Abstract
Despite its sometimes apparent tranquility, the Earth’s atmosphere is a complex chemical reactor, and chemicals released into it are oxidized by a series of chemical processes which are somewhat analogous to a low-temperature combustion system. Indeed, and fortunately, through these reactions the atmosphere acts as a “garbage-disposal” system to remove chemicals emitted into it. These chemical transformation processes involve a series of reactive oxygen-containing species, primarily ozone (O3), the hydroxyl radical (OH), and the nitrate radical (NO3) as the initiators together with an array of intermediate radicals including hydro-peroxyl (HO2), organic peroxy (RO2), and alkoxy (RO) radicals. Chemical compounds released into the atmosphere from anthropogenic and biogenic sources are subject to the physical removal processes of wet and dry deposition (Bidleman, 1988; Atkinson, 1988) and photolysis and chemical reaction (Atkinson, 1988, 1990, 1994), leading to such manifestations of air pollution as photochemical air pollution (Seinfeld, 1989; NRC., 1991), acidic deposition (Schwartz, 1989; Rodhe, 1989), forest decline and crop damage (Blank et al., 1988; Schulze, 1989; Frank, 1991), visibility reduction (Seinfeld, 1989; Larson et al., 1989), stratospheric ozone depletion (WMO, 1992), global atmospheric warming (IPCC., 1990), and the formation of toxic air pollutants (Atkinson and Arey, 1994).
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
Similar content being viewed by others
References
Anderson, J. G., Toohey, D. W., and Brune, W. H. (1991) Free Radicals Within the Antarctic Vortex: The Role of CFCs in Antarctic Ozone Loss. Science, 251, 39–46.
ARB (1992) Analysis of the Ambient VOC Data Collected in the Southern California Air Quality Study, Final Report to California Air Resources Board Contract No. A832–130, Sacramento, CA, February.
Arey, J., Atkinson, R., and Aschmann, S. M. (1990) Product Study of the Gas-Phase Reactions of Monoterpenes with the OH Radical in the Presence of NOx. J. Geophys. Res., 95, 18539–18546.
Arey, J., Winer, A. M., Atkinson, R., Aschmann, S. M., Long, W. D., and Morrison, C. L. (1991a) The emission of (Z)-3-hexen-1-ol, (Z)-3-hexenyla-cetate and other oxygenated hydrocarbons from agricultural plant species. Atmos. Environ., 25A, 1063–1075.
Arey, J., Winer, A. M., Atkinson, R., Aschmann, S. M., Long, W. D., Morrison, C. L., and Olszyk, D. M. (1991b) Terpenes emitted from agricultural species found in California’s Central Valley. J. Geophys. Res., 96, 9329–9336.
Atkinson, R. (1988) Atmospheric Transformations of Automotive Emissions, in Air Pollution, the Automobile, and Public Health (A. Y. Watson, R. R. Bates, and D. Kennedy, Eds.) National Academy Press, Washington, DC., pp. 99–132.
Atkinson, R. (1989) Kinetics and Mechanisms of the Gas-Phase Reactions of the Hydroxyl Radical with Organic Compounds. J. Phys. Chem. Ref. Data, Monograph 1, 1–246.
Atkinson, R. (1990) Gas-Phase Tropospheric Chemistry of Organic Compounds: A Review. Atmos. Environ., 24A, 1–41.
Atkinson, R. (1991) Kinetics and Mechanisms of the Gas-Phase Reactions of the NO3 Radical with Organic Compounds. J. Phys. Chem. Ref. Data, 20, 459–507.
Atkinson, R. (1994) Gas-Phase Tropospheric Chemistry of Organic Compounds. J. Phys. Chem. Ref. Data, Monograph 2, 1–216.
Atkinson, R., and Arey, J. (1994) Atmospheric Chemistry of Gas-Phase Polycyclic Aromatic Hydrocarbons: Formation of Atmospheric Mutagens. Environ. Health Persp., 102, (Suppl. 4) 117–126.
Atkinson, R., and Aschmann, S. M. (1993) OH Radical Production from the Gas-Phase Reactions of O3 with a Series of Alkenes under Atmospheric Conditions. Environ. Sci. Technol., 27, 1357–1363.
Atkinson, R., and Carter, W. P. L. (1991) Reactions of Alkoxy Radicals under Atmospheric Conditions: The Relative Importance of Decomposition Versus Reaction with O2. J. Atmos. Chem., 13, 195–210.
Atkinson, R., Winer, A. M., and Pitts, J. N., Jr. (1986) Estimation of Night-Time N2O5 Concentrations from Ambient NO2 and NO3 Radical Concentrations and the Role of N2O5 in Night-Time Chemistry. Atmos. Environ., 20, 331–339.
