Coffinite formation from UO2+x.

Most of the highly radioactive spent nuclear fuel (SNF) around the world is destined for final disposal in deep-mined geological repositories. At the end of the fuel's useful life in a reactor, about 96% of the SNF is still UO2. Thus, the behaviour of UO2 in SNF must be understood and evaluated under the weathering conditions of geologic disposal, which extend to periods of hundreds of thousands of years. There is ample evidence from nature that many uranium deposits have experienced conditions for which the formation of coffinite, USiO4, has been favoured over uraninite, UO2+x, during subsequent alteration events. Thus, coffinite is an important alteration product of the UO2 in SNF. Here, we present the first evidence of the formation of coffinite on the surface of UO2 at the time scale of laboratory experiments in a solution saturated with respect to amorphous silica at pH = 9, room temperature and under anoxic conditions.

Interaction of uranium with in situ anoxically generated magnetite on steel.

In the high level nuclear waste repository concept, spent nuclear fuel is designed to be encapsulated in steel canisters. Thus, it is necessary to study the influence of the steel and/or its corrosion products on the behaviour of the radionuclides released from the fuel. In this sense, the main objective of this work is to contribute to the knowledge of the influence of the steel and/or its corrosion products on the uranium(VI) retention. To this aim, magnetite (Fe(3)O(4)) has been generated by anaerobic steel corrosion in an autoclave reactor at an overpressure of 8atm of H(2)(g). After characterisation by X-ray diffraction (XRD), the obtained corroded steel coupons were contacted, at two different H(2)(g) pressures (1atm and 7.6atm), with a U(VI) solution. The evolution of the uranium concentration in solution is determined and a study of the composition of the coupons at the end of the experiments is carried out. The main conclusion obtained from this work is that magnetite generated on a steel coupon is able not only to retain uranium via sorption, but also to reduce hexavalent to tetravalent uranium in a higher extent than commercial magnetite, thus, providing an effective retardation path to the migration of uranium (and, potentially, other actinides) out of the repository.

Sorption of Th(IV) onto iron corrosion products: EXAFS study.

Long-term performance assessment of nuclear waste repositories is affected by the ability of the outer barrier systems to retain radionuclides after possible corrosive leakage of waste containers. The mobility of the radionuclides released from the spent fuel depends strongly on the processes that take place in the backfill material. The interaction of steel corrosion products and radionuclides is part of such a scenario. In this work, the sorption of Th(IV) onto 2-line-ferrihydrite (FeOOH x H2O) and magnetite (Fe3O4), used as models for steel corrosion products, has been studied using EXAFS spectroscopy. Sorption samples were prepared in 0.1 M NaClO4 solutions at acidic pH (initial pH values in the range 3.0-4.2) either from undersaturation and supersaturation conditions with respect to amorphous ThO2. Two oxygen subshells, one at 2.37 A and another at 2.54 A, were observed in the first hydration sphere of Th in the case of the ferrihydrite samples. Th-Fe distances for the different ferrihydrite samples are approximately 3.60 A. These results indicate a corner sharing surface complex of Th(IV) ion onto the ferrihydrite surface where the Th atom shares one O atom with each of two coordinated octahedra. The longer Th-O distance accounts for coordinated water molecules. No significant changes in the structural environment of Th in terms of coordination numbers and distances were detected as a function of Th(IV) concentration. Magnetite samples sorbing Th(IV) also showed also a strong distortion of the O shell, but in contrast to ferrihydrite, two types of nearest Fe atoms were detected at 3.50 A and 3.70 A. These results indicate that Th(IV) ion sorbs onto the magnetite surface as bidentate-corner sharing arrangements to [FeO6] octahedra and [FeO4] tetrahedra.

DFT studies of uranyl acetate, carbonate, and malonate, complexes in solution.

The aim of this work is to demonstrate that theoretical chemistry can be used as a complementary tool in determining geometric parameters of a number of uranyl complexes in solution, which are not observable by experimental methods. In addition, we propose plausible structures with partial geometric data from experimental results. A gradient corrected DFT methodology with relativistic effects is used employing a COSMO solvation model. The theoretical calculations show good agreement with experimental X-ray and EXAFS data for the triacetato-dioxo-uranium(VI) and tricarbonato-dioxo-uranium(VI) complexes and are used to assign possible geometries for dicalcium-tricarbonato-dioxo-uranium(VI) and malonato-dioxo-uranium(VI) complexes. The results of this exercise indicate that carbonate bonding in these complexes is mainly bidentate and that hydroxo bridging plays a critical role in the stabilization of the polynuclear uranyl complexes.

Evidence of uranium and associated trace element mobilization and retention processes at Oklo (Gabon), a naturally radioactive site.

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.