Abstract:
The microscopic reversibility of the sorption of Sm and Yb onto kaolinite and smectite is investigated by introducing an isotopic disequilibrium between the clay and the solution. The experiments are performed at 25°C, in 0.025 or 0.5 M NaClO4 and from pH 4 up to pH 7. The isotopic exchange is monitored as a function of time over a duration of 355 hours. The first stage of the experiment consists of equilibrating the clays with a natural or spiked lanthanide solution. The second stage consists of interchanging the solutions between twin phials (same clay, pH and ionic strength, but with different lanthanide isotopic compositions). The isotopic composition and concentration of aqueous lanthanides are analysed by ICP-MS. The results are as follows: (1) the lanthanide isotopic composition of the solution is rapidly modified and stabilised within 24 h; (2) the isotopic exchange between the solid and the solution is not always complete; (3) the degree of microscopic reversibility (isotopic exchange) decreases with increasing pH. These results are explained by the fact that exchange is easier for lanthanides linked to the surface as outer-sphere complexes (physical sorption), which predominate at low pH, than for atoms sorbed as inner-sphere complexes (chemical sorption) which predominate at high pH. The contrasted kinetics observed for the different kind of sites provide additional constraints for the modeling of migration processes in natural systems.
