Interlayered (<20 µm scale) vermiculite-smectite minerals were found in drill-cores from altered Otago schist basement up to 2 m from the contact with the overlying sediment. Mineral compositions defined a series from Fe2+-rich trioctahedral vermiculite to Fe2+-bearing dioctahedral smectite; in these, tetrahedral substitution of Al for Si was unusually high (up to 3·3/8 in the formula unit). The minerals formed as intermediates during the alteration of chlorite to kaolinite under non-oxidizing, possibly acid conditions. The source of the altering solutions may have been overlying lignite seams.

The Bertaut-Warren-Averbach (BWA) technique and high-resolution transmission electron microscopy (HRTEM) were used to characterize the products of dry-ground pyrophyllite. Mean crystallite thickness and crystallite thickness distributions were measured for each sample using the BWA technique. Mean crystallite thickness decreases during the treatment with respect to grinding time and energy applied per unit mass. The BWA data were checked by HRTEM measurements and good fits were obtained for samples having small mean particle thicknesses. Samples with thicker particles could not be measured properly by HRTEM because the number of particles counted from images is statistically insufficient. The shape of the crystallite and the particle-size distribution were used to determine the mechanism of pyrophyllite particle degradation. Particles initially having a lognormal size distribution are first delaminated randomly, then some are delaminated preferentially, thereby producing polymodal thickness distributions. Finally all particles undergo delamination yielding a lognormal thickness distribution.

Experimental alteration of a rhyolitic obsidian by solutions containing variable concentrations of Mg was carried out at 100, 150 and 200°C, for 30, 60 and 90 days, to investigate the mechanism of smectite formation. The smectite exhibits two distinct morphologies: (1) small flakes (aggregates of a few crystals); and (2) large flakes (massive groups). The small flakes are the earlier alteration products. Both morphological types have distinct chemical compositions: the smallest laminae are dioctahedral and contain more Fe, whereas the particles from the rose-shaped aggregates contain Mg and are trioctahedral. Intermediate compositions have been observed between the extreme compositions.

It is suggested that the two morphologies are the result of two distinct genetic processes: (1) the small flakes (Fe-rich smectite) form by solid state rearrangements of the hydrated external layer of glass and/or via the formation of domains within the glass; (2) the rose-shaped aggregates (Mg-rich smectite) form by precipitation from solution.

The structure of synthetic aluminosilicates prepared at pH 6 has been investigated by 29Si and 27Al high-resolution solid-state nuclear magnetic resonance (NMR) spectroscopy. Fourier transform infrared (FTIR) spectroscopy and electron microscopy have also been used to characterize the products. The amount of Si and Al in protoimogolite, disordered allophane and other structures has been measured. There is a fair correlation between the intensity of the 349 cm−1 band in the FTIR spectra and the proportion by weight of protoimogolite Si measured by NMR. It is shown that disordered allophanes have similar structures to those proposed by van Reeuwijk and de Villiers (Soil Sci. Soc. Am. Proc. 32 (1968) 238–240), i.e. octahedral Al surrounding a tetrahedral core. Moreover, it is clear that at high Al:Si ratios (⩾1:1), protoimogolite can compete with disordered allophane precursors for aluminum. The driving forces for formation of protoimogolite rather than allophane appear to be long range Al-Al repulsive forces through oxygen.

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.

Oxygen (18O/16O) and hydrogen (2H/1H) isotopic ratios were measured on 22 smectite separates from bentonite deposits of the Sierra de Gata and Serrata de Nijar, Almeria, Spain. In addition, 18O/16O and 2H/1H ratios were determined on some waters from springs and wells, and 18O/16O ratios were measured on quartz, plagioclase and biotite samples separated from the bentonites. The smectites displayed two distinct isotopic compositional groups which excluded an origin either by submarine alteration or weathering under normal surface conditions of the associated volcanic rocks. Bentonization processes caused by low-temperature fluids of meteoric origin could account for the stable isotopic contents. Argillization temperatures are estimated at ∼40°C and ∼70°C for the Serrata de Nijar and the Sierra de Gata deposits, respectively.

An Early Pliocene sedimentary succession in the Yenidoğan area, Sivrihisar, Turkey, consists of sepiolite, stevensite, kerolite, dolomite and magnesite. The geology, mineralogy and geochemistry of the succession was examined by extensive field work along several trenches and a representative measured section, followed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermal, and chemical analyses.

