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ENVIRONMENTAL
CHEMISTRY
NINTH EDITION
ENVIRONMENTAL
CHEMISTRY
NINTH EDITION

STANLEY E. MANAHAN

Boca Raton London New York

CRC Press is an imprint of the

Taylor & Francis Group, an informa business
The cover illustration depicts the pathway of solar energy captured by photosynthesis to convert atmospheric carbon
dioxide to biomass that can be used as a feedstock for the thermochemical production of methane. This synthetic natu-
ral gas product is the cleanest burning of all the carbon-based fuels. Methane made by the biomass pathway is neutral
with respect to the production of greenhouse gas carbon dioxide because any of that gas generated by combustion of
biomass-based synthetic natural gas was removed from the atmosphere by photosynthesis in producing the biomass
feedstock. Biomass-based synthetic fuel production and other sustainable energy technologies are discussed in detail in
Chapter 19, “Sustainable Energy: The Key to Everything.”

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Library of Congress Cataloging-in-Publication Data

Manahan, Stanley E.
Environmental chemistry / Stanley E. Manahan. -- 9th ed.
p. cm.
Includes bibliographical references and index.
ISBN 978-1-4200-5920-5 (hardcover : alk. paper)
1. Environmental chemistry. I. Title.

TD193.M36 2010
628--dc22 2009040939

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Contents

Preface ..................................................................................................................................... xxvii

Author ....................................................................................................................................... xxix

Chapter 1 The Environment and Sustainability Science .......................................................... 1

1.1 From the Sun to Fossil Fuels and Back Again .............................................. 1
1.1.1 The Brief but Spectacular Era of Fossil Fuels .................................. 2
1.1.2 Back to the Sun ................................................................................. 2
1.2 The Science of Sustainability ........................................................................ 3
1.2.1 Environmental Science ..................................................................... 4
1.2.2 Green Science and Technology ........................................................ 4
1.3 Chemistry and the Environment ................................................................... 4
1.4 Water, Air, Earth, Life, and Technology ....................................................... 5
1.4.1 Water and the Hydrosphere .............................................................. 5
1.4.2 Air and the Atmosphere ................................................................... 6
1.4.3 Earth, the Geosphere ........................................................................ 7
1.4.4 Life, the Biosphere ........................................................................... 7
1.4.5 Technology and the Environment .................................................... 7
1.5 Ecology, Ecotoxicology, and the Biosphere .................................................. 8
1.5.1 The Biosphere ................................................................................... 8
1.5.2 Ecology ............................................................................................. 9
1.5.3 Ecotoxicology ................................................................................... 9
1.6 Energy and Cycles of Energy ...................................................................... 10
1.6.1 Light and Electromagnetic Radiation ............................................ 10
1.6.2 Energy Flow and Photosynthesis in Living Systems ..................... 11
1.6.3 Energy Utilization .......................................................................... 11
1.7 Human Impact and Pollution ....................................................................... 12
1.7.1 Some Definitions Pertaining to Pollution ....................................... 12
1.7.2 Pollution of Various Spheres of the Environment .......................... 12
1.8 Chemical Fate and Transport ...................................................................... 12
1.8.1 Physical Transport .......................................................................... 14
1.8.2 Reactivity ........................................................................................ 14
1.8.3 Mass Balance Expression ............................................................... 14
1.8.4 Distribution among Phases ............................................................. 15
1.9 Chemical Fate and Transport in the Atmosphere, Hydrosphere,
and Geosphere ............................................................................................. 15
1.9.1 Pollutants in the Atmosphere ......................................................... 16
1.9.2 Pollutants in the Hydrosphere ........................................................ 16
1.9.3 Pollutants in the Geosphere ............................................................ 17
1.10 Environmental Mischief and Terrorism ...................................................... 17
1.10.1 Protection through Green Chemistry and Engineering ................. 17
1.11 Environmental Forensics ............................................................................. 18
Literature Cited ...................................................................................................... 19

v
vi Contents

Supplementary References ..................................................................................... 19

Questions and Problems ......................................................................................... 19

Chapter 2 Chemistry and the Anthrosphere: Environmental Chemistry

and Green Chemistry ............................................................................................. 23
2.1 Environmental Chemistry ........................................................................... 23
2.2 Matter and Cycles of Matter ........................................................................ 24
2.2.1 Carbon Cycle .................................................................................. 25
2.2.2 Nitrogen Cycle ................................................................................ 27
2.2.3 Oxygen Cycle ................................................................................. 28
2.2.4 Phosphorus Cycle ........................................................................... 28
2.2.5 Sulfur Cycle .................................................................................... 28
2.3 Anthrosphere and Environmental Chemistry ............................................. 29
2.3.1 Components of the Anthrosphere ................................................... 30
2.4 Technology and the Anthrosphere .............................................................. 31
2.4.1 Engineering ................................................................................... 32
2.5 Infrastructure ............................................................................................... 33
2.5.1 Vulnerable Infrastructure ............................................................... 34
2.6 Components of the Anthrosphere That Influence the Environment ........... 35
2.7 Effects of the Anthrosphere on Earth .......................................................... 37
2.8 Integration of the Anthrosphere into the Total Environment ...................... 38
2.8.1 Anthrosphere and Industrial Ecology ............................................ 39
2.9 Green Chemistry ......................................................................................... 40
2.9.1 Green Synthetic Chemistry ............................................................ 40
2.9.2 Risk Reduction ............................................................................... 41
2.9.3 Specific Aspects of Green Chemistry ............................................ 41
2.9.4 Three Undesirable Characteristics of Chemicals: Persistence,
Bioaccumulation, and Toxicity ....................................................... 42
2.9.5 Green Chemistry and Environmental Chemistry .......................... 42
Literature Cited ...................................................................................................... 42
Supplementary References ..................................................................................... 43
Questions and Problems ......................................................................................... 43

Chapter 3 Fundamentals of Aquatic Chemistry ..................................................................... 47

3.1 Importance of Water .................................................................................... 47
3.2 Water: From Molecules to Oceans .............................................................. 47
3.2.1 Sources and Uses of Water: The Hydrological Cycle .................... 47
3.2.2 Properties of Water, a Unique Substance ....................................... 50
3.2.3 Water Molecule .............................................................................. 50
3.3 Characteristics of Bodies of Water .............................................................. 52
3.4 Aquatic Life ................................................................................................. 52
3.5 Introduction to Aquatic Chemistry .............................................................. 53
3.6 Gases in Water ............................................................................................. 54
3.6.1 Oxygen in Water ............................................................................. 54
3.7 Water Acidity and Carbon Dioxide in Water .............................................. 55
3.7.1 Carbon Dioxide in Water ................................................................ 56
3.8 Alkalinity .................................................................................................... 59
3.8.1 Contributors to Alkalinity at Different pH Values ......................... 60
3.8.2 Dissolved Inorganic Carbon and Alkalinity .................................. 60
3.8.3 Influence of Alkalinity on CO2 Solubility ...................................... 61
Contents vii

