Uranium dioxide dissolution under acidic aqueous conditions

Abstract

Understanding of the long-term dissolution of waste forms in groundwater is required for the safe disposal of high level nuclear waste in a geologic repository, because waste-form radionuclides could be released by dissolution and transported in groundwater. The dissolution of the uranium dioxide (UO{sub 2}) matrix in spent nuclear fuel is considered the rate-limiting step for release of radioactive fission products. The intrinsic UO{sub 2} dissolution rate sets an upper limit on the aqueous radionuclide release rate. Unsaturated spent fuel tests have shown that pH`s of leachates have decreased to a range of 4 to 6, presumably due to air radiolysis that oxidizes nitrogen, producing nitric acid. Dissolution rates under such acidic conditions may be different than those previously reported for alkaline groundwater conditions. No dissolution rate measurements of UO{sub 2} or spent fuel have been reported for acidic conditions possibly relevant to a geologic repository. The purpose of our work has been to measure the intrinsic dissolution rates of uranium dioxide under acidic conditions that are relevant to a repository and allow for modeling. Experiments have been completed at room-temperature and 75 C, pH`s of 4 and 6, and air and oxygen saturated aqueous solutions. These are compared with earlier work on spent fuel and UO{sub 2} using alkaline solutions