For the first time microbial tDNA could be isolated from 50 g unperturbed Mont Terri Opalinus Clay. Based on the analysis of the tDNA the bacterial diversity of the unperturbed clay is dominated by representatives of Firmicutes, Betaproteobacteria, and Bacteriodetes. Firmicutes also dominate after treatment of the clay with R2A medium. Bacteria isolated from Mont Terri Opalinus Clay on R2A medium were related to Sporomusa spp., Paenibacillus spp., and Clostridium spp.. All further investigations are concentrated on the unique isolates Sporomusa sp. MT-2 and Paenibacillus sp. MT-2. Cells of the type Sporomusa sp. MT-2 and Paenibacillus sp. MT-2 were comprehensively analyzed in terms of growing, morphology, functional groups of the cell envelope, and cell membrane structure. Strong actinide(An)/lanthanide(Ln)-interactions with the Opalinus Clay isolates and the Äspö-strain Pseudomonas fluorescens (CCUG 32456) could be determined within a broad pH range (2-8). The metals bind as a function of pH on protonated phosphoryl, carboxyl and deprotonated phosphoryl sites of the respective cell membrane. The thermodynamic surface complexation constants of bacterial An/Ln-species were determined and can be used in modeling programs. Depending on the used An different interaction mechanisms were found (U(VI): biosorption, partly biomineralisation; Cm(III): biosorption, indications for embedded Cm(III); Pu: biosorption, bioreduction and indications for embedded Pu). Different strategies of coping with U(VI) were observed comparing P. fluorescens planktonic cells and biofilms under the chosen experimental conditions. An enhanced capability of the biofilm to form meta-autunite in comparison to the planktonic cells was proven. Conclusively, the P. fluorescens biofilm is more efficient in U(VI) detoxification. In conclusion, Mont Terri Opalinus Clay contains bacterial communities, that may influence the speciation and hence the migration behavior of selected An/Ln under environmental conditions.

For the first time microbial tDNA could be isolated from 50 g unperturbed Mont Terri Opalinus Clay. Based on the analysis of the tDNA the bacterial diversity of the unperturbed clay is dominated by representatives of Firmicutes, Betaproteobacteria, and Bacteriodetes. Firmicutes also dominate after treatment of the clay with R2A medium. Bacteria isolated from Mont Terri Opalinus Clay on R2A medium were related to Sporomusa spp., Paenibacillus spp., and Clostridium spp.. All further investigations are concentrated on the unique isolates Sporomusa sp. MT-2 and Paenibacillus sp. MT-2. Cells of the type Sporomusa sp. MT-2 and Paenibacillus sp. MT-2 were comprehensively analyzed in terms of growing, morphology, functional groups of the cell envelope, and cell membrane structure. Strong actinide(An)/lanthanide(Ln)-interactions with the Opalinus Clay isolates and the Äspö-strain Pseudomonas fluorescens (CCUG 32456) could be determined within a broad pH range (2-8). The metals bind as a function of pH on protonated phosphoryl, carboxyl and deprotonated phosphoryl sites of the respective cell membrane. The thermodynamic surface complexation constants of bacterial An/Ln-species were determined and can be used in modeling programs. Depending on the used An different interaction mechanisms were found (U(VI): biosorption, partly biomineralisation; Cm(III): biosorption, indications for embedded Cm(III); Pu: biosorption, bioreduction and indications for embedded Pu). Different strategies of coping with U(VI) were observed comparing P. fluorescens planktonic cells and biofilms under the chosen experimental conditions. An enhanced capability of the biofilm to form meta-autunite in comparison to the planktonic cells was proven. Conclusively, the P. fluorescens biofilm is more efficient in U(VI) detoxification. In conclusion, Mont Terri Opalinus Clay contains bacterial communities, that may influence the speciation and hence the migration behavior of selected An/Ln under environmental conditions.

