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Published February 16, 2016 | Supplemental Material + Published
Journal Article Open

"Sizing" Heterogeneous Chemistry in the Conversion of Gaseous Dimethyl Sulfide to Atmospheric Particles


The oxidation of biogenic dimethyl sulfide (DMS) emissions is a global source of cloud condensation nuclei. The amounts of the nucleating H_2SO_4(g) species produced in such process, however, remain uncertain. Hydrophobic DMS is mostly oxidized in the gas phase into H_2SO_4(g) + DMSO(g) (dimethyl sulfoxide), whereas water-soluble DMSO is oxidized into H_2SO_4(g) in the gas phase and into SO_4^(2–) + MeSO_3– (methanesulfonate) on water surfaces. R = MeSO_3–/(non-sea-salt SO_4^(2–)) ratios would therefore gauge both the strength of DMS sources and the extent of DMSO heterogeneous oxidation if R_(het) = MeSO_3–/SO_4^(2–) for DMSO(aq) + ·OH(g) were known. Here, we report that R_(het) = 2.7, a value obtained from online electrospray mass spectra of DMSO(aq) + ·OH(g) reaction products that quantifies the MeSO_3– produced in DMSO heterogeneous oxidation on aqueous aerosols for the first time. On this basis, the inverse R dependence on particle radius in size-segregated aerosol collected over Syowa station and Southern oceans is shown to be consistent with the competition between DMSO gas-phase oxidation and its mass accommodation followed by oxidation on aqueous droplets. Geographical R variations are thus associated with variable contributions of the heterogeneous pathway to DMSO atmospheric oxidation, which increase with the specific surface area of local aerosols.

Additional Information

© 2016 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: October 29, 2015. Revised: January 12, 2016. Accepted: January 13, 2016. Published: January 13, 2016. S.E. is grateful to the Iwatani Naoji Foundation's Research Grant, the Kurita Water and Environment Foundation, the Japan Science and Technology Agency (JST) PRESTO program, and JSPS KAKENHI grant number 15H05328. M.R.H. and A.J.C. acknowledge support from the National Science Foundation (U.S.A.) Grant AC-1238977. Aerosol measurements at Syowa Station, Antarctica were supported by "Observation Project of Global Atmospheric Change in the Antarctic" (Principal Investigator: T. Yamanouchi, NIPR), and Grant-in-Aid (16253001, Principal Investigator: T. Yamanouchi, and 15310012, Principle Investigator: K. Osada) from the Ministry of Education, Culture, Sports, Science, and Technology of Japan. Aerosol measurements on RV Umitaka-maru were supported by a Grant-in-Aid for Scientific Research in Priority Areas, grant number 18067005 (W-PASS), provided by the Ministry of Education, Culture, Sports, Science, and Technology of Japan. The authors declare no competing financial interest.

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Supplemental Material - es5b05337_si_001.pdf


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