La nature est complexe et c’est en toute modestie que les ingénieurs doivent chercher à prédire le comportement des ouvrages dans le sous-sol. La réalisation de projets industriels dans le domaine souterrain, à forts enjeux économiques et sociaux (traversées alpines, stockage de déchets nucléaires), nécessite d’évoluer vers une meilleure compréhension des mécanismes comportementaux des ouvrages à concevoir. Cette amélioration passe par une meilleure représentativité physique des mécanismes macroscopiques et par la mise à disposition d’outils de prédiction adaptés aux attentes et aux besoins des ingénieurs. Les outils de calculs développés dans ce travail s’inscrivent dans cette volonté de rapprocher les attentes de l’industrie et les connaissances liées à la rhéologie des géomatériaux. Ces développements ont ainsi débouché sur la proposition d’un modèle de comportement mécanique, adapté aux roches peu fissurées et assimilables à des milieux continus, intégrant, en particulier, l’effet du temps. Fil conducteur de cette étude, la problématique du sujet de thèse concerne précisément la prise en compte du comportement différé des massifs rocheux dans les modélisations et ses conséquences sur les ouvrages souterrains.Fondé sur des concepts physiques de référence, définis à différentes échelles (macro/méso/micro), le modèle rhéologique développé est transcrit dans un formalisme mathématique dans le but d’être mis en oeuvre numériquement.Les applications numériques proposées s’inscrivent principalement dans le contexte du stockage des déchets radioactifs. Elles concernent deux configurations d’ouvrages rigoureusement différentes : l’excavation du laboratoire souterrain canadien de l’AECL, dans le granite du Lac du Bonnet et le creusement de la galerie GMR du laboratoire de Bure (Meuse/Haute-Marne) dans l’argilite de l’Est. Dans les deux cas, l’utilisation du modèle a permis de mettre en évidence l’apport de la prise en compte du comportement différé sur la représentativité des prédictions numériques du comportement à court, moyen et long termes des ouvrages souterrains / Nature is complex and must be approached in total modesty by engineers seeking to predict the behavior of underground openings. The engineering of industrial projects in underground situations, with high economic and social stakes (Alpine mountain crossings, nuclear waste repository), mean striving to gain better understanding of the behavioral mechanisms of the openings to be designed. This improvement necessarily involves better physical representativeness of macroscopic mechanisms and the provision of prediction tools suited to the expectations and needs of the engineers. The calculation tools developed in this work is in step with this concern for satisfying industrial needs and developing knowledges related to the rheology of geomaterials. These developments led to the proposing of a mechanical constitutive model, suited to lightly fissured rocks, comparable to continuous media, while integrating more particularly the effect of time.Thread of this study, the problematics ensued from the subject of the thesis is precisely about the rock mass delayed behavior in numerical modeling and its consequences on underground openings design.Based on physical concepts of reference, defined in several scales (macro/meso/micro), the developed constitutive model is translated in a mathematical formalism in order to be numerically implemented.Numerical applications presented as illustrations fall mainly within the framework of nuclear waste repository problems. They concern two very different configurations of underground openings: the AECL’s underground canadian laboratory, excavated in the Lac du Bonnet granite, and the GMR gallery of Bure’s laboratory (Meuse/Haute-Marne), dug in argillaceous rock.In this two cases, this constitutive model use highlights the gains to be obtained from allowing for delayed behavior regarding the accuracy of numerical tunnel behavior predictions in the short, medium and long terms

This diploma thesis deals with nuclear energetics and its impact to the environment. Present state of the energetics, mainly nuclear energetics, in the Czech Republic is discussed here. Also perspective of nuclear energetics is given. The thesis describes nuclear power plant waste handling and also spent nuclear fuel handling. Nuclear power plant is compared with other sources of electric energy, which are counted to the energetic mix. The author focuses on fossil fuels and also on the renewable energy sources. The amount of produced waste to the unit of produced energy, built up area, safety and economic indicators and other parameters are followed for each source of energy.

