Atmospheric Chemistry and Physics: From Air Pollution to Climate Chang

Expanded and updated with new findings and new features* New chapter on Global Climate providing a self-contained treatment of climate forcing, feedbacks, and climate sensitivity* New chapter on Atmospheric Organic Aerosols and new treatment of the statistical method of Positive Matrix Factorization* Updated treatments of physical meteorology, atmospheric nucleation, aerosol-cloud relationships, chemistry of biogenic hydrocarbons* Each topic developed from the fundamental science to the point of application to real-world problems* New problems at an introductory level to aid in classroom teaching

Expanded and updated with new findings and new features Since the second edition of Seinfeld and Pandis' classic textbook, significant progress has taken place in the field of atmospheric chemistry and physics, particularly in the areas of tropospheric chemistry, aerosols, and the science of climate change. A new edition of this comprehensive work has been developed by the renowned author team. Atmospheric Chemistry and Physics, 3rd Edition, as the previous two editions have done, provides a rigorous and comprehensive treatment of the chemistry and physics of the atmosphere - including the chemistry of the stratosphere and troposphere, aerosol physics and chemistry, atmospheric new particle formation, physical meteorology, cloud physics, global climate, statistical analysis of data, and mathematical chemical/transport models of the atmosphere. Each of these topics is covered in detail and in each area the central results are developed from first principles. In this way the reader gains a significant understanding of the science underlying atmospheric processes and will be able to extend theories and results to solving real world problems. The 3rd edition includes new chapters on Atmospheric Organic Aerosols and Global Climate, as well as a significantly updated chapter on Physical Meteorology. Many chapters and topics have been updated and expanded from the Second Edition, including the Chemistry of Biogenic Hydrocarbons in the Troposphere, especially Isoprene Chemistry; Aqueous-Phase Organic Chemistry; mechanisms of Nucleation in the Atmosphere; Aerosol-Cloud relationships; and Chemistry of Mercury. A new section on Positive Matrix Factorization is included that carefully develops this powerful statistical method for aerosol data analysis. New problems have been added, especially ones at a basic level, to increase the utility of this text in classroom situations. All chapters develop results based on fundamental principles, enabling the reader to build a solid understanding of the science underlying atmospheric processes. Readers familiar with the book will discover a text with many new and revised additions. Atmospheric Chemistry and Physics, 3rd Edition is an ideal textbook for upper-level undergraduate and graduate students, as well as a reference for researchers in environmental and atmospheric science, chemistry, meteorology, and civil and environmental engineering. John H. Seinfeld is Louis E. Nohl Professor at the California Institute of Technology. He is a member of the U.S. National Academy of Engineering, the U.S. National Academy of Sciences, and a Fellow of the American Academy of Arts and Sciences. He is the recipient of numerous honors and awards, including the American Chemical Society Award for Creative Advances in Environmental Science and Technology, the NASA Public Service Award, the Nevada Medal, the Fuchs Award, and the 2012 Tyler Prize. Spyros N. Pandis is Professor of Chemical Engineering at the University of Patras, Greece, and Research Professor of Chemical Engineering and Engineering and Public Policy at Carnegie Mellon University. He is the recipient of the Whitby Award by the American Association for Aerosol Research and the European Research Council Advanced Investigator IDEAS award. He is a Fellow of the American Association for Aerosol Research.

