title: Mechanistic and kinetic studies on the OH-initiated atmospheric oxidation of fluoranthene.
abstract: The atmospheric oxidation of polycyclic aromatic hydrocarbons (PAHs) can generate toxic derivatives which contribute to the carcinogenic potential of particulate organic matter. In this work, the mechanism of the OH-initiated atmospheric oxidation of fluoranthene (Flu) was investigated by using high-accuracy molecular orbital calculations. All of the possible oxidation pathways were discussed, and the theoretical results were compared with the available experimental observation. The rate constants of the crucial elementary reactions were evaluated by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The main oxidation products are a range of ring-retaining and ring-opening chemicals containing fluoranthols, fluoranthones, fluoranthenequinones, nitro-fluoranthenes, dialdehydes and epoxides. The overall rate constant of the OH addition reaction is 1.72×10(-11) cm(3) molecule(-1) s(-1) at 298 K and 1 atm. The atmospheric lifetime of Flu determined by OH radicals is about 0.69 days. This work provides a comprehensive investigation of the OH-initiated oxidation of Flu and should help to clarify its atmospheric conversion.
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, PR China.
authors.forename: Juan
authors.initials: J
authors.lastname: Dang
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, PR China.
authors.forename: Xiangli
authors.initials: X
authors.lastname: Shi
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, PR China. Electronic address: zqz@sdu.edu.cn.
authors.forename: Qingzhu
authors.initials: Q
authors.lastname: Zhang
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, PR China.
authors.forename: Jingtian
authors.initials: J
authors.lastname: Hu
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, PR China.
authors.forename: Jianmin
authors.initials: J
authors.lastname: Chen
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, PR China.
authors.forename: Wenxing
authors.initials: W
authors.lastname: Wang
mesh_terms: D000393:Air Pollutants / Q000737:chemistry*; D001272:Atmosphere / Q000737:chemistry*; D005449:Fluorenes / Q000737:chemistry*; D007700:Kinetics; D008956:Models, Chemical; D010084:Oxidation-Reduction
chemical_list: D000393:Air Pollutants; D005449:Fluorenes; C007738:fluoranthene
keywords: Fluoranthene; OH radicals; Oxidation mechanism; Oxidation products; Rate constants