The clay fractions from a 1191-cm long sediment core in the SW Basin of the Atlantis II Deep, Red Sea, were investigated by XRD, electron microscopy and chemical analysis. Talc dominates in the botton portion of the core, near the brine discharge vent. At 1183 cm depth, the clay consists of vermiculite/chlorite and chrysotile. These minerals are of hydrothermal origin and two possible formation pathways are proposed: (i) vermiculite/chlorite and chrysotile formed by the submarine alteration of previously deposited talc; (ii) vermiculite/chlorite and chrysotile authigenically precipitated as a result of changes in the chemical composition of the brine. At 1170 cm depth, a new depositional sequence results from the progressive alteration of swelling 2:1 minerals into vermiculite. At 1025 cm, Mg-rich clay minerals such as chlorite, chrysotile and talc again become prominent. The upper part of the core is characterized by a transition from non-expanding Mg-rich clay minerals to Fe-rich expanding clays, principally nontronite. Periodically, the content of well-crystallized oxides such as hematite in the layers increases. At 1025 cm, some of the Fe-oxides have a morphology similar to that of akaganéite. In the uppermost part of the core, iron oxides appear to consist of a poorly crystalline hydrothermal hematite. An attempt has been made to correlate the various mineralogical assemblages geochemically.

Comprehensive X-ray photoelectron diffraction (XPD) studies have revealed octahedral cation ordering in a 1M lepidolite and in a 1M biotite. In the lepidolite (from Høydaler, Telemark, Norway), all three octahedral sites are differentiated, with Li and Mn concentrated in the trans M(1) site and Al in cis M(3); M(2) contains all three cations. In the biotite, the major cations do not order but Ti, present at only 1·2% concentration, preferentially occupies the two cis sites, information which is available uniquely from XPD. Long-range tetrahedral ordering should be detectable by XPD, but was not found in either mica.

The interaction of montmorillonite with sotalol hydrochloride (4-(1-hydroxy-N-isopropylaminoethyl) methane sulfanilide) was studied by means of adsorption isotherms, XRD and IR spectroscopy. The amount of sotalol adsorbed depended on pH, the maximum amount adsorbed (0·56 mEq g−1) being considerably less than the exchange capacity of the mineral (0·80 mEq g−1). XRD and IR data revealed that the sotalol is adsorbed into the interlayer space, forming a monolayer complex with a d001 spacing of 17·7 Å, and that the mechanisms involved are cation exchange and ion-dipole interactions. Experiments on the in vitro desorption of the drug from the sotalol-montmorillonite complex indicated that desorption is affected by pH, by the salt concentration of the electrolyte, and by the elimination rate of the desorbed organic cations.

The adsorption and desorption of water, the layer spacing of the montmorillonite with increasing water content and the heat of immersion with water have been measured for a Na-bentonite and two Ca-bentonites. The bentonite-water system is treated in terms of a micropore-filling process. Uptake of water occurs in discrete stages as the montmorillonite structure expands and the internal surface is calculated from these discrete stages of water adsorption.

Five montmorillonites were analysed by 57Fe Mössbauer spectroscopy and their Fe3+ occupation in tetrahedral and octahedral sites assigned. The montmorillonites, with a range of IVFe3+ contents, were used in an attempt to correlate IVFe3+ content with VIFe3+cis- and trans-OH site occupation to verify the assertion that increasing IVFe3+ content directs VIFe3+ to cis-OH sites. However, VIFe3+ in montmorillonite appears to be located essentially in the trans-OH sites. The two doublets computer-fitted to the VIFe3+ Mössbauer resonance for montmorillonite appear to represent a distribution of a continuum of slightly different Fe3+ resonances, which arise from the variable atomic environment surrounding the VIFe3+ sites, rather than discrete cis- and trans-OH sites. Therefore Mössbauer spectroscopy cannot be used to demonstrate whether an increasing IVFe3+ content directs VIFe3+ substitution into particular sites for montmorillonites.

A new approach to understanding illite-smectite interstratification is formulated which incorporates the concepts of interparticle diffraction and elementary illite particles. The analysis shows that nearest-neighbour ordering, non-nearest-neighbour ordering, ordering at the illite end of the composition scale, and the lack of ordering at the smectite end can be explained by expandable interfaces between elementary, i.e. two silicate layers, and larger illite particles. Ordering in I/S clays is significant only when the probability of occurrence of illite is ∼80%. New concepts proposed are an order parameter (ω) and an expansion parameter (β). Interparticle diffraction implies that I/S clays are unusual among all crystalline materials since their XRD size is equal to or larger than the size of their constituent physically separable particles.

