
249, 185
193.

Chapter 4 Food-rocessing wastewater treatment by membraneased operations

clarified fraction depleted in suspended solids and colloidal substances; the NF process was used for the recovery of lowmolecular-weight polyphenols and water from the MF permeate. Experimental results showed NF membrane rejection values higher than 98% toward dry matter, COD, antioxidant activity, and phenolic compounds independently by the final VCR that is achieved. Therefore a purified fraction (NF permeate) with low phenolic contents and COD very close to those requested for discharge into surface waters and a concentrated fraction (NF retentate) enriched in phenolic compounds useful for cosmeceutical or nutraceutical applications or as supplement in the food industry were obtained. Sedej et al. (2016) successfully used a novel vibratory sequential membrane system, including UF and RO processes, for the recovery of polyphenols and water from OMWWs. A polyethersulfone (PES) membrane with a MWCO of 7000 Da was selected for the UF treatment to remove suspended solids and high-molecular-weight molecules. The UF permeate was concentrated by a composite PA RO membrane, which was able to produce a purified permeate near to pure water suitable to be recycled into the milling process and a concentrated fraction enriched with biophenols. This stream was then dried using freeze drying, spray drying, and infrared drying to obtain a solid material. In a similar approach, UF and NF membranes in sequential design were employed for processing OMWWs aim to recover biologically active compounds (such as polyphenols) and clean water and at the same time to remove the polluting load (Alfano et al., 2018). The NF process led to a reduction of about 95% of the organic load and production of a retentate enriched in polyphenols. This fraction, dried by using the spray-drying technique, was tested for cell viability after oxidative stress induction on human keratinocytes model in vitro demonstrating an improved cell reparation in scratch assays assisted through time-lapse video microscopy. These results confirmed the suitability of these fractions as ingredients in cosmeceutical and nutraceutical preparations, while the NF permeate, characterized by low conductivity (5
15 μS cm21) could be reused in the productive cycle, contributing to a significant saving of water resources. The integration of MF and RO processes was investigated by Bottino et al. (2020). For this purpose, a multichannel ceramic MF membrane was used to retain suspended solids and to produce a clarified permeate to be treated with the RO membrane in order to separate dissolved substances from water. The RO

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membrane showed a high retention toward polyphenols (.99.3%) and COD (about 95%) and the production of a water stream (RO permeate) with low salinity and phytotoxicity (due to polyphenols removal). Recently, Tundis, Conidi, Loizzo, Sicari, and Cassano (2020) investigated a combination of MF, NF, and RO membranes to produce concentrated polyphenol-enriched fractions that were analyzed for their chemical profile and their potential biological activities, such as antioxidant, hypolipidemic, and hypoglycemic. In particular, OMMWs were first pretreated by MF to remove suspended solids and then fractionated and concentrated through a combination of NF and RO processes. The phenolic profile of permeate and retentate samples for each investigated process is reported in Table 4.2. The RO retentate exhibited the highest content of phenolic compounds, with hydroxytyrosol, tyrosol and oleuropein, the most abundant. In particular, a content of hydroxytyrosol of 1522.2 mg L21, about five times higher than that of the MF permeate, was found. This fraction showed the highest antioxidant activity as well as the highest hypoglycemic activity. It has been considered of interest for the development of functional products for the prevention of obesity and diabetes type 2. Savarese, De Marco, Falco, D’Antuoni, and Sacchi (2016) studied the integration of pressure-driven membrane processes and adsorbent resins for the separation and purification of phenolic compounds from OMWWs for large-scale implementation. For

Table 4.2 Treatment of olive mill wastewaters by integrated membrane process. Phenolic compounds MF permeate NF retentate NF permeate RO retentate RO permeate Caffeic acid p-Coumaric acid Ferulic acid Luteolin 4-Hydroxyphenyl acetate Hydroxytyrosol Oleuropein Tyrosol Vanillic acid Verbascoside

7.6 6 0.5 4.3 6 0.2 6.3 6 0.3 13.7 6 1.1 67.0 6 2.6 320.1 6 5.8 85.2 6 2.7 68.1 6 5.1 27.8 6 1.7 18.0 6 1.3

27.7 6 1.4 12.2 6 0.8 20.1 6 1.1 71.5 6 2.7 29.6 6 1.2 1017.5 6 8.8 263.2 6 4.2 157.3 6 4.3 97.0 6 2.5 82.8 6 3.4

1.8 6 0.2 2.6 6 0.2 n.d. n.d. 64.0 6 3.2 268.3 6 1.2 n.d. 64.8 6 1.2 6.5 6 0.9 n.d.

45.7 6 1.2 35.9 6 1.6 51.3 6 1.4 82.8 6 3.1 57.1 6 1.2 1522.2 6 7.3 510.0 6 5.5 519.0 6 6.2 116.2 6 3.1 130.9 6 1.2

Phenolic compounds in permeate and retentate samples (data expressed in mg L21) (Tundis et al., 2020). n.d., not detectable.

0.5 6 0.03 n.d. n.d. n.d. n.d. 18.8 6 1.2 n.d. 5.0 6 0.6 1.4 6 0.1 n.d.

Chapter 4 Food-rocessing wastewater treatment by membraneased operations

this purpose, an automated plant with a capacity of 1 m3 hour21 of incoming effluent was used. In the developed process, OMWWs were previously submitted to a pretreatment step (including decanter, lamellar flotator, filter press, and centrifugal separator) and then processed by spiral-wound UF, NF, and RO membranes in a sequential design. More in detail, the pretreated effluent was clarified by UF, and the obtained permeate was concentrated by NF. The NF retentate was submitted to an adsorption/desorption treatment by using a nonionic, highly cross-linked, adsorbent resin (polystyrene-divinylbenzene) with high specific surface area (800
1100 m2 g21) for the purification and concentration of polyphenols. Desorption of polyphenols was achieved by using ethanol and the ethanolic extract was then dried in evaporator under vacuum. The NF permeate, enriched in low-molecular-weight sugars, was treated by the RO membrane to obtain a concentrated fraction enriched in sugars, useful for biological treatment and purified water. The overall process allowed the production of a creamy phenolic extract with a content in polyphenols of about 9.5%, one-third of which (about 3.1%) is hydroxytyrosol. For plants with capacities of 20 m3 day21 and 200 m3 day21, total unit costs of h 125.01 m23 and h 58.61 m23, respectively, were estimated. The income from the sale of antioxidant extracts was estimated to be around h 200 kg21; further indirect benefits are represented by the avoided agronomic disposal of OMWWs and the value of the biogas. Pressure-driven membrane operations have been also combined with other membrane operations, such as osmotic distillation (OD) and membrane emulsification, to improve the final concentration of phenolic compounds in the purified fraction of OMWWs. In the process investigated by Bazzarelli et al. (2016). OMWWs were firstly acidified with sulfuric acid to achieve a complete removal of suspended solids before the MF step. The MF permeate was then fractionated by NF and the NF retentate was concentrated by OD by using a PP hollow fiber membrane contactor and calcium chloride dihydrate as stripping solution. The OD retentate was finally encapsulated in a water-in-oil emulsion by membrane emulsification. According to the mass balance of the process, about 1.5 kg of phenolic compounds (85% of the initial phenolic content) and 800 L of purified water can be recovered starting from 1 m3 of OMWW.

4.3.2

Fish-processing wastewaters

The fish-processing industry generates high amounts of process effluents as a result of operations such as washing, chilling,

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thawing, rinsing, blanching, fileting, and cooking. The volume and concentration of these effluents varies widely, depending on the fish to be processed, the additives used (e.g., brine, oil), and the unit processes involved (Cristo´va˜o, Botelho, Martins, Loureiro, & Boaventura, 2015). They contain high level of pollutants (e.g., organic contaminants in soluble, particulate, and colloidal form) with COD values up to 9 g L21, TN values up to 3 g L21, and salt content in the range 7
49 g L21. Consequently, the discharge of such untreated or inadequately treated fishprocessing wastewaters is likely to have significant environmental implications (Land et al., 2020). An adequate wastewater treatment process aimed at recycling water and recovering valuable nutrients is therefore crucial for a sustainable fish industry. Fish industry wastewaters are rich in bioactive molecules such as polyunsaturated fatty acids, proteins, carotenoids, aroma, and flavor compounds that can be potentially recovered and reused in the food sector (Venugopal, 2021). In this context, membrane technology is a useful approach for the recovery of these substances and water, reducing the risk of pollution and improving economic benefits for the fishery industry (Youravong & Li, 2009). An integrated membrane process based on the use of MF and UF (or NF) for the recovery of proteins from effluents of a fishmeal plant was studied by Afonso and Bo´rquez (Afonso & Borquez, 2002a). The MF pretreatment allowed the reduction of suspended matter, grease, and oil content from the original effluent. The subsequent treatment of the MF permeate by UF allowed recovery of valuable substances, including proteins, and reduction in the organic load. In particular, the selected tubular UF membrane (Carbosep M2, 15 kDa) showed a rejection rate toward proteins in the range 49%
62% depending on the operating conditions. A higher protein rejection rate, between 63% and 82%, was obtained when the MF permeate was treated with a ceramic multichannel NF membrane (Kerasep NanoN01A) (Afonso & Borquez, 2002b). According to the experimental results, a process based on the use of MF and UF membranes for the treatment of 10 m3 hour21 of fishmeal effluent, to obtain 1 m3 hour21 of concentrate containing 112 g L21 of proteins and 170 g L21 of solids, was designed. From an economic point of view, the proposed process, accomplished for production of 544 ton year21 of fishmeal (66% protein content), produced a net worth of US$160 3 103, an interest rate of return of 17%, and a payback time of 8 years, indicating its feasibility for both the recovery of proteins

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115

and the reduction of pollution (Afonso, Ferrer, & Bo´rquez, 2004). Mameri et al. (1996) measured an apparent rejection rate of about 70%
80% toward proteins of fishery washing water by using multichannel ceramic membranes with 0.1-μm pore size and tubular polysulfone membrane with MWCO of 20 kDa, despite their different pore diameters. The UF processes allowed a reduction on BOD of 80% and an increase in the protein concentration in the feed solution from 5 to 35 g dm23. Integrated membrane processes based on the use of UF, NF, or RO for the reduction of the pollution load and the concentration of flavor compounds from seafood cooking water (buckies, shrimps, and tuna) were investigated by Vandanjon, Cros, Jaouen, Que´me´neur, and Bourseau (2002). RO membranes were more efficient in retaining aroma compounds from buckies and shrimp cooking juices in comparison with 300-Da NF membranes, and showed also higher removals of COD (95% for buckies and shrimp and 85% for tuna juices). In another approach, Walha et al. (2011) studied the concentration of aroma compounds and the reduction of environmental load of tuna cooking juice with NF. In addition, the influence of pretreatment by MF on NF permeate fluxes and aroma quality was investigated. The MF pretreatment, performed with a ceramic multichannel membrane (Kerasep K01, Orelis) with pore size of 0.1 μm, positively affected NF permeation fluxes up to 90
100 L m22 h. In the NF permeate the overall juice intensity decreased; consequently, the aromatic properties of the juice were modified, but the marine note was well preserved. Recently, de Oliveira et al. (2021) successfully used a 30-kDa PES UF membrane in the treatment of surimi washing waters. The UF permeate showed a reduction in total solids, COD, and proteins of 63%, 99%, and 93.13%, respectively (Table 4.3). The

Table 4.3 Analyses of surimi washing water before and after UF treatment (de Oliveira et al., 2021). Parameter 21

Fixed solids (mg L ) Total solids (mg L21) COD (mg L21) Lipids Proteins (μg/10 μL) pH

Feed

UF permeate

Reduction (%)

1.1 6 0.15 7.9 6 0.96 142.7 6 32.52 0.7 6 0.15 19.2 6 0.92 6.5 6 0.01

0.9 6 0.16 2.9 6 0. 51 1.8 6 0.07 0.1 6 0.04 1.3 6 0.41 6.3 6 0.25

14 63 99 84 93


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selected membrane reduced the organic matter from surimi washing waters, allowing their disposal and potentially their reuse in the fish process and at the same time the recovery of proteins (.93%) that can be used as food supplements, owing to their high content of essential amino acids (leucine, lysine, valine, and phenylalanine).

4.3.3

Dairy-processing wastewaters

The dairy industry produces large quantities of liquid effluents deriving from material losses from the dairy products and wastewaters from cleaning, disinfection, washing, heating and cooling operations. Typically, dairy wastewaters have a turbid character, an unpleasant odor, a white color and contain high concentrations of organic and inorganic substances, suspended and dissolved solids, fat, oil, grease and are characterized by high BOD and COD values (Ahmad et al., 2019; Stasinakis, Charalambous, & Vyrides, 2022). This chemical composition makes these effluents extremely harmful and dangerous for the environment. Therefore appropriate treatment methods are required in order to meet effluent discharge standards and the implementation of strategies that ensure not only that valuable compounds are recovered but also that high-quality water is obtained for reuse (Oro, dos Santos, Dallago, & Tres, 2022; Passeggi, Lopez, & Borzacconi, 2009). Traditional biological and physicochemical dairy wastewater treatments, such as aerobic and anaerobic processes, coagulation, and flocculation, present many disadvantages, such as loss of nutrients and generation of greenhouse gases, and require many process steps, causing high processing time and costs (Kushwaha, Srivastava, & Mall, 2011; Slavov, 2017). On the other hand, membrane-based processes are a promising technology for water reuse, reduction of volume of produced dairy wastewater, and the recovery of valuable compounds (such as whey proteins), owing to their high separation efficiency, small footprint, and ease of operation (Caballero et al., 2021). In particular, the application of integrated pressure-driven membrane processes in decreasing order of MWCO has been investigated by different authors for the treatment of these effluents. For instance, a sequential combination of UF and NF processes has been studied by Luo et al. (Luo, Ding, Qi, Jaffrin, & Wan, 2011) for the treatment of dairy wastewaters, aiming at

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117

producing a concentrated fraction that is enriched in proteins and reusable water. In the first UF step, proteins and lipids were completely retained by the membrane and concentrated in the UF retentate. The NF membrane enabled concentration of lactose in the NF retentate, owing to the high retention rate that was measured (higher than 99%) and the production of reusable water. Three valuable fractions are produced according the proposed design (Fig. 4.5): 1. A concentrated fraction (UF retentate) enriched in proteins and lipids that is suitable as substrate for alga cultivation to produce biogas or biodiesel 2. A concentrated fraction (NF retentate) rich in lactose that is useful for anaerobic digestion to produce biogas 3. An aqueous fraction (NF permeate) with low electrical conductivity, that could be reused in the dairy industry

Figure 4.5 Sequential UF and NF process for the recovery of valuable compounds and water from dairy wastewaters. Adapted from Luo, J., Ding, L., Qi, B., Jaffrin, M.Y., Wan Y., 2011. A two-stage ultrafiltration and nanofiltration process for recycling dairy wastewater. Bioresource Technology, 102, 7437
7442.

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Chapter 4 Food-rocessing wastewater treatment by membraneased operations

In a similar approach, an integrated UF-NF process for recovering proteins and water from these effluents was investigated by Gong et al. (Gong, Zhang, & Cheng, 2012). The UF process allowed the removal of proteins (about 98.9% at pH 8.0), while lactose was completely recovered in the UF permeate and concentrated in the retentate of the NF membrane (NF 90, NF90 from Dow-Filmtec) with a recovery rate of 98.5%. The content of COD in the NF permeate was below 70 mg L21 (starting from an initial value in the UF feed of 2500
3900 mg L21). Bortoluzzi, Faita˜o, Di Luccio, Dallago, and Steffens (2017) studied an integrated membrane system based on sequential MF-NF (using two different NF membranes) or MF-RO at different applied pressures for treating dairy wastewaters. Results of filtration experiments showed that the combination of MF plus RO was more efficient in the removal of turbidity, color, total Kieldahl nitrogen, and total carbonic content (with average retention rates between 84% and 100%) working at low pressure values (1 bar for MF and 20 bar for RO). The RO permeate, depleted in organic matter, met characteristics to be reused in cleaning in place systems in dairy plants, following Brazilian environmental regulations. Chen et al. (2017) studied an integrated process based on isolelectric precipitation, UF, NF, and lactid acid fermentation for recovering proteins, cells, lactid acid and water from dairy wastewaters. The isoelectric precipitation, as pretreatment step, allowed to reduce concentration polarization and fouling during UF. Whey proteins were retained by the UF membrane. The treatment of the UF permeate by NF produced freshwater for reuse and a retentate enriched of lactose that was used as substrate for lactid acid fermentation by a thermophilic Bacillus coagulans IPE22. This step allowed to obtain 5.42 g L21 of cell mass and 37.6 g L21 of lactic acid, respectively, that could be used as animal food or raw material for bioplastics production. The proposed process is depicted in Fig. 4.6. More recently, Bria˜o, Salla, Miorando, Hemkemeier, and Favaretto (2019) investigated the use of NF and RO membranes for treating dairy rinse water aiming at recovering valuable compounds and water and improving the sustainability of the dairy industry from an economic and a technical point of view. The RO showed high retention toward all analyzed compounds (.99%) (Table 4.4), producing a water stream with a low organic content of potential use on side as

Chapter 4 Food-rocessing wastewater treatment by membraneased operations

119

Figure 4.6 Integrated process for the production of whey proteins and lactic acid (LA) from dairy wastewaters. Adapted from Chen, Z., Luo, J., Wang, Y., Cao, W., Qi, B., & Wan Y. (2017). A novel membrane-based integrated process for fractionation and reclamation of dairy wastewater. Chemical Engineering Journal, 313, 1061
1070.

cooling water and a milk-based retentate fraction, with a 9.4% of dry matter at VCR of 64, suitable to be added to fermented milk beverages, improving the sustainability of the dairy industry. From an economic perspective, processing 1000 m3 of milk per day, a potential profit of US$349,000 per year can be reached.

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Chapter 4 Food-rocessing wastewater treatment by membraneased operations

Table 4.4 Membrane rejection and characteristics of dairy rinse water before and after RO at a VCR of 64 (Bria˜o et al., 2019). Parameter 21

COD (mg L ) EC (μS cm21) Phosphorous (mg L21) Sodium (mg L21) Turbidity (NTU) Color (Hz) Hardness (mg L21) Nitrogen (mg L21) Potassium (mg L21) Proteins (mg L21) Lactose (mg L21) Oil and grease (mg L21)

Raw wastewater

RO retentate

RO permeate

Rejection (%)

2230 174 443 34 401 460 55 99.7 64 636 980 575

118,094 2200 443 1256 10,700 37,900 1050 3483 2730 22,221 42,890 21,550

88.3 95.0 0.5 108.2 2.0 2.0 48.0 17.9 105.5 114 31.0 18.0

99.93 95.68 99.88 99.13 99.98 99.99 99.54 99.49 96.15 99.47 99.92 99.91

4.4

Conclusions and future trends

The food industry is one of the most important industrial sectors worldwide. However, it consumes high volumes of waters and generates great quantity of polluting effluents that need to be treated before being discharged since cause damage to the environment and the ecosystem. On the other hand, the intensive research in the field of food industry wastewater management suggests that these effluents can be considered an important source of valued-added compounds and water that can be recovered. Particularly, given the increasing scarcity of freshwater, water recycling and reuse could help to reduce water consumption in the food industry, while the recovery of valuable compounds could be of interest for potential application in pharmaceuticals, food, and cosmetics industries. Pressure-driven membrane processes are a useful approach to recover water for recycling and high-value-added compounds from these effluents, helping to advance the food industry toward sustainable development. Over the course of this chapter, pressure-driven membrane operations were analyzed in light of their growing use for the recovery of value-added compounds from agro-food wastewater and high water quality with characteristics to be reused or recycled with significant advantages in terms of reduction of the environmental load.

Chapter 4 Food-rocessing wastewater treatment by membraneased operations

Case studies in the treatment of specific agro-food wastewaters have been reviewed and discussed, highlighting their advantages over conventional technologies, owing to their intrinsic properties in terms of reduction of the environmental impact, low energy consumption, high degree of selectivity, possibility of automation, and compact design. New perspectives and potentialities are expected from the combination of pressure-driven membrane processes and innovative membrane unit operations, such as forward osmosis, membrane distillation, and OD, contributing to redesign traditional flow sheets in the food-processing industry and providing fundamental support for the development of sustainable industrial growth in agreement with the process intensification and zero discharge strategies.

List of acronyms BOD COD MF MWCO NF OD OMWW PA PES PP RO TN UF VCR

biochemical oxygen demand chemical oxygen demand microfiltration molecular weight cut-off nanofiltration osmotic distillation olive mill wastewater polyamide polyethersulfone polypropylene reverse osmosis total nitrogen ultrafiltration volume concentration ratio

List of symbols Cf Cp R V0 Vf Vp Vr

feed concentration permeate concentration rejection initial volume feed volume permeate volume retentate volume

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452. Lafi, W. K., Shannak, B., Al-Shannag, M., Al-Anber, Z., & Al-Hasan, M. (2009). Treatment of olive mill wastewater by combined advanced oxidation and biodegradation. Separation and Purification Technology, 70, 141
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7442. Mameri, N., Abdessemed, D., Belhocine, D., Lounici, H., Gavach, C., Sandeaux, J., & Sandeaux, R. (1996). Treatment of fishery washing water by ultrafiltration. Journal of Chemical Technology & Biotechnology, 67, 169
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438. Obied, H. K., Allen, M. S., Bedgood, D. R., Prenzler, P. D., Robards, K., & Stockmann, R. (2005). Bioactivity and analysis of biophenols recovered from olive mill waste. Journal Agricultural and Food Chemistry, 53, 823
837. Oro, C. E. D., dos Santos, M. S. N., Dallago, R. M., & Tres, M. V. (2022). Membrane applications in the dairy industry. Biointerface Research in Applied Chemistry, 12, 5012
5020. Paraskeva, C. A., Papadakis, V. G., Tsarouchi, E., Kanellopoulou, D. G., & Koutsoukos, P. G. (2007). Membrane processing for olive mill wastewater fractionation. Desalination, 213, 218
229. Passeggi, M., Lopez, I., & Borzacconi, L. (2009). Integrated anaerobic treatment of dairy industrial wastewater and sludge. Water Science and Technology, 59, 501
506. Pervez, M. N., Mishu, M. R., Stylios, G. K., Hasan, S. W., Zhao, Y., Cai, Y., . . . Naddeo, V. (2021). Sustainable treatment of food industry wastewater using membrane technology: A short review. Water, 13, 3450. Razmjou, A., Mansouri, J., & Chen, V. (2011). The effects of mechanical and chemical modification of TiO2 nanoparticles on the surface chemistry, structure and fouling performance of PES ultrafiltration membranes. Journal of Membrane Science, 378, 73
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Savarese, M., De Marco, E., Falco, S., D’Antuoni, I., & Sacchi, R. (2016). Biophenol extracts from olive oil mill wastewaters by membrane separation and adsorption resin. International Journal of Food Science and Technology, 51, 2386
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5 Biorefineries to improve water and resource recovery in the seafood-processing industry J. Gonza´lez-Camejo1,2, C. Andreola1, V. Maceratesi1,3, G. Toscano3, A.L. Eusebi1 and F. Fatone1 1

Department of Science and Engineering of Materials, Environment and Urban Planning-SIMAU, Universita` Politecnica delle Marche, Ancona, Italy 2 CALAGUA—Unidad Mixta UV-UPV, Institut Universitari d’Investigacio´ d’Enginyeria de l’Aigua i Medi Ambient—IIAMA, Universitat Polite`cnica de Vale`ncia, Camı´ de Vera s/n, Valencia, Spain 3Department of Agricultural, Food and Environmental Sciences D3A, Universita` Politecnica delle Marche, Ancona, Italy

5.1

Introduction

Economic development based on the intensive consumption of resources is raising environmental awareness among citizens, scientists, and institutions. Current trends and practices in industrial agriculture for food and feed production do not guarantee a safe food supply for the 21st century. Moreover, with the perspectives of increasing resource consumption per capita and world population growth from 7.7 billion to 9.7 billion people in 2050 (Hong et al., 2018), the amount of water, energy, and food needed to serve the population is expected to increase exponentially in the next decades (Ait-Mouheb et al., 2018; Sorinolu, Tyagi, Kumar, & Munir, 2021). Resource consumption is also associated with the generation of wastes and wastewater that, despite the efforts of national and international authorities, are not decreasing. About 330 km3 of urban wastewater is generated worldwide each year. This water could be used to irrigate millions of hectares of crops or for other non-potable purposes if they are given appropriate treatments. However, the amount of wastewater that is reused is still far from the maximum possible (Khalid et al., 2018). With respect to solid waste, food wastage (Fig. 5.1) is one of the most abundant fractions of total municipal waste generated (European Environment Agency, 2013). Food loss includes the food wastage Advanced Technologies in Wastewater Treatment. DOI: https://doi.org/10.1016/B978-0-323-88510-2.00002-6 Copyright © 2023 Elsevier Inc. All rights reserved.

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Figure 5.1 Basic scheme of food wastage along the food supply chain. Based on Engelberth, A. S. (2020). Evaluating economic potential of food waste valorization: Onward to a diverse feedstock biorefinery. Current Opinion in Green and Sustainable Chemistry, 26, 100385. https://doi.org/10.1016/J.COGSC.2020.100385.

that is generated at the production, processing, and manufacturing stages, whereas food waste is the wastage that is generated at the retail and consumption stages (O’Connor et al., 2021), the latter accounting for 56% of the total food lost and wasted (Cristo´bal, Caldeira, Corrado, & Sala, 2018). Although it is hard to obtain precise numbers, it has been estimated that nearly 1.3 billion tons of food is lost along the food supply chain every year, which corresponds to one-third of the total production for human food consumption (FAO, IFAD, UNICEF, WFP, & WHO, 2020). These losses were estimated to be worth around 143 billion euros EU-28 in 2012 (Stenmarck, Jensen, Quested, & Moates, 2016). From an environmental point of view, inappropriate management of food wastage entails several issues: (1) pollution of natural water bodies, soils, and groundwater; (2) fire risk; (3) vector-borne disease proliferation (Mon˜ino Amoro´s, 2017); and (4) emissions of pollutant gases to the atmosphere. In fact, Scialabba (2015) reported that global food losses and wastes generated 4.4 GtCO2eq. annually, which is equivalent to the 8% of the total anthropogenic greenhouse gases (GHG) emissions. These numbers are expected to increase, since food wastage rises as population grows and living standards improve. Projections state that global food waste production will double by 2050 if consumption habits and food production practices do not change (Huang, Liu, & Hsu, 2020). For this, the United Nations has set the target of halving per capita global food wastage by 2030 (Cristo´bal et al., 2018).

Chapter 5 Biorefineries to improve water and resource recovery in the seafood-processing industry

Currently, most food wastage is either landfilled, incinerated, or simply left out to spoil with the subsequent environmental impacts (Bruno, Ekorong, Karkal, Cathrine, & Kudre, 2019; ¨ zogul, & Regenstein, 2016; Li, Xu, & Yu, 2018; Yadav Hamed, O et al., 2019). This is evidence of the urgent need for a shift in paradigm regarding economic and industrial development at the expense of depleting natural resources. Circularity must play a key role in this transformation toward climate neutrality and long-term competitiveness of all human activities. Within the circular economy concept, materials that are traditionally considered to be waste are used as raw matter, converting the economic activities into autoregenerative ones. In this respect, the Circular Economy Action Plan (COM, 2020) identified five priority sectors, food waste being one of them. A circular approach can significantly reduce negative environmental and social impacts associated with resource extraction while generating extra value, unlocking economic opportunities, and restoring biodiversity, making the economic model more efficient (Puyol et al., 2017; Spadaro & Rosenthal, 2020). With this approach, the zero pollution ambition, which is related to reducing pollutant emissions to negligible levels in soil, water, and ˇ marine ecosystems (Cavo sˇki, 2020), is also pursued. Both circularity and the zero pollution ambition are tightly related to the improvement in the efficiency of water and waste treatment processes, which is associated with carbon footprint reduction, digitalization tools for the water and waste treatment sectors, the transition of sustainable technologies from local regions to continent level and beyond, and the elaboration of policy guidelines and recommendations to boost their application. Food wastage has tremendous potential to be used in these new bio-based value chains, not only because of the huge amounts of food wastes produced, but also for their physicochemical characteristics. Implementation of biorefineries for food wastage and water valorization is an ideal option to pursue (Bhattacharya & Goswami, 2020; Tsang et al., 2019). Biorefineries (Fig. 5.2) refer to facilities where different conversion processes (using organic materials as feedstock) are integrated to obtain multiple bioproducts by taking advantage not only of the raw material but also of the residues generated in upstream processes (Cristo´bal et al., 2018). For instance, new and existing chemicals, biofertilizers, biofuels, and others can be produced, depending on the chemical composition of the raw material and on the transformation processes (Engelberth, 2020). The recovery of these sidestreams to obtain bioproducts adopts a circular approach, especially if they are coupled with wastewater treatment to produce reclaimed water. This

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Figure 5.2 General biorefinery scheme for resource recovery from water and food wastes.

approach enables taking advantage of key elements, reducing the GHG emissions associated with conventional production processes, and decreasing natural resource depletion (Matassa et al., 2020). For instance, biofertilizer production from biological resources helps to reduce the consumption of mineral phosphorus and nitrogen, which are very energy demanding and resource consuming. Conventional nitrogen fertilizers are produced by the Haber-Bosch process, which uses electrons derived from natural gas. In the early 2000s, 60% of its nitrogen manufacturing costs corresponded to natural gas, consuming around 1% 2% of the world’s total energy (Batstone, Hu¨lsen, Mehta, & Keller, 2015; Smil, 2000). Regarding phosphorus, predictions suggest that phosphorus production from mineral phosphates will start decreasing by 2035, owing to excessive demand (Cordell & White, 2013; Robles, 2013).

Chapter 5 Biorefineries to improve water and resource recovery in the seafood-processing industry

Engelberth (2020) distinguished between two main groups of biorefineries related to food wastage: biorefineries fed by food wastes from processing industries and biorefineries fed by domestic food waste. Domestic food wastes are heterogeneous in composition, variable in production, and usually vastly distributed geographically. Consequently, their collection is often difficult to manage (Engelberth, 2020). On the other hand, processing food waste, although it is only around 5% of the total bulk food waste (Kummu et al., 2012), is quite homogeneous, and constant in production, while it is produced at specific points. Consequently, it is often easier to collect (RedCorn, Fatemi, & Engelberth, 2018). Within all the food-processing activities, seafood industry is of high importance, especially in coastal regions (Zonn, Kostianoy, Semenov, Joksimovi´c, & DJurovi´c, 2021). The current demand for seafood is growing, which has led to increasing global seafood production from 134.3 MT in 2004 to 170.9 MT in 2016, including a raise in the aquaculture production from 41.9 to 80.0 MT (FAO, 2018). In the case of Europe, more than 6 million tons of fish are caught a year while more than 1.2 million tons are produced by aquaculture (Eurostat, 2019). This chapter focuses on the theoretical implementation of biorefineries fed by wastes from the seafood industry, including both processing activities and aquaculture, with the goal to obtain both bioproducts and reclaimed water.

5.2

Seafood industry

Seafood wastes include finfish, heads, skin, viscera, mollusk shells, and crustacean shells. This fraction can be even higher than 50%, such that around 25% 30% of the total seafood ends up as waste. These byproducts are commonly discarded (since they are considered waste) and processed by paying a disposal cost to a third party or specific waste management companies, not taking advantage of their high contents of proteins, polysaccharides, lipids, carotenoids, vitamins, minerals, and so on (Table 5.1). Recovering these biomolecules can be an important way to mitigate environmental problems associated with seafood processing (Bruno et al., 2019) and closing the loop in the seafood industry.

5.3

Processes to develop biorefinery schemes from seafood wastes

Plenty of processes and technologies can be used to recover biomaterials from seafood wastes. Some are based on the

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Table 5.1 Chemical characterization of mollusk byproducts. Parameter Unit of measure Meat residuea Mollusk shellb Fish waste Shrimp shelld (viscera, heads, bones, etc.)c Dry matter Ashes Crude protein Fats P Na Mg K Ca

% % d.b. % d.b. % d.b. g kg21 g kg21 g kg21 g kg21 g kg21

23.5 6.04 47.2 5.35 d.b. d.b. d.b. d.b. d.b.

6 6 6 6

6.2 3.3 18.4 2.03

97.97 6 1.9 79.4 6 21.9 3.4 6 2.1 0.18 6 0.1 0.16 6 0.05 4.35 6 1.5 1.5 6 1.3 0.13 6 0.05 483.5 6 185

36.29 6 10.7 8.8 6 8.6 38.5 6 9.8 54.5 6 10.6 13.9 6 4.1 2.89 6 2.40 0.76 6 0.81 3.88 6 2.59 32.7 6 18.2

87.7 6 0.1 26.6 6 0.0 32.5 6 0.1 9.8 6 0.7 0.85 6 0.22 3.86 6 1.70 1.67 6 1.28 44.61 6 5.56

a

Dare and Edwards (1975); Naik, Mora, and Hayes (2020); Tavares, Mello, Campos, de Morais, and Ostini (1998). Iriani, Hasan, and Sumarto (2020); Krutof, Bamdad, Hawboldt, and MacQuarrie (2020); Lertwattanaruk, Makul, and Siripattarapravat (2012); Naik et al. (2020); Papadimitriou, Anagnostopoulos, Anagnostopoulos, and Galinou-Mitsoudi (2020); Pecen˜o, Arenas, AlonsoFarin˜as, and Leiva (2019); Buasri, Chaiyut, Loryuenyong, Worawanitchaphong, and Trongyong (2013). c Ahuja, Dauksas, Remme, Richardsen, and Løes (2020); Esteban, Garcı´a, Ramos, and Ma´rquez (2007); Pateiro et al. (2020). d Samuthirapandian, Rameshkumar, and Prince (2009); Nu´n˜ez-Go´mez, Rodrigues, Lapolli, and Lobo-Recio, (2021). b

physical or chemical separation of the valuable components contained in seafood wastes, while others rely on chemical, thermal, or biological transformation of the components. Some of the most typical processes will be explained in this section.

5.3.1

Physical processes

Physical and mechanical separation techniques such as screening, shredding, sedimentation, and filtration do not usually obtain bioproducts directly from raw materials. These processes are mandatory in biorefinery schemes to pretreat waste by reducing the substrate size, separating solids from liquids, organic and inorganic fractions, materials with different sizes and densities, and so on (Battista et al., 2020). These techniques have been widely developed and are commonly used at various scales, from lab to industrial. Separation techniques are also important for the concentration and purification of the final bioproducts from wastes, which is usually a milestone step regarding the overall process (Lo´pez-Go´mez, Pe´rez-Rivero, & Venus, 2020). Apart from conventional techniques based on sedimentation, centrifugation, or thermal processes such as distillation and evaporation, purification by

Chapter 5 Biorefineries to improve water and resource recovery in the seafood-processing industry

means of membranes [microfiltration (MF), ultrafiltration (UF), reverse osmosis (RO), etc.] have been receiving increasing interest (Fan, Ebrahimi, & Czermak, 2017). In spite of the good solid-liquid separation yields achieved by membrane systems, they have to deal with fouling due to the cake-layer formation and the partial block of the membrane pores, which reduces membrane permeability (Zhang & Fu, 2018). To reduce fouling, gas-assisted membrane scouring, backwashing and/or chemical cleaning of the membrane can be applied (Gong et al., 2019; Porcelli & Judd, 2010), but it increases the operational and capital expenditures of the process. Membrane-based technology for waste treatment consists of dynamic membranes. They are formed on supporting porous materials with large pore sizes where influent solids are placed in and acting as the main barrier for the separation step. These membranes usually present larger pore size than MF, UF, or RO (although it decreases with the operating time). This makes fouling less severe, enabling them to operate at transmembrane fluxes as high as 100 L m22 h21 (Li et al., 2018), while systems based on MF and UF barely surpass 20 L m22 h21 (Robles, 2013). Apart from the solid-liquid separation, membranes are applied to recover gases from liquids. For instance, degassing membranes can be used to recover dissolved methane from effluents of anaerobic digestion systems (Crone, Garland, Sorial, & Vane, 2016; Sanchis-Perucho et al., 2021). Moreover, membrane contactors can be used to recover gases that are stripped from a liquid medium. Indeed, Noriega-Hevia, Serralta, Borra´s, Seco, and Ferrer (2020) used membrane contactors to recover stripped ammonia from a nitrogen-rich water stream, producing ammonium sulfate, an inorganic salt that is rich in directly available N and S. It can be thus used as marketable fertilizer (Bogdahn, 2015).

5.3.2

Chemical processes

Chemical processes refer to those in which chemical reactions occur; therefore the use of chemical reagents and/or enzymes is commonly needed. One example is the chemical extraction of chitin from crustacean or mollusk shells, which mainly involves three steps: deproteinization, demineralization, and decolorization (Hamed et al., 2016; Yadav et al., 2019). Deproteinization is processed by alkaline solutions with concentrations ranging from 0.125 M to 5.0 M OH2. The demineralization with acidic solutions consists of the decomposition of minerals, mainly calcium carbonate (CaCO3) into calcium chloride (CaCl2), releasing carbon dioxide (Nistico`, 2017; Yadav

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et al., 2019). The final step is the decolorization or depigmentation process, the goal of which is the removal of pigments such as carotenoids. The depigmentation process is usually performed by the addition of acetone or sodium hypochlorite (NaClO3) (Arbia, Arbia, Adour, & Amrane, 2013; Dhillon, Kaur, Brar, & Verma, 2013; Kaczmarek, Struszczyk-Swita, Li, Szcze˛sna-Antczak, & Daroch, 2019; Rameshthangam, Solairaj, Arunachalam, & Ramasamy, 2020). Chemical reagents can also be used to extract other valuable compounds such as lipids, proteins and carbohydrates (Ideia et al., 2020; Jayasinghe & Hawboldt, 2012). These compounds are useful to produce several value-added bioproducts (Section 5.4). However, chemical extraction processes usually have low production yields and a lot of negative impacts due to the commonly excessive use of reagents. Big efforts are therefore being carried out to improve the efficiency of these methods. It is worth mentioning that chemical processes can also be employed as pretreatment in biorefinery schemes. For instance, pretreatment of organic materials by acid or alkaline hydrolysis has been developed to increase biogas production through anaerobic digestion (Do˘gan & Sanin, 2009; Khanh Nguyen et al., 2021). Furthermore, extraction can be boosted by employing enzymes (substituting or complementing the chemical reagents) through a hydrolysis process. By way of example, proteolytic enzymes have been used to obtain protein hydrolysates from seafood wastes (Section 5.4). These enzymes hydrolyze proteins more gently than acids and alkalis, do not require high temperatures (,60 C), and usually target specific peptide bonds (Colla et al., 2015). Enzymatic hydrolysis usually starts by heating the raw material at 85 C 95 C to terminate the endogenous enzymes that are still active in the organic fraction of both whole fish and fish waste. Subsequently, exogenous enzymes must be carefully chosen and added to the solid to optimize the selective cleavage of its protein content into peptides. A variety of enzymes have been reported for this purpose, including Alcalases, Flavourzymes, Protamex, bromelain, thermolysin, proteinase, pepsin, papain, and chymotrypsin. Consequently, treatment conditions may be largely different; for instance, pepsin works at pH 5 2.0, and T 5 37 C, while trypsin and chymotrypsin require much higher pH and temperature, that is, 8.0 C and 60 C, respectively (Maschmeyer, Luque, & Selva, 2020). Protein hydrolysates can also be obtained by other methods than those using commercial enzymes. For example, Samaranayaka & Li-Chan (2008) prepared hydrolysates from Pacific hake fish through autolysis, using the high endogenous proteolytic activity from a parasitic infection.

Chapter 5 Biorefineries to improve water and resource recovery in the seafood-processing industry

Figure 5.3 Schematic diagram of protein hydrolysate (PH) production from seafood byproducts.

One of the advantages of protein hydrolyzation is the reduction of nitrogen concentration in seafood wastes, which is commonly high, owing to their protein content, which is around 15% 25% of the dry biomass. This is usually beneficial for downstream biological processes such as composting, anaerobic digestion, or fermentation, since excessive amounts of nitrogen can limit them (Valentino et al., 2017). A schematic summary of the different possibilities of hydrolysis to obtain protein hydrolysis is shown in Fig. 5.3.

5.3.3

Thermochemical and thermal processes

Thermochemical processes transform the biomaterials in less time as compared to biochemical methods. The production of thermal energy is their main driver, having four broad pathways: combustion (or incineration), pyrolysis, gasification, and liquefaction. Incineration is not a very interesting process in terms of resource recovery, since biomass is mostly transformed

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into carbon dioxide and ashes, so residual heat is the most valuable resource obtained from it. On the other hand, if the biomaterial that is obtained at any point of the biorefinery is submitted to pyrolysis, it can be transformed into more valueadded products such as biohydrogen, bio-oil, and/or biochar. Biomass pyrolysis (Fig. 5.4) is an emerging thermochemical technology that has the potential to serve as a viable pathway for converting sustainable biomass into advanced fuels and chemicals to displace fossil-based counterparts. Pyrolysis involves the thermal degradation of materials in the absence of an oxidizing agent, causing irreversible rupture of polymer structures into smaller molecules, leading to the formation of solid (char), liquid (bio-oils), and noncondensable gaseous products (i.e., CO, CO2, H2, CH4, C2H6) (Babu & Chaurasia, 2003; Bridgwater & Bridge, 1991; Bridgwater, Meier, & Radlein, 1999; Guran, Agblevor, & Brennan-Tonetta, 2018; Williams & Besler, 1996). The relative amounts of these products depend on several factors, including the heating rate and the final temperature reached by the biomass. Pyrolysis processes can be categorized according to the biomass conversion rate as slow pyrolysis in fixed-bed reactors, or fast/flash pyrolysis in fluidized-bed reactors (including bubbling bed and circulating bed), vacuum

Figure 5.4 Schematic diagram of seafood waste pyrolysis with combined heat & power (CHP) integration.

Chapter 5 Biorefineries to improve water and resource recovery in the seafood-processing industry

reactors, or transported beds. Slow heating rates and lower temperatures provide higher char yields, since slow heating and longer residence times in the reactor result in slower decomposition. Conversely, in fast pyrolysis the rapid heat transfer and short residence times coupled with medium and higher temperatures produce higher proportions of liquid products with decreased amount of biochar (Guran, 2018). Thermal techniques are also used to concentrate the bioproducts obtained from upstream processes. For instance, thermal drying and vacuum evaporation are based on removing water from the bioproducts to improve their purity. However, not all thermal processes in biorefineries are based on heating; freeze concentration consists of freezing the water contained in the biomass rather than evaporating it, consuming significantly less energy, that is, around 14% of the equivalent evaporation. Compared to membrane-based systems (one of the most implemented technologies to recover specific compounds from diluted effluents), freeze concentration requires similar or even lower operational energy consumption (Uald-Lamkaddam et al., 2021).

5.3.4

Biological processes

Biological processes consist of the biological degradation of the organic matter contained in biomaterials. Depending on the metabolism of the microorganisms, they can be divided in aerobic (in the presence of oxygen) and anaerobic (in the absence of oxygen).

5.3.4.1

Aerobic processes

A typical aerobic process to treat organic biomass is composting. Composting is a sustainable technique for waste stabilization, consisting of the biological decomposition and stabilization of organic substrates under conditions that enable to reach thermophilic temperatures (generally considered to be above 45 C) as a result of the heat that s produced biologically. Consequently, a stable bioproduct is obtained, which is free of pathogens and plant seeds, making it suitable to be applied to soils and arable lands (Akyol, Ince, & Ince, 2019). Factors such as pH, moisture, bulk density, and the carbonto-nitrogen (C/N) ratio need to be monitored to achieve successful composting (Ahuja et al., 2020). Special conditions of moisture and aeration are needed to produce thermophilic temperatures (Haug, 2018). In this respect, the high amount of water that is commonly present in seafood wastes can hinder

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reaching thermophilic conditions. The initial balance of the C/N ratio between 25 and 30 parts of carbon to one part of nitrogen is advocated as essential for the good initial course of composting (Haug, 2018). This C/N ratio is often much higher than that of seafood wastes, owing their high nitrogen concentrations. To solve this, seafood wastes can be mixed with bulking agents, such as woodchips, sawdust, wood shavings, bark, crop residues, rice hulls, leaves, crushed grass, wheat bran, and straw (Ahuja et al., 2020). This helps to improve composting performance, not only by adjusting the C/N ratio, but also by absorbing odor and improving the porosity and aeration conditions (Laos et al., 2002; Ros, Garcı´a, & Herna´ndez, 2006). Among different management strategies, windrow composting stands out as a simple and low-cost method (Brogaard, Petersen, Nielsen, & Christensen, 2015; Lalander, Nordberg, & Vinnera˚s, 2018), allowing the production of nutrient-rich biofertilizers that bring several benefits concerning soil fertility and soil recovery from degradation (Illera-Vives, Seoane Labandeira, Brito, Lo´pez-Fabal, & Lo´pez-Mosquera, 2015). A similar process to composting is biodrying. In this case, the metabolic heat is used to remove water from the waste matrix at the lowest possible residence time and minimal carbon biodegradation. Consequently, the final bioproduct will keep most of the gross calorific value of the raw waste material.

5.3.4.2 Anaerobic processes Owing to their high organic content, seafood residues can be used for biogas production through anaerobic digestion. The material that is fed to this process can be both raw materials and residues from previous processes (as long as they contain significant amounts of biodegradable organic matter). Anaerobic digestion is considered one of the best environmental solutions to manage large amounts of organic wastes, since the final residue (the digestate) is quite stable and a renewable source of energy (biogas or biomethane) is produced (Battista et al., 2020). To improve biogas production in biorefineries, the codigestion of seafood wastes with other organics, such as forestry and agricultural wastes, can be considered (Ivanovs, Spalvins, & Blumberga, 2018; Kafle & Kim, 2012). Substrate concentration is considered a key parameter regarding anaerobic digestion performance (Foglia et al., 2020). At low concentrations the activity of anaerobic microorganisms can be limited by the low availability of organic substrate. Moreover, anaerobic digestion of fish waste is sometimes complicated, since it contains

Chapter 5 Biorefineries to improve water and resource recovery in the seafood-processing industry

high amounts lipids, fatty acids, and nitrogen. Hence previous extraction steps of these compounds and/or combination with other substrates such as straw or manure (codigestion) can enhance anaerobic digestion performance. Substrate overloading might also lead to inhibition due to the accumulation of intermediate products such as volatile fatty acids (VFA) (Wainaina, Parchami, Mahboubi, Horva´th, & Taherzadeh, 2019; Zhang et al., 2014). One of the main drawbacks of anaerobic processes lies in the need to operate them at long solids retention time (SRT) and at mesophilic or thermophilic conditions due to the slow activity of anaerobic organisms at ambient conditions. This forces to have high reaction volumes (Gime´nez, 2014). Anaerobic treatment processes can be combined to membrane separation processes, commonly including MF and UF, to decouple the hydraulic retention time from sludge retention time. This way, anaerobic microorganisms can be retained in the reactor for longer, hence reducing the reacting volume without washing out the anaerobic biota. This technology is known anaerobic membrane bioreactor. As a consequence, the economic feasibility of the process improves (Liao, Kraemer, & Bagley, 2007; Stazi & Tomei, 2018). The main product of anaerobic digestion (i.e., biogas or biomethane) is not considered to be a highly valuable bioproduct. On the other hand, in fermentation processes, the methanogenesis step is hampered, so the production of hydrogen (actually, syngas) and/or VFAs (butyric, propionic, acetic, lactic, caprylic, caproic acids, etc.) is boosted (Lo´pez-Go´mez et al., 2020; Wainaina et al., 2019). Fermentation thus improves the added value of the final bioproducts, since VFAs and syngas offer significantly higher revenues than methane (Dai, Zhang, Zeng, & Zhang, 2019; Lo´pez-Go´mez et al., 2020). Although many of the processes that are explained in this section have been widely implemented at large scale, their combined use in biorefinery schemes is at an early technological stage. Hence, future research should focus on implementing the biorefinery concept to make it more competitive and to generate significant profits to users. In this respect, research projects such as H2020-SEA2LAND (101000402) are developing technologies in seven different pilot cases, the main goal of which is to recover resources from fishery and aquaculture biowastes.

5.4

Bioproducts obtained from seafood wastes

Different kind of bioproducts can be obtained from seafood wastes, that is, biostimulants or biofertilizers, intermediates,

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and other bioproducts such as chitin, minerals, VFAs, hydrolysates, polyhydroxyalkanoates (PHA), fuels (biogas, biomethane, biohydrogen), and even reclaimed water.

5.4.1

Biofertilizers and biostimulants

Since seafood wastes are rich in macronutrients and micronutrients (e.g., N, P, K, Ca, Cu, Zn, Mo), they are suitable raw material to obtain biofertilizers that can combat the increasing nutrient demands in agriculture and respect the environment simultaneously. They also contain bioactive compounds such as vitamins, amino acids, and antioxidants (Je, Park, Byun, Jung, & Kim, 2005; Jeon & Kim, 2002), the effect of which in food crops is not yet well established Indeed, these compounds could help mineralization and nutrient release or, conversely, could favor a slow release of nutritional compounds. Hence the biofertilizer effect of seafood-based compounds needs to be investigated. In this respect, project SEA2LAND is currently intending to improve and adapt technologies to recover nutrients from fish, mollusk, and crustacean biowastes to produce bio-based fertilizers, thus encouraging fertilizer production in Europe from nonimported organic or secondary raw materials. Protein hydrolysates obtained from enzymatic hydrolysis or autolysis (see Section 5.3.2) can act as biostimulants, that is, substances that are able to enhance crop quality parameters, nutrient efficiency, and abiotic stress tolerance, thus improving the productivity and product quality of horticultural crops. They are also effective tools for making horticulture more sustainable, owing to their benefits on growth, yield, product quality, resource use efficiency, and tolerance to environmental and chemical soil stresses of several horticultural crops (Colla et al., 2015). Compost, which is the stabilized bioproduct obtained from composting (Section 5.3.3), can be also used as a biofertilizer in agriculture or as soil amendment, depending on the characteristics and quality of the compost, which depend on the raw materials that are used, the composting conditions of the decomposition process, and the nutrient contents during composting. One promising option to enhance the quality and material properties of compost lies in the combination of compost with biochar (Fig. 5.5). Biochar is obtained by pyrolysis (see Section 5.3.3) and consists mainly of carbon. It can be used for soil amendment to improve the nutrient density of soils and the water-holding capacity, reduce fertilizer requirements, enhance soil microbiota, and increase crop yields (Allohverdi, Mohanty, Roy, & Misra, 2021).

Chapter 5 Biorefineries to improve water and resource recovery in the seafood-processing industry

Figure 5.5 Schematic diagram of seafood waste composting with forced aeration.

When biochar is combined with compost, its quality and material properties are improved by adding more stable carbon and creating a value-added product (biochar-compost blend) that can offset potential negative effects of both compost and biochar (Oldfield et al., 2018). Indeed, recent studies have reported the great potential of biochar to enhance compost production, since it can (1) promote compost mixture physicochemical properties; (2) enhance microbial activities, improving organic matter decomposition, and (3) increase the available nutrient content of the final bioproduct, decreasing phytotoxicity (Xiao et al., 2017). Metal content is one of the major issues related to the application of compost in soils. In this regard, seafood wastes usually have metal concentrations that are comparable to those of the organic fraction of municipal solid waste (Fisgativa, Tremier, & Dabert, 2016), which is commonly employed to produce commercial biofertilizers. It is worth noting that if shells from crustaceans and mollusks are used in biorefineries, they can serve as sources of calcium carbonate. Apart from its multiple industrial applications, this compound can be used in agricultural soils as a liming

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agent. In fact, renewable sources of CaCO3 are of interest in Europe, considering that the average pH is around 5.8 for the soils with depths of 0 20 cm (Fabian et al., 2014).

5.4.2

Biofuels

From the processes described in Section 5.3, it can be deduced that several biofuels could be produced in a seafoodbased biorefinery. For instance, biogas is the main bioproduct of anaerobic digestion processes. It is mainly composed of methane, carbon dioxide and other impurities such as H2S, CO, and H2. Thus biogas often needs an upgrading step to improve its quality. When this upgrading is also aimed at the removal of CO2, biogas achieves high methane concentrations and can be commercialized as biomethane, which is more valuable than biogas. In addition, pyrolysis processes can obtain combustible products, such as bio-oil and biohydrogen, that can be used as renewable fuels. The hydrogen stream in fact contains impurities such as CO2 and CO, so this bioproduct is commonly known as syngas. Syngas can also be obtained from dark fermentation together with VFAs (Dai et al., 2019; Elbeshbishy, Dhar, Nakhla, & Lee, 2017). In both cases, the syngas production will depend on the operating conditions, which will favor one bioproduct or another. The biochar that is obtained during pyrolysis could also be burned, as well as the syngas and bio-oil that are produced during the process to provide the heat required to sustain the pyrolysis, since the reaction heat is inadequate to meet all energy demand (Basu, 2010). Fadhil, Ahmed, and Salih (2017) produced liquid biofuels and activated carbons from fish waste: The fish waste was deoiled, and the obtained oil was transesterified separately with methanol and ethanol in the presence of potassium hydroxide to produce methylic and ethylic biodiesels; the deoiled fish waste was used in the production of bio-oil via pyrolysis, and the biochar was used as a precursor for production of mesoporous activated carbons.

5.4.3

Biocompounds

Bioactive compounds such as chitin, proteins, hydrolysates, and lipids, which have wide pharmaceutical and biotechnological applications, can also be obtained from fish waste (Ghaly, Vv, Brooks, Budge, & Dave, 2013). Their production will depend on the raw material (shells, viscera, heads, fish bones, etc.), the

Chapter 5 Biorefineries to improve water and resource recovery in the seafood-processing industry

transformation processes, and the operating conditions in the biorefinery. For instance, crustacean (prawns, crabs, shrimps, lobsters, etc.) shells are a suitable source of chitin. Chitin is used in many sectors, such as the agricultural, biochemical, food, and fertilizer industries. Other seafood residues, such as mollusk shells and fish scales, also contain chitin, although in lower concentrations, since the chitin is commonly mixed with proteins, lipids, and minerals. Hence they have a low degree of purity that must be improved by extracting the pure chitin from the corresponding seafood waste source (Abdulkarim, Isa, Abdulsalam, Muhammad, & Ameh, 2013; Alabaraoye, Achilonu, & Hester, 2018). Extraction is usually done by chemical processes (Section 5.3.2), although biological methods can be also used, usually achieving lower efficiencies (Kaczmarek et al., 2019; Rameshthangam et al., 2020; Yadav et al., 2019). Chitin is presented in nature mainly in three different crystalline types: α, β, and γ. In the case of seafood, α chitin is the most common. In α chitin, polysaccharide chains are structured in an antiparallel orientation, allowing the maximum amount of bonds; thus it is the most stable chitin form, having a high crystallinity index of 80% (Yadav et al., 2019). Chitin has low solubility in water and low porosity. It is therefore highly resistant to physical and chemical agents, but its application is limited in many cases. Therefore chitosan is often derived from chitin through partial deacetylation. Chitosan is soluble in both organic and inorganic acids (Hamed et al., 2016; Kaczmarek et al., 2019; Rameshthangam et al., 2020). Hydrolysates that are obtained from protein hydrolysis, apart from being able to be used as biostimulants (see Section 5.4.1), are relevant in food chemistry, particularly as functional ingredients of dietary supplements, owing to their antihypertensive, antioxidant, antimicrobial, immunomodulatory, and anticancer effects. Some of the trademarked nutraceuticals based on hydrolysates include Seacure, Amizate, Protizen, Vasotensin, and Peptace, which are commercially available products to alleviate body stress, support muscular and vascular functions, lower blood pressure, and control weight disorders (Maschmeyer et al., 2020). On the other hand, anaerobic fermentation produces a mixed of VFA that can be used in further valorization steps such as PHA production. PHA are polyesters that can be processed for bioplastic production, showing interesting properties such as high biodegradability and a recyclable nature. In fact, 1 kg of PHA can save 2 kg of CO2 emissions and around 30 MJ of fossil resources on average in comparison to fossil fuel plastic production (RodriguezPerez, Serrano, Pantio´n, & Alonso-Farin˜as, 2018).

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Fish biowaste, particularly the organic fraction, including viscera, heads, tails, and flesh residues, can have high lipid (triacylglycerols) contents, representing a rich source of omega3 fatty acids (Maschmeyer et al., 2020) and other “green” chemicals. Bio-oil, for instance, is mainly an energy source, but it may also be used as a feedstock for the production of “green chemicals” resulting in a “green” alternative in many applications where petro-oil is used (Basu, 2010).

5.4.4

Water streams

Seafood industry also produces great of amounts of liquid wastes that account for 5 35 m3 of water produced per ton of processed seafood (Pikaar et al., 2022). Some of these liquid wastes come from canning processes. These liquid sidestreams are difficult to manage, owing to their high content of organic matter, proteins, salinity, oils and fats, nitrogen, phosphorus, and suspended solids. One possibility to deal with these liquid streams is to recover the resources contained in them, for instance, by obtaining protein hydrolysates or other bioproducts through the concentration and further treatment of the compounds contained in them. The water fraction that is obtained during this step (or other separation and concentration steps of the biorefinery) normally contains high levels of biodegradable organic matter, showing great potential for a net energy production in the form of methane via anaerobic processes (Section 5.3.4.2). A possible alternative to treat this highly concentrated water streams can be an upflow anaerobic sludge blanket (UASB) reactor (PalenzuelaRollon, Zeeman, Lubberding, Lettinga, & Alaerts, 2002). In this reactor the influent stream passes through the sludge bed, where the suspended solids can be entrapped or adsorbed, and are partially hydrolyzed and acidified depending on the temperature and SRT. The influent flow constantly flushes the sludge bed, hence preventing possible accumulation of intermediate products, such as amino acids, which could otherwise be inhibitory to the hydrolysis or acidification steps of the anaerobic ˜ al process. A full-scale application of UASB was reported by Pun and Lema, 1999, where pretreatment of fats, consisting of alkaline hydrolysis, enabled the treatment of wastewater from a fish-canning factory without biomass washout or problems with the biogas evolution. In addition, the water effluent, if it was properly treated, could be theoretically be reused in the biorefinery scheme, since there are some processes, such as shredding and

Chapter 5 Biorefineries to improve water and resource recovery in the seafood-processing industry

hydrolysis, in which water addition is usually needed. This option could be very controversial, depending on the bioproducts that are obtained. If the bioproducts are intended to be in direct contact with humans and animals, legal requirements tend to be very restrictive in the use of reclaimed water, so it is normally not recommended to reuse water in those cases. Another option could be to reuse this water for irrigation or fertigation in agriculture (Jime´nez-Benı´tez et al., 2020). To do so in Europe, reclaimed water has to comply with Regulation 741/2020 on minimum requirements for water reuse (Foglia et al., 2021).

5.5

Conclusions and future trends

Novel biorefinery schemes are gaining importance for their role in the application of circular economy principles in the biowaste and water treatment sectors. Biorefinery schemes are generally in the early stages of development, and strong efforts are needed for their implementation. This chapter has focused on the theoretical implementation of biorefineries fed by wastes from the seafood industry. Plenty of processes and technologies can be used to recover biomaterials from seafood wastes. Physical processes such as screening, shredding, sedimentation, or filtration aim to pretreat waste by reducing its size, separating solids from liquids, separating organic and inorganic fractions, separating materials with different sizes and densities, and so on. They are also important for the concentration and purification of the final bioproducts. Chemical processes refer to those in which chemical reactions occur; thus the use of chemical reagents and/or enzymes is commonly needed. These processes enable extraction of valuable compounds from seafood wastes such as proteins, lipids, vitamins, and chitin. Biological treatments such as aerobic or anaerobic processes could be also submitted to produce biofuels, biofertilizers, biostimulants, and so on. On the other hand, thermochemical processes (combustion, pyrolysis, gasification, and liquefaction) transform the biomaterials from seafood wastes, but the production of thermal energy is commonly their main driver. Finally, valuable products can also be obtained from water streams produced in the seafood industry by both concentrating valuable compounds contained in the streams or producing energy (mainly biogas) and reclaimed water during its treatment. It must be noted that the biorefinery schemes will depend on the type of substrate that is used for feed and the

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bioproducts that the scheme is intended to produce. It is therefore essential to carry out deep assessment of each biorefinery case before proceeding to develop the system at industrial scale. It has also to be considered that biorefineries schemes are generally in the early stages of their technological readiness level. Strong efforts are therefore needed for their development and implementation at large scale.