Atkinson, R., Aschmann, S. M., Arey, J., and Carter, W. P. L. (1989) Formation of Ring-Retaining Products from the OH Radical-Initiated Reactions of Benzene and Toluene. Int. J. Chem. Kinet., 21, 801–827.
Atkinson, R., Baulch, D. L., Cox, R. A., Hampson, R. R., Jr., Kerr, J. A., and Troe, J. (1992a) Evaluated Kinetic and Photochemical Data for Atmospheric Chemistry: Supplement IV. J. Phys. Chem. Ref. Data, 21, 1125–1568.
Atkinson, R., Aschmann, S. M., Arey, J., and Shorees, B. (1992b) Formation of OH Radicals in the Gas Phase Reactions of O3 with a Series of Terpenes. J. Geophys. Res., 97, 6065–6073.
Ayers, G. P., Penkett, S. A., Gillett, R. W., Bandy, B., Galbally, I. E., Meyer, C. P., Elsworth, C. M., Bentley, S. T., and Forgan, B. W. (1992) Evidence for Photochemical Control of Ozone Concentrations in Unpolluted Marine Air. Nature, 360, 446–448.
Bidleman, T. F. (1988) Atmospheric Processes. Environ. Sci. Technol., 22, 361–367.
Blank, L. W., Roberts, T. M., and Skeffington, R. A. (1988) New Perspectives on Forest Decline. Nature, 336, 27–30.
Carter, W. P. L. (1990) A Detailed Mechanism for the Gas-Phase Atmospheric Reactions of Organic Compounds. Atmos. Environ., 24A, 481–518.
Carter, W. P. L., and Atkinson, R. (1989) Alkyl Nitrate Formation from the Atmospheric Photooxidation of Alkanes: A Revised Estimation Method. J. Attnos. Chem., 8, 165–173.
Chapman, S. (1930) A Theory of Upper Atmospheric Ozone. Mem. J. R. Met. Soc., 3, 103–125.
Cox, R. A., Patrick, K. F., and Chant, S. A. (1981) Mechanism of Atmospheric Photooxidation of Organic Compounds. Reactions of Alkoxy Radicals in Oxidation of n-Butane and Simple Ketones. Environ. Sci. Technol., 15, 587–592.
Crutzen, P. J. (1970) The Influence of Nitrogen Oxides on the Atmospheric Ozone Content. Quart. J. R. Met. Soc., 96, 320–325.
Dentener, F. J., and Crutzen, P. J. (1993) Reaction of N2O5 on Tropospheric Aerosols: Impact on the Global Distributions of NOx, O3, and OH. J. Geophys. Res., 98, 7149–7163.
Ehhalt, D. H., Dorn, H.-P., and Poppe, D. (1991) The Chemistry of the Hydroxyl Radical in the Troposphere. Proc. R. Soc. Edinburgh, 97B, 17–34.
Eisele, F. L., and Tanner, D. J. (1991) Ion-Assisted Tropospheric OH Measurements. J. Geophys. Res., 96, 9295–9308.
Felton, C. C., Sheppard, J. C., and Campbell, M. J. (1990) The Radiochemical Hydroxyl Radical Measurement Method. Environ. Sci. Technol., 24, 1841–1847.
Frank, H. (1991) Airborne Chlorocarbons, Photooxidants, and Forest Decline. Ambio, 20, 13–18.
Fung, I., John, J., Lerner, J., Matthews, E., Prather, M., Steele, L. P., and Fraser, P. J. (1991) Three-Dimensional Model Synthesis of the Global Methane Cycle. J. Geophys. Res., 96, 13033–13065.
Grosjean, D., and Fung, K. (1984) Hydrocarbons and Carbonyls in Los Angeles Air. J. Air Pollut. Control Assoc, 34, 537–543.
Hakola, H., Arey, J., Aschmann, S. M., and Atkinson, R. (1994) Product Formation from the Gas-Phase Reactions of OH Radicals and O3 with a Series of Monoterpenes. J. Atmos. Chem., 18, 75–102.
Hall, J. V., Winer, A. M., Kleinman, M. T., Lurmann, F. W., Brajer, V., and Colome, S. D. (1992) Valuing the Health Benefits of Clean Air. Science, 255, 812–817.
Harley, R. A., Hannigan, M. P., and Cass, G. R. (1992) Respeciation of Organic Gas Emissions and the Detection of Excess Unburned Gasoline in the Atmosphere. Environ. Sci. Technol., 26, 2395–2408.
Hatakeyama, S., Izumi, K., Fukuyama, T., and Akimoto, H. (1989) Reactions of Ozone with α-Pinene and β-Pinene in Air: Yields of Gaseous and Particulate Products. J. Geophys. Res., 94, 13013–13024.
