Thallium adsorption on three iron (hydr)oxides and Tl isotopic fractionation induced by adsorption on ferrihydrite.

Thallium (Tl) is an extraordinarily toxic metal, which is usually present with Tl(I) and highly mobile in aquatic environment. Limited knowledge is available on the adsorption and isotopic variations of Tl(I) to Fe-(hydr)oxides. Herein, the adsorption behavior and mechanism of Tl(I) on representative Fe-(hydr)oxides, i.e. goethite, hematite, and ferrihydrite, were comparatively investigated kineticly and isothermally, additional to crystal structure modelling and Tl isotope composition (Tl/Tl). The results showed that ferrihydrite exhibited overall higher Tl(I) adsorption capacity (1.11-10.86 mg/kg) than goethite (0.21-1.83 mg/kg) and hematite (0.14-2.35 mg/kg), and adsorption by the three prevalent Fe-minerals presented strong pH and ionic strength dependence. The magnitude of Tl isotopic fractionation during Tl(I) adsorption to ferrihydrite (α ≈ 1.00022-1.00037) was smaller than previously observed fractionation between Mn oxides and aqueous Tl(I) (α ≈ 1.0002-1.0015). The notable difference is likely that whether oxidation of Tl(I) occurred during Tl adsorption to the mineral surfaces. This study found a small but detectable Tl isotopic fractionation during Tl(I) adsorption to ferrihydrite and heavier Tl isotope was slightly preferentially adsorbed on surface of ferrihydrite, which was attributed to the formation of inner-sphere complex between Tl and ≡Fe-OH. The findings offer a new understanding of the migration and fate of Tl/Tl during Tl(I) adsorption to Fe (hydr)oxides.