Acknowledgments The authors acknowledge the European Union’s Horizon 2020 research and innovation program for their support to fund the SEA2LAND project under grant agreement 101000402. Coauthor J. Gonza´lez-Camejo acknowledges the Spanish Ministry of Universities and NextGenerationEU for their support via the postdoctoral Margarita Salas grant.

List of acronyms CHP C/N GHG MF OPT PH PHA RO SRT UASB UF VFA

Combined heat and power Carbon-Nitrogen ratio Greenhouse gases Microfiltration Option Protein hydrolysates Polyhydroxyalkanoates Reverse osmosis Solids retention time Upflow anaerobic sludge blanket Ultrafiltration Volatile fatty acids

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˜ as, B. (2018). Rodriguez-Perez, S., Serrano, A., Pantio´n, A. A., & Alonso-Farin Challenges of scaling-up PHA production from waste streams. A review. Journal of Environmental Management, 205, 215 230. Available from https:// doi.org/10.1016/J.JENVMAN.2017.09.083. Ros, M., Garcı´a, C., & Herna´ndez, T. (2006). A full-scale study of treatment of pig slurry by composting: Kinetic changes in chemical and microbial properties. Waste Management, 26(10), 1108 1118. Available from https://doi.org/ 10.1016/j.wasman.2005.08.008. Samaranayaka, A. G. P., & Li-Chan, E. C. Y. (2008). Autolysis-assisted production of fish protein hydrolysates with antioxidant properties from Pacific hake (Merluccius productus). Food Chemistry, 107(2), 768 776. Available from https://doi.org/10.1016/j.foodchem.2007.08.076. Samuthirapandian, R., Rameshkumar, G., & Prince, A. (2009). Biochemical composition of shell and flesh of the Indian white shrimp Penaeus indicus (H.milne Edwards 1837). American-Eurasian Journal of Scientific Research, 4, 191 194. ´ ., Dura´n, F., Rogalla, F., Ferrer, J., & Seco, A. (2021). Sanchis-Perucho, P., Robles, A Widening the applicability of AnMBR for urban wastewater treatment through PDMS membranes for dissolved methane capture: Effect of temperature and hydrodynamics. Journal of Environmental Management, 287, 112344. Available from https://doi.org/10.1016/J.JENVMAN.2021.112344. Scialabba, N. (2015). Food wastage footprint & climate change. Smil, V. (2000). Enriching the earth. The MIT Press. Available from https://doi. org/10.7551/mitpress/2767.001.0001. Sorinolu, A. J., Tyagi, N., Kumar, A., & Munir, M. (2021). Antibiotic resistance development and human health risks during wastewater reuse and biosolids application in agriculture. Chemosphere, 265, 129032. Available from https:// doi.org/10.1016/J.CHEMOSPHERE.2020.129032. Spadaro, P., & Rosenthal, L. (2020). River and harbor remediation: “polluter pays,” alternative finance, and the promise of a “circular economy. Journal of Soils and Sediments, 20(12), 4238 4247. Available from https://doi.org/ 10.1007/S11368-020-02806-W/FIGURES/1. Stazi, V., & Tomei, M. C. (2018). Enhancing anaerobic treatment of domestic wastewater: State of the art, innovative technologies and future perspectives. Science of the Total Environment, 635, 78 91. Available from https://doi.org/ 10.1016/j.scitotenv.2018.04.071. ˚ ., Jensen, C., Quested, T., & Moates, G. (2016). Estimates of European Stenmarck, A food waste levels. Available from https://doi.org/10.13140/RG.2.1.4658.4721. Tavares, M., Mello, M. R. P. d A., Campos, N. C., de Morais, C., & Ostini, S. (1998). Proximate composition and caloric value of the mussel Perna perna, cultivated in Ubatuba, Sa˜o Paulo State, Brazil. Food Chemistry, 62(4), 473 475. Available from https://doi.org/10.1016/S0308-8146(97)00177-5. Tsang, Y. F., Kumar, V., Samadar, P., Yang, Y., Lee, J., Ok, Y. S., . . . Jeon, Y. J. (2019). Production of bioplastic through food waste valorization. Environment International, 127, 625 644. Available from https://doi.org/10.1016/J. ENVINT.2019.03.076. Uald-Lamkaddam, I., Dadrasnia, A., Llenas, L., Ponsa´, S., Colo´n, J., Vega, E., & Mora, M. (2021). Application of freeze concentration technologies to valorize nutrient-rich effluents generated from the anaerobic digestion of agroindustrial wastes. Sustainability (Switzerland), 13(24), 13769. Available from https://doi.org/10.3390/SU132413769/S1. Valentino, F., Morgan-Sagastume, F., Campanari, S., Villano, M., Werker, A., & Majone, M. (2017). Carbon recovery from wastewater through bioconversion

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into biodegradable polymers. New Biotechnology, 37, 9 23. Available from https://doi.org/10.1016/J.NBT.2016.05.007. Wainaina, S., Parchami, M., Mahboubi, A., Horva´th, I. S., & Taherzadeh, M. J. (2019). Food waste-derived volatile fatty acids platform using an immersed membrane bioreactor. Bioresource Technology, 274, 329 334. Available from https://doi.org/10.1016/J.BIORTECH.2018.11.104. Williams, P. T., & Besler, S. (1996). The influence of temperature and heating rate on the slow pyrolysis of biomass. Renewable Energy, 7(3), 233 250. Available from https://doi.org/10.1016/0960-1481(96)00006-7. Xiao, R., Awasthi, M. K., Li, R., Park, J., Pensky, S. M., Wang, Q., . . . Zhang, Z. (2017). Recent developments in biochar utilization as an additive in organic solid waste composting: A review. Bioresource Technology, 246, 203 213. Available from https://doi.org/10.1016/j.biortech.2017.07.090. Yadav, M., Goswami, P., Paritosh, K., Kumar, M., Pareek, N., & Vivekanand, V. (2019). Seafood waste: A source for preparation of commercially employable chitin/chitosan materials. Bioresources and Bioprocessing, 6(1). Available from https://doi.org/10.1186/s40643-019-0243-y. Zhang, W., Lang, Q., Wu, S., Li, W., Bah, H., & Dong, R. (2014). Anaerobic digestion characteristics of pig manures depending on various growth stages and initial substrate concentrations in a scaled pig farm in Southern China. Bioresource Technology, 156, 63 69. Available from https://doi.org/10.1016/J. BIORTECH.2014.01.013. Zhang, Y., & Fu, Q. (2018). Algal fouling of microfiltration and ultrafiltration membranes and control strategies: A review. Separation and Purification Technology, 203, 193 208. Available from https://doi.org/10.1016/J. SEPPUR.2018.04.040. Zonn, I. S., Kostianoy, A. G., Semenov, A. V., Joksimovi´c, A., & DJurovi´c, M. (2021). Fishery in the Adriatic Sea. The Adriatic Sea encyclopedia (p. 133) Springer International Publishing. Available from https://doi.org/10.1007/ 978-3-030-50032-0_194.

6 A valorization approach of food industry wastewater using microwave-assisted extraction Halil Dertli1 and Didem Saloglu2 1

Department of Chemical Engineering, Faculty of Chemical and Metallurgical Engineering, Istanbul Technical University, Istanbul, Turkey 2Department of Disaster and Emergency Management, Disaster Management Institute, Istanbul Technical University, Istanbul, Turkey

6.1

Introduction

Food industry waste is one of the most produced biowaste in the world. As a huge amount of water is used at every manufacturing stage in food industry, it produces high amount of wastewater. Typically, food industry wastewater is in the form of solid and liquid materials that are difficult to manage. The efficient use of waste generated during food production not only contributes to the prevention of environmental pollution, but also creates economic value. Considering that the number of food-processing factories will increase in parallel with the population growth in the coming years, it can be assumed that wastewater problems may increase accordingly. Owing to the increasingly stringent discharge regulations and the increased costs of water treatment, many food-processing companies have taken actions to reduce, recycle, or treat their wastewater before discharging it. However, as treatment costs are very high, there is a great interest in methods to reduce treatment costs or provide products other than wastewater. As a clean technique, microwave-assisted extraction shows promise for the future for use in wastewater treatment. Food processing requires the large volumes of water for different purposes, such as cleaning, cooling, heating, processing, cooking, and dissolving. In the last decade, the food industry has become the third largest industrial user of water (Papadopoulos et al., 2020).

Advanced Technologies in Wastewater Treatment. DOI: https://doi.org/10.1016/B978-0-323-88510-2.00013-0 Copyright © 2023 Elsevier Inc. All rights reserved.

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The consumption of huge volumes of water in the production and processing of foodstuffs results in a high amount of wastewater. The composition and volumes of wastewater differ significantly with production factors, such as production scale and type of product (e.g., dairy, meat, olive oil, fruit, vegetables). Food industry wastewater is easily biodegradable and is characterized by the high concentrations of biological oxygen demand (BOD) and chemical oxygen demand (COD), oils, fats, grease, nitrogen (N), phosphorus (P), and minerals (Abdallh, Abdelhalim, & Abdelhalim, 2016). The high levels of COD and BOD, soluble organic matter, polyphenols, and dark pigments are described as environmentally hazardous for natural water; therefore wastewater should be treated properly for safe discharge (Antwi-Agyei et al., 2015). Soluble organic compounds, pigments, polyphenols, oils, and fats are among the major pollutants found in water, and there has been increasing interest in the removal of these contaminants in recent years. Polyphenols, organic materials, and oils present in the wastewater of the food industry are the most common chemical compounds in drinking water, groundwater, and surface water (Golovko et al., 2021). Even though these chemical compounds are present in ranges of micrograms per liter to milligrams per liter in water sources, they are considered a high environmental risk. Studies have shown that these chemical compounds persist for s long time in the aquatic environment, and unfortunately they can be removed only with low efficiency in conventional water treatment plants (Pompermaier et al., 2021). In recent years, many studies have been carried out by using several treatment methods, such as photocatalysis (Kanakaraju et al., 2015), ozonation, membrane filtration, adsorption (Saloglu & Ozcan, 2018), and extraction, for the removal of polyphenols, oils, and fats from the wastewater of food industry. Most of these methods are difficult to adapt to conventional treatment systems and their direct application in the field includes complex processes. Among these methods, the extraction process can easily and effectively be adapted to conventional water treatment systems. Extraction is the most important technique for the separation of various types of chemical compounds from solid and liquid phases. Many factors, such as solvent type, extraction temperature, extraction time, and solvent-to-solid ratio, can significantly influence the extraction yields of chemical compounds. In the last decade, ultrasound- and microwave-

Chapter 6 A valorization approach of food industry wastewater using microwave-assisted extraction

assisted extraction techniques have been applied conveniently for chemical compounds instead of the conventional solidliquid or liquid-liquid extraction method, owing to their simple and effective aspects. In addition, these new and advanced separation techniques increase extraction yields and decrease extraction times effectively. Microwave-assisted extraction has attracted great interest in recent years to obtain chemical compounds from industrial wastewater (Ruiz-Aceituno et al., 2016). Microwave-assisted extraction is a separation technique in which microwave energy is used to heat a solvent to be extracted from the solid and liquid phases. This method enables the diffusion of the active substance into solvent phase in a short time; therefore it increases the extraction yield and decreases both solvent consumption and extraction time (Nayak et al., 2015). In this chapter, microwave-assisted extraction method is discussed as an important extraction technique in the treatment of food industry wastewater.

6.2

Wastewater from the food industry

Food processing is used in a variety of industries, including dairy, meat, sweets, cheese, and beverages. Wastewater from these industries originates from different plant operations, such as production, cleaning, sanitizing, cooling, and materials transport. These operations result in high concentrations of BOD, COD, suspended solids, oil, grease, nitrogen, and phosphorus. Typical characteristic of wastewater of the food industry are listed in Table 6.1.

Table 6.1 Typical characteristics of wastewater of the food industry. Substance Oil and grease Biological oxygen demand Chemical oxygen demand Total suspended solids Total nitrogen Total phosphorus

Amount (mg L21) 10 50 250 50 10 2

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Chapter 6 A valorization approach of food industry wastewater using microwave-assisted extraction

6.2.1

Characterization of wastewater from the olive oil industry

Wastewater in generated in olive oil production in varying amounts depending on the system used. Blackwater has an acidic pH and contains high levels of organic matter. It is possible to use blackwater as a high-energy source, owing to the aromatic substances plus simple and complex sugars in its content. It is also known that it is a suitable medium for microorganisms because of its rich content (Sobhi, Yamini, & Abadi, 2007). Olive blackwater usually contains 83%
96% water, 3.5%
15% organic matter, and 0.5%
2.0% mineral salts. Owing to its high organic matter content, the blackwater consumes dissolved oxygen very quickly in receiving water sources. The organic fraction consists of sugars (1%
8%), N compounds (0.5%
2.4%), organic acids (0.5%
1.5%), fats (0.02%
1%), and phenols and pectins (1.0%
1.5%). The wastewater from olive oil production is also characterized by the high levels of BOD and COD. Maximum BOD and COD concentrations reach 100,000 mg L21 and 200,000 mg L21, respectively. For these reasons, it has been considered that blackwater can be used as a substrate in microwave-assisted extraction technique.

6.2.2

Characterization of wastewater from the sugar industry

Molasses is a kind of organic wastewater that is commonly produced in the food industry. Wastewater with molasses contains high concentrations of organic substances (52%
90%), such as sucrose (30%
40%), glucose (4%
9%), fructose (5%
12%), pectin, and protein, and when it is released directly into the rivers, it consumes a high amount of dissolved oxygen, leading to the water smelling bad and deterioration of the water quality. Since wastewater with molasses has high organic loading and chrome and is biodegradable, biological treatment methods can be applied to remove organic pollutants (Mischopoulou et al., 2016). The measurements revealed that the wastewater has a pH of 6.61, COD of 1529 mg L21, and BOD of 910 mg L21.

6.2.3

Characterization of wastewater from the cheese industry

Whey is a lactose-rich, aqueous byproduct of the cheese production, which contains nutrients and accounts for 85 to

Chapter 6 A valorization approach of food industry wastewater using microwave-assisted extraction

95% of the total milk volume. It contains lactose (4.5%
5%, w/v), soluble proteins (0.6%
0.8%, w/v), lipids (0.4%
0.5%, w/v), and mineral salts (8%
10% of dry extract). Owing to its high organic content, the removal of whey poses a serious environmental problem as lactose is responsible for the high COD values. Ntaikou et al. investigated whey and revealed its characteristics as follows: pH 6.1
7.7, BOD 9033 mg L21, COD 4958 mg L21, and total phosphorous 18
26.42 mg L21. Therefore the treatment of whey by the microwave-assisted extraction method represents an important approach (Ntaikou, Antonopoulou, & Lyberatos, 2010).

6.2.4

Characterization of wastewater from the slaughterhouse industry

Slaughterhouse wastewater was characterized and treated by Bustillo-Lecompte et al. (2016). The results of the characterization were reported in ranges as follows: pH 4.90
8.10, BOD 150
8500 mg L21, COD 1250
16000 mg L21, total suspended solids 300
2800 mg L21, total nitrogen 50
841 mg L21, and total phosphorus 25
200 mg L21.

6.2.5

Characterization of wastewater from the multiproduction food industry

Schmidt & Ahring (1997) characterized wastewater from multiproduct food processing of fruits and vegetables. They observed that wastewater from vegetable-processing plants had COD values of 1.5 and 7.7 mg L21, total solids of 1.7 and 11 mg L21, and volatile solids of 1.2 and 6.0 mg L21.

6.2.6

Characterization of wastewater from the seafood industry

Ribeiro et al. (2020) reported the physicochemical analysis of seafood-processing industry effluents. The test results were as follows: pH 6.8
7.5, total solid 2250
3800 mg L21, total suspended solids 190
680 mg L21, BOD 965
2250 mg L21, and COD 1440
2700 mg L21. The wastewater composition of the olive oil, sugar, cheese, slaughterhouse, and seafood industries is shown in Table 6.2.

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Table 6.2 Physicochemical analysis of the wastewater of food industry. Olive oil industry

Sugar industry

Cheese industry

TS 5900
6250 400
2000 60
270 (mg L21) TSS 1100
2010 540
4500 1000
1800 (mg L21) 20,000
100,000 700
1050 9000
12,500 BOD (mg L21) 30,000
200,000 1000
4600 4500
22,000 COD (mg L21) pH 4.5
5.1 4.0
6.65 3.86
7.7 300
870 18
370 15
60 TP (mg L21) 300
1150 100
1800 100
360 TN (mg L21)

6.3

Slaughterhouse Multiproduction industry food industry

Seafood industry

820
4000







300
2500




150
1500

150
8500

600
400

1000
6500

1250
16,000

800
8000

1200
8000

4.9
8.10 5
250

3.4
11.2 3
5

5.5
9.0


10
841

50
78

200
300

Removal of organic and inorganic compounds in food industry wastewater

The removal of organic and inorganic compounds such as oil, grease, nitrogen, phosphorus, and phenolic-based compounds from wastewater is a very popular valorization approach for these effluents (Galanakis & Kotsiou, 2017). Many techniques can be employed for the removal of these organic and inorganic compounds, including membrane separation, thermal and chemical processes, adsorption, solvent extraction, solid/liquid phase systems, and distillation (Frascari et al., 2019). Membranes are selectively permeable barriers, and they are structures that perform separation when different driving forces are applied. Various driving forces, such as pressure, temperature, concentration, vapor pressure, and electrical potential difference, are used to treat wastewater. Membrane technologies that are used in wastewater treatment applications include microfiltration, ultrafiltration, nanofiltration, reverse osmosis, membrane bioreactor, and electrodialysis. The sewage sludge is dried to a certain solid content in a thermal process and then hydrolyzed at 130 C
175 C. A study performed at a temperature of 170 C showed that the decomposition degree of sludge increased by 80% compared to the classical

Chapter 6 A valorization approach of food industry wastewater using microwave-assisted extraction

decomposition process. The energy that is given to the sludge in the thermal process is usually provided by a heat exchanger or by applying steam to the sludge. The Cambi/KREPRO process is used for the thermal disintegration of sludge. The thermal decomposition of sewage sludge has advantages, such as increasing the degree of stabilization with anaerobic decomposition process, improving the quenching properties of the sludge, and reducing the tendency of sludge to form foam. Adsorption processes using carbonaceous adsorbents, such as activated carbon, carbon fiber, carbon nanotubes, biochar, zeolite-rich composites, and nanoparticles, owing to their high surface areas and pore size distributions, are now more commonly utilized, as phenolic compounds, oil, and grease can be trapped on the surface of adsorbent and thus be easily separated from the liquid fraction. The most appropriate technique for wastewater treatment should be chosen, taking many parameters into account, including operation cost, initial concentration of the mixture to be purified, environmental impact, pH, chemicals to be used, removal efficiency, and economic feasibility. As was mentioned earlier, treatment methods using membrane technology include ultrafiltration, nanofiltration, microfiltration, reverse osmosis, forward osmosis, adsorption, chemical and thermal processes, and extraction. Adsorption is the most promising and widely used method for wastewater treatment, owing to ease of use, high rate of removal, and low cost of reusability. Compared to adsorption, the membrane method has some advantages because of its high efficiency; however, the separation cost and membrane fouling still cannot be minimized effectively. The chemicalbased methods, especially chemical precipitation, are considered both practical and cost-effective. The thermal method is highly advantageous, as it requires no (or less) chemical consumption and results in less sludge production, making it ecofriendly. Among treatment methods, extraction uses solvent- and diffusion-based techniques. Solvent extraction is a conventional method and yields high recovery efficiency of organic and inorganic compounds; on the other hand, it has some disadvantages, such as consumption of a huge amount of solvents, long extraction time, and potential degradation of organic and inorganic compounds. The recent advancements in extraction techniques, such as microwave-assisted extraction, ultrasound-assisted extraction, and supercritical fluid extraction, have helped to overcome the challenges of conventional methods.

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Chapter 6 A valorization approach of food industry wastewater using microwave-assisted extraction

6.3.1

Extraction methods of organic and inorganic compounds in food industry wastewater

New technologies have been studied as an alternative to classical extraction methods in wastewater treatment. These technologies have superior aspects compared to conventional methods. Microwave-assisted extraction, like ultrasound-assisted extraction, is an innovative technique that saves energy, is environmentally friendly, and is effective in obtaining high-quality water (Ameer, Shahbaz, & Kwon, 2017). Extraction methods are shown in Fig. 6.1.

6.3.1.1 Soxhlet extraction Soxhlet extraction was first proposed by the German chemist Franz Ritter von Soxhlet in 1879. It was designed primarily for lipid extraction but has also been widely used for the extraction of valuable bioactive compounds from various natural sources

Figure 6.1 Extraction methods.

Chapter 6 A valorization approach of food industry wastewater using microwave-assisted extraction

163

Figure 6.2 Soxhlet extraction apparatus.

164

Chapter 6 A valorization approach of food industry wastewater using microwave-assisted extraction

(Hewavitharana et al., 2020). In Soxhlet extraction the sample to be extracted is placed in a chamber, as shown in Fig. 6.2, and comes into contact with the fresh solvent descending from the continuous condenser. When the solvent system reaches the overflow level, a siphon aspirates it from the chamber and empties it back into distilling flask, thus carrying the extracted compounds into the bulk liquid (Azwanida, 2015). The most important factors affecting the extraction efficiency include the polarity of the target compound and the choice of solvent. In the selection of solvent for organic/inorganic compounds, such as oil, grease, nitrogen, phosphorus, and phenolic compounds, molecular affinity between solvent and organic/inorganic compounds, mass transfer, use of cosolvent, environmental safety, human toxicity, and financial feasibility should be considered. Organic and inorganic compounds extracted by using different solvents are presented in Fig. 6.3 (Hewavitharana et al., 2020).

6.3.1.2 Ultrasound-assisted extraction Ultrasound is sound waves with frequencies higher than 20 kHz. Ultrasound-assisted extraction is the use of ultrasonic wave energy in extraction applications. Unlike electromagnetic waves, ultrasound waves can move in solid, liquid, and gas phases (Ameer et al., 2017). As sound waves pass through the material, cavitation occurs (Fig. 6.4). The mechanical effect of acoustic cavitation from ultrasound increases the permeability of the cell wall by surface contact between solvent and sample.

Figure 6.3 Different solvents for extraction of organic and inorganic compounds.

Chapter 6 A valorization approach of food industry wastewater using microwave-assisted extraction

Figure 6.4 Ultrasound-assisted extraction mechanism.

The physical properties of materials exposed to ultrasound change. In this way, the contact of the solid/liquid and solvent system increases (Ameer et al., 2017), and the dissolution, diffusion, and heat transfer of the solvent are accelerated. In ultrasound-assisted extraction, the extraction efficiency depends on many factors, such as solvent, frequency, pressure, temperature, and sonication time. In ultrasound-assisted extraction applications the wavelength, frequency, wave width, and intensity of the ultrasonic equipment should be optimized. Ultrasound-assisted extraction has significant advantages over conventional extractions, that is, much less solvent consumption, shorter extraction time, rapid recovery of polyphenols, and low infrastructure and equipment costs (Ameer et al., 2017).

6.3.1.3

Supercritical fluid extraction

The supercritical phase is the state that occurs when the temperature and pressure of a substance rise above its critical value. Supercritical fluid has properties of both gases and liquids. Advantages of supercritical fluids compared to liquid solvents are as follows: • The resolving efficiency of the solvent can be adjusted with varying density by changing the pressure and/or temperature of the medium.

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Chapter 6 A valorization approach of food industry wastewater using microwave-assisted extraction

• Supercritical fluids have a higher diffusion coefficient and lower viscosity and surface tension than a liquid, resulting in faster mass transfer. The most important factors in supercritical fluid extraction are selection of supercrystalline fluid, preparation of material, and extraction conditions (Ameer et al., 2017). The selection of supercritical fluids is critical in the development of the process. Carbon dioxide is the main solvent used in supercritical extraction because of the limitations on the use of other organic solvents, because it has no residue and toxicity, and because of its appropriate critical temperature (304K) and critical pressure (7.3 MPa) (Lang & Wai, 2001). It is a good solvent for supercritical carbon dioxide extraction and for extraction of nonpolar compounds, such as hydrocarbons. Some solvents, such as Freon 22 and nitrous oxide, have been proposed for the extraction of polar compounds, but their use is limited, owing to their unfavorable properties in terms of safety and environmental considerations. Although supercritical water has higher extraction ability for polar compounds, it is not suitable for thermally unstable compounds (Nieto et al., 2010). In Fig. 6.5 the supercritical carbon dioxide phase diagram is presented. The most important parameters affecting the extraction efficiency in the supercritical extraction method are feed flow, temperature, pressure, particle size, moisture content, extraction time, CO2 flow rate, and solvent-to-solid ratio. For the maximum efficiency of this method, these parameters need to be precisely controlled (Hewavitharana et al., 2020). Although the extraction time varies according to the treated sample, the supercritical fluid extraction process is completed in less than 20 minutes. This method is advantageous, owing to the use of a low critical temperature supercritical fluid for the extraction of non-heat-resistant components (Andreu & Pico´, 2019).

Figure 6.5 The supercritical carbon dioxide phase diagram.

Chapter 6 A valorization approach of food industry wastewater using microwave-assisted extraction

The advantages of using supercritical fluids for the extraction of bioactive compounds are described below (Nieto et al., 2010). • Supercritical fluid has a higher diffusion coefficient, and lower viscosity and surface tension than a liquid solvent. Therefore mass transfer is increased by further penetrating into the sample matrix. • Extraction time is significantly reduced compared to conventional methods. • Repeated reflux of the supercritical fluid into the sample ensures complete extraction. • Selectivity of the supercritical fluid is higher than that of the liquid solvent, as the dissolving power can be adjusted by varying the temperature and/or pressure. • The conventional extraction process takes more time to separate the solute from the solution. By reducing the pressure of the supercritical fluid, the solvent is easily removed. • Supercritical extraction is an ideal method for thermostable compound extraction, owing to low operating temperatures. • It uses a small amount of organic solvents and is considered to be environmentally friendly. • Recycling and reuse of supercritical fluid is possible, thus minimizing waste generation. • It can be tailored for a specific purpose, from a few milligrams of samples in the lab to tons of samples in industries.

6.4

What are microwaves?

Microwaves are electromagnetic radiations with a frequency between 0.3 and 300 GHz (Sinquin Go¨rner, & Dellacherie, 1993). Domestic and industrial microwaves typically operate at 2.45 GHz. Because of their electromagnetic properties, microwaves have electric and magnetic fields that are perpendicular to each other. The electric field causes heating through two simultaneous mechanisms: dipolar rotation and ionic conduction. Dipole moments and dielectric constants of commonly used solvents are given in Table 6.3. The larger the dielectric constant of the solvent, the higher is the heating that occurs (Kaufmann & Christen, 2002). Since only polar molecules can be heated with microwaves, this heating system is selective. In this method, simultaneous heating takes place at every point of the sample. In classical (conductive) heating, the outer surface of the heated mass is first heated, while heating takes place in the center of the

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Table 6.3 Dipole moments and dielectric constants of commonly used solvents. Solvent Water Ethanol Methanol Chloroform Hexane Dichloromethane Ether Toluene Acetone

Dielectric constant (20˚C)

Dipole moment (25˚C) debye

80.4 24.5 32.7 4.81 1.89 8.93 4.33 2.40 21.0

1.87 1.69 2.87 1.15 0.08 1.14 1.15 0.36 2.69

Figure 6.6 Illustration of conventional and microwave heating.

solvent and matrix mixture in microwave heating. Thus unlike conductive heating, volumetric heating is achieved (Sinquin Go¨rner, & Dellacherie, 1993). This is illustrated in Fig. 6.6 for conventional and microwave heating. Compared to conventional thermal heat sources, microwave heating is highly effective for increasing the efficiency of many chemical reactions. In general, microwave effects cannot be achieved with conventional heating. Microwave effects are mainly classified as thermal or nonthermal. Thermal effects are

Chapter 6 A valorization approach of food industry wastewater using microwave-assisted extraction

caused by microwave heating, leading to a different temperature regime. Nonthermal effects are specific ones. Microwave thermal effects result from rapid heating, volumetric heating, overheating, hot spots, and selective heating. In contrast, nonthermal effects are associated with surface polarization. The rate increases in reactions or processes in microwaveapplied chemical reactions or processes can be attributed to simple thermal or kinetic effects. In heterogeneous catalysis the most important factor for the degradation efficiency is the interfacial polarization mechanism. Rapid pollutant degradation in the adsorbent microwave system occurs mainly by the formation of hot spots on the adsorbent surface, representing a unique microwave mechanism. This is useful for speeding up reactions in many processes. The acceleration of the reactions results from the movement of delocalized electrons on the adsorbent surface. During microwave irradiation the kinetic energy of the electrons on the adsorbent surface increases, which makes the electrons jump out of the material, leading to the ionization of the surrounding atmosphere and the formation of a hot spot. These hotspots are plasmas that are limited to a small region and last for fractions of a second. The temperature of the hot spot can usually reach 1200 C. This facilitates the destruction of complex chemical bonds by reducing the activation energy and increasing the reaction rate. The application of microwaves to remove contaminants reduces the reaction time and in many cases increases the yield and purity of the products. In addition, the use of powerful microwave absorbers, such as adsorbents, provides a rapid increase in temperature and an improvement in reaction rate. However, some studies reveal that microwaves do not induce relevant selective heating effects under the applied reaction conditions. This is because the dielectric property of target compound and matrix is similar, and the concentration of the compound on the catalyst surface prevents sufficient microwave heating. On the other hand, the quantum energy of the microwave causes the molecules to vibrate, helping to reduce the activation energy. As a process of removing pollutants, wastewater treatment can be easily done by using various techniques, systems and methods. A good wastewater treatment system should be costeffective and easy-to-use, and have high pollutant degradation and mineralization efficiency. The rapid and effective heating properties of the microwave make it useful in wastewater treatment. Microwaving oils has been a powerful tool in the breakdown of various organic compounds, including grease,

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nitrogen, phosphorus, and phenolic compounds. In the frequency range of 1
100 GHz the energy of 1 mol of photons from a microwave is equal to 0.4
40 J. However, the energy of the microwave is insufficient to break the chemical bonds of many organic compounds. Therefore microwaves are combined with adsorbents and catalysts to improve the efficiency of purification of various pollutants and shorten the reaction time. Microwaves have previously been combined with a wide variety of treatment processes, such as ultraviolet (UV), Fenton, UV/ Fenton, UV/H2O2, UV/TiO2, UV/Bi2WO6, and O3. The most commonly preferred microwave-assisted systems for wastewater treatment are (1) microwave alone; (2) microwave with oxidants; (3) microwave with catalysts, that is, microwaveenhanced catalytic degradation; (4) microwave with Fenton process; (5) microwave and direct photolysis; and (6) microwave with photocatalysis.

6.5

Microwave-assisted extraction

Advances in microwave-assisted extraction have resulted in a number of techniques, such as microwave-assisted solvent extraction, vacuum microwave hydrodistillation, microwave hydrodistillation, compressed air microwave distillation, and solvent-free microwave hydrodistillation. Over the years, procedures based on microwave-assisted extraction have replaced conventional methods and other extraction techniques in chemical laboratories (Proestos & Komaitis, 2008). In the extraction a solvent in which the target compound is soluble must first be selected. It has been reported that solvents with high dielectric constants absorb more microwave energy. In addition, the polarity of the solvent is very important in this technique (Lucchesi et al., 2004). Many substances, such as water, diethyl ether, petroleum ether, hexane, ethanol, methanol, acetone, and ethyl acetate, are used as solvents to perform extraction. An ideal solvent should have low viscosity and high solubility and should be specific to the component to be extracted, heatresistant, nontoxic, nonexplosive, economical, and harmless to the environment or human. In recent years, the application of microwave heating in solvent extraction has become increasingly common. Organic compounds, such as essential oils, flavors, pesticides, phenols, and dioxins, are effectively removed from matrices, such as soil, sediment, animal tissues, food, and wastewater. It has been reported that the extraction time is reduced, less solvent is used, and the

Chapter 6 A valorization approach of food industry wastewater using microwave-assisted extraction

amount of extracted phenolic compounds increases with the use of microwave-assisted extraction (Pan, Niu, & Liu, 2003). Microwave-assisted extraction is more advanced than conventional solvent extraction method, with the ability to efficiently and sparingly extract natural bioactive compounds by heating the matrix internally and externally without a thermal gradient and using less energy and solvent volume. The microwave treatment allows the water in the sample to evaporate, destroying the cellular system, thus allowing for a thorough extraction. Unlike conventional heating, no temperature gradient occurs in microwaveassisted extraction. Therefore even heating of the solution is ensured, thereby facilitating simultaneous heating of the entire sample. The hydrogen bond disruption due to the dipole spin of the molecule is an advantage in the case of extraction using microwaves. For microwave-assisted extraction the sample and/or solvent must have sufficient dielectric constant, as the microwave absorption capacity is dependent on the dielectric constant, that is, the greater the dielectric constant of the solvent, the more convenient the heating. Also, in some cases, the matrix itself interacts with microwaves because the surrounding solvent has a low dielectric constant. More specifically, when microwaves pass through the medium, their energy can be absorbed and converted into thermal energy. This principle was the basis for the development of microwaveassisted extraction, which works by heating and evaporating moisture inside the cell, creating high pressure on the cell wall. Pressure builds up inside the biomaterial and changes the physical properties of biological tissues, increasing the porosity of the biological matrix. This results in better penetration of the extraction solvent through the matrix and better mixing of the desired compounds. The solvents that are used for microwave-assisted extraction are present in a wide range of polarities. However, a combination of two or more solvents can be used to improve the extraction selectivity and the ability of the medium to interact with the microwave. Water has the highest microwave absorption, whereas hexane cannot be heated because it is completely transparent to microwaves. Consequently, the moisture content in the sample matrix enhances further extraction by locally superheating the water and promotes the release of the compounds into the surrounding environment. Two types of systems are commonly used, and different approaches are adopted in commercial microwave-assisted extraction process. The most common method is to perform the extraction in a closed vessel under controlled pressure and

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temperature. An alternative approach is to use an open extraction vessel under atmospheric pressure. It is not recommended to use a household microwave oven in laboratory studies. It has been indicated that the application of microwave energy to highly flammable organic solvents can cause serious hazards. In addition, homogeneity is not fully achieved in the microwave area of household ovens. Therefore it is reported that only equipment approved for microwave-assisted extraction should be used. Indoor microwaves are typically recommended for extraction, acid degradation, or digestion processes under harsh conditions. Because solvents can be heated above the atmospheric boiling point, both the extraction rate and efficiency are increased.

6.5.1

Specific applications of microwave-assisted extraction

Microwave irradiation has received great interest for household uses as well as industrial and medical applications. It has been used in various environmental applications, including phase separation by pyrolysis and extraction, soil remediation, remediation of hazardous and radioactive wastes, coal desulfurization, sewage sludge treatment, chemical catalysis, and organic/ inorganic syntheses. Microwaving is preferred because of its rapid and selective heating. For example, in pyrolysis-based applications a material with a relatively low porous structure is obtained from carbonaceous waste as a result of very high temperatures. The rapid heating is advantageous for soil remediation, remediation of hazardous and radioactive wastes, and chemical catalysis, while the selective heating is useful in coal desulfurization, separation, and purification. Microwaving is also a beneficial technique for the treatment of water and wastewater. It can be applied alone, combined with oxidants and catalysts, or coupled with advanced oxidation processes such as the Fenton process, UV radiation, or photocatalysis. In addition, it is used for drug extraction from both serum and skeletal tissues. Another use is the extraction of natural products, such as terpenes, alkaloids, essential oils, and carotenoids. Color pigments can also be extracted easily with this technique. Microwaving can be applied for rapid extraction of nitrated polycyclic aromatic hydrocarbons from soil. Microwave-assisted extraction is often used in environmental analysis. Extractions of polyaromatic hydrocarbons,

Chapter 6 A valorization approach of food industry wastewater using microwave-assisted extraction

polychlorobiphenyls, and organochlorine pesticides from sediment and soil can be performed. Microwaving has also been applied to food analysis. Oils and phenolic compounds present in foods can easily be extracted by using microwaveassisted extraction.

6.5.2

Kinetic modeling of microwave-assisted extraction

Many mathematical approaches have been used to model extraction kinetics. Models can be either derived theoretically, using Fick’s law and chemical kinetic equations, or formulated empirically. Diffusion in Fick’s law is an important property of mass transfer rate and very useful for equipment design. Another modeling approach is to use the chemical kinetic equation and empirical equations. The widely used Fick’s law of diffusion, chemical kinetic equations, and other parametric empirical equations are applied to most extraction curves. Depending on the nature of the solid sample in extraction, the kinetics of mass transfer may change. According to Fick’s law, the diffusion of soluble components depends on the concentration gradient between the solid and liquid phases. This gradient develops to create a balance between the two phases. Fick’s law formulation is as follows: N 52D

dC dx

ð6:1Þ

where N is the mass flow of the solute, C is the concentration of the solute, x is the distance in the direction of transfer, and D is the diffusion or diffusion coefficient of the solute in the solvent (Kayahan & Saloglu, 2020, 2021). New systems using microwave, ultrasound, and electric fields have been developed to increase the efficiency of solvent extraction. For this reason, empirical kinetic models developed in these extraction applications are used for scaling-up. Empirical models are considered more suitable for modeling nonconventional extraction processes such as microwaveassisted extraction because they cannot be accurately described by theoretical equations, such as those derived from diffusion and chemical kinetic theories. To determine the most suitable mathematical model for the microwave-assisted extraction method, the first-order kinetic model, the second-order kinetic model, Peleg’s model, and Page’s model were defined.

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The first-order kinetic model can be used for the modeling of extraction kinetics. Therefore the model was used to describe the microwave-assisted extraction kinetic model using the concentration values of the extracts (Kayahan & Saloglu, 2020, 2021). A kinetic approximation can be defined as follows: dCt =dt 5 k1 ðCe
Ct Þ

ð6:2Þ 21

where Ct is the solute concentration in the liquid (mg g ), Ce is the solute concentration at equilibrium in the liquid phase (mg g21), k1 is the mass transfer coefficient (1 time21), and t is the extraction time. The second-order kinetic model equation was used for solid/ liquid extraction kinetics. The second-order ratio can be defined as follows: dCt =dt 5 k2 ðCe
Ct Þ2

ð6:3Þ

where dCt/dt is the extraction rate (mg g21 . min), k2 is the rate constant of the extraction process (g mg21 . min), Ct is the solute concentration in liquid (mg g21), Ce is the solute concentration at equilibrium in liquid phase (mg g21), and t is the extraction time. The initial extraction rate, h, is equal to k2  Ce2 (Kayahan & Saloglu, 2020, 2021). The extraction mechanism of the second rate-order model is based on the idea that the microwave-assisted extraction occurs through two simultaneous processes. The amount of desired component that is extracted increases rapidly at the beginning of the extraction and then increases slowly until the end of the extraction. The first step is the equilibrium stage, in which the extracted component is removed from the surface at a constant rate and dissolution occurs. Then the mass transfer resistance at the interface appears. Mass transfer occurs through convection and diffusion. In the final step, the dissolved solvent diffuses toward it. The extraction rate in this step is low and is characterized by the extraction of the solute via a diffusion mechanism. In addition, the increase in solute concentration in the last step may explain the decrease in diffusion rate. Peleg’s model has been used to explain the kinetic behavior of extraction, as follows:
Ct 5 t= k1Peleg 1 k2Peleg t ð6:4Þ where Ct is the solute concentration (mg g21), t is the extraction time, k2Peleg is the Peleg’s rate constant (g mg21 per extraction time), and k2Peleg is the Peleg’s capacity constant (g mg21).

Chapter 6 A valorization approach of food industry wastewater using microwave-assisted extraction

Page’s model has also widely been used in extraction. Page’s model equation can be defined as follows:
ð6:5Þ Ct 5 exp 2kPage n where Ct (mg g21) is the solute concentration at the extraction time, kPage (mg g21) is the Page constant, and t is the extraction time (Kayahan & Saloglu, 2020, 2021).

6.6

Conclusion and future trends

The food industry is responsible for producing large volumes of wastewater. Evaluation of wastewater offers great environmental, economic, and social potential. It is seen that the techniques that are studied in the literature are still not widely applied to food industry wastewater; instead, it is disposed of with the techniques used by the municipalities to other types of industrial waste. Also, the choice of a valuation method for food wastewater should not be one-dimensional; rather, multiple key factors should be considered. Owing to the inherent variability in the composition of wastewater streams produced by different segments of food industry, the choice of an evaluation method for a given food industry wastewater is a complex process that must take many variables into account. However, anaerobic digestion is promising in the context of a circular economy and is probably the most used process in full-scale industrial settings. Food processing involves a range of production processes that are environmentally important, owing to high water consumption and use of variety of raw materials. Because of high organic matter, salt and nutrient content, treatment of food industry wastewater before discharging it into the receiving streams or water bodies is of great importance. For this purpose, food wastewater should be efficiently recycled or treated and discharged in a way that does not threaten the nature. Conventional methods that are used in the treatment of food wastewater are membrane filtration, adsorption, chemical, and thermal processes; electrochemical treatment; and extraction. The inadequacies, application difficulties, or costs of some of these methods have led the studies to find new methods in the field of environmental technologies. Among these methods, microwave-assisted extraction is a new and efficient type of extraction. There has been an increasing demand for microwave-assisted extraction because it has appropriate automation and is much faster and environmentally friendly.

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Microwave-assisted extraction can be used effectively as a significant treatment method in food wastewater in which oil, grease, polyphenols, and inorganic compounds are concentrated. The capabilities of microwave-assisted extraction suggest that it is a new and innovative method for the treatment of food wastewater. The best techniques to achieve efficient wastewater treatment with less environmental impact and low cost remain to be investigated in future research. Therefore it is important to use new and effective methods, such as microwave-assisted extraction, for the treatment of food industry wastewater.

List of acronyms BOD COD UV

Biological oxygen demand Chemical oxygen demand Ultraviolet

List of symbols N C x D Ct Ce k2 t h k1Peleg k2Peleg kPage

Mass flow of the solute Concentration of the solute Distance in the direction of transfer Diffusion or diffusion coefficient of the solute in the solvent Solute concentration in the liquid Solute concentration at equilibrium in the liquid phase Mass transfer coefficient Extraction time Initial extraction rate Peleg’s rate constant Peleg’s capacity constant Page constant

References Abdallh, M. N., Abdelhalim, W. S., & Abdelhalim, H. S. (2016). Industrial wastewater treatment of food industry using best techniques. International Journal of Engineering Science Invention, 5(8), 15
28. Ameer, K., Shahbaz, H. M., & Kwon, J. H. (2017). Green extraction methods for polyphenols from plant matrices and their byproducts: A review. Comprehensive Reviews in Food Science and Food Safety, 16(2), 295
315. Andreu, V., & Pico´, Y. (2019). Pressurized liquid extraction of organic contaminants in environmental and food samples. TrAC Trends in Analytical Chemistry, 118, 709
721. Antwi-Agyei, P., Cairncross, S., Peasey, A., Price, V., Bruce, J., Baker, K., & Ensink, J. (2015). A farm to fork risk assessment for the use of wastewater in agriculture in Accra, Ghana. PLoS One, 10(11), e0142346. Azwanida, N. N. (2015). A review on the extraction methods uses in medicinal plants, principle, strength and limitation. Medicinal & Aromatic Plants, 4 (196), 2167-0412.

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˜ ones-Bolan˜os, E. (2016). Bustillo-Lecompte, C., Mehrvar, M., & Quin Slaughterhouse wastewater characterization and treatment: An economic and public health necessity of the meat processing industry in Ontario, Canada. Journal of Geoscience and Environment Protection, 4(4), 175
186. Frascari, D., Molina Bacca, A. E., Wardenaar, T., Oertle´, E., & Pinelli, D. (2019). Continuous flow adsorption of phenolic compounds from olive mill wastewater with resin XAD16N: Life cycle assessment, cost
benefit analysis and process optimization. Journal of Chemical Technology & Biotechnology, 94(6), 1968
1981. Galanakis, C. M., & Kotsiou, K. (2017). Recovery of bioactive compounds from olive mill waste. Olive mill waste (pp. 205
229). Academic Press. ¨ rn, S., So¨renga˚rd, M., Frieberg, K., Nassazzi, W., Lai, F. Y., & Golovko, O., O Ahrens, L. (2021). Occurrence and removal of chemicals of emerging concern in wastewater treatment plants and their impact on receiving water systems. Science of the Total Environment, 754, 142122. Hewavitharana, G. G., Perera, D. N., Navaratne, S. B., & Wickramasinghe, I. (2020). Extraction methods of fat from food samples and preparation of fatty acid methyl esters for gas chromatography: A review. Arabian Journal of Chemistry, 13, 6865
6875. Kanakaraju, D., Motti, C. A., Glass, B. D., & Oelgemo¨ller, M. (2015). TiO2 photocatalysis of naproxen: Effect of the water matrix, anions and diclofenac on degradation rates. Chemosphere, 139, 579
588. Kaufmann, B., & Christen, P. (2002). Recent extraction techniques for natural products: Microwave-assisted extraction and pressurized solvent extraction. Phytochemical Analysis, 13(2), 105
113. Kayahan, S., & Saloglu, D. (2020). Optimization and kinetic modelling of microwave-assisted extraction of phenolic contents and antioxidants from Turkish artichoke. CyTA-Journal of Food, 18(1), 635
643. Kayahan, S., & Saloglu, D. (2021). Microwave-assisted extraction of antioxidant phenolic compounds from artichoke (Cynara scolymus L. cv Bayrampasa): Optimization and kinetic modelling. International Food Research Journal, 28 (4), 704
715. Lang, Q., & Wai, C. M. (2001). Supercritical fluid extraction in herbal and natural product studies-a practical review. Talanta, 53(4), 771
782. Lucchesi, M. E., Chemat, F., & Smadja, J. (2004). Solvent-free microwave extraction of essential oil from aromatic herbs: Comparison with conventional hydrodistillation. Journal of Chromatography. A, 1043(2), 323
327. Mischopoulou, M., Naidis, P., Kalamaras, S., Kotsopoulos, T. A., & Samaras, P. (2016). Effect of ultrasonic and ozonation pretreatment on methane production potential of raw molasses wastewater. Renewable Energy, 96, 1078
1085. Nayak, B., Dahmoune, F., Moussi, K., Remini, H., Dairi, S., Aoun, O., & Khodir, M. (2015). Comparison of microwave, ultrasound and accelerated-assisted solvent extraction for recovery of polyphenols from Citrus sinensis peels. Food Chemistry, 187, 507
516. Nieto, A., Borrull, F., Pocurull, E., & Marce´, R. M. (2010). Pressurized liquid extraction: A useful technique to extract pharmaceuticals and personal-care products from sewage sludge. TrAC Trends in Analytical Chemistry, 29(7), 752
764. Ntaikou, I., Antonopoulou, G., & Lyberatos, G. (2010). Biohydrogen production from biomass and wastes via dark fermentation: A review. Waste and Biomass Valorization, 1(1), 21
39. Pan, X., Niu, G., & Liu, H. (2003). Microwave-assisted extraction of tea polyphenols and tea caffeine from green tea leaves. Chemical Engineering and Processing: Process Intensification, 42(2), 129
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Papadopoulos, K. P., Economou, C. N., Dailianis, S., Charalampous, N., Stefanidou, N., Moustaka-Gouni, M., & Vayenas, D. V. (2020). Brewery wastewater treatment using cyanobacterial-bacterial settleable aggregates. Algal Research, 49, 101957. Pompermaier, A., Varela, A. C. C., Fortuna, M., Mendonc¸a-Soares, S., Koakoski, G., Aguirre, R., & Barcellos, L. J. G. (2021). Water and suspended sediment runoff from vineyard watersheds affecting the behavior and physiology of zebrafish. Science of the Total Environment, 757, 143794. Proestos, C., & Komaitis, M. (2008). Application of microwave-assisted extraction to the fast extraction of plant phenolic compounds. LWT-Food Science and Technology, 41(4), 652
659. Ribeiro, F., Okoffo, E. D., O’Brien, J. W., Fraissinet-Tachet, S., O’Brien, S., Gallen, M., & Thomas, K. V. (2020). Response to comment on quantitative analysis of selected plastics in high-commercial-value Australian seafood by pyrolysis gas chromatography mass spectrometry. Environmental Science & Technology, 54(23), 15556
15557. Ruiz-Aceituno, L., Garcı´a-Sarrio´, M. J., Alonso-Rodriguez, B., Ramos, L., & Sanz, M. L. (2016). Extraction of bioactive carbohydrates from artichoke (Cynara scolymus L.) external bracts using microwave assisted extraction and pressurized liquid extraction. Food Chemistry, 196, 1156
1162. Saloglu, D., & Ozcan, N. (2018). Activated carbon embedded chitosan/polyvinyl alcohol biocomposites for adsorption of nonsteroidal anti-inflammatory drug-naproxen from wastewater. Desalination and Water Treatment, 107, 72
84. Schmidt, J. E., & Ahring, B. K. (1997). Treatment of waste water from a multiproduct food processing company in upflow anaerobic sludge blanket (UASB) reactors: The effect of seasonal variation. Pure and Applied Chemistry, 69(11), 2447
2452. Sinquin, A., Go¨rner, T., & Dellacherie, E. (1993). L’utilisation des micro-ondes en chimie analytique. Analusis, 21(1), 1
10. Sobhi, H. R., Yamini, Y., & Abadi, R. H. H. B. (2007). Extraction and determination of trace amounts of chlorpromazine in biological fluids using hollow fiber liquid phase microextraction followed by high-performance liquid chromatography. Journal of Pharmaceutical and Biomedical Analysis, 45(5), 769
774.

7 Supercritical fluid extraction applied to food wastewater processing Luana Cristina dos Santos1, Talyta Mayara Silva Torres2, Daiane Ferreira Campos3, Filippo Giovanni Ghiglieno3 and Julian Martı´nez1 1

Department of Food Engineering and Technology, School of Food Engineering, University of Campinas, Campinas, Sa˜o Paulo, Brazil 2 Department of Chemical and Food Engineering, Federal University of Santa Catarina, Floriano´polis, Santa Catarina, Brazil 3Departament of Physics, Federal University of Sa˜o Carlos, Sa˜o Carlos, Sa˜o Paulo, Brazil

7.1

Introduction

In the food-processing industry, water is used for many purposes: in the production (agricultural irrigation), as a food ingredient for the final product, to be used as a thermal transfer medium (heating, chilling), as a transport medium, and in cleaning (washing, sanitation) (Kirby, Bartram, & Carr, 2003). Thus water consumption is excessive in the food processing industry, generating a large amount of wastewater, which is an environmental issue in the food plant alongside greenhouse gases, packaging, and food waste. According to FAO (2017), water use in the last century almost doubled in relation to the increase rate of the population, which is a growing trend. The alternatives to ease water consumption at higher scales, such as in the food industry, mainly focus on reuse, recycling, and improving layout design and processes (Bhagwat, 2019). For reuse in agriculture or other processes, a certain degree of purification and biological quality is needed to avoid contamination in the food chain. Wastewater treatment and sludge treatment are mainly focused on further uses as fertilizer or biodiesel rather than the potential of residues for the concentration of high value-added compounds. The food industry comprises segments with different structural, physicochemical, and biological characteristics. Therefore the use of Advanced Technologies in Wastewater Treatment. DOI: https://doi.org/10.1016/B978-0-323-88510-2.00007-5 Copyright © 2023 Elsevier Inc. All rights reserved.

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water is dependent on the product demand. For instance, the meat industry is responsible for using 24% of the total freshwater consumed by the food and beverage industry, almost twice the amount used by the beverage and dairy industries, the second and third most demanding freshwater industries (Bustillo-Lecompte & Mehrvar, 2015). Water is necessary for washing the carcasses at the slaughterhouses, in the evisceration process, and in general for cleaning and sanitization. Owing to the animal composition, the wastewater from this process is rich in fats, protein, and fibers, which can be detrimental to the environment. Dairy wastewater presents a similar problem. The effluent composition from these industries is also complex and contains a set of components and molecules with high value-added potential such as proteins. Around 80% of total industrial and domestic wastewater is discarded without pretreatment (Bhagwat, 2019). In the food industry, water treatment must be applied to adjust the concentration levels of organic matter so that it can be disposed of without harming the environment. There are also treatments to allow the reuse of water in the industry itself (e.g., water used to clean tanks and surfaces that undergo treatment to remove cleaning agents and heavy dirt by decanting). In both cases, a significant amount of sludge is generated. Depending on the industry segment, sludge can be rich in compounds with industrial application (e.g., residual lipids from the meat industry, tocopherols in the vegetable oil industry, essential oil in the industrial citrus, proteins in the dairy industry). In some cases, the industry can add these products to their manufacture chain; in other cases, they are simply considered to be industrial waste. The techniques that are used for wastewater and sludge treatment are based on a combination of physical, chemical, and biological processes (Crini & Lichtfouse, 2019). Some examples of physical-chemical treatments are gravity separation or concentration, evaporation, filtration and flotation, precipitation, oxidation, centrifugation, solvent extraction, carbon adsorption, ion exchange, membrane filtration, and electrochemistry. Biological processes usually need a preliminary removal of oils and solids before treatments, such as biodegradation by aerobic, anaerobic, or hybrid systems or phytoremediation (Barbera & Gurnari, 2018; Crini & Lichtfouse, 2019). Alternative technologies for wastewater treatment are included in the circular economy concept because they aim to reduce organic and pollutant solvents and usually demand lower energy than conventional technologies. Supercritical fluid

Chapter 7 Supercritical fluid extraction applied to food wastewater processing

technologies can be used for extraction, purification, oxidation, encapsulation, and other applications. Supercritical fluid extraction (SFE) is a clean technology that can be used to fractionate residual sludge, making some of these compounds of interest suitable for industrial applications, such as producing biodiesel, antioxidants, protein concentrates, or even eliminating toxic components from the liquid effluent. For instance, SFE has been applied to recover pesticides from wastewater (Yu, 2002) and, more recently, for the extraction of oil from olive mill wastewater (Dali et al., 2022). In this chapter the main characteristics of wastewater and sludge from the food industry are described, along with the SFE methodologies that could be used to separate the existing targeted compounds in effluents, representing an emergent alternative treatment to add value to this residue.

7.2

Wastewater and sludge from the food industry: composition and current issues

Wastewater is a significant problem in the food industry; therefore the correct treatment must be considered. The disposal of untreated or inadequately treated wastewater in water bodies can cause eutrophication in rivers, unleash poor conditions for aquatic life, contaminate surface water and groundwater, and contaminate the soil in addition to several other negative impacts on the natural environment (Bandeira, Esquerre, Bandeira, Brasileiro, & Borges, 2019; Kwon & Yoon, 2017; Memon, Soomro, Aziz, & Unar, 2012). To mitigate such impacts, national and international legislation determines parameters for the treatment of wastewater so that it will cause less harm to water bodies at the time of disposal. The treatment can occur through physicochemical and biological processes and can be subdivided into three stages of treatments. Preliminary and primary treatment involves grids, sieves, primary decanters, and so on. Secondary treatment involves stabilization and aeration ponds, activated sludges, and anaerobic reactors, among others. Tertiary or advanced wastewater treatment (ultrafiltration, ion exchange, reverse osmosis, electrolysis, nutrient removal, advanced oxidation processes, chlorination, etc.) usually occurs when the first two types of treatment fail to meet the desired conditions; applications vary according to the origin and characteristics of the effluents (Von Sperling, 2016). Biological treatments are widely

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used, mainly because they have microorganisms as active agents that are capable of degrading organic matter. In the effluent treatment process, the microbial biomass is generated, which concentrates most of the polluting components of the effluent (Von Sperling, 2016). This sludge from effluent treatment is considered an environmental liability with high fat content and organic matter, whose final disposal is commonly done in landfills (O’Kelly, 2005). Many studies have been carried out to find reuses of sludge in other industrial processes, with good alternatives in the civil construction and agriculture sectors. However, it is essential to highlight that most of the waste that is generated in effluent treatment plants is discarded without considering recovery and reuse alternatives, mainly because economically viable solutions are still in the development process. Owing to the characteristics of food industry products, the effluent sludge from these processes tends to be rich in minority compounds that, once extracted, have can provide added value in the pharmaceuticals, energy, food, and other sectors. The following subsections will discuss different types of effluents from the food industry and the characteristics of the sludge that is generated, emphasizing compounds with potential for recovery using supercritical fluid technologies.

7.2.1

Dairy

World milk production was estimated at almost 860 million tons in 2020, showing an increase of 1.4% compared to 2019, and this increase has been occurring continuously (FAO, 2021a). However, with the increase in milk production, there is also an increase in effluents and residues generated, which is already high compared to other industries in the food sector. Cheese whey from cheese production is an example of this because for each kilogram of milk that is used for cheese production, 0.9 kg of cheese whey residue is generated (Gonza´lez-Amado, Tavares, Freire, Soto, & Rodrı´guez, 2021). Therefore it becomes a problem that can damage conventional effluent treatment systems due to the high fat content. Altogether, about 1 2 m3 of wastewater is generated for each ton of milk that is processed in an industry’s production of dairy products (FEO, 2005). It is important to note that wastewater from the dairy industry is vulnerable to significant variations in quality and quantity, mainly because each dairy product needs a separate technological line, causing dairy effluents to be composed of milk and dairy products that are lost in the stages of production as well as byproducts of the processing operations.

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Cheese whey and other dairy products make the dairy industry effluents rich in numerous elements and functional biomolecules that can be recovered and reused as raw materials for new products. Table 7.1 lists the elements and biomolecules that are found in the sludge from the dairy wastewater treatment process. The biomolecules that are present in milk produce vital biotechnological substances. An example is lactase, whose sirups obtained from this enzyme can replace corn sirup or sucrose in the ice cream, confectionery, and bakery industries, thus improving the flavor of products without increasing their calories (Montiel, Carruyo, Marcano, & Mava´rez, 2005). Therefore different extraction techniques are used to recover these compounds, such as the method using toluene in phosphate buffer, as well as pressurized liquid extraction with ethanol-water at different temperatures, extraction using monolithic silica spin column, extraction by supercritical fluid, and several others (Kanamori-Kataoka et al., 2011; Montiel et al., 2005; Ruiz-Matute et al., 2007; Sa´nchez-Macı´as, Laubscher, Castro, Argu¨ello, & Jime´nez-Flores, 2013). To date, SFE has not been employed to recover elements or biomolecules from dairy wastewater. However, supercritical water gasification has been used in the dairy sludge to produce hydrogen as fuel. For instance, in a recent study, Khorasani, Khodaparasti, and Tavakoli (2021) evaluated hydrogen production from dairy

Table 7.1 Elements and biomolecules in dairy effluent sludge. Element or biomolecule Element P K Mg Al Ca Fe Biomolecule Lactate Lactose WP NCPC NCPC, native calcium phosphocaseinate; WP, whey protein.

References Daly, Fenton, Ashekuzzaman, and Fenelon (2019)

Sage, Daufin, and Ge´san-Guiziou (2006)

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wastewater using MnO2 and MgO as catalysts and formic acid as an additive.

