The fate of atmospheric phosgene and the stratospheric chlorine loadings of its parent compounds: CCl{sub 4}, C{sub 2}Cl{sub 4}, C{sub 2}HCl{sub 3}, CH{sub 3}CCL{sub 3} and CHCl{sub 3}
- Georgia Institute of Technology, Atlanta, GA (United States)
A study of the tropospheric and stratospheric cycles of phosgene is carried out to determine its fate and ultimate role in controlling the ozone depletion potentials of its parent compounds (CCl{sub 4}, C{sub 2}Cl{sub 4},CH{sub 3}CCl{sub 3},CHCl{sub 3}, and C{sub 2}HCl{sub 3}). Tropospheric phosgene is produced from the OH-initiated oxidation of C{sub 2}Cl{sub 4}, CH{sub 3}CCl{sub 3}, CHCl{sub 3}. Simulations using a two-dimensional model indicate that these processes produce about 90 pptv/yr of tropospheric phosgene with an average concentration of about 18 pptv, in reasonable agreement with observations. The authors estimate residence time of about 70 days for tropospheric phosgene, with the vast majority being removed by hydrolysis in cloudwater. Only about 0.4% of the phosgene produced in the troposphere avoids wet removal and is transported to the stratosphere, where its chlorine can be released to participate in the catalytic destruction of ozone. Stratospheric phosgene is produced from the photochemical degradation of CCl{sub 4}, C{sub 2}Cl{sub 4}, CHCl{sub 3}, and CH{sub 3}CCl{sub 3} and is removed by photolysis and downward transport to the troposphere. Model calculations, in good agreement with observations indicate that these processes produce a peak stratospheric concentration of about 25-30 pptv at an altitude of about 25 km. In contrast to tropospheric phosgene, stratospheric phosgene is found to have a lifetime against photochemical removal of the order of years. As a result, the authors find that a significant portion of the phosgene that is produced in the stratosphere is ultimately returned to the troposphere, where it is rapidly removed by clouds. This phenomenon effectively decreases the amount of reactive chlorine injected into the stratosphere and available for ozone depletion from phosgene`s parent compounds. 58 refs., 11 figs., 9 tabs.
- OSTI ID:
- 146843
- Journal Information:
- Journal of Geophysical Research, Journal Name: Journal of Geophysical Research Journal Issue: D1 Vol. 100; ISSN JGREA2; ISSN 0148-0227
- Country of Publication:
- United States
- Language:
- English
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