Atmos. Chem. Phys. Discuss., 11, 14233-14258, 2011
© Author(s) 2011. This work is distributed
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This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Multiple-sulfur isotope effects during photolysis of carbonyl sulfide
Y. Lin1,*, M. S. Sim1, and S. Ono1
1Department of Earth, Atmospheric and Planetary Sciences, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139, USA
*now at: School of Earth Sciences and Engineering, Nanjing University, Nanjing, Jiangsu 210093, China

Abstract. Laboratory experiments were carried out to determine sulfur isotope effects during ultraviolet photolysis of carbonyl sulfide (OCS) to carbon monoxide (CO) and elemental sulfur (S0). The OCS gas at 3.7 to 501 mbar was irradiated with or without a N2 bath gas using a 150 W Xe arc lamp. Sulfur isotope ratios for the product S0 and residual OCS were analyzed by an isotope ratio mass-spectrometer with SF6 as the analyte gas. The isotope effect after correction for the reservoir effects is −6.8 ‰ for the ratio 34S/32S, where product S0 is depleted in heavy isotopes. The magnitude of the overall isotope effect is not sensitive to the addition of N2 but increases to −9.5 ‰ when radiation of λ >285 nm is used. The measured isotope effect reflects that of photolysis as well as the subsequent sulfur abstraction (from OCS) reaction. The magnitude of isotope effects for the abstraction reaction is estimated by transition state theory to be between −18.9 and −3.1 ‰ for 34S which gives the photolysis isotope effect as −10.5 to +5.3 ‰. The measured isotope effects are found to be δ33S/δ34S = 0.534±0.005 and δ36S/δ34S = 1.980±0.021. These values are largely mass-dependent but statistically differ from canonical values for mass-dependent fractionation of 0.515 and 1.90, respectively. The result demonstrates that the OCS photolysis may not produce large isotope effect of more than about 10 \permil, and can be the major source of background stratospheric sulfate aerosol (SSA) during volcanic quiescence.

Citation: Lin, Y., Sim, M. S., and Ono, S.: Multiple-sulfur isotope effects during photolysis of carbonyl sulfide, Atmos. Chem. Phys. Discuss., 11, 14233-14258, doi:10.5194/acpd-11-14233-2011, 2011.
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