Reaction between CH3O2 and BrO Radicals: A New Source of Upper Troposphere Lower Stratosphere Hydroxyl Radicals

被引：18

作者：

Shallcross, Dudley E. ^{[1
]}

Leather, Kimberley E. ^{[2
]}

Bacak, Asan ^{[2
]}

Xiao, Ping ^{[1
]}

Lee, Edmond P. F. ^{[3
,4
]}

Ng, Maggie ^{[4
]}

Mok, Daniel K. W. ^{[4
]}

Dyke, John M. ^{[3
]}

Hossaini, Ryan ^{[5
]}

Chipperfield, Martyn P. ^{[5
]}

Khan, M. Anwar H. ^{[1
]}

Percival, Carl J. ^{[2
]}

机构：

[1] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England

[2] Univ Manchester, Sch Earth Atmospher & Environm Sci, Manchester M13 9PL, Lancs, England

[3] Univ Southampton, Sch Chem, Southampton SO17 1BJ, Hants, England

[4] Hong Kong Polytech Univ, Dept Appl Biol & Chem Technol, Kowloon, Hong Kong, Peoples R China

[5] Univ Leeds, Sch Earth & Environm, Leeds LS2 9JT, W Yorkshire, England

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2015年 / 119卷 / 19期

基金：

英国工程与自然科学研究理事会;

关键词：

INTERMEDIATES CRI MECHANISM; ACTIVE THERMOCHEMICAL TABLES; PRESSURE-DEPENDENCE; IONIZATION-POTENTIALS; OZONE PHOTOCHEMISTRY; DISSOCIATION-ENERGY; BROMINE MONOXIDE; BOUNDARY-LAYER; TRACE GAS; AB-INITIO;

D O I：

10.1021/jp5108203

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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 k(1) = (2.42(-0.72)(+1.02)) X 10(-14) exp[(1617 +/- 94)/T] cm(3) molecule(-1) s(-1). In addition, CH2OO and HOBr are believed to he 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 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.

引用

页码：4618 / 4632

页数：15

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