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- Bauhn, Lovisa, 1981, et al.
(författare)
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The fate of hydroxyl radicals produced during H2O2 decomposition on a SIMFUEL surface in the presence of dissolved hydrogen
- 2018
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Ingår i: Journal of Nuclear Materials. - : Elsevier BV. - 0022-3115. ; 507, s. 38-43
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Tidskriftsartikel (refereegranskat)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 UO 2 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 H 2 O 2 . 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 O 2 in the gas phase.
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- Bauhn, Lovisa, 1981, et al.
(författare)
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The interaction of molecular hydrogen with α-radiolytic oxidants on a (U,Pu)O2 surface
- 2018
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Ingår i: Journal of Nuclear Materials. - : Elsevier BV. - 0022-3115. ; 505, s. 54-61
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Tidskriftsartikel (refereegranskat)abstract
- In order to assess the impact of α-radiolysis of water on the oxidative dissolution of spent fuel, an un-irradiated, annealed MOX fuel pellet with high content of Pu (∼24 wt%), and a specific α-activity of 4.96 GBq/g MOX , was leached in carbonate-containing solutions of low ionic strength. The high Pu content in the pellet stabilizes the (U,Pu)O 2 (s) matrix towards oxidative dissolution, whereas the α-decays emitted from the surface are expected to produce ∼3.6 × 10 −7 mol H 2 O 2 /day, contributing to the oxidative dissolution of the pellet. Two sets of leaching tests were conducted under different redox conditions: Ar gas atmosphere and deuterium gas atmosphere. A relatively slow increase of the U and Pu concentrations was observed in the Ar case, with U concentrations increasing from 1·10-6 M after 1 h to ∼7 × 10-5 M after 58 days. Leaching under an atmosphere starting at 1 MPa deuterium gas was undertaken in order to evaluate any effect of dissolved hydrogen on the radiolytic dissolution of the pellet, as well as to investigate any potential recombination of the α-radiolytic products with dissolved deuterium. For the latter purpose, isotopic analysis of the D/H content was carried out on solution samples taken during the leaching. Despite the continuous production of radiolytic oxidants, the concentrations of U and Pu remained quite constant at the level of ∼3 × 10-8 M during the first 30 days, i.e. as long as the deuterium pressure remained higher than 0.8 MPa. These data rule out any oxidative dissolution of the pellet during the first month. The un-irradiated MOX fuel does not contain metallic ε-particles, hence it is mainly the interaction of ra diolytic oxidants and dissolved deuterium with the surface of the mixed actinide oxide that causes the neutralization of the oxidants. This conclusion is supported by the steadily increasing levels of HDO measured in the leachate samples.
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