The uranium deposit (1350 Ma) of Cigar Lake (Canada) is surrounded by a late hydrothermal alteration halo (330 Ma) containing Fe-illites and kaolinites. Crystallochemical characterization of the kaolinites has been carried on the microscale using XRD, electron microscopy (SEM and TEM) coupled with EDX spectrometry and EPR. The large, well-crystallized particles show large amounts of Fe (0.9–1.8%) and V (0.3–0.5%). According to EPR measurements performed on both random powders and oriented samples, V occurs as the vanadyl ion VO2+, in substitution within the octahedral sheet of the kaolinite structure in the same way as Fe3+. Kaolinite growth proceeded through the hydrothermal alteration of anterior phyllosilicates devoid of V, induced by fluids which leached V-rich titano-magnetites in the surrounding sandstones.

The K-Ar dates and oxygen isotope data of illite-to-mica mineral phases in Permian to Triassic sandstones from Germany and Libya have been compared to previously published results of similar minerals of Liassic ages taken from lithologically similar rocks in several sites in western Europe and northern Africa. The widespread Liassic age for the micaceous mineral phases can be related to abnormal heat pulses induced by pre-rifting conditions. The temperatures in most cases appeared to be in the 150–220°C range. Some of these hydrothermal activities were responsible for both gas generation and U and Pb-Zn concentrations.

An approach combining K-Ar isotope dates and oxygen isotope signatures provides a framework for the characterization of the clay separates used in isotopic investigations and for depicting any crystallization conditions. The trend in decreases in δ18O values relative to increases in K-Ar dates, while the size of the clay fractions in a single sample increases, is indicative of detrital contamination. Varied trends in the δ18O values at constant K-Ar dates for clay fractions with increase in size might be indicative of changes in the pore volume of the host rocks.

The mineralogy, crystallochemistry and microfabric of clay minerals from acidic soils were studied using transmission electron microscopy (TEM) and analytical electron microscopy (AEM). Soil profiles, developed on saprolites, sampled in the main crystalline massifs of France represent different pedological environments. The study focused on the microsystem of mica weathering, which appeared to be the main source of secondary clay minerals, and involves microdivision, transformation and dissolution. Microdivision begins with the splitting of large particles along layer planes and their shearing normal to the layers. This induces the breakdown of particles of one hundred layers into particles having only a few layers. The transformation of micas follows two steps: they first transform into 1–1.4 nm mixed-layer minerals and then into hydroxy-Al interlayered vermiculite. The formation of hydroxy-Al interlayered vermiculite derived from micas is dominant in acidic soils; particles are generally small, consisting of only three to seven layers, and always have a dioctahedral composition, whatever the type of the original mica (trioctahedral or dioctahedral). Dissolution affects the surface layers or large domains of the core of the particles and leads to the formation of multi-elementary gels rich in Fe and Al.

A series of reduced-charge montmorillonites (RCM), prepared from the same parent Li-montmorillonite (Jelšový Potok, Slovakia) by heating at various temperatures (105–210°C) for 24 h, was treated with 6 m HCl at 95°C for periods up to 30 h. Reaction solutions obtained were analysed for Al, Fe, Mg and Li and the solid reaction products were investigated by FTIR spectroscopy. Both analyses provided evidence that the extent of dissolution decreased with increased amounts of Li fixed within the montmorillonite structure, i.e. with increased heating temperature. Differences in the acid dissolution process were reflected in the structural changes which occurred within the RCM samples, due presumably to different positions of fixed Li. The ethylene glycol monoethyl ether (EGME) surface areas, and XRD and HRTEM analyses of the RCM series revealed an increased amount of non-swelling layers in the samples prepared at higher temperatures, which caused a substantially slower decomposition of M7 and M8 in HCl. The calculated XRD patterns of M6 and M7 confirmed the presence of 20% and 45% pyrophyllite-like layers, respectively, in these samples. Mixed-layer pyrophyllite-like-smectite and pyrophyllite-like crystals, containing only non-swelling layers, were found in sample M8. The results confirmed that the amount of swelling layers in RCM significantly affects their dissolution rate in HCl.

An organo-clay composite was prepared by contacting Na-montmorillonite and humic acid in aqueous solution which was of variable pH. After freeze-drying the precipitate of the solution, the detailed structure of the humic acid-montmorillonite composite was observed. Transmission electron micrographs and electron diffraction patterns indicate that the composite which was formed under acidic conditions has a characteristic microstructure. Humic acid, a large organic molecule, is combined with bent or curled thin foils of montmorillonite to form a spherical aggregate. The X-ray diffraction pattern supports this observation and suggests that the montmorillonite is cleaved into thin flakes as a silicate layer. The composite formed under alkaline conditions was in the form of a thin plate or lath and had a similar morphology to that of montmorillonite. The difference in the microstructure of the composite is reasonably attributed to the chemical flexibility of humic acid, i.e., conformation changes depending on the pH of the solution.

Model associations of layer silicates (kaolinite and montmorillonite) and iron oxyhydroxides were obtained by precipitating hydrous iron oxide in clay suspensions at different loading. The porosity of these clay-hydrous iron oxide associations was studied in the macro- and mesopore range by mercury intrusion porosimetry (MIP) and in the micropore region by nitrogen adsorption isotherms, being the fractal geometry applied to the approaches used in porosity studies. Results of nitrogen adsorption isotherms showed that surface area and microporosity of kaolinite and montmorillonite increased upon Fe precipitation, especially for montmorillonite. This process is accompanied by an increase in the surface fractal dimension Ds(N2) by the presence of hydrous iron oxide coating the clay particles. Results of MIP also showed a decrease in the pore volume by Fe precipitation on montmorillonite due to a decrease in the number of large pores and a development of new medium-size pores. An increase of the fractal dimension Ds(Hg) was also observed.

