Emerging Pollutants

Francisco García Calvo-Flores is Associate Professor in the Department of Organic Chemistry at the University of Granada. He has received his PhD at the University of Granada. After that he worked in the group of Professor Gabor Lukacs at the "Institut de Chemie des Substances Naturelles du CNRS" (Gif-sur-Yvette, France) before he got his current position. His main research areas are Green Chemistry and Carbohydrate Chemistry.Joaquín Isac-García is Associate Professor at the University of Granada. After having received his PhD in 1985, he became a postdoctoral fellow at the "Institut de Chemie des Substances Naturelles du CNRS" (Gif-sur-Yvette, France) (Professor Gabor Lukacs) before he started his academic career at the current position.José A. Dobado is Associate Professor in the Department of Organic Chemistry at the University of Granada. After having received his PhD he became Postdoc at Zurich University in the group of Professor Nonella and at the Helsinki University under Professor M. R. Sundberg before he started his independent career in Granada. His research area is Computational Chemistry.

• Epigraph xvAbbreviations xviiGlossary xxiiiPreface xxviiAcknowledgment xxix1 Introduction 11.1 Chemistry and Development 11.2 Pollution and Contamination 31.3 Chemical pollutants 41.4 Pollutants in the Environment 61.5 Concept of Emerging Pollutants 71.6 Historical Background of Emerging Pollutants 81.7 Classification of Emerging Pollutants 91.8 Regulations and Normatives 11References 132 Occurrence and Removal of Environmental Pollutants 192.1 Introduction 192.2 Pollutants in the Atmosphere 192.3 Pollutants in Ground and Surface Waters: Quality Parameters 202.4 Pollutants in the Ground and Soil 232.5 Sources of Emerging Pollutants or CECs 232.5.1 CECs from WWTPs 242.5.2 CECs in Wastewater Biosolids 252.5.3 CECs from Agriculture and Livestock 252.5.4 CECs in Soils 262.5.5 CECs in Groundwater 272.5.6 CECs in Landfill 282.5.7 CECs in Seawater 292.6 Treatment of CECs 302.6.1 Treatment of CECs in WWTPs 302.6.1.1 Physical Methods 302.6.1.2 Chemical Methods 312.6.1.3 Biological Methods 322.6.2 Treatment of CECs in Landfill Leachates 322.6.3 Wastewater Reuse 332.7 Toxicity of CECs 34References 373 Detection and Analysis of Chemical Pollutants 433.1 Introduction 433.2 Sample Preparation 433.2.1 Extraction with Organic Solvents 443.2.2 Microwave-Assisted Extraction (MAE) 443.2.3 Dispersive Liquid–Liquid Microextraction (DLLME) 453.2.4 Vortex-Assisted Liquid–Liquid Microextraction (VALLME) 453.2.5 Single-Drop Microextraction 453.2.6 Solid-Phase Extraction (SPE) 463.2.7 Solid-Phase Microextraction (SPME) 473.2.8 Dispersive Solid Phase Microextraction (DSPE/DSPME) 473.2.9 Matrix Solid-Phase Dispersion (MSPD) 483.2.10 Passive Sampling 483.2.11 Immunosorbent Extraction 493.2.12 Extraction of Volatile Compounds 493.2.13 Online Extraction 503.2.14 Extraction with Nanomaterials 503.2.15 Sampling from Biological Materials 503.3 Analytical Methods for Identifying EPs 503.3.1 Separation Methods 523.3.2 Characterization Methods 52References 534 Overview of Pharmaceutical Products as Emerging Pollutants 574.1 Introduction 574.2 Therapeutic