Atmospheric Chemistry and Physics
-15%
portes grátis
Atmospheric Chemistry and Physics
From Air Pollution to Climate Change
Seinfeld, John H.; Pandis, Spyros N.
John Wiley and Sons Ltd
03/2016
1152
Dura
Inglês
9781118947401
15 a 20 dias
Descrição não disponível.
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 ( -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 Force Field 376 9.5 Brownian Motion of Aerosol Particles 376 9.5.1 Particle Diffusion 379 9.5.2 Aerosol Mobility and Drift Velocity 381 9.5.3 Mean Free Path of an Aerosol Particle 384 9.6 Aerosol and Fluid Motion 385 9.6.1 Motion of a Particle in an Idealized Flow (90 Corner) 386 9.6.2 Stop Distance and Stokes Number 387 9.7 Equivalent Particle Diameters 388 9.7.1 Volume Equivalent Diameter 388 9.7.2 Stokes Diameter 390 9.7.3 Classical Aerodynamic Diameter 391 9.7.4 Electrical Mobility Equivalent Diameter 393 Problems 393 References 394 Chapter 10 | Thermodynamics of Aerosols 396 10.1 Thermodynamic Principles 396 10.1.1 Internal Energy and Chemical Potential 396 10.1.2 The Gibbs Free Energy G 398 10.1.3 Conditions for Chemical Equilibrium 400 10.1.4 Chemical Potentials of Ideal Gases and Ideal-Gas Mixtures 402 10.1.5 Chemical Potential of Solutions 404 10.1.6 The Equilibrium Constant 408 10.2 Aerosol Liquid Water Content 409 10.2.1 Chemical Potential of Water in Atmospheric Particles 411 10.2.2 Temperature Dependence of the DRH 412 10.2.3 Deliquescence of Multicomponent Aerosols 415 10.2.4 Crystallization of Single- and Multicomponent Salts 419 10.3 Equilibrium Vapor Pressure Over a Curved Surface: the Kelvin Effect 419 10.4 Thermodynamics of Atmospheric Aerosol Systems 423 10.4.1 The H2SO4 H2O System 423 10.4.2 The Sulfuric Acid Ammonia Water System 427 10.4.3 The Ammonia Nitric Acid Water System 430 10.4.4 The Ammonia Nitric Acid Sulfuric Acid Water System 434 10.4.5 Other Inorganic Aerosol Species 439 10.4.6 Organic Aerosol 440 10.5 Aerosol Thermodynamic Models 440 Problems 442 References 443 Chapter 11 | Nucleation 448 11.1 Classical Theory of Homogeneous Nucleation: Kinetic Approach 449 11.1.1 The Forward Rate Constant i 452 11.1.2 The Reverse Rate Constant i 453 11.1.3 Derivation of the Nucleation Rate 453 11.2 Classical Homogeneous Nucleation Theory: Constrained Equilibrium Approach 457 11.2.1 Free Energy of i-mer Formation 457 11.2.2 Constrained Equilibrium Cluster Distribution 459 11.2.3 The Evaporation Coefficient i 461 11.2.4 Nucleation Rate 461 11.3 Recapitulation of Classical Theory 464 11.4 Experimental Measurement of Nucleation Rates 465 11.4.1 Upward Thermal Diffusion Cloud Chamber 466 11.4.2 Fast Expansion Chamber 466 11.4.3 Turbulent Mixing Chambers 467 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 11.10.1 Molecular Constituency of New Particles 481 11.10.2 New-Particle Growth Rates 482 11.10.3 CLOUD Studies of Atmospheric Nucleation 482 11.10.4 Atmospheric Nucleation by Organic Species 487 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 12.1.1 The Continuum Regime 493 12.1.2 The Kinetic Regime 497 12.1.3 The Transition Regime 497 12.1.4 The Accommodation Coefficient 500 12.2 Mass Transport Limitations in Aqueous-Phase Chemistry 503 12.2.1 Characteristic Time for Gas-Phase Diffusion to a Particle 505 12.2.2 Characteristic Time to Achieve Equilibrium at the Gas Liquid Interface 506 12.2.3 Characteristic Time of Aqueous Dissociation Reactions 508 12.2.4 Characteristic Time of Aqueous-Phase Diffusion in a Droplet 510 12.2.5 Characteristic Time for Aqueous-Phase Chemical