Systematic XAS study on the reduction and uptake of Tc by magnetite and mackinawite


Systematic XAS study on the reduction and uptake of Tc by magnetite and mackinawite

Yalcintas, E.; Scheinost, A. C.; Gaona, X.; Altmaier, M.

Abstract

The mechanisms for the reduction and uptake of Tc by magnetite (Fe3O4) and mackinawite (FeS) are investigated using XAS techniques (XANES, EXAFS), in combination with thermodynamic calculations of the Tc/Fe systems and accurate characterization of the solution properties (pHm, pe, [Tc]). Batch sorption experiments were performed in the presence of freshly prepared magnetite and mackinawite in 0.1 M NaCl solutions with varying [Tc(VII)]0 (2·10–5 – 2·10–4 M) and loading of Tc (400–900 ppm ). XANES confirms the complete reduction of Tc(VII) to Tc(IV) in all investigated systems, as predicted by experimental (pHm + pe) measurements and thermodynamic calculations. Two Tc pure endmember species are identified by EXAFS in the magnetite system, corresponding to fully incorporated Tc in the magnetite structure and (likely) to a Tc-Tc dimeric structure with triple-bonding to the magnetite {111} faces. The latter endmember is favoured at higher [Tc], whereas incorporation prevails at low [Tc] and less alkaline pH conditions. The key role of pH in the uptake mechanism is interpreted in terms of magnetite solubility, with higher [Fe] and greater recrystallization rates occurring with decreasing pH values. A TcS2-like phase prevails in all investigated mackinawite systems, although the contribution of up to  20% of TcO2xH2O(s) (likely as surface precipitate) is observed for the highest investigated loadings (900 ppm). These results provide key inputs for an accurate mechanistic interpretation of the Tc uptake by magnetite and mackinawite, so far controversially discussed in the literature, and represent a very relevant contribution in the context of nuclear waste disposal.

Keywords: Tc; nuclear waste; XAS; XAFS; XANES; magnetite; mackinawite

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