A parallel reaction model is developed for describing the conversion of smectite to illite. Each reaction represents a group of similar smectite layers that require the same activation energy and have the same illitization rate. The model considers that the rate-determining reactant is smectite itself which follows first-order Arrhenius kinetics. By modelling the data from hydrothermal illitization experiments and from a Gulf Coast well, the activation energies are found to be distributed in the range of 11–24 kcal/mol with a maximum reaction at 18 kcal/mol, which involves 65% of reactive smectite. A frequency factor in the order of 10−3–10−4/s, obtained from the data fitting, appears to be adequate for modelling natural diagenesis in sedimentary basins. The distribution pattern of activation energies is considered to be controlled by the degree of heterogeneity of the initial smectite and the degree of electrostatic interactions between smectite layers and the newly formed illite layers during reaction.

Potassium-bentonites have been found in the Courceyan Lower Limestone Shales near Burrington Combe and Oakhill, Somerset, consisting of thin, greenish yellow, plastic clays interbedded within a mudrock and limestone sequence. Mineralogically, the clay fraction is composed of virtually monomineralic interstratified illite-smectite containing 7–10% smectite layers. The clay fraction of the surrounding mudrocks, however, consists of an illite-chlorite dominated assemblage. Their mineral composition, trace element content, and the relative abundance of zircon crystals suggest an origin from burial of montmorillonite originally formed from volcanic ash. The presence of anomalously high trace element contents with both euhedral and rounded zircon grains in the Oakhill K-bentonites suggests a secondary or reworked origin for these samples. In contrast, the presence of a non-anomalous trace element content and large (>100 μm) euhedral zircon grains suggests that the Burrington K-bentonite is primary in origin. Modelling of whole-rock rare-earth element (REE) patterns shows that the Oakhill REE pattern can be derived from the Burrington pattern by the addition of small contributions from zircon and monazite, two major heavy minerals present. These K-bentonites probably represent the oldest Carboniferous K-bentonites so far recorded in the British Isles.

The major and trace element contents and mineralogical composition of Cenozoic bentonites from the southern Apennines (Italy) have been determined, for the whole-rocks and the <2 µm size-fractions, in order to constrain parental affinities. The main mineralogical and chemical differences have been recognized in eleven samples allowing them to be grouped into two distinct subsets. The differences are based on smectite abundance, occurrence or lack of detrital clay phases, different contents of Ti, Fe, Mn, K, P, Rb, Sc, V, Cr and Ni and differences in the Eu/Eu* and Ti/Al elemental ratios. These ratios indicate an affinity for felsic volcanics for the subset showing high smectite contents. The low smectite subset shows, instead, an affinity for Cretaceous-Oligocene southern Apennine shales. A similar result is obtained using the La-Th-Sc and Th-Sc-Zr/10 diagrams. We suggest that during the deposition of the southern Apennine shales, episodic volcanic events took place. These were associated with the suture stage of the Tethyan ocean that promoted accumulation of felsic ash in the related basin and the diagenetic alteration of these materials produced bentonitic layers interbedded with shales.

Palygorskite has been identified as a major constituent of the clay fraction in mid-Cretaceous deposits of the Meseta, the Middle Atlas, and the Rif in central and northern Morocco. Two types of palygorskite are differentiated, based on the morphology of crystallites, bio- and lithofacies associations of the containing sediments. Type 1 occurs in sections of the Meseta and the Middle Atlas, where the mineral displays bundles of long fibres under the electron microscope and is associated with shallow marine carbonate and evaporite facies. Type 2 was found in the Rif, where palygorskite occurs mostly as bundles of shorter fibres in turbiditic sediments of a supposed deep-marine environment. Associated microfossils indicate reworking of the palygorskite-bearing sediment from shallower parts of the basin. Palygorskite apparently grew authigenically in the chemically restricted environments of the Meseta and the Middle Atlas, whereas it is of a detrital origin in the Rif section. We consider that sediments containing authigenically formed palygorskite (type 1) could be the source of detrital palygorskite (type 2). Type 1 deposits on the North African shelf were probably partly reworked and responsible for the supply of palygorskite to mid-Cretaceous Atlantic basins, where the mineral is well known from several DSDP sites. As in the case of various Recent deep-sea palygorskite occurrences, aeolian transport may have significantly contributed to palygorskite supply to the ocean basins.

Mineralogical and chemical heterogeneity within three standard clay mineral samples have been identified by X-ray diffraction and chemical analysis of various size-fractions. This heterogeneity is partly attributed to accessory minerals, but mostly to structural and compositional variations in the 2:1 layer minerals of different particle size in the same specimen.

The use of ground granulated blast furnace slag (ggbs) is well established in many cement applications where it provides enhanced durability, including high resistance to chloride penetration, resistance to sulphate attack and protection against alkali silica reaction (ASR). The use of ggbs in soil stabilization is, however, still a novel process in the UK although it has been used in South Africa. This paper reports on efforts to extend the use of ggbs to highway and other foundation layers by determining the beneficial effect which it has on the reduction of expansion due to the presence of sulphates. The paper describes the results of laboratory tests on lime-stabilized kaolinite containing different levels of added sulphate to which different amounts of ggbs have been added. The tests determine the strength development of compacted cylinders, moist cured in a humid environment at 30°C, and the linear expansion of these moist cured cylinders on soaking in water. The results illustrate that small additions of ggbs to sulphate containing clays which are stabilized with lime reduce substantially their expansion when exposed to water and have no significant deleterious effect on strength development.