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High Gas-Phase Methanesulfonic Acid Production in the OH-Initiated Oxidation of Dimethyl Sulfide at Low Temperatures

Shen, J. ; Roldin, P. LU ; Wollesen De Jonge, R. LU ; Bianchi, Federico and Worsnop, D.R. (2022) In Environmental Science and Technology 56(19). p.13931-13944
Abstract
Dimethyl sulfide (DMS) influences climate via cloud condensation nuclei (CCN) formation resulting from its oxidation products (mainly methanesulfonic acid, MSA, and sulfuric acid, H2SO4). Despite their importance, accurate prediction of MSA and H2SO4 from DMS oxidation remains challenging. With comprehensive experiments carried out in the Cosmics Leaving Outdoor Droplets (CLOUD) chamber at CERN, we show that decreasing the temperature from +25 to -10 °C enhances the gas-phase MSA production by an order of magnitude from OH-initiated DMS oxidation, while H2SO4 production is modestly affected. This leads to a gas-phase H2SO4-to-MSA ratio (H2SO4/MSA) smaller than one at low temperatures, consistent with field observations in polar regions.... (More)
Dimethyl sulfide (DMS) influences climate via cloud condensation nuclei (CCN) formation resulting from its oxidation products (mainly methanesulfonic acid, MSA, and sulfuric acid, H2SO4). Despite their importance, accurate prediction of MSA and H2SO4 from DMS oxidation remains challenging. With comprehensive experiments carried out in the Cosmics Leaving Outdoor Droplets (CLOUD) chamber at CERN, we show that decreasing the temperature from +25 to -10 °C enhances the gas-phase MSA production by an order of magnitude from OH-initiated DMS oxidation, while H2SO4 production is modestly affected. This leads to a gas-phase H2SO4-to-MSA ratio (H2SO4/MSA) smaller than one at low temperatures, consistent with field observations in polar regions. With an updated DMS oxidation mechanism, we find that methanesulfinic acid, CH3S(O)OH, MSIA, forms large amounts of MSA. Overall, our results reveal that MSA yields are a factor of 2-10 higher than those predicted by the widely used Master Chemical Mechanism (MCMv3.3.1), and the NOx effect is less significant than that of temperature. Our updated mechanism explains the high MSA production rates observed in field observations, especially at low temperatures, thus, substantiating the greater importance of MSA in the natural sulfur cycle and natural CCN formation. Our mechanism will improve the interpretation of present-day and historical gas-phase H2SO4/MSA measurements. © 2022 The Authors. Published by American Chemical Society. (Less)
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Contribution to journal
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published
subject
keywords
dimethyl sulfide (DMS), low temperatures, methanesulfinic acid (CH3S(O)OH, MSIA), methanesulfonic acid (MSA), OH-initiated oxidation, Gases, Organic acids, Oxidation, Acid production, Dimethyl sulphide, Dimethylsulphide, Gas-phases, Lows-temperatures, Methanesulphinic acid (CH3S(O)OH, MSIA), Methanesulphonic acid, OH -, Sulfur compounds
in
Environmental Science and Technology
volume
56
issue
19
pages
14 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85138953803
  • pmid:36137236
ISSN
0013-936X
DOI
10.1021/acs.est.2c05154
project
Continental Biosphere Aerosol Cloud climate feedback loop during the Anthropocene
Modelling atmospheric new particle formation from first principles – The role of Highly Oxygenated organic Molecules in clean and polluted air
language
English
LU publication?
yes
id
f1e4662f-d171-42ec-a7f5-95a4c12e1113
date added to LUP
2022-12-20 13:45:27
date last changed
2023-10-06 09:06:49
@article{f1e4662f-d171-42ec-a7f5-95a4c12e1113,
  abstract     = {{Dimethyl sulfide (DMS) influences climate via cloud condensation nuclei (CCN) formation resulting from its oxidation products (mainly methanesulfonic acid, MSA, and sulfuric acid, H2SO4). Despite their importance, accurate prediction of MSA and H2SO4 from DMS oxidation remains challenging. With comprehensive experiments carried out in the Cosmics Leaving Outdoor Droplets (CLOUD) chamber at CERN, we show that decreasing the temperature from +25 to -10 °C enhances the gas-phase MSA production by an order of magnitude from OH-initiated DMS oxidation, while H2SO4 production is modestly affected. This leads to a gas-phase H2SO4-to-MSA ratio (H2SO4/MSA) smaller than one at low temperatures, consistent with field observations in polar regions. With an updated DMS oxidation mechanism, we find that methanesulfinic acid, CH3S(O)OH, MSIA, forms large amounts of MSA. Overall, our results reveal that MSA yields are a factor of 2-10 higher than those predicted by the widely used Master Chemical Mechanism (MCMv3.3.1), and the NOx effect is less significant than that of temperature. Our updated mechanism explains the high MSA production rates observed in field observations, especially at low temperatures, thus, substantiating the greater importance of MSA in the natural sulfur cycle and natural CCN formation. Our mechanism will improve the interpretation of present-day and historical gas-phase H2SO4/MSA measurements. © 2022 The Authors. Published by American Chemical Society.}},
  author       = {{Shen, J. and Roldin, P. and Wollesen De Jonge, R. and Bianchi, Federico and Worsnop, D.R.}},
  issn         = {{0013-936X}},
  keywords     = {{dimethyl sulfide (DMS); low temperatures; methanesulfinic acid (CH3S(O)OH, MSIA); methanesulfonic acid (MSA); OH-initiated oxidation; Gases; Organic acids; Oxidation; Acid production; Dimethyl sulphide; Dimethylsulphide; Gas-phases; Lows-temperatures; Methanesulphinic acid (CH3S(O)OH, MSIA); Methanesulphonic acid; OH -; Sulfur compounds}},
  language     = {{eng}},
  number       = {{19}},
  pages        = {{13931--13944}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Environmental Science and Technology}},
  title        = {{High Gas-Phase Methanesulfonic Acid Production in the OH-Initiated Oxidation of Dimethyl Sulfide at Low Temperatures}},
  url          = {{http://dx.doi.org/10.1021/acs.est.2c05154}},
  doi          = {{10.1021/acs.est.2c05154}},
  volume       = {{56}},
  year         = {{2022}},
}