The influence of near field hydrogen on actinide solubilities and spent fuel leaching

Abstract

Large amounts of hydrogen are produced as a result of the anoxic corrosion of iron in the proposed container materials for some geologic repositories. Another hydrogen source, less important than the anoxic corrosion of iron, is the radiolysis of water by the spent fuel radiation. Gas phase formation occurs when the pressure of the hydrogen equals at least the hydrostatic pressure, around 5 MPa at 500 meters depth. The effects of 5 MPa hydrogen pressure on spent PWR fuel leaching and on uranium oxide solubility have been studied in carbonated solutions at 70 °C. The experiments were performed in a 1 liter autoclave, filled with 950 ml of a solution 10 mM NaCl, 2 mM NaHCO3 and with hydrogen at a pressure of 5 MPa in the remaining 50 ml free volume. The leaching behavior of 2 g PWR spent fuel powder of the 0.25-0.50 mm fraction, placed in a gold basket was studied during several months by analyzing 10 ml solution samples taken after regular time intervals. A few experiments were performed also with unirradiated U(IV) oxide. In both cases extremely low concentrations of uranium (less than 10-9 M were measured in the solution samples. Furthermore the uranium levels in solution remained practically constant during the whole leaching period (more than one year), indicating the absence of any oxidative dissolution of the spent fuel matrix. The same conclusion is confirmed by the constant (within analytical errors) levels of strontium, cesium, molybdenum, iodine and technetium during the whole leaching period. These results have been compared with the ones obtained during the leaching of a spent fuel pin in anoxic conditions, where the uranium and other radionuclides levels are several orders of magnitude higher. The surface of spent fuel or U(IV) oxide is partially oxidized during storage, giving rise to relatively high levels of U(VI) in solution even during leaching in anoxic conditions. No such effect could be observed in the presence of 5 MPa hydrogen, indicating that this initial amount of U(VI) should have been reduced to U(IV). The experimental study of the influence of various parameters as temperature and pressure is still in progress.