Examination of the cation-exchange capacity of a hydrated halloysite from Djebel Debar has disclosed no evidence for the proposed existence of exchangeable interlayer ions. A series of labile halloysite-salt complexes has been prepared. The requirements for effective intercalation of the salt are a high salt concentration in the external solution phase and a cation of low hydration energy.

The mineralogical and geochemical characteristics of Eocene continental sediments in south central Tunisia (Chebket Bouloufa and Jebel Hamri) and in north central Tunisia (Jebel Lessouda and Jebel Rhéouis), which contain considerable amounts of palygorskite, were studied. The clay fraction of the sediments also comprises illite, kaolinite, Mg smectite and Al smectite, together with carbonates (calcite and/or dolomite), quartz, gypsum and feldspars, all of which are present in extremely variable proportions.

The textural characteristics of the samples containing most palygorskite, as well as the chemical composition of the fibres and the contents of certain trace and rare earth elements suggest that the genesis of this fibrous clay is intimately linked to the diagenetic transformation of illite, mixedlayered minerals and/or Al smectite, as has also been observed in contemporaneous deposits in Morocco.

The effects of simultaneous additions of electrolyte and peptiser to dispersions of the synthetic hectorite-like clay, Laponite, have been studied. It has been unexpectedly discovered that whereas many cations cause gelling and flocculation of the dispersions as expected by colloid chemical theory, some cations actually stabilize the sols obtained with peptiser. A relationship has been found between the effectiveness of the cations in increasing sol stability and their size and charge.

The effects of time, temperature and peptiser concentration have also been examined, and explanations are offered for the phenomena observed.

Respirable forms of crystalline silica including the mineral cristobalite are known carcinogens and the subject of increasing regulation and codes of good practice. Some bentonites may contain cristobalite, but more commonly they contain opal-CT, or opal-C, which can be confused with cristobalite. In the light of increasing regulation there is a clear need for simple and reliable methods that can distinguish cristobalite from the opals in bentonites and other clay materials. Here we propose the use of a simple NaOH method that is easily applied to bulk samples of bentonites. The method consists of boiling the clay in 0.5 M NaOH for 10 min and measuring the weight of undissolved solid. The method is shown to be accurate for both the identification and quantification of opal in bentonites since these phases are soluble when thus treated. It is also a straightforward method to distinguish the opals from cristobalite as the latter is essentially insoluble. Adoption by industry of a simple operationally-defined method such as this would be preferable to ad hoc reliance on direct instrumental methods alone such as X-ray powder diffraction, as the latter almost always require a large element of judgement and experience on the part of the analyst, although direct methods do need to be used in a supporting role.

Halloysite-rich soils derived from in situ weathering of volcanic materials support steep stable slopes, but commonly fail under triggers of earthquakes or rainfall. Resulting landslides are slideflow processes, ranging from small translational slides to larger rotational failures with scarps characteristic of sensitive soils. Remoulding of failed materials results in high-mobility flows with apparent friction angles of 10–16°. The materials characteristically have high peak-friction angles (∼25– 37°), low cohesion (∼12–60 kN m−2) and plasticity ( plasticity index ∼10–48%), and low dry bulk density (∼480–1,080 kg m−3) with small pores due to the small size of the halloysite minerals. They remain saturated under most field conditions, with liquidity indexes frequently >1. Remoulded materials have limited cohesion (<5 kN m−2) and variable residual friction angles (15°–35°). Halloysite mineral morphology affects the rheology of remoulded suspensions: tubular minerals have greater viscosity and undrained shear strength than spherical morphologies.

The diagenetic conversion of smectite to illite in shales has been proposed as a mechanism for generating overpressure (fluid pressure above hydrostatic) in sedimentary basins. However, the mechanism and rate-controlling factors of the reaction and the magnitude of the resulting volume change are not known. In this paper the thermodynamics of the reversible hydration/dehydration of smectite are analysed in the pressure/temperature regime of sedimentary rocks. If the interlamellar water is more dense than bulk water, and the pressures on the solid and fluid phases are equal, the dehydration temperature should increase with increasing confining pressure via the Clapeyron-Clausius equation. However, either fluid pressures below the pressure on the solid matrix or high pore-fluid salinities can reduce the dehydration temperature. Experiments on Ca2+-montmorillonite compacted in the presence of distilled water in a steel autoclave fitted with a sensitive pressure transducer failed to detect any overall volume change due to dehydration up to 185°C and 1400 bar. This finding, which is consistent with recent high-pressure DTA and XRD studies on Na+-montmorillonite, suggests that reversible loss of the last two water layers does not occur in sedimentary basins except as part of the more complex diagenetic conversion of smectite to illite. Some recent evidence from high-resolution TEM and microprobe analyses regarding the mechanism of the reaction is also discussed.

