Preface to the First Edition xxiii Preface to the Third Edition xxv PART I The Atmosphere and Its Constituents Chapter 1 The Atmosphere 3 1.1 History and Evolution of Earth''s Atmosphere 3 1.2 Climate 5 1.3 Layers of the Atmosphere 5 1.4 Pressure in the Atmosphere 7 1.4.1 Units of Pressure 7 1.4.
2 Variation of Pressure with Height in the Atmosphere 7 1.5 Temperature in the Atmosphere 10 1.6 Expressing the Amount of a Substance in the Atmosphere 10 1.7 Airborne Particles 14 1.8 Spatial and Temporal Scales of Atmospheric Processes 14 Problems 16 References 17 Chapter 2 Atmospheric Trace Constituents 18 2.1 Atmospheric Lifetime 19 2.2 Sulfur-Containing Compounds 23 2.2.
1 Dimethyl Sulfide (CH3SCH3) 26 2.2.2 Carbonyl Sulfide (OCS) 26 2.2.3 Sulfur Dioxide (SO2) 27 2.3 Nitrogen-Containing Compounds 27 2.3.1 Nitrous Oxide (N2O) 28 2.
3.2 Nitrogen Oxides (NOx=NO+NO2) 29 2.3.3 Reactive Odd Nitrogen (NOy) 30 2.3.4 Ammonia (NH3) 31 2.3.5 Amines 32 2.
4 Carbon-Containing Compounds 32 2.4.1 Classification of Hydrocarbons 32 2.4.2 Methane 34 2.4.3 Volatile Organic Compounds 36 2.4.
4 Biogenic Hydrocarbons 36 2.4.5 Carbon Monoxide 39 2.4.6 Carbon Dioxide 40 2.5 Halogen-Containing Compounds 40 2.5.1 Methyl Chloride (CH3Cl) 42 2.
5.2 Methyl Bromide (CH3Br) 42 2.6 Atmospheric Ozone 44 2.7 Particulate Matter (Aerosols) 47 2.7.1 Stratospheric Aerosol 48 2.7.2 Chemical Components of Tropospheric Aerosol 48 2.
7.3 Cloud Condensation Nuclei (CCN) 49 2.7.4 Sizes of Atmospheric Particles 49 2.7.5 Carbonaceous Particles 51 2.7.6 Mineral Dust 53 2.
7.7 Biomass Burning 53 2.7.8 Summary of Atmospheric Particulate Matter 54 2.8 Mercury 55 2.9 Emission Inventories 55 Appendix 2.1 US Air Pollution Legislation 56 Appendix 2.2 Hazardous Air Pollutants (Air Toxics) 57 Problems 59 References 61 PART II Atmospheric Chemistry Chapter 3 Chemical Kinetics 69 3.
1 Order of Reaction 69 3.2 Theories of Chemical Kinetics 71 3.2.1 Collision Theory 71 3.2.2 Transition State Theory 74 3.2.3 Potential Energy Surface for a Bimolecular Reaction 75 3.
3 The Pseudo-Steady-State Approximation 76 3.4 Reactions of Excited Species 77 3.5 Termolecular Reactions 78 3.6 Chemical Families 81 3.7 Gas-Surface Reactions 83 Problems 84 References 87 Chapter 4 Atmospheric Radiation and Photochemistry 88 4.1 Radiation 88 4.2 Radiative Flux in the Atmosphere 91 4.3 Beer − Lambert Law and Optical Depth 93 4.
4 Actinic Flux 95 4.5 Atmospheric Photochemistry 97 4.6 Absorption of Radiation by Atmospheric Gases 100 4.7 Absorption by O2 and O3 105 4.8 Photolysis Rate as a Function of Altitude 109 4.9 Photodissociation of O3 to Produce O and O(1D) 112 4.10 Photodissociation of NO2 114 Problems 117 References 117 Chapter 5 Chemistry of the Stratosphere 119 5.1 Chapman Mechanism 122 5.
