Preprints
https://doi.org/10.5194/acp-2020-326
https://doi.org/10.5194/acp-2020-326
23 Apr 2020
 | 23 Apr 2020
Status: this preprint has been withdrawn by the authors.

Kinetics of dimethyl sulfide (DMS) reactions with isoprene-derived Criegee intermediates studied with direct UV absorption

Mei-Tsan Kuo, Isabelle Weber, Christa Fittschen, and Jim Jr-Min Lin

Abstract. Criegee intermediates (CIs) are formed in the ozonolysis of unsaturated hydrocarbons and play a role in atmospheric chemistry as a non-photolytic OH source or a strong oxidant. Using a relative rate method in an ozonolysis experiment, Newland et al. [Atmos. Chem. Phys., 15, 9521–9536, 2015] reported high reactivity of isoprene-derived Criegee intermediates towards dimethyl sulfide (DMS) relative to that towards SO2 with the ratio of the rate coefficients kDMS+CI / kSO2+CI = 3.5 ± 1.8. Here we reinvestigated the kinetics of DMS reactions with two major Criegee intermediates formed in isoprene ozonolysis, CH2OO and methyl vinyl ketone oxide (MVKO). The individual CI was prepared following reported photolytic method with suitable (diiodo) precursors in the presence of O2. The concentration of CH2OO or MVKO was monitored directly in real time through their intense UV-visible absorption. Our results indicate the reactions of DMS with CH2OO and MVKO are both very slow; the upper limits of the rate coefficients are 4 orders of magnitude smaller than that reported by Newland et al. These results suggest that the ozonolysis experiment could be complicated such that interpretation should be careful and these CIs would not oxidize atmospheric DMS at any substantial level.

This preprint has been withdrawn.

Mei-Tsan Kuo, Isabelle Weber, Christa Fittschen, and Jim Jr-Min Lin

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Interactive discussion

Status: closed
Status: closed
AC: Author comment | RC: Referee comment | SC: Short comment | EC: Editor comment
Printer-friendly Version - Printer-friendly version Supplement - Supplement
Mei-Tsan Kuo, Isabelle Weber, Christa Fittschen, and Jim Jr-Min Lin
Mei-Tsan Kuo, Isabelle Weber, Christa Fittschen, and Jim Jr-Min Lin

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Short summary
Dimethyl sulfide (DMS) is the major sulfur-containing species in the troposphere. Previous work by Newland et al. [Atmos. Chem. Phys., 15, 9521–9536, 2015] reported very high reactivity of isoprene-derived Criegee intermediates (CIs) towards DMS. By monitoring CIs with direct UV absorption, we found CI + DMS reactions are very slow, in contrast to the results of Newland et al., suggesting these CIs would not oxidize atmospheric DMS at any substantial level.
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