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THE FATE OF ATMOSPHERIC PHOSGENE AND THE STRATOSPHERIC CHLORINE LOADINGS OF ITS PARENT COMPOUNDS - CCL4, C2CL4, C2HCL3,CH3CCL3, AND CHCL3

Publication ,  Journal Article
KINDLER, TP; CHAMEIDES, WL; WINE, PH; CUNNOLD, DM; ALYEA, FN; FRANKLIN, JA
Published in: JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES
January 1995

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 (CCl4, C2Cl4, CH3CCl3, CHCl3, and C2HCl3). Tropospheric phosgene is produced from the OH-initiated oxidation of C2Cl4, CH3CCl3, CHCl3, and C2HCl3. 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. We estimate a 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 CCl4, C2Cl4, CHCl3, and CH3CCl3 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, we 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; we estimate approximate decreases of 14, 3, 15, and 25\% for the stratospheric chlorine loadings of CCl4, CH3CCl3, C2Cl4, and CHCl3, respectively. A similar phenomenon due to the downward transport of stratospheric COFCl produced from CFC-11 is estimated to cause a 7\% decrease in the amount of reactive chlorine injected into the stratosphere from this compound. Our results are potentially sensitive to a variety of parameters, most notably the rate of reaction of phosgene with sulfate aerosols. However, on the basis of the observed vertical distribution of COCl2, we estimate that the reaction of COCl2 with sulfate aerosol most likely has a gamma

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Published In

JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES

ISSN

0148-0227

Publication Date

January 1995

Volume

100

Issue

D1

Start / End Page

1235 / 1251

Related Subject Headings

  • Meteorology & Atmospheric Sciences
 

Citation

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KINDLER, T. P., CHAMEIDES, W. L., WINE, P. H., CUNNOLD, D. M., ALYEA, F. N., & FRANKLIN, J. A. (1995). THE FATE OF ATMOSPHERIC PHOSGENE AND THE STRATOSPHERIC CHLORINE LOADINGS OF ITS PARENT COMPOUNDS - CCL4, C2CL4, C2HCL3,CH3CCL3, AND CHCL3. JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 100(D1), 1235–1251.
KINDLER, T. P., W. L. CHAMEIDES, P. H. WINE, D. M. CUNNOLD, F. N. ALYEA, and J. A. FRANKLIN. “THE FATE OF ATMOSPHERIC PHOSGENE AND THE STRATOSPHERIC CHLORINE LOADINGS OF ITS PARENT COMPOUNDS - CCL4, C2CL4, C2HCL3,CH3CCL3, AND CHCL3.” JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES 100, no. D1 (January 1995): 1235–51.
KINDLER TP, CHAMEIDES WL, WINE PH, CUNNOLD DM, ALYEA FN, FRANKLIN JA. THE FATE OF ATMOSPHERIC PHOSGENE AND THE STRATOSPHERIC CHLORINE LOADINGS OF ITS PARENT COMPOUNDS - CCL4, C2CL4, C2HCL3,CH3CCL3, AND CHCL3. JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES. 1995 Jan;100(D1):1235–51.
KINDLER, T. P., et al. “THE FATE OF ATMOSPHERIC PHOSGENE AND THE STRATOSPHERIC CHLORINE LOADINGS OF ITS PARENT COMPOUNDS - CCL4, C2CL4, C2HCL3,CH3CCL3, AND CHCL3.” JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, vol. 100, no. D1, Jan. 1995, pp. 1235–51.
KINDLER TP, CHAMEIDES WL, WINE PH, CUNNOLD DM, ALYEA FN, FRANKLIN JA. THE FATE OF ATMOSPHERIC PHOSGENE AND THE STRATOSPHERIC CHLORINE LOADINGS OF ITS PARENT COMPOUNDS - CCL4, C2CL4, C2HCL3,CH3CCL3, AND CHCL3. JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES. 1995 Jan;100(D1):1235–1251.

Published In

JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES

ISSN

0148-0227

Publication Date

January 1995

Volume

100

Issue

D1

Start / End Page

1235 / 1251

Related Subject Headings

  • Meteorology & Atmospheric Sciences