Jarmo Lehikoinen

Porewater chemistry in compacted bentonite

Abstract The porewater chemistry in compacted bentonite was studied in solution–bentonite interaction experiments. The parameters varied in the experiments were the bentonite density, bentonite-to-water ratio (B/W), ionic strength of the solution, and the composition of bentonite. The bentonite types used in the experiments were Volclay MX80 and artificial bentonites prepared from purified MX-80 in sodium form where CaCO 3 and CaSO 4 were added. At the end of the experiment, the equilibrating external solution and the porewater squeezed out of the bentonite were analyzed to give information for interpretation of the interaction. The equilibrium was modelled with the HYDRAQL code. The evolution of porewater chemistry was determined by the dissolving components initially present in the bentonite together with the ions entering with water from the surroundings. Ion-exchange processes occurred between the bentonite and the porewater. The concentrations in the external solution and porewater strongly depended on the B/W used. The concentrations in the squeezed porewaters were clearly lower than in the equilibrating waters. The modelling results reasonably fit the experimental data.

Evaluation of factors affecting diffusion in compacted bentonite

The information available from the open literature and our studies on exclusion, sorption and diffusion mechanisms of ionic and neutral species in bentonite has been compiled and re-examined in relation to the microstructure of bentonite. The emphasis is placed on a more thorough understanding of the diffusion processes taking place in compacted bentonite. Despite the scarcity of experiments performed with neutral diffusants, these imply that virtually all the pores in compacted bentonite are accessible to neutral species. Anion exclusion, induced by the overlap of electrical double layers, may render the accessible porosity for anions considerably less than the porosity obtained from the water content of the clay. On the basis of the compiled data, it is highly probable that surface diffusion plays a significant role in the transport of cations in bentonite clays. Moreover, easily soluble compounds in bentonite can affect the ionic strength of porewater and, consequently, exclusion, equilibrium between cations, and surface diffusion.

Evolution of the Porewater Chemistry in Compacted Bentonite

The evolution of porewater chemistry in bentonite was studied in solution-bentonite interaction experiments under anaerobic conditions at room temperature. The parameters varied were the bentonite density, bentonite-to-water ratio (b/w), ionic strength of the solution, and the composition of bentonite. At the end of the experiment, the equilibrating solution and the porewater squeezed out of the bentonite samples were analysed. This paper presents the preliminary experimental results of these ongoing studies. The evolution of porewater chemistry was determined by the dissolving components initially present in the bentonite together with the ions coming with water from the surroundings. Ion-exchange processes occured between the exchangeable cations of montmorillonite and the cations in the water. The obtained concentrations in the external solution and porewater strongly depended on the b/w used. The concentrations in the squeezed porewaters were clearly lower than in the external waters and decreased with increasing density during squeezing.

Coupled chemical and diffusion model for compacted bentonite

A chemical equilibrium model has been developed for ion-exchange and to a limited extent for other reactions, such as precipitation or dissolution of calcite or gypsum, in compacted bentonite water systems. The model was successfully applied to some bentonite experiments, especially as far as monovalent ions were concerned. The fitted log-binding constants for the exchange of sodium for potassium, magnesium, and calcium were 0.27, 1.50, and 2.10, respectively. In addition, a coupled chemical and diffusion model has been developed to take account of diffusion in pore water, surface diffusion and ion-exchange.d the model was applied to the same experiments as the chemical equilibrium model, and its validation was found partly successful. The above values for binding constants were used also in the coupled model. The apparent (both for anions and cations) and surface diffusion (only for cations) constants yielding the best agreement between calculated and experimental data were 3.0 {times} 10{sup {minus}11} m{sup 2}/s and 6.0 {times} 10{sup {minus}12} m{sup 2}/s, respectively. These values are questionable, however, as experimental results good enough for fitting are currently not available.

Determination of Porewater Chemistry in Compacted Bentonite

Laboratory experiments were performed to study the interaction between groundwater and compacted sodium bentonite (Volclay MX-80). The solutions used were the fresh and saline groundwater simulants. The experiments were carried out in aerobic and anaerobic conditions at elevated temperature. Of main interest in the present study were the chemical changes in the reacting solution, bentonite porewater, and bentonite itself. The results for major cations display a principal difference between the interactions with fresh and saline solutions, while the differences between aerobic and anaerobic conditions within each solution case seem to be minor. The experimental results for the bentonite-water equilibria were interpreted in terms of a multi-site surface complexation model and the computer program HYDRAQL. The apparent diffusivities for sodium and sulfate in bentonite samples sandwiched between two filter plates were also determined.

Chemical Interactions in the Near-Field of a Repository for Spent Nuclear Fuel – A Modeling Study

The near-field chemistry of the repository for spent nuclear fuel arising from interactions between the groundwater, compacted bentonite clay, canister and the spent fuel was calculated using a three-successive-closed-systems approach. The calculations were performed for fresh granitic and saline groundwaters using the thermodynamic computer codes, HYDRAQL/CE and EQ3/6. The effects of water chemistry inside the canister as well as water radiolysis on fuel dissolution were taken into consideration. The groundwater and the three barriers of the near-field were accounted for by this approach, with particular emphasis given to the pH, Eh and actinide solubilities.

Diffusivity and Porosity in Rock Matrix—Laboratory Methods Using Artificial and Natural Tracers

The nature of diffusivity and porosity in crystalline rock was studied by electrical conductivity measurements, steady-state diffusion experiments, saturation-leaching of tracers with cylindrical rock samples and analysis of the concentrations of different elements from core samples or pore water near fractures. The phenomena of main interest were dead-end porosity, ion-exclusion, sorption, and the continuity of pore networks. The modelling of experimental results was based on a modified Fick`s second law for diffusion, which was solved either by analytical or numerical methods. The measured D{sub e} and {epsilon} were found to statistically follow an exponential presentation: Archie`s law. The existence of ion-exclusion for anions was confirmed. The connectivity of the pore network extended in the laboratory experiments at least six centimetres, in coarse of the pore network extended in the laboratory experiments at least six centimetres, in coarse-grained granite in nature several metres but in fine-grained rock samples of a uranium deposit the element mobilization effects could be seen only to the depth of 2-3 centimetres.

Diffusion of Uranium in Compacted Sodium Bentonite

In this study the diffusion of uranium dissolved from uranium oxide fuel was studied experimentally in compacted sodium bentonite (Wyoming bentonite MX-80). The parameters varied in the study were the density of bentonite, the salt content of the solution and the redox conditions. In the studies with non-saline water of total dissolved solids about 300 ppm, uranium was both in aerobic and anaerobic experiments as anionic complexes and followed the anionic diffusion mechanism. Anion exclusion decreased effective diffusion coefficients, especially in more dense samples. In the studies with saline water of total dissolves solids about 35000 ppm, uranium appeared in the aerobic experiments probably as cationic complexes and followed the cationic diffusion mechanism. Uranium in the saline, anaerobic experiment was probably U(OH) 4 and followed the diffusion mechanism of neutral species.