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Page 1: Chemistry of the environment - uscibooks.com · Chemistry of the environment / Thomas G. Spiro, Kathleen Purvis-Roberts, William M. Stigliani ; foreword by Harry Gray. — 3rd ed

Chemistry of the environment

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Page 3: Chemistry of the environment - uscibooks.com · Chemistry of the environment / Thomas G. Spiro, Kathleen Purvis-Roberts, William M. Stigliani ; foreword by Harry Gray. — 3rd ed

Chemistry of the environmentthird edition

thomas G. spiro

Kathleen L. Purvis-roberts

William m. stigliani

University sCienCe BooKs

www.uscibooks.com

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Page 4: Chemistry of the environment - uscibooks.com · Chemistry of the environment / Thomas G. Spiro, Kathleen Purvis-Roberts, William M. Stigliani ; foreword by Harry Gray. — 3rd ed

University Science Bookswww.uscibooks.com

Production Manager: Mark OngManuscript Editor: Jeannette Stiefel Illustrator: Laurel MullerBook and Cover Design: Yvonne Tsang Compositor: Asco TypesettersPrinter & Binder: Transcontinental

Copyright ©2012 by University Science Books

This book is printed on acid-free paper.

Reproduction or translation of any part of this work beyond that permitted by Section 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful. Requests for permission or further information should be addressed to the Permissions Department, University Science Books.

Library of Congress Cataloging-in-Publication Data

Spiro, Thomas G., 1935– Chemistry of the environment / Thomas G. Spiro, Kathleen Purvis-Roberts, William M. Stigliani ; foreword by Harry Gray. — 3rd ed. p. cm. ISBN 978-1-891389-70-2 (alk. paper) 1. Environmental chemistry. I. Purvis-Roberts, Kathleen. II. Stigliani, William M. III. Title. TD193.S7 2012 540—dc23 2011013139

Printed in North America10 9 8 7 6 5 4 3 2 1

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Page 5: Chemistry of the environment - uscibooks.com · Chemistry of the environment / Thomas G. Spiro, Kathleen Purvis-Roberts, William M. Stigliani ; foreword by Harry Gray. — 3rd ed

Dedicated to our children and grandchildren, and their generations.

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Page 7: Chemistry of the environment - uscibooks.com · Chemistry of the environment / Thomas G. Spiro, Kathleen Purvis-Roberts, William M. Stigliani ; foreword by Harry Gray. — 3rd ed

Contents in Brief

Foreword xviiPreface xix

Part i. sustainaBility and Green Chemistry 1

Chapter 1. Sustainability and Chemistry 3Chapter 2. Green Chemistry 11

Part ii. atmosPhere 21

Chapter 3. Air Pollution 23Chapter 4. Nitrogen Oxides, Ozone, and Gasoline 49Chapter 5. Stratospheric Ozone Shield 77Chapter 6. Climate Change 105

Part iii. enerGy and materials 155

Chapter 7. Energy Flows and Supplies 157Chapter 8. Fossil Fuels 169Chapter 9. Nuclear Energy 205Chapter 10. Renewable Energy 245Chapter 11. Energy Utilization 279

Part iV. hydrosPhere and lithosPhere 329

Chapter 12. Water Resources 331Chapter 13. Water as Solvent: Acids and Bases 349Chapter 14. Water and Lithosphere 369

vii

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viii Contents in Brief

Chapter 15. Oxygen and Life 399Chapter 16. Water Pollution and Treatment 435

Part V. BiosPhere 457

Chapter 17. Nitrogen and Food Production 459Chapter 18. Pest Control 491Chapter 19. Toxicity of Chemicals 523

Appendix A: Organic Structures 579Appendix B: Mathematical Fundamentals 589Index 595

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Contents

Foreword xviiPreface xix

Part i. sustainaBility and Green

Chemistry 1

Chapter 1. sustainability and Chemistry 3

1.1 What Is Sustainability? 31.2 From Environmentalism to Sustainability 41.3 Sustainability Connections among

Environmental Spheres 61.4 Applying Sustainability 7Additional Reading 8

Chapter 2. Green Chemistry 11

2.1 Sustainable Living through Chemistry 112.2 Green Chemistry Principles 122.3 Green Chemistry Examples 13

2.3a Eliminating Chlorofluorocarbons 132.3b Greener Solvents: Liquid and

Supercritical Carbon Dioxide 132.3b.i Dry Cleaning 142.3b.ii Cleaning Computer Chips 14

