The Carboniferous in Britain is diverse and this is reflected in the clay mineral assemblages. Several factors affecting the assemblages are identified including climate, rates of weathering and erosion, source rocks in the hinterland, preservation of palaeosols, whether the source rocks are nearby or distant, sorting during transportation, the presence of altered volcanic ash-falls in the depositional environment and the extent of burial diagenesis. There are temporal and geographic variations in the clay mineral assemblages in the mudrocks as a result of these controls. There are also clay-rich rocks that differ from the normal mudrocks and a knowledge of the clay mineralogy of these is a necessary prerequisite to a full understanding of their origins. Mudrocks falling in this category, and described below, include bauxitic clays, flint clays, fragmental clay rocks, tonsteins and K-bentonites and various palaeosols.

IR spectroscopy has been used to study the interaction of alkali metal hydroxides with dioctahedral smectites having iron contents of 0·7% (montmorillonite) to 22% (nontronite), in connection with the alkali-stabilization of soils. The results have shown that the alkalis (LiOH, NaOH, KOH and CsOH) deprotonate hydroxyl groups co-ordinated to octahedral ferric iron, causing distortion of tetrahedral and octahedral layers. This concept of distortion is supported by a striking change in Mössbauer spectra and a large increase in b cell dimensions. The perturbation of the smectite structure, shown by shifts in the Si-O and O-H stretching vibrations, is greater for Na, K and Cs than for Li, suggesting that the larger cations interact with surface oxygens around the hexagonal hole. IR spectra suggest that the effect of NaOH on nontronite is substantially reversed by treating the smectite with CO2 or acetic acid vapour or by washing it with dilute salt solution, although Mössbauer spectroscopy and XRD indicate that the structure of the regenerated smectite is more disordered than that of the original.

The Cu-triethylenetetramine-complex (Cutrien) is one of the commonly used index cations for CEC determination in clay science. Cutrien-exchanged smectites show basal spacings between 13.0 and 13.5 Å after correction for the Lorentz and polarization factors. The full width at half maximum (FWHM) of the d001 reflection is today related to the percentage of tetrahedral charge (beidellitic character) and/or to the Fe content of the smectites. The structural Fe content and the tetrahedral charge correlate, so their individual influence on d001 cannot be resolved. Nevertheless, the FWHM of Cutrien smectites should depend on the charge distribution rather than the Fe content.

X-ray diffraction (XRD) and water uptake capacity measurements showed that the interlayer of Cutrien-exchanged smectites does not swell any more, but can take up a few water molecules. Accordingly, the water uptake capacity of the external surface area can be determined independently from the interlayer water uptake capacity. Adjusting the pH of Cutrien-bentonite dispersion to different values allows for the determination of the variable charge.

In conclusion, Cutrien exchange of smectites appears to be suitable for the study of external surfaces area related phenomena (e.g. edge adsorption processes) without any influence of the interlayer region.

The distribution of rare earth elements (REE) in two different sediments, a marine clay and a till, was found to be dependent both on grain size and mineralogical composition. In the marine clay the REE content was highest in the coarsest fraction; in the till REE were markedly enriched in the finest fraction. Detrital and authigenic origins for different size fractions have been attributed on the basis of REE contents.

Kinetic studies have shown that the isothermal dehydration of the clay minerals proceeds according to a first order law enabling velocity constants to be evaluated for different temperatures. From these, the Arrhenius parameters have been determined and on this basis, the clay minerals may be classified into three main groups, viz., kaolinites, secondary mica clays and montmorillonites. No significant difference is shown by comparison of the Arrhenius plots for the kaolinites and halloysites but the secondary mica clays decompose more rapidly than the kaolinites at comparable temperatures. Evidence is provided to illustrate that the constants obtained are associated with the basic process involving interaction of hydroxyl groups in the clay mineral lattice. Indirect evidence also suggests that the irreversibility of the dehydration is due to lattice collapse resulting in the formation of highly stable configurations of Si4+, Al3−, and O2− atoms. The first order nature of the dehydration reaction is shown to be the underlying basis of the type of curve obtained in differential thermal analysis. Two important conclusions are that:—(a) The clay mineral is only approximately 70% decomposed at the peak on the thermal analysis curve. (b) Heating rate has a marked effect on the peak temperature. Mathematical equations have been developed to obtain the effect of heating at a constant rate on the progress of a reaction for which the isothermal velocity constants are known. The effect of sample weight and dilution factors are discussed, together with the kinetic problems associated with mixtures of clay minerals.

The distribution, mineralogy, petrology and bulk and stable isotope chemistry of altered volcanic ash beds in the marine sediments of Mid-Triassic age (Etalian) at Kaka Point, New Zealand, are described and related to lithofacies and the geological processes controlling their development.

