Geochemical Behaviour of Uranium in Sedimentary Formations: Insights From a Natural Analogue Study

Groundwater data from the natural analogue site Ruprechtov have been evaluated with special emphasis on the uranium behaviour in the so-called uranium-rich clay/lignite horizon. In this horizon in-situ Eh-values in the range of −160 to −280 mV seem to be determined by the $SO42−$/HS⁻ couple. Under these conditions U(IV) is expected to be the preferential redox state in solution. However, on-site measurements in groundwater from the clay/lignite horizon show only a fraction of about 20% occurring in the reduced state U(IV). Thermodynamic calculations reveal that the high CO₂ partial pressure in the clay/lignite horizon can stabilise hexavalent uranium, which explains the occurrence of U(VI). The calculations also indicate that the low uranium concentrations in the range between 0.2 and 2.1μg/l are controlled by amorphous UO₂ and/or the U(IV) phosphate mineral ningyoite. This confirms the findings from previous work that the uranium (IV) mineral phases are long-term stable under the reducing conditions in the clay/lignite horizon without any signatures for uranium mobilisation. It supports the current knowledge of the geological development of the site and is also another important indication for the long-term stability of the sedimentary system itself, namely of the reducing geochemical conditions in the near-surface (30m to 60 m deep) clay/lignite horizon. Further work with respect to the impact of changes in redox conditions on the uranium speciation is on the way.