The solid-state chemistry of uranium is essential to the nuclear fuel cycle. Uranyl nitrate is a key compound that is produced at various stages of the nuclear fuel cycle, both in front-end and backend cycles. It is typically formed by dissolving spent nuclear fuel in nitric acid or through a wet conversion process for the preparation of UF6. Additionally, uranium oxides are a primary consideration in the nuclear fuel cycle because they are the most commonly used nuclear fuel in commercial nuclear reactors. Therefore, it is crucial to understand the oxidation and thermal behavior of uranium oxides and uranyl nitrates. Under the ‘2023 Nuclear Global Researcher Training Program for the Back-end Nuclear Fuel Cycle,’ supported by KONICOF, several experiments were conducted at IMRAM (Institute of Multidisciplinary Research for Advanced Materials) at Tohoku University. First, the recovery ratio of uranium was analyzed during the synthesis of uranyl nitrate by dissolving the actual radioisotope, U3O8, in a nitric acid solution. Second, thermogravimetric-differential thermal analysis (TG-DTA) of uranyl nitrate (UO2(NO3)2) and hyper-stoichiometric uranium dioxide (UO2+X) was performed. The enthalpy change was discussed to confirm the mechanism of thermal decomposition of uranyl nitrate under heating conditions and to determine the chemical hydrate form of uranyl nitrate. In the case of UO2+X, the value of ‘x’ was determined through the calculation of weight change data, and the initial form was verified using the phase diagram for the U-O system. Finally, the formation of a few UO2+X compounds was observed with heat treatment of uranyl nitrate and uranium dioxide at different temperature intervals (450°C-600°C). As a result of these studies, a deeper understanding of the thermal and chemical behavior of uranium compounds was achieved. This knowledge is vital for improving the efficiency and safety of nuclear fuel cycle processes and contributes to advancements in nuclear science and technology.

In nuclear power plants and nuclear facilities, radioactive waste containing hazardous substances (Mixed waste) is continuously generated due to research such as radiochemical study and nuclide analysis. In addition, radioactive waste including heavy metals and asbestos is generated during the dismantling process of nuclear power plants. Mixed wastes have both radiation hazards and chemical hazards, and there’s a possibility of synergistic effects generation. However, in most countries except the United States, there are no regulatory standards for the chemical hazards of mixed waste. The regulations applicable to mixed waste in Korea include the Nuclear Safety Act and the Waste Management Act. The Nuclear Safety Act prohibits the acceptance of hazardous radioactive waste in disposal facilities, but there is no definition or characteristic identification procedure for “hazardous.” The Waste Management Act also does not state the regulation for radioactive waste. In the Gyeongju disposal facility in Korea, the leachate in the disposal facility is expected to be a groundwater saturated with concrete and is expected to irradiated by radioactive waste. On the other hands, most of the non-radioactive waste landfill facilities are built on the surface, and the leachate is expected to be rainwater that reacts with the soil. Due to the differences in leaching environments, there’s a potential to overestimate or underestimate the leaching properties of hazardous substances if the standard leaching test is applied. To show for this, a leaching test simulating disposal facility’s environment were applied to sample waste containing heavy metals. The leaching solution was groundwater collected from the area near the Gyeongju disposal facility, which is then saturated with concrete and adjusted to pH 12.5. In addition, gamma-ray irradiation was conducted during the leaching test to observe changes in the leaching behavior of heavy metals in the actual radioactive waste disposal environment. As a result, lead showed significantly increased leaching compared to the standard test method, and cadmium was not detected in all experimental conditions except heavy irradiation. This study suggested that regulations on the hazardous of mixed waste should be settled, which should be established in sufficient consideration of the types and characteristics of substances contained in the waste.