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Chemistry of Atmospheres

An Introduction to the Chemistry of the Atmospheres of Earth, the Planets, and their Satellites

Third Edition

Richard P. Wayne

Publication Date - 30 March 2000

ISBN: 9780198503750

808 pages


Atmospheric chemistry has been the focus of much research activity in recent years, and there is now heightened public awareness of the environmental issues in which it plays a part.

In a clear, readable style, this important book looks at the insights and interpretations afforded by the research, and places in context the exciting, dramatic, and sometimes disturbing findings.

Like its highly successful predecessor, this new edition lays down the principles of atmospheric chemistry and provides the necessary background for more detailed study. The text has been thoroughly revised and expanded throughout to take into account recent advances in atmospheric science that include a host of new atmospheric measurements, extended laboratory experiments, ever more sophisticated models, and ingenious interpretations of the phenomena. Heterogeneous processes are now known to be of great significance in the chemistry of the Earth's atmosphere, and new sections of the book discuss the influence o such processes on both the stratosphere and the troposphere. A major eruption, that of Mount Pinatubo, has highlighted how volcanoes can influence 'natural' atmospheric chemistry, and the opportunity is taken to examine the effects of the gases and particles produced in such eruptions. The startling discovery of the 'Antarctic ozone hole' has now been matched by observations of similar ozone losses in the Arctic; both phenomena are explored in more depth than before, and the whole question of trends in stratospheric ozone concentrations is updated. New topics in tropospheric chemistry that are discussed in this edition for the first time include the atmospheric chemistry of biogenic hydrocarbons, of aromatic compounds, and of halogens and halogen-containing species.

Several aspects have been added to the examination of air pollution, including the effects of biomass burning. Rapid changes in the composition of the Earth's atmosphere, apparently a result of man's activities, are apparently even having an effect on global climate, and recent assessments of the Intergovernmental Panel on Climate Change are presented in this context. Air transport continues to expand, and the influence of aircraft on atmospheric chemistry and, indeed, on climate has excited interest that is explained here. Moving away from Earth, information gathered by the Voyager, Galileo, and other space missions, which have provided a new understanding of the atmosphere of the planets other than our own, is also discussed and brought up to date.

This book does not attempt to suggest answers to the environmental problems facing us, but it lays the foundations for the study of atmospheric chemistry on which rational decisions will need to be based. A multidisciplinary approach is taken throughout in order to highlight the interplay between the atmosphere of a planet and other parts of the environment. This feature makes the book full of interest for chemists, physicists, biologists, and other scientists alike, and accessible to all of them. Readers will find the book an excellent introduction to an exciting topic, and a fascinating source of information about a part of science that is proving to be of key importance.

About the Author(s)

Richard P. Wayne is Dr Lee's Reader in Chemistry at Christ Church, Oxford, and Professor of Chemistry at the University of Oxford.

Previous Publication Date(s)