3.9 Calcium and Other Metals in Water ............................................................ 62

3.9.1 Hydrated Metal Ions as Acids ........................................................ 62
3.9.2 Calcium in Water ............................................................................ 63
3.9.3 Dissolved Carbon Dioxide and Calcium Carbonate Minerals ....... 64
3.10 Complexation and Chelation ....................................................................... 65
3.10.1 Occurrence and Importance of Chelating Agents in Water ........... 67
3.11 Bonding and Structure of Metal Complexes ............................................... 68
3.11.1 Selectivity and Specificity in Chelation ......................................... 68
3.12 Calculations of Species Concentrations ...................................................... 68
3.13 Complexation by Deprotonated Ligands ..................................................... 69
3.14 Complexation by Protonated Ligands ......................................................... 70
3.15 Solubilization of Lead Ion from Solids by NTA ......................................... 71
3.15.1 Reaction of NTA with Metal Carbonate ........................................ 73
3.15.2 Effect of Calcium Ion upon the Reaction of Chelating
Agents with Slightly Soluble Salts ................................................. 74
3.16 Polyphosphates and Phosphonates in Water ................................................ 75
3.16.1 Polyphosphates ............................................................................... 76
3.16.2 Hydrolysis of Polyphosphates ......................................................... 76
3.16.3 Complexation by Polyphosphates ................................................... 76
3.16.4 Phosphonates .................................................................................. 77
3.17 Complexation by Humic Substances ........................................................... 77
3.18 Complexation and Redox Processes ............................................................ 79
Literature Cited ...................................................................................................... 79
Supplementary References ..................................................................................... 79
Questions and Problems ......................................................................................... 80

Chapter 4 Oxidation–Reduction in Aquatic Chemistry............................................................ 83

4.1 The Significance of Oxidation–Reduction .................................................. 83
4.2 Electron and Redox Reactions ..................................................................... 85
4.3 Electron Activity and pE ............................................................................. 87
4.4 The Nernst equation .................................................................................... 88
4.5 Reaction Tendency: Whole Reaction from Half-Reactions ......................... 89
4.6 The Nernst Equation and Chemical Equilibrium ........................................ 90
4.7 The Relationship of pE to Free Energy ....................................................... 91
4.8 Reactions in Terms of One Electron-Mole .................................................. 91
4.9 The Limits of pE in Water ........................................................................... 93
4.10 pE Values in Natural Water Systems ........................................................... 94
4.11 pE–pH Diagrams ......................................................................................... 95
4.12 Humic Substances as Natural Reductants ................................................... 98
4.13 Photochemical Processes in Oxidation–Reduction ..................................... 99
4.14 Corrosion ..................................................................................................... 99
Literature Cited .................................................................................................... 100
Supplementary References ................................................................................... 100
Questions and Problems ....................................................................................... 101

Chapter 5 Phase Interactions in Aquatic Chemistry ............................................................... 103

5.1 Chemical Interactions Involving Solids, Gases, and Water ...................... 103
5.2 Importance and Formation of Sediments .................................................. 103
5.2.1 Formation of Sediments ............................................................... 104
5.2.2 Organic and Carbonaceous Sedimentary Materials .................... 105
viii Contents

5.3 Solubilities ................................................................................................. 106

5.3.1 Solubilities of Solids ..................................................................... 106
5.3.2 Solubilities of Gases ..................................................................... 107
5.4 Colloidal Particles in Water ....................................................................... 108
5.4.1 Contaminant Transport by Colloids in Water .............................. 109
5.4.2 Occurrence of Colloids in Water .................................................. 109
5.4.3 Kinds of Colloidal Particles ......................................................... 109
5.4.4 Colloid Stability ........................................................................... 110
5.5 Colloidal Properties of Clays ..................................................................... 112
5.6 Aggregation of Particles ............................................................................ 113
5.6.1 Flocculation of Colloids by Polyelectrolytes ................................ 114
5.6.2 Flocculation of Bacteria by Polymeric Materials ......................... 114
5.7 Surface Sorption by Solids ........................................................................ 115
5.8 Solute Exchange with Bottom Sediments ................................................. 116
5.8.1 Trace-Level Metals in Suspended Matter and Sediments ............ 117
5.8.2 Phosphorus Exchange with Bottom Sediments ............................ 118
5.8.3 Organic Compounds on Sediments and Suspended Matter ......... 119
5.8.4 Bioavailability of Sediment Contaminants .................................. 120
5.9 Interstitial Water ........................................................................................ 121
5.10 Phase Interactions in Chemical Fate and Transport .................................. 122
5.10.1 Rivers ............................................................................................ 122
5.10.2 Lakes and Reservoirs ................................................................... 122
5.10.3 Exchange with the Atmosphere .................................................... 122
5.10.4 Exchange with Sediments ............................................................ 123
Literature Cited .................................................................................................... 124
Supplementary References ................................................................................... 124
Questions and Problems ....................................................................................... 125

Chapter 6 Aquatic Microbial Biochemistry .......................................................................... 127

6.1 Aquatic Biochemical Processes ................................................................. 127
6.1.1 Microorganisms at Interfaces ....................................................... 128
6.2 Algae .......................................................................................................... 129
6.3 Fungi .......................................................................................................... 130
6.4 Protozoa ..................................................................................................... 130
6.5 Bacteria ...................................................................................................... 131
6.5.1 Autotrophic and Heterotrophic Bacteria ...................................... 131
6.5.2 Oxic and Anoxic Bacteria ............................................................ 132
6.5.3 Marine Bacteria ............................................................................ 132
6.6 The Prokaryotic Bacterial Cell .................................................................. 133
6.7 Kinetics of Bacterial Growth .................................................................... 134
6.8 Bacterial Metabolism ................................................................................ 134
6.8.1 Factors Affecting Bacterial Metabolism ...................................... 135
6.8.2 Microbial Oxidation and Reduction ............................................. 137
6.9 Microbial Transformations of Carbon ....................................................... 139
6.9.1 Methane-Forming Bacteria .......................................................... 139
6.9.2 Bacterial Utilization of Hydrocarbons ......................................... 140
6.9.3 Microbial Utilization of Carbon Monoxide ................................. 140
6.10 Biodegradation of Organic Matter ............................................................ 140
6.10.1 Oxidation ...................................................................................... 141
6.10.1.1 Microbial Oxidation of Hydrocarbons ......................... 141
6.10.2 Other Biochemical Processes in Biodegradation of Organics ..... 142
Contents ix

