Differences in the degradation behavior of disinfection by-products in UV/PDS and UV/H2O2 processes and the effect of their chemical properties

In this work, sixteen typical chlorinated and brominated aromatic disinfection by-products (DBPs) were selected as examples to investigate their different degradation mechanisms initiated by HO• and SO4•-. Addition reactions were the main mode of degradation of DBPs by HO•, while SO4•- dominated H-abstraction reactions and single electron transfer reactions. Chlorinated compounds had higher reactivity than brominated compounds. Furthermore, substituents with stronger electron-donating effects promoted the electrophilic reaction of DBPs with the two radicals. In addition, we developed a model based on the chemical properties LUMO, fmax−, and hardness for predicting the average reaction energy barriers for the initial reactions of DBPs with HO• and SO4•-. The model had good predictive performance for the difficulty of degradation of different DPBs by HO• and SO4•-, with R2 values of 0.85 and 0.87, respectively. Through the degradation efficiency simulation, we found that longer reaction times, higher oxidant concentrations and lower pollutant concentrations were more favorable for the removal of DBPs. The UV/PDS process showed better degradation of DBPs than the UV/H2O2 process. In addition, most degradation products of DBPs exhibited less toxicity to aquatic organisms than their parent compounds. This study provided theoretical guidance for the degradation and removal of other aromatic DBPs at the molecular level. © 2023