Insight into the mechanisms of trichloronitromethane formation by vacuum ultraviolet: QSAR model and FTICR-MS analysis.

• HO• and RNS during VUV photolysis of NO3− contributed to TCNM formation. • Solution pH, chloride and bicarbonate cannot effectively dimmish TCNM formation. • TCNM formation showed a linear relationship with the Hammett constant. • Newly formed 1161 nitrogen-containing compounds have higher aromaticity. • Results indicated TCNM formation risk of VUV applying in water treatment. Vacuum ultraviolet (VUV) photolysis is recognized as an environmental-friendly treatment process. Nitrate (NO 3 −) and natural organic matter (NOM) are widely present in water source. We investigated trichloronitromethane (TCNM) formation during chlorination after VUV photolysis, because TCNM is an unregulated highly toxic disinfection byproduct. In this study: (1) we found reactive nitrogen species that is generated under VUV photolysis of NO 3 − react with organic matter to form nitrogen-containing compounds and subsequently form TCNM during chlorination; (2) we found the mere presence of 0.1 mmol/L NO 3 − can result in the formation of up to 63.96 µg/L TCNM; (3) we found the changes in pH (6.0-8.0), chloride (1-4 mmol/L), and bicarbonate (1-4 mmol/L) cannot effectively diminish TCNM formation; and, (4) we established the quantitative structure-activity relationship (QSAR) model, which indicated a linear relationship between TCNM formation and the Hammett constant (σ) of model compounds; and, (5) we characterized TCNM precursors in water matrix after VUV photolysis and found 1161 much more nitrogen-containing compounds with higher aromaticity were generated. Overall, this study indicates more attention should be paid to reducing the formation risk of TCNM when applying VUV photolysis process at scale. [Display omitted]. [ABSTRACT FROM AUTHOR]