Ces travaux ont pour objectif de modéliser les mécanismes de dispersion dans les aquifères. L’hétérogénéité du champ de vitesse et le transfert de masse entre zones immobiles et mobiles sont deux origines possibles du comportement non-Fickéen, jusqu’alors étudiées de façon séparée. Notre hypothèse de départ est que ces deux mécanismes coexistent. Nos travaux comprennent : 1) des expériences de traçage sur colonnes de billes de verre et carottes de grès de Berea, en mode flow-through et push-pull, et 2) des simulations numériques réalisées à partir d’images en microtomographie RX segmentées en trois phases : solide, vide et microporosité. L’analyse du champ de vitesse (Stokes) montre l’importance de la discrétisation spatiale et de la prise en compte de la microporosité. Les résultats des simulations de transport (en utilisant la méthode time domain random walk) permettent de quantifier l’effet combiné de l’hétérogénéité du champ de vitesse et des transferts diffusifs dans la fraction micro-poreuse de la roche sur la dispersion non-Fickéenne, caractérisée à partir des courbes de restitution (BTC). Ces résultats sont cohérents avec les observations expérimentales. Nous concluons que ces deux effets doivent être pris en compte même si leur identification à partir de la forme des BTCs issues des traçages des milieux naturels (souvent caractérisés par de faible valeurs du nombre de Peclet ) reste difficile. Enfin, un modèle moyen macroscopique 1D est proposé dans le cadre d’une approche de type continuous time random walk dans laquelle des distributions spécifiques du temps de transfert des particules sont construites pour chacun des deux mécanismes de transport. / His work aims at modeling hydrodynamic dispersion mechanisms in aquifers. So far both flow field heterogeneity and mobile-immobile mass transfer have been studied separately for explaining the ubiquitously observed non-Fickian behaviors, but we postulate that both mechanisms contribute simultaneously. Our investigations combine laboratory experiments and pore scale numerical modeling. The experimental rig was designed to enable push-pull and flow through tracer tests on glass bead columns and Berea sandstone cores. Modeling consists in solving Stokes flow and solute transport on 3D X-ray microtomography images segmented into three phases: solid, void and microporosity. Transport is modeled using time domain random walk. Statistical analysis of the flow field emphasizes the importance of the mesh resolution and the inclusion of the microporosity. Results from the simulations show that both the flow field heterogeneity and the diffusive transport in the microporous fraction of the rock contribute to the overall non-Fickian transport behavior observed, for instance, on the breakthrough curves (BTC). These results are supported by our experiments. We conclude that, in general, this dual control must be taken into account, even if these different influences can hardly be distinguished from a qualitative appraisal of the BTC shape, specifically for the low values of the Peclet number that occurs in natural conditions. Finally, a 1D up-scaled model is developed in the framework of the continuous time random walk, where the influences of the flow field heterogeneity and mobile-immobile mass transfer are both taken into account using distinct transition time distributions.

Cette thèse se propose d'examiner les phénomènes de transport dans des milieux poreux colonisés par des biofilms. Ces communautés sessiles se développent dans les sols ou les roches souterraines, ou dans la zone hyporhéique des rivières et peuvent influencer significativement le transport de masse et de quantité de mouvement. Les biofilms modifient également très largement la spéciation chimique des éléments présents dans le milieu, menant à la biodégradation de nombreux polluants. Par conséquent, ces systèmes ont reçu une attention considérable en ingénierie environnementale. Pourtant, la recherche dans ce domaine a été très fortement limitée par notre incapacité à (1) observer directement les microorganismes dans des milieux poreux opaques réels et (2) prendre en compte la complexité multi-échelles des différents phénomènes. Cette thèse présente