Chemistry of the Upper and Lower Atmosphere

Description

Here is the most comprehensive and up-to-date treatment of one of the hottest areas of chemical research. The treatment of fundamental kinetics and photochemistry will be highly useful to chemistry students and their instructors at the graduate level, as well as postdoctoral fellows entering this new, exciting, and well-funded field with a Ph.D. in a related discipline (e.g., analytical, organic, or physical chemistry, chemical physics, etc.). Chemistry of the Upper and Lower Atmosphere provides postgraduate researchers and teachers with a uniquely detailed, comprehensive, and authoritative resource. The text bridges the "gap" between the fundamental chemistry of the earth's atmosphere and "real world" examples of its application to the development of sound scientific risk assessments and associated risk management control strategies for both tropospheric and stratospheric pollutants.

Serves as a graduate textbook and "must have" reference for all atmospheric scientists
Provides more than 5000 references to the literature through the end of 1998
Presents tables of new actinic flux data for the troposphere and stratospher (0-40km)
Summarizes kinetic and photochemical date for the troposphere and stratosphere
Features problems at the end of most chapters to enhance the book's use in teaching
Includes applications of the OZIPR box model with comprehensive chemistry for student use

Front Cover 2
Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications 5
Copyright Page 6
Contents 9
Preface 19
About the Authors 21
Acknowledgments 23
Chapter 1. Overview of the Chemistry of Polluted and Remote Atmospheres 25
- A. REGIONS AND CHARACTERISTICS OF THE ATMOSPHERE 26
- B. AIR POLLUTION AND THE CHEMISTRY OF OUR TROPOSPHERE 27
  - 2. "London" Smog: Sulfur Dioxide, Acidic Aerosols, and Soot 27
  - 1. Historical Perspectives: Ancient and Medieval Times 27
  - 3. "Los Angeles" Smog: Ozone and Photochemical Oxidants 28
  - 4. Acid Deposition 32
- C. CHEMISTRY OF THE NATURAL TROPOSPHERE: REMOTE ATMOSPHERES 33

