Item Details

Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications

Barbara J. Finlayson-Pitts, James N. Pitts, Jr.
Format
Book
Published
San Diego : Academic Press, c2000.
Language
English
ISBN
012257060X (acid-free paper)
Contents
  • 1 Overview of the Chemistry of Polluted and Remote Atmospheres
  • A. Regions and Characteristics of The Atmosphere 2
  • B. Air Pollution and the Chemistry of Our Troposphere 3
  • 1. Historical Perspectives: Ancient and Medieval Times 3
  • 2. "London" Smog: Sulfur Dioxide, Acidic Aerosols, and Soot 3
  • 3. "Los Angeles" Smog: Ozone and Photochemical Oxidants 4
  • 4. Acid Deposition 8
  • C. Chemistry of the Natural Troposphere: Remote Atmospheres 9
  • D. Chemistry of the Stratosphere 10
  • E. Global Climate Change 11
  • F. Indoor Air Pollution 13
  • G. Discussion Topic and OZIPR Model 13
  • 1. Discussion Topic: "Background Ozone" 13
  • 2. OZIPR Model 13
  • 2 Atmospheric System
  • A. Emissions 15
  • 1. Oxides of Nitrogen 17
  • 2. Volatile Organic Compounds (VOC) 18
  • 3. Carbon Monoxide 20
  • 4. Sulfur Compounds 20
  • 5. Total Suspended Particles (TSP), PM10, and PM2.5 21
  • 6. Lead 25
  • B. Meteorology 26
  • 1. Lapse Rate: Temperature and Altitude 26
  • 2. Potential Temperature 28
  • 3. Temperature Inversions 28
  • C. Removal from the Atmosphere: Wet and Dry Deposition 30
  • D. Typical Ambient Concentrations and Air Quality Standards 33
  • 1. Units of Concentrations and Conversions 33
  • 2. Criteria and Noncriteria Pollutants and Air Quality Standards 35
  • E. Effects on Visibility and Materials 37
  • F. Economics 38
  • G. Atmospheric Chemistry: Risk Assessments and Public Policies for Air Pollution Control 38
  • 3 Spectroscopy and Photochemistry: Fundamentals
  • A. Basic Principles 43
  • 1. Molecular Energy Levels and Absorption and Emission Spectroscopy 43
  • 2. Fates of Electronically Excited Molecules 50
  • B. Absorption of Light 52
  • 1. Basic Relationships 52
  • 2. Beer - Lambert Law 53
  • C. Atmospheric Photochemistry 55
  • 1. Solar Radiation and Its Transmission through the Atmosphere 55
  • 2. Calculating Photolysis Rates in the Atmosphere 61
  • 3. Procedure for Calculating Photolysis Rates 76
  • 4. Example: Photolysis of Acetaldehyde at the Earth's Surface 81
  • 4 Photochemistry of Important Atmospheric Species
  • A. Molecular Oxygen 86
  • 1. Absorption Spectra 86
  • 2. Photochemistry 89
  • B. Ozone 90
  • 1. Absorption Spectra 90
  • 2. Photochemistry 91
  • C. Nitrogen Dioxide 95
  • 1. Absorption Spectra 95
  • 2. Photochemistry 96
  • D. Nitric ACID 98
  • E. Nitrous ACID 99
  • F. Peroxynitric ACID 100
  • G. Nitrate Radical 100
  • H. Dinitrogen Pentoxide 101
  • I. Nitrous Oxide 101
  • J. Organic Nitrates and Peroxyacetyl Nitrate 102
  • 1. Organic Nitrates 102
  • 2. Peroxyacetyl Nitrate 103
  • K. Sulfur Dioxide and Sulfur Trioxide 103
  • 1. SO[subscript 2] 103
  • 2. SO[subscript 3] 105
  • L. Hydrogen Peroxide and Organic Hydroperoxides 107
  • M. Aldehydes and Ketones 107
  • N. Chlorine Nitrate (ClONO[subscript 2]) and Bromine Nitrate (BrONO[subscript 2]) 111
  • O. HCl and HBr 113
  • P. Halogens 114
  • Q. ClO, BrO, and IO 114
  • R. ClOOCl 114
  • S. OClO 115
  • T. HOCl, HOBr, and HOI 115
  • U. Nitrosyl Chloride (ClNO) and Nitryl Chloride (ClNO[subscript 2]) 117
  • V. Halogenated Methanes and Ethanes 117
  • 5 Kinetics and Atmospheric Chemistry
  • A. Fundamental Principles of Gas-Phase Kinetics 130
  • 1. Definitions 130
  • 2. Termolecular Reactions and Pressure Dependence of Rate Constants 133
  • 3. Temperature Dependence of Rate Constants 138
  • B. Laboratory Techniques for Determining Absolute Rate Constants for Gas-Phase Reactions 141
  • 1. Kinetic Analysis 142
  • 2. Fast-Flow Systems 142
  • 3. Flash Photolysis Systems 145
  • 4. Pulse Radiolysis 146
  • 5. Cavity Ring Down Method 147
  • 6. Static Techniques 148
  • C. Laboratory Techniques for Determining Relative Rate Constants for Gas-Phase Reactions 149
  • D. Reactions in Solution 151
  • 1. Interactionsn of Gaseous Air Pollutants with Atmospheric Aqueous Solutions 151
  • 2. Diffusion-Controlled Reactions of Uncharged Nonpolar Species in Solution 152
  • 3. Reactions of Charged Species in Solution 153
  • 4. Experimental Techniques Used for Studying Solution Reactions 155
  • E. Laboratory Techniques for Studying Heterogeneous Reactions 156
  • 1. Analysis of Systems with Gas- and Liquid-Phase Diffusion, Mass Accommodation, and Reactions in the Liquid Phase or at the Interface 158