Hatakeyama, S., Izumi, K., Fukuyama, T., Akimoto, H., and Wasmda, N. (1991) Reactions of OH with α-Pinene and β-Pinene in Air: Estimate of Global CO Production from the Atmospheric Oxidation of Terpenes. J. Geophys. Res., 96, 947–958.
Hofzumahaus, A., Dorn, H.-P., Callies, J., Platt, U., and Ehhalt, D. H. (1991) Tropospheric OH Concentration Measurements by Laser Long-Path Absorption Spectroscopy. Atmos. Environ., 25A, 2017–2022.
Horie, O., and Moortgat, G. K. (1991) Decomposition Pathways of the Excited Criegee Intermediates in the Ozonolysis of Simple Alkenes. Atmos. Environ., 25A, 1881–1896.
IPCC (1990) Climate Change: The IPCC Scientific Assessment, Intergovernmental Panel on Climate Change (J. T. Houghton, G. J. Jenkins, and J. J. Ephraums, Eds.), Cambridge University Press, Cambridge.
Isidorov, V. A., Zenkevich, I. G., and Ioffe, B. V. (1985) Volatile Organic Compounds in the Atmosphere of Forests. Atmos. Environ., 19, 1–8.
Jacob, D. J., and Wofsy, S. C. (1988) Photochemistry of Biogenic Emissions over the Amazon Forest. J. Geophys. Res., 93, 1477–1486.
Johnston, H. (1971) Reduction of Stratospheric Ozone by Nitrogen Oxide Catalysts from Supersonic Transport Exhaust. Science, 173, 517–522.
Kley, D., Drummond, J. W., McFarland, M., and Liu, S. C. (1981) Tropospheric Profiles of NOx. J. Geophys. Res., 86, 3153–3161.
Knispel, R., Koch, R., Siese, M., and Zetzsch, C. (1990) Adduct Formation of OH Radicals with Benzene, Toluene, and Phenol and Consecutive Reactions of the Adducts with NOx and O2. Ber. Bunsenges. Phys. Chem., 94, 1375–1379.
Lamb, B., Guenther, A., Gay, D., and Westberg, H. (1987) A National Inventory of Biogenic Hydrocarbon Emissions. Atmos. Environ., 21, 1695–1705.
Larson, S. M., Cass, G. R., and Gray, H. A. (1989) Atmospheric Carbon Particles and the Los Angeles Visibility Problem. Aerosol Sci. Technol., 10, 118–130.
Liu, S. C., Cicerone, R. J., Donahue, T. M., and Chameides, W. L. (1977) Sources and Sinks of Atmospheric N2O and the Possible Ozone Reduction due to Industrial Fixed Nitrogen Fertilizers. Tellus, 29, 251–263.
Logan, J. A. (1985) Tropospheric Ozone: Seasonal Behavior, Trends, and Anthropogenic Influence. J. Geophys. Res., 90, 10463–10482.
Logan, J. A., Prather, M. J., Wofsy, S. C., and McElroy, M. B. (1981) Tropospheric Chemistry: A Global Perspective. J. Geophys. Res., 86, 7210–7254.
Lonneman, W. A., Seila, R. L., and Meeks, S. A. (1986) Non-Methane Organic Composition in the Lincoln Tunnel. Environ. Sci. Technol., 20, 790–796.
Lowe, D. C., and Schmidt, U. (1983) Formaldehyde (HCHO) Measurements in the Nonurban Atmosphere. J. Geophys. Res., 88, 10844–10858.
Meyrahn, H., Pauly, J., Schneider, W., and Warneck, P. (1986) Quantum Yields for the Photodissociation of Acetone in Air and an Estimate for the Life lime of Acetone in the Lower Troposphere. J. Atmos. Chem., 4, 277–291.
McIlveen, R. (1992) Fundamentals of Weather and Climate, Chapman & Hall, London.
Möller, L., Schuetzle, D., and Autrup, H. (1994) Future Research Needs Associated with the Assessment of Potential Human Health Risks from Exposure to Toxic Ambient Air Pollutants. Environ. Health Persp., 102, (Suppl. 4), 193–210.
Mount, G. H., and Eisele, F. L. (1992) An Intercomparison of Tropospheric OH Measurements at Fritz Peak Observatory, Colorado. Science, 256, 1187–1190.
Niki, H., Maker, P. D., Savage, C. M., Breitenbach, L. P., and Hurley, M. D. (1987) FTIR Spectroscopic Study of the Mechanism for the Gas-Phase Reaction Between Ozone and Tetramethylethylene. J. Phys. Chem., 91, 941–946.
Noxon, J. R. (1983) NO3 and NO2 in the Mid-Pacific Troposphere. J. Geophys. Res., 88, 11017–11021.
NRC (1991) Rethinking the Ozone Problem in Urban and Regional Air Pollution, National Research Council, National Academy Press, Washington, DC.
