Dissolution behavior and aging of iron–uranium oxide

Abstract

Understanding the dissolution behavior of the fuel debris is necessary for the safe decommissioning of Fukushima Daiichi Nuclear Power Plants. The dissolution behavior of FeUO4 compounds formed by a high-temperature reaction of UO2 with iron, a stainless-steel component of reactor structural materials, was investigated under atmospheric conditions. The compounds were prepared in an electric furnace using U3O8 and Fe3O4 as starting materials, and their solid states were analyzed using X-ray diffraction, scanning electron microscopy–energy-dispersive X-ray spectroscopy, and X-ray absorption fine-structure spectroscopy. The fission products were produced via thermal-neutron irradiation. The concentration of nuclides dissolved in water was examined by performing static leaching tests of FeUO4 compounds for up to three months. A redox reaction was proposed to occur between trivalent Fe and pentavalent U ions in the early stage of FeUO4 dissolution. It was thermodynamically deduced that the reduced divalent Fe ion was finally oxidized into a trivalent ion in the presence of dissolved oxygen, and iron hydroxide limited the solubility of Fe. Meanwhile, the concentration of hexavalent U (i.e., uranyl ion) was limited owing to the presence of secondary minerals such as metaschoepite and sodium uranate and subsequently decreased, possibly owing to sorption on Fe oxides, for example. The concentrations of multivalent ions of fission products, such as Ru and Ce, also decreased, likely for the reason above. By contrast, the concentration of soluble Cs ions did not decrease. The validity of this interpretation was supported by comparing the results with the dissolution behavior of a reference sample (Fe-free U3O8).