2.3c Biomass Plastics 142.3c.i Polylactic Acid 152.3c.ii Cellulose 152.3c.iii Paint 16

2.3d Replacing Chlorine 162.3e Biodegradable Chelating Agent 17

2.3f Reducing Toxic Metals 172.3f.i Yttrium Replaces Lead in

Automobile Coatings 172.3f.ii Removing Arsenic and

Chromium from Pressure-Treated Wood 18

2.3g Atom Economy: Reducing Waste in Ibuprofen Manufacture 18

2.3h Materials Substitution: Recyclable Carpet 18

2.3i Environmentally Benign Pesticides 19Problems 20Additional Reading 20

Part ii. atmosPhere 21

Chapter 3. air Pollution 23

3.1 Pollutants and Their Effects 233.2 Carbon Monoxide 243.3 Sulfur Dioxide 27

3.3a Sulfur Dioxide Emission Controls 283.4 Toxic Organics 29

3.4a Formaldehyde and Acetaldehyde 293.4b Benzene 313.4c Polycyclic Aromatic Hydrocarbons 32

3.5 Particulate Matter 323.6 Nitrogen Oxides and Volatile Organics 363.7 Ozone and Other Oxidants 37

3.7a Control of Ozone Precursors 38

ix

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x Contents

3.8 Indoor Air Pollution 42Problems 45Additional Reading 46

Chapter 4. nitrogen oxides, ozone, and

Gasoline 49

4.1 Aerobic Earth 494.2 Nitrogen Oxides: Free Energy 50

4.2a Free Energy and Equilibrium 50Worked Problem 4.1: Atmospheric NO Concentration 52

4.2b Free Energy and Temperature 52Worked Problem 4.2: High-Temperature NO 53

4.3 Nitrogen Oxides: Kinetics 534.4 Free Radical Chain Reactions 564.5 Photochemistry 574.6 Photochemical Smog 59

4.6a Smog Photochemistry 594.6b The C   H Bond Strengths and

Photochemical Activity 614.6c Role of Olefins 644.6d Atmospheric Reactions of Organic

Radicals 644.6e Additional Smog Contributions 66

4.7 Gasoline and Its Formulations 674.7a Knocking and Octane 674.7b Diesels and Cetane 694.7c Lead in Gasoline 704.7d Reformulated Gasoline 71

Problems 73Additional Reading 74

Chapter 5. stratospheric ozone shield 77

5.1 Overview 775.2 Structure of the Atmosphere 79

Worked Problem 5.1: How Much Ozone? 825.3 Ultraviolet Radiation Damage 83

5.3a Transmission of UV Light through Ozone 85

5.4 Reactions that Create and Destroy Stratospheric Ozone 865.4a Calculating the Ozone Steady State 87

5.5 Catalytic Destruction of Ozone 905.5a Hydroxyl Radical 915.5b Chlorine and Bromine 915.5c Nitric Oxide 935.5d Summary of Ozone Destruction

Chemistry 945.6 Polar Ozone Destruction 955.7 Ozone Projections 985.8 The Chlorofluorocarbon Substitutes 98Problems 101Additional Reading 102

Chapter 6. Climate Change 105

6.1 Overview 1056.2 Energy Flows 1056.3 Radiation Balance and the Greenhouse

Effect 107Worked Problem 6.1: Human Energy and Earth’s Temperature 110

6.4 Infrared Absorption by Greenhouse Gases: Molecular Vibrations 111Worked Problem 6.2: Beer–Lambert Law and CO2 Saturation 114

