The modern world faces a number of challenges related to energy and the environment. Atmospheric levels of carbon dioxide have now surpassed the 400 ppm mark due to the burning of fossil fuels, yet despite its abundance and potential use as a C1 feedstock for value-added products, there are both thermodynamic and kinetic barriers associated with the strong carbon-oxygen bonds that preclude its widespread deployment in industry. Nuclear energy is an alternative power source that reduces carbon emissions by billions of tonnes each year, but there are widespread concerns regarding the treatment of the radioactive waste that it accrues (of which the main component is uranyl, [UO2]2+). Most of the work presented in this thesis concerns the synthesis of transition-metal complexes, with the aim of directing catalytic reactivity to convert CO2 to useful products. Part of this thesis also concerns the synthesis of uranyl complexes and the study of uranyl reduction chemistry, which is relevant to uranyl remediation and nuclear waste treatment at a fundamental level. Making use of Earth-abundant metals to carry out hydrocarbon oxidation catalysis is a further focus of this work, as the efficient production of oxygenated compounds under mild conditions is of importance to the fine-chemical industry. Chapter 1 reviews important complexes reported in the literature that successfully convert CO2 to useful products through molecular, homogenous electro-catalysis and ring-opening copolymerisation catalysis. Reactions that exemplify a two-electron reduction of uranyl (i.e. uranium(VI) to uranium(IV)) are reviewed, along with uranyl complexes that undergo ligand-centred redox to give ligand-based radicals. The state of the literature on hydrocarbon oxidation catalysis is reviewed in the introduction. The development of multinuclear, macrocyclic complexes and the reactivity of dinuclear Pacman complexes are also presented. Chapter 2 reports the synthesis and characterisation of a new set of Schiff-base macrocycles and acyclic dipyrrin ligands. A number of attempted synthetic routes towards incorporating a dipyrrin coordination compartment in a macro-cyclic setting are discussed. Differences in electronic structures between dipyrromethanes and dipyrromethenes are also examined by theoretical and experimental methods. Chapter 3 introduces the coordination chemistry of these new macrocycles with zinc(II), where the isolation of dinuclear and tetranuclear complexes is demonstrated using different zinc(II) precursors. Tetranuclear zinc-alkyl complexes presented here are shown to be resistant to insertion chemistry with small molecules, but readily form zinc-oxo, -hydroxyl and -alkoxide clusters upon protonolysis with water and alcohols. These molecular clusters display reactivity towards CO2: a zinc-hydroxyl complex precipitates ZnCO3 at high temperature; and zinc-alkoxide complexes have been used to catalyse the copolymerisation reaction between CO2 and cyclohexene oxide to form polycarbonates. Chapter 4 describes the synthesis of late-transition-metal complexes of macrocyclic ligands and dipyrrins, and explores the relationship between macrocycle geometry and electronic structure. Their reactivities towards CO2 are assessed here, using cyclic voltammetry to assess the electro-catalytic activity of a number of the complexes. Chapter 5 reports the oxidation chemistry of hydrocarbon substrates catalysed by copper(II) complexes. High-temperature catalysis occurs with bimetallic copper(II) complexes, and this chapter describes how added FeCl3 acts as a co-catalyst, leading to greater catalyst stability and allowing the catalytic reaction to occur at room temperature. A range of analytical methods have been used to deduce the catalytically active species, and chemical kinetic measurements have been used to deduce a possible reaction mechanism. Chapter 6 reports the synthesis of a uranyl(VI) dipyrrin complex and details characterisation of its electronic structure by theoretical and experimental methods. Theoretical modelling has indicated that the observed two-electron reduction of uranium(VI) to uranium(IV) is facilitated by the dipyrrin ligand, representing a novel uranyl reduction mechanism.

