气候变化领域集成服务门户(CCPortal): Atmospheric oxidation of gaseous anthracene and phenanthrene initiated by OH radicals

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DOI	10.1016/j.atmosenv.2020.117587
	Atmospheric oxidation of gaseous anthracene and phenanthrene initiated by OH radicals
	Zeng M.; Liao Z.; Wang L.
发表日期	2020
ISSN	1352-2310
卷号	234
英文摘要	Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental pollutants. In the atmosphere, PAHs are oxidized to oxygenated PAHs (OPAHs) and nitrated PAHs (NPAHs). However, the formation mechanism of OPAHs and NPAHs are unclear. Here we investigated the oxidation mechanism of anthracene (ANT) and phenanthrene (PHE) initiated by OH radical using quantum chemistry and chemical kinetic calculations. The oxidation starts by forming PAH-OH adducts which then react with O2 and NO2 in the atmosphere. Reactions of PAH-OH and O2 start mainly by reversible OO addition, forming PAH-OH-OO radicals, which then undergo backward decomposition to PAH-OH + OO, forward unimolecular isomerizations to OPAH products, and bimolecular reaction with NO. Effective rate of each route depends on the equilibrium constant of O2 addition and the rates of forward unimolecular and bimolecular reactions of PAH-OH-OO. We predicted that ANT-9-OH, PHE-4-OH, and PHE-1-OH would react slowly with O2 with effective rates at 298 K of ~18, ~50, and ~18 s−1, forming OPAH (2,10-AQ for ANT); therefore, they would also react with atmospheric NO2, forming significant amounts of 9-NANT, 3-NPHE, and 2-NPHE, respectively. ANT-1-OH and PHE-10-OH would react rapidly with O2, forming OPAHs only. Predicted formation of 9-NANT and 3-NPHE agrees with field measurements in urban atmosphere where NPAHs are more likely formed from reactions of PAHs with OH and/or NO3. On the other hand, observation of 9-NPHE might suggest a primary source of NPAHs such as biomass burning because 9-NPHE is highly unlikely formed in OH- and/or NO3-initiated reaction of PHE. © 2020 Elsevier Ltd
关键词	Nitro-PAHs OH Radical Oxidation mechanism Oxygenated PAHs PAHs
语种	英语
scopus关键词	Atmospheric chemistry; Equilibrium constants; Free radicals; Isomerization; Nitrogen oxides; Oxidation; Quantum chemistry; Atmospheric oxidation; Bimolecular reaction; Environmental pollutants; Formation mechanism; Kinetic calculations; Oxidation mechanisms; Polycyclic aromatic hydrocarbons (PAHS); Urban atmospheres; Anthracene; anthracene; hydroxyl radical; phenanthrene; biomass burning; hydroxyl radical; oxidation; phenanthrene; reaction kinetics; Article; atmosphere; biomass; chemical reaction kinetics; combustion; decomposition; equilibrium constant; gas; isomer; isomerization; oxidation; priority journal; quantum chemistry; urban area; Lamprididae
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/249094
作者单位	School of Chemistry & Chemical Engineering, South China University of Technology, Guangzhou, 510640, China; Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, South China University of Technology, Guangzhou, 510006, China
推荐引用方式 GB/T 7714	Zeng M.,Liao Z.,Wang L.. Atmospheric oxidation of gaseous anthracene and phenanthrene initiated by OH radicals[J],2020,234.
APA	Zeng M.,Liao Z.,&Wang L..(2020).Atmospheric oxidation of gaseous anthracene and phenanthrene initiated by OH radicals.ATMOSPHERIC ENVIRONMENT,234.
MLA	Zeng M.,et al."Atmospheric oxidation of gaseous anthracene and phenanthrene initiated by OH radicals".ATMOSPHERIC ENVIRONMENT 234(2020).