Oxidation State and Structure of Fe in Nontronite: From Oxidizing to Reducing Conditions.

The redox reaction between natural Fe-containing clay minerals and its sorbates is a fundamental process controlling the cycles of many elements such as carbon, nutrients, redox-sensitive metals, and metalloids (e.g., Co, Mn, As, Se), and inorganic as well as organic pollutants in Earth's critical zone. While the structure of natural clay minerals under oxic conditions is well-known, less is known about their behavior under anoxic and reducing conditions, thereby impeding a full understanding of the mechanisms of clay-driven reduction and oxidation (redox) reactions especially under reducing conditions. Here we investigate the structure of a ferruginous natural clay smectite, nontronite, under different redox conditions, and compare several methods for the determination of iron redox states. Iron in nontronite was gradually reduced chemically with the citrate-bicarbonate-dithionite (CBD) method. 57Fe Mössbauer spectrometry, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) spectroscopy including its pre-edge, extended X-ray absorption fine structure (EXAFS) spectroscopy, and mediated electrochemical oxidation and reduction (MEO/MER) provided consistent Fe(II)/Fe(III) ratios. By combining X-ray diffraction (XRD) and transmission electron microscopy (TEM), we show that the long-range structure of nontronite at the highest obtained reduction degree of 44% Fe(II) is not different from that of fully oxidized nontronite except for a slight basal plane dissolution on the external surfaces. The short-range order probed by EXAFS spectroscopy suggests, however, an increasing structural disorder and Fe clustering with increasing reduction of structural Fe.

Thallium adsorption onto phyllosilicate minerals.

The adsorption of thallium (Tl) onto phyllosilicate minerals plays a critical role in the retention of Tl in soils and sediments and the potential transfer of Tl into plants and groundwater. Especially micaceous minerals are thought to strongly bind monovalent Tl(I), in analogy to their strong binding of Cs. To advance the understanding of Tl(I) adsorption onto phyllosilicate minerals, we studied the adsorption of Tl(I) onto Na- and K-saturated illite and Na-saturated smectite, two muscovites, two vermiculites and a naturally Tl-enriched soil clay mineral fraction. Macroscopic adsorption isotherms were combined with the characterization of the adsorbed Tl by X-ray absorption spectroscopy (XAS). In combination, the results suggest that the adsorption of Tl(I) onto phyllosilicate minerals can be interpreted in terms of three major uptake paths: (i) highest-affinity inner-sphere adsorption of dehydrated Tl+ on a very low number of adsorption sites at the wedge of frayed particle edges of illite and around collapsed zones in vermiculite interlayers through complexation between two siloxane cavities, (ii) intermediate-affinity inner-sphere adsorption of partially dehydrated Tl+ on the planar surfaces of illite and muscovite through complexation onto siloxane cavities, (iii) low-affinity adsorption of hydrated Tl+, especially in the hydrated interlayers of smectite and expanded vermiculite. At the frayed edges of illite particles and in the vermiculite interlayer, Tl uptake can lead to the formation of new wedge sites that enable further adsorption of dehydrated Tl+. On the soil clay fraction, a shift in Tl(I) uptake from frayed edge sites (on illite) to planar sites (on illite and muscovite) was observed with increasing Tl(I) loading. The results from this study show that the adsorption of Tl(I) onto phyllosilicate minerals follows the same trends as reported for Cs and Rb and thus suggests that concepts to describe the retention of (radio)cesium by different types of phyllosilicate minerals in soils, sediments and rocks are also applicable to Tl(I).

Fundamental Research on Radiochemistry of Geological Nuclear Waste Disposal.

Currently, 5 · 1019 Bq of radioactive waste originating from the use of nuclear power for energy production, and medicine, industry and research, is maintained in Switzerland at intermediate storage facilities. Deep geological disposal of nuclear waste is considered as the most reliable and sustainable long-term solution worldwide. Alike the other European countries, the Swiss waste disposal concept embarks on the combination of engineered and geological barriers. The disposal cell is a complex geochemical system. The radionuclide mobility and consequently radiological impact depend not only on their chemical speciation but also on the background concentration of other stable nuclides and their behaviour in the natural environment. The safety assessment of the repository is thus a complex multidisciplinary problem requiring knowledge in chemical thermodynamics, structural chemistry, fluid dynamics, geo- and radiochemistry. Broad aspects of radionuclide thermodynamics and geochemistry are investigated in state-of-the-art radiochemical laboratories at the Paul Scherrer Institute. The research conducted over the last 30 years has resulted in a fundamental understanding of the radionuclides release, retention and transport mechanism in the repository system.

Fe(II) sorption on a synthetic montmorillonite. A combined macroscopic and spectroscopic study.

Extended X-ray absorption fine structure (EXAFS) and Mössbauer spectroscopy combined with macroscopic sorption experiments were employed to investigate the sorption mechanism of Fe(II) on an iron-free synthetic montmorillonite (Na-IFM). Batch sorption experiments were performed to measure the Fe(II) uptake on Na-IFM at trace concentrations as a function of pH and as a function of sorbate concentration at pH 6.2 and 6.7 under anoxic conditions (O2 < 0.1 ppm). A two-site protolysis nonelectrostatic surface complexation and cation exchange sorption model was used to quantitatively describe the uptake of Fe(II) on Na-IFM. Two types of clay surface binding sites were required to model the Fe(II) sorption, the so-called strong (≡S(S)OH) and weak (≡S(W)OH) sites. EXAFS data show spectroscopic differences between Fe sorbed at low and medium absorber concentrations that were chosen to be characteristic for sorption on strong and weak sites, respectively. Data analysis indicates that Fe is located in the continuity of the octahedral sheet at trans-symmetric sites. Mössbauer spectroscopy measurements confirmed that iron sorbed on the weak edge sites is predominantly present as Fe(II), whereas a significant part of surface-bound Fe(III) was produced on the strong sites (∼12% vs ∼37% Fe(III) species to total sorbed Fe).