Chemistry of the natural atmosphere / Peter Warneck.

Format:

Book

Author/Creator:

Warneck, Peter.

Series:

International geophysics series ; v. 71.

International geophysics series ; v. 71

Language:

English

Subjects (All):

Atmospheric chemistry.

Physical Description:

xvii, 927 pages : illustrations ; 24 cm.

Edition:

Second edition.

Place of Publication:

San Diego, Calif. : Academic Press, [2000]

Summary:

Knowledge of the chemical behavior of trace compounds in the atmosphere has grown steadily, and sometimes even spectacularly, in recent decades. These developments have led to the emergence of atmospheric chemistry as a new branch of science. This book covers all aspects of atmospheric chemistry on a global scale, integrating information from chemistry and geochemistry, physics, and biology to provide a unified account. For each atmospheric constituent of interest, the text summarizes the principal observations on global distribution, chemical reactions, natural and anthropogenic sources, and physical removal processes. Coverage includes processes in the gas phase, in aerosols and clouds, and in precipitation, as well as biogeochemical cycles and the evolution of the atmosphere. Chemistry of the Natural Atmosphere, Second Edition, will serve as a textbook for senior undergraduate and graduate courses, and as an essential reference for atmospheric chemists, meteorologists, and anyone studying the biogeochemical cycles of trace gases.

Contents:

