The aomogeneous and heterogeneous oxidation of organophosphate esters (OPEs) in the atmosphere: Take diphenyl...

Organophosphate esters (OPEs) are widely detected in the atmosphere. However, the atmospheric oxidative degradation mechanism of OPEs has not been closely examined. This work took density functional theory (DFT) to investigate the tropospheric ozonolysis of organophosphates, represented by diphenyl phosphate (DPhP), including adsorption mechanisms on the surface of titanium dioxide (TiO₂) mineral aerosols and oxidation reaction of hydroxyl groups (·OH) after photolysis. Besides, the reaction mechanism, reaction kinetics, adsorption mechanism, and ecotoxicity evaluation of the transformation products were also studied. At 298 K, the total reaction rate constants k_O3, k_OH, k_TiO2-O3, and k_TiO2-OH are 5.72 × 10^-15 cm³ molecule^-1 s^-1, 1.68 × 10^-13 cm³ molecule^-1 s^-1, 1.91 × 10^-23 cm³ molecule^-1 s^-1, and 2.30 × 10^-10 cm³ molecule^-1 s^-1. The atmospheric lifetime of DPhP ozonolysis in the near-surface troposphere is 4 min, much lower than that of hydroxyl radicals (·OH). Besides, the lower the altitude is, the stronger the oxidation is. The TiO₂ clusters carry DPhP promoting ·OH oxidation but inhibiting ozonolysis of DPhP. Finally, the main transformation products of this process are glyoxal, malealdehyde, aromatic aldehydes, etc., which are still ecotoxic. The findings shed new light on the atmospheric governance of OPEs.