Bentonite is often proposed as an engineered-buffer material in high-level radionuclide waste-management systems. For effective design of the barrier that will provide protection over the long time periods required, the physical/thermal/chemical processes taking place in the barrier material must be understood thoroughly. These processes, which interact, include the flow of water and gas, the flow of heat, and the transport and reaction of chemical constituents. The purpose of this study was to better understand the processes that occurred in a small-scale experiment within a confined bentonite space. A conceptual and mathematical model (FADES-CHEM) was built in order to simulate the results of an experiment conducted in 2000, and thereby to gain a better understanding of the controlling processes. In that experiment, a block of compacted bentonite was placed in an air-tight cell and subjected, for 6 months, to simultaneous heating and hydration from opposite sides. The bentonite block was then sliced into five sections each of which was then analyzed in order to obtain a series of physicochemical parameters illustrating the changes that had occurred. Before modeling, the chemical composition of the bentonite pore waters was restored in order to account for different processes such as gas outgassing and cell cooling. Modeling indicated that gas-pressure build up was a relevant process when computing the saturation of bentonite, and the computations in the present study suggested that evaporation/condensation processes played a crucial role in the final distribution of the water content. Gas pressure and evaporation/ condensation also affected the geochemical system, and the numerical model developed gives results that were consistent with the experimental values and trends observed. The model reproduced the results obtained and enable use at the repository scale and over longer time frames, provided that adequate data are available.

Clays are commonly used as liners in urban landfills. However, the reactive processes with landfill leachates, and in particular the role of accessory minerals is poorly known. The aim of this work is to evaluate the diffusion of a synthetic urban landfill leachate through compacted natural smectite-illitic clays containing carbonates and sulfates and to predict the functioning of the clay liner for different minor mineral proportions. The leachate, characterized by acidic pH conditions and high organic matter content, is a typical aqueous solution formed in the acetogenic phase of organic matter degradation in urban landfill areas. Medium-scale (11 cm) laboratory diffusion tests were performed over 77 days. Chloride diffusion coefficients, porosity changes, cation exchange constants and the sulfate reduction rate were quantitatively assessed by means of reactive transport modelling. The exchange capacity of the clays is responsible for NH4+ retention. However, the presence or absence of gypsum in the initial clay rock controls the functioning of the liner. Gypsum dissolution ensures a high sulfate concentration in the porewater and enhances the acetate consumption via sulfate reduction. Gypsum dissolution and the concomitant calcite precipitation do not significantly alter the porosity of the clay rock.

We introduce a discrete-time microscopic single-particle model for kinetic transport. The kinetics are modeled by a two-state Markov chain, and the transport is modeled by deterministic advection plus a random space step. The position of the particle after n time steps is given by a random sum of space steps, where the size of the sum is given by a Markov binomial distribution (MBD). We prove that by letting the length of the time steps and the intensity of the switching between states tend to 0 linearly, we obtain a random variable S(t), which is closely connected to a well-known (deterministic) partial differential equation (PDE), reactive transport model from the civil engineering literature. Our model explains (via bimodality of the MBD) the double peaking behavior of the concentration of the free part of solutes in the PDE model. Moreover, we show for instantaneous injection of the solute that the partial densities of the free and adsorbed parts of the solute at time t do exist, and satisfy the PDEs.