The Cs selectivity of several natural zeolitic tuffs and synthetic zeolites was measured. Phillipsite-rich tuffs from California and Nevada exchanged 13.5 and 23.7%, respectively, of the Cs present in simulated alkaline defense waste containing 0.00025 M CsCl in 5.5 M NaCl-NaOH solution from the Savannah River Plant, Aiken, South Carolina; whereas mordenite-rich tuffs from Arizona and Nevada exchanged less than 12.7%. The immobilization or fixation of Cs in phillipsite unlike other zeolites can be achieved by heating the zeolite at 600°C for 4 hr in air and collapsing the silicate (aluminate) tetrahedral rings around the Cs ions to produce a Cs-feldspar-type phase. Treatment of the Cs-exchanged phillipsite-rich tuff at 800° to 1000°C resulted in pollucite, CsAlSi2O6, which also “locks in” the Cs ions in its structure. The fixation of Cs exchanged in phillipsite can also be achieved by the formation of pollucite upon hydrothermal treatment at 300°C and 30 MPa pressure within 12 hr. These results suggest that phillipsite-rich tuffs are good candidates for Cs immobilization by heat treatment at low temperatures after they have been used as sorbents in waste decontamination.

Interaction between metal Fe and a variety of natural and synthetic smectite samples with contrasting crystal chemistry was studied by scanning electron microscopy and X-ray diffraction from experiments conducted at 80°C. These experiments demonstrate an important reactivity contrast as a function of smectite crystal chemistry. An XRD method involving the use of an internal standard allowed quantification of the relative proportion of smectite destabilized as a function of initial pH conditions as well as of smectite structural parameters. In mildly acidic to neutral pH conditions, a significant proportion of metal Fe is corroded to form magnetite without smectite destabilization. Under basic pH conditions, smectite and metal Fe are partly destabilized to form magnetite and newly-formed 1:1 phyllosilicate phases (odinite and crondstedtite). More specifically, systematic destabilization of both metal Fe and smectite is observed for dioctahedral smectites while trioctahedral smectites are essentially unaffected under similar experimental conditions. In addition, smectite reactivity is enhanced with increasing Fe3+ content and with the presence of Na+ cations in smectite interlayers. A conceptual model for smectite destabilization is proposed. This model involves first the release of protons from smectite structure, MeFe3+OH groups being deprotonated preferentially and metal Fe acting as proton acceptor. Corrosion of metal Fe results from its interaction with these protons. The Fe2+ cations resulting from this corrosion process sorb on the edges of smectite particles to induce the reduction of structural Fe3+ and migrate into smectite interlayers to compensate for the increased layer-charge deficit. Interlayer Fe2+ cations subsequently migrate to the octahedral sheet of smectite because of the extremely large layer-charge deficit. At low temperature, this migration is favored by the reaction time and by the absence of protons within the di-trigonal cavity. Smectite destabilization results from the inability of the tetrahedral sheets to accommodate the larger dimensions of the newly formed trioctahedral domains resulting from the migration of Fe2+ cations.

Bentonites are considered suitable backfill material for planned underground nuclear-waste repositories because of an inherent capacity to self-seal and retain contaminants when hydrated. Barrier effectiveness, however, depends on the physical properties of bentonite after placement in a repository site, where hydration state and bulk density can vary. The objective of the present study was to investigate commercial bentonite MX80 hydration rates and mechanisms during water infiltration into dry, moist, and wet samples using the ‘wet-cell’ X-ray diffraction technique. During experimentation, water enters a small flow-through cell and induces swelling within a confined reaction volume, analogous to clay barriers in excavated underground sites. Results demonstrated the importance of using dry, well compacted (>1.4 g/cm3) bentonite, which became saturated slowly (<2.0 ×10−9 m/s) with minimal water in noninterlayer sites (external-surface sites, or within pores). The significant degree of interlayer expansion dominated by the formation of two and eventually three water layers developed as hydration clusters with greater probabilities for the same thickness to lie in adjacent interlayer sites. The relatively thicker particles and the less accessible surface area of hydrated, initially dry bentonite probably resulted in less pore-controlled diffusion, but also less potential radionuclide adsorption by surface complexation. Moist MX80 had the greatest water uptake, the smallest (1.23 g/cm3) dry bulk density, and the greatest proportion of water in pores and on external surfaces. Water that initially accumulated in pore spaces subsequently acted as a reservoir for interlayer hydration and probable gel formation in trapped voids, which is expected to occur in more loosely filled gaps within an excavated repository.

In Sweden and in many other countries, a bentonite barrier will be used in the repository for spent nuclear fuel. In the event of canister failure, colloidal diffusion is a potential, but scarcely studied mechanism of radionuclide migration through the bentonite barrier. Column and in situ experiments are vital in understanding colloid diffusion and in providing information about the micro structure of compacted bentonite and identifying cut-off limits for colloid filtration. This study examined diffusion of negatively charged 2-, 5-, and 15-nm gold colloids in 4-month diffusion experiments using MX-80 Wyoming bentonite compacted to dry densities of 0.6–2.0 g/cm3. Breakthrough of gold colloids was not observed in any of the three diffusion experiments. In a gold-concentration profile analysis, colloid diffusion was only observed for the smallest gold colloids at the lowest dry density used (estimated apparent diffusivity Da ≈ 5 × 10−13 m2/s). The results from a microstructure investigation using low-angle X-ray diffraction suggest that at the lowest dry density used, interlayer transport of the smallest colloids cannot be ruled out as a potential diffusion pathway, in addition to the expected interparticle transport. In all other cases, with either greater dry densities or larger gold colloids, compacted bentonite will effectively prevent diffusion of negatively charged colloids due to filtration.