7.2.2

Fruit and vegetable industry

In 2018 the world produced 868 million tons of fruits and 1089 million tons of vegetables (FAOSTAT, 2020). Small family businesses, which account for 80% of the world’s food production, are also responsible for producing a large part of fruits and vegetables, with 50% of the total fruit and vegetable production being produced on farms of less than 20 hectares. Nevertheless, the large fruit and vegetable producers usually export and produce raw materials for the industry (FAO, 2020a). The processing industry in this sector involves the production of canned fruits and vegetables, frozen fruits and vegetables, juices, precut vegetables, ready-made salads, and dried and dehydrated foods. This sector also generates a significant amount of wastewater. For example, for each liter of fruit juice that is produced, 1.5 L of effluent is discarded (Santonja, Karlis, Stubdrup, Brinkmann, & Roudier, 2019). Therefore the effluents and residues that are generated in the production stages of this industry are concentrated in carbohydrates, minerals, vitamins, and dietary fibers that can be evaluated for their potential for the production of bioethanol, and enzymes; bioproduction of organic acids; pectin recovery; and use in biocoloring as well as for other compounds with commercial value in the food industry itself and in the pharmaceuticals and veterinary industries. Table 7.2 presents some of these compounds found in fruit and vegetable industry residues. Sterols, carotenoids, tocopherols, and other phytochemicals from fruit and vegetable seeds have interesting strengths from a commercial point of view (Alves, Simoes, & Domingues, 2021). Therefore using the supercritical CO2 extraction method for these compounds is a promising alternative (Dabrowski, Konopka, & Czaplicki, 2018; Panfili, Cinquanta, Fratianni, & Cubadda, 2003; Xu, Dong, Mu, & Sun, 2011). Overall, the solid waste that is generated from the fruit and vegetable industry has enormous potential to be used as raw material for SFE to recover high-value-added compounds.

7.2.3

Meat industry

Total world meat production in 2020 was estimated at 337.2 million tons. It remained similar to that of the previous year, as

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Table 7.2 Elements and biomolecules in residues from the fruit and vegetable industry. Type of waste

Element or biomolecule

References

Pretreated cane bagasse Sugars

Glucose Xylose

Krishnan et al. (2010)

Apple-processing waste Biomass components

Sugars

Cellulose Hemicellulose Lignin Pectin Glucose Fructose Arabinose

Dhillon, Kaur, and Brar (2013)

Lycopene β-Carotene α-Tocopherol (β 1 γ)-Tocopherol Δ-5-Avenasterol Campesterol Cholesterol Lanost-8-en-3-β-ol 24-Oxocholesterol β-Sitosterol Stigmasterol Cycloartenol β-Amyrin Oleanolic acid Ursolic acid

Kalogeropoulos, Chiou, Pyriochou, Peristeraki, and Karathanos (2012)

Tomato byproducts Carotenoids Tocopherols Sterols

Terpenes

a drop in beef and pork production was offset by an increase in poultry and sheep production (FAO, 2021b). The meat industry is a branch of the food industry that is responsible for significant environmental degradation; the amount of effluent that is generated for each slaughtered animal can reach 2900 L (Espinoza, Paz, Ribas, Sangoi, & Bursztejn, 2000). The effluent in this sector contains a variety of organic and inorganic pollutants and a high concentration of etheric extract, mainly owing to their organic byproduct composition, whose origin includes blood, stains from the removal of the rumen, intestinal residues from the evisceration process, fats from the meat cutting step, as well as

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Table 7.3 Elements and biomolecules present in the effluent sludge from the meat industry. Category

Component

References

Elements

N P K Cr Cd Cu Pb Zn Myristic acid Palmitic acid Stearic acid Oleic acid Cis-vaccenic acid Enrofloxacin Tetracycline Ceftiofur

Meehan, Maheswaran, and Phung (2001)

Fatty acids

Antibiotics

Okoro, Sun, and Birch (2017)

Carvalho, Pirra, Basto, and Almeida (2013)

the head and limbs, including bones, which makes it high in proteins and lipids (Banks & Wang, 2004; Miranda, Henriques, & Monteggia, 2005; Su & Chou, 2019). The tanning industry also uses chemicals to convert raw animal skins into commercial leather in a sequence of steps. Therefore a significant amount of organic waste is generated in slaughterhouses and the tanning industry. Their effluent is rich in soluble proteins, carbohydrates, lipids, and inorganic waste such as chromium, salts, solvents, and additives. Furthermore, like the elements and biomolecules presented previously, these compounds have value-added and applications in the food, pharmaceuticals, and veterinary industries. Table 7.3 presents some of these compounds found in the sludge from the meat industry. There is no documentation on the supercritical fluid treatment from meat industry wastewater. However, owing to the rich composition of this sludge, it would be interesting to conduct studies in this sector.

7.2.4

Oil industry

Global oilseed production in 2019 2020 was estimated at 584.3 million tons (FAO, 2020b). This production is represented mainly

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187

by the vegetable oil industry, whose effluent comes from the degumming, deacidification, and deodorization stages. However, the high concentration of fatty acids draws attention to fuel production. The focus on vegetable oils and animal fats to produce biodiesel has grown as new alternatives using low-cost raw materials have attracted interest in this sector. In this way, compounds that are found in recycled or used oils, byproducts from the refining of vegetable oils, and substances in wastewater from the oil industry have the potential to be reused in the fuel industry. Such potential is feasible because biodiesel is a transport fuel that is considered renewable, composed of a set of metal esters of fatty acids, which are present in vegetable and animal fats (Hoekman, Broch, Robbins, Ceniceros, & Natarajan, 2012). Table 7.4 presents the quantification of fatty acids in sludges from canola oil and palm oil production. The high content of fatty acids in vegetable oils makes oil industry wastewater a very interesting raw material for recovering nonpolar compounds by using supercritical CO2 extraction. Given the promising fatty acids applicability, including the molecules highlighted in Table 7.4, Yeo, Soetaredjo, Ismadji, and Sunarso (2021) performed a phase equilibrium experiment of several fatty acids in supercritical carbon dioxide (scCO2). The authors found that oleic acid had the greatest solubility and linolenic had the worst solubility in scCO2. Furthermore, Norulaini, Zaidul, Anuar, and Omar (2004) also performed SFE with scCO2 to fractionate fatty acids from palm kernel oil, corroborating their differences in solubility. Olive oil wastewater is another example of oil industry wastewater appropriate for applying supercritical technologies. Abbattista, Ventura, Calvano, Cataldi, and Losito (2021) presented a very well-structured review on the bioactive profile of olive mill wastewater. The authors observed that the phenolics were the major components in the wastewater profile, similar to

Table 7.4 Fatty acids content in effluent sludge from the oil industry. Fatty acid Palmitic acid Stearic acid Oleic acid Linoleic

Type Saturated Saturated Monounsaturated Polyunsaturated Reference

Canola oil (% by weight)

Palm oil (% by weight)

11 4 6 43 49 12 14 Ngoie, Oyekola, Ikhu-Omoregbe, and Welz (2020)

43 4 40 10 Hayyan et al. (2011)

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olive oil, showing that the wastewater can be well explored to recover such high value-added compounds. The supercritical CO2 technology can be applied to recover oiled samples that are enriched in fatty acids of industrial interest due to the high selectivity of nonpolar compounds.

7.2.5

Beverage industry

The beverage industry is a subsector of the food industry that supplies various products ranging from wine, beer, and liquors to mineral water and soft drinks. Markets worldwide are strongly affected by cultural differences, creating a favorable environment for the production of local products by small and medium-sized companies. However, large multinational companies can compete in markets worldwide (Guimara˜es, Klabjan, & Almada-Lobo, 2012). The wastewater that is generated by this industry has a wide range of characteristics due to the amount of water used, type of raw material used, type of product, and different additives such as salt, sugar, gelatin, colors, oil, dyes, and preservatives added (Srivastava, Gupta, Mehrotra, Choudhury, & Singh, 2016). In addition, a the significant amount of water that is used in the industry for washing and rinsing, especially when the industry reuses glass bottles that need water for cleaning before being refilled (Haroon, Waseem, & Mahmood, 2013). The manufacture of soft drinks, for example, generates approximately 1.75 L of wastewater for each liter of soft drink produced. In comparison, breweries generate around 3 6 L of effluent for each liter of beer produced (Santonja et al., 2019). Table 7.5 shows some of the compounds that are found in the effluent treatment sludge from the beverage industry. Substances such as perfluoroalkyl and polyfluoroalkyl are contaminants with a high risk of exposure and are extremely difficult to degrade naturally. However, they have highly valuable characteristics for many applications, such as high chemical resistance, hydrophobicity, lipophobicity, and heat resistance, that make them fundamental in the plastics, metals, electronics, herbicides, firefighting foams, cosmetics, paints, packaging, and other industries (Dhore & Murthy, 2021). Griffin, Aristizabal-Henao, and Bowden (2021) analyzed four extraction methods of perfluoroalkyl and polyfluoroalkyl substances, the methanol breakdown, ion pair, homogenized Folch, and chloroform methods. They found that concentrations were higher when the homogenized Folch method was used because these substances are similar to fatty acids, and homogenized Folch is an efficient method for extracting lipids.

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Table 7.5 Elements and biomolecules contents in brewery and wine sludge and wastewater. Biomolecule Perfluoroalkyl substances in brewery sludge Perfluoro-n-hexanoate Perfluorooctane sulfonate Perfluoro-n-octanoate Perfluoro-n-decanoate Phenolic compounds in wine wastewater Gallic acid 4-Hydroxybenzoic acid Caffeic acid Syringic acid

References 21

Amount (pg g ) 174.9 382.4 416.3 596.5 Amount (mg L21) 2.03 2.63 0.55 0.64

Sindiku, Orata, Weber, and Osibanjo (2013).

Can˜adas, Gonza´lez-Miquel, Gonza´lez, Dı´az, and Rodrı´guez (2021)

Nonetheless, in the performance requirement, supercritical carbon dioxide extraction could be satisfactory in addition to being able to reduce the use of toxic solvents.

7.3

Clean extraction technologies for wastewater and sewage sludge treatment: circular economy in high demand

The sustainability concept of a circular bioeconomy in the food industry aims to answer one question: What is the best recycling process/technology for the generated waste? There is no easy answer, since the generated residues need sustainable recycling options to make valuable products. Fig. 7.1 illustrates an overall idea of circular economy in food industry processes. Sustainable management became strictly related to corporate competitiveness (Porter & Van Der Linde, 1995). Consequently, considering the importance of ecologically friendly characteristics of the process, there is a continuously growing impact of food industry wastes on the environment, making it necessary to dig into further alternatives for those residues. Therefore it is crucial to find suitable processes and applications that are both environmentally and economically advantageous and easy to implement from this point of view. In this context, some emergent and clean technologies, such as subcritical and SFE, pressurized fluid extraction, ultrasound-assisted extraction, membrane separation,

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Figure 7.1 Circular economy in the food industry.

adsorption processes, and microwave-assisted extraction, have been discussed to guide sustainability along a correct path in food waste treatment (Bhagya Raj & Dash, 2020; dos Santos et al., 2021a, 2021b; Meng et al., 2021; Mezzomo, Martı´nez, Maraschin, & Ferreira, 2013; Pereira et al., 2020). Next, some beneficial aspects of using clean technologies to recover some value-added compounds present in food industry wastewater and sludge will be presented, focusing on biodiesel production and biotechnological application. A recent work reported by Deng et al. (2021) demonstrated the potential of soy fermentation wastewater as an excellent source of nutrients and N2, working perfectly as a growing medium for microalgae that could be used to feed fish. Such results suggest that alternatives for isolating those compounds from the whole matrices are possible. According to the global energy CO2 2019 report prepared by the International Energy Agency (IEA, 2019), the global oil demand increased by 1.3% in 2018, when liquefied petroleum gas, diesel, and gasoline were the main products. To reduce energy consumption from petroleum sources, oily wastes generated by meat, poultry, and dairy industries could be a great source of low-cost alternative feedstocks. However,

Chapter 7 Supercritical fluid extraction applied to food wastewater processing

exploring novel technologies to convert this waste into a product is challenging. Olkiewicz et al. (2015) used ionic liquid tetrakis(hydroxymethyl)phosphonium chloride (P(CH2OH)4]C) as a solvent to recover biodiesel from raw primary sludge without losing characteristics as observed in conventional Soxhlet methods. In addition, the process also achieved the elimination of the dewatering step, therefore reducing its production costs. Zohar et al. (2021) reported a recent work that used subcritical water as a green solvent to extract sewage sludge sampled from a wastewater treatment plant. The extracts showed herbicidal potential, and the highest temperature that was applied, namely, 300 C, was the most effective in inhibiting seeds germination of three different plant weed species. The gas chromatography analysis confirmed that the main compounds were pyrazines and their derivatives. A work reported by Bahari (2010) used subcritical water to obtain extracts with antioxidant capacity from a semisolid waste from cider production. After fermentation, phenolic compounds remained adsorbed into yeast cell walls, and subcritical water extraction was a clean alternative to recover these value-added compounds. The use of nonpolar solvents is known to offer some advantages over polar solvents in biodiesel extraction. Such effect is due to their ability to extract saponifiable lipids that are easier convertible to biodiesel. However, concerning supercritical fluid extraction using carbon dioxide (SFE-CO2) processes to recover oil for biodiesel production, only one reference using a crop was found in the literature to date, using Jatropha (Ferna´ndez, Fiori, Ramos, Pe´rez, & Rodrı´guez, 2015). Jatropha is currently considered the most appropriate plant in biodiesel production (Amit, Dahiya, Ghosh, Nigam, & Jaiswal, 2021). Microalgae is also a promising source to help the energy crisis in the future (Goswami, Mehariya, Verma, Lavecchia, & Zuorro, 2021). In the context of this chapter, food wastewaters can be excellent candidates for microalgae cultivation and therefore biodiesel production (Amit, Dahiya, Ghosh, Nigam, & Jaiswal, 2021). Unfortunately, only a few works reporting the use of supercritical fluids to extract lipids from sewage sludge or food wastewaters were found up to the present date, as seen in Section 7.4.3. Once this becomes an emerging technique, it requires more time and research for adequate processing that will show the advantages that justify proper technology investment in the industries. Integration of lipid extraction processes and further utilization of sewage sludge for the conversion of biomass (e.g., liquefaction) into energy is a current example of a cascading process with

191

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many advantages in the circular economy (Fan et al., 2021). Regarding food sludges, materials that are rich in crude protein instead of lipids are also being investigated, using liquefaction techniques of bio-oil with potential combustion characteristics (Chen et al., 2019). Prajitno, Zeb, Park, Ryu, and Kim (2017) investigated the effects of supercritical ethanol, methanol, and water in bio-oil conversion from sewage sludge. Using supercritical ethanol, the authors found an enhanced calorific value and a high yield of 87.8 (wt.%) for bio-oil production. The main compounds that were identified in this bio-oil were nitrogenated, fatty acid methyl and ethyl esters and short-chain mono alcohols. The latter were not found in bio-oils produced from supercritical methanol or water. Therefore the use of supercritical fluids in both lipid extraction and liquefaction might be an excellent example of a circular economy concept application, favoring energy balances and reducing biodiesel production costs. Besides biodiesel production, sewage sludge can also represent a potential source of value-added compounds. Although such targeted investigation has been widely applied to food byproducts (peel, seeds, pericarp), wastewater also presents an ´ lafsson, Helgason, opportunity. In this context, Stepnowski, O and Jastorff (2004) proposed a fully sustainable alternative for seafood processing. The authors performed wastewater treatment from Arctic shrimp processing to recover astaxanthins, potential antioxidants, carotenoid pigments, and precursors of vitamin A. They used a clean adsorption process, using fish scales as bioadsorbents compacted into a vertical column. Fractions were collected along the column, and 25 35 cm was the fraction with the best astaxanthin loading capacity, achieving a total of 362 mg of astaxanthin kg21 of dry fish scales. However, astaxanthin’s recovery from bound scales has been proposed from conventional extraction (using environmentally unfriendly solvents such as acetone). Since SFE-CO2 has effectively extracted carotenoids from different food matrices (dos Santos et al., 2021a, 2021b; Mezzomo et al., 2013), it could be a plausible post-treatment as an integrated process in such circumstances.

7.4

Supercritical fluid extraction

SFE will be discussed in the following subsections. First, in Section 7.4.1 a detailed description of the technology is provided, while Sections 7.4.2 and 7.4.3 focus on wastewater and sludge treatment alternatives using such fluids.

Chapter 7 Supercritical fluid extraction applied to food wastewater processing

7.4.1

Fundamentals of supercritical fluid extraction

The history of supercritical fluids started in 1822 with thermodynamic experiments at high temperatures and pressures by Charles Cagniard de la Tour in France. He observed that liquids tended to pass to the gaseous state even when the system’s pressure continuously increased, demonstrating the critical temperature. The physicochemical properties of a supercritical fluid were introduced by Hannay and Hogarth in 1879. However, supercritical fluids were not considered potential solvents to replace conventional ones until 1960, when precise analytical techniques confirmed the presence of residual organic solvents from conventional extractions, leading to serious concerns related to human health (Sovova´ & Stateva, 2011). Between the 1960s and 1980s, industrial applications of SFE in Germany included decaffeination of green coffee beans and hop extraction (Hubert & Vitzthum, 1978; Zosel, 1978). In the 1990s, SFE gained wide prominence with the investigation in academic research of crude and essential oil extraction from vegetable matrices without using toxic solvents (Reverchon & Osse´o, 1994; Reverchon, 1997; Reverchon, Daghero, Marrone, Mattea, & Poletto, 1999). Such remarkable outcomes were the first step of extensive works using supercritical fluids to extract value-added compounds from natural matter. The supercritical state of a pure compound is achieved when both pressure and temperature are above their respective critical values (Pc and Tc, respectively). In such conditions, the density of the pure substance is very similar to that of a pure liquid, whereas the viscosity is comparable to those of gases. In addition, diffusivity is considered in-between liquids and gases (Brunner, 2005). The modification of thermodynamic properties of supercritical fluids allows tunability in solubility and mass transfer properties, such as diffusivity, density, viscosity, and dielectric constant, contributing to the selectivity of the solvent. Therefore tuning the pressure and temperature of the processes based on this physical phenomenon can ease the selective extraction of a target class of compounds, which is usually done by previous analysis of the solubility of compounds in a supercritical medium (Bitencourt, Ferreira, Oliveira, Cabral, & Meirelles, 2018; dos Santos, Bitencourt, dos Santos, Vieira e Rosa, & Martı´nez, 2020; Maheshwari, Nikolov, White, & Hartel, ´ cka, Vacek, & Stra´nsky´, 2001). Even though 1992; Sovova´, Zarevu this seems to be a good strategy, in multicomponent systems with complex compositions, reaching the phase equilibrium

193

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becomes more challenging and unstable to predict, requiring the design of multiple experimental conditions to observe the concentration trend of the targeted compound. Despite its complexity, SFE is an excellent alternative to conventional extraction processes, mainly because of its environmentally friendly aspects related to the solvents’ physical and chemical properties (Knez et al., 2014). Carbon dioxide (CO2) is one of the most commonly used solvents in SFE, especially when the application is related to food ingredients, because of the solvent-free character of the extract, which is possible as a result of the depressurization at the end of the process, fully separating CO2 from the extract, dismissing purification steps (Pereda, Bottini, & Brignole, 2008). Supercritical CO2 is generally recognized as a safe (GRAS) promising solvent due to its manifold advantages: static nature, low toxicity, nonexplosive, and readily available in nature (Chemat et al., 2019). Another commonly used solvent in SFE is supercritical water (scH2O). However, owing to its high critical temperature (647.14 K), scH2O extraction requires high energy consumption and thus its application is somewhat limited. Supercritical H2O was the most studied solvent compared to supercritical methanol and ethanol in applications such as desulfurization of coal and recovery of liquid fuels from coal and oil shales (Marcus, 2018) and biomass liquefaction (Sharma et al., 2021). Supercritical H2O is also widely applied as a reactant in oxidation processes in a technique to replace incineration of waste products with a high amount of organic matter (Vadillo, Sa´nchez-Oneto, Portela, & Martı´nez de la Ossa, 2014). Besides extraction processes, supercritical ethanol and methanol were successfully applied for biodiesel production (Karki, Sanjel, Poudel, Choi, & Oh, 2017). Some thermodynamical properties of the most commonly used supercritical fluids are listed in Table 7.6. A generic SFE process using CO2 as solvent is presented in Fig. 7.2. The raw material usually has its moisture content removed (or reduced) and particle size reduced to improve mass transfer efficiency. The particle bed is packed into the extraction vessel, and occasionally, an inert material fills the void spaces. CO2 is cooled to ensure its liquid state before entering a pneumatic liquid pump driven by a compressed air pipeline. After CO2 is pressurized above its Pc, it passes through a serpentine submerged in a heating bath to achieve a temperature above its Tc. The same bath circulates water in the external chamber of the extractor vessel (sometimes being replaced by an electric heating system) to avoid temperature variations in the extraction system. Next, backpressure (or control

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Table 7.6 Critical properties of the most commonly used supercritical solvents in supercritical fluid extraction.

Carbon dioxide Ethanol Water

Molecular formula

Tc (˚C)

Pc (bar)

ρc (g cm23 )

Vc (cm3 mol21)

CO2 C2H6O H2O

30.97 240.77 373.99

73.74 61.48 220.64

0.468 0.276 0.322

94.07 167.00 55.95

Source: From Poling B. E., Prausnitz, J. M., & O’Connel, J. P. (2001). The properties of gases and liquids (5th ed.) New York: McGrawHill (Poling et al., 2001).

Figure 7.2 Process flow diagram of a generic supercritical fluid extraction (SFE) using CO2 as solvent. FI, Flow indicator; P, pressure indicator; T, temperature indicator (dos Santos, 2022). Adapted from dos Santos, L. C. (2022). Fractionation of extracts from industrial yellow passion fruit (Passiflora edulis Sims.) byproducts using supercritical CO2 and pressurized fluids. Universidade Estadual de Campinas. Food Engineering Department, Thesis, p. 222 (dos Santos, 2022).

pressure valve) is placed in the extraction vessel exit, and CO2 is partially depressurized in a cyclonic separator vessel, where the extract is precipitated. A flow indicator and a volume totalizer are placed at the end of the system to control the amount of spent CO2 and flow speed. Finally, CO2 recirculates in the process after a

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condensation and pressurization step, while the extract is collected at the bottom of the separator vessel. The study of mass transfer kinetics helps to define the solvent to feed mass ratio (S/F), an essential economic parameter that is used to scale up processes (Martı´nez, Rosa, & Meireles, 2007). In SFE, an important starting point is to establish the target compound and the characteristics of the raw material and the extract to be obtained. After that, gathering information on solubilization of the extract and its compounds in the supercritical solvent would play a key role in the design of experiments to achieve higher global and target compound yields, which means a maximum process efficiency. In addition, when aiming to recover volatile compounds, the extract collection is temperature-controlled (B10 C), and a trap could be added inside the collecting flask to adsorb the targeted compound (Lee, Peart, & Sarafin, 2003). Compounds that can be obtained from vegetable biomass through SFE include fatty acids, pigments, terpenes, tocols, sterols, fatty alcohols, and phenolics (de Melo, Silvestre, & Silva, 2014); the last are polar compounds owing to the hydroxyl groups in their molecules. Kumar et al. (2021) have recently compiled studies focusing on bioactive compounds recovery using green techniques, in which SFE is highlighted for phenolics concentration. To improve the extraction yield of this class of compounds, SFE can be performed with up to 15%, v/v cosolvent:scCO2 (Calvo, Morante, Pla´nder, & Sze´kely, 2007) of a solvent modifier or a cosolvent, which can be water, ethanol, or a mixture of them (Khaw, Parat, Shaw, & Falconer, 2017). Fractionation is sometimes performed coupled with the SFE process, depending on the raw material and the composition of the extract. Two or more separators can be coupled in series in this case. The backpressure valves are then put in the outlet of each separator to adjust pressure, while electric or heating baths will control the temperature. Thus the precipitation of extracts with different compositions is achieved in a single batch (Reverchon & Della Porta, 1997). As was described in Section 7.2, a typical process for food industries is removing solids and grease from food wastewater to avoid disturbing biological treatment. This procedure generates residues usually known as primary sludge. SFE would effectively separate the present compounds, improve food wastewater treatment efficacy, and generate value-added compounds simultaneously. In addition, SFE can be assisted with other unit operations such as membrane and ultrasound (dos ˚ gren, Mathiasson, & Bjo¨rklund, Santos et al., 2016; Eskilsson, A 2004), which could work as a pretreatment of wastewater

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Table 7.7 Advantages and drawbacks of supercritical fluid extraction over the conventional extraction process. Advantages Supercritical • Properties of CO2 can be easily tuned Fluid Extraction • CO2 available in nature • Sustainable process: CO2 is GRAS • Absence of toxic residue • Low process temperatures: suitable for thermolabile compounds (usually ,60 C) • Possibility of scaling-up processes • High diffusion • Substantially faster • Possibility of solvent recycling

Drawbacks • High investment costs (stainless steel equipment, pump, valves, cooling/heating system, and others) • High power consumption in comparison with solid-liquid conventional extraction or cold pressing • Needs cosolvents to extract polar compounds

treatment to remove protein, lipids, and other macro components to amend the separation procedures. The main SFE advantages and drawbacks are presented in Table 7.7.

7.4.2

Supercritical fluid extraction of liquid and semisolid mixtures

7.4.2.1

Supercritical fluid extraction using supercritical water (SFE-H2O)

Water is among the most used solvents that are considered environmentally friendly, since it is rapidly available, of high purity, nontoxic, nonflammable, and considerably cheaper than other solvents. Among the typical applications of scH2O, one can cite the treatment of coal and oil shales, allowing the recovery of liquid fuels by using a greener methodology (Marcus, 2018). Supercritical H2O has gained attention in the past decades, mainly owing to the solvent parameters, such as dielectric constant, which can be easily adjusted by variations in temperature and pressure (Malmberg & Maryott, 1956). SFE using ethanol was reported less often than water for wastewater treatment applications, being used mainly in their supercritical condition for improving reactions (Do, Prajitno, Lim, & Kim, 2019; Karki, Sanjel, Poudel, Choi, & Oh, 2017). Moreover, the utilization of EtOH in wastewater treatment processes seemed to be preferred under subcritical conditions

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Chapter 7 Supercritical fluid extraction applied to food wastewater processing

(Hadhoum, Burnens, Loubar, Balistrou, & Tazerout, 2019; Pagano et al., 2018).

7.4.2.2 Supercritical fluid extraction using supercritical carbon dioxide (SFE-CO2) It is well established that the mass transfer mechanism in SFE-CO2 of a high-water-content material has poor efficiency. Therefore wastewater from the food industry should be previously submitted to treatment. For instance, consolidated physicochemical systems (as mentioned in Section 7.2) allow the solids to precipitate, generating sewage sludge. In very particular cases, water content could be beneficial to achieve a high extraction yield. For instance, Ivanovic, Ristic, and Skala (2011) observed an increase of 40% in the yield of essential oil of Helichrysum italicum (a rich source of compounds with varied biological activities) when presoaking in water was performed, resulting in moisture content of 28.4% (w/w). Also, the characteristic of the substrate is essential before selecting the most suitable extraction method. The selection of CO2 implies the extraction of molecules that are considered nonpolar or have very low polar characteristics (Brunner, 2005), such as triglycerides, carotenoids, and aromas. In this context, the water content of liquid or semisolid substrates should be reduced by pretreatment (e.g., drying processes) if the targeted compounds are hydrophobic. Liquid samples are often submitted to continuous SFE in a countercurrent configuration. This process has a sample stream from the top and a solvent stream uprising so that the compounds can be distributed between the liquid sample and the supercritical solvent. Contact time is an important parameter, easily adjusted by extractor height, influencing the separation ˜ ez, 2013). One factor (Mendiola, Herrero, Castro-Puyana, & Iba´n of the most studied applications of countercurrent SFE-CO2 is oil refinement. This method was applied by Osse´o, Caputo, Gracia, and Reverchon (2004) to evaluate the separation of undesired compounds generated in frying processes. The authors reported optimum conditions at 35 MPa, 55 C, and S/F 5 53 (w/w), achieving a purified oil (94.5% of triacylglycerols) yield of 52%, indicating that this was an effective process for oil recycling. Similarly, Eisenmenger, Dunford, Eller, Taylor, and Martinez (2006) performed countercurrent SFE-CO2 to remove free fatty acids from wheat germ oil. The authors confirm the removal was achieved under conditions of 14 MPa and 80 C, preserving compounds such as tocopherols and sterols in

Chapter 7 Supercritical fluid extraction applied to food wastewater processing

the oil. Yasumoto et al. (2015) also applied countercurrent SFE to separate components from a citrus essential oil model composed of canola oil and D-limonene. The effects of pressure, temperature, CO2 flow rate, S/F, column height, and temperature gradient on D-limonene recovery were evaluated. The most effective separation was observed when a temperature gradient from 30 C to 60 C was induced. This result can be attributed to the changes in solubility of D-limonene (as reported by the same authors, D-limonene is about ten times less soluble in SFE at 60 C than at 30 C, at 10 MPa), which possibly favored mass transfer coefficient. All in all, it must be recognized that besides the importance of the previous characterization of the raw material in the selection of the separation method, knowing the target component’s solubility in CO2 (that is aimed to be recovered or removed) plays an essential role in finding the adequate separation conditions in a supercritical process.

7.4.3

Supercritical fluid extraction applied to wastewater and sludge from the food industry

Since the two most common green solvents in SFE are CO2 and water, the idea of developing a fully sustainable process also implies a byproduct or residue from the food and agriculture industry as raw material. For instance, the use of SFE in the recovery of bioactive compounds extracted from natural matter is a promising method in this context (Sodhi et al., 2022). Therefore the wastewater and sewage sludge from the food industry should be considered potential sources of compounds that can find technological application options (see Section 7.2 for composition aspects in leading food industry wastewater and sludge). Food residues also contain pollutants (e.g., heavy metals) that are very difficult to remove by conventional treatments. Therefore this section will focus mainly on the SFE of compounds from food and agroindustrial wastewater and sludge, although this technique has not yet been consolidated in this field. Solid or semisolid food byproducts such as seeds, peel, and bagasse, were not considered. Food-processing industry wastewater has been used as a potential substrate medium for producing value-added products such as pigments, biocontrol agents, biofloculant agents, and biopolymers (Sodhi et al., 2022). However, the utilization of wastewater or sludge as a raw material for extraction techniques aiming to recover those compounds is still poorly explored. In the food

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industry wastewater and sewage sludge, such compounds can be recovered (in enriched extracts) or removed from a matrix (toxic compounds), depending on necessity. Among the emerging extraction technologies, SFE can work as an alternative method to replace secondary treatments of wastewater, aiming to remove organic pollutants (Boukouvalas, Magoulas, & Tassios, 1998). In this context, scCO2 has been applied to extract pesticides and other toxic compounds from industrial wastewater, like polychlorinated biphenyls, a lipophilic pollutant used in transformers and capacitors (Lindholm-Lehto, Ahkola, & Knuutinen, 2017). Yu (2002) aimed to remove eight pesticides from samples of rice wastewater, achieving a complete removal of pesticides (99.99%) under the best condition found for a model system, which was 90 C, 320 bar, and 40 min extraction at 2 mL CO2 min21. Bisphenol A (BPA) (used in the production of commercial plastics) is confirmed to be highly toxic even if in low doses, causing health issues primarily related to coronary diseases (Gao & Wang, 2014). Therefore industries need to meet the criteria of their local government policies to adequate the wastewater before discharging. Lee and Peart (2000) suggested an alternative method to extract BPA from sewage sludge using SFE in an analytical scale (,0.5 g of sample). They first converted BPA into acetylated BPA molecules, and extraction was performed at a temperature range of 60 C 100 C at 37 MPa. In their findings, the maximum extraction yield of BPA reached 80% without temperature influence. Another application of SFE-CO2 is to determine organic contaminants (mainly lipophilic) in sewage sludge, which helps to find and eliminate health-risky molecules or even track information related to humans (Lin, Arunkumar, & Liu, 1999; Nahar, Uddin, Alam, & Sarker, 2021). Recently, Dali et al. (2022) performed SFE on a lab scale, using scCO2 to extract fatty acids from olive mill wastewater processed in Tunisia. To improve efficiency, the authors performed a freeze-drying process before the extraction, achieving yields of around 30% (g extract/100 g raw material, dry basis) under conditions of 30 MPa and 60 C. Such a step would be an issue in scaling-up processes, since huge amounts of wastewater are generated in the food industries. Therefore, alternatives should be considered. For instance, the use of different solvents or drying methods or even considering SFE as a secondary or tertiary treatment of previously treated sludge. When it comes to recovering value-added compounds, SFE is usually applied for biomass such as the solid residues from the food industry (seeds, peel, stems, etc.) (Duba & Fiori, 2015; Sodhi et al., 2022). On the other hand, separation methods are well established in analytical-scale processes. For instance, for

Chapter 7 Supercritical fluid extraction applied to food wastewater processing

organic pollutant determination in wastewater, analytes can be effectively separated from the sludge by employing scCO2 (You, Lao, & Wang, 1999), qualifying such extraction as a potential recovery method for high value-added compounds. Hence, scaling-up processes are required when such analytes are classified as value-added compounds or potential pollutants. In the scH2O medium, nonionic products are preferred over the ionic ones (Gu¨ngo¨ren et al., 2007). In other words, nonpolar compounds can be dissolved in scH2O. In the last two decades, researchers have dedicated themselves to find green alternatives to convert protein-rich biomasses into amino acids, with scH2O extraction being one of the main substitutes (Di Domenico Ziero et al., 2020). However, the decomposition of amino acids can reduce the recovery, so the process dynamics and configuration must be considered in selecting the extraction method, since scH2O conditions imply high temperatures and pressures (Table 7.6). Another application of scH2O extraction is related to drying processes of sewage sludge, where costs can be ¨ ngo¨ren et al. avoided when using this solvent. For example, Gu (2007) used scH2O to extract compounds from petrochemical sewage sludge with an optimum S/F 5 1. The authors observed a trend in increasing temperature and gas products, mainly formed by CH4, CO2, and H2. On the other hand, the oily part of the liquid products was mainly composed of hydrocarbons (C2 C4), which did not show a linear relationship between concentration (mole hydrocarbon kg21 sludge) and scH2O extraction temperature, suggesting an optimum of 450 C for all molecules. Their findings indicated that scH2O extraction increased recovered liquid hydrocarbons up to 44.4 wt.% while process residue decreased, reinforcing the sustainability of the technique. Unfortunately, at this point in time, there is no work reported in the literature using scH2O extraction to recover value-added compounds from food wastewater and food wastewater sludge. Metal contamination is another severe environmental concern, mainly because it can be hazardous when ingested. For instance, rivers located in big cities are continuously receiving wastewater from industries of all kinds, and the metal concentration can be dangerous for their aquatic ecosystems. Yabalak and Gizir (2013) tested different CO2 densities (ρCO2) in SFE applied to metal extraction from sewage sludge. They observed a positive effect in the demetalization of a generic sewage sludge with density increase, achieving the optimum result at 120 bar and 90 C (ρCO2 5 0.264 g mL21). The authors achieved an extraction yield removal between 40% and 50% of the metals Cr31, Cu21, Ni21,

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Pb21, and Zn21. The authors emphasize the necessity of adding a chelating agent, since solute-solvent affinity is very weak (owing to the differences in polarity). The positively charged metal ion must be chelated to become soluble in scCO2. Therefore extraction efficiency would also be related to the chelation ability and the molecule’s solubility in scCO2. Although only a few works have reported on the use of SFE to extract heavy metals from sewage sludge, some studies have proven to be highly efficient in remov¨ zel, ing heavy metals from contaminated soil (Geng et al., 2020). O Bartle, Clifford, and Burford (2000) achieved an efficiency of 27.5% of lead removal from soil contaminated with metals at SFE-CO2 conditions of 60 C and 400 bar. A less common application of SFE in food industry wastewater treatment includes a technique that was developed to replace a wet-salted skin treatment. For example, Marsal, Celma, Cot, and Cequier (2000) used scCO2 to dry and degrease sheepskin, observing a high extraction efficiency (94%) in higher CO2 densities, with an extract composition rich in lanolin, waxes, monoglycerides, diglycerides, triglycerides, fatty acids, and cholesterol. The next section will present some economic aspects of SFE applied for recovering value-added molecules found in wastewater and sludge from the food industry.

7.5

Technoeconomic evaluation of supercritical fluid extraction applied to the recovery of value-added molecules

As was illustrated in the previous sections, efforts to valorize food waste using supercritical fluid technologies have been made. Several studies have investigated SFE technology’s efficiency in recovering high value-added compounds from different food industry residues. However, there are fewer studies regarding economic feasibility, especially at the industrial scale. This section of the chapter will consider and discuss the technoeconomic aspects of supercritical technology. The first aspect of considering SFE production costs is the magnitude of the process, which can be at the analytical, pilot plant, or industrial scale. Most studies are focused on the laboratory and pilot plant scale. The investment cost of the SFE process is usually the most representative in the economic evaluation in considering both analytical and pilot plant scales. As the scales increase, the raw material cost is the most

Chapter 7 Supercritical fluid extraction applied to food wastewater processing

representative of the economic balance (Comim, Madella, Oliveira, & Ferreira, 2010). Technoeconomic evaluations of food wastewater using supercritical technologies to recover valuable compounds are scarce. Several studies involving natural products have shown the viability of SFE through cost-of-manufacturing analysis. Some of them are presented in Table 7.8. The cost of manufacturing (COM) concept was first presented by Turton, Bailie, Whiting, and Shaeiwitz (2008) and is a methodology that considers the costs of investment, labor, utilities, waste treatment, and raw material. The concept aims to calculate the total cost of the final product, therefore showing the viability of the investment and the payback time. It is a very resourceful tool for evaluating the economic impact of the application of new technology. For instance, Comim et al. (2010) found an economic route for recovering banana peel oil using supercritical CO2, with production costs lower than commercial oils with similar fatty acid content. Similarly, Santana et al. (2018) calculated an acai waste supercritical CO2 extract selling price equal to that of coldmechanical acai berries extract. Albarelli et al. (2018), when evaluating the integration of SFE on the sugarcane biorefinery, observed that the use of SFE for the recovery of wax from sugarcane filter cake residue significantly reduced the payback time, even in the worst-case scenario. The selling price of the product has a significant influence on the payback time, which is higher when product quality is also higher. In the case of SFE extracts, the selectivity of this extraction technique toward some target compounds, especially nonpolar compounds when the solvent used is CO2 neat, increased the value of the extracts Lefebvre, Destandau, and Lesellier (2021). In all the studies presented at Table 7.8, the COM decreased as the scale increased, which is the expected behavior. For example, Vigano´ et al. (2017) evaluated the COM of passion fruit bagasse SFE extraction at pilot and industrial scales of 1, 5, 50, and 500 L. The authors observed a decrease of COM when increasing scale. The authors simulated a sequential SFE (three steps) and pressurized liquid extraction (one step) extraction. Each step aimed at recovering an extract that was rich in a determined compound: tocol-rich extract, fatty-acid-rich extract, carotenoid-rich extract, and phenol-rich extract, respectively. The simulation aimed at high productivity (calculated as the sum of accumulated extract from each step) and low COM. All the COM presented are related to the industrial scale. Although the investment cost is usually significant, the raw material cost can influence the COM at an industrial scale. This behavior

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Table 7.8 Cost of manufacturing of SFE from food industry waste for the recovery of high value-added products. Target compound

SFE conditions

Extractor volumea (m3)

COM References (USD kg21)

Provitamin A compounds, carotenoids, flavonoids, polyunsaturated fatty acids, phytosterols, triterpenes. Phenolics

30 MPa, 50 C, 35 min, CO2.

0.4

13.69

Comim et al. (2010)

20 MPa, 40 C, 180 min, CO2.

0.5

133.16

Farı´asCampomanes, Rostagno, and Meireles (2013) Vigano´, Zabot, and Martı´nez (2017)

Lycopene

SFE 1 PLE:First step: 17 MPa, 2 3 0.5 60 C, 4.8 h, CO2;Second step: 17 MPa, 50 C, 4.8 h, CO2; Third step: 26 MPa, 60 C, 3.2 h, CO2;Fourth step: 10 MPa, 70 C, 2 h, EtOH/ Water. 50 MPa, 90 C, CO2. 1

Essential oils, flavonoids, alkaloids, beta-carotene

30 MPa, 35 C, CO2 1 5% EtOH.

0.5

Phenolic acids

30 MPa, 50 C, CO2.

1

First step: tocol-rich extractSecond step: fattyacid-rich extractThird step: carotenoid-rich extractFourth step: phenol-rich extract

Sugarcane wax extract (fatty 20 MPa, 50 C, CO2. alcohols and phytosterols)

Selina-1,3,7(11)-trien-8-one, oleic acid, phytol, and γ-sitosterol

25 MPa, 40 C, 60 min, CO2.

21.3

0.1

26.33

1.8 Silva, de kh kg21lycopene Melo, and Silva (2014) 5.91 Leita˜o, Prado, Veggi, Meireles, and Pereira (2013) 19.36 Santana et al. (2018) 26.5 Albarelli, Santos, and Meireles (2018) 1000 Canabarro, Veggi, Vardanega, Mazutti, and Ferreira (2020)

COM, Cost of manufacturing; PLE, Pressurized liquid extraction: USD, United States Dollars; h: euros. a Extractor volume simulated for COM calculation in a scaling-up process.

Chapter 7 Supercritical fluid extraction applied to food wastewater processing

was observed by Canabarro et al. (2020), when studying the COM of scCO2 pitanga leaf extracts. The authors observed a contribution of 73% and 80% of the COM’s raw material acquisition cost contribution for 50 and 100 L of production, respectively. Although the SFE presented an interesting alternative for pitanga leaf extract, the COM exceeded the assumed selling price of US$500 kg21, being profitable only if the extract selling price was stated as US$1000 kg21. In parallel, Leita˜o et al. (2013) evaluated the COM sc-CO2 1 5% EtOH extraction of cashew (Anacardium occidentale) leaves and calculated only 0.11% 0.17% of raw material cost influence on COM. The authors accounted for almost zero of the cost of the cashew leaves, as they were a residue from the cashew juice and cashew nut processing industry. However, the cost of drying, pretreatment, and transportation must be considered in the acquisition cost. Few technoeconomic evaluations of wastewater treatment using CO2 were found in the literature. A recent study by Jan and Wang (2020) evaluated the technoeconomic analysis of a scCO2 countercurrent system for the wastewater treatment of 250 ton d21 processing. The authors demonstrated the viability of the SFE process compared to current wastewater treatments, since the process presented a lower processing cost and lower processing time. Also, the scCO2 process advantage of releasing no chemical pollutants, the cost of the treatment being rated as 1.12 USD ton21, associated with a payback time of 1.29 years, with high chemical oxygen demand (COD) and oil removal rate (above 80%). COD is used as an indicator of the organic matter through oxygen accessible for oxidation at the liquid sample (Jan & Wang, 2020). Similarly, Xuan Do, Prajitno, Lim, and Kim (2019) did a technoeconomic analysis of supercritical ethanol and supercritical methanol on the production of bioheavy oil from sewage sludge. The authors evaluated the economic viability of a 100 ton d21 plant with 81% water content and calculated a cost of production of $11.2 and $8.6 million per year. Supercritical methanol is more economical than ethanol, owing to the solvent price, with a 21% annual return on investment. The payback times for ethanol and methanol used as solvents were 5.08 years and 3.68 years, respectively. The supercritical technology presented an interesting alternative to thermochemical technologies such as liquefaction and pyrolysis for the conversion of sewage sludge to bio-heavy-oils, especially the sc-MeOH, that presented a return of investment of over 10% and a payback time of under 5 years, that are the criteria used in the technoeconomic analysis that determine the feasibility of a plant.

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Overall, studies show the SFE technology’s feasibility for residues treatment from the food industry, as illustrated in the previous sections. However, more technoeconomic evaluations are needed to understand the economic viability of SFE compared to conventional technologies used for wastewater treatment. The more relevant costs of SFE are the cost of solvent (CO2) and electricity, which could be reduced by using recycling and alternative energy sources on an industrial scale.

7.6

Conclusions and future trends

Supercritical fluids have been widely applied in the past three decades, focusing mainly on extracting high-value compounds from vegetable matrices. However, several other applications have been discussed in the literature, such as removing heavy metals from electronic materials, particle formation, drying polymeric materials, and others. In this context, SFE represents a potential treatment for food industry wastewater and sludge, even though literature about this topic is still very scarce. There are two primary considerations regarding the use of SFE in this material: First, the recovered compounds may have biological potential, adding value to the product. Second, SFE offers some advantages regarding environmental concerns. For instance, SFE seems to be a potential method to remove organic pollutants such as BPA and toxic heavy metals from food industry sludge, therefore solving problems related to land application and local legislation. Besides, oil concentration in sludges can be intensely reduced. However, the use of supercritical CO2 requires some pretreatments (mainly drying), which could be a drawback for scaling-up processes of SFE applied to wastewater and sludge. The literature shows the potential of food industry wastewater and sludge as a new source of high value-added compounds (joining the circular economy model). Therefore new ideas to separate them, such as SFE, are welcomed. Even though scaling-up SFE processes to separate or extract compounds from wastewater and sludge is challenging, the association of pretreatments (e.g., membrane filtration, adsorption) might be a good alternative to reduce the overall operational cost, once the efficiency of the processes tends to improve.

Acknowledgments This study was financed in part by the Coordenac¸a˜o de Aperfeic¸oamento de Pessoal de Nı´vel Superior—Brasil (CAPES)—Finance Code 001. The authors also

Chapter 7 Supercritical fluid extraction applied to food wastewater processing

would like to thank the Sa˜o Paulo Research Foundation (FAPESP) for the doctorate scholarship (Process no. 2017/11245 5).

List of acronyms BPA COD COM scCO2 scH2O SFE SFE-CO2 SFE-H2O GRAS

bisphenol A chemical oxygen demand cost of manufacturing supercritical carbon dioxide supercritical water supercritical fluid extraction supercritical carbon dioxide extraction supercritical water extraction generally recognized as safe

List of symbols Pc ρ ρc S/F Tc

critical pressure density critical density solvent to feed ratio critical temperature

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Chapter 7 Supercritical fluid extraction applied to food wastewater processing

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8 Advances in ultrasound-assisted extraction of bioactive compounds (antioxidant compounds) from agrofood waste Abraham Osiris Martı´nez-Olivo, Alba Cecilia Dura´n-Castan˜eda, Francia Guadalupe Lo´pez-Ca´rdenas, Jose´ de Jesu´s Rodrı´guez-Romero, Jorge Alberto Sa´nchez-Burgos, Sonia Guadalupe Sa´yago-Ayerdi and Victor Manuel Zamora-Gasga National Technological Institute of Mexico, Technological Institute of Tepic, Nayarit, Mexico

8.1

Introduction

A residue (solid or liquid) that is deliberately or unintentionally unused, lost, or degraded throughout the food supply chain (preparation, storage, handling, or selling) is food waste (Rohini, Geetha, Vijayalakshmi, Mini, & Pasupathi, 2020). According to Chhandama, Chetia, Satyan, Ruatpuia, and Rokhum (2022), China (169 million tons/y), South Korea (4.28 million tons/y), India (11 billion tons/y), United Kingdom (15 million tons/y), United States of America (60 million tons/y), Germany (4 5 million tons/y), and France (5.8 9 million tons/y) are the leaders in food waste generation. The environmental impact of food waste is very considerable, representing almost 10% of global greenhouse gas emissions from human activities (Slorach, Jeswani, Cue´llar-Franca, & Azapagic, 2019). Agrofood industries generate a huge amount of organic waste (e.g., discarded fruits and vegetables, peels, leaves, seeds, whey, bones, blood, etc.), which usually ends up underutilized and accumulated (Fig. 8.1), causing environmental problems (Patel, Temgire, & Borah, 2021). Over the last decade, the recovery of food waste to obtain bioactive Advanced Technologies in Wastewater Treatment. DOI: https://doi.org/10.1016/B978-0-323-88510-2.00005-1 Copyright © 2023 Elsevier Inc. All rights reserved.

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Figure 8.1 Main residues and byproducts of the agrofood industry.

compounds (BC) has been the subject of extensive research (Panzella et al., 2020; Sagar, Pareek, Sharma, Yahia, & Lobo, 2018; Torres-Valenzuela, Ballesteros-Go´mez, & Rubio, 2020). The effective valorization of waste/byproducts from agrofood industries can help to reduce environmental stress by decreasing unwarranted pollution. Nowadays, the concept of circular economy has been proposed as the most efficient production system, since it allows for reducing and reutilizing different waste/byproducts (Fortunati, Morea, & Mosconi, 2020; Pagotto & Halog, 2016). Interestingly, these elements constitute a source of BC as such polyphenols, carotenoids, bioactive peptides, and polysaccharides, and their valorization leads to a circular economy that benefits industry and society (Aznar-Sa´nchez et al., 2020; Borrello, Lombardi, Pascucci, & Cembalo, 2016). Traditionally, the extraction of BC uses organic solvents (e.g., methanol, ethanol, or acetone) that have a negative impact on the environment. Therefore

Chapter 8 Advances in ultrasound-assisted extraction of bioactive compounds

it is necessary to modify the extraction methodologies involving ecological and sustainable technologies that lead to extracts rich in BC with a low environmental impact. Ultrasound-assisted extraction (UAE) is an alternative for the efficient recovery of BC in food waste. UAE using high-intensity sound waves to cause disruption in the fruit and vegetable tissues through physical forces developed during acoustic cavitation, helping the release of extractable components in a significant less amount of time by enhancing mass transport (Kumar, Srivastav, & Sharanagat, 2021). On this basis, this chapter provides a general description of the BC that are present in waste from the agrofood industry and the most commonly used ecological approaches for their recovery, highlighting the role of UAE as an efficient alternative with less processing time, low temperatures, and requirements of less energy and solvents. In addition, it provides information on the factors that affect extraction of BC and concludes with the new trends in the application of this extraction technology.

8.2

Main bioactive compounds from waste and byproducts of fruits and vegetables

Many of the fruit and vegetable industry’s waste and byproducts arise after the process of value-added products. Fruits and vegetables have the highest wastage rate (Gustavsson, Cederberg, Sonesson, Van Otterdijk, & Meybeck, 2011), and according to the latest statistics, the farming industry contributes more than 500 million tons of waste worldwide (Banerjee & Chattopadhyaya, 2017). Byproducts and residues generated from the inedible parts of fruits and vegetables are a valuable source of phytonutrients that remain undervalued. This waste is generated during the harvest or the postharvest stages (Das & Arora, 2017) and includes inedible parts such as leaves, peel, seeds, florets, and stems. Interestingly, these parts of crops often contain higher amounts of BC compared to the edible parts (Gorinstein, Martın-Belloso, et al., 2001; Gorinstein, Zachwieja, et al., 2001). Research on these byproducts has been highly significant, highlighting the fact that some fruits, such as grape, citrus fruit, mango, and apple peels are reported to contain 15% more BC content than in their pulp (Bertha, Alberto, Tovar, Sa´yago-Ayerdi, & Zamora-Gasga, 2019; Sa´yago-Ayerdi, Zamora-Gasga, & Venema, 2019; Soong & Barlow, 2004). The potential properties that some of these byproducts have are also described. It is important to mention that many of these properties and compounds are consistent in many other fruits and vegetables. That is why the characterization and

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identification of compounds of this type in various ethnic crops gains more strength and relevance. Some properties of these byproducts are mentioned below.

8.2.1

Pomace

Recognized for being a good source of pectin and dietary fiber, apple pomace contributes to the improvement of satiety and the reduction of blood glucose and cholesterol (Alongi, Melchior, & Anese, 2019). Also, significant amounts of phytochemicals with potential health benefits (phenolic acids, flavonols, flavanols, anthocyanins, and dihydrochalcones) have been found in apple pomace (Barreira, Arraibi, & Ferreira, 2019; Garcı´a, Valles, & Lobo, 2009; Lavelli & Corti, 2011). Similarly, berry pomace, obtained after juice extraction, contains significant amounts of polyphenols, such as anthocyanins. These compounds have been reported to prevent cardiovascular disease, renal artery stenosis, and some types of cancer. Similarly, anthocyanins, favonols, and phenolic acids from plum pomace have been recognized for their biological activities, mainly as antimicrobials and antioxidants (So´jka et al., 2015). Beetroot pomace is another industrial byproduct that is rich in flavonoids, carotenoids, and particularly betalains such as betacyanins and betaxanthins. It has been reported to have antioxidant activity as well as anti-inflammatory, anticarcinogenic, and antimicrobial properties (Rodriguez-Amaya, 2019; Vuli´c et al., 2014).

8.2.2

Peels and seeds

Fruit and vegetable peels and seeds also contain many phenolic compounds (Friedman, 1997). For example, it has been found that banana peel has a large group of flavonols, catechins, and catecholamines as well as phenolic acids such as ferulic, caffeic, and synaptic acids (Gonza´lez-Montelongo, Lobo, & Gonza´lez, 2010; Herna´ndez-Carranza et al., 2016; Rebello et al., 2014). Likewise, processing of citrus fruits generates a huge amount of waste, ranging from 50% to 70% of the wet weight of the processed fruit (Zema et al., 2018). Citrus fruit wastes such as seeds and peel are also a valuable source of phytochemicals and polyphenols with antioxidant, antiinflammatory, and anticancer properties, as has been demonstrated via in vitro and in vivo studies (Ishisono, Yabe, & Kitaguchi, 2017; Mahato, Sharma, Sinha, & Cho, 2018). In addition to phenolic acids and flavonoids, seeds found in citrus fruit waste contain limonoids, a unique class of BC (Liu et al., 2019).

Chapter 8 Advances in ultrasound-assisted extraction of bioactive compounds

Similarly, there are reports that state that mango peel and seed contain a great number of BC, such as phenolic acids, flavonoids, catechins, xanthonoids, and carotenoids (BallesterosVivas et al., 2019; Blancas-Benitez et al., 2015; Sa´yago-Ayerdi et al., 2019; Torres-Leo´n et al., 2016). Related to this, the potato peel has been distinguished by its high content of polyphenols compared with its pericarp, being mainly phenolic acids, to which antibacterial and antioxidant activity has been attributed (Friedman, Kozukue, Kim, Choi, & Mizuno, 2017; Wu et al., 2012). Moreover, chlorogenic acid stands out as a compound extracted from potato peels that is inversely associated with the risk of developing type 2 diabetes and cardiovascular diseases (Javed et al., 2019). Another important industrial waste is carrot peel, a valuable source of carotenoids, such as α- and β-carotenes, lutein, and tocopherols, with high antioxidant capacity (de Andrade Lima, Charalampopoulos, & Chatzifragkou, 2018).

8.2.3

Leaves and stems

Another interesting source of BC in farming waste is branches, leaves, and stems. Silva, Ferreira, and Nunes (2017) reported different compounds, such as anthocyanins, found in berry branches. Broccoli and cauliflower waste (leaves and stalk) are normally discarded, despite their composition being similar to that of florets (Ares, Bernal, Nozal, Turner, & Plaza, 2015). Nevertheless, Thomas, Badr, Desjardins, Gosselin, and Angers (2018) showed that broccoli byproducts have the potential for the extraction of compounds with biological interest such as polyphenols and glucosinolates. Also, broccoli byproducts, in comparison with florets, are an important source of macronutrients, highlighting their protein content close to 25% and carbohydrate content of almost 40% (Shi et al., 2019). The main phenolic acids that were found in cauliflower byproduct extracts were synaptic and ferulic acids. In addition, a high content of quercetin and kaempferol derivatives were also reported (Gonzales et al., 2014). Another type of residues from the fruit-processing industry are the exhausted calyxes from Hibiscus, which, according to Sa´yago˜i (2014) and Ayerdi, Vela´zquez-Lo´pez, Montalvo-Gonza´lez, and Gon (Amaya-Cruz, Pere´z-Ramı´rez, Pe´rez-Jime´nez, Nava, & ReynosoCamacho, 2019), contain manly organic acids, anthocyanins, and flavonols and are also a source of dietary fiber. Although there are plant byproducts that have already been extensively studied, many sources of vegetables waste/byproducts that may be useful for BC extraction, remain to be explored.

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8.3

Main bioactive compounds from waste and byproducts of animal product processing

Animal waste and byproducts generation mainly involve the milk and meat (livestock, poultry, and aquaculture) processing industries, and these byproducts have been undervalued (Leo´n, Marcilla, & Garcı´a, 2019). They are considered environmental and/or sanitary problems, and the costs of adequate treatment and disposal are high (Khalil, Berawi, Heryanto, & Rizalie, 2019). Therefore industry and researchers have focused on turning byproducts into useful sources of value-added inedible products, such as fertilizers and biodiesel, and edible products that include BC, such as peptides and oligosaccharides (Alao, Falowo, Chulayo, & Muchenje, 2017; Ozogul et al., 2021). Some compounds recovered from animal and marine product processing waste are shown in Table 8.1.

8.3.1

Dairy products

One of the main byproducts of dairy food production is whey (aqueous fraction obtained from the coagulation of casein in milk), and the generation of large volumes of whey in milk industry is considered a serious environmental problem. However, bioactive peptides obtained by enzymatic hydrolysis of whey proteins have shown antihypertensive and antioxidant properties (Correˆa et al., 2019; Sousa, Medeiros, Pintado, & Queiroga, 2019). In addition, it has been found that galactooligosaccharides that are produced from whey permeate by transgalactosylation of lactose using β-galactosidase have shown a promising prebiotic activity (Dzik et al., 2017; Mano, Paulino, & Pastore, 2019). In addition, an important source of bioactive oligosaccharides has been obtained in colostrum permeates after microfiltration treatments (de Moura Bell et al., 2018).Neuroprotective, antioxidant, antimicrobial, and antiinflammatory biological functions have been attributed to the protein fraction of colostrum, which contains a low-molecularweight glycoprotein called lactoferrin (Park, Moon, & Park, 2014).

8.3.2

Meat products

During the processing of meat, several byproducts are obtained (viscera, bone, horns, blood, skin) that could be used for the production of pet foods, biodiesel, and fertilizers, balancing treatment and disposal costs through added value (Toldra´, Mora, & Reig, 2016). Owing to their protein nature, meat byproducts can be used as a substrate to obtain bioactive

Table 8.1 Bioactive compounds from animal and marine processing wastes and byproducts. Industry

Type of waste

Bioactive compounds

References

Dairy products

Whey

Correˆa et al. (2019) Sousa et al. (2019)

Salmon nasal cartilage

Bioactive peptides from protein hydrolysate Bioactive from milk oligosaccharides; neutral oligosaccharides; acidic sialylated oligosaccharides Galactooligosaccharides Lactoferrin Oligosaccharides Bioactive peptides from protein hydrolysate Bioactive peptides from protein hydrolysate Collagen hydrolysate Chitooligosaccharides Astaxanthin Polyunsaturated fatty acids Proteoglycans

Salmon skin and trimmings

Bioactive peptides from protein hydrolysate

Colostrum Meat products

Marine products

Blood: hemoglobin and plasma Trimmings and cuttings Bones, horns,and skin Shrimp shells, heads, and tails

Mano et al. (2019) Park et al. (2014) de Moura Bell et al. (2018) Toldra´ et al. (2016) Mora et al. (2014) Ismail (2019) Hu et al. (2019) Amiguet et al. (2012) Hirose, Narita, Asano, and Nakane (2018); Kobayashi, Kakizaki, Nozaka, and Nakamura (2017); Tomonaga et al. (2017) Harnedy et al. (2018); Neves et al. (2017)

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peptides. In vitro and in vivo antimicrobial, antioxidant, and antihypertensive activity has been demonstrated in protein lysate from meat byproducts (Mora, Reig, & Toldra´, 2014).

8.3.3

Marine products

The fishing industry generates byproducts that range between 40% and 50% of the total weight of the raw material ¨ g˘ u¨t, & Kalemta¸s, 2018). Within marine (FAO, 2019; Terzio˘glu, O products, one of the most consumed shellfish is shrimp, from which BC can be extracted, including omega-3 polyunsaturated fatty acids, astaxanthin (a carotenoid with high antioxidant capacity), and chitooligosaccharides from chitin (Amiguet et al., 2012; Hu et al., 2019; Ismail, 2019). Bioactive peptides obtained from the hydrolysis of collagen from fish skin have been demonstrated to improve the learning and memory processes and include beneficial health properties, such as antihypertensive, antidiabetic, and antioxidant properties (Harnedy et al., 2018; Neves, Harnedy, O’Keeffe, & FitzGerald, 2017). However, with the available research information, studies on effective valorization of wastes and byproducts from animal resources remain limited when compared to fruits or vegetables.

