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.

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.

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.

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).

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.

The kinetics of the dehydration of ethanol on acidic Al3+-exchanged sepiolite has been studied. The product distribution indicates that the formation of diethylether and ethylene takes place by a series of consecutive and parallel reactions. A mechanism for the formation of both products has been derived by studying the influence of different operational variables on the reaction rates.

La décarboxylation de l'acide oxaloacétique en acide pyruvique a été étudiée en présence de montmorillonite saturée en cations différents et des mêmes cations à l'état libre (non incorporés). L'action catalytique dépend de la nature du cation, cést-à-dire de sa facilité à former des complexes avec l'acide oxaloacétique. Le réseau argileux intervient dans la catalyse essentiellement par les atomes d'aluminium (ou de fer) situés sur les bords des feuillets argileux. Il joue le rôle d'un métalloenzyme biologique. Le calcul des énergies d'activation pour les différents systèmes met bien en évidence l'activité catalytique de l'argile. En présence du phyllosilicate, la réaction a lieu avec un bon rendement jusqu'à une température de 60°C.

The dehydroxylation of kaolinite has been investigated by isothermal thermogravimetry. Kinetic analysis using the Avrami equation shows that a combination of atomic mechanisms operates throughout the temperature range 734 K to 890 K. An empirical activation energy of 222 kJ mol-1 was calculated from the Arrhenius relationship using rate constants based on diffusion and homogeneous models. The activation energy (Ea) was calculated for a series of degrees of dehydroxylation by the time to a given fraction method, showing an increase in Ea during the early stages of the reaction. The isothermal plots indicate that OH is retained in the final stages of the reaction. The observations are explained in terms of a reaction mechanism in which kaolinite grains dehydroxylate from the edges inwards, parallel to (001).

La détermination des complexes silico-ferriques, hydroxydes métalliques ou autres matériaux amorphes ou pseudocristallins contenus dans les sédiments marins est généralement difficile. La méthode décrite utilise la diffractométrie de RX et permet l'analyse quantitative de quelques-uns de ces matériaux tels que la silice biogène ou les cendres volcaniques. Cette phase amorphe constitue une composante majeure dans certains sédiments marins, d'où la nécessité de pouvoir la quantifier. La méthode reste suffisamment simple, fiable et précise pour permettre aussi la détermination quantitative de la phase cristallisée qui lui est généralement associée.

A method is described for IR spectroscopy whereby combining statistical analysis with the quantitative method described by Slonimskaya et al. (1986) results in more informative spectra. Application of this method to dioctahedral micaceous minerals with vacant trans octahedra has revealed a number of peculiarities in the octahedral cation distribution. This distribution is never completely disordered in the samples studied and shows maximum degree of short-range order in minerals having predominant Al.