Tracing nitrogenous byproducts during ozonation in the presence of bromide and ammonia using stable isotope labeling and high resolution mass spectrometry

Ammonia has been widely used to inhibit bromate formation during ozonation. However, our recent study found that during ozonation in the presence of bromide and ammonia, toxicity increased under certain conditions that might be attributed to the formation of nitrogenous byproducts. Herein, a typical structural moiety of natural organic matter (NOM), hydroquinone, was evaluated for its potential to form nitrogenous byproducts. During ozonation of the hydroquinone solution containing bromide and ammonia, toxicity of organic byproducts increased significantly. As organic bromine was hardly detected, organic nitrogen was responsible for the increased toxicity. An effective method combining ultra-performance liquid chromatography in tandem with high resolution mass spectrometry (UPLC-HRMS) with an isotope labeling strategy was used to trace nitrogenous byproducts. Four newly formed nitrogenous byproducts were detected, two of which were also detected in Suwannee River natural organic matter (SRNOM) solution treated under the same ozonation condition. Furthermore, the molecular structures and formation pathways of these nitrogenous byproducts were proposed. This study highlights that, despite the widespread use, adding ammonia to inhibit bromate formation during ozonation might increase the toxicity posed by nitrogenous byproducts. During ozonation in the presence of bromide and ammonia, particular attention should be paid to nitrogenous byproducts.