The phase behaviour of aqueous suspensions of NAu1 nontronite was studied on size-selected particles by combining osmotic pressure measurements, visual observations under polarized light, rheological experiments and Small Angle X-ray Scattering (SAXS). NAu1 suspensions display a liquid crystalline behaviour as they exhibit a Isotropic/Nematic (I/N) transition that occurs before the sol/gel transition for ionic strengths below 10–3 M/L. This I/N transition shifts towards lower volume fractions for increasing particle anisotropy and its position in the phase diagram agrees well with the theoretical predictions for platelets. SAXS measurements reveal the presence of characteristic interparticular distances in the isotropic, nematic and gel phases. In the gel phase a local lamellar order is observed which shows that the “house of cards” model is not appropriate for describing the gel structure in swelling clay materials at low ionic strength. Furthermore, by combining results from osmotic pressure measurements and X-ray scattering, it appears that the pressure of the system can be well described using a simple Poisson-Boltzmann treatment based on the repulsion between charged infinite parallel planes. In terms of rheological properties, even if the thermodynamical status of the sol/gel transition remains partially unclear, the yield stress and elasticity of the gels can be easily renormalized for all particle sizes on the basis of the volume of the particles. Furthermore, rheological modelling of the flow curves shows that for all the particles an approach based on excluded volume effects captures most features of nontronite suspensions.

Rhyolitic obsidian was reacted with natural waters to study the effect of water chemistry and biological activity on the composition and formation mechanisms of clay. Two sets of experiments (18 months, 6 years) used fresh, hypersaline water (Mg-Na-SO4-Cl- and NaCl-rich) and seawater. The 6-year experiments produced the transformation of obsidian into quartz, apparently by in situ re-crystallization (Cuadros et al., 2012). The most abundant neoformed clay was dioctahedral (typically montmorillonite), indicating chemical control by the glass (where Al > Mg). Altered glass morphology and chemistry in the 18-months experiments indicated in situ transformation to clay. Magnesium-rich (saponite) clay formed under water-chemistry control in the bulk and within biofilms with elevated Mg concentration (Cuadros et al., 2013). The contact between microbial structures and glass was very intimate. Glass transformation into quartz may be due to some characteristic of the obsidian and/or alteration conditions. Such combination needs not to be uncommon in nature and opens new possibilities of quartz origin.

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.

A new method for identifying the trioctahedral smectites saponite, stevensite and hectorite is proposed in this study. The method is based on differences in the X-ray diffraction (XRD) patterns of the three smectites after (a) heating at 500°C for 90 min and (b) glycerol solvation of the Cs-forms of the smectites for 20 h. After heating at 500°C, well below the dehydroxylation temperature of the three smectites, saponite and hectorite re-expand upon ethylene glycol (EG) solvation, whereas stevensite layers remain collapsed. Saponite forms one-layer and hectorite two-layer complexes after Cs-saturation and glycerol solvation. Cs-stevensite displays a gradual increase in d001 with increasing solvation time in glycerol vapours and forms two-layer glycerol complexes with prolonged solvation. Except for the individual Mg-smectites, the proposed method may be used to identify compositional heterogeneity that may exist in the smectites. Furthermore, it should be useful in identifying the individual trioctahedral Mg-smectites when present in mixtures, and in detecting interstratified layers of different Mg-trioctahedral smectites. Application of the method revealed that the SYnL-1 laponite (CMS Source Clay Project) is not homogeneous but consists of hectorite, stevensite and possibly mixed-layer hectorite/stevensite layers.

