Agence Nationale pour la Gestion des Déchets Radioactifs

Hydration of the <1 μm size fraction of SWy-1 source clay (low-charge montmorillonite) was studied by modeling of X-ray diffraction (XRD) patterns recorded under controlled relative humidity (RH) conditions on Li-, Na-, K-, Mg-, Ca-, and Sr-saturated specimens. The quantitative description of smectite hydration, based on the relative proportions of different layer types derived from the fitting of experimental XRD patterns, was consistent with previous reports of smectite hydration. However, the coexistence of smectite layer types exhibiting contrasting hydration states was systematically observed, and heterogeneity rather than homogeneity seems to be the rule for smectite hydration. This heterogeneity can be characterized qualitatively using the standard deviation of the departure from rationality of the 00l reflection series (ξ), which is systematically larger than 0.4 Å when the prevailing layer type accounts for ~70% or less of the total layers (~25% of XRD patterns examined). In addition, hydration heterogeneities are not distributed randomly within smectite crystallites, and models describing these complex structures involve two distinct contributions, each containing different layer types that are interstratifed randomly. As a result, the different layer types are partially segregated in the sample. However, these two contributions do not imply the actual presence of two populations of particles in the sample.

A set of triaxial compression tests on specimens of argillaceous rock were performed under tomographic monitoring at the European Synchrotron Radiation Facility in Grenoble, France, using an original experimental set-up developed at Laboratoire 3S, Grenoble. Complete 3D images of the specimens were recorded throughout each test using X-ray microtomography. Such images were subsequently analysed using a Volumetric Digital Image Correlation software developed at the Laboratoire de Me?canique des Solides in Palaiseau, France. Full-field incremental strain measurements were obtained, which allow to detect the onset of shear strain localisation and to characterise its development in a 3D complex pattern. Volumetric Digital Image Correlation revealed patterns which could not be directly observed from the original tomographic images, because the deformation process in the zones of localised deformation was essentially isochoric (i.e. without volumetric strain), hence not associated to density changes.

Abstract: A set of triaxial compression tests on specimens of argillaceous rock were performed under tomographic monitoring at the European Synchrotron Radiation Facility in Grenoble, France, using an original experimental set‐up developed at Laboratoire 3S , Grenoble. Complete 3D images of the specimens were recorded throughout each test using X‐ray microtomography. Such images were subsequently analysed using a Volumetric Digital Image Correlation software developed at the Laboratoire de Mécanique des Solides in Palaiseau, France. Full‐field incremental strain measurements were obtained, which allow to detect the onset of shear strain localisation and to characterise its development in a 3D complex pattern. Volumetric Digital Image Correlation revealed patterns which could not be directly observed from the original tomographic images, because the deformation process in the zones of localised deformation was essentially isochoric (i.e. without volumetric strain), hence not associated to density changes.

Core Ideas OZCAR is a network of sites studying the critical zone. OZCAR covers various disciplines. OZCAR will help disciplines to work together for a better representation and modeling of the critical zone. The French critical zone initiative, called OZCAR (Observatoires de la Zone Critique–Application et Recherche or Critical Zone Observatories–Application and Research) is a National Research Infrastructure (RI). OZCAR‐RI is a network of instrumented sites, bringing together 21 pre‐existing research observatories monitoring different compartments of the zone situated between “the rock and the sky,” the Earth's skin or critical zone (CZ), over the long term. These observatories are regionally based and have specific initial scientific questions, monitoring strategies, databases, and modeling activities. The diversity of OZCAR‐RI observatories and sites is well representative of the heterogeneity of the CZ and of the scientific communities studying it. Despite this diversity, all OZCAR‐RI sites share a main overarching mandate, which is to monitor, understand, and predict (“earthcast”) the fluxes of water and matter of the Earth's near surface and how they will change in response to the “new climatic regime.” The vision for OZCAR strategic development aims at designing an open infrastructure, building a national CZ community able to share a systemic representation of the CZ, and educating a new generation of scientists more apt to tackle the wicked problem of the Anthropocene. OZCAR articulates around: (i) a set of common scientific questions and cross‐cutting scientific activities using the wealth of OZCAR‐RI observatories, (ii) an ambitious instrumental development program, and (iii) a better interaction between data and models to integrate the different time and spatial scales. Internationally, OZCAR‐RI aims at strengthening the CZ community by providing a model of organization for pre‐existing observatories and by offering CZ instrumented sites. OZCAR is one of two French mirrors of the European Strategy Forum on Research Infrastructure (eLTER‐ESFRI) project.