Front Cover 2
Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications 5
Copyright Page 6
Contents 9
Preface 19
About the Authors 21
Acknowledgments 23
Chapter 1. Overview of the Chemistry of Polluted and Remote Atmospheres 25
- A. REGIONS AND CHARACTERISTICS OF THE ATMOSPHERE 26
- B. AIR POLLUTION AND THE CHEMISTRY OF OUR TROPOSPHERE 27
  - 2. "London" Smog: Sulfur Dioxide, Acidic Aerosols, and Soot 27
  - 1. Historical Perspectives: Ancient and Medieval Times 27
  - 3. "Los Angeles" Smog: Ozone and Photochemical Oxidants 28
  - 4. Acid Deposition 32
- C. CHEMISTRY OF THE NATURAL TROPOSPHERE: REMOTE ATMOSPHERES 33
- D. CHEMISTRY OF THE STRATOSPHERE 34
- E. GLOBAL CLIMATE CHANGE 35
- F. INDOOR AIR POLLUTION 37
- G. DISCUSSION TOPIC AND OZIPR MODEL 37
  - 1. Discussion Topic: "Background Ozone" 37
  - 2. OZIPR Model 37
- REFERENCES 37
Chapter 2. The Atmospheric System 39
- A. EMISSIONS 39
  - 1. Oxides of Nitrogen 41
  - 2. Volatile Organic Compounds (VOC) 42
  - 4. Sulfur Compounds 44
  - 3. Carbon Monoxide 44
  - 5. Total Suspended Particles (TSP), PM10, and PM2.5 45
  - 6. Lead 49
- B. METEOROLOGY 50
  - 1. Lapse Rate: Temperature and Altitude 50
  - 2. Potential Temperature 52
  - 3. Temperature Inversions 52
- C. REMOVAL FROM THE ATMOSPHERE: WET AND DRY DEPOSITION 54
- D. TYPICAL AMBIENT CONCENTRATIONS AND AIR QUALITY STANDARDS 57
  - 1. Units of Concentrations and Conversions 57
  - 2. Criteria and Noncriteria Pollutants and Air Quality Standards 59
- E. EFFECTS ON VISIBILITY AND MATERIALS 61
- G. ATMOSPHERIC CHEMISTRY: RISK ASSESSMENTS AND PUBLIC POLICIES FOR AIR POLLUTION CONTROL 62
- F. ECONOMICS 62
- H. PROBLEMS 63
- REFERENCES 63
Chapter 3. Spectroscopy and Photochemistry: Fundamentals 67
- A. BASIC PRINCIPLES 67
  - 1. Molecular Energy Levels and Absorption and Emission Spectroscopy 67
  - 2. Fates of Electronically Excited Molecules 74
- B. ABSORPTION OF LIGHT 76
  - 1. Basic Relationships 76
  - 2. The Beer – Lambert Law 77
- C. ATMOSPHERIC PHOTOCHEMISTRY 79
  - 1. Solar Radiation and Its Transmission through the Atmosphere 79
  - 2. Calculating Photolysis Rates in the Atmosphere 85
  - 3. Procedure for Calculating Photolysis Rates 100
  - 4. Example: Photolysis of Acetaldehyde at the Earth's Surface 105
- D. PROBLEMS 107
- REFERENCES 108
Chapter 4. Photochemistry of Important Atmospheric Species 110
- A. MOLECULAR OXYGEN 110
  - 1. Absorption Spectra 110
  - 2. Photochemistry 113
- B. OZONE 114
  - 1. Absorption Spectra 114
  - 2. Photochemistry 115
- C. NITROGEN DIOXIDE 119
  - 1. Absorption Spectra 119
  - 2. Photochemistry 120
- D. NITRIC ACID 122
- E. NITROUS ACID 123
- F. PEROXYNITRIC ACID 124
- G. NITRATE RADICAL 124
- H. DINITROGEN PENTOXIDE 125
- I. NITROUS OXIDE 125
- J. ORGANIC NITRATES AND PEROXYACETYL NITRATE 126
  - 1. Organic Nitrates 126
  - 2. Peroxyacetyl Nitrate 127
- K. SULFUR DIOXIDE AND SULFUR TRIOXIDE 127
  - 1. SO2 127
  - 2. SO3 129
- L. HYDROGEN PEROXIDE AND ORGANIC HYDROPEROXIDES 131
- M. ALDEHYDES AND KETONES 131
- N. CHLORINE NITRATE (ClONO2) AND BROMINE NITRATE (BrONO2) 135
- O. HCl AND HBr 137
- Q. ClO, BrO, AND IO 138
- R. ClOOCl 138
- P. THE HALOGENS 138
- T. HOCl, HOBr, AND HOI 139
- S. OClO 139
- W. PROBLEMS 141
- U. NITROSYL CHLORIDE (ClNO) AND NITRYL CHLORIDE (ClNO2) 141
- V. HALOGENATED METHANES AND ETHANES 141
- REFERENCES 150
Chapter 5. Kinetics and Atmospheric Chemistry 154
