Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications
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Table of contents
- Contentsvii
- Prefacexvii
- About the Authorsxix
- Acknowledgmentsxxi
- Chapter 1. Overview of the Chemistry of Polluted and Remote Atmospheres1
- A. REGIONS AND CHARACTERISTICS OF THE ATMOSPHERE2
- B. AIR POLLUTION AND THE CHEMISTRY OF OUR TROPOSPHERE3
- 1. Historical Perspectives: Ancient and Medieval Times3
- 2. "London" Smog: Sulfur Dioxide, Acidic Aerosols, and Soot3
- 3. "Los Angeles" Smog: Ozone and Photochemical Oxidants4
- 4. Acid Deposition8
- C. CHEMISTRY OF THE NATURAL TROPOSPHERE: REMOTE ATMOSPHERES9
- D. CHEMISTRY OF THE STRATOSPHERE10
- E. GLOBAL CLIMATE CHANGE11
- F. INDOOR AIR POLLUTION13
- G. DISCUSSION TOPIC AND OZIPR MODEL13
- 1. Discussion Topic: "Background Ozone"13
- 2. OZIPR Model13
- REFERENCES13
- Chapter 2. The Atmospheric System15
- A. EMISSIONS15
- 1. Oxides of Nitrogen17
- 2. Volatile Organic Compounds (VOC)18
- 3. Carbon Monoxide20
- 4. Sulfur Compounds20
- 5. Total Suspended Particles (TSP), PM10, and PM2.521
- 6. Lead25
- B. METEOROLOGY26
- 1. Lapse Rate: Temperature and Altitude26
- 2. Potential Temperature28
- 3. Temperature Inversions28
- C. REMOVAL FROM THE ATMOSPHERE: WET AND DRY DEPOSITION30
- D. TYPICAL AMBIENT CONCENTRATIONS AND AIR QUALITY STANDARDS33
- 1. Units of Concentrations and Conversions33
- 2. Criteria and Noncriteria Pollutants and Air Quality Standards35
- E. EFFECTS ON VISIBILITY AND MATERIALS37
- F. ECONOMICS38
- G. ATMOSPHERIC CHEMISTRY: RISK ASSESSMENTS AND PUBLIC POLICIES FOR AIR POLLUTION CONTROL38
- H. PROBLEMS39
- REFERENCES39
- Chapter 3. Spectroscopy and Photochemistry: Fundamentals43
- A. BASIC PRINCIPLES43
- 1. Molecular Energy Levels and Absorption and Emission Spectroscopy43
- 2. Fates of Electronically Excited Molecules50
- B. ABSORPTION OF LIGHT52
- 1. Basic Relationships52
- 2. The Beer – Lambert Law53
- C. ATMOSPHERIC PHOTOCHEMISTRY55
- 1. Solar Radiation and Its Transmission through the Atmosphere55
- 2. Calculating Photolysis Rates in the Atmosphere61
- 3. Procedure for Calculating Photolysis Rates76
- 4. Example: Photolysis of Acetaldehyde at the Earth's Surface81
- D. PROBLEMS83
- REFERENCES84
- Chapter 4. Photochemistry of Important Atmospheric Species86
- A. MOLECULAR OXYGEN86
- 1. Absorption Spectra86
- 2. Photochemistry89
- B. OZONE90
- 1. Absorption Spectra90
- 2. Photochemistry91
- C. NITROGEN DIOXIDE95
- 1. Absorption Spectra95
- 2. Photochemistry96
- D. NITRIC ACID98
- E. NITROUS ACID99
- F. PEROXYNITRIC ACID100
- G. NITRATE RADICAL100
- H. DINITROGEN PENTOXIDE101
- I. NITROUS OXIDE101
- J. ORGANIC NITRATES AND PEROXYACETYL NITRATE102
- 1. Organic Nitrates102
- 2. Peroxyacetyl Nitrate103
- K. SULFUR DIOXIDE AND SULFUR TRIOXIDE103
- 1. SO2103
- 2. SO3105
- L. HYDROGEN PEROXIDE AND ORGANIC HYDROPEROXIDES107
- M. ALDEHYDES AND KETONES107
- N. CHLORINE NITRATE (ClONO2) AND BROMINE NITRATE (BrONO2)111
- O. HCl AND HBr113
- P. THE HALOGENS114
- Q. ClO, BrO, AND IO114
- R. ClOOCl114
- S. OClO115
- T. HOCl, HOBr, AND HOI115