May 1991
June 1985

Table of Contents

    1. Chemical composition: a preliminary survey
    1.1. Earth's atmosphere in perspective
    1.2. Land, sea, and air
    1.3. Particles, aerosols, and clouds
    1.4. Ozone
    1.5. Cyclic processes
    1.5.1. Carbon cycle
    1.5.2. Oxygen cycle
    1.5.3. Nitrogen cycle
    1.5.4. Sulphur cycle
    1.6. Linking biosphere and atmosphere
    2. Atmospheric behavior as interpreted by physics
    2.1. Pressures
    2.2. Radiative heating
    2.2.1. Solar and planetary radiation
    2.2.2. Radiation trapping: the 'greenhouse effect'
    2.2.3. Models of radiation trapping and transfer
    2.2.4. Trapping in real atmospheres
    2.2.5. Unstable greenhouses: Venus, Earth, and Mars compared
    2.2.6. Diurnal and seasonal variations
    2.3. Temperature profiles
    2.3.1. Troposphere, stratosphere, and mesosphere
    2.3.2. Thermosphere, exosphere, and escape
    2.3.3. Vertical transport
    2.4. Winds
    2.5. Condensation and nucleation
    2.6. Light scattering
    3. Photochemistry and kinetics applied to atmospheres
    3.1. Photochemical change
    3.2. Photochemical primary processes
    3.2.1. Photodissociation and photoionization
    3.2.2. Reactions of electronically excited species
    3.3. Adiabatic processes and the correlation rules
    3.4. Chemical kinetics
    3.4.1. Bimolecular reactions
    3.4.2. Unimolecular and termolecular reactions
    3.4.3. Condensed-phase, surface, and heterogeneous reactions
    3.4.4. Liquid-phase reactions
    3.4.5. Heterogeneous reactions
    3.5. Multistep reaction schemes
    3.6. Models of atmospheric chemistry
    3.6.1. Lifetimes and transport
    3.6.2. Modelling and models
    3.6.3. Numerical models
    3.6.4. Families
    4. Ozone in Earth's stratosphere
    4.1. Introduction
    4.2. Observations
    4.3. Oxygen-only chemistry
    4.3.1. Reaction scheme
    4.3.2. Chapman layers
    4.3.3. Comparison of experiment and theory
    4.4. Influence of trace constituents
    4.4.1. Catalytic cycles
    4.4.2. Null cycles, holding cycles, and reservoirs
    4.4.3. Natural source sand sinks of catalytic species
    4.4.4. Heterogeneous chemistry
    4.4.5. Summary of homogeneous chemistry
    4.4.6. Comparison of experiment and theory
    4.5. Perturbations of the stratosphere
    4.5.1. Solar proton events
    4.5.2. Solar ultraviolet irradiance
    4.5.3. Quasi-biennial oscillation (QBO)
    4.5.4. El Ni-no
    4.5.5. Volcanoes
    4.6. Man's impact on the stratosphere
    4.6.1. Consequences of ozone perturbation
    4.6.2. Aircraft
    4.6.3. Rockets and the space shttle
    4.6.4. Halocarbons: basic chemistry
    4.6.5. Halocarbons: loading and ozone depletion potentials
    4.6.6. Halocarbons: control, legislation, and alternatives
    4.6.7. Halocarbons: future ozone depletions
    4.6.8. Nitrous oxide (N2O): agriculture
    4.6.9. Combined influences: gases, particles, and climate
    4.7. Polar ozone holes
    4.7.1. Discovery of abnormal depletion
    4.7.2. Special features of polar meteorology
    4.7.3. Anomalous chemical composition
    4.7.4. Polar stratospheric clouds
    4.7.5. Perturbed chemistry
    4.7.6. Origin of chlorine compounds; dynamics
    4.7.7. The Arctic stratosphere
    4.7.8. Implications of polar phenomena
    4.8. Ozone variations and trends
    5. The Earth's troposphere
    5.1. Introduction
    5.2. Sources, sinks, and transport
    5.2.1. Dry and wet deposition
    5.2.2. The boundary layer
    5.2.3. Transport in the troposphere
    5.3. Oxidation and transformation
    5.3.1. Photochemical chain initiation
    5.3.2. Oxidation steps
    5.3.3. Tropospheric ozone production
    5.3.4. The importance of NO[x
    5.3.5. The reaction OH + CO
    5.3.6. The nitrate readical
    5.3.7. Reactions with ozone
    5.4. Biogenic volatile organic compounds
    5.4.1. Methane
    5.4.2. Non-methane hydrocarbons and other compounds
    5.5. Aromatic compounds
    5.6. Compounds of sulfur
    5.7. Natural halogen-containing species
    5.8. Heterogeneous processes and cloud chemistry
    5.9. Models, observations, and comparisons
    5.9.1. Tropospheric models
    5.9.2. Tropospheric measurements of trace species
    5.9.3. Comparison of measurements and model predictiosn
    5.10.1. Clean and polluted air
    5.10.2. Effects of pollution
    5.10.3. Primary and secondary pollutants
    5.10.4. Sulphur dioxide chemistry
    5.10.5. Smoke and sulphur pollution
    5.10.6. Acid rain
    5.10.7. Photochemical ozone and smog
    5.10.8. Degradation of HFCs and HCFCs
    5.10.9. Polycyclic aromatic hydrocarbons (PAHs)
    5.10.10. Biomass burning
    6. Ions in the atmosphere
    6.1. Electrical charges in the atmosphere
    6.1.1. Aurora
    6.1.2. Geomagnetic fluctuations
    6.1.3. Radio propagation
    6.2. Ion chemistry in the atmosphere
    6.3. Ionization mechanisms
    6.4. Chemistry of specific regions
    6.4.1. F-region processes
    6.4.2. E-region processes
    6.4.3. D-region positive ion chemistry
    6.4.4. D-region negative-ion chemistry
    6.5. Ions in the stratosphere and troposphere
    7. The airglow
    7.1. Optical emission from planetary atmospheres
    7.2. Excitation mechanisms
    7.3. Airglow intensities and altitude profiles
    7.4. Specific emission sources
    7.4.1. Atomic and molecular oxygen
    7.4.2. Atomic sodium
    7.4.3. Hydroxyl radicals
    8. Extraterrestrial atmospheres
    8.1. Introduction
    8.2. Venus
    8.2.1. Atmospheric composition
    8.2.2. Clouds
    8.2.3. Lightning
    8.2.4. Sub-cloud chemistry
    8.2.5. Stratospheric chemistry
    8.3. Mars
    8.3.1. Atmospheric structure and composition
    8.3.2. Carbon dioxide photochemistry
    8.3.3. Ionospheric chemistry
    8.4. Jupiter and Saturn
    8.5. Titan, Io, Europa, and Callisto
    8.6. Uranus, Neptune, Triton, and Pluto
    8.7. Comets
    9. Evolution and change in atmospheres and climates
    9.1. Sources of atmospheric constituents
    9.1.1. Origin and development of atmospheres
    9.1.2. Interstellar clouds and their chemistry
    9.2. Noble gases and nitrogen in planetary atmospheres
    9.2.1. Inner planets
    9.2.2. Titan
    9.3. Isotopic enrichment
    9.4. Evolution of Earth's atmosphere
    9.5. Climates in the past
    9.6. Climates of the future
    9.6.1. Radiatively active gases and particles in the atmosphere
    9.6.2. Radiative forcing
    9.6.3. Feedbacks and models
    9.6.4. Detection of twentieth-century climate change
    9.6.5. Projected changes in concentrations forcing and climate
    9.6.6. Aircraft
    9.6.7. Impacts of climate change
    9.6.8. Legislation and policy
    9.7. A doomed biosphere?
    Each chapter ends with a Bibliography