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Environmental Chemistry
Eleventh Edition
Stanley E. Manahan
Eleventh edition published 2022
by CRC Press
6000 Broken Sound Parkway NW, Suite 300, Boca Raton, FL 33487-2742
and by CRC Press

4 Park Square, Milton Park, Abingdon, Oxon, OX14 4RN
CRC Press is an imprint of Taylor & Francis Group, LLC
© 2022 Taylor & Francis Group, LLC
[First edition published by Willard Grand Press of Boston]
Tenth edition published by CRC Press 2017
Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume
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Library of Congress Cataloging-in-Publication Data
Names: Manahan, Stanley E., author.

Title: Environmental chemistry / Stanley E. Manahan.
Description: Eleventh edition. | Boca Raton : Taylor and Francis, 2022. |
Includes bibliographical references and index.
Identifiers: LCCN 2021055239 | ISBN 9780367558871 (hardback) | ISBN
9780367560546 (paperback) | ISBN 9781003096238 (ebook)
Subjects: LCSH: Environmental chemistry.
Classification: LCC QD31.2 .M35 2022 | DDC 628--dc23/eng/20211208
LC record available at https://lccn.loc.gov/2021055239
ISBN: 978-0-367-55887-1 (hbk)

ISBN: 978-0-367-56054-6 (pbk)
ISBN: 978-1-003-09623-8 (ebk)
DOI: 10.1201/9781003096238
Typeset in Times
by KnowledgeWorks Global Ltd.
“This book is dedicated to the memory of Professor Reynold T. Iwamoto,
who served as a graduate faculty member of the University of Kansas
Department of Chemistry from 1956 to 1990. Dr. Iwamoto was born in
Hawaii in 1928 and died in Lawrence, Kansas in 2015. Everything that
I accomplished in life I owe to this man, a wonderful mentor and dear friend.”
Contents
Preface..........................................................................................................................................xxvii
Acknowledgments..........................................................................................................................xxxi
About the Author........................................................................................................................ xxxiii
Chapter 1 Environmental Chemistry: An Essential Discipline in Coping

with Challenges Facing Humankind.............................................................................1
1.1 A Catastrophic Year for Earth and Humankind................................................. 1
1.2 Earth and the Earth System................................................................................ 2
1.3 Biogeochemical Cycles in the Earth System......................................................3
1.3.1 Oxygen Cycle........................................................................................ 4
1.3.2 Nitrogen Cycle.......................................................................................4
1.3.3 Sulfur Cycle........................................................................................... 5
1.3.4 Phosphorus Cycle..................................................................................5
1.4 Natural Capital of the Earth System.................................................................. 5
1.5 What is Environmental Chemistry?...................................................................6
1.5.1 Environmental Chemistry and the Spheres
of the Earth System............................................................................... 7
1.6 Environmental Chemistry of Water and the Hydrosphere.................................7
1.7 Environmental Chemistry of Air and the Atmosphere......................................8
1.8 Environmental Chemistry of the Geosphere.................................................... 10
1.8.1 Soil...................................................................................................... 12
1.9 Environmental Chemistry of the Anthrosphere............................................... 13
1.10 Environmental Chemistry of the Biosphere..................................................... 14
1.11 Toxicological Chemistry and Biochemistry..................................................... 16
1.12 As We Enter the Anthropocene........................................................................ 17
1.13 Special Challenges to Environmental Chemistry
as Global Climate Change Becomes Reality................................................... 17
References................................................................................................................... 18
Further Reading........................................................................................................... 18
Chapter 2 The Hydrosphere and Water Chemistry...................................................................... 21

2.1 Water: An Essential Part of Earth’s Natural Capital........................................ 21
2.2 Sources and Uses of Water............................................................................... 23
2.2.1 The Groundwater Crisis......................................................................25
2.3 H2O: Simple Formula, Remarkable Molecule.................................................26
2.4 Life in Water..................................................................................................... 27
2.5 Chemistry of Water..........................................................................................28
2.6 Gases in Water.................................................................................................. 29
2.6.1 Oxygen in Water.................................................................................. 30
2.7 Water Acidity and Carbon Dioxide in Water................................................... 31
2.7.1 Carbon Dioxide in Water.................................................................... 31
2.8 Alkalinity.........................................................................................................34
2.8.1 Contributors to Alkalinity at Different pH Values.............................. 35
2.8.2 Dissolved Inorganic Carbon and Alkalinity....................................... 36
2.8.3 Influence of Alkalinity on CO2 Solubility.......................................... 37
vii
viii Contents
2.9 Calcium and Other Metals in Water................................................................. 37

2.9.1 Hydrated Metal Ions as Acids.......................................................... 37
2.9.2 Calcium in Water.............................................................................. 38
2.9.3 Dissolved Carbon Dioxide and Calcium Carbonate Minerals......... 39
2.10 Complexation and Chelation............................................................................40
2.10.1 Occurrence and Importance of Chelating
Agents in Water................................................................................ 42
2.11 Bonding and Structure of Metal Complexes.................................................... 43
2.11.1 Selectivity and Specificity in Chelation........................................... 43
2.12 Calculations of Species Concentrations...........................................................44
2.13 Complexation by Deprotonated Ligands.......................................................... 45
2.14 Complexation by Protonated Ligands..............................................................46
2.15 Solubilization of Lead Ion from Solids by NTA.............................................. 47
2.15.1 Reaction of NTA with Metal Carbonate.......................................... 48
2.15.2 Effect of Calcium Ion on the Reaction of Chelating
Agents with Slightly Soluble Salts................................................... 50
2.16 Polyphosphates and Phosphonates in Water..................................................... 51
2.16.1 Polyphosphates................................................................................. 51
2.16.2 Hydrolysis of Polyphosphates........................................................... 52
2.16.3 Complexation by Polyphosphates..................................................... 52
2.16.4 Phosphonates.................................................................................... 52
2.17 Complexation by Humic Substances................................................................ 53
2.18 Complexation and Redox Processes................................................................. 54
References................................................................................................................... 55
Further Readings......................................................................................................... 55
Chapter 3 Oxidation/Reduction in Aquatic Chemistry............................................................... 59

3.1 The Significance of Oxidation/Reduction in Aquatic Chemistry.................... 59
3.2 The Electron and Redox Reactions.................................................................. 61
3.3 Electron Activity and pE.................................................................................. 63
3.4 The Nernst Equation.........................................................................................64
3.5 Reaction Tendency: Whole Reaction from Half-Reactions.............................. 65
3.6 The Nernst Equation and Chemical Equilibrium.............................................66
3.7 The Relationship of pE to Free Energy............................................................ 67
3.8 Reactions in Terms of One Electron-Mole....................................................... 67
3.9 The Limits of pE in Water................................................................................ 69
3.10 pE Values in Natural Water Systems................................................................ 70
3.11 pE–pH Diagrams.............................................................................................. 71
3.12 Humic Substances as Natural Reductants........................................................ 74
3.13 Photochemical Processes in Oxidation/Reduction........................................... 74
3.14 Corrosion.......................................................................................................... 75
References................................................................................................................... 76
Chapter 4 Phase Interactions in Aquatic Chemistry.................................................................... 79

4.1 Chemical Interactions Involving Solids, Gases, and Water............................. 79
4.2 Importance and Formation of Sediments......................................................... 79
4.2.1 Formation of Sediments...................................................................... 79
4.2.2 Organic and Carbonaceous Sedimentary Materials........................... 81
Contents ix
4.3 Solubilities........................................................................................................ 81
4.3.1 Solubilities of Solids......................................................................... 82
4.3.2 Solubilities of Gases......................................................................... 83
4.4 Colloidal Particles in Water..............................................................................84
4.4.1 Colloids in Water and Contaminant
Transport by Colloids....................................................................... 85
4.4.2 Kinds of Colloidal Particles............................................................. 85
4.4.3 Colloid Stability................................................................................ 86
4.5 The Colloidal Properties of Clays.................................................................... 87
4.6 Aggregation of Colloidal Particles................................................................... 88
4.6.1 Flocculation of Colloids by Polyelectrolytes.................................... 88
4.6.2 Flocculation of Bacteria by Polymeric Materials............................. 89
4.7 Surface Sorption by Solids............................................................................... 89
4.8 Solute Exchange with Bottom Sediments........................................................90
4.8.1 Trace-Level Metals in Suspended Matter and Sediments................ 91
4.8.2 Phosphorus Exchange with Bottom Sediments................................92
4.8.3 Organic Compounds on Sediments and Suspended Matter.............92
4.8.4 Bioavailability of Sediment Contaminants......................................94
4.9 Interstitial Water............................................................................................... 95
4.10 Phase Interactions in Chemical Fate and Transport......................................... 95
4.10.1 Rivers................................................................................................ 95
4.10.2 Lakes and Reservoirs....................................................................... 95
4.10.3 Exchange with the Atmosphere........................................................96
4.10.4 Exchange with Sediments................................................................96
References...................................................................................................................97
Chapter 5 Aquatic Microbial Biochemistry............................................................................... 101

5.1 Aquatic Biochemical Processes...................................................................... 101
5.1.1 Microorganisms at Interfaces............................................................ 101
5.2 Algae............................................................................................................... 102
5.3 Fungi............................................................................................................... 104
5.4 Protozoa.......................................................................................................... 104
5.5 Bacteria........................................................................................................... 104
5.5.1 Autotrophic and Heterotrophic Bacteria........................................ 105
5.5.2 Oxic and Anoxic Bacteria.............................................................. 106
5.6 The Prokaryotic Bacterial Cell....................................................................... 106
5.7 Kinetics of Bacterial Growth......................................................................... 107
5.8 Bacterial Metabolism..................................................................................... 107
5.8.1 Factors Affecting Bacterial Metabolism........................................ 108
5.8.2 Microbial Oxidation and Reduction............................................... 109
5.9 Microbial Transformations of Carbon............................................................ 111
5.9.1 Methane-Forming Bacteria............................................................ 111
5.9.2 Bacterial Utilization of Hydrocarbons........................................... 112
5.9.3 Microbial Utilization of Carbon Monoxide.................................... 112
5.10 Biodegradation of Organic Matter................................................................. 113
5.10.1 Oxidation........................................................................................ 113
5.10.2 Microbial Oxidation of Hydrocarbons........................................... 113
5.10.3 Other Biochemical Processes in Biodegradation
of Organics..................................................................................... 114
x Contents
5.11 Microbial Transformations of Nitrogen.......................................................... 114

