ClO2 pre-oxidation changes dissolved organic matter at the molecular level and reduces chloro-organic byproducts and toxicity of water treated by the UV/chlorine process.

The formation of undesirable chloro-organic byproducts is of great concern in the UV/chlorine process. In this study, chlorine dioxide (ClO2) pre-oxidation was applied to control the formation of chloro-organic byproducts and the toxicity in UV/chlorine-treated water. The molecular-level changes in dissolved organic matter (DOM) were tracked by using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and ClO2 pre-oxidation was found to preferentially react with DOM moieties with high aromaticity level and with a carbon number of > 18, producing compounds with a higher degree of oxidation and lower aromaticity. The ClO2-treated DOM was found to be less susceptible to attack by radicals and free chlorine in the UV/chlorine process compared to the raw DOM. ClO2 pre-oxidation resulted in a significant decrease in the number of unknown chloro-organic byproducts (i.e., -17%) and the total intensity of organic chlorine detected by FT-ICR-MS (i.e., -31%). The molecular characteristics, such as O/C, aromaticity index, and the average number of chlorine atoms, of these unknown chloro-organic byproducts generated in the scenarios with and without ClO2 pre-oxidation were also different. Additionally, ClO2 pre-oxidation reduced the genotoxicity (SOS/umu test) and cytotoxicity (Hep G2 cytotoxicity assay) of UV/chlorine-treated water by 26% and 20%, respectively. The findings in this study highlight the merits of ClO2 pre-oxidation for controlling chloro-organic byproducts and reducing the toxicity of water treated by the UV/chlorine process in actual practice.