《environmental chemistry P753》求取 ⇩

Chapter 1The Environment and Sustainability Science1

1.1From the Sun to Fossil Fuels and Back Again1

1.1.1 The Brief but Spectacular Era of Fossil Fuels2

1.1.2 Back to the Sun2

1.2The Science of Sustainability3

1.2.1 Environmental Science4

1.2.2 Green Science and Technology4

1.3 Chemistry and the Environment4

1.4Water, Air, Earth, Life, and Technology5

1.4.1 Water and the Hydrosphere5

1.4.2 Air and the Atmosphere6

1.4.3 Earth, the Geosphere7

1.4.4 Life, the Biosphere7

1.4.5 Technology and the Environment7

1.5Ecology, Ecotoxicology, and the Biosphere8

1.5.1 The Biosphere8

1.5.2 Ecology9

1.5.3 Ecotoxicology9

1.6Energy and Cycles of Energy10

1.6.1 Light and Electromagnetic Radiation10

1.6.2 Energy Flow and Photosynthesis in Living Systems11

1.6.3 Energy Utilization11

1.7Human Impact and Pollution12

1.7.1 Some Definitions Pertaining to Pollution12

1.7.2 Pollution of Various Spheres of the Environment12

1.8Chemical Fate and Transport12

1.8.1 Physical Transport14

1.8.2 Reactivity14

1.8.3 Mass Balance Expression14

1.8.4 Distribution among Phases15

1.9Chemical Fate and Transport in the Atmosphere, Hydrosphere,and Geosphere15

1.9.1 Pollutants in the Atmosphere16

1.9.2 Pollutants in the Hydrosphere16

1.9.3 Pollutants in the Geosphere17

1.10Environmental Mischief and Terrorism17

1.10.1 Protection through Green Chemistry and Engineering17

1.11 Environmental Forensics18

Literature Cited19

Supplementary References19

Questions and Problems19

Chapter 2Chemistry and the Anthrosphere: Environmental Chemistry and Green Chemistry23

