TY - JOUR A1 - Hennig, Theresa A1 - Stockmann, Madlen A1 - Kühn, Michael T1 - Simulation of diffusive uranium transport and sorption processes in the Opalinus Clay JF - Applied geochemistry : journal of the International Association of Geochemistry and Cosmochemistry N2 - Diffusive transport and sorption processes of uranium in the Swiss Opalinus Clay were investigated as a function of partial pressure of carbon dioxide pCO(2), varying mineralogy in the facies and associated changes in porewater composition. Simulations were conducted in one-dimensional diffusion models on the 100 m-scale for a time of one million years using a bottom-up approach based on mechanistic surface complexation models as well as cation exchange to quantify sorption. Speciation calculations have shown, uranium is mainly present as U(VI) and must therefore be considered as mobile for in-situ conditions. Uranium migrated up to 26 m in both, the sandy and the carbonate-rich facies, whereas in the shaly facies 16 m was the maximum. The main species was the anionic complex CaUO2(CO3)(3)(2-) . Hence, anion exclusion was taken into account and further reduced the migration distances by 30 %. The concentrations of calcium and carbonates reflected by the set pCO(2) determine speciation and activity of uranium and consequently the sorption behaviour. Our simulation results allow for the first time to prioritize on the far-field scale the governing parameters for diffusion and sorption of uranium and hence outline the sensitivity of the system. Sorption processes are controlled in descending priority by the carbonate and calcium concentrations, pH, pe and the clay mineral content. Therefore, the variation in porewater composition resulting from the heterogeneity of the facies in the Opalinus Clay formation needs to be considered in the assessment of uranium migration in the far field of a potential repository. KW - reactive transport KW - facies KW - heterogeneity KW - carbonate KW - PHREEQC KW - Mont Terri KW - speciation Y1 - 2020 U6 - https://doi.org/10.1016/j.apgeochem.2020.104777 SN - 0883-2927 SN - 1872-9134 VL - 123 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Hennig, Theresa A1 - Kühn, Michael T1 - Surrogate model for multi-component diffusion of Uranium through Opalinus Clay on the host rock scale JF - Applied Sciences : open access journal N2 - Multi-component (MC) diffusion simulations enable a process based and more precise approach to calculate transport and sorption compared to the commonly used single-component (SC) models following Fick's law. The MC approach takes into account the interaction of chemical species in the porewater with the diffuse double layer (DDL) adhering clay mineral surfaces. We studied the shaly, sandy and carbonate-rich facies of the Opalinus Clay. High clay contents dominate diffusion and sorption of uranium. The MC simulations show shorter diffusion lengths than the SC models due to anion exclusion from the DDL. This hampers diffusion of the predominant species CaUO2(CO3)32-. On the one side, species concentrations and ionic strengths of the porewater and on the other side surface charge of the clay minerals control the composition and behaviour of the DDL. For some instances, it amplifies the diffusion of uranium. We developed a workflow to transfer computationally intensive MC simulations to SC models via calibrated effective diffusion and distribution coefficients. Simulations for one million years depict maximum uranium diffusion lengths between 10 m and 35 m. With respect to the minimum requirement of a thickness of 100 m, the Opalinus Clay seems to be a suitable host rock for nuclear waste repositories. KW - facies KW - uranium speciation KW - sorption KW - reactive transport KW - heterogeneity KW - PHREEQC KW - Mont Terri KW - repository far-field Y1 - 2021 U6 - https://doi.org/10.3390/app11020786 SN - 2076-3417 VL - 11 IS - 2 PB - MDPI CY - Basel ER -