Effect of Ca(II) on U(VI) and Np(VI) retention on Ca-bentonite and clay minerals at hyperalkaline conditions - New insights from batch sorption experiments and luminescence spectroscopy.

In deep geological repositories for radioactive waste, interactions of radionuclides with mineral surfaces occur under complex geochemical conditions involving complex solution compositions and high pH resulting from degradation of cementitious geo-engineered barriers. Ca cations have been hypothesized to play an important role as mediators for the retention of U(VI) on Ca-bentonite at (hyper)alkaline conditions, despite the anionic character of both the mineral surface and the aqueous uranyl species. To gain deeper insight into this sorption process, the effect of Ca on U(VI) and Np(VI) retention on alumosilicate minerals has been comprehensively evaluated, using batch sorption experiments and time-resolved laser-induced luminescence spectroscopy (TRLFS). Sorption experiments with Ca or Sr and zeta potential measurements showed that the alkaline earth metals sorb strongly onto Ca-bentonite at pH 8-13, leading to a partial compensation of the negative surface charge, thereby generating potential sorption sites for anionic actinyl species. U(VI) and Np(VI) sorption experiments in the absence and presence of Ca or Sr confirmed that these cations strongly enhance radionuclide retention on kaolinite and muscovite at pH ≥ 10. Concerning the underlying retention mechanisms, site-selective TRLFS provided spectroscopic proof for two dominating U(VI) species at the alumosilicate surfaces: (i) A ternary U(VI) complex, where U(VI) is bound to the surface via bridging Ca cations with the configuration surface ≡ Ca - OH - U(VI) and, (ii) U(VI) sorption into the interlayer space of calcium (aluminum) silicate hydrates (C-(A-)S-H), which form as secondary phases in the presence of Ca due to partial dissolution of alumosilicates under hyperalkaline conditions. Consequently, the present study confirms that alkaline earth elements, which are ubiquitous in geologic systems, enable strong retention of hexavalent actinides on clay minerals under hyperalkaline repository conditions.