Diffuse transport in clay media: µm to nm scale characterization of pore space and mineral spatial organization

In the framework of radioactive waste repository, clayrock formations are foreseen as barrier materials due to their diffusion properties. In clay materials, the dominant transport mode is diffusive and depends mainly on various parameters such as the mobility of the species in water, the accessible porosity, the pore space geometry and the retardation as a result of reactions such as sorption or ion exchange (Tournassat and Appelo, 2011). In this way, the European CATCLAY project (EURATOM FP7), in the context with research on transport in porous materials, was proposed to describe the cation migration processes in natural clayrocks. The project is structured along 3 RTD workpackages, combining modeling and experimental studies from a simpler, analogous system (monophasic compacted clay system) to clayrocks (Callovo-Oxfordian argillites, Opalinus Clay and Boom Clay). Part of this experimental studies focuses on small scale structure (µm - nm) property of rocks in order to determine how the spatial distribution of mineral and pores at small scales can influence diffusion driven transport of sorbing cations. The present study focuses on compacted illite properties (simpler analogous system) in hopes to extent this study to the natural clayrock formation. Illite was chosen by the way that is the main constituent of clayrock. Compacted illite material represents thus an analogy with the clay matrix constituting clay-rocks. Our approach is mainly based on imaging the small scale structural organization of compacted illite material and analyzing the obtained images in order to extract information on pore space and mineral spatial distribution. Techniques for imaging the texture of illite material like water saturated, in compacted state, were first developed. The first step was to improve classic resin impregnation method in order to preserve the texture without losing the clay confinement and modifying the pore space geometry. This has been done by taking into account the molecule size of the monomer, the low viscosity, the dipole moment (adapted for the clayrock with swelling clay content) and the controlled time polymerization. MMA monomer proved to be the most suitable resin in our study. The small scale structure of impregnated sample was then imaged in 2D using Transmission Electron Microscopy (TEM) and in 3D using Focused Ion Beam coupled to Scanning Electron Microscopy (FIB/SEM). For TEM observations, a set of ultra-thin serial sections (50 - 100 nm) were cut using a microtome. A set of 2D images were then acquired using a resolution ranged between 100 nm and 10 Å. TEM images clearly show us the multi-scale organization of clay materials (Figure 1 and 2); we observe the 10 Å spacing sheets constituting the illite particles, nanometer size illite clay particles more or less aggregated and the surrounding pores having a size ranging from few hundred nanometers to nanometer. FIB/SEM analysis is currently in progress. From FIB/SEM, a set of serial images can be acquired using the "slice and view" method (Keller et al., 2011). Then, 2D FIB/SEM images need to be aligned to reconstruct a 3D volume. Image resolution is limited to 10-20 nm. Both methodologies (FIB-tomography and TEM techniques) are thus complementary method for the up-scaling characterization of the structural organization of compacted clayey materials. TEM images analysis allow to scale down the resolution size since only a part of the pore space could thus be imaged with FIB/SEM method (Keller et al., 2011). Viewing and performing a qualitative description of images constitute a major result and can help us to better understand how the transfer pathways and retention sites are organized in the porous media. Thanks to image analysis method, pores and minerals can be thresholded from grey level TEM and FIB/SEM images. Quantitative parameters can be then computed based from segmented images. In this objective, we currently focus our analysis in order to determine the size and the morphology of pores, the main geometrical features of clay particles (number of layers, size, shape...), the spatial distribution of clay particles (individual/aggregates, type of contact between the clay particles, orientation...) and the pores connectivity. Quantitative parameters are expected to be used in various transfer modeling approaches. This will be done in the framework of SIMISOL project which is focused on the modeling cation diffusion from atomic to nanometer scales

A selection of thermodynamic properties for zeolites: application to the cement/clay interactions

