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The role of the SO2 oxidation for the background stratospheric sulfate layer in the light of new reaction rate data

Abstract

Presently available data on the reaction of SO2 with OH radicals (OH + SO2 +\(M\xrightarrow[{k_1 }]{}\) HSO3 +M) are critically reviewed in light of recent stratospheric sulfur budget calculations. These calculations impose that the net oxidation ratek of SO2 within the stratosphere should fall within the range 10−7k≤10−9, if the SO2 oxidation model for the stratospheric sulfate layer is assumed to be correct.

The effective reaction rate constantk 1 * =k 1[M] at the stratospheric temperature is estimated as

$$k_1^* = \frac{{(8.2 \pm 2.2) \times 10^{ - 13} \times [M]}}{{(0.79 \mp 0.34) \times 10^{ - 13} + [M]}}cm^3 /molecules sec$$

where [M] refers to the total number density (molecules/cm3).

Using the above limiting values ofk 1 * , and the estimated OH density concentrations, the net oxidation rate is calculated as 3.6×10−7k≤1.3×10−8 at 17 km altitude. This indicates that the upper limit of thesek values exceeds the tolerable range imposed by the model by a factor of about four. Obviously the uncertainty of thek 1 * values and of the OH concentrations in the stratosphere is still too large to make definite conclusions on the validity of the SO2 model.

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References

  1. [1]

    Atkinson, R., Perry, R. A. andPitts, J. N., Jr. (1976),Kinetics of the reaction of OH radicals with CO and N 2 O, Chem. Phys. Lett.44, 204–208.

  2. [2]

    Atkinson, R., Perry, R. A. andPitts, J. N., Jr. (1976),Rate constant for the reactions of the OH radical with NO 2 (M=Ar and N 2)and SO 2 (M=Ar), J. Chem. Phys.65, 306–310.

  3. [3]

    Castleman, A. W., Jr.,Davis, R. E., Munkelwitz, H. R., Tang, I. N. andWood, W. P. (1975),Kinetics of Association reactions pertaining to H 2 SO 4 aerosol formation, Proceedings of the Symposium on Chemical Kinetics Data for the Upper and Lower Atmosphere, Warrenton Va, Sept. 1974, Intern. J. Chem. Kin. Symp. No. 1, pp. 629–640.

  4. [4]

    Castleman, A. W., Jr. andTang, I. N. (1976/77),Kinetics of the association reaction of SO 2 with the hydroxyl radical, J. of Photochem.6, 349–354.

  5. [5]

    CIAP Report, Monograph 1, September 1975 Final Report Fig. 3.45.

  6. [6]

    Chan, W. H., Uselman, M., Calvert, J. G. andShaw, J. H. (1977),The pressure dependence of the rate constant for the reaction OH+CO→H+CO 2, Chem. Phys. Lett.45, 240–244.

  7. [7]

    Cox, R. A. (1975),The photolysis of gaseous nitrous acid, a technique for obtaining kinetic data on atmospheric photooxidation, Proceedings of the Symposium on Chemical Kinetics Data for the Upper and Lower Atmosphere, Warrenton, Va, Sept. 1974, Intern. J. Chem. Kin. Symp, No. 1, 379–398.

  8. [8]

    Crutzen, P. J. (1976),The possible importance of CSO for the sulfate layer of the stratosphere, Geophys. Res. Letters3, 73–76.

  9. [9]

    Davis, D. D. andKlauber, G. (1975),Atmospheric gas phase oxidation mechanisms for the molecule SO 2. Proceedings of the Symposium on Chemical Kinetics Data for the Upper and Lower Atmosphere, Warrenton, Va, Sept. 1974, Intern. J. Chem. Kin. Symp. No. 1, pp. 543–556.

  10. [10]

    Davis, D. D., McGee, T. andHeaps, W. (1976),Direct tropospheric OH radical measurements via an aircraft platform: laser induced fluorescence, Paper presented at 12th International symposium on free radicals, Laguna Beach, California, January 1976.

  11. [11]

    Davis, D. D. andSchiff, R. (1973), cited as unpublished data inPayne [22].

