Atmospheric Chemistry and Global Change

by Brasseur, Guy P.; Orlando, John J.; Tyndall, Geoffrey S.

• ISBN13: 9780195105216
• ISBN10: 0195105214
• Edition: 1st
• Format: Hardcover
• Copyright: 1999-03-04
• Publisher: Oxford University Press

Summary

Atmospheric Chemistry and Global Change presents an integrated examination of chemical processes in the atmosphere, focusing on global-scale problems and their role in the evolution of the Earth system. Taking a largely interdisciplinary approach, it features the collective efforts of a groupof scientists at the National Center for Atmospheric Research (NCAR), as well as other experts from several universities and national laboratories. Topics discussed include the fundamental physical, chemical, and biological processes that affect the atmospheric composition; the chemical mechanismsthat affect the production and the fate of important chemical compounds; and the techniques used to investigate the chemical processes in the atmosphere. The book concludes with discussions on global problems related to the atmosphere (stratospheric ozone depletion, changes in greenhouse gases, andglobal chemical pollution), the relationship between the atmosphere and the global climate, and the long-term chemical evolution of the atmosphere. Each chapter features a brief essay by a leader in the field and includes a large number of current references. Ideal for graduate courses inatmospheric chemistry and atmospheric science, Atmospheric Chemistry and Global Change also serves as an authoritative and practical reference for scientists studying the Earth's atmosphere. Support materials for the book are available via the website http://acd.ucar.edu/textbook

