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Enhanced production of stratospheric OH from methane oxidation at elevated reactive chlorine levels in northern midlatitudes

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Abstract

Examination of odd-hydrogen production and loss processes in the lower stratosphere reveals that the large abundances of midlatitude ClO recently measured requires a reassessment of the OH yield from methane oxidation due to a more rapid initiation of the methane oxidation sequence by atomic chlorine. Using a steady state calculation for OH and an iterative procedure for evaluating odd-hydrogen production from the methane oxidation sequence, we demonstrate that both OH and reactive chlorine are amplified below 25 km. The amplified values of OH and ClO are found to be consistent with recent measurements of ClO concentrations and of OH column abundances.

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References

  • Anderson, D. E., Meier, R. R., and Kumer, J. B., 1980, Improved model of Mie scattering contribution to troposphere and stratosphere photodissociation fluxes,Appl. Opt. 19, 1230–1231.

    Google Scholar 

  • Anderson, J. G., 1982, The measurement of trace reactive species in the stratosphere: A review of recent results, inCauses and Effects of Stratospheric Ozone Reduction: An Update, National Academy Press, Washington DC, pp. 206–305.

    Google Scholar 

  • Avallone, L. M., Toohey, D. W., Brune, W. H., Salawitch, R. J., Dessler, A. E., and Anderson, J. G., 1993, Balloon-borne in situ measurements of ClO and ozone: Implications for heterogeneous chemistry and mid-latitude ozone loss,Geophys. Res. Lett. 20, 1795–1798.

    Google Scholar 

  • Brasseur, G. and Solomon, S., 1986,Aeronomy of the Middle Atmosphere, D. Reidel, Dordrecht, Holland.

    Google Scholar 

  • Brune, W. H. and Anderson, J. G., 1986, In situ observations of midlatitude ClO and Bro,Geophys. Res. Lett. 13, 1391–1394.

    Google Scholar 

  • Burnett, C. R. and Burnett, E. B., 1981, Spectroscopic measurements of the vertical column abundance of hydroxyl (OH) in the Earth's atmosphere,J. Geophys. Res. 86, 5185–5202.

    Google Scholar 

  • Burnett, C. R. and Burnett, E. B., 1983, OH Pepsios,Appl. Opt. 22, 2887–2892.

    Google Scholar 

  • Burnett, C. R., Minschwaner, K. R., and Burnett, E. B., 1988, Vertical column abundance measurements of atmospheric hydroxyl from 26°, 40°, and 65° N,J. Geophys. Res. 93, 5241–5253.

    Google Scholar 

  • Burnett, C. R., Minschwaner, K. R., and Burnett, E. B., 1990, OH vertical column abundance: Tropical measurements,J. Geophys. Res. 95, 16491–16495.

    Google Scholar 

  • Burnett, C. R., Burnett, E. B., Wood, S. W., and Keep, D. J., 1994, Interhemispheric comparison of observed seasonal and diurnal behaviors of OH vertical column abundances,Eos. Trans. AGU (Suppl 75, 85.

    Google Scholar 

  • Burnett, E. B., 1986, Quasi-theoretical examination of the principal results of the Pepsios ground-based measurements of the vertical column abundance of atmospheric hydroxyl,Report FC-85-547, #3, Chemical Manufacturers' Association, Washington DC.

    Google Scholar 

  • Crutzen, P. J., Müller, R., Brühl, Ch., and Peter, Th., 1992, On the potential importance of the gas phase reaction CH3O2+ClO → ClOO + CH3O and the heterogeneous reaction HOCl+HCl → H2O+Cl2 in ‘Ozone Hole’ chemistry,Geophys. Res. Lett. 19, 1113–1116.

    Google Scholar 

  • DeMore, W. B., Sander, S. P., Golden, D. M., Molina, M. J., Hampson, R. F., Kurylo, M., Howard, C. J., and Ravishankara, A. R. (eds.), 1992, Chemical kinetics and photochemical data for use in stratospheric modeling: Evaluation 10,JPL Publ. 82-1, NASA Jet Propul. Lab., Pasadena, CA.

    Google Scholar 

  • Farman, J. C., Gardiner, B. G., and Shanklin, J. D., 1985, Large losses of total ozone in Antarctica reveal seasonal ClOx/NOx interaction,Nature 315, 207–210.

