A Spectroscopic Characterization and Quantification of M(III)/Clay Mineral Outer-Sphere Complexes

For the long-term safety assessment of deep radioactive waste repositories an understanding of the interactions of actinides with mineral surfaces at a molecular level is necessary. The retention/mobility of the released radionuclides is strongly dependent on sorption/desorption reactions at mineral surfaces. Thus, a quantitative understanding of the uptake mechanisms of actinides on clay minerals will make an important contribution to long-term safety assessments. Using time-resolved laser fluorescence spectroscopy (TRLFS), it was possible to differentiate between nonsorbed aquo ions and outer-sphere sorbed Cm(III) onto different montmorillonites. In addition, Cm(III)/clay outer-sphere complexation at different ionic strengths using NaCI as the background electrolyte is quantified. Finally, the results are verified by sorption model calculations.