- U. NITROSYL CHLORIDE (ClNO) AND NITRYL CHLORIDE (ClNO2)117
- V. HALOGENATED METHANES AND ETHANES117
- W. PROBLEMS117
- REFERENCES126
- Chapter 5. Kinetics and Atmospheric Chemistry130
- A. FUNDAMENTAL PRINCIPLES OF GAS-PHASE KINETICS130
- 1. Definitions130
- 2. Termolecular Reactions and Pressure Dependence of Rate Constants133
- 3. Temperature Dependence of Rate Constants138
- B. LABORATORY TECHNIQUES FOR DETERMINING ABSOLUTE RATE CONSTANTS FOR GAS-PHASE REACTIONS141
- 1. Kinetic Analysis142
- 2. Fast-Flow Systems142
- 3. Flash Photolysis Systems145
- 4. Pulse Radiolysis146
- 5. Cavity Ring Down Method147
- 6. Static Techniques148
- C. LABORATORY TECHNIQUES FOR DETERMINING RELATIVE RATE CONSTANTS FOR GAS-PHASE REACTIONS149
- D. REACTIONS IN SOLUTION151
- 1. Interactions of Gaseous Air Pollutants with Atmospheric Aqueous Solutions151
- 2. Diffusion-Controlled Reactions of Uncharged Nonpolar Species in Solution152
- 3. Reactions of Charged Species in Solution153
- 4. Experimental Techniques Used for Studying Solution Reactions155
- E. LABORATORY TECHNIQUES FOR STUDYING HETEROGENEOUS REACTIONS156
- 1. Analysis of Systems with Gas- and Liquid-Phase Diffusion, Mass Accommodation, and Reactions in th158
- 2. Knudsen Cells165
- 3. Flow Tube Studies167
- 4. Falling-Droplet Apparatus167
- 5. Bubble Apparatus168
- 6. Aerosol Chambers168
- 7. Liquid Jet Apparatus169
- 8. DRIFTS171
- 9. Surface Science Techniques171
- 10. Other Methods172
- F. COMPILATIONS OF KINETIC DATA FOR ATMOSPHERIC REACTIONS172
- G. PROBLEMS174
- REFERENCES175
- Chapter 6. Rates and Mechanisms of Gas-Phase Reactions in Irradiated Organic – NOx – Air Mixture179
- A. SOURCES OF OXIDANTS IN THE TROPOSPHERE: OH, O3, NO3, HO2, AND Cl179
- 1. OH179
- 2. O3180
- 3. NO3180
- 4. HO2180
- 5. Cl180
- B. LIFETIMES OF TYPICAL ORGANICS IN THE TROPOSPHERE181
- C. REACTIONS OF ALKANES182
- 1. Hydroxyl Radical (OH)182
- 2. Nitrate Radical (NO3)184
- 3. Chlorine Atoms (Cl)184
- D. REACTIONS OF ALKYL (R), ALKYLPEROXY (RO2), AND ALKOXY (RO) RADICALS IN AIR185
- 1. Alkyl Radicals (R)185
- 2. Alkylperoxy Radicals (RO2)185
- 3. Alkoxy Radicals (RO)188
- 4. Summary of R, RO2, and RO Radical Reactions in the Troposphere191
- E. REACTIONS OF ALKENES (INCLUDING BIOGENICS)191
- 1. Hydroxyl Radical (OH)191
- 2. Ozone (O3)196
- 3. Nitrate Radical (NO3)201
- 4. Chlorine Atoms (Cl)205
- 5. Nitrogen Dioxide (NO2)206
- F. REACTIONS OF ALKYNES206
- 1. Hydroxyl Radical (OH)206
- G. REACTIONS OF SIMPLE AROMATIC HYDROCARBONS207
- 1. Hydroxyl Radical (OH)207
- 2. Nitrate Radical (NO3)212
- 3. Chlorine Atoms (Cl)212
- H. REACTIONS OF OXYGEN-CONTAINING ORGANICS213
- 1. Reactions of OH, NO3, and Cl213
- 2. Hydroperoxyl Radical (HO2)216
- I. REACTIONS OF NITROGENOUS ORGANICS217
- 1. Peroxyacetyl Nitrate and Its Homologs217
- 2. Alkyl Nitrates and Nitrites220
- 3. Amines, Nitrosamines, and Hydrazines221
- J. CHEMISTRY OF REMOTE REGIONS225
- 1. Emissions of Biogenic Organics225
- 2. Chemistry231
- 3. Upper Troposphere239
- 4. Arctic241
- K. ATMOSPHERIC CHEMISTRY AND BIOMASS BURNING244
- L. PROBLEMS247
- REFERENCES248
- Chapter 7. Chemistry of Inorganic Nitrogen Compounds264
