In situ measurements were carried out to quantify montmorillonite dissolution rates at a compaction pressure ranging from 0.04 to 10.00 MPa and temperature of 70°C in 0.3 M NaOH solution (pH 12.1 at 70°C) using vertical scanning interferometry (VSI) and an auto-compaction cell. Ex situ measurements of the reacted samples using atomic force microscopy (AFM) were performed to quantify the ratio of edge surface area (ESA) to total surface area (TSA) (XESA = ESA/TSA). Accordingly, the actual ESA for the montmorillonite examined by in situ VSI could be estimated. The XESA value increases as a function of run duration or compaction pressure. At atmospheric pressure, XESA is approximately 0.0054 and converges to ∼0.0107 at 10 MPa, An expression that relates reactive surface area and montmorillonite compaction (XESA/XESA initial = kXESA, k: variable factor) is kXESA = 1.0 + 0.64628 P0.1527 where P is in MPa. Using the calculated XESA, dissolution rates from the in situ VSI measurements are obtained. The early dissolution (<1500 min) at less compaction pressure tends to show faster rates (>1.0 × 10-11 mol/m2/s) than that at higher compaction pressure. The rates after >1500 min are slower, with values of less than 3×6 10-12 mol/m2/s, but there is no significant dependency on the density in the range from 1.0 to 1.7 Mg/m3. These observed rates for compacted montmorillonite are two-orders of magnitude slower (2.63×10-13 mol/m2/s) than dissolution rates in the suspended state.

Highly alkaline environments induced by cement-based materials are likely to cause the physical and/or chemical properties of the bentonite buffer materials in radioactive waste repositories to deteriorate. Assessing long-term alteration of concrete/clay systems requires physicochemical models and a number of input parameters. In order to provide reliability in the assessment of the long-term performance of bentonite buffers under disposal conditions, it is necessary to develop and verify reactive transport codes for concrete/clay systems. In this study, a PHREEQC-based, reactive transport analysis code (MC-CEMENT ver. 2) was developed and was verified by comparing results of the calculations with in situ observations of the mineralogical evolution at the concrete/argillite interface. The calculation reproduced the observations such as the mineralogical changes in the argillite limited to within 1 cm in thickness from the interface, formation of CaCO3 and CSH, dissolution of quartz, decrease of porosity in the argillite and an increase in the concrete. These agreements indicate a possibility that models based on lab-scale (∼1 year) experiments can be applied to longer time scales although confidence in the models is necessary for much longer timescales. The fact that the calculations did not reproduce the dissolution of clays and the formation of gypsum indicates that there is still room for improvement in our model.

Highly alkaline environments induced by cementitious materials in radioactive waste repositories are likely to alter montmorillonite, the main constituent of bentonite buffer materials, and are likely to cause the physical and/or chemical properties of the buffer materials to deteriorate. The deterioration may cause variation in hydraulic conductivity of the buffer. However, empirical data on the variation of hydraulic conductivity are scarce, mainly because the alteration of compacted buffer materials, sand-bentonite mixtures, is extremely slow. In this study, laboratory experiments were performed to observe changes in hydraulic conductivity of sand-bentonite mixtures, accompanied by their alkaline alteration, using NaOH-based solutions at 80–90°C. Series-1 multi-step alteration/water conduction experiments resulted in an increase in the hydraulic conductivity by one order of magnitude over a 200 day period. Series-2 single step alteration/water conduction experiments revealed a decrease in the montmorillonite contents with time and a resulting increase in the hydraulic conductivity by 30 times over the 67 day period. Series-3 simultaneous alteration/water conduction experiment also demonstrated an increase in the hydraulic conductivity by 30 times over the 150 day period. The results proved that the alkaline alteration of the bentonite buffer can increase the hydraulic conductivity. The data obtained in this study are useful for verification of the code that will be used for assessing the alteration.

In situ migration experiments using different radiotracers have been performed in the HADES Underground Research Facility (URF), built at a depth of 225 m in the Boom Clay formation below the SCK–CEN nuclear site at Mol (Belgium). Small-scale experiments, mimicking laboratory experiments, were carried out with strongly retarded tracers (strontium, caesium, europium, americium and technetium). Contrary to europium, americium and technetium which are subjected to colloid mediated transport, the transport of strontium and caesium can be described by the classic diffusion retardation formalism. For these last two tracers, the transport parameters derived from the in situ experiments can be compared with the laboratory-derived values. For both tracers, the apparent diffusion coefficients measured in the in situ experiments agree well with the laboratory-derived values.