5.11.1 Nitrogen Fixation............................................................................ 116
5.11.2 Nitrification.................................................................................... 117
5.11.3 Nitrate Reduction............................................................................ 117
5.11.4 Denitrification................................................................................. 117
5.12 Microbial Transformations of Phosphorus and Sulfur................................... 118
5.12.1 Phosphorus Compounds................................................................. 118
5.12.2 Sulfur Compounds.......................................................................... 118
5.12.3 Oxidation of H2S and Reduction of Sulfate by Bacteria................ 119
5.12.4 Microorganism-Mediated Degradation of Organic Sulfur
Compounds..................................................................................... 119
5.13 Microbial Transformations of Halogens and Organohalides......................... 120
5.14 Microbial Transformations of Metals and Metalloids.................................... 121
5.14.1 Acid Mine Waters........................................................................... 122
5.14.2 Microbial Transitions of Selenium................................................. 123
5.14.3 Microbial Corrosion....................................................................... 123
References................................................................................................................. 124
Further Readings....................................................................................................... 124
Chapter 6 Water Pollutants and Water Pollution....................................................................... 129

6.1 Nature and Types of Water Pollutants............................................................ 129
6.1.1 Markers of Water Pollution............................................................ 129
6.2 Elemental Pollutants....................................................................................... 129
6.3 Heavy Metals.................................................................................................. 131
6.3.1 Cadmium........................................................................................ 131
6.3.2 Lead................................................................................................ 132
6.3.3 Mercury.......................................................................................... 132
6.4 Metalloids....................................................................................................... 133
6.5 Organically Bound Metals and Metalloids.................................................... 134
6.5.1 Organotin Compounds................................................................... 135
6.6 Inorganic Species........................................................................................... 136
6.6.1 Cyanide........................................................................................... 136
6.6.2 Ammonia and Other Inorganic Pollutants..................................... 136
6.6.3 Asbestos in Water........................................................................... 137
6.7 Algal Nutrients and Eutrophication................................................................ 137
6.8 Acidity, Alkalinity, and Salinity.................................................................... 138
6.9 Oxygen, Oxidants, and Reductants................................................................ 139
6.10 Organic Pollutants.......................................................................................... 140
6.10.1 Bioaccumulation of Organic Pollutants.......................................... 140
6.10.2 Sewage............................................................................................ 140
6.10.3 Soaps, Detergents, and Detergent Builders.................................... 141
6.10.3.1 Soaps............................................................................ 141
6.10.3.2 Detergents.................................................................... 142
6.10.3.3 Microbial Toxins.......................................................... 144
6.11 Pesticides in Water......................................................................................... 144
6.11.1 Natural Product Insecticides, Pyrethrins, and Pyrethroids............ 145
6.11.2 The Emergence of Neonicotinoid Insecticides............................... 145
6.11.3 DDT and Organochlorine Insecticides........................................... 148
6.11.4 Organophosphate Insecticides........................................................ 148
6.11.5 Carbamates..................................................................................... 149
Contents xi
6.11.6 Fungicides....................................................................................... 150

6.11.7 Herbicides....................................................................................... 150
6.11.8 Bipyridylium Compounds.............................................................. 151
6.11.9 Herbicidal Heterocyclic Nitrogen Compounds.............................. 151
6.11.10 Chlorophenoxy Herbicides............................................................. 151
6.11.11 Miscellaneous Herbicides............................................................... 152
6.12 Organochlorine Compounds in Water............................................................ 153
6.12.1 By-Products of Pesticide Manufacture........................................... 153
6.12.2 Polychlorinated Biphenyls.............................................................. 154
6.12.3 1,2,3-Trichloropropane in Groundwater......................................... 155
6.12.4 Naturally Occurring Chlorinated and Brominated
Compounds..................................................................................... 156
6.13 Emerging Water Pollutants, Pharmaceuticals, and Household
Wastes............................................................................................................. 156
6.13.1 Bactericides and Antibiotics........................................................... 157
6.13.2 Estrogenic Substances in Wastewater Effluents............................. 158
6.13.3 Biorefractory Organic Pollutants.................................................... 158
6.14 Radionuclides in the Aquatic Environment.................................................... 160
References................................................................................................................. 164
Chapter 7 World Water Crisis and Climate Change: Water Renovation and Recycling............ 169
7.1 The Most Important Body of Water—You..................................................... 169
7.2 Water Treatment and Water Use..................................................................... 170
7.3 Municipal Water Treatment............................................................................ 170
7.3.1 Failures in Water Treatment........................................................... 170
7.4 Treatment of Water for Industrial and Commercial Use................................ 171
7.5 Wastewater Treatment.................................................................................... 172
7.5.1 Industrial Wastewater Treatment.................................................... 172
7.6 Advanced Water Treatment............................................................................ 172
7.7 Aeration of Water........................................................................................... 173
7.8 Removal of Solids........................................................................................... 173
7.8.1 Dissolved Air Flotation.................................................................. 174
7.8.2 Membrane Filtration Processes...................................................... 175
7.9 Removal of Calcium and Other Metals.......................................................... 176
7.9.1 Removal of Iron and Manganese.................................................... 179
7.9.2 Removal of Heavy Metals from Water........................................... 179
7.10 Removal of Biodegradable Organics from Water and
Sewage Treatment........................................................................................... 180
7.10.1 Biodegradable Organics Removal from Wastewater...................... 180
7.10.2 Membrane Bioreactor..................................................................... 183
7.10.3 Sludge Handling and Disposal....................................................... 184
7.10.4 Chemical Sludges........................................................................... 185
7.10.5 Additional Purification of Water from Secondary
Wastewater Treatment.................................................................... 185
7.11 Removal of Dissolved Organics..................................................................... 185
7.11.1 Removal of Herbicides................................................................... 187
7.12 Removal of Dissolved Inorganics................................................................... 187
7.12.1 Ion Exchange.................................................................................. 187
7.12.2 Reverse Osmosis............................................................................. 188
xii Contents
7.12.3 Phosphorus Removal...................................................................... 189

7.12.4 Nitrogen Removal........................................................................... 190
7.13 Water Disinfection.......................................................................................... 190
7.13.1 Chlorine Dioxide............................................................................ 191
7.13.2 Green Ozone for Water Disinfection.............................................. 191
7.13.3 Ferrate and Percarbonate................................................................ 192
7.13.4 Disinfection with Ultraviolet Radiation
and Photocatalytic Processes......................................................... 193
7.13.5 Advanced Oxidation Processes for Water Treatment..................... 193
7.14 Natural Water Purification Processes............................................................. 193
7.14.1 Industrial Wastewater Treatment by Soil....................................... 194
7.15 Green Water and Total Water Recycle........................................................... 194
7.16 Water Conservation........................................................................................ 199
7.17 Protecting Water Supplies from Attack..........................................................200
References................................................................................................................. 201
Chapter 8 The Atmosphere and Atmospheric Chemistry..........................................................205

8.1 The Atmosphere and Atmospheric Chemistry...............................................205
8.1.1 Atmospheric Composition.................................................................206
8.1.2 Oxides of Nitrogen and Sulfur..........................................................207
8.1.3 Atmospheric Methane, Hydrocarbons,
and Photochemical Smog..................................................................207
8.1.4 Particulate Matter..............................................................................207
8.1.5 Primary and Secondary Pollutants...................................................207
8.2 How the Atmosphere Got That Way and its Natural Capital.........................208
8.2.1 Chemical and Biochemical Processes in Evolution
of the Atmosphere.............................................................................208
8.2.2 Self-Purification of the Atmosphere..................................................209
8.3 Physical Characteristics of the Atmosphere...................................................209
8.3.1 Variation of Pressure and Density with Altitude..............................209
8.3.2 Stratification of the Atmosphere....................................................... 211
8.4 Energy Transfer in the Atmosphere............................................................... 212
8.4.1 The Earth’s Radiation Budget........................................................... 213
8.5 Atmospheric Mass Transfer, Meteorology, and Weather............................... 214
8.5.1 Atmospheric Water in Energy and Mass Transfer............................ 214
8.5.2 Air Masses......................................................................................... 215
8.5.3 Topographical Effects....................................................................... 216
8.5.4 Movement of Air Masses.................................................................. 216
8.5.5 Global Weather.................................................................................. 217
8.5.6 Weather Fronts and Storms............................................................... 218
8.6 Inversions and Air Pollution........................................................................... 218
8.7 Global Climate and Microclimate.................................................................. 218
8.7.1 Atmospheric Carbon Dioxide and Human
Modifications of Climate.................................................................. 219
8.7.2 Microclimate..................................................................................... 219
8.7.3 Effects of Urbanization on Microclimate......................................... 220
8.8 Chemical and Photochemical Reactions in the Atmosphere......................... 220
8.8.1 Photochemical Processes.................................................................. 222
Contents xiii
8.8.2 Ions and Radicals in the Atmosphere.............................................224

8.8.3 Ions at Lower Altitudes in the Troposphere................................... 225
8.8.4 Free Radicals.................................................................................. 225
8.8.5 Hydroxyl and Hydroperoxyl Radicals in
the Atmosphere............................................................................... 225
8.9 Acid–Base Reactions in the Atmosphere..................................................... 228
8.10 Reactions of Atmospheric Oxygen............................................................... 228
8.10.1 Tropospheric Ozone in the Unpolluted Atmosphere...................... 229
8.11 Reactions of Atmospheric Nitrogen............................................................. 230
8.12 Atmospheric Water....................................................................................... 230
8.13 Influence of the Anthrosphere...................................................................... 231
8.14 Metals from Meteoroids in the Mesosphere................................................. 231
8.15 Chemical Fate and Transport in the Atmosphere......................................... 231
References................................................................................................................. 233
Chapter 9 Particles in the Atmosphere...................................................................................... 237

9.1 Particles in the Atmosphere............................................................................ 237
9.2 Physical Behavior of Particles in the Atmosphere......................................... 239
9.2.1 Size and Settling of Atmospheric Particles.......................................240
9.3 Physical Processes for Particle Formation.....................................................240
9.4 Chemical Processes for Particle Formation................................................... 241
9.4.1 Inorganic Particles............................................................................. 241
9.4.2 Organic Particles............................................................................... 242
9.5 The Composition of Inorganic Particles......................................................... 243
9.5.1 Fly Ash..............................................................................................244
9.5.2 Asbestos............................................................................................244
9.6 Toxic Metals in the Atmosphere..................................................................... 245
9.6.1 Atmospheric Mercury....................................................................... 245
9.6.2 Atmospheric Lead.............................................................................246
9.6.3 Atmospheric Beryllium.....................................................................246
9.7 Radioactive Particles......................................................................................246
9.8 Organic Particles in the Atmosphere.............................................................. 247
9.8.1 Polycyclic Aromatic Hydrocarbons...................................................248
9.8.2 Carbonaceous Particles from Diesel Engines................................... 249
9.9 Effects of Particles.......................................................................................... 249
9.9.1 The Asian Brown Cloud: Climate and
Health Effects.................................................................................... 250
9.9.2 Partitioning of Semivolatile Organic Substances
between Air and Particles................................................................. 251
9.10 Water as Particulate Matter.......................................................................... 251
9.11 Atmospheric Chemical Reactions Involving Particles................................. 252
9.12 Control of Particle Emissions....................................................................... 254
9.12.1 Particle Removal by Sedimentation and Inertia............................. 254
9.12.2 Particle Filtration............................................................................ 254
9.12.3 Scrubbers........................................................................................ 255
9.12.4 Electrostatic Removal..................................................................... 256
References................................................................................................................. 256
xiv Contents
Chapter 10 Gaseous Inorganic Air Pollutants............................................................................. 261