During recent decades, the search for possible repositories for high-level nuclear waste has yielded large amounts of sorption data for actinides on different minerals. Clays and clay minerals are of special interest as potential host-rock formations and backfill materials, by virtue of their good retardation properties. Neptunium (Np) is one of the actinides which is considered in long-term scenarios due to its long-lived nuclide 237Np (t1/2 = 2.1 × 106 y). Because neptunium sorption is heavily dependent on the experimental conditions, comparison of sorption data from different experiments is challenging. Normalizing reported data with respect to the surface area of the sorbent enables conversion of conventional distribution coefficients (Kd) to normalized (Ka) values, which improves comparability among the results of different experiments. The present review gives a detailed summary of sorption data of Np on clays and clay minerals and examines critically the applicability of the Ka approach.

The release and the speciation of carbon species from irradiated JRQ carbon steel samples, representative of the reactor pressure vessel of Belgian nuclear power plants, were studied in a saturated portlandite aqueous solution, relevant for the Belgian Supercontainer design, as perceived for the geological disposal of high-level nuclear waste. To achieve this, we performed simple immersion and potentiostatic corrosion tests. In addition, the corrosion rate (which determines the 14C release) was estimated by measuring the release of 60Co. Gas chromatography showed that during the static corrosion test, the carbonaceous species methane, carbon dioxide, ethene, and ethane were produced. Under the hypothesis that all the carbon released from the JRQ steel was transformed into carbon-base gaseous compounds, this corresponds to a corrosion rate of approximately 100 nm/yr, which is in good agreement with literature data.

Stalagmites and stalactites, as observed within natural caves, may develop inside geological repositories during constructional and post-operational periods. It is therefore important to understand actinide sorption within such materials. Towards this, experimental studies were carried out with 233U, 238Np (VI), 238Np (IV), 239Pu and 241Am radiotracers using natural speleothem samples collected from the Dharamjali cave of the Kumaon Lesser Himalayas, India. Petrological/mineralogical studies showed that natural speleothems have three general domains: (1) columnar calcite; (2) microcrystalline calcite; and (3) botryoidal aragonite – each with ferruginous materials. Results showed that all domains of speleothems can take up >99% actinides, irrespective of valence state and pH (1–6 range) of the solution. However, distribution coefficients were found to be at a maximum in aragonite for most of the actinides. Such data are very important for long-term performance and safety assessments of the deep geological repositories planned for the disposal of high-level nuclear wastes.

In safety assessments for nuclear waste disposal, the biosphere is a completely open system, whereas the bedrock can be treated with comparably simple boundary conditions. The bedrock has a vital role in providing and maintaining favourable conditions for the waste, but the public interest tends to focus on the biosphere. More importantly, the bedrock groundwater does arrive from the biosphere. Also, the regulations usually set the safety criteria in terms of doses occurring in the biosphere. Thus, it is reasonable to address the biosphere as a part of the disposal system, performance of which should be described based on conceptual models that cover phenomena and processes controlling radionuclide release and transport. From these, the actual assessment models and data are expected to be derived based on high-level research and expertise obtained through empirical study. In this paper, the complexity expected of a biosphere assessment within a mature safety case is discussed through the example of the Finnish regulations and recent safety cases for nuclear waste disposal. Both elaborate and complex presentations and stylised approaches have their benefits, and a balance needs to be sought.

Smectite-rich clays are to be used in nuclear repositories for sealing in the radioactive waste. As the radioactive decay produces heat it may affect the chemical, physical and hydromechanical properties of the clay components in the repository. An ‘alternative buffer material’ (ABM) experiment is a Svensk Kärnbränslehantering AB (SKB)-led in situ heating test placed in boreholes in the Äspö tunnel (Sweden). The 2nd ABM package was dismantled in April 2013, after 6.5 y of equilibration with Äspö groundwater and 5 y of heating. The objective was to investigate the long-term effects of the iron heater and Äspö groundwater on four of 31 compacted blocks made of MX-80, Deponit CaN and Friedland clays.

Compared to the starting materials, major changes in the exchangeable cation populations were observed. Within horizontal profiles, water-soluble sulfate, Ca, K and Mg increased; poorly crystalline Fe oxide contents decreased; total Mg, Ca and S increased; and a decrease in the amounts of total Na and K away from the host rock towards the heater was observed. At the boundary with the heater, an increase in the total Fe content, decreases in total Si and Al contents, precipitation of gypsum and anhydrite, dissolution of cristobalite and feldspars, and indications of the formation of trioctahedral clay minerals were observed. A decrease in swelling pressure for the Friedland clay (in drill-cored samples) was recorded which was recovered after grinding and recompaction. No effects of hydraulic conductivity were found, after 6.5 y of reaction time, in the subsurface of any of materials studied.

Two new solubility-limiting phases relevant to nuclear waste disposal are reported, namely CeSiO4 and Ca2Ce8(SiO4)O2, produced by hydrothermal synthesis at 180 °C. X-ray diffraction data are presented for both compounds. Rietveld refinement was performed for each of these phases. CeSiO4 was confirmed to be a zircon structure type, with space group I41/amd, unit celltype="bold">abold=6.9564(3),type="bold">cbold=6.1953(4) Å. Bond lengths for SiO4 are in excellent agreement with published values; Ce4+ is coordinated to eight oxygen atoms with four regular and four short bonds. Ca2Ce8(SiO4)O2 was shown to have an apatite structure, with space group P63/m and unit celltype="bold">abold=9.4343(3),type="bold">cbold=6.8885(4) Å. The unit cell and bond lengths were found to be slightly smaller than would be expected from other lanthanide-containing analogs; possible reasons for this are discussed.