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Chemistry of Ozone in Water and Wastewater Treatment

Chemistry of Ozone in Water and Wastewater Treatment

Clemens von Sonntag | Urs von Gunten

(2012)

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Abstract

Even though ozone has been applied for a long time for disinfection and oxidation in water treatment, there is lack of critical information related to transformation of organic compounds. This has become more important in recent years, because there is considerable concern about the formation of potentially harmful degradation products as well as oxidation products from the reaction with the matrix components. In recent years, a wealth of information on the products that are formed has accumulated, and substantial progress in understanding mechanistic details of ozone reactions in aqueous solution has been made. Based on the latter, this may allow us to predict the products of as yet not studied systems and assist in evaluating toxic potentials in case certain classes are known to show such effects. 
Keeping this in mind, Chemistry of Ozone in Water and Wastewater Treatment: From Basic Principles to Applications discusses mechanistic details of ozone reactions as much as they are known to date and applies them to the large body of studies on micropollutant degradation (such as pharmaceuticals and endocrine disruptors) that is already available. Extensively quoting the literature and updating the available compilation of ozone rate constants gives the reader a text at hand on which his research can be based. Moreover, those that are responsible for planning or operation of ozonation steps in drinking water and wastewater treatment plants will find salient information in a compact form that otherwise is quite disperse. A critical compilation of rate constants for the various classes of compounds is given in each chapter, including all the recent publications. 
This is a very useful source of information for researchers and practitioners who need kinetic information on emerging contaminants. Furthermore, each chapter contains a large selection of examples of reaction mechanisms for the transformation of micropollutants such as pharmaceuticals, pesticides, fuel additives, solvents, taste and odor compounds, cyanotoxins. 
Authors: Prof. Dr. Clemens von Sonntag, Max-Planck-Institut für Bioanorganische Chemie, Mülheim an der Ruhr, and Instrumentelle Analytische Chemie, Universität Duisburg-Essen, Essen, Germany and Prof. Dr. Urs von Gunten, Eawag, Swiss Federal Institute of Aquatic Science and Technology, Dübendorf, and Ecole Polytechnique Federal de Lausanne, Lausanne, Switzerland. 

