Surface Reaction of Sn~Ⅱ on Goethite (α-FeOOH): Surface Complexation, Redox Reaction, Reductive Dissolution, and Phase Transformation

摘要

To elucidate the potential risk of ~(126)Sn migration from nuclear waste repositories, we investigated the surface reactions of Sn~Ⅱ on goethite as a function of pH and Sn~Ⅱ loading under anoxic condition with O_2 level ＜ 2 ppmv. Tin redox state and surface structure were investigated by Sn K edge X-ray absorption spectroscopy (XAS), goethite phase transformations were investigated by high-resolution transmission electron microscopy and selected area electron diffraction. The results demonstrate the rapid and complete oxidation of Sn~Ⅱ by goethite and formation of Sn~Ⅳ ~1E and ~2C surface complexes. The contribution of ~2C complexes increases with Sn loading. The Sn~Ⅱ oxidation leads to a quantitative release of Fe~Ⅱ from goethite at low pH, and to the precipitation of magnetite at higher pH. To predict Sn sorption, we applied surface complexation modeling using the charge distribution multisite complexation approach and the XAS-derived surface complexes. Log K values of 15.5 ± 1.4 for the ~1E complex and 19.2 ± 0.6 for the ~2C complex consistently predict Sn sorption across pH 2-12 and for two different Sn loadings and confirm the strong retention of Sn~Ⅱ even under anoxic conditions.