Classes of PCs Detected in the Environment 594.3 Sources of PCs in the Environment 594.4 Detection and Analysis of PCs in the Environment 614.5 Occurrence of PCs in the Environment 634.5.1 Pharmaceuticals in WWTPs 644.5.2 PCs in Hospital Wastewater 644.5.3 PCs in Surface Water and Groundwater 664.5.4 PCs in Seawater 684.5.5 PCs in Drinking Water 684.5.6 PCs in Soil 694.6 Ecotoxicological Aspects of PCs on Environment 724.7 Removal of PCs 754.7.1 Conventional Systems for Removing PCs in Water-Treatment Systems 764.7.2 Adsorption on Activated Carbon 774.7.3 Technologies Based on Advanced Oxidation Processes (AOPs) 774.7.3.1 AOPs Based on Ozone 774.7.3.2 AOPs Based on UV Radiation 774.7.3.3 AOPs Based on γ-Radiation 794.7.3.4 Electro-Oxidation with and without Active Chlorine Generation 794.8 Conclusions 79References 805 Therapeutic Classes of PCs in the Environment 1035.1 Introduction 1035.2 Antibiotics (ABs) 1055.2.1 Chemical Classes of Antibiotics 1055.2.2 The Problem of the Resistance of Antibiotics 1145.2.3 Antibiotics in the Environment 1145.2.4 Degradation/Removal of Antibiotics 1165.2.5 An Example of ABs in the Environment: Sulfonamides 1165.3 Estrogens and Hormonal Compounds 1175.3.1 Estrogens in the Environment 1175.4 Drugs with Endocrine Disruption Properties 1205.5 Analgesic, Anti-inflammatory, Antiarthritic, and Antirheumatic Compounds 1245.5.1 Non-Narcotic Analgesics Drugs 1245.5.2 Narcotic Analgesics Drugs 1255.5.3 Non-Steroidal Anti-Inflammatory Drugs (NSAIDs) 1255.5.3.1 Diclofenac 1265.5.3.2 Ibuprofen 1275.5.3.3 Naproxen 1285.5.3.4 Ketoprofen 1285.5.3.5 Mefenamic Acid 1285.6 Psychotropic Drugs 1285.6.1 Environmental Impact of Psychotropic Drugs 1295.7 Antiepileptic Drugs 1315.8 β-Blockers/Diuretics 1335.8.1 β-Blockers in the Environment 1335.9 Lipid Regulators 1355.10 β2-Sympathomimetic Drugs 1365.11 Antidiabetic Drugs 1385.12 X-Ray Contrast Drugs: Diagnostic Agents 1395.13 Cytostatic PCs: Antineoplastics 1405.14 Veterinary Drugs: Anthelmintics 1415.14.1 Classes of Anthelmintics 1425.14.2 Anthelmintics in the Environment 145References 1466 Illegal Drugs, Occurrence, and Fate in Environment 1676.1 Introduction 1676.2 What is an Illicit Drug? 1686.2.1 Differences Between Licit and Illicit Drugs as Environmental Contaminants 1696.3 Classes of Illicit Drugs 1716.3.1 Opiates 1716.3.1.1 Opiates in the Environment 1716.3.2 Other Central Nervous System Depressants 1726.3.3 Central Nervous System Stimulants: Cocaine 1736.3.3.1 Cocaine in the Environment 1736.3.4 Central-Nervous-System Stimulants: Amphetamine-Type Substances (ATSs) 1736.3.4.1 Amphetamine-Type Substances in the Environment 1766.3.5 Hallucinogens 1766.3.6 Cannabis 1776.3.6.1 Cannabis and its Metabolites in the Environment 1776.4 Analytical Methods for Detecting of Illicit Drugs 1776.5 Illicit Drugs in the Environmental Compartments 1786.5.1 Illicit Drugs in Wastewater 1796.5.2 Illicit Drugs in Surface Water 1816.5.3 Illicit Drugs in Seawater 1826.5.4 Illicit Drugs in Drinking Water 1826.5.5 Illicit Drugs in Soil 1836.5.6 Illicit Drugs in Ambient Air 1846.5.7 Illicit Drugs on Currency Notes 1846.6 Estimation of Drug Consumption in Communities (Sewage-Based Epidemiology) 