Reactions 511 12.3 Mass Transport and Aqueous-Phase Chemistry 511 12.3.1 Gas-Phase Diffusion and Aqueous-Phase Reactions 512 12.3.2 Aqueous-Phase Diffusion and Reaction 514 12.3.3 Interfacial Mass Transport and Aqueous-Phase Reactions 515 12.3.4 Application to the S(IV) Ozone Reaction 517 12.3.5 Application to the S(IV) Hydrogen Peroxide Reaction 519 12.3.6 Calculation of Aqueous-Phase Reaction Rates 520 12.3.7 An Aqueous-Phase Chemistry/Mass Transport Model 525 12.4 Mass Transfer to Falling Drops 526 12.5 Characteristic Time for Atmospheric Aerosol Equilibrium 527 12.5.1 Solid Aerosol Particles 528 12.5.2 Aqueous Aerosol Particles 529 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 13.1.1 Discrete Distribution 537 13.1.2 Continuous Distribution 538 13.2 Condensation 538 13.2.1 The Condensation Equation 538 13.2.2 Solution of the Condensation Equation 540 13.3 Coagulation 544 13.3.1 Brownian Coagulation 544 13.3.2 The Coagulation Equation 551 13.3.3 Solution of the Coagulation Equation 553 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 14.1.1 Oxidation State of Organic Compounds 576 14.1.2 Generation of Highly Oxygenated Species by Autoxidation 579 14.2 Volatility of Organic Compounds 582 14.3 Idealized Description of Secondary Organic Aerosol Formation 583 14.3.1 Noninteracting Secondary Organic Aerosol Compounds 583 14.3.2 Formation of Binary Ideal Solution with Preexisting Aerosol 586 14.3.3 Formation of Binary Ideal Solution with Other Organic Vapor 588 14.4 Gas Particle Partitioning 590 14.4.1 Gas Particle Equilibrium 590 14.4.2 Effect of Aerosol Water on Gas-Particle Partitioning 594 14.5 Models of SOA Formation and Evolution 596 14.5.1 The Volatility Basis Set 597 14.5.2 Two-Dimensional SOA Models 603 14.6 Primary Organic Aerosol 605 14.7 The Physical State of Organic Aerosols 608 14.8 SOA Particle-Phase Chemistry 610 14.8.1 Particle-Phase Accretion Reactions 612 14.8.2 Heterogeneous Gas-Aerosol Reactions 612 14.9 Aqueous-Phase Secondary Organic Aerosol Formation 615 14.9.1 Gas- versus Aqueous-Phase Routes to SOA 616 14.9.2 Sources of OH Radicals in the Aqueous Phase 618 14.9.3 Glyoxal as a Source of aqSOA 619 14.10 Estimates of the Global Budget of Atmospheric Organic Aerosol 622 14.10.1 Estimate Based on Total VOC Emissions 622 14.10.2 Sulfate Lifetime and Ratio of Organic to Sulfate 622 14.10.3 Atmospheric Burden and Lifetime of SOA 623 14.10.4 Satellite Measurements 623 Problems 623 References 626 Chapter 15 | Interaction of Aerosols with Radiation 633 15.1 Scattering and Absorption of Light by Small Particles 633 15.1.1 Rayleigh Scattering Regime 638 15.1.2 Geometric Scattering Regime 640 15.1.3 Scattering Phase Function 640 15.1.4 Extinction by an Ensemble of Particles 640 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 16.3.1 The Gas Constant for Moist Air 671 16.3.2 Level of Cloud Formation: The Lifting Condensation Level 671 16.3.3 Dew-point and Wet-Bulb Temperatures 673 16.3.4 The Moist Adiabatic Lapse Rate 675 16.3.5 Stability of Moist Air 679 16.3.6 Convective Available Potential Energy (CAPE) 680 16.3.7 Thermodynamic Diagrams 681 16.4 Basic Conservation Equations for the Atmospheric Surface Layer 683 16.4.1 Turbulence 687 16.4.2 Equations for the Mean Quantities 688 16.4.3 Mixing-Length Models for Turbulent Transport 690 16.5 Variation of Wind with Height in the Atmosphere 692 16.5.1 Mean Velocity in the Adiabatic Surface Layer over a Smooth Surface 693 16.5.2 Mean Velocity in the Adiabatic Surface Layer over a Rough Surface 694 