Non-isothermal compositional two-phase flow is considered to be one of the fundamental physical processes in the field of water resources research. The strong non-linearity and discontinuity emerging from phase transition phenomena pose a serious challenge for numerical modeling. Recently, Lauser et al.[1] has proposed a numerical scheme, namely the Nonlinear Complementary Problem (NCP), to handle this strong non-linearity. In this work, the NCP is implemented at both local and global levels of a Finite element algorithm. In the former case, the NCP is integrated into the local thermodynamic equilibrium calculation. While in the latter one, it is formulated as one of the governing equations. The two different formulations have been investigated through several well established benchmarks and analyzed for their efficiency and robustness. In the second part of the thesis, the presented numerical formulations are applied for application and process studies in the context of nuclear waste disposal in Switzerland. Application studies comprehend the coupling between multiphase transport model and complex bio-geo-chemical process to investigate the degradation of concrete material due to two major reactions: carbonation and Aggregate Silica Reaction(ASR). The chemical processes are simplified into a lookup table and cast into the transport model via source and sink term. The efficiency and robustness of the look-up table are further compared with a fully reactive transport model.

The migration behavior of actinides and other radioactive contaminants in the environment is controlled by prominent molecular phenomena such as hydrolysis and complexation reactions in aqueous solutions as well as the diffusion and sorption onto minerals present along groundwater flow paths. These reactions significantly influence the mobility and bioavailability of the metal ions in the environment, in particular at liquid-solid interfaces. Hence, for the assessment of migration processes the knowledge of the mechanisms occurring at interfaces is crucial. The required structural information can be obtained using various spectroscopic techniques. In the present study, the speciation of uranium(VI) and neptunium(V) at environmentally relevant mineral – water interfaces of oxides of titania, alumina, silica, zinc, and alumosilicates has been investigated by the application of attenuated total reflection Fourier-transform infrared (ATR FT-IR) spectroscopy. Moreover, the distribution of the hydrolysis products in micromolar aqueous solutions of U(VI) and Np(V/VI) at ambient atmosphere has been characterized for the first time, by a combination of ATR FT-IR spectroscopy, near infrared (NIR) absorption spectroscopy, and speciation modeling applying updated thermodynamic databases. From the infrared spectra, a significant change of the U(VI) speciation is derived upon lowering the U(VI) concentration from the milli- to the micromolar range, strongly suggesting the dominance of monomeric U(VI) hydrolysis products in the micromolar solutions. In contradiction to the predicted speciation, monomeric hydroxo species are already present at pH ≥ 2.5 and become dominant at pH 3. At higher pH levels (> 6), a complex speciation is evidenced including carbonate containing complexes. For the first time, spectroscopic results of Np(VI) hydrolysis reactions are provided in the submillimolar concentration range and at pH values up to 5.3, and they are comparatively discussed with U(VI). For both actinides, the formation of similar species is suggested at pH ≤ 4, whereas at higher pH, the infrared spectra evidence structurally different species. At pH 5, the formation of a carbonate-containing dimeric complex, that is (NpO2)2CO3(OH)3−, is strongly suggested, whereas carbonate complexation occurs only under more alkaline conditions in the U(VI) system. The results from the experiments of the sorption processes clearly demonstrate the formation of stable U(VI) surface complexes at all investigated mineral phases. This includes several metal oxides, namely TiO2, Al2O3, and SiO2, serving as model systems for the elucidation of more complex mineral systems, and several alumosilicates, such as kaolinite, muscovite and biotite. From a multiplicity of in situ experiments, the impact of sorbent characteristics and