Calcium silicate hydrate (C-S-H) is the main product of cement hydration and has also been shown to be the main sorbing phase of actinide ions interacting with cement. U(IV) has been chosen as an exemplary actinide ion to study actinide sorption at C-S-H as U is the main element in highly active radioactive waste and because reducing conditions are foreseen in a deep geological repository for such waste. U(IV) surface adsorption, absorption in the interlayer, and incorporation into the calcium oxide layer of C-S-H has been modeled quantum mechanically, applying a density functional approach. For each sorption mode various sites have been considered and a combined dynamic equilibration and optimization approach has been applied to generate a set of representative stable sorption complexes. At the surface and in the interlayer similar U(IV) hydroxo complexes stabilized by Ca²⁺ ions have been determined as sorbates. Surface adsorption tends to be preferred over absorption in the interlayer for the same type of sites. Incorporation of U(IV) in the CaO layer yields the most favorable sorption site. This result is supported by good qualitative agreement of structures with EXAFS results for other actinides in the oxidation state IV, leading to a new interpretation of the experimental results.

Organophosphonates have manifold applications in the chemical industry, of which one of the most commonly used is 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC). It is widely used as a cement additive and may pose a potential risk of complexing radionuclides such as uranium in nuclear waste repositories. PBTC, in its fully deprotonated form, has four negatively charged groups, one phosphonate and three carboxylate groups, which makes it a superior ligand for metal ion complexation. In this study, for the first time, its complexation behavior towards hexavalent uranium, U(VI), in the pH range from 2 to 11, has been investigated using various spectroscopic methods. The structure-sensitive methods NMR, IR, and Raman spectroscopy were used to characterize the complex structure. The interpretation of the results was supported by density functional calculations. Over almost the entire pH range studied, U(VI) and PBTC form a chelate complex via the phosphonate and the geminal carboxylate group, highlighting the strong chelating ability of the ligand. UV-Vis spectroscopy combined with factor analysis was applied to determine the distribution of differently protonated chelate species and their stability constants. Time-resolved laser-induced luminescence spectroscopy (TRLFS) was additionally used as a complementary method.

To date, published studies have proven that the reactions at the iron/bentonite interface are complex and only partly understood. In the present study, mixtures of bentonite powder and iron powder were prepared, which allowed for varying individual parameters. The results confirmed some controversial previously reported conclusions and revealed new findings. More specifically, Na-exchanged samples showed a reduced extent of corrosion compared to Ca/Mg-exchanged ones, and the addition of reactive silica increased the extent of corrosion, which has not been reported to date. The negative temperature effect (less corrosion at higher temperatures), which was reported previously, could only be confirmed for Ca/Mg-bentonites. One Na-bentonite showed the opposite effect, but this sample also contained reactive silica in contrast to the others. The present study proves for the first time that the type of exchangeable cation can affect the type of corrosion product, which could be an explanation for why the 7 Å corrosion product was not reported in all corrosion tests (sometimes only magnetite was reported). In addition, experiments that ran for 36 months showed that the corrosion progress of six different bentonites was different. Three bentonite/iron mixtures did not show progress in corrosion after 12 months, whereas the other three showed ongoing corrosion. Using the former three bentonite/iron mixtures would significantly increase high-level radioactive waste canister lifetime, but future work should be devoted to the identification of the reason for this differing long-term performance, differing thermal behaviour and differing corrosion products resulting from different types of exchangeable cation.