Geological disposal is the preferred option for the final storage of high-level nuclear waste and spent nuclear fuel in most countries. The selected host rock may be different in individual national programs for radioactive-waste management and the engineered barrier systems that protect and isolate the waste may also differ, but almost all programs are considering an engineered barrier. Clay is used as a buffer that surrounds and protects the individual waste packages and/or as tunnel seal that seals off the disposal galleries from the shafts leading to the surface.

Bentonite and bentonite/sand mixtures are selected primarily because of their low hydraulic permeability in a saturated state. This ensures that diffusion will be the dominant transport mechanism in the barrier. Another key advantage is the swelling pressure, which ensures a self-sealing ability and closes gaps in the installed barrier and the excavation-damaged zone around the emplacement tunnels. Bentonite is a natural geological material that has been stable over timescales of millions of years and this is important as the barriers need to retain their properties for up to 106 y.

In order to be able to license a final repository for high-level radioactive waste, a solid understanding of how the barriers evolve with time is needed. This understanding is based on scientific knowledge about the processes and boundary conditions acting on the barriers in the repository. These are often divided into thermal, hydraulic, mechanical, and (bio)chemical processes. Examples of areas that need to be evaluated are the evolution of temperature in the repository during the early stage due to the decay heat in the waste, re-saturation of the bentonite blocks installed, build-up of swelling pressure on the containers and the surrounding rock, and degradation of the montmorillonite component in the bentonite. Another important area of development is the engineering aspects: how can the barriers be manufactured, subjected to quality control, and installed?

Geological disposal programs for radioactive waste have generated a large body of information on the safety-relevant properties of clays used as engineered barriers. The major relevant findings of the past 35 y are reviewed here.

Halloysite is used for targeted delivery of drugs and other biomolecules. Renewed interest in examination by X-ray diffraction (XRD) to predict the size of particles that can be loaded onto the nanotubes has resulted. Anhydrous halloysite consists of spiraled tubules the length and diameter of which can be determined by measurement using an electron microscope. In spite of ample evidence regarding the spiral structure of halloysite, current programs to evaluate the structure of halloysite nanotubes consider it to be a hollow tube or a cylinder which prevents accurate prediction of its structure and leads to misinformation about the sizes of materials that can be loaded onto the nanotubes. The overall objective of the current study was to derive equations to estimate the structure of halloysite nanotubes which take into consideration its spiral structure. The study of Fourier transform either by electron diffraction or XRD led to the measurement of the spiral thickness and the nature of the spiral. Calculations of the nanotube dimensions may determine the ability of these carriers to allow the mechanical delivery of certain drugs. Here the structure of hydrated halloysite (hollow cylindrical tubes with a doughnut-like cross-section) and anhydrous halloysite (spiraled or helical structure) are described as previously reported in the literature. The Fourier transform of the spiraled structure was selected based on three different kinds of spirals: the Archimedean spiral, the Power spiral, and the Logarithmic spiral. Programs used to define the crystal structure of materials and to calculate the Fourier transform need to take the spiral structure into consideration.

