Atmospheric oxidation of 1-butene initiated by OH radical: Implications for ozone and nitrous acid formations | |
Chen, Long1,2; Huang, Yu1,2; Xue, Yonggang1,2; Jia, Zhihui3; Wang, Wenliang4 | |
通讯作者 | Chen, Long(chenlong@ieecas.cn) ; Huang, Yu(huangyu@ieecas.cn) |
2020 | |
发表期刊 | ATMOSPHERIC ENVIRONMENT |
ISSN | 1352-2310 |
卷号 | 244页码:12 |
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 1butene 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 O-3 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. |
关键词 | 1-Butene Atmospheric oxidation Reaction mechanism Rate coefficients O-3 HONO |
DOI | 10.1016/j.atmosenv.2020.118010 |
关键词[WOS] | SECONDARY ORGANIC AEROSOL ; LOW-TEMPERATURE KINETICS ; H-ATOM ABSTRACTION ; GAS-PHASE ; MULTIFUNCTIONAL PRODUCTS ; CHEMICAL-REACTIONS ; OLIGOMER FORMATION ; RATE CONSTANTS ; DECOMPOSITION ; VOLATILITY |
收录类别 | SCI ; SCI |
语种 | 英语 |
资助项目 | National Natural Science Foundation of China[41805107] ; National Natural Science Foundation of China[21473108] ; National Key Research and Development Program of China[2016YFA0203000] ; Key Projects of Chinese Academy of Sciences, China[ZDRW-ZS-2017-6] ; Strategic Priority Research Program of the Chinese Academy of Sciences, China[XDA23010300] ; Strategic Priority Research Program of the Chinese Academy of Sciences, China[XDA23010000] ; Key Project of International Cooperation of the Chinese Academy of Sciences, China[GJHZ1543] ; Research Grants Council of Hong Kong, China[PolyU 152083/14E] ; CAS Light of West China Program[XAB 2019B01] ; General Project of Shaanxi Province[2020JQ-432] |
WOS研究方向 | Environmental Sciences & Ecology ; Meteorology & Atmospheric Sciences |
项目资助者 | National Natural Science Foundation of China ; National Key Research and Development Program of China ; Key Projects of Chinese Academy of Sciences, China ; Strategic Priority Research Program of the Chinese Academy of Sciences, China ; Key Project of International Cooperation of the Chinese Academy of Sciences, China ; Research Grants Council of Hong Kong, China ; CAS Light of West China Program ; General Project of Shaanxi Province |
WOS类目 | Environmental Sciences ; Meteorology & Atmospheric Sciences |
WOS记录号 | WOS:000591732600001 |
出版者 | PERGAMON-ELSEVIER SCIENCE LTD |
引用统计 | |
文献类型 | 期刊论文 |
条目标识符 | http://ir.ieecas.cn/handle/361006/15535 |
专题 | 粉尘与环境研究室 第四纪科学与全球变化卓越创新中心 |
通讯作者 | Chen, Long; Huang, Yu |
作者单位 | 1.Chinese Acad Sci, Key Lab Aerosol Chem & Phys, State Key Lab Loess & Quaternary Geol SKLLQG, Inst Earth Environm, Xian 710061, Peoples R China 2.Chinese Acad Sci, Ctr Excellence Quaternary Sci & Global Change, Xian 710061, Peoples R China 3.Shaanxi Normal Univ, Sch Mat Sci & Engn, Xian 710119, Shaanxi, Peoples R China 4.Shaanxi Normal Univ, Sch Chem & Chem Engn, Key Lab Macromol Sci Shaanxi Prov, Xian 710119, Shaanxi, Peoples R China |
推荐引用方式 GB/T 7714 | Chen, Long,Huang, Yu,Xue, Yonggang,et al. Atmospheric oxidation of 1-butene initiated by OH radical: Implications for ozone and nitrous acid formations[J]. ATMOSPHERIC ENVIRONMENT,2020,244:12. |
APA | Chen, Long,Huang, Yu,Xue, Yonggang,Jia, Zhihui,&Wang, Wenliang.(2020).Atmospheric oxidation of 1-butene initiated by OH radical: Implications for ozone and nitrous acid formations.ATMOSPHERIC ENVIRONMENT,244,12. |
MLA | Chen, Long,et al."Atmospheric oxidation of 1-butene initiated by OH radical: Implications for ozone and nitrous acid formations".ATMOSPHERIC ENVIRONMENT 244(2020):12. |
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