The influence of bicarbonate concentration and ionic strength on peroxide speciation and overall reactivity towards UO 2 .

H 2 O 2 produced from water radiolysis is expected to play a significant role in radiation induced oxidative dissolution of spent nuclear fuel under the anoxic conditions of a deep geological repository if the safety-barriers fail and ground water reaches the fuel. It was recently found that the coordination chemistry between U(vi), HCO 3 2- and H 2 O 2 can significantly suppress H 2 O 2 induced dissolution of UO 2 in 10 mM bicarbonate. This was attributed to the much lower reactivity of the U(vi)O 2 2+ -coordinated O 2 2- as compared to free H 2 O 2 . We have extended the study to lower bicarbonate concentrations and explored the impact of ionic strength to elucidate the rationale for the low reactivity of complexed H 2 O 2 . The experimental results clearly show that dissolution of U(vi) becomes suppressed at [HCO 3 - ] < 10 mM. Furthermore, we found that the reactivity of the peroxide in solutions containing U(vi) becomes increasingly more suppressed at lower carbonate concentration. The suppression is not influenced by the ionic strength, which implies that the low reactivity of O 2 2- in ternary uranyl-peroxo-carbonato complexes is not caused by electrostatic repulsion between the negatively charged complex and the negatively charged UO 2 -surface as we previously hypothesized. Instead, the suppressed reactivity is suggested to be attributed to inherently higher stability of the peroxide functionality as a ligand to UO 2 2+ compared to as free H 2 O 2 .