6.5 Water: Positive Feedback, Latent Heat, and Energy Flows 115Worked Problem 6.3: Energy in Rain 116

6.6 Greenhouse Computations: Radiative Forcing 117

6.7 Carbon Dioxide and the Carbon Cycle 1206.8 Reservoirs, Flows, and Residence Times 125

Worked Problem 6.4: Carbon Residence Time 125

6.9 Other Greenhouse Gases 1266.10 Albedo, Particles, and Clouds 129

6.10a Raindrops and Condensation Nuclei 131Worked Problem 6.5: Cloud Seeding 133

6.10b Aerosol Particles 133Worked Problem 6.6: Volcanic Cooling 135

6.10c Sulfur Cycle 1366.10d Black Carbon 138

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6.11 Geoengineering to Raise the Albedo 1406.12 Climate Modeling 1406.13 Global Warming Impacts 1456.14 International Agreements 146Problems 150Additional Reading 152

Part iii. enerGy and materials 155

Chapter 7. energy flows and supplies 157

7.1 Human Energy Consumption 1577.2 Exponential Growth 160

Worked Problem 7.1: World Energy Consumption 162

7.3 Human Energy Sources 163Problems 167Additional Reading 167

Chapter 8. fossil fuels 169

8.1 Closing the Carbon Cycle 169Worked Problem 8.1: Will We Run Out of Oxygen? 171

8.2 Origins of Fossil Fuels 1728.2a Petroleum and Natural Gas 1728.2b Coal 174

8.3 Fuel Energy 1748.3a Hydrogen Combustion and Bond

Enthalpies 1748.3b Comparison of Fuel Energies 177

Worked Problem 8.2: Methane Combustion 179

8.4 Petroleum 1808.4a Composition and Refining 1808.4b Advantages 1828.4c Disadvantages 182

8.4c.i Oil Spills 1828.4c.ii Carbon Dioxide Emissions 188

8.4d When Will the Oil Run Out? 1888.5 Gas 190

8.5a Advantages 1918.5b Disadvantages 1918.5c When Will the Gas Run Out? 192

8.6 Coal 1938.6a Advantages 194

8.6b Disadvantages 1958.6c When Will the Coal Run Out? 197

8.7 Coal-Derived Fuels 1978.8 Carbon Capture and Storage 199

8.8a Capture 1998.8b Geological Storage 2008.8c Biological Storage 202

Problems 203Additional Reading 204

Chapter 9. nuclear energy 205

9.1 Curve of Binding Energy 2059.2 Nuclei, Isotopes, and Radioactivity 2069.3 Half-Lives and Naturally Occurring

Radioisotopes 209Worked Problem 9.1: Radiocarbon Dating 210

9.4 Decay Chains: The Radon Problem 2119.5 Radioactivity: Biological Effects of Ionizing

Radiation 2139.5a Alpha Rays 2149.5b Beta and Gamma Rays, and Neutrons 215

9.6 Radiation Exposure 215Worked Problem 9.2: Radon Exposure 219

9.7 Power from Fission 2199.7a Fission Reactors 2219.7b Isotope Separation 2239.7c Breeder Reactor 2249.7d Reprocessing 225

9.8 Hazards of Nuclear Power 2269.8a Reactor Safety 2269.8b Weapons Proliferation 2299.8c Nuclear Waste Disposal 2319.8d New Reactor Designs and the Thorium

Fuel Cycle 2339.9 The Future of Nuclear Power 2369.10 Fusion 237

9.10a Fusion Reactions 2379.10b Inertial Confinement 2399.10c Magnetic Confinement 2409.10d Is Fusion the Energy Source of the

Future? 242Problems 242Additional Reading 243

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xii Contents

Chapter 10. renewable energy 245

10.1 Forms of Renewable Energy 24510.2 Solar Heating 24710.3 Solar Electricity 248

10.3a Solar Thermal Electricity and Solar Chemical Processing 248

10.3b Photovoltaic Electricity 25110.4 Principles of the Photovoltaic Cell 25210.5 Photosynthesis and

Photoelectrochemistry 25610.6 Biomass 258

10.6a Ethanol from Biomass 26010.6b Ethanol from Starch or Cellulose? 26110.6c Biodiesel 26310.6d Methane from Biomass 264

10.7 Hydroelectricity 265Worked Problem 10.1 267

10.8 Wind Power 26710.9 Ocean Energy 270

10.9a Tides 27010.9b Waves 27110.9c Salt Gradient 27110.9d Thermal Gradients 27110.9e Deep Ocean Current 272