  • 2. Knudsen Cells 165
  • 3. Flow Tube Studies 167
  • 4. Falling-Droplet Apparatus 167
  • 5. Bubble Apparatus 168
  • 6. Aerosol Chambers 168
  • 7. Liquid Jet Apparatus 169
  • 8. DRIFTS 171
  • 9. Surface Science Techniques 171
  • 10. Other Methods 172
  • F. Compilations of Kinetic Data for Atmospheric Reactions 172
  • 6 Rates and Mechanisms of Gas-Phase Reactions in Irradiated Organic-NO[subscript x]-Air Mixtures
  • A. Sources of Oxidants in the Troposphere: OH, O[subscript 3], NO[subscript 3], HO[subscript 2], and Cl 179
  • 1. OH 179
  • 2. O[subscript 3] 180
  • 3. NO[subscript 3] 180
  • 4. HO[subscript 2] 180
  • 5. Cl 180
  • B. Lifetimes of Typical Organics in the Troposphere 181
  • C. Reactions of Alkanes 182
  • 1. Hydroxyl Radical (OH) 182
  • 2. Nitrate Radical (NO[subscript 3]) 184
  • 3. Chlorine Atoms (Cl) 184
  • D. Reactions of Alkyl (R), Alkylperoxy (RO[subscript 2]), and Alkoxy (RO) Radicals in Air 185
  • 1. Alkyl Radicals (R) 185
  • 2. Alkylperoxy Radicals (RO[subscript 2]) 185
  • 3. Alkoxy Radicals (RO) 188
  • 4. Summary of R, RO[subscript 2], and RO Radical Reactions in the Troposphere 191
  • E. Reactions of Alkenes (Including Biocenics) 191
  • 1. Hydroxyl Radical (OH) 191
  • 2. Ozone (O[subscript 3]) 196
  • 3. Nitrate Radical (NO[subscript 3]) 201
  • 4. Chlorine Atoms (Cl) 205
  • 5. Nitrogen Dioxide (NO[subscript 2]) 206
  • F. Reactions of Alkynes 206
  • 1. Hydroxyl Radical (OH) 206
  • G. Reactions of Simple Aromatic Hydrocarbons 207
  • 1. Hydroxyl Radical (OH) 207
  • 2. Nitrate Radical (NO[subscript 3]) 212
  • 3. Chlorine Atoms (Cl) 212
  • H. Reactions of Oxygen-Containing Organics 213
  • 1. Reactions of OH, NO[subscript 3], and Cl 213
  • 2. Hydroperoxyl Radical (HO[subscript 2]) 216
  • I. Reactions of Nitrogenous Organics 217
  • 1. Peroxyacetyl Nitrate and Its Homologs 217
  • 2. Alkyl Nitrates and Nitrites 220
  • 3. Amines, Nitrosamines, and Hydrazines 221
  • J. Chemistry of Remote Regions 225
  • 1. Emissions of Biogenic Organics 225
  • 2. Chemistry 231
  • 3. Upper Troposphere 239
  • 4. Arctic 241
  • K. Atmospheric Chemistry and Biomass Burning 244
  • 7 Chemistry of Inorganic Nitrogen Compounds
  • A. Oxidation of No To NO[subscript 2] and the Leighton Relationship 265
  • B. Oxidation of NO[subscript 2] 266
  • 1. Daytime Gas-Phase Reaction with OH 266
  • 2. Nighttime Reactions to Form NO[subscript 3] and N[subscript 2]O[subscript 5] 267
  • 3. Reactions of NO and NO[subscript 2] with Water and Alcohols 268
  • 4. Other Reactions of NO[subscript 2] 272
  • C. Atmospheric Chemistry of Hono 273
  • 1. Formation of HONO 273
  • 2. Atmospheric Fates of HONO 274
  • D. Reactions of NO[subscript 3] and N[subscript 2]O[subscript 5] 276
  • 1. Reactions of NO[subscript 3] 276
  • 2. Reactions of N[subscript 2]O[subscript 5] 279
  • E. Atmospheric Chemistry of HNO[subscript 3] 281
  • 1. Formation 281
  • 2. Tropospheric Fates 281
  • F. "Missing" NO[subscript y] 286
  • G. Ammonia (NH[subscript 3]) 286
  • 8 Acid Deposition: Formation and Fates of Inorganic and Organic Acids in the Troposphere
  • A. Contribution of H[subscript 2]SO[subscript 4], HNO[subscript 3], HONO, and Organic Acids 294
  • B. Solubility of Gases in Rain, Fogs, and Clouds: Henry's Law and Aqueous-Phase Equilibria 295
  • C. Oxidation of SO[subscript 2] 296
  • 1.n Field Studies 296
  • 2. Oxidation in the Gas Phase 298
  • 3. Oxidation in the Aqueous Phase 301
  • 4. Oxidation on Surfaces 324
  • 5. Relative Importance of Various Oxidation Pathways for SO[subscript 2] 325
  • D. Organic Acids 326
  • E. Oxidation of Sulfur Compounds Other Than SO[subscript 2] 328
  • 1. Reactions of Dimethyl Sulfide (CH[subscript 3]SCH[subscript 3]) 329
  • 2. Dimethyl Disulfide (CH[subscript 3]SSCH[subscript 3]) 334
  • 3. Methyl Mercaptan (CH[subscript 3]SH) 334
  • 4. Hydrogen Sulfide (H[subscript 2]S) 335
  • 5. Carbon Disulfide (CS[subscript 2]) 335
  • 6. Carbonyl Sulfide (COS) 336
  • 9 Particles in the Troposphere
  • A. Physical Properties 349
  • 1. Some Definitions 349
  • 2. Size Distributions 351
  • 3. Particle Motion 362
  • 4. Light Scattering and Absorption and Their Relationship to Visibility Reduction 365
  • B. Reactions Involved in Particle Formation and Growth 375
  • 1. Nucleation, Condensation, and Coagulation 375
  • 2. Reactions of Gases at Particle Surfaces 379
  • 3. Reactions in the Aqueous Phase 380