Esta Tesis está dirigida al análisis teórico y experimental de problemas acoplados Termo-Hidro Mecánico (THM) que se desarrollan en formaciones geológicas profundas destinadas al almacenamiento de residuos radiactivos de alta actividad. En las últimas décadas, han sido estudiadas las formaciones arcillosas para ser utilizadas como barreras geológicas debido a su reducida conductividad hidráulica. La degradación de las rocas arcillosas producida por efectos de temperatura y por efectos de variación en el grado de saturación, es un factor de fundamental importancia, que es actualmente investigado en ensayos in situ a gran escala, como así también en ensayos de laboratorio. En ésta tesis, la roca Opalinus Clay ha sido ampliamente caracterizada mediante ensayos de laboratorios. Desde un punto de vista macro-estructural se ha obtenido la curva de retención de agua, conductividad hidráulica, resistencia y deformación. El análisis micro-estructural está enfocado a la caracterización mineralógica obtenida por difracción de rayos X, la distribución del tamaño de los poros determinada por porosimetría de mercurio (MIP) y microscopía electrónica (SEM). La tesis describe también un ensayo in situ de calentamiento diseñado para analizar la interacción entre la barrera de ingeniería (bloques de bentonita compactada) y la barrera geológica (Opalinus clay). Esta interacción ha sido analizada a través de simulaciones numéricas realizadas con el código de elementos finitos CODE_BRIGHT. Una célula termo-hidráulica fue especialmente diseñada para observar el comportamiento THM de la roca en condición drenada y no drenada, a través de pulsos de calor. Parámetros térmicos e hidráulicos de la roca fueron determinados por retro análisis a través de simulaciones numéricas realizadas con CODE_BRIGHT. Desde el punto de vista mecánico, un modelo constitutivo ha sido formulado en 3D e implementado en CODE_BRIGHT con el objetivo de reproducir el comportamiento mecánico anisótropo y rotura frágil de las rocas arcillosas. El modelo es formulado en un marco viscoplástico y considera la resistencia y deformabilidad de la matriz y de las juntas. El criterio de falla de la matriz y de las juntas es definido por superficies de fluencias hiperbólicas en el espacio de tensiones p-J y τ−σ, respectivamente. El comportamiento frágil de las rocas arcillosas es simulado por un reblandecimiento isótropo y cinemático definido en términos de trabajo de deformación plástico. El modelo constitutivo ha sido calibrado mediante ensayos triaxiales de laboratorio realizados en especimenes con diferentes ángulos de buzamiento. El modeloconstitutivo anisótropo ha sido aplicado a la simulación numérica en 3D de un ensayo de calentamiento in-situ. Una simulación numérica en 3D de un ensayo de ventilación in-situ realizado en un micro-túnel sin recubrimiento ha sido realizada para reproducir el brusco cambio de permeabilidad por efectos de secado de la roca. En este caso, un modelo hidráulico que considera la apertura de las juntas por efectos de secado ha sido implementado para reproducir los cambios de permeabilidad en excavaciones subterráneas. / This thesis deals with the theoretical and experimental analysis of the coupled Thermo- Hydro-Mechanical (THM) processes developed in geological formations suitable for the repository of radioactive waste of high activity. In the last decades, the argillaceous formations have been studied to be used as geological barriers, due to its reduced hydraulic conductivity. The degradation of clay shales induced by temperature and saturation effects is an important factor which is currently being investigated in large scale in situ tests as well as in laboratory studies. In this thesis, the Opalinus clay rock has been widely characterized by means of laboratory tests. From a macro-structural point of view, the water retention curve, hydraulic conductivity, strength and deformability parameters have been determined. The micro-structural analysis is focused to the mineralogical characterization obtained by means of X ray diffraction, pore size distribution (PSD) determined by means of mercury intrusion porosimetry (MIP) and scanning electronic microscopy (SEM). The thesis describes also a large scale heating in situ test designed to analyze the interaction between the engineer barrier (compacted bentonite blocks) and by the geological barrier, (Opalinus clay). This interaction has been analyzed by means of numerical simulations performed with the finite element code CODE_BRIGHT. A thermo hydraulic cell was specially designed to observe the coupled THM behaviour of the clay shale rock under drained and undrained conditions by means of heat pulses. Thermal and hydraulic parameters of rock were determined by means of back-analysis performed with the help of CODE_BRIGHT. In order to reproduce the anisotropic and brittle behaviour of the clay shale, a 3D mechanical constitutive model has been formulated and implemented in CODE_BRIGHT. The constitutive model is formulated in a viscoplastic framework and it considers the strength and deformability of both matrix and discontinuities (joints). The failure criterion of the matrix and the joints is defined by means of hyperbolic yield surfaces in the p-J and τ-σ stress space, respectively. The brittle behaviour of clay shale is simulated by means of isotropic and kinematic softening defined in terms of a workhardening criterion. The anisotropic constitutive model has been calibrated against triaxial laboratory tests performed on specimens with a main family of discontinuities having different dip angles. The constitutive model has been applied to a 3D numerical simulation of an "in-situ" heating test. A 3D numerical simulation of a ventilation test performed in an unlined micro tunnel was also performed in order to reproduce the changes of the rock permeability by drying effects. In this case, a hydraulic model able to consider the changes in joint thickness by drying effects has been developed to reproduce the changes of permeability in underground excavations.