des avancées théoriques et expérimentales permettant de surmonter ces deux difficultés. Une nouvelle stratégie, basée sur la microtomographie à rayons X assistée par ordinateur, a été utilisée pour obtenir des images en trois dimensions de la distribution spatiale du biofilm dans la structure poreuse. Ces informations topologiques peuvent être utilisées pour étudier la réponse de l'entité biologique à différents paramètres physiques, chimiques et biologiques à l'échelle du pore. De plus, ces images sont obtenues sur des volumes relativement importants et peuvent donc être utilisées pour étudier l'influence du biofilm sur le transport de solutés à plus grande échelle. Pour cela, les problèmes aux conditions limites décrivant le transport de matière à l'échelle du pore peuvent être moyennés en volume pour obtenir des équations homogénéisées à l'échelle de Darcy. Différents modèles, ainsi que leurs domaines de validité, sont présentés dans les cas réactifs et non-réactifs. Cette thèse se base sur la technique de prise de moyenne volumique, en conjonction avec des analyses utilisant les moments spatiaux, pour présenter une théorie complète de transport macroscopique ainsi qu'une analyse détaillée des relations entre les différents modèles, tout particulièrement entre les modèles à une et deux équations. Une décomposition non standard en terme de moyenne plus perturbation est présentée dans le but d'obtenir un modèle à une équation dans le cas du transport multiphasique avec des taux de réactions linéaires en fonction de la concentration. Finalement, la connexion entre l'analyse théorique et l'imagerie en trois dimensions est établie. Cette thèse illustre aussi brièvement comment la perméabilité peut être calculée numériquement en résolvant des problèmes de fermeture à partir des images en trois dimensions. / This dissertation examines transport phenomena within porous media colonized by biofilms. These sessile communities of microbes can develop within subsurface soils or rocks, or the riverine hyporheic zone and can induce substantial modification to mass and momentum transport dynamics. Biofilms also extensively alter the chemical speciation within freshwater ecosystems, leading to the biodegradation of many pollutants. Consequently, such systems have received a considerable amount of attention from the ecological engineering point of view. Yet, research has been severely limited by our incapacity to (1) directly observe the microorganisms within real opaque porous structures and (2) assess for the complex multiple-scale behavior of the phenomena. This thesis presents theoretical and experimental breakthroughs that can be used to overcome these two difficulties. An innovative strategy, based on X-ray computed microtomography, is devised to obtain three-dimensional images of the spatial distribution of biofilms within porous structures. This topological information can be used to study the response of the biological entity to various physical, chemical and biological parameters at the pore-scale. In addition, these images are obtained from relatively large volumes and, hence, can also be used to determine the influence of biofilms on the solute transport on a larger scale. For this purpose, the boundary-value-problems that describe the pore-scale mass transport are volume averaged to obtain homogenized Darcy-scale equations. Various models, along with their domains of validity, are presented in the cases of passive and reactive transport. This thesis uses the volume averaging technique, in conjunction with spatial moments analyses, to provide a comprehensive macrotransport theory as well as a thorough study of the relationship between the different models, especially between the two-equation and one-equation models. A non-standard average plus perturbation decomposition is also presented to obtain a one-equation model in the case of multiphasic transport with linear reaction rates. Eventually, the connection between the three-dimensional images and the theoretical multiple-scale analysis is established. This thesis also briefly illustrates how the permeability can be calculated numerically by solving the so-called closure problems from the three-dimensional X-ray images.