  • 4. Relative Importance of Various Aerosol Growth Mechanisms 380
  • C. Chemical Composition of Tropospheric Aerosols 380
  • 1. Inorganic Species 381
  • 2. Organics 393
  • D. GAS-Particle Distribution of Semivolatile Organics 412
  • 1. Adsorption on Solid Particles 413
  • 2. Absorption into Liquids 417
  • 3. Octanol - Air Partitioning Coefficients 420
  • 10 Airborne Polycyclic Aromatic Hydrocarbons and Their Derivatives: Atmospheric Chemistry and Toxicological Implications
  • A. Nomenclature and Selected Physical and Spectroscopic Properties of Polycyclic Aromatic Hydrocarbons (PAHs) and Polycyclic Aromatic Compounds (PACs) 440
  • 1. Combustion-Generated PAHs and PACs 440
  • 2. Structures and IUPAC Rules for Nomenclature 440
  • 3. Solubilities and Vapor Pressures 451
  • -- 4. Gas - Particle Partitioning, Sampling Techniques, and Ambient Levels of Selected PAHs and PACs 453
  • 5. Absorption and Emission Spectra of Selected PAHs and PACs 461
  • B. Biological Properties of PAHs and PACs I: Carcinogenicity 466
  • 1. Historical Perspective: Benzo[a]pyrene, the "Classic Chemical Carcinogen" 466
  • 2. Carcinogenicity of PAHs, Cancer Potencies, and Potency Equivalence Factors 467
  • 3. Carcinogenicity of Nitroarenes and Other Nitro-PACs 473
  • C. Biological Properties of PAHs and PACs II: Mutagenicity 475
  • 1. Short-Term Tests for Genetic and Related Effects 475
  • 2. Ames Salmonella typhimurium Reversion Assay 475
  • 3. Salmonella TM677 "Forward Mutation" Assay 483
  • 4. Human Cell Mutagenicities of PAHs and PACs 484
  • D. Bacterial and Human Cell Mutagenicities of Polluted Ambient Air 486
  • 1. Bacterial Mutagenicity of Urban Air: A Worldwide Phenomenon 486
  • 2. Sources, Ambient Levels, Transport, and Transformation: Some Case Studies 491
  • 3. Bioassay-Directed Chemical Analysis for PAHs and PACs in Fine Ambient Aerosols Using a Human Cell Assay 497
  • 4. Bioassay-Directed Chemical Analysis for Vapor-Phase and Particle-Phase PAHs and PACs in Ambient Air Using Bacterial Assays 502
  • E. Atmospheric Fates of Particle-Associated PAHs: Heterogeneous Reactions 504
  • 2. Theoretical and Experimental Structure - Reactivity Relationships 505
  • 3. Field Studies of Atmospheric Reactions: Transport and Transformation 507
  • 4. Photochemical Reactions of Particle-Associated PAHs 510
  • 5. Gas - Particle Reactions 513
  • 6. Atmospheric Fates of Particle-Associated Nitroarenes 518
  • F. Reactions of Gas-Phase PAHs: Atmospheric Formation of Mutagenic Nitroarenes 519
  • 1. Combustion-Generated Primary Emissions of Nitroarenes 519
  • 2. Atmospheric Formation of Nitro-PAHs and Nitro-PACs 520
  • 11 Analytical Methods and Typical Atmospheric Concentrations for Gases and Particles
  • A. Gases 548
  • 1. Optical Spectroscopic Techniques 548
  • 2. Mass Spectrometry 561
  • 3. Filters, Denuders, Transition Flow Reactors, Mist Chambers, and Scrubbers 567
  • 4. Methods for, and Tropospheric Levels of, Specific Gases 569
  • 5. Generation of Standard Gas Mixtures 607
  • B. Particles 608
  • 1. Sampling and Collection of Particles 608
  • 2. Measurement of Physical Characteristics: Mass and Size 612
  • 3. Measurement of Chemcial Composition 619
  • 4. Real-Time Monitoring Techniques for Particles 626
  • 5. Generation of Calibration Aerosols 632
  • 12 Homogeneous and Heterogeneous Chemistry in the Stratosphere
  • A. Chemistry of the Unperturbed Stratosphere 657
  • 1. Stratosphere - Troposphere Exchange (STE) 658
  • 2. Chapman Cycle and NO[subscript x] Chemistry 660
  • B. High-Speed Civil Transport (HSCT), Rockets, and the Space Shuttle 662
  • 1. HSCT 662
  • 2. Space Shuttle and Solid Rocket Motors 667
  • C. Chlorofluorocarbons 669
  • 1. Types, Nomenclature, and Uses 669
  • 2. Lifetimes and Atmospheric Fates of CFCs and Halons 670
  • 3. Gas-Phase Chemistry in the Stratosphere 673
  • 4. Antarctic "Ozone Hole" 675
  • 5. Polar Stratospheric Clouds (PSCs) and Aerosols 680
  • 6. Effects of Volcanic Eruptions 690
  • 7. Ozone Depletion in the Arctic 696
  • 8. Ozone Destruction in the Midlatitudes 700
  • D. Contribution of Brominated Organics 701
  • 1. Sources and Sinks of Brominated Organics 701
  • 2. Bromine Chemistry in the Stratosphere 702
  • E. Contribution of Iodine-Containing Organics 706
  • 13 Scientific Basis for Control of Halogenated Organics
  • A. International Agreements on Phaseout of Halogenated Organics 727
  • B. Ozone Depletion Potentials (ODP) 730