- A. OXIDATION OF NO TO NO2 AND THE LEIGHTON RELATIONSHIP265
- B. OXIDATION OF NO2266
- 1. Daytime Gas-Phase Reaction with OH266
- 2. Nighttime Reactions to Form NO3 and N2O5267
- 3. Reactions of NO and NO2 with Water and Alcohols268
- 4. Other Reactions of NO2272
- C. ATMOSPHERIC CHEMISTRY OF HONO273
- 1. Formation of HONO273
- 2. Atmospheric Fates of HONO274
- D. REACTIONS OF NO3 AND N2O5276
- 1. Reactions of NO3276
- 2. Reactions of N2O5279
- E. ATMOSPHERIC CHEMISTRY OF HNO3281
- 1. Formation281
- 2. Tropospheric Fates281
- F. "MISSING" NOy286
- G. AMMONIA (NH3)286
- H. PROBLEMS287
- REFERENCES288
- Chapter 8. Acid Deposition: Formation and Fates of Inorganic and Organic Acids in the Troposphere294
- A. CONTRIBUTION OF H2SO4, HNO3, HONO, AND ORGANIC ACIDS294
- B. SOLUBILITY OF GASES IN RAIN, FOGS, AND CLOUDS: HENRY'S LAW AND AQUEOUS-PHASE EQUILIBRIA295
- C. OXIDATION OF SO2296
- 1. Field Studies296
- 2. Oxidation in the Gas Phase298
- 3. Oxidation in the Aqueous Phase301
- 4. Oxidation on Surfaces324
- 5. Relative Importance of Various Oxidation Pathways for SO2325
- D. ORGANIC ACIDS326
- E. OXIDATION OF SULFUR COMPOUNDS OTHER THAN SO2328
- 1. Reactions of Dimethyl Sulfide (CH3SCH3)329
- 2. Dimethyl Disulfide (CH3SSCH3)334
- 3. Methyl Mercaptan (CH3SH)334
- 4. Hydrogen Sulfide (H2S)335
- 5. Carbon Disulfide (CS2)335
- 6. Carbonyl Sulfide (COS)336
- F. PROBLEMS336
- REFERENCES337
- Chapter 9. Particles in the Troposphere349
- A. PHYSICAL PROPERTIES349
- 1. Some Definitions349
- 2. Size Distributions351
- 3. Particle Motion362
- 4. Light Scattering and Absorption and Their Relationship to Visibility Reduction365
- B. REACTIONS INVOLVED IN PARTICLE FORMATION AND GROWTH375
- 1. Nucleation, Condensation, and Coagulation375
- 2. Reactions of Gases at Particle Surfaces379
- 3. Reactions in the Aqueous Phase380
- 4. Relative Importance of Various Aerosol Growth Mechanisms380
- C. CHEMICAL COMPOSITION OF TROPOSPHERIC AEROSOLS380
- 1. Inorganic Species381
- 2. Organics393
- D. GAS – PARTICLE DISTRIBUTION OF SEMIVOLATILE ORGANICS412
- 1. Adsorption on Solid Particles413
- 2. Absorption into Liquids417
- 3. Octanol – Air Partitioning Coefficients420
- E. PROBLEMS423
- REFERENCES423
- Chapter 10. Airborne Polycyclic Aromatic Hydrocarbons and Their Derivatives: Atmospheric Chemistry a436
- A. NOMENCLATURE AND SELECTED PHYSICAL AND SPECTROSCOPIC PROPERTIES OF POLYCYCLIC AROMATIC HYDROCARBO440
- 1. Combustion-Generated PAHs and PACs440
- 2. Structures and IUPAC Rules for Nomenclature440
- 3. Solubilities and Vapor Pressures451
- 4. Gas – Particle Partitioning, Sampling Techniques, and Ambient Levels of Selected PAHs and PACs453
- 5. Absorption and Emission Spectra of Selected PAHs and PACs461
- B. BIOLOGICAL PROPERTIES OF PAHs AND PACs. I: CARCINOGENICITY466
- 1. Historical Perspective: Benzo[a]pyrene, the "Classic Chemical Carcinogen"466
- 2. Carcinogenicity of PAHs, Cancer Potencies, and Potency Equivalence Factors467
- 3. Carcinogenicity of Nitroarenes and Other Nitro-PACs473
- C. BIOLOGICAL PROPERTIES OF PAHs AND PACs. II: MUTAGENICITY475