2.1 Environmental Chemistry23

2.2Matter and Cycles of Matter24

2.2.1 Carbon Cycle25

2.2.2 Nitrogen Cycle27

2.2.3 Oxygen Cycle28

2.2.4 Phosphorus Cycle28

2.2.5 Sulfur Cycle28

2.3Anthrosphere and Environmental Chemistry29

2.3.1 Components of the Anthrosphere30

2.4Technology and the Anthrosphere31

2.4.1 Engineering32

2.5Infrastructure33

2.5.1 Vulnerable Infrastructure34

2.6 Components of the Anthrosphere That Influence the Environment35

2.7 Effects of the Anthrosphere on Earth37

2.8Integration of the Anthrosphere into the Total Environment38

2.8.1 Anthrosphere and Industrial Ecology39

2.9Green Chemistry40

2.9.1 Green Synthetic Chemistry40

2.9.2 Risk Reduction41

2.9.3 Specific Aspects of Green Chemistry41

2.9.4 Three Undesirable Characteristics of Chemicals: Persistence,Bioaccumulation, and Toxicity42

2.9.5 Green Chemistry and Environmental Chemistry42

Literature Cited42

Supplementary References43

Questions and Problems43

Chapter 3Fundamentals of Aquatic Chemistry47

3.1 Importance of Water47

3.2Water: From Molecules to Oceans47

3.2.1 Sources and Uses of Water: The Hydrological Cycle47

3.2.2 Properties of Water, a Unique Substance50

3.2.3 Water Molecule50

3.3 Characteristics of Bodies of Water52

3.4 Aquatic Life52

3.5 Introduction to Aquatic Chemistry53

3.6Gases in Water54

3.6.1 Oxygen in Water54

3.7Water Acidity and Carbon Dioxide in Water55

3.7.1 Carbon Dioxide in Water56

3.8Alkalinity59

3.8.1 Contributors to Alkalinity at Different pH Values60

3.8.2 Dissolved Inorganic Carbon and Alkalinity60

3.8.3 Influence of Alkalinity on CO2 Solubility61

3.9Calcium and Other Metals in Water62

3.9.1 Hydrated Metal Ions as Acids62

3.9.2 Calcium in Water63

3.9.3 Dissolved Carbon Dioxide and Calcium Carbonate Minerals64

3.10Complexation and Chelation65

3.10.1 Occurrence and Importance of Chelating Agents in Water67

3.11Bonding and Structure of Metal Complexes68

3.11.1 Selectivity and Specitycity in Chelation68

3.12 Calculations of Species Concentrations68

3.13 Complexation by Deprotonated Ligands69

3.14 Complexation by Protonated Ligands70

3.15Solubilization of Lead Ion from Solids by NTA71

3.15.1 Reaction of NTA with Metal Carbonate73

3.15.2 Effect of Calcium Ion upon the Reaction of Chelating Agents with Slightly Soluble Salts74

3.16Polyphosphates and Phosphonates in Water75

3.16.1 Polyphosphates76

3.16.2 Hydrolysis of Polyphosphates76

3.16.3 Complexation by Polyphosphates76

3.16.4 Phosphonates77

3.17 Complexation by Humic Substances77

3.18 Complexation and Redox Processes79

Literature Cited79

Supplementary References79

Questions and Problems80

Chapter 4Oxidation-Reduction in Aquatic Chemistry83

4.1 The Significance of Oxidation-Reduction83

4.2 Electron and Redox Reactions85

4.3 Electron Activity and pE87

4.4 The Nernst equation88

4.5 Reaction Tendency: Whole Reaction from Half-Reactions89

4.6 The Nernst Equation and Chemical Equilibrium90

4.7 The Relationship of pE to Free Energy91

4.8 Reactions in Terms of One Electron-Mole91

4.9 The Limits of pE in Water93

4.10 pE Values in Natural Water Systems94

4.11 pE-pH Diagrams95

4.12 Humic Substances as Natural Reductants98

4.13 Photochemical Processes in Oxidation-Reduction99

4.14 Corrosion99

Literature Cited100

Supplementary References100

Questions and Problems101

Chapter 5Phase Interactions in Aquatic Chemistry103

5.1 Chemical Interactions Involving Solids, Gases, and Water103

5.2Importance and Formation of Sediments103

5.2.1 Formation of Sediments104

5.2.2 Organic and Carbonaceous Sedimentary Materials105

5.3Solubilities106

5.3.1 Solubilities of Solids106

5.3.2 Solubilities of Gases107

5.4Colloidal Particles in Water108

5.4.1 Contaminant Transport by Colloids in Water109

5.4.2 Occurrence of Colloids in Water109

5.4.3 Kinds of Colloidal Particles109

5.4.4 Colloid Stability110

5.5 Colloidal Properties of Clays112

5.6Aggregation of Particles113

5.6.1 Flocculation of Colloids by Polyelectrolytes114

5.6.2 Flocculation of Bacteria by Polymeric Materials114

5.7 Surface Sorption by Solids115

5.8Solute Exchange with Bottom Sediments116

5.8.1 Trace-Level Metals in Suspended Matter and Sediments117

5.8.2 Phosphorus Exchange with Bottom Sediments118

5.8.3 Organic Compounds on Sediments and Suspended Matter119

5.8.4 Bioavailability of Sediment Contaminants120

5.9 Interstitial Water121

5.10Phase Interactions in Chemical Fate and Transport122

5.10.1 Rivers122

5.10.2 Lakes and Reservoirs122

5.10.3 Exchange with the Atmosphere122

5.10.4 Exchange with Sediments123

Literature Cited124

Supplementary References124

Questions and Problems125

Chapter 6Aquatic Microbial Biochemistry127

6.1Aquatic Biochemical Processes127

6.1.1 Microorganisms at Interfaces128

6.2 Algae129

6.3 Fungi130

6.4 Protozoa130

6.5Bacteria131

6.5.1 Autotrophic and Heterotrophic Bacteria131