Mineralogical examination of a strongly chloritized amphibole-schist indicated that it had been subjected to two alteration episodes of different origin. Structural and petrographic evidence showed that the alteration processes operated per descensum from the bedrock surface down to shallow depth, thus eliminating any hydrothermal episode due to fluid ascension through deep fractures. The rock was first altered into interstratified chlorite-vermiculite minerals with potassic interlayers. These potassic clay minerals occur in an originally K-deficient rock and seem to have been generated by a marine alteration episode; this episode appears to be contemporaneous with the Cenomanian transgression which covered the amphibole-schist with sandy-clayey deposits. The potassic clay minerals were replaced during a later meteoric alteration episode by kaolinites, iron oxides, and smectites with Mg, Ca interlayer cations.

L'altération de biotites et de muscovites en halloysite a été mise en évidence par l'étude en MEB dans l'altération de roches granitiques et de micaschistes. Cette transformation débute par le développement d'un réseau losangique à la surface des feuillets de micas. La croissance par épitaxie de tubes d'halloysite est parfois accompagnée par celle de cristaux de goethite. Le MEB montre que l'halloysite se forme directement à partir du mica et qu'elle apparaît dans les tous premiers stades de l'altération, quelles que soient les conditions.

Absorption lines in the g ∼ 4 region of ESR spectra of three New Zealand halloysites were found to originate from similar paramagnetic centres as in kaolinites. Resonances in the g ∼ 4 region were not common to all the halloysites, although the signal at g = 2·0 for the Matauri Bay halloysite is probably due to a trapped positive hole or trapped ion. A 6-line resonance produced by Te Puke halloysite and removable by Na-saturation is attributed to exchangeable Mn on the clay surface. Low-temperature lines exhibited by all samples are due to V4+ or VO2+ replacing Al3+ in the octahedral sheet.

Three clay samples (a kaolinite, a halloysite and an inseparable mixture of kaolinite-palygorskite-illite-montmorillonite) were, after a mild pretreatment, successfully tested as catalysts in the polymerization of styrene. The catalytic activity of the clay (measured by the conversion rate), the MW and the colour of the polystyrene obtained depended not only on the chemical composition and the structure of the clay catalyst but also on its concentration in the medium. The polystyrenes obtained on the clay catalyst were composed of two groups of macromolecules, one with low MW and the other with high MW.

The interaction of chrysotile and crocidolite with water has been investigated in an attempt to identify the factors affecting the rate and the degree of dissolution of asbestos fibres within groundwater systems at landfill sites. Dissolution experiments were used to investigate rate laws and to obtain apparent activation energies for the dissolution of the two minerals. The activation energies related to transport-controlled processes, but as the overall dissolution occurred so slowly it was unlikely to be controlled by processes with such low activation energies. Congruent dissolution of both minerals tended to increase with temperature and time, suggesting that in the long-term environmental situation, congruent dissolution of these two asbestos minerals would occur. However these experiments show that, as the reaction was so slow, there is little likelihood of reduction of the asbestos pollution hazard by the complete dissolution of fibres on prolonged contact with natural waters.

This study of the Quaternary clay sedimentation in the Grenada Basin (Southeastern Caribbean) is based on six cores raised from depths of 1800 to 3000 m. Mineralogical analysis of <2 µm and <0·3 µm fractions revealed the presence of a four-component association — smectites, illite, kaolinite and chlorite — in which smectites were always dominant. These minerals were derived from two sources: the Lesser Antilles Arc, which contributed only smectites and kaolinite, and the South American continent, where smectites, kaolinite, chlorite and illite coexist. Geochemical data indicate that Ba and Cr are specific indicators of the South American minerals, whereas Cu characterizes the Antillean clays. The South American contribution, now prevailing, was less important during the Sangamon. The Antillean contribution was episodically predominant during the Wisconsin.

Sorption isotherms of ethylene glycol monoethyl ether (EGME) on homoionic Na−, K−, Mg− and Ca-montmorillonites at 25°C were determined. The extent of sorption was found to depend on the exchangeable cations, being larger for the bivalent ionic forms. Uptake of EGME was compared with the retention value obtained by evacuation of the sample wetted with EGME and also interpreted from XRD data. The results indicate that the montmorillonite-EGME complex formed by sorption at the saturation vapour pressure is stable and less ambiguous than after wetting by EGME. Montmorillonites are not suitable reference materials for surface area measurements.

According to field studies of the Pugu Hill kaolin deposit and mineralogical investigations (X-ray, SEM), two main types of Miocene sandstones are distinguished: (i) clayey-silty kaolinitic sandstones with stacks of idiomorphic pseudohexagonal kaolinite crystals; (ii) massive clayey-silty kaolinitic sandstones with irregular fabric of isolated kaolinite plates. The Precambrian metamorphic rocks of the Uluguru Mountains are a probable source for the kaolinitic sediments of the Pugu Hill Formation. Decomposition products of weathering profiles on meta-anorthosites are mainly 7Å- and 10Å-halloysite and gibbsite. It is suggested that the kaolinitic sandstones were deposited in a former delta. The first sandstone type is considered to have developed in situ from weathered arkosic sandstone, and the second represents channel deposits in an old river system (probably a Miocene predecessor of the Ruvu River) with kaolin transported from a hinterland and redeposited. The variable formation and fabric of the kaolinites in the Pugu Hill Formation are due to in situ weathering of transported primary minerals (fedspar), and to transported weathered material (with secondary halloysite).