- 1. Short-Term Tests for Genetic and Related Effects475
- 2. The Ames Salmonella typhimurium Reversion Assay475
- 3. The Salmonella TM677 "Forward Mutation" Assay483
- 4. Human Cell Mutagenicities of PAHs and PACs484
- D. BACTERIAL AND HUMAN CELL MUTAGENICITIES OF POLLUTED AMBIENT AIR486
- 1. Bacterial Mutagenicity of Urban Air: A Worldwide Phenomenon486
- 2. Sources, Ambient Levels, Transport, and Transformation: Some Case Studies491
- 3. Bioassay-Directed Chemical Analysis for PAHs and PACs in Fine Ambient Aerosols Using a Human Cell497
- 4. Bioassay-Directed Chemical Analysis for Vapor-Phase and Particle-Phase PAHs and PACs in Ambient A502
- E. ATMOSPHERIC FATES OF PARTICLE-ASSOCIATED PAHs: HETEROGENEOUS REACTIONS504
- 1. Background504
- 2. Theoretical and Experimental Structure – Reactivity Relationships505
- 3. Field Studies of Atmospheric Reactions: Transport and Transformation507
- 4. Photochemical Reactions of Particle-Associated PAHs510
- 5. Gas – Particle Reactions513
- 6. Atmospheric Fates of Particle-Associated Nitroarenes518
- F. REACTIONS OF GAS-PHASE PAHs: ATMOSPHERIC FORMATION OF MUTAGENIC NITROARENES519
- 1. Combustion-Generated Primary Emissions of Nitroarenes519
- 2. Atmospheric Formation of Nitro-PAHs and Nitro-PACs520
- REFERENCES527
- Chapter 11. Analytical Methods and Typical Atmospheric Concentrations for Gases and Particles547
- A. GASES548
- 1. Optical Spectroscopic Techniques548
- 2. Mass Spectrometry561
- 3. Filters, Denuders, Transition Flow Reactors, Mist Chambers, and Scrubbers567
- 4. Methods for, and Tropospheric Levels of, Specific Gases569
- 5. Generation of Standard Gas Mixtures607
- B. PARTICLES608
- 1. Sampling and Collection of Particles608
- 2. Measurement of Physical Characteristics: Mass and Size612
- 3. Measurement of Chemical Composition619
- 4. Real-Time Monitoring Techniques for Particles626
- 5. Generation of Calibration Aerosols632
- C. PROBLEMS635
- REFERENCES636
- Chapter 12. Homogeneous and Heterogeneous Chemistry in the Stratosphere657
- A. CHEMISTRY OF THE UNPERTURBED STRATOSPHERE657
- 1. Stratosphere – Troposphere Exchange (STE)658
- 2. Chapman Cycle and NOx Chemistry660
- B. HIGH-SPEED CIVIL TRANSPORT (HSCT), ROCKETS, AND THE SPACE SHUTTLE662
- 1. HSCT662
- 2. Space Shuttle and Solid Rocket Motors667
- C. CHLOROFLUOROCARBONS669
- 1. Types, Nomenclature, and Uses669
- 2. Lifetimes and Atmospheric Fates of CFCs and Halons670
- 3. Gas-Phase Chemistry in the Stratosphere673
- 4. Antarctic "Ozone Hole"675
- 5. Polar Stratospheric Clouds (PSCs) and Aerosols680
- 6. Effects of Volcanic Eruptions690
- 7. Ozone Depletion in the Arctic696
- 8. Ozone Destruction in the Midlatitudes700
- D. CONTRIBUTION OF BROMINATED ORGANICS701
- 1. Sources and Sinks of Brominated Organics701
- 2. Bromine Chemistry in the Stratosphere702
- E. CONTRIBUTION OF IODINE-CONTAINING ORGANICS706
- F. SUMMARY707
- G. PROBLEMS707
- REFERENCES708
- Chapter 13. Scientific Basis for Control of Halogenated Organics727
- A. INTERNATIONAL AGREEMENTS ON PHASEOUT OF HALOGENATED ORGANICS727
- B. OZONE DEPLETION POTENTIALS (ODP)730
- C. TRENDS IN CFCs, THEIR REPLACEMENTS, STRATOSPHERIC O3, AND SURFACE UV733