- A. FUNDAMENTAL PRINCIPLES OF GAS-PHASE KINETICS 154
  - 1. Definitions 154
  - 2. Termolecular Reactions and Pressure Dependence of Rate Constants 157
  - 3. Temperature Dependence of Rate Constants 162
- B. LABORATORY TECHNIQUES FOR DETERMINING ABSOLUTE RATE CONSTANTS FOR GAS-PHASE REACTIONS 165
  - 1. Kinetic Analysis 166
  - 2. Fast-Flow Systems 166
  - 3. Flash Photolysis Systems 169
  - 4. Pulse Radiolysis 170
  - 5. Cavity Ring Down Method 171
  - 6. Static Techniques 172
- C. LABORATORY TECHNIQUES FOR DETERMINING RELATIVE RATE CONSTANTS FOR GAS-PHASE REACTIONS 173
- D. REACTIONS IN SOLUTION 175
  - 1. Interactions of Gaseous Air Pollutants with Atmospheric Aqueous Solutions 175
  - 2. Diffusion-Controlled Reactions of Uncharged Nonpolar Species in Solution 176
  - 3. Reactions of Charged Species in Solution 177
  - 4. Experimental Techniques Used for Studying Solution Reactions 179
- E. LABORATORY TECHNIQUES FOR STUDYING HETEROGENEOUS REACTIONS 180
  - 1. Analysis of Systems with Gas- and Liquid-Phase Diffusion, Mass Accommodation, and Reactions in the Liquid Phase or at the Int 182
  - 2. Knudsen Cells 189
  - 4. Falling-Droplet Apparatus 191
  - 3. Flow Tube Studies 191
  - 6. Aerosol Chambers 192
  - 5. Bubble Apparatus 192
  - 7. Liquid Jet Apparatus 193
  - 9. Surface Science Techniques 195
  - 8. DRIFTS 195
  - 10. Other Methods 196
- F. COMPILATIONS OF KINETIC DATA FOR ATMOSPHERIC REACTIONS 196
- G. PROBLEMS 198
- REFERENCES 199
Chapter 6. Rates and Mechanisms of Gas-Phase Reactions in Irradiated Organic – NOx – Air Mixtures 203
- A. SOURCES OF OXIDANTS IN THE TROPOSPHERE: OH, O3, NO3, HO2, AND Cl 203
  - 1. OH 203
  - 2. O3 204
  - 5. Cl 204
  - 3. NO3 204
  - 4. HO2 204
- B. LIFETIMES OF TYPICAL ORGANICS IN THE TROPOSPHERE 205
- C. REACTIONS OF ALKANES 206
  - 1. Hydroxyl Radical (OH) 206
  - 3. Chlorine Atoms (Cl) 208
  - 2. Nitrate Radical (NO3) 208
- D. REACTIONS OF ALKYL (R), ALKYLPEROXY (RO2), AND ALKOXY (RO) RADICALS IN AIR 209
  - 2. Alkylperoxy Radicals (RO2) 209
  - 1. Alkyl Radicals (R) 209
  - 3. Alkoxy Radicals (RO) 212
  - 4. Summary of R, RO2, and RO Radical Reactions in the Troposphere 215
- E. REACTIONS OF ALKENES (INCLUDING BIOGENICS) 215
  - 1. Hydroxyl Radical (OH) 215
  - 2. Ozone (O3) 220
  - 3. Nitrate Radical (NO3) 225
  - 4. Chlorine Atoms (Cl) 229
  - 5. Nitrogen Dioxide (NO2) 230
- F. REACTIONS OF ALKYNES 230
  - 1. Hydroxyl Radical (OH) 230
- G. REACTIONS OF SIMPLE AROMATIC HYDROCARBONS 231
  - 1. Hydroxyl Radical (OH) 231
  - 2. Nitrate Radical (NO3) 236
  - 3. Chlorine Atoms (Cl) 236
- H. REACTIONS OF OXYGEN-CONTAINING ORGANICS 237
  - 1. Reactions of OH, NO3, and Cl 237
  - 2. Hydroperoxyl Radical (HO2) 240
- I. REACTIONS OF NITROGENOUS ORGANICS 241
  - 1. Peroxyacetyl Nitrate and Its Homologs 241
  - 2. Alkyl Nitrates and Nitrites 244
  - 3. Amines, Nitrosamines, and Hydrazines 245
- J. CHEMISTRY OF REMOTE REGIONS 249
  - 1. Emissions of Biogenic Organics 249
  - 2. Chemistry 255
  - 3. Upper Troposphere 263
  - 4. Arctic 265
- K. ATMOSPHERIC CHEMISTRY AND BIOMASS BURNING 268
- L. PROBLEMS 271
- REFERENCES 272
Chapter 7. Chemistry of Inorganic Nitrogen Compounds 288
- A. OXIDATION OF NO TO NO2 AND THE LEIGHTON RELATIONSHIP 289
- B. OXIDATION OF NO2 290
  - 1. Daytime Gas-Phase Reaction with OH 290
  - 2. Nighttime Reactions to Form NO3 and N2O5 291
  - 3. Reactions of NO and NO2 with Water and Alcohols 292
