NDMA formation during ozonation of metformin: Roles of ozone and hydroxyl radicals

Metformin, a high-consumed pharmaceutical for diabetes, has been reported to generate carcinogenic nitroso-dimethylamine (NDMA) during treatment of its containing wastewater. However, whether it would produce NDMA during ozonation or not is unclear, let alone discriminate roles of ozone (O₃) and hydroxyl radicals (OH). In this paper, effects of ozonation on NDMA formation from metformin were investigated, roles of O₃ and OH were also distinguished by adding tert-butyl alcohol (tBA) as OH scavenger. Moreover, various influencing factors and reaction mechanisms were demonstrated. The results indicated that NDMA could be directly formed from metformin during ozonation, the addition of OH scavenger significantly enhanced its formation (0-46.2 ng/L vs 0-139.1 ng/L). The formation of NDMA by O₃ and OH was more affected by bromide and HCO₃^- than those with only O₃; while the impacts of pH and sulphate on the latter were more notable. No matter without/with tBA in the solution, the formed NDMA during ozonation of metformin increased with raising pH (from 5 to 9) and achieved the maximum 69.6 ng/L and 235.9 ng/L at pH 9, respectively; small amount of bromide (0.1 μM) promoted NDMA production, high levels of bromide (10 μM) inhibited its formation; the existence of HCO₃^- enhanced the amounts of NDMA from 44.5 to 73.5 ng/L (raised by 65.2%) by O₃ and OH and from 102.9 to 130 ng/L with only O₃ (raised by 26.3%); with the addition of sulphate, NDMA concentration raised by 43.8% by O₃ and OH, while the value was high up to 134.6% with only O₃. Based on the result of UPLC-Q-TOF and density functional theory, the oxidation intermediates were identified and possible transformation pathways of metformin during ozonation were proposed. The findings in this paper would provide reference when treating metformin-containing water in future.