6.11 Microbial Transformations of Nitrogen ..................................................... 143

6.11.1 Nitrogen Fixation .......................................................................... 144
6.11.2 Nitrification .................................................................................. 145
6.11.3 Nitrate Reduction ......................................................................... 146
6.11.4 Denitrification .............................................................................. 146
6.11.5 Competitive Oxidation of Organic Matter by Nitrate Ion
and Other Oxidizing Agents ........................................................ 146
6.12 Microbial Transformations of Phosphorus and Sulfur .............................. 147
6.12.1 Phosphorus Compounds ............................................................... 147
6.12.2 Sulfur Compounds ....................................................................... 148
6.12.2.1 Oxidation of H2S and Reduction of Sulfate
by Bacteria .................................................................... 148
6.12.3 Microorganism-Mediated Degradation of Organic
Sulfur Compounds ....................................................................... 149
6.13 Microbial Transformations of Halogens and Organohalides .................... 149
6.14 Microbial Transformations of Metals and Metalloids ............................... 150
6.14.1 Acid Mine Waters ......................................................................... 151
6.14.2 Microbial Transitions of Selenium ............................................... 152
6.14.3 Microbial Corrosion ..................................................................... 153
Literature Cited .................................................................................................... 153
Supplementary References ................................................................................... 154
Questions and Problems ....................................................................................... 154

Chapter 7 Water Pollution ..................................................................................................... 159

7.1 Nature and Types of Water Pollutants ....................................................... 159
7.1.1 Markers of Water Pollution .......................................................... 159
7.2 Elemental Pollutants ................................................................................. 159
7.3 Heavy Metals ............................................................................................. 161
7.3.1 Cadmium ...................................................................................... 161
7.3.2 Lead .............................................................................................. 161
7.3.3 Mercury ........................................................................................ 162
7.4 Metalloids .................................................................................................. 163
7.5 Organically Bound Metals and Metalloids ............................................... 164
7.5.1 Organotin Compounds ................................................................. 165
7.6 Inorganic Species ...................................................................................... 165
7.6.1 Cyanide ......................................................................................... 165
7.6.2 Ammonia and Other Inorganic Pollutants ................................... 166
7.6.3 Asbestos in Water ......................................................................... 167
7.7 Algal Nutrients and Eutrophication ........................................................... 167
7.8 Acidity, Alkalinity, and Salinity ................................................................ 168
7.9 Oxygen, Oxidants, and Reductants ........................................................... 169
7.10 Organic Pollutants ..................................................................................... 170
7.10.1 Bioaccumulation of Organic Pollutants ....................................... 170
7.10.2 Sewage .......................................................................................... 170
7.10.3 Soaps, Detergents, and Detergent Builders .................................. 171
7.10.3.1 Soaps ............................................................................ 171
7.10.3.2 Detergents ..................................................................... 172
7.10.4 Naturally Occurring Chlorinated and Brominated
Compounds ................................................................................... 174
7.10.5 Microbial Toxins .......................................................................... 174
x Contents

7.11 Pesticides in Water ..................................................................................... 175

7.11.1 Natural Product Insecticides, Pyrethrins, and Pyrethroids .......... 175
7.11.2 DDT and Organochlorine Insecticides ......................................... 177
7.11.3 Organophosphate Insecticides ...................................................... 178
7.11.4 Carbamates ................................................................................... 179
7.11.5 Fungicides .................................................................................... 179
7.11.6 Herbicides ..................................................................................... 180
7.11.6.1 Bipyridilium Compounds ............................................. 180
7.11.6.2 Herbicidal Heterocyclic Nitrogen Compounds ............ 181
7.11.6.3 Chlorophenoxy Herbicides ........................................... 181
7.11.6.4 Miscellaneous Herbicides ............................................ 181
7.11.7 By-Products of Pesticide Manufacture ......................................... 182
7.12 Polychlorinated Biphenyls ......................................................................... 183
7.13 Emerging Water Pollutants, Pharmaceuticals, and
Household Wastes ...................................................................................... 184
7.13.1 Bactericides .................................................................................. 186
7.13.2 Estrogenic Substances in Wastewater Effluents ........................... 186
7.13.3 Biorefractory Organic Pollutants ................................................. 186
7.14 Radionuclides in the Aquatic Environment ............................................... 188
Literature Cited .................................................................................................... 192
Supplementary References ................................................................................... 192
Questions and Problems ....................................................................................... 193

Chapter 8 Water Treatment ................................................................................................... 197

8.1 Water Treatment and Water Use ................................................................ 197
8.2 Municipal Water Treatment ....................................................................... 197
8.3 Treatment of Water for Industrial Use ....................................................... 198
8.4 Sewage Treatment ...................................................................................... 199
8.4.1 Primary Waste Treatment ............................................................ 199
8.4.2 Secondary Waste Treatment by Biological Processes .................. 200
8.4.3 Membrane Bioreactor ................................................................... 203
8.4.4 Tertiary Waste Treatment ............................................................. 203
8.4.5 Physical-Chemical Treatment of Municipal Wastewater ............. 203
8.5 Industrial Wastewater Treatment ............................................................... 204
8.6 Removal of Solids ...................................................................................... 205
8.6.1 Dissolved Air Flotation ................................................................ 206
8.6.2 Membrane Filtration Processes .................................................... 206
8.7 Removal of Calcium and Other Metals ..................................................... 207
8.7.1 Removal of Iron and Manganese ................................................. 211
8.8 Removal of Dissolved Organics ................................................................ 212
8.8.1 Removal of Herbicides ................................................................. 213
8.9 Removal of Dissolved Inorganics .............................................................. 214
8.9.1 Ion Exchange ................................................................................ 214
8.9.2 Electrodialysis .............................................................................. 214
8.9.3 Reverse Osmosis ........................................................................... 215
8.9.4 Phosphorus Removal .................................................................... 216
8.9.5 Nitrogen Removal ......................................................................... 217
8.10 Sludge ........................................................................................................ 218
8.11 Water Disinfection ..................................................................................... 219
8.11.1 Chlorine Dioxide .......................................................................... 220
Contents xi

8.11.2 Ozone and Other Oxidants ........................................................... 221

8.11.3 Disinfection with Ultraviolet Radiation ....................................... 222
8.12 Natural Water Purification Processes ........................................................ 222
8.12.1 Industrial Wastewater Treatment by Soil ..................................... 223
8.13 Green Water ............................................................................................... 223
8.13.1 Reuse and Recycling of Wastewater ............................................ 224
8.14 Water Conservation ................................................................................... 226
8.15 Protecting Water Supplies from Attack ..................................................... 227
Literature Cited .................................................................................................... 228
Supplementary References ................................................................................... 228
Questions and Problems ....................................................................................... 229