Table of Contents

Section Title Page Action Price
Cover page 1
Half-title page 2
Title page 3
Copyright page 4
Contents 5
About the Authors 10
Chapter 1 11
Historical background and scope of the book 11
Chapter 2 16
Physical and chemical properties of ozone 16
2.1 INTRODUCTORY REMARKS 16
2.2 GENERATION OF OZONE 17
2.3 OZONE SOLUBILITY IN WATER 18
2.4 UV–VIS SPECTRUM OF OZONE 19
2.5 DETERMINATION OF THE OZONE CONCENTRATION 21
2.5.1 The N,N-diethyl-p-phenylenediamine (DPD) method 21
2.5.2 The indigo method 22
2.6 METHODS FOR MEASURING OZONE KINETICS 23
2.6.1 Ozone decay measurements 24
2.6.2 Quenching of ozone with buten-3-ol 25
2.6.3 Reactive absorption 25
2.6.4 Competition kinetics 26
2.7 REDUCTION POTENTIALS OF OZONE AND OTHER OXYGEN SPECIES 27
2.8 STABILITY OF OZONE SOLUTIONS 28
2.9 REACTIVITY OF OZONE 28
2.9.1 pH dependence of ozone reactions and the \"reactivity pK” 29
2.9.2 Multiple reaction sites within one molecule 30
Chapter 3 32
Ozone kinetics in drinking water and wastewater 32
3.1 STABILITY OF OZONE IN VARIOUS WATER SOURCES 32
3.2 MOLECULAR WEIGHT DISTRIBUTION OF DISSOLVED ORGANIC MATTER 40
3.3 MINERALISATION AND CHEMICAL OXYGEN DEMAND 42
3.4 FORMATION OF ASSIMILABLE ORGANIC CARBON 42
3.5 FORMATION AND MITIGATION OF DISINFECTION BY-PRODUCTS 44
3.6 UV ABSORBANCE OF DISSOLVED ORGANIC MATTER 45
3.7 RELEVANCE OF OZONE KINETICS FOR THE ELIMINATION OF MICROPOLLUTANTS 46
3.8 HYDROXYL RADICAL YIELD AND •OH-SCAVENGING RATE OF DISSOLVED ORGANIC MATTER 48
3.9 ELIMINATION OF OZONE-REFRACTORY MICROPOLLUTANTS BY THE •OH ROUTE 49
3.10 OZONE-BASED ADVANCED OXIDATION PROCESSES 51
3.10.1 Peroxone process 51
3.10.2 UV photolysis of ozone 54
3.10.3 Reaction of ozone with activated carbon 55
Chapter 4 57
Inactivation of micro-organisms and toxicological assessment of ozone-induced products of micropollutants 57
4.1 DISINFECTION KINETICS 57
4.2 INACTIVATION MECHANISMS: ROLE OF MEMBRANES AND DNA 60
4.3 REACTIONS WITH NUCLEIC ACID COMPONENTS 61
4.4 REACTION WITH DNA 62
4.5 APPLICATION OF OZONE FOR DISINFECTION IN DRINKING WATER AND WASTEWATER 63
4.6 TOXICOLOGICAL ASSESSMENT OF OZONE INDUCED TRANSFORMATION PRODUCTS 63
4.7 ENDOCRINE DISRUPTING COMPOUNDS 64
4.7.1 Laboratory studies 66
4.7.2 Full-scale studies 67
4.8 ANTIMICROBIAL COMPOUNDS 68
4.9 TOXICITY 70
Chapter 5 73
Integration of ozonation in drinking water and wastewater process trains 73
5.1 HISTORICAL ASPECTS 73
5.1.1 Drinking water 73
5.1.2 Municipal wastewater 73
5.2 DRINKING WATER TREATMENT SCHEMES INCLUDING OZONATION 74
5.3 MICROPOLLUTANTS IN WATER RESOURCES, DRINKING WATER AND WASTEWATER 78
5.4 ENHANCED WASTEWATER TREATMENT WITH OZONE 80
5.5 ENERGY REQUIREMENTS FOR MICROPOLLUTANT TRANSFORMATION IN DRINKING WATER AND WASTEWATER 81
5.6 SOURCE CONTROL 82
5.7 RECLAMATION OF WASTEWATER 83
5.8 COMPARISON OF THE APPLICATION OF OZONE IN THE URBAN WATER CYCLE 85
Chapter 6 88
Olefins 88
6.1 REACTIVITY OF OLEFINS 88
6.2 THE CRIEGEE MECHANISM 91
6.3 PARTIAL OXIDATION 94
6.4 DECAY OF THE OZONIDE VIA FREE RADICALS 95
6.5 DETECTION OF α-HYDROXYALKYLHYDROPEROXIDES 95
6.6 OZONE REACTIONS OF OLEFINS - PRODUCTS AND REACTIONS OF REACTIVE INTERMEDIATES 96
6.6.1 Methyland halogen-substituted olefins 96
6.6.2 Acrylonitrile, vinyl acetate, diethyl vinylphosphonate, vinyl phenyl sulfonate, vinylsulfonic acid and vinylene carbonate 98
6.6.3 Acrylic, methacrylic, fumaric, maleic and muconic acids 99
6.6.4 Muconic acids 103
6.6.5 Cinnamic acids 105
6.6.6 Dichloromaleic acid 106
6.6.7 Pyrimidine nucleobases 106
6.7 MICROPOLLUTANTS WITH OLEFINIC FUNCTIONS 109
