Interpretation of trace metal mobility in geological environments is often hampered by conflicting data from alternative experimental protocols and the lack of detailed mineralogical characterization of the host medium. To illustrate this issue, the release of uranium, thorium and the rare earth elements (REE) was investigated in polished rock slab samples from the U-Th deposit at the Palmottu Natural Analogue study site (SW Finland) by means of leaching experiments. The samples were sequentially leached with artificial groundwater of moderately high carbonate content at pH8, and nitric acid solutions at pH5 and pH3. The mineralogy and composition of the U, Th and REE mineral phases was studied using SEM-WDS and EDAX methods before and after each leaching step. In parallel, leaching was carried out on crushed material of the same samples and the leachates analysed by ICP-MS.
The most notable U minerals are uraninite, uranophane and two secondary U-Pb phases. Thorium occurs predominantly in monazite and at lower concentrations in uraninite. Accessory thorite is also present, which together with monazite contains most of the REE. Differential leaching of the elements was noted across all phases on the timescale of the experiments. Uraninite is partly dissolved at pH3. The main secondary uranium phase, uranophane, was stable in moderately acidic solution, but easily dissolved in the artificial groundwater and at pH3. Some release of REE was observed although the main REE-bearing phase, monazite, showed no evidence of degradation.
This study provides insights in the preferential release of radionuclides in granitic bedrock. An understanding of these processes is essential when assessing the safety of a spent fuel repository. Once released from the primary waste form U is expected to precipitate as secondary phases within micro fractures, as observed at Palmottu and numerous other deposits.