Skip to main content
Log in

The 1985 chlorine and fluorine inventories in the stratosphere based on ATMOS observations at 30° north latitude

  • Published:
Journal of Atmospheric Chemistry Aims and scope Submit manuscript

Abstract

The set of high-resolution infrared solar observations made with the Atmospheric Trace Molecule Spectroscopy (ATMOS)-Fourier transform spectrometer from onboard Spacelab 3 (30 April-1 May 1985) has been used to evaluate the total budgets of the odd chlorine and fluorine chemical families in the stratosphere. These budgets are based on volume mixing ratio profiles measured for HCl, HF, CH3Cl, ClONO2, CCl4, CCl2F2, CCl3F, CHClF2, CF4, COF2, and SF6 near 30° north latitude. When including realistic concentrations for species not measured by ATMOS, i.e., the source gases CH3CCl3 and C2F3Cl3 below 25 km, and the reservoirs ClO, HOCl and COFCl between 15 and 40 km (five gases actually measured by other techniques), the 30° N zonal 1985 mean total mixing ratio of chlorine, Cl, was found to be equal to (2.58±0.10) ppbv (parts per billion by volume) throughout the stratosphere, with no significant decrease near the stratopause. The results for total fluorine indicate a slight, but steady, decrease of its volume mixing ratio with increasing altitude, around a mean stratospheric value of (1.15±0.12) ppbv. Both uncertainties correspond to one standard deviation. These mean springtime 1985 stratospheric budgets are commensurate with values reported for the tropospheric Cl and F concentrations in the early 1980s, when allowance is made for the growth rates of their source gases at the ground and the time required for tropospheric air to be transported into the stratosphere. The results are discussed with emphasis on conservation of fluorine and chlorine and the partitioning among source, sink, and reservoir gases throughout the stratosphere.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  • Anderson J. G., Margitan J. J., and Stedman D. H., 1977, Atomic chlorine and the chlorine monoxide radical in the stratosphere: three in-situ observations, Science 198, 501–503.

    Google Scholar 

  • Anderson J. G., Grassl H. J., Shetter R. E., and Margitan J. J., 1980, Stratospheric free chlorine measured by balloon-borne in situ resonance fluorescence, J. Geophys. Res. 85, 2869–2887.

    Google Scholar 

  • Berg W. W., Crutzen P. J., Grahek F. E., Gitlen S. N., and Sedlacek W. A., 1980, First measurements of total chlorine and bromine in the lower stratosphere, Geophys. Res. Lett. 7, 937–940.

    Google Scholar 

  • Bischof W., Borchers R., Fabian P., and Küger B. C., 1985, Increased concentration and vertical distribution of carbon dioxide in the stratosphere, Nature 316, 708–710.

    Google Scholar 

  • Brown A., McKean D. C., and Duncan J. L., 1988, Vibrational anharmonicity and Fermi resonances in CHF2Cl, Spectrochim. Acta 44A, 553–565.

    Google Scholar 

  • Brown L. R., Farmer C. B., Rinsland C. P., and Toth R. A., 1987, Molecular line parameters for the atmospheric trace molecule spectroscopy experiment, Appl. Opt. 26, 5154–5182.

    Google Scholar 

  • Brown, L. R. and Cohen, E. A., 1989, Assignment of the γ1 and γ2 bands of COF2 at 5.2 μm, paper RE7 presented at 44th Symposium on Molecular Spectroscopy, Ohio State University, Columbus, 12–16 June.

  • Chance K. V., Johnson D. G., and Traub W. A., 1989, Measurement of stratospheric HOCl: concentration profiles, including diurnal variation, J. Geophys. Res. 94, 11059–11069.

    Google Scholar 

  • Cicerone R. J., Stolarski R. S. and Walters S., 1974, Stratospheric ozone destruction by man-made chlorofluoromethanes, Science 185, 1165–1167.

    Google Scholar 

  • Cicerone R. J., 1981, Halogens in the atmosphere, Rev. Geophys. Space Phys. 19, 123–139.

    Google Scholar 

  • Crutzen P. J., Isaksen I. S. A., and McAfee J. R., 1978, The impact of chlorocarbon industry on the ozone layer, J. Geophys. Res. 83, 345–363.

    Google Scholar 

  • Fabian P., Borchers R., Flentje G., Matthews W.A., Seiler W., Giehl H., Bunse K., Müller F., Schmidt U., Volz A., Khedim A., and Johnen F. J., 1981, The vertical distribution of stable trace gases at mid-latitudes, J. Geophys. Res. 86, 5179–5184.

    Google Scholar 

  • Fabian P., 1986, Halogenated hydrocarbons in the atmosphere in O. Hutzinger (ed.), Handbook of Environmental Chemistry, Vol. 4, Springer-Verlag, New York, 1986, part A, pp. 23–51.