6.5.2 Oxic and Anoxic Bacteria132

6.5.3 Marine Bacteria132

6.6 The Prokaryotic Bacterial Cell133

6.7 Kinetics of Bacterial Growth134

6.8Bacterial Metabolism134

6.8.1 Factors Affecting Bacterial Metabolism135

6.8.2 Microbial Oxidation and Reduction137

6.9Microbial Transformations of Carbon139

6.9.1 Methane-Forming Bacteria139

6.9.2 Bacterial Utilization of Hydrocarbons140

6.9.3 Microbial Utilization of Carbon Monoxide140

6.10Biodegradation of Organic Matter140

6.10.1Oxidation141

6.10.1.1 Microbial Oxidation of Hydrocarbons141

6.10.2 Other Biochemical Processes in Biodegradation of Organics142

6.11Microbial Transformations of Nitrogen143

6.11.1 Nitrogen Fixation144

6.11.2 Nitrification145

6.11.3 Nitrate Reduction146

6.11.4 Denitrification146

6.11.5 Competitive Oxidation of Organic Matter by Nitrate Ion and Other Oxidizing Agents146

6.12Microbial Transformations of Phosphorus and Sulfur147

6.12.1 Phosphorus Compounds147

6.12.2Sulfur Compounds148

6.12.2.1 Oxidation of H2S and Reduction of Sulfate by Bacteria148

6.12.3 Microorganism-Mediated Degradation of Organic Sulfur Compounds149

6.13 Microbial Transformations of Halogens and Organohalides149

6.14Microbial Transformations of Metals and Metalloids150

6.14.1 Acid Mine Waters151

6.14.2 Microbial Transitions of Selenium152

6.14.3 Microbial Corrosion153

Literature Cited153

Supplementary References154

Questions and Problems154

Chapter 7Water Pollution159

7.1Nature and Types of Water Pollutants159

7.1.1 Markers of Water Pollution159

7.2 Elemental Pollutants159

7.3Heavy Metals161

7.3.1 Cadmium161

7.3.2 Lead161

7.3.3 Mercury162

7.4 Metalloids163

7.5Organically Bound Metals and Metalloids164

7.5.1 Organotin Compounds165

7.6Inorganic Species165

7.6.1 Cyanide165

7.6.2 Ammonia and Other Inorganic Pollutants166

7.6.3 Asbestos in Water167

7.7 Algal Nutrients and Eutrophication167

7.8 Acidity, Alkalinity, and Salinity168

7.9 Oxygen, Oxidants, and Reductants169

7.10Organic Pollutants170

7.10.1 Bioaccumulation of Organic Pollutants170

7.10.2 Sewage170

7.10.3Soaps, Detergents, and Detergent Builders171

7.10.3.1 Soaps171

7.10.3.2 Detergents172

7.10.4 Naturally Occurring Chlorinated and Brominated Compounds174

7.10.5 Microbial Toxins174

7.11Pesticides in Water175

7.11.1 Natural Product Insecticides, Pyrethrins, and Pyrethroids175

7.11.2 DDT and Organochlorine Insecticides177

7.11.3 Organophosphate Insecticides178

7.11.4 Carbamates179

7.11.5 Fungicides179

7.11.6Herbicides180

7.11.6.1 Bipyridilium Compounds180

7.11.6.2 Herbicidal Heterocyclic Nitrogen Compounds181

7.11.6.3 Chlorophenoxy Herbicides181

7.11.6.4 Miscellaneous Herbicides181

7.11.7 By-Products of Pesticide Manufacture182

7.12 Polychlorinated Biphenyls183

7.13Emerging Water Pollutants, Pharmaceuticals, and Household Wastes184

7.13.1 Bactericides186

7.13.2 Estrogenic Substances in Wastewater Effluents186

7.13.3 Biorefractory Organic Pollutants186

7.14 Radionuclides in the Aquatic Environment188

Literature Cited192

Supplementary References192

Questions and Problems193

Chapter 8Water Treatment197

8.1 Water Treatment and Water Use197

8.2 Municipal Water Treatment197

8.3 Treatment of Water for Industrial Use198

8.4Sewage Treatment199

8.4.1 Primary Waste Treatment199

8.4.2 Secondary Waste Treatment by Biological Processes200

8.4.3 Membrane Bioreactor203

8.4.4 Tertiary Waste Treatment203

8.4.5 Physical-Chemical Treatment of Municipal Wastewater203

8.5 Industrial Wastewater Treatment204

8.6Removal of Solids205

8.6.1 Dissolved Air Flotation206

8.6.2 Membrane Filtration Processes206

8.7Removal of Calcium and Other Metals207

8.7.1 Removal of Iron and Manganese211

8.8Removal of Dissolved Organics212

8.8.1 Removal of Herbicides213

8.9Removal of Dissolved Inorganics214

8.9.1 Ion Exchange214

8.9.2 Electrodialysis214

8.9.3 Reverse Osmosis215

8.9.4 Phosphorus Removal216

8.9.5 Nitrogen Removal217

8.10 Sludge218

8.11Water Disinfection219

8.11.1 Chlorine Dioxide220

8.11.2 Ozone and Other Oxidants221

8.11.3 Disinfection with Ultraviolet Radiation222

8.12Natural Water Purification Processes222

8.12.1 Industrial Wastewater Treatment by Soil223

8.13Green Water223

8.13.1 Reuse and Recycling of Wastewater224

8.14 Water Conservation226

8.15 Protecting Water Supplies from Attack227

Literature Cited228

Supplementary References228

Questions and Problems229

Chapter 9The Atmosphere and Atmospheric Chemistry233

9.1Introduction233

9.1.1 Photochemistry and Some Important Terms233

9.1.2 Atmospheric Composition234

9.1.3 Gaseous Oxides in the Atmosphere234

9.1.4 Atmospheric Methane235

9.1.5 Hydrocarbons and Photochemical Smog236

9.1.6 Particulate Matter236

9.1.7 Primary and Secondary Pollutants236

9.2 Importance of the Atmosphere236

9.3Physical Characteristics of the Atmosphere237

9.3.1 Variation of Pressure and Density with Altitude237