Structurally, two distinct forms of sepiolites were distinguished by XRD: (a) well crystallized sepiolite with a 110 reflection at 12.07–12.3 Å , and (b) poorly crystallized sepiolite in which the 110 reflection occurs at 12.7–13.0 Å (denoted as sepiolite-13Å ). Differences in crystal chemistry, thermal and morphological properties of these forms, the vibrational spectra and XRD characterization of the related phyllosilicates were also documented.

Stevensite, kerolite and sepiolite were formed by direct precipitation from alkaline lake water rich in Mg and Si. Sepiolite-13Å was probably formed by transformation from precursor smectite via dissolution-precipitation, more likely during early diagenesis. Environmental conditions such as ion concentration, salinity and variations in pH may have controlled the formation of the phyllosilicates.

A survey of 060 spacings of dioctahedral smectites has shown that for nontronites with only iron on octahedral sites, a linear relationship exists between the b-axial dimension and the number of atoms of tetrahedrally coordinated Fe3+ per unit cell containing O20(OH)4. The slope, 0·0497 Å/Fe3+, is steeper than that for the increase in b resulting from Fe3+ on octahedral sites, 0·0377 Å/Fe3+, demonstrating the greater importance of tetrahedral substitution in influencing b. Factors that take account of the number of Fe3+ atoms on tetrahedral sites have been incorporated in existing formulae for calculating b-axis cell dimensions for smectites, but these are usually less successful in predicting b than a new formula involving only tetrahedral and octahedral iron contents.

Upper Jurassic claystones of Kimmeridgian-Volgian(-Ryazanian) age are the main source rocks for oil in the Central Trough, North Sea. Drill cuttings and cores from the depth interval 2368–4548 m, the interval from early-mature to peak oil generation, have been investigated by high-resolution transmission electron microscopy (HRTEM) of ion-milled rock samples, and by HRTEM and powder X-ray diffraction (XRD) of dispersed illite-smectite (I-S) mixed-layers isolated from the <0·2 µm fraction. Ordering parameters were determined by XRD profile simulation. TEM on shadowed particles, combined with XRD evidence, showed that dispersed I-S consists of a mixture of 10–70 Å thick particles, whereas HRTEM showed that intact bulk rock was dominated by 50–200 Å thick particles. Disruption, possibly along smectite planes, of the larger particles in the bulk rock formed the thin particles in dispersed I-S. HRTEM showed 20 and 30 Å periodic enhancement in the contrast of lattice fringes in bulk rock samples as well as in dispersed I-S crystals. These features were interpreted as ordered I-S crystals. Indications of disintegration of larger I-S particles during sample dispersion and of the presence of ordered I-S crystals in the intact bulk rock support the layer transformation mechanism for the conversion of smectite to illite.

L'étude des diffusions, en dehors des taches de Bragg, produites par les molécules d'eau et les cations échangeables des vermiculites magnésium bicouches (d001 ∼ 14·4 Å) permet de proposer un modèle de l'espace interlamellaire. Les groupements cation-molécules d'eau (Mg-12H2O) présentent une organisation bipériodique (maille centrée 3a,b) dans des domaines limités. Chaque motif est constitué par un octaèdre Mg-6H2O auquel est liée fortement une seconde ‘sphère’ d'hydratation, formée également par six molécules d'eau (distances entre atomes d'oxygène des deux sphères d'hydratation de l'ordre de 2·65 Å).

The alkylammonium adsorption method for the determination of layer-charge density was slightly modified and applied to mixtures of expandable clay minerals (i.e. predominantly 18 Å minerals after glycerol sorption) from two loess samples and two soils (Haplaquept and Aquentic Chromudert) having different K-adsorption properties. The layer-charge density of the so-called 18 Å minerals from these sediments and soil samples varied between −0·23 and −0·85 per formula unit, which suggested the presence of different amounts of vermiculite within the 18 Å minerals. The amounts of these vermiculites were related to K-fixing and K-buffering properties of the different samples. High-resolution electron micrographs of vermiculites saturated with tetradecylammonium exhibited a basal spacing of 25 Å. It was confirmed, that the alkylammonium ions in the interlayers of the vermiculites formed a paraffin-type structure. In the fine clay from the loess samples an interstratification of vermiculite and illitic layers was observed.

