Characterization of Carbonyl Disinfection By-Products During Ozonation, Chlorination, and Chloramination of Dissolved Organic Matters

Carbonyl compounds are an important class of byproducts that are generated in disinfection reactions. These chemicals are ingredients contributing to toxicology in the drinking water system, the compositions and structures of which are worthy of attention. In this study, a chemical derivatization method based on simultaneous light/heavy isotope labeling was established for general recognition of carbonyl compounds and carbonyl disinfection by-products (DBPs) as per the humic substance reference standard (Suwannee river fulvic acid II, SRFA) before and after ozonation, chlorination, and chloramination. Decomposition of macromolecular components into polar carbonyl species was observed to be the most prominent pathway in ozone treatment due to the efficient reactivity of ozone with phenols and alkoxy aromatic rings. As a result, alteration of molecular characteristics was noticed. For instance, ozone-induced carbonyl DBPs in the highly oxygenated compound classes (0.67 <= O/C <= 1.2, 0.6 < H/C <= 1.5) possessed higher O/C but contained less oxygen numbers and carbon numbers. Cl/Br-carbonyl-DBPs were identified after chlorination and chloramination, and I-carbonyl-DBPs were found in ozone and chloramine treatments. Several major halogenated carbonyl homologues were further recognized, including halogenated 4-oxobutenoic acid analogues, halogenated 2,5-dioxohex-3-enoic acid analogues, and halogenated 4-cyclopentene-1,3-diones analogues. These findings illustrate the presence of abundant carbonyl DBPs in water disinfection, and hence their impacts on human health deserve further investigation.