New insights into thallium(I) behaviors at birnessite surfaces: Effects of an organic buffer and goethite

Understanding the environmental behavior of thallium (Tl) is crucial due to its high toxicity and increasing anthropogenic presence. This study investigated the adsorption and redox behaviors of Tl(I) with acid birnessite (AcBi) in the presence of 1,4-piperazine-diethanesulfonic acid (PIPES) and goethite under diffusion-limited conditions using Donnan reactors in aerobic and anaerobic environments. Our findings indicate that Tl(I) preferentially adsorbs onto AcBi, with capacities 20 to 100 times higher than onto goethite, even when AcBi is partial reduced by PIPES. No net Tl(I) oxidation occurred in the Donnan reactors, likely due to complex electron transfer processes between Tl(I), birnessite, and PIPES. Any Tl(III) generated from Tl(I) oxidation by birnessite was rapidly reduced back to Tl(I) by PIPES. This was confirmed in batch experiments where reduced Tl(III) on birnessite surfaces and in Tl(III) salts. These findings highlight the need to assess the impact of Good's buffers on redox reactions involving manganese oxides and Tl, while also providing insights into the competitive retention of Tl on manganese and iron (hydr)oxides, with implications for Tl mobility and bioavailability in natural environments.