Chapter 7 115
Aromatic compounds 115
7.1 REACTIVITY OF AROMATIC COMPOUNDS 115
7.2 DECAY OF OZONE ADDUCTS 122
7.3 OZONE REACTIONS OF AROMATIC COMPOUNDS - PRODUCTS AND REACTIONS OF REACTIVE INTERMEDIATES 124
7.3.1 Methoxylated benzenes 124
7.3.2 Phenols 127
7.4 MICROPOLLUTANTS WITH AROMATIC FUNCTIONS 130
Chapter 8 137
Nitrogen-containing compounds 137
8.1 REACTIVITY OF NITROGEN-CONTAINING COMPOUNDS 137
8.2 GENERAL MECHANISTIC CONSIDERATIONS 144
8.2.1 Aliphatic amines 144
8.2.2 Aromatic amines (anilines) 149
8.2.3 Nitrogen-containing heterocyclic compounds 151
8.3 MICROPOLLUTANTS WITH NITROGEN-CONTAINING FUNCTIONS 152
8.3.1 The N-Nitrosodimethylamine (NDMA) puzzle 162
Chapter 9 166
Reactions of sulfur-containing compounds 166
9.1 REACTIVITY OF SULFUR-CONTAINING COMPOUNDS 166
9.2 THIOLS 167
9.3 SULFIDES, DISULFIDES AND SULFINIC ACIDS 168
9.4 SULFOXIDES 170
9.5 MICROPOLLUTANTS CONTAINING AN OZONE-REACTIVE SULFUR 171
Chapter 10 173
Compounds with C–H functions as ozone-reactive sites 173
10.1 REACTIVITY OF COMPOUNDS WITH C–H FUNCTIONS AS OZONE-REACTIVE SITES 173
10.2 GENERAL MECHANISTIC CONSIDERATIONS 175
10.3 FORMATE ION 177
10.4 2-METHYL-2-PROPANOL (TERTIARY BUTANOL) 179
10.5 2-PROPANOL 180
10.6 CARBOHYDRATES 184
10.7 DIHYDROGEN TRIOXIDE - PROPERTIES OF A SHORT-LIVED INTERMEDIATE 186
10.8 SATURATED MICROPOLLUTANTS LACKING OZONE-REACTIVE HETEROATOMS 188
Chapter 11 189
Inorganic anions and the peroxone process 189
11.1 INTRODUCTORY REMARKS 189
11.2 HYDROXIDE ION 191
11.3 HYDROPEROXIDE ION - PEROXONE PROCESS 192
11.4 FLUORIDE 193
11.5 CHLORIDE 194
11.6 HYPOCHLORITE 195
11.7 CHLORITE 196
11.8 BROMIDE 196
11.9 HYPOBROMITE 197
11.10 BROMITE 198
11.11 IODIDE 198
11.12 NITRITE 199
11.13 AZIDE 200
11.14 HYDROGEN SULFIDE 201
11.15 HYDROGEN SULFITE 202
11.16 BROMATE FORMATION AND MITIGATION IN WATER TREATMENT 202
11.17 BROMIDE-CATALYSED REACTIONS 205
11.18 MITIGATION OF IODIDE-RELATED PROBLEMS 206
Chapter 12 208
Reactions with metal ions 208
12.1 REACTIVITY OF METAL IONS 208
12.2 ARSENIC 209
12.3 COBALT 210
12.4 COPPER 210
12.5 IRON 210
12.6 LEAD 211
12.7 MANGANESE 211
12.8 SELENIUM 212
12.9 SILVER 212
12.10 TIN 214
12.11 METAL IONS AS MICROPOLLUTANTS 214
Chapter 13 216
Reactions with free radicals 216
13.1 REACTIVITY OF RADICALS 216
13.2 OZONE REACTIONS WITH REDUCING RADICALS 217
13.3 OZONE REACTIONS WITH CARBON-CENTERED RADICALS 218
13.4 OZONE REACTIONS WITH OXYGEN-CENTERED RADICALS 220
13.5 OZONE REACTIONS WITH NITROGENAND SULFUR-CENTRED RADICALS 222
13.6 OZONE REACTIONS WITH HALOGEN-CENTRED RADICALS 223
Chapter 14 228
Reactions of hydroxyl and peroxyl radicals 228
14.1 INTRODUCTORY REMARKS 228
14.2 HYDROXYL RADICAL REACTIONS 228
14.2.1 Addition reactions 228
14.2.2 H-abstraction reactions 230
14.2.3 Electron transfer reactions 231
14.3 DETERMINATION OF •OH RATE CONSTANTS 232
14.4 DETECTION OF •OH IN OZONE REACTIONS 233
14.5 DETERMINATION OF •OH YIELDS IN OZONE REACTIONS 235
14.6 FORMATION OF PEROXYL RADICALS 236
14.7 REDOX PROPERTIES OF PEROXYL RADICALS AND REACTION WITH OZONE 236
14.8 UNIMOLECULAR DECAY OF PEROXYL RADICALS 237
14.9 BIMOLECULAR DECAY OF PEROXYL RADICALS 238
14.10 REACTIONS OF OXYL RADICALS 239
14.11 INVOLVEMENT OF •OH RADICALS IN CHLORATE AND BROMATE FORMATION 240
14.11.1 Chlorate formation 240
14.11.2 Bromate formation 241
14.12 DEGRADATION OF OZONE-REFRACTORY MICROPOLLUTANTS BY •OH/PEROXYL RADICALS 244
14.12.1 Saturated aliphatic compounds 244
14.12.2 Aromatic compounds 246
14.12.3 Chlorinated olefins 248
14.12.4 Perfluorinated compounds 251
References 252
Index 289