Influence of salinity gradients on the diffusion of water and ionic species in dual porosity clay samples.

Most of the available data on diffusion in natural clayey rocks consider tracer diffusion in the absence of a salinity gradient despite the fact that such gradients are frequently found in natural and engineered subsurface environments. To assess the role of such gradients on the diffusion properties of clayey materials, through-diffusion experiments were carried out in the presence and absence of a salinity gradient using salt-diffusion and radioisotope tracer techniques. The experiments were carried out with vermiculite samples that contained equal proportions of interparticle and interlayer porosities so as to assess also the role played by the two types of porosities on the diffusion of water and ions. Data were interpreted using both a classical Fickian diffusion model and with a reactive transport code, CrunchClay that can handle multi-porosity diffusion processes in the presence of charged surfaces. By combining experimental and simulated data, we demonstrated that (i) the flux of water diffusing through vermiculite interlayer porosity was minor compared to that diffusing through the interparticle porosity, and (ii) a model considering at least three types of porous volumes (interlayer, interparticle diffuse layer, and bulk interparticle) was necessary to reproduce consistently the variations of neutral and charged species diffusion as a function of salinity gradient conditions.

Gas Porosimetry by Gas Adsorption as an Efficient Tool for the Assessment of the Shaping Effect in Commercial Zeolites.

A set of three commercial zeolites (13X, 5A, and 4A) of two distinct shapes have been characterized: (i) pure zeolite powders and (ii) extruded spherical beads composed of pure zeolite powders and an unknown amount of binder used during their preparation process. The coupling of gas porosimetry experiments using argon at 87 K and CO2 at 273 K allowed determining both the amount of the binder and its effect on adsorption properties. It was evidenced that the beads contain approximately 25 wt% of binder. Moreover, from CO2 adsorption experiments at 273 K, it could be inferred that the binder present in both 13X and 5A zeolites does not interact with the probe molecule. However, for the 4A zeolite, pore filling pressures were shifted and strong interaction with CO2 was observed leading to irreversible adsorption of the probe. These results have been compared to XRD, IR spectroscopy, and ICP-AES analysis. The effect of the binder in shaped zeolite bodies can thus have a crucial impact on applications in adsorption and catalysis.

Orientation measurements of clay minerals by polarized attenuated total reflection infrared spectroscopy.

The orientation and organization of molecular guests within the interlayer of clay minerals control the reactivity and performance of tailored organo-clay materials. Such a detailed investigation of hybrid structure on the molecular scale is usually provided by computational methods with limited experimental validation. In this study, polarized attenuated total reflection infrared spectroscopy was used to extract quantitative orientation measurements of montmorillonite particles. The validity of the evanescent electric field amplitude calculations necessary to derive the order parameter was critically evaluated to propose a methodology for determining the orientation of the normal to the clay layer relative to a reference axis, enabling comparison with the results obtained from X-ray scattering experiments and molecular dynamic simulations. Subsequently, the orientation of the interlayer water dipole and surface hydroxyls with respect to the normal of the clay layer was experimentally determined, showing good agreement with molecular simulations. This methodology may provide quantitative insights into the molecular-level description of interfacial processes between organic molecules and clay minerals.

A general orientation distribution function for clay-rich media.

The role of the preferential orientation of clay platelets on the properties of a wide range of natural and engineered clay-rich media is well established. However, a reference function for describing the orientation of clay platelets in these different materials is still lacking. Here, we conducted a systematic study on a large panel of laboratory-made samples, including different clay types or preparation methods. By analyzing the orientation distribution functions obtained by X-ray scattering, we identified a unique signature for the preferred orientation of clay platelets and determined an associated reference orientation function using the maximum-entropy method. This new orientation distribution function is validated for a large set of engineered clay materials and for representative natural clay-rich rocks. This reference function has many potential applications where consideration of preferred orientation is required, including better long-term prediction of water and solute transfer or improved designs for new generations of innovative materials.

Mesoscale Anisotropy in Porous Media Made of Clay Minerals. A Numerical Study Constrained by Experimental Data.

The anisotropic properties of clay-rich porous media have significant impact on the directional dependence of fluids migration in environmental and engineering sciences. This anisotropy, linked to the preferential orientation of flat anisometric clay minerals particles, is studied here on the basis of the simulation of three-dimensional packings of non-interacting disks, using a sequential deposition algorithm under a gravitational field. Simulations show that the obtained porosities fall onto a single master curve when plotted against the anisotropy value. This finding is consistent with results from sedimentation experiments using polytetrafluoroethylene (PTFE) disks and subsequent extraction of particle anisotropy through X-ray microtomography. Further geometrical analyses of computed porous media highlight that both particle orientation and particle aggregation are responsible of the evolution of porosity as a function of anisotropy. Moreover, morphological analysis of the porous media using chord length measurements shows that the anisotropy of the pore and solid networks can be correlated with particle orientation. These results indicate that computed porous media, mimicking the organization of clay minerals, can be used to shed light on the anisotropic properties of fluid transfer in clay-based materials.

