Arto Muurinen

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.

Diffusion of uranium in compacted sodium bentonite

Abstract Sorption and diffusion of uranium in sodium bentonite MX-80 were measured in aerobic conditions. The batch method was used for the sorption measurements and the steady state method for the diffusion measurements. Clear sorption was noticed only when high uranium concentrations were used so that the pH of the solution decreased. The diffusivities of uranium were strongly dependent on the compaction of bentonite so that in the highly compacted samples the diffusion was very restricted. Uranium shows both features of ion-exclusion and sorption. Further studies are, however, needed to explain the diffusion mechanisms of uranium.

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.

Long-term geochemical evolution of the near field repository: Insights from reactive transport modelling and experimental evidences

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept. In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution-precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.

Diffusivities of Cesium and Strontium in Concretes and in Mixtures of Sodium Bentonite and Crushed Rock

Diffusivities of Cs and Sr in concretes and in mixtures of sodium bentonite and crushed rock were measured. The order of magnitude of the apparent diffusivities (D a ) for Cs and Sr in concretes was −14 −10 −13 m 2 /s and in the mixtures of bentonite and crushed rock 10 −13 − 10 −11 m 2 /s. The calculated effective diffusivities (D e ) in the mixtures of bentonite and crushed rock seemed in some cases to exceed the corresponding values in water, which suggests that the pore diffusion/sorption model cannot explain the transport phenomena in all cases. The experiments where the sorption factors were varied in the diffusion samples suggest that the nuclides diffuse also while being sorbed. A combined pore diffusion-surface diffusion model has been used to explain the transport and the corresponding diffusivities have been evaluated. This paper will give the measured diffusion and sorption data and discuss the models used to describe diffusion in porous sorbing agents.

Bentonite pore distribution based on SAXS, chloride exclusion and NMR studies

Abstract Water-saturated bentonite is planned to be used in many countries as an important barrier component in high-level nuclear waste (HLW) repositories. Knowledge about the microstructure of the bentonite and the distribution of water between interlayer (IL) and non-interlayer (non-IL) pores is important for modelling of long-term processes. In this work the microstructure of water-saturated samples prepared from MX-80 bentonite was studied with nuclear magnetic resonance (NMR) and small-angle X-ray scattering spectroscopy (SAXS) coupled with chloride exclusion modelling. The sample dry densities ranged between 0.7 and 1.6 g/cm3. The NMR technique was used to get information about the relative amounts of different water types. Water in smaller volume domains has a shorter relaxation time than that in larger domains due to the average closer proximity of the water to the paramagnetic Fe at the layer surfaces. The results were obtained using 1H NMR T1ρ relaxation time measurements with the short inter-pulse CPMG method. The interpretation of the NMR results was made by fitting a sum of discrete exponentials to the observed decay curves. The SAXS measurement on bentonite samples was used to get information about the size distribution of the IL distance of montmorillonite. The chloride porosity measurements and Donnan exclusion calculations were used together with the SAXS results to evaluate the bentonite microstructure. In the model, the montmorillonite layers were organized in stacks having IL water between the layers and non-IL water between the stacks. In the modelling, the number of layers in the stacks was used as fitting parameters which determined the IL and non-IL surface areas. The fitting parameters were adjusted so that the modelled chloride concentration was equal to the measured one. The NMR studies and SAXS studies coupled with the Cl porosity measurements provided very similar pictures of how the porewater is divided in two phases in bentonite.

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.

Interaction of Water and Compacted Sodium-Bentonite in Simulated Nuclear Waste Disposal Conditions

Alteration of compacted sodium-bentonite (Volclay MX-80) caused by groundwater in simulated repository conditions for high level radioactive waste, was studied in an experiment where bentonite (wrapped by a copper cylinder) was let to react with two types (A,B) of synthetic granitic groundwater that are distinguished by their initial concentration of potassium and chloride. The reaction took place in ambient conditions at a temperature of 75 °C and proceeded during several time intervals up to 36 months. At the end of each time interval the water was chemically analysed for determination of possible changes in composition. Chemical and mineralogical changes in the bentonite were investigated by using NH 4 Cl extractions, XRD and microprobe (SEM, EDS) analyses and were studied as a function of the reaction time (months) as well as of the distance (mm) from the contact front with water. Sodium ions were found to migrate out from the bentonite while being replaced by other cations such as calcium, magnesium and to some extent, particularly during the reaction of the bentonite with water B, by potassium. No clear evidence was found for the fixation of potassium ions in the interlayer position of montmorillonite clay and the transformation to illite. The main mineralogical change in the bentonite was from Na- to Ca-rich montmorillonite. Secondary processes were the dissolution-precipitation of sulphur compounds, dissolution of gypsum and carbonates and the dissolution-precipitation of copper compounds.

Microstructural investigation of calcium montmorillonite

Abstract Bentonite clay is planned to form a part of deep-geological repositories of spent nuclear fuel in several countries. The extremely long operation time of the repository requires an indepth understanding of the structure and properties of used materials. In this work the microstructure of a simplified system of Ca-montmorillonite is investigated using a set of complementary methods: X-ray diffraction, small angle X-ray scattering, nuclear magnetic resonance, transmission electron microscopy and ion exclusion. The paper presents experimental results obtained from compacted, water saturated samples in the dry density range 0.6-1.5 g/cm3. It can be observed that different methods yield similar quantification of water present in the interlamellar space. Combined results support the multiple porosity concept of the bentonite structure.

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.