Reactions in the system basalt/simulated spent fuel/water

The Grande Ronde Basalts underlying the Hanford Site are being evaluated as a possible site for a high-level nuclear waste repository. Experiments, in which basalt from the Umtanum flow of the Grande Ronde Basalt and basalt with simulated spent fuel were reacted with synthetic Hanford groundwater, were conducted to determine steady state concentrations which can be used in radionuclide release-rate models. Tests were performed at temperatures of 1000, 2000, and 3000C; 30 MPa pressure, and a solution:solid mass ratio of 10:1 for durations up to 7000 hr. Solution aliquots were extracted periodically during the experiments for analysis. The pH was measured at 250C and recalculated to higher temperatures. In the basalt-water system the stable high-temperature pH values achieved were 7.2 (1000C), 7.5 (2000C), and 7.6 (3000C). Solution composition variations are due to mesostatis (glass) dissolution and precipitation of secondary phases. Solution measurements indicate a redox potential (Eh) of about -0.7 volts at 3000C. Secondary phases produced include silica, potassium feldspar, iron oxides, clays, scapolite, and zeolites. Tests in the basalt + simulated spent fuel + water system show that calculated pH values stabilized near 7.6 (1000C), 7.2 (2000C), and 7.7 (3000C). At higher temperatures, solution concentrations were controlled by secondary phases similar to those found in basalt-water tests. Less than 1% of uranium, thorium, samarium, rhenium, cerium, and palladium were released to solution while somewhat higher amounts of iodine, molybdenum, and cesium were released. The UO2 component was unreactive; however, other components (e.g., cesium-bearing phases) were almost completely dissolved. Secondary phases incorporating radionuclide-analog elements include clays, palladium sulfide, powellite, coffinite, and a potassium-uranium silicate. 11 references, 5 figures, 1 table