The increasing levels of industrial wastewater released to the environment present a serious threat to human health, living resources, and ecological systems. Fe-modified zeolites were developed and tested for removal of Cu2+ and Zn2+ from contaminated water. The surfaces of the naturally occurring zeolite, clinoptilolite, were modified with Fe(III) oxyhydroxides using three different methods, denoted I, II, and III (FeCli1, FeCli2, and FeNaCli1, respectively). The oxyhydroxides were prepared in Method I using 0.1 M FeCl3·6H2O in an acetate buffer (pH = 3.6); in Method II, using 10ai] FeCl3·6H2O solution in 0.1 M KOH (pH = 10); and Method III was the same as Method I except the clinoptilolite was pretreated with NaCl. Newly synthesized materials from these three methods were then tested for their ability to enhance the sorption capacity for Cu and Zn compared to the natural sample (Cli). Powder X-ray diffraction measurements and the chemical composition of these modified samples confirmed that clinoptilolite maintained its structure while amorphous Fe3+ species were synthesized. The specific surface area (BET method) of both the natural and modified clinoptilolite increased by 2 and 7.5 times for Methods I and II, respectively. Scanning electron microscopy and energy dispersive X-ray spectroscopy revealed that CaO was formed during Method I (FeClii). Throughout the adsorption process, the hydrolysis of CaO and the release of OH− caused the precipitation of Cu and Zn hydroxide, which made the determination of the sorption capacity of FeClii impossible. This phenomenon was avoided in Method III (FeNaClii) because of the absence of exchangeable Ca2+. The adsorption experiments with Method II resulted in double-enchanced adsoprtion capacity. Laboratory batch experiments revealed that the sorption capacities increased in the following order: Cli < FeCli2 < FeNaCli1, for Cu: 0.121 mmol/g < 0.251 mmol/g < 0.403 mmol/g and for Zn: 0.128 mmol/g < 0.234 mmol/g < 0.381 mmol/g.

The early and sensitive detection of microbial contamination of kaolinite slurries is needed for timely treatment to prevent spoilage. The sensitivity, reproducibility, and time required by current methods, such as the dip-slide method, do not meet this challenge. A more sensitive, reproducible, and efficient method is required. The objective of the present study was to develop and validate such a method. The new method is based on the measured growth kinetics of indigenous kaolinite-slurry microorganisms. The microorganisms from kaolinite slurries with different contamination levels were eluted and quantified as colony-forming units (CFUs). Known quantities of E. coli (ATCC 11775) were inoculated into sterilized kaolinite slurries to relate kaolinite-slurry CFUs to true microbial concentrations. The inoculated slurries were subsequently incubated, re-extracted, and microbial concentrations quantified. The ratio of the known inoculated E. coli concentration to the measured concentration was expressed as the recovery efficiency coefficient. Indigenous microbial communities were serially diluted, incubated, and the growth kinetics measured and related to CFUs. Using the new method, greater optical densities (OD) and visible microbial growth were measured for greater dilutions of kaolinite slurries with large microbial-cell concentrations. Growth conditions were optimized to maximize the correlation between contamination level, microbial growth kinetics, and OD value. A Standard Bacterial Unit (SBU) scale with five levels of microbial contamination was designed for kaolinite slurries using the experimental results. The SBU scale was validated using a blind test of 50 unknown slurry samples with various contamination levels provided by the Imerys Company. The validation tests revealed that the new method using the SBU scale was more time efficient, sensitive, and reproducible than the dip-slide method.

The conventional cauliflower-like shape of magadiite imposes serious limitations on its applications in adsorption, catalysis, ion exchange, etc. To overcome this problem, a method to prepare it with plate-like structures was developed. This novel approach is based on an interface-controlled heterogeneous nucleation process. Zirconia grinding balls with diameters of 2.0 mm were dispersed in the starting solution to provide solid-liquid interfaces. Then the starting solution with a SiO2:NaOH:H2O molar ratio of 9:2:75 was subjected to hydrothermal treatment at 433 K for 96 h. The presence of the solid-liquid interface improved the crystallization yield and controlled the morphology and specific surface area of the crystals. With the zirconia balls, the yield and sizes of the plate-like magadiite were 52 wt.% and 1–3 μm, respectively. In the absence of zirconia balls, the yield was smaller (45 wt.%) and magadiite shaped like cauliflower was formed. The plate-like magadiite had a specific surface area of 66 m2 g−1 and a pore-size distribution between 4 and 5 nm, compared with a surface area of 28 m2 g−1 for the cauliflower-like magadiite. In addition, the plate-like magadiite was a more effective ion exchanger than the cauliflower-like magadiite with a cation exchange capacity of 64.5 mmol/100 g (compared to 53.8 mmol/100 g for the cauliflower-like form) and it had a faster sorption rate for calcium ions.