Deep disposal concepts are usually based on a multibarrier concept that may involve a physical contact between clayey and cementitious materials. In such context, zeolites are a group of important phases, which group most of the transition phases between cement and the clayey barrier since zeolites have been shown to form readily after the weathering of clays in a hyperalkaline environment [1]. Thermodynamic properties can be found in the literature for some of the zeolites of interest in deep disposal contexts. However, there is still a lack of consistency among the available thermodynamics datasets. A first task realized in the present work consists in a critical selection of the thermodynamic datasets published so far. The selection could be achieved with some confidence for a rather large list of minerals. Some questions and uncertainties still remain for phases like phillipsite, chabazite or gismondine. Cases from the previous critical selection indicate the role of kinetics in the precipitation of zeolites, which can help in moderating the phase relations indicated by thermodynamics and can be related to field observations or experimental results. In addition, the concept of rock acidity can applied with success in order to investigate the phase relations between cements, zeolites and clayey materials

Thermodynamics of hydration of MX80-Na: an experimental study of the hydration energies

Hydration properties of swelling clay minerals may be very variable depending on the chemical composition of the clay, on the nature of the interlayer cations and on the interlayer charge (Berend et al., 1995; Vieillard et al., 2011). The Wyoming smectite has been largely studied, notably for assessing its hydration behavior as a function of the interlayer cations, in connection with its structural characteristics (Ferrage et al., 2005; Salles et al., 2007). In the present work, carried out as part of a collaborative Andra/BRGM/HydrASA research program for ThermoChimie project, we propose an original experimental study, based on adsorption and desorption isotherms performed on MX80 clay samples. The goal is to determine energetic contributions to the reactions of hydration, which have been revealed to be non-negligible with respect to the stability of the clay minerals (Gailhanou et al., submitted). In particular, the present work addresses the problems of the hysteresis loop between adsorption and desorption isotherms and of the irreversibility of hydration reactions. This is directly related to the application of classical thermodynamics to the hydration reactions of clay minerals. In a first stage, an experimental study is dedicated to better understand the origin of the hysteresis loop which is systematically observed for the adsorption-desorption isotherms at 25°C. The development of the hysteresis loop has been studied by considering several kinetically related parameters: stabilization periods, temperatures (from 25°C to 60°C) and hydration steps (Figure 1). No sensible change was observed in the hysteresis loop. Therefore, the amount of adsorbed water depends on the followed reaction pathway (adsorption or desorption). The variations in microstructures and in the distribution of hydration layers (0/1/2 water layers; Ferrage et al., 2005) as a function of relative humidity (RH) could provide a possible explanation for this phenomenon

Extending the prediction of the thermodynamic properties of clay minerals to the trapping of trace elements