16.5.3 Mean Velocity Profiles in the Nonadiabatic Surface Layer 695 16.5.4 The Pasquill Stability Classes Estimation of L 698 16.5.5 Empirical Equation for the Mean Windspeed 700 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 17.1.1 Equilibrium of a Pure Water Droplet 708 17.1.2 Equilibrium of a Flat Water Solution 710 17.1.3 Atmospheric Equilibrium of an Aqueous Solution Drop 712 17.1.4 Atmospheric Equilibrium of an Aqueous Solution Drop Containing an Insoluble Substance 717 17.2 Cloud and Fog Formation 719 17.2.1 Isobaric Cooling 720 17.2.2 Adiabatic Cooling 720 17.2.3 A Simplified Mathematical Description of Cloud Formation 721 17.3 Growth Rate of Individual Cloud Droplets 723 17.4 Growth of a Droplet Population 726 17.5 Cloud Condensation Nuclei 730 17.5.1 Ambient CCN 733 17.5.2 The Hygroscopic Parameter Kappa 733 17.6 Cloud Processing of Aerosols 736 17.6.1 Nucleation Scavenging of Aerosols by Clouds 736 17.6.2 Chemical Composition of Cloud Droplets 737 17.6.3 Nonraining Cloud Effects on Aerosol Concentrations 739 17.6.4 Interstitial Aerosol Scavenging by Cloud Droplets 742 17.7 Other Forms of Water in the Atmosphere 743 17.7.1 Ice Clouds 743 17.7.2 Rain 747 Appendix 17 Extended Kohler Theory 751 17A.1 Modified Form of Kohler Theory for a Soluble Trace Gas 751 17A.2 Modified Form of Kohler Theory for a Slightly Soluble Substance 754 17A.3 Modified Form of Kohler 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 18.4.1 Eulerian Approaches 767 18.4.2 Lagrangian Approaches 769 18.5 Solution of the Atmospheric Diffusion Equation for an Instantaneous Source 771 18.6 Mean Concentration from Continuous Sources 772 18.6.1 Lagrangian Approach 772 18.6.2 Eulerian Approach 776 18.6.3 Summary of Continuous Point Source Solutions 777 18.7 Statistical Theory of Turbulent Diffusion 778 18.7.1 Qualitative Features of Atmospheric Diffusion 778 18.7.2 Motion of a Single Particle Relative to a Fixed Axis 780 18.8 Summary of Atmospheric Diffusion Theories 783 18.9 Analytical Solutions for Atmospheric Diffusion: the Gaussian Plume Equation and Others 784 18.9.1 Gaussian Concentration Distributions 784 18.9.2 Derivation of the Gaussian Plume Equation as a Solution of the Atmospheric Diffusion Equation 786 18.9.3 Summary of Gaussian Point Source Diffusion Formulas 791 18.10 Dispersion Parameters in Gaussian Models 791 18.10.1 Correlations for y and z Based on Similarity Theory 791 18.10.2 Correlations for y and z Based on Pasquill Stability Classes 795 18.11 Plume Rise 796 18.12 Functional Forms of Mean Windspeed and Eddy Diffusivities 798 18.12.1 Mean Windspeed 800 18.12.2 Vertical Eddy Diffusion Coefficient Kzz 800 18.12.3 Horizontal Eddy Diffusion Coefficients Kxx and Kyy 803 18.13 Solutions of the Steady-State Atmospheric Diffusion Equation 803 18.13.1 Diffusion from a Point Source 804 18.13.2 Diffusion from a Line Source 805 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 19.4.1 Gases 836 19.4.2 Particles 836 19.5 Surface Resistance 839 19.5.1 Surface Resistance for Dry Deposition of Gases to Water 841 19.5.2 Surface Resistance for Dry Deposition of Gases to Vegetation 845 19.6 Measurement of Dry Deposition 849 19.6.1 Direct Methods 849 19.6.2 Indirect Methods 850 19.6.3 Comparison of Methods 851 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 20.2.1 Below-Cloud Scavenging of an Irreversibly Soluble Gas 861 20.2.2 Below-Cloud Scavenging of a Reversibly Soluble Gas 864 20.3 Precipitation Scavenging of Particles 868 20.3.1 Raindrop Aerosol Collision Efficiency 