Interpretation of dissolution behavior at the surface of uranium-zirconium oxide solid solutions

Tonna, Ryutaro*; Sasaki, Takayuki*; Okamoto, Yoshihiro; Kobayashi, Taishi*

Journal of Nuclear Materials, 612, p.155820_1 - 155820_11, 2025/06

https://doi.org/10.1016/j.jnucmat.2025.155820

The dissolution behavior of (U,Zr)O, the primary uranium solid phase in the fuel debris from the Fukushima Daiichi nuclear power plant accidents, was investigated thermodynamically and kinetically under atmospheric conditions. Cubic (U,Zr)O samples with a uniform solid solution of Zr were prepared using wet chemistry methods, and static batch immersion tests were conducted. In strongly acidic conditions, where the solubility of U and Zr exceeded their concentrations, congruent dissolution of both elements was observed with (U,Zr)O dissolving at the same rate as UO. In moderately acidic conditions, where the U solubility was higher than its concentration with Zr reaching a steady state at lower solubility, the U dissolution rate from (U,Zr)O decreased compared to UO. In the presence of oxalic acid, with increased Zr solubility due to the formation of complexes, the U dissolution rate from (U,Zr)O did not decrease. This indicates that Zr in (U,Zr)O formed a secondary solid phase on the solid surface under conditions of lower Zr solubility, which in turn suppressed the oxidative dissolution of U.

Dissolution behavior of calcium uranate under oxidizing and reducing conditions

Kato, Yuto*; Sasaki, Takayuki*; Tonna, Ryutaro*; Kobayashi, Taishi*; Okamoto, Yoshihiro

Applied Geochemistry, 175, p.106196_1 - 106196_9, 2024/11

https://doi.org/10.1016/j.apgeochem.2024.106196

Dissolution behavior and aging of iron-uranium oxide

Tonna, Ryutaro*; Sasaki, Takayuki*; Okamoto, Yoshihiro; Kobayashi, Taishi*; Akiyama, Daisuke*; Kirishima, Akira*; Sato, Nobuaki*

Journal of Nuclear Materials, 589, p.154862_1 - 154862_10, 2024/02

https://doi.org/10.1016/j.jnucmat.2023.154862

The dissolution behavior of FeUO compounds formed by a high-temperature reaction of UO with iron, a stainless-steel component of reactor structural materials, was investigated under atmospheric conditions. The compounds were prepared in an electric furnace using UO and FeO 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 concentration of nuclides dissolved in water was examined by performing static leaching tests of FeUO 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 FeUO 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 UO).

Research on the stability of fuel debris consisting of oxides and alloys, 10; Leaching behavior of nuclides from simulated fuel debris in the UO-Zr-SS system; Irradiation or addition method

Sasaki, Takayuki*; Tonna, Ryutaro*; Kobayashi, Taishi*; Akiyama, Daisuke*; Kirishima, Akira*; Sato, Nobuaki*; Watanabe, Masayuki; Kumagai, Yuta; Kusaka, Ryoji

no journal, , 

We synthesized simulated fuel debris which containing stainless steel and zirconium. The fission of Uranium by the irradiation of thermal neutron or non-radioactive elements was fed in the simulated fuel debris as fission products (FP), and the sample was immersed in pure water or artificial sea water. In this presentation, we would report the behavior of the solubility of the FP and the interpretation of its results.

Leaching behavior of simulated fuel debris in the UO-SUS system prepared by irradiation or tracer doping method

Sasaki, Takayuki*; Tonna, Ryutaro*; Kobayashi, Taishi*; Akiyama, Daisuke*; Kirishima, Akira*; Sato, Nobuaki*; Kumagai, Yuta; Kusaka, Ryoji; Watanabe, Masayuki

no journal, , 

Dissolution behavior of iron-uranium oxide

Tonna, Ryutaro*; Sasaki, Takayuki*; Okamoto, Yoshihiro; Kobayashi, Taishi*; Akiyama, Daisuke*; Kirishima, Akira*; Sato, Nobuaki*

no journal, , 

Since fuel debris recovered from the Fukushima Daiichi Nuclear Power Plant may be directly disposed of in deep geological strata, knowledge of dissolution reactions of fuel debris in water and chemical states of dissolved nuclides is essential for safety assessment of disposals. The chemical composition and physical properties of fuel debris depend on the atmosphere and temperature, but the formation of FeUO has been suggested at conditions under which air enters the reactor from outside. Uranium in FeUO is reported to be pentavalent, but no dissolution reaction in water has been investigated. In this study, FeUO was synthesized by heating at a predetermined temperature and oxygen pressure, immersed in nitric acid to remove unreacted uranium oxides, and then immersed in a solution of pH2-8. After the prescribed period, pH and Eh values were measured, and dissolved iron and uranium concentrations were measured by ICP-MS. X-ray absorption fine structure (XAFS) and powder X-ray diffraction (XRD) were used to evaluate the solid state before and after immersion. From these results, it was interpreted that the dissolution of FeUO was accompanied by a redox reaction between Fe(III)/Fe(II) and U(V)/U(VI) during dissolution.