Water and ion diffusion in partially-water saturated compacted kaolinite: Role played by vapor-phase diffusion in water mobility.

Diffusion is the main transport process of water and solutes in clay-rich porous media owing to their very low permeability, so they are widely used as barriers against contaminant spreading. However, the prediction of contaminant mobility can be very complicated when these media are partially water-saturated. We conducted diffusion experiments for water (HTO and HDO) and ions (22Na+ and 125I-) through partially water saturated compacted kaolinite, a weakly charged clay material, to quantify the distinct diffusive behavior of these species. The osmosis method was used to set kaolinite samples at 67, 86 and 100% saturation. The results showed that desaturation led to a sharp decrease in diffusive rates by factors of 6.5, 18 and 35 for HTO, 125I- and 22Na+, respectively, from 100 to 67% of the degree of saturation. Thus, to interpret water diffusivities, we proposed a model taking into account the diffusion of water in both gas and liquid phases, using diffusion data obtained for ions, considered as inert species. This model was capable of properly predicting water diffusive flux, especially at a low degree of saturation (67% saturation), for which the assumption made for the occurrence of air phase continuity throughout the sample appears to be more relevant than at 86% saturation.

Uranium retention in a Callovo-Oxfordian clay rock formation: From laboratory-based models to in natura conditions.

For the performance assessment of radioactive waste disposal, it is critical to predict the mobility of radionuclides in the geological barrier that hosts it. A key challenge consists of assessing the transferability of current knowledge on the retention properties deduced from model systems to in natura situations. The case of the redox-sensitive element uranium in the Callovo-Oxfordian clay formation (COx) is presented herein. Extensive experimental work was carried out with respect to parameters affecting uranium speciation (pH, PCO2, [Ca] and redox potential) with illite, COx clay fraction and raw COx claystone. The "bottom-up" approach implemented, with illite and montmorillonite as reactive phases, quantitatively explains the adsorption results of U(VI) and U(IV) on COx. While retention is high for U(IV) (Rd∼104 L kg-1), it remains very low for U(VI) (Rd∼4 L kg-1) due to the formation of soluble ternary Ca(Mg)-U(VI)-carbonate complexes. The applicability of the sorption model was then assessed by comparing predictive analyses with data characterizing the behavior of naturally-occurring U (<3 mg kg-1). The COx clay phase is the largest reservoir of naturally-occurring U (∼65%) but only a small fraction appears to be adsorbed (∼1%). Under representative site conditions (especially with respect to reducing conditions), we have concluded that ternary U(VI) complexes control U speciation in solution while U(IV) surface species dominate U adsorption, with Rd values > 70 L kg-1.

Diffusion of organic anions in clay-rich media: Retardation and effect of anion exclusion.

The transport of emerging organic contaminants through the geosphere is often an environmental issue. The sorption of organic compounds slows their transport in soils and porous rocks and retardation is often assessed by extrapolation of batch experiments. However, transport experiments are preferable to strengthen migration data and modelling. In this context, we evaluated the adsorption of various organic acids by means of through-diffusion experiments in a sedimentary clay-rich rock (Callovo-Oxfordian, East of Paris Basin, France). A low diffusivity of organic anions was quantified with effective diffusion coefficients, De, ranged between 0.5 and 7 10-12 m2 s-1. These values indicated an organic anion exclusion. As for chloride, the porosity accessible to organic anions was lower than that of water: εa(organic anions) < ε(water). The partial exclusion of organic anions from rock porosity was linked to both charge and size effects. A significant retardation was observed for organic anions such as oxalate, citrate or α-isosaccharinate. Yet, retardation measured by diffusion experiments was significantly lower than expected from batch experiments on crushed samples. An empirical correction factor is proposed to account for a possible decrease of retardation with accessible porosity of diffusing solute. This feature has significant implications for the estimation of migration parameters of organic compounds in the environment.

How mobile is tritiated water through unsaturated cement-based materials? New insights from two complementary approaches.

This work presents two complementary approaches (for low and high desaturation) to study tritiated water (HTO) diffusion through unsaturated cement-based materials. The first approach was based on through-diffusion experiments where suction was controlled by osmosis. In the second approach, diffusion experiments were performed in humidity chambers controlled by under-saturated saline solutions. Results revealed a decrease of effective diffusion coefficient by a factor of 10 from 100% to 23% of saturation degree. Comparison with gaseous H2 suggests that HTO diffuses through unsaturated cement-based materials at rates 4 orders of magnitude lower.

The influence of a pressure wavepacket's characteristics on its acoustic radiation.

Noise generation by flows is modeled using a pressure wavepacket to excite the acoustic medium via a boundary condition of the homogeneous wave equation. The pressure wavepacket is a generic representation of the flow unsteadiness, and is characterized by a space envelope of pseudo-Gaussian shape and by a subsonic phase velocity. The space modulation yields energy in the supersonic range of the wavenumber spectrum, which is directly responsible for sound radiation and directivity. The influence of the envelope's shape on the noise emission is studied analytically and numerically, using an acoustic efficiency defined as the ratio of the acoustic power generated by the wavepacket to that involved in the modeled flow. The methodology is also extended to the case of acoustic propagation in a uniformly moving medium, broadening possibilities toward practical flows where organized structures play a major role, such as co-flow around cruising jet, cavity, and turbulent boundary layer flows. The results of the acoustic efficiency show significant sound pressure levels, especially for asymmetric wavepackets radiating in a moving medium.

Direct simulation of heterogeneous diffusion and inversion procedure applied to an out-diffusion experiment. Test case of Palmottu granite.

An out-diffusion laboratory experiment using a non-reactive tracer was fitted using the Time Domain Diffusion (TDD) method. This rapid particle tracking method allows simulation of the heterogeneous diffusion based on pore-scale images and local values of diffusivities. The superimposed porosity and mineral 2D maps act as computation grids to condition diffusion pathways. We focused on a Palmottu granite sample, in which the connected pore space has a composite microstructure with cracks linking microporous minerals and is above the percolation threshold. Three main results were achieved: (i) When compared to the fitting obtained with one coefficient (best mean square residual R = 1.6 x 10(-2)), diffusion is shown to be suitably characterised with two coefficients related to cracks and microporous minerals (best R = 6.5 x 10(-4)), (ii) rather than imposing a local apparent diffusion coefficient D(a) independent of the local porosity Phi, a best fit is obtained by applying Archie's relationship D(a) = D(0) x G with G = Phi(m) to each pixel of the calculation grids (G is the geometry factor, D(0) is the diffusion coefficient in free fluid, and m is Archie's exponent), and (iii) the order of magnitude of the fitted diffusion coefficient or Archie's exponents (m=0 for microcracks and m=1.82 for microporous minerals) is physically realistic.