variations in the aqueous U(VI) system on the sorption processes was considered. A preferential formation of an inner-sphere complex is derived from the spectra of the TiO2 and SiO2 phases. In addition, since the in situ FT-IR experiments provide an online monitoring of the absorption changes of the sorption processes, the course of the formation of the U(VI) surface complexes can be observed spectroscopically. It is shown that after prolonged sorption time on TiO2, resulting in a highly covered surface, outer-sphere complexation predominates the sorption processes. The prevailing crystallographic modification, namely anatase and rutile, does not significantly contribute to the spectra, whereas surface specific parameters, e.g. surface area or porosity are important. A significant different surface complexation is observed for Al2O3. The formation of inner-spheric species is assumed at low U(VI) surface coverage which is fostered at low pH, high ionic strength and short contact times. At proceeded sorption the surface complexation changes. From the spectra, an outer-spheric coordination followed by surface precipitation or polymerization is deduced. Moreover, in contrast to TiO2, the appearance of ternary U(VI) carbonate complexes on the γ-Al2O3 surface is suggested. The first results of the surface reactions on more complex, naturally occurring minerals (kaolinite, muscovite and biotite) show the formation of U(VI) inner-sphere sorption complexes. These findings are supported by the spectral information of the metal oxide surfaces. In this work, first spectroscopic results from sorption of aqueous Np(V) on solid mineral phases are provided. It is shown that stable inner-sphere surface species of NpO2+ are formed on TiO2. Outer-sphere complexation is found to play a minor role due to the pH independence of the sorption species throughout the pH range 4 – 7.6. The comparative spectroscopic experiments of Np(V) sorption onto TiO2, SiO2, and ZnO indicate structurally similar bidentate surface complexes. The multiplicity of IR spectroscopic experiments carried out within this study yields a profound collection of spectroscopic data which will be used as references for future investigations of more complex sorption systems in aqueous solution. Furthermore, from a methodological point of view, this study comprehensively extends the application of ATR FT-IR spectroscopic experiments to a wide range in the field of radioecology. The results obtained in this work contribute to a better understanding of the geochemical interactions of actinides, in particular U(VI) and Np(V/VI), in the environment. Consequently, more reliable predictions of actinides migration which are essential for the safety assessment of nuclear waste repositories can be performed. / Das Migrationsverhalten von Aktiniden und anderen radioaktiven Schadstoffen in der Umwelt wird von wichtigen molekularen Prozessen entlang der Grundwasserfließwege reguliert. Dazu gehören sowohl die Hydrolyse und Komplexierung in wässrigen Lösungen als auch Diffusion und Sorption der Schwermetalle an Mineralen. Diese Reaktionen beeinflussen entscheidend die Mobilität und Bioverfügbarkeit der Metallionen in der Umwelt, insbesondere an den fest-flüssig Grenzflächen. Genaue Kenntnisse über die an diesen Grenzflächen stattfindenden Mechanismen sind somit entscheidend, um Migrationsprozesse verlässlich abschätzen zu können. Die benötigten strukturellen Informationen können mit verschiedenen spektroskopischen Techniken ermittelt werden. Das Ziel der vorliegenden Arbeit war die Untersuchung der Speziation von Uran(VI) und Neptunium(V) an umweltrelevanten Grenzflächen von Oxiden des Titans, Aluminiums, Siliziums und Zinks und von Alumosilikaten mittels ATR FT-IR Spektroskopie. Des Weiteren wurde die Verteilung aquatischer Spezies in mikromolaren Lösungen des U(VI) und Np(V/VI) unter Normalbedingungen charakterisiert. Diese erstmalige Untersuchung wurde mit einer Kombination aus Speziationsmodellierung unter Anwendung aktueller thermodynamischer Daten und ATR FT-IR und NIR Absorptionsspektroskopie realisiert. Die Infrarotspektren zeigen eine deutliche Änderung der Speziesverteilung im Konzentrationsverlauf vom millimolaren zum mikromolaren Bereich. Dies verweist auf die Bildung monomerer U(VI) Hydrolyseprodukte. Im Gegensatz zu