[Show abstract][Hide abstract] ABSTRACT: Disposal of Finnish spent nuclear fuel is planned to be based on the KBS-3 repository concept. The role of the bentonite buffer in this concept is essential, and thus the behaviour of the bentonite has to be known. The experiments in this paper concentrated on providing information about the effects of carbon dioxide CO2(g) partial pressure on compacted sodium bentonite, giving an insight into the buffering capacity. The experimental setup consisted of a hermetic box which had a CO2-adjusted atmosphere, and the bentonite was in contact with this atmosphere through water reservoirs. The results indicated that it is possible to measure online the changing pH in the porewater inside compacted bentonite using IrOx electrodes. It was found that the pH fell if the CO2 partial pressure increased above atmospheric conditions. The experimental results indicated a greater fall in pH than in our model in the test cases where CO2 was present. The pH in the experiment with 0 PCO2 remained nearly constant throughout the 5 month period. On the other hand, the pH dropped to near 6 with 0.3 PCO2 and to 5.5 with 1 PCO2.
[Show abstract][Hide abstract] 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 T 1ρ 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.
[Show abstract][Hide abstract] 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 0.6–5 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.
[Show abstract][Hide abstract] ABSTRACT: Bentonite is planned to be used in many countries as an important barrier in high-level waste repositories. Assessment of the barrier with regard to, inter alia, its ability to hinder transport of dissolved radionuclides leaking from a damaged canister containing spent nuclear fuel, requires quantitative data about the pore structure inside bentonite. The present NMR study was made in order to determine the number of distinguishable porewater phases in compacted water-saturated samples of MX-80 bentonite and Na-montmorillonite. The samples were compacted to dry densities in the interval 0.7-1.6 g/cm3 and subsequently saturated with Milli-Q water or 0.1 M NaCl solution in equilibrium cells. The NMR measurements were performed with a high-field 270 MHz NMR spectrometer using a short inter-pulse CPMG method to study proton T1ρ relaxation. The measured relaxation curves were found to consist of one faster and one slower proton relaxation. Subsequent analysis of the data indicated that the faster relaxation was associated with interlayer (IL) water between montmorillonite unit layers, while the slower one was associated with non-interlayer (non-IL) water located outside the interlayer spaces. The results indicate for compacted samples with a dry density of ≥ 1.0 g/cm3, that Na montmorillonite contains a larger relative volume of non-IL water than the corresponding MX-80 bentonite. This in turn, suggests that the stacking number in Na-montmorillonite is smaller than in MX-80 bentonite. Changing the porewater chemistry seemed to have some effect on the non-IL water content in the Na montmorillonite but not in the MX-80 bentonite.
[Show abstract][Hide abstract] ABSTRACT: The Finnish spent nuclear fuel disposal is based on the Swedish KBS-3 concept in crystalline bedrock. The concept aims at long-term isolation and containment of spent fuel in copper canisters surrounded by bentonite buffer which mostly consists of montmorillonite. For the long-term modelling of the chemical processes in the buffer, the cation-exchange selectivity coefficients have to be known at different temperatures. In this work, the cation-exchange selectivity coefficients and cation-exchange isotherms were determined in batch experiments for montmorillonite at three different temperatures (25 °C, 50 °C and 75 °C). Five different ratios of NaClO4/Ca(ClO4)2 were used in the experimental solutions. After equilibration the solution and montmorillonite were separated and the solution analysed to get the desired exchange parameters. The experiments were modelled with a computational model capable of taking into account the physicochemical processes that take place in the experiment.
[Show abstract][Hide abstract] ABSTRACT: The low-content free water and high swelling pressure in compacted bentonite, planned to be used as a buffer in nuclear waste repositories, create adverse conditions for direct measurements of the chemical conditions. This paper presents laboratory results from online measurements with Eh and pH electrodes in water-saturated compacted MX-80 bentonite. The Eh was measured with Au and Pt wires as electrodes, while the pH was determined with IrOx electrodes. The latter were prepared in accordance with the method by Yao et al. . The measurements were carried out in two types of cells: 'squeezing cells' and 'diffusion cells'. The squeezing cell excludes almost completely all chemical interactions between the sample and the surrounding environment outside the cell. The diffusion cell, on the other hand, contains a sample that stays in contact with an external solution and therefore allows following of the physico-chemical interaction between the sample and the external solution. The measuring electrodes were positioned inside the cell in the compacted bentonite, while the reference electrode was positioned outside the cell. (authors)
[Show abstract][Hide abstract] ABSTRACT: 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 nearfield were accounted for by this approach, with particular emphasis given to the pH, Eh and actinide solubilities.
[Show abstract][Hide abstract] ABSTRACT: 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.