Paulson, S. E., and Seinfeld, J. H. (1992) Atmospheric Photochemical Oxidation of 1-Octene: OH, O3, and 0(3P) Reactions. Environ. Sci. Technol., 26, 1165–1173.
Paulson, S. E., Flagan, R. C., and Seinfeld, J. H. (1992a) Atmospheric Photooxidation of Isoprene. Part I: The Hydroxyl Radical and Ground State Atomic Oxygen Reactions. Int. J. Chem. Kinet., 24, 79–101.
Paulson, S. E., Flagan, R. C., and Seinfeld, J. H. (1992b) Atmospheric Photooxidation of Isoprene. Part II: The Ozone-Isoprene Reaction. Int. J. Chem. Kinet., 24, 103–125.
Prinn, R., Cunnold, D., Rasmussen, R., Simmonds, P., Alyea, R., Crawford, A., Fraser, P., and Rosen, R. (1990) Atmospheric Emissions and Trends of Nitrous Oxide Deduced from 10 Years of ALE-GAGE Data. J. Geophys. Res., 95, 18369–18385.
Prinn, R., Cunnold, D., Simmonds, P., Alyea, F., Boldi, R., Crawford, A., Fraser, P., Gutzler, D., Hartley, D., Rosen, R., and Rasmussen, R. (1992) Global Average Concentration and Trend for Hydroxyl Radicals Deduced from ALE/GAGE Trichloroethane (Methyl Chloroform) Data for 1978–1990. J. Geophys. Res., 97, 2445–2461.
Rodhe, H. (1989) Acidification in a Global Perspective. Ambio, 18, 155–160.
Rogers, J. D. (1990) Ultraviolet Absorption Cross Sections and Atmospheric Photodissociation Rate Constants of Formaldehyde. J. Phys. Chem., 94, 4011–4015.
Rowland, F. S. (1990) Stratospheric Ozone Depletion by Chlorofluorocarbons. Ambio, 19, 281–292.
Rowland, F. S. (1991) Stratospheric Ozone Depletion. Annu. Rev. Phys. Chem., 42, 731–768.
Schulze, E.-D. (1989) Air Pollution and Forest Decline in a Spruce (Picea abies) Forest. Science, 244, 776–783.
Schwartz, S. E. (1989) Acid Deposition: Unraveling a Regional Phenomenon. Science, 243, 753–763.
Seinfeld, J. H. (1989) Urban Air Pollution: State of the Science. Science, 243, 745–752.
Sigsby, J. E., Jr., Tejada, S., Ray, W., Lang, J. M., and Duncan, J. W. (1987) Volatile Organic Compound Emissions from 46 In-Use Passenger Cars. Environ. Sci. Technol., 21, 466–475.
Smith, I. W. M. (1977) The Mechanism of the OH + CO Reaction and the Stability of the HOCO Radical. Chem. Phys. Lett, 49, 112–115.
Thompson, A. M. (1992) The Oxidizing Capacity of the Earth’s Atmosphere: Probable Past and Future Changes. Science, 256, 1157–1165.
Tuazon, E. C., and Atkinson, R. (1989) A Product Study of the Gas-Phase Reaction of Methyl Vinyl Ketone with the OH Radical in the Presence of NOx. Int. J. Chem. Kinet, 21, 1141–1152.
Tuazon, E. C., and Atkinson, R. (1990a) A Product Study of the Gas-Phase Reaction of Isoprene with the OH Radical in the Presence of NOx. Int. J. Chem. Kinet, 22, 1221–1236.
Tuazon, E. C., and Atkinson, R. (1990b) A Product Study of the Gas-Phase Reaction of Methacrolein with the OH Radical in the Presence of NOx. Int. J. Chem. Kinet., 22, 591–602.
WMO (1990) Scientific Assessment of Stratospheric Ozone: 1989, World Meteorological Organization Global Ozone Research and Monitoring Project, Report No. 20, Volume II, Appendix: AFEAS Report, Geneva.
WMO (1992) Scientific Assessment of Ozone Depletion: 1991, World Meteorological Organization Global Ozone Research and Monitoring Project, Report No. 25, Geneva.
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1995 Chapman & Hall
About this chapter
Cite this chapter
Atkinson, R. (1995). Reactions of Oxygen Species in the Atmosphere. In: Foote, C.S., Valentine, J.S., Greenberg, A., Liebman, J.F. (eds) Active Oxygen in Chemistry. Structure Energetics and Reactivity in Chemistry Series (SEARCH Series), vol 2. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-0874-7_7
Download citation
DOI: https://doi.org/10.1007/978-94-007-0874-7_7
Publisher Name: Springer, Dordrecht
Print ISBN: 978-0-7514-0371-8
Online ISBN: 978-94-007-0874-7
eBook Packages: Springer Book Archive