10.10 Geothermal Energy 272Problems 276Additional Reading 277

Chapter 11. energy utilization 279

11.1 Efficiency and Heat: The Role of Entropy 27911.1a Heat Engine Efficiencies 280

Worked Problem 11.1: Power Plant Efficiency 282

11.1b Energy to Heat: The Heat Pump 28311.2 Chemical Energy: Fuel Cells 285

Worked Problem 11.2: Fuel Cell Efficiency 28611.2a A PEM Fuel Cell 28811.2b Other Fuel Cells 29111.2c Microbial Fuel Cell 292

11.3 Space Heating, Cogeneration 29311.4 Electricity Storage 294

11.4a Batteries 295

11.4b Hydrogen Storage 29711.5 The Materials Connection 299

11.5a Materials Properties: Paper versus Plastics 300

11.5b Recycling 30211.5b.i Energy of Refining Al versus

Fe 30411.5c Concrete 30511.5d Dematerialization 306

11.6 Systems Efficiency 30711.6a Industrial Ecology 30911.6b Transportation 31111.6c Energy Efficiency in Automobiles 31411.6d The “Smart Grid” 31611.6e Hydrogen Economy 317

11.7 Connecting Energy Use and Climate Change: Stabilization Wedges and Cost Curves 319

Problems 324Additional Reading 326

Part iV. hydrosPhere and

lithosPhere 329

Chapter 12. Water resources 331

12.1 Global Perspective 33112.2 Irrigation 33412.3 “Virtual” Water and the Issue of Meat

Production 33712.4 Groundwater 33812.5 United States Water Resources 34012.6 The Oceans 34112.7 Water as Solvent and as a Biological

Medium 344Problems 345Additional Reading 346

Chapter 13. Water as solvent: acids and

Bases 349

13.1 Unique Properties of Water 34913.1a Hydrogen Bonding 34913.1b Clathrates and Water Miscibility 352

13.2 Ions, Autoionization, and pH 35413.2a The pH Scale 355

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13.3 Weak Acids and Bases: Buffers 35713.3a Weak Acids 35713.3b The pH of a Weak Acid 357

Worked Problem 13.1: The pH of a Weak Acid 358

13.3c Weak Bases 35813.3d The pH of a Weak Base 359

Worked Problem 13.2: The pH of a Weak Base 359

13.3e Conjugate Acids and Bases: Buffers 359

13.4 Water in the Atmosphere: Acid Rain 36113.5 Polyprotic Acids 362

Worked Problem 13.3: Phosphate Protonation 365Worked Problem 13.4: Ocean Carbonate 366

13.6 Alkalinity 366Problems 367Additional Reading 368

Chapter 14. Water and the lithosphere 369

14.1 The Earth as an Acid–Base Reactor 36914.2 Organic and Inorganic Carbon Cycles 372

14.2a The Carbonate Control 37314.2b Carbonate Sequestration 37514.2c Carbon Dioxide, Water, and Earth’s

Planetary Neighbors 37714.3 Weathering and Solubilization

Mechanisms 37714.3a Ionic Solids and the Solubility

Product 377Worked Problem 14.1: Barium Sulfate Solubility 378

14.3b Solubility and Basicity 379Worked Problem 14.2: Calcium Carbonate Solubility in Equilibrium with the Atmosphere 379

14.3c Ocean Acidification 38014.4 Ion Exchange: Clays and Humic

Substances 38214.5 Effects of Freshwater Acidification 386

14.5a Soil Neutralization 38614.5b Hardness and Detergents 388

14.5c Acid Deposition and Watershed Buffering 390

14.5d Ecosystem Effects of Acid Rain 39314.5e Acid Mine Drainage 39414.5f Global Acidification 395

Problems 396Additional Reading 397

Chapter 15. oxygen and life 399

15.1 Redox Reactions and Energy 39915.2 Biological Oxygen Demand 400

Worked Problem 15.1: Biological Oxygen Demand 401

15.3 Oxidation Levels and Water 401Worked Problem 15.2: Calculating the Oxidation State and Balancing Redox Equations 402

