Experimental study and modeling of the sorption of uranium(VI) onto olivine-rock

The sorption of U(VI) onto the surface of olivine has been experimentally investigated at 25 degreesC under an air atmosphere as a function of pH, solid surface to volume ratio and total U concentration. Sorption has been observed to decrease as the extent of carbonate complexation of U(VI) in solution increases, which is attributed to the competition between aqueous and solid ligands for the coordination of U. The experimental results have been interpreted by means of two different approaches: (1)a semi-empirical model, exemplified by the application of a Langmuir isotherm and (2) a non-electrostatic thermodynamic surface complexation model which includes the formation of the surface species: >SO-UO2+ and >SO-UO2(OH). The following stability constants for these species have been determined from the thermodynamic analysis: K(> SO-UO2+) = 289+/-71 and K(> SO-UO2(OH)) = (3.4+/-10.4)x10(-6). The comparison of the sorption of U onto olivine with granites of different origin indicate that the use of this mineral as additive to the backfill of deep high level nuclear waste repositories could retard the migration of U from the repository to the geosphere. (C) 2002 Elsevier Science Ltd. All rights reserved.