Atmospheric oxidation of phenanthrene initiated by OH radicals in the presence of O2 and NOx - A theoretical study

Phenanthrene (Pile) is one of the most abundant polycyclic aromatic hydrocarbons (PAHs) observed in polluted urban atmosphere. The most important atmospheric loss process of Phe is the reaction with OH radicals. The present work investigated OH radical-initiated atmospheric degradation of Phe in the presence of O-2 and NOx. The possible reaction mechanism was elucidated by density functional theory (DFT) calculations. Calculations show that the main products are a series of ring-retaining and ring-opening oxygenated PAHs containing phenanthrol, phenanthones, phenanthrenequinone, and dialdehydes. Rice-Ramsperger-Kassel-Marcus (RRKM) theory was employed to evaluate the rate constants for the initial steps of Phe with OH. The atmospheric lifetime of Phe relative to gas-phase reactions with OH is estimated to be 4.6 h, based on the calculated overall rate constant of 3.02 x 10(-11) cm(3) molecule(-1) s(-1) at 298 K and 1 atm. Combined with available experimental data, this work also provides a comprehensive investigation of the formation mechanism of oxygenated PAHs in the atmospheric oxidation process of phenanthrene and should help to clarify its potential health risk. (C) 2016 Elsevier B.V. All rights reserved.