Le stockage des déchets radioactifs dans les formations géologiques profondes peu perméables comme les argilites et les argiles plastiques est envisagée comme une solution possible et fait l'objet de nombreuses études depuis une trentaine d'années. Dans le cadre du projet européen TIMODAZ, l'accent a été mis sur l'étude des effets d'une augmentation de la température engendrée par les déchets exothermiques sur la zone endommagée autour d'une galerie souterraine de stockage. Dans le cadre de ce projet, une étude expérimentale sur le comportement thermique de l'argile de Boom et de l'argile à Opaline a été réalisée. Afin de surmonter les difficultés reliées à l'étude expérimentale des matériaux peu perméables en laboratoire, une nouvelle cellule triaxiale à court chemin de drainage a été mise en œuvre. Les essais ainsi qu'une modélisation numérique montrent que la re-saturation des échantillons désaturés par le processus d'excavation, transport, stockage et préparation peut être réalisée beaucoup plus rapidement par ce dispositif. Les essais de chargement mécanique et thermique en condition drainée (c'est-à-dire avec une surpression interstitielle engendrée négligeable) peuvent être réalisés également dans cette cellule avec des vitesses de chargement plus élevée comparée aux cellules triaxiales classiques. La possibilité de réactivation d'une bande de cisaillement par pressurisation thermique du fluide interstitiel dans un échantillon de l'argile de Boom est mise en évidence. On observe qu'un plan de rupture préexistant dans l'échantillon agit comme un plan de faiblesse pouvant être réactivé de façon préférentielle au moment de la rupture. La résistance au cisaillement obtenue sur le plan de rupture est inférieure à celle de matériau intact pour l'argile de Boom. Le comportement thermique de l'argile à Opaline a été étudié à partir d'essais de chauffage en condition drainée et non drainée sur des échantillons saturés. L'essai de chauffage drainé montre un comportement thermo-elasto-plastique avec limite expansion/contraction à 65°C. Ce comportement est similaire au comportement des argiles faiblement surconsolidées. L'analyse des résultats de l'essai de chauffage non drainé met en évidence que l'eau interstitielle dans l'argile à Opaline a un coefficient de dilation thermique plus important comparé à celui de l'eau libre. Dans la gamme de températures étudiées (25°C-80°C), les mesures de perméabilité sur les échantillons endommagés par un chargement déviatorique ne montrent aucun effet de l'endommagement sur la perméabilité, ce qui prouve la bonne capacité de scellement de l'argile de Boom et l'argile à Opaline saturées / Storage of exothermic radioactive waste in deep low permeability geological formations such as clayey rocks and plastic clays is a solution considered for long term repositories. However the excavation of underground galleries creates a damaged zone (EDZ). The effect of the damage zone on the transport properties of the geological barrier has been widely studied. Within the framework of the TIMODAZ European project, emphasis has been put on the effect of temperature. As a partner of this project, the current work is performed to investigate the coupling effect between temperature, damage and permeability on Boom clay and Opalinus clay through an experimental study. View to the experimental difficulties related to the low permeability materials, a new hollow cylinder triaxial cell with short drainage path specifically designed to study the thermo-hydro-mechanical behaviour of very low permeable materials is developed during this work. The tests and the numerical analysis show that the short sample drainage path reduces significantly the time needed to resaturate an initially unsaturated sample and it also permits to achieve drained conditions (i.e. negligible excess pore pressure during testing) with a higher loading rate. For Boom clay, the effect of the pore water thermal pressurisation on a sample with a pre-existing shear band is investigated. The undrained heating under shear stress decreases the effective stress on the sample which leads to its failure. An existing failure plane in the sample behaves like a preferential weakness plane which can be reactivated by pore water thermal pressurisation. The estimated shearing resistance along the sheared plane is smaller than that of the intact material. For the Opalinus claystone, drained heating on a saturated sample shows that this claystone behaves like a slightly overconsolidated material (thermo-elasto-plastic behaviour) with transition from expansion to contraction at 65°C. The decrease of the permeability of the sample before and after the heating-cooling cycles proves the irreversible volumetric compaction of the sample. The undrained heating test on the Opalinus claystone induces an excess pore pressure in the sample which cannot be explained by the difference between the free water thermal expansion coefficient and that of the solid matrix. The back analysis of the results shows a higher value for the water thermal expansion coefficient as compared to that of free water. Permeability measurements at 25°C and 80°C on samples previously damaged by deviatoric loading show no significant effect of damage on the permeability of the samples. These results confirm the good sealing capacity of both clays at various temperatures

The objective of this project was the study of basic interaction processes in the systems actinide - clay organics - aquifer and actinide - natural clay - clay organics - aquifer. Thus, complexation, redox, sorption and diffusion studies were performed. To evaluate the influence of nitrogen, phosphorus and sulfur containing functional groups of humic acid (HA) on the complexation of actinides in comparison to carboxylic groups, the Am(III) and U(VI) complexation by model ligands was studied by UV-Vis spectroscopy and TRLFS. The results show that Am(III) is mainly coordinated via carboxylic groups, however, probably stabilized by nitrogen groups. The U(VI) complexation is dominated by carboxylic groups, whereas nitrogen and sulfur containing groups play a minor role. Phosphorus containing groups may contribute to the U(VI) complexation by HA, however, due to their low concentration in HA they play only a subordinate role compared to carboxylic groups. Applying synthetic HA with varying sulfur contents (0 to 6.9 wt.%), the role of sulfur functionalities of HA for the U(VI) complexation and Np(V) reduction was studied. The results have shown that sulfur functionalities can be involved in U(VI) humate complexation and act as redox-active sites in HA for the Np(V) reduction. However, due to the low content of sulfur in natural HA, its influence is less pronounced. In the presence of carbonate, the U(VI) complexation by HA was studied in the alkaline pH range by means of cryo-TRLFS (-120°C) and ATR FT-IR spectroscopy. The formation of the ternary UO2(CO3)2HA(II)4− complex was detected. The complex formation constant was determined with log β0.1 M = 24.57 ± 0.17. For aqueous U(VI) citrate and oxalate species, luminescence emission properties were determined by cryo-TRLFS and used to determine stability constants. The existing data base could be validated. The U(VI) complexation by lactate, studied in the temperature range 7 to 65°C, was found to be endothermic and entropy-driven. In contrast, the complex stability constants determined for U(VI) humate complexation at 20 and 40°C are comparable, however, decrease at 60°C. For aqueous U(IV) citrate, succinate, mandelate and glycolate species stability constants were determined. These ligands, especially citrate, increase solubility and mobility of U(IV) in solution due to complexation. The U(VI) sorption onto crushed Opalinus Clay (OPA, Mont Terri, Switzerland) was studied in the absence and presence of HA or low molecular weight organic acids, in dependence on temperature and CO2 presence using OPA pore water as background electrolyte. Distribution coefficients (Kd) were determined for the sorption of U(VI) and HA onto OPA with (0.0222 ± 0.0004) m3/kg and (0.129 ± 0.006) m3/kg, respectively. The U(VI) sorption is not influenced by HA (50 mg/L), however, decreased by low molecular weight organic acids (> 1×10-5 M), especially by citrate and tartrate. With increasing temperature, the U(VI) sorption increases both in the absence and in the presence of clay organics. The U(VI) diffusion in compacted OPA is not influenced by HA at 25 and 60°C. Predictions of the U(VI) diffusion show that an increase of the temperature to 60°C does not accelerate the migration of U(VI). With regard to uranium-containing waste, it is concluded that OPA is suitable as host rock for a future nuclear waste repository since OPA has a good retardation potential for U(VI).

