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A discussion of the chemistry of some minor constituents in the stratosphere and troposphere


A discussion is given of atmospheric reactions in the H2O−CH4−O2−O3−NO x system. In the lower troposphere such reactions may lead to significant production of ozone. Their role in the odd hydrogen balance, especially of the troposphere and lower stratosphere, is discussed. CH3OH may be an intermediate in the oxidation cycle of methane, especially in the cold stratosphere. Its photodissociation into H2 and CH2O may consequently provide an important source for stratospheric H2. Catalytic photochemical chains of reactions involving NO x and HO x may also lead to tropospheric destruction of ozone. Due to lack of knowledge it is not possible at present to evaluate the importance of the before-mentioned reactions.

With the aid of model calculations it is indicated that stratospheric ozone is most sensitive to changes in the adopted lower boundary values of N2O and that an increase in water vapour concentrations in the lower stratosphere will indeed cause some increase in ozone as predicted.

Fluctuations in the flux of solar radiation near 190 nm may cause significant variations in stratospheric ozone concentrations.

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  1. [1]

    M. Ackerman andC. Muller,Stratospheric methane and nitrogen dioxide from infrared spectra, Pure and Appl. Geophys.106–108 (1973), 1325.

  2. [2]

    P. Crutzen,The influence of nitrogen oxides on the atmospheric ozone content, Quart. J. Roy. Met. Soc.96 (1970), 320–327.

  3. [3]

    H. Johnston,Redvction of stratospheric ozone by nitrogen oxide catalysis from SST exhaust, Science173 (1971), 517–522.

  4. [4]

    P. Crutzen,Ozone production rates in oxygen-hydrogen-nitrogen oxide atmosphere, J. Geophys. Res.76 (1971), 7311–7327.

  5. [5]

    H. Johnston,The Concorde, oxides of nitrogen, and stratospheric ozone, Search3 (1972), 276–282.

  6. [6]

    P. Crutzen,SST's—A threat to Earth's ozone shield, Ambiol1 (1972), 41–51.

  7. [7]

    S. Chapman,A theory of upper atmospheric ozone, Quart. J. Roy. Met. Soc.3 (1930), 103.

  8. [8]

    M. Nicolet,Ozone and hydrogen reactions, Ann. Geophys.26 (1970), 531–546.

  9. [9]

    K. F. Preston andR. F. Barr,Primary processes in the photolysis of nitrous oxide, J. Chem. Phys.54 (1971), 3347.

  10. [10]

    R. I. Greenberg andJ. Heickien,Reaction of O(1 D) with N 2 O, Int. J. Chem. Kin.2 (1970), 185.

  11. [11]

    M. B. McElroy andJ. C. McConnell,Nitrous oxide: A natural source of stratospheric NO, J. Atm. Sci.28 (1971), 1095–1098.

  12. [12]

    P. Warneck,Cosmic radiation as a source of odd nitrogen in the stratosphere, J. Geophys. Res.77 (1972), 6589–6591.

  13. [13]

    C. E. Junge,Air Chemistry and Radioactivity (Academic Press, New York 1963).

  14. [14]

    D. G. Murcray, T. G. Kyle, F. H. Murcray andW. J. Williams,Presence of HNO 3 in the upper atmosphere, J. Opt. Soc. America59 (1969), 1131–1134.

  15. [15]

    D. F. Strobel,Odd nitrogen in the mesosphere, J. Geophys. Res.76 (1971), 8384–8386.

  16. [16]

    G. Brasseur andS. Cieslik, On the Absorption of Nitric Oxide Bands in the Mesosphere and its Distribution in the Stratosphere, Paper presented at this meeting, August 1972.