9.3.2 Stratification of the Atmosphere238

9.4Energy Transfer in the Atmosphere240

9.4.1 The Earth’s Radiation Budget241

9.5Atmospheric Mass Transfer, Meteorology, and Weather241

9.5.1 Atmospheric Water in Energy and Mass Transfer243

9.5.2 Air Masses243

9.5.3 Topographical Effects244

9.5.4 Movement of Air Masses244

9.5.5 Global Weather245

9.5.6 Weather Fronts and Storms246

9.6 Inversions and Air Pollution247

9.7Global Climate and Microclimate247

9.7.1 Atmospheric Carbon Dioxide and Human Modifications of Climate248

9.7.2 Microclimate248

9.7.3 Effects of Urbanization on Microclimate249

9.8Chemical and Photochemical Reactions in the Atmosphere249

9.8.1 Photochemical Processes251

9.8.2Ions and Radicals in the Atmosphere253

9.8.2.1 Free Radicals254

9.8.3 Hydroxyl and Hydroperoxyl Radicals in the Atmosphere254

9.8.4 Chemical and Biochemical Processes in Evolution of the Atmosphere256

9.9 Acid-Base Reactions in the Atmosphere257

9.10 Reactions of Atmospheric Oxygen258

9.11 Reactions of Atmospheric Nitrogen259

9.12 Atmospheric Water260

9.13 Influence of the Anthrosphere260

9.14 Chemical Fate and Transport in the Atmosphere261

Literature Cited262

Supplementary References262

Questions and Problems263

Chapter 10Particles in the Atmosphere265

10.1 Introduction265

10.2Physical Behavior of Particles in the Atmosphere266

10.2.1 Size and Settling of Atmospheric Particles267

10.3 Physical Processes for Particle Formation267

10.4Chemical Processes for Particle Formation268

10.4.1 Inorganic Particles269

10.4.2 Organic Particles270

10.4.3 Polycyclic Aromatic Hydrocarbon Synthesis270

10.5The Composition of Inorganic Particles271

10.5.1 Fly Ash272

10.5.2 Asbestos272

10.6Toxic Metals in the Atmosphere273

10.6.1 Atmospheric Mercury273

10.6.2 Atmospheric Lead273

10.6.3 Atmospheric Beryllium274

10.7 Radioactive Particles274

10.8The Composition of Organic Particles275

10.8.1 PAHs275

10.8.2 Carbonaceous Particles from Diesel Engines276

10.9Effects of Particles276

10.9.1 Partitioning of Semivolatile Organic Substances between Air and Particles277

10.10 Water as Particulate Matter277

10.11 Atmospheric Chemical Reactions Involving Particles278

10.12Control of Particulate Emissions280

10.12.1 Particle Removal by Sedimentation and Inertia280

10.12.2 Particle Filtration280

10.12.3 Scrubbers281

10.12.4 Electrostatic Removal282

Literature Cited282

Supplementary References283

Questions and Problems283

Chapter 11Gaseous Inorganic Air Pollutants285

11.1 Inorganic Pollutant Gases285

11.2Production and Control of Carbon Monoxide285

11.2.1 Control of Carbon Monoxide Emissions285

11.3 Fate of Atmospheric CO286

11.4 Sulfur Dioxide Sources and the Sulfur Cycle286

11.5Sulfur Dioxide Reactions in the Atmosphere287

11.5.1 Effects of Atmospheric Sulfur Dioxide289

11.5.2 Sulfur Dioxide Removal290

11.6Nitrogen Oxides in the Atmosphere292

11.6.1 Atmospheric Reactions of NO294

11.6.2 Harmful Effects of Nitrogen Oxides296

11.6.3 Control of Nitrogen Oxides297

11.7 Acid Rain299

11.8 Ammonia in the Atmosphere299

11.9Fluorine, Chlorine, and their Gaseous Compounds299

11.9.1 Chlorine and Hydrogen Chloride300

11.10 Reduced Sulfur Gases301

Literature Cited303

Supplementary References303

Questions And Problems304

Chapter 12Organic Air Pollutants307

12.1Organic Compounds in the Atmosphere307

12.1.1 Loss of Organic Substances from the Atmosphere307

12.1.2 Global Distillation and Fractionation of Persistent Organic Pollutants (POP)307

12.2Biogenic Organic Compounds308

12.2.1 Removal of Atmospheric Organic Compounds by Plants310

12.3Pollutant Hydrocarbons310

12.3.1 Aromatic Hydrocarbons313

12.3.2 Reactions of Atmospheric Aromatic Hydrocarbons314

12.4 Carbonyl Compounds: Aldehydes and Ketones315

12.5Miscellaneous Oxygen-Containing Compounds317

12.5.1 Alcohols317

12.5.2 Phenols318

12.5.3 Ethers318

12.5.4 Oxides319

12.5.5 Carboxylic Acids319

12.6 Organonitrogen Compounds320

12.7Organohalide Compounds322

12.7.1 Chlorofluorocarbons323

12.7.2 Atmospheric Reactions of Hydrofluorocarbons and Hydrochlorofluorocarbons324

12.7.3 Perfluorocarbons325

12.7.4 Marine Sources of Organohalogen Compounds325

12.7.5 Chlorinated Dibenzo-p-dioxins and Dibenzofurans325

12.8 Organosulfur Compounds326

12.9 Organic Particulate Matter327

12.10 Hazardous Air Pollutants Organic Compounds327

Literature Cited329

Supplementary References330

Questions and Problems330

Chapter 13Photochemical Smog333

13.1 Introduction333

13.2Smog-Forming Emissions334

13.2.1 Control of Exhaust Hydrocarbons334

13.2.2 Automotive Emission Standards337

13.2.3 Polluting Green Plants337

13.3Smog-Forming Reactions of Organic Compounds in the Atmosphere338

13.3.1 Photochemical Reactions of Methane338

13.4 Overview of Smog Formation340

13.5Mechanisms of Smog Formation341

13.5.1 Nitrate Radical347

