Interfacial reaction of Sn(II) on mackinawite (FeS).

The interaction of Sn(II) with metastable, highly reactive mackinawite is a complex process due to transient changes of the mackinawite surface in the sorption process. In this work, we show that tin redox state and local structure as investigated by Sn-K X-ray absorption spectroscopy (XAS) change with pH. We observe at pH<7 that divalent Sn forms two short (2.38 Å) Sn-S bonds to the S-terminated surface of mackinawite, and two longer (2.59 Å) Sn-S bonds pointing most likely towards the solution phase, in line with a SnS4 innersphere sorption complex. Precipitation of SnS or formation of a solid solution with mackinawite could be excluded. At pH>9, Sn(II) is completely oxidized to Sn(IV) by an Fe(II)/Fe(III) (hydr)oxide, most likely green rust, forming on the surface of mackinawite. Six O atoms at 2.04 Å and 6 Fe atoms at 3.29 Å indicate a structural incorporation by green rust, with Sn(IV) substituting for Fe in the crystal structure. The transition between Sn(II) and Sn(IV) and between sulfur and oxygen coordination takes place at a pH of 7 to 8 and an Eh of -250 mV, close to the thermodynamically predicted transitions from mackinawite to Fe (hydr)oxide and from sulfide to sulfate. The uptake processes of Sn(II) by mackinawite are largely in line with the uptake processes of divalent cations with soft Lewis-acid character like Cd, Hg and Pb, and lead to a strong retention of Sn with logRd values from 5 to 7 across the investigated pH range of 5 to 11.

Surface reaction of SnII on goethite (α-FeOOH): surface complexation, redox reaction, reductive dissolution, and phase transformation.

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 O2 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) (1)E and (2)C surface complexes. The contribution of (2)C 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 (1)E complex and 19.2 ± 0.6 for the (2)C 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.

Surface complexation and oxidation of Sn(II) by nanomagnetite.

The long-lived fission product 126Sn is of substantial interest in the context of nuclear waste disposal in deep underground repositories. However, the prevalent redox state, the aqueous speciation as well as the reactions at the mineral-water interface under the expected anoxic and reducing conditions are a matter of debate. We therefore investigated the reaction of Sn(II) with a relevant redox-reactive mineral, magnetite (Fe(II)Fe(III)2O4) at <2 ppmv O2, and monitored Sn uptake as a function of pH and time. Tin redox state and local structure were investigated by Sn­K X-ray absorption spectroscopy (XAS). We observed a rapid uptake (<30 min) and oxidation of Sn(II) to Sn(IV) by magnetite. The local structure determined by XAS showed two Sn­Fe distances of about 3.15 and 3.60 Å in line with edge and corner sharing arrangements between octahedrally coordinated Sn(IV) and the magnetite surface, indicative of formation of tetradentate inner-sphere complexes between pH 3 and 9. Based on the EXAFS-derived surface structure, we could successfully model the sorption data with two different complexes, (Magn_sO)4Sn(IV)(OH)2­2 (logK(2,0)(­2) −14.97 ± 0.35) prevailing from pH 2 to 9, and (Magn_sO)4Sn(IV)(OH)2Fe (logK(2,1)(0) −17.72 ± 0.50), which forms at pH > 9 by coadsorption of Fe(II), thereby increasing sorption at this high pH.