This thesis focuses on solute transport upscaling. Upscaling of solute transport is usually required to obtain computationally efficient numerical models in many field applications such as, remediation of aquifers, environmental risk to groundwater resources or the design of underground repositories of nuclear waste. The non-Fickian behavior observed in the field, and manifested by peaked concentration profiles with pronounced tailing, has questioned the use of the classical advection-dispersion equation to simulate solute transport at field scale using numerical models with discretizations that cannot capture the field heterogeneity. In this context, we have investigated the use of the advection-dispersion equation with mass transfer as a tool for upscaling solute transport in a general numerical modeling framework. Solute transport by groundwater is very much affected by the presence of high and low water velocity zones, where the contaminant can be channelized or stagnant. These contrasting water velocity zones disappear in the upscaled model as soon as the scale of discretization is larger that the size of these zones. We propose, for the modeling solute transport at large scales, a phenomenological model based on the concept of memory functions, which are used to represent the unresolved processes taking place within each homogenized block in the numerical models. We propose a new method to estimate equivalent blocks, for which transport and mass transfer parameters have to be provided. The new upscaling technique consists in replacing each heterogeneous block by a homogeneous one in which the parameters associated to a memory functions are used to represent the unresolved mass exchange between highly mobile and less mobile zones occurring within the block. Flow upscaling is based on the Simple Laplacian with skin, whereas transport upscaling is based in the estimation of macrodispersion and mass transfer parameters as a result of the interpretation of the r / Llerar Meza, G. (2009). Upscaling nonreactive solute transport [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/5848 / Palancia

Ce travail de thèse porte sur la modélisation mathématique et la simulation numérique de la migration par gravité et capillarité du CO₂ supercritique injecté dans un site de séquestration géologique hétérogène. Les simulations sont réalisées à l'aide du code DuMux. Particulièrement, on s'intéresse à la mise à l'échelle, de l'échelle de la cellule à l'échelle du réservoir, d'un modèle d'écoulement diphasique CO₂ -saumure, au sein d'un milieu stratifié périodique constitué d'un réseau de barrières peu perméables horizontales, continues ou discontinues. La mise à l'échelle est effectuée par la méthode asymptotique à double échelle. Dans un premier temps, on considère le cas d'une colonne verticale parfaitement stratifiée. Un modèle homogénéisé est développé puis validé par simulation numérique pour différentes valeurs du nombre capillaire et du flux incident de CO₂ . La méthode d'homogénéisation est appliquée au cas d'un écoulement dans un milieu bidimensionnel constitué de strates discontinues. Par l'effet de gravité, le CO₂ s'accumule sous les strates peu perméables, ce qui conduit à un problème mathématique local non standard. Cette stratification est modélisée à l'aide de l'approche des courants de gravité. L'approche est étendue au cas des strates semi-perméables et en prenant en compte la capillarité. Le modèle mis à l'échelle est comparé à des simulations numériques effectuées pour différents types de strates, avec ou sans pression capillaire, et sa limite de validité est discutée pour chacun de ces cas. La dernière partie de la thèse est dédiée à l'étude des performances du code DuMux pour simuler par calcul parallèle l'injection et la migration de CO₂ dans des milieux hétérogènes tridimensionnels (milieu périodique stratifié, milieu fluviatile et milieu réservoir SPE10). / This work deals with the mathematical modeling and the numerical simulation of the migration under gravity and capillarity effects of the supercritical CO₂ injected into a geological heterogeneous sequestration site. The simulations are performed with the code DuMux. Particularly, we consider the upscaling, from the cell scale to the reservoir scale, of a two-phase (CO₂ -brine) flow model within a periodic stratified medium made up of horizontal low permeability barriers, continuous or discontinuous. The upscaling is done by the two-scale asymptotic method. First, we consider perfectly layered media. An homogenized model is developed and validated by numerical simulation for different values of capillary number and the incident flux of CO₂ . The homogenization method is then applied to the case of a two-dimensional medium made up of discontinuous layers. Due to the gravity effect, the CO₂ accumulates under the low permeability layers, which leads to a non-standard local mathematical problem. This stratification is modeled using the gravity current approach. This approach is then extended to the case of semi-permeable stratas taking into account the capillarity. The upscaled model is compared with numerical simulations for different types of layers, with or without capillary pressure, and its limit of validity is discussed in each of these cases. The final part of this thesis is devoted to the study of the parallel computing performances of the code DuMux to simulate the injection and migration of CO₂ in three-dimensional heterogeneous media (layered periodic media, fluvial media and reservoir model SPE 10).

