In the case of early canister failure, actinide chemistry in the near-field of a repository for the disposal of high-level radioactive waste (HLW) will be affected by elevated temperatures of up to 200☌, depending upon host-rock system and repository concept. These results provide new insights on the interlink between solubility, structure, surface and thermodynamics in the ThO 2(s, hyd)–H 2O(l) system, with special emphasis on the transformation of the amorphous hydrous/hydroxide solid phases into the thermodynamically stable crystalline oxides. Solubility data are used to derive the thermodynamic properties (log * K° s,0, Δ f G° m) of the investigated solid phases, and discussed in terms of particle size using the Schindler equation. These observations can be consistently explained considering a solubility control by the outermost surface of the ThO 2(s, hyd) solid, which cannot be properly probed by any of the techniques considered in this work.
In contrast to the observations gained by solid phase characterization, the ageing time and ageing pH significantly affect the solubility measured at T = 22☌. Solubility experiments conducted at T = 22☌ with fresh and aged Th(IV) solid phases show a systematic decrease in the solubility of the solid phases aged at T = 80☌. However, while clear differences between the structure of freshly precipitated ThO 2(am, hyd) and aged samples were observed, the characterization methods used in this work are unable to resolve clear differences between solid phases aged for different time periods or at different pH values.
TG-DTA and XPS support that the ageing process is accompanied by an important decrease in the number of hydration waters/hydroxide groups in the original amorphous Th(IV) hydrous oxide. XRD and EXAFS confirm that ageing of ThO 2(am, hyd) at T = 80☌ promotes a significant increase of the particle size and crystallinity. The impact of temperature on a freshly precipitated ThO 2(am, hyd) solid phase was investigated using a combination of undersaturation solubility experiments and a multi-method approach for the characterization of the solid phase.
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