1 Bulk Composition, Structure, and Dynamics of the Atmosphere

1.1 Observational Data and Averages 1

1.2 Temperature Structure and Atmospheric Regions 7

1.3 Pressure, Density, and Mixing Ratio 10

1.4 Global Circulation and Transport 15

1.4.1 Atmospheric Mean Motions 16

1.4.2 Eddy Diffusion 19

1.4.3 Molecular Diffusion 30

1.5 Air Mass Exchange between Principal Atmospheric Domains 31

1.6 The Planetary Boundary Layer 42

2 Photochemical Processes and Elementary Reactions

2.1 Fundamentals of Reactions Kinetics 55

2.2 Properties of Rate Coefficients 60

2.3 Photochemical Processes 67

2.4 Attenuation of Solar Radiation in the Atmosphere 69

2.5 Photodissociation of Oxygen and Ozone 79

2.6 Photochemistry of Minor Atmospheric Constituents 85

3 Chemistry of the Stratosphere

3.1 Historical Survey 100

3.2 Ozone Observations 104

3.2.1 Principal Features and Behavior of the Ozone Layer 104

3.2.2 Global Trends in Total Ozone 109

3.3 The Chapman Model 113

3.4 Trace Gases Other Than Ozone 118

3.4.1 Nitrogen Oxides 119

3.4.2 Water Vapor, Methane, and Hydrogen 126

3.4.3 Halocarbons 131

3.4.4 Carbonyl Sulfide and Sulfur Dioxide 136

3.5 Heterogeneous and Polar Stratospheric Chemistry 140

3.6 The Budget of Ozone in the Stratosphere 151

4 Chemistry of the Troposphere: The Methane Oxidation Cycle

4.1 The Tropospheric Reservoir 158

4.2 Hydroxyl Radicals in the Troposphere 163

4.3 The Budget of Methane 174

4.4 Formaldehyde 189

4.5 Carbon Monoxide 192

4.6 Hydrogen 205

5 Ozone in the Troposphere

5.2 Photochemical Air Pollution 213

5.3 Distribution and Behavior of Tropospheric Ozone 230

5.3.1 Balloon Soundings 231

5.3.2 Aircraft Observations 236

5.3.3 Surface Measurements 238

5.4 A Minimum Tropospheric Ozone Budget 249

5.4.1 Influx of Ozone from the Stratosphere 249

5.4.2 Destruction of Ozone at the Ground Surface 252

5.5 Photochemical Production and Loss of Ozone in the Unperturbed Troposphere 255

5.5.1 Reaction Mechanism 255

5.5.2 Combined Tropospheric Ozone Budget 261

6 Hydrocarbons, Halocarbons, and Other Volatile Organic Compounds

6.1 Hydrocarbons and Some Other Organic Volatiles 265

6.1.1 Hydrocarbon Lifetimes 265

6.1.2 Anthropogenic Sources of Atmospheric Hydrocarbons 270

6.1.3 Natural Sources of Hydrocarbons and Other Organic Compounds 275

6.1.4 Hydrocarbon Mixing Ratios over the Continents 283

6.1.5 Hydrocarbons in the Marine Atmosphere 292

6.1.6 Formic and Acetic Acid 300

6.2 Hydrocarbon Oxidation Mechanisms 309

6.2.1 Alkylperoxy Radicals 310

6.2.2 Alkoxy Radicals 314

6.2.3 Oxidation of Alkanes 318

6.2.4 Oxidation of Alkenes 321

6.2.5 Aromatic Compounds 330

6.3 Halocarbons 331

6.3.1 Methyl Chloride 334

6.3.2 Chlorofluorocarbons 336

6.3.3 Fully Fluorinated Compounds 339

6.3.4 Methyl Chloroform and Carbon Tetrachloride 340

6.3.5 Methyl Bromide and Methyl Iodide 342

7 The Atmospheric Aerosol

7.2 Particulate Size Distribution 348

7.3 The Physical Behavior of Particles 355

7.3.1 Coagulation and Condensation 355

7.3.2 Interaction of Aerosol Particles with Water Vapor 364

7.4 Aerosol Sources and Global Production Rates 373

7.4.1 Mineral Sources 373

7.4.2 Sea Salt 378

7.4.3 Gas-to-Particle Conversion 383

7.4.4 Miscellaneous Sources 397

7.4.5 Global Aerosol Production Rates 401

7.5 The Chemical Constitution of the Aerosol 405

7.5.1 The Inorganic Fraction, Soluble and Insoluble 408

7.5.2 The Organic Fraction 428

7.6 Global Distribution, Physical Removal, and Residence Time of the Tropospheric Aerosol 438

7.6.1 Vertical Aerosol Distribution and Global Budget 438

7.6.2 Residence Times of Aerosol Particles 441

7.6.2 Sedimentation and Dry Deposition 447

8 Chemistry of Clouds and Precipitation

8.1 The Water Cycle 451

8.2 Cloud and Rain Formation 455

8.3 The Incorporation of Particulate Matter into Cloud and Raindrops 461

8.3.1 Nucleation Scavenging 461

8.3.2 Below Cloud Scavenging of Particles 463

8.4 The Scavenging of Gases by Cloud and Raindrops 468

8.4.1 Gas-Liquid Equilibria in Clouds 469

8.4.2 Time Constants for the Adjustment to Equilibrium 478

8.5 Inorganic Chemical Composition and pH of Cloud and Rain Water 484

8.6 Chemical Reactions in Cloud and Fog Waters 493

8.6.1 Basic Photochemistry in Clouds 494

8.6.2 Reactions of Nitrogen Compounds 496

8.6.3 The Role of Transition Metals 499

8.6.4 The Oxidation of Sulfur Dioxide in Aqueous Solution 503

9 Nitrogen Compounds in the Troposphere

9.1 Biochemical Processes 511

9.2 Ammonia 515

9.2.1 Distribution in the Troposphere 516

9.2.2 Sources and Sinks of Atmospheric NH[subscript 3] 520

9.3 Nitrous Oxide 530

9.4 Nitrogen Dioxide, NO[subscript 2], and Related Nitrogen Compounds 541

9.4.1 Nitrogen Oxide Chemistry 542

9.4.2 The Tropospheric Distribution of NO[subscript x] 553

9.4.3 Peroxyacetyl Nitrate 561

9.4.4 Nitric Acid and Particulate Nitrate 566

9.4.5 Total Oxidized Nitrogen 572

9.4.6 Sources and Sinks of Oxidized Nitrogen in the Troposphere 574

10 Sulfur Compounds in the Atmosphere

10.2 Reduced Sulfur Compounds 589

10.2.1 Atmospheric Abundances, Behavior, Sources, and Sinks 589

10.2.2 Atmospheric Reactions and Life Times 598

10.2.3 Terrestrial Biosphere-Atmosphere Exchange 603

10.2.4 Summary of Natural Sources of Sulfur 610

10.3 Sulfur Dioxide, SO[subscript 2], and Particulate Sulfate 611

10.3.1 Anthropogenic Emissions 611

10.3.2 Sulfur Emissions from Volcanoes 614

10.3.3 Chemical Conversion of SO[subscript 2] to Particulate Sulfate 618

10.3.4 Distribution of SO[subscript 2] and SO[superscript 2-][subscript 4] in the Troposphere 624

10.3.5 Wet and Dry Deposition of Sulfate 639

10.4 Tropospheric Sulfur Budgets 647

10.4.1 The Regionally Polluted Continental Atmosphere 647

10.4.2 The Circulation of Sulfur in the Unperturbed Marine Atmosphere 650

10.4.3 The Global Tropospheric Sulfur Budget 652

11 Geochemistry of Carbon Dioxide

11.2 The Major Carbon Reservoirs 658

11.2.1 Carbon Dioxide in the Atmosphere 659

11.2.2 The Oceans 660

11.2.3 Carbon in Sedimentary Rocks 666

11.2.4 The Terrestrial Biosphere 672

11.3 The Global Carbon Cycles 675

11.3.1 The Geochemical Cycles 677

11.3.2 Exchange of CO[subscript 2] between Atmosphere and Ocean 686

11.3.3 Interaction between the Atmosphere and the Terrestrial Biosphere 694

11.3.4 Long-Term Atmosphere-Biosphere Interactions and Current CO[subscript 2] Budget 698

12 The Evolution of the Atmosphere

12.1 The Noble Gases 712

12.2 The Primitive Atmosphere 721

12.3 Nitrogen 730

12.4 Oxygen 734

12.4.1 Sources of Oxygen 734

12.4.2 The Budget and Cycles of Oxygen 736

12.4.3 The Rise of Atmospheric Oxygen 744

12.5 Atmospheric Gases: Cumulative Versus Cyclic Behavior 750.

Notes:

Previous ed.: 1988.

Includes bibliographical references (pages 777-904) and index.

ISBN:

0127356320

OCLC:

42622164