Generality and diversity on the kinetics, toxicity and DFT studies of sulfate radical-induced transformation of BPA and its analogues

Abstract

The international campaign to ban bisphenol A (BPA) has resulted in increasing application of BPA substitutes. However, investigations have mainly been confined to the removal of single contaminant from the water, resulting in an inefficient burden. Furthermore, systematic study and synthetical discussion of bisphenol analogues (BPs) kinetics and transformation pathways were largely underemphasized. Chemical oxidation of BPA and four typical alternatives (i.e., bisphenol AF, bisphenol E, bisphenol F and bisphenol S) in a UV-activated persulfate system was examined in this study. The effects of persulfate (PS) dosage, pH and water matrix constituents (i.e., bicarbonate, chloride and natural organic matter) were comprehensively examined using a combination of laboratory experiments and mathematical modeling. According to our findings, the removal characteristics of different BPs employing SO4•−-induced removal technology, including degradation mechanisms and influencing trends by water matrix, revealed similarly. The second order-rate constants of SO4•– reacting with BPs served as the main variables mediating the variation in degradation kinetics. Frontier molecular orbital theory and density functional theory suggested BPs molecules possessed the same susceptible positions to free radicals. In the UV-activated PS process, transformation pathways included hydroxylation, electron-transfer, substitution, and rearrangement triggered by ortho-cleavage, with certain intermediates exhibiting higher toxicity than the parent chemicals. The findings of this study provided valuable information to estimate potential environmental risks of using BPA alternatives.