2 Nitrogen Oxide Cycles 129 5.2.1 Stratospheric Source of NOx from N2O 129 5.2.2 NOx Cycles 131 5.3 HOx Cycles 134 5.4 Halogen Cycles 139 5.4.
1 Chlorine Cycles 140 5.4.2 Bromine Cycles 143 5.5 Reservoir Species and Coupling of the Cycles 144 5.6 Ozone Hole 146 5.6.1 Polar Stratospheric Clouds (PSCs) 149 5.6.
2 PSCs and the Ozone Hole 150 5.6.3 Arctic Ozone Hole 153 5.7 Heterogeneous (Nonpolar) Stratospheric Chemistry 155 5.7.1 The Stratospheric Aerosol Layer 155 5.7.2 Heterogeneous Hydrolysis of N2O5 155 5.
7.3 Effect of Volcanoes on Stratospheric Ozone 160 5.8 Summary of Stratospheric Ozone Depletion 162 5.9 Transport and Mixing in the Stratosphere 165 5.10 Ozone Depletion Potential 167 Problems 168 References 173 Chapter 6 Chemistry of the Troposphere 175 6.1 Production of Hydroxyl Radicals in the Troposphere 176 6.2 Basic Photochemical Cycle of NO2, NO, and O3 179 6.3 Atmospheric Chemistry of Carbon Monoxide 181 6.
3.1 Low-NOx Limit 183 6.3.2 High-NOx Limit 184 6.3.3 Ozone Production Efficiency 184 6.3.4 Theoretical Maximum Yield of Ozone from CO Oxidation 188 6.
4 Atmospheric Chemistry of Methane 188 6.5 The NOx and NOy Families 192 6.5.1 Daytime Behavior 192 6.5.2 Nighttime Behavior 193 6.6 Ozone Budget of the Troposphere and Role of NOx 195 6.6.
1 Ozone Budget of the Troposphere 195 6.6.2 Role of NOx 195 6.6.3 Global Hydroxyl Radical Budget 197 6.7 Tropospheric Reservoir Molecules 203 6.7.1 H2O2, CH3OOH, and Hydroperoxides 203 6.
7.2 Nitrous Acid (HONO) 204 6.7.3 Peroxyacyl Nitrates (PANs) 204 6.8 Relative Roles of VOC and NOx in Ozone Formation 208 6.8.1 Importance of the VOC/NOx Ratio 208 6.8.
2 Ozone Isopleth Plot 209 6.8.3 Weekend Ozone Effect 211 6.9 Simplified Organic/NOx Chemistry 212 6.10 Chemistry of Nonmethane Organic Compounds in the Troposphere 214 6.10.1 Alkanes 215 6.10.
2 Alkenes 222 6.10.3 Aromatics 228 6.10.4 Aldehydes 230 6.10.5 Ketones 230 6.10.
6 Ethers 231 6.10.7 Alcohols 231 6.10.8 Tropospheric Lifetimes of Organic Compounds 232 6.11 Atmospheric Chemistry of Biogenic Hydrocarbons 233 6.11.1 Atmospheric Chemistry of Isoprene 233 6.
11.2 Monoterpenes (α-Pinene) 241 6.12 Atmospheric Chemistry of Reduced Nitrogen Compounds 244 6.12.1 Amines 245 6.12.2 Nitriles 246 6.12.
3 Nitrites 246 6.13 Atmospheric Chemistry (Gas Phase) of Sulfur Compounds 246 6.13.1 Sulfur Oxides 246 6.13.2 Reduced Sulfur Compounds (Dimethyl Sulfide) 247 6.14 Tropospheric Chemistry of Halogen Compounds 249 6.14.
1 Chemical Cycles of Halogen Species 249 6.14.2 Tropospheric Chemistry of CFC Replacements: Hydrofluorocarbons (HFCs) and Hydrochlorofluorocarbons (HCFCs) 251 6.15 Atmospheric Chemistry of Mercury 253 Appendix 6 Organic Functional Groups 254 Problems 256 References 259 Chapter 7 Chemistry of the Atmospheric Aqueous Phase 265 7.1 Liquid Water in the Atmosphere 265 7.2 Absorption Equilibria and Henry''s Law 268 7.3 Aqueous-Phase Chemical Equilibria 271 7.3.
