Introduction to atmospheric chemistry

Cover\n......Page 1
INTRODUCTION TO ATMOSPHERIC CHEMISTRY......Page 2
Title\n......Page 4
Copyright......Page 5
Contents......Page 6
Preface......Page 12
1.1 Mixing Ratio......Page 16
1.2 Number Density......Page 17
1.3 Partial Pressure......Page 21
1.3 The Ozone Layer......Page 24
2.2 Mass of the Atmosphere......Page 27
2.3 Vertical Profiles of Pressure and Temperature......Page 29
2.4 Barometric Law......Page 31
2.5 The Sea-Breeze Circulation......Page 34
2.2 Scale Height and Atmospheric Mass......Page 35
3 – Simple Models......Page 37
3.1.1 Concept of Lifetime......Page 38
3.1.2 Mass Balance Equation......Page 40
3.2 Multibox Models......Page 43
3.3 Puff Models......Page 46
3.1 Atmospheric Steady State......Page 49
3.3 Stratosphere-Troposphere Exchange......Page 50
3.5 Long-Range Transport of Acidity......Page 52
3.7 The Montreal Protocol......Page 53
4.1.1 Coriolis Force......Page 55
4.1.2 Geostrophic Balance......Page 59
4.2 The General Circulation......Page 61
4.3.1 Buoyancy......Page 66
4.3.2 Atmospheric Stability......Page 68
4.3.3 Adiabatic Lapse Rate......Page 69
4.3.4 Latent Heat Release from Cloud Formation......Page 71
4.3.5 Atmospheric Lapse Rate......Page 73
4.4 Turbulence......Page 76
4.4.2 Turbulent Flux......Page 77
4.4.3 Parameterization of Turbulence......Page 80
4.4.4 Time Scales for Vertical Transport......Page 83
4.1 Dilution of Power Plant Plumes......Page 84
4.2 Short Questions on Atmospheric Transport......Page 85
4.3 Seasonal Motion of the ITCZ......Page 86
4.5 Breaking a Nighttime Inversion\n......Page 87
4.6 Wet Convection......Page 88
4.8 Global Source of Methane......Page 89
4.9 Role of Molecular Diffusion in Atmospheric Transport......Page 90
4.10 Vertical Transport near the Surface......Page 91
5.1.1 Derivation\n......Page 92
5.1.2 Discretization......Page 94
5.2 Lagrangian Form......Page 97
5.1 Turbulent Diffusion Coefficient......Page 98
6.1 Geochemical Cycling of Elements......Page 100
6.2 Early Evolution of the Atmosphere......Page 102
6.3 The Nitrogen Cycle......Page 103
6.4 The Oxygen Cycle......Page 107
6.5.2 Carbonate Chemistry in the Ocean......Page 110
6.5.3 Uptake of CO2 by the Ocean......Page 113
6.5.4 Uptake of CO2 by the Terrestrial Biosphere......Page 117
6.5.5 Box Model of the Carbon Cycle......Page 118
6.1 Short Questions on the Oxygen Cycle......Page 120
6.3 Atmospheric Residence Time of Helium......Page 121
6.4 Methyl Bromide......Page 122
6.6 Ocean pH......Page 124
6.7 Cycling of CO2 with the Terrestrial Biosphere......Page 125
6.9 Fossil Fuel CO2 Neutralization by Marine CaCO3......Page 126
7 – The Greenhouse Effect......Page 128
7.1 Radiation......Page 131
7.2.1 Solar and Terrestrial Emission Spectra......Page 134
7.2.2 Radiative Balance of the Earth......Page 135
7.3.1 Spectroscopy of Gas Molecules......Page 139
7.3.2 A Simple Greenhouse Model......Page 141
7.3.3 Interpretation of the Terrestrial Radiation Spectrum......Page 144
7.4.1 Definition of Radiative\n Forcing......Page 146
7.4.2 Application......Page 148
7.4.3 Radiative Forcing and Surface Temperature......Page 150
7.5.1 Water Vapor......Page 151
7.6 Optical Depth......Page 153