In the Recent sediments of the Congo River estuary, the green Fe-bearing peloids containing 7 Å phases are nearer to the river mouth than the 10 Å phyllosilicates. Measurements of d060 for 7 Å minerals in various density fractions indicated a progressive transformation of kaolinite into trioctahedral 1:1 phyllosilicates in the zone with a high sedimentation rate. Projection of the chemical composition from the approximate crystallochemical formula on to a classification field confirmed the transformation of kaolinite into a 7 Å Fe-rich phase via substitution of Fe2+ and Mg for Al in the octahedral sheet, with insignificant changes in the tetrahedral sheet. The resultant transition phase has a composition closer to greenalite than berthierine. The possible advancement of the evolution process was stopped by massive formation of goethite. The 10 Å minerals formed in the grains deposited in the off-shore sediments have a homogenous composition and occur in association with goethite and quartz. These peloids show an enrichment in Al although no kaolinite is present.

A report is given of the decisions reached at a meeting on the classification and nomenclature of clay minerals held under the auspices of Comité International pour l’Etude des Argiles at Brussels in July 1958. Tables of recently-proposed classification systems are included and some comments made on problems requiring agreement.

The synthesis of clay minerals has been studied for decades in an attempt to better understand their formation in natural environments and more recently to obtain clay minerals with controlled compositions and properties. Even though nontronite has been synthesized successfully since 1935, the process is not a straightforward and has been poorly documented. In the present review concerning the synthesis of nontronite and other Fe-rich smectites, the experiments attempted in the past are discussed critically in light of the most recent data. Most notably, the application of relationships established recently, thanks to synthetic smectitic series, have allowed us to refine the chemical compositions of some nontronites synthesized previously.

Diffuse reflectance spectra in the near-infrared region are presented for Li-saturated smectites heated up to 200°C. The smectites included three montmorillonites, an Fe-beidellite and a ferruginous smectite. Unheated samples showed a complex band near 7060 cm-1 assigned to the first overtone of the OH-stretching mode of structural hydroxyl groups and bound H2O. The OH combination bands appeared in the 4600-4300 cm-1 region. Spectra of heated montmorillonites showed an upward shift and splitting of the OH-overtone band into two components near 7170 and 7110 cm-1. The presence of a band near 7170 cm-1, assigned to the overtone of the AlMgLiOH-stretching vibration, implied that local trioctahedral domains were created upon Li(I) fixation in the previously vacant octahedral positions of montmorillonites. The OH combination bands were shifted to higher frequencies and a new band appeared near 4472 cm-1 in the spectra of montmorillonites heated to temperatures in excess of 130°C. No features indicating Li(I) in the structure of Fe-beidellite or ferruginous smectite were observed in the NIR spectra.

Lower Palaeozoic mudstones from Cwmcadian, Gwynedd are dominantly composed of quartz, illite and chlorite, with subordinate albite, orthoclase and rutile. Chemical formulae are determined for chlorite and illite using a combination of chemical and X-ray data. The formulae indicate that the illite is dioctahedral and suggest that the chlorite structure contains one dioctahedral and one trioctahedral layer. The hypothesis is put forward that both minerals formed from a dioctahedral mineral; illite from a non-expanded form and chlorite from an 'open' form by precipitation of a Fe2+/Mg hydroxide interlayer.

In Upper Jurassic sandstones of the Magnus Sandstone Member from the Magnus Oilfield in the North Sea, diagenetic kaolinite morphology and isotopic composition vary away from the Late Cimmerian unconformity. Near the unconformity, coarse-grained (15-30 μm) vermiform kaolinite morphology is most common, whereas downdip, 3 km away, fine-grained (∼10 μm) blocky morphology is prevalent. Kaolinite abundances increase downdip, away from the unconformity, and kaolinite near the unconformity has low δ18O (12·5-14·9%o smow) compared to that downdip (15·9−17·5%o). This reflects replacement of marine depositional pore-waters by meteoric water near the erosion surface. However, isotopic temperature estimates suggest that the majority of kaolinite formed at elevated burial temperatures of ~80°C, and not during subaerial exposure of the sandstone. The δD of kaolinite close to the unconformity is also lower than that downdip. Kaolinite morphology and isotopic composition record meteoric water ingress during Late Cimmerian subaerial erosion and retention of meteoric-derived water in the crest of the Magnus structure during burial diagenesis. Kaolinite formation during subaerial exposure is not of significance to the sandstone reservoir quality.

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.

Rocks above and below the Precambrian-Palaeozoic unconformity at the base of many Palaeozoic sedimentary basins of mid-continental North America are distinguished by secondary K-feldspar, chlorite and illite. Thrusting of the Appalachian foreland is generally considered responsible for the fluid migrations which caused this alteration. We have examined secondary chlorite and illite from Cambro-Ordovician rocks which overlie the unconformity in southern Ontario, Canada. This area is situated along the interface between the Michigan and Appalachian basins. Water involved in chloritic alteration at ~150°C has an O isotope composition compatible with a basinal brine evolved from seawater. Brine migration was probably triggered by the Taconic Orogeny to the east. In comparison, the secondary illite (365–321 Ma) largely postdates the Acadian Orogeny, and the illite-forming fluids have stable isotopic compositions typical of tepid (~40–55°C) meteoric water. We suggest that basement arches beneath southern Ontario were reactivated by this orogeny, which facilitated introduction of meteoric water. Similar alteration in underlying Precambrian rocks shows that fluid flow was focused along the unconformity during the regional Ordovician brine migration, as well as during the localized Mississippian introduction of fresh water.