8.4

Emerging technologies for obtaining bioactive compounds

The extraction of BC is usually carried out from different matrices, which can include plants (seeds, leaves, fruits), tree bark, or other sources, including marine organisms such as algae (Kuhn, de Azevedo, Frazzon, & Noren˜a, 2021). Extraction methods for these matrices are usually considered empirical exercises, using different solvents and varying conditions, such as temperature, concentration of the plant material, solvent mixtures of different polarity, and particle size of the plant material (Ingle et al., 2017). Once these compounds have been obtained, it is necessary to perform a correct separation of the element of interest, using different methodological strategies, depending on the chemical nature of the BC. The extraction of BC has transformed the way in which these byproducts are considered and has led to the search for technologies that are more ecofriendly and allow better use of all the residues. Fig. 8.2 shows the general scheme for obtaining BC from any type of organic matter (Galanakis, 2012; Gil-Martı´n et al., 2021). The first stage includes the preparation of the biological material

Chapter 8 Advances in ultrasound-assisted extraction of bioactive compounds

from which the BC of interest will be obtained. Usually, this stage involves reduction of the particle size by operations such as grinding, thermal or vacuum concentration, lyophilization, centrifugation, or microfiltration. The main objective at this point is to provide the necessary characteristics so that the separation of the macromolecules or micromolecules of interest is more efficient. The second stage consists of separation through the use of organic solvents, alcohol precipitation, or solubilization and precipitation, to mention some of the most common processes. Meanwhile, other methodologies, known as emerging strategies, involve the use of UAE, crystallization, microwave-assisted extraction, or extraction using eutectic solvents or the so-called green extraction (using only water or ethanol). The third stage enables a more precise extraction of the BC of interest, in which the chemical characteristics, biological properties, and net concentration of these compounds have already been considered. It is at this stage that greater efficiency is allowed in the extraction process. The fourth stage involves the separation and purification of the BC of interest, using established techniques such as adsorption, size exclusion chromatography, electrodialysis, and ionexchange chromatography, to name a few. Finally, the fifth stage contemplates the preparation of the final product, obtained after separating the nonuseful components. This step is where obtaining powders as a final product is usually carried out by spray drying, lyophilization, emulsification, etc., with the objective to preserve the technological and biological quality of the compounds for their later use. However, there are several problems

Figure 8.2 Recovery stages of bioactive compounds.

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that usually appear in each of the stages; overheating of the matrix of interest, high energy consumption and costs during the stages of the obtaining process, loss of activity of the metabolites of interest and low stability of the final product, legal restrictions regarding toxicity, or safety of the solvents used during the production processes, are examples of these issues. All of these affect the use of technologies that are considered conventional to obtain these BC, hence the reason to consolidate emerging technologies, which are based on nonthermal processes, controlled thermal processes, high or low energy, use of GRAS (Generally Recognized As Safe) solvents, ohmic heating, supercritical fluids, and so on. The most important and most advanced emerging technologies in terms of application are UAE, microwave-assisted extraction (MAE), electric pulse assisted extraction (EPAE), pressurized liquid extraction (PLE), supercritical fluids extraction (SFE), and enzyme-assisted extraction (EAE), which are considered clean and green and have higher efficiency compared to conventional extraction technologies (Azmir et al., 2013; Wen, Zhang, Sun, Sivagnanam, & Tiwari, 2020). Ultrasound is a type of sound wave that usually ranges from 20 kHz to 100 MHz, which, when passing through a medium, creates a phenomenon of compression and expansion. The bubbles that are generated in a liquid or mixed (liquid with solids) medium can reach a temperature of up to 5000 K and a pressure of 1000 atm. Ultrasound extraction mechanisms involve two main physical phenomena: diffusion through the cell wall and release of cell content once the walls are broken. In this mechanism the factors that have the most influence are the particle size, the humidity of the sample and the solvent. MAE is a technology in which electromagnetic fields are used in a range of frequencies ranging from 300 MHz to 300 GHz. This system is made up of two oscillatory fields that are perpendicular (e.g., an electric field and a magnetic field), and the heating is generated as a result of the direct impact of the microwaves on the polar materials. This electromagnetic energy is converted to heat followed by ionic conduction and dipole rotation mechanisms. The mechanisms of MAE are through three main stages: separation of solutes from the active sites of the matrix with a subsequent increase in pressure and temperature, a diffusion of the solvents in the matrix, and finally the liberation of the solutes toward the solvents. EPAE mainly uses electric fields to disrupt the structure of the cell membrane by passing an electric potential through a suspension of cells. Since the molecules that constitute the cell membranes have a dipolar nature, an electrical potential can separate

Chapter 8 Advances in ultrasound-assisted extraction of bioactive compounds

these molecules according to their charge, once a variation of approximately 1 V of the transmembrane potential occurs, a repulsion between the charges of the carrier molecules will generate pores and cause an increase in cell permeability. In this case, the process parameters such as field strength, specific input energy, number of pulses, treatment temperature, and material properties are some of these parameters to consider. PLE is also known as pressurized fluid extraction, accelerated fluid extraction, enhanced solvent extraction, and highpressure solvent extraction. Extraction efficiency can be improved at elevated temperatures by increasing analyte diffusion to the matrix surface, favoring mass transfer of organic compounds to the solvent through increased solubility of target analytes and breakdown of matrix-analyte interactions. Thus solvents with these conditions show an increase in their extraction yield directly proportional to the increase in solvation power. The effect of high pressure and high temperature allows the solvent to be kept in its liquid state, increasing the mass transfer from the plant material matrix to the solvent. This technology uses small amounts of solvent (water or ethanol) and can be combined with other environmentally friendly technologies. SFE is an extraction technology that uses the solid state of liquids and gases. In principle, the supercritical state is a state that is achieved when a substance is subjected to a temperature and pressure close to its critical point; achieving this critical temperature (Tc) and pressure (Pc) of the substance will not allow to distinguish between its liquid and gaseous phase. Carbon dioxide is considered an ideal solvent for SFE because it has a low critical temperature (31 C) and a low critical pressure (74 bars), with which it can work in a range of pressures ranging from 100 to 450 bar. Owing to its low polarity, it is ideal for compounds such as lipids, fats, and other nonpolar substances. EAE is one of the best strategies to obtain BC that are in interactions with complex matrices such as lignins, polysaccharides, or other biopolymers that hinder the entry of solvents that are normally used in an extraction process in both traditional and emerging technologies. This technology is based on the use of specific enzymes, such as cellulase, α-amylase, and pectinase, which allow the breaking of specific bonds by hydrolysis to release the compounds of interest, thereby increasing their recovery by precipitation or other separation techniques. Usually, the EAE uses water as a solvent and is called enzymeassisted aqueous extraction or enzyme-assisted cold pressing. This technology is very useful in the recovery of BC from

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agroindustrial waste or byproducts, where it is possible to use not only an enzyme but also enzyme consortia.

8.5

Fundamentals for ultrasound-assisted extraction

Several advantages have been reported in using UAE to obtain BC: short extraction times, relatively easy operation, lower solvent and temperature consumption, energy savings, and high performance. UAE has the potential to increase extraction yields through cavitation and mass transfer phenomena (Riciputi et al., 2018). However, there are many considerations involved in UAE, such as frequency, sonication power, time, and wave distribution. In some cases, maximum performance has been obtained at a relatively longer extraction time. The intensity also depends on the amplitude and frequency. Greater amplitude at any given frequency improves intensity production; the same is true for a higher frequency at a given amplitude. The importance of the amplitude in the intensification of the extraction has been demonstrated; by increasing the amplitude, the number of compression cycles and the dilation of the ultrasonic wave increase, and as a consequence, there is a greater delivery of the ultrasonic effect (Sharayei, Azarpazhooh, Zomorodi, & Ramaswamy, 2019). However, Meullemiestre, Breil, Abert-Vian, and Chemat (2016) also pointed out that in addition to the turbulence and abrasive effects caused by ultrasonic waves, physical effects such as cavitation in the ultrasonic process increase BC permeability in plant tissues, increasing the extraction yield. In contrast, a decrease in the extraction yield caused by the decomposition of BC in some plant materials has been observed at higher ultrasonic intensity (Ali et al., 2019); therefore it is necessary to perform an optimization process in the extraction of the compounds of interest with a specific plant matrix. Acoustic energy density (Wcm23 or WmL21), intensity (Wcm22), and power (W) represent different ways to express the energy propagated in the ultrasonic system. However, the most common way to evaluate power levels in ultrasonic systems is through acoustic energy density (Wen et al., 2020). During UAE, physical phenomena such as vibrations, mixing, crushing, and especially cavitation, can occur. Choosing the proper frequency is important for UAE; some studies indicate that high amplitude causes probe erosion and reduces cavitation formation (Chemat et al., 2017). Cavitation is improved at lower extraction temperature, but high temperature could lead to disruption of the solvent-matrix interaction.

Chapter 8 Advances in ultrasound-assisted extraction of bioactive compounds

However, high temperature also improves the diffusion rates of the solvent (Dzah et al., 2020). Therefore the temperature of the solvent must be controlled. On the other hand, an additional increase in power can generate a decrease in extraction efficiency. Sengar, Rawson, Muthiah, and Kalakandan (2020) reported a low pectin recovery yield at 750 W of power compared to 450 W. This illustrates that higher-energy treatment conditions produce accelerated structural breakdown of the dissolved pectin side chain. In addition, the decrease in extraction performance was observed with increasing power, which may be due to a higher concentration of bubble volume or is probably due to the formation of cavity bubbles around the probe tip that could filter and create a reduction in the transmission of energy to the environment. This is considered to be a saturation effect (Sengar et al., 2020). The solvent or mixture of solvents that are used in UAE plays an important role in synergy with the swelling effect caused by the effect of ultrasound, since it increases the contact surface between the extraction solvent and the compounds of interest (Martı´nez-Ramos et al., 2020). It has been observed that the polarity of the solvent proportionally influences the extraction of polyphenols in the following order: polar protic solvents . polar aprotic solvents . nonpolar aprotic solvents. Particularly, ethanol is used for the extraction of glucosidic and nonglucosidic phenols, while acetone is used for nonglucosidic phenols (Ali et al., 2019). The extraction time is another condition that must be optimized during the process, since it has been observed that long times favor BC extraction but can cause unwanted structural changes in them (Kumar et al., 2021). In addition, the BC migration length outside the matrix and the contact surface determined by the particle size of the plant material may also affect the extraction yields (Sun, Zhang, Zhang, Tian, & Chen, 2020). Therefore to optimize this technique, it is important to consider both the chemical nature of the compound or compounds of interest in the research and the composition of the plant matrix that contains them.

8.6

Variables associated with ultrasoundassisted extraction

Agrofood waste is composed of plant material with a complex chemical composition that limits the performance of the UAE. For this reason, there is no standard method, and it is necessary to study the optimal conditions for each

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biological material. Several variables, such as ultrasonic power, ultrasonic frequency, solvent type, extraction temperature, liquid-to-solid ratio, and extraction time can affect biological activity and extraction yield of BC when using UAE. The influence of these variables on bioactive extraction using UAE is described below.

8.6.1

Ultrasonic power

This variable is described as the amplitude percentage in the range of 0% 100%, where 100% indicates the rated power of the equipment and power density, calculated as the power dissipated per unit volume of the extraction medium (Palma & Barroso, 2002). The power that is applied for UAE of BC depends upon the desired compound and the types of food matrix selected for the extraction; this power can be varied from 20 to 700 W (Samaram et al., 2015; Zhang et al., 2008). The performance of UAE increases with the power density and then decreases after reaching a peak by the so-called effect of cavitation, which turns into a violent bubble collapse with the increase of power. The size of the resonant bubble is proportional to the ultrasonic wave and power, leading to major impact of implosion as the size of the bubble increases. This causes fragmentation, pore formation, and mixing in the tissue, increasing diffusivity and improving extraction performance (Maran et al., 2017). Also, in increasing the ultrasonic power, it is recommended to evaluate the effect of the temperature of the process and decrease the moisture content in the sample, which causes an increase in the contact surface with the solvent, leading to better efficiency and decrease the UAE time. It has even been found that the variation in potency produces selectivity for the extraction of some molecules (Chemat et al., 2017). However, when the power increases to a very high level, the number of bubbles formed increases, leading to a large bubble collision, deformation, and nonspherical collapse, which reduce the impact of bubble implosion (Dezhkunov, Francescutto, Ciuti, & Sturman, 2005).

8.6.2

Ultrasonic frequency

Frequency (expressed in units of hertz) used in the UAE of BC ranges between 20 and 120 kHz (Kumar et al., 2021). The number of cavitation bubbles is lower when low sound frequencies are used; however, their diameter is larger, so the physical effects are more relevant than the chemical ones at these conditions

Chapter 8 Advances in ultrasound-assisted extraction of bioactive compounds

(Leong, Ashokkumar, & Kentish, 2011; Mason, Cobley, Graves, & Morgan, 2011). On the other hand, the rarefaction and compression-rarefaction cycles in cavitation bubbles are short, preventing bubble growth when high frequencies are used in the process, since higher amplitudes and intensities are required to generate the cavitation phenomenon. Currently, most ultrasound equipment operates at determined frequencies (20 kHz). (Chemat et al., 2017; Leong et al., 2011).

8.6.3

Solvents

The choice of the solvent to be used during the UAE must be made through physical properties, such as the pressure value in the medium, surface tension, and viscosity, as well as chemical properties, such as the solubility of the analytes, since these considerations influence the acoustic cavitation phenomenon (Rutkowska, Namie´snik, & Konieczka, 2017). In this way, in highly viscous samples, it is necessary to increase the amplitude, which allows obtaining the mechanical waves that produce cavitation. The increase in amplitude is necessary to overcome the natural cohesive forces between the molecules that make up the liquid whenever it has high viscosity or high surface tension (Santos, Lodeiro, & Capelo-Martinez, 2009). Different solvents (acidified water, ethanol, alcohols, acetone, water) have been used for the extraction of different compounds during UAE. Ethanol and acetone (mixed with different levels of water) are the most used for the extraction of BC; and ethanol has been found to possess the highest affinity for phenolics and is preferred, owing its classification as GRAS (Kumar et al., 2021; Rodrigues, Fernandes, de Brito, Sousa, & Narain, 2015).

8.6.4

Temperature of ultrasound-assisted extraction

Temperature has an effect on the solvent properties and performance of UAE. An increase in the vapor pressure of the solvent is produced by an increase in temperature and a decrease in surface tension and viscosity. This implies that the cavitation bubbles are filled with solvent vapor and collapse less violently, reducing the extraction yield (Chemat et al., 2017). It is important to choose the temperature using as criteria the thermolabile characteristics of the BC to be extracted, since it has been observed that an increase in the initial temperature causes a lower performance of the UAE, similar to the effect that occurs

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with an increase in ultrasonic power (Zhang, Yang, Zhao, & Wang, 2009).

8.6.5

Liquid (solvent) to solid ratio

The solvent concentration parameter is expressed in two ways: liquid-solid ratio (LSR) and solid-liquid ratio (SLR). The LSR is a relationship that exists between the volume of the solvent (in milliliters) and the amount of sample taken (in grams); therefore the SLR is the reciprocal of LSR. The performance of the UAE increases as a result the increase in LSR, however this increase has a limit, since it decreases after reaching a maximum point. When the LSR decreases, the viscosity of the solution increases, and manifests itself as a difficulty in the cavitation effect. In a solution with high viscosity, the cohesive forces that must overcome the negative pressure in the rarefaction cycle is greater. The reduction of the concentration of the medium or the viscosity are favored by an increase in the LSR, increasing the effects of cavitation in the system. An increase in the solute concentration difference affects the diffusivity and the solubility of the solute in the solvent, leading to greater extraction yields, due to the phenomena of fragmentation, erosion and pore formation. Another factor to consider is the contact area between the material and the solvent, since the greater the contact area, the greater the performance. The enhanced cavitation effect is the result of degradation of the desirable solute itself, to this effect it can be observed as a decrease in LSR performance (Maran et al., 2017; Samaram et al., 2015; Xu et al., 2014).

8.6.6

Time of ultrasound-assisted extraction

The time in the UAE has been extensively studied for BC and has been described as a parameter that can affect performance. Similar to power and temperature, time unexpectedly increases yield and then, as extraction is prolonged, efficiency decreases. At first, ultrasound cavitation will enhance the swelling, hydration, fragmentation, and pore formation of the plant tissue matrix from which the solute was extracted; this is a key factor to increase the exposure of the solute and the solvent and, consequently, the extraction. However, prolonged exposure from long ultrasound times causes structural damage to the matrix and the overall performance of the process (Nishad, Saha, & Kaur, 2019; Raza, Li, Xu, & Tang, 2017).

Chapter 8 Advances in ultrasound-assisted extraction of bioactive compounds

8.7

Effect of variables associated with ultrasound-assisted extraction on the extraction of bioactive compounds from byproducts

The variables associated with UAE such as power, frequency, solvent type, temperature, liquid-to-solid ratio and time needs precise control for optimal extraction. All these variables can affect the process, since they interact with each other, affecting the concentrations of BC and their potential biological activity (Medina-Torres, Ayora-Talavera, Espinosa-Andrews, Sa´nchezContreras, & Pacheco, 2017). Therefore it is important to highlight that not only the extraction yield factor must be considered in the UAE, but also its effect on biological activity (i.e., antioxidant, antimicrobial, anticancer activity) and the profile of BC (M’hiri, Ioannou, Boudhrioua, & Ghoul, 2015). A statistical tool that has allowed analysis of the collective effects of the UAE variables as well as its optimization and size reduction of the experiments is the response surface methodology (RSM), which has been widely used in extraction processes (Chen, Zhao, & Yu, 2015). Therefore the individual as well as the interaction effects of these variables have been studied by several researchers on the extraction of BC supported by RSM in fruit and vegetables byproducts (Table 8.2).

8.8

Commercial patents: ultrasound and innovative techniques for the extraction of bioactives

Several UAE methodologies have been used for the extraction of BC in different food residues, obtaining useful patents for the food and pharmaceutical industries. Some examples of patents that include ultrasound and other BC extraction techniques are included below. Madhavamenon and Maliakel (2017) patented a commercial-scale, continuous, and automated process for the complete zero-residue fractionation of cocoa beans using various enzymes in combination with ultrasonication at critical steps and water-based ion-exchange adsorption chromatography for polyphenol extraction and soluble dietary fiber with high yield and purity, involving minimal cost and labor. Wang and Han (2021) developed an ultrasound-assisted cyclic double-solvent extraction technique to obtain resveratrol and

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Table 8.2 Optimal extraction conditions for ultrasound-assisted extraction of bioactive compounds from fruit and vegetable byproducts. Bioactive Byproduct Ultrasound-assisted compound source extraction factors

Optimum conditions and major effects

Polyphenols

Treatment with 76% amplitude, Castan˜eda80% ethanol, 10 min of Valbuena et al. sonication and 50 mLg21 of (2021) solid showed more total polyphenol content

Mango peel and seed

Phenols and Orange peel flavonoids

Carotenoids

Mandarin epicarp

Polyphenols

Date palm spikelets

Polyphenols

Orange peel

Polyphenols and flavonoids

Sage herbal dust

Polyphenols Jabuticaba and peel anthocyanins

30 treatments with 4 factors: ethanol concentration (20% 95%), extraction time (10 15 min), amplitude (40% 94%), solvent-to-solid ratio (1 g/30 1 g/60 mL) 17 treatments with 3 factors: extraction time (15 35 min), amplitude (60% 100%), and solvent-to-solid ratio (1 g/ 20 1 g/40 mL) 20 treatments with 3 factors: temperature (40 C 60 C), extraction time (40 60 min), and solid-to-solvent ratio (0.0004 0.0012 gmL21) 17 treatments with 3 factors: temperature (25 C 60 C), extraction time (20 40 min), and ethanol concentration (25% 50%) 27 treatments with 4 factors: ethanol concentration (0% 100%), extraction time (5 45 min), amplitude (20% 100%) 17 treatments with 3 factors: temperature (40 C 80 C), extraction time (40 80 min), and power (24 60 WL21) 17 treatments with 3 factors: pH, ethanol concentration (%), and extraction time (min)

Treatment with 35 min of extraction, 80% of amplitude, and 40 mLg21 of solid showed more phenol and flavonoid content Treatment with 50 C temperature, 50 min of extraction, and 0.0004 gmL21 of solvent showed more carotenoid content Treatment with 42.5 C of temperature, 20 min of extraction, and 50% of ethanol concentration showed more total polyphenol content Treatment with 45% of ethanol concentration, 35 min of extraction, 90% of amplitude, and 100% of pulse showed more total polyphenol content Treatment with 75.4 C of temperature, 80 min of extraction, and 42.54 WL21 of power showed more phenol and flavonoid content Treatment with a pH of 3.5, 46.86% of ethanol concentration, and 40 min of extraction showed more phenol and anthocyanin content

References

Nishad et al. (2019)

Ordo´n˜ez-Santos, EsparzaEstrada, and VanegasMahecha (2021) Almusallam et al. (2021)

Razola-Dı´az et al. (2021)

Zekovi´c et al. (2017)

Rodrigues et al. (2015)

(Continued )

Chapter 8 Advances in ultrasound-assisted extraction of bioactive compounds

235

Table 8.2 (Continued) Bioactive Byproduct Ultrasound-assisted compound source extraction factors

Optimum conditions and major effects

References

Polyphenols

Treatment with 14.4 min of extraction, 10% of amplitude, and 10 g/100 mL of solvent showed more polyphenol content Treatment with 17 min of extraction, 32 C of temperature, and 51% of ethanol concentration showed more carotenoid content Treatment with 206.64 W of power, 70 C of temperature, and 80.1 min of extraction showed more polyphenol content

Ben-Othman et al. (2021)

Carotenoids

Polyphenols

Apple tree leaves

17 treatments with 3 factors: extraction time (5 30 min), amplitude (10% 100%), and solid-to-solvent ratio (1 100 g/ 100 mL) Carrot 17 treatments with 3 factors: pomace extraction time (3 37 min), temperature (10 C 60 C), ethanol concentration (13% 97%) 17 treatments with 3 factors: Aronia melanocarpa ultrasonic power (72 216 W), temperature (30 C 70 C), and herbal dust extraction time (30 90 min)

grape skin pigment that has the advantages of high extraction efficiency, low extraction cost, and low energy consumption and includes the following steps: drying, pulverizing, ultrasonic wave resveratrol extraction, ultrasonic wave pigment extraction, and purification. Augustin, Juliano, Mawson, Swiergon, and Knoerzer (2014) developed a technique for extracting oil from plant material based on heating, screw pressing, double sonication (one below 1 MHz and the second above 1 MHz), and decanting. Bates, Mcloughlin, and Sin Ju Yap (2009) presented a method and apparatus for the aqueous extraction of anthocyanins in grape skins in which the solid material is entrained in a liquid extraction phase that flows around submerged sonotrodes that emit high-energy radial or focused ultrasonic waves. In addition, a recent method uses a naturally occurring eutectic solvent combined with ultrasound to dissolve and extract one or more compounds from plant, fungal, animal, and/or microbial material (Chemat, Fabiano-Tixier, Imbert, Khadhraoui, & Robinet, 2020). Wang and Han (2021) patented a method to extract anthocyanin from Perilla frutescens (L.) Britton leaves through the use of a deep eutectic solvent and a method to extract anthocyanin with the help of ultrasound, microwave, and ultraviolet light, increasing the extraction yield.

Umair et al. (2021)

Rami´c et al. (2015)

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8.9

Current trends in the extraction of bioactive compounds

The current trend for obtaining BC considers the emerging technologies as a challenge because there are many scientific studies that support the great advantages that these technologies have. However, it is necessary to develop strategies to persuade industry to bet on these technologies to apply them in their processes. It can be observed from the bibliometric analysis of research articles published in 2020 21, including some that were to come out in early 2022, that research into the application of emerging technologies in different fields, such as the food industry, pharmaceuticals, and cosmetology, is increasing. An analysis of the co-occurrence and the “total link strength attribute” was performed by using the VOSviewer software (version 1.6.10) (Yu et al., 2020), using the information on the year of publication, keywords, co-occurrence, and summary of the articles available in the Scopus database. Table 8.3 shows the search keywords that were used. A total of 324 publications in the years 2020 21 and some close to being published in 2022 were analyzed. With the keywords provided by the authors of the articles and the appearances more than five times obtained in the bibliometric analysis, a total of 189 items were classified in seven clusters: cluster 1 (43 items), cluster 2 (39 items), cluster 3 (37 items), cluster 4 (32 items), cluster 5 (18 items), cluster 6 (11 items), and cluster 7 (9 items). Fig. 8.3 shows the most relevant keywords that are intertwined with the observed clusters. It was observed that in cluster 1 (Quadrants III and IV) the investigations are associated with the use of strategies such as experiment designs to be able to carry out more efficient procedures in terms of obtaining BC

Table 8.3 Search key in the Scopus database. ALL ((extraction) AND (polyphenols) AND (emerging AND technologies)) AND (LIMIT-TO (EXACTSRCTITLE, "Innovative Food Science And Emerging Technologies") OR LIMIT-TO (EXACTSRCTITLE, "Foods") OR LIMIT-TO (EXACTSRCTITLE, "Trends In Food Science And Technology") OR LIMIT-TO (EXACTSRCTITLE, "Food Research International") OR LIMIT-TO (EXACTSRCTITLE, "Critical Reviews In Food Science And Nutrition") OR LIMIT-TO (EXACTSRCTITLE, "Lwt") OR LIMIT-TO (EXACTSRCTITLE, "Journal Of Food Processing And Preservation") OR LIMITTO (EXACTSRCTITLE, "Industrial Crops And Products")) AND (LIMIT-TO (PUBYEAR, 2022) OR LIMIT-TO (PUBYEAR, 2021) OR LIMIT-TO (PUBYEAR, 2020)) AND (LIMIT-TO (SUBJAREA, "AGRI") OR LIMIT-TO (SUBJAREA, "ENVI")) AND (LIMIT-TO (EXACTKEYWORD, "Extraction") OR LIMIT-TO (EXACTKEYWORD, "Phenols") OR LIMIT-TO (EXACTKEYWORD, "Polyphenols"))

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using emerging technologies, such as EAE, extraction with eutectic solvents, simultaneous extractions, and UAE, aimed at developing green strategies to obtain these BC. Cluster 2 (Quadrants I and IV) is associated with investigations related to PLE extractions, using byproducts as raw material, considering that under these methodologies, volatile compounds that are important for the industry of the food can be obtained. In cluster 3 (Quadrants II and III), research is focused on obtaining compounds with antimicrobial activity, their characterization by methodologies such as gas chromatography, and their obtainment process through MAE and UAE, in combination with supercritical fluids. In cluster 4 (Quadrants I and II), investigations are related to the

Figure 8.3 Bibliometric analysis in publications based on co-occurrence of the keywords identified by quadrant (Q). The size of a node indicates the frequency of occurrence. The lines between the nodes represent their cooccurrence in the same publication. The shorter the distance between two nodes, the larger the number of cooccurrences of the two keywords.

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chemometric evaluation and chromatographic characterization of compounds with antioxidant activity, in which the bioaccessibility and bioavailability of compounds obtained from fruits, mainly phenolic compounds, were evaluated. In cluster 5 (Quadrants I and II) the investigations are focused on evaluating by conventional methods the activity of BC, their stability depending on environmental conditions and polyphenols and pigments that are usually reference for the elaboration of products food or food storage. In cluster 6 (Quadrants I and IV) and cluster 7 (Quadrant II), research is focused precisely on stability during high-pressure processing, biological activity against specific enzymes, as well as low temperature drying and heating microwaves, and these factors were found to affect bioactivity. In general, research on the application of emerging technologies is focused on the extraction of phenolic compounds with proven antioxidant capacity, followed by obtaining pigments from different matrices.

8.10

Conclusions and future trends

The widespread perspective of insignificant value of food waste in the food industry has been modified over the last few years, with the encouraging of its use for the recovery of components with high biological activities, sustainable development, and protection of the environment through the use of ecological technologies, such as UAE. Nonetheless, it must be recognized that technological advances allow the incorporation of hybrid technologies to industrial processes that improve extraction yields, more efficient times, and lower energy consumption. However, for each type of food waste, the effects of ultrasound conditions must be optimized to avoid damage to the restructuring of BC and decrease in their biological activity. It is also necessary to continue research around the search of waste food sources in which these technologies can be applied to recover valuable compounds for the pharmaceuticals, cosmetic, or food industries. The demand for BC in these industries can be satisfied through the continuous improvement of technology and processes of basic and applied research that allow an easier understanding of the mechanisms involved.

List of acronyms BC EAE EPAE

bioactive compounds enzyme-assisted extraction electric pulse assisted extraction

Chapter 8 Advances in ultrasound-assisted extraction of bioactive compounds

FAO GRAS LSR MAE Pc PLE RSM SFE SLR Tc UAE

Food and Agricultural Organization generally recognized as safe liquid-solid ratio microwave-assisted extraction critical pressure pressurized liquid extraction response surface methodology supercritical fluids extraction solid-liquid ratio critical temperature ultrasound-assisted extraction

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Chapter 8 Advances in ultrasound-assisted extraction of bioactive compounds

Rohini, C., Geetha, P., Vijayalakshmi, R., Mini, M., & Pasupathi, E. (2020). Global effects of food waste. Journal of Pharmacognosy and Phytochemistry, 9(2), 690 699. Rutkowska, M., Namie´snik, J., & Konieczka, P. (2017). Ultrasound-assisted extraction. The application of green solvents in separation processes (pp. 301 324). Elsevier. Sagar, N. A., Pareek, S., Sharma, S., Yahia, E. M., & Lobo, M. G. (2018). Fruit and vegetable waste: Bioactive compounds, their extraction, and possible utilization. Comprehensive Reviews in Food Science and Food Safety, 17(3), 512 531. Samaram, S., Mirhosseini, H., Tan, C. P., Ghazali, H. M., Bordbar, S., & Serjouie, A. (2015). Optimisation of ultrasound-assisted extraction of oil from papaya seed by response surface methodology: Oil recovery, radical scavenging antioxidant activity, and oxidation stability. Food Chemistry, 172, 7 17. Santos, H. M., Lodeiro, C., & Capelo-Martinez, J.-L. (2009). The power of ultrasound. Ultrasound in Chemistry: Analytical Applications, 1 16. ˜ i, I. Sa´yago-Ayerdi, S. G., Vela´zquez-Lo´pez, C., Montalvo-Gonza´lez, E., & Gon (2014). By-product from decoction process of Hibiscus sabdariffa L. calyces as a source of polyphenols and dietary fiber. Journal of the Science of Food and Agriculture, 94(5), 898 904. Sa´yago-Ayerdi, S. G., Zamora-Gasga, V. M., & Venema, K. (2019). Prebiotic effect of predigested mango peel on gut microbiota assessed in a dynamic in vitro model of the human colon (TIM-2). Food Research International, 118, 89 95. Sengar, A. S., Rawson, A., Muthiah, M., & Kalakandan, S. K. (2020). Comparison of different ultrasound assisted extraction techniques for pectin from tomato processing waste. Ultrasonics Sonochemistry, 61, 104812. Sharayei, P., Azarpazhooh, E., Zomorodi, S., & Ramaswamy, H. S. (2019). Ultrasound assisted extraction of bioactive compounds from pomegranate (Punica granatum L.) peel. LWT, 101, 342 350. Shi, M., Ying, D.-Y., Hlaing, M. M., Ye, J.-H., Sanguansri, L., & Augustin, M. A. (2019). Development of broccoli by-products as carriers for delivering EGCG. Food Chemistry, 301, 125301. Silva, P., Ferreira, S., & Nunes, F. M. (2017). Elderberry (Sambucus nigra L.) byproducts a source of anthocyanins and antioxidant polyphenols. Industrial Crops and Products, 95, 227 234. Slorach, P. C., Jeswani, H. K., Cue´llar-Franca, R., & Azapagic, A. (2019). Environmental sustainability of anaerobic digestion of household food waste. Journal of Environmental Management, 236, 798 814. So´jka, M., Kołodziejczyk, K., Milala, J., Abadias, M., Vin˜as, I., Guyot, S., & Baron, A. (2015). Composition and properties of the polyphenolic extracts obtained from industrial plum pomaces. Journal of Functional Foods, 12, 168 178. Soong, Y.-Y., & Barlow, P. J. (2004). Antioxidant activity and phenolic content of selected fruit seeds. Food Chemistry, 88(3), 411 417. Sousa, Y. R., Medeiros, L. B., Pintado, M. M. E., & Queiroga, R. C. (2019). Goat milk oligosaccharides: Composition, analytical methods and bioactive and nutritional properties. Trends in Food Science & Technology, 92, 152 161. Sun, X., Zhang, W., Zhang, L., Tian, S., & Chen, F. (2020). Molecular and emulsifying properties of arachin and conarachin of peanut protein isolate from ultrasound-assisted extraction. LWT, 132, 109790. ¨ g˘ u¨t, H., & Kalemta¸s, A. (2018). Natural calcium phosphates from Terzio˘glu, P., O fish bones and their potential biomedical applications. Materials Science and Engineering: C, 91, 899 911. Thomas, M., Badr, A., Desjardins, Y., Gosselin, A., & Angers, P. (2018). Characterization of industrial broccoli discards (Brassica oleracea var. italica)

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9 Integrated advanced technologies for olive mill wastewater treatment: a biorefinery approach Marı´a del Mar Contreras1,2, Juan Carlos Lo´pez-Linares1,2 and Eulogio Castro1,2 1

Department of Chemical, Environmental and Materials Engineering, Universidad de Jae´n, Jae´n, Spain 2Center for Advanced Studies in Earth Sciences, Energy and Environment (CEACTEMA), Universidad de Jae´n, Jae´n, Spain

9.1

Introduction

Olive oil is a traditional product of the Mediterranean basin. It is obtained from the olive fruit by physical treatments and has a distinctive flavor, valuable nutritional quality, and positive effects on human health (Mazzocchi, Leone, Agostoni, & PaliScho¨ll, 2019). This fact has made its demand to be increased worldwide for food and cosmetics applications (Global Marketing Associates, 2021). Olive oil is not only the key fat source of the Mediterranean diet, but also a source of income for these countries. The production of olive oil was around 3.2 million tons in the last three campaigns, the major producer countries being Spain, Greece, Italy, and Portugal, with around 50%, 9%, 8%, and 3% of the world production, respectively, along with Tunisia, Morocco, Turkey, Syria, and Algeria (FAO, 2019; International Olive Oil Council, 2020) (Fig. 9.1). The oil content of the olive fruit is around 12% to nearly 20% on a fresh basis, depending on the cultivar, ripening time, and climate conditions (Talhaoui et al., 2015). The production of olive oil is characterized by the generation of a large quantity of residues. In addition, these residues are produced during a short period of time (generally, between October to January in the Northern Hemisphere), causing management problems due to their phytotoxic properties and organic load (Cassano, Conidi, Galanakis, & Advanced Technologies in Wastewater Treatment. DOI: https://doi.org/10.1016/B978-0-323-88510-2.00006-3 Copyright © 2023 Elsevier Inc. All rights reserved.

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Figure 9.1. Olive oil production based on the International Olive Oil Council data, 2020.

˜oz, 2016; Ferna´ndez-Herna´ndez, Roig, Serramia´, Castro-Mun Civantos, & Sa´nchez-Monedero, 2014). The type, quantity, and composition of olive oil residues depend mainly on the olive processing (Contreras, del, Romero, Moya, & Castro, 2020). Concerning the latter factor, the oil extraction could be performed in three ways: in the traditional pressure system and in continuous two- or three-phase decanters. Fig. 9.2 shows the main residues that are generated in these extraction modes: a semisolid residue, olive pomace, and olive mill wastewater (OMWW) (also known as alpechin, blackwater, vegetation water, or vegetable water) (Obied, Allen, R, Prenzler, & Robards, 2005). Wastewater is also generated as a result of the cleaning of the olives and the olive oil at the initial and final step of the production chain of the olive oil (Fig. 9.2). It has been estimated that around 30 million m3 of OMWW could be generated in the Mediterranean basin (Jeguirim et al., 2020), a volume similar to that of the Quiebrajano reservoir in Jae´n, Spain (iAgua, 2021). The hydraulic pressing system is used in around 40% of the oil mills in Portugal and around 15% and 30% of the production of Italy and Tunisia, respectively, is generated by this more traditional mode. In other countries, its use is decreasing, for example, in Jordan. Alternatively, the three-phase extraction mode is commonly used in Mediterranean countries (e.g., 79% in Jordan, 55% in Italy, 82% in Greece, and 40% in Portugal) (Contreras et al., 2020; Jellali, Hachicha, & Aljuaid, 2021; Khdair, Abu-rumman, & Khdair, 2019; Tesla, n.d.). In the case of twophase extraction, the Spanish mills started to invest in this

Chapter 9 Integrated advanced technologies for olive mill wastewater treatment: a biorefinery approach

249

Olives

Washing wastewater

Air cleaning / Washing

Olive mill leaves

Traditional mode

Crushing/milling

Water

Pressing Malaxation Decantation/vertical centrifugation

Olive pomace

Water Olive mill wastewater

Horizontal centrifugation

Horizontal centrifugation

Three-phase mode

Two-phase mode

Olive oil

Olive mill wastewater

Olive pomace

Water

Olive oil phase

Vertical centrifugation

Oil-wasting wastewater

Figure 9.2 Olive oil processing and residues generated.

system as a result of a failure to develop an efficient and economical treatment technology for OMWW in the 1990s (Borja et al., 2006; Pedro, Moral, Victoria, & Me´ndez, 2006). Almost all olive oil mills in Spain (99%) use two-phase decanters, and the use of this system is increasing in other countries, for example, in Greece, Italy, Portugal, and Jordan, the two-phase system is applied in around 15%, 18%, 20%, and 22% of the mills, respectively (Contreras et al., 2020; Khdair et al., 2019; Tesla, n.d.). This is considered a more ecologically friendly extraction system, which uses no (or a low quantity of) process water and separates the oil from olive pomace (known

Olive oil

Olive pomace

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Chapter 9 Integrated advanced technologies for olive mill wastewater treatment: a biorefinery approach

as alperujo), a semisolid byproduct. The latter has a moisture content of over 60% 70%, higher than those for olive pomace obtained by the three-phase system (48% 54%) and pressing (25% 30%). Therefore the consumption and production of residual water are lower than those produced by the threephase system (Table 9.1). In addition, the organic load of the new effluent is reduced to 6% 15% (Borja et al., 2006; Cabrera, 1995; Toscano & Montemurro, 2012). Moreover, the quality of the olive oil is the highest compared to that obtained by other extraction methods, with a good economic profitability (Jellali et al., 2021). As a more general term, OMWW can also refer to the liquid stream that is generated in the production of olive oil (Khdair et al., 2019). OMWW is composed of the water that is utilized to clean the processed olives and the mill (about 5% 10% and 5% of the weight of processed olives, respectively), olive pulp water (40% 50% of the initial weight of processed olives), and the water that is added to the olive paste in the extraction step (Cassano et al., 2016). It also contains soft tissues from olive pulp, pectin, and oil in the form of emulsion (Tsagaraki, Lazarides, & Petrotos, 2007). In the case of the two-phase extraction the residual water stream consists of the waters that derive from the washing of the olives, the olive oil, and the industry installation. In some countries, OMWW is collected in open-air pools, evaporation ponds, lagoons and dry bends, and the residue collected for soil amendments (Fig. 9.3A C). The discharge of OMWW to the municipal drain system is not allowed because

Table 9.1 Water consumption and generation in olive mills (Di Giovacchino, 2013). Parameter 21

Water consumption (L ton ) Wastewater generated (L ton21)

Pressing

Three-phase system

Two-phase system

320 600 560a580a

350 700 800a1240b

120a350 100a250c

Around 400a500 Lton21 comes from the horizontal decanter. Around 500a900 Lton21 comes from the horizontal decanter. c Around 100a200 Lton21 comes from the vertical decanter. Source: Based on Borja, B. R., Raposo, F., Rinco´n, B., De, I., Csic, G., Padre, A., & Tejero, G., (2006). Treatment technologies of liquid and solid wastes from two-phase olive oil mills. Grasas Y Aceites, 3495, 32 46; Di Giovacchino, L., 2013. Technological Aspects, in: Aparicio, R., Harwood, J. (Eds.), Handbook of olive oil (pp. 57 96). Boston: Springer; Khdair, A. I., Abu-Rumman, G., & Khdair, S.I. (2019). Pollution estimation from olive mills wastewater in Jordan. Heliyon, 5, e02386; Toscano, P., & Montemurro, F. (2012). Olive mill byproducts management. In: I. Muzzalupo (Ed.), Olive germplasm the olive cultivation, table olive and olive oil industry in Italy. IntechOpen. https://doi.org/10.5772/52039. a b

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251

Figure 9.3 Open-air evaporation methods of oil mill wastewater and spring contaminated with this residue (Khdair & Abu-Rumman, 2020): (A) Concrete pool, (B) Evaporation lagoon, (C) Sealed drying pond for OMMW (D) Sprong polluted with OMWW.

of the pollution level and suspended solid load of this residue, which can clog the water network (Khdair et al., 2019). Other wastewater treatments have been proposed such as distillation, filtering or flocculation, application on the soil and disposal in the water bodies (Toscano & Montemurro, 2012). However, the two latter have limitations; in particular, OMWW discharge into soil can provoke physical changes due to its potassium content and detrimental effects on plant and microbial metabolism (Tsagaraki et al., 2007). However, the application of diluted

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Chapter 9 Integrated advanced technologies for olive mill wastewater treatment: a biorefinery approach

OMWW could be beneficial for soils (Ahmed, Ferna´ndez, Figueroa, & Pajot, 2019). Uncontrolled disposal in the water bodies generates toxicity for organisms, causes eutrophication, and alters the color of the water (Fig. 9.3D) because of the high content of phenolic compounds, reducing sugars, and phosphorus (Ahmed et al., 2019; Tsagaraki et al., 2007). Considering that a satisfactory solution from a point of view of both environment and economy is still to be found (Elmekawy, Diels, Bertin, & Heleen De Wever, 2014; Tsagaraki et al., 2007), research focused on its valorization by alternative processes has been published. At this point the management of OMWW is a priority in Mediterranean regions (Khdair et al., 2019). Therefore this chapter presents updated information on the chemical composition of OMWW and its applications to obtain bioenergy and bioproducts as a renewable bioresource. Some methods of integration of these applications in a biorefinery context are detailed, that is, multiproduct processes to maximize the valorization of OMWW and the integral use of its constituents.

9.2

Chemical composition of olive mill wastewater

Besides the processing method, the characteristics of this residue depend on the olive variety or cultivar, growing technique, harvesting period, pedoclimatic conditions, the use of pesticides and fertilizers, fermentation during the storage, and so on. OMWW is violet dark brown to black in color (Fig. 9.2) with a strong acidic olive oil smell and pH values below neutrality (Borja et al., 2006; Cassano et al., 2016). The main chemical characteristics of OMWW are shown in Table 9.2. OMWW contains a huge quantity of organic compounds, including phenolic compounds, biochemical oxygen demand and chemical oxygen demand (COD). The latter parameters can reach 110 and 170 gL21, respectively. In general, these values, along with the content of phosphorus, phenolic compounds, and potassium, are higher in wastewater from traditional mills, and the lowest values are found in wastewater from two-phase mills. This can be related to the presence of fruit residue, lower production process efficiency, and more contact of the oil phase with water in the former extraction type and in three-phase extraction (Khdair et al., 2019). In addition, the pH, conductivity, and COD values of OMWW can increase if it is mixed with the wastewater from the table olives industry (Hodaifa et al., 2015). Besides potassium, other

Chapter 9 Integrated advanced technologies for olive mill wastewater treatment: a biorefinery approach

253

Table 9.2 Composition of wastewater generated in the olive mills. Parameter

Pressing

Three-phase system

Two-phase system

pH Dry matter (%) Total suspended solids (gL21) Electrical conductivity (mScm21) Biochemical oxygen demand (gL21) Chemical oxygen demand (gL21) Phosphorus (%) Potassium (%) Phenols (gL21) Oil/grease (%)

4.5a5.7 8a20 51.6

4a6.7 4a24 1a46 35.1 20a110 40a170 0.02a0.06 0.1a0.5 0.01a10.1 0.03a2.3

2.3a9.01 3 0.2 1a178.1a 0.06 0.4 38a 0.0002 — 0.0008a0.45a 0.002 0.1

41a100 65.7a130 0.03a0.10 0.25a0.4 0.04a24 0.03a1.3

a Higher values due to wastewater from olive oil industry being mixed with wastewater from table olives industry. Source: According to (Borja, B. R., Raposo, F., Rinco´n, B., De, I., Csic, G., Padre, A., & Tejero, G. (2006). Treatment technologies of liquid and solid wastes from two-phase olive oil mills. Grasas Y Aceites, 3495, 32 46; Di Giovacchino, L. (2013). Technological aspects. In R. Aparicio & J. Harwood (Eds.), Handbook of olive oil (pp. 57 96). Boston: Springer; El-Abbassi, A., Saadaoui, N., Kiai, H., Raiti, J., & Hafidi, A. (2017). Potential applications of olive mill wastewater as biopesticide for crops protection. The Science of the Total Environment, 576, 10 21; Hodaifa, G., Agabo, C., Moya, A.J., Pacheco, R., Mateo, S. (2015). Treatment of olive oil mill wastewater by UV-light and UV/H2O2 system. International Journal of Green Technology, 1, 46 53; Khdair, A.I., Abu-rumman, G., & Khdair, S.I. (2019). Pollution estimation from olive mills wastewater in Jordan. Heliyon, 5, e02386; Massadeh, M. I., & Modallal, N. (2008). Ethanol Production from Olive Mill Wastewater (OMW) Pretreated with Pleurotus sajor-caju. Energy & Fuels, 22, 150 154; Tsagaraki, E., Lazarides, H. N., & Petrotos, K. B. (2007). Olive mill wastewater treatment, In V. Oreopoulou, & W. Russ (Eds.), Utilization of by-products and treatment of waste in the food industry. Boston: Springer.

minerals are found in OMWW, including magnesium, calcium, and sodium, while copper, zinc, iron, and manganese are present in minor proportion. In some cases, heavy metals, such as lead and cadmium, have been detected in OMWW, thus limiting its use for food and beverage applications (Zbakh & El, 2012). In addition to minerals and phenolic compounds, OMWW contain sugars, which can constitute up to 60% of the dry solid, including fructose, mannose, glucose, and saccharose (Borja et al., 2006). Other studies have shown that OMWW from the traditional extraction process has the following in a dry basis: cellulose (19.5%a30.4%), hemicellulose (21.6%a36.9%), lignin (28.6%a 43.5%), fat (14.30%), and ash (4.5%a21.9%). OMWW from this process also has a higher heating value (HHV) of 24.3 MJkg21 (Guida et al., 2015; Hadhoum, Burnens, Loubar, Balistrou, & Tazerout, 2019). Paredes and coworkers found neither cellulose nor hemicellulose and lignin, but the origin of the wastewater was not reported (Paredes, Bernal, Cegarra, & Roig, 2002). Flocculated fractions from two- and three-phase OMWW, particularly olive oil washing and alpechin, contained 9.7% and 22.6% of cellulose, 39.3% and 40.0%

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Chapter 9 Integrated advanced technologies for olive mill wastewater treatment: a biorefinery approach

of hemicellulose, and 44.9% and 40.0% of lignin, respectively (Garcı´a-Go´mez, Roig, & Bernal, 2003).

9.3

Reuse, applications, and technologies employed

The chemical composition of OMWW suggests that this liquid waste can be successfully considered for many applications, such as for the production of biofuels, such as bio-oil; polysaccharides such as pectin and exopolysaccharides; compounds with high added value, such as antioxidants compounds (mainly hydroxytyrosol, tyrosol, verbascoside, and nu¨zhenide); citric acid and lipids; polyhydroxyalkanoates (PHA); biosurfactants, such as surfactin and rhamnolipid; enzymes (e.g., L-asparaginases, endocellulase, endoxylanase, feruloyl esterase activity, and laccase); and materials such as bioflocculants) (Ahmed et al., 2019; Contreras et al., 2020; Foti et al., 2021) (Table 9.2).

9.3.1

Biofuels

OMWW can be bioresource to obtain biofuels such as bioethanol, bio-oil or biodiesel, biomethane and biohydrogen could be obtained from this waste (Ahmed et al., 2019) (Table 9.3). In this way, for example, bio-oil could be obtained from OMWW through a thermochemical liquefaction process with alcohol (ethanol or methanol/water at 50% (w/w) ratio) mixtures in an autoclave reactor at 240 C 320 C. In this way, up to 92.3% and 78% of bio-oil yield (calculated as the mass of bio-oil over the mass of dry OMMW multiplied by 100) were obtained from OMWW at 280 C, 30 min, and 50% solvent/water ratio when ethanol and methanol, respectively, were used. Moreover, it is worth highlighting the high energy content found in both bio-oil generated (39.21 and 43.20 MJkg21 for bio-oil obtained by using 50% ethanol and 50% methanol, respectively, as solvents) (Hadhoum et al., 2019). Moreover, bioethanol can also be generated from OMWW (Massadeh & Modallal, 2008; Sarris, Matsakas, Aggelis, Koutinas, & Papanikolaou, 2014). In this context, for instance, Massadeh and Modallal (2008) achieved a high ethanol concentration (14.2 gL21 ethanol) when OMWW was 50% diluted and heat-pretreated with the basidiomycete fungus Pleurotus sajor-caju to reduce the phenolic compounds content and using Saccharomyces cerevisiae in the fermentation process.

Chapter 9 Integrated advanced technologies for olive mill wastewater treatment: a biorefinery approach

255

Table 9.3 Examples of applications and technologies from OMWW. Feedstock

Extraction Application type

Technology used

Result

OMWW

Pressing

Bio-oil

Yield: 92.3% Hadhoum et al. Energy content: (2019) 39.21 MJ/kg

OMWW

Three-phase system

Biomethane

Thermochemical liquefaction (280 C, 30 min, 50% ethanol) Two-phase anaerobic digestion (37 C, 24 d, 8.17 g COD L21d21) Photofermentation [cylindrical photobioreactors, 30 C, 406 h, Rhodopseudomonas palustris (strain 6 A)] Fermentation (30 C, 200 rpm, 5 d, 10% (v/v) Xanthomonas campestris NRRL B-1459 S4LII) Ultrafiltration (membranes of 25 and 100 kDa) Multistage recovery process (acidification 1 delipidization 1 solvent extraction 1 solid-phase extraction) Liquid fermentation (30 C, 150 rpm, 2 d, pH 8, 0.5 gL21 Bacillus aryabhattai BA03) Fermentation (37 C, 160 rpm, 7 d, 5% (v/v) Bacillus subtilis N1)

OMWW (25% v/v)

Biohydrogen

OMWW (30% v/v)

Horizontal centrifuge

Polysaccharides (exopolysaccharides)

OMWW

Three-phase system

Polysaccharides (pectin)

OMWW

Two-phase system

Phenolic and antioxidant compounds

OMWW (25% w/w)

Three-phase system

Enzymes (L-asparaginases)

OMWW (2 v/v)

Biosurfactants (surfactin)

References

Productivity: 32 L LOMWW21

Fezzani and Ben Cheikh (2010)

Production: 0.53 L

Ena et al. (2010)

Concentration: 7 gL21

Lo´pez et al. (2001)

Concentration: 87 mgL21

Galanakis, Tornberg, and Gekas (2010)

Hydroxytyrosol: C¸elik, Saygın, and 6.6 mg g21 Balcıoglu (2021)

Enzymatic activity: 11.6 UmL21

Paz, Nikolaivits, and Topakas (2021)

Concentration: 3.12 mgL21

Ramı´rez et al. (2015)

(Continued )

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Chapter 9 Integrated advanced technologies for olive mill wastewater treatment: a biorefinery approach

Table 9.3 (Continued) Feedstock

Extraction Application type

OMWW

Three-phase system

Result

References

Citric acid: 54 gL21 (yield: 0.82 gg21) Lipids: 2.5 gL21

Tzirita, Kremmyda, Sarris, Koutinas, and Papanikolaou (2019)

Yield: 43% Concentration: 0.2 gL21

Alsafadi and AlMashaqbeh (2017)

OMWW (1M 1 SOMW)

Fermentation (28 C, 3 Hz agitation rate, pH 6, Yarrowia lipolytica ACA-YC 5031, glycerol, and salt) Polyhydroxyalkanoates Single-stage fermentation (37 C, 170 rpm, 22% NaCl, 4 d, Haloferax mediterranei DSM 1411) Fertilizers (compost) Cocomposting (200 d)

Germination index: 80%

OMWW

Biopesticides

OMWW (0.75 gkg21)

Food supplement (white meat burgers)

Pathogens inhibition (Phelipanche ramose weed) Antimicrobial activity

Makni, Ayed, Ben Khedher, and Bakhrouf (2010) Disciglio et al. (2016)

OMWW (80 mgkg21)

Food supplement (butter)

OMWW (15% v/v)

Citric acid lipids

Technology used

Oxidative processes enhance

Veneziani, Novelli, Esposto, Taticchi, and Servili (2017) Mikdame et al. (2020)

COD, Chemical oxygen demand. M, manures of poultry, sheep, cow and horse. SOMW, solid olive mill waste.

OMWW has a high level of organic matter, so many studies have been reported about biomethane production from this waste (Azbar, Keskin, & Yuruyen, 2008; Fezzani & Ben Cheikh, 2007; Fezzani & Ben Cheikh, 2010) by anaerobic digestion and using different microorganisms. For example, some authors achieved a biomethane productivity of up to 32 L LOMWW21 in a two-phase anaerobic digestion process, employing five semicontinuous digesters, a loading rate of 8.17 g COD L21 per day, a temperature of 37 C, and a hydraulic retention time of 24 days (Fezzani & Ben Cheikh, 2010). Anaerobic codigestion of OMWW with other residues can increase the nitrogen content

Chapter 9 Integrated advanced technologies for olive mill wastewater treatment: a biorefinery approach

to favor the process yield in terms of volume of biomethane produced. For example, El Gnaoui et al. (2020) showed that by using a ratio of 20% OMWW/80% food waste, the biomethane yield was 302 mL, 38% higher than that the yield when solely OMWW was used as feedstock. Biohydrogen is another interesting biofuel that can be obtained from OMWW by photofermentation (Ahmed et al., ˜ ez, & Byrne, 2019; Rioja-Cabanillas, Valdesueiro, Ferna´ndez-Iba´n 2021). With this objective, diverse microorganisms can be used, such as Rhodobacter sphaeroides, Rhodopseudomonas palustris, and Chlamydomonas reinhardtii (Foti et al., 2021). In this way, different authors have reported the biohydrogen production from OMWW (Ena, Pintucci, & Carlozzi, 2010; Faraloni, Ena, Pintucci, & Torzillo, 2011), highlighting the high biohydrogen production (0.31 0.53 L) using cylindrical and flat photobioreactors at 30 C, and Rhodopseudomonas palustris (Ena et al., 2010). Some limitations of this method of production are the low yields and formation rates as a result of slow bacterial metabolisms. An alternative procedure can be the application of electrohydrolysis. The use of direct current voltages at 2 V produced around 0.6 L of hydrogen per day along with COD removal (44%) (Kargi & Catalkaya, 2011). Another study suggests the application of supercritical water gasification using hydroxide catalysts at 530 C, 230 bar, and 20 min to obtain a gas fuel that is rich in biohydrogen (76.7 mol kg21 dry matter). Unlike other thermal treatments, a prior drying step is not required (Casademont, Garcı´a-Jarana, Sa´nchez-Oneto, Portela, & Martı´nez de la Ossa, 2018).

9.3.2

Polysaccharides

OMWW have also been studied as an important source of polysaccharides, highlighting the presence of exopolysaccharides. These compounds (e.g., xanthan), which are formed mainly by glucose (and galactose, arabinose, rhamnose, and galacturonic acid), are used in cosmetics, as supplements and thickening compounds, and in the pharmaceuticals and bioremediation fields (Ahmed et al., 2019; Foti et al., 2021). Exopolysaccharides have been successfully obtained from OMWW by a fermentation process using different microorganisms, such as Xanthomonas campestris (Lo´pez, Moreno, & Ramos-Cormenzana, 2001), Paenibacillus jamilae sp. (Lopez & Ramos-Cormenzana, 1996), P. jamilae CECT 5266 (Morillo, Del ´ guila, Aguilera, Ramos-Cormenzana, & Monteoliva-Sa´nchez, A 2007), and P. jamilae CP-7 (Ruiz-Bravo, Jimenez-Valera, Moreno,

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Guerra, & Ramos-Cormenzana, 2001), among others. The highest concentration was achieved with the former microorganism, over 7 gL21 (Table 9.3). Pectin is another interesting polymer that can be obtained from OMWW (Contreras et al., 2020; Gebreyohannes, Mazzei, & Giorno, 2016). It is usually used as a stabilizer, gelling agent, prebiotic, anti-inflammatory, and emulsifier (Contreras et al., 2020). Galanakis et al. (2010) were able to obtain pectin from OMWW by ultrafiltration (2a100 kDa) and nanofiltration, reaching values of up to 87 mgL21 when membranes of 25 and 100 kDa were used (Table 9.3).

9.3.3

Phenolic compounds and other antioxidants

Recently, there has been great interest in phenolic compounds produced from natural raw materials because of their antioxidant properties. In this context, the content of phenolic compounds in OMWW has been widely studied (Ahmed et al., 2019; Contreras et al., 2020; Foti et al., 2021). The concentrations of antioxidant compounds in OMWW, which are shown as colored pigments, depend on different factors, such as olive variety, cultivation type, fruit ripeness, climate, oil-obtaining process, and methods carried out about OMWW, among others (Ahmed et al., 2019). The main phenolic compounds that are found in OMWW are phenolic alcohols, phenolic acids, secoiridoids, and flavonoid, such as hydroxytyrosol, tyrosol, 4-methylcatechol, homovanillic alcohol, 3,4-dihydroxyphenylglycol, luteolin, quercetin, cyanidin, verbascoside, caffeic acid, p-coumaric acid, vanillic acid, syringic acid, gallic acid, 4-hydroxybenzoic acid, and protocatechuic acid. These compounds have great properties for the treatment of hypertension, cholesterol, cancer, diabetes, obesity, and inflammatory processes as well as for the treatment against bacteria and fungus (Ahmed et al., 2019; Contreras et al., 2020; Foti et al., 2021). Phenolic and antioxidant compounds can be extracted from OMWW by using different methods, for example, by bioconversion using an enzyme obtained from Aspergillus niger and Trichoderma atroviride (formed mainly by β-glucosidase and esterase activity), achieving up to 0.56 gL21 (Ramı´rez et al., 2015) and 1.1 gL21 (Hamza, Khoufi, & Sayadi, 2012) of hydroxytyrosol, respectively; using biofilters (Azolla and activated carbon), enabling the great adsorption of hydroxytyrosol (Ena, Pintucci, & Carlozzi, 2012); through solvent extraction assisted by ultrasound, obtaining mainly hydroxytyrosol, tyrosol, verbas´ jo, Pimentel, Alves, & Oliveira, 2015); ¨ zhenide (Arau coside, and nu

Chapter 9 Integrated advanced technologies for olive mill wastewater treatment: a biorefinery approach

by ultrafiltration (25 kDa) and nanofiltration, the ultrafiltration being a better method to maintain the antioxidant properties (Galanakis et al., 2010); and using OMWW from lagoon and decanter (which were previously concentrated with a evaporator) by a multistage recovery process, the steps carried out being the following: acidification, delipidization, solvent extraction, and solid-phase extraction, reaching up to 6.6 mgg21 of hydroxytyrosol with an ethanol/(NH4)2SO4-based aqueous two-phase system (C ¸ elik et al., 2021) (Table 9.3).