  • C. Trends in CFCs, Their Replacements, Stratospheric O[subscript 3], and Surface UV 733
  • 1. Trends in CFCs and Their Replacements 733
  • 2. Trends in Stratospheric O[subscript 3] 736 --n 3. Trends in Surface Ultraviolet Radiation 741
  • D. Tropospheric Chemistry of Alternate CFCs 744
  • 1. Kinetics of OH Reactions 744
  • 2. Tropospheric Chemistry 746
  • 14 Global Tropospheric Chemistry and Climate Change
  • A. Radiation Balance of the Atmosphere: The Greenhouse Effect 763
  • 1. Global Absorption and Emission of Radiation 763
  • 2. Radiative Transfer Processes in the Atmosphere 766
  • 3. Dependence of Net Infrared Absorption on Atmospheric Concentrations 769
  • B. Contribution of Trace Gases to the Greenhouse Effect 770
  • 1. Infrared Absorption by Trace Gases 770
  • 2. Trends in Trace Gas Concentrations 773
  • 3. Radiative Forcing by Greenhouse Gases and Global Warming Potentials 783
  • C. Aerosol Particles, Atmospheric Radiation, and Climate Change 788
  • 1. Direct Effects 789
  • 2. Indirect Effects of Aerosol Particles 799
  • D. Some Other Factors Affecting Global Climate 814
  • 1. Absorption of Solar Radiation by Clouds 814
  • 2. Feedbacks: Water Vapor, Clouds, and the "Supergreenhouse Effect" 819
  • 3. Solar Variability 821
  • 4. Volcanic Eruptions 822
  • 5. Oceans 822
  • E. Observations of Climate Changes 823
  • 1. Observed Temperature Trends 823
  • 2. Other Climate Changes 828
  • F. Future 828
  • 15 Indoor Air Pollution: Sources, Levels, Chemistry, and Fates
  • A. Radon 844
  • B. Oxides of Nitrogen 846
  • 1. Levels of NO[subscript x] 846
  • 2. HONO and HNO[subscript 3] 847
  • C. CO and SO[subscript 2] 849
  • D. Volatile Organic Compounds 850
  • E. Ozone 859
  • F. Indoor VOC-NO[subscript x]-O[subscript 3] Chemistry 859
  • G. Particles 861
  • 16 Applications of Atmospheric Chemistry: Air Pollution Control Strategies and Risk Assessments for Tropospheric Ozone and Associated Photochemical Oxidants, Acids, Particles, and Hazardous Air Pollutants
  • A. Tropospheric Ozone and Associated Photochemical Oxidants 871
  • 1. Environmental Chambers 872
  • 2. Isopleths for Ozone and Other Photochemically Derived Species 882
  • 3. Models 886
  • B. Reactivity of VOC 907
  • 1. Typical Reactivity Scales 907
  • 2. Application to Control of Mobile Source Emissions 909
  • C. Field Observations of VOC, NO[subscript x], and O[subscript 3] 913
  • D. Alternate Fuels 918
  • 1. Reformulated Gasolines 918
  • 2. Compressed Natural Gas (CNG) 919
  • 3. Liquefied Petroleum Gas (LPG) 920
  • 4. Alcohol Fuels and Blends with Gasoline 920
  • 5. Hydrogen 921
  • 6. Electric Vehicles 921
  • E. Control of ACIDS 921
  • F. Control of Particles 923
  • G. Atmopsheric Chemistry and Risk Assessments of Hazardous Air Pollutants 925
  • Appendix I Enthalpies of Formation of Some Gaseous Molecules, Atoms, and Free Radicals at 298 K 943
  • Appendix II Bond Dissociation Energies 945
  • Appendix III Running the OZIPR Model 947.
Description
xxii, 969 p. : ill. ; 29 cm.
Notes
Includes bibliographical references and index.
Technical Details
  • Access in Virgo Classic

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    g| 1 t| Overview of the Chemistry of Polluted and Remote Atmospheres -- g| A. t| Regions and Characteristics of The Atmosphere g| 2 -- g| B. t| Air Pollution and the Chemistry of Our Troposphere g| 3 -- g| 1. t| Historical Perspectives: Ancient and Medieval Times g| 3 -- g| 2. t| "London" Smog: Sulfur Dioxide, Acidic Aerosols, and Soot g| 3 -- g| 3. t| "Los Angeles" Smog: Ozone and Photochemical Oxidants g| 4 -- g| 4. t| Acid Deposition g| 8 -- g| C. t| Chemistry of the Natural Troposphere: Remote Atmospheres g| 9 -- g| D. t| Chemistry of the Stratosphere g| 10 -- g| E. t| Global Climate Change g| 11 -- g| F. t| Indoor Air Pollution g| 13 -- g| G. t| Discussion Topic and OZIPR Model g| 13 -- g| 1. t| Discussion Topic: "Background Ozone" g| 13 -- g| 2. t| OZIPR Model g| 13 -- g| 2 t| Atmospheric System -- g| A. t| Emissions g| 15 -- g| 1. t| Oxides of Nitrogen g| 17 -- g| 2. t| Volatile Organic Compounds (VOC) g| 18 -- g| 3. t| Carbon Monoxide g| 20 -- g| 4. t| Sulfur Compounds g| 20 -- g| 5. t| Total Suspended Particles (TSP), PM10, and PM2.5 g| 21 -- g| 6. t| Lead g| 25 -- g| B. t| Meteorology g| 26 -- g| 1. t| Lapse Rate: Temperature and Altitude g| 26 -- g| 2. t| Potential Temperature g| 28 -- g| 3. t| Temperature Inversions g| 28 -- g| C. t| Removal from the Atmosphere: Wet and Dry Deposition g| 30 -- g| D. t| Typical