185References 1877 Pesticides as Pollutants 1977.1 Introduction 1977.2 Classification of Pesticides 1987.2.1 Classification of Pesticides by Activity 1997.2.2 Classification of Pesticides by Toxicity 1997.2.3 Classification of Pesticides by Chemical Structure 2007.3 Organic Pesticides 2007.3.1 Organochlorine Pesticides 2007.3.2 Organophosphorus Pesticides 2027.3.3 Carbamates 2037.3.4 Thiocarbamates 2047.3.5 Pyrethrins and Pyrethroids 2057.3.6 Phenoxy Carboxylic Acids 2057.3.7 Triazines 2067.3.8 Uracils and Ureas 2077.3.9 Azoles and Related Compounds 2087.3.10 Morpholine Derivatives 2097.3.11 Bipyridines 2107.3.12 Amides 2117.3.13 Neonicotinoids 2117.3.14 Other Classes of Herbicides 2137.3.14.1 Pyridazines and Pyridazinones 2137.3.14.2 Nitrile Herbicides 2137.3.14.3 Dinitroanilines 2137.3.14.4 Pyridine Herbicides 2147.3.14.5 Pyrimidines 2147.4 Pesticides in the Environment 2157.4.1 Degradation and Transformation of Pesticides in Environment 2177.4.2 Pesticide TPs in the Environment 2177.4.3 Analysis of Pesticides 2187.4.4 Pesticides in Water 2207.5 An Example of National Survey: Pesticides in Italy 2217.6 An Example of Pesticides in the Environment: NeonicotinoidInsecticides 223References 2248 Lifestyle Products as Emerging Pollutants 2338.1 Introduction 2338.2 Stimulants 2338.2.1 Caffeine 2348.2.1.1 Caffeine in the Environment 2348.2.2 Nicotine 2368.2.2.1 Cigarettes in the Environment 2378.2.2.2 Nicotine in the Environment 2378.3 Food Additives 2388.3.1 Toxicology of Food Additives 2398.3.2 Global Regulation on Food Additives 2408.4 Classes of Food Additives 2418.4.1 Substances with Nutritive and Other Dietary Effects 2418.4.1.1 Vitamins and Provitamins 2418.4.1.2 Amino Acids 2428.4.1.3 Minerals and Trace Elements 2428.4.1.4 Bulking Agents 2428.4.2 Substances with Stabilizing Effects 2428.4.2.1 Preservatives 2428.4.2.2 Antioxidants 2428.4.2.3 Synergists and Sequestrants 2438.4.2.4 Packaging Gases 2438.4.2.5 Stabilizers 2448.4.3 Substances with Sensory Effects (Organoleptic Substances) 2458.4.3.1 Coloring Agents 2458.4.3.2 Color Stabilizers 2458.4.3.3 Bleaching Agents 2468.4.3.4 Intense Sweeteners 2468.4.3.5 Nutritive Sweeteners 2468.4.3.6 Acidulants 2468.4.3.7 Substances with a Salty Taste 2468.4.3.8 Substances with a Bitter Taste 2468.4.3.9 Substances with an Alkaline Taste 2468.4.3.10 Flavor Enhancers 2468.4.3.11 Spices and Flavorings 2478.4.3.12 Chewing-Gum Bases 2478.4.4 Substances as Processing Aids 2478.4.4.1 Extractants 2478.4.4.2 Clarifying Agents 2488.4.4.3 Filter Aids 2488.4.4.4 Propellants 2488.4.4.5 Cooling Agents and Cryogens 2488.4.4.6 Mold-Release Agents 2488.4.4.7 Antifoaming Agents 2488.4.4.8 Acidity Regulators 2498.4.4.9 Emulsifying Salts 2498.4.4.10 Dough Conditioners and Flour Improvers 2498.4.4.11 Leavening Agents 2498.4.4.12 Enzymes 2498.4.4.13 Microbial Cultures 2498.4.5 Dietary Supplements 2498.5 Food Additives as Emerging Organic Contaminants 2508.6 Antioxidants in the Environment 2508.7 Artificial Sweeteners in the Environment 2518.7.1 Metabolism of Artificial Sweeteners 2528.7.2 Occurrence of the Artificial Sweeteners in the Environment 2538.7.3 Artificial Sweeteners as Pollution Markers 2558.7.3.1 Ecotoxicological