Cation exchange capacity measurements on illite using the sodium and cesium isotope dilution technique: Effects of the index cation, electrolyte concentration and competition: Modeling

The isotope dilution technique using Na and Cs as index cations was used to determine the cation exchange capacity (CEC) of illite du Puy as a function of background electrolyte composition. The work showed, in accord with previous studies, that the CEC values were in the order Cs-CEC > Na-CEC. Sodium is commonly chosen as the index cation in CEC determinations using the isotope dilution method. The experimentally measured Na-CEC values for Na-illite increased from similar to75 to similar to200 meq kg(-1) for NaClO4 concentrations in the range 5.6 x 10(-4) to 1.25 x 10(-2) M. Cesium CEC determinations showed a much less pronounced trend over a CsNO3 concentration range from 10(-3) to 10(-2) M. A reference Cs-CEC value of 225 meq kg(-1) was chosen. Careful chemical analyses of the supernatant solutions revealed that Ca and Mg at the (sub)mumolar level were present in all the determinations, despite the extensive conditioning procedures used. Competition between (Ca + Mg) and Na for the exchange sites was put forward as an explanation for the variation of Na-CEC values. This hypothesis was confirmed in a series of single (Ca-45) and double (Ca-45 plus Na-22) labeling experiments. Calcium-sodium selectivity coefficients (K-Ca(Na)c) were calculated from the experimental data for NaClO4 concentrations from 5.6 x 10(-4) to 0.1 M and exhibited a variation from 1.6 to 14.3. A two-site cation exchange model was developed with site capacities and K-Ca(Na)c values for each site: planar site capacity = 180 meq kg(-1), K-Ca(Na)c(PS) = 2; type II site capacity = 45 meq kg(-1), K-Ca(Na)c(II) = 80. The model was able to predict the Na and Ca occupancies in the Na-CEC experiments over the whole range of NaClO4 concentrations. It is recommended that Cs should be used instead of Na as the index cation for determining the CEC of illite.