15.4 Reduction Potentials 40315.5 Natural Sequence of Biological

Reductions 40515.6 Concentration Dependence of the Potential:

pH and Eh 408Worked Problem 15.3: Eh and Ksp of Fe(OH)3 409Worked Problem 15.4: Effective Oxygen Potential 409

15.7 Electron and Proton Affinities Are Linked: pE versus pH 410

15.8 Biological Oxidations 41315.9 Aerobic Earth 41315.10 Water as an Ecological Medium 416

15.10a The Euphotic Zone and the Biological Pump 416

15.10b Eutrophication in Freshwater Lakes 418

15.10c Nitrogen and Phosphorus: The Limiting Nutrients 420

15.10d Anoxia and Its Effects on Coastal Marine Waters 423

15.10e Wetlands as Chemical Sinks 42715.10f Redox Effects on Metals

Pollution 42915.10g Fertilizing the Ocean with Iron 430

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xiv Contents

Problems 431Additional Reading 433

Chapter 16. Water Pollution and Water

treatment 435

16.1 Water Use and Water Quality: Point and Nonpoint Sources of Pollution 435

16.2 Regulation of Water Quality 43916.3 Water and Sewage Treatment 44116.4 Desalinization of Seawater 44316.5 Health Hazards 445

16.5a Pathogens and Disinfection 44516.5b Organic and Inorganic Contaminants 448

16.5b.i Waste Sites 44816.5b.ii Agriculture 449

16.6 Low-Cost Water Technology for Developing Countries 450

16.7 Trace Pollutants 45116.8 Perchlorate Pollution 45216.9 Summary of Hydrosphere–Lithosphere

Interactions 452Problems 453Additional Reading 454

Part V. BiosPhere 457

Chapter 17. nitrogen and food Production 459

17.1 Nitrogen Cycle 45917.2 Agriculture 463

17.2a Fertilizer and the Green Revolution 463

17.2b Environmental Degradation 46817.2c Confined Animal Feeding

Operations 46917.2d Organic Farming and Sustainable

Agriculture 47017.3 Nutrition 472

17.3a Energy and Calories 47217.3b Protein 47317.3c Minerals and Vitamins 47817.3d Antioxidants 48317.3e Antioxidant Mechanisms 484

Problems 486Additional Reading 487

Chapter 18. Pest Control 491

18.1 Insecticides 49118.1a Persistent Insecticides:

Organochlorines 49218.1b Molecular Shape and Biological

Activity 49418.1c Ecosystem Effects:

Bioaccumulation 49518.1d Bioaccumulation and the Partition

Coefficient 49818.1e Nonpersistent Insecticides:

Organophosphates and Carbamates 49918.1f Molecular Mechanism of

Cholinesterase Inhibitors 50118.1g Natural Insecticides 50318.1h Integrated Pest Management 504

18.2 Herbicides 50618.2a Molecular Mechanism of Glyphosate

Inhibition; Genetic Engineering 50918.3 Genetically Modified Organisms 511

18.3a Genetically Modified Plants: Actualities and Potential 511

18.3b Resistance to Genetically Modified Foods 51418.3b.i Moral Issues 51418.3b.ii Political Issues 51618.3b.iii Health and Environment

Issues 516Problems 519Additional Reading 520

Chapter 19. toxicity of Chemicals 523

19.1 Acute and Chronic Toxicity 52319.2 Cancer 526

19.2a Mechanisms 52719.2b Cancer Incidence and Testing 532

19.3 Hormonal Effects 53619.3a Bisphenol A 539

19.4 Persistent Organic Pollutants: Dioxins and Polychlorinated Biphenyls 54119.4a Dioxins and Furans 542

19.4a.i Toxicity 53419.4a.ii Paper Bleaching and

Combustion Sources 544

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19.4a.iii Natural Sources? 54619.4a.iv Exposure 548

19.4b Polychlorinated Biphenyls 54919.4c Polybrominated Diphenyl Ethers 55219.4d Perflouroctanoic Sulfonate 55219.4e Global Transport 553