13.5.2 Photolyzable Compounds in the Atmosphere347

13.6 Reactivity of Hydrocarbons348

13.7 Inorganic Products from Smog348

13.8 Effects of Smog349

Literature Cited352

Supplementary References352

Questions and Problems353

Chapter 14 The Endangered Global Atmosphere355

14.1Climate Change and Anthropogenic Effects355

14.1.1 Changes in Climate356

14.2Global Warming357

14.2.1 Methane and Other Greenhouse Gases360

14.2.2 Particles and Global Warming360

14.2.3 The Outlook for Global Warming and Associated Effects361

14.3Green Science and Technology to Alleviate Global Warming361

14.3.1 Minimization362

14.3.2 Counteracting Measures364

14.3.3 Adaptation364

14.4 Acid Rain365

14.5Stratospheric Ozone Destruction368

14.5.1 Shielding Effect of the Ozone Layer369

14.5.2 Ozone Layer Destruction369

14.5.3 Green Chemistry Solutions to Stratospheric Ozone Depletion372

14.6Atmospheric Brown Clouds373

14.6.1 Yellow Dust374

14.7 Atmospheric Damage by Photochemical Smog375

14.8Nuclear Winter377

14.8.1 Doomsday Visitors from Space379

14.9 What Is to Be Done?379

Literature Cited381

Supplementary References381

Questions and Problems382

Chapter 15 The Geosphere and Geochemistry385

15.1Introduction385

15.2The Nature of Solids in the Geosphere386

15.2.1 Structure and Properties of Minerals386

15.2.2 Kinds of Minerals387

15.2.3 Evaporites387

15.2.4 Volcanic Sublimates388

15.2.5Igneous, Sedimentary, and Metamorphic Rock388

15.2.5.1 Rock Cycle389

15.2.5.2 Stages of Weathering389

15.3Physical Form of the Geosphere389

15.3.1 Plate Tectonics and Continental Drift390

15.3.2 Structural Geology390

15.4Internal Processes391

15.4.1 Earthquakes392

15.4.2 Volcanoes392

15.4.3 Surface Processes393

15.5 Sediments393

15.6 Clays394

15.7Geochemistry395

15.7.1 Physical Aspects of Weathering396

15.7.2 Chemical Weathering396

15.7.3 Biological Aspects of Weathering397

15.8Groundwater in the Geosphere397

15.8.1 Water Wells399

15.8.2 Qanats400

15.9Environmental Aspects of the Geosphere400

15.9.1 Natural Hazards401

15.9.2 Anthropogenic Hazards401

15.10 Earthquakes401

15.11Volcanoes403

15.11.1 Mud Volcanoes404

15.12 Surface Earth Movement404

15.13 Stream and River Phenomena406

15.14Phenomena at the Land/Ocean Interface407

15.14.1 The Threat of Rising Sea Levels408

15.15 Phenomena at the Land/Atmosphere Interface409

15.16 Effects of Ice409

15.17Effects of Human Activities410

15.17.1 Extraction of Geospheric Resources: Surface Mining411

15.17.2 Environmental Effects of Mining and Mineral Extraction411

15.18 Air Pollution and the Geosphere411

15.19 Water Pollution and the Geosphere412

15.20Waste Disposal and the Geosphere413

15.20.1 Municipal Refuse413

Literature Cited415

Supplementary References415

Questions and Problems416

Chapter 16 Soil and Agricultural Environmental Chemistry419

16.1Soil and Agriculture419

16.1.1 Agriculture419

16.1.2 Pesticides and Agriculture421

16.2Nature and Composition of Soil421

16.2.1 Water and Air in Soil422

16.2.2 The Inorganic Components of Soil424

16.2.3 Organic Matter in Soil424

16.2.4 Soil Humus426

16.2.5 The Soil Solution426

16.3Acid-Base and Ion-Exchange Reactions in Soils427

16.3.1 Adjustment of Soil Acidity428

16.3.2 Ion-Exchange Equilibria in Soil428

16.4 Macronutrients in Soil429

16.5Nitrogen, Phosphorus, and Potassium in Soil430

16.5.1 Nitrogen430

16.5.2 Phosphorus432

16.5.3 Potassium433

16.6 Micronutrients in Soil433

16.7Fertilizers434

16.7.1 Fertilizer Pollution435

16.8 Pollutants from Livestock Production436

16.9Pesticides and Their Residues in Soil436

16.9.1 Soil Fumigants437

16.10Wastes and Pollutants in Soil438

16.10.1 Biodegradation and the Rhizosphere440

16.11Soil Loss and Degradation440

16.11.1 Soil Sustainability and Water Resources441

16.12Saving the Land442

16.12.1 Agroforestry443

16.12.2 Soil Restoration443

16.13 Genetic Engineering and Agriculture444

16.14 Green Chemistry and Sustainable Agriculture445

16.15Agriculture and Health447

16.15.1 Food Contamination448

16.16 Protecting the Food Supply from Attack448

Literature Cited449

Supplementary References449

Questions and Problems450

Chapter 17 Green Chemistry and Industrial Ecology453

17.1Changing the Bad Old Ways453

17.2Green Chemistry454

17.2.1 Twelve Principles of Green Chemistry454

17.3Reduction of Risk: Hazard and Exposure456

17.3.1 The Risks of Not Taking Risks458

17.4 Waste Prevention and Green Chemistry458

17.5Green Chemistry and Synthetic Chemistry459

17.5.1 Yield and Atom Economy459

17.6Feedstocks461

17.6.1 Biological Feedstocks461

17.7 Reagents463

17.8 Stoichiometric and Catalytic Reagents464

17.9Media and Solvents465

17.9.1 Water, the Greenest Solvent466

17.9.2 Dense Phase Carbon Dioxide as a Solvent467

17.9.3 Gas-Expanded Solvents468

17.10 Enhancing Reactions468

17.11 Industrial Ecology470

17.12 The Five Major Components of an Industrial Ecosystem472

