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The reaction between CH3O2 and BrO radicals: a new source of upper troposphere-lower stratosphere hydroxyl radicals

The reaction between CH3O2 and BrO radicals: a new source of upper troposphere-lower stratosphere hydroxyl radicals
The reaction between CH3O2 and BrO radicals: a new source of upper troposphere-lower stratosphere hydroxyl radicals
Over the last two decades it has emerged that measured hydroxyl radical levels in the upper troposphere are often underestimated by models, leading to the assertion that there are missing sources. Here we report laboratory studies of the kinetics and products of the reaction between CH3O2 and BrO radicals that shows that this could be an important new source of hydroxyl radicals:BrO + CH3O2 ? products (1). The temperature dependent value in Arrhenius form of k(T) is k1 = (2.42–0.72+1.02) × 10–14?exp[(1617 ± 94)/T] cm3 molecule–1 s–1. In addition, CH2OO and HOBr are believed to be the major products. Global model results suggest that the decomposition of H2COO to form OH could lead to an enhancement in OH of up to 20% in mid-latitudes in the upper troposphere and in the lower stratosphere enhancements in OH of 2–9% are inferred from model integrations. In addition, reaction 1 aids conversion of BrO to HOBr and slows polar ozone loss in the lower stratosphere.
1089-5639
4618-4632
Shallcross, Dudley
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Leather, Kimberley
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Bacak, Asan
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Xiao, Ping
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Lee, Edmond
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Ng, Maggie
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Mok, Daniel
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Dyke, John
46393b45-6694-46f3-af20-d7369d26199f
Chipperfield, Martyn
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Khan, M. Anwar
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Percival, Carl
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Hossaini, Ryan
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Shallcross, Dudley
f706d4ac-11ea-4f20-b0d9-644ae8611dc5
Leather, Kimberley
6849144d-c2ae-44d6-94e0-b250a644a8c3
Bacak, Asan
6a17f49e-e33c-4041-8d9a-12acb3de8e34
Xiao, Ping
2426bc85-81a6-4d81-9783-54d2ef041e2d
Lee, Edmond
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Ng, Maggie
bc203fa1-3eb7-4b63-b1e9-78faca2e5c30
Mok, Daniel
89c78a4b-6c37-4f0c-8026-57246a407d35
Dyke, John
46393b45-6694-46f3-af20-d7369d26199f
Hossaini, Ryan
5ec1c900-b93f-4fd5-ad71-62015a25bdd9
Chipperfield, Martyn
95071ffe-eaec-4860-a63f-751214676ce4
Khan, M. Anwar
90babf30-2651-4f1c-ac29-35d3146b64dd
Percival, Carl
8d8fc5c3-0d6a-4d89-9ed2-2f7b9157afee

Shallcross, Dudley, Leather, Kimberley, Bacak, Asan, Xiao, Ping, Lee, Edmond, Ng, Maggie, Mok, Daniel, Dyke, John, Chipperfield, Martyn, Khan, M. Anwar and Percival, Carl , Hossaini, Ryan (ed.) (2015) The reaction between CH3O2 and BrO radicals: a new source of upper troposphere-lower stratosphere hydroxyl radicals. Journal of Physical Chemistry A, 119 (19), 4618-4632. (doi:10.1021/jp5108203).

Record type: Article

Abstract

Over the last two decades it has emerged that measured hydroxyl radical levels in the upper troposphere are often underestimated by models, leading to the assertion that there are missing sources. Here we report laboratory studies of the kinetics and products of the reaction between CH3O2 and BrO radicals that shows that this could be an important new source of hydroxyl radicals:BrO + CH3O2 ? products (1). The temperature dependent value in Arrhenius form of k(T) is k1 = (2.42–0.72+1.02) × 10–14?exp[(1617 ± 94)/T] cm3 molecule–1 s–1. In addition, CH2OO and HOBr are believed to be the major products. Global model results suggest that the decomposition of H2COO to form OH could lead to an enhancement in OH of up to 20% in mid-latitudes in the upper troposphere and in the lower stratosphere enhancements in OH of 2–9% are inferred from model integrations. In addition, reaction 1 aids conversion of BrO to HOBr and slows polar ozone loss in the lower stratosphere.

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Accepted/In Press date: 13 March 2015
e-pub ahead of print date: 13 March 2015
Published date: 14 May 2015
Organisations: Computational Systems Chemistry

Identifiers

Local EPrints ID: 383094
URI: http://eprints.soton.ac.uk/id/eprint/383094
ISSN: 1089-5639
PURE UUID: caa72434-8e92-4664-bb15-92994c3c6aca
ORCID for John Dyke: ORCID iD orcid.org/0000-0002-9808-303X

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Date deposited: 27 Oct 2015 14:09
Last modified: 15 Mar 2024 02:35

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Contributors

Author: Dudley Shallcross
Author: Kimberley Leather
Author: Asan Bacak
Author: Ping Xiao
Author: Edmond Lee
Author: Maggie Ng
Author: Daniel Mok
Author: John Dyke ORCID iD
Editor: Ryan Hossaini
Author: Martyn Chipperfield
Author: M. Anwar Khan
Author: Carl Percival

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