Chapter 9 The Atmosphere and Atmospheric Chemistry ..................................................... 233

9.1 Introduction ............................................................................................... 233
9.1.1 Photochemistry and Some Important Terms ................................ 233
9.1.2 Atmospheric Composition ............................................................ 234
9.1.3 Gaseous Oxides in the Atmosphere ............................................. 234
9.1.4 Atmospheric Methane .................................................................. 235
9.1.5 Hydrocarbons and Photochemical Smog ..................................... 236
9.1.6 Particulate Matter ......................................................................... 236
9.1.7 Primary and Secondary Pollutants ............................................... 236
9.2 Importance of the Atmosphere .................................................................. 236
9.3 Physical Characteristics of the Atmosphere .............................................. 237
9.3.1 Variation of Pressure and Density with Altitude ......................... 237
9.3.2 Stratification of the Atmosphere .................................................. 238
9.4 Energy Transfer in the Atmosphere ........................................................... 240
9.4.1 The Earth’s Radiation Budget ..................................................... 241
9.5 Atmospheric Mass Transfer, Meteorology, and Weather .......................... 241
9.5.1 Atmospheric Water in Energy and Mass Transfer ....................... 243
9.5.2 Air Masses .................................................................................... 243
9.5.3 Topographical Effects .................................................................. 244
9.5.4 Movement of Air Masses ............................................................. 244
9.5.5 Global Weather ............................................................................. 245
9.5.6 Weather Fronts and Storms .......................................................... 246
9.6 Inversions and Air Pollution ...................................................................... 247
9.7 Global Climate and Microclimate ............................................................. 247
9.7.1 Atmospheric Carbon Dioxide and Human Modifications
of Climate ..................................................................................... 248
9.7.2 Microclimate ................................................................................ 248
9.7.3 Effects of Urbanization on Microclimate ..................................... 249
9.8 Chemical and Photochemical Reactions in the Atmosphere ..................... 249
9.8.1 Photochemical Processes ............................................................. 251
9.8.2 Ions and Radicals in the Atmosphere ........................................... 253
9.8.2.1 Free Radicals ................................................................ 254
9.8.3 Hydroxyl and Hydroperoxyl Radicals in the Atmosphere ........... 254
9.8.4 Chemical and Biochemical Processes in Evolution
of the Atmosphere ........................................................................ 256
9.9 Acid–Base Reactions in the Atmosphere .................................................. 257
9.10 Reactions of Atmospheric Oxygen ............................................................ 258
9.11 Reactions of Atmospheric Nitrogen .......................................................... 259
xii Contents

9.12 Atmospheric Water .................................................................................... 260

9.13 Influence of the Anthrosphere ................................................................... 260
9.14 Chemical Fate and Transport in the Atmosphere ...................................... 261
Literature Cited .................................................................................................... 262
Supplementary References ................................................................................... 262
Questions and Problems ....................................................................................... 263

Chapter 10 Particles in the Atmosphere ................................................................................. 265

10.1 Introduction ............................................................................................... 265
10.2 Physical Behavior of Particles in the Atmosphere .................................... 266
10.2.1 Size and Settling of Atmospheric Particles .................................. 267
10.3 Physical Processes for Particle Formation ................................................ 267
10.4 Chemical Processes for Particle Formation .............................................. 268
10.4.1 Inorganic Particles ........................................................................ 269
10.4.2 Organic Particles .......................................................................... 270
10.4.3 Polycyclic Aromatic Hydrocarbon Synthesis ............................... 270
10.5 The Composition of Inorganic Particles .................................................... 271
10.5.1 Fly Ash ......................................................................................... 272
10.5.2 Asbestos ....................................................................................... 272
10.6 Toxic Metals in the Atmosphere ............................................................... 273
10.6.1 Atmospheric Mercury .................................................................. 273
10.6.2 Atmospheric Lead ........................................................................ 273
10.6.3 Atmospheric Beryllium ................................................................ 274
10.7 Radioactive Particles ................................................................................. 274
10.8 The Composition of Organic Particles ...................................................... 275
10.8.1 PAHs ............................................................................................. 275
10.8.2 Carbonaceous Particles from Diesel Engines .............................. 276
10.9 Effects of Particles ..................................................................................... 276
10.9.1 Partitioning of Semivolatile Organic Substances
between Air and Particles ............................................................ 277
10.10 Water as Particulate Matter ....................................................................... 277
10.11 Atmospheric Chemical Reactions Involving Particles .............................. 278
10.12 Control of Particulate Emissions ............................................................... 280
10.12.1 Particle Removal by Sedimentation and Inertia ........................... 280
10.12.2 Particle Filtration .......................................................................... 280
10.12.3 Scrubbers ...................................................................................... 281
10.12.4 Electrostatic Removal ................................................................... 282
Literature Cited .................................................................................................... 282
Supplementary References ................................................................................... 283
Questions and Problems ....................................................................................... 283

Chapter 11 Gaseous Inorganic Air Pollutants ........................................................................ 285

11.1 Inorganic Pollutant Gases .......................................................................... 285
11.2 Production and Control of Carbon Monoxide ........................................... 285
11.2.1 Control of Carbon Monoxide Emissions ...................................... 285
11.3 Fate of Atmospheric CO ............................................................................ 286
11.4 Sulfur Dioxide Sources and the Sulfur Cycle ........................................... 286
11.5 Sulfur Dioxide Reactions in the Atmosphere ............................................ 287
11.5.1 Effects of Atmospheric Sulfur Dioxide ........................................ 289
11.5.2 Sulfur Dioxide Removal ............................................................... 290
Contents xiii

11.6 Nitrogen Oxides in the Atmosphere .......................................................... 292

11.6.1 Atmospheric Reactions of NOx ..................................................... 294
11.6.2 Harmful Effects of Nitrogen Oxides ............................................ 296
11.6.3 Control of Nitrogen Oxides .......................................................... 297
11.7 Acid Rain ................................................................................................... 299
11.8 Ammonia in the Atmosphere .................................................................... 299
11.9 Fluorine, Chlorine, and their Gaseous Compounds .................................. 299
11.9.1 Chlorine and Hydrogen Chloride ................................................. 300
11.10 Reduced Sulfur Gases ............................................................................... 301
Literature Cited .................................................................................................... 303
Supplementary References ................................................................................... 303
Questions And Problems ...................................................................................... 304

Chapter 12 Organic Air Pollutants ......................................................................................... 307

