Single-phase monazite-type ceramics are discussed as waste forms for the safe disposal of surplus plutonium or separated minor actinides. To derive a fundamental understanding of the long-term stability of these materials under repository relevant conditions, the dissolution kinetics of synthetic lanthanum monazite (LaPO4) were studied in dynamic dissolution experiments in the temperature range from 50 to 90°C under acidic conditions. The surface area normalised dissolution rates increased with temperature from 3.2·10-5 g m-2 d-1 at 50°C to 1.8·10-4 g m-2 d-1 at 90°C. The apparent activation energy Ea of the dissolution process was determined to be about 44 kJ mol-1, indicating a predominantly surface reaction controlled dissolution process in this temperature range. From thermodynamic considerations it can be inferred that the dissolution of the LaPO4 ceramics is governed by the dissolution of a thin layer of La-rhabdophane (LaPO4 · 0.667H2O) forming at the monazite surface in low temperature aqueous environments.

Development of an iodine immobilization technique that can fix radioactive iodine in waste form for a long period and constrain its leaching into pore water is necessary in order to secure the long-term safety of geological disposal of transuranic (TRU) waste.

Lead borate glass vitrified at a low temperature is regarded as one of the promising immobilization materials of Iodine-129 which will be removed from spent AgI filters generated from reprocessing plants and may have a significant effect on long term safety of geological disposal.

Leaching experiments in bentonite-equilibrium water have been conducted to understand the lead borate glass dissolution behaviors in possible geological disposal conditions. Boron dissolved with the highest rate in all types of the solutions and was regarded as an index element to represent the glass dissolution rate. On the other hand, lead dissolved with a far slower rate. The chemical species and possible precipitating minerals of lead were examined by a geochemical calculation code for typical underground water. Altered glass surfaces were investigated by SEM, TEM and XRD. XRD analysis showed that the main constituent phase of the altered layer was hydrocerussite, Pb3(CO3)2(OH)2, that was predicted by the geochemical simulation as well.

The dissolution of a soda-lime silicate glass in two cement leachate compositions, Young Cement Water (YCW) and Ca(OH)2, was investigated, as an analogue for dissolution of vitrified nuclear waste in a cementitious geological disposal facility. Dissolution was performed at repository temperatures (50°C) and under CO2-exclusion. Dissolution rates were observed to be a factor of 20 times higher in YCW than in Ca(OH)2, as result of the high potassium content of YCW solutions. The precipitation of the zeolite phase, K-phillipsite (K(Si,Al)8O16·6H2O), is thought to be responsible for elevated dissolution rates. Conversely, in Ca(OH)2 solutions, the precipitation of calcium- and silica-containing phases, such as tobermorite (Ca5Si6O16(OH)·4H2O), acted to reduce rates of dissolution by forming a barrier to diffusion. These results show that dissolution of vitrified nuclear waste materials in a cementitous repository may be significant during the early stages of cement leaching in groundwater.

The apparent diffusion coefficients of La, Nd, Eu, Dy, Er, and Lu in compacted bentonites were investigated at various bicarbonate concentrations. The apparent diffusion coefficients of these lanthanides tended to decrease with increasing dry density. At bicarbonate concentrations below 0.25 M, lanthanum had the largest diffusion coefficient (ca. 10-13 m2/s) at 1.0 Mg/m3, and the diffusion coefficient decreased with increasing atomic number. On the other hand, at bicarbonate concentrations above 0.25 M, lutetium had the largest diffusion coefficient, and the diffusion coefficient decreased with decreasing atomic number. In particular, lanthanum and neodymium had diffusion coefficients below 10-14 m2/s, even at 1.0 Mg/m3. The diffusion coefficient of europium was around 10-13 m2/s at 1.0 Mg/m3 and was influenced less by the bicarbonate concentration. The diffusion coefficient of lutetium increased from 2 × 10-14 to 10-12 m2/s as the bicarbonate concentration was increased to 1.0 M. The concentration of carbonate ion in the pore water of bentonite is estimated to be much lower than that in solutions in contact with bentonite from the viewpoints of solubility and chemical species of lanthanides.