berechneten Speziationen werden diese monomeren Komplexe schon bei pH ≥ 2,5 gebildet und dominieren die Speziation bei pH 3. Bei höheren pH-Werten (> 6) konnte eine komplexe Speziesverteilung mit Anteilen von Karbonatkomplexen nachgewiesen werden. Erstmals konnten im Rahmen dieser Arbeit spektroskopische Befunde der Hydrolysereaktionen des Np(VI) im submillimolaren Konzentrationsbereich bis pH 5,3 erhalten werden. Diese wurden im Vergleich mit der U(VI) Speziation diskutiert. Obwohl im sauren Bereich (pH ≤ 4) die Bildung ähnlicher Komplexe nachgewiesen wurde, zeigen die bei höheren pH-Werten erhaltenen Spektren eine unterschiedliche Speziesverteilung. Im Gegensatz zum U(VI) bildet das Np(VI) schon bei pH 5 karbonathaltige aquatische Spezies wie (NpO2)2CO3(OH)3−. Die Ergebnisse der Sorptionsexperimente von U(VI) zeigen die Bildung stabiler Oberflächenkomplexe an allen untersuchten Mineralphasen. Dies umfasst mehrere als Modellsystem dienende Metalloxide wie TiO2, Al2O3 und SiO2, als auch komplexere Alumosilikate wie Kaolinit, Muskovit und Biotit. Für eine detaillierte Charakterisierung der Oberflächenkomplexe wurde eine Vielzahl von in situ Sorptionsexperimenten durchgeführt, die den Einfluss unterschiedlicher Parameter der mineralischen Phase als auch des wässrigen U(VI) Systems berücksichtigen. Die bevorzugte Bildung von innersphärischen Komplexen an TiO2 und SiO2 wird aus den spektroskopischen Daten abgeleitet. Da die in situ FT-IR Spektroskopie eine kontinuierliche Registrierung der Absorptionsänderungen während der ablaufenden Sorptionsprozesse erlaubt, kann somit der Verlauf dieser Prozesse quasi in Echtzeit spektroskopisch verfolgt werden. Es konnte gezeigt werden, dass mit fortschreitender Sorptionsdauer, d.h. bei hohen Beladungsdichten, die Bildung einer weiteren außersphärischen Spezies die Sorption dominert. Die vorliegende kristallographische Modifikation, Anatas und Rutil, ist nicht maßgeblich für das Auftreten unterschiedlicher Sorptionsprozesse verantwortlich, obwohl Parameter wie die spezifische Oberfläche und die Porosität für den Sorptionsprozess von Bedeutung sind. Deutlich verschiedene Oberflächenreaktionen werden für Al2O3 beobachtet. Aus den Spektren kann die Ausbildung einer innersphärischen Spezies bei sehr niedrigen U(VI) Beladungen, niedrigen pH-Werten, hohen Ionenstärken und kurzen Kontaktzeiten abgeleitet werden. Bei fortschreitender Sorption ändert sich die Art der Oberflächenkomplexe. Zunächst bilden sich außersphärische Spezies, während im weiteren Verlauf die Spektren auf eine beginnende Oberflächenausfällung bzw. Polymerisation hinweisen. Weiterhin wird das Auftreten von ternären U(VI) Karbonatkomplexen an γ-Al2O3 aus den spektroskopischen Daten abgeleitet. Die ersten Ergebnisse der Sorptionsexperimente an komplexeren, natürlich auftretenden Mineralphasen (Kaolinit, Muskovit und Biotit) zeigen eine bevorzugte Ausbildung von innersphärischen U(VI) Komplexen. Diese Resultate werden durch die spektralen Befunde der Experimente der Metalloxide gestützt. Erstmalig werden in dieser Arbeit spektroskopische Ergebnisse der Sorptionsprozesse von wässrigen Np(V) an verschiedenen Mineralphasen präsentiert. Wie U(VI) bildet Np(V) stabile innersphärische Oberflächenkomplexe an TiO2. Die Speziesverteilung an der TiO2 Oberfläche ist im pH Bereich 4 – 7,6 konstant. Daher ist zu erwarten, dass eine außersphärische Komplexierung hier nur eine untergeordnete Rolle spielt. Der Vergleich von Spektren der Np(V) Sorptionskomplexe an TiO2, SiO2 und ZnO weist auf die Bildung strukturell ähnlicher bidentater Komplexe hin. Die Vielzahl der hier vorgestellten infrarotspektroskopischen Experimente bietet eine fundierte Sammlung spektroskopischer Daten, die für zukünftige Untersuchungen komplexer aquatischer und mineralischer Systeme unerlässlich ist. Gleichzeitig wurde der Anwendungsbereich der ATR FT-IR Technik auf dem Gebiet der Radioökologie umfassend erweitert. Die im Rahmen dieser Arbeit gewonnenen Ergebnisse tragen zu einem besseren Verständnis der geochemischen Wechselwirkungen von Aktiniden, im Speziellen von U(VI) und Np(V) in der Umwelt bei. Damit unterstützen sie den Aufklärungsprozess der Migration von radioaktiven Kontaminationen und dienen als Grundlage für zuverlässige Prognosen für die Sicherheitsbewertung von Endlagern für nukleare Abfälle.