Studies on Sucralose 256References 2579 Industrial Chemicals as Emerging Pollutant 2659.1 Introduction 2659.2 Perfluorinated Alkyl Substances (PFASs) 2669.2.1 PFASs in the Environment 2689.2.2 Analysis of PFASs 2699.2.3 Toxicology and Regulation of PFASs 2709.3 Plasticizers 2719.3.1 Bisphenol A (BPA) 2719.3.1.1 BPA in the environment 2729.3.1.2 Toxicology and regulation of bisphenol A (BPA) 2739.3.2 Phthalates 2749.3.2.1 Phthalates in the environment 2769.3.2.2 Toxicology and regulation of phthalates 2799.3.3 N-Butylbenzenesulfonamide (NBBSA) 2809.3.3.1 NBBSA in the Environment 2809.4 Flame Retardants 2819.5 Brominated Flame Retardants (BFRs) 2819.5.1 Polybrominated Diphenyl Ether (PBDE) 2829.5.2 Tetrabromobisphenol A (TBBPA) 2899.5.3 Polybrominated Biphenyls (PBBs) 2919.5.4 Hexabromobenzene (HBB) 2919.5.5 Hexabromocyclododecane (HBCD) 2929.5.6 Decabromodiphenyl Ethane (DBDPE) 2929.5.7 1,2-Bis(2,4,6-Tribromophenoxy)ethane (BTBPE) 2929.6 Polychlorinated Alkanes (C10–C13) 2929.6.1 Use and Consumption of PCAs 2939.6.2 Properties of PCAs 2949.6.3 PCAs in the Environment 2959.6.4 Toxicology and Regulations of PCAs 2969.7 Organophosphate Flame Retardants (OPFRs) 2979.7.1 Use and Demand of OPFRs 2979.7.2 Properties of OPFRs 2989.7.3 OPFRs in the Environment 2999.7.4 Toxicology and Regulations of OPFRs 3009.8 Corrosion Inhibitors: Benzothiazoles and Benzotriazoles 3029.8.1 Benzotriazoles 3029.8.2 Benzothiazoles 3039.9 Polycyclic Aromatic Hydrocarbons (PAHs) 3049.10 Volatile Organic Compounds (VOCs) 3069.10.1 Hazardous Compounds Originating from Oil Products 3089.10.2 Gasoline Additives: MTBE 3099.11 Other Industrial Chemicals 3109.11.1 Siloxanes 3109.11.2 1,4-Dioxane 3119.11.3 Nitroaromatic Compounds 3119.11.3.1 2,4-Dinitrophenol 3129.11.4 Naphthenic Acids 3129.11.5 Other Chlorinated Compounds 3129.11.6 Perchlorate 313References 31410 Surfactants in the Environment 34110.1 Introduction 34110.2 Structure and Classification 34210.3 Nonionic Surfactants 34310.3.1 Fatty Alcohols 34410.3.2 Alcohol Ethoxylates 34410.3.3 Ethylene Oxide/Propylene Oxide-Block Polymers 34510.3.4 Alkylphenol Ethoxylates 34510.3.5 Ethoxylated Oils and Fats 34610.3.6 Alkanolamides 34610.3.7 Esters 34710.3.8 Nonionic Surfactants Derived from Carbohydrates and Related Compounds 34710.3.8.1 Alkyl Polyglucosides 34810.3.8.2 Sorbitan Esters 34810.3.8.3 Alkyl Carbohydrate Esters 34910.3.9 Ester/Ether Surfactants 34910.3.9.1 Ethoxylated Glycol and Glycerol Esters 35010.3.9.2 Ethoxylated Sorbitan Esters 35010.3.9.3 Ethoxylated Pentaerythritol Esters 35010.3.9.4 Polyglycerol Monoester 35010.3.10 Amine Oxides 35110.4 Anionic Surfactants 35110.4.1 Carboxylic Acids Derivatives 35110.4.1.1 Carboxylic Acid Salts 35110.4.1.2 Ether Carboxylic Acids 35210.4.2 Sulfuric and Sulfonic Acid Derivatives 35310.4.2.1 Alkyl Sulfates 35310.4.2.2 Alkyl Sulfonates 35310.4.2.3 Alkylbenzene Sulfonates 35410.4.2.4 Sulfosuccinates 35410.4.2.5 Sulfo Fatty Acid Esters 35510.4.2.6 Fatty Acid Isethionates and Taurides 35510.4.3 Phosphoric Acid Esters and Salts 35610.4.4 Acylamino Acids and Salts 35610.5 Cationic Surfactants 35710.5.1 Alkyl Amines 35710.5.2 Alkylimidazolines 35810.5.3 Quaternary Ammonium