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

The mechanisms for the reduction and uptake of Tc by magnetite (Fe3O4) and mackinawite (FeS) are investigated using X-ray absorption spectroscopy (XANES and 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 under strictly anoxic conditions using freshly prepared magnetite and mackinawite in 0.1 M NaCl solutions with varying initial Tc(VII) concentrations (2 × 10−5 and 2 × 10−4 M) and Tc loadings (400–900 ppm). XANES confirms the complete reduction of Tc(VII) to Tc(IV) in all investigated systems, as predicted from experimental (pHm + pe) measurements and thermodynamic calculations. Two Tc endmember species are identified by EXAFS in the magnetite system, Tc substituting for Fe in the magnetite structure and Tc–Tc dimers sorbed to the magnetite {111} faces through a triple bond. The sorption 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 at lower pH values. A TcSx-like phase is predominant 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 highly relevant contribution to the investigation of Tc retention processes in the context of nuclear waste disposal

Thermodynamic description of U(IV) solubility and hydrolysis in chloride systems: Pitzer activity model for the system U4+^{4+}–Na+^+–Mg2+^{2+}–Ca2+^{2+}–H+^+–Cl−^-–OH−^-–H2_2O(l)

This study presents updated chemical, thermodynamic, and activity models for the system U$^{4+}$–Na$^+$–Mg$^{2+}$–Ca$^{2+}$–H$^+$–Cl$^-$–OH$^-$–H$_2$O(l)derived using the Pitzer formalism and a strict ion interaction approach. The models build on comprehensive solubility datasets in dilute to concentrated NaCl, MgCl$_2$, and CaCl$_2$ solutions. The Nuclear Energy Agency-Thermochemical Database (NEA-TDB) selection of solubility and hydrolysis constants in the reference state were taken as anchoring point, and were extended further with the solid nanocrystalline phase UO$_2$∙H$_2$O(ncr) and the ternary complex Ca$_4$[U(OH)$_8$]$^{4+}$. The former was identified in long-term solubility experiments at ambient conditions, whereas the latter has been selected in analogy to Th(IV), Np(IV), and Pu(IV) considering experimental evidences available for these An(IV) in alkaline, concentrated CaCl$_2$ solutions. These models represent an improved tool for the calculation of U(IV) solubility and aqueous speciation in a variety of geochemical conditions including concentrated brine systems relevant in salt-based repositories for nuclear waste disposal

Recent advances in the aqueous chemistry of the calcium(II)-gluconate system – Equilibria, structure and composition of the complexes forming in neutral and in alkaline solutions

Of the sugar carboxylates, D-gluconate is clearly the most significant representative: the world’s annual production of this organic compound is estimated to be in the order of 10$^{5}$ tonnes. The reason of its mass production is due to its outstandingly broad range of practical (medical, pharmaceutical, industrial, etc.) applications. D-gluconate is a well-known and exceptionally popular complexing agent; accordingly, it has been the subject of a large number of coordination chemical research investigations. Its complexation properties are specially remarkable in alkaline to hyperalkaline pH conditions, where the deprotonation of one or more of its alcoholic OH groups provides a favourable frame for the formation of very stable chelate complexes with a large variety of metal cations. With the aim to show the state of the art of some relevant issues in the aqueous chemistry of the D-gluconate ion, the current paper focusses on the acidbase properties and calcium(II) complexation of the compound encompassing the entire experimentally available pH-range in water. The accessible literature on the deprotonation of carboxylic and alcoholic OH groups is collected and critically evaluated. The lactonization equilibria of D-gluconic acid are also scrutinized. The available data on the calcium complexes forming in neutral and in (hyper)alkaline solutions (both in terms of composition, formation constants and solution structure) are also discussed. Where feasible, some of these properties are compared with those of D-glucose and its derivatives as well as some less common sugar carboxylates, structurally related to D-gluconate, (i.e., D-heptagluconate, Lgulonate and α-D-isosaccharinate). Special emphasis is laid on the relationship between complex stability and the type of metal-binding groups