870 20.3.2 Scavenging Rates 871 20.4 In-Cloud Scavenging 873 20.5 Acid Deposition 874 20.5.1 Acid Rain Overview 874 20.5.2 Surface Water Acidification 876 20.5.3 Cloudwater Deposition 877 20.5.4 Fogs and Wet Deposition 877 20.6 Acid Deposition Process Synthesis 878 20.6.1 Chemical Species Involved in Acid Deposition 878 20.6.2 Dry versus Wet Deposition 878 20.6.3 Chemical Pathways for Sulfate and Nitrate Production 878 20.6.4 Source Receptor Relationships 879 20.6.5 Linearity 880 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 21.4.1 Buys Ballot s Law 899 21.4.2 Ekman Spiral 900 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 22.2.1 Carbon Dioxide 912 22.2.2 Compartmental Model of the Global Carbon Cycle 914 22.2.3 Atmospheric Lifetime of CO2 921 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 23.2.1 Climate Sensitivity 934 23.2.2 Climate Feedbacks 935 23.2.3 Timescales of Climate Change 935 23.3 The Greenhouse Effect 936 23.4 Climate-Forcing Agents 942 23.4.1 Solar Irradiance 942 23.4.2 Greenhouse Gases 945 23.4.3 Radiative Efficiencies of Greenhouse Gases 946 23.4.4 Aerosols 946 23.4.5 Summary of IPCC (2013) Estimated Forcing 947 23.4.6 The Preindustrial Atmosphere 948 23.5 Cosmic Rays and Climate 949 23.6 Climate Sensitivity 950 23.7 Simplified Dynamic Description of Climate Forcing and Response 951 23.7.1 Response to a Perturbation of Earth s Radiative Equilibrium 951 23.7.2 Physical Interpretation of Feedback Factors 954 23.8 Climate Feedbacks 955 23.8.1 Water Vapor Feedback 955 23.8.2 Lapse Rate Feedback 956 23.8.3 Cloud Feedback 956 23.8.4 Arctic Sea Ice Feedback 958 23.8.5 Summary of Feedbacks 958 23.9 Relative Radiative Forcing Indices 960 23.10 Atmospheric Chemistry and Climate Change 961 23.10.1 Indirect Chemical Impacts 962 23.10.2 Atmospheric Lifetimes and Adjustment Times 963 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 24.8.1 Stratocumulus Clouds 991 24.8.2 Simplified Model for Cloud Albedo 993 24.8.3 Albedo Susceptibility: Simplified Model 995 24.8.4 Albedo Susceptibility: Additional Considerations 997 24.8.5 A General Equation for Cloud Albedo Susceptibility 999 24.8.6 Estimating Indirect Aerosol Forcing on Climate 1003 Problems 1004 References 1004 PART VII | Chemical Transport Models and Statistical Models Chapter 25 | Atmospheric Chemical Transport Models 1011 25.1 Introduction 1011 25.1.1 Model Types 1012 25.1.2 Types of Atmospheric Chemical Transport Models 1013 25.2 Box Models 1014 25.2.1 The Eulerian Box Model 1015 25.2.2 A Lagrangian Box Model 1017 25.3 Three-Dimensional Atmospheric Chemical Transport Models 1020 25.3.1 Coordinate System Uneven Terrain 1020 25.3.2 Initial Conditions 1022 25.3.3 Boundary Conditions 1023 25.4 One-Dimensional Lagrangian Models 1024 25.5 Other Forms of Chemical Transport Models 1026 25.5.1 Atmospheric Diffusion Equation Expressed in Terms of Mixing Ratio 1026 25.5.2 Pressure-Based Coordinate System 1029 25.5.3 Spherical Coordinates 1031 25.6 Numerical Solution of Chemical Transport Models 1031 25.6.1 Coupling Problem Operator Splitting 1032 25.6.2 Chemical Kinetics 1037 25.6.3 Diffusion 1041 25.6.4 Advection 1042 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 26.2.1 CMB Evaluation 1058 26.2.2 CMB Resolution 1059 26.2.3 CMB Codes 1059 26.3 Factor Analysis 1059 26.3.1 Principal-Component Analysis (PCA) 1061 26.3.2 Positive Matrix Factorization (PMF) 1064 26.4 Methods Incorporating Wind Information 1067 26.4.1 Potential Source Contribution Function (PSCF) 1068 26.4.2 Empirical Orthogonal Function (EOF) 1070 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
