Atmospheric Chemistry and Physics

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 1.5 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 2.3 Nitrogen-Containing Compounds 27 2.4 Carbon-Containing Compounds 32 2.5 Halogen-Containing Compounds 40 2.6 Atmospheric Ozone 44 2.7 Particulate Matter (Aerosols) 47 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 3.3 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 5.3 HOx Cycles 134 5.4 Halogen Cycles 139 5.5 Reservoir Species and Coupling of the Cycles 144 5.6 Ozone Hole 146 5.7 Heterogeneous (Nonpolar) Stratospheric Chemistry 155 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 6.4 Atmospheric Chemistry of Methane 188 6.5 The NOx and NOy Families 192 6.6 Ozone Budget of the Troposphere and Role of NOx 195 6.7 Tropospheric Reservoir Molecules 203 6.8 Relative Roles of VOC and NOx in Ozone Formation 208 6.9 Simplified Organic/NOx Chemistry 212 6.10 Chemistry of Nonmethane Organic Compounds in the Troposphere 214 6.11 Atmospheric Chemistry of Biogenic Hydrocarbons 233 6.12 Atmospheric Chemistry of Reduced Nitrogen Compounds 244 6.13 Atmospheric Chemistry (Gas Phase) of Sulfur Compounds 246 6.14 Tropospheric Chemistry of Halogen Compounds 249 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 7.4 Aqueous-Phase Reaction Rates 284 7.5 S(IV)-S(VI) Transformation and Sulfur Chemistry 286 7.6 Dynamic Behavior of Solutions with Aqueous-Phase Chemical Reactions 295 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 8.2 Ambient Aerosol Size Distributions 342 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 9.2 The Drag on a Single Particle: Stokes' Law 368 9.3 Gravitational Settling of an Aerosol Particle 372 9.4 Motion of an Aerosol Particle in an External Force Field 376 9.5 Brownian Motion of Aerosol Particles 376 9.6 Aerosol and Fluid Motion 385 9.7 Equivalent Particle Diameters 388 Problems 393 References 394 Chapter 10 | Thermodynamics of Aerosols 396 10.1 Thermodynamic Principles 396 10.2 Aerosol Liquid Water Content 409 10.3 Equilibrium Vapor Pressure Over a Curved Surface: the Kelvin Effect 419 10.4 Thermodynamics of Atmospheric Aerosol Systems 423 10.5 Aerosol Thermodynamic Models 440 Problems 442 References 443 Chapter 11 | Nucleation 448 11.1 Classical Theory of Homogeneous Nucleation: Kinetic Approach 449 11.2 Classical Homogeneous Nucleation Theory: Constrained Equilibrium Approach 457 11.3 Recapitulation of Classical Theory 464 11.4 Experimental Measurement of Nucleation Rates 465 11.5 Modifications of the Classical Theory and More Rigorous Approaches 467 11.6 Binary Homogeneous Nucleation 468 11.7 Binary Nucleation in the H2SO4-H2O System 473 11.8 Nucleation on an Insoluble Foreign Surface 475 11.9 Ion-Induced Nucleation 478 11.10 Atmospheric New-Particle Formation 480 Appendix 11 The Law of Mass Action 487 Problems 489 References 490 Chapter 12 | Mass Transfer Aspects of Atmospheric Chemistry 493 12.1 Mass and Heat Transfer to Atmospheric Particles 493 12.2 Mass Transport Limitations in Aqueous-Phase Chemistry 503 12.3 Mass Transport and Aqueous-Phase Chemistry 511 12.4 Mass Transfer to Falling Drops 526 12.5 Characteristic Time for Atmospheric Aerosol Equilibrium 527 Appendix 12 Solution of the Transient Gas-Phase Diffusion Problem: Equations (12.4)-(12.7) 532 Problems 533 References 535 Chapter 13 | Dynamics of Aerosol Populations 537 13.1 Mathematical Representations of Aerosol Size Distributions 537 13.2 Condensation 538 13.3 Coagulation 544 13.4 The Discrete General Dynamic Equation 557 13.5 The Continuous General Dynamic Equation 558 Appendix 13.1 Additional Mechanisms of Coagulation 560 13A.1 Coagulation in Laminar Shear Flow 560 13A.2 Coagulation in Turbulent Flow 560 13A.3 