Analyzing disinfection by-products yield and mechanisms in UV/Cl2 using response surface methodology and quantitative structure-activity relationship models.

The study aimed to investigate the formation of halogenated disinfection byproducts (DBPs) during applying UV/chlorine (UV/Cl2) and unravel the interactive impacts of critical operational parameters and the mechanisms behind DBPs formation. Response surface methodology and quantitative structure-activity relationship models were developed to evaluate the contribution of electrophilic, nucleophilic, and free radical reactions to the formation of DBPs in UV/Cl2. The study found that Cl2 and its interactions dominated the total DBPs and non-Br-DBPs formation, while Br- and the Cl2-Br- interaction played a decisive role in the Br-DBPs formation. The study also observed significant interactions of Br, Cl2, and pH on chloroform, bromodichloromethane, dichloroacetonitrile, 1,1-dichloro-2-propanone, trichloroactic acid, and chlorodibromoacetic acid formations, while no evident interaction on chloral hydrate, dibromochloromethane, trichloroacetone, dibromoacetic acid, and bromodichloroacetic acid formations. The electrophilic substitution of HOBr mainly controlled the formation of trihalomethanes, and the contribution of nucleophilic, electrophilic, and free radical (•OH, Cl•, Cl2•- and ClO•) reactions depended on the molar ratio of Cl2 to Br, and pH-determined hydrolysis rate constants of DBPs and the types of free radicals. Overall, the response surface methodology and quantitative structure-activity relationship models provided a reference for revealing DBPs formation mechanisms in other disinfection processes.