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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 ( -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 Force Field 376 9.5 Brownian Motion of Aerosol Particles 376 9.5.1 Particle Diffusion 379 9.5.2 Aerosol Mobility and Drift Velocity 381 9.5.3 Mean Free Path of an Aerosol Particle 384 9.6 Aerosol and Fluid Motion 385 9.6.1 Motion of a Particle in an Idealized Flow (90 Corner) 386 9.6.2 Stop Distance and Stokes Number 387 9.7 Equivalent Particle Diameters 388 9.7.1 Volume Equivalent Diameter 388 9.7.2 Stokes Diameter 390 9.7.3 Classical Aerodynamic Diameter 391 9.7.4 Electrical Mobility Equivalent Diameter 393 Problems 393 References 394 Chapter 10 | Thermodynamics of Aerosols 396 10.1 Thermodynamic Principles 396 10.1.1 Internal Energy and Chemical Potential 396 10.1.2 The Gibbs Free Energy G 398 10.1.3 Conditions for Chemical Equilibrium 400 10.1.4 Chemical Potentials of Ideal Gases and Ideal-Gas Mixtures 402 10.1.5 Chemical Potential of Solutions 404 10.1.6 The Equilibrium Constant 408 10.2 Aerosol Liquid Water Content 409 10.2.1 Chemical Potential of Water in Atmospheric Particles 411 10.2.2 Temperature Dependence of the DRH 412 10.2.3 Deliquescence of Multicomponent Aerosols 415 10.2.4 Crystallization of Single- and Multicomponent Salts 419 10.3 Equilibrium Vapor Pressure Over a Curved Surface: the Kelvin Effect 419 10.4 Thermodynamics of Atmospheric Aerosol Systems 423 10.4.1 The H2SO4 H2O System 423 10.4.2 The Sulfuric Acid Ammonia Water System 427 10.4.3 The Ammonia Nitric Acid Water System 430 10.4.4 The Ammonia Nitric Acid Sulfuric Acid Water System 434 10.4.5 Other Inorganic Aerosol Species 439 10.4.6 Organic Aerosol 440 10.5 Aerosol Thermodynamic Models 440 Problems 442 References 443 Chapter 11 | Nucleation 448 11.1 Classical Theory of Homogeneous Nucleation: Kinetic Approach 449 11.1.1 The Forward Rate Constant i 452 11.1.2 The Reverse Rate Constant i 453 11.1.3 Derivation of the Nucleation Rate 453 11.2 Classical Homogeneous Nucleation Theory: Constrained Equilibrium Approach 457 11.2.1 Free Energy of i-mer Formation 457 11.2.2 Constrained Equilibrium Cluster Distribution 459 11.2.3 The Evaporation Coefficient i 461 11.2.4 Nucleation Rate 461 11.3 Recapitulation of Classical Theory 464 11.4 Experimental Measurement of Nucleation Rates 465 11.4.1 Upward Thermal Diffusion Cloud Chamber 466 11.4.2 Fast Expansion Chamber 466 11.4.3 Turbulent Mixing Chambers 467 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 11.10.1 Molecular Constituency of New Particles 481 11.10.2 New-Particle Growth Rates 482 11.10.3 CLOUD Studies of Atmospheric Nucleation 482 11.10.4 Atmospheric Nucleation by Organic Species 487 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 12.1.1 The Continuum Regime 493 12.1.2 The Kinetic Regime 497 12.1.3 The Transition Regime 497 12.1.4 The Accommodation Coefficient 500 12.2 Mass Transport Limitations in Aqueous-Phase Chemistry 503 12.2.1 Characteristic Time for Gas-Phase Diffusion to a Particle 505 12.2.2 Characteristic Time to Achieve Equilibrium at the Gas Liquid Interface 506 12.2.3 Characteristic Time of Aqueous Dissociation Reactions 508 12.2.4 Characteristic Time of Aqueous-Phase Diffusion in a Droplet 510 12.2.5 Characteristic Time for Aqueous-Phase Chemical Reactions 511 12.3 Mass Transport and Aqueous-Phase Chemistry 511 12.3.1 Gas-Phase Diffusion and Aqueous-Phase Reactions 512 12.3.2 