Durability of U-Zr oxide solid solution in aqueous HO solution

Kumagai, Yuta   ; Kusaka, Ryoji  ; Takano, Masahide ; Watanabe, Masayuki   

Uranium-zirconium oxide solid solution, (U, Zr)O, is a representative matrix phase found in fuel debris formed during severe nuclear reactor accidents. Understanding its chemical behavior in oxidative aqueous environments is important for evaluating the potential release of radionuclides during water contact. In this study, we investigated the reactivity of (U, Zr)O with hydrogen peroxide (HO) in pure water to assess its resistance to oxidative dissolution, because HO is the dominant oxidant produced by water radiolysis. The dissolution behavior of uranium and zirconium was monitored through repeated HO exposure experiments, and the solid phases were characterized using Raman micro-spectroscopy and X-ray diffraction. Kinetic modeling was performed to interpret experimental data. The results showed that uranium dissolution occurred initially but decreased significantly upon repeated HO exposure, while zirconium dissolution proceeded more slowly. Raman analysis revealed only minor surface changes, with limited formation of uranyl peroxide phases. The kinetic simulation reproduced the experimental trends by assuming a small fraction of redox-active surface sites. These findings suggest that the observed durability of (U, Zr)O against HO-induced oxidative dissolution is not due to the formation of a protective surface layer, but rather reflects the limited redox reactivity of most of the surface. This study provides a quantitative basis for understanding the HO-induced oxidation of (U, Zr)O in water, relevant to the long-term behavior of fuel debris.