9.3.4

Enzymes

In the last 20 years, there has been great interest in the biotechnological use of enzymes, especially from agroindustrial residues (Ahmed et al., 2019). In this context, diverse enzymes (of particular interest in the food, pharmaceuticals, and biotechnologyl industries) have been generated from OMWW (Contreras et al., 2020) (Table 9.3). For example, Paz et al. (2021) got to obtain L-asparaginases (with an enzymatic activity of 11.6 UmL21) from OMWW diluted at 25% (w/w) in a liquid fermentation process by Bacillus aryabhattai. Other enzymes, such as feruloyl esterase, laccase, endocellulase, and endoxylanas, up to 89.5, 6.4, 6.8, and 3.1 UmL21, respectively, were also obtained from OMWW, using in this case a solid-state fermentation and different microorganisms, such as Aspergillus spp., Funalia trogii, and Trametes versicolor (Boran & Ye¸silada, 2011; Salgado, Abrunhosa, Venaˆncio, Domı´nguez, & Belo, 2014). D’Annibale, Sermanni, Federici, and Petruccioli (2006) was also able to produce lipase (9.23 Ucm23), using OMWW and Candida cylindracea NRRL Y-17506. Laccase and manganese peroxidase (with activities of up to 134 and 20 UL21, respectively) were also generated by Hericium erinaceus, using OMWW as a substrate at 50%, v/v (Koutrotsios, Larou, Mountzouris, & Zervakis, 2016). Also, using the latter proportion, Zerva, Zervakis, Christakopoulos, and Topakas (2017) reported the production of laccase (1048.9 UL21) and manganese peroxidase (303.7 UL21) from OMWW, but in this case using Pleurotus citrinopileatus LGAM 28684, at pH 6, 150 rpm, and corn steep liquor (3 gL21) to increase the nitrogen content.

9.3.5

Biosurfactants

Biosurfactants are surface-active compounds that are obtained as secondary byproducts in a fermentation process by

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microorganisms. Owing to the stability of these compounds at very high levels of pH, temperature, and salt concentration, they can be used in numerous applications, such as for soil bioremediation and heavy metals recovery as well as in the food, cosmetics, detergent, and pharmaceuticals industries (Ahmed et al., 2019; Contreras et al., 2020). OMWW contains residual oils and polysaccharides; therefore it can be used as a carbon source to obtain biosurfactants, such as rhamnolipids and surfactins (Ahmed et al., 2019) (Table 9.3). For instance, surfactin and rhamnolipid (3.12 and 191.46 mgL21, respectively) were achieved from OMWW (at 2 and 10% v/v loading, respectively), using Bacillus subtilis and Pseudomonas aeruginosa, respectively (Ramı´rez et al., 2015). The latter compound has also been obtained by using Pseudomonas spp. (Ahmed et al., 2019), while a glycoprotein complex was produced with surfactant properties by a fungal strain, Aspergillus sp. FS11 (Derguine-Mecheri & KebboucheGana, 2020).

9.3.6

Citric acid and lipids

Organic acids, such as citric acid, are very interesting compounds, especially in recent years, as they are considered to be excellent building blocks. Therefore they are very useful in diverse sectors, such as the food, pharmaceuticals, and plastic sectors (Contreras et al., 2020). OMWW is regarded as a great carbon source, and citric acid can be obtained from this waste through a fermentation process. With this objective, Yarrowia lipolytica strains have been reported in the literature as very good producers of citric acid from OMWW supplemented with glycerol and salt, reaching concentrations of up to 54 gL21 citric acid (Papanikolaou, Galiotou-Panayotou, Fakas, Komaitis, & Aggelis, 2008; Sarris, Galiotou-Panayotou, Koutinas, Komaitis, & Papanikolaou, 2011; Tzirita et al., 2019) (Table 9.3). Yarrowia lipolytica strains are also able to produce other high-value added compounds, such as lipids and mannitol, as byproducts, using media limited in nitrogen (Sarris et al., 2011; Tzirita et al., 2019) (Table 9.3). For instance, Tzirita et al. (2019) obtained up to 54 gL21 citric acid as a byproduct of a lipid concentration of 2.5 gL21.

9.3.7

Polyhydroxyalkanoates

PHAs are considered to be “green” plastics. Compared to conventional plastics, and regarding the production and

Chapter 9 Integrated advanced technologies for olive mill wastewater treatment: a biorefinery approach

recycling processes, these compounds have recently become of interest, both socially and environmentally (Contreras et al., 2020). PHAs can be obtained by using OMWW as a substrate and different microorganisms, such as Haloferax mediterranei and Pseudomonas spp., in both single-step and multistep fermentations (Alsafadi & Al-Mashaqbeh, 2017; Kourmentza, Ntaikou, Lyberatos, & Kornaros, 2015) (Table 9.3). For example, Alsafadi and Al-Mashaqbeh (2017) achieved 43% polyhydroxyalkanoates/cell dry mass (0.2 gL21) from OMWW (15% v/v), using H. mediterranei, NaCl (22%), and a single-stage process. PHAs (0.1 gL21) were also generated from OMWW (25% v/v), but in this case, Pseudomonas spp. and a multistep process (anaerobic, acidogenic first step, Pseudomonas spp. second step) were employed (Kourmentza et al., 2015).

9.3.8

Use in agriculture: fertilizers, biopesticides, and irrigation

The use of OMWW in organic fertilizers and biopesticides has been considered to be one of the most interesting, appropriate and sustainable applications of OMWW, owing to the high organic matter content and presence of mineral nutrient in this waste (Ahmed et al., 2019; Chatzistathis & Koutsos, 2017; El-Abbassi et al., 2017; Foti et al., 2021). OMWW could be also used for irrigation of olive trees, which might be profitable considering both agronomic and economic aspects and could solve water scarcity problems in areas with low rainfall (Pedrero, Grattan, Ben-Gal, & Vivaldi, 2020) (Table 9.3). Concerning organic fertilizers, different processes (physicochemical and/or biological) can be applied to OMWW. Regarding physicochemical processes, treatments with flocculants, coagulants, membrane filtration, reverse osmosis, oxidation cryogenesis, electrocoagulation, or photochemical systems could be performed (Foti et al., 2021). OMWW could also be used directly even as a bioflocculant (Bouaouine, Bourven, Khalil, & Baudu, 2020). Considering biological processes, it highlights the cocomposting technique, which is a process in which organic solid residues from OMWW (combined with lignocellulosic residues, such as sawdust and cereal straws) are degraded by microorganisms under aerobic or anaerobic conditions, generating compost as a result (Ahmed et al., 2019). The compost can increase the water-holding capacity of soil as well

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as its stability, its microbial activity, and pesticide degradation (Cerda et al., 2018). Numerous studies have been reported about compost production using OMWW, alone or mixed with other residues. For example, compost with phytostimulant properties was generated from long-term storage OMWW (Sa´ez et al., 2021). Using also OMWW (mixed with manures of poultry, sheep, cow and horse, and solid olive mill waste), Makni et al. (2010) also got to produce compost (after 200 days of cocomposting) with a germination index of 80%, which indicates that the compost that is generated can be considered mature or very mature. With regard to biopesticides, OMWW has been widely reported as a great biopesticide against plant pathogens, inhibiting the growth of phytopathogenic bacteria, fungi, weeds, and pests (e.g., nematodes, mollusks and arthropods). Furthermore, no negative effects have been observed on crop growth (El-Abbassi et al., 2017). Some examples of pathogens that are inhibited by OMWW are Pectobacterium carotovorum phytopathogenic bacteria (Yangui, Sayadi, & Dhouib, 2013); Aspergillus, Botrytis, Fusarium, and Penicillium spp. phytopathogenic fungi (Lykas, Vagelas, & Gougoulias, 2014); Phelipanche ramose weed (Disciglio et al., 2016); and Aphis citricola and Euphyllura olivine pests (Larif, Zarrouk, Soulaymani, & Elmidaoui, 2013).

9.3.9

Food and beverage supplement

Another important application of OMWW is as ingredients in the food production in diverse agro-food chains, enhancing hygienic conditions and rheological properties (Foti et al., 2021). For example, OMWW has been added in the manufacturing of fermented sausages (2.5% OMWW), providing antifungal activity (Lopez et al., 2015); white meat burgers (0.75 1.50 g OMWW/kg), achieving antimicrobial activity (Veneziani et al., 2017); lard (100 200 ppm OMWW) and butter (80 mg OMWWkg21), improving the oxidative processes (Mikdame et al., 2020); cheese (250 500 μg OMWWmL21), enhancing shelf life (Roila et al., 2019); bread and rusks (200 mg OMWWkg21 flour), inhibiting the growth of microorganisms such as Escherichia coli and enhancing the oxidative processes during cooking (Galanakis, 2018); and pasta (30% w/w OMWW), attaining antioxidant properties and food fortification (Cedola, Cardinali, D’Antuono, Conte, & Del Nobile, 2019) (Table 9.3). Another study suggests that phenolic

Chapter 9 Integrated advanced technologies for olive mill wastewater treatment: a biorefinery approach

compounds from OMWW can be the basis to produce functional beverages. For these applications, to guarantee a better quality of OMWW, olive-washing wastewater and that generated during the cleaning of the mill should not be mixed with OMWW (the water from the decanter). Therefore it important to clarify what type of water is used in each application.

9.4

Process integration: biorefinery examples

An investigation of OMWW addressed its treatment through techniques that were able to minimize the initial pollution charge and reduce the environmental impacts of its disposal, but it requires the combination of chemical, biological and physical processes to remove solids, odor, and color. Although the treatment of OMWW could be more or less solved technologically, practical/economic reasons had made its valorization not still set on (Elmekawy et al., 2014). Therefore other investigations are being conducted to treat or valorize OMWW. For example, a recent study reported that the use of ultrasound oxidation (or sonolysis) combined with other oxidation methods, including physical ones such as ultraviolet radiation and chemical treatments with hydrogen peroxide and titanium oxide as catalysts, can reach up to 59% COD removal (Al-bsoul et al., 2020). Another trend is that shown in Section 9.3, based on the development of one single process to obtain a valuable byproduct. However, a more promising possibility is to integrate two or more processes in a scheme in which the biomass is utilized to produce a variety of bioproducts, trying to be self-sustaining and environmentally friendly (Saral, Ajmal, & Ranganathan, 2022). Although OMWW is an interesting bioresource for a lignocellulosic biorefinery, its moisture content (78.5% or higher) could be a limitation for applications that requires solid raw material. In other cases, some studies have found opportunities for exploiting its liquid nature, such as the study by Jeguirim et al. (2020). In this case, OMWW and olive pomace from three-phase extraction were mixed to be raw material to recover water for irrigation by convective drying, condensation, and a tertiary treatment and then a thermochemical conversion of the dry material by pyrolysis (2 hours at 500 C) to obtain biogas that is rich in methane, biochar, and bio-oil with a yield of 60.5% carbon and HHV of 26 MJkg21 (Fig. 9.4A). The biogas and the bio-oil, after upgrading, can be applied as fuels, while the

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Water

(A)

Biogas OMWW

Drying

Biochar

Pyrolysis

OP Bio-oil

(B)

Hydrochar

OMWW

Hydrothermal carbonization Liquid fraction

(C)

OMWW

Hemicellulase treatment

Microfiltration/ Biochar Ultrafiltration

Phenolic compounds

Fermentation T. ochracea

Laccase and Mn-dependent peroxidase (D)

OMWW

Adsorption by activated carbon

Photofermentation Rhodopseudomonas

H2 and poly-βhydroxybutyrate

Elution by acidified ethanol Phenolic compounds

Figure 9.4 Potential biorefinery schemes to valorize OMWW. OP, olive pomace; T. ochracea, Trametes ochracea.

biochar, with high nutrients levels including potassium and phosphorus, could be used as a fertilizer (Jeguirim et al., 2020). In another work, using a single process, hydrothermal carbonization (HTC) at 200 C and a residence time of 24 hours, two bioproducts were obtained from three-phase OMWW: a hydrochar with HHV of 35.7 MJkg21 as biofuel and a liquid fraction suitable for agricultural applications (Fig. 9.4B). This type of treatment enables the use of the OMWW in itself, without the

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265

requirement of a drying step, which increases the costs (Amine Azzaz et al., 2020). Another direct wet conversion treatment, hydrothermal liquefaction (HTL), has been suggested to be suitable to produce biofuels from microalgae cultivation on OMWW, which could provide ´ lvareza bio-oil with a production cost around 2.5 hL21 (Delrue, A Dı´az, Fon-Sing, Fleury, & Sassi, 2016). The difference between HTL and HTC techniques is that HTC reactions are governed at a temperature ranging from 180 C to 250 C, while it varies between 250 C and 375 C in HTL (Fig. 9.5).

Amines

Peptides and amino acids

Lactic acid

Hydrolysis

Amides

Glucose Hydrolysis

Hydroxymethylfurfural

Aminolysis Cellulose Proteins

Breakage

Fatty acids

Hydrolysis Xylose and other Hemicellulose sugar monomers Dehydration

Hydrolysis

Glycerol

Lipids

Lignocellulose

Lignin

Furfural

Depolymerization and hydrolysis Aromatic oligomers and benzene derivatives

Hydrochar Bio-oil

Formic acid

Aqueous phase

Figure 9.5 Reactions produced in hydrothermal processes Hydrothermal carbonization mainly lead to generation of hydrochar and hydrothermal liquefaction to a biocrude (or bio-oil) (Lachos-Perez, Paulo, Abaide, Zabot, Castilhos, 2022). Based on Lachos-Perez, D., Paulo, C., Abaide, E. R., Zabot, G. L., Castilhos, F. De (2022). Hydrothermal carbonization and liquefaction: Differences, progress, challenges, and opportunities. Bioresource Technology, 343, 126084.

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The application of OMWW for microalgae cultivation is interesting, since microalgae can become a renewable energy source and a feedstock to produce oils, intermediate compounds to obtain biofuels, and a source for biohydrogen and other high-value bioproducts (Kant Bhatia et al., 2021; Moreno Garcı´a, Garie´py, Barnabe, & Raghavan, 2020). The use of wastewater as the main source of nutrients can reduce the cost of this process, which is one of the current disadvantages of the application of microalgae (Moreno Garcı´a et al., 2020). OMWW can also be a substrate for other microorganisms such as bacteria and yeasts in biorefining models (Carlozzi et al., 2019; Vaidya, Carota, Calonzi, Petruccioli, & Annibale, 2019). For example, a recent study developed a biorefinery approach to obtain hydroxytyrosol, poly-β-hydroxybutyrate (PHB), and hydrogen from three-phase OMWW based on the use of photosynthetic bacteria. In a first step, by using activated carbon as an adsorbent material and acidified ethanol (pH 3.1) as eluent at 50 C, 2.0 gL21 of hydroxytyrosol was obtained, which is a promising antioxidant for food and cosmetics applications. Then the dephenolized waste was applied as substrate (culture broth containing 50%) of the purple bacteria Rhodopseudomonas sp. S16-FVPT5 to coproduce PHB (0.3 gLd-OMWW21) and hydrogen (2.2 L H2Ld-OMWW21) (Carlozzi et al., 2019) (Fig. 9.4D). This process is a very interesting way to obtain two valuable products: PHB to produce bioplastics and hydrogen to meet decarbonization goals. Moreover, the latter authors suggest that this bioenergy production method based on microorganisms and using a waste liquid stream as substrate is attractive because it does not compete with food crops, the waste does not require pretreatment, and the photobioreactors can be placed in marginal areas to avoid competition with agricultural lands. Another possibility, proposed by Vaidya et al., is a two-step biorefinery based on three-phase OMWW to recover phenolic compounds by membrane separation technology, while the retentate was applied as based medium to obtain ligninmodifying enzymes. This combines a mature and cost-effective technology, which is the use of membranes for fractionation, with a good performance fermentative process with Trametes ochracea (Fig. 9.4C) (Vaidya et al., 2019). This study was done at reactor scale to facilitate the transfer to large scale. Although a certain amount of fouling occurred, high enzyme production levels were obtained.

Chapter 9 Integrated advanced technologies for olive mill wastewater treatment: a biorefinery approach

9.5

Conclusions and future trends

OMWW has a multitude of potential applications, but its chemical characteristics are highly variable, depending, among other factors, on the source of the wastewater. This fact should be considered to reproduce the technology, especially when two or more processes are going to be concatenated. In this context, it is desirable that future OMWW management strategies integrate a combination of processes in a complementary manner that enables the production of a variety of valuable bioproducts whose revenues offset the costs of treatment and the transition to a more sustainable sector with zero residue. The exploitation of OMWW can reduce the environmental impact of the olive sector, especially using sustainable technologies, but technoeconomic and lifecycle analyses are required to assess the potential scalability of these processes and their environmental impact. The application of microorganisms that are able to both capture CO2 and use OMWW to generate bioproducts and biofuels is also an attractive option, but these carbon capture and utilization technologies have some limitations that need to be overcome (Lu, Alam, Liu, Xu, & Parra Saldivar, 2020). Another option is for governments to favor the transition to the two-phase olive oil extraction, for example, giving economical support to the olive oil industry to invest in this technology. It generates a lower volume of polluted water. In this case, the advance in technology should be addressed to manage olive pomace and exhausted olive pomace (or defatted olive pomace), and again implementation of biorefinery schemes could be promising.

Acknowledgments M.d.M. Contreras would like to express gratitude to the Ministry of Science and Innovation of Spain for her Ramo´n y Cajal grant (RYC2018 026177-I / AEI / 10.13039/501100011033). Some images have been obtained from open databases PubChem (https://pubchem.ncbi.nlm.nih.gov/) and UniProtKB (https://www. uniprot.org /uniprot/).

List of acronyms COD HHV HTC HTL OMWW PHA PHB

chemical oxygen demand higher heating value hydrothermal carbonization hydrothermal liquefaction olive mill wastewater polyhydroxyalkanoates poly-β-hydroxybutyrate

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Faraloni, C., Ena, A., Pintucci, C., & Torzillo, G. (2011). Enhanced hydrogen production by means of sulfur-deprived Chlamydomonas reinhardtii cultures grown in pretreated olive mill wastewater. International Journal of Hydrogen Energy, 36(10), 5920 5931. Ferna´ndez-Herna´ndez, A., Roig, A., Serramia´, N., Civantos, C.G., Sa´nchezmonedero, M.A., (2014). Application of compost of two-phase olive mill waste on olive grove: Effects on soil, olive fruit and olive oil quality 34, 1139 1147. Fezzani, B., & Ben Cheikh, R. (2007). Anaerobic co-digestion of olive mill wastewater with olive mill solid waste in a tubular digester at a mesophilic temperature. Bioresource Technology, 98, 769 774. Fezzani, B., & Ben Cheikh, R. (2010). Two-phase anaerobic co-digestion of olive mill wastes in semi-continuous digesters at mesophilic temperature. Bioresource Technology, 101(6), 1628 1634. Foti, P., Romeo, F. V., Russo, N., Pino, A., Vaccalluzzo, A., Caggia, C., & Randazzo, C. L. (2021). Olive mill wastewater as renewable raw materials to generate high added-value ingredients for agro-food industries. Applied Sciences, 11(16), 7511. Galanakis, C. M. (2018). Phenols recovered from olive mill wastewater as additives in meat products. Trends in Food Science and Technology, 79, 98 105. Galanakis, C. M., Tornberg, E., & Gekas, V. (2010). Clarification of high-added value products from olive mill wastewater. Journal of Food Engineering, 99, 190 197. Garcı´a-Go´mez, A., Roig, A., & Bernal, M. P. (2003). Composting of the solid fraction of olive mill wastewater with olive leaves: Organic matter degradation and biological activity. Bioresource Technology, 86, 59 64. Gebreyohannes, A. Y., Mazzei, R., & Giorno, L. (2016). Trends and current practices of olive mill wastewater treatment: Application of integrated membrane process and its future perspective. Separation and Purification Technology, 162, 45 60. Global Marketing Associates (2021). Global olive oil market: Export opportunity analysis export/import analysis. ,http://www.globalmarketing1.com/blog/ global-olive-oil-market-export-opportunity-analysis/. (accessed 20.11.21). Guida, M. Y., Bouniak, H., Tabal, A., Hannioui, A., Solhy, A., Barakat, A., . . . El harfi, K. (2015). Thermochemical treatment of olive mill solid waste and olive mill wastewater. Pyrolysis kinetics. Journal of Thermal Analysis and Calorimetry, 123, 1657 1666. Hadhoum, L., Burnens, G., Loubar, K., Balistrou, M., & Tazerout, M. (2019). Biooil recovery from olive mill wastewater in sub-/supercritical alcohol-water system. Fuel, 252, 360 370. Hamza, M., Khoufi, S., & Sayadi, S. (2012). Fungal enzymes as a powerful tool to release antioxidants from olive mill wastewater. Food Chemistry, 131(4), 1430 1436. Hodaifa, G., Agabo, C., Moya, A. J., Pacheco, R., & Mateo, S. (2015). Treatment of olive oil mill wastewater by UV-light and UV/H2O2 system. International Journal of Green Technology, 1, 46 53. iAgua (2021). Embalse de Quiebrajano. ,https://www.iagua.es/data/ infraestructuras/embalses/quiebrajano. Accessed 21.11.21. International Olive Oil Council (2020). HUILES D ’ Olive—Olive oils. ,https:// www.internationaloliveoil.org/wp-content/uploads/2020/12/HO-W901-23-112020-P.pdf. Accessed 11.20.21. Jeguirim, M., Goddard, M.-L., Tamosiunas, A., Tamosiunas, A., Berrich-Betouche, E., Azzaz, A. A., . . . Jellali, S. (2020). Olive mill wastewater: From a pollutant to

Chapter 9 Integrated advanced technologies for olive mill wastewater treatment: a biorefinery approach

green fuels, agricultural water source and bio-fertilizer. Biofuel prodution. Renew. Energy, 149, 716 724. Jellali, A., Hachicha, W., & Aljuaid, A. M. (2021). Sustainable configuration of the Tunisian olive oil supply chain using a fuzzy TOPSIS-based approach. Sustainability, 13, 1 20. Kant Bhatia, S., Mehariya, S., Kant, R., Kumar, M., Pugazhendhi, A., Kumar, M., . . . Yang, Y. (2021). Wastewater based microalgal biorefinery for bioenergy production: Progress and challenges. The Science of the Total Environment, 751, 141599. Kargi, F., & Catalkaya, E. C. (2011). Hydrogen gas production from olive mill wastewater by electrohydrolysis with simultaneous COD removal. International Journal of Hydrogen Energy, 36, 3457 3464. Khdair, A., & Abu-Rumman, G. (2020). Sustainable environmental management and valorization options for olive mill byproducts in the Middle East and North Africa (MENA) Region. Processes, 8, 671. Khdair, A. I., Abu-rumman, G., & Khdair, S. I. (2019). Pollution estimation from olive mills wastewater in Jordan. Heliyon, 5, e02386. Kourmentza, C., Ntaikou, I., Lyberatos, G., & Kornaros, M. (2015). Polyhydroxyalkanoates from Pseudomonas sp. using synthetic and olive mill wastewater under limiting conditions. International Journal of Biological Macromolecules, 74, 202 210. Koutrotsios, G., Larou, E., Mountzouris, K. C., & Zervakis, G. I. (2016). Detoxification of olive mill wastewater and bioconversion of olive crop residues into high-value-added biomass by the choice edible mushroom Hericium erinaceus. Applied Biochemistry and Biotechnology, 180(2), 195 209. Lachos-Perez, D., Paulo, C., Abaide, E. R., Zabot, G. L., & Castilhos, F. De (2022). Hydrothermal carbonization and Liquefaction: Differences, progress, challenges, and opportunities. Bioresource Technology, 343, 126084. Larif, M., Zarrouk, A., Soulaymani, A., & Elmidaoui, A. (2013). New innovation in order to recover the polyphenols of olive mill wastewater extracts for use as a biopesticide against the Euphyllura olivina and Aphis citricola. Research on Chemical Intermediates, 39, 4303 4313. Lopez, C. C., Serio, A., Mazzarrino, G., Martuscelli, M., Scarpone, E., & Paparella, A. (2015). Control of household mycoflora in fermented sausages using phenolic fractions from olive mill wastewaters. International Journal of Food Microbiology, 207, 49 56. Lopez, M., & Ramos-Cormenzana, A. (1996). Xanthan production from olivemill wastewaters. International Biodeterioration and Biodegradation, 38, 263 270. Lo´pez, M. J., Moreno, J., & Ramos-Cormenzana, A. (2001). Xanthomonas campestris strain selection for xanthan production from olive mill wastewaters. Water Research, 35(7), 1828 1830. Lu, W., Alam, M. A., Liu, S., Xu, J., & Parra Saldivar, R. (2020). Critical processes and variables in microalgae biomass production coupled with bioremediation of nutrients and CO2 from livestock farms: A review. The Science of the Total Environment, 716, 135247. Lykas, C., Vagelas, I., & Gougoulias, N. (2014). Effect of olive mill wastewater on growth and bulb production of tulip plants infected by bulb diseases. Spanish Journal of Agricultural Research, 12, 233. Makni, H., Ayed, L., Ben Khedher, M., & Bakhrouf, A. (2010). Evaluation of the maturity of organic waste composts. Waste Management & Research, 28(6), 489 495.

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Massadeh, M. I., & Modallal, N. (2008). Ethanol Production from Olive Mill Wastewater (OMW) pretreated with Pleurotus sajor-caju. Energy & Fuels, 22, 150 154. Mazzocchi, A., Leone, L., Agostoni, C., & Pali-Scho¨ll, I. (2019). The secrets of the mediterranean diet. Does [only] olive oil matter? Nutrients, 11, 1 14. Mikdame, H., Kharmach, E., Mtarfi, N. E., Alaoui, K., Ben Abbou, M., Rokni, Y., . . . Rais, Z. (2020). By-products of olive oil in the service of the deficiency of food antioxidants: The case of butter. Journal of Food Quality, 2020, 1 10. Moreno Garcı´a, L., Garie´py, Y., Barnabe, S., & Raghavan, V. (2020). Biorefinery of microalgae biomass cultivated in wastewaters. In R. Praveen Kumar, E. Gnansounou, J. K. Raman, & G. Baskar (Eds.), Refining biomass residues for sustainable energy and bioproducts (pp. 149 180). Academic Press. ´ guila, V. G., Aguilera, M., Ramos-Cormenzana, A., & Morillo, J. A., Del A Monteoliva-Sa´nchez, M. (2007). Production and characterization of the exopolysaccharide produced by Paenibacillus jamilae grown on olive millwaste waters. World Journal of Microbiology and Biotechnology, 23, 1705 1710. Obied, H. K., Allen, M. S., R, B. D., Prenzler, P. D., & Robards, K. (2005). Investigation of Australian olive mill waste for recovery of biophenols. Journal of Agricultural and Food Chemistry, 53, 9911 9920. Papanikolaou, S., Galiotou-Panayotou, M., Fakas, S., Komaitis, M., & Aggelis, G. (2008). Citric acid production by Yarrowia lipolytica cultivated on olive-mill wastewater-based media. Bioresource Technology, 99, 2419 2428. Paredes, C., Bernal, M. P., Cegarra, J., & Roig, A. (2002). Bio-degradation of olive mill wastewater sludge by its co-composting with agricultural wastes. Bioresource Technology, 85, 1 8. Paz, A., Nikolaivits, E., & Topakas, E. (2021). Valorization of olive mill wastewater towards the production of L-asparaginases. Biomass Conversion and Biorefinery, 11, 539 546. Pedrero, F., Grattan, S. R., Ben-Gal, A., & Vivaldi, G. A. (2020). Opportunities for expanding the use of wastewaters for irrigation of olives. Agricultural Water Management, 241, 106333. Pedro, B., Moral, S., Victoria, M., & Me´ndez, R. (2006). Production of pomace olive oil. Grasas Y Aceites, 57, 47 55. Ramı´rez, I. M., Tsaousi, K., Rudden, M., Marchant, R., Alameda, E. J., Roman, M. G., & Banat, I. M. (2015). Rhamnolipid and surfactin production from olive oil mill waste as sole carbon source. Bioresource Technology, 198, 231 236. ˜ ez, P., & Byrne, J. A. (2021). Rioja-Cabanillas, A., Valdesueiro, D., Ferna´ndez-Iba´n Hydrogen from wastewater by photocatalytic and photoelectrochemical treatment. JPhys Energy, 3(1), 012006. Roila, R., Valiani, A., Ranucci, D., Ortenzi, R., Servili, M., Veneziani, G., & Branciari, R. (2019). Antimicrobial efficacy of a polyphenolic extract from olive oil by-product against “Fior di latte” cheese spoilage bacteria. International Journal of Food Microbiology, 295, 49 53. Ruiz-Bravo, A., Jimenez-Valera, M., Moreno, E., Guerra, V., & RamosCormenzana, A. (2001). Biological response modifier activity of an exopolysaccharide from Paenibacillus jamilae CP-7. Clinical and Diagnostic Laboratory Immunology, 8, 706 710. Sa´ez, J. A., Pe´rez-Murcia, M. D., Vico, A., Martı´nez-Gallardo, M. R., AndreuRodrı´guez, F. J., Lo´pez, M. J., . . . Moral, R. (2021). Olive mill wastewaterevaporation ponds long term stored: Integrated assessment of in situ

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bioremediation strategies based on composting and vermicomposting. Journal of Hazardous Materials, 402, 123481. Salgado, J. M., Abrunhosa, L., Venaˆncio, A., Domı´nguez, J. M., & Belo, I. (2014). Screening of winery and olive mill wastes for lignocellulolytic enzyme production from Aspergillus species by solid-state fermentation. Biomass Conversion and Biorefinery, 4, 201 209. Saral, J. S., Ajmal, R. S., & Ranganathan, P. (2022). Bioeconomy of hydrocarbon biorefinery processes—Sustainable processing of biomass for hydrocarbon biofuels. In S. K. Maity, T. K. Bhowmick, & K. Gayen (Eds.), Hydrcarbon biorefinery (pp. 355 385). Elsevier. Sarris, D., Galiotou-Panayotou, M., Koutinas, A. A., Komaitis, M., & Papanikolaou, S. (2011). Citric acid, biomass and cellular lipid production by Yarrowia lipolytica strains cultivated on olive mill wastewater-based media. Journal of Chemical Technology and Biotechnology (Oxford, Oxfordshire: 1986), 86, 1439 1448. Sarris, D., Matsakas, L., Aggelis, G., Koutinas, A. A., & Papanikolaou, S. (2014). Aerated vs non-aerated conversions of molasses and olive mill wastewaters blends into bioethanol by Saccharomyces cerevisiae under non-aseptic conditions. Industrial Crops and Products, 56, 83 93. Talhaoui, N., Go´mez-Caravaca, A. M., Leon, L., De, R., Fernandez-Gutierrez, A., & Segura-Carretero, A. (2015). Pattern of variation of fruit traits and phenol content in olive fruits from six different cultivars. Journal of Agricultural and Food Chemistry, 63, 10466 10476. Tesla (n.d.). Transfering energy save laid on agroindustry. ,http://teslaproject. chil.me/download-doc/63246. Accessed 11.20.21. Toscano, P., & Montemurro, F. (2012). Olive mill by-products management. In I. Muzzalupo (Ed.), Olive germplasm—The olive cultivation, table olive and olive oil industry in Italy. IntechOpen. Available from https://doi.org/10.5772/52039. Tsagaraki, E., Lazarides, H. N., & Petrotos, K. B. (2007). Olive mill wastewater treatment. In V. Oreopoulou, & W. Russ (Eds.), Utilization of by-products and treatment of waste in the food industry. Boston: Springer. Tzirita, M., Kremmyda, M., Sarris, D., Koutinas, A. A., & Papanikolaou, S. (2019). Effect of salt addition upon the production of metabolic compounds by Yarrowia lipolytica cultivated on biodiesel-derived glycerol diluted with olivemill wastewaters. Energies, 12, 3649. Vaidya, V., Carota, E., Calonzi, D., Petruccioli, M., & Annibale, A. D. (2019). Production of lignin-modifying enzymes by Trametes ochracea on highmolecular weight fraction of olive mill wastewater, a byproduct of olive oil biorefinery. New Biotechnology, 50, 44 51. Veneziani, G., Novelli, E., Esposto, S., Taticchi, A., & Servili, M. (2017). Applications of recovered bioactive compounds in food products. Olive mill waste (pp. 231 253). Cambridge, MA: Academic Press. Yangui, T., Sayadi, S., & Dhouib, A. (2013). Sensitivity of Pectobacterium carotovorum to hydroxytyrosol-rich extracts and their effect on the development of soft rot in potato tubers during storage. Crop Protection (Guildford, Surrey), 53, 52 57. Zbakh, H., & El, A. (2012). Potential use of olive mill wastewater in the preparation of functional beverages: A review. Journal of Functional Foods, 4, 53 65. Zerva, A., Zervakis, G. I., Christakopoulos, P., & Topakas, E. (2017). Degradation of olive mill wastewater by the induced extracellular ligninolytic enzymes of two wood-rot fungi. Journal of Environmental Management, 203, 791 798.

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10 Advanced strategies for dairy wastewater treatment: a perspective Adriano Gomes da Cruz1, Tatiana Colombo Pimentel2, Geraldo Lippel Sant’Anna Junior3 and Simone Maria Ribas Vendramel1 1

Federal Institute of Education, Science and Technology of Rio de Janeiro (IFRJ), Department of Food, Rio de Janeiro, Brazil 2Federal Institute of Education, Science and Technology of Parana´ (IFPR), Department of Food, Parana´, Brazil 3Federal University of Rio de Janeiro (UFRJ), Alberto Luiz Coimbra Institute of Graduate Studies and Research in Engineering (COPPE), Rio de Janeiro, Brazil

10.1

Introduction

Humans are mammals; therefore milk has always been a primordial source of nutrients for our species. Since the emergence of human communities thousands of years ago, raising animals to produce milk has been an ordinary activity. Over time, humans learned to obtain milk-derived products. Global milk production was approximately 906 million tons in 2020, up 2% from 2019 (FAO-UN, 2021). The milk production chain starts in the dairy farms and follows a heterogeneous processing system. The production of milk-derived products is carried out by various producers, including small artisanal cheese makers, local industries, and large multinational companies. Thus the scenario of milk-derived production is highly heterogeneous. In recent years, the environmental impacts of the dairy chain have been highlighted by environmentalists and governmental agencies. For example, there has been criticism regarding animal breeding and live conditions, gas emissions by cattle, intensive fuel consumption in farming, and the transportation of milk and final products to markets. Another concern is the pollution impact of the wastewaters and wastes generated by the dairy industry on natural ecosystems.

Advanced Technologies in Wastewater Treatment. DOI: https://doi.org/10.1016/B978-0-323-88510-2.00012-9 Copyright © 2023 Elsevier Inc. All rights reserved.

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In particular, the global food industries are committed to the growing interest of investors and business players in environmental, social, and governance (ESG) criteria. However, the degree of commitment varies from company to company in the dairy segment. The small and least capitalized dairy enterprises, in general, have difficulties adopting ESG criteria. The fact is that the dairy industry is concerned about the current demands of investors and consumers regarding sustainability. However, concerns should lead to practical actions. The dairy industry’s adequate management of wastes and wastewaters is the first step toward demonstrating commitment to sustainability and environmental protection. Nowadays, such management can be made with a high degree of quality, owing to the considerable advances in the techniques that ensure the recovery of materials and substances from these residues. These techniques offer an extensive portfolio of environmental solutions that are available for implementation. After the recovery steps, the residual wastes or wastewaters should be efficiently processed or treated because the treatment technologies have also made substantial progress over the years. The dairy sector is very dynamic and attentive to consumption trends, including dietary products and/or lower-calorie products. The increase in the number of minidairies worldwide reflects the consumption trend of searching for artisanal and sophisticated products. However, large national and multinational dairy companies widely dominate the market. The diversity of the dairy industry makes environmental commitment more complex. The requirements for wastewater treatment, for instance, may vary depending on the industry location and the local wastewater discharge regulations.

10.2

Some guidelines for wastewater treatment in the dairy industry

To address industrial wastewater treatment, two classical concepts can be applied: in-plant design and the end-of-pipe process. Both approaches were detailed by Ramalho (1977) and, in simplified terms, have the following meanings: The end-of-pipe process does not argue how the wastewater was generated, the streams that contribute to the final effluent, their volume, and characteristics. Briefly, it just looks for technologies and processes that can treat given wastewater. On the other hand, the in-plant-design approach is based on the analysis of all streams that contribute to the final effluent and looks for volume reduction, stream

Chapter 10 Advanced strategies for dairy wastewater treatment: a perspective

segregation, and other actions that will reduce treatment costs and facilitate last treatment, which, in addition, will generate treated wastewater presenting a higher quality. Some guidelines for a more consistent wastewater treatment approach are as follows: 1. All the streams that contribute to the industrial wastewater should be characterized (flow rate, chemical, physical properties, etc.) 2. Industrial operation practices should be analyzed judiciously to verify unnecessary losses of raw materials or products. The amount of water that is used in vessels and equipment flushing, cleaning of the floor, and other related activities should be monitored. The possibility of water consumption reduction should be evaluated. 3. Wastewaters from the dairy industry are rich in organic material, mainly proteins, fats, and carbohydrates. The opportunity to recover these substances from wastewaters or residual liquids, such as whey, should be analyzed in cooperation with the industrial staff (for feasibility, economics, and other factors), since this could significantly reduces the organic load applied to the treatment system. 4. The installation of a storage tank should be considered to collect spills and leaks from pipelines and, mainly, batches of products or raw materials that should be discarded owing to poor quality, contamination, or other production problem. Streams containing large amounts of sanitizing agents or similar products that can hinder wastewater biological treatment steps must be sent to this tank. The content of this tank can be pumped gradually and mixed with the industrial wastewater to avoid detrimental impacts on the wastewater treatment system. 5. Including an equalization tank upstream of the treatment system is strongly recommended because the wastewater characteristics vary during the production journey. This tank allows absorbing peaks and reduces fluctuations in the concentration of pollutants. 6. Before a treatment system is installed or an existing one is modified, it is advisable to do treatability tests in conjugation with equipment suppliers or process designers. For example, if the dairy industry chooses a treatment step based on membrane technology, care should be taken concerning membrane-fouling problems. In this case, experiments in cooperation with the technology supplier should be done to ensure that the projected process performance will be attained. Likewise, one should have the same concern regarding treatment techniques based on chemical coagulation, adsorption, and chemical oxidation.

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7. Pretreatments are usually needed and cannot be underestimated. They ensure the correct operation of processes located downstream in the treatment system. In general, these pretreatments generate slurries or solid wastes that should have adequate treatment or disposal.

10.3

Dairy wastewater characteristics

The dairy industry is based on milk, and its chemical composition depends mainly on the type of animal (cow, sheep, goat) and many other factors, such as animal nutrition and stage of lactation Table 10.1 shows some reported components of different milks. The data shown in Table 10.1 should be understood as indication values of each milk component. Significant variation occurs in the amount of these components, as has already been mentioned. For instance, the sampling campaign conducted by Merlin Jr. et al. (2015) in two different dairy farms located in the same region of the country revealed that the contents of fat and protein in the sheep milk varied as follows: 5.0% 8.5% and 3.4% 6.6%, respectively, in one dairy farm and 6.5% 9.0% and 4.7% 6.9%, respectively, in the other one. Alichanidis et al. (2016) presented variations of fat and protein contents for cow milk in the ranges of 2.5% 6.0% and 2.9% 5.0%, respectively. Milk also contains many other organics, such as α-lactoalbumin, β-lactoalbumin, serum albumin, lactoferrin,

Table 10.1 Major components of cow, sheep, and goat milks. Components

Cowa

Cowb

Sheepc

Sheepd

Goatc

Goatb

Crude protein (%) Casein (%) Whey protein (%) Fat (%) Lactose (%) Phosphorus (g L21) Calcium (g L21)

3.4 2.6 0.6 3.8 4.8 0.9 1.3

3.3 2.7 0.6 3.6 4.6 1.2 1.2

5.2 4.0 0.9 5.8 4.6 1.5 1.8

5.8 4.5 1.1 7.3 3.4

3.2 2.4 0.5 3.7 4.3 1.0 1.3

3.5 2.1 0.6 3.8 4.1 1.4 1.3

a

Alichanidis et al. (2016). Park (2011). Mayer and Fiechter (2012). d Merlin Jr. et al. (2015) (average data of two regions). b c

Chapter 10 Advanced strategies for dairy wastewater treatment: a perspective

vitamins, and minerals such as calcium, phosphorus, potassium, magnesium, and low amounts of iron, zinc, and copper. All these organic substances and minerals can be found in dairy wastewaters in different amounts. Ingredients used in milk-derived products may also be found in the water, including sweeteners, dyes, stabilizers, thickeners, and fruits debris. Cleaning and sanitizing agents also can reach the wastewater stream. The components shown in Table 10.1 are biodegradable, and most of the minor components and ingredients are used by the dairy industry. This result indicates that biological processes are well suited to treating dairy wastewaters. However, other industrial sectors (oil, pharmaceuticals, chemical, pulp, and paper) generate wastewaters that pose challenges to their adequate treatment, since they contain toxic and recalcitrant pollutants. Whey is the liquid stream that is generated during curd manufacturing. If a particular dairy plant does not recover or process whey, this voluminous stream will affect the treatment system with a high organic load, since it has elevated chemical oxygen demand (COD) and biochemical oxygen demand (BOD). The volume of whey corresponding to the production of 1 kg of cheese may be up to 9 L (Lappa et al., 2019). Whey composition varies according to the type of product being made and the production conditions. Sweet whey, acid whey, and salty whey have some differences in composition. The acid whey results from producing cottage cheese, strained yogurt, casein, and other products. Salty whey is generated during the production of cheddar cheese and different dry-salted dairy cheeses (Blaschek et al., 2007). Sweet whey is generated when enzymes are used in the curdling process to produce cheese or casein. The whey composition is variable and depends on milk characteristics and composition and on the curdling process. In general, the organic content of whey is high. Values of COD and BOD in the range of 65 80 g L21 and 20 35 g L21, respectively, were reported by Britz et al. (2004). A compilation of published data made by Carvalho et al. (2013) revealed a large variation in whey characteristics. The ranges of variation of some parameters were as follows: pH (3.8 6.5), BOD (27 60 g L21), COD (50 102 g L21), total suspended solids (TSS) (1.3 21.8 g L21), and lactose (42 60 g L21). If whey is not processed with the aiming of producing byproducts and is not consistently pretreated, it will severely affect any treatment system. An industrial stream presenting such high organic matter levels is undoubtedly a source of raw

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Table 10.2 Dairy industry wastewater characteristics. pH 3.4 5.6 3.4 5.8 6.0 4.0

8.1 8.3 9.5 7.2 9.0 11.0

TSS (g L21)

Fat (g L21)

COD (g L21)

BOD (g L21)

References

0.2 0.5 0.3 0.1 0.5 0.06

0.3 5.0

0.2 1.1 0.9 0.4 0.2 0.5

0.6 8.0 0.3 4.8 0.7 5.0

Britz et al. (2004) Shete and Shinkar (2013) Goli et al. (2019) Vourch et al. (2008) Yonar et al. (2018) Slavov (2017)

3.6 5.8 2.6 0.8 5.8 5.8

0.01 0.03 0.02 1.9

6.2 10.3 9.2 9.5 10.3 10.4

0.05 4.8 0.24 5.9

materials or products. A remark frequently made by technicians working with wastewater treatment states that “a high organic matter content in the wastewater means that the industry is losing raw materials, products or both.” Thus if the cheese industry does not process whey, the high organic load of the wastewater will affect the treatment system. Other dairy industry products (e.g., evaporated milk, ice cream, whey powders, yogurt) also may generate wastewaters with high organic matter and/or high-fat contents. Thus it is challenging to establish typical characteristics of dairy wastewaters. Each dairy industry, small or large, producing one or several products will generate specific wastewater. Data published on dairy wastewater characteristics reflect the industry’s variety of products, processes, and waste management techniques. Table 10.2 summarizes data surveys made by different authors. Values in the table were selected from surveys disregarding data of whey or whey-containing streams. Extreme values reported by the authors were judiciously disregarded too. In the case of the data reported in the last row of the table, only the results reported as “mixed dairy” by the author were considered. The parameters of dairy wastewater shown in Table 10.2 have large ranges of variation, indicating, as was mentioned earlier, that the wastewater characteristics are particular to a given industry. In addition, these characteristics can vary with time, production schedule, cleaning periods, and other factors.

10.4 10.4.1

Dairy industry wastewater treatments Preliminary treatments

Preliminary treatments are necessary to remove coarse and fine particles from the industrial effluents in the production

Chapter 10 Advanced strategies for dairy wastewater treatment: a perspective

units. The equipment that is used to remove such materials is simple and easy to operate and includes a bar screen, a grit chamber, or similar devices. This treatment step is essential to remove undesirable material that can clog pipes or channels and damage pumps and other equipment. An essential item that should be present upstream of the treatment system is the flow rate measurement device. Modern ultrasonic flowmeters can be used as well as classical meters such as a Parshall flume. Determining the wastewater flow rate is fundamental to controlling the treatment system and reporting the occurring daily flow variations. Instrumentation and automation of processes have had a considerable advance in the last decades. If exceptionally performing systems are in operation internally in the industrial sector, there is no reason not to install similar systems in the wastewater treatment processes. Recording the flow rate, pH, and temperature are fundamental to have correct control of the treatment operation. As has already been mentioned, a stirred equalization tank is also essential equipment. It can be installed after the flow rate measurement device to reduce the range of variation of wastewater parameters. In addition, if mixing is adequate, pH adjustment can be performed in that tank.

10.4.2

Physicochemical treatments

Coagulation/flocculation is a technique that has been intensively investigated in lab-scale experiments. Its use on an industrial scale is frequent in small and middle-sized industries. Alum, ferrous sulfate, and ferric chloride are the inorganic coagulants that have been most investigated. They promote high removal of turbidity and suspended solids and moderate removal of COD. Sludge is produced and should be disposed of or processed. The presence of metals in the sludge, mainly aluminum, is a concern because the health risks associated with this element are not completely clear and deserve more investigation (Willhite et al., 2014). Organic coagulants have also been investigated in lab-scale experiments. Tannins, chitosan, and powdered Moringa oleifera were employed in small-scale experiments with dairy wastewaters. Table 10.3 summarizes some results obtained in experiments of coagulation of industrial and synthetic dairy wastewaters. As seen in the table, high percentages of TSS and turbidity are removed ( . 90%), but COD removal rarely exceeds 70%. In addition, the adjustment of the raw wastewater pH would require volumes of acid or alkaline solutions. The coagulant

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Table 10.3 Reported performance of coagulation treatment of dairy wastewater. Wastewater

Coagulant

pH

Dose (mg L21)

Removal (%) COD TSS

Industrial

Ferric chloride Aluminum sulfate Calcium hydroxide Polyaluminum chloridea Chitosan Polyaluminum chloride Ferrous sulfate Potash alum Ferrous sulfate Aluminum sulfate Ferric chloride Aluminum Ferrous sulfate Alum 1 polyferric sulfate Alum 1 polyacrylamide

7 6.5 11 4 4 8 8 8 8.5 7.0 4.4 5 5

600 1000 630 1500 10 300 800 500 250 1000 250 1000 1000 1000 1 (20) 600 1 (20)

35 39 40 60 68 40 69 67 64 50 40 40 50 68 62 83 86

Industrial Synthetic

Industrial

Synthetic

91 89 94

References

Hamdani et al. (2004)

Sarkar et al. (2006) Kushwaha et al. (2010a)

93 91 75 95a 95a

Rivas et al. (2010)

Loloei et al. (2014)

a

Turbidity removal.

doses shown in the table reveal that large amounts of coagulants would be necessary to promote the reported removal efficiencies on an industrial scale because in many dairies the daily dose of wastewater surpasses hundreds of cubic meters. Electrocoagulation (EC), a physicochemical process, was investigated by several authors to treat dairy wastewaters. A survey of results obtained by this process was presented by Reilly et al. (2019). Wastewaters from the dairy industry, ice cream production, and synthetic effluents were submitted to EC in different lab-scale systems. Reported data were scattered: reaction time (20 120 min), removals of COD (49% 98%), TSS (65% 95%), turbidity (50% 100%). Wastewater characteristics also presented large variations. For instance, COD varied from 1200 to 18,300 mg L21 in different experiments. COD removal of 74% was obtained by treating industrial dairy wastewater using Fe-Al plate electrodes in an electrolytic cell (1-L). When air was injected during the reaction, a slight improvement in COD removal was attained (79.3%), and when the voltage was doubled to 5 V, a better result was achieved (86.4%). However, the

Chapter 10 Advanced strategies for dairy wastewater treatment: a perspective

bottom sludge and supernatant material amount corresponded to 8% and 25%, respectively, of the cell volume. The combination of EC with other processes was also investigated; the other processes included powdered carbon adsorption (Qasim and Mane, 2013), phytoremediation (Akansha et al., 2020) and Fenton oxidation (Torres-Sa´nches et al., 2014). Although many academic works on EC have been published, there is a lack of information about process performance in pilot or industrial-scale plants. As remarked in the in-depth review of EC made by Moussa et al. (2017), besides the advantages of high efficiency in removal of pollutants, no addition of chemicals, and less sludge production, some disadvantages are observed, such as the need to regularly replace the sacrificial anode, cathode passivation, and the dependence on electricity supply at a reasonable cost. Dissolved air flotation (DAF) is a physicochemical treatment that is used mainly in the dairy industry. Some of the biggest water technology companies have commercialized DAF cells and installations, which have been improved over time. DAF has been used for a long time to treat different wastewaters. A consistent review of DAF fundamentals has been presented by Edzwald (2010). Besides developing high-rate DAF, polymeric flocculants, synthetic or natural, are commercially available to enhance the separation process that occurs in the flotation cell. Since dairy wastewaters are rich in soluble organic matter, DAF, like other primary treatments, removes only part of the amount of organic matter that is present in the water phase. As shown in Table 10.4, COD removals rarely surpass 75% for industrial wastewaters. However, removal of turbidity, TSS, and oils and greases (O&G) may reach higher values. Data presented in the table were selected from articles published after 2010. Both preliminary and primary treatments generate sludges, which differ in composition and quantity. Grit chambers produce a sandy residue, generally in modest amounts, which can be sent to landfills. Bar screens retain coarse solids that can have the same destination as grit chamber residue. More voluminous sludges are produced in the chemical treatment with coagulants and flocculants. If mineral coagulants are used, metals like iron and aluminum will be present in these sludges, which may be carefully used in land application. Electrocoagulation also produces sludge that may contain metals. The sludge generated by DAF of dairy wastewater is usually scrapped from the top of the cell and sent to a container. The moisture content of this sludge may be high, and it has an increased range of fats, proteins, and other organic

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Table 10.4 Some reported results of DAF applied to dairy wastewaters. Wastewater

Removals (%) COD TSS O&G turbidity

References

Industrial Industrial Synthetic Industrial Industrial Synthetic Industrial Industrial Industrial Syntheticb

65.9 64 87.5 75 49 87.5 74.8 34.6 34.5 48.3 50.3 70

Babatola et al. (2011) Falletti et al. (2015) Pereira et al. (2018) Nagappan et al. (2018) Zylka et al. (2018) Pereira et al. (2020) Pereira et al. (2020) Pereira et al. (2020) Pereira et al. (2020) Muniz et al. (2020) Muniz et al. (2020) Yapicioglu and Yesilnakar (2020)

Syntheticc Industrial

92.2 65 97.8 37.7a

92.6 86.1 43.3

94.9

84.5 96.6

80.7 91.1 91.5 97

a

Total solids. Coagulant: ripe okra (Abelmoschus esculentus). Coagulant: passion fruit seeds (Passiflora edulis).

b c

substances, being a candidate for anaerobic digestion. The utilization of these sludges produced in the primary treatment of dairy wastewaters and the recovery of products from these residues will be discussed later in this chapter.

10.4.3

Biological treatments

Biological processes (anaerobic and aerobic) are often used to treat dairy wastewaters. Since most components of these streams are biodegradable, such processes are well suited to promote their depuration. In addition, they have affordable costs in comparison with other treatment techniques, which utilize chemicals and intensive energy for pollutants removal. However, the high organic loads and composition variability of dairy wastewaters may lead to operation problems and unsatisfactory performance of biological processes. Therefore the choice of anaerobic or aerobic biological treatment may consider the technical limitations of each one together with the wastewater characteristics, mainly quality and amount, aiming to achieve the highest performance possible. Aerobic processes have many advantages but cannot be operated at high organic loads (kgCOD m23 d21) as the

Chapter 10 Advanced strategies for dairy wastewater treatment: a perspective

anaerobic processes can. When intensive aeration is necessary, energy consumption contributes heavily to operation costs ˙ (Zyłka et al., 2021). High sludge production is also a drawback of aerobic processes, and sludge separation by sedimentation may be difficult in some cases, especially in activated sludge systems (Slavov, 2017). However, aerobic processes are robust enough, are easy to operate and start up, and achieve elevated organic matter and ammonium nitrogen removals. In some cases, the effluent has the quality required by local regulations for disposal in water bodies. Anaerobic processes can operate with high organic loads and low energy requirements. Additionally, sludge production is significantly lower than that observed in aerobic processes. Furthermore, biogas, a vital energy source, is produced under anaerobic conditions. However, several toxic substances and environmental conditions may inhibit the anaerobic microbial community, such as pH and temperature. Wastewaters that contain high levels of fats, as observed in the dairy industry, can pose challenges to anaerobic treatment. Long-chain fatty acids (LCFA) are slowly degraded and inhibit biodigestion (Cirne et al., 2007). In addition, their biodisponibility is small in the reaction medium (Battimelli et al., 2010). Fats may also cause operation problems, such as sludge flotation. Although some works suggest upper limits for fats contents in the feeding stream of anaerobic reactors, these values should be regarded with prudence, since fat composition is a complex and microbial adaptation is a common event. The complexity of the anaerobic microbial community requires careful process control. Therefore the organic load, hydraulic retention time, pH, alkalinity, and temperature should be monitored and controlled to ensure that the process will reach and keep the designed efficiency. Even the feed strategy of anaerobic reactors may have an essential effect on sludge properties (Tan et al., 2021a). The bibliography on the biological treatment of dairy wastes and wastewaters is vast, as reported by Goli et al. (2019), who made a compilation of published works on the subject. They verified that from 2000 to 2016, according to the database ISI Web of Knowledge, more than 1500 papers focused on aerobic treatment, and more than 5000 papers investigated anaerobic techniques. However, it should be underlined that the compilation refers to all wastes generated by the dairy production chain, including farm wastes. Biological treatments are preceded by physicochemical techniques and may be combined with posttreatments if the

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Figure 10.1 Schematic diagram showing biological process possibilities to dairy wastewater treatment.

requirements for effluent disposal are stringent or if water reuse is targeted. Considering the characteristics of anaerobic and aerobic processes, the combination of both is commonly made in the dairy industry. The technological development of wastewater treatment techniques (biological processes and reactors) makes a broad portfolio of technologies available. Thus the most appropriate system for a given dairy industry can be selected. Fig. 10.1 shows some biological treatment techniques that have been applied to dairy wastewater as reported in the technical literature. Although anaerobic processes are very suitable to treat dairy wastewaters, there is growing interest in aerobic processes based on batch reactors and/or immobilized biomass. Two treatment systems that have gained diffusion are the sequencing batch reactor (SBR) and the moving-bed biofilm reactor. The SBR can use one or several tanks and may be operated sequentially at different conditions: oxic and anoxic or anoxic and oxic. Such versatility allows removal of organic matter and performing of nitrification and denitrification. The reaction time at each condition can be monitored and controlled to keep the necessary process efficient. The utilization of immobilized biomass in SBR results in a biofilm sequencing batch reactor (BSBR). Ozturk et al. (2019) observed an improvement in COD and ammonium nitrogen removal treating industrial dairy wastewater when the conventional SBR was filled with plastic biofilm carriers. Khalaf et al. (2021) compared different pilotscale systems treating synthetic dairy wastewater: BSBR, SBR, conventional activated sludge, and biofilm activated sludge. The

Chapter 10 Advanced strategies for dairy wastewater treatment: a perspective

results showed that all systems led to high COD ( . 93%) and ammonium nitrogen ( . 89%) removal. The highest reductions were observed in the BSBR system: 97.8% COD and 93.2% ammonium nitrogen. Although the aerobic processes, which have developed considerably in the last decades, can be effectively applied to treat dairy wastewaters, anaerobic processes are always considered during the treatment plant design. Weights in this choice can operate with high organic loads and their potential to produce methane and even hydrogen as energy sources (Chandra et al., 2018). The Bulletin of the International Dairy Federation 500/ 2019, as cited by Brazzalle et al. (2019), indicated that the dairy industry is showing more interest in anaerobic processes (68% of the questionnaire responses). Stanchev et al. (2020) underlined the positive insertion of the anaerobic treatment in the context of the circular economy. The upflow anaerobic sludge bed reactor (UASB) has been extensively used to reduce the environmental impact of waste and wastewaters generated in the production chain of the dairy industry (Slavov, 2017). The research that has been conducted in recent years showed that excellent levels of organic matter removal can be achieved by using anaerobic hybrid reactors and biofilm reactors (Karadag et al., 2015; Goli et al., 2019). These treatment systems combine the typical configurations of consolidated reactor models (continuous stirred tank reactor, UASB, and expanded granular sludge bed) with mobile biofilm carriers or fixed media. A hybrid reactor fed with hydrolyzed synthetic dairy wastewater was investigated by De˛bowski et al. (2018). The reaction system consisted of a stirred tank to promote hydrolysis and a fluidized bed mechanically stirred anaerobic reactor. According to the authors, the utilization of microporous magnetic carriers was essential to increase process performance. The carriers were made of polyvinyl chloride modified with a blowing agent and blended with chemically pure copper and iron powder. The reaction system satisfactorily removed COD (maximum 77.5%) and phosphorus (about 90%). However, the removal of ammonium nitrogen in the proposed system was not achieved, as expected. Only 26% of the reduction was attained. The aggregation of metals to the carriers, according to the authors, seems to favor biodegradation by changing the redox potential due to metal oxidation and by increasing the buffering capacity of the reaction medium. Furthermore, as argued by the authors, the presence of metals can contribute to the formation of insoluble phosphate and ammonium ions, reducing the concentration of phosphorus and nitrogen in the water. Despite

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these arguments, the removal of ammonium nitrogen, as commented, was low in the reaction system. The search for new carriers for biofilm reactors and the development of hybrid reactors are very pertinent subjects; however, experiments with industrial wastewaters in pilot or full-scale systems are highly advisable for comparison with existing systems, determining operating costs, and process performance. Furthermore, an important aspect to be examined in biofilm anaerobic reactors is the production of scum, which is considered a frequent event (Mainardis et al., 2020). Another point that has been observed is methane production, since this energy source can be essential for the process economy. Wastewater quality is becoming an essential parameter because of the stricter requirements for effluent disposal and the growing interest in water reuse. In this context, membrane processes play an indispensable role. They complement the treatment process, generating high-quality effluent. The versatility of processes (microfiltration, ultrafiltration, nanofiltration, reverse osmosis) allows obtaining reuse water for different application purposes. The membrane processes may be used in a wastewater treatment plant aiming at other goals, such as effluent polishing, removal of specific pollutants, and biological treatment. In the last case, they constitute the category of membrane bioreactors (MBR). Two standard MBR configurations are available according to the membrane module localization, namely, submerged and sidestream, when the module is inside or outside the reaction tank, respectively. The main advantages of MBR over other technologies are the high levels of pollutant removal, resulting in an effluent with improved quality, and the effective separation of sludge from the liquid phase (Ozgun et al., 2013). However, some limitations associated with the MBR technology are membrane fouling and limited values of the ratio of food to microorganisms when highloaded wastewaters are treated aerobically (Erkan et al., 2018). Since the advantages overcome the disadvantages of MBR technology, its spread has been fast in several industrial sectors, including the dairy industry. Investigating several aspects of the technology and possible applications resulted in many published works about anaerobic and aerobic MBR systems. As a result, some international waste treatment companies have proposed environmental solutions based on aerobic MBR and/or anaerobic MBR (AnMBR). As an example, the dairy industry in Japan installed a membrane bioreactor to increase the capacity of its treatment plant. The results showed a significant improvement in effluent quality (COD ,7 mg L-1) and sludge

Chapter 10 Advanced strategies for dairy wastewater treatment: a perspective

separation, which was previously made by sedimentation (Brazzalle et al., 2019). An essential challenge to anaerobic treatment is the high level of fats in the wastewater. As was mentioned earlier, LCFAs have inhibitory effects on the biodigestion process. To overcome this challenge, some proposals have been made. Researchers at Minho University filed for a patent on a novel type of reactor that operates with an internal chamber for fat separation, named the inverted anaerobic sludge blanket reactor (Alves et al., 2007). A vital water technology company proposed a reactor (UASB) model with an internal chamber for fat flotation with biogas, which has the commercial name of BIOPACAFR. Leal et al. (2006) proposed a two-step process: hydrolysis of wastewater using an enzymatic preparation containing lipase and anaerobic treatment on a lab scale UASB. The supplementation of granular activated carbon to lipid-rich wastewater showed increased methanogenesis in lab-scale tests measuring biomethane potential (Tan et al., 2021b). Although the subject of fats influence on anaerobic reactor has been intensively studied, when designing or installing a treatment plant is advisable to consider and evaluate the possible adverse effect of these substances on anaerobic treatment performance. A compilation of bioreactor systems applied to the treatment of dairy wastewaters is shown in Table 10.5. The type of reactor and wastewater, the equipment scale, the organic load applied, and the removal efficiency are listed in that table. This compilation was restricted to works published in the last 5 years and illustrates the diversity of biological treatment alternatives for dairy wastewaters. In the review paper of Joshiba et al. (2019), classical bioreactors like aerated lagoons, trickling filters, anaerobic filters were presented and discussed together with more recent models of bioreactors (UASB, SBR, fluidized bed, etc.). Regardless of the process or the bioreactor type, process monitoring and control are essential for satisfactory operation and performance. As has already been noted, the instrumentation of the treatment process is fundamental, and nowadays, the availability of sensors and monitoring devices is abundant. The offline determination of crucial process parameters is also essential. Thus laboratory analysis and findings of critical parameters are necessary, such as BOD, COD, suspended solids, sludge volume index, extracellular polymeric substances (EPS), alkalinity, methane content in the biogas, volatile acids, ammonium, and phosphorus concentrations among others. The recent development of molecular techniques can shed light on the complex microbial ecology that is found in biological

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Table 10.5 Proposed bioreactors for dairy wastewater treatment. Bioreactor typea

Wastewater (scale)

Organic loading rate (kg CODm23 d21)

Removal efficiency (%)

References

SB-FFBR ICB-AnGS

Industrial Industrial full) Synthetic Synthetic

(lab) (lab and

0.38 8.19 20.0

COD (86.8 97.5) COD (80.0)

(lab) (pilot)

3.0 10.0 6.0 8.0

COD (75.0 95.0) COD (66.5 77.5) PT (82.9 90.7) COD (98.2) NH3-N (95.4) PO4-P (88.9) NH41-N (.95.0) PO4 3-P (.95.0) COD (93.5 6 8.1) NO3 (99.2 6 19) TKN (87.5 6 16.1) NH41 (55.8 6 8.3) COD (99.0)

Abdulgader et al. (2020) Charalambous et al. (2020) Couras et al. (2015) De˛bowski et al. (2018)

UASB HAnBR AsMBR

Primary industrial (lab)

7.5

IASBR

Industrial (pilot)

FBBR

Synthetic (lab)

2.62 6 0.36

AnMBR

Synthetic (lab)

4.7

Erkan et al. (2018)

Leonard et al. (2018) Hamdani et al. (2020)

Szabo-Corbacho et al. (2021)

a

AnMBR, Anaerobic membrane bioreactor; AsMBR, aerobic submerged membrane bioreactor; FBBR, fixed-bed bioreactor; HAnBR, hybrid anaerobic biofilm reactor; IASBR, intermittently aerated sequencing batch reactor; ICB-AnGS, internal circulation bioreactor— anaerobic granular sludge; SB-FFBR, sequencing batch flexible fiber biofilm reactor; UASB, upflow anaerobic sludge bed reactor.

reactors. A deep discussion of these techniques was presented by Bassin et al. (2018), which includes the fundamentals of polymerase chain reaction, denaturing gradient gel electrophoresis, fluorescent in situ hybridization, DNA microarray, and others. The cost of these techniques should soon decrease, and their utilization, as mentioned, will supply essential tools to monitor and control biological treatment processes.