Ce travail porte sur le fractionnement des produits de fission et les actinides mineurs (simulées par des terres rares) dans une vitrocéramique borosilicate riche en molybdène contenant des cristallites de powellite (CaMoO4) étudié par techniques d'analyse élémentaire (LIBS, LA-ICP-MS, et l'EMPA). Il a été montré que des terres rares et Sr (émetteur bêta) sont incorporés préférentiellement dans la phase powellite, tandis que Al, Fe, Zr, Zn et Cs (sources bêta-decay) restent dans le verre. Le comportement de monocristaux orientés de powellite dopé en terres rares (simulants des actinides mineurs) sous irradiations est décrit et commenté afin de comprendre son comportement à long terme dans des conditions de stockage, en utilisant l'interférométrie optique, la spectroscopie Raman, TEM, et la spectroscopie de photoluminescence. On observe que l'irradiation induit un gonflement dans powellite augmentant avec la dose d'irradiation (de 0,012 à 1,2 dpa). La saturation est atteinte à 1,2 dpa. Une contrainte anisotrope associée à un changement du volume de la maille dans le monocristal de powellite a été mis en évidence et analysée par suivi de la position des raies v1 (Ag) et v3 (Eg) des modes Raman. Le désordre induit dans la structure de powellite irradiée est signé par l'augmentation de la largeur des raies Raman. La caractérisation fine par TEM indique que les dommages structuraux induits dans la powellite irradiée suivent l'évolution suivante de la structure cristalline : défauts ponctuels, dislocations, mosaïcité. Il a été confirmé à la fois par Raman et par TEM que la structure powellite résiste fortement à l'irradiation et n'atteint jamais l'état d'amorphisation dans la gamme dpa étudiée (0,012 à 5,0) / The fractionation of fission products and minor actinides (simulated by rare-earth elements) is studied in a Morich borosilicate glass-ceramic containing powellite (CaMoO4) crystallites, using elemental analysis techniques (LIBS, LA-ICPMS, and EMPA). For Mo-rich borosilicate glass-ceramic containing powellite crystallites, it was suggested that rare earth elements and Sr (beta-decay source) are prone to incorporate into the powellite phase, while Al, Fe, Zr et Cs (beta-decay source) and Zn remain in the glass matrix. The behavior of rare-earth (surrogates of radioactive minor actinides) doped powellite single crystal under irradiations figure out its longterm behavior in storage conditions, using optical interferometry, Raman spectroscopy, TEM, and luminescent spectroscopy. It is observed that the irradiation-induced swelling in powellite first increased with irradiation dose (0.012 to 1.2 dpa), then reached saturation after 1.2 dpa Anisotropic stress and lattice volume change induced by irradiation in powellite single crystal were found and analyzed by determining the peak position of V1 (Ag) et V3 (Eg) Raman modes. Structure disorder of irradiated powellite in medium-range order was represented by the Raman linewidth broadening. According to the TEM characterization, the structural damages of irradiated powellite followed an evolution of crystalline structure, point defects, dislocations, mosaicity. It was confirmed by both Raman and TEM that powellite resisted strongly and never reached amorphization within the studied dpa range (0.012 to 5.0)

Rhetorical choices and strategies are central to democratic decision-making, especially regarding decisions on matters that are open for argumentation depending on perspective. The thesis considers public meetings on Swedish nuclear waste management as an example of rhetorical argumentation, specifically in relation to the project of finding a place for final deposition of the high-level spent nuclear fuel – with local geological investigation as a critical part of that project. Project managers have met with other organizations such as protest groups, associations of experts and authorities on several occasions, mainly through local and national hearings. The thesis is guided by a research question regarding the most salient challenges to a resilient rhetorical dialogue for nuclear waste management. The concept of rhetorical dialogue is applied in two ways. Firstly to explain the lack of dialogue that is experienced by participants despite arrangements to reach consensus-oriented dialogue in the Habermasian sense. Secondly in a discussion of rhetorical relations that might explain ambiguity in participants’ interpretations of each other. Three meetings are compared: two local meetings at sites of geological investigation (Kynnefjäll 1979 and Kolsjön 1985) and one national meeting held in Stockholm in 2008. Research materials have been collected from the archives of participating organizations and from interviews with participants. Analyses of these materials are combined with a rhetorical analysis of meeting recordings, with a specific focus on question-reply argumentation. One main conclusion is that the principal rhetorical challenges concern the roles of participants in relation to the rhetorical situation, the establishment of rhetorical genre in the format of hearings, and inclusion of relevant perspectives in the early project phase.

A nuclear waste stream is the complete flow of waste material from origin to treatment facility to final disposal. The objective of this study was to design and develop a Geographic Information Systems (GIS) module using Google Application Programming Interface (API) for better visualization of nuclear waste streams that will identify and display various nuclear waste stream parameters. A proper display of parameters would enable managers at Department of Energy waste sites to visualize information for proper planning of waste transport. The study also developed an algorithm using quadratic Bézier curve to make the map more understandable and usable. Microsoft Visual Studio 2012 and Microsoft SQL Server 2012 were used for the implementation of the project. The study has shown that the combination of several technologies can successfully provide dynamic mapping functionality. Future work should explore various Google Maps API functionalities to further enhance the visualization of nuclear waste streams.

