RESUMEN
Unsymmetrical dimethylhydrazine (UDMH) is found to generate substantial carcinogenic nitroso-dimethylamine (NDMA) during ozonation, moreover, its formation is promoted by ubiquitous bromide ions (Br-) in water matrixes, but the mechanism is still unclear. In this study, effects of Br- on NDMA formation during ozonation of UDMH were studied, meanwhile, its promotion pathways were also determined. The results demonstrated that Br- promoted NDMA formation from UDMH during ozonation, the formation rate constant with Br- is over 7 times of that without Br-. NDMA amount raised from 142.5 to 327.5 µg/L when Br- dosages increased from 0 to 100 µM. No matter with or without Br-, the augment of O3 dosages facilitated NDMA formation; the maximum value was achieved at pH 8. NDMA decreased dramatically from 173.8 to 123.5 µg/L with HCO3- raising from 0 to 160 µM, while increasing remarkably to 222.5 µg/L with SO42- dosing. In addition, NOM inhibited NDMA formation from UDMH during ozonation. The mass spectrum of LC-MS/MS verified that the generation of Br-UDMH was main cause for promoting NDMA formation. Moreover, hypobromous acid (HBrO) was confirmed to be responsible for Br-UDMH formation. In addition, the position that oxidants and Br- attacked was demonstrated based on Gaussian calculation. The results of this study could provide theoretical basis for the application of ozonation in bromine-containing water matrixes.