10.1 Inorganic Pollutant Gases.......................................................................... 261
10.2 Production and Control of Carbon Monoxide........................................... 261
10.2.1 Control of Carbon Monoxide Emissions................................ 262
10.3 Fate of Atmospheric CO ........................................................................... 262
10.4 Sulfur Dioxide Sources and the Sulfur Cycle........................................... 262
10.5 Sulfur Dioxide Reactions in the Atmosphere............................................264
10.5.1 Effects of Atmospheric Sulfur Dioxide..................................266
10.5.2 Sulfur Dioxide Removal.........................................................266
10.5.3 Oxy-Fuel Combustion for Sulfur Dioxide
and Carbon Dioxide Recovery................................................ 268
10.6 Nitrogen Oxides in the Atmosphere.......................................................... 269
10.6.1 Atmospheric Reactions of NOx ............................................. 271
10.6.2 Harmful Effects of Nitrogen Oxides...................................... 273
10.6.3 Control of Nitrogen Oxides..................................................... 274
10.6.4 Limiting Production and Emissions of Nitrogen Oxides........ 274
10.6.5 Removal of Nitrogen Oxides from Stack Gas
and Engine Exhaust Gases...................................................... 275
10.7 Acid Rain................................................................................................... 276
10.8 Ammonia in the Atmosphere.................................................................... 276
10.9 Fluorine, Chlorine, and their Gaseous Compounds.................................. 277
10.9.1 Chlorine and Hydrogen Chloride............................................ 278
10.9.2 Hydrogen Chloride in the Atmosphere................................... 278
10.10 Reduced Sulfur Gases............................................................................... 279
References................................................................................................................. 281
Chapter 11 Organic Air Pollutants.............................................................................................. 285

11.1 Organic Compounds in the Atmosphere................................................... 285
11.1.1 Loss of Organic Substances from the Atmosphere................ 285
11.1.2 Persistent Organic Pollutants.................................................. 285
11.1.3 Global Distillation and Fractionation of POPs....................... 286
11.2 Biogenic Organic Compounds................................................................... 286
11.2.1 Biogenic Methane................................................................... 287
11.2.2 Biogenic Hydrocarbons from Plants....................................... 287
11.2.3 Removal of Atmospheric Organic Compounds by Plants...... 289
11.3 Pollutant Hydrocarbons............................................................................. 290
11.3.1 Aromatic Hydrocarbons.......................................................... 292
11.3.2 Reactions of Atmospheric Aromatic Hydrocarbons............... 293
11.4 Carbonyl Compounds................................................................................ 294
11.5 Miscellaneous Oxygen-Containing Compounds....................................... 296
11.5.1 Alcohols.................................................................................. 297
11.5.2 Phenols.................................................................................... 297
11.5.3 Ethers...................................................................................... 298
11.5.4 Oxides..................................................................................... 298
11.5.5 Carboxylic Acids..................................................................... 298
11.6 Organonitrogen Compounds...................................................................... 299
11.7 Organohalide Compounds......................................................................... 301
11.7.1 CFCs and Halons.................................................................... 303
Contents xv
11.7.2 Atmospheric Reactions of Hydrofluorocarbons and

Hydrochlorofluorocarbons......................................................304
11.7.3 Perfluorocarbons.....................................................................304
11.7.4 Chlorinated Dibenzo-p-Dioxins and Dibenzofurans............. 305
11.8 Organosulfur Compounds......................................................................... 305
11.9 Organic Particulate Matter........................................................................306
11.10 Hazardous Air Pollutant Organic Compounds..........................................307
References.................................................................................................................307
Further Readings.......................................................................................................308
Chapter 12 Photochemical Smog................................................................................................. 311

12.1 Reduced Visibility When the Sun Shines.................................................. 311
12.2 Smog-Forming Emissions......................................................................... 312
12.2.1 Control of Exhaust Hydrocarbons.......................................... 313
12.2.2 Automotive Emission Standards............................................. 315
12.2.3 Polluting Green Plants............................................................ 316
12.3 Smog-Forming Reactions of Organic Compounds in the Atmosphere..... 317
12.3.1 Photochemical Reactions of Methane.................................... 317
12.3.2 Addition Reactions in the Atmosphere................................... 318
12.4 Overview of Smog Formation................................................................... 319
12.5 Mechanisms of Smog Formation............................................................... 321
12.5.1 Nitrate Radical........................................................................ 326
12.5.2 Photolyzable Compounds in the Atmosphere......................... 327
12.6 Reactivity of Hydrocarbons....................................................................... 327
12.7 Importance of HOx/VOC Ratios............................................................... 328
12.8 Inorganic Products from Smog.................................................................. 328
12.9 Effects of Smog......................................................................................... 329
References................................................................................................................. 332
Chapter 13 The Endangered Global Atmosphere........................................................................ 337

13.1 Saving the Atmosphere to Save Ourselves................................................ 337
13.1.1 Preservation of the Atmosphere’s Natural Capital................. 338
13.2 The Earth’s Evolving Atmosphere and Climate Change........................... 338
13.2.1 Changes in Climate................................................................. 339
13.3 Effects of the Anthrosphere on the Atmosphere and Climate...................340
13.3.1 Destroying the Earth’s Lungs: Destruction of the
Amazon Forest........................................................................340
13.4 The Greatest Threat to the Atmosphere and the Earth System:
Global Warming........................................................................................ 341
13.4.1 Methane and Other Greenhouse Gases.................................. 343
13.4.2 Particles and Global Warming................................................ 345
13.5 Consequences of Global Climate Change................................................. 345
13.5.1 Increasing Temperature.......................................................... 345
13.5.2 Passing the Tipping Points...................................................... 347
13.5.3 Loss of Ice Cover.................................................................... 347
13.5.4 Glaciers and Water Supply......................................................348
13.5.5 Expansion of Subtropical Arid Regions and Drought............ 348
13.5.6 Some Other Effects of Global Climate Change...................... 348
xvi Contents
13.6 Green Science and Technology to Alleviate Global Warming.................. 349

13.6.1 Minimization.......................................................................... 349
13.6.2 Counteracting Measures......................................................... 351
13.6.3 Adaptation............................................................................... 352
13.7 Acid Rain................................................................................................... 352
13.8 Stratospheric Ozone Destruction............................................................... 355
13.8.1 Shielding Effect of the Ozone Layer....................................... 356
13.8.2 Ozone Layer Destruction........................................................ 357
13.8.3 Green Chemistry Solutions to Stratospheric
Ozone Depletion..................................................................... 359
13.9 Atmospheric Brown Clouds.......................................................................360
13.9.1 Yellow Dust............................................................................. 361
13.10 Atmospheric Damage by Photochemical Smog........................................ 362
13.11 The Urban Aerosol.................................................................................... 363
13.12 Nuclear Winter...........................................................................................364
13.12.1 “Doomsday Visitors” from Space........................................... 366
13.13 What Is to Be Done?.................................................................................. 366
References................................................................................................................. 368
Chapter 14 The Geosphere and Geochemistry............................................................................ 373

14.1 The Geosphere........................................................................................... 373
14.1.1 The Fragile Solid Earth and its Relationship
with the Other Environmental Spheres................................... 373
14.2 Physical Form of the Geosphere................................................................ 375
14.2.1 Plate Tectonics and Continental Drift.................................... 375
14.2.2 Structural Geology.................................................................. 376
14.3 The Nature of Solids in the Geosphere..................................................... 377
14.3.1 Structure and Properties of Minerals..................................... 377
14.3.2 Kinds of Minerals................................................................... 377
14.3.3 Igneous, Sedimentary, and Metamorphic Rock
in the Rock Cycle.................................................................... 378
14.3.4 Rock Cycle.............................................................................. 379
14.4 Geochemistry and Weathering of Rock in the Geosphere........................ 379
14.4.1 Physical Aspects of Weathering............................................. 380
14.4.2 Chemical Weathering............................................................. 380
14.4.3 Biological Aspects of Weathering.......................................... 382
14.5 Clays: Especially Important Weathering Products
and Secondary Minerals............................................................................ 383
14.6 Sediments.................................................................................................. 384
14.7 Groundwater in the Geosphere.................................................................. 385
14.7.1 Water Wells............................................................................. 387
14.7.2 Water Wells and the Arsenic Problem.................................... 387
14.8 The Geosphere as a Source of Natural Capital......................................... 388
14.8.1 The Extraordinary Importance of Lithium............................. 389
14.9 Environmental Phenomena of the Geosphere........................................... 389
14.9.1 Natural Hazards...................................................................... 390
14.9.2 Anthropogenic Hazards.......................................................... 390
14.10 Volcanoes................................................................................................... 391
14.11 Earthquakes............................................................................................... 392
Contents xvii
14.12 Surface Earth Movement........................................................................... 394

14.13 Effects of Human Activities...................................................................... 396
14.13.1 Extraction of Geospheric Resources: Surface Mining........... 396
14.13.2 Environmental Effects of Mining and Mineral
Extraction................................................................................ 396
14.14 Air Pollution and the Geosphere............................................................... 397
14.15 Water Pollution and the Geosphere........................................................... 398
14.16 The Geosphere as a Waste Repository...................................................... 399
References.................................................................................................................400
Chapter 15 Soil: Earth’s Lifeline.................................................................................................403

