Transformation of bisphenol AF by chlorination: kinetic study and product identification

Bisphenol AF (BPAF), commonly used as a substitute for bisphenol A (BPA), is also an endocrine disruptor with cytotoxicity, neurotoxicity, genotoxicity, and biotoxicity. In this study, we found that BPAF could be effectively degraded by free chlorine. The second order rate constant of the reaction ranged from 1.67 to 126.67 M^-1·s^-1 in the pH range of 5.0-11.0. Nineteen products were detected by LC-Q-TOF-MS analysis, including chlorinated BPAF (i.e., mono/di/tri/tetrachloro-BPAF), 8 dimers, and 6 trimers. According to the identified products, two transformation pathways of electrophilic substitution and electron transfer are proposed. Humic acid (HA) could inhibit the degradation rate of BPAF due to its ability to reduce the reactive BPAF radical intermediates to the parent compound. The addition of low concentrations of Br^- and I^- accelerates the reaction rate of BPAF, due to the formation of HOBr and HOI with a higher oxidizing capacity. In seawater, BPAF degraded rapidly, and 16 new halogenated products were formed. Theoretical calculation shows that electrophilic substitution is more prone to occur at the ortho position of the hydroxyl group to form chlorinated products, while electron transfer tends to occur at the hydroxyl oxygen, resulting in the formation of BPAF radical and its subsequent coupling products.