    Google Scholar 

  • Fenn, R. W., Clough, S. A., Gallery, W. O., Good, R. E., Kneizys, F. X., Mill, J. D., Rothman, L. S., Shettle, E. P., and Volz, F. E., 1985, Optical and infrared properties of the atmosphere, in A. S. Jursa (ed.),Handbook of Geophysics and the Space Environment, Air Force Geophysics Laboratory, Bedford, MA.

    Google Scholar 

  • Frederick, J. E., Serafino, G. N., and Douglass, A. R., 1984, An analysis of the annual cycle in upper stratospheric ozone,J. Geophys. Res. 89, 9547–9555.

    Google Scholar 

  • Froidevaux, L., Allen, M., and Yung, Y. L., 1985, A critical analysis of ClO and O3 in the mid-latitude stratosphere,J. Geophys. Res. 90, 12999–13029.

    Google Scholar 

  • Garcia, R. R. and Solomon, S., 1983, A numerical model of the zonally averaged dynamical and chemical structure of the middle atmosphere,J. Geophys. Res. 88, 1379–1400.

    Google Scholar 

  • Gunson, M. R., Farmer, C. B., Norton, R. H., Zander, R., Rinsland, C. P., Shaw, J. H., and Gao, B. C., 1990, Measurements of CH4, N2O, CO, H2O, and O3 in the middle atmosphere by the Atmospheric Trace Molecule Spectroscopy experiment on Spacelab 3,J. Geophys. Res. 95, 13867–13882.

    Google Scholar 

  • Johnston, P. V. and McKenzie, R. L., 1989, NO2 observations at 45° S during the decreasing phase of solar cycle 21 from 1980–1987,J. Geophys. Res. 94, 3473–3486.

    Google Scholar 

  • Kawa, S. R., Fahey, D. W., Solomon, S., Brune, W. H., Proffitt, M. H., Toohey, D. W., Anderson, D. E. Jr., Anderson, L. C., and Chan, K. R., 1990, Interpretation of aircraft measurements of NO, ClO, and O3 in the lower stratosphere,J. Geophys. Res. 95, 18597–18609.

    Google Scholar 

  • Kondo, Y., Iwata, A., Pirre, M., Ramorosen, R., Delannoy, C., Matthews, W. A., Koike, M., and Suzuki, R., 1989, Diurnal variation of nitric oxide at 26 km,Geophys. Res. Lett. 16, 867–870.

    Google Scholar 

  • LeTexier, H., Solomon, S., and Garcia, R. R., 1988, The role of molecular hydrogen and methane oxidation in the water vapour budget of the stratosphere,Q. J. Roy. Meteor. Soc. 114, 281–295.

    Google Scholar 

  • Liu, Y., 1990, Examination of observed OH column abundance behaviors using a mesospheric model, MS thesis, Florida Atlantic University, Boca Raton, FL, 117 pp.

    Google Scholar 

  • Logan, J. A., Prather, M. J., Wofsy, S. C., and McElroy, M. B., 1978, Atmospheric chemistry: Response to human influence,Phil. Trans. Roy. Soc. 290, 187–234.

    Google Scholar 

  • Meier, R. R., Anderson, D. E., and Nicolet, M., 1982, Radiation field in the troposphere and stratosphere from 240–1000 nm, 1, General analysis,Planet. Space Sci. 30, 923–933.

    Google Scholar 

  • Mergenthaler, J. L., Kuner, J. B., Roche, A. E., Nightingale, R. W., Wuebbles, D. J., and Connell, P. S., 1994, Observations of the diurnal behaviour of stratospheric ClONO2 by the UARS CLAES experiment,Eos Trans. AGU (Suppl. 75, 96.

    Google Scholar 

  • Minschwaner, K. R., 1987, Observations of atmospheric OH and their significance to middle atmospheric photochemistry, MS thesis, Florida Atlantic University, Boca Raton, FL, 98 pp.

    Google Scholar 

  • Minschwaner, K. R., Salawitch, R. J., and McElroy, M. B., 1993, Absorption of solar radiation by O2: Implications for O3 and lifetimes of N2O, CFCl3, and CF2Cl2,J. Geophys. Res. 98, 10543–10561.

    Google Scholar 

  • Mount, G. H. and Eisele, F. L., 1992, An intercomparison of tropospheric OH measurements at Fritz Peak Observatory, Colorado,Science 256, 1187–1189.