Diffusion of Water through the Dual-Porosity Swelling Clay Mineral Vermiculite.

Prediction of water and solute migration in natural clay-based materials requires a detailed understanding of the roles played by different porosity types (around or inside clay particles) on the overall transfer process. For smectite, a reference material for the design of migration models, this discrimination is complex because of osmotic swelling of the structure under water-saturated conditions. Diffusion experiments with a water tracer (HDO) were conducted on 0.1-0.2, 1-2, and 10-20 µm size fractions of Na-vermiculite, a swelling clay mineral with no osmotic swelling. Results obtained for the two finest fractions suggest that osmotic swelling and the associated impact on pore structure are responsible for the low De values reported in the literature for smectite compared to those of vermiculite. When considering only interparticle porosity, De values for vermiculite are similar to those reported for nonporous grains (Na-kaolinite and Na-illite). This indicates that interparticle porosity has a primary effect on the overall water diffusion process, whereas interlayer porosity is shown to imply a small proportion of HDO adsorption. This study provides evidence that vermiculite is a promising reference mineral for the understanding of the roles played by pore structure and mineral-water interaction in the transport properties of water in claystones and for associated refinement of dual-porosity diffusion models.

Water Mobility within Compacted Clay Samples: Multi-Scale Analysis Exploiting 1H NMR Pulsed Gradient Spin Echo and Magnetic Resonance Imaging of Water Density Profiles.

1H NMR pulsed gradient spin echo attenuation and water density profile analysis by magnetic resonance imaging are both used to determine the mobility of water molecules confined within a porous network of compacted kaolinite clay sample (total porosity of ∼50%). These two complementary experimental procedures efficiently probe molecular diffusion within time scales varying between milliseconds and few hours, filling the gap between the time scale of diffusion dynamics measured by traditional quasi elastic neutron scattering and through-diffusion methods. Furthermore, magnetic resonance imaging is a nondestructive investigation tool that is able to assess the effect of the local structure on the macroscopic mobility of the diffusing probe.

Crystal structure control of aluminized clay minerals on the mobility of caesium in contaminated soil environments.

Radioactive caesium pollution resulting from Fukushima Dai-ichi and Chernobyl nuclear plant accidents involves strong interactions between Cs+ and clays, especially vermiculite-type minerals. In acidic soil environments, such as in Fukushima area, vermiculite is subjected to weathering processes, resulting in aluminization. The crystal structure of aluminized clays and its implications for Cs+ mobility in soils remain poorly understood due to the mixture of these minerals with other clays and organic matter. We performed acidic weathering of a vermiculite to mimic the aluminization process in soils. Combination of structure analysis and Cs+ extractability measurements show that the increase of aluminization is accompanied by an increase in Cs+ mobility. Crystal structure model for aluminized vermiculite is based on the interstratification of unaltered vermiculite layers and aluminized layers within the same particle. Cs+ in vermiculite layers is poorly mobile, while the extractability of Cs+ is greatly enhanced in aluminized layers. The overall reactivity of the weathered clay (cation exchange capacity, Cs+ mobility) is then governed by the relative abundance of the two types of layers. The proposed layer model for aluminized vermiculite with two coexisting populations of caesium is of prime importance for predicting the fate of caesium in contaminated soil environments.

Effect of Water on Elastic and Creep Properties of Self-Standing Clay Films.

We characterized experimentally the elastic and creep properties of thin self-standing clay films, and how their mechanical properties evolved with relative humidity and water content. The films were made of clay montmorillonite SWy-2, obtained by evaporation of a clay suspension. Three types of films were manufactured, which differed by their interlayer cation: sodium, calcium, or a mixture of sodium with calcium. The orientational order of the films was characterized by X-ray diffractometry. The films were mechanically solicited in tension, the resulting strains being measured by digital image correlation. We measured the Young's modulus and the creep over a variety of relative humidities, on a full cycle of adsorption-desorption for what concerns the Young's modulus. Increasing relative humidity made the films less stiff and made them creep more. Both the elastic and creep properties depended significantly on the interlayer cation. For the Young's modulus, this dependence must originate from a scale greater than the scale of the clay layer. Also, hysteresis disappeared when plotting the Young's modulus versus water content instead of relative humidity. Independent of interlayer cation and of relative humidity greater than 60%, after a transient period, the creep of the films was always a logarithmic function of time. The experimental data gathered on these mesoscale systems can be of value for modelers who aim at predicting the mechanical behavior of clay-based materials (e.g., shales) at the engineering macroscopic scale from the one at the atomistic scale, for them to validate the first steps of their upscaling scheme. They provide also valuable reference data for bioinspired clay-based hybrid materials.