Table of Contents

Preface	x	(2)
Contributing Authors	xii	(3)
List of Frequently Used Symbols	xv
1. ATMOSPHERIC CHEMISTRY AND THE EARTH SYSTEM	1	(22)
1.1 Introduction	1	(4)
1.2 The Earth System	5	(12)
Further Reading	17	(2)
Essay: Atmospheric Chemistry and the Earth System	19	(4)
Ralph J. Cicerone
Part 1: Fundamentals	23	(186)
2. ATMOSPHERIC DYNAMICS AND TRANSPORT	23	(62)
2.1 Introduction	23	(2)
2.2 The Governing Equations	25	(7)
2.3 Constraints on Atmospheric Motion	32	(12)
2.4 Zonal Means and Eddies	44	(9)
2.5 Atmospheric Waves	53	(11)
2.6 Tropospheric Circulation and Transport	64	(9)
2.7 Stratospheric Circulation and Transport	73	(5)
2.8 Stratosphere-Troposphere Exchange	78	(2)
Further Reading	80	(2)
Essay: Why Understand Dynamics -- And What Is "Understanding" Anyway?	82	(3)
Michael E. McIntyre
3. CHEMICAL AND PHOTOCHEMICAL PROCESSES	85	(32)
3.1 Introduction	85	(1)
3.2 Radiation	86	(8)
3.3 Photophysical and Photochemical Processes	94	(1)
3.4 Chemical Reactions	95	(11)
3.5 Catalytic Cycles	106	(2)
3.6 Role of Excited States	108	(1)
3.7 Measurement of Rate Coefficients	109	(3)
3.8 The Steady State Approximation	112	(1)
3.9 Lifetimes in the Atmosphere	112	(2)
Further Reading	114	(1)
Essay: When Do We Know Enough about Atmospheric Chemistry?	115	(2)
Harold Schiff
4. AEROSOLS AND CLOUDS	117	(42)
4.1 Introduction	117	(1)
4.2 Overview of the Atmospheric Aerosol	117	(9)
4.3 The Role of Clouds in Tropospheric Chemistry	126	(3)
4.4 Single-Particle Physical Characteristics	129	(8)
4.5 Gas-to-Particle Conversion	137	(4)
4.6 Acid-Base Reactions of Aerosol Particles	141	(1)
4.7 Removal Processes Associated with Aerosols	142	(2)
4.8 Solubility of Gases in Droplets	144	(4)
4.9 Mass Transfer Rates	148	(3)
4.10 Aqueous Reactions	151	(3)
Further Reading	154	(1)
Essay: Aerosols and Clouds: A Postscript	155	(4)
Richard P. Turco
5. TRACE GAS EXCHANGES AND BIOGEOCHEMICAL CYCLES	159	(50)
5.1 Introduction	159	(2)
5.2 Surface Exchanges	161	(4)
5.3 The Global Water Cycle	165	(2)
5.4 The Global Carbon Cycle	167	(21)
5.5 The Global Nitrogen Cycle	188	(7)
5.6 The Global Sulfur Cycle	195	(6)
5.7 Halogens	201	(2)
Further Reading	203	(1)
Essay: The View from Outside	204	(5)
James Lovelock
Part 2: Chemical Families	209	(166)
6. HYDROGEN COMPOUNDS	209	(26)
6.1 Importance of Atmospheric Hydrogen Compounds	209	(1)
6.2 Scope and Definitions	210	(1)
6.3 Sources of Hydrogen to the Atmosphere	210	(2)
6.4 Chemistry of Hydrogen Species in the Middle Atmosphere	212	(4)
6.5 Chemistry of Hydrogen Compounds in the Troposphere	216	(4)
6.6 Concentrations of Hydrogen Compounds in the Stratosphere	220	(6)
6.7 Concentrations of Hydrogen Compounds in the Troposphere	226	(5)
6.8 Summary	231	(1)
Further Reading	232	(1)
Essay: Hydrogen Compounds	233	(2)
Dieter Ehhalt
7. NITROGEN COMPOUNDS	235	(56)
7.1 Importance of Atmospheric Odd Nitrogen	235	(1)
7.2 Scope and Definitions	235	(2)
7.3 The Role of Odd Nitrogen in the Stratosphere	237	(11)
7.4 Odd Nitrogen in the "Contemporary" Stratosphere	248	(6)
7.5 Odd Nitrogen in the Troposphere	254	(22)
7.6 Experimental Summary of the Influence of Odd Nitrogen in the Continental Boundary Layer	276	(1)
7.7 NO(3) Chemistry	277	(4)
7.8 Gaseous Acid and Particulate Nitrate Formation	281	(1)
7.9 Chemistry of Organic Nitrates	282	(5)
Further Reading	287	(1)
Essay: Time's Arrow	288	(3)
Ian Galbally
8. HALOGEN COMPOUNDS	291	(34)
8.1 Introduction	291	(1)
8.2 Scope and Definitions	291	(1)
8.3 Sources of Halogens	292	(6)
8.4 Loss Processes of Halogen Source Gases	298	(3)
8.5 Inorganic Chemistry of Halogen Species	301	(15)
8.6 Controlling the Detrimental Effects of Halogens on the Atmosphere: Future Outlook	316	(5)
Further Reading	321	(1)
Essay: CFC(s) and Stratospheric Ozone Depletion	322	(3)
Mario Molina
9. CARBON-CONTAINING COMPOUNDS	325	(24)
9.1 Introduction	325	(1)
9.2 Scope and Definitions	325	(1)
9.3 Atmospheric Photochemistry of Hydrocarbons	326	(12)
9.4 Distribution of Hydrocarbons	338	(7)