Thermal transformations of kaolinite were studied by 29Si- and 27Al-MAS/NMR and ESR techniques. In metakaolin, Si is still dominantly in the Q3 state (three Si atoms bonded to an Si-O4 tetrahedron) and Al detectable by NMR is in both 4-coordination and 6-coordination. Coordination polyhedra around Al or Fe replacing Al are much distorted. Metakaolin crystallizes into γ-alumina and mullite exothermically at ∼980°C, this crystallization being preceded by a faint endothermic reaction. The latter is due to segregation of SiO2 and Al2O3, which results in an increase of Si in the Q4 state and an increase of 6-coordinated Al2O3.

Les nontronites ne présentent pas les propriétés caractéristiques des phyllosilicates 2:1 magnésiens ou alumineux à substitutions tétraédriques: domaines d'hydratation homogène, isotherme de désorption d'eau avec paliers, organisation structurale ordonnée ou semi-ordonnée. Or les analyses structurales montrent que ce sont des beidellites ferriffères et l'étude de l'effet Hofmann–Klemen confirme le taux très faible de lacunes et de substitutions octaédriques. Diverses hypothèses justifiant ces propriétés sont présentées et discutées.

A series of experiments has been carried out to investigate the possible formation of magnetite, Fe3O4, under ambient soil-forming conditions. Rapid and easy synthesis of magnetite was achieved through controlled oxidation of Fe2+ solutions at room temperatures and near neutral pH values. The synthetic products were found to range in size between 0·01–0·07 µm (mean diameter) and hence span the theoretical superparamagnetic-single-domain grain-size boundary.

Temperature-programmed desorption (TPD) and IR spectroscopy were used to characterize the number and strength of acid sites in Al3+-, Cr3+- and Fe3+-exchanged montmorillonite. The bases pyridine and n-butylamine occupied three different sites in the interlamellar space: (i) physisorbed base, (ii) base bound to Lewis acid sites, and (iii) protonated base. TPD profiles for pyridine were characterized by maxima at 40°, 150° and 340°C, whilst those for n-butylamine occurred at 30°, 200° and 410°C. The Al3+- and Cr3+-exchanged forms were stable up to pretreatment temperatures of 300°C, but the Fe3+-form required > 3 day exposure to base vapour to re-establish the high-temperature desorption peak. Variable-temperature IR studies showed that the number of Brönsted-bound pyridine molecules increased with increased outgassing temperature.

The filtration of suspensions containing clay and other particles in water is a common process in drinking water treatment. Such filtration processes are very efficient, producing clear water containing less than 1 mg/l from suspensions with particle concentrations of up to 100 mg/l. This filtration is not straining, but a process of collection of clay particles on the sand surfaces in the pores. The clays may range in size from sub-micron to ∼20 µm, and may be flocculated, and are retained in pores ∼200 µm in size within sand grains ∼500 µm in diameter. The collection process has three principal components (i) transport of clay particles across laminar water streamlines by diffusion, gravity and hydrodynamic forces, (ii) attachment by electrical or van der Waals' forces with hydrodynamic forces intervening, (iii) detachment by fluid shear or instabilities caused by arriving particles. Mathematical and physical models relate suspension concentration, quantity of deposit and permeability to depth in a filter, and time of operation. Fibre-optic endoscopes with CCTV enable video recordings to be made of the behaviour of clay particles in the filter pores, at magnifications up to 500 ×.

Hofmann & Klemen ont observé qu'en chauffant modérément (200-220°C) une smectite dioctaèdrique à substitutions octaàdriques saturée par du lithium, celle-ci perdait sa capacité d'échange cationique et son pouvoir de solvatation. Les auteurs ont attribué cet effet à la migration des cations Li vers la couche octaèdrique. Nous avons, en utilisant essentiellement la diffraction X aux grands angles et la microscopie électronique, caractérisé de manière quantitative la structure d'une smectite à déficit de charge mixte (c'est-à.-dire ayant 30% de substitutions dans les couches téraèdriques et 70% dans les couches octaèdriques) saturée par du nickel, avant et après chauffage. Nous avons ainsi pu montrer en éudiant les réflexions 00l qu'après un chauffage à 400°C, les cations interfoliaires migrent vers la cavité octaèdrique vacante pour compenser la totalité des charges négatives dues aux substitutions Al → Mg et qu'il existe une distribution inhomogène de la charge entre les couches octaèdriques et tétraèdriques au sein d'un même cristal. Certains feuillets ont des substitutions uniquement dans la couche octaèdrique, d'autres uniquement dans la couche tétraèdrique, et toutes les possibilités peuvent exister entre ces deux pôles extrèmes.