Kinetics of dimethyl sulfide (DMS) reactions with isoprene-derived Criegee intermediates studied with direct UV absorption
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Published:2020-11-06
Issue:21
Volume:20
Page:12983-12993
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ISSN:1680-7324
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Container-title:Atmospheric Chemistry and Physics
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language:en
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Short-container-title:Atmos. Chem. Phys.
Author:
Kuo Mei-Tsan, Weber IsabelleORCID, Fittschen ChristaORCID, Vereecken LucORCID, Lin Jim Jr-MinORCID
Abstract
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. (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 the 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 the rate coefficient reported by Newland et al. (2015) 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.
Funder
Academia Sinica Ministry of Science and Technology, Taiwan
Publisher
Copernicus GmbH
Subject
Atmospheric Science
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