The thermodynamic properties of clay minerals, which control the stability of these minerals in solution, are still a matter of debate in spite of recent advances (Gailhanou et al., submitted). This is especially the case for the minerals that may structurally include trace elements and potential radionuclides such like Ni, Cd, Co, Cr, Mn, Pb, ... The usual methods developed in order to predict thermodynamic properties are parameterised using a given set of minerals. For clay minerals, the latter are mainly composed by Si, Al, Fe and Mg, apart from the alkalis elements (Chermak and Rimstidt, 1989), which means that predictions are limited to minerals whose layers are composed by Si, Al, Fe and Mg. At the vicinity of H&ILW disposal cells, the possible interactions between clay rock or engineered barrier and waste degradation products can result in the appearance of clay minerals that may structurally include radionuclides within an irreversible trapping process. This work aims at proposing a method for predicting the thermodynamic properties of such minerals. Theoretical principle and selection of calibration phases Vieillard (1994) has developed a methodology of estimation based on the difference of electronegativity by considering three scales of values of the parameter HO=(Mz+clay) in the three sites of phyllosilicates. We have considered the work of Vieillard (1994) that originally applies to the estimate of H0f and extended it to the estimate of Cp(T), S0 and V. Some popular estimate methods (Chermak and Rimstidt, 1989) are based on the hypothesis that the thermodynamic property of a mineral can be obtained by combining the properties of its components. An improvement of this principle had consisted in decomposing minerals into their polyhedral components (Chermak and Rimstidt, 1989). Now, we can write the fictive solution equilibrium with a basic polyhedral component MxOy as: and assumming the entropy of this fictive reaction is zero, we can define a SO= parameter as: . The value for the oxide analog of the polyhedral unit is obtained by implementing S0 of the oxide in the S0(MxOy) term. We have also defined, from the same reasoning, similar parameters for heat capacity and volume of the basic polyhedral components: ; . Results and discussion On Figure 1, we have displayed, for entropy, the correlation obtained between calculated values of SO= for the polyhedral unit and for the oxide analog. A straight line and a second-order function are obtained, for the interlayer and octahedral cations, respectively, with a good correlation coefficient. Fig. 1 - Development of predictive capacity for entropy estimates The implementation of the derived semi-empirical, first or second order relations allows to estimate the thermodynamic properties of a clay mineral, MX80 (Na0.409K0.024Ca0.009(Si3.738Al0.262)(Al1.598Mg0.214Fe3+0.173Fe2+0.035)O10(OH)2) in the present case, loaded by 6 radionuclides and to compare the values with the results obtained by Gailhanou et al. (submitted).The results can be expressed in terms of the concentrations for the elements Ni, Cd, Co, Cr, Mn and Pb and in terms of energetic potential with respect to the measurements performed by Gailhanou et al. (submitted)

Rapport final du projet européen CatClay sur les processus de migration des cations dans les roches argileuses indurées

International audienceIn the framework of the feasibility studies on the radioactive waste disposal in deep argillaceous formations, it isnow well established that the transport properties of solutes in clay rocks, i.e. parameter values for Fick’s law, are mainlygoverned by the negatively charged clay mineral surface. While a good understanding of the diffusive behaviour of non-reactiveanionic and neutral species is now achieved, much effort has to be placed on improving understanding of coupledsorption/diffusion phenomena for sorbing cations. Indeed, several cations known to form highly stable surface complexes withsites on mineral surfaces migrate more deeply into clay rock than expected. Therefore, the overall objective of the EC CatClayproject is to address this issue, using a ‘bottom-up’ approach, in which simpler, analogous systems (here a compacted clay,‘pure’ illite) are experimentally studied and modelled, and then the transferability of these results to more complex materials, i.e.the clay rocks under consideration in France, Switzerland and Belgium for hosting radioactive waste disposal facilities, isverified. The cations of interest were chosen for covering a representative range of cations families: from a moderately sorbingcation, the strontium, to three strongly sorbing cations, Co(II), Zn(II) and Eu(III). For the 4 years of this project, much effort wasdevoted to developing and applying specific experimental methods needed for acquiring the high precision, reliable data neededto test the alternative hypotheses represented by different conceptual-numerical models. The enhanced diffusion of the sorbingcations of interest was confirmed both in the simpler analogous illite system for Sr2+, Co(II) and Zn(II), but also in the naturalclay rocks, except for Eu(III). First modelling approach including diffusion in the diffuse double layer (DDL) promisinglysucceeded in reproducing the experimental data under the various conditions both in illite and clay rocks, even though someassumptions made have to be verified. In parallel, actual 3D geometrical pore size distributions of compacted illite, and in lessextent, clay rock samples, were successfully determined by combining TEM and FIB-nt analyses on materials maintained in awater-like saturation state by means of an extensive impregnation step. Based on this spatial distribution of pores, first numericaldiffusion experiments were carried at the pore scale through virtual illite, enabling a better understanding of how transferpathways are organized in the porous media. Finally, the EC CatClay project allowed a better understanding of the migration ofstrongly sorbing tracers through low permeability ‘clay rock’ formations, increasing confidence in our capacity to demonstratethat the models used to predict radionuclide migration through these rocks are scientifically sound

