Structural insight into iodide uptake by AFm phases.

The ability of cement phases carrying positively charged surfaces to retard the mobility of (129)I, present as iodide (I(-)) in groundwater, was investigated in the context of safe disposal of radioactive waste. (125)I sorption experiments on ettringite, hydrotalcite, chloride-, carbonate- and sulfate-containing AFm phases indicated that calcium-monosulfate (AFm-SO(4)) is the only phase that takes up trace levels of iodide. The structures of AFm phases prepared by coprecipitating iodide with other anions were investigated in order to understand this preferential uptake mechanism. X-ray diffraction (XRD) investigations showed a segregation of monoiodide (AFm-I(2)) and Friedel's salt (AFm-Cl(2)) for I-Cl mixtures, whereas interstratifications of AFm-I(2) and hemicarboaluminate (AFm-OH-(CO(3))(0.5)) were observed for the I-CO(3) systems. In contrast, XRD measurements indicated the formation of a solid solution between AFm-I(2) and AFm-SO(4) for the I-SO(4) mixtures. Extended X-ray absorption fine structure spectroscopy showed a modification of the coordination environment of iodine in I-CO(3) and in I-SO(4) samples compared to pure AFm-I(2). This is assumed to be due to the introduction of stacking faults in I-CO(3) samples on one hand and due to the presence of sulfate and associated space-filling water molecules as close neighbors in I-SO(4) samples on the other hand. The formation of a solid solution between AFm-I(2) and AFm-SO(4), with a short-range mixing of iodide and sulfate, implies that AFm-SO(4) bears the potential to retard (129)I.

Soft X-ray spectromicroscopy of cobalt uptake by cement.

Scanning transmission X-ray microscopy was used to investigate the speciation and spatial distribution of Co in a Co(II)-doped cement matrix. The aim of this study was to improve the understanding of the heavy metals immobilization process in cement on the molecular level. The Co-doped cement samples hydrated for 30 days with a Co loading of 5000 mg/kg were prepared under normal atmosphere to simulate conditions used for cement-stabilized waste packages. Co 2p(3/2) absorption edge signals were used to determine the spatial distributions of the metal species in the Co(II)-doped cement. The speciation of Co was determined by collecting near-edge X-ray absorption fine structure spectra. On the basis of the shape of the absorption spectra, it was found that Co(II) is partly oxidized to Co(III). The correlation, respectively the anticorrelation with elements such as Al, Si, and Mn, show that Co(II) is predominantly present as Co-hydroxide-like phase as well as Co-phyllosilicate, whereas Co(III) tends to be incorporated only into a CoOOH-like phase. Thus, this study suggests that thermodynamic calculations of Co(II)-immobilization by cementitious systems should take into consideration not only the solubility of Co(II)-hydroxides but also Co(III) phases.