The vast majority of oil and gas reserves are trapped in fractured carbonate reservoirs. Most carbonate reservoirs are naturally fractured, with fractures ranging from millimeter- to kilometer-scale. These fractures create complex flow behaviors which impact reservoir characterization, production performance, and, eventually, total recovery. As we know, bridging the gas from plug to near-wellbore, eventually to field scales, is a persisting challenge in modeling Naturally Fractured Reservoirs (NFRs). This dissertation will focus on assessing the fundamental flow mechanisms in fractured rocks at the plug scale, understanding the governing upscaling parameters, and ultimately, developing fit-for-purpose upscaling tools for field-scale implementation. In this dissertation, we first focus on the upscaling of rock fractures under the laminar flow regime. A novel analytical model is presented by incorporating the effects of normal aperture, roughness, and tortuosity. We then investigate the stress-dependent hydraulic behaviors of rock fractures. A new and generalized theoretical model is derived and verified by a dataset collected from public experimental resources. In addition, an efficient coupled flow-geomechanics algorithm is developed to further validate the proposed analytical model. The physics of matrix-fracture interaction and fluid leakage is modeled by a high-resolution, micro-continuum approach, called extended Darcy-Brinkman-Stokes (DBS) equations. We observe the back-flow phenomena for the first time. Machine learning is then implemented into our traditional upscaling work under complex physics (e.g., initial and Klinkenberg effects). We finally consolidate the lab-scale upscaling tools and scale them up to the field scale. We develop a fully coupled hydro-mechanical model based on the Discrete-Fracture Model (DFM) in fractured reservoirs, in which we incorporate localized effects of fracture roughness at the field-scale.

The objective of this project was to study the influence of increased salinities on interaction processes in the system radionuclide – organics – clay – aquifer. For this purpose, complexation, redox, sorption, and diffusion studies were performed under variation of the ionic strength (up to 4 mol/kg) and the background electrolyte. The U(VI) complexation by propionate was studied in dependence on ionic strength (up to 4 mol/kg NaClO4) by TRLFS, ATR FT-IR spectroscopy, and DFT calculations. An influence of ionic strength on stability constants was detected, depending on the charge of the respective complexes. The conditional stability constants, determined for 1:1, 1:2, and 1:3 complexes at specific ionic strengths, were extrapolated to zero ionic strength. The interaction of the bacteria Sporomusa sp. MT-2.99 and Paenibacillus sp. MT-2.2 cells, isolated from Opalinus Clay, with Pu was studied. The experiments can be divided into such without an electron donor where biosorption is favored and such with addition of Na-pyruvate as an electron donor stimulating also bioreduction processes. Moreover, experiments were performed to study the interactions of the halophilic archaeon Halobacterium noricense DSM-15987 with U(VI), Eu(III), and Cm(III) in 3 M NaCl solutions. Research for improving process understanding with respect to the mobility of multivalent metals in systems containing humic matter was focused on the reversibility of elementary processes and on their interaction. Kinetic stabilization processes in the dynamics of humate complexation equilibria were quantified in isotope exchange studies. The influence of high salinity on the mobilizing potential of humic-like clay organics was systematically investigated and was described by modeling. The sorption of Tc(VII)/Tc(IV) onto the iron(II)-containing minerals magnetite and siderite was studied by means of batch sorption experiments, ATR FT-IR and X-ray absorption spectroscopy. The strong Tc retention at these minerals could be attributed to surface-mediated reduction of Tc(VII) to Tc(IV). An influence of ionic strength was not observed. The influence of ionic strength (up to 3 mol/kg) and background electrolyte (NaCl, CaCl2, MgCl2) on U(VI) sorption onto montmorillonite was studied. The U(VI) sorption is influenced by the background electrolyte, the influence of ionic strength is small. Surface complexation modeling was performed applying the 2SPNE SC/CE model. Surface complexation constants were determined for the NaCl and CaCl2 system and were extrapolated to zero ionic strength. Surface complexation in mixed electrolytes can be modeled applying surface complexation constants derived for pure electrolytes. The influence of citrate on U(VI) diffusion in Opalinus Clay was studied using Opalinus Clay pore water as background electrolyte. The diffusion parameter values obtained for the HTO through-diffusion and the U(VI) in-diffusion in the absence of citric acid were in agreement with literature data. In the presence of citric acid, U(VI) diffusion was significantly retarded, which was attributed to a change in speciation, probably U(VI) was reduced to U(IV). Larger-scale heterogeneous material effects on diffusive transport were investigated with PET. Diffusion parameters were derived by optimum fit of a FEM-model to the measurement. These parameters are in accordance with the results from 1D-through-diffusion experiments. Deviations from the simple transversal-isotropic behavior, which are identified as residuals from the model, are indications for heterogeneous transport on the mm-scale. PET measurements were also conducted in order to display the improvement of the EDZ with waterglass injections. These experiments enable to draw conclusions on the complex reactive transport process and thus an estimation of the achieved improvement of the barrier function. The image reconstruction procedure was largely improved, mainly with the aid of Monte-Carlo simulations, and now allows quantitative analysis and error estimation.