We report a molecular dynamics study of the structure and dynamics of water at a clay surface. The negative charge of the surface and the presence of surface oxygen atoms perturbs water over two to three molecular layers, while the nature of the counterions (Na(+)or Cs(+)) has only a small effect. In the first molecular layer, approximately half of the water molecules are H-bonded to the surface. We also analyze the H-bond network between surface water molecules. The diffusion of water molecules along the surface is slowed down compared to the bulk case. As far as the orientational order and dynamics of the water dipole are concerned, only the component normal to the clay surface is perturbed. We investigate the surface H-bond formation and dissociation dynamics and their coupling to the release of molecules from the first molecular layer. We introduce a simple kinetic model in the spirit of Luzar and Chandler [Nature, 1996, 379, 55] to allow for a comparison with bulk water dynamics. This model semi-quantitatively reproduces the molecular simulation results and suggests that H-bond formation is faster with the surface than in the bulk, while H-bond dissociation is slower.

In the context of global warming, nuclear energy is a carbon-free source of power and so is a meaningful option for energy production without CO2 emissions. Currently, there are more than 440 commercial nuclear reactors, accounting for about 15% of electric power generation in the world, and there has not been a major accident in over 20 years. The world's fleet of nuclear power plants is, on average, more than 20 years old. Even though the design life of a nuclear power plant is typically 30 or 40 years, it is quite feasible that many nuclear power plants will be able to operate for longer than this.

Abstract The description and identification of corrosion products formed on archaeological iron artefacts need various approaches at different observation scales. For this study, samples from five sites were prepared using two techniques. The first consists in cutting cross‐sections perpendicular to corrosion layers. This allows local observations and analysis of the corrosion layer stratigraphy at different levels. The second consists in performing manual grinding or abrading of the corrosion layers starting from the current surface of the excavated artefact to the metal core. It allows the description of the successive layers and is well adapted for the analysis on a larger scale. In addition to these two observation scales, the identification of the iron oxides formed needs the coupling of several complementary techniques. Elementary compositions were determined by scanning electron microscopy–energy‐dispersive x‐ray (SEM–EDX) analysis and electron probe microanalysis (EPMA). Structural identification was performed by x‐ray micro‐diffraction under synchrotron radiation (µXRD) and micro‐Raman spectroscopy. These analyses were performed on the same samples with both x‐ray diffraction and Raman spectroscopy in order to ensure a reliable characterization. In some cases there are some ambiguities or overlapping between signatures of different phases by µXRD (such as maghaemite–magnetite) or Raman spectroscopy (such as goethite–magnetite) which can be overcome by the association of the two methods. The final aim is to set up an analytical methodology that will be optimal for the study of ancient iron corrosion products. It is the first step in the study of long‐term mechanisms of iron in soil. Copyright © 2004 John Wiley &amp; Sons, Ltd.

Geologic repositories for radioactive waste are designed as multi-barrier disposal systems that perform a number of functions including the long-term isolation and containment of waste from the human environment, and the attenuation of radionuclides released to the subsurface. The rock laboratory at Mont Terri (canton Jura, Switzerland) in the Opalinus Clay plays an important role in the development of such repositories. The experimental results gained in the last 20 years are used to study the possible evolution of a repository and investigate processes closely related to the safety functions of a repository hosted in a clay rock. At the same time, these experiments have increased our general knowledge of the complex behaviour of argillaceous formations in response to coupled hydrological, mechanical, thermal, chemical, and biological processes. After presenting the geological setting in and around the Mont Terri rock laboratory and an overview of the mineralogy and key properties of the Opalinus Clay, we give a brief overview of the key experiments that are described in more detail in the following research papers to this Special Issue of the Swiss Journal of Geosciences. These experiments aim to characterise the Opalinus Clay and estimate safetyrelevant parameters, test procedures, and technologies for repository construction and waste emplacement. Other aspects covered are: bentonite buffer emplacement, high-pH concrete-clay interaction experiments, anaerobic steel corrosion with hydrogen formation, depletion of hydrogen by microbial activity, and finally, release of radionuclides Editorial handling: A. G.