The present study investigated the use of local and affordable clinoptilolite for the removal of persistent dyes from water. To improve its adsorption capacity, Na-clinoptilolite was modified chemically with two N-terminated siloxanes (molar mass: 2600 and 11000 g/mol) and used to adsorb the dye phenol red. The results of Fourier-transform infrared spectroscopy (FTIR) showed that N-terminated siloxanes were grafted successfully onto clinoptilolite. Examination by X-ray diffraction and scanning electron microscopy supported the suggestion of modifications observed by FTIR. The modified clinoptilolite showed improved adsorption properties for phenol red: up to 0.32 mg of phenol red were removed per g of clinoptilolite modified with N-terminated siloxanes from water, while HCl-treated clinoptilolite removed only 0.15 mg after 4 h. Langmuir and Freundlich models were used to obtain isotherm parameters. Results (with R2 > 0.84) from pseudo-first and pseudo-second order equations suggested that adsorption could have involved chemisorption and physisorption, probably because of the mineral-organic nature of the materials prepared.

A major problem with polymeric membranes is low hydrophilicity and consequently a tendency to fouling. Preparing composite membranes is one way to improve the properties and performance of the neat membrane. In the present study, the effects of coagulation-bath temperature (CBT) and the hydrophilic nanoclay concentration of montmorillonite (MMT) on the morphology and performance of asymmetric cellulose acetate butyrate (CAB) membranes were investigated. The membranes were prepared via phase inversion induced by immersion precipitation in a water-coagulation bath. The morphology of the membranes prepared was studied by scanning electron microscopy (SEM). The permeation performance of the membranes prepared was studied by experiments using pure water and bovine serum albumin (BSA) solutions as feeds. The results showed that the membrane thickness and pure water flux (PWF) were increased by adding up to 2 wt.% MMT nanoclay to the casting solution. These two parameters decreased with further addition of MMT, however. In addition, the results obtained in the case of filtration of BSA solution indicated that the addition of MMT in the casting solution increased permeate flux and reduced BSA rejection slightly. Furthermore, increasing the MMT nanoclay concentration in the casting solution increased pure water flux recovery and consequently decreased the fouling. Decreasing the CBT in the presence of MMT during membrane preparation resulted in the formation of a more porous structure and consequently increased the flux and simultaneously decreased the BSA rejection.

Reconstructing the origin of bentonitic clays is often a challenging and rather complicated undertaking, but the analysis of certain predictor clay minerals is proving to be an excellent method to simplify this process. The goal of the present investigation was to use abundance changes of five X-ray diffraction (XRD) predictor minerals to determine the relative contributions of weathering and parent-rock changes to the origin of clay minerals in Egyptian bentonitic clays as the test case. The XRD predictor minerals, selected in an earlier discriminant function analysis of quantitative abundances of 14 minerals, provided a simpler approach to the interpretation of clay-mineral origins because they are the minerals that were most responsible for statistically significant differences among the samples. Changes in mineral composition were basically a function of parent-rock lithology, drainage, and climate interactions. A Paleo-Climate Index (CI; the ratio of coarsely crystalline kaolinite to Fe-rich smectite), and a Parent-Rock Index (PI; the ratio of the illitic phases and quartz abundances to pure smectite) were established to track the paleo-climate and parent-rock changes, respectively. Low CI values indicated that a long, seasonally dry climate prevailed during the Middle Eocene, uppermost Eocene, Lower Miocene, and Upper Pliocene bentonitic clay deposition. Lowermost Upper Eocene and the Middle Miocene bentonitic clays were produced when a wet climate prevailed throughout the year. Moderate to high PI values suggested derivation of the clays from the acidic basement crystalline rocks at Uweinat-Bir Safsaf uplift and Lower Paleogene shales during the Middle Eocene and lowermost Upper Eocene. The youngest Upper Eocene and Lower Miocene materials contained abundant Fe-smectite and low PIs indicating derivation from tholeiitic basalts. Diagenetic and sedimentary segregation modifications were not apparent. Direct evidence for in situ derivation from volcanic precursor materials was lacking in general, but volcanic eruptions were common in the region. The minerals in the Egyptian bentonitic clays formed as weathering products on land and have been transported by north-flowing streams and rivers to the sites of accumulation.

