DOI: 10.1016/j.atmosenv.2020.117587
论文题名: Atmospheric oxidation of gaseous anthracene and phenanthrene initiated by OH radicals
作者: Zeng M. ; Liao Z. ; Wang L.
刊名: Atmospheric Environment
ISSN: 1352-2310
出版年: 2020
卷: 234 语种: 英语
英文关键词: 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
; biomass burning
; hydroxyl radical
; oxidation
; phenanthrene
; reaction kinetics
; Lamprididae
学科: Nitro-PAHs
; OH Radical
; Oxidation mechanism
; Oxygenated PAHs
; PAHs
中文摘要: 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 Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/160712
Appears in Collections: 气候变化与战略
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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
Recommended Citation:
Zeng M.,Liao Z.,Wang L.. Atmospheric oxidation of gaseous anthracene and phenanthrene initiated by OH radicals[J]. Atmospheric Environment,2020-01-01,234