Stellan Holgersson

Effects of gluco-isosaccharinate on Cs, Ni, Pm and Th sorption onto, and diffusion into cement

The conditions in the Swedish design for a repository of intermediate to low level radioactive waste include a high alkalinity buffer from the concrete construction in combination with cellulose materials in the waste. Experiments have been undertaken in order to quantify the effects of cellulose degradation products on the radionuclide retention capability of the concrete enclosure. Studies of the sorption of Cs, Ni, Pm and Th onto crushed cement and the diffusion of Cs, Ni and Pm in cement and concrete discs of 2 cm thickness were made in a nitrogen-flushed glovebox facility, using different cellulose degradation product additives to the alkaline pore-water. Samples of the liquid phases were taken during a period of 12 months and the sorption and diffusion behaviour was evaluated by radioanalytical methods. In the experiments of alkaline degradation of cellulose the major constituent was found to be D-gluco-isosaccharinate, a potential metal complexing agent, which was synthesized as its Ca salt and used as a 5mM additive in sorption and diffusion experiments. The other additives were leachates of 5 kg/m3 and 100 kg/m3 cellulose in alkaline water. The results show that the additives caused a significant, but transient reduction of the sorption of Pm and Th. The sorption of Cs and Ni were not influenced. The diffusion of D-gluco-isosaccharinate itself was also studied and this indicates that its apparent diffusivity in cement is low, probably due to its strong sorption on cement. This would explain the transient reduction of the radionuclide sorption.

A method for preparation and purification of 234Th

An improved method to recover 234Th from depleted uranium has been developed. The method is based on solvent extraction and ion-exchange separations. The final thorium fraction has a high specific activity, about 1-3 PBq/mol Th, which makes it well suited for investigations, where a low thorium concentration is essential. The method is comparably fast, with a total processing time of 2 days. Another advantage is that the uranium fraction can be used as a 234Th generator for several years.

Dependency of BET surface area on particle size for some granitic minerals.

Abstract In order to assess the geochemical retention properties of rocks, which will be the final barrier for radionuclide transport to the biosphere in the case of a failed deep underground repository for spent nuclear fuel, radionuclide sorption experiments are usually made with crushed material. This raises the issue of extrapolating results obtained from laboratory experiments to the field scale. As sorption is generally related to the surface area of the geological material, it is then important to consider the dependency of the specific surface area on the particle size. In this work, BET surface area determinations of samples of different particle sizes are conducted on two minerals commonly found in granite: labradorite and magnetite. The results show a linear relationship between BET surface area and the inverse of the particle size, up to a certain particle size. Furthermore, results also show that the specific surface area for intact, larger pieces is much smaller than the one predicted by a linear extrapolation of results on crushed material. Therefore, extrapolation of BET area for fine particles to the field situation will lead to an overestimation of the surface area and thereby also the radionuclide sorption, if sorption coefficients are extrapolated as well. Also of importance is that these results show that sorption experiments on crushed material may dominantly reflect properties of new surface, created during the mechanically treatment of the samples.

Diffusion of HTO and cement pore fluids through host rock

Summary In the post-closure period of a deep disposal facility for low- to intermediate-level radioactive waste, highly alkaline pore-fluids chemically equilibrated with cementious components of the engineered barriers will migrate into the surroundings. Primary minerals in the host rock could dissolve and secondary calcium silicate hydrate (CSH) phases might be formed in the micro pore system of the rock and change the available porosity for radionuclides and hence the permeability. Since the retardation of radionuclides in the host rock depends on sorption and matrix diffusion, the study of the mineral reactions is of importance. Experiments with diffusion of HTO and synthetic cementitious pore-waters through 1 cm thick discs of Äspö diorite have been made in a nitrogen-flushed glovebox facility. Synthetic cementitious pore-waters representative of fresh and leached concrete were used. For the fresh pore-water the results show that hydroxide ion diffusion is retarded relative to HTO tracer, indicating that reactions between hydroxide and host rock take place. The result can be interpreted as hydroxide sorption in the rock. Al and Si did also accumulate on the sampling side which was attributed to mineral dissolution. For the evolved pore-water, no through-diffusion of hydroxide ions or accumulation of other elements in the sampling cell was observed during the sampling period, indicating that the through-diffusion of hydroxide is hindered by this type of pore-water.

Interactions of Cement Pore Fluids with Host Rock and the Effects on HTO, Na and Cs Diffusion

In the post-closure period of a deep disposal facility for low- and intermediate-level radioactive waste, pore-fluids chemically equilibrated with cementious components of the engineered barriers will migrate into the surroundings. Secondary calcium silicate hydrate (CSH) phases might be formed in the micro pore system of the rocks and change the available porosity for radionuclides and hence permeability. Since the retardation of radionuclides in host rock is dependent on the sorption and matrix diffusion, these chemical reactions are of concern. Experiments have been undertaken to react discs of Aspo diorite with alkaline cement porewaters. These experiments provided aged material for through diffusion experiments and samples for studies of chemical reactions. 1 cm thick discs of Aspo diorite were reacted with waters representative for fresh and leached concrete at 70C in nitrogen filled vessels for six months. Analysis of the waters indicates dissolution of primary minerals and precipitation of secondary CSH phases. HTO, Na and Cs diffusion experiments were then undertaken with both reacted and unreacted discs in a nitrogen-flushed glovebox facility. The effects of alkaline degradation of Aspo diorite on tracer through-diffusion was found to be small and of the same order of magnitude as natural variations in rock heterogenity between undegraded samples.

Activity coefficients in deep eutectic solvents: implications for the solvent extraction of metals

An understanding of the effects of the water content on the solvent extraction of metals from the deep eutetic formed from choline chloride and lactic acid has been obtained. This change can be rationalised as being due to a change in the activity coefficient of chloride in the deep eutetic.