15 Aug 2022
15 Aug 2022
Status: this preprint is currently under review for the journal ACP.

Product distribution, kinetics, and aerosol formation from the OH oxidation of dimethyl sulfide under different RO2 regimes

Qing Ye1,a, Matthew B. Goss1, Jordan E. Krechmer2, Francesca Majluf2, Alexander Zaytsev3, Yaowei Li3, Joseph R. Roscioli4, Manjula Canagaratna2, Frank N. Keutsch3,5, Colette L. Heald1, and Jesse H. Kroll1 Qing Ye et al.
  • 1Department of Civil and Environmental Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
  • 2Center for Aerosol and Cloud Chemistry, Aerodyne Research Incorporated, Billerica, Massachusetts 01821, United States
  • 3John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138, United States
  • 4Center for Atmospheric and Environmental Chemistry, Aerodyne Research Incorporated, Billerica, Massachusetts 01821, United States
  • 5Department of Chemistry and Chemical Biology, Department of Earth and Planetary Sciences, Harvard University, Cambridge, Massachusetts 02138, United States
  • anow at: the Atmospheric Chemistry Observations and Modeling Laboratory, National Center for Atmospheric Research, Boulder, Colorado 80301, United States

Abstract. The atmospheric oxidation of dimethyl sulfide (DMS) represents a major natural source of atmospheric sulfate aerosols. However, there remain large uncertainties in our understanding of the underlying chemistry that governs the product distribution and sulfate yield from DMS oxidation. Here, chamber experiments were conducted to simulate gas-phase OH-initiated oxidation of DMS under a range of reaction conditions. Most importantly, the bimolecular lifetime (τbi) of the peroxy radical CH3SCH2OO was varied over several orders of magnitude, enabling the examination of the role of peroxy radical isomerization reactions on product formation. An array of analytical instruments was used to measure nearly all sulfur-containing species in the reaction mixture, and results were compared with a near-explicit chemical mechanism. When relative humidity was low, “sulfur closure” was achieved under both high-NO (τbi < 0.1 s) and low-NO (τbi > 10 s) conditions, though product distributions were substantially different in the two cases. Under high-NO conditions, approximately half the product sulfur was in the particle phase, as methane sulfonic acid (MSA) and sulfate, with most of the remainder as SO2 (which in the atmosphere would eventually oxidize to sulfate or be lost to deposition). Under low-NO conditions, hydroperoxymethyl thioformate (HPMTF, HOOCH2SCHO), formed from CH3SCH2OO isomerization, dominates the sulfur budget over the course of the experiment, suppressing or delaying the formation of SO2 and particulate matter. The isomerization rate constant of CH3SCH2OO at 295 K is found to be 0.13 ± 0.03 s-1, in broad agreement with other recent laboratory measurements. The rate constants for the OH oxidation of key first-generation oxidation products (HPMTF and methyl thioformate, MTF) were also determined (kOH+HPMTF = 2.1 × 10-11 cm3 molec-1 s-1, kOH+MTF = 1.35 × 10-11 cm3 molec-1 s-1). Product measurements agree reasonably well with mechanistic predictions in terms of total sulfur distribution and concentrations of most individual species, though the mechanism overpredicts sulfate and underpredicts MSA under high-NO conditions. Lastly, results from high-RH conditions suggest efficient heterogenous loss of at least some gas-phase products.

Qing Ye et al.

Status: final response (author comments only)

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on acp-2022-566', Anonymous Referee #1, 25 Aug 2022
  • RC2: 'Comment on acp-2022-566', Anonymous Referee #2, 26 Aug 2022
  • RC3: 'Comment on acp-2022-566', Anonymous Referee #3, 22 Sep 2022
  • CC1: 'Comment on acp-2022-566', Bernadette Rosati, 23 Sep 2022

Qing Ye et al.


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Short summary
The atmospheric oxidation of dimethyl sulfide (DMS) represents a major natural source of sulfate aerosols, and thus plays an important role in global aerosol climate effects. However, the mechanism is poorly constrained. In this work, laboratory measurements were conducted to comprehensively investigate DMS oxidation products. The results show that peroxy radical (RO2) fate has a controlling influence on product distributions, and the isomerization of RO2 suppresses aerosol formation.