La Tomographie à Emission de Positrons (TEP) permet d'obtenir une mesure dynamique et résolue en espace de la concentration d'un traceur radioactif injecté au patient. La quantification du débit sanguin cérébral par TEP repose sur l'utilisation d'un modèle cinétique le reliant à la variation spatio-temporelle de la concentration du traceur dans le cerveau. Différents modèles cinétiques sont proposés dans la littérature. Cependant, la majorité d'entre eux repose sur une modélisation compartimentale de l'organe observé. Dans ce cas, l'organe est subdivisé en un compartiment capillaire échangeant avec un compartiment tissulaire par une cinétique le plus souvent du premier ordre. Les résultats obtenus avec ce type de modèle sous-estiment le débit et ne permettent pas de prédire les premiers instants de la dynamique de répartition du traceur. Ces faiblesses ont été confirmées suite à l'amélioration de la résolution temporelle des tomographes, conduisant à l'élaboration de modèles incorporant plus de réalité physiologique. Cependant, tous ces modèles sont développés pour modéliser les échanges entre la micro-circulation et le tissu environnant à l'échelle d'un capillaire (échelle microscopique). Or la résolution spatiale des tomographes utilisés en clinique ne permet pas de distinguer la micro-circulation et le tissu. L'utilisation de ces modèles cinétiques avec des mesures de concentrations macroscopiques dépasse donc leur cadre théorique de validité et peut introduire des résultats faussés. Dans ce contexte, nous proposons un modèle cinétique basé sur le changement d'échelle (utilisant la méthode de prise de moyenne volumique). Ce changement d'échelle permet de remplacer l'ensemble micro-circulation/tissu par un volume fictif, homogène, dont les propriétés macroscopiques sont calculées à partir des propriétés microscopiques d'un Volume Elémentaire Représentatif (VER) du milieu. Dans un premier temps, afin de pouvoir comparer les résultats de ce modèle avec ceux du modèle compartimental standard, le VER considéré est constitué d'un capillaire unique et de son enveloppe de tissu, puis une complexité géométrique supplémentaire est introduite en considérant un réseau de capillaire isotrope à l'échelle de Darcy. Ces modèles sont utilisés pour identifier le débit à l'aide d'une méthode inverse. Pour cela, l'évolution temporelle du champ de concentration dans notre géométrie de référence, qui ne peut être mesurée par TEP en raison de sa faible résolution spatiale, est déterminée par des simulations numériques ainsi que par des mesures in vitro à l'aide d'un modèle expérimental, également développé au cours de ce travail, permettant de reproduire l'écoulement dans un canal traversant une matrice diffusante (gel d'alginate). / Positron Emission Tomography (PET) provides a dynamic and space-resolved measurement of the concentration field of a radioactive tracer previously injected to the patient. Quantification of cerebral blood flow by PET is based on the use of a kinetic model linking cerebral blood flow to the spatial and temporal variations of tracer concentration in the brain. Various kinetic models have been proposed in the literature. However, most of the mare based on a compartmental approach of the observed organ In this case, the organ is divided in two compartments, the capillary and the tissue, and the exchanges between these two compartments are often described by a first order kinetic model. Results obtained with this kind of model under estimate the flow rate and are notable to predict the first instants of the tracer dynamics distribution. With the continuous improvement of the temporal resolution of PET, these weaknesses have been confirmed, which led to the development of models incorporating more physiological reality. However, all these models have been developed to describe exchanges between micro-circulation and surrounding tissue at the scale of capillary vessels (microscopic scale). Because the spatial resolution of PET inclinical practice is insufficient to allow the distinction between micro-circulation and tissue, using of these models with kinetic measurement of macroscopic concentrations exceeds their theoretical validity and can introduce false results. In this context, we propose a kinetic model based on up-scaling (using the method of volume averaging). This up-scaling technique allows to replace the two previous compartments (tissue and micro-circulation) by an homogeneous fictive volume, whose macroscopic properties are calculated from the microscopic properties of are presentative elementary volume (REV) of the medium. First, in order to compare the results of this model with those of the standard compartmental model, the considered REV consists of a single capillary and its surrounding tissue. Second, additional geometric complexity is introduced by considering an isotropic capillary network at the Darcy scale. These models are used to identify the flow rate using an inverse method. For that purpose, the temporal evolution of concentration field in a geometry of reference, which can't be measured by PET due to its low spatial resolution, is determined by numerical simulations and by in vitro measurements. These measurements are performed using an experimental model developed during this work to reproduce the flow in a channel passing through a diffusive matrix (alginate gel).