The paper presents an interpretation of an in situ heating test carried out on Opalinus clay in the Mont Terri underground laboratory. Opalinus clay is a stiff, strongly bedded, Mesozoic clay of marine origin. When subjected to thermal loading, saturated stiff clays exhibit a strong pore pressure response that significantly affects the hydraulic and mechanical behaviour of the material. The observations gathered in the in situ test have provided an opportunity to examine the integrated thermo-hydro-mechanical (THM) response of this sedimentary clay. Coupled THM numerical analyses have been carried out to provide a structured framework for interpretation, and to enhance understanding of THM clay behaviour. Numerical analyses have been based on a coupled theoretical formulation that incorporates a constitutive law especially developed for this type of material. The law includes degradation of bonding by damage. By performing three-dimensional computations, it has been possible to incorporate anisotropy of material parameters and of in situ stresses. The 3D simulation has proved able to furnish a satisfactory representation of the development of the in situ test and of the main observed patterns of behaviour. A sensitivity analysis has also been carried out to examine the potential effect of various key or uncertain parameters. The critical examination of test observations and the results of the numerical analyses have allowed the classification, by differing degrees of significance, of the various coupled phenomena present in the problem.

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We have developed a mechanistic model to interpret spectral induced polarization data of partially saturated clay-rocks. This model accounts for the polarization of the grains through an electrical double layer model with a polarization model of the inner part of the electrical double layer called the Stern layer. The polarization model accounts also for the Maxwell-Wagner polarization at frequencies higher than 100 Hz. The Maxwell-Wagner polarization is modelled by using a conductivity model modified to account for the presence of a non-wetting immiscible phase like air in the pore space. The resulting model is consistent with the first and second Archie's laws in the case where surface conductivity can be neglected. The volumetric charge density of the diffuse layer at saturation is divided by the saturation of the water phase to account for the partial water saturation of the porous material. The model comprises seven fundamental parameters: the formation factor, the second Archie's exponent, a critical water saturation level, the mean electrical potential of the pore space at saturation, the density of the counterions in the Stern layer, and at least two parameters describing the grain size distribution. Most of these parameters can be derived independently using alternative measurements and electrochemical models. Measurements were performed in the frequency range 10 mHz-45 kHz using five samples from the Callovo-Oxfordian formation in the eastern part of the Paris Basin, France. The model agrees fairly well with the experimental data at saturation and for partially saturated clay-rocks down to 1 Hz. Most of the seven physical parameters entering the model were independently evaluated.

Models of swelling clays are studied by computer simulations (Monte Carlo and molecular dynamics). We focus on the comparison of structural and dynamic properties of two montmorillonites with different kinds of counterions Na+ and Cs+. The calculated values are compared with available experimental quantities such as interlayer spacing as a function of water content and diffusion coefficients of both water molecules and counterions in the monohydrated state. The results are consistent with experimental values and previous simulations. For the dynamics, the short time behavior of water as observed with quasielastic neutron scattering is in agreement with simulated one. For the ions, the experimental values are related to macroscopic long time motions and are much smaller than the short time values calculated from MD. Thus, the present study provides a detailed insight in the microscopic dynamics of ions related to the structure of the clay: it is shown that Cs+ diffuse faster than Na+ and that the arrangement of clay surfaces plays a significant role in the choice of the sites occupied by the cations as well as in their mobility.

X-ray diffraction (XRD) patterns were calculated and compared to literature data with the aim of investigating the crystal structure of nanocrystalline calcium silicate hydrates (C-S-H), the main binding phase in hydrated Portland cement pastes. Published XRD patterns from C-S-H of Ca/Si ratios ranging from ~ 0.6 to ~ 1.7 are fully compatible with nanocrystalline and turbostratic tobermorite. Even at a ratio close or slightly higher than that of jennite (Ca/Si = 1.5) this latter mineral, which is required in some models to describe the structure of C-S-H, is not detected in the experimental XRD patterns. The 001 basal reflection from C-S-H, positioned at ~ 13.5 Å when the C-S-H structural Ca/Si ratio is low (< 0.9), shifts towards smaller d values and sharpens with increasing Ca/Si ratio, to reach ~ 11.2 Å when the Ca/Si ratio is higher than 1.5. Calculations indicate that the sharpening of the 001 reflection may be related to a crystallite size along c* (i.e. a mean number of stacked layers) increasing with the C-S-H Ca/Si ratio. Such an increase would contribute to the observed shift of the 001 reflection, but fails to quantitatively explain it. It is proposed that the observed shift could result from interstratification of at least two tobermorite-like layers, one having a high and the other a low Ca/Si ratio with a basal spacing of 11.3 and 14 Å, respectively.