Compounds 35810.5.3.1 Tetraalkyl(-aryl) Ammonium Salts 35810.5.3.2 Heterocyclic Ammonium Salts 35810.5.4 Ethoxylated Alkyl Amines 35910.5.5 Esterified Quaternaries 36010.6 Amphoteric Surfactants 36010.6.1 Acyl Ethylenediamines and Derivatives 36010.6.2 N-Alkyl Amino Acids or Imino Diacids 36110.6.3 Alkyl Betaines 36110.7 Alkoxylated Polysiloxanes 36210.8 Fluorosurfactants 36210.9 Toxicological Aspects (Environmental Impact) of Surfactants 36310.9.1 Environmental Impact of Alkylphenol Ethoxylates (APEOs) 36410.10 Environmental Occurrence of the Surfactants 36510.10.1 Alkylphenol Ethoxylates (APEOs), and Their Degradation Products in the Environment 36610.10.2 LASs and Their Degradation Products 36810.11 Biodegradation of Surfactants 36810.11.1 Aerobic Biodegradation 37110.11.2 Anerobic Biodegradation 371References 37311 Personal-Care Products 38511.1 Introduction 38511.2 Musks: Fragrances 38511.3 Biocides 38811.3.1 Triclosan 38911.3.2 Chlorophene and Dichlorophene 39111.3.3 Parabens 39211.4 Sunscreen Agents: UV Filters 39611.4.1 Analysis of UV-Filters 39711.4.2 UV-Filters as Endocrine Disrupters 39811.4.3 UV Filters in the Environment 39911.4.3.1 Benzophenone Derivatives in the Environment 40111.4.3.2 3-Benzylidene- and 4-Methylbenzylidene-Camphor in the Environment 40211.5 Insect Repellents: N,N-diethyl-m-toluamide (DEET) 40311.6 Other PCPs 405References 40712 Water Disinfectant By-Products 42312.1 Introduction 42312.2 Wastewater Treatments 42412.2.1 Water Reuse 42512.2.2 Drinking Water Treatments 42512.2.3 Water Disinfection 42512.3 Disinfection Methods 42612.3.1 Chlorination 42612.3.2 Chlorine Dioxide 42712.3.3 Chloramination 42812.3.4 Sodium Dichloroisocyanurate 42812.3.5 Ozonization 42912.3.6 UV Irradiation 42912.3.7 Other Methods of Disinfection 42912.4 Water DPBs 43012.4.1 DBPs from Chlorination 43012.4.2 Other Halogenated DBPs 43212.4.3 Nitrogenous DBPs 43312.4.4 Carbonaceous DPBs from Ozonation 43512.5 Methods of Analysis of DBPs 43512.6 Disinfection By-Products (DBPs) in Drinking Water 43712.7 Disinfection By-Products in Swimming Pools 43812.8 Changes in Oxidation/Disinfection Strategies 43912.9 Toxicological Studies on DBPs 44112.10 Regulations/Guidelines of DBPs in Drinking Water 442References 44413 Other Contaminants of Emerging Concern 45313.1 Introduction 45313.2 Nanotechnology as a Pollution Source 45313.2.1 Detection of NMs 45413.2.2 NMs in the Environment 45613.2.3 Toxicity of NMs 45713.3 Microplastics (MPs) 45813.4 Toxic Elements and Elemental Species 46013.4.1 Arsenic (As) 46213.4.2 Cadmium (Cd) 46213.4.3 Lead (Pb) 46313.4.4 Mercury (Hg) 46413.4.5 Manganese (Mn) 46513.4.6 Antimony (Sb) 46613.4.7 Technology-Critical Elements 46613.4.8 Radionuclides 46713.5 Biotoxins 46713.5.1 Mycotoxins 46813.5.2 Algal Toxins 46913.5.3 Other Marine Toxins 47213.5.3.1 Cyclic Imines 47213.5.3.2 Ciguatoxins 47213.5.3.3 Azaspiracids (AZAs) 47213.5.3.4 Tetrodoxin (TTX) 47213.5.3.5 Palitoxins 47313.5.4 Bacterial Toxins 47313.5.5 Naturally Occurring Toxins in Vegetable Foodstuffs 47313.6 Microorganisms 47313.7 Contaminants on the Horizon: Ionic Liquids and Prions 474References 475A InChI Key for the Most Relevant Compounds in this Book 487Index 493