10.4.4

Complementary treatments

In some industries the final effluent does not fulfill the quality requirements for disposal in water bodies even after primary and secondary treatments. Thus additional or complementary treatments are required. In this case, it is essential to determine what quality parameters surpass the limits of the local regulations to decide what type of treatment will be necessary. Some authors refer to this additional treatment as effluent or

Chapter 10 Advanced strategies for dairy wastewater treatment: a perspective

wastewater polishing. However, a different approach is adopted when the industry is interested in water reuse, since, depending on the reuse purpose, a more sophisticated treatment would be necessary. Membrane processes will not be commented on in this section; they will be addressed further in a case that will focus specifically on water reuse. The literature about tertiary treatment of biologically treated dairy wastewater is relatively scarce. However, wetlands have been investigated. Their advantages of low cost, ease of operation, and reasonable capacity to remove nutrients; their disadvantages are the need for careful vegetation management and sediment monitoring. In addition, their installation will require the availability of land, and their startup time can be long. In a study performed with small-scale wetlands, three macrophytes were used to treat the dairy effluent coming from an aerated basin (Triphati and Upadhyay, 2003). The best results were achieved with the combination of Eichhornia crassipes and Lemna minor, resulting in about 79% and 69% of nitrogen and phosphorus removals, respectively. In more recent work, Schierano et al. (2020) used a horizontal constructed wetland planted with Typha domingensis for tertiary treatment of dairy wastewater. The removal results that were obtained during 7 months of operation were approximately as follows: BOD (58%), COD (69%), nitrates (48%), and total phosphorus (30%). Thus the authors concluded that the investigated wetland might constitute an alternative for the tertiary treatment of dairy wastewater. Another tertiary treatment, based on the cultivation of microalgae, continues to attract the interest of many investigators. A review on this subject that enhanced the potential of microalgae to treat different wastewaters was presented by Mohsenpour et al. (2021). These authors consider that the algal treatment is environmentally friendly and economically viable. Kothari et al. (2012) cultivated the unicellular algae Chlorella pyrenoidosa in the effluent coming from an oxidation pond of a dairy industry. The following removals were attained after 10 days of cultivation: TSS (80%), nitrate (49%), and phosphate (83%). The cultivation of two species of Chlorella was investigated using the effluent from a dairy industry treatment plant under controlled temperature and luminous flux (Asadi et al., 2019). Removals of phosphate, nitrate, and ammonia were higher than 80%. Zkeri et al. (2021) reported the utilization of microalgae as a tertiary treatment of the dairy effluent from an anaerobic moving bed biofilm reactor (AnMBBR). The system consisting of the AnMBBR and the algal reactor generated an effluent with 26 mg.L21 COD and removed 65% of ammonium nitrogen and 31% of phosphate.

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Although there is broad interest in tertiary treatment using microalgae, the nonsterile condition and the variability of the wastewater characteristics (pH, temperature, composition) can cause process failure. Furthermore, most published results were obtained in lab-scale experiments. Long-term monitoring and operation of full-scale systems are necessary to validate microalgae technology applied to dairy wastewater treatment.

10.5

Recovery and valorization of wastewater components and treatment wastes

Dairy wastewaters contain many valuable compounds that can be recovered using techniques that are not very sophisticated. A critical component of the wastewaters is whey, which is discussed in detail in this section. Sludges or residues that are generated during wastewater treatment by physicochemical and biological processes can also be a source of energy or can be utilized for soil amendment. Depending on the treatment process used, the amount of residue that is produced is significant and calls for adequate management and disposal. Finally, the relevant issue of water reuse will be discussed in this section. Climate change is imposing more significant and severe drought periods in many countries, highlighting the need to focus on water reuse with extreme seriousness. Fig. 10.2 gives an overall view of the possibilities of valorization of dairy

Figure 10.2 Schematic diagram showing alternatives for valorization of dairy wastewater components.

Chapter 10 Advanced strategies for dairy wastewater treatment: a perspective

wastewater components that will be subsequently commented on in more detail.

10.5.1

Whey: recovering and processing

As was mentioned in Section 10.3, the physical and chemical characteristics of cheese whey impose careful management based on two principal facts: its high pollution impact if disposed inappropriately in the environment and the possibility of using whey in natura or in processed forms to generate new products or to recover valuable compounds. In addition, whey is a differentiated waste stream containing components with nutritional, functional, and biological properties. Whey management issues are related to the size of the cheese-making industry. Small and medium-scale producers, which are responsible for a large proportion of the cheese made worldwide, may have technical and economic difficulties even installing simple treatment systems. It is not rare to observe whey being disposed of on land as a soil conditioner, being used to feed animals, or being discarded in water bodies, causing severe pollution. These are not the best practices to be adopted. Discharge into water bodies without previous treatment should be prohibited, as is the case in many countries having well-established environmental regulations. The utilization of whey as a soil conditioner can damage the chemical and physical properties of soil as a result of its high content of salts and solids. The utilization of animal feed should be judiciously controlled, since high whey amounts on a diet can harm animal health. Whey processing, keeping in view economic and sustainability issues open a large window of opportunities. This is especially true because there was an enormous advance in the techniques used to process and recover valuable products from whey. It is interesting to note that the mid-70s United States and the United Kingdom have commercialized whey protein concentrate. However, only a tiny portion of the produced whey was processed to get that product. Nevertheless, in developing countries, some initiatives to recover valuable substances from whey were made (Marwaha and Kennedy, 1988). Despite the progress observed on the recovering and purification techniques, the valorization of whey components presents some challenges due to its chemical complexity, variable volumes daily produced, cost, and efficiency of the recovering processes. The magnitude of these challenges depends on the size of the dairy industry. Fortunately, science and technology have been

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developing whey processing techniques that provide an adequate cost-benefit ratio to small and medium-scale producers. When whey is not processed, it joins other streams that the industry produces. In such a case, whey largely contributes to the organic content of the global dairy wastewater. If whey is segregated and treated individually, the treatment system will receive a high organic load. It will operate in extreme conditions and increase costs, mainly with chemicals in coagulation or precipitation steps. High energy consumption will occur in the electrocoagulation process, and if membrane processes are used, fouling will increase, resulting in higher operating costs. Regarding biological processes, it is not advisable to treat raw whey without dilution with other wastewaters. Satisfactory performance of biological processes may be attained by submitting whey to previous treatments or coprocessing with other streams. Even so, the treated effluent will probably require further treatment before being discharged to water bodies. Aerobic biological process performance is highly affected by whey. Respirometric studies revealed 2.5-fold lower degradation rates when whey was incorporated into other dairy wastewaters (Janczukowicz et al., 2008). Treating whey by aerobic processes requires intense aeration and produces large amounts of sludge, resulting in an unfavorable technique (Asunis et al., 2020). Anaerobic processes can treat very charged wastewaters operating with high organic loads. Whey treatment by anaerobic routes will require high hydraulic retention times, in general greater than 1 day and possibly reaching 20 days in some cases. Supplementation of alkalinity is often necessary. Some problems should be overcome, such as biodegradation process instability, methanogenic inhibition caused by the accumulation of volatile fatty acids, and difficulty of granular sludge formation due to medium acidification (Prazeres et al., 2012; Asunis et al., 2020). The possibilities of recovering whey components besides the production of whey powder are very promising. Fig. 10.3 presents an overview of possible techniques for whey valorization. Whey processing is feasible because whey is rich in proteins, functional peptides, lipids, vitamins, minerals, and lactose. These substances can be the platform to obtain by chemical or biotechnological processes a variety of compounds and products, including functional foods, nutraceuticals, pharmaceutical and cosmetic products, biopolymers, and biofuels. Powdered whey, lactose, and whey proteins are valuable items with a consolidated market and well-established production methods. However, the cost of the processing techniques and the availability of large volumes of whey to reach high

Chapter 10 Advanced strategies for dairy wastewater treatment: a perspective

Figure 10.3 Schematic diagram showing possible techniques for whey valorization.

yields are limiting factors for small dairy companies. Large dairy companies have better conditions to conduct whey processing and obtain more valuable products. Powdered whey preserves whey properties for long periods, facilitating transportation and utilization with less loss of nutritional benefits (Ryan and Walsh, 2016). In addition, whey powder can be added to a broad range of food products for the general public or specifically for athletes or children. Lactic acid production by whey has been investigated for decades. Although there is a large and growing market for this product, many substrates have advantages over whey, such as sugarcane, cassava, and corn (Gran View Research, 2021). Some challenges of lactic acid production by fermentation are the necessity of hydrolyzing lactose, the inhibition caused by the substrate and product, and the formation of byproducts (Taleghani et al., 2018). Investigations to overcome such challenges are being conducted because lactic acid is an essential product and can produce polylactic acid. This polymer has applications as sustainable packaging to reduce the carbon footprint because it is made from renewable sources. Deproteinized hydrolyzed cheese whey was utilized to produce carotenoids using the fungus Blakeslea trispora (Roukas et al., 2015). Three carotenoids were obtained: β-carotene,

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lycopene, and γ-carotene. In addition, the culture medium was supplemented with Tween 80, Span 80, and β-ionone. The economic viability of the process needs to be evaluated and compared with that of other pathways used to produce carotenoids. Another exciting product that can be produced by using whey is bacterial cellulose. This product has many applications, and its production by the bacterial strain Gluconacetobacter sucrofermentans was investigated by Revin et al. (2018). Reasonable yields were obtained in a shaker incubator after 3 days of cultivation. A summary of works focusing on the production of bacterial cellulose using whey and its relevance was provided by Lappa et al. (2019).

10.5.1.1

Proteins

The high molar mass of these whey components favors the use of membrane techniques to recover these substances. The membrane ultrafiltration process can obtain the product known as whey protein. Whey protein concentrate may have 85% of proteins and significant amounts of lactose and carbohydrates. The whey protein isolate has a higher protein content (95%), and the whey protein hydrolysate has improved nutritional properties (Lu and Zhou, 2019). The different attributes of membrane processes can enhance the separation of whey components. For example, using previous centrifugation to remove fats and solids followed by microfiltration, ultrafiltration, and nanofiltration, Das et al. (2016) recovered proteins, lactose, and salts from whey at high yields, attenuating membrane fouling. An extensive review of the utilization of lactose and whey proteins to develop new products for the food industry, keeping in view process sustainability, was made by Lappa et al. (2019). Promising applications of whey proteins based on their specific properties include surface-active agents, texture modifiers, thickening agents, and emulsifiers. In addition, processing of whey proteins can generate macrostructures, microstructures, and nanostructures for use as delivery vehicles for bioactive ingredients: edible films and coatings, microgels, microspheres, nanohydrogels, and nanoparticles. Bioactive peptides can be obtained through the enzymatic hydrolysis of whey proteins. These substances have been studied because they can have health benefits (De Jesus et al., 2015). However, although promising properties are attributed to these peptides, there are also several challenges concerning biopeptide discovery and identification (Nongonierma et al., 2017).

Chapter 10 Advanced strategies for dairy wastewater treatment: a perspective

10.5.1.2

Lactose

The carbohydrate lactose is relatively abundant in whey (4.5% 5.8% w/v) and can be recovered and commercialized after purification or may be used to obtain sirups (lactose or lactose-hydrolyzed). In addition, galactooligosaccharides (GOS) and other particular carbohydrates with nutraceutical properties can be obtained from lactose. Enzymes or inorganic catalysts catalyze the transformation of lactose in such compounds. Some lactose-derived products that can be produced are GOS, lactulose, lactosucrose, lactitol, lactobionic acid, and tagatose (Lifran et al., 2009). The research on the production of particular carbohydrates obtained from lactose is intense. Lactose fatty acid esters constitute compounds produced by esterification reactions catalyzed by lipases (Lappa et al., 2019). High yields of ester synthesis were achieved when palmitic and lauric acids were used (Enayati et al., 2018). However, long reaction times were necessary to reach these yields under the investigated reaction conditions. Despite the large number of products that can be obtained from lactose, a byproduct of the dairy industry, most companies do not have the necessary expertise and structure to produce these fine chemicals manufactured by the pharmaceuticals and chemical industries. Therefore the more superficial chemical transformation that is done by many dairy companies is the hydrolysis of lactose to produce lactose-free milks, milk powders, and yogurts. As a result, the market for lactose-free products grew about 7.3% in recent years, as reported by Dekker et al. (2019). Ethanol can be produced by fermentation of culture media containing lactose. Several companies around the world make this fuel from whey. In general, whey is submitted to ultrafiltration, resulting in a permeate containing lactose and a concentrate that is rich in whey proteins. The permeate that is obtained by ultrafiltration or further concentrate is generally used in the fermentation process. Some yeasts can convert lactose in ethanol, particularly some organisms of the genus Kluyveromyces. Large-scale production of ethanol from whey started in 1978 in Ireland (Ling, 2008). Since then, other dairy companies have started ethanol production utilizing different microbial strains and fermentation systems. This subject has aroused many researchers investigating genetically modified bacteria and yeasts with increased ability to produce ethanol and resistance to high ethanol and salt concentrations in the fermentation medium.

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Filamentous fungi generally have a low assimilative capacity for lactose; however, a strain of basidiomycete fungus (Neolentinus lepideus) could produce ethanol from whey, diluted whey, and whey concentrate at yields of 0.35, 0.38, and 0.32 g ethanol, respectively, per gram of lactose (Okamoto et al., 2019). These results, albeit promising, are inferior to those obtained by the process developed by a US innovation company that uses ethanol and salttolerant yeast strains in its reaction system, which can reach yields of 0.46 0.49 g ethanol per gram of lactose (Ling, 2008). Although ethanol is not a high-value product, it has environmental importance as a substitute for fossil fuels. During its distillation, a concentrate liquid, stillage, is produced and can be anaerobically digested to produce methane. As was previously reported, there are many possibilities to process whey and obtain useful or valuable products. However, each possible valorization route should be carefully examined concerning its economic and technical viability. Even the wastes that are generated in a given route can make it unfeasible. A contribution to an integrated vision of whey valorization is provided by the concept of biorefinery, which may combine physical, chemical, and biological processes. According to this concept, several chemical substances can be obtained from whey, such as lactic acid, probiotics, hydrolyzed proteins, and bioactive peptides. Furthermore, biogas can be produced from wastes. Asunis et al. (2020) and Sebastia´n-Nicola´s et al. (2020) have done an in-depth review on whey biorefinery issues and highlighted the promising results that can be achieved by applying this concept in the dairy industry. However, these authors also stated that more studies are necessary to confirm the economic and technical viability of the biorefinery approach, in particular for large-scale dairies.

10.5.2

Sludges from primary and secondary treatments

Dairy wastewater offers several opportunities for recovering substances and products. However, it is difficult to find uses for some residues, since their intrinsic value is not high. This is the case for the wastes that are produced in the primary treatment, including chemical coagulation, electrocoagulation, or DAF. Reports about the amounts and composition of the wastes produced in such treatments are scarce. Kushwaha et al. (2010b) studied the electrochemical treatment of synthetic dairy wastewater and gave attention to the

Chapter 10 Advanced strategies for dairy wastewater treatment: a perspective

elemental composition of the sludge and the scum produced by the process. The sludge had the following elemental composition: 60.5% carbon, 26.5% oxygen, 0.72% aluminum, 0.21% sulfur, 0.32% potassium, 0.89% calcium, and 10.9% iron. The scum had a higher content of carbon (82.7%) and 10.4% oxygen, 0.85% aluminum, 0.5% sulfur, 0.2% potassium, 0.91% calcium, and 4.45% iron. The authors determined that the ignition temperature of both residues was 200 C. They suggested that these residues can be dried and used as fuel in industrial activities or the production of fuel briquettes. Sludges from the coagulation process are potential candidates for application in soil, but agricultural regulations should be judiciously observed, as was pointed out by Hamdani et al. (2004). These authors also suggested incineration and landfilling as adequate destinations of coagulation sludges. On the other hand, Kushwaha et al. (2010a) considered that the sludges from the coagulation of dairy wastewaters, like the slurries from the electrochemical process, could be used as fuel or production fuel-briquettes. The floated material that is obtained during dairy wastewater’s DAF was investigated for biogas production. This residue has a consistency of mousse and high moisture content, but it is difficult to filter. The composition of this residue was reported by Pascale et al. (2019), as follows: density 0.94 kg L21, moisture 84.5%, pH 5.3, alkalinity 1.27 gCaCO3 L21, proteins 10.2 g L21, O&G 12.5%, lipids 54.8 g L21, total LCFA 5.85 g L21. These authors investigated the hydrolysis of the residue using a commercial lipase before anaerobic treatment. The maximum specific methane production attained in 5-day digestion assays was 2.46 mL g21 of residue. Bila et al. (2016) presented the following characteristics for the floated material of the dairy industry: density 0.95 kg L21, pH 6.0, moisture 94.5%, total solids 54 g L21, volatile solids 45.4 g L21. The specific methane production that was attained after 63 days of digestion was 35 mL g21 of residue when enzymatic prehydrolysis was performed. The addition of flotation residue to sewage sludge to feed an anaerobic digester was investigated by Hubert et al. (2020). The results indicate that the digestor that was provided with the more significant amount of flotation residue, corresponding to the highest organic load applied, could operate adequately. Its organic load was almost twice that of the control digester, which was fed exclusively with sewage solids. However, the adaptation of the digestion process to high amounts of flotation waste in the feed mixture should be carefully performed to avoid digester failure. In addition, high levels of ammonium

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nitrogen were found in the effluent when flotation residue was fed to the digester. The dried residue that was obtained from DAF using tannin as a coagulant was investigated by Justina et al. (2018). Promising results indicated that the sludge had excellent potential for soil conditioning. However, in a later study, Justina and Skoronski (2020) determined that some pollutants are solubilized from the residue and concluded that limits should be considered for its successful agronomical application. Sludges that are produced during biological treatment of dairy wastewaters differ from primary treatment sludges in their composition, properties, and characteristics. Sludges from aerobic and anaerobic treatment systems also present many differences. The aerobic treatment produces large amounts of sludge that may be submitted to conventional treatments, including sludge thickening, sludge drying, and further solids disposal. The anaerobic treatment of the aerobic wasted sludge may be an alternative to enhance methane production. However, the hydrolysis of the EPS that is present in the sludge flocs is slow. Therefore several techniques have been proposed to promote floc disintegration and liberation of substrates for anaerobic conversion. Based on thermal, chemical, ultrasonic, and thermochemical processes, these techniques have been investigated to enhance the anaerobic digestion efficiency of biosolids from the conventional activated sludge process (Kim et al., 2003). The application of sono-alkalization was examined to treat dairy waste-activated sludge, and a significant improvement (80%) in biogas production was obtained (Rani et al., 2014). In addition, microwave disintegration of sludge with hydrogen peroxide in an acidic medium was investigated by Eswari et al. (2017). According to the authors, this treatment enhanced sludge EPS dissociation and improved methane yield in the anaerobic digestion process. A different approach was adopted by Balasubramanian et al. (2018), who investigated the production of biodiesel from dairy wastewater sludge. Before biodiesel production assays, the dewatered and dried sludge was processed (lipid extraction, degumming, dewaxing). The best results led to the production yield of 13.6% of biodiesel (on a weight basis) from dairy sludge.

10.5.3

Water reuse

Reusing water in the dairy industry reduces wastewater treatment costs and environmental impacts related to the disposal of large volumes of effluents in water bodies. In addition,

Chapter 10 Advanced strategies for dairy wastewater treatment: a perspective

it reduces the consumption of water by the industry, favoring a circular economy and promoting more sustainable production processes. However, as has already been mentioned, the complexity and variability of the characteristics of dairy industry effluents pose difficulties for the practice of water reuse, especially for small-scale producers. In general, reuse practices remain limited to internal applications that do not require water that has a high level of quality. Some typical applications are washing of floors or external parts of trucks, replacing water in cooling towers or boilers, rinsing outside areas, and sanitary discharges in toilets (Velpula et al., 2017). In the food industry, to avoid contamination, the applications of reused water are strictly limited and even prohibited in the production steps (Galva˜o, 2018). A barrier preventing the extension of water reuse internally is the strict requirement of removing microorganisms, chiefly pathogenic ones (Finnegan et al., 2018). Disinfection of water at levels required for utilization in dairy processing steps can have unaffordable costs. To reach the chemical and physical characteristics required for simple applications such as washing, cooling, or heating, membrane processes are well suited, as was noted in Section 10.4.3. Membranes are versatile because they can be made of different materials and present varied pore sizes and module configurations. They can be designed to operate in microfiltration, ultrafiltration, and nanofiltration processes and reverse osmosis systems. Therefore membrane technology is a fundamental tool to separate molecules and ions from wastewater. If water reuse is targeted, membrane techniques are always potential candidates for this purpose. However, they are not the only solution available in some cases and can be combined with other techniques. As has already been mentioned, MBR technology combines biological processes with separation by membranes. In general, the MBR effluent has better quality than that of effluent from conventional biological treatment. The quality of MBR effluent can be improved if it is submitted to nanofiltration. Andrade et al. (2015) utilized this combination to obtain water for cooling towers, steam generation in low-pressure boilers, and cleaning floors and external areas of a dairy company. A survey conducted with 11 French dairy companies revealed that potable water from the public network supplied 11% 75% of the water consumed by all industries, except one supplied mainly with groundwater. The contribution of vapor condensate in 10 industries ranged from 20% to 48% of the total water consumption. Reverse osmosis generated water with a

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quality similar to vapor condensates for cooling, heating, and cleaning purposes (Vourch et al., 2008). In some cases, the strict regulation on wastewater disposal demands efficient treatment techniques that generate effluents with a level of quality compatible with reuse waters. Working with a pilot MBR with an external tubular ultrafiltration module, Fraga et al. (2017) obtained an effluent with enough quality to be discharged and/or reused by the dairy industry. The utilization of membrane technology in the dairy industry has operating and capital costs as adverse aspects. In addition, membrane fouling affects filtration rates and membrane lifetime, increasing costs. Energy consumption by MBRs may reach 6 kWh m23 of treated effluent, and membranes need to be replaced every 2 5 years (Brazzalle et al., 2019). However, membrane supply companies research antifouling materials, module design, and cleaning strategies, ensuring more stable operation. These companies are also seeking to reduce operating costs and develop more robust systems. In the context of the dairy industry, if water reuse is the goal, membrane processes will undoubtedly be chosen for such a purpose.

10.6

Conclusions and future trends

The dairy industry is very diverse in terms of production capacity, revenues, types of milk processed, portfolio of products, technological level, and environmental concerns. Currently, the industry should be very attentive to society’s demands, which include ESG criteria. Consumers are not just demanding high-quality of products. Many countries observe the entire production chain and call for transparency, environmental commitment, and responsible social engagement. Due to their diversity, not all dairy companies have conditions to respond to the new demands of society, but they need to strive to face these new challenges. Concerning environmental issues, knowledge and resoluteness are essential attributes to face problems and challenges. In wastewater treatment, which was the object of this chapter, a deep preliminary investigation on water uses and losses and the pollution impact of every production sector is highly advisable (Bria˜o and Tavares, 2008). Many technologies are available to generate a final effluent that meets the disposal or discharge requirements. The choice of the treatment methods should consider process efficiency and sustainability, costs, availability of space or land, among other factors.

Chapter 10 Advanced strategies for dairy wastewater treatment: a perspective

The way wastewaters are viewed currently differs from the end-of-pipe approach that was often adopted in the past. It is possible to look at wastewaters as sources of energy, chemical substances, and water. The concept of “recover, recycle, and reuse” is gaining diffusion within waste and wastewater management. In the dairy industry, wastewater can be a source of different products, energy, and water. If whey is the focus, for instance, proteins have a high value, and several products based on whey proteins are found in the market, presenting nutraceutical properties. Lactose obtained from whey may be processed to give sirups that can be used in the food industry. From lactose, other valuable carbohydrates can be obtained, such as GOS. Other valuable products can be obtained by using biotechnological processes, and the concept of biorefinery can be used to prove the whey potential as a source of energy and chemicals. Some promising chemicals obtained from whey biotransformation are carotenoids and bacterial cellulose (Lappa et al., 2019). A broad class of compounds can be obtained by fermentation, such as ethanol, lactic acid, and volatile fatty acids. Some additional bioprocesses can convert these substances into lactic acid polymers or polyhydroxyalkanoates (Asunis et al., 2020). Whey-to-fuel ethanol has been a necessary process in operation since the 1980s, as reported by Ling (2008). The report states that the process is technically feasible, mature, and economically viable. Industrial plants are in operation in several countries, including New Zealand, the United States, and Ireland. Dairy wastewaters, with or without whey recovery, can be anaerobically treated, generating methane. This energy source can replace the utilization of oil fuel and/or reduce electricity consumption by the industry. Water for industrial use can also be obtained from wastewaters. It is worth mentioning that the development of membrane processes had many beneficial effects on the dairy industry. The membrane-based process can recover proteins, concentrate streams, remove solids and generate water with the level of quality required for industrial reuse purposes. Even the retentate stream of membrane processes can be a source of inorganic or organic substances of interest. Small dairy companies should be prepared and attentive to avoid environmental impacts. If they do not treat their wastewaters adequately and damage the natural water receiving systems, the consequences will negatively affect their reputation. As reviewed in this chapter, there is an arsenal of efficient treatment techniques with affordable costs that must and can be installed by the industries. Thus the dairy industries can strictly

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control their wastewaters and advance sustainability by recovering, recycling, and reusing water and materials.

List of acronyms AnMBBR AnMBR AsMBR BOD BSBR COD DAF EC EPS ESG FBBR GOS HAnBR IASBR ICB-AnGS LCFA MBR MBBR O&G RRR SBR SB-FFBR TSS UASB

anaerobic moving bed biofilm reactor anaerobic membrane bioreactor aerobic submerged membrane bioreactor biochemical oxygen demand biofilm sequencing batch reactor chemical oxygen demand dissolved air flotation electrocoagulation extracellular polymeric substances environmental, social, and governance fixed-bed bioreactor galactooligosaccharides hybrid anaerobic biofilm reactor intermittently aerated sequencing batch reactor internal circulation bioreactor—anaerobic granular sludge long-chain fatty acids membrane bioreactors moving-bed biofilm reactor oils and greases recover, recycle, and reuse sequencing batch reactor sequencing batch flexible fiber biofilm reactor total suspended solids upflow anaerobic sludge bed

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UASB reactors: Influence of effluent recirculation. Environmental Technology, 36(17), 2272-2238. Das, B., Sarkara, S., Sarkara, A., Bhattacharjeeb, S., & Bhattacharjee, C. (2016). Recovery of whey proteins and lactose from dairy waste: A step towards green waste management. Process Safety and Environmental, 101, 27 33. De Jesus, C. S. A., Ruth, V. G. E., Daniel, S.-F. R., & Sharma, A. (2015). Biotechnological alternatives for the utilization of dairy industry waste products. Advances in Bioscience and Biotechnology, 6, 223 235. ´ De˛bowski, M., Zielinski, M., Kisielewska, M., Krzemieniewski, M., Makowska, M., ´ ˛tek, A. (2018). Simulated dairy wastewater Gra˛dkowski, M., & Tor-Swia treatment in a pilot plant scale magneto-active anaerobic biofilm reactor (MA-HABR). Brazilian Journal of Chemical Engineering, 359(02), 553 562. Dekker, P. J. T., Koenders, D., & Bruins, M. J. (2019). Lactose-free dairy products: Market developments, production, nutrition and health benefits. Nutrition (Burbank, Los Angeles County, Calif.), 11(551), 11030551. Edzwald, J. K. (2010). Dissolved air flotation and me. Water Research, 44, 2077 2106. Enayati, M., Gong, Y., Goddard, J. M., & Abbaspourrad, A. (2018). Synthesis and characterization of lactose fatty acid ester biosurfactants using free and immobilized lipases in organic solvents. Food Chemistry, 266(15), 508 513. Erkan, H. S., Turan, N. B., & Engin, G. O. (2018). Chapter Five—Membrane bioreactors for wastewater treatment. Comprehensive Analytical Chemistry., 81, 151 200. Eswari, A. P., Kavitha, S., Banu, J. R., Karthikeyen, O. P., & Yeom, I.-T. (2017). H2O2 induced cost effective microwave disintegration of dairy waste activated sludge in acidic environment for efficient biomethane generation. Bioresource Technology, 244(1), 688 697. Falletti, L., Conte, L., Zaggia, A., Battistini, T., & Garosi, D. (2015). Food industry wastewater treatment plant based on flotation and MBBR. Modern Environmental Science and Engineering, 1(2), 94 98. FAO-UN (2021, April). Food and Agriculture Organization of the United Nations, Dairy Market Review ,http://www.fao.org/3/cb4230en/cb4230en.pdf. Accessed 21.08.18. Finnegan, W., Clifford, E., Goggins, J., O’Leary, N., Dobson, A., Rowan, N., . . . Zhan, X. (2018). Dairywater: Striving for sustainability within the dairy processing industry in the Republic of Ireland. The Journal of Dairy Research, 85, 366 374. Fraga, F. A., Garcı´a, H. A., Hooijmans, C. M., Mı´guez, D., & Brdjanovic, D. (2017). Evaluation of a membrane bioreactor on dairy wastewater treatment and reuse in Uruguay. International Biodeterioration and Biodegradation, 119, 552 564. Available from https://doi.org/10.1016/j.ibiod.2016.11.025. Galva˜o, D. F. (2018). Membrane technology and water reuse in a dairy industry, technological approaches for novel applications in dairy processing. Nurcan Koca. IntechOpen. Available from http://doi.org/10.5772/intechopen.76464. Available from https://www.intechopen.com/chapters/61182. Goli, A., Shamiri, A., Khosroyar, S., Talaiekhosani, A., Sanaye, R., & Azizi, K. (2019). A review on aerobic and anaerobic treatment methods in dairy industry wastewater. Journal of Environmental Treatment Techniques, 6(1), 113 141. Gran View Research (2021). Polylactic acid market size, share & trends analysis report by end-use (packaging, textile, agriculture, automotive & transport, electronics). By region (North America, APAC, Europe), and segment forecasts, 2021 2028, ,https://www.grandviewresearch.com/industryanalysis/lactic-acid-and-poly-lactic-acid-market. Accessed 21.31.08.

Chapter 10 Advanced strategies for dairy wastewater treatment: a perspective

Hamdani, A., Amrane, A., Yettefi, I. K., Mountadar, M., & Assobhei, O. (2020). Carbon and nitrogen removal from a synthetic dairy effluent in a vertical-flow fixed bed bioreactor. Bioresource Technology Reports, 12, 100581. Hamdani, A., Chennaoui, M., Assobhei, O., & Mountadar, M. (2004). Caracte´risation et traitement par coagulation-de´cantation d’un effluent de laiterie. Le Lait, 84, 317 328. Hubert, C., Steiniger, B., & Schaum, C. (2020). Residues of the dairy industry as cosubstrate for the flexibilization of digester operation. Water Environment Research: A Research Publication of the Water Environment Federation, 92, 534 540. Janczukowicz, W., Zielinsk, M., & Debowski, M. (2008). Biodegradability evaluation of dairy effluents originated in selected sections of dairy production. Bioresource Technology, 99(10), 4199-4125. Joshiba, G. J., Kumar, P. S., Femina, C. C., Jayashree, E., Rocchana, R., & Sivanesan, S. (2019). Critical review on biological treatment strategies of dairy wastewater. Desalination and Water Treatment, 160, 94 109. Justina, M. D., Alves, M. V., & Skoronski, E. (2018). Applying different doses of tannin coagulated dairy sludge in soil: Influences on selected pollutants leaching and chemical agronomic attributes. Agricultural Water Management, 209, 11 19. Justina, M. D., & Skoronski, E. (2020). Environmental and agronomical aspects of sludge produced from tannin-based coagulants in dairy industry wastewater treatment. Waste Biomass Valorization, 11, 1385 1392. Karadag, D., Ko¨ruglu, O. E., Ozkaya, B., & Cakmakci, M. (2015). A review on anaerobic biofilm reactors for the treatment of dairy industry wastewater. Process Biochemistry, 50, 262 271. Khalaf, A. H., Ibrahim, W. A., Fayed, M., & Eloffy, M. G. (2021). Comparison between the performance of activated sludge and sequence batch reactor systems for dairy wastewater treatment under different operating conditions. Alexandria Engineering Journal, 60(1), 1433 1445. Kim, J., Park, C., Kim, T.-H., Lee, M., Kim, S., Kim, S.-W., & Lee, J. (2003). Effects of various pretreatments for enhanced anaerobic digestion with waste activated sludge. Journal of Bioscience and Bioengineering, 95(3), 271 275. Kothari, R., Pathak, V. V., Kumar, V., & Singh, D. P. (2012). Experimental study for growth potential of unicellular alga Chlorella pyrenoidosa on dairy wastewater: An integrated approach for treatment and biodiesel production. Bioresource Technology, 116, 466 470. Kushwaha, J. P., Srivastava, V. C., & Mall, I. D. (2010a). Organics removal from dairy wastewater by electrochemical treatment and residue disposal. Separation and Purification Technology, 76, 198 205. Kushwaha, J. P., Srivastava, V. C., & Mall, I. D. (2010b). Treatment of dairy wastewater by inorganic coagulants: Parametric and disposal studies. Water Research, 44, 5867 5874. Lappa, I. K., Papadaki, A., Kachrimanidou, V., Terpou, A., Koulougliotis, D., Eriotou, E., & Kopsahelis, N. (2019). Cheese whey processing: Integrated biorefinery concepts and emerging food applications. Foods MDPI, 8(8), 37. Leal, M. C. M. R., Freire, D. M. G., Cammarota, M. C., & Sant’Anna, G. L., Jr. (2006). Effect of enzymatic hydrolysis on anaerobic treatment of dairy wastewater. Process Biochemistry, 41, 1173 1178. Leonard, P., Tarpey, E., Finnegan, W., & Zhan, X. (2018). Efficient treatment of dairy processing wastewater in a pilot scale intermittently aerated sequencing batch reactor (IASBR). The Journal of Dairy Research, 85(3), 384 387. Lifran, E. V., Hourigan, J. A., & Sleigh, R. W. (2009). Lactose derivatives: Turning waste into foods. Australian Journal of Dairy Technology, 64(1), 89 93.

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Ling, K. C. (2008). Whey to ethanol: A biofuel role for dairy cooperatives? United States development agency. Rural Development. Res. Rep, 214, 27. Loloei, M., Alidadi, H., Nekonam, G., & Kor, Y. (2014). Study of the coagulation process in wastewater treatment of dairy industries. International Journal of Environmental Health Engineering, 2(5), 17 21. Lu, N., & Zhou, P. (2019). Whey protein-based nutrition bars. In H. C. Deeth, & N. Bansal (Eds.), Whey proteins: from milk to medicine (pp. 495 517). Cambridge: Academic Press. Mainardis, M., Buttazzoni, M., & Goi, D. (2020). Up-flow anaerobic sludge blanket (UASB) technology for energy recovery: A review on state-of-the-art and recent technological advances. Bioeng, 7(43), 7020043. Marwaha, S. S., & Kennedy, J. F. (1988). Whey-pollution problem and potential utilization. Institute of Food Science and Technology (IFST), 23(4), 323 336. Mayer, H. K., & Fiechter, G. (2012). Physical and chemical characteristics of sheep and goat milk in Austria. International Dairy Journal, 24(2), 57 63. Merlin Jr., I. A., dos Santos, J. S., Costa, L. G., Costa, R. G., Ludovico, A., Rego, F. C. A., & Santana, E. H. W. (2015). Sheep milk: Physical-chemical and microbiological quality. Archivos Latinoamericanos de Nutricion, 65(3), 193 198. Mohsenpour, S. F., Hennige, S., Willoughby, N., Adeloye, A., & Gutierrez, T. (2021). Integrating micro-algae into wastewater treatment: A review. The Science of the Total Environment, 752, 142168. Moussa, D. T., El-Naas, M. H., Nasser, M., & Al-Marri, M. J. (2017). A comprehensive review of electrocoagulation for water treatment: Potentials and challenges. Journal of Environmental Management, 186(1), 24 41. Muniz, G. L., da Silva, T. C. F., & Borges, A. C. (2020). Assessment and optimization of the use of a natural coagulant (Guazuma ulmifolia) for dairy wastewater treatment. The Science of the Total Environment, 744, 140864. Nagappan, S., Phinney, D. M., & Heldman, D. R. (2018). Management of waste streams from dairy manufacturing operations using membrane filtration and dissolved air flotation. Applied Sciences, 8(12), 2694. Nongonierma, A. B., Lalmahomed, M., Paolella, S., & FitzGerald, R. J. (2017). Milk protein isolate (MPI) as a source of dipeptidyl peptidase IV (DPP-IV) inhibitory peptides. Food Chemistry, 231, 202 211. Okamoto, K., Nakagawa, S., Kanawaku, R., & Kawamura, S. (2019). Ethanol production from cheese whey and expired milk by brown rot fungus Neolentinus lepideus. Fermentation, 5(2), 49, 5020049. Ozgun, H., Dereli, R. K., Ersahin, M. E., Kinaci, C., Spanjers, H., & van Lier, J. B. (2013). A review on anaerobic membrane bioreactors for municipal wastewater treatment: Integration options, limitations and expectations. Separation and Purification Technology, 118, 89 104. Ozturk, A., Aygun, A., & Nas, B. (2019). Application of sequencing batch reactor biofilm reactor (SBBR) in dairy wastewater treatment. Korean Journal of Chemical Engineering, 36(2), 248 254. Park, Y. W. (2011). Goat milk: Composition and characteristics, . (2nd ed., pp. 537 540). Encyclopedia of animal science, (II, pp. 537 540). CRC Press. Pascale, N. C., Chastinet, J. J., Bila, D. M., Sant’Anna, G. L., Jr., Quite´rio, S. L., & Vendramel, S. M. R. (2019). Enzymatic hydrolysis of floatable fatty wastes from dairy and meat food-processing industries and further anaerobic digestion. Water Science and Technology: A Journal of the International Association on Water Pollution Research, 79(5), 985 992. Pereira, M. S., Borges, A. C., Heleno, F. F., Squillace, L. F. A., & Faroni, L. R. D. (2018). Treatment of synthetic milk industry wastewater using dissolved air flotation. Journal of Cleaner Production, 189(10), 729 737.

Chapter 10 Advanced strategies for dairy wastewater treatment: a perspective

Pereira, M. S., Borges, A. C., Muniz, G. L., Heleno, F. F., & Faroni, L. R. D. (2020). Dissolved air flotation optimization for treatment of dairy effluents with organic coagulants. Journal of Water Process Engineering, 36, 101270. Prazeres, A. R., Carvalho, F., & Rivas, J. (2012). Cheese whey management: A review. Environmental Management, 110, 48 68. Qasim, W., & Mane, A. V. (2013). Characterization and treatment of selected food industrial effluents by coagulation and adsorption techniques. Water Resources and Industry, 4, 1 12. Ramalho, R. S. (1977). Introduction to wastewater treatment processes. New York: Academic Press Inc. Rani, R. U., Kumar, S. A., Kaliappan, S., Yeom, I.-T., & Banu, J. R. (2014). Enhancing the anaerobic digestion potential of dairy waste activated sludge by two step sono-alkalinization pretreatment. Ultrasonics Sonochemistry, 21, 1065 1074. Reilly, M., Cooley, A. P., Tito, D., Tassou, S. A., & Theodorou, M. K. (2019). Electrocoagulation treatment of dairy processing and slaughterhouse wastewaters. Energy Procedia, 161, 343 351. Revin, V., Liyaskina, E., Nazarkina, M., Bogatyreva, A., & Shchankin, M. (2018). Cost-effective production of bacterial cellulose using acidic food industry byproducts. Brazilian Journal of Microbiology, 49S, 151 159. Rivas, J., Prazeres, A. R., Carvalho, F., & Beltra´n, F. (2010). Treatment of cheese whey wastewater: Combined coagulation-flocculation and aerobic biodegradation. Journal of Agricultural and Food Chemistry, 58(13), 7871 7877. Roukas, T., Varzakakou, M., & Kotzekidou, P. (2015). From cheese whey to carotenes by Blakeslea trispora in a bubble column reactor. Applied Biochemistry and Biotechnology, 175(1), 182 193. Ryan, M. P., & Walsh, G. (2016). The biotechnological potential of whey. Reviews in Environmental Science and Biotechnology, 15, 478 498. Sarkar, B., Chakrabarti, P. P., Vijaykumar, A., & Kale, V. (2006). Wastewater treatment in dairy industries—Possibility of reuse. Desalination, 195, 141 152. Schierano, M. C., Panigatti, M. C., Maine, M. A., Griffa, C. A., & Boglione, R. (2020). Horizontal subsurface flow constructed wetland for tertiary treatment of dairy wastewater: Removal efficiencies and plant uptake. Journal of Environmental Management, 272, 111094. Sebastia´n-Nicola´s, J. L., Gonza´lez-Olivares, L. G., Va´zquez-Rodrı´guez, G. A., ˜ eda-Ovando, A. (2020). Valorization of whey Lucho-Constatino, C. A., & Castan using a biorefiner, . Biofuels, Bioproducts and Biorefining (14, pp. 1010 1027). . Available from http://doi.org/10.1002/bbb.2100. Shete, B. S., & Shinkar, N. P. (2013). Dairy industry wastewater sources, characteristics & its effects on environment. International Journal of Current Engineering and Technology, 3(5), 1611 1615. Slavov, A. K. (2017). General characteristics and treatment possibilities of dairy wastewater—A review. Food Technology and Biotechnology., 55(1), 14 28. Stanchev, P., Vasilaki, V., Egas, D., Colon, J., Ponsa´, S., & Katsou, E. (2020). Multilevel environmental assessment of the anaerobic treatment of dairy processing effluents in the context of circular economy. Journal of Cleaner Production, 261, 121139. Szabo-Corbacho, M. A., Pacheco-Ruiz, S., Miguez, D., Hooijmans, C. M., Garcia, H. E., Brdjanovic, D., & van Lier, J. B. (2021). Impact of solids retention time on the biological performance of an AnMBR treating lipid-rich synthetic dairy wastewater. Environmental Technology, 42(4), 597 608.

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11 Winery wastewater treatment for biomolecules recovery and water reuse purposes Alexandre Giacobbo1,2, Margarida Oliveira3,4, Andre´a Moura Bernardes1 and Maria Norberta de Pinho2,5 1

Post-Graduation Program in Mining, Metallurgical and Materials Engineering, (PPGE3M), Federal University of Rio Grande do Sul (UFRGS), Porto Alegre, Brazil 2Center of Physics and Engineering of Advanced Materials (CeFEMA), Instituto Superior Te´cnico, University of Lisbon, Lisbon, Portugal 3ESAS, UIIPS, Instituto Polite´cnico de Santare´m, Santare´m, Portugal 4LEAF—Linking Landscape, Environment, Agriculture and Food—Research Center, Associated Laboratory TERRA, Instituto Superior de Agronomia, University of Lisbon, Lisbon, Portugal 5Chemical Engineering Department, Instituto Superior Te´cnico, University of Lisbon, Lisbon, Portugal

11.1

Introduction

Viniculture is a very important agroindustrial activity worldwide, especially in the Mediterranean region where the three largest wine producing countries are located, namely Italy, France and Spain. Such is the economic importance of this sector that, in the last decade (2011 20), the average global wine production was approximately 270 MhL, from which about 100 MhL were destined for exports (OIV, 2021). According to data from the Food and Agriculture Organization of the United Nations, in 2019 the world export value of wine exceeded US$33 billion (FAO, 2021). Without a doubt, viniculture plays an important economic role in many countries, but like any agroindustrial activity, it also causes environmental impacts, such as the generation of wastes and wastewaters throughout the production process (Giacobbo et al., 2019; Giacobbo, Bernardes, Rosa, & de Pinho, 2018). Sometimes there can be some difficulty in managing this environmental liability, since more than 60% of these wastes and wastewaters are generated in a short period of up to 3 months during the vintage and in the first racking

Advanced Technologies in Wastewater Treatment. DOI: https://doi.org/10.1016/B978-0-323-88510-2.00001-4 Copyright © 2023 Elsevier Inc. All rights reserved.

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(Devesa-Rey et al., 2011; Oliveira & Duarte, 2016), demanding a greater effort from the treatment system. In this regard, wineries typically generate about 0.2 4 L of wastewater per liter of wine produced (Welz, Holtman, Haldenwang, & le Roes-Hill, 2016), but this figure can reach 14 L of wastewater per liter of wine produced (Ioannou, Puma, & Fatta-Kassinos, 2015), varying with the dimensions of the facilities, the type of wine produced (e.g., red, white, or special wines), and the winemaking and cleaning technologies (Giacobbo et al., 2013b; Lofrano & Meric, 2016; Oliveira, Costa, Fragoso, & Duarte, 2019). Winery wastewaters mainly originate from cleaning procedures for reception hoods, destemmers, tanks, presses, vats, barrels, floors, and other equipment and surfaces (Costa et al., 2020). Therefore they are predominantly composed of residues of skins, seeds, stems, lees, losses of wines and musts, cleaning products, and filtration aids (Giacobbo, Meneguzzi, Bernardes, & de Pinho, 2017b; Rodrigues et al., 2006). In fact, winery wastewater has a high pollutant load and can reach values of chemical oxygen demand (COD) and total solids of up to 49 g L21 and 18 g L21, respectively (Conradie, Sigge, & Cloete, 2014). The wastewater can contain various contaminants, such as sugars, ethanol, glycerol, organic acids, esters, phenolic compounds, and minerals (Conradie et al., 2014; Mosse, Verheyen, Cruickshank, Patti, & Cavagnaro, 2013). Nevertheless, some of these contaminants are value-added compounds liable to recovery, such as phenolic compounds (Giacobbo, Bernardes, & de Pinho, 2013a). Furthermore, the treated wastewater is an important and low-cost resource that can be reused for irrigation, representing a source of water and nutrients for agriculture (Albornoz, Centuria˜o, Giacobbo, Zoppas-Ferreira, & Bernardes, 2020). Summing up, the recovery of biomolecules and other substances from winery wastewater and the reuse of treated wastewater reduce the environmental impact of wineries and represent a significant advance in terms of sustainability, with gains in environmental and economic issues and promotion of the circular economy (Giacobbo et al., 2017b; Martins, Arau´jo, Grac¸a, Caetano, & Mata, 2018). On the basis of these considerations, this chapter will present an overview of winery wastewater and its treatment processes aiming at biomolecule recovery and water reuse purposes. The identification of the best processes for the recovery of byproducts, the definition of their sequencing, as well as the selection of the treatment system for this generated wastewater will also be developed in this chapter.

Chapter 11 Winery wastewater treatment for biomolecules recovery and water reuse purposes

11.2

Winemaking process and wastewater generation

Annually, wineries generate large volumes of wastewater, which depends on the winery dimension, the winemaking technology, and the specific operation that is being performed (Andreottola, Foladori, Ragazzi, & Villa, 2002; Brito et al., 2007; Coetzee, Malandra, Wolfaardt, & Viljoen-Bloom, 2004; Day et al., 2011; Malandra, Wolfaardt, Zietsman, & Viljoen-Bloom, 2003; Oliveira et al., 2019). Winemaking typically involves receiving grapes, crushing and pressing, processing (including maturation and stabilization), and bottling (Fig. 11.1). During each working period, wastewater volumes are generated from crushing and pressing of grapes and rinsing of fermentation tanks, barrels, other equipment (racking operations), and surfaces (Brito et al., 2007; Oliveira & Duarte, 2016; Zacharof, 2017), differing in their composition and quality. Briefly, the main stages of the winemaking process and contamination sources are as follows: 1. Grape reception. The wastewater generated at this stage is mostly related to the washing of equipment and surfaces. It is rich in suspended solids, dissolved sugars, potassium, and sodium (Day et al., 2011; Oliveira et al., 2019). 2. Crushing and pressing (must production). The grapes are pressed to produce must and solid residues (grape pomace), which consists mostly of skins, seeds, and stems (Genisheva, Macedo, Mussatto, Teixeira, & Oliveira, 2012). Wastewater is generated during the prewashing of the fermentation tanks and the washing of the equipment and the production hall. It can also contain must loss as a result of the racking operation. In this stage, the wastewater is rich in dissolved sugars, potassium, and sodium (Day et al., 2011; Oliveira et al., 2019). 3. Fermentation. At this stage, wastewater is generated mostly from rinsing of fermentation tanks. It is rich in suspended solids, grape solids, dissolved sugars, wine, potassium, and sodium (Day et al., 2011; Oliveira et al., 2019). 4. Decanting. During this process, the wine is decanted from the wine lees (Giacobbo et al., 2019). Wastewater is generated during prewashing and washing of the stabilization tanks and production room and during pump cleaning. At this stage product losses can occur (Vlyssides, Barampouti, & Mai, 2005). The wastewater is rich in suspended solids, grape solids, dissolved sugars, wine, potassium, and sodium (Day et al., 2011; Oliveira et al., 2019).

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Figure 11.1 Diagram of the winemaking process for white wine and red wine. Adapted from Devesa-Rey, R., Vecino, X., Varela-Alende, J. L., Barral, M. T., Cruz, J. M., & Moldes, A. B. (2011). Valorization of winery waste vs. the costs of not recycling. Waste Management (New York, N.Y.), 31, 2327 2335. https://doi.org/10.1016/j.wasman.2011.06.001; Oliveira, M., & Duarte, E. (2016). Integrated approach to winery waste: Waste generation and data consolidation. Frontiers of Environmental Science & Engineering,10, 168 176. https://doi.org/10.1007/s11783-014-0693-6; Zacharof, M.-P. (2017). Grape winery waste as feedstock for bioconversions: Applying the biorefinery concept. Waste and Biomass Valorization, 8, 1011 1025. https://doi.org/10.1007/s12649016-9674-2.

Chapter 11 Winery wastewater treatment for biomolecules recovery and water reuse purposes

5. Maturation-stabilization. Wastewater comes from the washing of the tanks and is rich in tartrate solids, fining agents, polyphenols, polysaccharides, potassium, and sodium (Day et al., 2011; Giacobbo et al., 2013b; Oliveira et al., 2019). 6. Tartaric stabilization. The excess of potassium hydrogen tartrate is removed from the wine by subtractive or additive methods. One of the methods uses a membrane process, electrodialysis, which gives rise to two different flows, the electrodialysis-treated wine and the wastewater flow, mainly containing potassium hydrogen tartrate and calcium tartrate. Besides this wastewater flow, wastewater is generated during the washing of the tanks and cleaning of the membranes, pumps, and production room. At this stage, wine can also be lost (Bories et al., 2011; Day et al., 2011; Gonc¸alves, Fernandes, Cameira dos Santos, & de Pinho, 2003). 7. Filtration. The wine is filtered to improve its quality. Wastewater comes from the washing of the tanks, from the prewashing of the storage tanks, from the cleaning of filters, from the transportation pump, and from the washing of the production room as well as from the possible wine losses during its transfer (Vlyssides et al., 2005; Zacharof, 2017). At this stage, the wastewater is rich in suspended solids, filtration earths, alcohol, polyphenols, polysaccharides, potassium, and sodium (Day et al., 2011; Giacobbo et al., 2013b; Oliveira et al., 2019). 8. Bottling. The produced wine is sold either in bulk or as bottled, which is charged from tanks to transportation trucks or in the packaging unit. At this stage, wastewater comes from the washing of tanks, the washing of equipment, and the washing of the packaging room (Vlyssides et al., 2005). At this stage, the wastewater is rich in suspended solids, polyphenols, and sodium (Day et al., 2011). This diversity of compounds that constitute winery wastewater, the spatiotemporal dynamics of the wastewater generation between and within wineries, and its potential for recovery and reuse pose real challenges to technologists (Ioannou et al., 2015; Mosse, Patti, Christen, & Cavagnaro, 2011). As was mentioned earlier, the quality and volume of wastewater, the end use for treated wastewater, the local environment and the implementing and operation costs are the main parameters to be considered in the winery wastewater management (Pirra, 2005; Braz, Pirra, Lucas, & Peres, 2010). The qualitative composition of winery wastewater is displayed in Table 11.1.

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Table 11.1 Physicochemical composition of winery wastewater. Parameter

Unit

Chemical oxygen demand Biochemical oxygen demand Total organic carbon Total solids Total suspended solids Turbidity Total nitrogen Total phosphorus Potassium Conductivity pH Total phenolic compounds Total sugars

21

mg O2 L mg O2 L21 mg C L21 mg L21 mg L21 NTU mg L21 mg L21 mg L21 mS cm21 mg L21 GAE mg L21 GE

Minimum

Maximum

320 203 41.0 748 66.0 251 10.0 2.10 5.00 1.10 2.50 0.51 100

49,105 22,418 7363 18,332 8600 782 415 280 2105 5.60 12.9 3531 8000

GAE, gallic acid equivalent; GE, glucose equivalent. Source: Adapted from Braz, R., Pirra, A., Lucas, M. S., & Peres, J.A. (2010). Combination of long term aerated storage and chemical coagulation/flocculation to winery wastewater treatment. Desalination, 263, 226 232. https://doi.org/10.1016/j.desal.2010.06.063; Ioannou, L. A., Puma, G. L., & Fatta-Kassinos, D. (2015). Treatment of winery wastewater by physicochemical, biological and advanced processes: A review. Journal of Hazardous Materials, 286, 343 368. https://doi.org/10.1016/j.jhazmat.2014.12.043; Pirra, A. J. D. (2005). Characterization and treatment of winery effluents from the Douro Wine Region (Caracterizac¸a˜o e tratamento de efluentes vinı´colas da Regia˜o Demarcada do Douro). University of Tra´s-os-Montes and Alto Douro. Vila Real, Portugal; Shilpi, S., Seshadri, B., Sarkar, B., Bolan, N., Lamb, D., & Naidu, R. (2018). Comparative values of various wastewater streams as a soil nutrient source. Chemosphere, 192, 272 281. https://doi.org/10.1016/j.chemosphere.2017.10.118; Welz, P.J., Holtman, G., Haldenwang, R., & le Roes-Hill, M. (2016). Characterisation of winery wastewater from continuous flow settling basins and waste stabilisation ponds over the course of 1 year: Implications for biological wastewater treatment and land application. Water Science and Technology: A Journal of the International Association on Water Pollution Research, 74, 2036 2050. https://doi.org/10.2166/wst.2016.226.