7.1 Climate Response to Changes in Ozone......Page 155
7.2 Interpretation of the Terrestrial Radiation Spectrum......Page 156
7.4 The ‘‘Faint Sun’’ Problem......Page 157
7.6 Absorption in the Atmospheric Window......Page 158
8.1 Sources and Sinks of Aerosols......Page 159
8.2.1 Scattering of Radiation......Page 161
8.2.2 Visibility Reduction......Page 163
8.2.3 Perturbation to Climate......Page 164
Further Reading......Page 167
8.2 Aerosols and Radiation......Page 168
9.1.1 Bimolecular Reactions......Page 170
9.1.2 Three-Body Reactions......Page 171
9.2 Reverse Reactions and Chemical Equilibria......Page 172
9.3 Photolysis......Page 173
9.4 Radical-Assisted Reaction Chains......Page 174
Further Reading......Page 176
10.1.1 The Mechanism......Page 177
10.1.2 Steady-State Solution......Page 179
10.2.1 Hydrogen Oxide Radicals (HOx)......Page 184
10.2.2 Nitrogen Oxide Radicals (NOx)......Page 185
10.2.3 Chlorine Radicals (ClOx)......Page 190
10.3 Polar Ozone Loss......Page 192
10.3.1 Mechanism for Ozone Loss......Page 194
10.3.2 PSC Formation......Page 196
10.3.3 Chronology of the Ozone Hole......Page 198
10.4 Aerosol Chemistry......Page 200
10.2 The Chapman Mechanism and Steady State......Page 204
10.3 The Detailed Chapman Mechanism......Page 205
10.5 Chlorine Chemistry at Midlatitudes......Page 206
10.6 Partitioning of Cly......Page 208
10.7 Bromine-Catalyzed Ozone Loss......Page 209
10.8 Limitation of Antarctic Ozone Depletion......Page 210
10.9 Fixing the Ozone Hole......Page 211
10.10 PSC Formation......Page 212
11 – Oxidizing Power of the Troposphere......Page 213
11.1.1 Tropospheric Production of OH......Page 214
11.1.2 Global Mean OH Concentration......Page 216
11.2 Global Budgets of CO and Methane......Page 218
11.3.2 CO Oxidation Mechanism......Page 220
11.3.3 Methane Oxidation Mechanism......Page 223
11.4 Global Budget of Nitrogen Oxides......Page 225
11.5 Global Budget of Tropospheric Ozone......Page 228
11.6 Anthropogenic Influence on Ozone and OH......Page 229
11.1 Sources of CO......Page 232
11.2 Sources of Tropospheric Ozone......Page 233
11.3 Oxidizing Power of the Atmosphere......Page 234
11.5 Acetone in the Upper Troposphere......Page 236
11.6 Transport, Rainout, and Chemistry in the Marine Upper Troposphere......Page 238
11.7 Bromine Chemistry in the Troposphere......Page 240
11.8 Nighttime Oxidation of NOx......Page 241
11.9 Peroxyacetylnitrate (PAN) as a Reservoir for NOx......Page 242
12.1 Air Pollution and Ozone......Page 244
12.2 Ozone Formation and Control Strategies......Page 246
12.3 Ozone Production Efficiency......Page 253
12.1 NOx- and Hydrocarbon-Limited Regimes for Ozone Production......Page 255
12.2 Ozone Titration in a Fresh Plume......Page 256
13.1.1 Natural Precipitation......Page 258
13.1.2 Precipitation over North America......Page 259
13.2 Sources of Acids: Sulfur Chemistry......Page 262
13.3 Effects of Acid Rain......Page 263
13.4 Emission Trends......Page 265
13.3 Aqueous-Phase Oxidation of SO2 by Ozone......Page 266
13.4 The Acid Fog Problem......Page 267
13.5 Acid Rain: The Preindustrial Atmosphere......Page 268
Numerical Solutions to Problems......Page 270
Appendix. Physical Data and Units......Page 272
Index......Page 274