Excavated bentonite from two large iron-bentonite field experiments at Äspö Hard Rock Laboratory in Sweden was investigated with respect to iron redox chemistry and mineralogy. The iron redox chemistry was studied by Fe K-edge X-ray absorption near edge structure spectroscopy and the mineral phases were studied using X-ray diffraction. Bentonite is to be used as a buffer material in high-level radioactive waste repositories to protect the waste containers from their surroundings. Montmorillonite, which is responsible for the sealing properties in the bentonite, is susceptible to redox reactions. A change in the montmorillonite iron redox chemistry may affect its layer charge and hence its properties. The experiments included are the first Alternative Buffer Material test (ABM1) and the Temperature Buffer Test (TBT). The clays were heated to a maximum of ~130°C (ABM1) or ~150°C (TBT) for 2.5 and 7 y, respectively. In the central part of the compacted clay blocks was placed an iron heater and the distance from the heater to the rock was ~10 cm (ABM1) and ~50 cm (TBT), respectively. Eleven different clay materials were included in the ABM1 experiment and five were analyzed here. In the ABM1 experiment, the Fe(II)/Fe(III) ratio was increased in several samples from the vicinity of the heater. Kinetic data were collected and showed that most of the Fe(II)-rich samples oxidized rapidly when exposed to atmospheric oxygen. In the TBT experiment the corrosion products were dominated by Fe(III) and no significant increase in Fe(II) was seen. In ABM1, reducing conditions were achieved, at least in parts of the experiment; in TBT, reducing conditions were not achieved. The difference was attributed to the larger scale of the TBT experiment, providing more oxygen after the installation, and to the longer time taken for water saturation; oxidation of the samples during excavation cannot be ruled out. Minor changes in the bentonite mineral phases were found in some cases where direct contact was made with the iron heater but no significant impact on the bentonite performance in high-level radioactive waste applications was expected as a result.

Supercritical carbon dioxide (scCO2) processing has been proven as a method for preparing polymer/montmorillonite (MMT) nanocomposites with improved platelet dispersion. The influence of scCO2 processing on the shape and size of the MMT tactoid/platelet, which is of great importance to the final platelet dispersion in the polymer matrix, is scarcely reported in the literature. In the present study, the pristine MMT was first surface modified with 3-glycidoxypropyltrimethoxysilane (the grafted MMT is labeled as GMMT), and then intercalated using three kinds of intercalating agents, myristyltrimethyl-ammonium bromide (MTAB), tetradecyltrihexylphosphonium chloride (TDTHP), and ethoxyltriphenyl-phosphonium chloride (ETPC), in water or scCO2, to study the effect of intercalating agent type and intercalation method on the morphology and thermal properties of GMMT, as a part of a program devoted to the synthesis of polymer/MMT nanocomposites. The structure of intercalated GMMT was characterized by thermogravimetric analysis, X-ray powder diffraction, and scanning electron microscopy (SEM). The optimum intercalation conditions in scCO2 were established by trying a range of reaction times and pressures. The structures of intercalated GMMT obtained under optimum scCO2 conditions and water were compared. The basal spacing of GMMT intercalated in scCO2 was almost the same as that in water, and both were obviously larger than that of GMMT. The GMMT exhibited a compact spherical morphology (examined using SEM), and the surface structures (including surface morphology, surface roughness, and surface compactness) of samples intercalated in water became ‘less compact’ and the degree of the ‘compactness’ of samples intercalated in scCO2 decreased further. Whether in water or scCO2, samples intercalated with TDTHP exhibited a larger basal spacing and the extent of disorder increased compared to that for samples intercalated with MTAB. The pristine MMT was also intercalated for comparison and silane grafting was proven to contribute to the increased basal spacing and ‘less compact’ surface structure.