Highly weathered soils of the tropics and subtropics commonly have kaolinitedominated clay fractions. Under acidic conditions prevailing in these soils kaolinite dissolution occurs, contributing to the high levels of soluble Al in these soils. This study evaluates the dissolution behaviour of kaolinites from subsurface horizons of highly weathered soils from Thailand, along with a soil kaolinite from Western Australia (WA kaolinite) and Georgia kaolinite (KGa-2). Kaolinite-dominated clay fractions were isolated from soils by sedimentation and chemically treated to remove iron oxides. The dissolution rate of kaolinites was measured in 0.01 M NaCl as a function of pH (1–4; HCl) at 25±1°C using non-stirred flow-through reactors. Kaolinite dissolution rates were calculated from the release of Al and Si at the steady state. In most of the experiments and at all pH values, the release of both Si and Al underwent a distinct transition from an initial period of rapid release to significantly slower release at the steady state. Aluminium and Si concentrations at the steady state were higher for soil kaolinites than the reference sample (KGa-2). At the steady state the dissolution of all kaolinites was stoichiometric except for the soil kaolinites from Thailand at pH 4, where the Al/Si ratio was well below the stoichiometric ratio. Log dissolution rate (RSi) of soil kaolinites ranged from –13.75 to –12.51, with the dissolution rate increasing significantly with decreasing solution pH. However, the dissolution rate was similar or pH independent between pH 2 and 3, which is the pH range of the point of zero net charge (PZNC) for both soil and reference kaolinites. The dissolution rate of soil kaolinite was significantly higher than the KGa-2 sample at pH < 3. The results obtained on kaolinite samples from highly weathered soils show that in highly acidic systems kaolinite is a source of soluble Al. Soil kaolinites with poorly ordered small crystals dissolve faster than better crystalline reference kaolinite (KGa-2) with larger crystals.

Detailed multi-scale characterization of the kaolin quality and the controlling depositional environment is crucial for optimal quality upgrading and for prioritizing potential exploitation areas. In the present work, the quality of El-Tih kaolin, Egypt, was investigated using the chemical/mineralogical characteristics as well as the field observations of the clay. Chemical analysis of major oxides was carried out using energy dispersive X-ray fluorescence (EDS-XRF) spectrometry. Mineralogical analyses were carried out using X-ray diffraction (XRD) and scanning electron microscopy coupled with wavelength-dispersive X-ray spectroscopy (SEM-WDS). Spatial heterogeneity of the quality was evaluated applying kriging geostatistical techniques and potential zones were identified.

Results clarified an upward gradual deterioration of the quality via a decrease in the Al2O3 content and thickness of the clay layers, and an increase in the TiO2 content. According to the kriging maps, areas of high potentiality indices (PI) characterized by high Al2O3 and low SiO2 content and maximum thickness of the kaolin are located to the west and east, and decrease toward the central part of the study area. The high PI zones are dominated by pseudo-hexagonal platy kaolinite, often forming accordion- and book-like aggregates with subordinate quartz and traces of Fe and Ti oxides, yielding minimal TiO2 and Fe2O3 contents. These zones of high PI are considered optimal for exploitation. Kaolinite was formed as a result of intensive weathering of rhyolite/granite and basalt in the source area, and subsequent erosion, transportation and deposition of the weathering mantles in a flood environment with marked depositional energy variations. Results allowed comparison with worldwide kaolin occurrences, and suggested the suitability of the studied kaolins for use in paper coating and filling and in higher-grade ceramics, after removal of free Fe- and Ti-oxide impurities.

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.

Intercalation of cationic surfactants hexadecylpyridinium (HDPy+) and hexadecyltrimethylammonium (HDTMA+) into the interlayer space of homoionic (Na-, Ca- and Zn-) smectites by solid-solid reactions was investigated. These reactions were complete within 15 min. Changes in the surface and structure of the smectites modified with different surfactants were characterized using XRD, FTIR and DSC. The intercalation of surfactant is controlled by the exchangeable cation of smectite and monofunctional ammonium cation type. HDPy+ and HDTMA+ surfactants were retained by Zn-exchanged smectite, suggesting important surface properties (CEC = 80 meq/100 g clay, SBET = 116.5 m2/g) and acid-base properties (point of zero proton charge PZC, density charge σH). HDPy cation loading was effective, suggesting that the aromatic polar group is favoured for intercalation. Comparing with original clay, modification with surfactants increased the basal spacings d001. Based on the d001 spacing of modified smectites, different configurations of surfactants within smectite interlayer were proposed as a function of surfactant concentration, which were examined by FTIR and DSC.

The purpose of this paper was to prepare purified Na- bentonite with improved properties for use in the pharmaceutical industry. Calcium bentonite from the Shagia region of Karak district, Pakistan, was activated with various proportions of sodium carbonate (2, 3, 5 and 8 wt.%) and purified by sedimentation to remove impurities, especially quartz. X-ray diffraction (XRD), and swelling volume confirmed the conversion of raw bentonite to sodium bentonite by using 5% Na2CO3. The sodium bentonite (K5) obtained by activation met the chemical and microbiological requirements set by the pharmacopeias regarding the toxic trace elemental content (Pb and As), absence of E. coli, total aerobic microbial contents and physicochemical properties such as swelling volume, pH and sedimentation volume. Therefore K5 bentonite could be designated as potentially suitable for pharmaceutical applications. The CEC, surface area, porosity, pH, gel formation and swelling volume indicated that K5 bentonite could be used in the formulation of oral suspension and in topical application.

