Adsorption of Eu³⁺ and Gd³⁺ on high-charge micas as inner-sphere complexes

High-charge micas exhibit improved adsorption properties and are a promising alternative clay material for the engineered barrier in deep geological repositories. When combined with Eu³⁺ cations, they serve as an in situ luminescent probe for tracking the physical-chemical changes occurring in this engineered barrier over the long term. Therefore, a better understanding of the local environment of the lanthanide is highly desirable to comprehend the specific behavior of these systems. A combination of different techniques, (X-ray diffraction, thermogravimetry, fluorescence, and X-ray absorption spectroscopy), has allowed the study of the local environment of two luminescent lanthanide cations, Eu³⁺ and Gd³⁺_, embedded in the galleries of two high-charge micas with different Si/Al tetrahedral ratio. The results show that the hydration state of these cations is primarily influenced by the layer charge of the aluminosilicate, and secondarily by the cation's hydration enthalpy. High-charge micas doped with trivalent lanthanide cations are more hydrated compared to the original clays with Na⁺ in the interlayer. Nevertheless, both Eu³⁺ and Gd³⁺ are adsorbed as inner-sphere complexes in the galleries of high-charge micas. They are located inside the distorted hexagonal cavity in all cases, coordinated by 3 oxygens from the tetragonal sheet, one fluorine from the octahedral sheet, and by 2-4 oxygens from water molecules, all at distances around 2.4 Å. An additional oxygen atom at a distance of 3.45-3.50 Å, is proposed from an H₂O molecule in the second coordination shell.