Investigations towards incorporation of Eu3+ and Cm3+ during ZrO2 crystallization in aqueous solution

Abstract

Nuclear energy provides a widely applied carbon-reduced energy source. Following operation, the spent nuclear fuel (SNF), containing a mixture of radiotoxic elements such as transuranics, needs to be safely disposed of. Safe storage of SNF in a deep geological repository (DGR) relies on multiple engineered and natural retention barriers to prevent environmental contamination. In this context, zirconia (ZrO2) formed on the SNF rod cladding, could be employed as an engineered barrier for immobilization of radionuclides via structural incorporation. This study investigates the incorporation of Eu3+ and Cm3+, representatives for trivalent transuranics, into zirconia by co-precipitation and crystallization in aqueous solution at 80 °C. Complementary structural and microstructural characterization has been carried out by powder X-ray diffraction (PXRD), spectrum imaging analysis based on energy-dispersive X-ray spectroscopy in scanning transmission electron microscopy mode (STEM-EDXS), and luminescence spectroscopy. The results reveal the association of the dopants with the zirconia particles and elucidate the presence of distinct bulk and superficially incorporated species. Hydrothermal aging for up to 460 days in alkaline media points to great stability of these incorporated species after initial crystallization, with no indication of phase segregation or release of Eu3+ and Cm3+ over time. These results suggest that zirconia would be a suitable technical retention barrier for mobilized trivalent actinides in a DGR.