    Google Scholar 

  • Fabian P., Borchers R., Krüger B. C., and Lal S., 1987, CF4 and C2F6 in the atmosphere, J. Geophys. Res. 92, 9831–9835.

    Google Scholar 

  • Farmer C. B., 1987, High resolution infrared spectroscopy of the sun and the earth's atmosphere from space, Mikrochim. Acta [Wien] III, 189–214.

    Google Scholar 

  • Farmer C. B., Raper O. F., and O'Callaghan F. G., 1987, Final report on the first flight of the ATMOS instrument during the Spacelab 3 mission, 29 April through 6 May 1985; JPL Publication 87–32, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, California.

    Google Scholar 

  • Gallagher C. C., Forsberg C. A., Mason A. S., Gandrud B. W., and Janhorbani M., 1985, Total chlorine content in the lower stratosphere, J. Geophys. Res. 90, 10747–10752.

    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 

  • Heidt L. E., Vedder J. F., Pollock W. H., Lueb R. A., and Henry B. E., 1989, Trace gases in the Antarctic atmosphere, J. Geophys. Res. 94, 11599–11611.

    Google Scholar 

  • Kaye J. A., Douglas A. R., Jackman C. H., Stolarski R. S., Zander R., and Roland G., 1991, Two-dimensional model calculation of fluorine-containing reservoir species in the stratosphere, J. Geophys. Res. 96, 12865–12881.

    Google Scholar 

  • Ko M. K. W., and Sze N. D., 1984, Diurnal variation of ClO: implications for the stratospheric chemistries of ClONO2, HOCl, and HCl, J. Geophys. Res. 89, 11619–11632.

    Google Scholar 

  • Lazrus A. L., Gandrud B. W., Greenberg J., Bonelli J., Mroz E., and Sedlacek W. A., 1977, Midlatitude seasonal measurements of stratospheric acidic chlorine vapor, Geophys. Res. Lett. 4, 587–589.

    Google Scholar 

  • Mankin W. G. and Coffey M. T., 1983, Latitudinal distributions and temporal changes of stratospheric HCl and HF, J. Geophys. Res. 88, 10776–10784.

    Google Scholar 

  • McDaniel A. H., Cantrell C. A., Davidson J. A., Shetter R. E. and Calvert J. A., 1991, The temperature dependent absorption cross sections for the chlorofluorocarbons: CFC-11, CFC-12, CFC-13, CFC-14, CFC-22, CFC-113, CFC-114, and CFC-115, J. Atmos. Chem. 12, 211–227.

    Google Scholar 

  • Molina M. J. and Rowland F. S., 1974, Stratospheric sink for chlorofluoromethanes: chlorine atomcatalysed destruction of ozone, Nature 249, 810–812.

    Google Scholar 

  • Mroz E. J., Lazrus A. L., and Bonelli J. E., 1977, Direct measurements of stratospheric fluoride, Geophys. Res. Lett. 4, 149–150.

    Google Scholar 

  • Norton R. H. and Rinsland C. P., 1991, ATMOS data processing and science analysis methods, Appl. Opt. 30, 389–400.

    Google Scholar 

  • Park J. H., Zander R., Farmer C. B., Rinsland C. P., Russell J. M.III, Norton R. H., and Raper O. F., 1986, Spectroscopic detection of CH3Cl in the upper troposphere and lower stratosphere, Geophys. Res. Lett. 13, 765–768.

    Google Scholar 

  • Prather M. J. and Watson R. T., 1990, Stratospheric ozone depletion and future levels of atmospheric chlorine and bromine, Nature 344, 729–734.

    Google Scholar 

  • Prinn R. G., 1988, How have the atmospheric concentrations of the halocarbons changed?, in F. S. Rowland and I. S. A. Isaksen (eds.), The Changing Atmosphere, Wiley, New York, pp. 33–48.

    Google Scholar 

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

    Google Scholar 

  • Rinsland C. P., Zander R., Brown L. R., Farmer C. B., Park J. H., Norton R. H., Russell J. M.III, and Raper O. F., 1986, Detection of carbonyl fluoride in the stratosphere, Geophys. Res. Lett. 13, 769–772.

    Google Scholar 

  • Rinsland C. P., Brown L. R., and Farmer C. B., 1990, Infrared spectroscopic detection of sulfur hexafluoride (SF6) in the lower stratosphere and upper troposphere, J. Geophys. Res. 95, 5577–5585.

    Google Scholar 

  • Rinsland C. P., Levine J. S., Goldman A., Sze N. D., Ko M. K. W., and Johnson D. W., 1991, Infrared measurements of HF and HCl total column abundances above Kitt Peak, 1977–1990: seasonal cycles, long-term increases, and comparison with model calculations, J. Geophys. Res. 96, 15523–15540.