17.13 Industrial Metabolism474

17.14 Materials Flow and Recycling in an Industrial Ecosystem475

17.15 The Kalundborg Industrial Ecosystem475

17.16 Consideration of Environmental Impacts in Industrial Ecology476

17.17Life Cycles: Expanding and Closing the Materials Loop477

17.17.1 Product Stewardship479

17.17.2 Embedded Utility479

17.18Life-Cycle Assessment480

17.18.1 Scoping in Life-Cycle Assessment480

17.19Consumable, Recyclable, and Service (Durable) Products481

17.19.1 Desirable Characteristics of Consumables481

17.19.2 Desirable Characteristics of Recyclables481

17.19.3 Desirable Characteristics of Service Products482

17.20Design for Environment482

17.20.1 Products, Processes, and Facilities483

17.20.2 Key Factors in Design for Environment483

17.20.3 Hazardous Materials in Design for Environment484

17.21Inherent Safety484

17.21.1 Increased Safety with Smaller Size485

17.22 Industrial Ecology and Ecological Engineering486

Literature Cited486

Supplementary References486

Questions and Problems488

Chapter 18Resources and Sustainable Materials491

18.1 Where to Get the Stuff We Need?491

18.2Minerals in the Geosphere492

18.2.1 Evaluation of Mineral Resources492

18.3 Extraction and Mining493

18.4 Metals494

18.5Metal Resources and Industrial Ecology496

18.5.1 Aluminum497

18.5.2 Chromium497

18.5.3 Copper498

18.5.4 Cobalt498

18.5.5 Lead498

18.5.6 Lithium498

18.5.7 Potassium499

18.5.8 Zinc500

18.6 Nonmetal Mineral Resources500

18.7 Phosphates501

18.8Sulfur502

18.8.1 Gypsum503

18.9 Wood: A Major Renewable Resource503

18.10Extending Resources through the Practice of Industrial Ecology504

18.10.1 Metals504

18.10.2 Plastics and Rubber505

18.10.3 Lubricating Oil506

Literature Cited506

Supplementary References506

Questions and Problems507

Chapter 19Sustainable Energy: The Key to Everything509

19.1 Energy Problem509

19.2 Nature of Energy510

19.3 Sources of Energy Used in the Anthrosphere511

19.4Energy Devices and Conversions513

19.4.1 Fuel Cells516

19.5 Green Technology and Energy Conversion Efficiency517

19.6 Energy Conservation and Renewable Energy Sources518

19.7 Petroleum and Natural Gas520

19.8Coal521

19.8.1 Coal Conversion521

19.9 Carbon Sequestration for Fossil Fuel Utilization523

19.10 Industrial Ecology for Energy and Chemicals524

19.11Nuclear Energy526

19.11.1 Nuclear Fusion528

19.12 Geothermal Energy528

19.13 The Sun: An Ideal, Renewable Energy Source529

19.14Energy from Moving Air and Moving Water531

19.14.1 Surprising Success of Wind Power531

19.14.2 Energy from Moving Water533

19.14.3 Energy from Moving Water without Dams534

19.15Biomass Energy534

19.15.1 Ethanol Fuel535

19.15.2 Biodiesel Fuel535

19.15.3 Unrealized Potential of Lignocellulose Fuels536

19.15.4 Biogas539

19.16 Hydrogen as a Means to Store and Utilize Energy540

19.17 Combined Power Cycles540

19.18 A System of Industrial Ecology for Methane Production541

Literature Cited542

Supplementary References542

Questions and Problems543

Chapter 20 Nature, Sources, and Environmental Chemistry of Hazardous Wastes545

20.1Introduction545

20.1.1 History of Hazardous Substances545

20.1.2 Legislation546

20.2Classification of Hazardous Substances and Wastes547

20.2.1 Characteristics and Listed Wastes547

20.2.2Hazardous Wastes548

20.2.2.1 Hazardous Wastes and Air and Water Pollution Control548

20.3Sources of Wastes549

20.3.1 Types of Hazardous Wastes550

20.3.2 Hazardous Waste Generators550

20.4Flammable and Combustible Substances551

20.4.1 Combustion of Finely Divided Particles552

20.4.2 Oxidizers552

20.4.3 Spontaneous Ignition553

20.4.4 Toxic Products of Combustion553

20.5Reactive Substances553

20.5.1 Chemical Structure and Reactivity554

20.6Corrosive Substances555

20.6.1 Sulfuric Acid556

20.7Toxic Substances556

20.7.1 Toxicity Characteristic Leaching Procedure556

20.8 Physical Forms and Segregation of Wastes557

20.9 Environmental Chemistry of Hazardous Wastes558

20.10 Physical and Chemical Properties of Hazardous Wastes559

20.11Transport, Effects, and Fates of Hazardous Wastes559

20.11.1 Physical Properties of Wastes560

20.11.2 Chemical Factors560

20.11.3 Effects of Hazardous Wastes560

20.11.4 Fates of Hazardous Wastes561

20.12 Hazardous Wastes and the Anthrosphere561

20.13 Hazardous Wastes in the Geosphere562

20.14 Hazardous Wastes in the Hydrosphere564

20.15 Hazardous Wastes in the Atmosphere566

20.16Hazardous Wastes in the Biosphere567

20.16.1 Microbial Metabolism in Waste Degradation567

20.16.2 Ecotoxicology of Hazardous Wastes568

20.17Hazardous Substances in Terrorism569

20.17.1 Detection of Hazardous Substances570

20.17.2 Removing Hazardous Agents571

Literature Cited571

Supplementary References572

Questions and Problems572

Chapter 21Industrial Ecology for Waste Minimization, Utilization, and Treatment575