In the large-scale experiments (of the order of metres) performed in the URF, non-retarded or slightly retarded tracers (HTO, iodide and H14CO3–) were used. The migration behaviour of these tracers was predicted based on models applied in performance assessment calculations (classic diffusion retardation) using migration parameter values measured in laboratory experiments. These blind predictions of large-scale experiments agree well in general with the experimental measurements. Fitting the experimental in situ data leads to apparent diffusion coefficients close to those determined by the laboratory experiments. The iodide and H14CO3– data were fitted with a simple analytical expression, and the HTO data were additionally fitted numerically with COMSOL multiphysics, leading to about the same optimal values.

Some recent works dealing with the concept of order-disorder in clay minerals are considered, including those aspects of order-disorder which appeared in the Brindley & Brown (1980) monograph, i.e. disorder in the distribution of cations, disorder in layer stacking, orderdisorder in mixed-layer systems and finite crystal size as a lattice disorder. Heterogeneity of samples and polymorphous transformations are also considered as other types of disorder. Most of these works emphasize that accurate structural characterization can only be obtained if several techniques are combined (e.g. XRD and IR, EXAFS and Mo¨ssbauer spectroscopies, etc.). Another conclusion is that accurate structural determination provides the key to the genesis of clays.

Bentonite clay is planned to form a part of deep-geological repositories of spent nuclear fuel in several countries. The extremely long operation time of the repository requires an indepth understanding of the structure and properties of used materials. In this work the microstructure of a simplified system of Ca-montmorillonite is investigated using a set of complementary methods: X-ray diffraction, small angle X-ray scattering, nuclear magnetic resonance, transmission electron microscopy and ion exclusion. The paper presents experimental results obtained from compacted, water saturated samples in the dry density range 0.6–1.5 g/cm3. It can be observed that different methods yield similar quantification of water present in the interlamellar space. Combined results support the multiple porosity concept of the bentonite structure.

In recent years, experimental and theoretical methods have provided new insights into the size, shape, reactivity, and stability of clay minerals. Although diverse and complex, the surface chemistry of all clay minerals is defined spatially on a common scale of nanometres. This review is organized around the nanoscale architecture of clay minerals examined at several different length scales. The first, and perhaps most important, is the length scale associated with Hbonding in clay minerals. Hbonding interactions define the size and shape of 1:1 phyllosilicates and dominate the surface chemistry of many clay minerals. Structural and surface OHgroups contained within and on the surface of clay minerals provide a type of ‘molecular reporter group’ and are sensitive to subtle changes in their local environment. Examples of OH-reporter group studies in clay minerals, and the spatial scales at which they provide diagnostic information, are examined. The second length scale considered here is that associated with clay–water and clay–organic interactions. Inorganic and organic solutes can be used to explore the surface chemistry of clay minerals. Similar to the use of reporter groups, molecular probes have diagnostic properties that are sensitive to changes in their molecular environment. Clay–water interactions occur at a length scale that extends from the size of the H2O molecule (~0.3 nm) to the larger scales associated with clay-swelling (>10 nm). Similarly, clay–organic interactions are also defined, in part, on the basis of their molecular size, in addition to the type of chemical bonding interactions that take place between the organic solute and the clay surface. Examples illustrating the use of clay–water and clay–organic solute interactions as molecular probes are presented. The largest scale to be considered is that of the particles themselves, with scales that approach micrometres. Recent developments in the synthesis and characterization of ultrathin hybrid films of clay minerals provide complementary information about the nature and distribution of active sites on clay minerals, as well as providing new opportunities to exploit the surface chemistry of clay minerals in the design of functional materials.

The present special issue of Clay Minerals contains 19 full papers of scientific studies presented at the 5th conference on “Clays in natural and engineered barriers for radioactive waste confinement” held at Montpellier 2012. Since 2002, ANDRA, the French National Radioactive Waste Management Agency, developed this conference into the most important event for all kinds of scientists from all over the world dealing with the disposal of highly and longlived radioactive waste (HLRW). With these conferences, ANDRA contributed significantly to the outstanding scientific level of European research in this field. Therefore, Clay Minerals is happy to be able to provide the present compilation of recent HLRW disposal research articles in clay mineralogy. The 19 papers published in this special Montpellier 2012 issue were classified according to different areas within the field of HLRW disposal research.