    Google Scholar 

  • Russell J. M.III, Farmer C. B., Rinsland C. P., Zander R., Froidevaux L., Toon G. C., Gao B., Shaw J., and Gunson M., 1988, Measurements of odd nitrogen compounds in the stratosphere by the ATMOS experiment on Spacelab 3, J. Geophys. Res. 93, 1718–1736.

    Google Scholar 

  • Schmidt, U., Jebsen, C., Johnen, F. J., Khedim, A., Klein, E., Knapska, D., Kulessa, G., Rudolph, J., Schumacher, G., and Schunck, E., 1986, Stratospheric observations of long-lived trace gases at mid-latitudes 1982–1985, Data Report-Jül-Spez-375.

  • Schmidt, U., Bauer, R., Khedim, A., Klein, E., Kulessa, G., and Schubert, B., 1989, In situ observations of long-lived trace gases in the arctic stratosphere during winter, in R. D. Bojkov and P. Fabian (eds.), Ozone in the Atmosphere, A. Deepak Publishers, pp. 298–301.

  • Schmidt U. and Khedim A., 1991, In situ measurements of carbon dioxide in the winter Arctic vortex and at midlatitudes: an indicator of the ‘age’ of the stratosphere, Geophys. Res. Lett. 18, 763–766.

    Google Scholar 

  • Stolarski R. S. and Rundel R. D., 1975, Fluorine photochemistry in the stratosphere, Geophys. Res. Lett. 2, 443–444.

    Google Scholar 

  • Symonds R. B., Rose W. I., and Reed M. H., 1978, Contribution of Cl- and F-bearing gases to the atmosphere by volcanoes, Nature 344, 415–418.

    Google Scholar 

  • Sze N. D., 1978, Stratospheric fluorine: a comparison, Geophys. Res. Lett. 5, 781–783.

    Google Scholar 

  • Toon G. C. and Farmer C. B., 1989, Detection of HOCl in the Antarctic stratosphere, Geophys. Res. Lett. 16, 1375–1377.

    Google Scholar 

  • Wallace L. and Livingston W., 1991, Spectroscopic observations of atmospheric trace gases over Kitt Peak. 3. The long-term trends of hydrogen chloride and hydrogen fluoride from 1978 to 1990, J. Geophys. Res. 96, 15513–15521.

    Google Scholar 

  • Waters J. W., Stachnik R. A., Hardy J. C., and Jarnot R. F., 1988, ClO and O3 stratospheric pro balloon microwave measurements, Geophys. Res. Lett. 15, 780–783.

    Google Scholar 

  • Watson R. T., Smokler P. E., and DeMore W. B., 1978, An assessment of an F2 or N2O4 atmospheric injection from an aborted space shuttle mission, JPL Publication 77–81, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, Calif.

    Google Scholar 

  • Wilson, S. R., Schuster, G., and Helas, G., 1989, Measurements of COFCl and CCl2O near the tropopause, in R. D. Bojkov and P. Fabian (eds.), Ozone in the Atmosphere, A. Deepak Publisher, pp. 302–305.

  • WMO Report, 1986, No. 16, Atmospheric ozone 1985: Assessment of our understanding of the processes controlling its present distribution and change, World Meterological Organization, Geneva, Switzerland.

  • WMO, 1990a, Report No. 18, Report of the International Ozone Trends Panel 1988, World Meteorological Organization, Geneva, Switzerland.

    Google Scholar 

  • WMO, 1990b, Report No. 20, Scientific Assessment of Stratospheric Ozone: 1989, World Meteorological Organization, Geneva, Switzerland.

    Google Scholar 

  • Zander R., Rinsland C. P., Farmer C. B., Brown L. R., and Norton R. H., 1986, Observation of several chlorine nitrate (ClONO2) bands in stratospheric infrared spectra, Geophys. Res. Lett. 13, 757–761.

    Google Scholar 

  • Zander R., Rinsland C. P., Farmer C. B., and Norton R. H., 1987a, Infrared spectroscopic measurements of halogenated source gases in the stratosphere with the ATMOS instrument, J. Geophys. Res. 92, 9836–9850.

    Google Scholar 

  • Zander R., Roland G., Delbouille L., Sauval A., Farmer C. B., and Norton R. H., 1987b, Monitoring of the integrated column of hydrogen fluoride above the Jungfraujoch station since 1977 — the HF/HCl column ratio, J. Atmos. Chem. 5, 385–394.

    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 ATMOS/Spacelab 3 observations — An update, J. Geophys. Res. 95, 20519–20525.

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints and permissions

About this article

Cite this article

Zander, R., Gunson, M.R., Farmer, C.B. et al. The 1985 chlorine and fluorine inventories in the stratosphere based on ATMOS observations at 30° north latitude. J Atmos Chem 15, 171–186 (1992). https://doi.org/10.1007/BF00053758

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00053758

Key words

Navigation