Lanthanide(III) and actinide complexes with the N-donor extractants which are proposed for se in next generation separation processes, CyMe4-BTPhen and CyMe4-BTBP, have been synthesised and characterised in idealised synthetic and real extraction conditions. Next generation spent nuclear fuel reprocessing is necessary in order to reduce the longevity of activity (from 100,000’s to 100-1,000’s years) through re-use as fuel in GenIV reactor programs. The N donor extractants have been previously shown to preferentially extract the trivalent An ions over the Ln ions in biphasic acidic extraction processes, a necessary task due to the large neutron capture crosssections of the lanthanides, and the reasons behind this selectivity have been investigated here. Proposed processes that use these extractants are called SANEX and GANEX. The SANEX process is undertaken after a PUREX-style process where only the trivalent minor actinides and the lanthanides are present during the separation. Whereas, in the GANEX process the organic phase contains the N-donor molecule and another extractant, such as TBP, with the aqueous phase containing the entire An series in various oxidation states. Speciation of the Ln3+ ions with the N-donor molecules has been shown to be dominated by 1:2 (M:L) complexes in the bulk organic phase post extraction and coordination is completed by a small ligand, either H2O or NO3-. Spectrophotometric titration yielded logβ values for the 1:2 (M:L) complexes of Pr3+, Eu3+ and Tb3+ nitrate salts. In all cases it was shown that the CyMe4-BTPhen molecule has a greater affinity than the CyMe4-BTBP molecule for the Ln3+ ions, as expected given the ‘locked’ design of CyMe4-BTPhen. The uranyl ion was shown to only form 1:1 (M:L) complexes in solution with the N-donor molecules but structural characterisation showed it to also form 2:1 (M:L) complexes with the metal ions bridged by a peroxide anion. The formation of this species was found to require a protic solvent, light and molecular dioxygen. Again, binding was shown, by spectrophotometric titration, to be stronger with CyMe4-BTPhen than CyMe4-BTBP.The speciation of the tetravalent An ions, Pu4+ and Th4+ was studied using 1H NMR and X-ray absorption spectroscopy in GANEX style conditions. When the organic phase contains TBP and the N donor extractants, complexation is completed by TBP in the post extraction organic phase and the extraction of Th4+ is exclusively completed by TBP but by both extractants for Pu4+. In both cases, the major bulk species was identified as Pu/Th(NO3)4.3TBP, although complexes of the N donor extractants and the An4+ have been observed in idealised conditions, in both 1:1 and 1:2 (M:L) stoichiometries, depending on the solution composition. U4+ was shown to form a variety of complexes of a myriad of M:L stoichiometries.

Apresentamos um estudo de solidificaçaõ e lixiviacão de matrizes de vidros porosos de alto teor de sílica armazenando 20% em peso de solução aquosa simuladora de rejeitos nucleares de alto nível de radioatividade do tipo Savanah River Labratory. A matriz porosa foi preparada após o tratamento térmico de um vidro de 65% SiO2-27%B2O3-8%Na2O, que sofreu separação de fase à 560°C por 20 horas e lixiviado em HCl - 3N à 90°C. O tamanho dos poros (tipicamente de 100 à 250Å de diâmetro) , foi determinado utilizando o método BET. Após sinterização à 1300°C em ar, as amostras foram caracterizadas física e quimicamente através de testes de lixiviação padronizados MCC1, Soxhlet (MCC5) e Estagnante durante cerca de 28 dias. Determinamos a perda de peso total, o pH, as taxas de lixiviação diferencial e as concentrações acumuladas para os seguintes elementos: Si, Na, B, Ca, Mn, Al, Fe e Ni com técnicas de ICP e espectroscopia de chama para o caso do Na. Os resultados são comparados com os obtidos com vidros borosilicatos de referência, fabricados por fusão convencional (SRL 131, PNL 76-68, MCC 76-68, SRL TDS 131, AVM-Ml à M7), vidros fabricados pela técnica sol-gel (TDS 211), vidros de alto teor de sílica (CU PGM), synroc-D, cerâmicas manufaturadas, concreto FUETAP e matrizes metálicas. Os valores obtidos são similares àqueles obtidos com os melhores vidros borosilicato presentemente usados. / We present a study of the sinterization and of the leaching behavior of a high silica porous glass matrix containing 20 weight % of simulated solution of high level liquid nuclear waste of the type Savanah River Laboratory. The porous matrix has been prepared after heat treatment of a 65% SiO2-27%B2O3-8%Na2O glass, phase separate at 560°C for 20 hours and leached in 3N HCl at 90°C. The pore size (typically 100-250Å in diameter) has been determined by the BET method. After sinterization in air at 1300°C, the samples have been physically and chemically characterized during 28 days using the MCC1, Estagnant and Soxhlet (MCC5) standard tests. We have determined thetotal weight loss, the pH, the diferential leaching rate and the cumulative concentrations for the following elements: Si, Na, B, Ca, Mn, Al, Fe and Ni by ICP technique, for Na flames spectroscopy. The results are compared with these obtained with other reference borosilicate glasses made by conventional fusion techniques (SRL 131, PNL 76-68, MCC 76-68, SRL TDS 131, AVM-M1 to M7), glasses made by sol-gel technique (TDS-211), porous glasses matrix (CU PGM), synroc-D, tailored ceramics, FUETAP concrete and metallic matrix. The values obtained are similar to those found for the best borosilicate glass presently used.