[Show abstract][Hide abstract] ABSTRACT: The low content of free water and high swelling pressure in compacted bentonite, planned to be used as a buffer in nuclear waste repositories, create adverse conditions for direct measurements of the chemical conditions. This paper presents results from on-line measurements with Eh and pH electrodes in water-saturated compacted MX-80 bentonite. The Eh was measured with Au- and Pt-wires as electrodes, while the pH was determined with IrOx electrodes. The measurements have been carried out in closed bentonite cells and in cells where the bentonite is in contact with an outside solution through a filter plate, so that the experimental conditions can be changed during the experiment. The results suggest that it is possible to measure pH and Eh in compacted bentonite, which improves the possibilities of obtaining information about the chemical processes occurring in the bentonite.
[Show abstract][Hide abstract] ABSTRACT: 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.
[Show abstract][Hide abstract] ABSTRACT: Materials Research Society Symposium Proceedings. Vol. 1124 : Scientific Basis for Nuclear Waste Management XXXII. Materials Research Society. Warrendale, PA, USA, 251-256 After closure, the near-field of a nuclear waste repository contains large amounts of oxygen in tunnels and deposition holes. The bentonite buffer/backfill will contain oxygen as a gas phase in unsaturated pores as well as dissolved gas in porewater. The redox conditions in the bentonite filling after post-closure will change towards reducing conditions. In the initial stage, the development of the redox state is mainly governed by the depletion of oxygen. The main mechanisms of oxygen depletion in the bentonite are: 1) diffusion into the surrounding rock and 2) reactions with accessory minerals and by microbial aerobic consumption of organic matter [1,2]. The reactions leading to oxygen depletion are not, however, well understood. The objective of this work was to gather new information concerning oxygen depletion in MX-80. This was done by measuring oxygen depletion and changes in the redox state in suspensions of 1) MX-80, 2) a heavy fraction of MX-80, or 3) a light fraction of MX-80. 2008 MRS Fall Meeting. Boston, MA, USA, 1-5 Dec. 2008
[Show abstract][Hide abstract] ABSTRACT: In the present work, the effect of homogenization on the microstructure and exclusion of chloride in compacted bentonite was studied. The experiments were performed with MX-80 bentonite, from which easily dissolving components, e.g. chlorides and gypsum, had been removed to ensure that the excess ions in the pore water came from the external solution alone. In the first case, the bentonite was homogenized by dispersing the clay powder in deionized water with ultrasound. The extra water was subsequently squeezed out in order to obtain the desired clay density. In the second case, the samples were compacted to the desired density at the outset and then saturated with deionized water. Thereafter, both sample types were equilibrated with 0.1 M NaCl solution through filter plates. In the third case, the compacted samples were equilibrated directly with 0.1 M NaCl solution. The concentrations in the pore water at the end of equilibration were determined by dispersing the bentonite samples in deionized water. The concentrations in the pore water of the samples saturated first with deionized water were clearly lower than those saturated directly with 0.1 M NaCl solution. This probably reflects the effect of homogenization and a smaller size of the external pores on the chloride concentrations. The model results calculated with the Donnan model by assuming a homogenous bentonite structure were lower than the measured values. Excellent agreement between experimental and model results could be obtained by assuming a dual-porosity structure.
Physics and Chemistry of the Earth Parts A/B/C 01/2007; 32(1):485-490. DOI:10.1016/j.pce.2006.02.058 · 1.48 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: This work describes the development of an on-line method for studying the chemical conditions in compacted water-saturated bentonite. The equipment includes a squeezing cell, measurement electrodes, a reference electrode, and a data-logging system. IrOx wire was used for the pH measurements and Au and Pt wires for the redox measurements. The electrodes were made in-house at VTT. The reference electrode was a commercial leak-free electrode. The measurement electrodes were installed in the bentonite, while the reference electrode was placed in water outside the clay. The contact between the reference electrode and the measurement electrodes was established via the solution in a tube.The work included first a test and calibration of the electrodes in various standard solutions. The performance of the electrodes was subsequently studied in compacted MX-80 in squeezing cell experiments. The squeezing cell initially contained MX-80 mixed with different solutions at a dry density of 0.8–0.9Mg/m3. The pore water was then slowly squeezed out from the clay until the final density of 1.5Mg/m3 was reached. The measurement electrodes were then placed in the clay and the potential measurements were started. At the end of the experiments the electrodes were removed from bentonite and recalibrated. The pH and Eh in the squeezed pore waters were determined for comparison.The results obtained so far have led to the conclusion that it is possible to perform pH measurements in compacted bentonite by using IrOx electrodes. The electrode can survive the swelling pressure inside compacted water-saturated clay without losing its ability to function as a pH electrode. It is also possible to perform Eh measurements in compacted clay by using Au and Pt electrodes.
Physics and Chemistry of the Earth Parts A/B/C 01/2007; 32(1):241-246. DOI:10.1016/j.pce.2006.02.059 · 1.48 Impact Factor