The mesostructure (millimeter to micrometer scale) of clay‐rich sedimentary rocks is generally characterized by a connected fine‐grained clay matrix embedding coarser nonclay minerals. We use the Callovo‐Oxfordian clay‐rich rock formation (France) to illustrate how mesostructure influences solute transfer in clay‐rich rocks at larger scales. Using micrometer resolution imaging techniques (SEM and micro‐CT) major mineral phases (clay matrix, carbonates, tectosilicates, and heavy minerals) were mapped both in two dimensional (2‐D) and three dimensional (3‐D) at the mesoscale. Orientation and elongation distributions of carbonate and tectosilicate grains measured on mineral maps reveal an anisotropic mesostructure relative to the bedding plane, in agreement with the geological history of the sedimentary rock. Diffusion simulations were performed based on the 3‐D mineral maps using a random walk method thus allowing direct computation of mesoscopic scale‐related diffusion anisotropy and tortuosity. Considering an isotropic clay matrix, simulated diffusion anisotropy (1.11–1.26) was found lower than the one experimentally measured on macroscopic samples (1.5 to 2), due to the anisotropy feature of pores within the clay matrix. The effects of the mineral content variations on diffusion properties were then investigated by numerical modifications of a mineral map combined with diffusion simulations. Evolution of the tortuosity and diffusion anisotropy with the clay matrix content were successfully interpreted by the Koponen percolation/diffusion model, whereas the Archie approach fails to reproduce diffusion properties at low clay contents. A comparison of fitting parameters with those obtained experimentally indicates that diffusion coefficient variations observed at a large scale could be mainly controlled by the mesostructure.

Dry and in situ (fluid-cell) Atomic Force Microscopy (AFM) and Low-Pressure Gas Adsorption experiments were used to investigate the surfaces of pure Na-smectite particles. These two techniques permit the identification of different surfaces of the platelets (lateral, basal, and interlayer surfaces) and to quantify their surface area. Calculation of the surface area was done for AFM, by measuring directly the dimensions of the clay particles on AFM images, and for gas adsorption experiments, by applying the Derivative Isotherm Summation (DIS) procedure designed by Villiéras et al. (Villiéras et al. 1992, 1997a, 1997b).

Since 2000, the French National Radioactive Waste Management Agency (ANDRA) has been constructing an Underground Research Laboratory (URL) at Bure (east of the Paris Basin) to perform experiments in order to obtain in situ data necessary to demonstrate the feasibility of geological repository in the Callovo-Oxfordian claystone. An important experimental program is planned to characterize the response of the rock to different drift construction methods. Before 2008, at the main level of the laboratory, most of the drifts were excavated using pneumatic hammer and supported with rock bolts, sliding steel arches and fiber shotcrete. Other techniques, such as road header techniques, stiff and flexible supports, have also been used to characterize their impacts. The drift network is developed following the in situ major stresses. The parallel drifts are separated enough so as they can be considered independently when their hydromechanical (HM) behaviors are compared. Mine-by experiments have been performed to measure the HM response of the rock and the mechanical loading applied to the support system due to the digging and after excavation. Drifts exhibit extensional (mode I) and shear fractures (modes II and III) induced by excavation works. The extent of the induced fracture networks depends on the drift orientation versus the in situ stress field. This paper describes the drift convergence and deformation in the surrounding rock walls as function of time and the impact of different support methods on the rock mass behavior. An observation based method is finally applied to distinguish the instantaneous and time-dependent parts of the rock mass deformation around the drifts.