High-resolution electron microscopy and microanalytical studies were performed on clay and bulk soil samples developed on various igneous and metamorphic rocks from Galicia in the Coruna province in NW Spain. Two mineralogical microsystems can be distinguished showing different stages of weathering. For feldspars, exsolution and mass transformation lead to the delineation of parallel domains, and to formation of gel or paracrystalline minerals. For micas, alteration starts with a physical breakdown, i.e. exfoliation and crystal microdivision; individualization of monolayers is followed by gel formation. A solid phase diffusion phenomenon can explain the formation of 1 : 1 phyllosilicates inside 2 : 1 phyllosilicates or within the continuum of the original crystals. Evidence of such weathering stages in crystalline rocks can be related to the occurrence of specific climatic conditions between temperate and tropical areas.

Carbonate cements in Tertiary reservoir sandstones from the northern North Sea have distinctive carbon isotopic compositions (δ13C). Oil migration up faults from deeper structures and biodegradation of oil pools are factors of particular importance in influencing the δ13C of carbonate cements in these sandstones. As a result, δ13C can be used as an exploration guide to locating the positions of vertical leakoff points from the Jurassic source rocks. The histogram distribution of δ13C in these carbonate cements is trimodal, with peaks at around −26, −3 and +12‰ (ranges −22 to −30, +2 to −10 and +8 to +18‰, respectively). Bacterial processes played major roles in determining this distribution, with oxidative biodegradation of oil resulting in carbonate cements with very negative compositions and bacterial fermentation resulting in the positive δ13C cements. δ13C distribution patterns may be used to differentiate Tertiary reservoir sandstones from Jurassic in the northern North Sea, and these regional carbonate cement δ13C datasets allow geologically useful inferences to be drawn from δ13C data from new sample locations.

Bentonites are candidate materials for the encapsulation of radioactive waste. In the ‘Alternative Buffer Material test’ (ABM), compacted ring-shaped blocks of eleven different buffer materials (mainly bentonites) were packed vertically on top of each other with an iron tube as heater in the centre. These buffer materials started with various exchangeable cation populations (ECpopulation). The first ‘ABM package’ was terminated 28 months after installation and the bentonites had been exposed to the maximum temperature (130°C) for about one year. The aim of the present study is first: to describe modification of the cation exchange population, and second to understand the influence of the groundwater on cation exchange at different scales. No significant horizontal variation of any exchangeable cation (EC) was detected between 1 and 7 cm distance from contact with the iron tube. Large total differences of the ECpopulations, however, were observed for the individual blocks after the field experiment (n = 21 blocks) with respect to the composition of the reference materials. The average cation exchange capacity (CEC) values of the analysed bentonites (n = 9 blocks) decreased by 5.5 meq/100 (1.1 – 8.8 meq/100 g) after the experiment. Exchangeable Na+ and Mg2+ decreased on average, whereas Ca2+ increased. This trend was pronounced in the top region of the parcel (upper seven blocks). Although most changes occurred on the large scale of the whole test parcel, small but important changes were also recorded in the vertical direction on the centimetre scale. The observed differences cannot be explained assuming simply that a bentonite reacts only with neighbouring blocks, which would mean that the system was more or less closed. The differences are much larger and the only conclusion from this observation is that the whole package seems to be influenced by the groundwater which was added from a water tank at the experiment site, enabling at least partial equilibration between the different blocks.

The procedure for synthesizing proto-imogolite (an acid-soluble hydroxy-aluminium orthosilicate complex) and imogolite (a tubular aluminosilicate mineral) was used to produce ferruginous aluminosilicates over a range of Al/Fe ratios to determine whether Fe3+ can be incorporated in the imogolite structure. Analysis of the synthesized products by transmission electron microscopy, electron diffraction, and IR spectroscopy indicated that, while imogolite was formed in the presence of iron, increased Fe3+ in the systems caused the formation of ferrihydrite and poorly-organized aluminosilicates resembling proto-imogolite allophane. Treatment of these materials with Na-citrate/dithionite/bicarbonate dissolved the ferrihydrite and poorly-organized aluminosilicate, and concentrated products with tubular morphology. Analysis of the structural Fe3+ by ESR spectroscopy suggested that little or no Fe3+ was incorporated in the structure of imogolite, although the less crystalline proto-imogolite allophane may have accommodated some structural Fe3+. A separate iron-rich product, identified as ferrihydrite, was formed at low Al/Fe ratios. Mössbauer spectroscopic analysis of 57Fe3+ doped at very low levels into proto-imogolite and imogolite indicated that the sites of substitution were better defined in the latter. At least part of this Fe3+ may have been incorporated in the structure of boehmite, an impurity formed during synthesis.

