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  4. Hypobromous Acid as an Unaccounted Sink for Marine Dimethyl Sulfide?
 
research article

Hypobromous Acid as an Unaccounted Sink for Marine Dimethyl Sulfide?

Muller, Emanuel
•
von Gunten, Urs  
•
Bouchet, Sylvain
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November 19, 2019
Environmental Science & Technology

Marine emissions of dimethyl sulfide (DMS) to the atmosphere play a fundamental role in the global sulfur (5) cycle and have important consequences for the Earth's radiative balance. In the ocean, DMS is mainly produced by marine algae and bacteria via cleavage of the precursor compound dimethylsulfoniopropionate (DMSP). Here, we studied the reaction between DMS and the strong oxidant hypobromous acid (HOBr), which is also produced by marine algae. Further, reactions between DMS oxidation products and HOBr were studied. The second-order rate constants were determined in competition kinetic experiments using sulfite as a competitor. In addition, we developed a new HPLC-ICP-MS/MS method to identify and quantify the oxidation products of DMS and related compounds. We found that HOBr reacts very fast with DMS to dimethyl sulfoxide (DMSO), with a second-order rate constant of 1.6 X 10(9) M-1 s(-1), while the subsequent oxidation of DMSO to dimethyl sulfone (DMSO2) is much slower (0.4 M-1 s(-1)). Concentrations of DMSP, DMSO2, and methanesulfonic acid (MSA) did not decrease when exposed to excess concentrations of HOBr, implying that these S-containing compounds are not or only slightly reactive toward HOBr. A quantitative comparison of known DMS sinks shows that HOBr may be an important, hitherto neglected sink for marine DMS that needs to be considered in ocean-atmosphere chemistry models.

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Type
research article
DOI
10.1021/acs.est.9b04310
Web of Science ID

WOS:000498279400019

Author(s)
Muller, Emanuel
von Gunten, Urs  
Bouchet, Sylvain
Droz, Boris
Winkel, Lenny H. E.
Date Issued

2019-11-19

Publisher

AMER CHEMICAL SOC

Published in
Environmental Science & Technology
Volume

53

Issue

22

Start page

13146

End page

13157

Subjects

Engineering, Environmental

•

Environmental Sciences

•

Engineering

•

Environmental Sciences & Ecology

•

bromide-containing waters

•

natural organic-matter

•

reactive bromine

•

rate constants

•

oceanic dms

•

equatorial pacific

•

oxidation

•

kinetics

•

sulfur

•

mechanism

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LTQE  
Available on Infoscience
December 7, 2019
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/163834
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