12.1 Organic Compounds in the Atmosphere ................................................... 307
12.1.1 Loss of Organic Substances from the Atmosphere ...................... 307
12.1.2 Global Distillation and Fractionation of Persistent
Organic Pollutants (POP) ............................................................. 307
12.2 Biogenic Organic Compounds ................................................................... 308
12.2.1 Removal of Atmospheric Organic Compounds by Plants ............ 310
12.3 Pollutant Hydrocarbons ............................................................................. 310
12.3.1 Aromatic Hydrocarbons ............................................................... 313
12.3.2 Reactions of Atmospheric Aromatic Hydrocarbons .................... 314
12.4 Carbonyl Compounds: Aldehydes and Ketones ........................................ 315
12.5 Miscellaneous Oxygen-Containing Compounds ....................................... 317
12.5.1 Alcohols ........................................................................................ 317
12.5.2 Phenols ......................................................................................... 318
12.5.3 Ethers ............................................................................................ 318
12.5.4 Oxides ........................................................................................... 319
12.5.5 Carboxylic Acids .......................................................................... 319
12.6 Organonitrogen Compounds ..................................................................... 320
12.7 Organohalide Compounds ......................................................................... 322
12.7.1 Chlorofluorocarbons ..................................................................... 323
12.7.2 Atmospheric Reactions of Hydrofluorocarbons
and Hydrochlorofluorocarbons ..................................................... 324
12.7.3 Perfluorocarbons .......................................................................... 325
12.7.4 Marine Sources of Organohalogen Compounds .......................... 325
12.7.5 Chlorinated Dibenzo-p-dioxins and Dibenzofurans .................... 325
12.8 Organosulfur Compounds ......................................................................... 326
12.9 Organic Particulate Matter ........................................................................ 327
12.10 Hazardous Air Pollutants Organic Compounds ........................................ 327
Literature Cited .................................................................................................... 329
Supplementary References ................................................................................... 330
Questions and Problems ....................................................................................... 330

Chapter 13 Photochemical Smog ............................................................................................ 333

13.1 Introduction ............................................................................................... 333
13.2 Smog-Forming Emissions ......................................................................... 334
13.2.1 Control of Exhaust Hydrocarbons ................................................ 334
13.2.2 Automotive Emission Standards .................................................. 337
13.2.3 Polluting Green Plants .................................................................. 337
xiv Contents

13.3 Smog-Forming Reactions of Organic Compounds in the Atmosphere ..... 338

13.3.1 Photochemical Reactions of Methane .......................................... 338
13.4 Overview of Smog Formation ................................................................... 340
13.5 Mechanisms of Smog Formation ............................................................... 341
13.5.1 Nitrate Radical ............................................................................. 347
13.5.2 Photolyzable Compounds in the Atmosphere .............................. 347
13.6 Reactivity of Hydrocarbons ....................................................................... 348
13.7 Inorganic Products from Smog .................................................................. 348
13.8 Effects of Smog ......................................................................................... 349
Literature Cited .................................................................................................... 352
Supplementary References ................................................................................... 352
Questions and Problems ....................................................................................... 353

Chapter 14 The Endangered Global Atmosphere ................................................................... 355

14.1 Climate Change and Anthropogenic Effects ............................................. 355
14.1.1 Changes in Climate ...................................................................... 356
14.2 Global Warming ........................................................................................ 357
14.2.1 Methane and Other Greenhouse Gases ........................................ 360
14.2.2 Particles and Global Warming ..................................................... 360
14.2.3 The Outlook for Global Warming and Associated Effects .......... 361
14.3 Green Science and Technology to Alleviate Global Warming ................. 361
14.3.1 Minimization ................................................................................ 362
14.3.2 Counteracting Measures ............................................................... 364
14.3.3 Adaptation .................................................................................... 364
14.4 Acid Rain ................................................................................................... 365
14.5 Stratospheric Ozone Destruction ............................................................... 368
14.5.1 Shielding Effect of the Ozone Layer ............................................ 369
14.5.2 Ozone Layer Destruction .............................................................. 369
14.5.3 Green Chemistry Solutions to Stratospheric
Ozone Depletion ........................................................................... 372
14.6 Atmospheric Brown Clouds ...................................................................... 373
14.6.1 Yellow Dust .................................................................................. 374
14.7 Atmospheric Damage by Photochemical Smog ........................................ 375
14.8 Nuclear Winter .......................................................................................... 377
14.8.1 Doomsday Visitors from Space .................................................... 379
14.9 What Is to Be Done? .................................................................................. 379
Literature Cited .................................................................................................... 381
Supplementary References ................................................................................... 381
Questions and Problems ....................................................................................... 382

Chapter 15 The Geosphere and Geochemistry ....................................................................... 385

15.1 Introduction ............................................................................................... 385
15.2 The Nature of Solids in the Geosphere ..................................................... 386
15.2.1 Structure and Properties of Minerals ........................................... 386
15.2.2 Kinds of Minerals ........................................................................ 387
15.2.3 Evaporites ..................................................................................... 387
15.2.4 Volcanic Sublimates ..................................................................... 388
15.2.5 Igneous, Sedimentary, and Metamorphic Rock ........................... 388
15.2.5.1 Rock Cycle ................................................................... 389
15.2.5.2 Stages of Weathering .................................................... 389
Contents xv

15.3 Physical Form of the Geosphere ................................................................ 389

15.3.1 Plate Tectonics and Continental Drift .......................................... 390
15.3.2 Structural Geology ....................................................................... 390
15.4 Internal Processes ...................................................................................... 391
15.4.1 Earthquakes .................................................................................. 392
15.4.2 Volcanoes ..................................................................................... 392
15.4.3 Surface Processes ......................................................................... 393
15.5 Sediments .................................................................................................. 393
15.6 Clays .......................................................................................................... 394
15.7 Geochemistry ............................................................................................ 395
15.7.1 Physical Aspects of Weathering ................................................... 396
15.7.2 Chemical Weathering ................................................................... 396
15.7.3 Biological Aspects of Weathering ................................................ 397
15.8 Groundwater in the Geosphere .................................................................. 397
15.8.1 Water Wells .................................................................................. 399
15.8.2 Qanats ........................................................................................... 400
15.9 Environmental Aspects of the Geosphere ................................................. 400
15.9.1 Natural Hazards ........................................................................... 401
15.9.2 Anthropogenic Hazards ............................................................... 401
15.10 Earthquakes ............................................................................................... 401
15.11 Volcanoes ................................................................................................... 403
15.11.1 Mud Volcanoes ............................................................................. 404
15.12 Surface Earth Movement ........................................................................... 404
15.13 Stream and River Phenomena ................................................................... 406
15.14 Phenomena at the Land/Ocean Interface .................................................. 407
15.14.1 The Threat of Rising Sea Levels .................................................. 408
15.15 Phenomena at the Land/Atmosphere Interface .......................................... 409
15.16 Effects of Ice .............................................................................................. 409
15.17 Effects of Human Activities ...................................................................... 410
15.17.1 Extraction of Geospheric Resources: Surface Mining ................. 411
15.17.2 Environmental Effects of Mining and
Mineral Extraction ....................................................................... 411
15.18 Air Pollution and the Geosphere ............................................................... 411
15.19 Water Pollution and the Geosphere ........................................................... 412
15.20 Waste Disposal and the Geosphere ........................................................... 413
15.20.1 Municipal Refuse ......................................................................... 413
Literature Cited .................................................................................................... 415
Supplementary References ................................................................................... 415
Questions and Problems ....................................................................................... 416