Aqueous-Phase Diffusion and Reaction 514 12.3.3 Interfacial Mass Transport and Aqueous-Phase Reactions 515 12.3.4 Application to the S(IV) Ozone Reaction 517 12.3.5 Application to the S(IV) Hydrogen Peroxide Reaction 519 12.3.6 Calculation of Aqueous-Phase Reaction Rates 520 12.3.7 An Aqueous-Phase Chemistry/Mass Transport Model 525 12.4 Mass Transfer to Falling Drops 526 12.5 Characteristic Time for Atmospheric Aerosol Equilibrium 527 12.5.1 Solid Aerosol Particles 528 12.5.2 Aqueous Aerosol Particles 529 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 13.1.1 Discrete Distribution 537 13.1.2 Continuous Distribution 538 13.2 Condensation 538 13.2.1 The Condensation Equation 538 13.2.2 Solution of the Condensation Equation 540 13.3 Coagulation 544 13.3.1 Brownian Coagulation 544 13.3.2 The Coagulation Equation 551 13.3.3 Solution of the Coagulation Equation 553 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 14.1.1 Oxidation State of Organic Compounds 576 14.1.2 Generation of Highly Oxygenated Species by Autoxidation 579 14.2 Volatility of Organic Compounds 582 14.3 Idealized Description of Secondary Organic Aerosol Formation 583 14.3.1 Noninteracting Secondary Organic Aerosol Compounds 583 14.3.2 Formation of Binary Ideal Solution with Preexisting Aerosol 586 14.3.3 Formation of Binary Ideal Solution with Other Organic Vapor 588 14.4 Gas Particle Partitioning 590 14.4.1 Gas Particle Equilibrium 590 14.4.2 Effect of Aerosol Water on Gas-Particle Partitioning 594 14.5 Models of SOA Formation and Evolution 596 14.5.1 The Volatility Basis Set 597 14.5.2 Two-Dimensional SOA Models 603 14.6 Primary Organic Aerosol 605 14.7 The Physical State of Organic Aerosols 608 14.8 SOA Particle-Phase Chemistry 610 14.8.1 Particle-Phase Accretion Reactions 612 14.8.2 Heterogeneous Gas-Aerosol Reactions 612 14.9 Aqueous-Phase Secondary Organic Aerosol Formation 615 14.9.1 Gas- versus Aqueous-Phase Routes to SOA 616 14.9.2 Sources of OH Radicals in the Aqueous Phase 618 14.9.3 Glyoxal as a Source of aqSOA 619 14.10 Estimates of the Global Budget of Atmospheric Organic Aerosol 622 14.10.1 Estimate Based on Total VOC Emissions 622 14.10.2 Sulfate Lifetime and Ratio of Organic to Sulfate 622 14.10.3 Atmospheric Burden and Lifetime of SOA 623 14.10.4 Satellite Measurements 623 Problems 623 References 626 Chapter 15 | Interaction of Aerosols with Radiation 633 15.1 Scattering and Absorption of Light by Small Particles 633 15.1.1 Rayleigh Scattering Regime 638 15.1.2 Geometric Scattering Regime 640 15.1.3 Scattering Phase Function 640 15.1.4 Extinction by an Ensemble of Particles 640 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 16.3.1 The Gas Constant for Moist Air 671 16.3.2 Level of Cloud Formation: The Lifting Condensation Level 671 16.3.3 Dew-point and Wet-Bulb Temperatures 673 16.3.4 The Moist Adiabatic Lapse Rate 675 16.3.5 Stability of Moist Air 679 16.3.6 Convective Available Potential Energy (CAPE) 680 16.3.7 Thermodynamic Diagrams 681 16.4 Basic Conservation Equations for the Atmospheric Surface Layer 683 16.4.1 Turbulence 687 16.4.2 Equations for the Mean Quantities 688 16.4.3 Mixing-Length Models for Turbulent Transport 690 16.5 Variation of Wind with Height in the Atmosphere 692 16.5.1 Mean Velocity in the Adiabatic Surface Layer over a Smooth Surface 693 16.5.2 Mean Velocity in the Adiabatic Surface Layer over a Rough Surface 694 16.5.3 Mean Velocity Profiles in the Nonadiabatic Surface Layer 695 16.5.4 The Pasquill Stability Classes Estimation of L 698 16.5.5 