Uranium Uptake by Hectorite and Montmorillonite: a Solution Chemistry and Polarized EXAFS Study

The mechanism of U(VI) retention on montmorillonite and hectorite at high ionic strength (0.5 M NaCl) was investigated by solution chemistry and, at near-neutral pH, polarized EXAFS spectroscopy. Uranium(VI) sorption increases from pH 3 to 7 on the two clays, but with a steeper edge for hectorite. Uranium(VI) is no longer retained at pH > 9, presumably owing to the formation of soluble anionic complexes. Polarized EXAFS showed that U(VI) retains its uranyl conformation on montmorillonite (U_mont) and hectorite (U_hect), with uranyl O at 1.79(2) A for U_mont and 1.82(2) A for U_hect, and split equatorial O shells at 2.29(2) and 2.47(2) A (U_mont), or 2.35(2) and 2.53(2) A (U_hect). An additional atomic shell of approximately 0.5 Al/Si at 3.3 A is detected for U_mont, but neither the oxygen nor the cationic shell exhibit clear angular dependence. These results indicate the formation of mononuclear complexes at the edges of montmorillonite platelets, with the orientation of the uranyl axis equal to the magic angle, as constrained by the edges' structural properties. In contrast to U_mont, the U-O signal varies with the polarization angle in U_hect, and the cationic Mg/Si contribution at 3.2 A is weak. The structure of this surface complex is not completely elucidated; it may correspond either to sorption on silanol sites, or to coprecipitation. These results lay out the fundamental molecular-scale basis to understand U retention by neoformed clay layers of nuclear glasses.