Technetium immobilization by chukanovite and its oxidative transformation products: Neural network analysis of EXAFS spectra

Abstract

The uptake of the fission product technetium (Tc) by chukanovite, an FeII hydroxy carbonate mineral formed as a carbon steel corrosion product in anoxic and carbonate-rich environments, was studied under anoxic, alkaline to hyperalkaline conditions representative for nuclear waste repositories in deep geological formations with cement-based inner linings. The retention potential of chukanovite towards TcVII is high in the pH range 7.8 to 12.6, evidenced by high solid-water distribution coefficients, log Rd ~ 6, and independent of ionic strength (0.1 or 1 M NaCl). Using Tc K-edge X-ray absorption spectroscopy (XAS) two series of samples were investigated, Tc chukanovite sorption samples and coprecipitates, prepared with varying Tc loadings, pH values and contact times. From the resulting 37 XAS spectra, spectral endmembers and their dependence on chemical parameters were derived by self-organizing (Kohonen) maps (SOM), a neural network-based approach of machine learning. X-ray absorption near-edge structure (XANES) data confirmed the complete reduction of TcVII to TcIV by chukanovite under all experimental conditions. Consistent with mineralogical phases identified by X-ray diffraction (XRD), SOM analysis of the extended X-ray absorption fine-structure (EXAFS) spectra revealed the presence of three species in the sorption samples, the speciation predominately controlled by pH: Between pH 7.8 and 11.8, TcO2-dimers form inner-sphere sorption complexes at the surface of the initial chukanovite as well as on the surface of secondary magnetite formed due to redox reaction. At pH ≥ 11.9, TcIV is incorporated in a mixed, chukanovite-like, Fe/Tc hydroxy carbonate precipitate. The same species formed when using the coprecipitation approach. Reoxidation of sorption samples resulted in a small remobilization of Tc, demonstrating that both the original chukanovite mineral and its oxidative transformation products, magnetite and goethite, contribute to the immobilization of Tc in the long term, thus strongly attenuating its environmental transport.