Os nanotubos naturais da paligorsquita, por apresentarem propriedades físicas e químicas específicas, têm potencial uso como nano sorventes e matrizes para imobilização, retenção, e solidificação de radionuclídeos presentes em efluentes nucleares. No processo de desenvolvimento de materiais com propriedades de sorção visando a incorporação e imobilização de radionuclídeos, as etapas mais importantes são a geração de sítios ativos simultaneamente com o aumento da área superficial específica e tratamento térmico adequado para conduzir ao colapso estrutural. Neste estudo foram avaliados parâmetros e condições determinantes no processo de ativação dos nanotubos naturais da paligorsquita visando a sorção de radionuclídeos de interesse na estrutura dos nanotubos e a avaliação posterior dos parâmetros que afeitam ao colapso estrutural por tratamento térmico. Por este estudo constatou-se que a otimização do processo de ativação ácida é fundamental para o aumento da capacidade de sorção de níquel usando estruturas de nanotubos naturais ativados. A condição otimizada de ativação superficial, mantendo a integridade estrutural foi removido cerca de 33,3% dos cátions de magnésio, equivalente a 6,30·10-4 mol·g-1 de magnésio em massa, aumentando a área superficial específica em 42,8%. Este aspecto permitiu a incorporação de mesma concentração molar de níquel presente nos rejeitos radioativos líquidos em um tempo de processo de 80min. / Natural palygorskite nanotubes show suitable physical and chemical properties and characteristics to be use as potential nanosorbent and immobilization matrix for the concentration and solidification of radionuclides present in nuclear wastes. In the development process of materials with sorption properties for the incorporation and subsequent immobilization of radionuclides, the most important steps are related with the generation of active sites simultaneously to the increase of the specific surface area and suitable heat treatment to producing the structural folding. This study evaluated the determining parameters and conditions for the activation process of the natural palygorskite nanotubes aiming at the sorption of radionuclides in the nanotubes structure and subsequent evaluation of the parameters involve in the structural folding by heat treatments. The optimized results about the maximum sorption capacity of nickel in activated natural nanotubes show that these structures are apt and suitable for incorporation of radionuclides similar to nickel. By this study is verified that the optimization of the acid activation process is fundamental to improve the sorptions capacities for specifics radionuclides by activated natural nanotubes. Acid activation condition optimized maintaining structural integrity was able to remove around 33.3 wt.% of magnesium cations, equivalent to 6.30·10-4 g·mol-1, increasing in 42.8% the specific surface area and incorporating the same molar concentration of nickel present in the liquid radioactive waste at 80 min.