Preface to the First Edition xxiiiPreface to the Third Edition xxvPART I | The Atmosphere and Its ConstituentsChapter 1 | The Atmosphere 31.1 History and Evolution of Earth's Atmosphere 31.2 Climate 51.3 Layers of the Atmosphere 51.4 Pressure in the Atmosphere 71.5 Temperature in the Atmosphere 101.6 Expressing the Amount of a Substance in the Atmosphere 101.7 Airborne Particles 141.8 Spatial and Temporal Scales of Atmospheric Processes 14Problems 16References 17Chapter 2 | Atmospheric Trace Constituents 182.1 Atmospheric Lifetime 192.2 Sulfur-Containing Compounds 232.3 Nitrogen-Containing Compounds 272.4 Carbon-Containing Compounds 322.5 Halogen-Containing Compounds 402.6 Atmospheric Ozone 442.7 Particulate Matter (Aerosols) 472.8 Mercury 552.9 Emission Inventories 55Appendix 2.1 US Air Pollution Legislation 56Appendix 2.2 Hazardous Air Pollutants (Air Toxics) 57Problems 59References 61PART II | Atmospheric ChemistryChapter 3 | Chemical Kinetics 693.1 Order of Reaction 693.2 Theories of Chemical Kinetics 713.3 The Pseudo-Steady-State Approximation 763.4 Reactions of Excited Species 773.5 Termolecular Reactions 783.6 Chemical Families 813.7 Gas-Surface Reactions 83Problems 84References 87Chapter 4 | Atmospheric Radiation and Photochemistry 884.1 Radiation 884.2 Radiative Flux in the Atmosphere 914.3 Beer . Lambert Law and Optical Depth 934.4 Actinic Flux 954.5 Atmospheric Photochemistry 974.6 Absorption of Radiation by Atmospheric Gases 1004.7 Absorption by O2 and O3 1054.8 Photolysis Rate as a Function of Altitude 1094.9 Photodissociation of O3 to Produce O and O(1D) 1124.10 Photodissociation of NO2 114Problems 117References 117Chapter 5 | Chemistry of the Stratosphere 1195.1 Chapman Mechanism 1225.2 Nitrogen Oxide Cycles 1295.3 HOx Cycles 1345.4 Halogen Cycles 1395.5 Reservoir Species and Coupling of the Cycles 1445.6 Ozone Hole 1465.7 Heterogeneous (Nonpolar) Stratospheric Chemistry 1555.8 Summary of Stratospheric Ozone Depletion 1625.9 Transport and Mixing in the Stratosphere 1655.10 Ozone Depletion Potential 167Problems 168References 173Chapter 6 | Chemistry of the Troposphere 1756.1 Production of Hydroxyl Radicals in the Troposphere 1766.2 Basic Photochemical Cycle of NO2, NO, and O3 1796.3 Atmospheric Chemistry of Carbon Monoxide 1816.4 Atmospheric Chemistry of Methane 1886.5 The NOx and NOy Families 1926.6 Ozone Budget of the Troposphere and Role of NOx 1956.7 Tropospheric Reservoir Molecules 2036.8 Relative Roles of VOC and NOx in Ozone Formation 2086.9 Simplified Organic/NOx Chemistry 2126.10 Chemistry of Nonmethane Organic Compounds in the Troposphere 2146.11 Atmospheric Chemistry of Biogenic Hydrocarbons 2336.12 Atmospheric Chemistry of Reduced Nitrogen Compounds 2446.13 Atmospheric Chemistry (Gas Phase) of Sulfur Compounds 2466.14 Tropospheric Chemistry of Halogen Compounds 2496.15 Atmospheric Chemistry of Mercury 253Appendix 6 Organic Functional Groups 254Problems 256References 259Chapter 7 | Chemistry of the Atmospheric Aqueous Phase 2657.1 Liquid Water in the Atmosphere 2657.2 Absorption Equilibria and Henry's Law 2687.3 Aqueous-Phase Chemical Equilibria 2717.4 Aqueous-Phase Reaction Rates 2847.5 S(IV)-S(VI) Transformation and Sulfur Chemistry 2867.6 Dynamic Behavior of Solutions with Aqueous-Phase Chemical Reactions 295Appendix 7.1 Thermodynamic and Kinetic Data 301Appendix 7.2 Additional Aqueous-Phase