Combined effects of Fe(II) and oxidizing radiolysis products on UO2 and PuO2 dissolution in a system containing solid UO2 and PuO2

The stability of UO2 spent nuclear fuel in an oxygen-free geological repository depends on the absence of oxidizing reaction partners in the near field. This work investigates the reactions between the products of water radiolysis by alpha radiation and Fe(II) an the effect on UO2 dissolution. Solid (PuO2)-Pu-238 powder and UO2 pellet were allowed to react in Fe(II) solution in oxygen-free batch reactor tests and kinetics of the subsequent redox reactions were measured. Depending on the concentration of Fe(II) (tests with 10(-5) and 10(-4) mol L-1 were made), the induced redox reactions took place between 20 and 400 h. Dissolved uranium concentrations went first through a minimum caused by reduction, followed by a maximum caused by radiolytic oxidation, and eventually reached another minimum, probably due to sorption on precipitated Fe(III). Plutonium concentrations were decreasing steadily after going through a maximum about 70 h from the start of the experiments. The results show that in the presence of the strong alpha-radiolytic field induced by the presence of solid Pu-238, the behavior of the system is largely governed by Fe(II) as it controls the H2O2 concentration, reduces U(VI) in solution and drives the Fenton reaction leading to the oxidation of Pu(IV). (C) 2012 Elsevier B.V. All rights reserved.