Evidence obtained from ESR and IR studies is presented for the presence of structural Cr in two natural kaolinites (MILO and GEY) formed in an hydrothermal environment in Sonoma County, California. The XRD patterns show a greater structural disorder for GEY than for MILO, but both have the usual hexagonal shapes as shown by TEM observations. On the basis of EDX analysis of different particles, GEY, on average, appears to be richer in Cr (2.1% Cr203) than MILO (0.6% Cr203). The presence of Fe oxide particles containing some Cr, Ni and V is also indicated by EDX analysis. By FT-IR observation, the octahedral Cr 3+ position was easily detected by a well resolved spectral feature at 3586 cm -1. The adsorbed Cr 3+ kaolinite (KMRXCR) presents no band at 3586 cm -1, but two other bands situated at 3527 and 3477 cm -1. The main features of the ESR spectra of these two kaolinites are a set of resonances near geff4; a broad resonance centred near geff2 with some modulations; and a set of resonances near gcffl. The broad resonance centred near geff2 is interpreted as the free iron oxide signal with modulations due to VO 2+. The set of resonances near geff4 is similar to that observed for octahedral Fe 3+, but the position is shifted compared to that of octahedral Fe 3+. This set of resonances near geff4 is, therefore, interpreted as belonging to Cr 3+ in octahedral position. The resonances at geff1 are also interpreted as belonging to Cr 3-. Comparison with the Cr 3+ surface-adsorbed ESR signal of a Cr-saturated kaolinite (which is a broad resonance centred near geff2) strengthens the interpretation of the geff4 resonances belonging to Cr 3+ in the octahedral position. The results obtained by the combination of FT-IR and ESR spectroscopics indicate that Cr 3+ is present in the octahedral position of the MILO and GEY kaolinites.

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.

Mineralogical trends have been investigated on a detailed scale in two Westphalian fluvial sandstone sequences in contact with either a coal seam or shales. The evolution in an authigenic clay mineral assemblage can be related to changes in the pH of the pore-water. Firstly, kaolinite formed early in diagenesis, mainly as a result of K-feldspar dissolution and alteration. This process, which took place under acidic conditions, consumed protons. Subsequently the pH of the pore-water increased and after compaction, illitization of kaolinite occurred under near neutral conditions. Deep burial is marked by dickite formation, which again reflects acidic conditions. Distribution of clay minerals is related to meteoric water flux through the sediments and the release of organic acids and CO2 from coalification of organic matter in the underlying strata.

A bluish-green clay found in veins cutting across brecciated slates of the Llanvirnian stage at Huy, Belgium, is shown by X-ray diffraction and chemical analysis to be a lithium-bearing, aluminium-rich, regular mixed layer montmorillonite-chlorite with associated pyrophyllite, nacrite and quartz and smaller amounts of calcite and ankerite. The cation exchange capacity of the purified air-dry magnesium saturated clay is 49 mEq/100 g and its structural formula is

The problem of the nomenclature of regular mixed layer montmorillonite-chlorites is discussed.

Radiometric dating of fault gouges has become a useful tool for regional tectonics studies and for exploring and understanding fault and earthquake processes. Methods to define the absolute age of faults achieved a solid scientific foundation almost 25 years ago when the development and application of illite age analysis for investigating sedimentary burial and thermal histories found a new potential application – defining the age of fold-and-thrust development. Since then, the methods have benefitted from further development and incorporation of the 40Ar/39Ar micro-encapsulation method and quantitative clay mineral evaluation to distinguish polytypes (Wildfire). These refinements to the methods have improved their application in fold-and-thrust terrains and have opened up applications in normal and strike-slip fault environments. Another important development is the use of absolute dating methods in retrograde clay gouges in which clays in a fault develop from igneous or metamorphic wall rocks that contain no clays. In addition, the method has also been shown to be useful at dating folds in fold-and-thrust belts. We think the method is now an established part of the geological toolkit, look forward to future fault structural and tectonic studies that incorporate fault ages and hope that researchers continue to probe and discover ways that the method can assist fault process studies, including earthquake fault studies.