Sulfur Chemistry 3057A.1 S(IV) Oxidation by the OH Radical 3057A.2 Oxidation of S(IV) by Oxides of Nitrogen 3087A.3 Reaction of Dissolved SO2 with HCHO 309Appendix 7.3 Aqueous-Phase Nitrite and Nitrate Chemistry 3117A.4 NOx Oxidation 3117A.5 Nitrogen Radicals 311Appendix 7.4 Aqueous-Phase Organic Chemistry 312Appendix 7.5 Oxygen and Hydrogen Chemistry 313Problems 314References 317PART III | AerosolsChapter 8 | Properties of the Atmospheric Aerosol 3258.1 The Size Distribution Function 3258.2 Ambient Aerosol Size Distributions 3428.3 Aerosol Chemical Composition 3528.4 Spatiotemporal Variation 354Problems 357References 359Chapter 9 | Dynamics of Single Aerosol Particles 3629.1 Continuum and Noncontinuum Dynamics: the Mean Free Path 3629.2 The Drag on a Single Particle: Stokes' Law 3689.3 Gravitational Settling of an Aerosol Particle 3729.4 Motion of an Aerosol Particle in an External Force Field 3769.5 Brownian Motion of Aerosol Particles 3769.6 Aerosol and Fluid Motion 3859.7 Equivalent Particle Diameters 388Problems 393References 394Chapter 10 | Thermodynamics of Aerosols 39610.1 Thermodynamic Principles 39610.2 Aerosol Liquid Water Content 40910.3 Equilibrium Vapor Pressure Over a Curved Surface: the Kelvin Effect 41910.4 Thermodynamics of Atmospheric Aerosol Systems 42310.5 Aerosol Thermodynamic Models 440Problems 442References 443Chapter 11 | Nucleation 44811.1 Classical Theory of Homogeneous Nucleation: Kinetic Approach 44911.2 Classical Homogeneous Nucleation Theory: Constrained Equilibrium Approach 45711.3 Recapitulation of Classical Theory 46411.4 Experimental Measurement of Nucleation Rates 46511.5 Modifications of the Classical Theory and More Rigorous Approaches 46711.6 Binary Homogeneous Nucleation 46811.7 Binary Nucleation in the H2SO4-H2O System 47311.8 Nucleation on an Insoluble Foreign Surface 47511.9 Ion-Induced Nucleation 47811.10 Atmospheric New-Particle Formation 480Appendix 11 The Law of Mass Action 487Problems 489References 490Chapter 12 | Mass Transfer Aspects of Atmospheric Chemistry 49312.1 Mass and Heat Transfer to Atmospheric Particles 49312.2 Mass Transport Limitations in Aqueous-Phase Chemistry 50312.3 Mass Transport and Aqueous-Phase Chemistry 51112.4 Mass Transfer to Falling Drops 52612.5 Characteristic Time for Atmospheric Aerosol Equilibrium 527Appendix 12 Solution of the Transient Gas-Phase Diffusion Problem: Equations (12.4)-(12.7) 532Problems 533References 535Chapter 13 | Dynamics of Aerosol Populations 53713.1 Mathematical Representations of Aerosol Size Distributions 53713.2 Condensation 53813.3 Coagulation 54413.4 The Discrete General Dynamic Equation 55713.5 The Continuous General Dynamic Equation 558Appendix 13.1 Additional Mechanisms of Coagulation 56013A.1 Coagulation in Laminar Shear Flow 56013A.2 Coagulation in Turbulent Flow 56013A.3 Coagulation from Gravitational Settling 56113A.4 Brownian Coagulation and External Force Fields 562Appendix 13.2 Solution of (13.73) 567Problems 568References 571Chapter 14 | Atmospheric Organic Aerosols 57314.1 Chemistry of Secondary Organic Aerosol Formation 57414.2 Volatility of Organic Compounds 58214.3 Idealized Description of Secondary Organic Aerosol Formation 58314.4 Gas-Particle Partitioning 59014.5 Models of SOA Formation and Evolution 59614.6 Primary Organic Aerosol 60514.7 The Physical State of Organic Aerosols 60814.8 