The fate of hydroxyl radicals produced during H2O2 decomposition on a SIMFUEL surface in the presence of dissolved hydrogen

Abstract

Over geologic timescales hydrogen peroxide will be one of the most important radiolytic oxidants challenging the spent fuel integrity in a deep repository. Consequently, the reaction between hydrogen peroxide and different kinds of UO2 based materials has been the subject of several studies over recent decades. Parts of these studies have investigated the effect of dissolved hydrogen on this reaction, as large amounts of hydrogen are expected to be produced by anoxic corrosion of iron in the deep repositories. In some of the studies hydrogen has been shown to offset the radiolysis-driven oxidative dissolution of the fuel despite the expected inertia of hydrogen at repository temperatures. However, the underlying mechanism is primarily based on the effect of the metallic particles contained in the spent fuel.One clue to the mechanistic understanding is whether or not a reaction takes place between dissolved hydrogen and hydroxyl radicals adsorbed to a fuel surface resulting from the decomposition of H2O2. In the study presented here this reaction could be confirmed in an autoclave system with SIMFUEL, a hydrogen peroxide spiked solution, and deuterium gas.The results show that the studied reaction does not only occur, but accounts for a substantial part of the hydrogen peroxide consumption in the system. Only a very minor part, 0.02%, of the total consumed hydrogen peroxide caused oxidative dissolution of the SIMFUEL. The conclusion is supported by quantitative measurements of HDO, dissolved U in solution and O2 in the gas phase.