11.3

Value-added biomolecules found in winery wastewaters

As was previously mentioned, winery wastewater contains several contaminants, including commercially important biomolecules that originate from grapes and wine-processing operations, such as phenolic compounds, which are known to have antioxidant properties (Bhise, Kaur, Gandhi, & Gupta, 2014; Giacobbo et al., 2017b). Polyphenols and other phenolic compounds are secondary metabolites of plants (Can˜adas, Gonza´lez-Miquel, Gonza´lez, Dı´az, & Rodrı´guez, 2021). They comprise a wide variety of molecules and may contain only one phenolic ring, such as phenolic acids, or a polyphenolic structure with several hydroxyl groups on aromatic rings, forming a very diverse group (e.g., flavonoids, stilbenes, and

Chapter 11 Winery wastewater treatment for biomolecules recovery and water reuse purposes

lignans) containing several subgroups (Manach, Scalbert, Morand, Re´me´sy, & Jime´nez, 2004). Phenolic compounds may also be associated with one another or with various carbohydrates and organic acids; that more than 4000 flavonoids and 8000 phenolic structures have been identified so far (Cheynier, 2005; Tsao, 2010). Thus this large variety of interactions possibilities between and within groups of molecules results in compounds with a wide molecular weight (MW) range, covering small solutes such as benzoic acid (MW 5 122 Da) and proanthocyanidins (tannins) with a degree of polymerization of 80 (Souquet, Cheynier, Brossaud, & Moutounet, 1996), which corresponds to a MW on the order of 25,000 Da. Considering this wide variety of phenolic compounds, they are usually analyzed and quantified as total phenolic content, and gallic acid is conventionally used as a reference standard, so the results are expressed in mg L21 or mg kg21 of gallic acid equivalent as displayed in Table 11.1. The antioxidant activity of the extract/wastewater is sometimes also analyzed, and the result is usually expressed in mg L21 or mg kg21 of Trolox equivalent. The phenolic compounds derived from wine production are usually divided in flavonoids and nonflavonoids, the former being the most important (Oliveira, Ferreira, De Freitas, & Silva, 2011). The flavonoid structure is composed of a C6-C3-C6 skeleton, in which two aromatic rings (A and B) are connected by a central pyran ring (C) (Jackson, 2008; Santos-Buelga & Feliciano, 2017), as illustrated in Fig. 11.2. The most common flavonoids (Fig. 11.3) in wine are flavonols (kaempferol, quercetin, and myricetin), flavan-3-ols (catechins and proanthocyanidins or condensed tannins), and anthocyanins (Kammerer, Kammerer, Valet, & Carle, 2014). Small amounts of flavan-3,4-diols are also found (Jackson, 2008), while the nonflavonoids (Fig. 11.4) are mainly derivatives

3' 4'

2' 8 7

A

1

O C

6

2 3

5

Figure 11.2 Basic flavonoid structure.

1'

4

B 6'

5'

317

318

Chapter 11 Winery wastewater treatment for biomolecules recovery and water reuse purposes

Figure 11.3 Most common flavonoids found in wine. Adapted from (Oliveira et al., 2011; Tsao, 2010). Molecular weight (MW) data from (Pubchem, 2021).

Chapter 11 Winery wastewater treatment for biomolecules recovery and water reuse purposes

319

Figure 11.4 Most common non-flavonoids found in wine. Adapted from (Oliveira et al., 2011; Tsao, 2010). MW data from (Pubchem, 2021).

of benzoic and cinnamic acids, although stilbenes, as transresveratrol, are also present (Oliveira et al., 2011).

11.4

Winery wastewater treatment systems

In general, wastewater treatments are based on physical, physicochemical, biological, membrane filtration, and advanced oxidation processes (AOPs) (Colin, Bories, Sire, & Perrin, 2005; Ioannou et al., 2015; Mosse et al., 2011). They may be used in different combinations (and sequences) and are generally grouped as primary, secondary, and tertiary treatments.

11.4.1

Physical treatments

Almost all the wastewater treatment operations in wineries involve at least one physical step, predominantly to screen out

320

Chapter 11 Winery wastewater treatment for biomolecules recovery and water reuse purposes

or settle out the large solids, including grape seeds, stalks, and leaves, thus preventing other treatment machinery from getting clogged with solids, during the primary treatment. The applicability of various physical treatments, such as evaporation (natural or forced), evapoconcentration by fractional condensation, microfiltration (MF), ultrafiltration (UF), electrodialysis, and reverse osmosis (RO) for wastewater wineries have been studied (Durham, Bourbigot, & Pankratz, 2001; Giacobbo et al., 2013b; Jacob et al., 2010; Portilla Rivera, Saavedra Leos, Solis, & Domı´nguez, 2021; Rengaraj, Yeon, & Moon, 2001; Zhang, Ghyselbrecht, Meesschaert, Pinoy, & Van der Bruggen, 2011), as secondary and tertiary treatments. In the Mediterranean regions, natural evaporation ponds have been used for a long time in wineries, owing to the low investment and maintenance costs. Although technically simple, this methodology has several drawbacks, including the emission of malodors and contamination of soil and groundwater. The evaporation ponds act as a reservoir of wastewater that is subjected to an evaporation effect, which may be natural or forced, leading to the concentration of suspended particulate organic matter. The forced evaporation system is composed of a buffer tank of small size and high surface alveolar panels (which increase the amount evaporated) with automated injection of a biocide cleaning solution (Clerc, 2004). The effluent from this process can be used in agriculture, applied through irrigation (Clerc, 2004; Masi, Conte, Martinuzzi, & Pucci, 2002). In areas with high land value, the footprint associated with this technology is a relevant issue (Mosse et al., 2011). Saraiva et al. (2020) reported an average water footprint of 2.6 L/FU,1 which depends on the year under study. The evapoconcentration to fractional condensation (ECCF; abbreviation from French) is a new biophysical process comprising two stages; in the first the fermentation of sugars occurs by forming ethanol (a biological process,) and the second stage consists in the separation of ethanol from the final effluent. This process can be used as a complete treatment or pretreatment. For complete treatment, which includes demineralization of purified water, Colin et al. (2005) reported an efficiency of COD removal of 99% 99.7%, and for pretreatment (involving only the separation of ethanol), 80% of COD removal was achieved. The final effluent can be reused (e.g., washing operations and industrial applications). The alcoholic 1

FU: functional unit. The functional unit (FU) selected by Saraiva et al. (2020) was the 0.75 L bottle that is commonly used for wine.

Chapter 11 Winery wastewater treatment for biomolecules recovery and water reuse purposes

product may be sold or used as fuel. Also, the residual product can be used as a fertilizer because of the content in organic compounds and inorganic compounds. Thus the ECCF appears as a new concept for the treatment of winery wastewater, opening the way for a new generation of wastewater treatment, with a view to sustainable development through the enhancement of the compounds produced and reuse of the final effluent (Colin et al., 2005; Fillaudeau, Bories, & Decloux, 2008). Physical treatments are used for salt removal, an important step when high sodium ion concentration is present in the wastewater, and the treated water is reused or disposed onto land (Tillman & Surapaneni, 2002). As reviewed by Mosse et al. (2011), there are several technologies for salt removal, such as electrodialysis, ion exchange, and RO, which tend to be disadvantageous for use in most wineries, owing to the high energy consumption and maintenance costs, mainly for the smaller ones. Moreover, the desalination process produces highly concentrated brine, which requires disposal, and to our knowledge, these technologies are not yet being employed in winery wastewater treatment plants. Nevertheless, electrodialysis, ion exchange, and RO are already well-known technologies with large-scale application in a wide variety of industries for the desalination of wastewater for industrial reuse purposes. These methods, although essentially physical, are included in Sections 11.5 and 11.6.

11.4.2

Physicochemical treatments

Within the physicochemical methods there are some processes that are applicable to winery wastewater treatment, in particular chemical precipitation with the addition of chelating agents, sedimentation with the addition of flocculants, coagulation/flocculation, and electrocoagulation and AOPs. As reviewed by Ioannou et al. (2015) there are several parameters that influence the removal efficiency of the treatment process. However, the electrocoagulation process was shown to be a suitable technology, achieving removal efficiencies very close to those of biological processes. On the other hand, the search for more sustainable treatment technologies showed that the use of the natural coagulant chitosan could be an alternative to chemical coagulants, achieving a COD removal of up to 73% (Ioannou et al., 2015; Rizzo, Bresciani, Martinuzzi, & Masi, 2020).

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The AOPs are innovative technologies that have received increasing attention in the research and development of wastewater treatment in the last decades. They provide an alternative for wastewater treatment for the removal or degradation of toxic pollutants. This process can be used as pretreatment to convert recalcitrant pollutants into biodegradable compounds to be treated by a biological process or as posttreatment after a biological step to remove the recalcitrant contaminants. The efficacy of AOPs depends on the generation of reactive free radicals, the most important of which is the hydroxyl radical (HO•) used for the oxidation process (Wang & Xu, 2012). Radiation, photolysis and photocatalysis, sonolysis, electrochemical oxidation technologies, Fenton-based reactions, and ozone-based processes are the main types of AOPs that have been described for wastewater treatment in general (Ioannou et al., 2015; Sevillano, Chiappero, Gomez, Fiore, & Martı´nez, 2020). Photocatalysis reactions are a subset of AOPs that rely on a catalyst and ultraviolet (UV) or visible radiation to cause oxidation. Commonly, the most widespread catalysts used are Fenton’s reagent, titanium dioxide, or ozone; each of them gives different characteristics to the photocatalysis process (de Heredia, Torregrosa, Dominguez, & Partido, 2005; Gernjak, Krutzler, Malato, Caceres, & Bauer, 2001; Ioannou et al., 2015; Lucas, Dias, Bezerra, & Peres, 2008; Ormad, Mosteo, Ibarz, & Ovelleiro, 2006). Although associated with a low cost, the main disadvantage is that Fenton’s reagent is a homogeneous catalyst, added as salts of iron, which may remain dissolved, causing additional water pollution. To overcome this issue, the heterogeneous photo-Fenton process emerged, characterized by the use of a semiconductor oxide in the presence of UV or visible radiation, capable of interacting with the Fenton’s reagent. Lucas, Mosteo, Maldonado, Malato, and Peres (2009) suggested that the efficacy of the photo-Fenton reaction could be increased if ethanol were previously eliminated from winery wastewater by air stripping. Other authors also reported the use of AOPs with Fenton’s reagent as pretreatment, making certain organic compounds more degradable by further biological treatment (Agustina, Ang, & Pareek, 2008; Mosteo, Ormad, Gale´, Sarasa, & Ovelleiro, 2004). The main advantages of photocatalysis with titanium dioxide are the availability of sunlight and the availability, stability, and low price of the catalyst (TiO2). Moreover, TiO2 is capable of oxidating of a wide range of organic compounds into harmless compounds such as CO2 and H2O (Chatterjee & Dasgupta, 2005).

Chapter 11 Winery wastewater treatment for biomolecules recovery and water reuse purposes

Among the drawbacks associated with TiO2 photocatalysis are the difficulty of separating final particles from the aqueous TiO2 matrix and loss of radiation after recombination. To overcome these drawbacks, coating the surface of the reactor with TiO2 particles and the use of oxygen excess or addition of inorganic H2O2 to prevent light loss have been proposed (Gimeno, Rivas, Beltra´n, & Carbajo, 2007). Photocatalytic ozonation (O3/UV/TiO2) is a powerful chemical oxidation method that involves two major pathways of degradation: ozonation (O3) and direct photolysis. This method is considered superior to ozonation and photocatalysis (UV/TiO2), owing to synergistic effects (Giri, Ozaki, Taniguchi, & Takanami, 2008), and is emerging as a promising oxidation method for recalcitrant organic contaminants, including pesticides, due to the large number of HO• that are generated (Agustina et al., 2008; de Heredia et al., 2005; Farre´ et al., 2005; Gimeno et al., 2007; Li, Zhu, Chen, Zhang, & Chen, 2005). The advantages of this method arise mainly from the properties of ozone, a strong oxidizing agent that is not a source of pollution and whose degradation leads to a lower formation of toxic elements. The ozonation process reduces recalcitrant organic matter and enhances the biodegradability of organic compounds, since it allows the formation of smaller and less toxic molecules, which are more easily metabolized by microorganisms. The effectiveness of different ozone-based AOPs in winery wastewater treatment was investigated in a bubble column reactor (Lucas, Peres, & Li Puma, 2010). The O3/UV/H2O2 treatment was shown to be the most efficient for total organic carbon and COD removal, especially if the system is operated at alkaline pH (pH 10), and the most economical process when compared to O3 or O3/UV treatments. However, according to Mosse et al. (2011) it is unlikely that ozone-based processes will be used in the winery industry at this stage, since they are rather expensive, require safety precautions (ventilation, maintenance, frequent monitoring), and are relatively complex. Despite some drawbacks, wastewater treatment with ozone has been recommended both as pretreatment and as tertiary treatment. When used as a pretreatment, it promotes increased biodegradability of the effluent and permits the removal of toxic compounds and inhibitors. When used as tertiary treatment, it allows the removal of the remaining recalcitrant compounds (Beltran-Heredia, Torregrosa, Dominguez, & Garcia, 2000). According to Ioannou et al. (2015), combined biological and advanced processes (pretreatment and posttreatment) present the most effective technologies applied for the treatment of winery wastewater with a COD removal efficiency of 98% 99.5%.

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11.4.3

Natural biological treatments

Biological processes have proven to be efficient to the treatment of wastewaters with high organic loads (Bolzonella, Papa, Da Ros, Anga Muthukumar, & Rosso, 2019). The organic matter in winery wastewater is essentially soluble and quickly biodegradable. For this reason, biological treatment systems are particularly interesting options for this type of effluents (Bolzonella & Rosso, 2009; Torrijos, Moletta, & Delgenes, 2004). Nevertheless, the variable nature of wastewater composition and quantity should be faced, and the treatment plants must be able to handle fluctuations in influent composition and volumes. Concerning the wastewater composition, the toxicity of the wastewater may lead to a partial inhibition of biodegradability because some microorganisms are particularly sensitive to phenolic compounds and some intermediates of their degradation, pesticides, and chemical compounds (de Heredia et al., 2005; Stricker & Racault, 2005). In a broad sense, biological treatments can be divided into aerobic and anaerobic processes. The first is based on oxygen to facilitate microbial-mediated breakdown of organic matter present in wastewaters; the second occurs in the absence of oxygen, relying on alternative metabolic pathways utilized by a consortium of different microorganisms (Mosse et al., 2011). Nevertheless, the combined use of anaerobic and aerobic treatments is referred as the best option to be used on winery wastewater treatment (Ferna´ndez et al., 2007), as Ioannou et al. (2015) advocate the combined use of biological treatment and AOPs. The preference for anaerobic processes is associated with their proper performance and economy of operation (Rodrigues et al., 2006). When aerobic and anaerobic systems are compared, the aeration costs are proportional to the content of organic matter to be removed, which may lead to quite significant operating costs. In contrast, the anaerobic systems require no aeration, and in the case of use of the biogas that is generated, anaerobic digestion can present a positive energy balance. Also, the anaerobic systems have the advantage of lower production of sludge, owing to the slower growth of anaerobic microbes, have a slower kinetics, thus reflecting higher hydraulic retention times and larger volumes of reactors. They are more sensitive to pH variation and biomass transfer problems and have limitations with respect to degradation of some compounds. Moreover, the startup of anaerobic reactors is often considered to be unstable and dependent on several factors, including wastewater composition, available inoculum, reactor

Chapter 11 Winery wastewater treatment for biomolecules recovery and water reuse purposes

operating conditions, and reactor configuration (Alkarimiah, Mahat, Yuzir, Din, & Chelliapan, 2011; Duarte, Reis, & Martins, 2004; Kalyuzhnyi, Gladchenko, Sklyar, Kurakova, & Shcherbakov, 2000; Oliveira, Neves, & Duarte, 2007; Pe´rez-Garcı´a, RomeroGarcı´a, Rodrı´guez-Cano, & Sales-Ma´rquez, 2005; Sevillano et al., 2020). Often, after an anaerobic treatment, is advisable to apply an aerobic treatment as a thinning process that is used to remove organic matter, which is still in the wastewater. Anaerobic processes can also be used as a pretreatment, allowing the reduction of energy and sludge management costs (Rodrigues et al., 2006). For economic reasons and for their simplicity, the aerobic systems are referred as the most appropriate choice for small wineries (Mosse et al., 2011). In this case, the wastewater generation is low, and expenses associated with aerobic treatment will not be as significant as with anaerobic digestion. For winery wastewaters, another aspect that is not always optimized involves the removal of inorganic suspended solids, since they can affect the mechanical equipment (e.g., pumps, Venturi type aerators) by abrasion. In addition, as biological processes are not very effective for insoluble compounds; a preliminary treatment is always desirable to also remove the organic suspended solids (Rodrigues et al., 2006).

11.4.3.1

Anaerobic treatment systems

The anaerobic treatment systems show better adaptation to the winery wastewaters than aerobic systems, owing to the high COD/N/P ratio, that is these effluents have low nitrogen and phosphorus contents as compared to carbon. Moreover, by anaerobic digestion it is possible to minimize the energy costs through the recovery of biogas that is produced during the process (Artiga, Carballa, Garrido, & Me´ndez, 2007; Brito et al., 2007; Mace, Bolzonella, Cecchi, & Mata-Alvarez, 2004; Moletta, 2005). However, the anaerobic systems are often affected by the need to maintain the operating temperature (mesophilic or thermophilic), which is significantly higher than room temperature. Anaerobic reactors operating at low temperatures have been developed (Kalyuzhnyi et al., 2001, 2000). Of the anaerobic digestion technologies that are available for this type of effluents, emphasis is given to those listed in Table 11.2. One of the most significant drawbacks of anaerobic digestion is the production of volatile fatty acids (VFAs) and other compounds, which are responsible for malodors in the vicinity of wineries (Bories, Sire, & Colin, 2005). To control the odor

325

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Table 11.2 Removal efficiencies of various anaerobic treatment systems System

Advantages

Drawbacks COD Removal (%)

Polyphenol removal (%)

References

Upflow anaerobic filters Relatively High sludge Upflow high activity, low anaerobic sludge blanket sludge production installation costs Upflow Sludge blanket filter

70 87 90

Moletta (2005) Ferna´ndez et al. (2007)

90 60 2 703 571, 682, 703 96 2 98

Kalyuzhnyi et al. (2000) Kalyuzhnyi et al. (2000) Kalyuzhnyi et al. (2001)

Continuous stirred tank digester Anaerobic fluidized bed reactor Upflow anaerobic floating filter

62 2 66

201, 392,403

Molina, Ruiz-Filippi, Garcı´a, Roca, and Lema (2007) Mace et al. (2004)

81.5 2 92.5

Pe´rez-Garcı´a et al. (2005)

47.89 2 75.5

Pe´rez-Garcı´a et al. (2005)

1

Temperature: 4˚C. Temperature: 7˚C. Temperature: 10˚C.

2 3

emission, nitrate salts (e.g., calcium nitrate) can be added to the wastewater, thus preventing the formation of VFAs (Bories et al., 2007). However, this process requires large quantities of added nitrate salt, which is expensive and degrades the final quality of the wastewater. In addition, there is an increased risk of nitrogen runoff into streams and subsequent eutrophication, which represents a threat to the aquatic ecosystems (Burgin & Hamilton, 2007). Therefore the use of nitrate salts should be limited to emergency/backup situations, owing to both economic and environmental impacts (Mosse et al., 2011).

11.4.3.2

Aerobic treatment systems

The high efficiency and versatility that aerobic treatment processes provide allow them to often be the most selected

Chapter 11 Winery wastewater treatment for biomolecules recovery and water reuse purposes

option. The aerobic processes are generally preferred for degrading phenolic compounds because of the lower costs associated with this option and the possibility of complete mineralization of xenobiotic compounds (Ruiz-Ordaz et al., 2001). Several aerobic treatment systems have been developed, as summarized in the Table 11.3. The lagooning system usually requires large surface areas, frequently in land with high value, and has also problems related to the generation of malodors due to deprived oxygen mass transfer (Agustina et al., 2008; de Heredia et al., 2005; Pirra, 2008). The aerated lagoons are similar to the previous system, but a mechanical stirrer is responsible for oxygenation. The large land areas that are required to implement stabilization ponds makes these systems more advantageous in regions where the cost and availability of land are not a constraint (Mosse et al., 2011). This process is widely used in France for very small wineries. To reduce the tank volume and the treatment time, the performance of this process may be optimized by combining it with another treatment, such as decantation or thinning treatment with sand filtration, membrane filtration, filtration combined with constructed ponds, or physicochemical processes. This method has advantages such as small production of sludge and absence of sludge recirculation, reduced need for manual labor, and low cost of setting up and maintenance (Racault & Stricker, 2004). Constructed wetlands (CWs) are classified as a biological treatment based on the principle of infiltration-percolation. These ponds behave like a biofilter in which bacteria located on the surface of carrier material (sand, gravel) degrade the organic matter that is present in the effluent. They can be settled as vertical filters (water is injected into the surface of the system, which promotes oxygen and prevents saturation) or as horizontal filters (the system is permanently saturated). These filters can be used separately or in combination (Kerner & Rochard, 2004). This process can provide considerable efficiency, low cost, low maintenance, and low energy consumption. Furthermore, it is well adapted to accept seasonal flows without adversely affecting functional aspects of the treatment system. According to Shepherd (1998) and Grismer, Carr, and Shepherd (2003), this system was effective in the treatment of winery wastewaters with 5 g COD L21, and COD loads up to 160 g COD m22 d21. Removal efficiencies of 85% 97% for COD and 50% for total suspended solids (TSS) were achieved 9.4 days after the startup. Higher COD concentrations may be

327

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Table 11.3 Advantages, drawbacks, and removal efficiencies of various aerobic treatment systems. System

Advantages

Drawbacks

COD References removal (%)

Aerated lagoons

Easy management; widespread

Easy management; high sludge activity; widespread

91 99 87.5 97.8 87 90 93 95

Montalvo et al. (2010) Kerner and Rochard (2004) Masi et al. (2002)

Activated sludge

Energy intensive; do not always meet the requirements during vintage Relatively high installation costs; energy intensive; supplementation with N and P for microbial growth Requires storage tanks for batch feeding

90 95

Brucculeri et al. (2005) Ferna´ndez et al. (2007)

Packed-bed bioreactor Fluidized-bed bioreactor (FBB) Air bubble column bioreactor (ABB) Jet-loop reactor (JLR)

Low area requirement Low area requirement High efficiency; low area requirement

Lab scale

91.1

Lab scale

88.7

Brito et al. (2007); Lo´pez-Palau et al. (2009); Pirra et al. (2004); Torrijos & Moletta (1997); Torrijos et al. (2004) Petruccioli, Duarte and Federici (2000) Petruccioli et al. (2000)

Lab scale

92.2

Petruccioli et al. (2000)

High efficiency; lowered energy requirements

Limited number of application to date

94 98

Rotating biological contactor (RBC) Membrane bioreactor (MBR)

Easy to operate; small startup

Maintenance during treatment process

41 43

Euse´bio, Mateus, Baeta-Hall, Almeida-Vara, and Duarte (2005); Eusebio, Petruccioli, Lageiro, Federici, and Duarte (2004); Petruccioli, Cardoso Duarte, Eusebio, and Federici (2002) Coetzee et al. (2004) Malandra et al. (2003)

Sequencing batch Low capital costs; reactor simple automation

95 High efficient; higher High installation cost; organic loading rate high energy requirement; 97 membrane fouling. and F/M; small footprint; lower sludge production

Bolzonella et al. (2010) Artiga et al. (2005)

(Continued )

Chapter 11 Winery wastewater treatment for biomolecules recovery and water reuse purposes

329

Table 11.3 (Continued) System

Advantages

Drawbacks

COD References removal (%)

Fixed-bed biofilm reactor (FBBR) Air microbubble bioreactor (AMBB) Sequencing batch biofilm reactor (SBBR)

Simple management; no bulking problems. High efficiency; lower energy requirements High organic loads; sludge recirculation not required; no bulking problems; simple management

Limited number of application to date Limited number of application to date

91 98

Andreottola, Foladori, Nardelli, and Denicolo (2005) Oliveira et al. (2007, 2009)

High installation cost; requires large area

86 99

Andreottola et al. (2002)

applied if the recirculation of treated wastewater is performed (Kerner & Rochard, 2004). However, this system should be considered only when the wineries have large viable areas (Kerner & Rochard, 2004; Masi et al., 2002). Moreover, experiments simulating a wetland microcosm, in which three macrophyte wetland species (Phragmites australis, Schoenoplectus validus, and Juncus ingens) were tested, revealed the phytotoxicity of the treated wastewater for concentrations greater than 25%. Cress (Lepidium sativum) and onion (Allium cepa) were similarly sensitive to the treated wastewater (Arienzo, Christen, & Quayle, 2009b). Nevertheless, the same authors showed that this system, when combined with a previous sedimentation or aerobic process, could be used for small wineries located in rural areas, achieving a 72% COD removal rate (Arienzo, Christen, Quayle, & Di Stefano, 2009a). Options such as lagooning and CWs may constitute interesting solutions for winery wastewater treatment if there has been the previous removal of suspended solids and if the local edaphoclimatic conditions are favorable (Rochard, 2017; Rodrigues et al., 2006). Ferna´ndez et al. (2007) studied an activated sludge system model in which the COD removal efficiency ranged from 93% to 95%. The implementation of this system required the nutrient adjustment and the sludge production was about 0.3 0.6 g TSS g21 COD (Jourjon, Racault, & Rochard, 2001; Racault, Cornet, & Vedrenne, 1998). Although this system was able to

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Chapter 11 Winery wastewater treatment for biomolecules recovery and water reuse purposes

provide substantial removal yields, the sludge sedimentation was poor, and the long retention times were often problematic (Agustina et al., 2008; Artiga et al., 2007; Jourjon et al., 2001). A long-term activated sludge system may provide a COD removal rate between 97% and 99% (Fumi, Parodi, Parodi, Silva, & Marchetti, 1995). In addition to a good removal efficiency, the system is simple (not very labor-intensive and dispensing with the need for skilled personnel), flexible and economical (with costs that were approximately one-half of those resulting from a conventional activated sludge system). This system can also operate by utilizing two reactors in series, the first one corresponding to the conventional treatment (F/M between 0.25 and 0.60 g COD g21 VSS d21), with a hydraulic retention time of 3 5 days, and the second operating under extended aeration (F/M between 0.05 and 0.15 g COD g21 VSS d21), with a hydraulic retention time of about 4 8 days. The overall treatment allows a COD removal efficiency of 96% 99% (Bolzonella et al., 2019; Jourjon et al., 2001; Racault et al., 1998; Rochard, Racault, & Canler, 2000). According to Rodrigues et al. (2006), the sequencing batch reactor (SBR) is the most suitable technology for this type of industry. The system is characterized by a sequential operation, consisting of the periodic repetition of the operation cycle. Each stage of operation is under non-steady-state conditions, where the biomass retention within the system is performed by introducing a sedimentation phase under fully quiescent conditions, by combining different operations in a single tank. Trials conducted in a full-scale SBR showed the suitability of this system for winery wastewater treatment with a feed of 0.8 g COD L21 d21 and a ratio F/M of 0.25 g COD g21 VSS d21, showing a COD removal efficiency of 93% 97% (Torrijos et al., 2004). Similar results were obtained by other authors (Wilderer, Irvine, & Goronszy, 2001). Further, Pirra, Arroja, and Capela (2004) showed that the SBR can operate with higher organic loads (5 18 g COD L21 d21), achieving a COD removal of 95%, although some problems during the biomass sedimentation have been observed. Winery wastewater often requires adjustment of the C/N/P ratio, as the carbon loads are usually higher. This high organic load also leads to oxygen transfer efficiency problems (Lo´pez´ lvarez, 2009). Also, to optimize the Palau, Dosta, & Mata-A sludge settling time, the formation of granules can be performed based on feast and famine periods (Lo´pez-Palau et al., 2009). In fact, the high organic load promotes microbial growth and increases the biomass concentration, thus causing aeration

Chapter 11 Winery wastewater treatment for biomolecules recovery and water reuse purposes

problems in the reactor. Consequently, to achieve good performance, the aeration must be proportional to the COD load. Another strategy to optimize the SBR cycle for total organic carbon and ammonia removal is based on dissolved oxygen (DO) control (Puig et al., 2006). The cycle consisted of three phases: reaction (under aerobic and anoxic conditions), settling, and discharge. During the aerobic phase, the set-point was DO 2.0 mg L21, with an On/Off control. Reactor optimization was performed on pH, DO, and oxygen uptake rate (OUR). This model allowed the ammonia valley to be detected during pH evolution and the end of nitrification, using the OUR plot. By identifying the bending points for the pH (ammonia valley) and the calculated OUR, it is possible to optimize the aerobic phase of the SBR cycle for organic matter and ammonia removal (Puig et al., 2006).

11.4.4

Membrane bioreactors

Membrane bioreactors (MBRs) represent an important technical option for wastewater treatment and reuse, being very compact and efficient systems for separation of suspended and colloidal matter (Delgado, Villarroel, Gonza´lez, & Morales, 2011; Valderrama et al., 2012). This technology is based on the combination of biological treatment, usually conventional activated sludge, with a membrane process of MF or UF. The membrane is a barrier that retains all particles, colloids, and microorganisms, providing complete disinfection of treated wastewater, enabling a highquality effluent. The advantages of this system include the elimination of foaming and suspended solids in the effluent, the smaller footprint, the lower sludge production, and the improvement in treated wastewater quality (Artiga et al., 2005; Guglielmi, Andreottola, Foladori, & Ziglio, 2009). MBR treatment of winery wastewater has been shown to be highly effective, with COD removal rates higher than 97% (Artiga et al., 2005). According to Bolzonella et al. (2010), the MBR was able to handle hydraulic and organic loading peaks without changes in the reactor’s performance. Even for an organic loading rate up to 2 g COD L21 d21, the COD removal efficiency was over 95%, and nitrogen removal was also reported (Bolzonella et al., 2010). The growing interest in this system has led to its application in several full-scale wastewater treatment plants (Andreottola, Foladori, & Ziglio, 2009; Bolzonella et al., 2010; Delgado et al., 2011; Ferre, Trepin, Gime´nez, & Lluch, 2009). Also, a combined MBR RO plant demonstrated the viability of integrating membrane technology with a bioreactor to enable significant water savings (Dolar et al., 2012; Vanossi & Durante, 2009).

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11.4.5

Other bioreactors

There are some specific aerobic treatments systems that have been studied for winery wastewater; among them are the fixed bed biofilm reactor, the air microbubble bioreactor (AMBB) or the jetloop reactor (JLR), using self-adapted microbial population, either free or immobilized (Eusebio et al., 2004; Euse´bio et al., 2005; Oliveira, Queda, & Duarte, 2009; Petruccioli et al., 2000). In the JLR and AMBB (vertical reactors) the oxygen supply is performed by recirculation of the reactor effluent through a Venturi injector, which permits a good oxygen diffusion rate, overcoming the energetic costs associated with the aeration systems, with the advantage of requiring a small area. However, the high shear stress applied on the Venturi injector influences the composition of the microbial population (Euse´bio et al., 2005; Oliveira & Duarte, 2011; Oliveira et al., 2009; Petruccioli et al., 2000), leading in some cases to settling sludge problems. These reactors achieve a COD removal efficiency up to 95%, for an applied organic load of 0.4 5.9 g COD L21 d21. Vertical reactors appears to be among the most promising technologies, not only because of the economy of space but also because they are characterized by a good oxygen transfer capability and a high biological conversion rate (Duarte et al., 2004; Petruccioli et al., 2000; Xu, Zhou, Qu, Yang, & Liu, 2010). Data from the literature point to several challenges related to winery wastewater treatment systems, namely, the wastewater’s seasonality, volume and quality variations, and high oxygen transfer requirements as well as the presence of recalcitrant compounds. Criteria for the selection of the treatment technology include winery size, location, land and water availability, energy costs, and quality required in the treated wastewater. Moreover, the quantification and characterization of new fluxes from wine production need to be evaluated. Because of the variability and unique characteristics of these fluxes, the selection of the most adequate treatment system is of paramount importance. In fact, the most suitable method is to use processes that allow simultaneous treatment of the effluents and recovery of the bioproducts.

11.5

Membrane separation based processes for biomolecules recovery from winery wastewater

Membrane separation processes such as MF, UF, nanofiltration (NF) and RO are unit operations in which a pressure

Chapter 11 Winery wastewater treatment for biomolecules recovery and water reuse purposes

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gradient that is applied between the two sides of a permselective membrane promotes the physical separation of a feed stream into two others: retentate and permeate streams. The retentate stream comprises the components rejected by the membrane, while the permeate stream contains the components that get through the membrane. In these operations the separation mechanism in UF is governed mainly by steric hindrances, also known as sieving mechanism, in which the components that are smaller than the pores size or the MW cutoff (MWCO) of the membrane get through into the permeate stream and the larger ones remain in the retentate. Conventionally, MWCO determines the selectivity of a membrane and is related to the MW of a solute whose rejection is higher than 90% (Baker, 2012). However, other mechanisms, such as solute-solute and solute-membrane interactions, can also occur, interfering with the process. Table 11.4 shows the operating principles and applications of pressure-driven separation processes (de Pinho and Minhalma, 2019). In fact, membrane separation processes, especially those driven by pressure gradient, have been proposed for the recovery of biomolecules from diverse wastewaters and extracts of

Table 11.4 Pressure-driven membrane processes: operating principles, and applications. Separation Pore size or process MWCO

Operating pressure (bar)

Range of application

Rejected material

Microfiltration 10 0.1 µm

0.1 1.0

Sterilization, Clarification Separation of macromolecular solutes Separation of ions and small organic solutes

Particles, colloids, and bacteria

Ultrafiltration

350,000 1000 Da 0.5 8.0

Nanofiltration 1000 200 Da

Reverse osmosis

, 200 Da

5 40

20 100

Proteins, polysaccharides, polyphenols, and other macromolecules Glucose, fructose, amino acids, small organic solutes, and bivalent ions Separation of ions and Ions and small organic solutes microsolutes

Source: Adapted from Cassano, A., Conidi, C., Ruby-Figueroa, R., & Castro-Mun˜oz, R. (2018). Nanofiltration and tight ultrafiltration membranes for the recovery of polyphenols from agro-food by-products. International Journal of Molecular Sciences, 19, 351. https:// doi.org/10.3390/ijms19020351; de Pinho, M. N., Minhalma, M. (2019). Introduction in membrane technologies. In: C. M. Galanakis (Ed.), Separation of functional molecules in food by membrane technology (pp. 1 29). Chennai: Academic Press. https://doi.org/10.1016/B9780-12 815056-6.00001-2; Habert, A. C., Borges, C. P., No´brega, R. (2006). Processos de separac¸a˜o por membranas. Editora E-papers, Rio de Janeiro.

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agroindustrial byproducts (Cassano, Conidi, & Ruby-Figueroa, 2014; Garcia-Castello, Cassano, Criscuoli, Conidi, & Drioli, 2010). Nevertheless, concerning the wine industry, the recovery of biomolecules by membrane technologies has been the focus mostly of studies involving solid byproducts, such as lees (Cassano et al., 2019; Giacobbo, Bernardes, & de Pinho, 2017a; Giacobbo, do Prado, Meneguzzi, Bernardes, & de Pinho, 2015) and grape pomace (Mora et al., 2019; Pereira et al., 2020), while studies addressing wastewater are still incipient. Despite that, winery wastewater (Table 11.1) can also be seen as a source for biomolecules recovery, and membrane technologies have emerged as a promising alternative for this purpose (Cassano, Conidi, Ruby-Figueroa, Castro-Mun˜oz, 2018). Therefore considering the precepts presented in studies with extracts from wine industry byproducts and also those with wastewater from other agroindustrial activities, it is possible to propose membranebased processes that will be capable of recovering biomolecules from winery wastewater. In a process for biomolecules recovery using a cascade of membrane technologies, MF or loose UF may be used to remove the components responsible for the turbidity of wastewater, such as suspended solids and colloids, resulting in a permeate stream containing phenolic compounds, organic acids, sugars, and minerals. Subsequently, the permeate of MF and loose UF can be concentrated by tight NF or RO, and the retentate can be used as food additives and pharmaceutical and cosmetic products, while the tight NF/RO permeate can be water for reuse (Fig. 11.5). Additionally, by adding a loose NF step between MF/loose UF and tight NF/RO, the MF/loose UF permeate could be fractionated, resulting in a concentrate that is rich in polyphenols and polysaccharides and a permeate containing monosaccharides (glucose, fructose, sucrose) and small

Figure 11.5 Conceptual framework of a cascade membrane process for the recovery of phenolic compounds from winery wastewater.

Chapter 11 Winery wastewater treatment for biomolecules recovery and water reuse purposes

organic acids, which can then be subjected to the final concentration step via tight NF or RO to be used later as a food additive (Fig. 11.6). Moreover, the operations shown in Figs. 11.5 and 11.6 may be conducted in diafiltration mode, resulting in a greater recovery of target compounds in the MF/loose UF permeate stream and obtaining concentrate streams with a greater degree of purity in subsequent steps. Alternatively, an extraction step can also be employed, aiming at the selective extraction of target compounds (e.g., phenolic compounds), and integrated with membrane technologies, which would act as a concentration step for the target com˜ adas pounds present in the extract (Fig. 11.7). In this sense, Can et al. (2021) assessed chloride ammonium salts based hydrophobic eutectic solvents as a greener alternative to organic solvents for the recovery of phenolic compounds from winery wastewater. By using trimethyloctylammonium chloride-DLmenthol, at a molar ratio of 1:2, and trimethyloctylammonium chloride-octanoic acid at a molar ratio of 1:1, the authors achieved recovery efficiencies of phenolic compounds up to 83.64% and 84.10%, respectively, from a winery wastewater. They performed the liquid-liquid extraction, at a solvent/wastewater ratio of 1, extraction time of 15 min under agitation at 500 rpm, and posterior centrifugation for 15 min at 3500 rpm, in which the phenolic compound enriched fraction (less dense)

Figure 11.6 Conceptual framework of a cascade membrane process for the recovery and fractionation of biomolecules from winery wastewater.

Figure 11.7 Conceptual framework of an integrated membrane process for the selective recovery of phenolic compounds from winery wastewater.

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was recovered on the top and the water-rich fraction remained at the bottom. Indeed, the recovery of biomolecules is considered a promising alternative for the valorization of byproducts of the wine industry, as in addition to providing an improvement in environmental performance, owing to the reduction of the pollutant load of wastewater, it also facilitates its treatment in downstream stages, mainly owing to the removal of phenolic compounds, which have been considered toxic to microorganisms present in biological treatments (Mosse et al., 2013). In this way, it is possible to obtain treated wastewater with a better quality, which allows its reuse in agriculture. Reports have pointed out that polyphenols have also shown phytotoxic effects on plants and soil microorganisms (Mosse, Patti, Christen, & Cavagnaro, 2010; Shilpi et al., 2018), being recommended the removal of these compounds prior to using the winery wastewater for irrigation purposes. Furthermore, membrane technologies also play an important role in terms of water and wastewater reuse, which will be discussed in the next section.

11.6

Wastewater reuse

Water is becoming increasingly scarce, mainly in regions that suffer droughts and have experienced increased levels of irrigation (European Commission, 2012). Actually, irrigation in the vineyard is a practice of increasing use in many regions. The Mediterranean region is identified as one of the most prominent hotspots in future climate change projections, and projected climate changes will have a direct impact on water resources and crop irrigation requirements (Costa et al., 2020; Diffenbaugh & Giorgi, 2012; Giorgi, 2006). In 2006 the World Health Organization (WHO) has published guidelines for the safe use of wastewater in agriculture (WHO, 2006). However, these guidelines do not address the concerns of the wine industry, as the main focus is on heavy metals and human pathogens. Similarly, the European regulations are more directed to microbiological parameters, since their focus has been on the reuse of domestic wastewater (Brissaud, 2008). Microbiological parameters have great relevance from a public health point of view, but they must be considered only in treatment systems receiving domestic wastewater. In this sense, wineries that plan to reuse treated wastewater for irrigation must segregate flows and treat industrial and domestic wastewater separately, since the domestic effluent flow is about 100-fold to

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1000-fold smaller. This avoids the need for the disinfection step in the total flow generated, reducing treatment costs. The analytical parameters of the treated winery wastewater are usually in agreement with these guidelines. However, sodium and potassium compounds from sanitizing agents and measured as sodium adsorption ratio and potassium adsorption ratio are typically higher than the allowed parametric value (Laurenson, Bolan, Smith, & McCarthy, 2010; Oliveira et al., 2009). These substances are a concern when the treated wastewater is to be reused for irrigation, since conventional treatment processes do not significantly reduce salt concentrations (Hirzel, Steenwerth, Parikh, & Oberholster, 2017; Mosse, Patti, Smernik, Christen, & Cavagnaro, 2012). A study conducted in South Africa revealed that in regions with low rainfall, irrigation with winery wastewater would lead to the spread of cations, increasing soil salinity (Mulidzi, Clarke, & Myburgh, 2020). Studies on the long-term effects of the use of untreated winery wastewater in the irrigation process showed a negative impact on soil structural stability (Liang, Rengasamy, Smernik, & Mosley, 2021; Mosse et al., 2012, 2013). When the treated wastewater was applied, no significant differences in nitrogen and carbon cycling were detected in the short-term analysis (Mosse et al., 2012, 2013). Considering the treatment processes that were identified in Section 11.4 and constraints highlighted previously, the most relevant processes applied for the reuse of treated wastewater will be outlined (Fig. 11.8). Mitigation strategies should be adopted at the winery level. The reuse of the wash water to exhaustion, at which point it ceases to be effective as a bitartrate dissolving agent, could be very useful in preventing contamination. Also, it is advisable to replace disinfectants and cleaning agents by ozone (Cullen & Norton, 2012; Guillen, Kechinski, & Manfroi, 2010; Pascual, Llorca, & Canut, 2007). It is probable that the ozone treatment will allow decreases in both conductivity and COD, thus contributing to compliance with the legal limits for beneficial crop irrigation (Cullen & Norton, 2012; Lucas et al., 2009). Also, the reduction in

Figure 11.8 Treatment strategy for winery wastewater reuse, based on reviewed literature.

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COD can be achieved by screening out solids larger than 0.5 1.0 mm with basket screens as a pretreatment and by reducing the contact period between solids and wastewater. The reuse of wastewater in irrigation is limited to a maximum concentration of organic matter of 500 mg L21, expressed as biochemical oxygen demand (BOD). The WHO guidelines further state that the application of wastewater with a BOD between 110 and 400 mg L21 can be beneficial to cultures (WHO, 2006). MBR technology was applied to wine wastewater and compared with conventional activated sludge systems, revealing similar COD removal rates. The MBR was very effective in removing suspended solids and microbiological contamination, producing treated wastewater that met the requirements for reuse in agricultural practices (Valderrama et al., 2012) and all kinds of industrial applications (To¨re & Sesler, 2021). In addition, treated wastewater from SBR was used for irrigation purposes, and no negative impacts were detected (Mosse et al., 2012). Regarding COD removal, a treatment system consisting of hydrolytic upflow sludge blanket (HUSB) and CWs allowed reuse of the treated wastewater for irrigation as long as the influent did not exceed COD values higher than 2000 mg L21 (Pascual et al., 2021). Although the treatment system treated industrial and domestic flow in combination, the study did not evaluate the removal of Escherichia coli. From the results it can be concluded that the combination of CWs and HUSB can be adapted to treat the high and variable organic load from the wine industry while producing water that is suitable for agricultural irrigation (Pascual et al., 2021). Given the relevance of the salt content in these wastewaters, it becomes urgent to evaluate the efficiency of wine wastewater treatment systems against these parameters. Studies conducted in CWs have shown the potential application of halophytes in removing the salt content from wine wastewater, namely, Na1 and K1 (Mader, Holtman, & Welz, 2022; Matinzadeh, Akhani, Abedi, & Palacio, 2019). However, the composition and concentration of contaminants should be known prior to selection of the halophytic plant species. The potential ecological risk associated with the application of treated wastewater cannot be assessed by chemical characterization alone, as this does not allow an assessment of the possible combined effects of the different contaminants mixed together as well as an evaluation of their bioavailability. One of the methods that is used is phytotoxicity assessment through germination and growth of seedlings (L. sativum) to understand the ability of plants to compete and survive in their environment (APHA, 2005). Therefore to evaluate the potential phytotoxicity of

Chapter 11 Winery wastewater treatment for biomolecules recovery and water reuse purposes

wastewater after treatment, due to possible synergistic and deleterious effects of various water contaminants, bioassays should be envisaged, such as cress as a plant indicator (Fja¨llborg, Ahlberg, Nilsson, & Dave, 2005; Mekki, Dhouib, & Sayadi, 2007; Mosse et al., 2010; Muyen, Moore, & Wrigley, 2011; Oliveira et al., 2009; Stutte, Eraso, Anderson, & Hickey, 2006; van Gestel et al., 2001). Studies conducted with the AMBB showed that the diluted treated wastewater was suitable for irrigation. These conclusions were based on physicochemical analyses and phytotoxicity tests (Oliveira et al., 2009). As posttreatment, various methods such as ion exchange and RO can be used, which are effective in removing salt in winery wastewaters. The ion-exchange process is characterized by the exchange of ions between the solution to be treated and an immobilized resin; it is a widespread process in wastewater treatment systems for the removal of ions, including ammonium (Jorgensen & Weatherley, 2003), chromium (Rengaraj et al., 2001) and boron (Kabay et al., 2004). Ion-exchange resins can be generated synthetically or by using natural zeolites (clinoptolites), which are also effective in removing cationic contaminants (Pitcher, Slade, & Ward, 2004). This natural mineral shows high and moderate specificity for K1 and Na1, respectively, suggesting its applicability to the removal of these inorganic ions from winery wastewater. RO is the most suitable technology for salt removal and water purification, being used in wastewater treatment for potable water production. Although RO is very effective, pretreatment by MF (Durham et al., 2001) or UF (van Hoof, Hashim, & Kordes, 1999) is necessary to prevent biofouling of the RO membrane and ensure that the RO system will operate at design capacity (Jacob et al., 2010). Another key issue in membrane treatment is the high energy demand for operation, although pretreatment stages have been shown to reduce the energy requirements (Pearce, 2007). Although RO is appropriated to wastewater treatment (Dolar et al., 2012; Ioannou et al., 2013; Jacob et al., 2010; Zhang et al., 2011), the economic and environmental costs should be taken into account (Mosse et al., 2011). Nevertheless, if a membrane system is used to recover biomolecules and other products, in addition to water (Section 11.5), this can be compensated for. The selection of the appropriate treatment system that allows compliance with legal requirements for reuse and at the same time prevents negative impacts on the ecosystem is crucial. To valorize the value-added compounds of the wine

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Figure 11.9 Conceptual approach for value-added compound recovery and wastewater reuse in a winery.

wastewater and to produce high-quality treated wastewater, we propose a sequence of separation and treatment processes (Fig. 11.9). This management model will enable the recovery of valueadded compounds and water saving, with obvious benefits for the environment and no apparent risk to public health.

11.7

Conclusions and future trends

The wine industry is one of the most important food and beverage industries in the world and also one with great polluting potential due to the high volume and load of wastewater that is generated. Therefore considering average values of wastewater generation, 2.2 L per liter of wine produced (Oliveira et al., 2019; Welz et al., 2016), the average wine production of the last decade, 270 MhL (OIV, 2021), and moderate values for the concentration of phenolic compounds in wastewater, 5 mg L21 (see Table 11.1), it is estimated that the wine industry annually generates about 54 billion liters of wastewater containing about 297,000 kg of phenolic compounds. Currently, these wastewaters are seen as environmental liabilities that must be treated before being discharged into the environment when in fact they are important and inexpensive sources of raw materials such as phenolic compounds and water. Although this is a rough and simplistic calculation, it serves to give an idea of the amount of resources wasted annually in wastewater from the wine sector, since these phenolic compounds are not recovered and only a small fraction of this water is reused for irrigation. In this regard, membrane technologies have been shown to be effective in the recovery, purification, and concentration of phenolic compounds and other biomolecules from wastewater and agroindustrial waste extracts, emerging as a promising

Chapter 11 Winery wastewater treatment for biomolecules recovery and water reuse purposes

alternative for the recovery and valorization of biomolecules from winery wastewater. Furthermore, membrane technologies can be integrated with other wastewater treatment methods, resulting in high-quality treated effluent for industrial or agricultural reuse, meeting the concepts of a circular economy. It is important to highlight that actions of this magnitude, associated with those that already exist in the context of recovering value-added compounds from solid wastes, tend to bring a traditional winery closer to the concept of biorefinery, in which losses are minimized and resources are used to the full, providing achievements in economic, environmental, and social areas, as preconized in the Sustainable Development Goals of the United Nations for 2030.

List of acronyms ABB AMBB AOP BOD COD CW DO ECCF FAO FBB FBBR F/M FU GAE GE HUSB JLR NF MBR MF MW MWCO OIV OUR RBC RO SBBR SBR TSS UF VFA WHO

air bubble column bioreactor air microbubble bioreactor advanced oxidation process biochemical oxygen demand chemical oxygen demand constructed wetland dissolved oxygen evapoconcentration to fractional condensation (abbreviation from French, evapoconcentration a` condensation fractionne´e) Food and Agriculture Organization fluidized-bed bioreactor fixed-bed biofilm reactor food-to-microorganism ratio functional unit gallic acid equivalent glucose equivalent hydrolytic upflow sludge blanket jet-loop reactor nanofiltration membrane bioreactor microfiltration molecular weight molecular weight cutoff International Organization of Vine and Wine (abbreviation from French, Organisation internationale de la vigne et du vin) oxygen uptake rate rotating biological contactor reverse osmosis sequencing batch biofilm reactor sequencing batch reactor total suspended solids ultrafiltration volatile fatty acid World Health Organization

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Bhise, S., Kaur, A., Gandhi, N., & Gupta, R. (2014). Antioxidant property and health benefits of grape byproducts. Journal of Postharvest Technology, 2, 1 11. Bolzonella, D., Fatone, F., Pavan, P., & Cecchi, F. (2010). Application of a membrane bioreactor for winery wastewater treatment. Water Science and Technology: A Journal of the International Association on Water Pollution Research, 62, 2754 2759. Available from https://doi.org/10.2166/wst.2010.645. Bolzonella, D., Papa, M., Da Ros, C., Anga Muthukumar, L., & Rosso, D. (2019). Winery wastewater treatment: A critical overview of advanced biological processes. Critical Reviews in Biotechnology, 39, 489 507. Available from https://doi.org/10.1080/07388551.2019.1573799. Bolzonella, D., & Rosso, D. (2009). Winery wastewater characterisation and biological treatment options. In: Proceedings of the fifth international specialized conference on sustainable viticulture and winery wastes management (pp. 19 26). Trento-Verona, Italy. Bories, A., Guillot, J.-M., Sire, Y., Couderc, M., Lemaire, S.-A., Kreim, V., & Roux, J.-C. (2007). Prevention of volatile fatty acids production and limitation of odours from winery wastewaters by denitrification. Water Research, 41, 2987 2995. Available from https://doi.org/10.1016/j.watres.2007.03.022. Bories, A., Sire, Y., Bouissou, D., Goulesque, S., Moutounet, M., Bonneaud, D., & Lutin, F. (2011). Environmental impacts of tartaric stabilisation processes for wines using electrodialysis and cold treatment. South African Journal of Enology and Viticulture, 32, 174 182. Available from https://doi.org/10.21548/32-2-1377. Bories, A., Sire, Y., & Colin, T. (2005). Odorous compounds treatment of winery and distillery effluents during natural evaporation in ponds. Water Science and Technology: A Journal of the International Association on Water Pollution Research, 51, 129 136. Available from https://doi.org/10.2166/wst.2005.0016. Braz, R., Pirra, A., Lucas, M. S., & Peres, J. A. (2010). Combination of long term aerated storage and chemical coagulation/flocculation to winery wastewater treatment. Desalination, 263, 226 232. Available from https://doi.org/ 10.1016/j.desal.2010.06.063. Brissaud, F. (2008). Criteria for water recycling and reuse in the Mediterranean countries. Desalination, 218, 24 33. Available from https://doi.org/10.1016/j. desal.2006.07.016. Brito, A. G., Peixoto, J., Oliveira, J. M., Oliveira, J. A., Costa, C., Nogueira, R., & Rodrigues, A. (2007). Brewery and winery wastewater treatment: Some focal points of design and operation. In V. Oreopoulou, & R. Winfred (Eds.), Utilization of by-products and treatment of waste in the food industry (pp. 109 131). New York: Springer. Available from https://doi.org/10.1007/978-0-387-35766-9_7. Brucculeri, M., Bolzonella, D., Battistoni, P., & Cecchi, F. (2005). Treatment of mixed municipal and winery wastewaters in a conventional activated sludge process: A case study. Water Science and Technology: A Journal of the International Association on Water Pollution Research, 51, 89 98. Available from https://doi.org/10.2166/wst.2005.0011. Burgin, A. J., & Hamilton, S. K. (2007). Have we overemphasized the role of denitrification in aquatic ecosystems? A review of nitrate removal pathways. Frontiers in Ecology and the Environment, 5, 89 96. Available from https:// doi.org/10.1890/1540-9295(2007)5[89:HWOTRO]2.0.CO;2. ˜ adas, R., Gonza´lez-Miquel, M., Gonza´lez, E. J., Dı´az, I., & Rodrı´guez, M. Can (2021). Hydrophobic eutectic solvents for extraction of natural phenolic antioxidants from winery wastewater. Separation and Purification Technology, 254, 117590. Available from https://doi.org/10.1016/j.seppur.2020.117590. Cassano, A., Bentivenga, A., Conidi, C., Galiano, F., Saoncella, O., & Figoli, A. (2019). Membrane-based clarification and fractionation of red wine lees

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Journal of the International Association on Water Pollution Research, 60, 1217 1223. Available from https://doi.org/10.2166/wst.2009.558. Ormad, M. P., Mosteo, R., Ibarz, C., & Ovelleiro, J. L. (2006). Multivariate approach to the photo-Fenton process applied to the degradation of winery wastewaters. Applied Catalysis B: Environmental, 66, 58 63. Available from https://doi.org/10.1016/j.apcatb.2006.02.014. Pascual, A., Llorca, I., & Canut, A. (2007). Use of ozone in food industries for reducing the environmental impact of cleaning and disinfection activities. Trends in Food Science and Technology, 18, S29 S35. Available from https:// doi.org/10.1016/j.tifs.2006.10.006. Pascual, A., Pena, R., Go´mez-Cuervo, S., de la Varga, D., Alvarez, J. A., Soto, M., & Arias, C. A. (2021). Nature based solutions for winery wastewater valorisation. Ecological Engineering, 169, 106311. Available from https://doi.org/10.1016/j. ecoleng.2021.106311. Pearce, G. (2007). Introduction to membranes: Water and wastewater—RO pretreatment. Filtration & Separation, 44, 28 31. Available from https://doi.org/ 10.1016/S0015-1882(07)70216-1. Pereira, D. T. V., Vollet Marson, G., Ferna´ndez Barbero, G., Gadioli Tarone, A., Bau´ Betim Cazarin, C., Dupas Hubinger, M., & Martı´nez, J. (2020). Concentration of bioactive compounds from grape marc using pressurized liquid extraction followed by integrated membrane processes. Separation and Purification Technology, 250, 117206. Available from https://doi.org/10.1016/j.seppur.2020.117206. Pe´rez-Garcı´a, M., Romero-Garcı´a, L. I., Rodrı´guez-Cano, R., & Sales-Ma´rquez, D. (2005). High rate anaerobic thermophilic technologies for distillery wastewater treatment. Water Science and Technology: A Journal of the International Association on Water Pollution Research, 51, 191 198. Available from https://doi.org/10.2166/wst.2005.0024. Petruccioli, M., Cardoso Duarte, J., Eusebio, A., & Federici, F. (2002). Aerobic treatment of winery wastewater using a jet-loop activated sludge reactor. Process Biochemistry, 37, 821 829. Available from https://doi.org/10.1016/ S0032-9592(01)00280-1. Petruccioli, M., Duarte, J., & Federici, F. (2000). High-rate aerobic treatment of winery wastewater using bioreactors with free and immobilized activated sludge. Journal of Bioscience and Bioengineering, 90, 381 386. Available from https://doi.org/10.1016/S1389-1723(01)80005-0. Pirra, A. (2008). Manual de boas pra´ticas ambientais na adega. In: APHVINGHEVID—Associac¸a˜o Portuguesa Da Histo´ria Da Vinha e Do Vinho, p. 231. Pirra, A., Arroja, L., & Capela, I. (2004). Winery effluents treatment using SBR technology. In: Proceedings of the third international specialized conference on sustained viticulture and winery. Wastes management (pp. 167 174). Barcelona, Spain. University of Barcelona, Barcelona, Spain. Pirra, A. J. D. (2005). Characterization and treatment of winery effluents from the Douro Wine Region (Caracterizac¸a˜o e tratamento de efluentes vinı´colas da Regia˜o Demarcada do Douro). University of Tra´s-os-Montes and Alto Douro. Vila Real, Portugal. Pitcher, S. K., Slade, R. C. T., & Ward, N. I. (2004). Heavy metal removal from motorway stormwater using zeolites. The Science of the Total Environment, 334 335, 161 166. Available from https://doi.org/10.1016/j. scitotenv.2004.04.035. Portilla Rivera, O. M., Saavedra Leos, M. D., Solis, V. E., & Domı´nguez, J. M. (2021). Recent trends on the valorization of winemaking industry wastes. Current Opinion in Green and Sustainable Chemistry, 27, 100415. Available from https://doi.org/10.1016/j.cogsc.2020.100415.

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Pubchem (2021). PubChem source information. ,https://pubchem.ncbi.nlm. nih.gov/. Accessed 8.16.21. Puig, S., Corominas, L., Traore, A., Colomer, J., Balaguer, M. D., & Colprim, J. (2006). An on-line optimisation of a SBR cycle for carbon and nitrogen removal based on on-line pH and OUR: The role of dissolved oxygen control. Water Science and Technology: A Journal of the International Association on Water Pollution Research, 53, 171 178. Available from https://doi.org/ 10.2166/wst.2006.121. Racault, Y., Cornet, D., & Vedrenne, J. (1998). Application du traitement biologique ae´robie double e´tage aux effluents vinicoles: Evaluation de deux proce´de´s lors des vendanges en bordelais. In: Actes Du 2e´me Congre`s International Sur Le Traitement Des Effluents Vinicole (Cemagref Editions, pp. 197 206). France: Bourdeaux. Racault, Y., & Stricker, A.E. (2004). Combining membrane filtration and aerated storage: Assessment of two full scale processes treating winery effluents. In: Proceedings of the third international specialised conference on sustainable viticulture and winery wastes management (pp. 105 112). University of Barcelona, Barcelona, Spain. Rengaraj, S., Yeon, K.-H., & Moon, S.-H. (2001). Removal of chromium from water and wastewater by ion exchange resins. Journal of Hazardous Materials, 87, 273 287. Available from https://doi.org/10.1016/S0304-3894(01)00291-6. Rizzo, A., Bresciani, R., Martinuzzi, N., & Masi, F. (2020). Online monitoring of a long-term full-scale constructed wetland for the treatment of winery wastewater in Italy. Applied Sciences. Available from https://doi.org/10.3390/ app10020555. Rochard, J. (2017). Processes of treatment of wineries effluents adapted to the organic wine sector: Current situation and prospects. In: Proceedings of the fortieth World Congress of Vine and Wine (6 pp.). OIV, Sofia, Bulgaria. Rochard, J., Racault, Y., & Canler, J.P. (2000). Les filie`res d’e´puration des effluents vinicoles. Rodrigues, A. C., Oliveira, J. M., Oliveira, J. A., Peixoto, J., Nogueira, R., & Brito, A. G. (2006). Tratamento de efluentes vitivinı´colas: uma caso de estudo na ´ stria e Ambient, 40, 20 25. regia˜o dos vinhos verdes. Revista. Indu ˜o´n-Gonza´lez, J. H., Herna´ndez-Manzano, Ruiz-Ordaz, N., Ruiz-Lagunez, J. C., Castan E., Cristiani-Urbina, E., & Galı´ndez-Mayer, J. (2001). Phenol biodegradation using a repeated batch culture of Candida tropicalis in a multistage bubble column. Revista Latinoamericana de Microbiologia, 43, 19 25. Santos-Buelga, C., & Feliciano, A. S. (2017). Flavonoids: From structure to health issues. Molecules (Basel, Switzerland), 22, 477. Available from https://doi.org/ 10.3390/molecules22030477. Saraiva, A., Presumido, P., Silvestre, J., Feliciano, M., Rodrigues, G., Silva, P. O., . . . Oliveira, M. (2020). Water footprint sustainability as a tool to address climate change in the wine sector: A methodological approach applied to a Portuguese case study. Atmosphere (Basel). Available from https://doi.org/ 10.3390/atmos11090934. Sevillano, C. B. A., Chiappero, M., Gomez, X., Fiore, S., & Martı´nez, E. J. (2020). Improving the anaerobic digestion of wine-industry liquid wastes: Treatment by electro-oxidation and use of biochar as an additive. Energies. Available from https://doi.org/10.3390/en13225971. Shepherd, H. (1998). Performance evaluation of a pilot scale constructed wetland used for treatment of winery process wastewater. In: Actes Du 2e´me Congre`s International Sur Le Traitement Des Effluents Vinicole (pp. 155 163). Bourdeaux, France: CEMAGREF.