Ambient Concentrations and Air Quality Standards g| 33 -- g| 1. t| Units of Concentrations and Conversions g| 33 -- g| 2. t| Criteria and Noncriteria Pollutants and Air Quality Standards g| 35 -- g| E. t| Effects on Visibility and Materials g| 37 -- g| F. t| Economics g| 38 -- g| G. t| Atmospheric Chemistry: Risk Assessments and Public Policies for Air Pollution Control g| 38 -- g| 3 t| Spectroscopy and Photochemistry: Fundamentals -- g| A. t| Basic Principles g| 43 -- g| 1. t| Molecular Energy Levels and Absorption and Emission Spectroscopy g| 43 -- g| 2. t| Fates of Electronically Excited Molecules g| 50 -- g| B. t| Absorption of Light g| 52 -- g| 1. t| Basic Relationships g| 52 -- g| 2. t| Beer - Lambert Law g| 53 -- g| C. t| Atmospheric Photochemistry g| 55 -- g| 1. t| Solar Radiation and Its Transmission through the Atmosphere g| 55 -- g| 2. t| Calculating Photolysis Rates in the Atmosphere g| 61 -- g| 3. t| Procedure for Calculating Photolysis Rates g| 76 -- g| 4. t| Example: Photolysis of Acetaldehyde at the Earth's Surface g| 81 -- g| 4 t| Photochemistry of Important Atmospheric Species -- g| A. t| Molecular Oxygen g| 86 -- g| 1. t| Absorption Spectra g| 86 -- g| 2. t| Photochemistry g| 89 -- g| B. t| Ozone g| 90 -- g| 1. t| Absorption Spectra g| 90 -- g| 2. t| Photochemistry g| 91 -- g| C. t| Nitrogen Dioxide g| 95 -- g| 1. t| Absorption Spectra g| 95 -- g| 2. t| Photochemistry g| 96 -- g| D. t| Nitric ACID g| 98 -- g| E. t| Nitrous ACID g| 99 -- g| F. t| Peroxynitric ACID g| 100 -- g| G. t| Nitrate Radical g| 100 -- g| H. t| Dinitrogen Pentoxide g| 101 -- g| I. t| Nitrous Oxide g| 101 -- g| J. t| Organic Nitrates and Peroxyacetyl Nitrate g| 102 -- g| 1. t| Organic Nitrates g| 102 -- g| 2. t| Peroxyacetyl Nitrate g| 103 -- g| K. t| Sulfur Dioxide and Sulfur Trioxide g| 103 -- g| 1. t| SO[subscript 2] g| 103 -- g| 2. t| SO[subscript 3] g| 105 -- g| L. t| Hydrogen Peroxide and Organic Hydroperoxides g| 107 -- g| M. t| Aldehydes and Ketones g| 107 -- g| N. t| Chlorine Nitrate (ClONO[subscript 2]) and Bromine Nitrate (BrONO[subscript 2]) g| 111 -- g| O. t| HCl and HBr g| 113 -- g| P. t| Halogens g| 114 -- g| Q. t| ClO, BrO, and IO g| 114 -- g| R. t| ClOOCl g| 114 -- g| S. t| OClO g| 115 -- g| T. t| HOCl, HOBr, and HOI g| 115 -- g| U. t| Nitrosyl Chloride (ClNO) and Nitryl Chloride (ClNO[subscript 2]) g| 117 -- g| V. t| Halogenated Methanes and Ethanes g| 117 -- g| 5 t| Kinetics and Atmospheric Chemistry -- g| A. t| Fundamental Principles of Gas-Phase Kinetics g| 130 -- g| 1. t| Definitions g| 130 -- g| 2. t| Termolecular Reactions and Pressure Dependence of Rate Constants g| 133 -- g| 3. t| Temperature Dependence of Rate Constants g| 138 -- g| B. t| Laboratory Techniques for Determining Absolute Rate Constants for Gas-Phase Reactions g| 141 -- g| 1. t| Kinetic Analysis g| 142 -- g| 2. t| Fast-Flow Systems g| 142 -- g| 3. t| Flash Photolysis Systems g| 145 -- g| 4. t| Pulse Radiolysis g| 146 -- g| 5. t| Cavity Ring Down Method g| 147 -- g| 6. t| Static Techniques g| 148 -- g| C. t| Laboratory Techniques for Determining Relative Rate Constants for Gas-Phase Reactions g| 149 -- g| D. t| Reactions in Solution g| 151 -- g| 1. t| Interactionsn of Gaseous Air Pollutants with Atmospheric Aqueous Solutions g| 151 -- g| 2. t| Diffusion-Controlled Reactions of Uncharged Nonpolar Species in Solution g| 152 -- g| 3. t| Reactions of Charged Species in Solution g| 153 -- g| 4. t| Experimental Techniques Used for Studying Solution Reactions g| 155 -- g| E. t| Laboratory Techniques for Studying Heterogeneous Reactions g| 156 -- g| 1. t| Analysis of Systems with Gas- and Liquid-Phase Diffusion, Mass Accommodation, and Reactions in the Liquid Phase or at the Interface g| 158 -- g| 2. t| Knudsen Cells g| 165 -- g| 3. t| Flow Tube Studies g| 167 -- g| 4. t| Falling-Droplet Apparatus g| 167 -- g| 5. t| Bubble Apparatus g| 168 -- g| 6. t| Aerosol Chambers g| 168 -- g| 7. t| Liquid Jet Apparatus g| 169 -- g| 8. t| DRIFTS g| 171 -- g| 9. t| Surface Science Techniques g| 171 -- g| 10. t| Other Methods g| 172 -- g| F. t| Compilations of Kinetic Data for Atmospheric Reactions g| 172 -- g| 6 t| Rates and Mechanisms of Gas-Phase Reactions in Irradiated Organic-NO[subscript x]-Air Mixtures -- g| A. t| Sources of Oxidants in the Troposphere: OH, O[subscript 3], NO[subscript 3], HO[subscript 2], and Cl g| 179 -- g| 1. t| OH g| 179 -- g| 2. t| O[subscript 3] g| 180 -- g| 3. t| NO[subscript 3] g| 180 -- g| 4. t| HO[subscript 2] g| 180 -- g| 5. t| Cl g| 180 -- g| B. t| Lifetimes of Typical Organics in the Troposphere g| 181 -- g| C. t| Reactions of Alkanes g| 182 -- g| 1. t| Hydroxyl Radical (OH) g| 182 -- g| 2. t| Nitrate Radical (NO[subscript 3]) g| 184 -- g| 3. t| Chlorine Atoms (Cl) g| 184 -- g| D. t| Reactions of Alkyl (R), Alkylperoxy (RO[subscript 2]), and Alkoxy (RO) Radicals in Air g| 185 -- g| 1. t| Alkyl Radicals (R) g| 185 -- g| 2. t| Alkylperoxy Radicals (RO[subscript 2]) g| 185 -- g| 3. t| Alkoxy Radicals (RO) g| 188 -- g| 4. t| Summary of R, RO[subscript 2], and RO Radical Reactions in the Troposphere g| 191 -- g| E. t| Reactions of Alkenes (Including Biocenics) g| 191 -- g| 1. t| Hydroxyl Radical (OH) g| 191 -- g| 2. t| Ozone (O[subscript 3]) g| 196 -- g| 3. t| Nitrate Radical (NO[subscript 3]) g| 201 -- g| 4. t| Chlorine Atoms (Cl) g| 205 -- g| 5. t| Nitrogen Dioxide (NO[subscript 2]) g| 206 -- g| F. t| Reactions of Alkynes g| 206 -- g| 1. t| Hydroxyl Radical (OH) g| 206 -- g| G. t| Reactions of Simple Aromatic Hydrocarbons g| 207 -- g| 1. t| Hydroxyl Radical (OH) g| 207 -- g| 2. t| Nitrate Radical (NO[subscript 3]) g| 212 -- g| 3. t| Chlorine Atoms (Cl) g| 212 -- g| H. t| Reactions of Oxygen-Containing Organics g| 213 -- g| 1. t| Reactions of OH, NO[subscript 3], and Cl g| 213 -- g| 2. t| Hydroperoxyl Radical (HO[subscript 2]) g| 216 -- g| I. t| Reactions of Nitrogenous Organics g| 217 -- g| 1. t| Peroxyacetyl Nitrate and Its Homologs g| 217 -- g| 2. t| Alkyl Nitrates and Nitrites g| 220 -- g| 3. t| Amines, Nitrosamines, and Hydrazines g| 221 -- g| J. t| Chemistry of Remote Regions g| 225 -- g| 1. t| Emissions of Biogenic Organics g| 225 -- g| 2. t| Chemistry g| 231 -- g| 3. t| Upper Troposphere g| 239 -- g| 4. t| Arctic g| 241 -- g| K. t| Atmospheric Chemistry and Biomass Burning g| 244 -- g| 7 t| Chemistry of Inorganic Nitrogen Compounds -- g| A. t| Oxidation of No To NO[subscript 2] and the Leighton Relationship g| 265 -- g| B. t| Oxidation of NO[subscript 2] g| 266 -- g| 1. t| Daytime Gas-Phase Reaction with OH g| 266 -- g| 2. t| Nighttime Reactions to Form NO[subscript 3] and N[subscript 2]O[subscript 5] g| 267 -- g| 3. t| Reactions of NO and NO[subscript 2] with Water and Alcohols g| 268 -- g| 4. t| Other Reactions of NO[subscript 2] g| 272 -- g| C. t| Atmospheric Chemistry of Hono g| 273 -- g| 1. t| Formation of HONO g| 273 -- g| 2. t| Atmospheric Fates of HONO g| 274 -- g| D. t| Reactions of NO[subscript 3] and N[subscript 2]O[subscript 5] g| 276 -- g| 1. t| Reactions of NO[subscript 3] g| 276 -- g| 2. t| Reactions of N[subscript 2]O[subscript 5] g| 279 -- g| E. t| Atmospheric Chemistry of HNO[subscript 3] g| 281 -- g| 1. t| Formation g| 281 -- g| 2. t| Tropospheric Fates g| 281 -- g| F. t| "Missing" NO[subscript y] g| 286 -- g| G. t| Ammonia (NH[subscript 3]) g| 286 -- g| 8 t| Acid Deposition: Formation and Fates of Inorganic and Organic Acids in the Troposphere -- g| A. t| Contribution of H[subscript 2]SO[subscript 4], HNO[subscript 3], HONO, and Organic Acids g| 294 -- g| B. t| Solubility of Gases in Rain, Fogs, and Clouds: Henry's Law and Aqueous-Phase Equilibria g| 295 -- g| C. t| Oxidation of SO[subscript 2] g| 296 -- g| 1.n t| Field Studies g| 296 -- g| 2. t| Oxidation in the Gas Phase g| 298 -- g| 3. t| Oxidation in the Aqueous Phase g| 301 -- g| 4. t| Oxidation on Surfaces g| 324 -- g| 5. t| Relative Importance of Various Oxidation Pathways for SO[subscript 2] g| 325 -- g| D. t| Organic Acids g| 326 -- g| E. t| Oxidation of Sulfur Compounds Other Than SO[subscript 2] g| 328 -- g| 1. t| Reactions of Dimethyl Sulfide (CH[subscript 3]SCH[subscript 3]) g| 329 -- g| 2. t| Dimethyl Disulfide (CH[subscript 3]SSCH[subscript 3]) g| 334 -- g| 3. t| Methyl Mercaptan (CH[subscript 3]SH) g| 334 -- g| 4. t| Hydrogen Sulfide (H[subscript 2]S) g| 335 -- g| 5. t| Carbon Disulfide (CS[subscript 2]) g| 335 -- g| 6. t| Carbonyl Sulfide (COS) g| 336 -- g| 9 t| Particles in the Troposphere -- g| A. t| Physical Properties g| 349 -- g| 1. t| Some Definitions g| 349 -- g| 2. t| Size Distributions g| 351 -- g| 3. t| Particle Motion g| 362 -- g| 4. t| Light Scattering and Absorption and Their Relationship to Visibility Reduction g| 365 -- g| B. t| Reactions Involved in Particle Formation and Growth g| 375 -- g| 1. t| Nucleation, Condensation, and Coagulation g| 375 -- g| 2. t| Reactions of Gases at Particle Surfaces g| 379 -- g| 3. t| Reactions in the Aqueous Phase g| 380 -- g| 4. t| Relative Importance of Various Aerosol Growth Mechanisms