Six samples of ‘Vermiculite’ have been studied to investigate the mechanism of its well known but poorly understood property to exfoliate. The samples were analysed quantitatively by XRD to determine their precise mineralogical composition. Electron microprobe methods, including elemental mapping of native potassium and of caesium (introduced by cation exchange) were used to examine variation in the chemical composition of the particles. Most of the samples examined show heterogeneous mineralogical compositions which occur as distinct zones within the volume of individual particles, presenting a mosaic texture. Exfoliation is related to this mosaic distribution of the different mineral phases within the particles. Lateral phase boundaries between vermiculite and mica layers, or vermiculite and chlorite layers are postulated to prevent or impede the escape of gas from a particle, resulting in exfoliation when the pressure exceeds the interlayer bonding forces that hold the layers together. This mechanism provides a common explanation for the exfoliation of ‘Vermiculite’ by thermal methods or by treatment with H2O2. Paradoxically, one sample which consists of pure vermiculite, in the mineralogical sense of the term, demonstrates that pure vermiculite does not and should not exhibit the property of exfoliation. Our explanation of the mechanism of exfoliation explains the commonly observed particle size dependence of exfoliation and the tendency for obviously poly-phase ‘Vermiculite’ samples to show the largest coefficients of expansion.

During the installation of the buffer in a deposition hole of an HLW repository, it is necessary to control water flow from the fractured rock into the deposition hole. Water flow with inflow rate greater than 0.001 l/min may cause piping and erosion of the buffer, and may trigger mass redistribution of the buffer, sedimentation and material separation of bentonite materials. This paper describes the condition of parameters which cause piping and erosion; revised conditions which keep advection, inflow rate, buffer component, gap between buffer materials, gap between outside wall and buffer block, and type of water. The results from the experiment show the condition of the self-sealing function of bentonite materials, formation of piping, allowable limit of inflow rate in the case of an Na type bentonite block of 70 wt.% Kunigel V1 and 30 wt.% silica sand, or a pellet of 100 wt.% Kunigel V1. Piping and erosion continue until the engineered barrier (EB) is filled with water, and then the hydraulic gradient becomes small. Piping may lead to erosion and redistribution of material which needs to be taken into account in the long-term performance assessment.

Disposal of Finnish spent nuclear fuel is planned to be based on the KBS-3 repository concept. The role of the bentonite buffer in this concept is essential, and thus the behaviour of the bentonite has to be known. The experiments in this paper concentrated on providing information about the effects of carbon dioxide CO2(g) partial pressure on compacted sodium bentonite, giving an insight into the buffering capacity. The experimental setup consisted of a hermetic box which had a CO2-adjusted atmosphere, and the bentonite was in contact with this atmosphere through water reservoirs. The results indicated that it is possible to measure online the changing pH in the porewater inside compacted bentonite using IrOx electrodes. It was found that the pH fell if the CO2 partial pressure increased above atmospheric conditions. The experimental results indicated a greater fall in pH than in our model in the test cases where CO2 was present. The pH in the experiment with 0 PCO2 remained nearly constant throughout the 5 month period. On the other hand, the pH dropped to near 6 with 0.3 PCO2 and to 5.5 with 1 PCO2.

Bentonite is one of the more safety-critical components of the engineered barrier system in the disposal concepts developed for many types of radioactive waste. It is used due to its favourable properties (including plasticity, swelling capacity, colloid filtration, low hydraulic conductivity, high retardation of key radionuclides) and its stability in relevant geological environments. However, bentonite is unstable under alkaline conditions and this has driven interest in low-alkali cements (leachate pH of 10–11). To build a robust safety case, it is important to have supporting natural analogue data to confirm understanding of the likely long-term performance of bentonite. In Cyprus, the presence of natural bentonite in close proximity to natural alkaline groundwaters permits the zones of potential bentonite/alkaline water reaction to be studied as an analogy of the potential reaction zones in the repository. Here, the results indicate minimal volumetric reaction of bentonite, with production of a palygorskite secondary phase.