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Shilpi, S., Seshadri, B., Sarkar, B., Bolan, N., Lamb, D., & Naidu, R. (2018). Comparative values of various wastewater streams as a soil nutrient source. Chemosphere, 192, 272 281. Available from https://doi.org/10.1016/j. chemosphere.2017.10.118. Souquet, J.-M., Cheynier, V., Brossaud, F., & Moutounet, M. (1996). Polymeric proanthocyanidins from grape skins. Phytochemistry, 43, 509 512. Available from https://doi.org/10.1016/0031-9422(96)00301-9. Stricker, A.-E., & Racault, Y. (2005). Application of Activated Sludge Model No. 1 to biological treatment of pure winery effluents: Case studies. Water Science and Technology: A Journal of the International Association on Water Pollution Research, 51, 121 127. Available from https://doi.org/10.2166/wst.2005.0015. Stutte, G. W., Eraso, I., Anderson, S., & Hickey, R. D. (2006). Bioactivity of volatile alcohols on the germination and growth of radish seedlings. HortScience: A Publication of the American Society for Horticultural Science, 41, 108 112. Available from https://doi.org/10.21273/HORTSCI.41.1.108. Tillman, R. W., & Surapaneni, A. (2002). Some soil-related issues in the disposal of effluent on land. Australian Journal of Experimental Agriculture, 42, 225 235. Available from https://doi.org/10.1071/EA00133. To¨re, G. Y., & Sesler, S¸ . K. (2021). Developments in membrane bioreactor technologies and evaluation on case study applications for recycle and reuse of miscellaneous wastewaters. In M. P. Shah, & S. B. T.-M.-B. H. P. RodriguezCouto (Eds.), Membrane-based hybrid processes for wastewater treatment (pp. 503 575). Elsevier, for W. T. Available from https://doi.org/10.1016/B9780-12-823804-2.00006-9. Torrijos, M., & Moletta, R. (1997). Winery wastewater depollution by sequencing batch reactor. Water Science and Technology: A Journal of the International Association on Water Pollution Research, 35, 249 257. Available from https:// doi.org/10.1016/S0273-1223(96)00903-1. Torrijos, M., Moletta, R., & Delgenes, J.P. (2004). Treatment of winery effluents in sequencing batch reactors (SBR). In: Proceedings of the 3rd international specialised conference on sustainable viticulture and winery wastes management (pp. 393 396). University of Barcelona, Barcelona, Spain. Tsao, R. (2010). Chemistry and biochemistry of dietary polyphenols. Nutrients. Available from https://doi.org/10.3390/nu2121231. Valderrama, C., Ribera, G., Bahı´, N., Rovira, M., Gime´nez, T., Nomen, R., . . . Martinez-Llado´, X. (2012). Winery wastewater treatment for water reuse purpose: Conventional activated sludge vs membrane bioreactor (MBR): A comparative case study. Desalination, 306, 1 7. Available from https://doi. org/10.1016/j.desal.2012.08.016. van Gestel, C. A. M., van der Waarde, J. J., Derksen, J. G. M., (Anja)., van der Hoek, E. E., Veul, M. F. X. W., . . . Stokman, G. N. M. (2001). The use of acute and chronic bioassays to determine the ecological risk and bioremediation efficiency of oil-polluted soils. Environmental Toxicology and Chemistry/SETAC, 20, 1438 1449. Available from https://doi.org/10.1002/etc.5620200705. van Hoof, S. C. J. M., Hashim, A., & Kordes, A. J. (1999). The effect of ultrafiltration as pretreatment to reverse osmosis in wastewater reuse and seawater desalination applications. Desalination, 124, 231 242. Available from https://doi.org/10.1016/S0011-9164(99)00108-3. Vanossi, M., & Durante, F. (2009). Recycling of process wastewater in the beverages industry using membrane bioreactors (MBR). In: Proceedings of the fifth international specialised conference on sustainable viticulture: Winery wastes and ecological impacts management (pp. 295 300). University of Trento, Trento and Verona, Italy.

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Vlyssides, A. G., Barampouti, E. M., & Mai, S. (2005). Wastewater characteristics from Greek wineries and distilleries. Water Science and Technology: A Journal of the International Association on Water Pollution Research, 51, 53 60. Available from https://doi.org/10.2166/wst.2005.0007. Wang, J. L., & Xu, L. J. (2012). Advanced oxidation processes for wastewater treatment: Formation of hydroxyl radical and application. Critical Reviews in Environmental Science and Technology, 42, 251 325. Available from https:// doi.org/10.1080/10643389.2010.507698. Welz, P. J., Holtman, G., Haldenwang, R., & le Roes-Hill, M. (2016). Characterisation of winery wastewater from continuous flow settling basins and waste stabilisation ponds over the course of 1 year: Implications for biological wastewater treatment and land application. Water Science and Technology: A Journal of the International Association on Water Pollution Research, 74, 2036 2050. Available from https://doi.org/10.2166/wst.2016.226. WHO—World Health Organization. (2006). Guidelines for the safe use of wastewater, excreta and greywater. Wastewater use in agriculture (2). WHO. Wilderer, P., Irvine, R., & Goronszy, M. C. (2001). Sequencing batch reactor technology. London: IWA Publishing. Xu, Y., Zhou, J., Qu, Y., Yang, H., & Liu, Z. (2010). Dynamics and oxygen transfer of a novel vertical tubular biological reactor for wastewater treatment. Chemical Engineering Journal., 156, 92 97. Available from https://doi.org/ 10.1016/j.cej.2009.10.002. Zacharof, M.-P. (2017). Grape winery waste as feedstock for bioconversions: Applying the biorefinery concept. Waste and Biomass Valorization, 8, 1011 1025. Available from https://doi.org/10.1007/s12649-016-9674-2. Zhang, Y., Ghyselbrecht, K., Meesschaert, B., Pinoy, L., & Van der Bruggen, B. (2011). Electrodialysis on RO concentrate to improve water recovery in wastewater reclamation. Journal of Membrane Science, 378, 101 110. Available from https://doi.org/10.1016/j.memsci.2010.10.036.

12 Nanomaterials for the removal of organic pollutants from agrofood wastewaters Roxana-Ioana Brazdis1,2, Radu Claudiu Fierascu1,2, Sorin-Marius Avramescu3 and Irina Fierascu1,4 1

Emerging Nanotechnologies Group, National Institute for Research & Development in Chemistry and Petrochemistry—ICECHIM, Bucharest, Romania 2Department of Science and Engineering of Oxide Materials and Nanomaterials, University Politehnica of Bucharest, Bucharest, Romania 3 Research Center for Environmental Protection and Waste Management, University of Bucharest, Bucharest, Romania 4University of Agronomic Sciences and Veterinary Medicine of Bucharest, Bucharest, Romania

12.1

Introduction

Until around three decades ago, natural resources were considered readily available at no or little cost except those of exploitation and processing. Over the years, anthropic activities (industrialization, intensive agriculture practices, population growth, etc.) resulted in a significant pollution of natural ecosystems, decrease in biodiversity, and resources depletion. Agroindustrial practices have the highest impact on environmental equilibria, since they are directly linked to the basic human survival needs and the overconsumerism of modern society. Global water supplies are most affected, owing to high consuming and pollution phenomena induced by large amount of wastewaters resulting from foodprocessing activities (Rajagopal et al., 2013). The food processing industry is known as the third consumer of water resources , one of the main reasons being the high number of stages from farm to supermarket associated with this industry. Most processing operation steps in agroindustry are water-based (washing the raw materials, processes after peeling, sanitation cleanup, cooking or processed product cooling). Thus processing the raw materials, along with packaging activities require large amounts of aqueous effluents and produce process wastewater, which often contain large amounts of pesticides and other compounds used as Advanced Technologies in Wastewater Treatment. DOI: https://doi.org/10.1016/B978-0-323-88510-2.00008-7 Copyright © 2023 Elsevier Inc. All rights reserved.

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˜as et al., 2019). adjuvants in the plants’ growth (Campos-Man Organic chemical products such as imazalil, thiabendazole, and ortho-phenylphenol, usually persist after the treatment processes and return to the environment (Ko¨ck-Schulmeyer et al., 2014). Thus the quantities of wastewaters that result from these processes are significant and requires adequate treatment technologies. In the absence of appropriate preventive measures, the detrimental effect of pollution are likely to get a considerable boost in the next years ( Kuzmanovi´c et al., 2015; Łozowicka et al., 2016). There are several aspects that account for food-processing wastewaters patterns and characteristics (Liu et al., 2021a, 2021b): 1. High variability of wastewater discharges volumes, including significant differences between households comparing with large factories (a hundred or a thousand times more). 2. Many organic and inorganic compounds are found in these wastewaters (oils, fats, proteins, carbohydrates, heavy metal, pesticides, nitrogen, phosphorus, etc.) (Tekerlekopoulou et al., 2020). They are transferred from raw materials or from different adjuvants required in the fabrication process. Some of these compounds are biodegradable, and others are nonbiodegradable or even toxic; hence the treatment of these effluents is a difficult process. This is also a source of biological hazard due to presence of pathogenic or nonpathogenic microorganisms; 3. These streams present high pollutant concentrations, which are generally expressed as global parameters: total solids (TS), total phosphorus (TP), chemical oxygen demand (COD), and biological oxygen demand (BOD). These parameters and their correlations (e.g., COD/BOD ratio) provide us with information about the treatment strategies to be adopted. There are three main production sections of food industry that generates wastewaters: 1. The cleaning section of raw materials could contain sand, soil debris, leaves, skin, hairs, feathers, oils, heavy metals, and natural pigments; 2. The production section could contain organic substances because of the raw materials that could not be entirely processed; 3. The forming section could contain additives, pigments, and aromas. At the end of food processing, all these pollutants reach the aquatic environment, causing biological and health problems on long-term.

Chapter 12 Nanomaterials for the removal of organic pollutants from agrofood wastewaters

In this context, this chapter discusses the agro-food industries that are responsible for water pollution along with the achievements in the field of materials/nanomaterials used for wastewater depollution. This chapter is a critical discussion of issues related to water decontamination in terms of environmental protection, using novel materials with recovery capacities and, if possible, low costs involved.

12.2

Slaughterhouse wastewater

It is known that meat represents the first choice of animal protein for lots of people around the world, and the consumption of meat is increasing daily. This industry continues to grow rapidly, owing to world population growth and therefore higher consumer demand (Valta et al., 2015). For example, the poultry meat production worldwide increased by 3% from 2018 to 2019, reaching approximately 128 million metric tons (FAO, 2020; Hilares et al., 2021). The wastewater derived from this industry is characterized by its strong color index and turbidity and by high levels of organic matter, suspended solids, and mixtures of fats (Alfonso-Muniozguren et al., 2021), requiring special care before its disposal into the environment. A considerable amount of wastewater is discharged from slaughter industries, being the result of slaughtering, meat processing or equipment cleaning, such as the animal holding, slaughter, or freezing rooms (Aziz et al., 2019). It has been reported that directly or indirectly, approximately 29% of the total freshwater is used for the manufacturing of animal products, both meat and dairy products (Gerbens-Leenes, Mekonnen, & Hoekstra, 2013). Fig. 12.1 presents the processing steps in a slaughterhouse, from the raw material to the final product, all of them generating wastewater. Slaughterhouse wastewaters are rich in carbohydrates, proteins, lipids, and the most concerning of all, pathogens and antibiotic-resistant microbes, which enable the spreading of the pollutants in the environment (Deng et al., 2022). More than that, there is a compelling presence of veterinary pharmaceutical products in this type of wastewater (Zahedi et al., 2021).

12.3

Dairy wastewater

Another product that is frequently used as an ingredient around the world is milk, an essential source of nutrients without which the human body cannot perform its vital functions.

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Figure 12.1 Meat-processing steps in a slaughterhouse.

The overall process of the dairy industry includes the proper processing of milk to different products, packaging, storage of products, and final distribution, in the end playing an important role in environmental pollution (Kaur, 2021). Some reports state that for every 1 kg of milk, between 8.0 and 35.0 L of water are used for the milk processing, and 0.2 10 L of wastewater per liter of processed milk is discharged into the environment (Custodio et al., 2022; Mansoorian et al., 2016). The processing of butter, cheese, and cream and the washing of drying equipment represent the most polluting processes (Shi et al., 2021). Fig. 12.2 illustrates several examples of dairy industry discharges: Recently, it was demonstrated that the dairy industry has serious effects upon aquatic systems, accelerating the multiplication of pathogens and eutrophication (Sharma et al., 2018). These aspects are creating a great impact on the environment because of the high consumption of water and, most important, high effluent production. Generally, the wastewaters that are produced by the dairy industry are neutral or lightly alkaline and high in dissolved organic substances, such as lactose, which is the principal pollutant, colloidal protein suspensions, and mineral salts (Charalambous, 2020). As a result of lactose fermentation, the wastewater may suffer pH transformations, becoming acidic (Shi et al., 2021).

Chapter 12 Nanomaterials for the removal of organic pollutants from agrofood wastewaters

Figure 12.2 Examples of dairy industry discharges.

The COD concentrations in this kind of wastewater varies from 2000 to 4000 mg L21, and the BOD varies from 2000 to 3000 mg L21 (Custodio et al., 2022), while the pH values range from 4.7 to 11 as a result of the content of sterilizing agents or alkaline detergents used in the cleaning process (Ahmad et al., 2019). The biological degradation of dairy discharges takes place faster than that of municipal wastewaters, owing to its higher temperature (17 C 25 C for dairy wastewater and 10 C 20 C for municipal water) (Slavov, 2017). The repulsive odor and the yellow green color are also the result of biological degradation.

12.4

Fish processing

The fish industry represents another industry that generates wastewater in large quantities. It is discharged into the aquatic environment, where it is likely to cause adverse effects on the marine ecosystem. This type of wastewater is made of fish blood, seawater, and some residues of seafood resulting from the cleaning process.

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Usually, fish markets use water spray or air guns and scrapers to clean their floors, which are provided with sieves to prevent the drain of solid residues, such as fish heads or bones (Jamal & Pugazhendi, 2021). Picos-Benı´tez et al. (2019) determined that the COD concentration in this type of wastewater ranges between 0.3 and 42 mg L21, while the solids concentration is approximately 6%; these values are explained by the presence of blood and bowels. Fish processing brings out the most unpleasant smell, first because of organic decay and second because of the presence of ammonia, hydrogen sulfide, and mercaptans (Ching & Redzwan, 2017). When the water is rich in nutrients, such as fish excreta, nitrogen, phosphorus, and ammonia, the eutrophication phenomenon occurs (Ahmad et al., 2022). This means that the cyanobacteria (known as blue-green algae) start their activity to produce secondary metabolites, such as cyanobacteria toxins, which are toxic to organisms (Jing et al., 2021). The possible effects of human activities in the aquaculture industry are presented in Fig. 12.3. Some antibiotics, such as oxytetracycline, sulfadimethoxine, trimethoprim, norfloxacine, and ofloxacin, have reached high levels of administration; therefore they are frequently found in the aquatic environment, causing health problems such as allergies and toxicity (Ahmad et al., 2022; Done & Halden, 2015). Oxytetracycline concentrations in water bodies range between 0.5 and 25 µg L21, having the capacity to disrupt the aquatic

Figure 12.3 Possible effects of human activities on the aquaculture.

Chapter 12 Nanomaterials for the removal of organic pollutants from agrofood wastewaters

plant physiological functions under longer exposure (Vilvert et al., 2017). Owing to inaccurate feeding practices and unconsciousness in terms of pharmaceuticals’ administration, the environment has been placed at risk by human activities.

12.5

Olive oil manufacturing

The refinery processes of oil comes with the development of agricultural byproducts, which are therefore found in the wastewater resulted from the mills. The wastewater’s characteristics and quantities differ from one mill to another (Lee et al., 2019). After sunflower oil, olive oil is the second most consumed oil product consumed, but the wastes that are generated during its production are not taken into account. According to Solomakou and Goula (2020), the Mediterranean countries produce approximately 95% of the overall world production of olives per year. The olive mill wastewater is recognized by its dark color, with high turbidity and a harsh odor (Solomakou & Goula, 2020). Ververi and Goula (2019) reported that, owing to the presence of high concentrations of lignin and tannins, phenolic compounds, and fatty acids, the treatment process of olive mill wastewater is complex and difficult. The acidic nature of olive mill wastewater is a result of its high concentration of phenols (Aly et al., 2018). Olive oil can be obtained by three methods of extraction, namely, discontinuous press process, two-phase and threephase centrifugation systems, the last two being the most encountered methods. Fig. 12.4 presents the two- and threephase centrifugation systems that are used for olive oil extraction (Al-Hmoud, 2020; Tsagaraki, Lazarides, & Petrotos, 2007), including the processing steps for each method of extraction. Even if olives are known for their high antioxidant potential, only approximately 2% of the bioactive compounds pass into the oil during the extraction processes. The highest percentage of phenolic compounds is therefore found in the wastewater, ranging from simple phenol to polyphenols (al Bsoul et al., 2019). Some of them are illustrated in Fig. 12.5. Because of the high concentrations of phenols, olive mill wastewater has high COD and BOD (Loncˇ ari´c, Habuda-Stani´c, & Molnar, 2021). These compounds have high toxicity, which can affect aquatic organisms and plants, even disrupting bacterial activity (Lee et al., 2019). Therefore olive mill wastewater should go through thorough treatment processes before being discharged in order to prevent negative effects on the aquatic environment.

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Figure 12.4 Schematic mass balance of two- and three-phase centrifugation systems used for the extraction of olive oil.

Figure 12.5 Examples of phenolic compounds found in olive mill wastewater.

Chapter 12 Nanomaterials for the removal of organic pollutants from agrofood wastewaters

12.6

Sugar manufacturing

The presence of sugar in food matrices, as an additive or a natural ingredient, affects the environment, human health, and aquatic life. The sugar industry is one of the oldest ones in the entire world, owing to the increased demand for food, being a necessary ingredient for human diet. Generally, sugar is the main product obtained after the processing of sugarcane crops. Beside sugar, there are also obtained secondary products, such as bagasse, which results from sugarcane pressing, press mud, which represents the result of juice purification, and the final residue from sugar crystallization, molasses (Fito, Tefera, & van Hulle, 2019). The sugarcane production steps are presented in Fig. 12.6. Approximately 80% of sugar factories are annexed to ethanol distilleries; for example, in Brazil 90% of sugarcane harvest is used for this purpose. In order to obtain 1 liter of ethanol, an amount of 8 16 L of wastewater is discharged (Martinelli et al., 2013). Like every industry, sugar processing generates high quantities of wastewater, loaded with organic compounds (Patel et al., 2021). Obtaining 1 ton of raw sugar requires 2 m3 of water, which generates approximately 1 m3 of wastewater, with COD concentration ranging between 6100 and 6700 mg L21 and BOD concentrations of approximately 2500 2600 mg L21 (Alkaya & Demirer, 2011; Patel, 2021).

Figure 12.6 Sugarcane-processing scheme and the obtained byproducts.

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The wastewater from sugar mills is dark yellowish, with acidic pH, and it is rich in oxidized or reduced forms of chloride, sodium, potassium, calcium, magnesium, iron, and sulfur (Singh et al., 2019). If it is used for irrigation systems, the presence of these compounds can affect the plants and the soil’s properties in negative ways. Similar results are obtained when it is discharged into aquatic bodies, such as rivers, lakes, oceans, or groundwater sources, disturbing the aquatic ecosystem.

12.7

Wine making

Worldwide, wine production is a common practice. It is one of the leading sectors in the agro-food industry, mostly in agricultural areas of the Mediterranean and the Atlantic coasts of Europe, but also of Central and East Europe, and the Western Hemisphere (Ioannou, Li Puma, & Fatta-Kassinos, 2015). Along with the environmentally friendly perspective that it has received over time, wine production comes with some drawbacks, negatively affecting the ecosystem. The first step in wine production is the harvesting of grapes, followed by crushing and fermentation, straining of skins and seeds, and finally storage, clarification, and wine maturation (Kyzas, Symeonidou, & Matis, 2016). Wine-making procedures require considerable amounts of resources, such as water, energy, and fertilizers, while producing large volumes of wastewater and organic wastes (Amor et al., 2019a, 2019b; Ioannou et al., 2015). According to a study, for every1 L of produced wine, a winery discharges between 0.5 and 14 L of wastewater (Marcha˜o et al., 2021), mainly originating from the cleaning activities during the crushing and pressing of grapes, but also from washing the fermentation tanks. Generally, winery wastewater contains a variety of pollutants, mainly sugars, ethanol, organic acids, yeasts, polyphenols, specifically, tannins, and pesticides (Lofrano & Meric, 2016; Lucas et al., 2009). The presence of organic acids provides the low pH value (3 6), while the high COD concentration is due to the presence of ethanol, sugars, and polyphenolic compounds (Agustina, Ang, & Pareek, 2008). Polyphenols are present in winery wastewater in the range 13 700 mg L21; they include p-coumaric, caffeic, ferulic acids, resveratrol, catechin, epicatechin, and quercetin, which have good biological properties for human nutrition and favor the inhibition of aerobic biological processes (Bolzonella et al., 2019). Another group of pollutants that are found in this type of effluent are pesticides, which are used in vineyards for

Chapter 12 Nanomaterials for the removal of organic pollutants from agrofood wastewaters

controlling grapevine diseases. Examples of these compounds consist of carbendazim, cymoxanil, cyprodinil, quinoxyfen, and others (Massot et al., 2010). The processing steps in wine making are presented in Fig. 12.7. Regarding the environmental impact related to the improper discharge of winery wastewater, ground and surface water pollution, vegetation damage, and soil degradation are some examples (Kyzas et al., 2016).

Figure 12.7 The steps and a schematic mass balance of the wine-making process.

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Chapter 12 Nanomaterials for the removal of organic pollutants from agrofood wastewaters

All these presented sources of agrofood water contamination follow different steps during their processing, each of them generating effluents that differ in physicochemical characteristics.

12.8

Materials for wastewater treatment

The agrofood industry is one of the major contributors to environmental contamination because of the large volume of discharged effluents, during different kinds of processes. They can be generated from raw material cleaning, cooling, and heating processes or from equipment washing activities. The scientific area is still searching for suitable depollution technologies for this wastewater. Generation of these type of effluents is inevitable, since food production and processing activities are ubiquitous in our society and require a large amount of water. Treatment of these effluents is a difficult task, owing to complex composition and high concentration of pollutants. Biological treatments (aerobic or anaerobic) represent the first line of defense against these streams and are quite effective. However, there are some important drawbacks associated with this type of technologies, which prevented them from fulfilling the main objective (clean water as defined by to the environmental authorities and legal and regulatory requirements): 1. Biological processes are rather slow and very demanding regarding the optimization of operational parameters. Every sudden change in the effluent characteristics leads can to a wrong response in the treatment process. 2. Seasonal characteristic of activities from which these effluents are generated represent a negative impact on their continuity in good condition. 3. A large number of agroindustrial effluents are not suitable for biological treatment, since they contain biorefractory or even toxic compounds for the microorganisms used in these processes. Materials used in depollution processes are complex and varied based on the nature of contaminant removal method usually used, such as coagulation-flocculation, chemical precipitation, ion exchange, neutralization, filtration, ultrafiltration, nanofiltration, reverse osmosis, adsorption, ozonation, advanced oxidation processes (AOP) (Puri, Gupta, & Mishra, 2021). These materials should present some physicochemical characteristics, such as large surface to volume ratio, easy functionalization ability to enhance affinity and selectivity, and high sorbent capabilities (Zhang, Zhang, & Liang, 2019) for heavy metals and antibiotics,

Chapter 12 Nanomaterials for the removal of organic pollutants from agrofood wastewaters

which are the most common additives in the livestock industry (Liu et al., 2021a, 2021b; Oyewale, Adesakin, & Aduwo, 2019). The ultrafiltration method can be successfully used for the removal of phenolic compounds found in the wastewaters generated from agro-food sector (Cassini et al., 2010; El-Abbassi, 2014). For the removal of colloidal materials of coagulation and flocculation processes, materials such as Fe2(SO4)3 and Al2(SO4)3 can be used (Aguilar et al., 2002). AOP are a good alternative for the reduction of the organic compounds generated in agro waste waters from olive oil mill (Amor et al., 2019a), winery (Amor et al., 2019b) and palm oil mill (Bashir et al., 2017). Among AOPs, Fenton process has attracted great interest to the disadvantage of other methods such as ozonation (methods which could result in the formation of harmful byproducts) or ozone and ultraviolet (UV) light (which can activate H2O2 to form radical •OH) (Sani, Dashti, & Adnan, 2020). For these types of waters, the removal efficiency is evaluated in terms of COD, BOD, TS/TSS, TN, and TP (Tekerlekopoulou et al., 2020). However, these techniques have some limitations in terms of high costs, their inability to efficiently remove contaminants from complex matrix water to satisfactory levels, and the sludge that is generated (Ihsanullah et al., 2016). To solve the limitations of these techniques (Table 12.1), nanomaterials are most often developed to be used in agro-food wastewater depollution. For phenolic and aromatic substances, for which conventional wastewater treatment processes are not efficient, coupled systems such as photocatalytic and biological processes offer synergistic effects toward an improved depollution efficiency (Zhang et al., 2021). Of these techniques, adsorption and catalytic ozonation are two good candidates for treating agroindustrial wastewater in order to comply with environmental regulations. Therefore in the last decade, numerous studies have led to the development of solid materials that can be applied in these two processes. Owing to their low cost and high efficiency, adsorbent materials such as zeolites and clays are frequently used in the depollution processes (Crini, 2006). Therefore some other complementary or even standalone techniques are used to tackle with this environmental burden. The main methods that are used for these tasks are catalytic ozonation and adsorption, and they are all mature and very efficient technologies. Their application requires an entirely different approach for pollutant removal from water: by destruction of toxics (catalytic ozonation) along with a strong oxidant agent and by transfer of unwanted compound from liquid

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Table 12.1 Water treatment technologies with their advantages and drawbacks. Treatment method

Advantages

Limitations

Processes based on pollutant transfer from one phase to another

Membrane filtration: microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), reverse osmosis (RO)

Flocculation and coagulation

Ion exchange

Adsorption

Flotation Chemical precipitation

High separation selectivity and efficiency; eliminates from coarse particle to small molecules; small footprint; low energy consumption; mature technology; no additives required; large variations in feed quality have little influence on permeate quality Removal of different classes of chemical compounds

High costs of membrane materials; require multiple stages as a function of particle/molecules dimensions; retentate is more concentrated than input effluent; low flow rate

Applicable mainly for turbid water; the necessity to be used in tandem with other depollution methods; require expensive polymer-based coagulant and flocculants for higher efficiency; optimization of adjuvant dose is critical; secondary pollution is possible Good efficiency and selectivity High costs of commercial ion exchange materials; low mechanical resistance; swelling phenomena occurNecessity of regeneration;obtaining secondary effluents after regeneration Wide range of pH; high efficiency; low Necessity of regeneration; solid waste costs of materials; readily available for after deactivation any application; large range of materials can be used, including in house manufactured solids; applicable at different scale and in remote places; extended to all types of materials not only for ionic species.Valuable compounds recovery is possible High selectivity and efficiency High costs Low cost; simple operating system Time consuming; secondary pollution possible; applicable for cations and anions; organic pollutants may interfere

Processes based on pollutant destruction

Incineration

Supercritical water treatment

Applicable for very concentrated effluents or residual sludge; high efficiency

Energy consumption; secondary pollution may occur due to exhaust gases Energy consumption (Continued )

Chapter 12 Nanomaterials for the removal of organic pollutants from agrofood wastewaters

Table 12.1 (Continued) Treatment method

Advanced oxidation processes

Advantages

Limitations

Applicable for medium concentrated effluents or residual sludge; effective for removal of organic compounds resistant to oxidation; catalysts can be used; alternative to biological processes if the effluents contain toxic compounds High energy consumption Applicable for medium to low concentrated effluents; represent a cluster of techniques based on generation of hydroxyl radical using different combination of energy sources, oxidant agents, and catalysts; catalytic ozonation is the core of this group of methods, since it is very effective and versatile; an alternative to biological processes if the effluents contain toxic compounds

(water) to solid (adsorbent) phase. There are also important similarities between the two technologies: 1. The core of these methods is represented by solid materials that act as catalysts (in the oxidation processes) or as adsorbents. The solid materials for both techniques are carefully selected and synthesized to attain appropriate structural and morphological features. The development of these materials takes place according to two main directions: their synthesis from scratch or the use of solid agroindustrial waste with or without additional processing. 2. There is a large base for selection or synthesis of these materials; therefore the methods can be applied to a large range of pollutants. 3. The solids that are selected can be used to a large extent for both processes with caution that the material properties must remain as intact as possible in the oxidizing environment. An important example is represented by activated carbon (modified or not) with high performances in adsorption and oxidation tests. 4. They can operate in batch or in continuous mode. 5. Operational parameters (pH, flow rate, temperature, pollutant concentration, pollutants type, etc.) can be extended on broad domains.

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6. They are flexible and versatile and can be integrated into complex treatment systems. 7. For both processes, advanced modeling is available with respect with kinetic and thermodynamic aspects. Hence optimization is more easily achieved based on a large amount of data collected from numerous studies. 8. They are cost-effective methods and are applicable at different scales. These techniques are complementary in terms of the final results, since catalytic ozonation can be used only for compounds that are amenable to total oxidation (CO2 and H2O) and is ineffective for destruction of heavy metals or of different oxyanions in a superior state of oxidation (arsenate, nitrate, etc.), while in the adsorption process, most pollutants can be retained, yet a regeneration step is required. Catalytic ozonation represents an interesting tandem between ozone and some solids that are able to transform this oxidant agent into a more active chemical species: OH radicals. Owing to the significant difference between their oxidation potentials, these radicals are able to destroy the organic pollutants at a higher rate compared to a single ozonation method. Moreover, there are numerous species that are not oxidized by single ozonation and require radicals to be generated in the catalytic process. Ozone can be transformed in radicals by using other forms of energy (UV radiation, ultrasound, etc.), oxidant agents (H2O2, persulfate, etc.), or basic pH, but the main route is by using appropriate catalysts. The rates of oxidation of pollutants by hydroxyl radical are very different (Table 12.2); therefore the

Table 12.2 Redox potential of oxidizing agents. Substance

Potential (V)

Fluorine (F) Hydroxyradical (OH) Oxygen atom (O) Ozone molecule (O3) Hydrogen peroxide (H2O2) Chlorine (Cl) Chlorine dioxide (ClO2) Oxygen molecule (O2)

2.87 2.86 2.42 2.07 1.78 1.36 1.27 1.23

Chapter 12 Nanomaterials for the removal of organic pollutants from agrofood wastewaters

catalytic systems are needed to provide a high flux of active species and to prevent ozone consumption by different scavengers. In general, agroindustrial effluents are highly concentrated in term of COD, total phenols (TPh), and BOD and require a preliminary dilution. For example, live processing wastewaters contain large amounts of COD (2900 135,000 mg O2 L21), TPh (40 2500 mg L21), and BOD (650 52000 mg O2 L21). In Table 12.3 the performances of several catalyst in the treatment of wastewaters resulting from agroindustrial activities are presented, while in Table 12.4 some examples of reaction rate constants during the interaction between radical hydroxyl and of some common pollutants are presented. For the winery wastewater treatment, the best results were achieved by Gimeno et al. (2007), using TiO2, obtaining a COD removal of 80% 95% and TOC 5 60% 65%. Carbajo et al. (2007), after the catalytic ozonation of olive processing wastewater with perovskite, reached a COD removal ranging between 70% and 75%. Post biologically treated milk whey wastewater treatment was performed by Martins and Quinta-Ferreira (2010), who obtained 70% COD removal using Mn-Ce-O as a catalyst, compared to 66% COD removal using Fe-Mn-O. Outstanding results were obtained for the removal of sulfamethazine-containing effluents by Chen and Wang (2021), with a 100% targeted pollutant removal in 4 minutes. Roshani et al. (2014) successfully removed benzotriazole in 15 minutes using Mn/Al2O3 and Cu/Al2O3. Use of adsorbents represent in these days the main approach for removal of pollutants from wastewater, owing to their significant advantages compared with other methods. Almost all prepared adsorbents are very efficient in pollutant removal. In general, adsorbents are cost effective or even free, since they originate from different solid waste. The adsorption capacity and selectivity can be easily modulated, and the overall process occurs with low energy consumption. The regeneration step is relatively simple, and in most cases, it can be a source of valuable compounds. Adsorption represent the single option for small-scale installation, households, and remote applications. Generally, the adsorbents that are used nowadays fall in three main categories: 1. Adsorbents with low cost: This category contains in general natural sources (organic or inorganic) that are readily available with little or processing, such as zeolites, clay, chitin, peat, and wood.

371

Table 12.3 Examples of solid systems used in catalytic ozonation processes for wastewater treatment. Wastewater type

Operating parameters

Performances

References

Olive-processing wastewater: COD0 5 33600 mg L21; BOD0 5 13100 mg L21; TPh0 5 268 mg L21; pH 5 11.2 Olive-processing wastewater COD0 5 3844 mg L21; BOD0 5 730 mg L21; TPh0 5 285 mg L21

Perovskite (LaTi0.15Cu0.85O3) CCat 5 1 g L21 CO3(inlet) 5 50 g m3

COD removal 5 70% 75%

Carbajo et al. (2007)

Mn-Ce-O; Fe-Mn-O CCat 5 10 g L21 CO3 (inlet) 5 40 g m23 Flow rate 5 500 mL min21 tR 5 180 min Catalyst: TiO2 (Degussa) Catalyst load: 0.5 3.0 g L21 Flow rate 5 50 L h21; CO3 (inlet) 5 50 mg L21; T 5 293K; pH 5 3 11. Fenton’s process: [H2O2] 5 1 14 g L21 [Fe21] 5 0 5.5 g L21 pH 5 3 Perovskite (LaTi0.15Cu0.85O3) CCat 5 1 g L21 CO3 (inlet) 5 50 g m23 Qgas 5 40 L h21 Qgas 5 59.5 L min21 CO3 (inlet) 5 39.7 mg L21 100 g/1.5 L of catalyst (TOCCATAprocess supported cobalt catalyst)

Catalytic ozonation (Fe-Mn-O) XCOD 5 27% BOD5/COD 5 0.43

Martins and QuintaFerreira (2011)

Light/ozonation/TiO2 XCOD 5 80% 95% XTOC 5 60% 95%

Gimeno et al. (2007)

Ozonation 1 Fenton: XCOD 5 73% XTSS 5 94%

Martins et al. (2009)

XCOD 5 50% 90%

Carbajo et al. (2007)

XTOC 5 84% (better ozone usage)

Fontanier et al. (2006)

Catalytic ozonation (Mn-Ce-O) XCOD 5 70% Catalytic ozonation (Fe-Mn-O) XCOD 5 66%

Martins and QuintaFerreira (2010)

Winery wastewater: COD0 5 9250 mg L21; BOD0 5 7100 mg L21; TPh0 5 268 mg L21; pH 5 7.1 Winery wastewater: COD0 5 4047 8827 mg L21; TPh0 5 28 134 mg L21; pH 5 4.7 5.3 Wine distillery wastewaters: COD0 5 9250 mg L21; BOD0 5 7100 mg L21; TPh0 5 268 mg L21 Effluent from a secondary biological treatment of a Kraft pulp mill: COD0 5 173 mg L21; TOC0 5 53 mg L21; pH 5 7.3 Post biologically treated milk whey wastewater: COD0 5 520 mg L21; BOD0 5 151 mg L21; TOC0 5 215 mg L21

Catalyst: Mn-Ce-O; Fe-Mn-O CCat 5 10 g L21 CO3 (inlet) 5 10 g m23 Qgas 5 500 mL min21 pH 5 2 10 [H2O2] 5 16.5 66.0 mM;

(Continued )

Table 12.3 (Continued) Wastewater type

Operating parameters

Performances

References

Phenacetin (PNT)

CuFe2O4 pH: 7.72 Catalyst dosage: 2.0 g L21; [O3]: 0.36 mg min21; [PNT]0: 0.2 mM Modified C-doped MgO eggshell membrane powder CCa t 5 0.125 1 g L21

TOC removal: 90% (3 h) PNT removal: 100% (5 min)

Wang and Zhiyong (2016)

TOC removal 5 80%

Asgari et al. (2019)

Target pollutant 100% removal in 4 min; TOC removal 60% Benzotriazole 100% removal in 15 min TOC removal 80%

Chen & Wang (2021) Roshani et al. (2014)

Industrial textile wastewater: pH 5 10.45, total organic carbon 445 mg L21, ADMI 1450, and BOD5/COD 0.12. Effluents containing sulfamethazine 20 mg L21 Effluents containing benzotriazole 10 mg L21; TOC 5 6 mg L21 2,4-Dichlorophenoxyacetic acid

2,4-Dichlorophenoxyacetic acid (2,4-D)

Omethoate (OMT)

Ibuprofen

Catalyst 0.05 g L21; O3 4.5 mg min21; initial pH 5.2 Mn/Al2O3 Cu/Al2O3 Mn Cu/Al2O3 2.6 g h21 while oxygen flow rate was controlled at 3 L min21 Co/Mn/c-Fe2O3 pH 5 6; Catalyst dosage: 1 g L21; [O3]: 20 mg21 L; flow rate: 12 L h21; [2,4-D]0: 20 mg L21 Reaction time: 40 min Fe Co/ZrO2 pH: 7; Catalyst dosage: 2 g L21; [O3]: 30 mg L21; flow rate: 12 L h21; [p-CBA]0: 50 mg L21 Fe(III)/AC Reaction time: 120 min; pH: 8; Catalyst dosage: 0.2 g L21; [O3]0:15 mg min21; [OMT]0: 10 mg/ L21 Fe2O3/Al2O3@SB-15 pH: 7.0; Catalyst dosage: 1.5 g L21; [O3]: 30 mg21

TOC removal: 32% (SO), 93% (CO) Lv et al. (2012)

2,4-D removal: 30% (SO); 90% (CO)

Nie et al. (2012)

OMT removal: 50% (CO

Qiang, Ling, and Tian (2013)

TOC removal: 90% (CO)

Bing et al. (2015)

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Chapter 12 Nanomaterials for the removal of organic pollutants from agrofood wastewaters

Table 12.4 Example reaction rate constants during the interaction between radical hydroxyl and of some common pollutants. Pollutant

Pollution source

kOH (M21s21) with reference

References

1,2,3Trichlorobenzene 1,2-Butanediol 1-Nonyl-4-phenol or 4-nonylphenol 2,4-dichlorophenol

Dyes and textiles industry Agroindustrial sources Detergent

6.1 3 109 at 20 C and pH 9

Mandal (2018)

2.3 3 109 at 25 C 10 3 109 at 20 C

Herbicide

2.65 3.80 3 1010 20 C

Hoffmann et al. (2009) Zimmermann et al. (2012) Shu et al. (2013)

Table 12.5 The adsorption capacity of different adsorbents used for wastewater treatment. Adsorbents

Pollutants

Capacity

Performance References

Activated carbon

Violet dye

84.11

85% 90%

Fe3O4 nanoparticles DS-Zn/Al layered double hydroxides Montmorillonite-supported nanoparticles Modified biogas residue Waste-based biosorbent TiO2 nanotubes and carbon nanotubes Fungal and bacterial biomass

Pd Organic pollutant Cr

367.0 520.6 98% 87 149.3 81%

Sarabadan, Bashiri, and Mousavi (2019) Xin et al. (2012) Grover et al. (2019)

15

Xu et al. (2017)

Nitrate Fluoxetine Cu

65.12 83% 21.86 233.5 78% 83 124 91%

Pan et al. (2019)

Organic pollutants

374 620

Cheng et al. (2020)

78%

Sadegh et al. (2017)

2. Nanomaterials: These include metallic oxides synthesized by top-down or bottom-up methods and different nanocomposites. 3. Adsorbents based on biomass. Table 12.5 lists some examples of adsorbents and their performances in removal of toxic pollutants from agrofood industries.

Chapter 12 Nanomaterials for the removal of organic pollutants from agrofood wastewaters

12.9

Conclusions and future trends

Agroindustrial wastewater depollution is a challenging issue, especially due to the variable composition of waters, which depends mainly on the raw material composition (which varies according to a series of other factors) and industrial processing. These waters can cause great impacts in different ecological systems. Providing new and sustainable materials for depollution processes, with enhanced recovery possibilities, represents a “must” of research activities. Future trends in this scientific area of development of new materials for water treatment can be represented by agricultural waste, which can be used for water treatments instead of hazardous chemical compounds, thus solving an environmental pollution problem at low cost by an efficient method. This chapter was intended to be a critical discussion of some aspects related to different types of agrofood wastewaters and materials used in the treatment processes. The depollution processes in the food industry requires special care and presents many difficulties, mainly because of potential biological and chemical contamination of the products with the obtained water. It is necessary to supervise the quality of the water that will come into contact with edible products, for which a potable quality water is required. To obtain water with adequate quality, it is necessary to characterize the effluent, identify and quantify the substances that can pose risks to public health, and remove the pollutants with specific, tailored materials. Owing to the spread and resistance of environmental pollutants in the world’s agro-food systems, systemic management strategies are required.

Acknowledgments This work was supported by Romanian Ministry of Research and Innovation, MCI (Ministry of Research, Innovation and Digitization, MCID) through INCDCP ICECHIM Bucharest 2019 2022 Core Program PN. 19.23 ChemErgent, Project No.19.23.03. The authors gratefully acknowledge the support obtained by grants of the Romanian National Authority for Scientific Research and Innovation, CCCDI UEFISCDI, project number PN-III-P2 2.1-PTE2019 0222, contract 26PTE/2020, project number PN-III-P2-2.1-PTE-2021-0309, contract 81PTE/2022, and project number PN-III-P2 2.1-PED-2019 3166, contract 299PED/2020, within PNCDI III.

List of acronyms AOPs BOD

advanced oxidation processes biological oxygen demand

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CCat COD D kOH MF NF OMT PNT Qgas RO TN TP TPh tR TS TSS UF

catalyst concentration chemical oxygen demand dichlorophenoxyacetic acid reaction rate constant microfiltration nanofiltration omethoate phenacetin gas flow rate reverse osmosis total nitrogen total phosphorus total phenols retention time total solids total solids suspended ultrafiltration

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Chapter 12 Nanomaterials for the removal of organic pollutants from agrofood wastewaters

Aziz, A., et al. (2019). Biological wastewater treatment (anaerobic-aerobic) technologies for safe discharge of treated slaughterhouse and meat processing wastewater. Science of the Total Environment, 686, 681 708. Bashir, M. J. K., et al. (2017). Electro persulphate oxidation for polishing of biologically treated palm oil mill effluent (POME). Journal of Environmental Management, 193, 458 469. Bing, J., et al. (2015). Mechanism of catalytic ozonation in Fe(2)O(3)/Al(2)O(3)@SBA-15 aqueous suspension for destruction of ibuprofen. Environmental Science & Technology, 49(3), 1690 1697. Bolzonella, D., et al. (2019). Winery wastewater treatment: A critical overview of advanced biological processes. Critical Reviews in Biotechnology, 39(4), 489 507. ˜ as, M. C., et al. (2019). Determination of pesticide levels in Campos-Man wastewater from an agro-food industry: Target, suspect and transformation product analysis. Chemosphere, 232, 152 163. Carbajo, M., et al. (2007). Ozonation of phenolic wastewaters in the presence of a perovskite type catalyst. Applied Catalysis B: Environmental, 74(3 4), 203 210. Cassini, A. S., et al. (2010). Ultrafiltration of wastewater from isolated soy protein production: A comparison of three UF membranes. Journal of Cleaner Production, 18, 260 265. Charalambous, P. (2020). Anaerobic digestion of industrial dairy wastewater and cheese whey: Performance of internal circulation bioreactor and laboratory batch test at PH 5 6. Renewable Energy, 147, 1 10. Chen, H., & Wang, J. (2021). Catalytic ozonation for degradation of sulfamethazine using NiCo2O4 as catalyst. Chemosphere, 268, 128840. Cheng, Z., et al. (2020). Novel biosorbents synthesized from fungal and bacterial biomass and their applications in the adsorption of volatile organic compounds. Bioresource Technology, 300, 122705. Ching, Y. C., & Redzwan, G. (2017). Biological treatment of fish processing saline wastewater for reuse as liquid fertilizer. Sustainability (Switzerland), 9(7). Crini, G. (2006). Non-conventional low-cost adsorbents for dye removal: A review. Bioresource Technology, 97(9), 1061 1085. Custodio, M., et al. (2022). Treatment of dairy industry wastewater using bacterial biomass isolated from Eutrophic lake sediments for the production of agricultural water. Bioresource Technology Reports, 17. Deng, J., et al. (2022). Enhanced treatment of organic matter in slaughter wastewater through live Bacillus velezensis strain using nano zinc oxide microsphere. Environmental Pollution, 292(A), 118306. Done, H. Y., & Halden, R. U. (2015). Reconnaissance of 47 antibiotics and associated microbial risks in seafood sold in the United States. Journal of Hazardous Materials, 282, 10 17. El-Abbassi, A. (2014). Application of ultrafiltration for olive processing wastewaters treatment. Journal of Cleaner Production, 65, 432 438. FAO—Food and Agriculture Organization of the United Nation (2020). Food outlook biannual report on global food markets. Roma. Fito, J., Tefera, N., & van Hulle, S. W. H. (2019). Sugarcane biorefineries wastewater: Bioremediation technologies for environmental sustainability. Chemical and Biological Technologies in Agriculture, 6(1), 6. Fontanier, V., et al. (2006). Simulation of pulp mill wastewater recycling after tertiary treatment. Environmental Technology, 26, 1335 1344.

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381

Index Note: Page numbers followed by “f” and “t” refer to figures and tables, respectively.

A Adsorption, 68, 161 Aerobic digestion, 68 Aerobic processes, 137 138, 284 285 Aerobic treatment systems, 326 331 Agro-food wastewaters (AFWWs), 67 68, 229 230 anaerobic filter, 71 72 anaerobic hybrid reactors, 87 88 anaerobic membrane bioreactor, 81 87 anaerobic moving bed biofilm reactor, 78 79 characteristics, 70 expanded granular sludge bed reactor, 76 78 external circulation sludge bed reactor, 79 81 high-rate anaerobic systems, 88 89 upflow anaerobic sludge blanket reactor, 72 76 wastewater treatment, challenges of, 90 91 Agroindustrial practices, 355 356 Agroindustrial residues, 3 4 Almond (Prunus dulcis), 30 31, 39 41 Anaerobic digestion, 67 68, 90 91 Anaerobic fermentation, 143 Anaerobic filter (AF), 71 72 Anaerobic hybrid reactors, 68, 87 88

Anaerobic membrane bioreactor (AnMBR), 68, 81 87, 139 Anaerobic moving bed biofilm reactor (AMBBR), 68, 78 79, 291 Anaerobic processes, 285, 287, 294 Anaerobic treatment systems, 325 326 Animal wastes, 3 Antioxidant compounds, 220. See also Bioactive compounds (BC) Antioxidants, 46 47, 181 Aroma compounds, 115 Aromas, 367 Atmospheric pollutants, 7

B Beverage industry, 188 189 Bioactive compounds (BC), 27 28, 196, 199, 217 219 of animal product processing dairy products, 222 marine products, 224 meat products, 222 224 current trends in, 236 238 dairy-processing wastewaters, 116 119 emerging technologies for, 224 228 fish-processing wastewaters, 113 116 from fruits and vegetables, 219 220 leaves and stems, 221 peels and seeds, 220 221 pomace, 220

olive mill wastewaters, 108 113 ultrasound-assisted extraction, 233 Biocompounds, 142 144 Biodegradable garden, 2 Biodiesel, 181 Biofertilizers, 129 130, 140 142 Biofilm sequencing batch reactor (BSBR), 286 287 Biogas production, 68, 74 76, 79 81 Biological processes, 180 182 Biological treatments, 181 182, 284 290 Biomass pyrolysis, 136 137 Biomolecules recovery, 332 336 Bioproducts, 252, 267 Biorefineries, 129 131, 263 266 from seafood wastes aerobic processes, 137 138 anaerobic processes, 138 139 chemical processes, 133 135 physical processes, 132 133 thermochemical and thermal processes, 135 137 Biostimulants, 140 142 Biowaste agroindustrial sector, 2 6 bioactive compounds, 8 11 environmental contamination and disposal of, 6 11 Bisphenol A (BPA), 199 200 Bottling, 315

383

384

Index

C Carotenoids, 184 Catalytic ozonation, 370 371 Cereal-based beverages, 26 Cereals and pulses, 4 5 Cheese whey, 183 Chemical oxygen demand (COD), 67 68, 205 Chemical reagents, 134 Chitin, 143 Chitosan, 143 Circular economy, 13, 13f, 217 219 Circular Economy Action Plan, 129 Climate change, 292 293 C/N ratio, 137 138 Coagulation, 68 Coagulation/flocculation, 281 Complementary treatments, 290 292 Compost, 140 Conventional methods, 14, 161, 175 Conventional nitrogen fertilizers, 129 130 Crushing and pressing, 313

D Dairy-processing wastewaters, 116 119 Dairy products, 222 Dairy wastewater treatment, 179 180, 357 359 biological treatments, 284 290 characteristics, 278 280 complementary treatments, 290 292 global milk production, 275 guidelines for, 276 278 physicochemical treatments, 281 284 preliminary treatments, 280 281 recovery and valorization of sludges from primary and secondary treatments, 298 300 water reuse, 300 302

whey, 293 298 sustainability and environmental protection, 276 Decanting, 313 314 Depollution, 366 Dissolved air flotation (DAF), 283 Domestic food wastes, 131

E Ecological disturbances, 2 Electrocoagulation (EC), 282 283 Emulsion stabilizers, 51 Environmental protection, 2 Enzymatic hydrolysis, 134 Enzyme-assisted extraction (EAE), 227 228 Ethanol, 229, 297 European Union, 7, 27 Eutrophication, 252 Expanded granular sludge bed (EGSB) reactor, 76 78 External circulation sludge bed (ECSB) reactor, 68, 79 81 Extra-cellular polymeric substances (EPS), 81

F Fat replacers, 49 Fermentation, 313 Fiber supplement and glycemic index reducer, 47 48 Fick’s law of diffusion, 173 Filamentous fungi, 298 Filtration, 315 Fish-processing wastewaters, 113 116, 359 361 Flocculation, 68 Food and Agriculture Organization of the United Nations (FAO), 2 3 Food industry wastewater characterization from cheese industry, 158 159 from multiproduction food industry, 159

from olive oil industry, 158 from seafood industry, 159 from slaughterhouse industry, 159 from sugar industry, 158 extraction methods, of organic and inorganic compounds Soxhlet extraction, 162 164 supercritical fluid extraction, 165 167 ultrasound-assisted extraction, 164 165 Food losses and waste, 2 6, 127 128 Food-manufacturing processes, 67 68 Food-processing industry characteristics, 101, 102t Food supply chain, 128 Food wastage, 128f, 129 130 environmental impact of, 217 219 Fractionation, 196

G Generally Recognized As Safe (GRAS) solvents, 225 226 Gluten-free products, 49 51 Grape reception, 313

H Haber-Bosch process, 129 130 High-rate anaerobic processes (HRAnPs), 68 Household waste, 5 Hydraulic pressing system, 248 249 Hydrolysates, 143

I Incineration, 135 136 Industrial operation practices, 277 Inorganic solid waste, 3 4 Insoluble dietary fiber (IDF), 37 Integrated membrane processes, 115

Index

International Energy Agency, 190 191 Irrigation, 312 Isolelectric precipitation, 118

J Jatropha, 191

L Lactic acid production, 295 Lactose, 297 298 Leaves and stems, 221 Legume-based beverages, 26 Liquid samples, 198 199 Liquid-solid ratio (LSR), 232 Liquid wastes, 27 biofuel, 54 55 direct use ingredient, 56 57 nutrient extraction, 55 56 reuse, 51 Long-chain fatty acids (LCFA), 285

M Marine products, 224 Maturation-stabilization, 315 Meat industry, 184 186 Meat products, 222 224 Mediterranean diet, 247 Membrane-based operations. See Pressure-driven membrane processes Membrane bioreactors (MBR), 288, 331 Membrane filtration, 68 Membrane separation, 332 336 Membrane technology, 331 335 Metal contamination, 201 202 Metal content, 141 Microfiltration (MF), 85 87, 102 103 membranes, 104 Microwave-assisted extraction, 170 175 applications of, 172 173 kinetic modeling of, 173 175 Microwave irradiation, 172 Microwaves, 167 170 Microwaving, 172

Mixed liquor suspended solids (MLSS), 81 Molecular weight cutoff (MWCO), 102 103 Moringa oleifera, 281

N Nanofiltration (NF), 102 103 membranes, 105 Natural biological treatments, 324 331 Natural resources, 355 356 Nonpolar solvents, 191 Nut-based beverages, 26 Nutrient composition, 33 42 almond, 39 41 oat, 39 okara, 37 38 rice, 38 39 tiger nut, 41 42

O Oat (Avena sativa), 30, 39 Oil industry, 186 188 Okara, 28 29, 37 38 Olive mill wastewater (OMWW), 108 113, 247, 250 252 chemical composition of, 252 254 process integration, 263 266 reuse, applications, and technologies biofuels, 254 257 biosurfactants, 259 260 citric acid and lipids, 260 enzymes, 259 fertilizers, biopesticides, and irrigation, 261 262 food and beverage supplement, 262 263 phenolic compounds and other antioxidants, 258 259 polyhydroxyalkanoates, 260 261 polysaccharides, 257 258 water consumption and generation in, 250t Olive oil, 247 248, 248f, 361

385

manufacturing, 361 362 Open-air evaporation methods, 251f Organic compounds, 170 171 Organic residues, 3 4 Organic solvents, 217 219 Organic waste, 4 Osmotic distillation (OD), 113 Oxidation, 68

P Page’s model, 175 Parshall flume, 281 Peels and seeds, 220 221 Peleg’s model, 174 Phenolic compounds, 9 11, 312, 316 317 Phenolic compounds class, 1 Physical-chemical treatments, 180 181 Physical treatments, 319 321 Physicochemical treatments, 281 284, 321 323 Pigments, 356 Plant-based beverages, 25 applications in, food industry antioxidants, 46 47 emulsion stabilizers, 51 fat replacers, 49 fiber supplement and glycemic index reducer, 47 48 ingredients in gluten-free products, 49 51 solid wastes/byproducts, 42 51 water-holding ingredients, 48 49 bioactive compounds, 27 28 cereal-based beverages, 26 consumption pattern, 25 26 legume-based beverages, 26 liquid wastes, 27 biofuel, 54 55 direct use ingredient, 56 57 nutrient extraction, 55 56 reuse, 51 nut-based beverages, 26

386

Index

Plant-based beverages (Continued) nutrient composition, 33 42 almond, 39 41 oat, 39 okara, 37 38 rice, 38 39 tiger nut, 41 42 pseudo-cereal-based beverages, 26 research evolution, 28 33 seed-based beverages, 26 solid byproducts/wastes, 27 28 soy drinks, 26 Polyamide (PA) membrane, 109 110 Polyethersulfone (PES) membrane, 111 Polyphenols, 316 317, 364 Pomace, 220 Preliminary treatments, 280 281 Press cake, 27 Pressure-driven membrane processes cross-flow filtration system, 104f membrane fouling, 107 membrane performance in, 106 MF membranes, 104 module design, 106 107 NF membranes, 105 rejection values, 106 RO membranes, 105 separation capabilities of, 105, 105f separation mechanism, 104 spiral-wound and plate-andframe modules, 106 107 UF membranes, 104 Pressurized fluid extraction, 227 Protein concentrates, 181 Protein hydrolyzation, 135 Proteins, 296 Pseudo-cereal-based beverages, 26 Pyrolysis processes, 142

R Recovery and valorization sludges from primary and secondary treatments, 298 300 water reuse, 300 302 whey, 293 298 Residual water, 249 250 Resource consumption, 127 128 Response surface methodology (RSM), 233 Reverse osmosis (RO), 102 103 membranes, 105 Rice (Oryza sativa), 29, 38 39

S Sampling campaign, 278 SARS-CoV-2 infection, 10 11 Seafood industry, 131 Seafood wastes bioproducts biocompounds, 142 144 biofertilizers and biostimulants, 140 142 biofuels, 142 water streams, 144 145 biorefineries aerobic processes, 137 138 anaerobic processes, 138 139 chemical processes, 133 135 physical processes, 132 133 thermochemical and thermal processes, 135 137 Secondary treatment, 181 182 Seed-based beverages, 26 Separation techniques, 132 133 Sequencing batch reactor (SBR), 286 287 Sewage sludge, 160 161 Slaughterhouse wastewater, 159, 357 Sludge treatment, 179

Solid byproducts/wastes, 27 28, 42 51 Solids retention time (SRT), 139 Solvents, 231 extraction, 161 Soxhlet extraction, 162 164 Soy drinks, 26 Spanish mills, 248 249 Sterols, 184 Stream segregation, 276 277 Substrate concentration, 138 139 Sugar manufacturing, 363 364 Supercritical fluid extraction, 165 167, 227 fundamentals of, 193 197 of liquid and semisolid mixtures SFE-CO2, 198 199 SFE-H2O, 197 198 technoeconomic evaluation of, 202 206 wastewater and sludge, 199 202 Supercritical fluid technologies, 180 181 Sustainable biotechnology, 17

T Tartaric stabilization, 315 Thermal techniques, 137 Tiger nut (Cyperus esculentus), 31, 41 42 Tocopherols, 184 Total phosphorus (TP), 68

U Ultrafiltration (UF), 85 87, 102 103 membranes, 104, 109 110 retentate fractions, 109 110 Ultrasonic frequency, 230 231 Ultrasonic power, 230 Ultrasound-assisted extraction, 164 165 commercial patents, 233 235 fundamentals for, 228 229 variables

Index

liquid (solvent) to solid ratio, 232 solvents, 231 temperature of, 231 232 time of, 232 ultrasonic frequency, 230 231 ultrasonic power, 230 Ultrasound-assisted extraction (UAE), 217 219 Untreated wastewater, 12, 15 Upflow anaerobic sludge blanket (UASB) reactor, 68, 72 76, 287

V Valorization and recovery sludges from primary and secondary treatments, 298 300 water reuse, 300 302 whey, 293 298 Value-added compounds, 179 Volatile fatty acids (VFA), 76 78, 89 90

W Wastewater discharge, 67 68

Wastewater quality, 288 Wastewater treatment, 6 AFWWs, challenges of, 90 91 and applications, 13 16 beverage industry, 188 189 clean extraction technologies for, 189 192 from dairy industry, 182 184 dairy-processing wastewaters, 116 119 emergence and potential of, 11 17 fish-processing wastewaters, 113 116 fruit and vegetable industry, 184 materials for, 366 374 meat industry, 184 186 oil industry, 186 188 olive mill wastewaters, 108 113 properties and benefits, 16 17 and sludge treatment, 179 winery wastewater treatment. See Winery wastewater treatment Water consumption, 67 68

387

Water-holding ingredients, 48 49 Water reuse, 101 103, 300 302 Water streams, 144 145 Whey, 279, 293 298 Wine making, 364 366 Winery wastewater treatment aerobic treatment systems, 326 331 anaerobic treatment systems, 325 326 membrane bioreactors, 331 membrane separation, 332 336 natural biological treatments, 324 331 physical treatments, 319 321 physicochemical treatments, 321 323 process and wastewater generation, 313 315 value-added biomolecules, 316 319 wastewater reuse, 336 340