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The potential impact of the reaction OH+ClO→HCl+O2 on polar ozone photochemistry

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Abstract

We call attention to the likely importance of the potential reaction OH+ClO→HCl+O2. It may only be a minor channel for the reaction of OH with ClO, which is often ignored in models, but if it occurs it considerably increases the rate of recovery of HCl after an air parcel has encountered a polar stratospheric cloud (PSC). The net effect of this reaction on the ozone concentration depends on the relative HCl concentration and whether the air parcel is in a PSC. When an air parcel is in a PSC and the HCl concentration is less than the sum of the HOCl and ClONO2 concentrations, heterogeneous ClO x production is rate limited by the production of HCl. Under these conditions the reaction allows HCl to be reprocessed more rapidly by the heterogeneous reactions of HCl with HOCl and ClONO2. This allows high ClO x concentration to be maintained for longer, and at a slightly higher level, than would otherwise be possible which in turn leads to more ozone depletion. When there are PSCs but HCl is in excess, or outside of the PSC regions (i.e. during the recovery phase), the reaction will always reduce the ClO/HCl ratio and hence slightly reduce the ozone loss.

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References

  • Anderson, D. E., 1983, The troposphere to stratosphere radiation field at twilight: A spherical model,Planetary Space Science 31 (12), 1517–1523.

    Google Scholar 

  • Atkinson, R., Baulch, D. I., Cox, R. A., Hampson, R. F., Kerr, J. A., Troe, J., 1992, Evaluated kinetic and photochemical data for atmospheric chemistry — Supplement IV, IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry,J. Phys. Chem. Ref. Data 21 (6), 1125.

    Google Scholar 

  • Austin, J., Butchart, N., Shine, K. P., 1992, Possibility of an arctic ozone hole in a doubled-CO2 climate,Nature 360 (6401), 221–225.

    Google Scholar 

  • Burrows, J. P., Cox, R. A., 1981, Kinetics of chlorine oxide radical reactions using modulated photolysis. Part 4. — The reactions of Cl + Cl2O → Cl2 + ClO and ClO + HO2 → products studied at 1 atm and 300 K,J. Chem. Soc. Faraday Trans. 1 77, 2465.

    Google Scholar 

  • Chandra, S., Jackman, C. H., Douglass, A. R., Fleming, E. L., Considine, D. B., 1993, Chlorine catalyzed destruction of ozone — implications for ozone variability in the upper-stratosphere,Geophys. Res. Lett. 20 (5), 351–354.

    Google Scholar 

  • Cattell, F. C., Cox, R. A., 1986, Pressure dependence of the reaction of HO2 with Cl and ClO,J. Chem. Soc. Faraday Trans. 2 82, 1413.

    Google Scholar 

  • Chipperfield, M. P., Cariolle, D., Simon, P., Ramaroson, R., and Lary, D. J., 1993, A three-dimensional modelling study of trace species in the Arctic lower stratosphere during winter 1989–90,J. Geophys. Res. 98, 7199–7218.

    Google Scholar 

  • Chipperfield, M. P., Cariolle, D., and Simon, P., 1994a, A 3D chemical transport model study of chlorine activation during EASOE,Geophys. Res. Lett. 21, 1467–1470.

    Google Scholar 

  • Chipperfield, M. P., Pyle, J. A., Blom, C. E., Glatthor, N., Höpfner, M., Gulde, T., Piesch, Ch., and Simon, P., 1994b, The variability of ClONO2 and HNO3 in the Arctic polar vortex: Comparison of Transall MIPAS Measurements and 3D model results,J. Geophys. Res., (submitted).

  • Chipperfield, M. P., 1994c, A 3D model comparison of PSC processing during the Arctic winters of 1991/92 and 1992/93,Annal. Geophys. 12, 342–354.

    Google Scholar 

  • DeMore, W. B., Howard, C. J., Sander, S. P., Ravishankara, A. R., Golden, D. M., Kolb, C. E., Hampson, R. F., Molina, M. J., Kurylo, M. J., 1992, Chemical kinetics and photochemical data for use in stratospheric modeling, evaluation number 10, JPL publication 92-20.

  • Fisher, M., Lary, D. J., 1994, Langrangian four dimensional variational assimilation of chemical species, submitted to theQuart. J. Royal Meteorol. Soc.

  • Gear, C. W., 1971,Numerical Initial Value Problems in Ordinary Differential Equations, Prentice-Hall, Englewood Cliffs, NJ, Chapter 9, 1971.

    Google Scholar 

  • Hanson, D. and Mauersberger, K., 1988, Laboratory studies of the nitric acid trihydrate: Implications for the south polar stratosphere,Geophys. Res. Lett. 15, 855–858.