15.1 Have You Thanked A Clod Today?...........................................................403
15.1.1 What Is Soil?...........................................................................403
15.1.2 Agriculture and Soil................................................................403
15.2 Structure of Soil.........................................................................................405
15.3 Composition of Soil...................................................................................406
15.3.1 Water in Soil...........................................................................406
15.3.2 The Soil Solution....................................................................408
15.3.3 Air in Soil...............................................................................408
15.3.4 Inorganic Solids in Soil...........................................................408
15.3.5 Soil Organic Matter................................................................408
15.4 Acid–Base and Ion-Exchange Reactions in Soil....................................... 410
15.4.1 Acid–Base Reactions of Soil................................................... 410
15.4.2 Adjustment of Soil Acidity..................................................... 412
15.4.3 Ion-Exchange Equilibria in Soil............................................. 412
15.5 Macronutrients in Soil............................................................................... 413
15.5.1 Sulfur in Soil and as a Macronutrient..................................... 414
15.6 Nitrogen, Phosphorus, and Potassium in Soil............................................ 414
15.6.1 Nitrogen.................................................................................. 414
15.6.2 Phosphorus.............................................................................. 417
15.6.3 Potassium................................................................................ 417
15.7 Micronutrients in Soil................................................................................ 417
15.8 Fertilizers................................................................................................... 418
15.8.1 Fertilizer Pollution.................................................................. 420
15.9 Pesticides and their Residues in Soil......................................................... 421
15.9.1 Soil Fumigants........................................................................ 422
15.10 Wastes and Pollutants and their Degradation on Soil............................... 422
15.10.1 Soil Pollutants from Livestock Production............................. 424
15.10.2 Biodegradation and the Rhizosphere...................................... 425
15.11 Soil Loss and Degradation......................................................................... 425
15.11.1 Soil Sustainability and Water Resources................................ 426
15.12 Saving the Land......................................................................................... 427
15.12.1 Agroforestry............................................................................ 427
15.12.2 Soil Restoration....................................................................... 428
15.12.3 Poduculture in Soil Restoration.............................................. 429
15.13 Green Chemistry and Sustainable Agriculture......................................... 430
15.14 Genetics and Agriculture........................................................................... 433
15.14.1 Recombinant DNA and Genetic Engineering
in Agriculture.......................................................................... 433
xviii Contents
15.14.2 The Major Transgenic Crops and Their Characteristics......... 435

15.14.3 Crops versus Pests................................................................... 435
15.14.4 Future Crops........................................................................... 436
15.15 Agriculture and Health.............................................................................. 438
15.15.1 Food Contamination............................................................... 438
15.16 Protecting the Food Supply from Attack................................................... 438
References................................................................................................................. 439
Chapter 16 The Anthrosphere: Industrial Ecology and Green Chemistry.................................. 443

16.1 Changing the Bad Old Ways...................................................................... 443
16.2 Green Chemistry.......................................................................................444
16.3 Reduction of Risk: Hazard and Exposure.................................................446
16.3.1 The Risks of Not Taking Risks............................................... 447
16.4 Waste Prevention and Green Chemistry....................................................448
16.5 Green Chemistry and Synthetic Chemistry...............................................448
16.5.1 Yield and Atom Economy.......................................................449
16.6 Feedstocks................................................................................................. 450
16.6.1 Biological Feedstocks............................................................. 451
16.7 Reagents..................................................................................................... 452
16.8 Stoichiometric and Catalytic Reagents...................................................... 453
16.9 Media and Solvents.................................................................................... 453
16.9.1 Water, the Greenest Solvent.................................................... 454
16.9.2 Dense Phase Carbon Dioxide as a Solvent............................. 455
16.9.3 Gas-Expanded Solvents.......................................................... 456
16.10 Enhancing Reactions................................................................................. 456
16.11 Industrial Ecology..................................................................................... 458
16.12 The Five Major Components of an Industrial Ecosystem......................... 459
16.13 Industrial Metabolism................................................................................460
16.14 The Kalundborg Industrial Ecosystem......................................................460
16.15 Attributes of Successful Industrial Ecosystems........................................ 461
16.15.1 Diversity.................................................................................. 462
16.16 Environmental Impacts in Industrial Ecology.......................................... 463
16.17 Life Cycles: Expanding and Closing the Materials Loop.........................464
16.17.1 Product Stewardship...............................................................465
16.17.2 Embedded Utility....................................................................465
16.18 Design for Environment............................................................................466
16.18.1 Products, Processes, and Facilities.........................................466
16.18.2 Key Factors in Design for Environment................................. 467
16.18.3 Hazardous Materials in Design for Environment...................468
16.19 Inherent Safety...........................................................................................468
16.19.1 Increased Safety with Smaller Size........................................469
16.20 Industrial Ecology and Ecological Engineering........................................469
References................................................................................................................. 470
Chapter 17 Resources and Sustainable Materials........................................................................ 475

17.1 Where to Get the Stuff We Need?............................................................. 475
17.2 Extraction of Materials from the Geosphere............................................. 476
Contents xix
17.3 Environmental Effects of Mining and Mineral Extraction....................... 477

17.4 Sustainable Utilization of Geospheric Mineral Resources........................ 477
17.4.1 Metals...................................................................................... 478
17.5 Metal Resources and Industrial Ecology................................................... 479
17.5.1 Aluminum............................................................................... 479
17.5.2 Chromium...............................................................................480
17.5.3 Copper..................................................................................... 481
17.5.4 Cobalt...................................................................................... 481
17.5.5 Lead........................................................................................ 481
17.5.6 Lithium.................................................................................... 482
17.5.7 Zinc......................................................................................... 482
17.5.8 Rare Earths............................................................................. 483
17.6 Nonmetal Mineral Resources.................................................................... 483
17.7 Phosphates.................................................................................................484
17.8 Sulfur......................................................................................................... 485
17.8.1 Gypsum................................................................................... 486
17.9 Wood: An Abundant Renewable Resource............................................... 486
17.10 Extending Resources with Industrial Ecology.......................................... 487
17.10.1 Metals...................................................................................... 487
17.10.2 Plastics and Rubber................................................................. 488
17.10.3 Lubricating Oil........................................................................ 488
References................................................................................................................. 489
Chapter 18 Sustainable Energy: The Key to Everything............................................................. 493

18.1 The Energy Problem.................................................................................. 493
18.2 Nature of Energy....................................................................................... 494
18.3 Sustainable Energy: Away from the Sun and Back Again........................ 494
18.3.1 The Brief Era of Fossil Fuels.................................................. 495
18.3.2 Back to the Sun....................................................................... 496
18.4 Sources of Energy Used in the Anthrosphere: Present and Future........... 497
18.5 Energy Devices and Conversions.............................................................. 499
18.5.1 Fuel Cells................................................................................ 502
18.6 Energy Conservation and Renewable Energy Sources.............................. 502
18.6.1 Renewable Energy.................................................................. 505
18.6.2 Heavy Oil................................................................................506
18.6.3 Shale Oil................................................................................. 507
18.6.4 Natural Gas Liquids................................................................507
18.7 Natural Gas................................................................................................ 507
18.8 Coal............................................................................................................ 508
18.8.1 Coal Conversion......................................................................509
18.9 Carbon Sequestration for Fossil Fuel Utilization......................................509
18.10 The Great Plains Synfuels Plant: Industrial Ecology
in Practice to Produce Energy and Chemicals.......................................... 511
18.11 Nuclear Energy.......................................................................................... 512
18.11.1 Thorium-Fueled Reactors....................................................... 515
18.11.2 Nuclear Fusion........................................................................ 515
18.12 Geothermal Energy................................................................................... 516
18.13 The Sun: An Ideal, Renewable Energy Source......................................... 516
18.13.1 Solar Photovoltaic Energy Systems........................................ 517
xx Contents
18.13.2 Artificial Photosynthesis for Capturing Solar Energy............ 520

18.14 Energy from the Earth’s Two Great Fluids in Motion............................... 520
18.14.1 The Success of Wind Power................................................... 521
18.14.2 Energy from Moving Water.................................................... 522
18.14.3 Energy from Moving Water without Dams............................ 523
18.15 Biomass Energy: An Overview of Biofuels and their Resources.............. 523
18.15.1 Processing of Biofuel to More Compact Forms...................... 526
18.15.2 Decarbonization with Biomass Utilization............................. 526
18.15.3 Conversion of Biomass to Other Fuels.................................... 527
18.15.4 Ethanol Fuel............................................................................ 528
18.15.5 Biodiesel Fuel.......................................................................... 528
18.15.6 Fuel from Algae...................................................................... 529
18.15.7 The Potential of Lignocellulose Fuels.................................... 530
18.15.8 Chemical Conversion of Biomass to Synthetic Fuels............. 532
18.15.9 Biogas...................................................................................... 533
18.15.10 Biorefineries and Utilizing Biomass for Energy..................... 533
18.15.11 A System of Industrial Ecology for Methane Production
from Renewable Sources........................................................ 534
18.16 Hydrogen as a Means to Store and Utilize Energy.................................... 534
18.17 Combined Power Cycles............................................................................ 536
References................................................................................................................. 537
Chapter 19 The Nature, Sources, and Environmental Chemistry of Hazardous Wastes............ 541
19.1 Introduction............................................................................................... 541
19.1.1 History of Hazardous Substances........................................... 541
19.1.2 Legislation............................................................................... 542
19.2 Classification of Hazardous Substances and Wastes................................. 543
19.2.1 Characteristics and Listed Wastes.......................................... 543
19.2.2 Hazardous Wastes...................................................................544
19.2.3 Hazardous Wastes and Air and Water Pollution Control.......544
19.3 Sources of Wastes...................................................................................... 545
19.3.1 Types of Hazardous Wastes.................................................... 545
19.3.2 Hazardous Waste Generators..................................................546
19.4 Flammable and Combustible Substances.................................................. 547
19.4.1 Combustion of Finely Divided Particles................................. 547
19.4.2 Oxidizers................................................................................. 548
19.4.3 Spontaneous Ignition.............................................................. 548
19.4.4 Toxic Products of Combustion................................................ 549
19.5 Reactive Substances................................................................................... 549
19.5.1 Chemical Structure and Reactivity......................................... 550
19.6 Corrosive Substances................................................................................. 551
19.6.1 Sulfuric Acid........................................................................... 551
19.7 Toxic Substances........................................................................................ 552
19.7.1 Toxicity Characteristic Leaching Procedure.......................... 552
19.8 Physical Forms and Segregation of Wastes............................................... 553
19.9 Environmental Chemistry of Hazardous Wastes...................................... 554
19.10 Physical and Chemical Properties of Hazardous Wastes.......................... 555
19.11 Transport, Effects, and Fates of Hazardous Wastes.................................. 555
19.11.1 Physical Properties of Wastes................................................. 556
Contents xxi
19.11.2 Chemical Factors.................................................................... 556