Chapter 16 Soil and Agricultural Environmental Chemistry ................................................. 419

16.1 Soil and Agriculture .................................................................................. 419
16.1.1 Agriculture ................................................................................... 419
16.1.2 Pesticides and Agriculture ............................................................ 421
16.2 Nature and Composition of Soil ................................................................ 421
16.2.1 Water and Air in Soil ................................................................... 422
16.2.2 The Inorganic Components of Soil .............................................. 424
16.2.3 Organic Matter in Soil .................................................................. 424
16.2.4 Soil Humus ................................................................................... 426
16.2.5 The Soil Solution .......................................................................... 426
xvi Contents

16.3 Acid–Base and Ion-Exchange Reactions in Soils ...................................... 427

16.3.1 Adjustment of Soil Acidity ........................................................... 428
16.3.2 Ion-Exchange Equilibria in Soil ................................................... 428
16.4 Macronutrients in Soil ............................................................................... 429
16.5 Nitrogen, Phosphorus, and Potassium in Soil ........................................... 430
16.5.1 Nitrogen ........................................................................................ 430
16.5.2 Phosphorus ................................................................................... 432
16.5.3 Potassium ...................................................................................... 433
16.6 Micronutrients in Soil ................................................................................ 433
16.7 Fertilizers ................................................................................................... 434
16.7.1 Fertilizer Pollution ....................................................................... 435
16.8 Pollutants from Livestock Production ....................................................... 436
16.9 Pesticides and Their Residues in Soil ........................................................ 436
16.9.1 Soil Fumigants ............................................................................. 437
16.10 Wastes and Pollutants in Soil .................................................................... 438
16.10.1 Biodegradation and the Rhizosphere ........................................... 440
16.11 Soil Loss and Degradation ........................................................................ 440
16.11.1 Soil Sustainability and Water Resources ..................................... 441
16.12 Saving the Land ......................................................................................... 442
16.12.1 Agroforestry ................................................................................. 443
16.12.2 Soil Restoration ............................................................................ 443
16.13 Genetic Engineering and Agriculture ....................................................... 444
16.14 Green Chemistry and Sustainable Agriculture ......................................... 445
16.15 Agriculture and Health .............................................................................. 447
16.15.1 Food Contamination ..................................................................... 448
16.16 Protecting the Food Supply from Attack ................................................... 448
Literature Cited .................................................................................................... 449
Supplementary References ................................................................................... 449
Questions and Problems ....................................................................................... 450

Chapter 17 Green Chemistry and Industrial Ecology ............................................................. 453

17.1 Changing the Bad Old Ways ..................................................................... 453
17.2 Green Chemistry ....................................................................................... 454
17.2.1 Twelve Principles of Green Chemistry ........................................ 454
17.3 Reduction of Risk: Hazard and Exposure ................................................. 456
17.3.1 The Risks of Not Taking Risks .................................................... 458
17.4 Waste Prevention and Green Chemistry .................................................... 458
17.5 Green Chemistry and Synthetic Chemistry .............................................. 459
17.5.1 Yield and Atom Economy ............................................................ 459
17.6 Feedstocks ................................................................................................. 461
17.6.1 Biological Feedstocks ................................................................... 461
17.7 Reagents ..................................................................................................... 463
17.8 Stoichiometric and Catalytic Reagents ...................................................... 464
17.9 Media and Solvents .................................................................................... 465
17.9.1 Water, the Greenest Solvent ......................................................... 466
17.9.2 Dense Phase Carbon Dioxide as a Solvent ................................... 467
17.9.3 Gas-Expanded Solvents ................................................................ 468
17.10 Enhancing Reactions ................................................................................. 468
17.11 Industrial Ecology ..................................................................................... 470
17.12 The Five Major Components of an Industrial Ecosystem ......................... 472
Contents xvii

17.13 Industrial Metabolism ............................................................................... 474

17.14 Materials Flow and Recycling in an Industrial Ecosystem ....................... 475
17.15 The Kalundborg Industrial Ecosystem ...................................................... 475
17.16 Consideration of Environmental Impacts in Industrial Ecology ............... 476
17.17 Life Cycles: Expanding and Closing the Materials Loop ......................... 477
17.17.1 Product Stewardship ..................................................................... 479
17.17.2 Embedded Utility ......................................................................... 479
17.18 Life-Cycle Assessment .............................................................................. 480
17.18.1 Scoping in Life-Cycle Assessment ............................................... 480
17.19 Consumable, Recyclable, and Service (Durable) Products ....................... 481
17.19.1 Desirable Characteristics of Consumables ................................... 481
17.19.2 Desirable Characteristics of Recyclables ..................................... 481
17.19.3 Desirable Characteristics of Service Products ............................. 482
17.20 Design for Environment ............................................................................ 482
17.20.1 Products, Processes, and Facilities ............................................... 483
17.20.2 Key Factors in Design for Environment ....................................... 483
17.20.3 Hazardous Materials in Design for Environment ........................ 484
17.21 Inherent Safety .......................................................................................... 484
17.21.1 Increased Safety with Smaller Size .............................................. 485
17.22 Industrial Ecology and Ecological Engineering ........................................ 486
Literature Cited .................................................................................................... 486
Supplementary References ................................................................................... 486
Questions and Problems ....................................................................................... 488

Chapter 18 Resources and Sustainable Materials ................................................................... 491