g| 380 -- g| C. t| Chemical Composition of Tropospheric Aerosols g| 380 -- g| 1. t| Inorganic Species g| 381 -- g| 2. t| Organics g| 393 -- g| D. t| GAS-Particle Distribution of Semivolatile Organics g| 412 -- g| 1. t| Adsorption on Solid Particles g| 413 -- g| 2. t| Absorption into Liquids g| 417 -- g| 3. t| Octanol - Air Partitioning Coefficients g| 420 -- g| 10 t| Airborne Polycyclic Aromatic Hydrocarbons and Their Derivatives: Atmospheric Chemistry and Toxicological Implications -- g| A. t| Nomenclature and Selected Physical and Spectroscopic Properties of Polycyclic Aromatic Hydrocarbons (PAHs) and Polycyclic Aromatic Compounds (PACs) g| 440 -- g| 1. t| Combustion-Generated PAHs and PACs g| 440 -- g| 2. t| Structures and IUPAC Rules for Nomenclature g| 440 -- g| 3. t| Solubilities and Vapor Pressures g| 451 --
    505
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    g| 4. t| Gas - Particle Partitioning, Sampling Techniques, and Ambient Levels of Selected PAHs and PACs g| 453 -- g| 5. t| Absorption and Emission Spectra of Selected PAHs and PACs g| 461 -- g| B. t| Biological Properties of PAHs and PACs I: Carcinogenicity g| 466 -- g| 1. t| Historical Perspective: Benzo[a]pyrene, the "Classic Chemical Carcinogen" g| 466 -- g| 2. t| Carcinogenicity of PAHs, Cancer Potencies, and Potency Equivalence Factors g| 467 -- g| 3. t| Carcinogenicity of Nitroarenes and Other Nitro-PACs g| 473 -- g| C. t| Biological Properties of PAHs and PACs II: Mutagenicity g| 475 -- g| 1. t| Short-Term Tests for Genetic and Related Effects g| 475 -- g| 2. t| Ames Salmonella typhimurium Reversion Assay g| 475 -- g| 3. t| Salmonella TM677 "Forward Mutation" Assay g| 483 -- g| 4. t| Human Cell Mutagenicities of PAHs and PACs g| 484 -- g| D. t| Bacterial and Human Cell Mutagenicities of Polluted Ambient Air g| 486 -- g| 1. t| Bacterial Mutagenicity of Urban Air: A Worldwide Phenomenon g| 486 -- g| 2. t| Sources, Ambient Levels, Transport, and Transformation: Some Case Studies g| 491 -- g| 3. t| Bioassay-Directed Chemical Analysis for PAHs and PACs in Fine Ambient Aerosols Using a Human Cell Assay g| 497 -- g| 4. t| Bioassay-Directed Chemical Analysis for Vapor-Phase and Particle-Phase PAHs and PACs in Ambient Air Using Bacterial Assays g| 502 -- g| E. t| Atmospheric Fates of Particle-Associated PAHs: Heterogeneous Reactions g| 504 -- g| 2. t| Theoretical and Experimental Structure - Reactivity Relationships g| 505 -- g| 3. t| Field Studies of Atmospheric Reactions: Transport and Transformation g| 507 -- g| 4. t| Photochemical Reactions of Particle-Associated PAHs g| 510 -- g| 5. t| Gas - Particle Reactions g| 513 -- g| 6. t| Atmospheric Fates of Particle-Associated Nitroarenes g| 518 -- g| F. t| Reactions of Gas-Phase PAHs: Atmospheric Formation of Mutagenic Nitroarenes g| 519 -- g| 1. t| Combustion-Generated Primary Emissions of Nitroarenes g| 519 -- g| 2. t| Atmospheric Formation of Nitro-PAHs and Nitro-PACs g| 520 -- g| 11 t| Analytical Methods and Typical Atmospheric Concentrations for Gases and Particles -- g| A. t| Gases g| 548 -- g| 1. t| Optical Spectroscopic Techniques g| 548 -- g| 2. t| Mass Spectrometry g| 561 -- g| 3. t| Filters, Denuders, Transition Flow Reactors, Mist Chambers, and Scrubbers g| 567 -- g| 4. t| Methods for, and Tropospheric Levels of, Specific Gases g| 569 -- g| 5. t| Generation of Standard Gas Mixtures g| 607 -- g| B. t| Particles g| 608 -- g| 1. t| Sampling and Collection of Particles g| 608 -- g| 2. t| Measurement of Physical Characteristics: Mass and Size g| 612 -- g| 3. t| Measurement of Chemcial Composition g| 619 -- g| 4. t| Real-Time Monitoring Techniques for Particles g| 626 -- g| 5. t| Generation of Calibration Aerosols g| 632 -- g| 12 t| Homogeneous and Heterogeneous Chemistry in the Stratosphere -- g| A. t| Chemistry of the Unperturbed Stratosphere g| 657 -- g| 1. t| Stratosphere - Troposphere Exchange (STE) g| 658 -- g| 2. t| Chapman Cycle and NO[subscript x] Chemistry g| 660 -- g| B. t| High-Speed Civil Transport (HSCT), Rockets, and the Space Shuttle g| 662 -- g| 1. t| HSCT g| 662 -- g| 2. t| Space Shuttle and Solid Rocket Motors g| 667 -- g| C. t| Chlorofluorocarbons g| 669 -- g| 1. t| Types, Nomenclature, and Uses g| 669 -- g| 2. t| Lifetimes and Atmospheric Fates of CFCs and Halons g| 670 -- g| 3. t| Gas-Phase Chemistry in the Stratosphere g| 673 -- g| 4. t| Antarctic "Ozone Hole" g| 675 -- g| 5. t| Polar Stratospheric Clouds (PSCs) and Aerosols g| 680 -- g| 6. t| Effects of Volcanic