19.11.3 Effects of Hazardous Wastes.................................................. 556
19.11.4 Fates of Hazardous Wastes. .................................................... 557
19.12 Hazardous Wastes and the Anthrosphere.................................................. 557
19.13 Hazardous Wastes in the Geosphere......................................................... 558
19.14 Hazardous Wastes in the Hydrosphere...................................................... 560
19.15 Hazardous Wastes in the Atmosphere....................................................... 562
19.16 Hazardous Wastes in the Biosphere........................................................... 563
19.16.1 Microbial Metabolism in Waste Degradation......................... 563
19.16.2 Ecotoxicology of Hazardous Wastes......................................564
19.17 Hazardous Substances in Terrorism..........................................................564
19.17.1 Detection of Hazardous Substances....................................... 566
19.17.2 Removing Hazardous Agents................................................. 567
References................................................................................................................. 567
Chapter 20 Industrial Ecology for Waste Minimization, Utilization,

and Treatment............................................................................................................ 571
20.1 Introduction............................................................................................... 571
20.2 Waste Reduction and Minimization.......................................................... 571
20.3 Recycling................................................................................................... 573
20.3.1 Examples of Recycling........................................................... 573
20.3.2 Waste Oil Utilization and Recovery....................................... 574
20.3.3 Waste Oil Fuel........................................................................ 575
20.3.4 Waste Solvent Recovery and Recycle..................................... 575
20.3.5 Recovery of Water from Wastewater...................................... 575
20.4 Physical Methods of Waste Treatment...................................................... 576
20.4.1 Methods of Physical Treatment.............................................. 577
20.4.2 Phase Separations................................................................... 577
20.4.3 Phase Transition...................................................................... 578
20.4.4 Phase Transfer......................................................................... 578
20.4.5 Molecular Separation.............................................................. 579
20.5 Chemical Treatment: An Overview........................................................... 580
20.5.1 Acid/Base Neutralization........................................................ 580
20.5.2 Chemical Precipitation............................................................ 580
20.5.3 Coprecipitation of Metals....................................................... 581
20.5.4 Oxidation/Reduction............................................................... 582
20.5.5 Electrolysis.............................................................................. 582
20.5.6 Hydrolysis............................................................................... 583
20.5.7 Chemical Extraction and Leaching........................................ 584
20.5.8 Ion Exchange........................................................................... 584
20.6 Green Waste Treatment by Photolysis and Sonolysis................................ 585
20.7 Thermal Treatment Methods..................................................................... 586
20.7.1 Incineration Systems............................................................... 587
20.7.2 Wet Air Oxidation................................................................... 588
20.7.3 UV-Enhanced Wet Oxidation................................................. 588
20.7.4 Destruction of Hazardous Wastes in Cement
Manufacture............................................................................ 589
20.8 Biodegradation of Wastes.......................................................................... 589
20.9 Phytoremediation....................................................................................... 590
xxii Contents
20.10 Land Treatment and Composting.............................................................. 591

20.10.1 Land Treatment....................................................................... 591
20.10.2 Composting............................................................................. 591
20.11 Preparation of Wastes for Disposal........................................................... 592
20.12 Ultimate Disposal of Wastes..................................................................... 594
20.12.1 Disposal Aboveground............................................................ 594
20.12.2 Landfill.................................................................................... 594
20.12.3 Surface Impoundment of Liquids........................................... 595
20.12.4 Deep-Well Disposal of Liquids............................................... 595
20.13 Leachate and Gas Emissions..................................................................... 596
20.14 In Situ Treatment....................................................................................... 596
20.14.1 In Situ Thermal Processes...................................................... 598
References................................................................................................................. 598
Chapter 21 The Biosphere: Environmental Biochemistry...........................................................603

21.1 Life and the Biosphere...............................................................................603
21.1.1 The Biosphere in Stabilizing the Earth System:
The Gaia Hypothesis...............................................................604
21.2 Metabolism and Control in Organisms.....................................................604
21.2.1 Enzymes in Metabolism.........................................................604
21.2.2 Nutrients..................................................................................605
21.2.3 Control in Organisms..............................................................606
21.3 Reproduction and Inherited Traits.............................................................606
21.4 Stability and Equilibrium of the Biosphere...............................................607
21.5 Biochemistry..............................................................................................607
21.5.1 Biomolecules...........................................................................608
21.6 Biochemistry and the Cell.........................................................................608
21.6.1 Major Cell Features................................................................609
21.7 Proteins...................................................................................................... 610
21.7.1 Protein Structure..................................................................... 612
21.7.2 Denaturation of Proteins......................................................... 613
21.8 Carbohydrates............................................................................................ 613
21.9 Lipids......................................................................................................... 615
21.10 Enzymes.................................................................................................... 617
21.11 Nucleic Acids............................................................................................. 619
21.11.1 Nucleic Acids in Protein Synthesis......................................... 621
21.11.2 Modified DNA........................................................................ 621
21.12 Recombinant DNA and Genetic Engineering .......................................... 621
21.13 Metabolic Processes.................................................................................. 622
21.13.1 Energy-Yielding Processes...................................................... 622
21.14 Metabolism of Xenobiotic Compounds..................................................... 623
21.14.1 Phase I and Phase II Reactions............................................... 623
References................................................................................................................. 624
Chapter 22 Toxicological Chemistry........................................................................................... 627

22.1 Introduction to Toxicology and Toxicological Chemistry......................... 627
22.1.1 Toxicology............................................................................... 627
Contents xxiii
22.1.2 Synergism, Potentiation, and Antagonism.............................. 629

22.2 Dose–Response Relationships................................................................... 629
22.3 Relative Toxicities...................................................................................... 630
22.3.1 Nonlethal Effects.................................................................... 630
22.4 Reversibility and Sensitivity...................................................................... 632
22.4.1 Hypersensitivity and Hyposensitivity..................................... 632
22.5 Xenobiotic and Endogenous Substances................................................... 632
22.6 Toxicological Chemistry............................................................................ 633
22.6.1 Toxicants in the Body............................................................. 633
22.6.2 Phase I Reactions.................................................................... 634
22.6.3 Phase II Reactions................................................................... 634
22.7 Kinetic Phase and Dynamic Phase............................................................ 635
22.7.1 Kinetic Phase.......................................................................... 635
22.7.2 Dynamic Phase....................................................................... 635
22.7.3 Primary Reaction in the Dynamic Phase................................ 636
22.7.4 Biochemical Effects in the Dynamic Phase............................ 637
22.7.5 Responses to Toxicants........................................................... 637
22.8 Teratogenesis, Mutagenesis, Carcinogenesis, and Effects on the
Immune and Reproductive Systems.......................................................... 638
22.8.1 Teratogenesis........................................................................... 638
22.8.2 Mutagenesis............................................................................ 638
22.8.3 Biochemistry of Mutagenesis.................................................. 638
22.8.4 Carcinogenesis........................................................................ 639
22.8.5 Biochemistry of Carcinogenesis.............................................640
22.8.6 Alkylating Agents in Carcinogenesis..................................... 642
22.8.7 Testing for Carcinogens.......................................................... 642
22.8.8 Bruce Ames Test..................................................................... 642
22.8.9 Immune System Response...................................................... 643
22.8.10 Endocrine Disruption.............................................................. 643
22.9 Health Hazards.......................................................................................... 643
22.9.1 Assessment of Potential Exposure.......................................... 643
22.9.2 Epidemiological Evidence......................................................644
22.9.3 Estimation of Health Effects Risks......................................... 645
22.9.4 Risk Assessment..................................................................... 645
References................................................................................................................. 645
Chapter 23 Toxicological Chemistry of Chemical Substances.................................................... 649

23.1 Introduction............................................................................................... 649
23.1.1 ATSDR Toxicological Profiles................................................ 649
23.2 Toxic Elements and Elemental Forms....................................................... 649
23.2.1 Ozone...................................................................................... 649
23.2.2 White Phosphorus................................................................... 649
23.2.3 Elemental Halogens................................................................ 651
23.2.4 Heavy Metals.......................................................................... 651
23.3 Toxic inorganic Compounds...................................................................... 652
23.3.1 Cyanide................................................................................... 652
23.3.2 Carbon Monoxide................................................................... 653
23.3.3 Nitrogen Oxides...................................................................... 653
23.3.4 Hydrogen Halides................................................................... 653
xxiv Contents
23.3.5 Hydrogen Fluoride.................................................................. 654

23.3.6 Hydrogen Chloride.................................................................. 654
23.3.7 Interhalogen Compounds and Halogen Oxides...................... 654
23.3.8 Inorganic Compounds of Silicon............................................ 655
23.3.9 Asbestos.................................................................................. 655
23.3.10 Inorganic Phosphorus Compounds......................................... 655
23.3.11 Inorganic Compounds of Sulfur............................................. 656
23.3.12 Perchlorate.............................................................................. 656
23.3.13 Organometallic Compounds................................................... 657
23.3.14 Organolead Compounds......................................................... 657
23.3.15 Organotin Compounds............................................................ 657
23.3.16 Carbonyls................................................................................ 657
23.3.17 Reaction Products of Organometallic Compounds................ 658
23.4 Toxicology of Organic Compounds........................................................... 658
23.4.1 Alkane Hydrocarbons............................................................. 658
23.4.2 Alkene and Alkyne Hydrocarbons......................................... 658
23.4.3 Benzene and Aromatic Hydrocarbons.................................... 658
23.4.4 Toluene.................................................................................... 659
23.4.5 Naphthalene............................................................................ 659
23.4.6 Polycyclic Aromatic Hydrocarbons........................................660
23.4.7 Oxygen-Containing Organic Compounds..............................660
23.4.7.1 Oxides..................................................................660
23.4.7.2 Alcohols............................................................... 661
23.4.7.3 Phenols................................................................. 661
23.4.7.4 Aldehydes and Ketones........................................ 662
23.4.7.5 Carboxylic Acids.................................................. 663
23.4.7.6 Ethers................................................................... 663
23.4.7.7 Acid Anhydrides.................................................. 663
23.4.7.8 Esters.................................................................... 663
23.4.8 Organonitrogen Compounds...................................................664
23.4.8.1 Aliphatic Amines.................................................664
23.4.8.2 Carbocyclic Aromatic Amines............................ 665
23.4.8.3 Pyridine................................................................ 665
23.4.8.4 Melamine............................................................. 665
23.4.8.5 Acrylamide: Toxic Potato Chips?......................... 665
23.4.8.6 Nitriles..................................................................666
23.4.8.7 Nitro Compounds.................................................666
23.4.8.8 Nitrosamines........................................................666
23.4.8.9 Isocyanates and Methyl Isocyanate......................666
23.4.8.10 Organonitrogen Pesticides...................................666
23.4.9 Organohalide Compounds...................................................... 667
23.4.9.1 Alkyl Halides....................................................... 667
23.4.9.2 Alkenyl Halides....................................................668
23.4.9.3 Aryl Halides.........................................................668
23.4.10 Organohalide Pesticides.......................................................... 669
23.4.10.1 TCDD................................................................... 669
23.4.10.2 Chlorinated Phenols............................................. 670
23.4.11 Organosulfur Compounds...................................................... 670
23.4.11.1 Sulfur Mustards................................................... 670
23.4.12 Organophosphorus Compounds.............................................. 671
23.4.12.1 Organophosphate Esters....................................... 671
Contents xxv
23.4.12.2 Phosphorothionate and Phosphorodithioate

Ester Insecticides................................................. 672
23.4.12.3 Organophosphorus Military Poisons................... 672
23.5 Toxic Natural Products.............................................................................. 673
References................................................................................................................. 673
Chapter 24 Chemical Analysis in Environmental and Toxicological Chemistry........................ 679