18.1 Where to Get the Stuff We Need? ............................................................. 491
18.2 Minerals in the Geosphere ........................................................................ 492
18.2.1 Evaluation of Mineral Resources ................................................. 492
18.3 Extraction and Mining ............................................................................... 493
18.4 Metals ........................................................................................................ 494
18.5 Metal Resources and Industrial Ecology .................................................. 496
18.5.1 Aluminum .................................................................................... 497
18.5.2 Chromium .................................................................................... 497
18.5.3 Copper .......................................................................................... 498
18.5.4 Cobalt ........................................................................................... 498
18.5.5 Lead .............................................................................................. 498
18.5.6 Lithium ......................................................................................... 498
18.5.7 Potassium ...................................................................................... 499
18.5.8 Zinc ............................................................................................... 500
18.6 Nonmetal Mineral Resources .................................................................... 500
18.7 Phosphates ................................................................................................. 501
18.8 Sulfur ......................................................................................................... 502
18.8.1 Gypsum ........................................................................................ 503
18.9 Wood: A Major Renewable Resource ........................................................ 503
18.10 Extending Resources through the Practice of Industrial Ecology ............ 504
18.10.1 Metals ........................................................................................... 504
18.10.2 Plastics and Rubber ...................................................................... 505
18.10.3 Lubricating Oil ............................................................................. 506
Literature Cited .................................................................................................... 506
Supplementary References ................................................................................... 506
Questions and Problems ....................................................................................... 507
xviii Contents

Chapter 19 Sustainable Energy: The Key to Everything ........................................................ 509

19.1 Energy Problem ......................................................................................... 509
19.2 Nature of Energy ....................................................................................... 510
19.3 Sources of Energy Used in the Anthrosphere ........................................... 511
19.4 Energy Devices and Conversions .............................................................. 513
19.4.1 Fuel Cells ...................................................................................... 516
19.5 Green Technology and Energy Conversion Efficiency .............................. 517
19.6 Energy Conservation and Renewable Energy Sources .............................. 518
19.7 Petroleum and Natural Gas ....................................................................... 520
19.8 Coal ............................................................................................................ 521
19.8.1 Coal Conversion ........................................................................... 521
19.9 Carbon Sequestration for Fossil Fuel Utilization ...................................... 523
19.10 Industrial Ecology for Energy and Chemicals .......................................... 524
19.11 Nuclear Energy .......................................................................................... 526
19.11.1 Nuclear Fusion .............................................................................. 528
19.12 Geothermal Energy ................................................................................... 528
19.13 The Sun: An Ideal, Renewable Energy Source ......................................... 529
19.14 Energy from Moving Air and Moving Water ............................................ 531
19.14.1 Surprising Success of Wind Power .............................................. 531
19.14.2 Energy from Moving Water ......................................................... 533
19.14.3 Energy from Moving Water without Dams .................................. 534
19.15 Biomass Energy ......................................................................................... 534
19.15.1 Ethanol Fuel ................................................................................. 535
19.15.2 Biodiesel Fuel ............................................................................... 535
19.15.3 Unrealized Potential of Lignocellulose Fuels .............................. 536
19.15.4 Biogas ........................................................................................... 539
19.16 Hydrogen as a Means to Store and Utilize Energy ................................... 540
19.17 Combined Power Cycles ............................................................................ 540
19.18 A System of Industrial Ecology for Methane Production ......................... 541
Literature Cited .................................................................................................... 542
Supplementary References ................................................................................... 542
Questions and Problems ....................................................................................... 543

Chapter 20 Nature, Sources, and Environmental Chemistry of Hazardous Wastes ............... 545
20.1 Introduction ............................................................................................... 545
20.1.1 History of Hazardous Substances ................................................ 545
20.1.2 Legislation .................................................................................... 546
20.2 Classification of Hazardous Substances and Wastes ................................. 547
20.2.1 Characteristics and Listed Wastes ................................................ 547
20.2.2 Hazardous Wastes ........................................................................ 548
20.2.2.1 Hazardous Wastes and Air and Water
Pollution Control .......................................................... 548
20.3 Sources of Wastes ...................................................................................... 549
20.3.1 Types of Hazardous Wastes .......................................................... 550
20.3.2 Hazardous Waste Generators ....................................................... 550
20.4 Flammable and Combustible Substances .................................................. 551
20.4.1 Combustion of Finely Divided Particles ...................................... 552
20.4.2 Oxidizers ...................................................................................... 552
20.4.3 Spontaneous Ignition .................................................................... 553
20.4.4 Toxic Products of Combustion ..................................................... 553
Contents xix

20.5 Reactive Substances .................................................................................. 553

20.5.1 Chemical Structure and Reactivity .............................................. 554
20.6 Corrosive Substances ................................................................................. 555
20.6.1 Sulfuric Acid ................................................................................ 556
20.7 Toxic Substances ....................................................................................... 556
20.7.1 Toxicity Characteristic Leaching Procedure ............................... 556
20.8 Physical Forms and Segregation of Wastes ............................................... 557
20.9 Environmental Chemistry of Hazardous Wastes ...................................... 558
20.10 Physical and Chemical Properties of Hazardous Wastes .......................... 559
20.11 Transport, Effects, and Fates of Hazardous Wastes .................................. 559
20.11.1 Physical Properties of Wastes ...................................................... 560
20.11.2 Chemical Factors .......................................................................... 560
20.11.3 Effects of Hazardous Wastes ........................................................ 560
20.11.4 Fates of Hazardous Wastes ........................................................... 561
20.12 Hazardous Wastes and the Anthrosphere .................................................. 561
20.13 Hazardous Wastes in the Geosphere ......................................................... 562
20.14 Hazardous Wastes in the Hydrosphere ...................................................... 564
20.15 Hazardous Wastes in the Atmosphere ....................................................... 566
20.16 Hazardous Wastes in the Biosphere .......................................................... 567
20.16.1 Microbial Metabolism in Waste Degradation .............................. 567
20.16.2 Ecotoxicology of Hazardous Wastes ............................................ 568
20.17 Hazardous Substances in Terrorism .......................................................... 569
20.17.1 Detection of Hazardous Substances ............................................. 570
20.17.2 Removing Hazardous Agents ....................................................... 571
Literature Cited .................................................................................................... 571
Supplementary References ................................................................................... 572
Questions and Problems ....................................................................................... 572

Chapter 21 Industrial Ecology for Waste Minimization, Utilization, and Treatment ............ 575
21.1 Introduction ............................................................................................... 575
21.2 Waste Reduction and Minimization .......................................................... 575
21.3 Recycling ................................................................................................... 577
21.3.1 Examples of Recycling ................................................................. 578
21.3.2 Waste Oil Utilization and Recovery ............................................. 578
21.3.2.1 Recycling Waste Oil ..................................................... 578
21.3.2.2 Waste Oil Fuel .............................................................. 579
21.3.3 Waste Solvent Recovery and Recycle ........................................... 579
21.3.4 Recovery of Water from Wastewater ............................................ 580
21.4 Physical Methods of Waste Treatment ...................................................... 580
21.4.1 Methods of Physical Treatment .................................................... 581
21.4.1.1 Phase Separations ......................................................... 582
21.4.1.2 Phase Transition ........................................................... 582
21.4.1.3 Phase Transfer .............................................................. 583
21.4.1.4 Molecular Separation ................................................... 584
21.5 Chemical Treatment: An Overview ........................................................... 584
21.5.1 Acid–Base Neutralization ............................................................ 584
21.5.1.1 Acid Recovery .............................................................. 584
21.5.2 Chemical Precipitation ................................................................. 585
21.5.2.1 Precipitation of Metals ................................................. 585
21.5.2.2 Coprecipitation of Metals ............................................. 586
21.5.3 Oxidation–Reduction ................................................................... 586
xx Contents

