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DOI	10.1016/j.atmosenv.2020.118010
	Atmospheric oxidation of 1-butene initiated by OH radical: Implications for ozone and nitrous acid formations
	Chen L.; Huang Y.; Xue Y.; Jia Z.; Wang W.
发表日期	2021
ISSN	1352-2310
卷号	244
英文摘要	The present study combines (i) field measurements of 1-butene over Xi'an and surrounding areas during a heavy ozone pollution episode with (ii) quantum chemical calculations on the photochemical transformation of 1-butene initiated by OH radical. The measurements show that the diurnal variation of both 1-butene and ozone exhibits a negative relationship during the sampling campaign. The concentrations of 1-butene vary from 0.04 to 0.67 ppbv, and the lowest and highest values emerge in the noon time (1 p.m.–3 p.m.) and in the night time (1 a.m.–3 a.m.). The concentrations of O3 range from 32.36 to 88.82 ppbv, and the high values appear in the noon time. Quantum chemical calculations show that the OH-addition pathways are more energetically preferable than H-abstraction channels, and the rate coefficient exhibits a negative T-dependence in the temperature range of 273–400 K. The autoxidation of peroxy radicals (RO2) formed from the addition of molecular oxygen to OH-addition products S2 and S3 leads to the formation of highly oxygenated molecules (HOMs), C4H9O5, in which the 1,5-H shift reaction is favoured. In the low-NOx regions, RO2 radicals mainly react with HO2 radical leading to hydroperoxide ROOH on both the singlet and triplet PESs, in which the triplet PES is preferable. In the high-NOx regions, RO2 radicals mainly react with NO leading to the formation of RO· + NO2, aldehyde + HONO and organic nitrate, in which the HONO formation appears to be previously unconsidered in the photochemical transformation of alkenes. The branching ratio of RO· + NO2 increases slowly with increasing temperature (from 51.3 to 52.7%), whereas aldehyde + HONO gradually decreases with the temperature rising (from 48.7 to 47.3%). The formation of organic nitrate is negligible over the temperature range of 273–400 K. These findings are expected to deepen our understanding the photochemistry oxidation of alkene under realistic atmospheric conditions. © 2020 Elsevier Ltd
关键词	1-Butene Atmospheric oxidation HONO O3 Rate coefficients Reaction mechanism
语种	英语
scopus关键词	Air pollution; Aldehydes; Atmospheric chemistry; Butenes; Free radicals; Inorganic acids; Molecular oxygen; Nitrates; Nitrogen oxides; Olefins; Ozone; Quantum chemistry; Atmospheric conditions; Atmospheric oxidation; Diurnal variation; Increasing temperatures; Photochemical transformations; Quantum chemical calculations; Sampling campaigns; Temperature rising; Atmospheric temperature; 1 butene; aldehyde; alkene derivative; hydroperoxide; hydroxyl radical; nitrogen dioxide; nitrous acid; organic nitrate; ozone; peroxy radical; propionaldehyde; unclassified drug; chemical reaction; concentration (composition); detection method; hydroxyl radical; nitrous acid; oxidation; ozone; photochemistry; temperature effect; Article; autooxidation; circadian rhythm; concentration (parameter); enthalpy; photochemistry; priority journal; quantum chemistry; reaction analysis; temperature; China; Shaanxi; Xian
来源期刊	ATMOSPHERIC ENVIRONMENT
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/248793
作者单位	Key Lab of Aerosol Chemistry & Physics, State Key Lab of Loess and Quaternary Geology (SKLLQG), Institute of Earth Environment, Chinese Academy of Sciences (CAS), Xi'an, 710061, China; CAS Center for Excellence in Quaternary Science and Global Change, Xi'an, 710061, China; School of Materials Science and Engineering, Shaanxi Normal University, Xi'an, Shaanxi 710119, China; School of Chemistry and Chemical Engineering, Key Laboratory for Macromolecular Science of Shaanxi Province, Shaanxi Normal University, Xi'an, Shaanxi 710119, China
推荐引用方式 GB/T 7714	Chen L.,Huang Y.,Xue Y.,et al. Atmospheric oxidation of 1-butene initiated by OH radical: Implications for ozone and nitrous acid formations[J],2021,244.
APA	Chen L.,Huang Y.,Xue Y.,Jia Z.,&Wang W..(2021).Atmospheric oxidation of 1-butene initiated by OH radical: Implications for ozone and nitrous acid formations.ATMOSPHERIC ENVIRONMENT,244.
MLA	Chen L.,et al."Atmospheric oxidation of 1-butene initiated by OH radical: Implications for ozone and nitrous acid formations".ATMOSPHERIC ENVIRONMENT 244(2021).