24.1 Analytical Chemistry................................................................................ 679
24.2 The Chemical Analysis Process................................................................ 679
24.3 Major Categories of Chemical Analysis....................................................680
24.4 Error and Treatment of Data...................................................................... 681
24.5 Gravimetric and Volumetric Analyses...................................................... 682
24.6 Spectrophotometric Methods of Analysis.................................................684
24.6.1 Absorption Spectrophotometry...............................................684
24.6.2 Atomic Absorption and Emission Analyses........................... 685
24.6.3 Atomic Emission Techniques................................................. 685
24.7 Electrochemical Methods of Analysis....................................................... 687
24.8 Chromatography........................................................................................ 688
24.8.1 High-Performance Liquid Chromatography........................... 689
24.8.2 Ion Chromatography...............................................................690
24.9 Methods for Water Analysis......................................................................690
24.10 Mass Spectrometry....................................................................................690
24.11 Automated Analyses.................................................................................. 691
24.12 Immunoassay Screening............................................................................ 692
24.13 Total Organic Carbon in Water................................................................. 692
24.14 Measurement of Radioactivity in Water.................................................... 693
24.15 Analysis of Wastes and Solids................................................................... 693
24.15.1 Toxicity Characteristic Leaching Procedure.......................... 694
24.16 Atmospheric Monitoring........................................................................... 694
24.16.1 Methods for Sampling and Analyzing Atmospheric
Pollutants................................................................................. 695
24.16.2 Atmospheric Carbon Monoxide by Infrared Absorption....... 696
24.16.3 Determination of Hydrocarbons and Organics in the
Atmosphere............................................................................. 697
24.16.4 Direct Spectrophotometric Analysis of Gaseous Air
Pollutants................................................................................. 697
24.17 Analysis of Biological Materials and Xenobiotics.................................... 698
24.17.1 Indicators of Exposure to Xenobiotics.................................... 698
24.17.2 Immunological Methods of Xenobiotics Analysis.................. 699
References................................................................................................................. 699
Index............................................................................................................................................... 703
Preface
The year 2020 has been a particularly momentous one in which to undertake a revision of
Environmental Chemistry. That is because the year saw two particularly earth-shattering phe-
nomena of great consequence for Planet Earth and its human population. First, numerous events
around the globe have forcefully brought home the reality of global climate change. For example,
on February 20, 2020, an all-time record high temperature of 18.3°C (64.9°F) was set in Antarctica;
unprecedented wildfires ravished the US west coast and Colorado; and so many hurricanes occurred
in the Gulf of Mexico that it was necessary to go deep into the Greek alphabet to name them all.
On November 3, Hurricane Eta hit Central America as a powerful Category 4 storm, and just two
weeks later, Category 5 Hurricane Iota traversed an almost identical path, leaving the populace
devastated. The second momentous event characterizing 2020 is that the human population that
depends on Planet Earth for its existence and well-being has been devastated by the worst pandemic
to hit in more than a century, the deadly COVID-19 coronavirus. Either individually or in combina-
tion, these phenomena have altered living conditions on the Earth, toppled governments, threatened
wars, resulted in mass migrations, and generally changed the complexion of Planet Earth and its
population of humans and other species.
Environmental Chemistry, Eleventh Edition, generally retains the organization and approach
that have proven popular in earlier editions. This includes viewing the Earth System as consist-
ing of five closely interacting spheres—the hydrosphere, atmosphere, geosphere, anthrosphere, and
biosphere, that part of the Earth System constructed and operated by humans. The book acknowl-
edges the importance of the Earth’s natural capital, which includes materials, water resources, air
resources, biological resources, and conditions generally conducive to life on the planet.
Environmental Chemistry recognizes that the Earth is entering a new epoch, leaving the
Holocene epoch in which humankind has existed in relative comfort for the last approximately
10,000 years, and is well into a new epoch, the Anthropocene, in which conditions on the Earth are
determined largely by human influences. Of overwhelming importance in the Anthropocene are
human influences on climate, especially global warming, which is largely attributed to emissions to
the atmosphere of carbon dioxide from fossil fuel combustion.
Environmental chemistry deals with chemical phenomena and conditions in the five spheres
of the Earth System and how human activities influence these phenomena. The tenth and now the
eleventh edition of Environmental Chemistry differed from the preceding edition in that it goes
directly to the topic of environmental chemistry. In order to understand the environmental chemis-
try and phenomena that occur in each of the five environmental spheres, it is useful to have a general
understanding of environmental chemistry. Therefore, Chapter 1, “Environmental Chemistry: An
Essential Discipline in Coping with Challenges Facing Humankind,” is a general survey of environ-
mental chemistry as a whole. Though deemed essential to provide perspective on the remainder of
the book, Chapter 1 needs to be as short and concise as possible to enable the reader to quickly move
on to the remaining chapters, which pertain to the body of knowledge that comprise environmental
chemistry. Therefore, Chapter 1 has been revised significantly for brevity and conciseness.
Chapters 2–7 address the environmental chemistry of the hydrosphere. Chapter 2, “The
Hydrosphere and Water Chemistry,” provides an overview of the hydrosphere and the nature of
water that composes it. This chapter deals with some of the key aspects of aquatic chemistry, includ-
ing the nature of the water molecule, which determines the physical nature of the hydrosphere, and
the chemistry of water in the hydrosphere. Aspects of aquatic chemistry addressed in this chapter
include acid–base reactions and equilibria, carbon dioxide in water, alkalinity, water hardness, and
complexation and chelation.
Chapter 3, “Oxidation/Reduction in Aquatic Chemistry,” discusses oxidation and reduction reac-
tions in water. It emphasizes the importance of microorganisms as catalysts that mediate oxidation
xxvii
xxviii Preface
and reduction in water and the concept of pE, analogous to pH and defined as the negative log of
the activity of the electron in water. A simplified pE/pH diagram for iron is used to illustrate the
pE concept and its interaction with pH. The concept of expressing energy transitions for oxidation–
reduction reactions on the basis of one electron-mole of reaction is introduced, enabling the energy
changes in such reactions to be expressed on a common basis.
Chapter 4, “Phase Interactions in Aquatic Chemistry,” addresses the interactions that occur
between species in water and those in solid and gaseous phases. The importance of sediments in
determining water quality is stressed. This chapter also explains the important roles played by col-
loids in water.
Chapter 5, “Aquatic Microbial Biochemistry,” provides details regarding the crucial role played
by microorganisms in the environmental chemistry of water, including algae, bacteria, protozoa,
and fungi. Also considered are microbial transformations of carbon; the microorganism-mediated
biodegradation of organic matter; and the transformations of nitrogen, sulfur, and phosphorus spe-
cies carried out by bacteria. This chapter concludes with a discussion of the influence bacteria have
on metal species and water, including the formation of pollutant acid mine water from the bacteri-
ally mediated oxidation of iron pyrite, FeS2.
Chapter 6, “Water Pollutants and Water Pollution,” covers the nature and effects of various kinds
of water pollutants. The chapter covers inorganic pollutants, organic pollutants, organometallics,
and pesticides among the topics pertinent to water pollution.
The emphasis of Chapter 7, “World Water Crisis and Climate Change: Water Renovation and
Recycling,” is on the worldwide water crisis, which has been exacerbated by global climate change.
Various water treatment processes are covered in this chapter. Also covered are means for dealing
with water shortages, including schemes for the complete recycling of water.
Chapter 8, “The Atmosphere and Atmospheric Chemistry,” is the first chapter that addresses the
atmosphere. This chapter covers general characteristics of the atmosphere, including stratification
of the atmosphere into the troposphere, the stratosphere, and higher layers. A number of general
topics pertaining to the atmosphere are addressed, including movement of masses of air, transport
of energy, and weather and climate. Basic photochemistry and the role of solar radiation in deter-
mining atmospheric phenomena such as photochemical smog are introduced.
Chapter 9, “Particles in the Atmosphere,” deals with particulate matter suspended in the atmo-
sphere. It includes a discussion of particles as air pollutants and the role of particulate matter in
determining atmospheric chemistry. Also discussed is the influence of the anthrosphere in intro-
ducing pollutant particles into the atmosphere, which cause pollutant phenomena such as the Asian
brown cloud.
“Gaseous Inorganic Air Pollutants” addressed in Chapter 10 include prominently oxides of sul-
fur and nitrogen, which, as primary air pollutants, may devolve into more harmful secondary air
pollutants, such as acid rain and corrosive sulfate and nitrate salts. The chapter discusses the impor-
tance of nitrogen dioxide in capturing photons of sunlight, thus initiating the process of the forma-
tion of photochemical smog.
Chapter 11, “Organic Air Pollutants,” discusses the wide variety of organic compounds that
pollute the atmosphere, including hydrocarbons, oxygen-containing organics, organonitrogen com-
pounds, and organosulfur compounds. Sources of organic air pollutants, from both the anthrosphere
and the biosphere, especially plants, are discussed.
Chapter 12, “Photochemical Smog,” deals with arguably the most annoying air pollution phe-
nomenon, the photochemical smog that forms when reactive hydrocarbons, nitrogen oxides, and
sunlight interact to produce a noxious mixture of ozone, organic oxidants, aldehydes, and particles
that constitute photochemical smog. Sources of the primary pollutants that are precursors to the
formation of photochemical smog are discussed, as is their control.
Chapter 13, “The Endangered Global Atmosphere,” addresses climate change and its effects,
which may pose the greatest danger to the Earth System and the biosphere in modern times. Carbon
dioxide emission to the atmosphere as a major contributor to global climate change is discussed.
Preface xxix
Various trends pertaining to global climate change, including temperatures, ice cover, and precipi-
tation are discussed. The chapter also addresses means for slowing global climate change and for
dealing with it as it occurs.
Chapter 14, “The Geosphere and Geochemistry,” introduces the geosphere as one of the major
environmental spheres. The nature and behavior of the geosphere and of the rocks and solids that
compose it are discussed. The crucial role of the geosphere in providing the Earth’s natural capital is
covered in this chapter. Also covered are hazards from the geosphere, including devastating earth-
quakes and potentially climate-altering volcanic eruptions.
Chapter 15, “Soil: Earth’s Lifeline,” addresses the most important part of the geosphere for life
on the Earth, the soil upon which humans and many other organisms depend to provide the food
necessary for their existence. The chapter explains what soil is and the kinds of mineral matter that
compose it. Various soil characteristics, such as the layers called soil horizons, are discussed. Also
covered are the challenges involved with managing soil during an era of global climate change.
The sphere of the environment made and controlled by humans is introduced in Chapter 16, “The
Anthrosphere: Industrial Ecology and Green Chemistry.” This chapter defines what the anthrosphere
is and how it has come to be recognized as an integral sphere of the Earth System to the extent that
the Earth is entering a new epoch, the Anthropocene. The chapter discusses in some detail the inter-
actions of the anthrosphere with the other spheres of the Earth System. Two important approaches
to making the anthrosphere compatible with other environmental spheres—industrial ecology and
its environmental chemistry aspect, green chemistry—are introduced and explained.
The anthrosphere is a voracious consumer of the Earth’s resources and its natural capital, as
discussed in Chapter 17, “Resources and Sustainable Materials.” This chapter deals with resources
such as metals, some of which are in short supply, and how renewable alternatives to some of these
resources may be developed. The roles played by the practices of industrial ecology and green
chemistry in extending limited resources are discussed.
The availability of abundant, environmentally friendly energy is of utmost importance in the
achievement of sustainability as discussed at length in Chapter 18, “Sustainable Energy: The Key
to Everything.” Reflecting the importance of energy, this chapter is relatively long and emphasizes
renewable sources of energy, including wind, water, solar, and biological energy sources.
For decades, a major problem posed by the anthrosphere has been the generation and disposal of
hazardous wastes as discussed in Chapter 19, “The Nature, Sources, and Environmental Chemistry
of Hazardous Wastes.” Dealing with hazardous wastes sustainably is discussed in Chapter 20,
“Industrial Ecology for Waste Minimization, Utilization, and Treatment.”
The first of three chapters on the biosphere is Chapter 21, “The Biosphere: Environmental
Biochemistry.” This chapter introduces basic biochemistry. A very important aspect of the biosphere
as related to environmental chemistry is the influence of toxic substances, discussed in Chapter 22,
“Toxicological Chemistry.” The toxic effects and toxicological chemistry of specific substances are
discussed in Chapter 23, “Toxicological Chemistry of Chemical Substances.”
The book concludes with an overview of chemical analysis in environmental chemistry,
Chapter 24, “Chemical Analysis in Environmental and Toxicological Chemistry.” This chapter also
includes brief coverage of the determination of toxicants and their products in living systems.
PowerPoint presentations are available for each of the chapters to users of the book free of charge
by request from CRC Press or from the author. The author welcomes input from readers and may be
contacted by e-mail at [email protected].
Acknowledgments
The author gratefully acknowledges the excellent work over a number of years and several volumes
of books by Taylor & Francis editor Hilary LaFoe. Hilary has been not only an outstanding editor
and collaborator but also a true and valued friend. He would also like to acknowledge the excellent
work of several copy editors who have worked so hard to bring the project to fruition, especially
Ms. Suzanne Pfister.
xxxi
About the Author
Stanley E. Manahan is Professor Emeritus of Chemistry at the University of Missouri, Columbia,
where he has been on the faculty since 1965. He earned an Bachelor of Arts (BA) degree in chem-
istry at Emporia State University in Kansas in 1960 and a PhD in analytical chemistry at the
University of Kansas in 1965. Since 1968, his primary research and professional activities have
been in environmental chemistry, with recent emphasis on hazardous waste treatment. His latest
research has involved gasification of wastes and gasification of sewage sludge and crop by-product
biomass for energy production. He is the author of approximately 90 research papers. Professor
Manahan has taught courses on environmental chemistry, hazardous wastes, toxicological chem-
istry, and analytical chemistry, and has lectured on these topics throughout the United States as
an American Chemical Society Local Sections tour speaker and in countries abroad, including
France, Italy, Austria, Japan, Mexico, and Venezuela. Since 1970, Professor Manahan has written
books in his areas of expertise, including printed works and more recently electronic versions. His
longest standing and most popular book has been Environmental Chemistry, the first of its kind,
initially published in 1972 through numerous editions, of which this work is the eleventh edition.
Other topics on which the author has written books include general chemistry, applied chemistry,
toxicological chemistry, toxicology, quantitative chemical analysis, sustainable chemical science,
green chemistry, water chemistry, energy, environmental geology and geochemistry, global climate
change, environmental and sustainability science, the anthrosphere and the Anthropocene epoch,
hazardous wastes, and industrial ecology.
xxxiii
1 An Essential Discipline in Coping
with Challenges Facing Humankind
1.1 A CATASTROPHIC YEAR FOR EARTH AND HUMANKIND