SOA Particle-Phase Chemistry 61014.9 Aqueous-Phase Secondary Organic Aerosol Formation 61514.10 Estimates of the Global Budget of Atmospheric Organic Aerosol 622Problems 623References 626Chapter 15 | Interaction of Aerosols with Radiation 63315.1 Scattering and Absorption of Light by Small Particles 63315.2 Visibility 64415.3 Scattering, Absorption, and Extinction Coefficients From Mie Theory 64715.4 Calculated Visibility Reduction Based on Atmospheric Data 651Appendix 15 Calculation of Scattering and Extinction Coefficients by Mie Theory 654Problems 654References 656PART IV | Physical and Dynamic Meteorology, Cloud Physics, and Atmospheric DiffusionChapter 16 | Physical and Dynamic Meteorology 66116.1 Temperature in the Lower Atmosphere 66116.2 Atmospheric Stability 66516.3 The Moist Atmosphere 67016.4 Basic Conservation Equations for the Atmospheric Surface Layer 68316.5 Variation of Wind with Height in the Atmosphere 692Appendix 16.1 Properties of Water and Water Solutions 70116A.1 Specific Heat of Water and Ice 70116A.2 Latent Heats of Vaporization and Melting for Water 70116A.3 Water Surface Tension 701Appendix 16.2 Derivation of the Basic Equations of Surface-Layer Atmospheric Fluid Mechanics 702Problems 705References 706Chapter 17 | Cloud Physics 70817.1 Equilibrium of Water Droplets in the Atmosphere 70817.2 Cloud and Fog Formation 71917.3 Growth Rate of Individual Cloud Droplets 72317.4 Growth of a Droplet Population 72617.5 Cloud Condensation Nuclei 73017.6 Cloud Processing of Aerosols 73617.7 Other Forms of Water in the Atmosphere 743Appendix 17 Extended Köhler Theory 75117A.1 Modified Form of Köhler Theory for a Soluble Trace Gas 75117A.2 Modified Form of Köhler Theory for a Slightly Soluble Substance 75417A.3 Modified Form of Köhler Theory for a Surface-Active Solute 75517A.4 Examples 756Problems 759References 760Chapter 18 | Atmospheric Diffusion 76318.1 Eulerian Approach 76318.2 Lagrangian Approach 76618.3 Comparison of Eulerian and Lagrangian Approaches 76718.4 Equations Governing the Mean Concentration of Species in Turbulence 76718.5 Solution of the Atmospheric Diffusion Equation for an Instantaneous Source 77118.6 Mean Concentration from Continuous Sources 77218.7 Statistical Theory of Turbulent Diffusion 77818.8 Summary of Atmospheric Diffusion Theories 78318.9 Analytical Solutions for Atmospheric Diffusion: the Gaussian Plume Equation and Others 78418.10 Dispersion Parameters in Gaussian Models 79118.11 Plume Rise 79618.12 Functional Forms of Mean Windspeed and Eddy Diffusivities 79818.13 Solutions of the Steady-State Atmospheric Diffusion Equation 803Appendix 18.1 Further Solutions of Atmospheric Diffusion Problems 80718A.1 Solution of (18.29)-(18.31) 80718A.2 Solution of (18.50) and (18.51) 80918A.3 Solution of (18.59)-(18.61) 810Appendix 18.2 Analytical Properties of the Gaussian Plume Equation 811Problems 815References 823PART V | Dry and Wet DepositionChapter 19 | Dry Deposition 82919.1 Deposition Velocity 82919.2 Resistance Model for Dry Deposition 83019.3 Aerodynamic Resistance 83419.4 Quasilaminar Resistance 83519.5 Surface Resistance 83919.6 Measurement of Dry Deposition 84919.7 Some Comments on Modeling and Measurement of Dry Deposition 851Problems 852References 854Chapter 20 | Wet Deposition 85620.1 General Representation of Atmospheric Wet Removal Processes 85620.2 Below-Cloud Scavenging