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Ce travail contribue à mieux connaître et contraindre la minéralogie du plomb. L’incorporation du plomb dans des minéraux du manteau terrestre a été étudiée ; on observe que deux phases importantes du globe sont des candidates pour accueillir le plomb : la phase CAS dans les plaques en subduction et la phase pérovskite CaSiO3 troisième minéral majeur du manteau inférieur. D’autres minéraux du manteau supérieur ont été également étudiés pour une incorporation du plomb. Des calculs ab-initio ont été réalisés sur un composé simple de plomb, PbO2. Ces calculs permettent de mettre en évidence l’évolution de PbO2 à hautes pressions jusqu’à 130 GPa. La spéciation du plomb dans des minéraux naturels métamictes a aussi été explorée : cette étude de l’élément fils des éléments radioactifs U et Th, dans ces minéraux naturels permet de mieux contraindre l’immobilisation durable des déchets nucléaires / This work helps to better understand and constrain the mineralogy of lead. The incorporation of lead in mantle minerals has been studied, we observe that two important mineral phases of the globe are candidates to accommodate lead in their structures : the CAS phase present in subducted plates and the CaSiO3 perovskite which is the third major mineral phase of the Earth’s lower mantle. Other minerals present in the upper mantle have also been studied for the incorporation of lead. Ab-initio calculations have been performed on a simple compound of lead, PbO2. These calculations help to better constrain the evolution of PbO2 at high pressures up to 130 GPa. The speciation of lead in natural metamict minerals has also been explored : this study on lead the daughter product of radioactive U and Th in these minerals improves our knowledge of the long-term immobilization of nuclear wastes

The focus of this work is to investigate the dissolution of MW25, a non-radioactive simulant of UK high-level nuclear waste borosilicate glass, and to predict its performance in the near field of a geological repository. A single-pass flow-through (SPFT) experimental system was used to measure the forward dissolution rates of MW25. Experiments were conducted in two parts. Experiment Part 1 considers the dissolution of the waste glass in deionised water at 40 and 90 oC and circum-neutral pH. Experiment Part 2 considers the dissolution of the waste glass in simulant groundwaters, with similar compositions to groundwaters of Callovo-Oxfordian clay (lower-strength sedimentary rock (LSSR)) and Borrowdale Volcanic Group rocks (higher-strength rock (HSR)), at 40 oC and pH 7. The forward dissolution rate measured in deionised water was found to be approximately one order of magnitude higher at 90 oC than at 40 oC. A similar release was observed for Si, Mg and Al at 40 oC and 90 oC, whereas the B, Cs, Na, Li and Mo showed an order of magnitude increase when the temperature was increased from 40 to 90 oC for low q/S values. The activation energy (Ea) of the reactions shows that the dissolution process is a surface phenomenon. At 90 oC the net effect of the processes governing MW25 dissolution led to the preferential release of boron and alkali metals relative to the release of Si during the transient dissolution stage, accompanied by an increase in the concentration of silicic acid. This suggests that the solution activity of silicic acid at a higher temperature has a weak influence on the release of the mobile elements. The forward dissolution rate measured in LSSR simulant groundwater was found to be slightly higher than that measured in HSR simulant groundwater. The dissolution behaviour of MW25 in both groundwaters is consistent with its behaviour in deionised water at 40 oC, with the dissolution rates of elements increasing as flow rates were increased. However, forward dissolution rates measured in the simulant groundwaters were lower than the forward dissolution rates measured in deionised water under these experimental conditions. This is attributable to the interaction of the components of the simulant groundwaters with the glass, as revealed by post-reaction surface analyses, and a consequential lower alkalinity of the leachates collected in the experiments with simulant groundwater than in deionised water. Reactive chemical transport simulations of waste glass dissolution and radionuclide release in a hypothetical near field were conducted over a time span of a million years with GoldSim. The results showed that enclosing the waste glass in a steel canister covered by a copper canister and emplacing the waste package in a granite host rock is optimal for the long-term isolation of the radionuclides. The waste glass was found to play a significant role in the overall performance of the near field. This study features a new method for estimating the surface area of reacted glass powder more accurately than the geometric surface area estimate, which is the preferred standard method among researchers.

