Formation of disinfection byproducts upon chlorine dioxide preoxidation followed by chlorination or chloramination of natural organic matter

Chlorine dioxide (ClO2) is often used as an oxidant to remove taste, odor and color during water treatment. Due to the concerns of the chlorite formation, chlorination or chloramination is often applied after ClO2 preoxidation. We investigated the formation of regulated and emerging disinfection byproducts (DBPs) in sequential ClO2-chlorination and ClO2-chloramination processes. To clarify the relationship between the formation of DBPs and the characteristics of natural organic matter (NOM), changes in the properties of NOM before and after ClO2 oxidation were characterized by fluorescence, Fourier transform infrared spectroscopy (FTIR), and size and resin fractionation techniques. ClO2 preoxidation destroyed the aromatic and conjugated structures of NOM and transformed large aromatic and long aliphatic chain organics to small and hydrophilic organics. Treatment with ClO2 alone did not produce significant amount of trihalomethanes (THMs) and haloacetic acids (HAAs), but produced chlorite. ClO2 preoxidation reduced THMs, HAAs, haloacetonitriles (HANs) and chloral hydrate (CH) during subsequent chlorination, but no reduction of THMs was observed during chloramination. Increasing ClO2 doses enhanced the reduction of most DBPs except halonitromethanes (HNMs) and haloketones (HKs). The presence of bromide increased the formation of total amount of DBPs and also shifted DBPs to more brominated ones. Bromine incorporation was higher in ClO2 treated samples. The results indicated that ClO2 preoxidation prior to chlorination is applicable for control of THM, HAA and HAN in both pristine and polluted waters, but chlorite formation is a concern and HNMs and HKs are not effectively controlled by ClO2 preoxidation.

► ClO2 transformed large aromatic and long aliphatic chain organics to small and hydrophilic ones.
► ClO2 alone did not generate significant amount of THMs and HAAs, but chlorite.
► ClO2 prior to chlorination reduced THMs, HAAs, HANs and CH, but not HNMs and HKs.
► Bromine incorporation in THM and HAA was higher in ClO2 pretreated samples.
► ClO2 prior to chlorination is suitable for certain DBP control in both pristine and polluted water.