Cesium adsorption on clay minerals: an EXAFS spectroscopic investigation

Cesium adsorption on the clay minerals vermiculite and montmorillonite is described as a function of surface coverage using extended X-ray adsorption fine structure spectroscopy (EXAFS). Cesium (Cs) possessed a variable coordination environment consisting of Cs-O distances between 3.2 and 4.3 A; however, disorder typical of the Cs coordination environments prevented the resolution of all oxygen shells. On the basis of the influence of Cs loading and exchangeability on this structural arrangement, we could recognize both inner-sphere and outer-sphere adsorption complexes. The shorter Cs-O bond distance belongs to outer-sphere complexes typical of hydrated ions. In inner-sphere complexes, partially or fully dehydrated Cs coordinates directly to siloxane groups of the clay minerals forming longer Cs-O bonds. The inner-sphere adsorption complexes may have occurred within the interlayer or at frayed edge sites and were less extractable than the outer-sphere complexed Cs. Both coordination number ratios and linear combination fitting of EXAFS spectra were useful in estimating the fractions of inner-sphere and outer-sphere adsorption complexes. Our results show that X-ray absorption spectroscopy (XAS), and particularly EXAFS, is a valuable technique for exploring the type of Cs binding in environmental samples.