Experimental sorption of Ni2+, Cs+ and Ln3+ onto a montmorillonite up to 150°C

The effect of temperature on the sorption of cations onto a dioctahedral smectite was investigated by running batch experiments at 25, 40, 80 and 150 degrees C. We measured the distribution coefficient (Kd) of Cs+, Ni2(+) and 14 lanthanides (Ln(3+)) between solutions and the montmorillonite fraction of the MX80 bentonite at various pH and ionic strengths. Up to 80 degrees C we used a conventional experimental protocol derived from Coppin et al. (2002). At 150 degrees C, the experiments were conducted in a PTFE reactor equipped with an internal filter allowing the sampling of clear aliquots of solution. The results show a weak but measurable influence of the temperature on the elements sorption. Kd's for Ni2+ and Ln(3+) increase by a factor 2 to 5 whereas temperature raises from 25 to 150 degrees C. This effect seems higher at high ionic strength. The estimated apparent endothermic sorption enthalpies are 33 +/- 10 kJ.mol(-1) and 39 +/- 15 kJ.mol(-1) for Ni2+ and Eu3+, respectively. On the other hand, the temperature effect on Cs+ sorption is only evidenced at low ionic strength and under neutral conditions where the Kd decreases by a factor 3 between 25 and 150 degrees C. Apparent exothermic sorption enthalpy for Cs+ on the montmorillonite is - 19 +/- 5 kJ.mol(-1). Experiments conducted at the four temperatures with the coexistence of all of the cations in the reacting solution (100 ppb of each element in the starting solution) or only one of them, produced similar values of Kd. This suggests the absence of competition between the sorbed cations, and consequently a low degree of saturation of the available sites. A fractionation of the lanthanides spectrum is also observed at high pH and high ionic strength whatever the temperature. The conclusion of this study is that the temperature dependence on sorption reflects, as the fractionation of REE or the pH and ionic strength effects, the chemical process which controls the overall reaction. In the case of an exchange dominated reaction (low pH and low ionic strength), the temperature effect is negligible. In the case of surface complexation (high pH and high ionic strength), the observed increase of Kd with temperature reflects either an increase of the sorption equilibrium constant with temperature or an endothermic property for reactions describing the montmorillonite surface chemistry. Copyright (c) 2005 Elsevier Ltd