21.1 Introduction575

21.2 Waste Reduction and Minimization575

21.3Recycling577

21.3.1 Examples of Recycling578

21.3.2Waste Oil Utilization and Recovery578

21.3.2.1 Recycling Waste Oil578

21.3.2.2 Waste Oil Fuel579

21.3.3 Waste Solvent Recovery and Recycle579

21.3.4 Recovery of Water from Wastewater580

21.4Physical Methods of Waste Treatment580

21.4.1Methods of Physical Treatment581

21.4.1.1 Phase Separations582

21.4.1.2 Phase Transition582

21.4.1.3 Phase Transfer583

21.4.1.4 Molecular Separation584

21.5Chemical Treatment: An Overview584

21.5.1Acid-Base Neutralization584

21.5.1.1 Acid Recovery584

21.5.2Chemical Precipitation585

21.5.2.1 Precipitation of Metals585

21.5.2.2 Coprecipitation of Metals586

21.5.3 Oxidation-Reduction586

21.5.4 Electrolysis587

21.5.5 Hydrolysis588

21.5.6 Chemical Extraction and Leaching588

21.5.7 Ion Exchange589

21.6 Green Waste Treatment by Photolyis and Sonolysis589

21.7Thermal Treatment Methods590

21.7.1Incineration591

21.7.1.1 Incinerable Wastes591

21.7.2 Hazardous Waste Fuel591

21.7.3 Incineration Systems591

21.7.4 Types of Incinerators592

21.7.5 Combustion Conditions592

21.7.6 Effectiveness of Incineration593

21.7.7 Wet Air Oxidation593

21.7.8 UV-Enhanced Wet Oxidation593

21.7.9 Destruction of Hazardous Wastes in Cement Manufacture593

21.8Biodegradation of Wastes594

21.8.1 Biodegradability594

21.8.2 Aerobic Treatment595

21.8.3 Anaerobic Treatment595

21.8.4 Reductive Dehalogenation595

21.9 Phytoremediation596

21.10Land Treatment and Composting596

21.10.1 Land Treatment596

21.10.2 Composting597

21.11Preparation of Wastes for Disposal597

21.11.1 Immobilization597

21.11.2 Stabilization597

21.11.3Solidification597

21.11.3.1 Sorption to a Solid Matrix Material598

21.11.3.2 Thermoplastics and Organic Polymers598

21.11.3.3 Vitrification598

21.11.3.4 Solidification with Cement599

21.11.3.5 Solidification with Silicate Materials599

21.11.3.6 Encapsulation599

21.11.4 Chemical Fixation599

21.12Ultimate Disposal of Wastes600

21.12.1 Disposal Aboveground600

21.12.2 Landfill600

21.12.3 Surface Impoundment of Liquids601

21.12.4 Deep-Well Disposal of Liquids601

21.13Leachate and Gas Emissions601

21.13.1 Leachate601

21.13.2 Hazardous Waste Leachate Treatment602

21.13.3 Gas Emissions602

21.14In Situ Treatment602

21.14.1 In Situ Immobilization602

21.14.2 Vapor Extraction603

21.14.3 Solidification In Situ603

21.14.4 Detoxification In Situ603

21.14.5 Permeable Bed Treatment603

21.14.6 In Situ Thermal Processes604

21.14.7 Soil Washing and Flushing604

Literature Cited604

Supplementary References605

Questions and Problems606

Chapter 22Environmental Biochemistry609

22.1Biochemistry609

22.1.1 Biomolecules609

22.2Biochemistry and the Cell610

22.2.1 Major Cell Features610

22.3Proteins611

22.3.1 Protein Structure613

22.3.2 Denaturation of Proteins614

22.4 Carbohydrates614

22.5 Lipids616

22.6 Enzymes618

22.7Nucleic Acids620

22.7.1 Nucleic Acids in Protein Synthesis623

22.7.2 Modified DNA623

22.8 Recombinant DNA and Genetic Engineering623

22.9Metabolic Processes624

22.9.1 Energy-Yielding Processes624

22.10Metabolism of Xenobiotic Compounds625

22.10.1 Phase Ⅰ and Phase Ⅱ Reactions625

Literature Cited626

Supplementary References626

Questions and Problems626

Chapter 23 Toxicological Chemistry629

23.1Introduction to Toxicology and Toxicological Chemistry629

23.1.1 Toxicology629

23.1.2 Synergism, Potentiation, and Antagonism631

23.2 Dose-Response Relationships631

23.3Relative Toxicities632

23.3.1 Nonlethal Effects632

23.4Reversibility and Sensitivity634

23.4.1 Hypersensitivity and Hyposensitivity634

23.5 Xenobiotic and Endogenous Substances634

23.6Toxicological Chemistry635

23.6.1 Toxicological Chemistry Defined635

23.6.2Toxicants in the Body635

23.6.2.1 Phase Ⅰ Reactions635

23.6.2.2 Phase Ⅱ Reactions636

23.7Kinetic Phase and Dynamic Phase637

23.7.1 Kinetic Phase637

23.7.2Dynamic Phase637

23.7.2.1 Primary Reaction in the Dynamic Phase637

23.7.2.2 Biochemical Effects in the Dynamic Phase638

23.7.2.3 Responses to Toxicants639

23.8Teratogenesis, Mutagenesis, Carcinogenesis, and Effects On the Immune and Reproductive Systems639

