1Helmholtz-Zentrum Dresden-Rossendorf Bautzner Landstraße 400 01328 Dresden (Germany)
2The Rossendorf Beamline at ESRF, 71 Ave. des Martyrs, 38043 Grenoble (France)
To assess the safety of nuclear waste repositories, possible incidents have to be considered like canister corrosion and as a consequence the release of radionuclides. Among them, the fission product 99Tc is of high concern due to its long half-life (2.13∙105 years) and the high mobility of the Tc(VII)O4- oxoanion that is barely adsorbed by common mineral phases. However, Tc migration decreases under reducing conditions due to formation of Tc(IV), whose main species is a highly insoluble solid TcO2. Under the reducing and corrosive conditions in the near-field of the repository, Fe2+ will act as a reducing agent for redox sensitive radionuclides (when present in the groundwater or sorbed on mineral surfaces). Furthermore, secondary mineral phases like Fe(II)-Al(III)-Cl, a layered double hydroxide (LDH), can be formed when Fe2+ interacts with Al2O3 at circumneutralalkaline pH [1]. LDH phases are so-called anionic clays and
they are known to retain pollutants by anion exchange, incorporation, surface complexation and in the case of Fe(II)-Al(III)-Cl via reduction promoted by the structural Fe2+ [2]. We have analysed the 99Tc uptake by Fe(II)-Al(III)-Cl LDH under varying pH (4 to 11), ionic strength (0 to 0.1 M) and Tc concentration (10-9 to 10-3 M). At pH < 6.5, the solid to liquid distribution coefficient, (log Kd in mL/g), ranges from (2 to 6) and increases with decreasing ionic strength and increasing pH. At pH > 6.5, log Kd (6.5±0.3) are independent of pH and ionic strength. Tc K-edgeX-ay absorption spectroscopy showed in all cases a reduction to Tc(IV) and enabled us to elucidate the surface bound speciation of Tc on a molecular level.
We thank the German Federal Ministry of Economic Affairs and Energy (BMWi) for the VESPA II project funding and Dr. K. Dardenne and Dr. J. Rothe for their help at KARA.
[1] E. J. Elzinga,” Environ. Sci. Technol., vol. 46, no. 9, pp. 4894–4901, 2012.
[2] C. Forano, U. Costantino, V. Prévot, and C. T. Gueho, Layered double hydroxides (LDH), vol. 5. 2013.