Les sulfates phosphates d'aluminium hydratés (APS) dans l'environnement des gisements d'uranium associés à une discordance protérozoïque (caractérisation cristallochimique et signification pétrogénétique)

Les sulfates phosphates d'aluminium (APS) sont des minéraux ubiquistes, généralement observés dans les altérations hydrothermales dans l'environnement des gisements d'uranium associés à une discordance protérozoïque de l'East Alligator River Uranium Field (Territoire du Nord, Australie) et du bassin d'Athabasca (Saskatchewan, Canada). L'objectif de cette étude est de: 1) caractériser la nature et l'origine des APS de chaque côté de la discordance, au niveau de la couverture gréseuse et du socle métamorphique sous-jacent, hôtes de plusieurs corps minéralisés, 2) caractériser ces minéraux sur leur capacité à indiquer les paléoconditions (redox, pH) relatives à la formation des gisements d'uranium. La formation des APS résulte principalement de l'interaction entre des saumures oxydantes, relativement acides et des roches riches en monazite et en minéraux alumineux. De même, la nature des assemblages APS-argiles et la cristallochimie des APS varient en fonction de leur position relative aux corps minéralisés en uranium et de leur distance à la discordance où ont opéré les interactions fluide/roche, à l'origine de la minéralisation. L'un des résultats majeurs de cette étude repose sur le fait que les assemblages minéralogiques, récemment utilisés dans la littérature pour décrire les zones d'altération autour des gisements d'uranium, peuvent être reconstitués par le biais d'une modélisation thermodynamique simulant différentes étapes d'interaction fluide/roche liées à l'infiltration des saumures, acides et oxydantes, dans les unités gréseuses basales du bassin et dans le socle métamorphique. De même, les différentes compositions chimiques d'APS dépendent des conditions de pH et de fO2, pour lesquelles l'uranium peut soit être transporté en solution, soit précipité sous forme d'uraninite. Par conséquent, les APS sont non seulement de bons marqueurs du degré d'altération des roches mais surtout de bons indicateurs des conditions de pH et de fO2 pour lesquelles les gisements d'uranium associés à une discordance protérozoïque se sont formés.Aluminium phosphate sulfate minerals (APS) are particularly widespread and spatially associated with hydrothermal clay alteration in both the East Alligator River Uranium Field (Northern Territory, Australia) and the Athabasca basin (Saskatchewan, Canada), in the environment of proterozoic unconformity-related uranium deposits (URUD). The purpose of this study is both: 1) to characterize the nature and the origin of the APS minerals on both sides of the middle proterozoic unconformity between the overlying sandstones and the underlying metamorphic basement rocks that host the uranium orebodies, 2) to improve our knowledge on the suitability of these minerals to indicate the paleoconditions (redox, pH) at which the alteration processes relative to the uranium deposition operated. The APS minerals result from the interaction of oxidising and relatively acidic fluids with aluminous host rocks enriched in monazite. Several APS-bearing clay assemblages and APS crystal-chemistry have also been distinguished as a function of the distance from the uranium ore bodies or from the structural discontinuities which drained the hydrothermal solutions during the mineralisation event. One of the main results of this study is that the index mineral assemblages, used in the recent literature to describe the alteration zones around the uranium ore bodies, can be theoretically predicted by a set of thermodynamic calculations which simulate different steps of fluid-rock interaction processes related to a downward penetrating of hypersaline, oxidizing and acidic diagenetic fluids through the lower sandstone units of the basins and then into the metamorphic basement rocks. The above considerations and the fact that APS with different crystal-chemical compositions crystallised in a range of fO2 and pH at which uranium can either be transported in solution or precipitated as uraninite in the host-rocks make these minerals not only good markers of the degree of alteration of the basement rocks but also very good indicators of the fO2 and pH paleoconditions at which the formation of the U-ore bodies took place.POITIERS-BU Sciences (861942102) / SudocSudocFranceF

