Identification of N-Nitrosamines and Nitrogenous Heterocyclic Byproducts during Chloramination of Aromatic Secondary Amine Precursors

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 N-14/N-15-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. CI-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.