This work presents model development and model analyses of CO2 storage in deep saline aquifers. The goal has been two-fold, firstly to develop models and address the system behaviour under geological heterogeneity, second to tackle the issues related to problem scale as modelling of the CO2 storage systems can become prohibitively complex when large systems are considered. The work starts from a Monte Carlo analysis of heterogeneous 2D domains with a focus on the sensitivity of two CO2  storage performance measurements, namely, the injectivity index (Iinj) and storage efficiency coefficient (E), on parameters characterizing heterogeneity. It is found that E and Iinj are determined by two different parameter groups which both include correlation length (λ) and standard deviation (σ) of the permeability. Next, the issue of upscaling is addressed by modelling a heterogeneous system with multi-modal heterogeneity and an upscaling scheme of the constitutive relationships is proposed to enable the numerical simulation to be done using a coarser geological mesh built for a larger domain. Finally, in order to better address stochastically heterogeneous systems, a new method for model simulations and uncertainty analysis based on a Gaussian processes emulator is introduced. Instead of conventional point estimates this Bayesian approach can efficiently approximate cumulative distribution functions for the selected outputs which are CO2 breakthrough time and its total mass. After focusing on reservoir behaviour in small domains and modelling the heterogeneity effects in them, the work moves to predictive modelling of large scale CO2  storage systems. To maximize the confidence in the model predictions, a set of different modelling approaches of varying complexity is employed, including a semi-analytical model, a sharp-interface vertical equilibrium (VE) model and a TOUGH2MP / ECO2N model. Based on this approach, the CO2 storage potential of two large scale sites is modelled, namely the South Scania site, Sweden and the Dalders Monocline in the Baltic Sea basin. The methodologies developed and demonstrated in this work enable improved analyses of CO2 geological storage at both small and large scales, including better approaches to address medium heterogeneity. Finally, recommendations for future work are also discussed.

The objective of this project was to study the influence of increased salinities on interaction processes in the system radionuclide – organics – clay – aquifer. For this purpose, complexation, redox, sorption, and diffusion studies were performed under variation of the ionic strength (up to 4 mol/kg) and the background electrolyte. The U(VI) complexation by propionate was studied in dependence on ionic strength (up to 4 mol/kg NaClO4) by TRLFS, ATR FT-IR spectroscopy, and DFT calculations. An influence of ionic strength on stability constants was detected, depending on the charge of the respective complexes. The conditional stability constants, determined for 1:1, 1:2, and 1:3 complexes at specific ionic strengths, were extrapolated to zero ionic strength. The interaction of the bacteria Sporomusa sp. MT-2.99 and Paenibacillus sp. MT-2.2 cells, isolated from Opalinus Clay, with Pu was studied. The experiments can be divided into such without an electron donor where biosorption is favored and such with addition of Na-pyruvate as an electron donor stimulating also bioreduction processes. Moreover, experiments were performed to study the interactions of the halophilic archaeon Halobacterium noricense DSM-15987 with U(VI), Eu(III), and Cm(III) in 3 M NaCl solutions. Research for improving process understanding with respect to the mobility of multivalent metals in systems containing humic matter was focused on the reversibility of elementary processes and on their interaction. Kinetic stabilization processes in the dynamics of humate complexation equilibria were quantified in isotope exchange studies. The influence of high salinity on the mobilizing potential of humic-like clay organics was systematically investigated and was described by modeling. The sorption of Tc(VII)/Tc(IV) onto the iron(II)-containing minerals magnetite and siderite was studied by means of batch sorption experiments, ATR FT-IR and X-ray absorption spectroscopy. The strong Tc retention at these minerals could be attributed to surface-mediated reduction of Tc(VII) to Tc(IV). An influence of ionic strength was not observed. The influence of ionic strength (up to 3 mol/kg) and background electrolyte (NaCl, CaCl2, MgCl2) on U(VI) sorption onto montmorillonite was studied. The U(VI) sorption is influenced by the background electrolyte, the influence of ionic strength is small. Surface complexation modeling was performed applying the 2SPNE SC/CE model. Surface complexation constants were