As this is being written at the end of 2020, it has been an annus horribilis (a term popularized by
Queen Elizabeth II of England in 1992), a truly horrible year for Earth, its environment, its cli-
mate, and its human residents. COVID-19 coronavirus, a deadly pathogen that, by the end of the
year 2021, had killed over 1 million people worldwide, afflicted tens of millions, and disrupted the
global economy, has spread throughout the planet. Out-of-control wildfires, exacerbated by global-
warming-induced drought on the US West coast and later in Colorado, have spread an evil yellow
haze across the nation causing the sun to appear as a dull red circle resting on the horizon just before
sunset. Later, in October 2020, fire outbreaks in southern California, fueled by hurricane-force
Santa Ana winds approaching 100 miles per hour in some cases, have prompted evacuation orders.
Because of rapidly approaching wildfires, Colorado’s Rocky Mountain National Park had to be
abandoned in October 2020. Regulations requiring wearing of masks in public to prevent the spread
of coronavirus sparked civil unrest in some places, fueled in part by the economic burden posed
by measures taken to contain the coronavirus, resulting in rioting and destruction of infrastructure.
By mid-November of 2021, the deadly COVID-19 virus had swept the world with a steeply rising
toll of deaths. The United States was leading the world in total cases and deaths, although several
other smaller nations had the dubious distinction of having larger numbers of cases and deaths per
100,000 population. It is no exaggeration to assert that as 2020 was coming to a close, humankind
was in a deadly race between this raging pandemic and the development and deployment of effec-
tive vaccines and treatments for it.
In 2018, some disease experts warned of a “Disease X” that could devastate humankind on
Earth. The hypothetical disease that was the subject of the warning had characteristics remark-
ably like those of COVID-19 sweeping the world in 2020. It is estimated that there are more than
700 coronaviruses carried by bats, 50 of them closely related to severe acute respiratory syndrome
(SARS) of which COVID-19 is a prime example. It is not improbable that more pandemics similar
to COVID-19 are on the way. Humans need to be more intelligent in their appreciation of such
onslaughts and develop rapid and effective responses to them.
In 2021, the reality of global warming and climate change was obvious to all thinking people.
Climate change has been very apparent in higher, normally colder latitudes. In the first half of
2020, normally frigid Siberia experienced a time of very high temperatures. On June 20, the town
of Verkhoyansk reached a record-breaking temperature of 38°C (100°F). Effects of excessive heat
in the fragile Siberian environment included wildfires, loss of permafrost with release of methane,
a powerful greenhouse gas, and an invasion of pests. In September 2020, augmented by global
warming and record-high temperatures in Siberia, the ice of Arctic Ocean reached its second lowest
level ever of 3.74 million square kilometers, next to 2012’s record-low level. And according to some
authoritative reports, Greenland’s ice sheet has melted to a point of no return, such that it is too late
to make any efforts to slow global warming to stop it.
On August 17, 2020, the temperature in Death Valley, California, hit 54.4°C (130°F), which
some weather experts contend is the highest temperature ever recorded anywhere on the Earth
(two higher temperatures reported in Death Valley in 1913 and in Tunisia in 1931 are not deemed
DOI: 10.1201/9781003096238-1 1
2 Environmental Chemistry
to be from reliable readings). Warming climate and drought are contributing to mass move-
ments of “climate refugees,” such as a flood of Central American refugees to the United States in
2020. These movements are expected to reach epic proportions in future years, causing daunting
humanitarian and political problems with major wars a real possibility. It is possible that some
areas will become uninhabitable, including Saudi Arabia hit by record heat and a total lack of
rainfall and parts of Bangladesh permanently flooded by raising sea levels. The year also saw a
record hurricane season in the Gulf of Mexico (the farthest in history that the naming of Gulf
hurricanes has had to go so far into the Greek alphabet), and at least one record-strongest typhoon
ravishing parts of Southeast Asia.1
An interesting change in demographics is underway and expected to accelerate in the future as
the human population on the Earth is likely to stop growing or even fall in decades to come with
falling fertility rates, that is, the number of live births per woman.2 Better education and career
opportunities for women, access to means to limit births, and lower child mortality rates mean
women will have fewer children on average. That is generally good news for the planet Earth,
which already has reached a level of human population that exceeds its comfortable carrying capac-
ity. Lower birth rates tend to go with enhanced economic development. For countries with lower
income, this should mean higher living standards with better health and education for each child
born. In some countries that have experienced lower fertility rates for decades, further shrinkage
could be problematic. These countries must cope with caring for an older population, with fewer
young people to provide care and to pay into the system.
So, it is obvious that planet Earth and those of us who live on it are in for interesting times in
decades to come. To cope with the changes that will occur, humans must apply all they can of
human ingenuity and science. A key science will be environmental chemistry, the topic of this book.
1.2 EARTH AND THE EARTH SYSTEM

This book is about environmental chemistry, the chemical processes, reactions, and conditions that
occur in Earth’s environment. So, what is the environment? The Earth’s environment may be con-
sidered consisting of five closely related and interacting spheres: (1) the hydrosphere, consisting of
water; (2) the atmosphere, composed mostly of air that envelopes the Earth’s surface, the bulk of
which lies in proximity to the surface; (3) the geosphere, which makes up the rock, mineral mat-
ter, and soil on or below the Earth’s surface; (4) the anthrosphere, consisting of the many parts
of the Earth that have been made, modified, and operated by humans employing their ingenuity
and technology; and (5) the biosphere, consisting of living organisms. These five spheres shown
in Figure 1.1 make up the Earth System.3 It is logical to discuss environmental chemistry on the
basis of the five major environmental spheres, keeping in mind that they compose a total Earth
System and interact strongly with each other, including robust exchanges of matter and energy
(Figure 1.1). Since this is a book about environmental chemistry, it goes directly and specifically
into environmental chemistry as it applies primarily to each of the environmental spheres. But to
discuss the environmental chemistry of any segment of the Earth System, account must be taken
of all the other segments; thus, each is defined and briefly described at the beginning within this
introductory chapter.
As noted above, a particularly important aspect of the Earth System is the continuous exchange
of matter and energy among the five major environmental spheres. One of the major factors in
these exchanges consists of two great fluids that circulate in the Earth System: (1) surface water,
especially in the oceans and rivers, and (2) air in the atmosphere, both of which transport matter
and energy. Air heated in equatorial regions expands and flows away from the equator carrying heat
energy as sensible heat in the air molecules and latent heat in water vapor toward polar regions. The
Gulf Stream, a plume of relatively warm water, heated in the Caribbean region flows northward
near the surface of the Atlantic Ocean along the east coast of North America and releases heat off
the coast of Europe before sinking and flowing back at greater depths. This phenomenon, called
Environmental Chemistry 3
FIGURE 1.1 The Earth’s environment (the Earth System) may be viewed as consisting of five spheres, which
interact with robust exchanges of matter and energy among them.
the thermohaline circulation of the North Atlantic, is responsible in part for the relatively warm
temperatures of Ireland, England, and Western Europe despite their more northern latitudes, and its
possible demise is of concern with respect to global climate change. In addition to large quantities
of water, flowing rivers carry sediments and are very much involved in the transport of waterborne
pollutants.
1.3 BIOGEOCHEMICAL CYCLES IN THE EARTH SYSTEM