  17. [17]

    A. B. Callear andI. W. M. Smith,Fluorescence of nitric oxide, Trans. Far. Soc.60 (1964), 96–111.

  18. [18]

    H. Johnston,Formation and stability of nitric acid in the stratosphere, J. Atm. Sciences, to be published.

  19. [19]

    H. Levy,Normal atmosphere: Large radical and formaldehyde concentrations predicted, Science173 (1971), 141–143.

  20. [20]

    H. Levy,Photochemistry of the lower troposphere, Planet. Space Sci.20 (1972), 919–935.

  21. [21]

    B. Weinstock andH. Niki,Carbon monoxide balance in nature, Science176 (1972), 290–292.

  22. [22]

    J. C. McConnell, M. B. McElroy andS. C. Wofsy,Natural sources of atmospheric CO, Nature233 (1971), 187–188.

  23. [23]

    H. Levy,Photochemistry of minor constitutents in the troposphere, J. Atm. Science, in press.

  24. [24]

    S. C. Wofsy, J. C. McConnell andM. B. McElroy,Atmospheric CH 4 ,CO, and CO 2 , J. Geophys. Res.77 (1972), 477–4493.

  25. [25]

    D. F. Heath, Satellite Observations of the Long-Term Variability and Intensity of the Near and Far Ultraviolet Solar Flux, Paper presented at the IUGG Conference, Moscow, August 1971.

  26. [26]

    Report of the Study of Man's Impact on Climate (The MIT Press, Cambridge, Mass. 1971), p. 276.

  27. [27]

    A. E. Bainbridge andL. E. Heidt,Measurement of methane in the tropopause and lower stratosphere, Tellus18 (1966), 221.

  28. [28]

    E. Robinson andR. C. Robbins,Sources, Abundance, and Fate of Gaseous, Atmospheric Pollutants, Stanford Research Project PR-6755 (American Petroleum Institute, Washington, D.C. 1968).

  29. [29]

    P. Fabian andC. E. Junge,Global rate of ozone destruction at the earth's surface, Arch. Met. Geoph. Biok. A,19 (1970), 161–172.

  30. [30]

    A. W. Brewer andA. W. Wilson,The regions of formation of atmospheric ozone, Quart. J. Roy. Met. Soc.94 (1968), 249–265.

  31. [31]

    C. W. Spicer, A. Villa, H. A. Wiebe andJ. Heicklen,The Reactions of Methylperoxy radicals with NO and NO 2 , CAES Report No 223-71 (Center for Air Environment Studies, The Pennsylvania State University, 1972), 30 pp.

  32. [32]

    H. A. Wiebe, A. Villa, T. M. Hellman andJ. Heicklen,Photolysis of Methyl Nitrite in the Presence of NO, NO 2 , and O 2 , CASE Report No 170-70 (Center for Air Environment Studies, The Pennsylvania State University, 1972), 30 pp.

  33. [33]

    S. C. Schmidt, R. C. Amme, D. G. Murcray andA. Goldman,Ultraviolet absorption by nitric acid vapour, Nature238 (1972), 109.

  34. [34]

    H. S. Johnston andR. Graham,Gas Phase Ultraviolet Absorption Spectrum of Nitric Acid Vapour, to be published.

  35. [35]

    G. Witt, Rocket Measurements, to be published.

  36. [36]

    K. Schütz, C. Junge, R. Beck andB. Albrecht,Studies of atmospheric N 2 O, J. Geophys. Res.75 (1970), 2230–2246.

  37. [37]

    E. J. Williamson andJ. T. Houghton,Radiometric measurements of emission from stratospheric water vapour, Quart. J. Roy. Met. Soc.91 (1965), 330.

  38. [38]

    D. H. Ehhalt andL. E. Heidt,The concentration of molecular H 2 and CH 4 in the stratosphere, Pure and Appl. Geophys.106–108 (1973), 1352.

  39. [39]

    W. Seiler andC. E. Junge,Carbon monoxide in the atmosphere, J. Geophys. Res.75 (1970), 2217–2226.

  40. [40]

    M. Ackerman,Ultraviolet Absorption Related to Mesospheric Processes, Mesospheric Models and Related Experiments, edited byG. Fiocco (Reidel Publishing Company, Dordrecht, Holland 1971), pp. 149–159.

  41. [41]

    G. Kockarts,Penetration of Solar Radiation in the Schumann-Runge Bands of Molecular Oxygen Mesospheric Models and Related Experiments, edited byG. Fiocco (Reidel Publishing Company, Dordrecht, Holland 1971), pp. 160–176.