21.5.4 Electrolysis ................................................................................... 587

21.5.5 Hydrolysis ..................................................................................... 588
21.5.6 Chemical Extraction and Leaching .............................................. 588
21.5.7 Ion Exchange ................................................................................ 589
21.6 Green Waste Treatment by Photolyis and Sonolysis ................................. 589
21.7 Thermal Treatment Methods ..................................................................... 590
21.7.1 Incineration .................................................................................. 591
21.7.1.1 Incinerable Wastes ........................................................ 591
21.7.2 Hazardous Waste Fuel .................................................................. 591
21.7.3 Incineration Systems .................................................................... 591
21.7.4 Types of Incinerators .................................................................... 592
21.7.5 Combustion Conditions ................................................................ 592
21.7.6 Effectiveness of Incineration ........................................................ 593
21.7.7 Wet Air Oxidation ........................................................................ 593
21.7.8 UV-Enhanced Wet Oxidation ...................................................... 593
21.7.9 Destruction of Hazardous Wastes in Cement Manufacture ......... 593
21.8 Biodegradation of Wastes .......................................................................... 594
21.8.1 Biodegradability ........................................................................... 594
21.8.2 Aerobic Treatment ........................................................................ 595
21.8.3 Anaerobic Treatment .................................................................... 595
21.8.4 Reductive Dehalogenation ............................................................ 595
21.9 Phytoremediation ....................................................................................... 596
21.10 Land Treatment and Composting .............................................................. 596
21.10.1 Land Treatment ............................................................................ 596
21.10.2 Composting .................................................................................. 597
21.11 Preparation of Wastes for Disposal ........................................................... 597
21.11.1 Immobilization ............................................................................. 597
21.11.2 Stabilization .................................................................................. 597
21.11.3 Solidification ................................................................................ 597
21.11.3.1 Sorption to a Solid Matrix Material ............................. 598
21.11.3.2 Thermoplastics and Organic Polymers ........................ 598
21.11.3.3 Vitrification .................................................................. 598
21.11.3.4 Solidification with Cement ........................................... 599
21.11.3.5 Solidification with Silicate Materials ........................... 599
21.11.3.6 Encapsulation ............................................................... 599
21.11.4 Chemical Fixation ........................................................................ 599
21.12 Ultimate Disposal of Wastes ..................................................................... 600
21.12.1 Disposal Aboveground ................................................................. 600
21.12.2 Landfill ........................................................................................ 600
21.12.3 Surface Impoundment of Liquids ................................................ 601
21.12.4 Deep-Well Disposal of Liquids .................................................... 601
21.13 Leachate and Gas Emissions ..................................................................... 601
21.13.1 Leachate ....................................................................................... 601
21.13.2 Hazardous Waste Leachate Treatment ......................................... 602
21.13.3 Gas Emissions ............................................................................. 602
21.14 In Situ Treatment ...................................................................................... 602
21.14.1 In Situ Immobilization ................................................................. 602
21.14.2 Vapor Extraction .......................................................................... 603
21.14.3 Solidification In Situ ..................................................................... 603
21.14.4 Detoxification In Situ ................................................................... 603
21.14.5 Permeable Bed Treatment ........................................................... 603
Contents xxi

21.14.6 In Situ Thermal Processes ............................................................ 604

21.14.7 Soil Washing and Flushing ......................................................... 604
Literature Cited .................................................................................................... 604
Supplementary References ................................................................................... 605
Questions and Problems ....................................................................................... 606

Chapter 22 Environmental Biochemistry ............................................................................... 609

22.1 Biochemistry .............................................................................................. 609
22.1.1 Biomolecules ................................................................................ 609
22.2 Biochemistry and the Cell ......................................................................... 610
22.2.1 Major Cell Features ...................................................................... 610
22.3 Proteins ...................................................................................................... 611
22.3.1 Protein Structure .......................................................................... 613
22.3.2 Denaturation of Proteins .............................................................. 614
22.4 Carbohydrates ............................................................................................ 614
22.5 Lipids ......................................................................................................... 616
22.6 Enzymes .................................................................................................... 618
22.7 Nucleic Acids ............................................................................................. 620
22.7.1 Nucleic Acids in Protein Synthesis .............................................. 623
22.7.2 Modified DNA .............................................................................. 623
22.8 Recombinant DNA and Genetic Engineering ........................................... 623
22.9 Metabolic Processes .................................................................................. 624
22.9.1 Energy-Yielding Processes ........................................................... 624
22.10 Metabolism of Xenobiotic Compounds ..................................................... 625
22.10.1 Phase I and Phase II Reactions ..................................................... 625
Literature Cited .................................................................................................... 626
Supplementary References ................................................................................... 626
Questions and Problems ....................................................................................... 626

Chapter 23 Toxicological Chemistry ...................................................................................... 629

23.1 Introduction to Toxicology and Toxicological Chemistry ......................... 629
23.1.1 Toxicology .................................................................................... 629
23.1.2 Synergism, Potentiation, and Antagonism ................................... 631
23.2 Dose–Response Relationships ................................................................... 631
23.3 Relative Toxicities ...................................................................................... 632
23.3.1 Nonlethal Effects .......................................................................... 632
23.4 Reversibility and Sensitivity ...................................................................... 634
23.4.1 Hypersensitivity and Hyposensitivity .......................................... 634
23.5 Xenobiotic and Endogenous Substances ................................................... 634
23.6 Toxicological Chemistry ............................................................................ 635
23.6.1 Toxicological Chemistry Defined ................................................. 635
23.6.2 Toxicants in the Body ................................................................... 635
23.6.2.1 Phase I Reactions ......................................................... 635
23.6.2.2 Phase II Reactions ........................................................ 636
23.7 Kinetic Phase and Dynamic Phase ............................................................ 637
23.7.1 Kinetic Phase ................................................................................ 637
23.7.2 Dynamic Phase ............................................................................. 637
23.7.2.1 Primary Reaction in the Dynamic Phase ..................... 637
23.7.2.2 Biochemical Effects in the Dynamic Phase ................. 638
23.7.2.3 Responses to Toxicants ................................................. 639
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