Revisiting the chloramination of phenolic compounds: Formation of novel high-molecular-weight nitrogenous disinfection byproducts

Abstract

• Identified about 100 unreported N-DBPs during chloramination of phenolic compounds. • Revealed structural diversity of the novel N-DBPs using HRMS and DFT calculations. • Proposed novel formation pathways of N-DBPs through experiments and computations. • Explored the unreported bonding mechanisms of coupling heterocyclic N-DBPs. Disinfection is critical for ensuring water safety; however, the potential risks posed by disinfection byproducts (DBPs) have raised public concern. Previous studies have largely focused on low-molecular-weight DBPs with one or two carbon atoms, leaving the formation of high-molecular-weight DBPs (HMW DBPs, with more than two carbon atoms) less understood. This study explores the formation of HMW DBPs during the chloramination of phenolic compounds using a novel approach that combines high-resolution mass spectrometry with density functional theory (DFT) calculations. For the first time, we identified nearly 100 previously unreported HMW nitrogenous DBPs (N-DBPs), with nearly half of those being halogenated N-DBPs. These N-DBPs were tentatively identified as heterocyclic (e.g., pyrrole and pyridine analogs) and coupling heterocyclic N-DBPs. Through detailed structure analysis and DFT calculations, the key formation steps of heterocyclic N-DBPs (monochloramine-mediated ring-opening reactions of halobenzoquinones) and new bonding mechanisms (C–N, C–O, and C–C bonding) of the coupling heterocyclic N-DBPs were elucidated. The selective formation of these novel N-DBPs was significantly influenced by factors such as contact time, monochloramine dosage, pH, and bromide concentration. Our findings emphasize the occurrence of diverse HMW heterocyclic N-DBPs, which are likely toxicologically significant, underscoring the need for further research to evaluate and mitigate their potential health risks in water disinfection.

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