Abstract. Aerosol particles are essential constituents of the Earth's atmosphere, impacting the earth radiation balance directly by scattering and absorbing solar radiation, and indirectly by acting as cloud condensation nuclei. In contrast to most greenhouse gases, aerosol particles have short atmospheric residence times, resulting in a highly heterogeneous distribution in space and time. There is a clear need to document this variability at regional scale through observations involving, in particular, the in situ near-surface segment of the atmospheric observation system. This paper will provide the widest effort so far to document variability of climate-relevant in situ aerosol properties (namely wavelength dependent particle light scattering and absorption coefficients, particle number concentration and particle number size distribution) from all sites connected to the Global Atmosphere Watch network. High-quality data from almost 90 stations worldwide have been collected and controlled for quality and are reported for a reference year in 2017, providing a very extended and robust view of the variability of these variables worldwide. The range of variability observed worldwide for light scattering and absorption coefficients, single-scattering albedo, and particle number concentration are presented together with preliminary information on their long-term trends and comparison with model simulation for the different stations. The scope of the present paper is also to provide the necessary suite of information, including data provision procedures, quality control and analysis, data policy, and usage of the ground-based aerosol measurement network. It delivers to users of the World Data Centre on Aerosol, the required confidence in data products in the form of a fully characterized value chain, including uncertainty estimation and requirements for contributing to the global climate monitoring system.

Bacterial respiration of nitrate is a natural process of nitrate reduction, which has been industrialized to treat anthropic nitrate pollution. This process, also known as “microbial denitrification”, is widely documented from the fundamental and engineering points of view for the enhancement of the removal of nitrate in wastewater. For this purpose, experiments are generally conducted with heterotrophic microbial metabolism, neutral pH and moderate nitrate concentrations (&lt;50 mM). The present review focuses on a different approach as it aims to understand the effects of hydrogenotrophy, alkaline pH and high nitrate concentration on microbial denitrification. Hydrogen has a high energy content but its low solubility, 0.74 mM (1 atm, 30 °C), in aqueous medium limits its bioavailability, putting it at a kinetic disadvantage compared to more soluble organic compounds. For most bacteria, the optimal pH varies between 7.5 and 9.5. Outside this range, denitrification is slowed down and nitrite (NO2−) accumulates. Some alkaliphilic bacteria are able to express denitrifying activity at pH levels close to 12 thanks to specific adaptation and resistance mechanisms detailed in this manuscript, and some bacterial populations support nitrate concentrations in the range of several hundred mM to 1 M. A high concentration of nitrate generally leads to an accumulation of nitrite. Nitrite accumulation can inhibit bacterial activity and may be a cause of cell death.

Abstract In this study, Raman spectroscopy was used to precisely understand the mechanisms of oxidation of mackinawite (FeS). Two experimental conditions were considered: (1) oxidation in air at room temperature and (2) oxidation in acidic anoxic solutions at 80 °C. In both cases, the oxidation process began by the in situ oxidation of Fe(II) cations inside the crystal structure of mackinawite and led to Fe(III)‐containing mackinawite, Fe II 1−3 x Fe III 2 x S. The oxidation in air finally led to Fe(III) oxyhydroxides and elemental sulfur α‐S 8 , but greigite (Fe 3 S 4 ) was observed as an intermediate compound. In anoxic acidic solutions, the product of the oxidation was proved to depend on the Fe/S concentration ratio. For Fe/S = 3/4, greigite was the only product obtained, and this allowed us to determine unambiguously the Raman spectrum of this compound. Copyright © 2010 John Wiley &amp; Sons, Ltd.

In ANDRA's studies to characterize the Callovian–Oxfordian formation, porewater chemistry is a key topic. Indeed, chemistry determines the durability of the repository materials (bentonite, concrete, metals, nuclear glass) and the speciation (and thus the mobility) of radionuclides. The method developed in the frame of the THERMOAR project enables the acquisition of a complete set of data from core samples to model the porewater chemistry. The method requires a detailed mineralogical study, a model of free-water/bound-water distribution, leaching experiments, adsorbed ion measurements, ion-exchange constant acquisition, and CO 2 partial-pressure measurements. These experiments and measurements were done on samples from the site of the Meuse/Haute-Marne laboratory and from ANDRA's regional boreholes. The regional stability of a great number of parameters can be observed, except for a decrease of the Na and Cl concentration following a NE–SW axis passing through the laboratory. The water/rock equilibrium model makes it possible to calculate the chemical composition of interstitial waters of the formation.