19.5 Toxic Metals 55419.5a Mercury 55719.5b Cadmium 56219.5c Arsenic 56519.5d Lead 567

19.5d.i Exposure 56719.5d.ii Bioavailability 57119.5d.iii Toxicity 571

Problems 574Additional Reading 575

aPPendiCes

appendix a: organic structures 579

appendix B: mathematical fundamentals 589

Index 595

Contents xv

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foreWord

Chemistry of the Environment by Spiro, Purvis-Roberts, and Stigliani fills a critical need by providing a coherent chemical account of the environmental issues we face. From air pollution and climate change, to acid rain and oil spills, to food security and genetically modified plants, to carcinogens and lead poisoning, Chemistry of the Environment puts the environmental story in chemical context, showing how the problems arise, and pointing ways to their solutions.

I am particularly pleased that the authors have devoted an entire unit of their book to Energy and Materials, as I firmly believe that energy production and utilization are key to human welfare as well as the source of most envi-ronmental problems. The Energy and Materials unit sets out the challenges we face, and points to the many opportunities to develop new chemistry for effi-cient energy production and use. It will be especially helpful to young inves-tigators entering the field.

Spiro, Purvis-Roberts, and Stigliani write in a clear and engaging style. They organize the material in a logical and compelling manner, emphasizing the many cross-connections among environmental topics.

The bottom line is that this is the book on environmental chemistry that we all have been waiting for! It is a must read for young and old alike.

Harry Gray

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PrefaCe

environmental Chemistry lessons

“Here’s a short chemistry lesson”, wrote Bill McKibben in a 1995 New York Times Magazine feature story.a “Grasp it and you will grasp the reason the environmental era has barely begun. . . .” McKibben’s lesson is about the dif-ference between two molecules, carbon monoxide (CO) and carbon dioxide (CO2). Today’s automobiles release half a pound of carbon as CO per gallon of gasoline burned, around half as much as they did a generation ago, and the rate is going down with continuing improvements in technology. As a result, the air is now cleaner than it used to be in Los Angeles and in many other c ities. But the same gallon of gasoline releases almost five and one-half pounds of carbon as CO2, and this rate cannot be decreased. The atmospheric concentration of CO2 is increasing worldwide, and bringing global warming with it. The two molecules capture two sides of the environmental coin, local versus global effects of human activity. Environmental quality has improved in many localities, thanks to environmental controls and new technologies, but the global problems are just beginning to be addressed, and they are much more difficult to solve. Carbon monoxide is a side product of combustion, and is subject to emission controls, but CO2 is the end product of combustion and is the inevitable accompaniment of our reliance on fossil fuels. “Carbon mon-oxide versus carbon dioxide,” says McKibben, “one damn oxygen atom, and all the difference in the world”.

McKibben’s story is a wonderful illustration of the power of chemistry to illuminate environmental issues. Chemistry is all around us, and it really does make a difference. The chemical cycles of the planet are increasingly dis-turbed by human activities. These disturbances can degrade the quality of life, as when auto emissions overwhelm the atmosphere’s capacity to clean the air over our cities. We are capable of ameliorating these effects, as the experience

a B. McKibben, “Not So Fast”, New York Times Magazine, July 23, 1995, pp. 24 –25.

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of Los Angeles demonstrates. But first we must understand the chemistry. In the case of Los Angeles, initial attempts to alleviate smog back in the 1960s actually made things worse. Standards were imposed on CO and hydrocarbon levels in auto emissions, and auto makers met those standards by increasing the air/fuel ratio to burn the fuel more completely. But smog levels increased because higher air/fuel ratios made combustion hotter, thereby increasing the nitrogen oxide ( NOx) emissions. Only then was it discovered that nitrogen oxides and hydrocarbons are both key players in smog formation and that both have to be controlled. This kind of surprise is not unusual in environmental affairs. The world is a marvelously complex place, chemically, as in other ways. We are just beginning to understand how it works.