of Gases 86020.3 Precipitation Scavenging of Particles 86820.4 In-Cloud Scavenging 87320.5 Acid Deposition 87420.6 Acid Deposition Process Synthesis 878Problems 881References 886PART VI | The Global Atmosphere, Biogeochemical Cycles, and ClimateChapter 21 | General Circulation of the Atmosphere 89121.1 Hadley Cell 89321.2 Ferrell Cell and Polar Cell 89321.3 Coriolis Force 89521.4 Geostrophic Windspeed 89721.5 The Thermal Wind Relation 90221.6 Stratospheric Dynamics 90521.7 The Hydrologic Cycle 905Problems 906References 907Chapter 22 | Global Cycles: Sulfur and Carbon 90822.1 The Atmospheric Sulfur Cycle 90822.2 The Global Carbon Cycle 91222.3 Solution for a Steady-State Four-Compartment Model of the Atmosphere 923Problems 927References 929Chapter 23 | Global Climate 93123.1 Earth's Energy Balance 93123.2 Radiative Forcing 93323.3 The Greenhouse Effect 93623.4 Climate-Forcing Agents 94223.5 Cosmic Rays and Climate 94923.6 Climate Sensitivity 95023.7 Simplified Dynamic Description of Climate Forcing and Response 95123.8 Climate Feedbacks 95523.9 Relative Radiative Forcing Indices 96023.10 Atmospheric Chemistry and Climate Change 96123.11 Conclusion 964Problems 965References 967Chapter 24 | Aerosols and Climate 97024.1 Scattering-Absorbing Model of an Aerosol Layer 97224.2 Cooling Versus Heating of an Aerosol Layer 97524.3 Scattering Model of an Aerosol Layer for a Nonabsorbing Aerosol 97724.4 Upscatter Fraction 97924.5 Optical Depth and Column Forcing 98124.6 Internal and External Mixtures 98524.7 Top-of-the-Atmosphere Versus Surface Forcing 98724.8 Indirect Effects of Aerosols on Climate 990Problems 1004References 1004PART VII | Chemical Transport Models and Statistical ModelsChapter 25 | Atmospheric Chemical Transport Models 101125.1 Introduction 101125.2 Box Models 101425.3 Three-Dimensional Atmospheric Chemical Transport Models 102025.4 One-Dimensional Lagrangian Models 102425.5 Other Forms of Chemical Transport Models 102625.6 Numerical Solution of Chemical Transport Models 103125.7 Model Evaluation 104625.8 Response of Organic and Inorganic Aerosols to Changes in Emission 1047Problems 1048References 1050Chapter 26 | Statistical Models 105126.1 Receptor Modeling Methods 105126.2 Chemical Mass Balance (CMB) 105426.3 Factor Analysis 105926.4 Methods Incorporating Wind Information 106726.5 Probability Distributions for Air Pollutant Concentrations 107226A.1 The Lognormal Distribution 107326A.2 The Weibull Distribution 107426.6 Estimation of Parameters in the Distributions 107426A.1 Method of Quantiles 107526A.2 Method of Moments 107626.7 Order Statistics of Air Quality Data 107826A.1 Basic Notions and Terminology of Order Statistics 107826A.2 Extreme Values 107926.8 Exceedances of Critical Levels 108026.9 Alternative Forms of Air Quality Standards 108026.10 Relating Current and Future Air Pollutant Statistical Distributions 1083Problems 1085References 1087AppendixesAppendix A: | Units and Physical Constants 1091A.1 SI Base Units 1091A.2 SI Derived Units 1092A.3 Fundamental Physical Constants 1094A.4 Properties of the Atmosphere and Water 1094A.5 Units for Representing Chemical Reactions 1096A.6 Concentrations in the Aqueous Phase 1096A.7 Symbols Denoting Concentration 1097References 1097Appendix B: | Rate Constants of Atmospheric Chemical Reactions 1098References 1106Appendix C: | Abbreviations 1107Index 1112