Photodegradation of phthalic acid esters under simulated sunlight: Mechanism, kinetics, and toxicity change

Abstract

The photodegradation of two phthalic acid esters (PAEs), dimethyl phthalate (DMP) and di-n-octyl phthalate (DOP), under simulated sunlight in aqueous or organic phases (n-hexane (HEX) and dichloromethane (DCM)) was investigated. The mean photodegradation rates were ranked by half-lives as follows: DOP in DCM (3.77 h) < DMP in DCM (9.62 h) < DOP in H2O (3.99 days) < DMP in H2O (19.2 days) < DOP in HEX (21.0 days) < DMP in HEX (>30 days). Compound-specific stable isotope analysis (CSIA) combined with intermediate analysis was employed to explore the involved initial photoreaction mechanism. C–O bond cleavage, chlorine radical adduction to the aromatic ring, competing reactions of chlorine radical adduction to the aromatic ring and side chain, and a singlet oxygen-mediated pathway were mainly responsible for initial photodegradation mechanism of PAEs in H2O, DMP in DCM, DOP in DCM, and DOP in HEX, respectively. Furthermore, distinct isotope fractionation patterns of PAEs photodegradation open the possibility of using CSIA to differentiate the involved solvents in the field. More toxic and recalcitrant intermediates emerged during the photodegradation of DMP in DCM, while the risk to human health was reduced during the photochemical transformation of DOP in organic solvents.