1 Water 271 7.3.2 Carbon Dioxide-Water Equilibrium 272 7.3.3 Sulfur Dioxide-Water Equilibrium 274 7.3.4 Ammonia-Water Equilibrium 278 7.3.
5 Nitric Acid-Water Equilibrium 280 7.3.6 Equilibria of Other Important Atmospheric Gases 281 7.4 Aqueous-Phase Reaction Rates 284 7.5 S(IV)-S(VI) Transformation and Sulfur Chemistry 286 7.5.1 Oxidation of S(IV) by Dissolved O3 286 7.5.
2 Oxidation of S(IV) by Hydrogen Peroxide 289 7.5.3 Oxidation of S(IV) by Organic Peroxides 290 7.5.4 Uncatalyzed Oxidation of S(IV) by O2 291 7.5.5 Oxidation of S(IV) by O2 Catalyzed by Iron and Manganese 291 7.5.
6 Comparison of Aqueous-Phase S(IV) Oxidation Paths 293 7.6 Dynamic Behavior of Solutions with Aqueous-Phase Chemical Reactions 295 7.6.1 Closed System 296 7.6.2 Calculation of Concentration Changes in a Droplet with Aqueous-Phase Reactions 298 Appendix 7.1 Thermodynamic and Kinetic Data 301 Appendix 7.2 Additional Aqueous-Phase Sulfur Chemistry 305 7A.
1 S(IV) Oxidation by the OH Radical 305 7A.2 Oxidation of S(IV) by Oxides of Nitrogen 308 7A.3 Reaction of Dissolved SO2 with HCHO 309 Appendix 7.3 Aqueous-Phase Nitrite and Nitrate Chemistry 311 7A.4 NOx Oxidation 311 7A.5 Nitrogen Radicals 311 Appendix 7.4 Aqueous-Phase Organic Chemistry 312 Appendix 7.5 Oxygen and Hydrogen Chemistry 313 Problems 314 References 317 PART III Aerosols Chapter 8 Properties of the Atmospheric Aerosol 325 8.
1 The Size Distribution Function 325 8.1.1 The Number Distribution nN(Dp) 328 8.1.2 The Surface Area, Volume, and Mass Distributions 330 8.1.3 Distributions Based on ln Dp and log Dp 331 8.1.
4 Relating Size Distributions Based on Different Independent Variables 333 8.1.5 Properties of Size Distributions 334 8.1.6 Definition of the Lognormal Distribution 335 8.1.7 Plotting the Lognormal Distribution 338 8.1.
8 Properties of the Lognormal Distribution 339 8.2 Ambient Aerosol Size Distributions 342 8.2.1 Urban Aerosols 343 8.2.2 Marine Aerosols 344 8.2.3 Rural Continental Aerosols 347 8.
2.4 Remote Continental Aerosols 348 8.2.5 Free Tropospheric Aerosols 348 8.2.6 Polar Aerosols 349 8.2.7 Desert Aerosols 349 8.
3 Aerosol Chemical Composition 352 8.4 Spatiotemporal Variation 354 Problems 357 References 359 Chapter 9 Dynamics of Single Aerosol Particles 362 9.1 Continuum and Noncontinuum Dynamics: the Mean Free Path 362 9.1.1 Mean Free Path of a Pure Gas 363 9.1.2 Mean Free Path of a Gas in a Binary Mixture 365 9.2 The Drag on a Single Particle: Stokes'' Law 368 9.
2.1 Corrections to Stokes'' Law: the Drag Coefficient 371 9.2.2 Stokes'' Law and Noncontinuum Effects: Slip Correction Factor 371 9.3 Gravitational Settling of an Aerosol Particle 372 9.4 Motion of an Aerosol Particle in an External Forc.