  12. [12]

    Davis, D. D., Schiff, R., Bollinger, W. andFischer, S. (1974), Paper presented at the Symposium on Chemical Kinetics Data for the Upper and Lower Atmosphere, Warrenton, Va. Sept.

  13. [13]

    Erler, K., Field, D. andZellner, R. (1975),Rate measurements by fast flow method with resonance fluorescence detection; some recombination reactions involving OH radicals, Fourth International Conference on Gas Kinetics, Edinburgh, August.

  14. [14]

    Fair, R. W. andThrush, B. A. (1969),Reactions between hydrogen atoms and sulphur dioxide, Trans. Faraday Soc.65, 1550–1556.

  15. [15]

    Gordon, S. andMulac, W. A. (1975),Reaction of the OH (X 2)radical produced by the pulse radiolysis of water vapor, Proceedings of the symposium on Chemical Kinetics Data for the Upper and Lower Atmosphere, Warrenton, Va, Sept. 1974, Intern. J. Chem. Kin. Symp. No. 1, pp. 289–299.

  16. [16]

    Hampson, R. F., Jr. andGarwin, D. (1975), NBS Technical note 866, U.S. Department of Commerce, pp. 56–57.

  17. [17]

    Harris, G. W. andWayne, R. P. (1975),Reaction of hydroxyl radicals with NO, NO 2 and SO 2, Faraday Trans. I,71, 610–617.

  18. [18]

    Jaeschke, W., Schmitt, R. andGeorgii, H. W. (1976),Preliminary results of stratospheric SO 2 measurements, submitted to Geophys Rev. letters.

  19. [19]

    Junge, C. (1974),Sulfur budget of the stratospheric aerosol layer, Proceedings of the IAMAP Conference on Structure, Composition and General Circulation of the Upper and Lower Atmospheres, Melbourne, January 1974, Vol. 1, pp. 85–97.

  20. [20]

    RRKM (abbreviation forRice, Rampsberger, Kassel andMarcus) is a useful approximation method, which allows the calculation of the limiting low pressure (k 1 0 ) and high pressure rate constants by means of a statistical theory. SeeSetser, D. W. (1972),Chemical Kinetics MTP International Review of Science,Physical Chemistry, Series one, Vol. 9, pp. 1–43 (Butterworths University Park Press).

  21. [21]

    McAndrew, T. andWheeler, R. (1962),The recombination of atomic hydrogen in propane flame gases, J. Phys. Chem.66, 229–232.

  22. [22]

    Payne, W. A., Stief, L. J. andDavis, D. D. (1973),A kinetics study of the reaction of HO 2 with SO 2 and NO, J. Amer. Chem. Soc.95, 7614–7619.

  23. [23]

    Sie, B. K. T., Simonaitis, R. andHeicklen, J. (1976),The reaction of OH with CO, Intern. J. Chem. Kin.8, 85–98.

  24. [24]

    Shimazaki, T. andOgawa, T. (1974),A theoretical model of minor constituent distributions in the stratosphere including diurnal variations, J. Geophys. Res.79, 3411–3423.

  25. [25]

    Shimazaki, T. andWhitten, R. C. (1976),A comparison of one-dimensional theoretical models of stratospheric minor constituents, Rev. Geoph. and Space Phys.14, 1–12.

  26. [26]

    Troe, J. inPhysical Chemistry. An advanced treatise (H. Eyring, D. Henderson and W. Jost, eds.), (Academic Press, New York 1975).

  27. [27]

    Wheeler, R. (1968),On the radical recombination rates in SO 2-doped flames, J. Phys. Chem.72, 3359–3360.

  28. [28]

    Zellner, R. (1977),Recombination reactions in atmospheric chemistry, Paper presented at the NATO Advanced Study Institute, held in Arabba, Italy. March.

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Moortgat, G.K., Junge, C.E. The role of the SO2 oxidation for the background stratospheric sulfate layer in the light of new reaction rate data. PAGEOPH 115, 759–774 (1977). https://doi.org/10.1007/BF00881209

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Key words

  • Sulfate layer
  • Photo-chemistry
  • Stratospheric aerosol
  • Reaction rate