Theoretical and Kinetic Properties of OH Radical-Initiated Oxidation of Galaxolide in the Atmosphere.

Abstract

Galaxolide (HHCB), an important emerging contaminant, has attracted great environmental concern owing to its widespread occurrence and potential toxicity. In this study, the detailed multichannel mechanism of OH radical-initiated atmospheric degradation reactions of HHCB has been investigated by employing density functional theory (DFT). The reactants, transition states, intermediates, and products were optimized at the MPWB1K/6-31+G(d,p) level, and single-point energies were further refined at the MPWB1K/6-311+G(3df,2p) level of theory. The canonical variational transition-state (CVT) theory combined with the small curvature tunneling (SCT) was performed to evaluate the Arrhenius expressions and rate constants of key elementary reactions over a suitable range of 180-370 K. The thermodynamic and kinetic calculation results show that OH addition and hydrogen abstraction reactions are competitive pathways for HHCB. The dominant products in the presence of O2/NO are epoxide, dialdehyde, alcohol ketone, cyclolactone compounds, and HO2 radicals. At 298 K, the total rate constant of OH-initiated degradation of HHCB is 2.71 × 10-11 cm3 molecule-1 s-1. The atmospheric lifetime of HHCB determined by OH-initiated reactions is 10.09 h, which is in favor of the phenomenon of medium-range transport for HHCB in the atmosphere.