We present a two-step procedure for treating contaminated liquid waste generated during the processing of uranium, specifically residual uranium-contaminated liquid after precipitation. After precipitating U(IV) as sodium diuranate under alkaline conditions, the resulting solution was solidified by immobilising it in an alkali-activated material. Static leaching tests indicated excellent material stability in water. Exposing the material to aggressive chemical conditions (nitric acid) resulted in slow and incomplete dissolution of uranium (and of structural elements) from a thin superficial layer with further passivation. Characterisation of the solid phase was performed to assess the stability of the alkali-activated material under the tested conditions.

We show that a homogeneous single-phase mixed oxide is obtained by blending and sintering commercial UO₂ and nanocrystalline PuO₂ powder; whereas, under the same conditions, conventional PuO₂ powder obtained from oxalate precipitation and composed of platelets, yields two-phase mixed oxide. The use of nanometric PuO₂ results in a larger final grain size.

We compare typical reductive sintering conditions for U, Pu mixed oxides (4 h at 1700 °C in Ar/6 % H2 + 1200 ppm H2O) with lower temperature and mildly oxidative conditions (2 h at 1200 °C in CO/CO2 = 1/9) and report on the resulting microstructures and homogeneity. We show that lower temperature and mildly oxidative conditions, without cover gas change, can give close-to stoichiometric, crack-free MOX pellets with a relative density of ∼ 95 %, and we propose ways to improve the homogenisations of PuO2 and UO2 and increase the grain size.

The low-temperature heat capacity of (U_1−yTh_y)O₂ and ²³⁸Pu-doped UO₂ samples were determined using hybrid adiabatic relaxation calorimetry. Results of the investigated systems revealed the presence of the magnetic transition specific for UO₂ in all three intermediate compositions of the uranium-thorium dioxide (y = 0.05, 0.09 and 0.12) and in the ²³⁸Pu-doped UO₂ around 25 K. The magnetic behaviour of UO₂ exposed to the high alpha dose from the ²³⁸Pu isotope was studied over time and it was found that 1.6% ²³⁸Pu affects the magnetic transition substantially, even after short period of time after annealing. In both systems the antiferromagnetic transition changes intensity, shape and Néel temperature with increasing Th-content and radiation dose, respectively, related to the increasing disorder on the crystal lattice resulting from substitution and defect creation.

The physicochemical properties of the potassium neptunate K₂NpO₄ have been investigated in this work using X-ray diffraction, X-ray absorption near edge structure (XANES) spectroscopy at the Np-L₃ edge, and low-temperature heat capacity measurements. A Rietveld refinement of the crystal structure is reported for the first time. The Np(VI) valence state has been confirmed by the XANES data, and the absorption edge threshold of the XANES spectrum has been correlated to the Mössbauer isomer shift value reported in the literature. The standard entropy and heat capacity of K₂NpO₄ have been derived at 298.15 K from the low-temperature heat capacity data. The latter suggest the existence of a magnetic ordering transition around 25.9 K, most probably of the ferromagnetic type.

The electronic structure of U^V- and U^VI-containing uranates NaUO₃and Pb₃UO₆was studied by using an advanced technique, namely X-ray absorption spectroscopy (XAS) in high-energy-resolution fluorescence-detection (HERFD) mode. Due to a significant reduction in core–hole lifetime broadening, the crystal-field splittings of the 5f shell were probed directly in HERFD-XAS spectra collected at the U 3d edge, which is not possible by using conventional XAS. In addition, the charge-transfer satellites that result from U 5f–O 2p hybridization were clearly resolved. The crystal-field parameters, 5f occupancy, and degree of covalency of the chemical bonding in these uranates were estimated by using the Anderson impurity model by calculating the U 3d HERFD-XAS, conventional XAS, core-to-core (U 4f–3d transitions) resonant inelastic X-ray scattering (RIXS), and U 4f X-ray photoelectron spectra. The crystal field was found to be strong in these systems and the 5f occupancy was determined to be 1.32 and 0.84 electrons in the ground state for NaUO₃and Pb₃UO₆, respectively, which indicates a significant covalent character for these compounds.