Torbjörn Carlsson

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.

Coprecipitation of Ni With Calcite: An Experimental Study

At the Finnish candidate sites for a nuclear waste repository calcite (CaCO 3 ) is a common fracture mineral, that may participate in coprecipitation processes. The objective of this work was to study the coprecipitation of the trace element Ni with CaCO 3 under controlled conditions. The experiments were carried out at 30 °C in vessels closed to the atmosphere. Calcite-saturated 0.05 M NaCI solutions containing trace amounts of Ni 2+ were contacted with calcite for periods of up to 42 days. The experimental data indicate that Ni coprecipitates with calcite as a result of recrystallization. The amounts of coprecipitated Ni and recrystallized calcite were determined using liquid scintillation counting and the isotopes 63 Ni and 45 Ca. The results are supported by a complementary SEM/EDS analysis of the solid phase.

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.

Experimental Study of Nickel Solubility in Sulfidic Groundwater under Anoxic Conditions

This paper presents the results from an experimental study of the nickel solubility in sulfidic groundwater under anoxic conditions. The waters used were natural groundwater from Olkiluoto and synthetic saline groundwater, to which sulfide had been added. Two sulfide concentrations, 3.1.10 −6 M and 9.4.10 −5 M, were used. The possible influence of ferrous iron on the nickel concentration was also studied by adding small amounts of iron chloride, which yielded ferrous iron concentrations of 1.8.10 −5 M or less. The initial nickel concentrations in the water samples were 1.0.10 −6 M and 1.0.10 −3 M. The nickel concentrations were determined using 63 Ni and liquid scintillation counting. The duration of the experiments was 177 days. The results for the waters differed markedly. The nickel concentration in the natural groundwater decreased in all samples to roughly 10% of the initial value. The nickel concentration in the synthetic groundwater was found to decrease in those samples having initial sulfide and nickel concentrations of 9.4.10 −5 M and 1.0.10 −6 M, respectively. The nickel concentration was in this case reduced to about 1% of its initial value. For the other synthetic groundwater samples, the nickel concentration remained at its original initial level. The variation of the ferrous iron concentration did not have any observable effect on the measured nickel concentrations.

Influence of Colloids in Experimental Solubility Studies of Ni in Natural and Synthetic Aqueous Media

The estimation of nickel solubility values for performance assessment is impaired by the lack of experimentally verified solubility values in conditions relevant to actual nuclear waste disposal sites. For this reason, experimental nickel solubility studies were conducted in conditions relevant to a possible Finnish disposal site, Olkiluoto. Using an initial nickel concentration of 10 −3 M, nickel solubility was approached from over-saturation in three aqueous media – natural fresh groundwater, synthetic saline groundwater, and cement-conditioned groundwater with added ferrous iron and sulfide. In addition to the nickel solubility values, nickel association with the particle and colloidal phases was measured. Almost 100%of the initial nickel was found associated with the separated particle phase in the natural groundwater and the cement-conditioned groundwater, and in only the natural groundwater about 0.04%or 0.4%with the separated colloidal fraction depending on the initially added amount of ferrous iron and sulfide. In the synthetic saline groundwater, all the nickel was found in the soluble fraction except for a minor fraction sorbed onto the walls of the sample bottle. Colloid-bound nickel did not have any practical influence on the solubility values obtained. The inverse behavior of Ni solubility and sorption in the natural groundwater compared to that in the other two aqueous phases studied was suspected to be caused by the unidentified yellow color of the groundwater for which indications of both possible organic and inorganic nature was obtained. Based on the measured results, the presence of sulfide and ferrous iron would decrease the amount of mobile nickel, both soluble and colloidal, in non-saline natural and cement-conditioned groundwater, whereas in saline groundwater nickel remains in the mobile phases.

Coprecipitation of Sr, Ni and U with CaCO 3 : An Experimental Study

At the Finnish candidate sites for a nuclear waste repository, calcite (CaCO{sub 3}) is a common fracture mineral that may participate in coprecipitation processes. The objective of this preliminary work was to study the coprecipitation of the trace elements Sr, Ni, and U with CaCO{sub 3} under controlled conditions. The experiments were made in a titration vessel at room temperature under pure N{sub 2} or a 0.1% CO{sub 2}/N{sub 2} mixture. The water phase contained CaCl{sub 2} (0.01M) and NaCl (0.05 M) to which trace amounts of Ni{sup 2+}, Sr{sup 2+} and UO{sub 2}{sup 2+} were initially added. CaCO{sub 3} was precipitated by the addition of Na{sub 2}CO{sub 3} and the use of CaCO{sub 3} seed crystals. When about 10{sup {minus}4} mol of precipitate had formed, the solution and solid phases were analyzed with ICP-MS. The results seem to indicate that Ni coprecipitated with CaCO{sub 3} under the experimental conditions, while U did not. In the case of Sr, further data are needed in order to make any conclusions from the experiments.