Effect of bromide on molecular transformation of dissolved effluent organic matter during ozonation, UV/H2O2, UV/persulfate, and UV/chlorine treatments

Ozonation and ultraviolet-based advanced oxidation processes (UV-AOPs) play important roles in advanced treatment of municipal wastewater for water reuse. Bromide is widely present in wastewater at different concentration levels (ranging from mu g/L to mg/L). However, the effect of bromide on molecular transformation of dissolved effluent organic matter (dEfOM) in real wastewater during ozonation and UV-AOPs treatments still remains unclear. Herein, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) was utilized to characterize the overall molecular transformation of dEfOM and the formation of unknown halogenated byproducts (X-BPs) in ozonation, UV/H2O2, UV/persulfate (UV/PS), and UV/chlorine (UV/CI) processes in the presence of additional bromide. Compared with the same oxidation processes without additional bromide, the degree of dEfOM oxygenation had some extent decrement with the effect of bromide. A slightly increment of the number of unknown brominated byproducts (BrBPs) was observed during ozonation, UV/H2O2, and UV/PS treatments in the presence of additional bromide, and the largest increment of these compounds was found in UV/Cl process. A total of 82 chlorinated byproducts (Cl-BPs) and 183 Br-BPs were detected in all oxidation processes with the effect of bromide, and the number of Br-BPs was significantly higher than that of Cl-BPs. Based on mass difference analysis, 69 pairs of possible precursors/Br-BPs were identified. In addition, the additional bromide did not remarkably increase the concentrations of trihalomethanes (THMs) and haloacetic acids (HAAs) in ozonation, UV/H2O2, and UV/PS treatments, while the production of THMs and HAAs significantly decreased by 68.06% and 54.55%, respectively, during UV/Cltreatment. The calculated cytotoxicity increased to some extent for each treatment, especially for UV/Cl treatment, and the compound with largest contribution to cytotoxicity was monobromoacetic acid. This study provides new insights into the formation and transformation of X-BPs during advanced treatment of real wastewater with the effect of bromide.

Automated summary

This study used FT-ICR-MS to investigate the impact of bromide on the overall molecular transformation of dissolved effluent organic matter (dEfOM) and the formation of unknown halogenated byproducts (X-BPs) during different oxidation processes. The presence of additional bromide led to a slight decrease in dEfOM oxygenation and a slight increase in the number of unknown brominated byproducts (BrBPs) in various oxidation processes, with the largest increment observed in the UV/Cl process. The study also found that the additional bromide did not significantly increase the concentrations of trihalomethanes (THMs) and haloacetic acids (HAAs) in most treatments, except for a significant decrease during UV/Cl treatment.