Groundwater chemistry of the Okélobondo uraninite deposit area (Oklo, Gabon): two-dimensional reactive transport modelling.

The stability of uranium-bearing minerals in natural environments is of interest to evaluate the feasibility of radioactive waste repositories. The uraninite bodies, UO2(s), in the Oklo district (Gabon) are the result of a natural fission process, which took place 1970 Ma ago. These deposits can be regarded as natural analogues for spent fuel. One of the uraninite bodies, the Okélobondo deposit, is located at a depth of 300 m. Groundwater samples from boreholes located at shallow depths (100-200 m) show neutral to basic pH, anoxic conditions (Eh = 0.10 to -0.05 V) and are saturated with respect to uraninite. In contrast, deeper samples collected in the vicinity of the ore body are oxidising (Eh = 0.32-0.47 V), slightly basic (pH = 7.0-8.5) and undersaturated with respect to uraninite. These oxidising conditions at depth, if present under repository conditions, may affect the stability of uranium oxide. In order to improve our understanding of the observed site geochemistry, the available information on the lithology and groundwater flow was integrated in a reactive transport model. The chemical composition and the pH-Eh values of the water sampled above and in the western side of the Okélobondo deposit can be explained by the interaction of meteoric recharge with pelites, dolomites and sandstones. The dissolution of Fe(II)-silicates and the oxidation of the Fe(II)-aqueous species maintained the pH-Eh distribution along the Fe(2+)-Fe(OH)3(am) equilibrium, with the result that uraninite does not dissolve. This may explain the lower uranium content in the water samples from pelites and dolomites above the Okélobondo deposit. The high Mn/Fe ratio and the high pH-Eh values of the water sampled at depth, close to the Okélobondo deposit, suggest a control by the Mn(2+)-MnOOH(s) equilibrium. This control is attributed to the dissolution of a large rhodochrosite, MnCO3(s), and manganite, MnOOH(s) deposit in the recharge area on the eastern side.