Europium sorption on zirconia at elevated temperatures: experimental study and modeling

Full text of publication follows: Direct disposal of spent nuclear fuel in deep underground repository is being considered by several countries. The waste package maintains an elevated temperature for thousands of years. As sorption is one of the main phenomenon limiting the dispersion of radionuclides in the environment, it has to be studied at elevated temperatures. Zirconia is an oxide produced by cladding oxidation which is suspected in the near field of a nuclear repository. It then could possibly be in contact with waste elements as Europium (III), the sorption of which is therefore studied on zirconia. Experiments were performed by the batch method at a solid/liquid ratio of 10 g.L-1. The sorption edges were recorded in the pH-range from 2 to 10 at 2.10-5 mol.L-1 Eu(NO3)3 (I = 0.1 mol.L-1 KNO3). An over-pressure device in an autoclave with an incorporated filtering system allowed the experiments, carbonate free, at 25 deg. C, 50 deg. C, 80 deg. C, 120 deg. C and 150 deg. C and in situ pH measurements. Filtrates were analyzed by the ICP-AES method. Sorption isotherms show an increase in the sorption phenomenon when the temperature raises. The half sorption pH decreases from 7 at 25 deg. C to 3,6 at 150 deg. C. The distribution coefficients that were obtained at elevated temperatures enriched the databases of integrated performance assessment codes. Raw data were modeled with the surface complexation theory using the double layer model (DLM). Several possible surface complexes were examined and discussed, taking into account aqueous hydrolyzed and precipitated species of Europium. A good agreement between experimental values and modeled isotherms was found at all studied temperatures. Results were consistent with a bidentate complex formed by Europium (III) on the zirconia surface. Associated formation constants were then determined with the geochemical computer code CHESS. (authors)