Empirical Equation for the Mean Windspeed 700 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 17.1.1 Equilibrium of a Pure Water Droplet 708 17.1.2 Equilibrium of a Flat Water Solution 710 17.1.3 Atmospheric Equilibrium of an Aqueous Solution Drop 712 17.1.4 Atmospheric Equilibrium of an Aqueous Solution Drop Containing an Insoluble Substance 717 17.2 Cloud and Fog Formation 719 17.2.1 Isobaric Cooling 720 17.2.2 Adiabatic Cooling 720 17.2.3 A Simplified Mathematical Description of Cloud Formation 721 17.3 Growth Rate of Individual Cloud Droplets 723 17.4 Growth of a Droplet Population 726 17.5 Cloud Condensation Nuclei 730 17.5.1 Ambient CCN 733 17.5.2 The Hygroscopic Parameter Kappa 733 17.6 Cloud Processing of Aerosols 736 17.6.1 Nucleation Scavenging of Aerosols by Clouds 736 17.6.2 Chemical Composition of Cloud Droplets 737 17.6.3 Nonraining Cloud Effects on Aerosol Concentrations 739 17.6.4 Interstitial Aerosol Scavenging by Cloud Droplets 742 17.7 Other Forms of Water in the Atmosphere 743 17.7.1 Ice Clouds 743 17.7.2 Rain 747 Appendix 17 Extended Kohler Theory 751 17A.1 Modified Form of Kohler Theory for a Soluble Trace Gas 751 17A.2 Modified Form of Kohler Theory for a Slightly Soluble Substance 754 17A.3 Modified Form of Kohler 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 18.4.1 Eulerian Approaches 767 18.4.2 Lagrangian Approaches 769 18.5 Solution of the Atmospheric Diffusion Equation for an Instantaneous Source 771 18.6 Mean Concentration from Continuous Sources 772 18.6.1 Lagrangian Approach 772 18.6.2 Eulerian Approach 776 18.6.3 Summary of Continuous Point Source Solutions 777 18.7 Statistical Theory of Turbulent Diffusion 778 18.7.1 Qualitative Features of Atmospheric Diffusion 778 18.7.2 Motion of a Single Particle Relative to a Fixed Axis 780 18.8 Summary of Atmospheric Diffusion Theories 783 18.9 Analytical Solutions for Atmospheric Diffusion: the Gaussian Plume Equation and Others 784 18.9.1 Gaussian Concentration Distributions 784 18.9.2 Derivation of the Gaussian Plume Equation as a Solution of the Atmospheric Diffusion Equation 786 18.9.3 Summary of Gaussian Point Source Diffusion Formulas 791 18.10 Dispersion Parameters in Gaussian Models 791 18.10.1 Correlations for y and z Based on Similarity Theory 791 18.10.2 Correlations for y and z Based on Pasquill Stability Classes 795 18.11 Plume Rise 796 18.12 Functional Forms of Mean Windspeed and Eddy Diffusivities 798 18.12.1 Mean Windspeed 800 18.12.2 Vertical Eddy Diffusion Coefficient Kzz 800 18.12.3 Horizontal Eddy Diffusion Coefficients Kxx and Kyy 803 18.13 Solutions of the Steady-State Atmospheric Diffusion Equation 803 18.13.1 Diffusion from a Point Source 804 18.13.2 Diffusion from a Line Source 805 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 19.4.1 Gases 836 19.4.2 Particles 836 19.5 Surface Resistance 839 19.5.1 Surface Resistance for Dry Deposition of Gases to Water 841 19.5.2 Surface Resistance for Dry Deposition of Gases to Vegetation 845 19.6 Measurement of Dry Deposition 849 19.6.1 Direct Methods 849 19.6.2 Indirect Methods 850 19.6.3 Comparison of Methods 851 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 20.2.1 Below-Cloud Scavenging of an Irreversibly Soluble Gas 861 20.2.2 Below-Cloud Scavenging of a Reversibly Soluble Gas 864 20.3 Precipitation Scavenging of Particles 868 20.3.1 Raindrop Aerosol Collision Efficiency 870 20.3.2 Scavenging Rates 871 20.4 In-Cloud Scavenging 873 20.5 Acid Deposition 874 20.5.1 Acid Rain Overview 874 20.5.2 Surface