A comprehensive study of the sorption mechanism and thermodynamics of f-element sorption onto K-feldspar

The mobility of heavy metal contaminants and radionuclides in the environment is directly controlled by their interactions with charged mineral surfaces, hence an assessment of their potential toxicity, e.g. in the context of nuclear waste disposal sites, requires understanding of sorption processes on the molecular level. Here, we investigate the sorption of a variety of rare earth elements (REE) and trivalent actinides (Am, Cm) on K-feldspar using batch sorption and column transport experiments, time-resolved laser-induced fluorescence spectroscopy (TRLFS), and a surface complexation model. Initially, a reliable pKa for K-feldspar’s surface deprotonation reaction was determined as 2.5 ± 0.02, in excellent agreement with a measured pHIEP of 2.8. Batch sorption experiments over a broad range of experimental conditions in terms of mineral grain size, pH, [M3+], ionic radius, solid/liquid ratio, ionic strength, and equilibration procedures were carried out to quantify macroscopic immobilization. Similar pH-dependent uptake behavior was found for all investigated trivalent REE and actinides. In parallel, spectroscopic investigations provided insight into surface speciation. Cm TRLFS spectra indicate the formation of three inner-sphere sorption complexes with increasing hydrolysis. Additionally, a ternary K-feldspar/Cm/silicate complex was found for pH > 10, and batch and spectroscopic data at low pH (< 4) point to small amounts of outer sphere sorption complexes. Based on TRLFS data, batch sorption, and titration data, a generic geochemical sorption model was developed, that describes sorption edges for all investigated M3+/K-feldspar systems satisfactorily. The derived stability constants for the binary sorption complexes (logK1-4 = −3.6, −7.7, −11.5, and −17.4, respectively) are in good agreement with previous studies on similar systems, and could successfully be used to reproduce literature data. The stability constants obtained for the surface complexes were included into the database for the Smart Kd-concept, which will further improve the safety assessment of potential repositories for radioactive waste.