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With diminishing pristine water, wastewater-affected waters that contain complex anthropogenic compounds are becoming important sources of drinking water and the compounds will inevitably react with disinfectants to form disinfection byproducts (DBPs). Secondary amines such as diphenylamine (DPA) analogues are considered as potential precursors of N-nitrosamines. In this study, an in situ 14N/15N-labeling and screening workflow was used to systematically investigate the formation of nitrogenous DBPs (N-DBPs) and putative reaction pathways. Twenty-four pairs of N-DBPs were generated and identified from chloramination of DPA through two main pathways, in which chloramines reacted with the amino and phenyl functional groups to form N-nitrosodiphenylamine and monochlorinated 5,10-dihydro-phenazine (Cl-DiH-Phe), respectively. Cl-DiH-Phe could further produce phenazine and the coupling products with another DPA molecule. Selective N-DBP formation was pH and dose-dependent, and the same reactions were observed for additional two aromatic DPA analogues. Effects of alkyl substituents on the formation pathways were investigated using a series of dialkyl and N-alkyl aromatic analogues. Only the amino pathway to form nitrosamines was noticed for dialkyl amines, nevertheless, both the main reactions occurred for N-alkyl aromatic amines. These findings suggested that the reaction with chloramines through a phenyl pathway was likely to be crucial for novel nitrogenous heterocyclic byproducts.

Carbonyl compounds are an important class of by-products 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.