The storage of nuclear waste in deep geological formations is discussed worldwide as the main strategy for nuclear waste management. To ensure the confinement of the nuclear waste, a multiple barrier system which consists of engineered, geo-engineered, and geological barriers will be applied. Thereby, in Germany the definition of the isolating rock zone represents an important safety function indicator. Clay rock is internationally investigated as potential host rock for a repository and represents a part of the geological barrier. In the present work, the natural clay rock Opalinus Clay from the Mont Terri rock laboratory, Switzerland, was studied. In Germany, the direct disposal of the spent nuclear fuel without the reprocessing of the spent fuel is preferred. In case of water ingress, radionuclides can be released from the nuclear waste repository into its surroundings, namely the host rock of the repository. Humic acids, ubiquitous in nature, can be found associated with the inorganic components in natural clay rock (1.5×10–3 wt.% in Opalinus Clay). They can be released under certain conditions. Due to their variety of functional groups, humic acids are very strong complexing agents for metal ions. They have inherent redox abilities and a colloidal conformation in solution. Because of these characteristics, humic acids can affect the mobility of metal ions such as actinides. Furthermore, in the near-field of a repository elevated temperatures have to be considered due to the heat production resulting from the radioactive decay of the various radionuclides in the nuclear waste. This work focuses on the interaction of uranium, as main component of spent nuclear fuel, with Opalinus Clay and studies the influence of humic acid and elevated temperature on this interaction. For investigation of the retention behavior of the clay and the mobility of U(VI) in the system, batch sorption and diffusion experiments were performed. To clarify which U(VI) and humic acid species were present under the applied conditions, aqueous speciation modeling was used. Additionally, the U(VI) speciation in solution and on the clay surface was investigated by spectroscopic methods. Prior to the investigation of the ternary system U(VI) / humic acid / clay, the applied batches of Opalinus Clay were characterized (e.g., specific surface area, carbon content, cation exchange capacity, elemental composition, particle size distribution). Leaching studies with Opalinus Clay in synthetic Opalinus Clay pore water (pH 7.6, It = 0.34 mol/L) and in NaClO4 (pH 3 – 10, I = 0.1 mol/L) were performed to identify the competing ions and their concentrations in the background electrolytes. These data were used to calculate the U(VI) and humic acid speciation in solution. Calcium and carbonate ions are present under pore water conditions as well as in 0.1 mol/L NaClO4 from pH 7 to 8.5, due to dissolution of calcite (mineral fraction in Opalinus Clay). Thus, the U(VI) speciation is dominated by the aquatic Ca2UO2(CO3)3 complex. In the case of pore water, Ca2UO2(CO3)3(aq) is also the dominant U(VI) species in the presence of humic acid, which was corroborated by time-resolved laser-induced fluorescence spectroscopic measurements. A significantly changed speciation was found in 0.1 mol/L NaClO4 in the presence of humic acid. At pH > 7, the negatively charged UO2(CO3)2HA(II)4– complex determines the U(VI) speciation, thus repressing the Ca2UO2(CO3)3(aq) complex. In addition, the speciation of humic acid is influenced from ions leached out from Opalinus Clay. The CaHA(II) complex is the dominating humic acid species in solution. Batch sorption experiments in 0.1 mol/L NaClO4 showed that Opalinus Clay has the strongest retardation effect on U(VI) in the pH range from pH 4.5 to 7. However, under environmentally relevant conditions (pH > 7), the sorption of U(VI) onto Opalinus Clay is very weak. Under pore water conditions, a distribution coefficient (Kd) of 0.0222 ± 0.0004 m3/kg was determined, which was shown to be independent of solid-to-liquid ratios ≥ 60 g/L. In addition, in pore water, the U(VI) sorption onto Opalinus Clay is not influenced by humic acid, which is supported by the speciation results. Extended X ray absorption fine-structure investigations confirmed this batch sorption result. The U(VI) diffusion experiments performed in pore water at 25 °C with Opalinus Clay bore core samples confirmed the Kd value obtained by batch sorption experiments. In the diffusion experiments at 60 °C, a change in the U(VI) speciation occurred. Beside Ca2UO2(CO3)3(aq), a colloidal U(VI) species was formed. Almost equivalent apparent diffusion coefficient (Da) values were determined for the diffusion of the aqueous U(VI) species at 25 and 60 °C through Opalinus Clay. Thus, based on the investigations in the present study the breakthrough of U(VI) through Opalinus Clay is expected to be independent of the temperature and should occur nearly at the same