Imaging a pore network in a clay-rock at the sub-nanometer scale

International audienceMini-Symposium Description (2.22) Clayey rocks properties are the focus of an ever-increasing interest from the geoscience community. These fine-grained sedimentary rocks (mudstone, argillite, shalesetc.) are recognized as key-components for energy-related technologies, for which they could serve as isolation material (in radioactive waste disposal), caprocks (in CO 2 capture and storage systems), or as reservoir rocks for hydrocarbons (gas and oil shales) (Bourg, 2015; Tournassat et al., 2015b). For all of these applications, accurate predictions of mechanical, flow, and reactive properties at the field scale are necessary. However, macroscale properties of clayey rocks arise for a large part from the surface properties of their nano-sized clay minerals constituents and from the characteristics of associated microstructure and pore network. Pore networks in clayey rocks are highly heterogeneous with pore widths/diameters ranging in the categories of micropores ( 2 nm and 50 nm). The fact that the pore size distribution in clayey rocks encompasses all of these pore size categories evinces the multiplicity of coupled physical processes that must be taken into account to explain observations at the core and field scales. Even if, FIB-SEM has enabled to improve the nanoscale characterization up to 5 nm (Gaboreau et al.,2016) must of the smallest pores, ensuring the connectivity, are not probed at this scale. One of the biggest challenges in the present downscaling approaches is a lack of understanding of the pore structure down to the (sub)nanometer pore sizes, which can contain up to 30 % of the total porosity, and which is also hypothesized to ensure most of the connectivity between bigger pores (Ma et al., 2016). In this study, we imaged in three dimensions the structure of a clayey rock down to the sub-nanometer scale using electron tomography. Pore network connectivity was extracted at the nanometer scale, providing key information for the building of future pore scale models. References Bourg, I.C., 2015.Sealing shales versus brittle shales: A sharp threshold in the material properties and energy technology uses of fine-grained sedimentary rocks.Environmental Science &TechnologyLetters 2, 255–259. Gaboreau, S., Robinet, J.-C., Prêt, D., 2016. Optimization of pore network characterization of compacted clay materials by TEM and FIB/SEM imaging.Microporous and Mesoporous Materials 224, 116–128., Courtois, L., 2016. Novel 3D centimetre-to nano-scale quantification of an organic-rich mudstone: The Carboniferous Bowland Shale, Northern England. Marine and Petroleum Geology 72, 193–205

Diffusion in clays. Continuum and micro-continuum approaches

International audienc

From microstructure description to macro-scale properties of clay barriers

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Optimization of pore network characterization of compacted clay materials by TEM and FIB/SEM imaging

International audienceThe transport properties of clay-rocks are controlled by their complex pore network and the reactive and negatively charged clay mineral surfaces. The Pore Size Distribution (PSD) and the geometrical features of the pore network constitute key parameters governing the migration of solvate elements through the clay formations. Upon the last few years, some works have contributed to improve the knowledge of some clay-rich rock pore networks by using innovative microscopic imaging techniques (FIB-nt, BIB, X-ray…). Even if these techniques allow imaging the mesostructure scale organization of clay-rocks and clay materials, these studies have however highlighted several limitations to fully represent the spatial distribution of pores in terms of PSD, geometry and connectivity. In the present work, we demonstrate that a multi-scale characterization of pore network of clay materials based on FIB-nt and TEM techniques is feasible and could be robustly achieved for providing some useful input data in order to assess a future modeling task. The studied material was a compacted clay materials composed of illite, a non-swelling mineral. Illite was chosen in order to represent an analog system mimicking the clay matrix of the clay-rocks. This compacted clay plug allows working on homogeneous system with a controlled porosity, facilitating the comparison between different methods. All the techniques used in the present work whether bulk or microscopic methods show that all results converge to a similar and entire PSD (figure 1). The main improvement of this work was to demonstrate how the usual resolution limitations and the data handling of the FIB-nt techniques could be improved in order to recognize a fully connected pore network