Further Reading	345	(1)
Essay: Hydrocarbons	346	(3)
Hanwant Singh
10. SULFUR COMPOUNDS	349	(26)
10.1 Introduction	349	(1)
10.2 Scope and Definitions	350	(1)
10.3 Sulfur Compounds	351	(1)
10.4 Tropospheric Chemistry of Sulfur Compounds	351	(10)
10.5 Measurements of Sulfur Gas Abundances and Distributions	361	(6)
10.6 SO(2) and Acid Precipitation	367	(1)
10.7 Stratospheric Sulfur Chemistry	368	(2)
10.8 Gas-Phase Ionic Chemistry in the Stratosphere	370	(1)
Further Reading	370	(1)
Essay: Sulfur, Aerosols, Clouds, and Rain	371	(4)
Robert J. Charlson
Part 3: Tools	375	(90)
11. OBSERVATIONAL METHODS: INSTRUMENTS AND PLATFORMS	375	(48)
11.1 Introduction	375	(1)
11.2 Instrumentation for Constituent Measurements	375	(24)
11.3 Flux Measurements	399	(4)
11.4 Measurements of Atmospheric Radiation	403	(2)
11.5 Instrumentation for Aerosol and Cloud Measurements	405	(1)
11.6 Observing Platforms	406	(13)
Further Reading	419	(1)
Essay: From Individual Measurements to Scale Integration Strategies	420	(3)
Gerard Megie
12. MODELING	423	(42)
12.1 Introduction	423	(1)
12.2 Model Equations	424	(3)
12.3 Modeling Chemical Processes	427	(6)
12.4 Modeling Atmospheric Transport	433	(7)
12.5 Examples and Illustrations	440	(10)
12.6 Modeling Global Budgets and Biogeochemical Cycles	450	(4)
12.7 Data Assimilation	454	(4)
12.8 Inverse Modeling	458	(1)
12.9 Chemical-Transport Models in the Future	459	(1)
Further Reading	460	(1)
Essay: How Complex Do Models Need to Be?	461	(4)
Henning Rodhe
Part 4: Ozone, Climate, and Global Change	465	(88)
13. TROPOSPHERIC OZONE	465	(22)
13.1 Introduction	465	(2)
13.2 Distribution and Trends	467	(5)
13.3 Production and Loss of Ozone	472	(12)
13.4 Major Uncertainties and Research Needs	484	(1)
Further Reading	485	(1)
Essay: Tropospheric Ozone	486	(1)
Paul Crutzen
14. MIDDLE ATMOSPHERIC OZONE	487	(28)
14.1 Introduction	487	(4)
14.2 The Ozone Distribution	491	(2)
14.3 Ozone Production	493	(1)
14.4 Ozone Destruction	494	(6)
14.5 Transport Effects	500	(1)
14.6 Polar Ozone	501	(5)
14.7 Ozone Perturbations	506	(3)
14.8 Impact of Ozone Depletion on UV Radiation	509	(2)
Further Reading	511	(2)
Essay: Ozone Depletion: From Pole to Pole	513	(2)
Susan Solomon
15. ATMOSPHERIC CHEMISTRY AND CLIMATE	515	(24)
15.1 Introduction	515	(1)
15.2 Radiation in the Atmosphere	516	(6)
15.3 Natural Variations: Past Climates	522	(1)
15.4 Impact of Anthropogenic Trace Gases on Climate	523	(5)
15.5 Global Warming Potentials (GWPs)	528	(2)
15.6 Radiative Effects of Aerosols	530	(4)
15.7 Response of the Climate System to Radiative Forcing	534	(2)
Further Reading	536	(1)
Essay: Can Climate Models Be Validated?	537	(2)
Stephen H. Schneider
16. ATMOSPHERIC EVOLUTION AND GLOBAL PERSPECTIVE	539	(14)
16.1 Introduction	539	(1)
16.2 Atmospheric Evolution on Geological Timescales	539	(4)
16.3 Human Influences on the Atmosphere	543	(3)
16.4 Future Trends	546	(3)
16.5 Global Perspective	549	(1)
Further Reading	549	(1)
Essay: The Atmospheric Humankind: Our Related Futures	551	(2)
Daniel L. Albritton
APPENDIXES	553	(44)
Appendix A: Physical Constants and Other Data	555	(3)
Appendix B: Units, Conversion Factors, and Multiplying Prefixes	558	(2)
Appendix C: Atmospheric Parameters and Mixing Ratios of Chemical Constituents	560	(7)
Appendix D: Chemical Species in the Atmosphere	567	(3)
Appendix E: Rate Coefficients for Second-Order Gas-Phase Reactions	570	(4)
Appendix F: Rate Coefficients for Association Gas-Phase Reactions	574	(1)
Appendix G: Mass Accommodation Coefficients	575	(1)
Appendix H: Surface Reaction Probability	576	(2)
Appendix I: Atmospheric Humidity	578	(2)
Appendix J: Henry's Law Coefficients	580	(1)
Appendix K: Aqueous Equilibrium Constants	581	(1)
Appendix L: Rate Coefficients for Aqueous-Phase Reactions	582	(3)
Appendix M: Spectrum of Solar Extraterrestrial Actinic Flux (120-730 nm)	585	(3)
Appendix N: Photolysis Frequencies	588	(9)
Sample Problems	597	(18)
References	615	(34)
Index	649