University of Oulu

T. Berndt et al. Fast peroxy radical isomerization and OH recycling in the reaction of OH radicals with dimethyl sulfide. J. Phys. Chem. Lett. 2019, 10, 6478−6483.

Fast peroxy radical isomerization and OH recycling in the reaction of OH radicals with dimethyl sulfide

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Author: Berndt, T.1; Scholz, W.2,3; Mentler, B.2;
Organizations: 1Atmospheric Chemistry Department (ACD), Leibniz Institute for Tropospheric Research (TROPOS), 04318 Leipzig, Germany
2Institute for Ion Physics and Applied Physics, University of Innsbruck, 6020 Innsbruck, Austria
3IONICON Analytik GmbH, 6020 Innsbruck, Austria
4Nano and Molecular Systems Research Unit, University of Oulu, 90014 Oulu, Finland
Format: article
Version: accepted version
Access: open
Online Access: PDF Full Text (PDF, 0.6 MB)
Persistent link:
Language: English
Published: American Chemical Society, 2019
Publish Date: 2020-10-07


Dimethyl sulfide (DMS), produced by marine organisms, represents the most abundant, biogenic sulfur emission into the Earth’s atmosphere. The gas-phase degradation of DMS is mainly initiated by the reaction with the OH radical forming first CH3SCH2O2 radicals from the dominant H-abstraction channel. It is experimentally shown that these peroxy radicals undergo a two-step isomerization process finally forming a product consistent with the formula HOOCH2SCHO. The isomerization process is accompanied by OH recycling. The rate-limiting first isomerization step, CH3SCH2O2 → CH2SCH2OOH, followed by O2 addition, proceeds with k = (0.23 ± 0.12) s–1 at 295 ± 2 K. Competing bimolecular CH3SCH2O2 reactions with NO, HO2, or RO2 radicals are less important for trace-gas conditions over the oceans. Results of atmospheric chemistry simulations demonstrate the predominance (≥95%) of CH3SCH2O2 isomerization. The rapid peroxy radical isomerization, not yet considered in models, substantially changes the understanding of DMS’s degradation processes in the atmosphere.

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Series: Journal of physical chemistry letters
ISSN: 1948-7185
ISSN-E: 1948-7185
ISSN-L: 1948-7185
Volume: 10
Pages: 6478 - 6483
DOI: 10.1021/acs.jpclett.9b02567
Type of Publication: A1 Journal article – refereed
Field of Science: 114 Physical sciences
116 Chemical sciences
Funding: The project was partly funded by the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program, Project SURFACE (Grant Agreement No. 717022). N.H. and N.L.P. also gratefully acknowledge the financial contribution from the Academy of Finland (Grant Nos. 308238 and 314175). W.S. received funding from the European Union’s Horizon 2020 research and innovation program (Marie Skłodowska-Curie Grant Agreement No. 764991).
EU Grant Number: (717022) SURFACE - The unexplored world of aerosol surfaces and their impacts.
Academy of Finland Grant Number: 308238
Detailed Information: 308238 (Academy of Finland Funding decision)
314175 (Academy of Finland Funding decision)
Copyright information: © 2019 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see