In Finland and Sweden the KBS-3 concept has been chosen for the disposal of spent nuclear fuel in crystalline rock. Recent experiments have shown that heterogeneity of rock may play a major role in the transport of radionuclides. Autoradiographic methods have been proven to be able to assist the characterization of heterogeneous structures. In this study we tested a novel filmless autoradiographic device called BeaverTM which applies a micro patterned gaseous detector in order to quantitatively map beta emissions from C-14 atoms. The studied samples were impregnated with C-14-labelled methylmethacrylate (C-14-MMA) and polymerized to C-14-PMMA with thermal initiator. The BeaverTM was then used to determine the spatial distribution of the C-14-PMMA by measuring the C-14 emissions. The porosity is determined from the amount of C-14-PMMA in the rock sample and results were compared to ones from phosphor imaging plate autoradiography. The resulting images show a heterogeneous distribution of porosity which arises from the different minerals. The samples were chosen from three sites that have been used recently for in situ diffusion experiments: Olkiluoto (Finland), Äspö (Sweden) and Grimsel (Switzerland).

Shale formations are considered by a number of countries as the most suitable media to dispose of high-level radioactive waste. This is mainly due to the impermeable, self-sealing, chemical reducing, and sorption properties that tend to retard radionuclide migration. However, shale formations can also contain highly connected fault zones with permeabilities that can differ of several orders of magnitudes with respect to the undeformed host rock. The objective of this work is to use the 14C-PMMA autoradiography method combined with SEM-EDS measurements to understand the porosity variations in and around fault gouges and to define their relationship to mechano-chemical processes. The studied samples were taken from a low permeability shale in a small-scale vertical strike-slip fault at the Tournemire underground research laboratory. Results display significant variations in porosity and mineralogy along the studied gouge zone due to polyphased tectonics and paleo-fluid circulations.

For the UK geological disposal facility (GDF) concept in a high strength crystalline rock, Nirex Reference Vault Backfill (NRVB) has been considered to use as a cementitious backfill material. The lifetime performance of this high pH material is required to be extremely long, and as a consequence of the interaction with the geological environment (e.g. groundwater), the backfill material will evolve and age with time. In this paper, we present the results of a leaching experiment, where NRVB is placed in contact with three different groundwater compositions representative of granitic, clay and saline groundwater for 35 days. Some differences were observed related with the mineralogy. X-ray Diffraction results showed the formation of more ettringite, mainly in the NRVB samples leached in clay and saline groundwater. An increase of the pH was also observed in the NRVB samples leached with the three different ground waters, being these results in accordance with the reactive transport modelling performed.

The dynamics of the gas release at thermal oxidation of the two-phase systems of 30% solution of tri-n-butyl phosphate (TBP) in isoparaffinic diluent Isopar M – aqueous solution of 4.3, 8.2 and 12 mol/L of HNO3 has been investigated within the temperature range from 70°C to 110°C. The effect of pre-irradiation of the system TBP–Isopar-M–HNO3 on the kinetics of its thermolysis has been determined. All of the samples were irradiated with an electron accelerator at a dose rate of 10 kGy/h up to integrated doses of 0.5, 1 and 2 MGy. The parameters of heat and gas emission during thermolysis of the tested extraction system in an open apparatus have been determined experimentally. It has been demonstrated, that there are no conditions for extension of autocatalytic oxidation under heat treatment of two-phase extraction systems in open vessels.

Though not often discussed explicitly in literature, sample handling and preparation for advanced characterization techniques is a significant challenge for radiological materials. In this contribution, a detailed description is given of method development associated with characterization of highly radioactive and, in some cases, hygroscopic oxides of technetium. Details are given on developed protocols, fixtures, and tooling designed for x-ray and neutron diffraction, x-ray absorption, Raman spectroscopy, magic angle spinning nuclear magnetic resonance, and electron paramagnetic resonance. In some cases, multiple iterations of improved sample holder design are described. Lessons learned in handling Tc compounds for these and similar characterization methods are discussed.