Ce travail est consacré à l’analyse et au développement de concepts et d’outils mathématiques en vue de leur application à des problématiques propres aux sites de stockage géologique profond de déchets radioactifs. La première partie porte sur l’estimation en champ lointain de la concentration de radionucléides issus du relâchement des colis de confinement, lorsque les incertitudes sur le relâchement sont prises en compte. En s’appuyant sur les travaux de A. Bourgeat et A. Piatniski sur l’homogénéisation d’une équation de convection-diffusion avec second membre aléatoire, on développe des outils numériques permettant d’approcher le comportement probabiliste du champ de concentration dans une configuration du type site de stockage. Dans une seconde partie, on s’intéresse à la migration de gaz dans et autour d’un site de stockage. Après une revue sur la modélisation physique des écoulements diphasiques de type eau/hydrogène en milieu poreux, on propose une nouvelle formulation mathématique du problème qui décrit, dans un même jeu d’équations, les écoulements à une (liquide) et deux (liquide/gaz) phases. Une étude de l’existence de solutions de cette formulation est menée à l’aide de la théorie générale des équations différentielles quasilinéaires elliptiques-paraboliques introduite par H.W. Alt et S. Luckhaus. Une méthode de résolution numérique du problème est mise en oeuvre pour la simulation de différents cas test, des plus simples au plus représentatif d’un site de stockage géologique. Enfin, l’homogénéisation périodique du modèle est effectuée et appliquée à la simulation de l’exercice Couplex-Gaz proposé par l’ANDRA / The purpose of this work is to analyze and develop mathematical concepts and tools in application to performance assessment of an underground nuclear waste disposal. The first part is concerned with estimating the far field concentration of radionuclides released by containers of waste when uncertainties on the release are taking in account. Using the work of A. Bourgeat and A. Piatniski about homogenization of a convection-diffusion equation with random source term, numerical tools are developed to approximate the random behavior of the concentration field in an underground disposal configuration. In a second part, we are interested in gas migration in and around an underground nuclear waste disposal. After a review on physical models of two-phase flow in porous media for water/hydrogen mixture, we propose a new mathematical formulation describing one- (liquid) and two- (liquid/gas) phase flow with a unique set of equation. Considering the general theory of quasilinear elliptic-parabolic differential equations introduced by H.W. Alt and S. Luckhaus, we study existence of solutions for this formulation. A numerical method to solve the problem is implemented to simulate several test cases. These test cases run from very simple situations to a representative configuration of an underground nuclear waste disposal. Finally, the periodic homogenization of the model is done and applied to simulate the Couplex-Gas exercise proposed by ANDRA.

La gestion des colis de déchets radioactifs représente un enjeu majeur pour l’industrie nucléaire. La solution de gestion d’un colis est déterminée en fonction de ses caractéristiques radiologiques. L’une de ces principales caractéristiques est l’activité α qui est principalement due aux actinides. Les méthodes non destructives actives, reposant sur le principe de la réaction de fission, permettent de quantifier les actinides. Ces méthodes sont mises en œuvre lorsque les techniques non-destructives passives deviennent inapplicables. Dans un premier temps, les méthodes actives consistent à irradier le colis afin d’entraîner des réactions de fission sur les actinides. Dans un second temps, les particules promptes et retardées émises suite aux réactions de fission sont détectées. Cette thèse a pour objectif d’optimiser le flux de neutrons, destiné à interroger les colis, en étudiant la possibilité d’utiliser un accélérateur d’électrons comme source de neutrons en lieu et place d’un générateur de type deutérium-tritium (gain attendu de l’ordre de deux décades en termes d’intensité d’émission). Un accélérateur d’électrons permettrait par ailleurs d’améliorer la caractérisation des colis de déchets radioactifs en rendant compatible, à l’aide du même dispositif d’irradiation, les mesures par interrogation neutronique active, par interrogation photonique active, et l’imagerie haute énergie.Dans un premier temps, nous avons caractérisé et optimisé le flux de photoneutrons émis par un accélérateur d’électrons en utilisant les codes de calculs Monte Carlo MCNPX et TRIPOLI-4. Nous avons considéré des cibles de conversion en tungstène ou en tantale et avons déterminé les paramètres suivants : intensité moyenne d’émission ; spectre en énergie ; et distribution angulaire. La cohérence de nos résultats a été évaluée par comparaison entre calculs et mesures d’activation neutronique. Nous avons ensuite évalué la faisabilité des mesures par interrogation neutronique active, en utilisant la cible d’un accélérateur d’électrons de 17 MeV en tant que générateur de neutrons, sur des échantillons d’uranium et de plutonium. Nous nous sommes intéressés à la détection des neutrons prompts, des neutrons retardés, et des gamma retardés. Nous avons également réalisé l’association de résultats de mesures par interrogations neutronique et photonique actives non-simultanées. Nous avons appliqué cette technique à la mesure de l’enrichissement de l’uranium. Enfin, nous avons dimensionné par simulation