In addition to the two great fluids discussed above, a second pathway for the exchange of matter and
energy among the environmental spheres through the Earth System is by way of biogeochemical
cycles.4 These are commonly expressed in terms of key elements, including essential nutrient ele-
ments. Often, as is the case with the nitrogen cycle, they contain an atmospheric component, though
in some cases, such as the phosphorus cycle, the atmospheric component is not significant. Before
humans’ appearance on the Earth, the anthrospheric compartment did not exist, but now, as is the
case of carbon dioxide emitted to the atmosphere by fossil fuel combustion, the anthrosphere is a
very significant component of the Earth System. The anthrosphere is likewise a significant factor in
the nitrogen cycle, in which atmospheric elemental N2 is incorporated as chemically bound nitro-
gen fixed initially as ammonia (NH3) in synthetic chemical facilities in amounts comparable to the
nitrogen bound by living organisms (nitrogen-fixing bacteria).
Figure 1.2 illustrates an important example of a biogeochemical cycle, the carbon cycle. As shown
in the figure, a small, but very significant fraction of the Earth’s carbon is held in the atmosphere as
CO2 gas. This gas is transferred to the biosphere through the leaf surfaces of plants that photosyn-
thetically convert it to biomass using solar energy. It also enters the hydrosphere by dissolving in
surface water and enters the geosphere by precipitating as solid carbonate salts (CaCO3) from water;
the Earth’s oceans constitute a large sink for atmospheric carbon dioxide. Carbon dioxide enters
the atmosphere from the biosphere as organisms produce it as a product of their respiratory bio-
chemical oxidation of organic matter and from the anthrosphere by the combustion of fossil fuels.
Volcanoes and geothermal vents (such as those in Yellowstone National Park) emit carbon dioxide
from the geosphere to the atmosphere. (Sudden emissions of large quantities of geospheric carbon
dioxide underlying volcanic lakes have killed many people in Africa.) Carbon dioxide dissolved in
water as HCO3− is converted to CO32− , which, in the presence of dissolved Ca2+, precipitates CaCO3
(limestone) that ends up as solid rock in the geosphere. Carbon goes back into the hydrosphere as
4 Environmental Chemistry
FIGURE 1.2 The carbon cycle showing the various reservoirs and conduits of carbon species in the environ-
ment. Biomass, which contains carbon, is represented by the general formula {CH2O}. The carbon cycle is
closely related to the oxygen cycle.
acidic CO2 from the atmosphere or from the biodegradation of organic matter, reacting with solid
CaCO3 to produce dissolved HCO3− .
Several other important biogeochemical cycles involving elements that are important in living
organisms may be noted here. Below are summarized cycles of four other elements that are impor-
tant to living organisms.
1.3.1 Oxygen Cycle

The atmosphere, which is 21% elemental O2 by volume, is a vast reservoir of this element. Oxygen
is removed from the atmosphere as carbon dioxide by respiration process of organisms and by com-
bustion and is returned to the atmosphere by plant photosynthesis in which oxygen is released from
atmospheric CO2 in the production of biomass. Oxygen is a component of biomass in the biosphere,
and most rocks in the Earth’s crust are composed of oxygen-containing compounds. Water or H2O
in the hydrosphere is predominantly oxygen.
1.3.2 Nitrogen Cycle
Nitrogen, as chemically very stable elemental N2, composes approximately 80% of the Earth’s
atmosphere. Nitrogen from the atmosphere becomes chemically combined with other elements,
especially H and O, by the synthesis of NH3 in the anthrosphere, from N2 and H2 over a catalyst at
high temperatures and very high pressures, as a by-product of combustion of fuels as gaseous NO
and NO2, and as nitrogen in biomass by some bacteria, including Rhizobium bacteria attached to the
roots of legume plants growing under very mild conditions. Elemental N2 and N2O are returned to
the atmosphere in the biodegradation of biomass, which also releases NH +4 to soil.
Environmental Chemistry 5
1.3.3 Sulfur Cycle

Chemically combined sulfur enters the atmosphere as pollutant gases such as H2S and SO2 gases,
which are also emitted by natural sources, including volcanoes. Large quantities of H2S are pro-
duced and released to the atmosphere by anoxic microorganisms degrading organic compounds
and using sulfate, SO24−, as an oxidizing agent. Volatile dimethyl sulfide, (CH3)2S, is released to
the atmosphere by marine microorganisms. In the atmosphere, gaseous sulfur compounds are oxi-
dized to sulfate, largely in the forms of H2SO4 (pollutant acid rain) and corrosive ammonium salts
(NH4HSO4), which settle from the atmosphere or are washed out with precipitation. The geosphere
is a vast reservoir of sulfur minerals, including sulfate salts (CaSO4), sulfide salts (FeS), and even
elemental sulfur. Sulfur is a small, though essential constituent of biomolecules.
1.3.4 Phosphorus Cycle

The phosphorus cycle does not have an atmospheric component. Phosphorus is an essential life
element and ingredient of cellular DNA as well as ATP and ADP, molecules through which energy
is transferred in organisms. Dissolved phosphate in the hydrosphere is required as a nutrient for
aquatic organisms, although excessive phosphate may result in too much algal growth, causing an
unhealthy condition called eutrophication. Phosphorus is abundant in the geosphere, especially as
the mineral hydroxyapatite, Ca5OH(PO4)3. Significant deposits of phosphorus-rich material have
been formed from the feces of birds and bats (guano).
1.4 NATURAL CAPITAL OF THE EARTH SYSTEM

Every person in that very small group of humans who have been privileged to view the Earth from
outer space has been struck with a sense of awe at the sight. Photographs of the Earth taken at
altitudes high enough to capture its entirety reveal a marvelous sphere, largely blue in color, white
where covered by clouds, with desert regions showing up in shades of brown, yellow, and red. But
the Earth is far more than a beautiful globe that inspires artists and poets. In a very practical sense,
it is a source of the life support systems that sustain humans and all other known forms of life.
The Earth obviously provides the substances required for life including water, atmospheric oxygen,
carbon dioxide from which billions of tons of biomass are made each year by photosynthesis, and
ranging all the way down to the trace levels of micronutrients, such as iodine and chromium that
organisms require for their metabolic processes. The Earth provides temperature conditions con-
ducive to life and a shield against incoming ultraviolet radiation; its potentially deadly photons are
absorbed by molecules in the atmosphere and their energy is dissipated as heat. The Earth also has
a good capacity to deal with waste products that are discharged to the atmosphere, into water, or
the geosphere.
As the industrial revolution gathered force from around 1800, unrestricted development put a
rapidly increasing burden on natural capital, which continued during an era in which there was
recognition of the problem. This eventually led to regulations that began to alleviate somewhat
the impact on natural capital. To an extent, the regulatory approach was supplemented by pollu-
tion prevention and recycling. In an optimistic view of the future, sustainable development and
green technology will further reduce the burden on natural capital even with increased economic
development.
The capacity of the Earth System to provide materials, protection, and conditions conducive to
life is known as its natural capital, which can be regarded as the sum of two major components:
natural resources and ecosystem services. Early hunter–gatherer and agricultural human societies
made few demands upon the Earth’s natural capital. (However, they did modify it in some ways. For
example, indigenous people in parts of North America regularly burned sections of forests so that
grass would grow to support game animals.) As shown in Figure 1.3, as the industrial revolution
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ISBN: 978-0-367-55887-1 (hbk)

Chapter 1 Environmental Chemistry: An Essential Discipline in Coping

Chapter 2 The Hydrosphere and Water Chemistry...................................................................... 21

2.9 Calcium and Other Metals in Water................................................................. 37

Chapter 3 Oxidation/Reduction in Aquatic Chemistry............................................................... 59

Chapter 4 Phase Interactions in Aquatic Chemistry.................................................................... 79

Chapter 5 Aquatic Microbial Biochemistry............................................................................... 101

5.11 Microbial Transformations of Nitrogen.......................................................... 114

Chapter 6 Water Pollutants and Water Pollution....................................................................... 129

6.11.6 Fungicides....................................................................................... 150

7.12.3 Phosphorus Removal...................................................................... 189

Chapter 8 The Atmosphere and Atmospheric Chemistry..........................................................205

8.8.2 Ions and Radicals in the Atmosphere.............................................224

Chapter 9 Particles in the Atmosphere...................................................................................... 237

Chapter 10 Gaseous Inorganic Air Pollutants............................................................................. 261

Chapter 11 Organic Air Pollutants.............................................................................................. 285

11.7.2 Atmospheric Reactions of Hydrofluorocarbons and

Chapter 12 Photochemical Smog................................................................................................. 311

Chapter 13 The Endangered Global Atmosphere........................................................................ 337

13.6 Green Science and Technology to Alleviate Global Warming.................. 349

Chapter 14 The Geosphere and Geochemistry............................................................................ 373

14.12 Surface Earth Movement........................................................................... 394

Chapter 15 Soil: Earth’s Lifeline.................................................................................................403

15.14.2 The Major Transgenic Crops and Their Characteristics......... 435

Chapter 16 The Anthrosphere: Industrial Ecology and Green Chemistry.................................. 443

Chapter 17 Resources and Sustainable Materials........................................................................ 475

17.3 Environmental Effects of Mining and Mineral Extraction....................... 477

Chapter 18 Sustainable Energy: The Key to Everything............................................................. 493

18.13.2 Artificial Photosynthesis for Capturing Solar Energy............ 520

19.11.2 Chemical Factors.................................................................... 556

Chapter 20 Industrial Ecology for Waste Minimization, Utilization,

20.10 Land Treatment and Composting.............................................................. 591

Chapter 21 The Biosphere: Environmental Biochemistry...........................................................603

Chapter 22 Toxicological Chemistry........................................................................................... 627

22.1.2 Synergism, Potentiation, and Antagonism.............................. 629

Chapter 23 Toxicological Chemistry of Chemical Substances.................................................... 649

23.3.5 Hydrogen Fluoride.................................................................. 654

23.4.12.2 Phosphorothionate and Phosphorodithioate

Chapter 24 Chemical Analysis in Environmental and Toxicological Chemistry........................ 679

with Challenges Facing Humankind