Local chemotherapy with biocompatible drug-delivery systems prolongs survival in patients. Due to the biocompatibility and high loading capacity, bentonite nanoclay is a good candidate for the fabrication of drug-delivery vehicles. In this study, doxorubicin-bentonite nanoclay complex (DOX-Bent complex) was prepared for the first time as a sustained-release drug-delivery system for intratumoural chemotherapy of melanoma. An efficient loading of DOX on 1 mg of bentonite nanoclay as high as 994.45 ± 4.9 µg was obtained at a 30:1 DOX:bentonite nanoclay mass ratio. The DOX-Bent complex showed a low initial burst release of DOX in the first 24 h of release, followed by a sustained-release pattern for 21 days. The cumulative in vitro release of DOX from the DOX-Bent complex at pHs 6.5 and 7.4 revealed that the DOX-Bent complex can distinguish between tumour and normal tissues and express specific drug release at the tumour site. The results of cytotoxicity experiments indicated that the release pattern of DOX can supply sufficient DOX to inhibit growth of the melanoma cancer cell with an IC50 of 0.29 ± 0.07 µg/mL. It is thus suggested that the DOX-Bent complex be introduced as a drug-delivery system for effective local cancer therapy.

Dehydration and rehydration of a phlogopitic Mg-vermiculite were studied by thermo-analysis (TG, DSC) and in situ X-ray powder diffractometry. A detailed analysis of the relation between temperature and state of hydration of the vermiculite was rendered possible by use of slow heating rates in combination with a fast-recording position-sensitive detector. The results confirm the existence of a number of definite states of hydration characterized by basal spacings of 1.441,1.429,1.376, 1.165, 1.151,1.002 and 0.926 nm, all of which have already been described in the literature. In addition, so far undetected regular 1 : 1 interstratifications have been found. They formed during those transformations which lead to a change in the number of sheets of interlayer water molecules. These structures exhibit integral series of 00l reflections and d(001) spacings of 2.54 and 2.15 nm for the 2 : 1 and 1 : 0 transitions in the ratio of molecular layers of water, respectively.

Clay from Fourges has been selected by the Commissariat à l'Energie Atomique as a support in radioactive waste disposal studies. This material was activated by adding Na2CO3, then compacted at 60 MPa. Subsequently, its swelling behaviour was monitored at 90°C and 145°C for 330 days and at the end of this period the samples were examined by transmission electron microscopy (TEM). For this, they were embedded in a resin then sectioned with an ultramicrotome for mineralogical and chemical analyses. The initial material is essentially composed of kaolinite and smectite. Addition of Na2CO3 at room temperature induces a replacement of Ca ions by Na ions and the precipitation of finely divided carbonates on the surface of the constituents. At the end of 330 days at 90°C under a hydraulic pressure of 1 MPa, the initial particles combine and the material exerts a swelling pressure of 20 MPa. A complete reorganisation of the clay crystallites is observed without significant dissolution of the solid phases. After the same time at 145°C under a hydraulic pressure of 10 MPa, in a basic medium, the combined conditions are such that a high proportion of the clay is dissolved with formation of amorphous aluminosilicates correlated with a marked drop in the swelling pressure to 5 MPa. This work establishes the advantages of following the macroscopic properties in parallel with the microstructure variations for understanding the changes in the properties of clays.

The milling process in the solid-state 2:1 clay minerals, montmorillonite and talc, which have different cation exchange capacities, is reported here. Several instrumental techniques were used to monitor systematically the products formed. The dehydroxylation/amorphization of the montmorillonite and talc structures occurs within 3 and 6 h of milling, respectively. Electron paramagnetic resonance spectra indicated that structural Mn2+ was oxidized more quickly in the montmorillonite structure than in talc, while the paramagnetic defects increased during milling. Nuclear magnetic resonance was also used to monitor the environmental changes for Si and Al during milling.

Modification of clay minerals by exchange, intercalation, calcination and imbibition of organics followed by their polymerization and carbonization was studied. The surface properties of the clays were investigated by inverse gas chromatography at infinite dilution employing alkanes and alkenes as probes; the structural properties were measured directly by X-ray diffraction and inferred from the results of high pressure hydrogen adsorption. Calcination of pillared smectites prior to polymerization and carbonization of organic material in the interlayer space leads to a microporous “activated carbon” that demonstrates unique properties as an adsorbent for hydrogen, significantly different from clays that have not been calcined.

Aluminium-substituted goethites are found in many soils and can also be synthesised readily in the laboratory. In recent years, synthetic substituted goethites have been examined by various techniques including XRD, IR, TEM and dissolution kinetics (Thiel, 1963; Jonas & Solymar, 1970; Fey & Dixon, 1981; Fysh & Fredericks, 1983; Schulze & Schwertmann, 1984; Schwertmann, 1984). Transmission electron microscopy (TEM) studies have shown that as Al substitution rises above 10%, the goethite needles become shorter and also thicker in the a direction. Furthermore, crystals which at zero substitution consist of domains parallel to the c axis become less domainic with increasing Al substitution (Schulze & Schwertmann, 1984).