Virtually all 2:1 clay minerals contain some Fe in their crystal structure, which may undergo redox reaction with surrounding redox-active species causing potentially significant changes in the chemical and physical properties of the clay mineral and its surrounding matrix. This phenomenon was originally of interest mostly as a laboratory experiment using strong inorganic reduction agents, but the discovery that the structural Fe could be reduced by microorganisms in natural soils and sediments opened the way for this to become a practical method for altering the chemical and physical properties of soils and sediments in situ. The purpose of this report was to review the body of literature that has been published since the inception of this field of inquiry and to complement, update, and complete three other reviews that have been published during the intervening years. Studies of microbial reduction of structural Fe in smectites have revealed the extent of reduction, effects on chemical and physical properties, reversibility (or lack thereof) of microbial reduction, stoichiometry, possible reaction mechanism, and types of organisms involved. Some organisms are also capable of oxidizing structural Fe, such as in biotite or reduced smectite, while one appears to be able to do both. Illitic layers resist reduction by microorganisms, but this can be partially overcome by the presence of an electron shuttle compound such as anthraquinone-2,6-disulfonate, which also enhances the extent of reduction in smectites. Microorganisms may be employed as an in situ reducing agent to drive redox cycles for structural Fe in constituent clay minerals of soils and sediments, which in turn can serve as an abiotic source for redox-mediated remediation of environmental contaminants.

The impact of diagenetic processes on petroleum entrapment and recovery efficiency has focused the vast majority of the world's conventional oil and gas resources into relatively narrow thermal intervals, which we call Earth's energy “Golden Zone”. Two key mineralogical research breakthroughs, mainly from the North Sea, underpinned this discovery. The first is the fundamental particle theory of clay mineralogy, which showed the importance of dissolution/precipitation mechanisms in the formation of diagenetic illitic clays with increasing depth and temperature. The second is the surface area precipitation-rate-controlled models for the formation of diagenetic cements, primarily quartz, in reservoirs. Understanding the impacts of these geological processes on permeability evolution, porosity loss, overpressure development, and fluid migration in the subsurface, lead to the realization that exploration and production risks are exponential functions of reservoir temperature. Global compilations of oil/gas reserves relative to reservoir temperature, including the US Gulf Coast, have verified the “Golden Zone” concept, as well as stimulated further research to determine in greater detail the geological/mineralogical controls on petroleum migration and entrapment efficiency within the Earth's sedimentary basins.

The interaction of two different bulk bentonites (Na- and Ca-types) with three types of simulated cement waters (pH 9.7, 11.3 and 12.0) and one saline groundwater simulate (pH 8.3) as a reference, was studied in batch reactors at 25°C. The solution pH was monitored in order to keep the pH as steady as possible by replacing the leaching solution with fresh one when needed. After 554 days, one set of parallel samples was removed from the experiment in order to investigate the possible changes in the bentonite materials.

The buffering capacity of bentonite was clearly observed, especially at the beginning of the high-pH experiments, as the pH of the leaching solutions decreased quite dramatically due to interaction with bentonite. The solution chemistry results showed a decrease of Ca content in all leachate samples, but especially in pH 12.0 experiments. Small amounts of silica were released throughout the experiment. Both bentonites in pH 12.0 experiments also released detectable amounts of Al, while in the lower pH experiments the levels were below detection limit. These observations were also supported by chemical analyses of the bentonite materials. Only minor changes were detected in the mineralogy, and they were mainly concentrated on experiments at pH 11.3 and pH 12.0. The measured swelling pressure showed an increase in pH 12.0 experiments. The results obtained in this research may facilitate modelling of bentonite interaction with high-pH solutions.

In order to evaluate the long-term behaviour of the engineered barriers in geological disposal sites for transuranic element-bearing (TRU) waste, an evaluation by numerical analysis is required. Although chemical and hydraulic/mechanical analyses have been conducted independently until now, essentially both type of phenomena occur simultaneously and produce synergistic effects. Therefore, we focused attention on the buffer (bentonite) engineered barrier and conducted a study of which involved incorporating hydraulic/mechanical phenomena into the chemical analysis of bentonite alteration. The simulations employed weakly-coupled chemical and hydraulic/mechanical effects to study the behaviour in one dimension.

The results showed that the dissolution of the montmorillonite is suppressed in the buffer section nearest the cement material. Moreover, in order to achieve a fully coupled analysis in future, the present study also identifies issues that need to be resolved.