  - 4. Other Reactions of NO2 296
- C. ATMOSPHERIC CHEMISTRY OF HONO 297
  - 1. Formation of HONO 297
  - 2. Atmospheric Fates of HONO 298
- D. REACTIONS OF NO3 AND N2O5 300
  - 1. Reactions of NO3 300
  - 2. Reactions of N2O5 303
- E. ATMOSPHERIC CHEMISTRY OF HNO3 305
  - 2. Tropospheric Fates 305
  - 1. Formation 305
- F. "MISSING" NOy 310
- G. AMMONIA (NH3) 310
- H. PROBLEMS 311
- REFERENCES 312
Chapter 8. Acid Deposition: Formation and Fates of Inorganic and Organic Acids in the Troposphere 318
- A. CONTRIBUTION OF H2SO4, HNO3, HONO, AND ORGANIC ACIDS 318
- B. SOLUBILITY OF GASES IN RAIN, FOGS, AND CLOUDS: HENRY'S LAW AND AQUEOUS-PHASE EQUILIBRIA 319
- C. OXIDATION OF SO2 320
  - 1. Field Studies 320
  - 2. Oxidation in the Gas Phase 322
  - 3. Oxidation in the Aqueous Phase 325
  - 4. Oxidation on Surfaces 348
  - 5. Relative Importance of Various Oxidation Pathways for SO2 349
- D. ORGANIC ACIDS 350
- E. OXIDATION OF SULFUR COMPOUNDS OTHER THAN SO2 352
  - 1. Reactions of Dimethyl Sulfide (CH3SCH3) 353
  - 2. Dimethyl Disulfide (CH3SSCH3) 358
  - 3. Methyl Mercaptan (CH3SH) 358
  - 4. Hydrogen Sulfide (H2S) 359
  - 5. Carbon Disulfide (CS2) 359
  - 6. Carbonyl Sulfide (COS) 360
- F. PROBLEMS 360
- REFERENCES 361
Chapter 9. Particles in the Troposphere 373
- A. PHYSICAL PROPERTIES 373
  - 1. Some Definitions 373
  - 2. Size Distributions 375
  - 3. Particle Motion 386
  - 4. Light Scattering and Absorption and Their Relationship to Visibility Reduction 389
- B. REACTIONS INVOLVED IN PARTICLE FORMATION AND GROWTH 399
  - 1. Nucleation, Condensation, and Coagulation 399
  - 2. Reactions of Gases at Particle Surfaces 403
  - 3. Reactions in the Aqueous Phase 404
  - 4. Relative Importance of Various Aerosol Growth Mechanisms 404
- C. CHEMICAL COMPOSITION OF TROPOSPHERIC AEROSOLS 404
  - 1. Inorganic Species 405
  - 2. Organics 417
- D. GAS – PARTICLE DISTRIBUTION OF SEMIVOLATILE ORGANICS 436
  - 1. Adsorption on Solid Particles 437
  - 2. Absorption into Liquids 441
  - 3. Octanol – Air Partitioning Coefficients 444
- REFERENCES 447
- E. PROBLEMS 447
Chapter 10. Airborne Polycyclic Aromatic Hydrocarbons and Their Derivatives: Atmospheric Chemistry and Toxicological Implication 460
- A. NOMENCLATURE AND SELECTED PHYSICAL AND SPECTROSCOPIC PROPERTIES OF POLYCYCLIC AROMATIC HYDROCARBONS (PAHs) AND POLYCYCLIC ARO 464
  - 1. Combustion-Generated PAHs and PACs 464
  - 2. Structures and IUPAC Rules for Nomenclature 464
  - 3. Solubilities and Vapor Pressures 475
  - 4. Gas – Particle Partitioning, Sampling Techniques, and Ambient Levels of Selected PAHs and PACs 477
  - 5. Absorption and Emission Spectra of Selected PAHs and PACs 485
- B. BIOLOGICAL PROPERTIES OF PAHs AND PACs. I: CARCINOGENICITY 490
  - 1. Historical Perspective: Benzo[a]pyrene, the "Classic Chemical Carcinogen" 490
  - 2. Carcinogenicity of PAHs, Cancer Potencies, and Potency Equivalence Factors 491
  - 3. Carcinogenicity of Nitroarenes and Other Nitro-PACs 497
- C. BIOLOGICAL PROPERTIES OF PAHs AND PACs. II: MUTAGENICITY 499
  - 1. Short-Term Tests for Genetic and Related Effects 499
  - 2. The Ames Salmonella typhimurium Reversion Assay 499
  - 3. The Salmonella TM677 "Forward Mutation" Assay 507
  - 4. Human Cell Mutagenicities of PAHs and PACs 508
- D. BACTERIAL AND HUMAN CELL MUTAGENICITIES OF POLLUTED AMBIENT AIR 510
