The present work reports experimental data for trivalent metal cation (Cm/Eu) sorption onto illite (Illite du Puy) and montmorillonite (Na-SWy-2) in NaCl solutions up to 4.37molal (m) in the absence of carbonate. Batch sorption experiments were carried out for a given ionic strength at fixed metal concentration (mEu=2×10-7m, labeled with152Eu for γ-counting) and at a constant solid to liquid ratio (S:L=2g/L) for 3<pHm<12 (pHm=-logmH+). The amount of clay sorbed Eu approaches almost 100% (with logKD>5) for pHm>8, irrespective of the NaCl concentration. Variations in Eu uptake are minor at elevated NaCl concentrations. Time-resolved laser fluorescence spectroscopy (TRLFS) studies on Cm sorption covering a wide range of NaCl concentrations reveal nearly identical fluorescence emission spectra after peak deconvolution, i.e. no significant variation of Cm surface speciation with salinity. Beyond the three surface complexes already found in previous studies an additional inner-sphere surface species with a fluorescence peak maximum at higher wavelength (λ~610nm) could be resolved. This new surface species appears in the high pH range and is assumed to correspond to a clay/curium/silicate complex as already postulated in the literature for kaolinite. The 2 site protolysis non-electrostatic surface complexation and cation exchange sorption model (2SPNE SC/CE) was applied to describe Eu sorption data by involving the Pitzer and SIT (specific ion interaction) formalism in the calculation of the activities of dissolved aqueous species. Good agreement of model and experiment is achieved for sorption data at pHm<6 without the need of adjusting surface complexation constants. For pHm>6 in case of illite and pHm>8 in case of montmorillonite calculated sorption data systematically fall below experimental data with increasing ionic strength. Under those conditions sorption is almost quantitative and deviations must be discussed considering uncertainties of measured Eu concentrations in the range of analytical detection limits.
Schnurr, A., Marsac, R., Rabung, T., Lützenkirchen, J., & Geckeis, H. (2015). Sorption of Cm(III) and Eu(III) onto clay minerals under saline conditions: Batch adsorption, laser-fluorescence spectroscopy and modeling. Geochimica et Cosmochimica Acta, 151, 192–202. https://doi.org/10.1016/j.gca.2014.11.011