MCNPX une cellule de mesure, basée sur un accélérateur d’électrons, dédiée à l’interrogation neutronique active. La cellule a ensuite été construite et une campagne d’expérimentations a permis d’évaluer les performances de cette dernière lors de mesures réalisées sur des colis de déchets radioactifs maquettes de type 220 L contenant différentes matrices. / Management of nuclear waste packages is a crucial task for the nuclear industry. The solution for management of a nuclear waste package is chosen according to its radiological characteristics. One of the most important of these features is the α-activity which is mainly due to actinides. Non-destructive active methods based on the fission process enable to quantify the actinides. These methods are implemented when non-destructive passive methods become inapplicable. First, these methods consist in irradiating a package in order to induce fission reactions on the actinides, and then, to detect the prompt and delayed particles which are emitted further to these reactions. This thesis aims at optimizing the neutron flux, which is intended to interrogate a package, by studying the potentialities of using an electron accelerator as a neutron source instead of a deuterium-tritium neutron generator (expected gain in terms of emission intensity on the order of two decades higher). Furthermore, an electron accelerator would enable to improve nuclear waste packages characterization by making compatible, on the same irradiation setup, neutron interrogation measurements, photon interrogation measurements, and high-energy imaging.First, we characterized and optimized the photoneutron flux emitted by an electron accelerator using MCNPX and TRIPOLI-4 Monte Carlo codes. We considered tungsten and tantalum conversion targets and focused on the following parameters: average emission intensity; mean energy; and angular distribution. The consistency of our results has been verified by comparing neutron activation calculations and measurements. We have then evaluated the feasibility of neutron interrogation measurements on uranium and plutonium samples using the target of a 17 MeV electron accelerator as a neutron generator. We detected prompt neutrons, delayed neutrons, and delayed gamma-rays. We also combined photon and neutron interrogation non-simultaneous measurements. We applied such technique to the measurement of uranium enrichment. Finally, we designed by MCNPX simulation a neutron interrogation setup based on an electron accelerator. The cell was then built and an experimentation campaign enabled to evaluate performances of the latter. Measurements were carried out on 220 liter nuclear waste mock-up drums containing different matrices.

In this thesis, fractured rock masses are treated asequivalent continua for large-scale analyses of rockengineering projects. Systematic developments are made for thedetermination of equivalent mechanical and hydraulic propertiesof fractured rock masses using a hybrid discrete fracturenetwork - distinct element method (DFN-DEM) approach. Thedetermined equivalent properties are then used for a far-fieldfinite element analysis of the thermo-mechanical impacts on thestress, deformation and permeability of fractured rockssurrounding a hypothetical geological repository of nuclearwaste. The geological data were extracted from the results ofan extensive site investigation programme at Sellafield, UK,conducted by Nirex UK Ltd. The scale dependencies of the hydraulic and mechanicalproperties were investigated by using multiple realizations ofthe fracture system geometry with increasing model sizes untilproperly defined hydraulic and mechanical representativeelementary volumes (REVs) were reached. The validity of thesecond order permeability tensor and the fourth-ordermechanical compliance tensor were tested for continuum analysesat larger scales. The REV was determined to be around 5 m formechanical and hydraulic data in this study. Analysis of the stress-dependent mechanical and hydraulicproperties shows that the effect of rock stresses is crucial.The elastic moduli increase significantly with the increase ofstress and an empirical equation of stress-dependent elasticmodulus is suggested based on results of numerical experiments.Calculations of the Poisson's ratios suggest greater valuesthan are normally assumed in practice. Depending on the stateof stress, permeability decreases or increases with increasingcompressive stress. Stress-induced flow channeling effect iscaptured by numerical modeling for the first time and detailedmechanisms of shear dilation of fractures are provided. Basedon the numerical experiments, a set of empirical equations wassuggested for the stress-dependent permeability, consideringboth normal deformation and shear dilation of fractures. Thermo-mechanical impact on the performance of ahypothetical repository at a far-field scale (5 km by 1 km) wasinvestigated with the stress-dependent equivalent propertiesdetermined at the REV scale. This analysis shows thatmechanical responses vary significantly depending on how themechanical properties were determined. The change ofpermeability due to the thermal loading is, however, notsignificant in this particular case. The thesis provides a framework for systematic analysis oflarge-scale engineering applications in fractured rock masses,such as geological repositories of nuclear wastes. Keyword:Fractured rock masses, Equivalent Continuum,Discrete Fracture Network (DFN), Distinct Element Method (DEM),Finite Element Method (FEM), Nuclear Waste Disposal, CoupledThermo-Hydro-Mechanical Processes