Bentonites are candidate materials for the encapsulation of radioactive waste. In the ‘Alternative Buffer Material test’ (ABM), compacted ring-shaped blocks of eleven different buffer materials (mainly bentonites) were packed vertically on top of each other with an iron tube as heater in the centre. These buffer materials started with various exchangeable cation populations (ECpopulation). The first ‘ABM package’ was terminated 28 months after installation and the bentonites had been exposed to the maximum temperature (130°C) for about one year. The aim of the present study is first: to describe modification of the cation exchange population, and second to understand the influence of the groundwater on cation exchange at different scales. No significant horizontal variation of any exchangeable cation (EC) was detected between 1 and 7 cm distance from contact with the iron tube. Large total differences of the ECpopulations, however, were observed for the individual blocks after the field experiment (n = 21 blocks) with respect to the composition of the reference materials. The average cation exchange capacity (CEC) values of the analysed bentonites (n = 9 blocks) decreased by 5.5 meq/100 (1.1 – 8.8 meq/100 g) after the experiment. Exchangeable Na+ and Mg2+ decreased on average, whereas Ca2+ increased. This trend was pronounced in the top region of the parcel (upper seven blocks). Although most changes occurred on the large scale of the whole test parcel, small but important changes were also recorded in the vertical direction on the centimetre scale. The observed differences cannot be explained assuming simply that a bentonite reacts only with neighbouring blocks, which would mean that the system was more or less closed. The differences are much larger and the only conclusion from this observation is that the whole package seems to be influenced by the groundwater which was added from a water tank at the experiment site, enabling at least partial equilibration between the different blocks.

This paper describes the ways in which the major rock-forming primary minerals (olivine, pyroxenes, amphiboles, feldspars, micas and chlorites) break down during weathering, the products that develop during this breakdown and the rates at which this breakdown occurs. The perspective chosen to illustrate this vast topic is that of the residual soil weathering profile. Different physical and chemical conditions characterize the various parts of such a profile. Thus, in the slightly weathered rock at the base of the profile, mineral weathering will take place in microfissures and narrow solution channels and the capillary water in such spatially restricted volumes may be expected to be close to equilibrium with the primary mineral. In these circumstances, the weathering product formed may be closely related to the primary mineral both compositionally and structurally. The saprolite higher up in the weathering profile may or may not retain the fabric and structure of the original parent rock, but in either case the close relationship observed between primary mineral and weathering product in the slightly weathered rock may be lost. This part of the profile will usually be affected by freely flowing drainage waters, the composition of which will be far from equilibrium with specific primary minerals. Weathering products which do form are likely to reflect the interaction between bulk water and bulk parent material. In the soil profile, the situation will be further complicated by organic ligands derived from decomposing organic matter or from the direct activities of soil microbes or plant roots. Thus, biological weathering will assume a much greater significance in this part of the profile compared with the mainly inorganic processes dominating in the saprolite and the slightly weathered rock. The general nature of any particular weathering profile will reflect the interactions between climate, topography, parent material, soil biota and time and superimposed upon this complexity, when considering how individual primary minerals break down in detail, will be factors related to the nature of the mineral itself. Particularly important in this respect is the inherent susceptibility of the mineral to weathering, which is related to overall chemical composition and structure, as well as the distribution and density of defects, dislocations and exsolution features, which often control the progress of the weathering reaction.

The effects of simulant groundwater composition, pH and temperature on the dissolution and alteration of Na- and Ca-montmorillonite have been studied. Prior to the experiments, Wyoming type Na-montmorillonite, Swy-2, was purified to decrease the amount of accessory minerals. For Ca-montmorillonite experiments, the interlayer cation Na+ of purified Swy-2 was exchanged with Ca2+. The batch experiments were conducted with the purified montmorillonites in simulated fresh and saline waters at 25°C and 60°C under anaerobic conditions in an Ar atmosphere. The concentrations of Si, Al, Fe and Mg were analysed from ultra-filtered solution samples with High Resolution Inductively Coupled Plasma Mass Spectrometry (HR-ICP-MS) as a function of dissolution time. The pH evolution was also measured. The solid smectite phases were analysed with X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). XRD analyses indicated that the nature of the smectite mineral did not change over 140 days. However, the experimental conditions, more or less, modified the structure (e.g. the layer stacking of montmorilllonite; the partial dissolution of the smectite), which cannot be detected by XRD but was evidenced by chemical data, and can be considered as a possible contributor to the stacking faults of the montmorillonite. The log rates (mol g–1 s–1), based on the dissolved amount of Si, varied between –10.64 and –12.13 depending on the experimental conditions.