Water Acidification 876 20.5.3 Cloudwater Deposition 877 20.5.4 Fogs and Wet Deposition 877 20.6 Acid Deposition Process Synthesis 878 20.6.1 Chemical Species Involved in Acid Deposition 878 20.6.2 Dry versus Wet Deposition 878 20.6.3 Chemical Pathways for Sulfate and Nitrate Production 878 20.6.4 Source Receptor Relationships 879 20.6.5 Linearity 880 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 21.4.1 Buys Ballot s Law 899 21.4.2 Ekman Spiral 900 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 22.2.1 Carbon Dioxide 912 22.2.2 Compartmental Model of the Global Carbon Cycle 914 22.2.3 Atmospheric Lifetime of CO2 921 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 23.2.1 Climate Sensitivity 934 23.2.2 Climate Feedbacks 935 23.2.3 Timescales of Climate Change 935 23.3 The Greenhouse Effect 936 23.4 Climate-Forcing Agents 942 23.4.1 Solar Irradiance 942 23.4.2 Greenhouse Gases 945 23.4.3 Radiative Efficiencies of Greenhouse Gases 946 23.4.4 Aerosols 946 23.4.5 Summary of IPCC (2013) Estimated Forcing 947 23.4.6 The Preindustrial Atmosphere 948 23.5 Cosmic Rays and Climate 949 23.6 Climate Sensitivity 950 23.7 Simplified Dynamic Description of Climate Forcing and Response 951 23.7.1 Response to a Perturbation of Earth s Radiative Equilibrium 951 23.7.2 Physical Interpretation of Feedback Factors 954 23.8 Climate Feedbacks 955 23.8.1 Water Vapor Feedback 955 23.8.2 Lapse Rate Feedback 956 23.8.3 Cloud Feedback 956 23.8.4 Arctic Sea Ice Feedback 958 23.8.5 Summary of Feedbacks 958 23.9 Relative Radiative Forcing Indices 960 23.10 Atmospheric Chemistry and Climate Change 961 23.10.1 Indirect Chemical Impacts 962 23.10.2 Atmospheric Lifetimes and Adjustment Times 963 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 24.8.1 Stratocumulus Clouds 991 24.8.2 Simplified Model for Cloud Albedo 993 24.8.3 Albedo Susceptibility: Simplified Model 995 24.8.4 Albedo Susceptibility: Additional Considerations 997 24.8.5 A General Equation for Cloud Albedo Susceptibility 999 24.8.6 Estimating Indirect Aerosol Forcing on Climate 1003 Problems 1004 References 1004 PART VII | Chemical Transport Models and Statistical Models Chapter 25 | Atmospheric Chemical Transport Models 1011 25.1 Introduction 1011 25.1.1 Model Types 1012 25.1.2 Types of Atmospheric Chemical Transport Models 1013 25.2 Box Models 1014 25.2.1 The Eulerian Box Model 1015 25.2.2 A Lagrangian Box Model 1017 25.3 Three-Dimensional Atmospheric Chemical Transport Models 1020 25.3.1 Coordinate System Uneven Terrain 1020 25.3.2 Initial Conditions 1022 25.3.3 Boundary Conditions 1023 25.4 One-Dimensional Lagrangian Models 1024 25.5 Other Forms of Chemical Transport Models 1026 25.5.1 Atmospheric Diffusion Equation Expressed in Terms of Mixing Ratio 1026 25.5.2 Pressure-Based Coordinate System 1029 25.5.3 Spherical Coordinates 1031 25.6 Numerical Solution of Chemical Transport Models 1031 25.6.1 Coupling Problem Operator Splitting 1032 25.6.2 Chemical Kinetics 1037 25.6.3 Diffusion 1041 25.6.4 Advection 1042 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 26.2.1 CMB Evaluation 1058 26.2.2 CMB Resolution 1059 26.2.3 CMB Codes 1059 26.3 Factor Analysis 1059 26.3.1 Principal-Component Analysis (PCA) 1061 26.3.2 Positive Matrix Factorization (PMF) 1064 26.4 Methods Incorporating Wind Information 1067 26.4.1 Potential Source Contribution Function (PSCF) 1068 26.4.2 Empirical Orthogonal Function (EOF) 1070 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
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