Chlorination of bisphenol S: Kinetics, products, and effect of humic acid

Bisphenol S (BPS), as a main alternative of bisphenol A for the production of industrial and consumer products, is now frequently detected in aquatic environments. In this work, it was found that free chlorine could effectively degrade BPS over a wide pH range from 5 to 10 with apparent second-order rate constants of 7.6-435.3 M^-1s^-1. A total of eleven products including chlorinated BPS (i.e., mono/di/tri/tetrachloro-BPS), 4-hydroxybenzenesulfonic acid (BSA), chlorinated BSA (mono/dichloro-BSA), 4-chlorophenol (4CP), and two polymeric products were detected by high performance liquid chromatography and electrospray ionization-tandem quadrupole time-of-flight mass spectrometry. Two parallel transformation pathways were tentatively proposed: (i) BPS was attacked by stepwise chlorine electrophilic substitution with the formation of chlorinated BPS. (ii) BPS was oxidized by chlorine via electron transfer leading to the formation of BSA, 4CP and polymeric products. Humic acid (HA) significantly suppressed the degradation rates of BPS even taking chlorine consumption into account, while negligibly affected the products species. The inhibitory effect of HA was reasonably explained by a two-channel kinetic model. It was proposed that HA negligibly influenced pathway i while appreciably inhibited the degradation of BPS through pathway ii, where HA reversed BPS phenoxyl radical (formed via pathway ii) back to parent BPS.