Geochemical interactions of Np and Pu with pyrite heterogeneities in Opalinus Clay in the context of deep geological repositories

The safety case for the final disposal of high-level radioactive waste in a deep geological repository involves a thorough understanding of the geochemical interactions of the potentially mobilized waste inventory with components of a proposed multi-barrier concept. Argillaceous rock is considered as a potential host rock and final barrier to the biosphere. Opalinus Clay (OPA) from the Mont Terri rock laboratory (St-Ursanne, Switzerland) serves as a reference material for a natural clay rock. As a sedimentary rock and porous medium, OPA exhibits characteristic properties such as a low hydraulic conductivity, limiting the transport of solutes to diffusion, as well as structural and compositional heterogeneities in a range of length scales [1]. To address the influence of the potentially reactive microstructure on solute transport, spatially resolved sorption and diffusion studies of Np(V) and Pu(V,VI) with bulk OPA samples were performed, utilizing synchrotron-based microscopic chemical imaging at the microXAS beamline (Swiss Light Source, Paul Scherrer Institute, Villigen, Switzerland), simultaneously obtaining chemical information about the OPA microstructure as well as the distribution and transport patterns of Np and Pu [2-5]. In these studies, domains of pyrite, contained in OPA to about 1 wt. % as microstructural, Fe(II)-bearing heterogeneities, were identified exhibiting an enhanced reactivity regarding redox transformation and immobilization of the solute species as reduced, predominantly tetravalent and therefore less mobile species. Further sorption studies with isolated pyrite heterogeneities, extracted from the OPA matrix as sub-100 µm sized particles, indicate a reactivity depending on the morphology of the heterogeneities, including the crystallite size distribution (framboidal) and cementing phase of these pyrite aggregates. The results of these studies should add to an enhanced understanding of reactive transport in a natural clay rock in the context of a deep geological repository.   References [1] Nagra (2002). Tech. Ber. 02-03. Projekt Opalinuston. Wettingen, Switzerland. [2] Fröhlich, D.R., Amayri, S., Drebert, J., Grolimund, D., Huth, J., Kaplan, U., Krause, J. and Reich, T. (2012). Speciation of Np(V) uptake by Opalinus Clay using synchrotron microbeam techniques. Anal. Bioanal. Chem. 404: 2151-2162. [3] Kaplan, U., Amayri, S., Drebert, J., Rossberg, A., Grolimund, D. and Reich, T. (2017). Geochemical interactions of Plutonium with Opalinus Clay studied by spatially resolved synchrotron radiation techniques. Environ. Sci. Technol. 51: 7892-7902. [4] Börner, P.J.B. (2017). Sorption and diffusion of Neptunium in Opalinus Clay. PhD thesis. Johannes Gutenberg-Universität Mainz, Mainz, Germany. [5] Kaplan, U., Amayri, S., Drebert, J., Grolimund, D. and Reich, T. (2024). Plutonium mobility and reactivity in a heterogeneous clay rock barrier accented by synchrotron-based microscopic chemical imaging. Sci. Rep., accepted.   Acknowledgements Funding from the German Federal Ministry of Education and Research (BMBF) under contract number 02NUK044B, from the Federal Ministry for the Environment, Nature Conservation, Nuclear Safety and Consumer Protection (BMUV) under contract numbers 02E11415A and 02E11860A, and from the European Union’s Horizon 2020 project EURAD (WP FUTuRE), EC Grant agreement no. 847593, is acknowledged.