| Abstract: |
Batch experiments were conducted to study the sorption of uranium on selected clay minerals (KGa-1b and KGa-2 reference kaolinite, SWy-2 and STx-1b reference montmorillonite, and IBECO natural bentonite) as a function of pH (4–9) and 0.001, 0.01, and 0.025 M NaCl in equilibrium with the CO2 partial pressure of the atmosphere. Uranium concentrations were kept below 100 μg L−1 to avoid precipitation of amorphous Uranium-hydroxides. Solely PTFE containers and materials were used, because experiments showed significant sorption at higher pH on glass ware. All batch experiments were performed over a period of 24 h, since kinetic experiments proved that the common 10 or 15 min are in many cases by far not sufficient to reach equilibrium. Kaolinite showed much greater uranium sorption than the other clay minerals due to the more aluminol sites available. Sorption on the poorly crystallized KGa-2 was higher than on the well-crystallized KGa-1b. Uranium sorption on STx-1b and IBECO exhibited parabolic behavior with a sorption maximum around pH 6.5. Sorption of uranium on montmorillonites showed a distinct dependency on sodium concentrations because of the effective competition between uranyl and sodium ions, whereas less significant differences in sorption were found for kaolinite. The presence of anatase as impurity in kaolinite enhanced the binding of uranyl-carbonate complexes with surface sites. The kinetic of uranium sorption behavior was primarily dependent on the clay minerals and pH. A multisite surface complexation model without assuming exchange is based on the binding of the most dominant uranium species to aluminol and silanol edge sites of montmorillonite, respectively to aluminol and titanol surface sites of kaolinite. For eight surface species, the log_k was determined from the experimental data using the parameter estimation code PEST together with PHREEQC. |
