OH-Initiated Oxidation of Acetylacetone: Implications for Ozone and Secondary Organic Aerosol Formation

被引：59
作者：
Ji, Yuemeng [1 ]
Zheng, Jun [2 ]
Qin, Dandan [1 ]
Li, Yixin [3 ,4 ]
Gao, Yanpeng [1 ]
Yao, Meijing [1 ]
Chen, Xingyu [1 ]
Li, Guiying [1 ]
An, Taicheng [1 ]
Zhang, Renyi [3 ,4 ]
机构：
[1] Guangdong Univ Technol, Sch Environm Sci & Engn, Inst Environm Hlth & Pollut Control, Guangzhou Key Lab Environm Catalysis & Pollut Con, Guangzhou 510006, Guangdong, Peoples R China
[2] Nanjing Univ Informat Sci & Technol, Collaborat Innovat Ctr Atmospher Environm & Equip, Nanjing 210044, Jiangsu, Peoples R China
[3] Texas A&M Univ, Dept Atmospher Sci, College Stn, TX 77843 USA
[4] Texas A&M Univ, Dept Chem, College Stn, TX 77843 USA
来源：
ENVIRONMENTAL SCIENCE & TECHNOLOGY | 2018年 / 52卷 / 19期
基金：
中国国家自然科学基金;
关键词：
METHYL VINYL KETONE; HETEROGENEOUS REACTIONS; ATMOSPHERIC CHEMISTRY; RATE CONSTANTS; WALL LOSS; METHYLGLYOXAL; RADICALS; MECHANISM; KINETICS; SOA;
D O I：
10.1021/acs.est.8b03972
中图分类号：
X [环境科学、安全科学];
学科分类号：
08 ; 0830 ;
摘要：
Acetylacetone (AcAc) is a common atmospheric oxygenated volatile organic compound due to broad industrial applications, but its atmospheric oxidation mechanism is not fully understood. We investigate the mechanism, kinetics, and atmospheric fate of the OH-initiated oxidation for the enolic and ketonic isomers of AcAc using quantum chemical and kinetic rate calculations. OH addition to enol-AcAc is more favorable than addition to keto-AcAc, with the total rate constant of 1.69 X 10(-13) exp(1935/T) cm(3) molecule(-1) s(-1 )over the temperature range of 200-310 K. For the reaction of the enol-AcAc with OH, the activation energies of H-abstraction are at least 4 kcal mol(-1) higher than those of OH-addition, and the rate constants for OH-addition are by 2-3 orders of magnitude higher than those for H-abstraction. Oxidation of AcAc is predicted to yield significant amounts of acetic acid and methylglyoxal, larger than those are currently recognized. A lifetime of less than a few hours for AcAc is estimated throughout the tropospheric conditions. In addition, we present field measurements in Beijing and Nanjing, China, showing significant concentrations of AcAc in the two urban locations. Our results reveal that the OH-initiated oxidation of AcAc contributes importantly to ozone and SOA formation under polluted environments.
引用
收藏
页码：11169 / 11177
页数：9
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