Uranium redox chemistry and its importance in nuclear waste disposal

For the safety assessment of geological disposal of spent nuclear fuels, to predict and prevent migration of uranium in the geo-sphere is very important. Uranium can take oxidation states IV, V, and VI in aqueous solution. Its solubility differ several orders of magnitude depending on its oxidation state, but also depends strongly on pH and Eh of the solution and concentrations of co-existing organic/inorganic ligands. In this study, quantum chemical methods (MP2, CASPT2) were used to estimate the redox potential of the U(VI)/U(V) couple and the result was compared with experimental data. Similarly, An(VI)/An(V) redox potentials were also calculated for An = Np, Pu, and Am, and the importance of multi-configurational calculations and the role of spin-orbit effect were discussed.
Uranium may coordinate with various organic/inorganic ligands, and this is also a determining factor of the redox potential. We studied the complexation of uranium(VI) with several inorganic ligands (sulfate, carbonate, etc.) by DFT calculations and also by electrochemistry experiments. The structures of uranium complexes were characterized using EXAFS (extended X-ray absorption fine structure) spectroscopy at the Rossendorf Beamline, European Synchrotron Radiation Facility, in Grenoble, France. DFT and EXAFS were found to provide complementary structural information.