The aim of the present paper is to clarify previous results showing that selectivity coefficients determined for the exchange of Na(+) for Ca(2+) in montmorillonite were dependent on the solid/solution ratio. The organization of montmorillonite suspensions upon Na(+)/Ca(II) exchange was analyzed by combining optical microscopy, small-angle X-ray scattering and X-ray diffraction. All samples displayed flocculated characteristics, eliminating the possibility of contrasting accessibility of sorption sites with the solid/solution ratio. Modeling of experimental X-ray diffraction patterns was used to quantify the relative proportions of interlayer Ca(2+) and Na(+) cations along the exchange isotherm. The results further confirmed the influence of the solid/solution ratio on the degree of interlayer Ca(II)-for-Na(+) exchange, and specific selectivity coefficients for interlayer sites were determined. The effect of the solid/solution ratio was finally interpreted by the resulting local changes in the solution chemistry. We demonstrated that by accounting for the Donnan effect, the different data can be interpreted using a single selectivity coefficient. The obtained Kc constant was successfully applied to interpret existing hydrogeochemical data on a natural aquitard. This most likely represents a more constrained and valid approach for the modeling of reactive element transport in natural media than does the poorly defined Kd parameter.
Copyright © 2011 Elsevier Inc. All rights reserved.