time. Modeling calculations showed that it would take about 10 years until a detectable amount of 233U(VI) (1×10–9 mol/L) migrates through an 11 mm thick Opalinus Clay sample. Two distinct humic acid size fractions – a large- and a small-sized colloid fraction – diffused through the Opalinus Clay samples. Within three months, the high molecular size humic acid colloids migrated only about 500 µm into the clay, whereas the low molecular size fraction diffused through the entire Opalinus Clay samples and were consequently detected in the receiving reservoirs. These findings demonstrate a filtration effect of the compacted clay. The diffusion experiments revealed that the effect of humic acid on U(VI) diffusion is negligible and, under the studied conditions, independent of temperature. The obtained results contribute to data bases used for modeling of interaction and migration processes in uranium / clay rock systems. Thus, the collected sorption and diffusion data are not only relevant for safety assessment of nuclear waste repositories but also for any clay-containing system present in the environment, where the geochemical interaction with uranium contaminated water plays a role. Concerning the suitability of Opalinus Clay as host rock for a nuclear waste repository, it can be concluded, that Opalinus Clay has a relatively high retardation potential for U(VI). In case of water ingress U(VI) as part of the nuclear waste is released into the clay formation. Under near-neutral pH conditions, it will be complexed by calcium and carbonate ions leached out from Opalinus Clay, whereby Ca2UO2(CO3)3(aq) is formed. This complex is only weakly retarded by sorption onto the clay, which can contribute to an enhanced mobility of U(VI) in the host rock. However, the U(VI) migration through the clay rock is governed by molecular diffusion. This decelerates the migration of Ca2UO2(CO3)3(aq) through Opalinus Clay and thus it represents the decisive retardation process in the investigated system. Additionally, under environmentally relevant conditions, humic acid has no significant influence on U(VI) / Opalinus Clay interaction even at an elevated temperature of 60 °C. This was shown by speciation, sorption, as well as diffusion experiments. / Eine weltweit diskutierte Strategie zum Umgang mit radioaktiven Abfällen ist deren Endlagerung in tiefen geologischen Formationen. Zur Abschirmung der Umwelt vor den schädlichen Einflüssen des radioaktiven Abfalls soll ein Multibarrierensystem bestehend aus technischen, geotechnischen und geologischen Barrieren im Endlager dienen. Dabei ist in Deutschland die Definition des einschlusswirksamen Gebirgsbereichs ein wichtiger sicherheitstechnischer Indikator. Tongestein wird als potentielles Endlagerwirtsgestein und Teil der geologischen Barriere international erforscht. In der vorliegenden Arbeit wurde das natürliche Tongestein Opalinuston aus dem Mont Terri Felslabor, Schweiz, untersucht. In Deutschland wird die direkte Endlagerung des abgebrannten Kernbrennstoffes ohne Wiederaufarbeitung des Brennstoffs favorisiert. Bei Wassereinbruch können Radionuklide aus dem Abfall in die Umgebung des Endlagers freigesetzt werden, d. h. sie können in Kontakt mit dem Wirtsgestein kommen. Ubiquitär in der Natur vorkommende Huminsäuren können mit den anorganischen Komponenten des natürlichen Tongesteins vergesellschaftet sein (1.5×10–3 Gew.-% in Opalinuston). Unter bestimmten Bedingungen können die Huminsäuren freigesetzt werden. Ihre Struktur enthält eine Vielzahl von funktionellen Gruppen, was sie zu starken Komplexbildnern für Metallionen macht. Sie besitzen Redoxeigenschaften und bilden in Lösung eine kolloidale Konformation aus. Aufgrund dieser Charakteristika können sie die Mobilität von Metallionen wie den Actinoiden beeinflussen. Weiterhin sind im Nahfeld eines Endlagers erhöhte Temperaturen zu erwarten, welche aus der Wärmefreisetzung beim radioaktiven Zerfall der verschiedenen Radionuklide im radioaktiven Abfall resultieren. Die vorliegende Studie konzentriert sich auf die Untersuchung der Wechselwirkung von Uran, als Hauptkomponente des endgelagerten abgebrannten Kernbrennstoffs, mit Opalinuston und untersucht dabei den Einfluss von Huminsäure und erhöhter Temperatur. Um das Rückhaltevermögen des Tongesteins gegenüber U(VI) und die U(VI)-Mobilität im System zu ermitteln, wurden Sorptions- und Diffusionsversuche durchgeführt. Zur Klärung, welche U(VI)- und Huminsäurespezies unter den untersuchten Bedingungen vorliegen, wurde die aquatische Speziation berechnet. Zusätzlich wurde die U(VI)-Speziation in Lösung und an der Tonoberfläche mit spektroskopischen Methoden untersucht. Vor der Untersuchung des ternären Systems U(VI) / Huminsäure / Ton wurden die eingesetzten Opalinuston-Chargen charakterisiert (z. B. spezifische Oberfläche, Kohlenstoffgehalt, Kationenaustauschkapazität, elementare Zusammensetzung, Partikelgrößenverteilung). Anschließend wurden Auslaugungsversuche mit Opalinuston in