Eruptions g| 690 -- g| 7. t| Ozone Depletion in the Arctic g| 696 -- g| 8. t| Ozone Destruction in the Midlatitudes g| 700 -- g| D. t| Contribution of Brominated Organics g| 701 -- g| 1. t| Sources and Sinks of Brominated Organics g| 701 -- g| 2. t| Bromine Chemistry in the Stratosphere g| 702 -- g| E. t| Contribution of Iodine-Containing Organics g| 706 -- g| 13 t| Scientific Basis for Control of Halogenated Organics -- g| A. t| International Agreements on Phaseout of Halogenated Organics g| 727 -- g| B. t| Ozone Depletion Potentials (ODP) g| 730 -- g| C. t| Trends in CFCs, Their Replacements, Stratospheric O[subscript 3], and Surface UV g| 733 -- g| 1. t| Trends in CFCs and Their Replacements g| 733 -- g| 2. t| Trends in Stratospheric O[subscript 3] g| 736 --n g| 3. t| Trends in Surface Ultraviolet Radiation g| 741 -- g| D. t| Tropospheric Chemistry of Alternate CFCs g| 744 -- g| 1. t| Kinetics of OH Reactions g| 744 -- g| 2. t| Tropospheric Chemistry g| 746 -- g| 14 t| Global Tropospheric Chemistry and Climate Change -- g| A. t| Radiation Balance of the Atmosphere: The Greenhouse Effect g| 763 -- g| 1. t| Global Absorption and Emission of Radiation g| 763 -- g| 2. t| Radiative Transfer Processes in the Atmosphere g| 766 -- g| 3. t| Dependence of Net Infrared Absorption on Atmospheric Concentrations g| 769 -- g| B. t| Contribution of Trace Gases to the Greenhouse Effect g| 770 -- g| 1. t| Infrared Absorption by Trace Gases g| 770 -- g| 2. t| Trends in Trace Gas Concentrations g| 773 -- g| 3. t| Radiative Forcing by Greenhouse Gases and Global Warming Potentials g| 783 -- g| C. t| Aerosol Particles, Atmospheric Radiation, and Climate Change g| 788 -- g| 1. t| Direct Effects g| 789 -- g| 2. t| Indirect Effects of Aerosol Particles g| 799 -- g| D. t| Some Other Factors Affecting Global Climate g| 814 -- g| 1. t| Absorption of Solar Radiation by Clouds g| 814 -- g| 2. t| Feedbacks: Water Vapor, Clouds, and the "Supergreenhouse Effect" g| 819 -- g| 3. t| Solar Variability g| 821 -- g| 4. t| Volcanic Eruptions g| 822 -- g| 5. t| Oceans g| 822 -- g| E. t| Observations of Climate Changes g| 823 -- g| 1. t| Observed Temperature Trends g| 823 -- g| 2. t| Other Climate Changes g| 828 -- g| F. t| Future g| 828 -- g| 15 t| Indoor Air Pollution: Sources, Levels, Chemistry, and Fates -- g| A. t| Radon g| 844 -- g| B. t| Oxides of Nitrogen g| 846 -- g| 1. t| Levels of NO[subscript x] g| 846 -- g| 2. t| HONO and HNO[subscript 3] g| 847 -- g| C. t| CO and SO[subscript 2] g| 849 -- g| D. t| Volatile Organic Compounds g| 850 -- g| E. t| Ozone g| 859 -- g| F. t| Indoor VOC-NO[subscript x]-O[subscript 3] Chemistry g| 859 -- g| G. t| Particles g| 861 -- g| 16 t| Applications of Atmospheric Chemistry: Air Pollution Control Strategies and Risk Assessments for Tropospheric Ozone and Associated Photochemical Oxidants, Acids, Particles, and Hazardous Air Pollutants -- g| A. t| Tropospheric Ozone and Associated Photochemical Oxidants g| 871 -- g| 1. t| Environmental Chambers g| 872 -- g| 2. t| Isopleths for Ozone and Other Photochemically Derived Species g| 882 -- g| 3. t| Models g| 886 -- g| B. t| Reactivity of VOC g| 907 -- g| 1. t| Typical Reactivity Scales g| 907 -- g| 2. t| Application to Control of Mobile Source Emissions g| 909 -- g| C. t| Field Observations of VOC, NO[subscript x], and O[subscript 3] g| 913 -- g| D. t| Alternate Fuels g| 918 -- g| 1. t| Reformulated Gasolines g| 918 -- g| 2. t| Compressed Natural Gas (CNG) g| 919 -- g| 3. t| Liquefied Petroleum Gas (LPG) g| 920 -- g| 4. t| Alcohol Fuels and Blends with Gasoline g| 920 -- g| 5. t| Hydrogen g| 921 -- g| 6. t| Electric Vehicles g| 921 -- g| E. t| Control of ACIDS g| 921 -- g| F. t| Control of Particles g| 923 -- g| G. t| Atmopsheric Chemistry and Risk Assessments of Hazardous Air Pollutants g| 925 -- g| Appendix I t| Enthalpies of Formation of Some Gaseous Molecules, Atoms, and Free Radicals at 298 K g| 943 -- g| Appendix II t| Bond Dissociation Energies g| 945 -- g| Appendix III t| Running the OZIPR Model g| 947.
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    a| Atmospheric chemistry.
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    a| Pitts, James N.
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    a| QC879.6 .F57 2000 w| LC i| X004522593 k| CHECKEDOUT l| STACKS m| SCI-ENG t| BOOK
    999
      
      
    a| QC879.6 .F57 2000 w| LC i| X004972551 k| CHECKEDOUT l| STACKS m| SCI-ENG t| BOOK

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