This book tells the environmental story in the language of chemicals. It is grounded in the flows of chemicals and energy through nature on the one hand, and through our industrial civilization on the other. The parts of the book, Sustainability and Green Chemistry, Atmosphere, Energy and M aterials, Hydrosphere and Lithosphere, and Biosphere, reflect this holistic perspective. Environmental issues frequently cut across these divisions, and the resulting interconnections add richness to the story. For example, leaded gasoline is linked to the issue of auto emission controls, a subject that arises in Part II, the Atmosphere, but it is also a major health hazard, as discussed in Part V, the Biosphere.

Interconnections are even more numerous at the level of the underlying chemistry. For example, the reactivity of dioxygen (O2) is a leitmotif for all parts of the book. Thus energy flow through industrial civilization (as well as through the biosphere itself  ) depends on the oxygen–oxygen bond being rela-tively weak, so that energy is released when O2 combines with organic mole-cules. Yet, because of its unusual electronic structure, O2 is quite unreactive until it encounters a free radical or a transition metal ion. These O2 activators determine most aspects of atmospheric chemistry, including how smog is formed. They are also vitally important for the biosphere, since O2 metabo-lism gone awry is a threat to the integrity of biological molecules and has been implicated as a factor in cancer and aging.

These interconnections provide a satisfying context for understanding the chemical world we live in and the environmental issues we face.

What this Book is about

This book is about the natural chemical cycles that form our world, and how humans are altering these cycles. Our world contains many chemical ele-ments, which combine into a much larger number of compounds. Under the influence of the energy flowing out of earth’s molten core and from the sun, these compounds are continually transformed into one another and back. These transformations occur in earth’s crust, in its waters, and in its atmo-sphere. The cycles are linked, one reaction depending on others, according to the laws of chemistry.

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Life evolved in harmony with these cycles, and has also altered them substantially. The rise of human civilizations has magnified this impact, first through the spread of agriculture, and then through the development of manu-facturing technologies. The modern industrial era accelerated the pace of chemical change, and now we see evidence everywhere of chemical imbal-ances that threaten human well-being, and even the continued existence of entire ecosystems. Increasingly, we are concerned whether our practices are sustainable.

What are the key threats to our environment, and how can they be averted? How can chemistry contribute to the sustainablility of our world? These are the questions that animate this book. It is organized around the environmental story, and it brings science in as needed to illuminate that story. Some famil-iarity with chemistry is assumed, but freshman chemistry, or a good high school course should be sufficient.

The book considers the following topics:

• Sustainability, and the role of “green chemistry” in reducing human impacts.

• The chemistry of the atmosphere, and how it determines the issues of climate change, protection from ultraviolet (UV) radiation, and air pollution.

• Energy, and how we obtain and use it, with emphasis on how we can reduce its environmental impact, particularly on climate.

• The chemistry of the hydrosphere, and the problems of acidification of fresh and ocean waters, and of water overfertilization and pollution.

• The biosphere, focusing on the role of agriculture and the spread of toxic compounds, both organic and inorganic.

Through these chapters, readers will learn about the critical role of chemistry in the great environmental issues of our time. This understanding can help to inform their actions as participants in our human enterprise.

acknowledgments

This book is a successor to Chemistry of the Environment, eds. 1 and 2 by Spiro and Stigliani (Prentice Hall, 1996, 2003). The material has been exten-sively revised, reflecting the rapid evolution of all areas of environmental sci-ence and of environmental concerns. Much of the text has been rewritten for clarity, and the organization has been simplified for smoother flow. Additional worked and end-of-chapter problems have been provided, and the lists of ad-ditional readings have been updated.

We are indebted to a number of individuals who helped us improve the book. Douglas Fox, John Perona, and Richard Treptow, read parts or all of the book, and provided extensive suggestions. Keith Kuwata tested several sec-tions of the book in class, and provided thoughtful feedback from his students.

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Special thanks go to Kirk Smith, Jim Purvis, Alexandra Soldatova, and Robert Socolow, for help with the Air Pollution, Nuclear Energy, Renewable Energy and Energy Utilization chapters, and to Bruce Ames and Lois Gold for a help-ful critique of the material on carcinogens in Chapter 19, Toxicity of C hemicals.

We are especially grateful to Helen Spiro and Jon Roberts for reading and helping revise some of the material, and for their patient and loving support and advice during the long and arduous process of crafting the book.

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