synthetischem Opalinustonporenwasser (pH 7.6, It = 0.34 mol/L) und in NaClO4 (pH 3 – 10, I = 0.1 mol/L) durchgeführt, um relevante Konkurrenzionen zu identifizieren und deren Konzentration in den Hintergrundelektrolyten zu bestimmen. Die erhaltenen Daten wurden zur Berechnung der U(VI)- und Huminsäurespeziation in Lösung verwendet. Unter Porenwasserbedingungen sowie in 0.1 mol/L NaClO4 von pH 7 bis 8.5 liegen, durch die Auflösung von Calcit (Mineralphase im Opalinuston), Calcium- und Carbonationen in Lösung vor. Dadurch wird die U(VI)-Speziation von dem aquatischen Ca2UO2(CO3)3-Komplex dominiert. Im Falle des Porenwassers ist Ca2UO2(CO3)3(aq) auch in Gegenwart von Huminsäure die dominierende U(VI)-Spezies. Dies wurde durch zeitaufgelöste laserinduzierte fluoreszenzspektroskopische Messungen nachgewiesen. Eine signifikante Änderung der U(VI)-Speziation tritt in 0.1 mol/L NaClO4 in Gegenwart von Huminsäure auf. Bei pH > 7 bestimmt der negativ geladene UO2(CO3)2HA(II)4–-Komplex die U(VI)-Speziation, wobei der Anteil von Ca2UO2(CO3)3(aq) zurückgedrängt wird. Auch die Huminsäurespeziation wird durch die vom Opalinuston ausgelaugten Ionen beeinflusst. So ist der CaHA(II)-Komplex die dominierende Huminsäurespezies in Lösung. Sorptionsversuche in 0.1 mol/L NaClO4 zeigten, dass Opalinuston gegenüber U(VI) den stärksten Retardationseffekt im pH-Bereich 4.5 bis 7 aufweist. Unter umweltrelevanten Bedingungen hingegen (pH > 7) ist die U(VI)-Sorption an Opalinuston sehr schwach. Unter Porenwasserbedingungen wurde ein Verteilungskoeffizient (Kd) von 0.0222 ± 0.0004 m3/kg ermittelt, der von Fest-Flüssig-Verhältnissen ≥ 60 g/L unabhängig ist. Außerdem wird die U(VI)-Sorption an Opalinuston in Porenwasser nicht von Huminsäure beeinflusst. Dies wird durch die Ergebnisse aus den Speziations-rechnungen unterstützt. Röntgenabsorptionsspektroskopische Untersuchungen bestätigten ebenfalls dieses Sorptionsergebnis. Die U(VI)-Diffusionsexperimente in Porenwasser bei 25 °C unter Verwendung von Opalinustonbohrkernstücken bestätigten den Kd-Wert der Sorptionsexperimente. In den Diffusionsexperimenten bei 60 °C trat eine Änderung in der U(VI)-Speziation auf. Neben Ca2UO2(CO3)3(aq) wurde eine kolloidale U(VI)-Spezies gebildet. Für die Diffusion der aquatischen U(VI)-Spezies durch Opalinuston bei 25 und 60 °C wurden annähernd gleiche scheinbare (apparente) Diffusionskoeffizienten (Da) bestimmt. Das bedeutet, der Durchbruch von U(VI) durch Opalinuston ist unabhängig von den hier untersuchten Temperaturen und wird deshalb etwa zum gleichen Zeitpunkt erwartet. Modellierungen zeigten, dass es etwa zehn Jahre dauern würde, bis eine detektierbare Menge an 233U(VI) (1×10–9 mol/L) durch ein 11 mm-dickes Opalinustonbohrkernstück migrieren würde. Zwei verschiedene Huminsäuregrößenfraktionen diffundierten durch die Opalinustonproben – eine große und eine kleine kolloidale Größenfraktion. Innerhalb von drei Monaten migrierten die hochmolekularen Huminsäurekolloide nur 500 µm in den Ton, während die niedermolekularen Huminsäurekolloide durch die gesamten Opalinustonproben diffundierten und dadurch im Auffangreservoir detektiert werden konnten. Diese Resultate demonstrieren den Filtrationseffekt des Tongesteins. Die Diffusionsversuche zeigten, dass der Einfluss von Huminsäure auf die U(VI)-Diffusion, unabhängig von der in dieser Arbeit verwendeten Temperatur, vernachlässigbar ist. Die erhaltenen Ergebnisse tragen zu Datenbanken bei, die für die Modellierung von Wechselwirkungs- und Migrationsprozessen in Uran / Tongestein-Systemen genutzt werden. Das bedeutet, die gesammelten Sorptions- und Diffusionsdaten sind nicht nur für den Langzeitsicherheitsnachweis eines Endlagers für radioaktive Abfälle von Relevanz, sondern auch für jedes tonhaltige System in der Umwelt, bei dem die geochemische Wechselwirkung mit urankontaminierten Wässern eine Rolle spielt. Bezüglich der Eignung von Opalinuston als Wirtsgestein für ein Endlager radioaktiver Abfälle lässt sich schlussfolgern, dass Opalinuston ein relativ hohes Retardationspotential bezüglich U(VI) aufweist. Wenn U(VI) als Bestandteil des radioaktiven Abfalls bei Wassereinbruch im Endlager in die Umgebung freigesetzt wird, wird es unter umweltrelevanten Bedingungen von Calcium- und Carbonationen, welche aus dem Opalinuston herausgelöst werden, komplexiert. Dabei bildet sich Ca2UO2(CO3)3(aq). Dieser Komplex wird nur schwach durch Sorption am Tongestein zurückgehalten, was zu einer erhöhten U(VI)-Mobilität im Wirtsgestein führen kann. Im untersuchten System wird die U(VI)-Migration durch das Tongestein jedoch durch molekulare Diffusion bestimmt. Sie verzögert die Migration von Ca2UO2(CO3)3(aq) durch Opalinuston und stellt somit den maßgeblichen Retardationsprozess im System dar. Huminsäure hat keinen signifikanten Einfluss auf die U(VI) / Opalinuston-Wechselwirkung, sogar bei einer erhöhten Temperatur von 60 °C. Dies wurde mittels Speziationsmodellierungen sowie durch Sorptions- und Diffusionsversuche gezeigt.