- 1. Trends in CFCs and Their Replacements733
- 2. Trends in Stratospheric O3736
- 3. Trends in Surface Ultraviolet Radiation741
- D. TROPOSPHERIC CHEMISTRY OF ALTERNATE CFCs744
- 1. Kinetics of OH Reactions744
- 2. Tropospheric Chemistry746
- E. SUMMARY753
- F. PROBLEMS753
- REFERENCES753
- Chapter 14. Global Tropospheric Chemistry and Climate Change762
- A. RADIATION BALANCE OF THE ATMOSPHERE: THE GREENHOUSE EFFECT763
- 1. Global Absorption and Emission of Radiation763
- 2. Radiative Transfer Processes in the Atmosphere766
- 3. Dependence of Net Infrared Absorption on Atmospheric Concentrations769
- B. CONTRIBUTION OF TRACE GASES TO THE GREENHOUSE EFFECT770
- 1. Infrared Absorption by Trace Gases770
- 2. Trends in Trace Gas Concentrations773
- 3. Radiative Forcing by Greenhouse Gases and Global Warming Potentials783
- C. AEROSOL PARTICLES, ATMOSPHERIC RADIATION, AND CLIMATE CHANGE788
- 1. Direct Effects789
- 2. Indirect Effects of Aerosol Particles799
- D. SOME OTHER FACTORS AFFECTING GLOBAL CLIMATE814
- 1. Absorption of Solar Radiation by Clouds814
- 2. Feedbacks: Water Vapor, Clouds, and the "Supergreenhouse Effect"819
- 3. Solar Variability821
- 4. Volcanic Eruptions822
- 5. Oceans822
- E. OBSERVATIONS OF CLIMATE CHANGES823
- 1. Observed Temperature Trends823
- 2. Other Climate Changes828
- F. THE FUTURE828
- G. PROBLEMS829
- REFERENCES829
- Chapter 15. Indoor Air Pollution: Sources, Levels, Chemistry, and Fates844
- A. RADON844
- B. OXIDES OF NITROGEN846
- 1. Levels of NOx846
- 2. HONO and HNO3847
- C. CO AND SO2849
- D. VOLATILE ORGANIC COMPOUNDS850
- E. OZONE859
- F. INDOOR VOC – NOx – O3 CHEMISTRY859
- G. PARTICLES861
- H. PROBLEMS865
- REFERENCES865
- Chapter 16. Applications of Atmospheric Chemistry: Air Pollution Control Strategies and Risk Assessm871
- A. TROPOSPHERIC OZONE AND ASSOCIATED PHOTOCHEMICAL OXIDANTS871
- 1. Environmental Chambers872
- 2. Isopleths for Ozone and Other Photochemically Derived Species882
- 3. Models886
- B. REACTIVITY OF VOC907
- 1. Typical Reactivity Scales907
- 2. Application to Control of Mobile Source Emissions909
- C. FIELD OBSERVATIONS OF VOC, NOx , AND O3913
- D. ALTERNATE FUELS918
- 1. Reformulated Gasolines918
- 2. Compressed Natural Gas (CNG)919
- 3. Liquefied Petroleum Gas (LPG)920
- 4. Alcohol Fuels and Blends with Gasoline920
- 5. Hydrogen921
- 6. Electric Vehicles921
- E. CONTROL OF ACIDS921
- F. CONTROL OF PARTICLES923
- G. ATMOSPHERIC CHEMISTRY AND RISK ASSESSMENTS OF HAZARDOUS AIR POLLUTANTS925
- H. PROBLEMS930
- REFERENCES932
- Appendix I: Enthalpies of Formation of Some Gaseous Molecules, Atoms, and Free Radicals at 298 K943
- Appendix II: Bond Dissociation Energies945
- Appendix III: Running the OZIPR Model947
- Appendix IV: Some Relevant Web Sites949
- Appendix V: Pressures and Temperatures for Standard Atmosphere951
- Appendix VI: Answers to Selected Problems952
- Subject Index957
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.
Key Features
*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
Key Features
*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