Oxidizing dissolution of spent MOX47 fuel subjected to water radiolysis: Solution chemistry and surface characterization by Raman spectroscopy

The mechanisms of oxidizing dissolution of spent MOX fuel (MIMAS TU2(R)) subjected to water radiolysis were investigated experimentally by leaching spent MOX47 fuel samples in pure water at 25 degrees C under different oxidizing conditions (with and without external gamma irradiation); the leached surfaces were characterized by Raman spectroscopy. The highly oxidizing conditions resulting from external gamma irradiation significantly increased the concentration of plutonium (Pu(V)) and uranium (U(VI)) compared with a benchmark experiment (without external irradiation). The oxidation behavior of the plutonium-enriched aggregates differed significantly from that of the UO2 matrix after several months of leaching in water under gamma irradiation. The plutonium in the aggregates appears to limit fuel oxidation. The only secondary phases formed and identified to date by Raman spectroscopy are uranium peroxides that generally precipitate on the surface of the UO2 grains. Concerning the behavior of plutonium, solution analysis results appear to be compatible with a conventional explanation based on an equilibrium with a Pu(OH)(4(am)) phase. The fission product release - considered as a general indicator of matrix alteration - from MOX47 fuel also increases under external gamma irradiation and a change in the leaching mode is observed. Diffusive leaching was clearly identified, coinciding with the rapid onset of steady-state actinide concentrations in the bulk solution. (C) 2010 Elsevier B.V. All rights reserved.