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. https://doi.org/10.1021/acs.jpclett.9b02567
Fast peroxy radical isomerization and OH recycling in the reaction of OH radicals with dimethyl sulfide
|Author:||Berndt, T.1; Scholz, W.2,3; Mentler, B.2;|
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
|Persistent link:|| http://urn.fi/urn:nbn:fi-fe2019101733541
American Chemical Society,
|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.
Journal of physical chemistry letters
|Pages:||6478 - 6483|
|Type of Publication:||
A1 Journal article – refereed
|Field of Science:||
114 Physical sciences
116 Chemical sciences
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 (Academy of Finland Funding decision)
314175 (Academy of Finland Funding decision)
© 2019 American Chemical Society.