  - 1. Bacterial Mutagenicity of Urban Air: A Worldwide Phenomenon 510
  - 2. Sources, Ambient Levels, Transport, and Transformation: Some Case Studies 515
  - 3. Bioassay-Directed Chemical Analysis for PAHs and PACs in Fine Ambient Aerosols Using a Human Cell Assay 521
  - 4. Bioassay-Directed Chemical Analysis for Vapor-Phase and Particle-Phase PAHs and PACs in Ambient Air Using Bacterial Assays 526
- E. ATMOSPHERIC FATES OF PARTICLE-ASSOCIATED PAHs: HETEROGENEOUS REACTIONS 528
  - 1. Background 528
  - 2. Theoretical and Experimental Structure – Reactivity Relationships 529
  - 3. Field Studies of Atmospheric Reactions: Transport and Transformation 531
  - 4. Photochemical Reactions of Particle-Associated PAHs 534
  - 5. Gas – Particle Reactions 537
  - 6. Atmospheric Fates of Particle-Associated Nitroarenes 542
- F. REACTIONS OF GAS-PHASE PAHs: ATMOSPHERIC FORMATION OF MUTAGENIC NITROARENES 543
  - 1. Combustion-Generated Primary Emissions of Nitroarenes 543
  - 2. Atmospheric Formation of Nitro-PAHs and Nitro-PACs 544
- REFERENCES 551
Chapter 11. Analytical Methods and Typical Atmospheric Concentrations for Gases and Particles 571
- A. GASES 572
  - 1. Optical Spectroscopic Techniques 572
  - 2. Mass Spectrometry 585
  - 3. Filters, Denuders, Transition Flow Reactors, Mist Chambers, and Scrubbers 591
  - 4. Methods for, and Tropospheric Levels of, Specific Gases 593
  - 5. Generation of Standard Gas Mixtures 631
- B. PARTICLES 632
  - 1. Sampling and Collection of Particles 632
  - 2. Measurement of Physical Characteristics: Mass and Size 636
  - 3. Measurement of Chemical Composition 643
  - 4. Real-Time Monitoring Techniques for Particles 650
  - 5. Generation of Calibration Aerosols 656
- C. PROBLEMS 659
- REFERENCES 660
Chapter 12. Homogeneous and Heterogeneous Chemistry in the Stratosphere 681
- A. CHEMISTRY OF THE UNPERTURBED STRATOSPHERE 681
  - 1. Stratosphere – Troposphere Exchange (STE) 682
  - 2. Chapman Cycle and NOx Chemistry 684
- B. HIGH-SPEED CIVIL TRANSPORT (HSCT), ROCKETS, AND THE SPACE SHUTTLE 686
  - 1. HSCT 686
  - 2. Space Shuttle and Solid Rocket Motors 691
- C. CHLOROFLUOROCARBONS 693
  - 1. Types, Nomenclature, and Uses 693
  - 2. Lifetimes and Atmospheric Fates of CFCs and Halons 694
  - 3. Gas-Phase Chemistry in the Stratosphere 697
  - 4. Antarctic "Ozone Hole" 699
  - 5. Polar Stratospheric Clouds (PSCs) and Aerosols 704
  - 6. Effects of Volcanic Eruptions 714
  - 7. Ozone Depletion in the Arctic 720
  - 8. Ozone Destruction in the Midlatitudes 724
- D. CONTRIBUTION OF BROMINATED ORGANICS 725
  - 1. Sources and Sinks of Brominated Organics 725
  - 2. Bromine Chemistry in the Stratosphere 726
- E. CONTRIBUTION OF IODINE-CONTAINING ORGANICS 730
- G. PROBLEMS 731
- F. SUMMARY 731
- REFERENCES 732
Chapter 13. Scientific Basis for Control of Halogenated Organics 751
- A. INTERNATIONAL AGREEMENTS ON PHASEOUT OF HALOGENATED ORGANICS 751
- B. OZONE DEPLETION POTENTIALS (ODP) 754
- C. TRENDS IN CFCs, THEIR REPLACEMENTS, STRATOSPHERIC O3, AND SURFACE UV 757
  - 1. Trends in CFCs and Their Replacements 757
  - 2. Trends in Stratospheric O3 760
  - 3. Trends in Surface Ultraviolet Radiation 765

Author's affiliation

Barbara J. Finlayson-Pitts: University of California at Irvine; School of
James N. Pitts, Jr.: University of California at Irvine; School of

Theory, Experiments, and Applications

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