    Google Scholar 

  • Mount, G. H. and Rottman, G. J., 1983a, The solar absolute spectral irradiance 1150–3173A: May 17, 1982,J. Geophys. Res. 88, 5403–5410.

    Google Scholar 

  • Mount, G. H. and Rottman, G. J., 1983b, The solar absolute spectral irradiance at 1216A and 1800–3173A: January 12, 1983,J. Geophys. Res. 88, 6807–6811.

    Google Scholar 

  • Mount, G. H. and Rottman, G. J., 1985, The solar absolute spectral irradiance 118–300 nm: July 25, 1985,J. Geophys. Res. 90, 13031–13036.

    Google Scholar 

  • Nicolet, M., 1975, Stratospheric ozone: An introduction to its study,Rev. Geophys. Space Phys. 13, 593–636.

    Google Scholar 

  • Nicolet, M., 1984, On the molecular scattering in the terrestrial atmosphere: An empirical formula for its calculation in the homosphere,Planet. Space Sci. 32, 1467–1468.

    Google Scholar 

  • Prather, M. and Jaffe, A. H., 1990, Global impact of the Antarctic ozone hole: Chemical propagation,J. Geophys. Res. 95, 3473–3492.

    Google Scholar 

  • Raper, O. F., Farmer, C. B., Zander, R., and Park, J. H., 1987, Infrared spectroscopic measurements of halogenated sink and reservoir gases with the ATMOS instrument,J. Geophys. Res. 92, 9851–9858.

    Google Scholar 

  • Stimpfle, R. M., Wennberg, P. O., Lapson, L. B., and Anderson, J. G., 1990, Simultaneous in situ measurements of OH and HO2 in the stratosphere,Geophys. Res. Lett. 17, 1905–1908.

    Google Scholar 

  • Thomas, R. J., 1990, Seasonal ozone variations in the upper mesosphere,J. Geophys. Res. 95, 7395–7401.

    Google Scholar 

  • Toohey, D. W., Avallone, L. M., Allen, N. T., Demusz, J. N., Hazen, J. N., Hazen, N. L., and Anderson, J. G., 1993, The performance of a new instrument for in situ measurements of ClO in the lower stratosphere,Geophys. Res. Lett. 18, 1791–1794.

    Google Scholar 

  • Waters, J. W., Froidevaux, L., Read, W. G., Manney, G. L., Elson, L. S., Flower, D. A., Jarnot, R. F., and Harwood, R. S., 1993, Stratospheric ClO and ozone from the Microwave Limb Sounder on the Upper Atmospheric Research Satellite,Nature 362, 597–602.

    Google Scholar 

  • Wennberg, P. O., Stimpfle, R. M., Weinstock, E. M., Dessler, A. E., Lloyd, S. A., Lapson, L. B., Schwab, J. J., and Anderson, J. G., 1990, Simultaneous in situ measurements of OH, HO2, and H2O: A test of modeled stratospheric HO x ,Geophys. Res. Lett. 17, 1909–1912.

    Google Scholar 

  • Wood, S. W., Keep, D. J., Burnett, C. R., and Burnett, E. B., 1994, Column abundance measurements of atmospheric hydroxyl at 45° S,Geophys. Res. Lett. 21, 1607–1610.

    Google Scholar 

  • World Meteorological Organization (WMO), 1982, The Stratosphere 1981,Report 11, Global Ozone Research and Monitoring Project, Geneva, Switzerland.

    Google Scholar 

  • World Meteorological Organization (WMO), 1986, Atmospheric Ozone 1985,Report 16, Global Ozone Research and Monitoring Project, Geneva, Switzerland.

    Google Scholar 

  • Zander, R., Gunson, M. R., Foster, J. C., Rinsland, C. P., and Namkung, J., 1990, Stratospheric ClONO2, HCl, and HF concentration profiles derived from Atmospheric Trace Molecule Spectroscopy Experiment Spacelab 3 observations,J. Geophys. Res. 95, 20519–20525.

    Google Scholar 

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Burnett, E.B., Burnett, C.R. Enhanced production of stratospheric OH from methane oxidation at elevated reactive chlorine levels in northern midlatitudes. J Atmos Chem 21, 13–41 (1995). https://doi.org/10.1007/BF00712436

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  • DOI: https://doi.org/10.1007/BF00712436

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