Minerals with the general formula Cu4(OH)6A2/nn ± pH2O (A = Cl–, NO3–, SO42–) were synthesized and their behaviour following treatment with chloride, nitrate and sulfate solutions was studied by powder XRD and SEM. Two types of transformation were found: (1) an ion-exchange reaction manifested by preservation of both the precursor's morphology and structural type; (2) a dissolution-crystallization mechanism characterized by changes in the structural type and the morphology.

The results were considered by simultaneous application of the binary presentation of the structures, a bond valence approach and the ion-exchange ability. It was found that the structures of minerals with ion-exchange properties are built from similar layered structural unit of edge-shared and corner-shared Jahn-Teller square frameworks and different interstitial complexes of exchangeable ions, water molecules and cation-water groups. On the basis of their structural features the position of the investigated minerals in mineralogical classifications is also discussed.

The mineralogical, geochemical and micromorphological features of an isalteritic clay facies, which originated from weathering of an anorthosite, were compared to those of clay facies derived from the degradation of a bauxite developed from the same rock. The isalteritic clay was formed by the hydrolytic alteration of plagioclase, whereas the degraded clays were formed by decomposition of gibbsite and neoformation of kaolinite. This resilification process resulted from the reintroduction of silica via the oscillation of the phreatic level and/or the decomposition of organic matter on the surface. The degradation process was gradual and yielded two different facies: (a) degraded clays with almost total decomposition of gibbsite, and (b) degraded clays with gibbsite nodules. Morphologically, the isalteritic clays differ from the degraded clays because they contain larger hexagonal and pseudo-hexagonal crystals. The degraded clays have more irregular crystal shapes, ranging from laths to anhedral shapes.

Basalts and other mafic rocks are frequently used for road construction. The aggregates have to provide intrinsic mechanical strength and skid resistance. However, smectite contents stemming from alteration processes may deteriorate these mechanical properties considerably because of the resulting contrast in hardness. Quantitative relationships between smectite content, kind of distribution, and aggregate stability are rare except for a recent study by Kaufhold et al. (2012). In this work thirteen basalt and andesite samples from German quarries were analysed by X-ray diffraction (XRD) for their mineral contents (including clay minerals), their cation exchange capacities (CEC) and their resistance against disaggregation in dimethyl sulfoxide. Smectite contents from XRD exceeded those calculated from the CEC regardless of the kind of occurrence of smectite observed in thin sections. The hypothesis that rocks with smectites occurring mostly in patches should differ in terms of CEC and mechanical properties from those rocks where smectites are more disseminated could not be confirmed. However, the amounts of smectite accessible to cation exchange correlated with the DMSO losses. Therefore, the fast CEC determination with Cu-Trien exchange can be substituted for the time-consuming DMSO test.

In the post-closure period of a geological disposal facility for radioactive waste, leaching of cement components is likely to give rise to an alkaline plume which will be in chemical disequilibrium with the host rock (which is clay in some concepts) and other engineered barrier system materials used in the facility, such as bentonite. An industrial analogue for cement-clay interaction can be found at Tournemire, southern France, where boreholes filled with concrete and cement remained in contact with the natural mudstone for 15–20 years. The boreholes have been overcored, extracted and mineralogical characterization has been performed. In this study, a reactive-transport model of the Tournemire system has been set up using the general-purpose modelling tool QPAC. Previous modelling work has been built upon by using the most up-to-date data and modelling techniques, and by adding both ion exchange and surface complexation processes in the mudstone. The main features observed at Tournemire were replicated by the model, including porosity variations and precipitation of carbonates, K-feldspar, ettringite and calcite. It was found that ion exchange needed to be included in order for C-S-H minerals to precipitate in the mudstone, providing a better match with the mineralogical characterization. The additional inclusion of surface complexation, however, led to limited calcite growth at the concrete-mudstone interface unlike samples taken from the Tournemire site that have a visible line of crusty carbonates along the interface.