Coagulation from Gravitational Settling 561 13A.4 Brownian Coagulation and External Force Fields 562 Appendix 13.2 Solution of (13.73) 567 Problems 568 References 571 Chapter 14 | Atmospheric Organic Aerosols 573 14.1 Chemistry of Secondary Organic Aerosol Formation 574 14.2 Volatility of Organic Compounds 582 14.3 Idealized Description of Secondary Organic Aerosol Formation 583 14.4 Gas-Particle Partitioning 590 14.5 Models of SOA Formation and Evolution 596 14.6 Primary Organic Aerosol 605 14.7 The Physical State of Organic Aerosols 608 14.8 SOA Particle-Phase Chemistry 610 14.9 Aqueous-Phase Secondary Organic Aerosol Formation 615 14.10 Estimates of the Global Budget of Atmospheric Organic Aerosol 622 Problems 623 References 626 Chapter 15 | Interaction of Aerosols with Radiation 633 15.1 Scattering and Absorption of Light by Small Particles 633 15.2 Visibility 644 15.3 Scattering, Absorption, and Extinction Coefficients From Mie Theory 647 15.4 Calculated Visibility Reduction Based on Atmospheric Data 651 Appendix 15 Calculation of Scattering and Extinction Coefficients by Mie Theory 654 Problems 654 References 656 PART IV | Physical and Dynamic Meteorology, Cloud Physics, and Atmospheric Diffusion Chapter 16 | Physical and Dynamic Meteorology 661 16.1 Temperature in the Lower Atmosphere 661 16.2 Atmospheric Stability 665 16.3 The Moist Atmosphere 670 16.4 Basic Conservation Equations for the Atmospheric Surface Layer 683 16.5 Variation of Wind with Height in the Atmosphere 692 Appendix 16.1 Properties of Water and Water Solutions 701 16A.1 Specific Heat of Water and Ice 701 16A.2 Latent Heats of Vaporization and Melting for Water 701 16A.3 Water Surface Tension 701 Appendix 16.2 Derivation of the Basic Equations of Surface-Layer Atmospheric Fluid Mechanics 702 Problems 705 References 706 Chapter 17 | Cloud Physics 708 17.1 Equilibrium of Water Droplets in the Atmosphere 708 17.2 Cloud and Fog Formation 719 17.3 Growth Rate of Individual Cloud Droplets 723 17.4 Growth of a Droplet Population 726 17.5 Cloud Condensation Nuclei 730 17.6 Cloud Processing of Aerosols 736 17.7 Other Forms of Water in the Atmosphere 743 Appendix 17 Extended Köhler Theory 751 17A.1 Modified Form of Köhler Theory for a Soluble Trace Gas 751 17A.2 Modified Form of Köhler Theory for a Slightly Soluble Substance 754 17A.3 Modified Form of Köhler Theory for a Surface-Active Solute 755 17A.4 Examples 756 Problems 759 References 760 Chapter 18 | Atmospheric Diffusion 763 18.1 Eulerian Approach 763 18.2 Lagrangian Approach 766 18.3 Comparison of Eulerian and Lagrangian Approaches 767 18.4 Equations Governing the Mean Concentration of Species in Turbulence 767 18.5 Solution of the Atmospheric Diffusion Equation for an Instantaneous Source 771 18.6 Mean Concentration from Continuous Sources 772 18.7 Statistical Theory of Turbulent Diffusion 778 18.8 Summary of Atmospheric Diffusion Theories 783 18.9 Analytical Solutions for Atmospheric Diffusion: the Gaussian Plume Equation and Others 784 18.10 Dispersion Parameters in Gaussian Models 791 18.11 Plume Rise 796 18.12 Functional Forms of Mean Windspeed and Eddy Diffusivities 798 18.13 Solutions of the Steady-State Atmospheric Diffusion Equation 803 Appendix 18.1 Further Solutions of Atmospheric Diffusion Problems 807 18A.1 Solution of (18.29)-(18.31) 807 18A.2 Solution of (18.50) and (18.51) 809 18A.3 Solution of (18.59)-(18.61) 810 Appendix 18.2 Analytical Properties of the Gaussian Plume Equation 811 Problems 815 References 823 PART V | Dry and Wet Deposition Chapter 19 | Dry Deposition 829 19.1 Deposition Velocity 829 19.2 Resistance Model for Dry Deposition 830 19.3 Aerodynamic Resistance 834 19.4 Quasilaminar Resistance 835 19.5 Surface Resistance 