No abstract

The thermodynamic and kinetic dissolution properties of a synthetically obtained soddyite have been determined at different bicarbonate concentrations. This uranium-silicate is expected to be a secondary solid phase of the oxidative alteration pathway of uranium dioxide in waters with low phosphate content and, consequently, it is likely to constitute one of the long-term uranium solubility limiting solid phases.The experimental data obtained at the end of the experiments correspond fairly well to the theoretical model calculated with a log K0S0 of 3.9±0.7.On the other hand, the general trend of the total uranium in solution measured in the experiments as a function of time has been fitted by using a kinetic equation obtained from the principle of detailed balancing of the dissolution reaction. In addition, the EQ3/6 code has also been used to model the uranium concentrations as a function of time. In both modeling exercises comparable results were obtained. The dissolution rate, normalized to the total surface area used in the experiments as measured with the BET method, gave an average value of 6.8 (±4.4) 10−14 mol cm−2 s−1.

The processes that affect the mobility of uranium and other radionuclides in the environment have been largely studied at both the laboratory and the field scales. The natural reactors found at the Oklo uranium mine in Gabon constitute a unique investigation setting as spontaneous fission reactions occurred two billion years ago. Oklo uraninites contain a large amount of other radionuclides as a result of the fission process. We have investigated the dissolution behavior of four uraninite samples from Oklo as a function of temperature (25 and 60 degrees C) and bicarbonate concentration (2.7-30 mmol/L). We have also investigated the dissolution behavior of minor components of the uraninites (i.e., Nd, Cs, Mo, Yb, and Sb) in relation to the dissolution of uranium. The results of the reported work are in good agreement with the kinetic rate laws derived from other uranium(IV) dioxide studies. Some of the minor components are found to be congruently released from the uraninite phase, while it is postulated that dissolution from segregated phases might affect the final concentrations of some of the rare earth elements, i.e., Nd and Yb. In addition, we have performed dissolution studies at 60 degrees C with two uraninites representative of different geochemical environments at Oklo, to study the uranium dissolution rates as a function of the temperature. This has allowed derivation of apparent activation energies for the bicarbonate-promoted oxidative dissolution of the Oklo uraninites. The dissolution behavior of the minor components of the uraninites at 60 degrees C was found to closely follow the behavior observed at 25 degrees C. This indicates that similar codissolution mechanisms operate in the temperature range studied. The implications for the mobility of uranium and other radionuclides in natural and anthropogenic environments are discussed.