determined for the NaCl and CaCl2 system and were extrapolated to zero ionic strength. Surface complexation in mixed electrolytes can be modeled applying surface complexation constants derived for pure electrolytes. The influence of citrate on U(VI) diffusion in Opalinus Clay was studied using Opalinus Clay pore water as background electrolyte. The diffusion parameter values obtained for the HTO through-diffusion and the U(VI) in-diffusion in the absence of citric acid were in agreement with literature data. In the presence of citric acid, U(VI) diffusion was significantly retarded, which was attributed to a change in speciation, probably U(VI) was reduced to U(IV). Larger-scale heterogeneous material effects on diffusive transport were investigated with PET. Diffusion parameters were derived by optimum fit of a FEM-model to the measurement. These parameters are in accordance with the results from 1D-through-diffusion experiments. Deviations from the simple transversal-isotropic behavior, which are identified as residuals from the model, are indications for heterogeneous transport on the mm-scale. PET measurements were also conducted in order to display the improvement of the EDZ with waterglass injections. These experiments enable to draw conclusions on the complex reactive transport process and thus an estimation of the achieved improvement of the barrier function. The image reconstruction procedure was largely improved, mainly with the aid of Monte-Carlo simulations, and now allows quantitative analysis and error estimation.

The need to consider groundwater and surface water as a single resource has fostered the interest of the scientific community on the interactions between surface water and groundwater. The region below and alongside rivers where surface hydrology and subsurface hydrology concur is the hyporheic zone. This is the region where water exchange determines many biogeochemical and ecological processes of great impact on the functioning of rivers. However, the complex processes taking place in the hyporheic zone require a multidisciplinary approach. The combination of innovative point and distributed techniques originally developed in separated disciplines is of great advantage for the indirect identification of water exchange in the hyporheic zone. Distributed techniques using temperature as a tracer such as fiber-optic distributed temperature sensing can identify the different components of groundwater-surface water interactions based on their spatial and temporal thermal patterns at the sediment-water interface. In particular, groundwater, interflow discharge and local hyporheic exchange flows can be differentiated based on the distinct size, duration and sign of the temperature anomalies. The scale range and resolution of fiber-optic distributed temperature sensing are well complemented by geophysics providing subsurface structures with a similar resolution and scale. Thus, the use of fiber-optic distributed temperature sensing to trace flux patterns supported by the exploration of subsurface structures with geophysics enables spatial and temporal investigation of groundwater-surface water interactions with an unprecedented level of accuracy and resolution. In contrast to the aforementioned methods that can be used for pattern identification at the interface, other methods such as point techniques are required to quantify hyporheic exchange fluxes. In the present PhD thesis, point methods based on hydraulic gradients and thermal profiles are used to quantify hyporheic exchange flows. However, both methods are one-dimensional methods and assume that only vertical flow occurs while the reality is much more complex. The study evaluates the accuracy of the available methods and the factors that impact their reliability. The applied methods allow not only to quantify hyporheic exchange flows but they are also the basis for an interpretation of the sediment layering in the hyporheic zone. For upscaling of the previous results three-dimensional modelling of flow and heat transport in the hyporheic zone combines pattern identification and quantification of fluxes into a single framework. Modelling can evaluate the influence of factors governing groundwater-surface water interactions as well as assess the impact of multiple aspects of model design and calibration of high impact on the reliability of the simulations. But more importantly, this modelling approach enables accurate estimation of water exchange at any location of the domain with unparalleled resolution. Despite the challenges in 3D modelling of the hyporheic zone and in the integration of point and distributed data in models, the benefits should encourage the hyporheic community to adopt an integrative approach comprising from the measurement to the upscaling of hyporheic processes.