Clay shales are currently being assessed as possible host rock formations for the deep geological disposal of radioactive waste. However, one main concern is that the favourable long-term isolation properties of the intact rock mass could be negatively affected by the formation of an excavation damaged zone (EDZ) around the underground openings. This thesis investigated the deformation and failure process of a clay shale, namely Opalinus Clay, with particular focus on the influence of anisotropy on the short-term response of circular tunnels. To achieve this goal, a hybrid continuum-discontinuum numerical approach was used in combination with new field measurements from the Mont Terri underground research laboratory. The response of Opalinus Clay during the excavation of a full-scale emplacement (FE) test tunnel was characterized by geodetic monitoring of wall displacements, radial extensometers and longitudinal inclinometers. The deformation measurements indicated strong directionality induced by the combined effect of in situ stress field and presence of bedding planes striking parallel to the tunnel axis, with the most severe deformation occurring in the direction approximately perpendicular to the material layering. Computer simulations were conducted using a newly-extended combined finite-discrete element method (FEM/DEM), a numerical technique which allows the explicit simulation of brittle fracturing and associated seismicity. The numerical experimentation firstly focused on the laboratory-scale analysis of failure processes (e.g., acoustic activity) in brittle rocks, and on the role of strength and modulus anisotropy in the failure behaviour of Opalinus Clay in tension and compression. The fracturing behaviour of unsupported circular excavations in laminated rock masses was then analyzed under different in situ stress conditions. Lastly, the modelling methodology was applied to the aforementioned FE tunnel to obtain original insights into the possible EDZ formation process around emplacement tunnels for nuclear waste. The calibrated numerical model suggested delamination along bedding planes and subsequent extensional fracturing as key mechanisms of the damage process potentially leading to buckling and spalling phenomena. Overall, the research findings may have a potential impact on the constructability and support design of an underground repository as well as implications for its long-term safety assessment procedure.

Clay shales are currently being assessed as possible host rock formations for the deep geological disposal of radioactive waste. However, one main concern is that the favourable long-term isolation properties of the intact rock mass could be negatively affected by the formation of an excavation damaged zone (EDZ) around the underground openings. This thesis investigated the deformation and failure process of a clay shale, namely Opalinus Clay, with particular focus on the influence of anisotropy on the short-term response of circular tunnels. To achieve this goal, a hybrid continuum-discontinuum numerical approach was used in combination with new field measurements from the Mont Terri underground research laboratory. The response of Opalinus Clay during the excavation of a full-scale emplacement (FE) test tunnel was characterized by geodetic monitoring of wall displacements, radial extensometers and longitudinal inclinometers. The deformation measurements indicated strong directionality induced by the combined effect of in situ stress field and presence of bedding planes striking parallel to the tunnel axis, with the most severe deformation occurring in the direction approximately perpendicular to the material layering. Computer simulations were conducted using a newly-extended combined finite-discrete element method (FEM/DEM), a numerical technique which allows the explicit simulation of brittle fracturing and associated seismicity. The numerical experimentation firstly focused on the laboratory-scale analysis of failure processes (e.g., acoustic activity) in brittle rocks, and on the role of strength and modulus anisotropy in the failure behaviour of Opalinus Clay in tension and compression. The fracturing behaviour of unsupported circular excavations in laminated rock masses was then analyzed under different in situ stress conditions. Lastly, the modelling methodology was applied to the aforementioned FE tunnel to obtain original insights into the possible EDZ formation process around emplacement tunnels for nuclear waste. The calibrated numerical model suggested delamination along bedding planes and subsequent extensional fracturing as key mechanisms of the damage process potentially leading to buckling and spalling phenomena. Overall, the research findings may have a potential impact on the constructability and support design of an underground repository as well as implications for its long-term safety assessment procedure.

