Atmospheric Autoxidation of Organophosphate Esters

Organophosphate esters (OPEs), widely used as flame retardants and plasticizers, have frequently been identified in the atmosphere. However, their atmospheric fate and toxicity associated with atmospheric transformations are unclear. Here, we performed quantum chemical calculations and computational toxicology to investigate the reaction mechanism of peroxy radicals of OPEs (OPEs-RO₂^•), key intermediates in determining the atmospheric chemistry of OPEs, and the toxicity of the reaction products. TMP-RO₂^• (R₁) and TCPP-RO₂^• (R₂) derived from trimethyl phosphate and tris(2-chloroisopropyl) phosphate, respectively, are selected as model systems. The results indicate that R₁ and R₂ can follow an H-shift-driven autoxidation mechanism under low NO concentration ([NO]) conditions, clarifying that RO₂^• from esters can follow an autoxidation mechanism. The unexpected autoxidation mechanism can be attributed to the distinct role of the ─(O)₃P(═O) phosphate-ester group in facilitating the H-shift of OPEs-RO₂^• from commonly encountered ─OC(═O)─ and ─ONO₂ ester groups in the atmosphere. Under high [NO] conditions, NO can mediate the autoxidation mechanism to form organonitrates and alkoxy radical-related products. The products from the autoxidation mechanism have low volatility and aquatic toxicity compared to their corresponding parent compounds. The proposed autoxidation mechanism advances our current understanding of the atmospheric RO₂^• chemistry and the environmental risk of OPEs.