Light- and HO-Mediated Redox Transformation of Thallium in Acidic Solutions Containing Iron: Kinetics and Mechanistic Insights.

The redox transformation between the oxidation states of thallium (Tl(I) and Tl(III)) is the key to influencing its toxicity, reactivity, and mobility. Dissolved iron (Fe) is widely distributed in the environment and coexists at a high level with Tl in acidic mine drainages (AMDs). While ultraviolet (UV) light and HO can directly (by inducing Tl(III) reduction) and indirectly (by inducing Fe(III) to form reactive intermediates) impact the redox cycles of Tl in Fe(III)-containing solutions, the kinetics and mechanism remain largely unclear. This study is the first to investigate the UV light- and HO-mediated Tl redox kinetics in acidic Fe(III) solutions. The results demonstrate that UV light and HO could directly reduce Tl(III) to Tl(I), with the extent of reduction dependent on the presence of Fe(III) and the solution pH. At pH 3.0, Tl(I) was completely oxidized to Tl(III), which can be ascribed to the generation of hydroxyl radicals (OH) from the Fe(III) photoreduction or Fe(III) reaction with HO. The kinetics of Tl(I) oxidation were strongly affected by the Fe(III) concentration, pH, light source, and water matrix. Kinetic models incorporating Tl redox kinetics with Fe redox kinetics were developed and satisfactorily interpreted Tl(III) reduction and Tl(I) oxidation under the examined conditions. These findings emphasize the roles of the UV light- and HO-driven Fe cycles in influencing the redox state of Tl, with implications for determining its mobility and fate in the environment.