Kinetics of Thallium(I) Oxidation by Free Chlorine in Bromide-Containing Waters: Insights into the Reactivity with Bromine Species.

The oxidation of thallium [Tl(I)] to Tl(III) by chlorine (HOCl) is an important process changing its removal performance in water treatment. However, the role of bromide (Br-), a common constituent in natural water, in the oxidation behavior of Tl(I) during chlorination remains unknown. Our results demonstrated that Br- was cycled and acted as a catalyst to enhance the kinetics of Tl(I) oxidation by HOCl over the pH range of 5.0-9.5. Different Tl(I) species (i.e., Tl+ and TlOH(aq)) and reactive bromine species (i.e., HOBr/BrO-, BrCl, Br2O, and BrOCl) were kinetically relevant to the enhanced oxidation of Tl(I). The oxidation by free bromine species became the dominant pathway even at a low Br- level of 50 μg/L for a chlorine dose of 2 mg of Cl2/L. It was found that the reactions of Tl+/BrCl, Tl+/BrOCl, and TlOH(aq)/HOBr dominated the kinetics of Tl(I) oxidation at pH < 6.0, pH 6.0-8.0, and pH > 8.0, respectively. The species-specific rate constants for Tl+ reacting with individual bromine species were determined and decreased in the order: BrCl > Br2 > BrOCl > Br2O > HOBr. Overall, the presented results refine our knowledge regarding the species-specific reactivity of TI(I) with bromine species and will be useful for further prediction of thallium mobility in chlorinated waters containing bromide.