@phdthesis{Hennig2022,
  author    = {Hennig, Theresa},
  title     = {Uranium migration in the Opalinus Clay quantified on the host rock scale with reactive transport simulations},
  doi       = {10.25932/publishup-55270},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-552700},
  school      = {Universit{\"a}t Potsdam},
  pages     = {161},
  year      = {2022},
  abstract  = {Humankind and their environment need to be protected from the harmful effects of spent nuclear fuel, and therefore disposal in deep geological formations is favoured worldwide. Suitability of potential host rocks is evaluated, among others, by the retention capacity with respect to radionuclides. Safety assessments are based on the quantification of radionuclide migration lengths with numerical simulations as experiments cannot cover the required temporal (1 Ma) and spatial scales (>100 m). Aim of the present thesis is to assess the migration of uranium, a geochemically complex radionuclide, in the potential host rock Opalinus Clay. Radionuclide migration in clay formations is governed by diffusion due to their low permeability and retarded by sorption. Both processes highly depend on pore water geochemistry and mineralogy that vary between different facies. Diffusion is quantified with the single-component (SC) approach using one diffusion coefficient for all species and the process-based multi-component (MC) option. With this, each species is assigned its own diffusion coefficient and the interaction with the diffuse double layer is taken into account. Sorption is integrated via a bottom-up approach using mechanistic surface complexation models and cation exchange. Therefore, reactive transport simulations are conducted with the geochemical code PHREEQC to quantify uranium migration, i.e. diffusion and sorption, as a function of mineralogical and geochemical heterogeneities on the host rock scale. Sorption processes are facies dependent. Migration lengths vary between the Opalinus Clay facies by up to 10 m. Thereby, the geochemistry of the pore water, in particular the partial pressure of carbon dioxide (pCO2), is more decisive for the sorption capacity than the amount of clay minerals. Nevertheless, higher clay mineral quantities compensate geochemical variations. Consequently, sorption processes must be quantified as a function of pore water geochemistry in contact with the mineral assemblage. Uranium diffusion in the Opalinus Clay is facies independent. Speciation is dominated by aqueous ternary complexes of U(VI) with calcium and carbonate. Differences in the migration lengths between SC and MC diffusion are with +/-5 m negligible. Further, the application of the MC approach highly depends on the quality and availability of the underlying data. Therefore, diffusion processes can be adequately quantified with the SC approach using experimentally determined diffusion coefficients. The hydrogeological system governs pore water geochemistry within the formation rather than the mineralogy. Diffusive exchange with the adjacent aquifers established geochemical gradients over geological time scales that can enhance migration by up to 25 m. Consequently, uranium sorption processes must be quantified following the identified priority: pCO2 > hydrogeology > mineralogy. The presented research provides a workflow and orientation for other potential disposal sites with similar pore water geochemistry due to the identified mechanisms and dependencies. With a maximum migration length of 70 m, the retention capacity of the Opalinus Clay with respect to uranium is sufficient to fulfill the German legal minimum requirement of a thickness of at least 100 m.},
  language  = {en}
}
@article{HennigKuehn2021,
  author    = {Hennig, Theresa and K{\"u}hn, Michael},
  title     = {Surrogate model for multi-component diffusion of Uranium through Opalinus Clay on the host rock scale},
  series = {Applied Sciences : open access journal},
  volume    = {11},
  journal   = {Applied Sciences : open access journal},
  number    = {2},
  publisher = {MDPI},
  address   = {Basel},
  issn      = {2076-3417},
  doi       = {10.3390/app11020786},
  pages     = {21},
  year      = {2021},
  abstract  = {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.},
  language  = {en}
}
@article{HennigStockmannKuehn2020,
  author    = {Hennig, Theresa and Stockmann, Madlen and K{\"u}hn, Michael},
  title     = {Simulation of diffusive uranium transport and sorption processes in the Opalinus Clay},
  series = {Applied geochemistry : journal of the International Association of Geochemistry and Cosmochemistry},
  volume    = {123},
  journal   = {Applied geochemistry : journal of the International Association of Geochemistry and Cosmochemistry},
  publisher = {Elsevier},
  address   = {Oxford},
  issn      = {0883-2927},
  doi       = {10.1016/j.apgeochem.2020.104777},
  pages     = {9},
  year      = {2020},
  abstract  = {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.},
  language  = {en}
}
@article{HennigKuehn2021,
  author    = {Hennig, Theresa and K{\"u}hn, Michael},
  title     = {Potential uranium migration within the geochemical gradient of the opalinus clay system at the Mont Terri},
  series = {Minerals},
  volume    = {11},
  journal   = {Minerals},
  number    = {10},
  publisher = {MDPI},
  address   = {Basel},
  issn      = {2075-163X},
  doi       = {10.3390/min11101087},
  pages     = {22},
  year      = {2021},
  abstract  = {Transport properties of potential host rocks for nuclear waste disposal are typically determined in laboratory or in-situ experiments under geochemically controlled and constant conditions. Such a homogeneous assumption is no longer applicable on the host rock scale as can be seen from the pore water profiles of the potential host rock Opalinus Clay at Mont Terri (Switzerland). The embedding aquifers are the hydro-geological boundaries, that established gradients in the 210 m thick low permeable section through diffusive exchange over millions of years. Present-day pore water profiles were confirmed by a data-driven as well as by a conceptual scenario. Based on the modelled profiles, the influence of the geochemical gradient on uranium migration was quantified by comparing the distances after one million years with results of common homogeneous models. Considering the heterogeneous system, uranium migrated up to 24 m farther through the formation depending on the source term position within the gradient and on the partial pressure of carbon dioxide pCO2 of the system. Migration lengths were almost equal for single- and multicomponent diffusion. Differences can predominantly be attributed to changes in the sorption capacity, whereby pCO2 governs how strong uranium migration is affected by the geochemical gradient. Thus, the governing parameters for uranium migration in the Opalinus Clay can be ordered in descending priority: pCO2, geochemical gradients, mineralogical heterogeneity.</p>},
  language  = {en}
}