Formation and enhanced photodegradation of chlorinated derivatives of bisphenol A in wastewater treatment plant effluent

There are many reports on the detection and removal of emerging pollutants in the wastewater effluents, while the fate of their chlorinated derivatives generated during chlorination is not well understood. Here we investigated the photodegradation of chlorinated derivatives of bisphenol A (CDBPAs), mainly including 3-chlorobisphenol A, 3,3′-dichlorobisphenol A, 3,5-dichlorobisphenol A, 3,3′,5-trichlorobisphenol A, and 3,3′,5,5′-tetrachlorobisphenol A, under simulated sunlight. Distinct from BPA, CDBPAs underwent rapid direct photodegradation due to a pronounced bathochromic shift of UV absorption. The photodegradation of CDBPAs was significantly enhanced by effluent organic matter (EfOM) from the wastewater effluent. A series of quenching experiments and laser flash photolysis analysis verified the contribution of triplet states of EfOM (3EfOM∗) for the indirect photodegradation of CDBPAs with rate constant of ∼109 M−1 s−1. Both direct and EfOM-induced indirect photodegradation of CDBPAs increased with a higher degree of chlorination. Furthermore, high-resolution mass spectrometry showed similar photoproducts for direct and indirect photodegradation of CDBPAs, mainly ascribed to the cleavage of C–Cl bond and hydroxylation with further cleavage of the benzene ring. The estrogenic activity of the photoproducts was diminished. These findings suggest that photodegradation is an important pathway for the removal and detoxication of CDBPAs from effluents and receiving natural waters under sunlight. [Display omitted] •CDBPAs underwent rapid direct photodegradation under sunlight.•3EfOM∗ accounted for the photosensitized degradation of CDBPAs.•Photolysis of CDBPAs increased with a higher degree of chlorination.•Cleavage of C–Cl bond and hydroxylation were major photolysis processes.•The estrogenic activity of the photoproducts was diminished.