<p>Accelerator-driven systems for transmutation of nuclear waste have been suggested as a means for dealing with spent fuel components that pose potential radiological hazard for long periods of time. While not entirely removing the need for underground waste repositories, this nuclear waste incineration technology provides a viable method for reducing both waste volumes and storage times. Potentially, the time spans could be diminished from hundreds of thousand years to merely 1.000 years or even less. A central aspect for accelerator-driven systems design is the prediction of safety parameters and fuel economy. The simulations performed rely heavily on nuclear data and especially on the precision of the neutron cross section representations of essential nuclides over a wide energy range, from the thermal to the fast energy regime. In combination with a more demanding neutron flux distribution as compared with ordinary light-water reactors, the expanded nuclear data energy regime makes exploration of the cross section sensitivity for simulations of accelerator-driven systems a necessity. This fact was observed throughout the work and a significant portion of the study is devoted to investigations of nuclear data related effects. The computer code package EA-MC, based on 3-D Monte Carlo techniques, is the main computational tool employed for the analyses presented. Directly related to the development of the code is the extensive IAEA ADS Benchmark 3.2, and an account of the results of the benchmark exercises as implemented with EA-MC is given. CERN's Energy Amplifier prototype is studied from the perspectives of neutron source types, nuclear data sensitivity and transmutation. The commissioning of the n_TOF experiment, which is a neutron cross section measurement project at CERN, is also described.</p>

Accelerator-driven systems for transmutation of nuclear waste have been suggested as a means for dealing with spent fuel components that pose potential radiological hazard for long periods of time. While not entirely removing the need for underground waste repositories, this nuclear waste incineration technology provides a viable method for reducing both waste volumes and storage times. Potentially, the time spans could be diminished from hundreds of thousand years to merely 1.000 years or even less. A central aspect for accelerator-driven systems design is the prediction of safety parameters and fuel economy. The simulations performed rely heavily on nuclear data and especially on the precision of the neutron cross section representations of essential nuclides over a wide energy range, from the thermal to the fast energy regime. In combination with a more demanding neutron flux distribution as compared with ordinary light-water reactors, the expanded nuclear data energy regime makes exploration of the cross section sensitivity for simulations of accelerator-driven systems a necessity. This fact was observed throughout the work and a significant portion of the study is devoted to investigations of nuclear data related effects. The computer code package EA-MC, based on 3-D Monte Carlo techniques, is the main computational tool employed for the analyses presented. Directly related to the development of the code is the extensive IAEA ADS Benchmark 3.2, and an account of the results of the benchmark exercises as implemented with EA-MC is given. CERN's Energy Amplifier prototype is studied from the perspectives of neutron source types, nuclear data sensitivity and transmutation. The commissioning of the n_TOF experiment, which is a neutron cross section measurement project at CERN, is also described.