  42. [42]

    R. E. Huie, J. T. Herron andD. D. Davis,The rate of the reaction O+O 2 +M→O 3 +M, J. Phys. Chem.76 (1972), 2653–2658.

  43. [43]

    I. T. N. Jones andR. P. Wayne,The photolysis of ozone by ultraviolet radiation: Effect of photolysis wavelength on primary step, Proc. Roy. Soc. London. A,319 (1970), 273–287.

  44. [44]

    J. L. McCrumb andF. Kaufman,Kinetics of the O+O 3 reaction, to be published in J. Chem. Phys.

  45. [45]

    D. D. Davis, J. T. Herron andR. E. Huie,Absolute Rate constants for the reaction O( 3 P)+NO 2 →NO+O 2 over the temperature range 339–230 K, to be published in J. Chem. Phys.

  46. [46]

    H. S. Johnston, Laboratory Experiments, private communication, 1972.

  47. [47]

    G. Paraskevopoulos andR. J. Cvetanovic,Relative rate of reaction of O(1D) with H2O, Chem. Phys. Lett.9 (1971), 603–605.

  48. [48]

    C. J. Hochanadel, J. A. Ghormley andP. J. Orgren,Absorption spectrum and reaction kinetics of the HO 2 radical in the gas phase, J. Chem. Phys.56 (1972), 4426–4432.

  49. [49]

    R. Simonaitis andJ. Heicklen,The Reaction of OH with NO 2, to be published.

  50. [50]

    C. J. Fortin, D. R. Snelling andA. Tardif,The Ultraviolet Flash Photolysis of Ozone and the Reaction of O(1D) with H2O, to be published.

  51. [51]

    K. F. Langley andW. D. McGrath,The ultraviolet photolysis of ozone in the presence of water vapour, Planet. Space. Sci.19 (1971), 413.

  52. [52]

    M. J. Kurylo,Absolute Rate Constants for the Reaction H+O 2+M→HO2+M Over the Temperature Range 203–404 K, to be published.

  53. [53]

    I. M. Campbell andB. A. Thrush,Effects of water, carbon dioxide and nitrous oxide on active nitrogen, Trans. Far. Soc.64 (1968), 1275–1286.

  54. [54]

    J. Heicklen,Gas phase reactions of alkyl peroxy and alkoxy radicals, Adv. Chem. Ser.76 (1968), 23–39.

  55. [55]

    J. G. Calvert, J. A. Kerr, K. L. Demerjian andR. D. McQuigg,Photolysis of formaldehyde as a hydrogen atom source in the lower atmosphere, Science175 (1972), 751–752.

  56. [56]

    E. D. Morris, Jr. andH. Niki,Mass spectrometric study of the reaction of the hydroxyl radical with formaldehyde, J. Chem. Phys.55 (1971), 1991–1992.

  57. [57]

    Chemical Kinetics Data Survey (National Bureau of Standard Reports 10692, 10828, 10867, U.S. Department of Commerce, 1972).

  58. [58]

    D. L. Baulch, D. D. Drysdale, A. C. Lloyd andD. G. Horne,High temperature reaction rate data, No. 1, May 1968; No. 2, Nov. 1968; No. 3, April 1969; No. 4, Dec. 1969; No. 5, July 1970 (Department of Physical Chemistry, The University, Leeds 2, England).

  59. [59]

    K. Schofield,An evaluation of kinetic rate data for reactions of neutrals of atmospheric interest, Planet. Space Sci.15 (1967), 643–670.

  60. [60]

    F. Kaufman,Neutral reactions involving hydrogen and other minor constitutents, Con. J. Chem.47 (1969), 1917–1924.

  61. [61]

    J. G. Calvert andJ. N. Pitts, Jr.,Photochemistry (John Wiley and Sons, Inc., New York 1967), p. 444.

  62. [62]

    W. B. DeMore andO. F. Raper,Reaction of O(1D) with methane, J. Chem. Phys.46 (1967), 2500–2505.

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Crutzen, P. A discussion of the chemistry of some minor constituents in the stratosphere and troposphere. PAGEOPH 106, 1385–1399 (1973). https://doi.org/10.1007/BF00881092

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  • Ozone
  • Lower Troposphere
  • Minor Constituent
  • Total Ozone
  • Stratospheric Ozone