Modeling the arrangement of particles in natural swelling-clay porous media using three-dimensional packing of elliptic disks.

Swelling clay minerals play a key role in the control of water and pollutant migration in natural media such as soils. Moreover, swelling clay particles' orientational properties in porous media have significant implications for the directional dependence of fluid transfer. Herein we investigate the ability to mimic the organization of particles in natural swelling-clay porous media using a three-dimensional sequential particle deposition procedure [D. Coelho, J.-F. Thovert, and P. M. Adler, Phys. Rev. E 55, 1959 (1997)]. The algorithm considered is first used to simulate disk packings. Porosities of disk packings fall onto a single master curve when plotted against the orientational scalar order parameter value. This relation is used to validate the algorithm used in comparison with existing ones. The ellipticity degree of the particles is shown to have a negligible effect on the packing porosity for ratios ℓ(a)/ℓ(b) less than 1.5, whereas a significant increase in porosity is obtained for higher values. The effect of the distribution of the geometrical parameters (size, aspect ratio, and ellipticity degree) of particles on the final packing properties is also investigated. Finally, the algorithm is used to simulate particle packings for three size fractions of natural swelling-clay mineral powders. Calculated data regarding the distribution of the geometrical parameters and orientation of particles in porous media are successfully compared with experimental data obtained for the same samples. The results indicate that the obtained virtual porous media can be considered representative of natural samples and can be used to extract properties difficult to obtain experimentally, such as the anisotropic features of pore and solid phases in a system.

Nature of the sites involved in the process of cesium desorption from vermiculite.

Three particle size fractions of sodium-saturated vermiculite (10-20, 1-2 and 0.1-0.2 µm), differing only in their ratios of external-to-total sorption sites, were used to probe the nature of the sites involved in desorption of cesium ions. The sorption was investigated for initial aqueous concentrations of cesium ranging from 5.6×10(-4) to 1.3×10(-2) mol/L, and the cesium desorption was probed by exchange with ammonium ions. The results showed that (1) the amounts of desorbed cesium were strongly dependent on the particle size for a given initial aqueous cesium concentration and (2) the amounts of desorbed cations (Na(+) and Cs(+)) strongly decreased with increasing initial cesium aqueous concentration, irrespective of the particle size investigated. Quantitative analysis of these results suggested that cesium ions sorbed on external (edge+basal) sorption sites can be desorbed by ammonium ions. As a contrast, most of cesium ions sorbed on interlayer sites remain fixed due to the collapse of the structure under aqueous conditions. This study provides important information, such as the nature of the sites involved in the exchange process, when the thermodynamic formalism is considered to describe the ion-exchange process involving cesium and high-charge swelling clay minerals in polluted soil environments.

The titration of clay minerals II. Structure-based model and implications for clay reactivity.

The potentiometric titration and CEC data presented in part I are modeled in this paper, part II. Two models are compared: the two pK, three complexation sites plus exchange sites nonelectrostatic model developed by Baeyens and Bradbury and a model based on the MUSIC approach developed by Hiemstra and Van Riemsdijk. Both morphological and structural information is used to develop this new model. Morphological information is taken from the literature, while structural information is taken from the literature and constrained by supporting FTIR experiments. The Baeyens and Bradbury model is found to reproduce the general tendency of the titration curve, whereas the model based on the Hiemstra and Van Riemsdijk MUSIC approach provides a better fit to the experimental data. The former uses only 3 edge reaction sites, whereas the latter uses at least 27 edge reaction sites. Five main reactive sites are sufficient to fit the MUSIC model curve, but the model allows us to derive the properties of 22 other reactive sites. Logically, the greater the number of sites, the better the fit. Nevertheless, fewer adjustable parameters are necessary for the Hiemstra and Van Riemsdijk MUSIC model than for the Baeyens and Bradbury model, thanks to structural and morphological constraints. The precision of the potentiometric titration curve is insufficient to verify that the properties of the 27 sites given by the MUSIC model are effective. Thus, we coupled some properties of clay minerals, such as dissolution, to the modeled acid-base properties of these sites to assess our model. We then questioned the ability of simplified models such as the Baeyens and Bradbury model to predict the interactions between clay minerals and solutions in natural environments. In addition, we derived the cation exchange selectivity coefficients for CaCl+ ionic pairs and H+ from our CEC data and gave an estimate for the CaOH+ selectivity coefficient.