    Google Scholar 

  • Hills, A. J. and Howard, C. J., 1984, Rate coefficient temperature dependence and branching ratio for the OH-ClO reaction,J. Chem. Phys. 81, 4458–4465.

    Google Scholar 

  • Lary, D. J. and Pyle, J. A., 1991, Diffuse radiation, twilight and photochemistry — I,J. Atmos. Chem. 13, 373–392.

    Google Scholar 

  • Lary, D. J. and Pyle, J. A., 1991, Diffuse radiation, twilight and photochemistry — II,J. Atmos. Chem. 13, 393–406.

    Google Scholar 

  • Leck, T. J., Cook, Jac.-E. L., and Birks, J. W., 1980, Studies of reactions of importance in the stratosphere, III. Rate constant and products of the reaction between ClO and HO2 radicals at 298 K,J. Chem. Phys. 72, 2364.

    Google Scholar 

  • Leu, M. T. and Lin, C. L., 1979, Rate constants for the reactions of OH with ClO, Cl2, and Cl2O at 298 K,Geophys. Res. Lett. 6, 425.

    Google Scholar 

  • Leu, M. T., 1980, Product distribution for the reaction of HO2 with ClO,Geophys. Res. Lett. 7, 173.

    Google Scholar 

  • McElroy, M. B. and Salawitch, R. J., 1989, Changing composition of the global stratosphere,Science 243 (4892), 763–770.

    Google Scholar 

  • Meier, R. R., Anderson, D. E., and Nicolet, M., 1982, The radiation field in the troposphere and stratosphere from 240 nm to 1000 nm: General analysis,Planetary Space Sci. 30 (9), 923–933.

    Google Scholar 

  • Natarajan, M. and Callis, L. B., 1990, Stratospheric photochemical studies with Atmospheric Trace Molecule (ATMOS) measurements,J. Geophys. Res. 96, 9361–9370.

    Google Scholar 

  • Nicolet, M., Meier, R. R., and Anderson, D. E., 1982, The radiation field in the troposphere and stratosphere from 240 nm to 1000 nm: Numerical Analysis,Planetary Space Sci. 30 (9), 935–983.

    Google Scholar 

  • Poulet, G., Laverdet, G., Le Bras, G., 1986, Rate constant and branching ratio for the reaction of OH and ClO,J. Phys. Chem. 90, 159.

    Google Scholar 

  • Press, W. H., Teukolsky, S. A., Vetterling, W. T., Flannery, B. P., 1992,Numerical Recipes in Fortran — The Art of Scientific Computing, 2nd edn; Cambridge University Press.

  • Ravishankara, A. R., Eisele, F. L., Wine, P. H., 1983, The kinetics of the reaction of OH with ClO,J. Chem. Phys. 78, 1140–1144.

    Google Scholar 

  • Stimpfle, R. M., Perry, R. A., and Howard, C. J., 1979, Temperature dependence of the reaction of ClO and HO2 radicals,J. Chem. Phys. 71, 5183.

    Google Scholar 

  • Stoer, J. and Bulirsch, R., 1980,Introduction to Numerical Analysis, Springer-Verlag, New York, Chapter 7.

    Google Scholar 

  • Toon, G. C., Blavier, J.-F., Solario, J. N., Szeto, J. T., 1992, Airborne observations of the 1992 Arctic winter stratosphere by FTIR solar absorption spectroscopy,SPIE Optical Methods in Atmos. Chem. 1715, 457–467.

    Google Scholar 

  • Toumi, R. and Bekki, S., 1993, The importance of the reactions between OH and ClO for stratospheric ozone,Geophys. Res. Lett. 20 (22), 2447–2450.

    Google Scholar 

  • Toumi, R., Jones, R. L., and Pyle, J. A., 1993, Stratospheric ozone depletion by ClONO2 photolysis,Nature 365 (6441), 331–333.

    Google Scholar 

  • von Clarmann, T., Fisher, H., Friedlvallon, F., Linden, A., Oelhaf, H., Piesch, C., and Seefeldner, M., 1993, Retrieval of stratospheric O3, HNO3 and ClONO2 profiles from 1992 MIPAS-B limb emission-spectra — method, results, and error analysis,J. Geophys. Res. 98, D11, 20495–20506.

    Google Scholar 

  • Webster, C. R.et al., 1993, Chlorine chemistry on polar stratospheric cloud particles in the Arctic winter,Science 261 (5125), 1130–1134.

    Google Scholar 

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Lary, D.J., Chipperfield, M.P. & Toumi, R. The potential impact of the reaction OH+ClO→HCl+O2 on polar ozone photochemistry. J Atmos Chem 21, 61–79 (1995). https://doi.org/10.1007/BF00712438

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