Hydroxyl radical and UV-induced reactions of bisphenol analogues inwater: Kinetics, transformation products and estrogenic activity estimation

Abstract

There is currently a concern about the endocrine-disrupting capacity of many bisphenol A substitutes, such as BPAF, BPAP, BPB, BPC, BPC-Cl, BPE, BPF, BPS and BPZ in natural waters. However, fundamental data (i.e., kinetics and mechanisms) about the performance of advanced oxidation processes and UV radiation for water decontamination are scarce. In this study, the removal of bisphenol A substitutes was evaluated by UV/H2O2 and UV treatments under neutral pH conditions. Reactivity of hydroxyl radical (·OH) with bisphenol analogues was studied by competition kinetics and their quantum yield was determined at 254 nm. Results revealed similar values of the second-order rate constants of ·OH with all bisphenols (5.89–14.1 × 109 M−1 s−1), as well as comparable values of the quantum yields (4.8–28.7 × 10−3 mol E−1), except for BPC-Cl. This compound showed a remarkably high quantum yield (4.7 × 10−1 mol E−1), which resulted in a removal higher than 60 % at typical UV disinfection doses (ca. 40 mJ cm−2). The transformation products formed by ·OH and UV-induced reactions were also assessed. Catechol and ortho-quinone derivatives were suggested as the main intermediates from the reaction of bisphenols with ·OH. Excluding BPC-Cl, the resulting photolysis products of bisphenols coincided with those from the ·OH reaction. A distinguished mechanism was proposed for the formation of the photolysis products of BPC-Cl, based on the favoured cleavage of the C–Cl bonds under UV irradiation. Phenanthrene-3,6-diol was suggested as main initial photolysis byproduct of BPC-Cl. Estrogenicity of bisphenols and detected intermediates was predicted using a Quantitative Structure-Activity Relationship (QSAR) approach. Certain byproducts produced during bisphenols reaction with ·OH, such as catechol derivatives, may exhibit estrogenic activity, as they were predicted as very strong binders. Similarly, all photolysis intermediates of BPC-Cl were predicted as very strong binders as well, suggesting that estrogenicity could persist after the treatment.