Ceramic tile production by the wet route requires clay suspensions with a high solid content and low viscosity. In this work the deflocculation of clays in aqueous suspensions was investigated by varying the type of clay and additive. Three kaolinitic and two illitic clays were characterized and dispersed with deflocculants based on lithium, sodium and potassium silicates and polyacrylates. The clays were characterized by chemical and mineralogical analyses, particle size distribution, zeta potential, organic carbon content, cation exchange capacity (CEC) and specific surface area (BET). Deflocculation curves were determined by measuring the viscosity for 50 wt.% clay slips. The results indicate that additive consumption is closely related to CEC and BET, which correspond respectively to the chemical and physical characteristics of the clay mineral's surface. Moreover, viscosity values at the deflocculation point are closely related to BET.

The mineralogy of the silt fraction of a 1.5 m-deep, well developed, intensely weathered, greyish soil profile from a toposequence on a tableland covered by agricultural crops in the upper valley of the Jequitinhonha river basin, Minas Gerais, Brazil, has been studied by X-ray powder diffraction, 57Fe Mössbauer spectroscopy at 298 K and 80 K, and vibrating sample magnetometry. Mössbauer data collected at room temperature indicated about 17 atom% of the iron content of the sample to be structural Fe2+ in phyllosilicates, which X-ray diffraction showed to be mainly halloysite and kaolinite. The magnetization curve also indicates the presence of a ferrimagnetic phase, tentatively identified by Mössbauer spectroscopy as maghemite (γ-Fe2O3).

These findings support a pedogenetic model for this soil profile, by which the remaining Fe2+ bearing minerals were first formed under relatively anoxic palaeo-conditions of an intense hydric regime. Subsequent drier local conditions, due to a much improved drainage, favoured intensive weathering, leading to the presently developed Oxisol. Even under the more oxidative conditions, part of the Fe2+ -containing phyllosilicates still remained in the profile, which is believed to impart the rather unusual greyish colour (Munsell 10YR 3/2) to this deep tropical soil.

This research work deals with chlorite-vermiculite mixed-layer stability under hydrothermal and metamorphic conditions. We used as a case study a clayey flysch unit cropping out in an active geothermal area near to a Recent volcano (Mt. Amiata) in central Italy. The geothermal gradient is higher than the world average and temperatures over 100°C can occur at less than 1 km depth. The mineralogical data, obtained from X-Ray Power Diffraction (XRPD) analysis of clay samples from the same geologic unit, show that the primary anchimetamorphic mineral assemblage (illite, chlorite, illite-smectite mixed layers) is accompanied by secondary phases, such as chlorite-vermiculite mixed-layers and calcite. Reactive flow modelling was used to outline a realistic water-rock (W/R) interaction process able to generate the new minerals. In the numerical simulation, the pristine shale was made to react with a local thermal spring, at an estimated but realistic carbonate reservoir temperature. The simulation predicts that, at a temperature of 120°C, clinochlore dissolves and vermiculite crystallizes, a good proxy of the chlorite-vermiculite crystallization process. Under low water/rock conditions the proportions of the clay minerals (illite, chlorite, smectite and vermiculite) are comparable with the analytical results. The simulation also shows that temperatures higher than 120°C enhance the vermiculite formation. We conclude that the chlorite-vermiculite mixed-layers formed in the recent past due to the upflow of thermal water which permeated the flysch unit. This result indicates that the alteration of the clayey cap-rocks of geothermal reservoirs is enhanced by the interaction with geothermal fluids, and can be used as a prospecting tool.

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.

The influence of Zn on the adsorption and desorption of Cry1Ab toxin from Bacillus thuringiensis (Bt) on palygorskite and montmorillonite was studied. The adsorption of the toxin gradually increased with increasing Zn concentration from 0 to 1.0 mmol L–1, and then decreased with further increase in Zn concentration. The adsorption isotherms of the toxin in the absence and presence of Zn were well described by the Langmuir equation (R2 > 0.9810–0.9991). The separation factor (RL) decreased with increase of Zn concentration, suggesting that the irreversibility of the adsorption increases. The XRD results showed that the treatment by Tris buffer or Zn(NO3)2 solution caused an expansion of the interlayer space of montmorillonite but did not affect palygorskite. The IR spectra suggest that Zn was likely to be combined with amino groups on the surface of the toxin. The presence of Zn during the adsorption of the toxin decreased desorption, suggesting that the residual risk of toxin would be exacerbated if soil is polluted by zinc.