Experimental and simulation investigations of UV/persulfate treatment in presence of bromide: Effects on degradation kinetics, formation of brominated disinfection byproducts and bromate

Abstract

Bromide (Br−), which is omnipresent in water bodies, can not only affect the degradation kinetics of target pollutants but may also form undesired byproducts (such as bromate (BrO3-) and brominated disinfection byproducts (Br-DBPs)) through sulfate radical (SO4∙-)-based advanced oxidation processes (AOPs). This study found that Br− significantly suppressed the degradation of diethyl phthalate (DEP) based on the ultraviolet (UV)/persulfate (PS) treatment and was efficiently converted into reactive species (radicals and free bromine) by the SO4∙- or hydroxyl radical (HO) generated in the UV/PS system. These reactive bromine species could, in turn, brominate the phenolic degradation intermediates of DEP as well as natural organic matter (NOM), yielding Br-DBPs, including tribromomethane (TBM), which was observed when Br−, DEP and/or NOM coexisted in this UV/PS system. However, the Br-DBPs were a short-lived form of bromine during the transformation of Br– and were degraded by the excessive oxidants (e.g., SO4∙- and HO). Instead, Br− was eventually transformed into BrO3-, with free bromine acting as the requisite intermediate. The BrO3- formation initially showed a delay before increasing monotonically. In general, raising the PS dosage and the initial Br− concentrations enhanced both the maximum concentration of TBM and the formation of BrO3-, while increasing the amounts of DEP and NOM facilitated the former and inhibited the latter. The maximum concentration of TBM increased while the formation of BrO3- was suppressed with increasing pH from 5.0 to 8.0. In addition, through simulating the steady-state concentration of radicals, it was found that the contribution of bromine atom radical (Br) towards oxidizing free bromine to BrO3- was far greater than those of SO4∙- and HO. The findings demonstrate the potential negative effects of Br− on SO4∙--based AOPs, which need to be considered when this technology is applied in practice.