La sûreté des installations de stockage profond des déchets radioactifs repose sur l’évaluation des propriétés de confinement de la barrière géologique et des processus qui y régissent le transport des radionucléides. La thèse est menée dans le cadre de l’expérience Deep Borehole du projet Mont Terri. Elle vise à renforcer l’évaluation de l’importance relative des phénomènes de transfert convectifs et diffusifs au sein de l’Argile à Opalines (OPA) et à apporter des éclaircissements concernant l’impact des phénomènes transitoires chimique et hydraulique sur ces transferts et la génération d’anomalies de pression. Un premier volet expérimental a permis d’acquérir les paramètres de transport advectifs, diffusifs, et les forces motrices associées, nécessaires à l’estimation des flux d’eau et de solutés entre l’OPA et les aquifères adjacents. Les données de température et de pression révèlent un gradient géothermique de 8.5°C/100 m et un excès de charge d’au moins 60 m. L’inversion du profil de chlorure par méthode Bayésienne de type Monte Carlo Markov Chain valide l’évolution paléohydrogéologique du site proposé dans la littérature en considérant un transport diffusif pur à travers la formation. La contribution des phénomènes de transport osmotique a été déterminée en interprétant le profil de pression à l’aide de simulations transitoires considérant l’évolution temporelle de la chlorinité et de la pression au cours du scénario géologique et de simulations en pseudo régime permanent. Ce profil est reproduit en évaluant le flux advectif couplé incluant l’advection de Darcy, la chemo-osmose et la thermo-osmose, avec une contribution majeure de ce dernier processus. / The safety of radioactive waste disposal facilities in deep geological formation depends on the evaluation of the rock confining properties and the processes governing radionuclides transfer. The thesis is conducted in the framework of Deep Borehole experiment of the Mont Terri project. The purpose of this research is to build confidence with regard to understanding relative importance of diffusive and convective phenomena withine the Opalinus Clay (OPA) and to identify the impact of a hydraulic and chemical transient behaviour on the transfers of fluid and solutes, and anomalous pressures generation.A first experimental stage enabled to acquire the advective and diffusive transport parameters, and the associated driving forces, necessary to the evaluation of fluid and solute fluxes between the OPA and its adjacent aquifers. Temperature and pressure measurements revealed a geothermal gradient of 8.5 °C/100 m and an excess of hydraulic head of at least 60 m.The chloride profile inversion by a Bayesian method with a Monte Carlo Markov Chain algorithm validates the paleohydrological evolution proposed in the litterature, considering a pure diffusive transport through the argillaceous formation. The contribution of osmotic transport phenomena was assessed by interpreting the pressure profile, using transient simulations that takes into account the temporal evolution of chlorinity and pressure during the geological scenario, and pseudo steady-state simulations. This profile is reproduced by evaluating the coupled advective flux, including pure advection, chemo-osmosis and thermo-osmosis, with a major contribution of the latter process.

The objective of this project was the study of basic interaction processes in the systems actinide - clay organics - aquifer and actinide - natural clay - clay organics - aquifer. Thus, complexation, redox, sorption and diffusion studies were performed. To evaluate the influence of nitrogen, phosphorus and sulfur containing functional groups of humic acid (HA) on the complexation of actinides in comparison to carboxylic groups, the Am(III) and U(VI) complexation by model ligands was studied by UV-Vis spectroscopy and TRLFS. The results show that Am(III) is mainly coordinated via carboxylic groups, however, probably stabilized by nitrogen groups. The U(VI) complexation is dominated by carboxylic groups, whereas nitrogen and sulfur containing groups play a minor role. Phosphorus containing groups may contribute to the U(VI) complexation by HA, however, due to their low concentration in HA they play only a subordinate role compared to carboxylic groups. Applying synthetic HA with varying sulfur contents (0 to 6.9 wt.%), the role of sulfur functionalities of HA for the U(VI) complexation and Np(V) reduction was studied. The results have shown that sulfur functionalities can be involved in U(VI) humate complexation and act as redox-active sites in HA for the Np(V) reduction. However, due to the low content of sulfur in natural HA, its influence is less pronounced. In the presence of carbonate, the U(VI) complexation by HA was studied in the alkaline pH range by means of cryo-TRLFS (-120°C) and ATR FT-IR spectroscopy. The formation of the ternary UO2(CO3)2HA(II)4− complex was detected. The complex formation constant was determined with log β0.1 M = 24.57 ± 0.17. For aqueous U(VI) citrate and oxalate species, luminescence emission properties were determined by cryo-TRLFS and used to determine stability constants. The existing data base could be validated. The U(VI) complexation by lactate, studied in the temperature range 7 to 65°C, was found to be endothermic and entropy-driven. In contrast, the complex stability constants determined for U(VI) humate complexation at 20 and 40°C are comparable, however, decrease at 60°C. For aqueous U(IV) citrate, succinate, mandelate and glycolate species stability constants were determined. These ligands, especially citrate, increase solubility and mobility of U(IV) in solution due to complexation. The U(VI) sorption onto crushed Opalinus Clay (OPA, Mont Terri, Switzerland) was studied in the absence and presence of HA or low molecular weight organic acids, in dependence on temperature and CO2 presence using OPA pore water as background electrolyte. Distribution coefficients (Kd) were determined for the sorption of U(VI) and HA onto OPA with (0.0222 ± 0.0004) m3/kg and (0.129 ± 0.006) m3/kg, respectively. The U(VI) sorption is not influenced by HA (50 mg/L), however, decreased by low molecular weight organic acids (> 1×10-5 M), especially by citrate and tartrate. With increasing temperature, the U(VI) sorption increases both in the absence and in the presence of clay organics. The U(VI) diffusion in compacted OPA is not influenced by HA at 25 and 60°C. Predictions of the U(VI) diffusion show that an increase of the temperature to 60°C does not accelerate the migration of U(VI). With regard to uranium-containing waste, it is concluded that OPA is suitable as host rock for a future nuclear waste repository since OPA has a good retardation potential for U(VI).