839 19.6 Measurement of Dry Deposition 849 19.7 Some Comments on Modeling and Measurement of Dry Deposition 851 Problems 852 References 854 Chapter 20 | Wet Deposition 856 20.1 General Representation of Atmospheric Wet Removal Processes 856 20.2 Below-Cloud Scavenging of Gases 860 20.3 Precipitation Scavenging of Particles 868 20.4 In-Cloud Scavenging 873 20.5 Acid Deposition 874 20.6 Acid Deposition Process Synthesis 878 Problems 881 References 886 PART VI | The Global Atmosphere, Biogeochemical Cycles, and Climate Chapter 21 | General Circulation of the Atmosphere 891 21.1 Hadley Cell 893 21.2 Ferrell Cell and Polar Cell 893 21.3 Coriolis Force 895 21.4 Geostrophic Windspeed 897 21.5 The Thermal Wind Relation 902 21.6 Stratospheric Dynamics 905 21.7 The Hydrologic Cycle 905 Problems 906 References 907 Chapter 22 | Global Cycles: Sulfur and Carbon 908 22.1 The Atmospheric Sulfur Cycle 908 22.2 The Global Carbon Cycle 912 22.3 Solution for a Steady-State Four-Compartment Model of the Atmosphere 923 Problems 927 References 929 Chapter 23 | Global Climate 931 23.1 Earth's Energy Balance 931 23.2 Radiative Forcing 933 23.3 The Greenhouse Effect 936 23.4 Climate-Forcing Agents 942 23.5 Cosmic Rays and Climate 949 23.6 Climate Sensitivity 950 23.7 Simplified Dynamic Description of Climate Forcing and Response 951 23.8 Climate Feedbacks 955 23.9 Relative Radiative Forcing Indices 960 23.10 Atmospheric Chemistry and Climate Change 961 23.11 Conclusion 964 Problems 965 References 967 Chapter 24 | Aerosols and Climate 970 24.1 Scattering-Absorbing Model of an Aerosol Layer 972 24.2 Cooling Versus Heating of an Aerosol Layer 975 24.3 Scattering Model of an Aerosol Layer for a Nonabsorbing Aerosol 977 24.4 Upscatter Fraction 979 24.5 Optical Depth and Column Forcing 981 24.6 Internal and External Mixtures 985 24.7 Top-of-the-Atmosphere Versus Surface Forcing 987 24.8 Indirect Effects of Aerosols on Climate 990 Problems 1004 References 1004 PART VII | Chemical Transport Models and Statistical Models Chapter 25 | Atmospheric Chemical Transport Models 1011 25.1 Introduction 1011 25.2 Box Models 1014 25.3 Three-Dimensional Atmospheric Chemical Transport Models 1020 25.4 One-Dimensional Lagrangian Models 1024 25.5 Other Forms of Chemical Transport Models 1026 25.6 Numerical Solution of Chemical Transport Models 1031 25.7 Model Evaluation 1046 25.8 Response of Organic and Inorganic Aerosols to Changes in Emission 1047 Problems 1048 References 1050 Chapter 26 | Statistical Models 1051 26.1 Receptor Modeling Methods 1051 26.2 Chemical Mass Balance (CMB) 1054 26.3 Factor Analysis 1059 26.4 Methods Incorporating Wind Information 1067 26.5 Probability Distributions for Air Pollutant Concentrations 1072 26A.1 The Lognormal Distribution 1073 26A.2 The Weibull Distribution 1074 26.6 Estimation of Parameters in the Distributions 1074 26A.1 Method of Quantiles 1075 26A.2 Method of Moments 1076 26.7 Order Statistics of Air Quality Data 1078 26A.1 Basic Notions and Terminology of Order Statistics 1078 26A.2 Extreme Values 1079 26.8 Exceedances of Critical Levels 1080 26.9 Alternative Forms of Air Quality Standards 1080 26.10 Relating Current and Future Air Pollutant Statistical Distributions 1083 Problems 1085 References 1087 Appendixes Appendix A: | Units and Physical Constants 1091 A.1 SI Base Units 1091 A.2 SI Derived Units 1092 A.3 Fundamental Physical Constants 1094 A.4 Properties of the Atmosphere and Water 1094 A.5 Units for Representing Chemical Reactions 1096 A.6 Concentrations in the Aqueous Phase 1096 A.7 Symbols Denoting Concentration 1097 References 1097 Appendix B: | Rate Constants of Atmospheric Chemical Reactions 1098 References 1106 Appendix C: | Abbreviations 1107 Index 1112