23.8.1 Teratogenesis639

23.8.2Mutagenesis639

23.8.2.1 Biochemistry of Mutagenesis640

23.8.3Carcinogenesis641

23.8.3.1 Biochemistry of Carcinogenesis642

23.8.3.2 Alkylating Agents in Carcinogenesis642

23.8.4Testing for Carcinogens643

23.8.4.1 Bruce Ames Test644

23.8.5 Immune System Response644

23.8.6 Endocrine Disruption644

23.9Health Hazards644

23.9.1 Assessment of Potential Exposure645

23.9.2 Epidemiological Evidence645

23.9.3 Estimation of Health Effects Risks646

23.9.4 Risk Assessment646

Literature Cited646

Supplementary References646

Questions and Problems647

Chapter 24Toxicological Chemistry of Chemical Substances649

24.1Introduction649

24.1.1 ATSDR Toxicological Profiles649

24.2Toxic Elements and Elemental Forms649

24.2.1 Ozone649

24.2.2 White Phosphorus651

24.2.3 Elemental Halogens651

24.2.4 Heavy Metals651

24.3Toxic Inorganic Compounds652

24.3.1 Cyanide652

24.3.2 Carbon Monoxide652

24.3.3 Nitrogen Oxides653

24.3.4Hydrogen Halides653

24.3.4.1 Hydrogen Fluoride653

24.3.4.2 Hydrogen Chloride654

24.3.5 Interhalogen Compounds and Halogen Oxides654

24.3.6 Inorganic Compounds of Silicon654

24.3.7 Asbestos655

24.3.8 Inorganic Phosphorus Compounds655

24.3.9 Inorganic Compounds of Sulfur655

24.3.10 Perchlorate656

24.3.11Organometallic Compounds656

24.3.11.1 Organolead Compounds656

24.3.11.2 Organotin Compounds657

24.3.11.3 Carbonyls657

24.3.11.4 Reaction Products of Organometallic Compounds657

24.4Toxicology of Organic Compounds657

24.4.1 Alkane Hydrocarbons657

24.4.2 Alkene and Alkyne Hydrocarbons658

24.4.3Benzene and Aromatic Hydrocarbons658

24.4.3.1 Toluene659

24.4.3.2 Naphthalene659

24.4.3.3 Polycyclic Aromatic Hydrocarbons659

24.4.4Oxygen-Containing Organic Compounds660

24.4.4.1 Oxides660

24.4.4.2 Alcohols660

24.4.5Phenols661

24.4.5.1 Aldehydes and Ketones661

24.4.5.2 Carboxylic Acids662

24.4.5.3 Ethers662

24.4.5.4 Acid Anhydrides662

24.4.5.5 Esters662

24.4.6Organonitrogen Compounds663

24.4.6.1 Aliphatic Amines663

24.4.6.2 Carbocyclic Aromatic Amines664

24.4.6.3 Pyridine664

24.4.6.4 Acrylamide: Toxic Potato Chips?664

24.4.6.5 Nitriles665

24.4.6.6 Nitro Compounds665

24.4.6.7 Nitrosamines665

24.4.6.8 Isocyanates and Methyl Isocyanate665

24.4.6.9 Organonitrogen Pesticides665

24.4.7Organohalide Compounds666

24.4.7.1 Alkyl Halides666

24.4.7.2 Alkenyl Halides667

24.4.7.3 Aryl Halides667

24.4.8Organohalide Pesticides668

24.4.8.1 TCDD668

24.4.8.2 Chlorinated Phenols669

24.4.9Organosulfur Compounds669

24.4.9.1 Sulfur Mustards669

24.4.10Organophosphorus Compounds670

24.4.10.1 Organophosphate Esters670

24.4.10.2 Phosphorothionate and Phosphorodithioate Ester Insecticides670

24.4.10.3 Organophosphorus Military Poisons671

24.5 Toxic Natural Products671

Literature Cited672

Supplementary References672

Questions and Problems673

Chapter 25Chemical Analysis of Water and Wastewater677

25.1General Aspects of Environmental Chemical Analysis677

25.1.1 Error and Quality Control677

25.1.2 Water Analysis Methods678

25.2 Classical Methods678

25.3Spectrophotometric Methods679

25.3.1 Absorption Spectrophotometry679

25.3.2 Atomic Absorption and Emission Analyses680

25.3.3 Atomic Emission Techniques682

25.4 Electrochemical Methods of Analysis682

25.5Chromatography683

25.5.1 High-Performance Liquid Chromatography685

25.5.2 Chromatographic Analysis of Water Pollutants686

25.5.3 Ion Chromatography686

25.6 Mass Spectrometry686

25.7Analysis of Water Samples687

25.7.1 Physical Properties Measured in Water687

25.7.2Water Sampling687

25.7.2.1 Extractors688

25.7.3 Water Sample Preservation689

25.7.4 Total Organic Carbon in Water689

25.7.5 Measurement of Radioactivity in Water690

25.7.6 Biological Toxins690

25.7.7 Summary of Water Analysis Procedures690

25.8 Automated Water Analyses692

25.9 Speciation692

25.10 Emerging Contaminants in Water Analysis693

25.11 Chiral Contaminants694

Literature Cited695

Supplementary References695

Questions and Problems696

Chapter 26 Analysis of Wastes and Solids697

26.1Introduction697

26.2 Sample Digestion for Elemental Analysis698

26.3Analyte Isolation for Organics Analysis698

26.3.1 Solvent Extraction698

26.3.2 Supercritical Fluid Extraction699

26.3.3 Pressurized Liquid Extraction and Subcritical Water Extraction699

26.4 Sample Cleanup700

26.5 Sample Preparation for VOCs701

26.6 Bioassay and Immunoassay Screening of Wastes702

26.7 Determination of Chelating Agents702

26.8 Toxicity Characteristic Leaching Procedure703

Literature Cited704

Supplementary References704

Questions and Problems705

Chapter 27 Analysis of the Atmosphere and Air Pollutants707

27.1Atmospheric Monitoring707

27.1.1 Air Pollutants Measured707

27.2 Sampling708

27.3 Methods of Analysis709

27.4 Determination of Sulfur Dioxide710

27.5 Nitrogen Oxides711

27.6 Analysis of Oxidants712

27.7 Analysis of Carbon Monoxide713

27.8Determination of Hydrocarbons and Organics714

27.8.1 Determination of Specific Organics in the Atmosphere714

27.9Analysis of Particulate Matter714

27.9.1 Filtration714

27.9.2 Collection by Impactors716

27.9.3 Particle Analysis716

27.9.4 X-Ray Fluorescence716

27.9.5 Determination of Lead in Particulate Matter717

27.10 Direct Spec trophotometric Analysis of Gaseous Air Pollutants718

Literature Cited719

Supplementary References720

Questions and Problems720

Chapter 28Analysis of Biological Materials and Xenobiotics723

28.1 Introduction723

28.2 Indicators of Exposure to Xenobiotics723

28.3Determination of Metals725

28.3.1 Direct Analysis of Metals725

28.3.2 Metals in Wet-Ashed Blood and Urine725

28.3.3 Extraction of Metals for Atomic Absorption Analysis725

28.4 Determination of Nonmetals and Inorganic Compounds726

28.5 Determination of Parent Organic Compounds726

28.6Measurement of Phase Ⅰ and Phase Ⅱ Reaction Products727

28.6.1 Phase Ⅰ Reaction Products727

28.6.2 Phase Ⅱ Reaction Products728

28.6.3 Mercapturates729

28.7 Determination of Adducts729

28.8 The Promise of Immunological Methods730

Literature Cited732

Supplementary References732

Questions and Problems733

Index735

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