Three varieties of altered ash occur in the Kaka Point sediments — porcellanite, claystone (bentonite) and albite-rich. Porcellanites are quartz-rich and may contain analcime and heulandite: they are restricted mainly to the on-shore facies. Claystones are rich in smectitic clay minerals and occur in both the on-shore and off-shore facies. They often contain diagenetic nodules of analcime, quartz, apatite and carbonates. The authigenic carbonates of the on-shore facies are variable in composition (sideritic, rhodochrositic, calcitic), whereas in the off-shore facies they consist only of calcite. The albite-rich lithology is very rare and is known only from the off-shore facies.

The development of the porcellanite and albite-rich lithologies was restricted to slowly deposited, relatively coarse-grained ash sediments in which extensive interchange took place between the sediment's pore-waters and ambient seawater, resulting in enhanced microbial activity and high pH throughout the pore-waters of the suboxic zone beneath the water-sediment interface. The high pH increased the rate of volcanic ash hydrolysis and provided the conditions necessary for the precipitation of zeolite, feldspar and quartz. The development of smectitic claystones was associated with more rapid deposition and limited interchange between the pore-waters of the parent ash and ambient seawater. The pore-water alkalinity was generally lower and enhanced microbial activity and high pHs were restricted to patches of sediment at which quartz, analcime, apatite and carbonates formed diagenetic nodules. Modelling of the stable isotopes of the smectitic clays (δ18O, δD) and diagenetic carbonates (δ18O, δ13C) suggest that: (1) ash argillization in the on-shore facies took place in brackish water (∼25% meteoric water) at an average temperature of ∼50°C and in the off-shore facies in marine pore-waters (∼10% meteoric waters) at ∼40°C and (2) diagenetic carbonate precipitation in the near-shore facies took place at ∼30°C and in the off-shore facies at 60–80°C.

The pattern of ash alteration in the marine Triassic sediments at Kaka Point is considered to represent an early stage in the development of the zeolite pattern associated with the classic area of zeolite facies metamorphism in the Taringatura and Hokonui Hills.

The mineralogical characteristics of authigenic palygorskite occurring with chlorite and illite in Miocene sediments in Linxia basin were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM). The XRD results suggest that the mineral composition of the sediments includes mainly quartz, chlorite, illite, calcite, plagioclase, orthoclase, minor palygorskite and small amounts of gypsum and ankerite. Two kinds of palygorskite were observed in the sediments, relatively straight fibrous particles found in matted, felted masses associated with platy chlorite and silky aggregates found in the void spaces. The former probably replaces chlorite grains, growing from the edges or the fissures of chlorite particles. Chlorite grains exhibit bay-shaped or rounded edges, with ambiguous felted boundaries between chlorite particles, indicative of an intensive dissolution process and the growth of palygorskite at the expense of chlorite. Palygorskite is also observed as inclusions within calcite, sprouting from or coating calcite surfaces, suggesting that palygorskite crystallized from solution. The textural relations of palygorskite and the occurrence of ankerite and the characteristically Fe-bearing palygorskite in the sediments suggest the destruction and hydrolysis of chlorite. The ankerite seems to be preferentially present in the void spaces, closely associated with chlorite and illite; fibrous palygorskite crystallizes at the edges of these clay mineral particles and the platy clay mineral particles are gradually replaced by fibrous palygorskite crystals, suggesting that alteration of chlorite to palygorskite involves an interaction with water during the diagenetic process.

Smectite formation in a vertisol developed from a granitic parent rock in the Kaélé region of Cameroon in a tropical, dry climate was studied by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), chemical analyses, cation exchange capacity (CEC) and low temperature gas adsorption. The soil profile comprises three horizons (from base to top): (1) a saprolite, (2) an intermediate horizon, and (3) an upper dark grey horizon. In the saprolite, the progressive alteration of feldspars gave rise to the exclusive neoformation of beidellite exhibiting a typical honeycomb fabric. This process resulted in Al, Fe, Ca, Mg, Ti and Mn enrichment, a depletion of Si and Na and a significant negative Eu anomaly. In the upper horizons, beidellite evolves and is transformed into montmorillonite and kaolinite, probably through a series of smectite-kaolinite mixed layers. This transformation, from the saprolite to the upper horizons, causes the observed decrease in the CEC and the increase in specific surface area and mesoporosity of the clay. The REE patterns of the bulk soil and clay fraction display similar behaviour, indicating that the three horizons, and hence the clay minerals, have a common source in the underlying granite. Mass-balance calculations show that the intense weathering of the granite leads to a mass reduction of ~80–90%.

The incomplete miscibility of Al into the ferrihydrite structure has been a recurring issue in understanding the environmental geochemistry of this important oxyhydroxide. During co-precipitation from acidic aqueous solution, ferrihydrite has been observed to accept only up to ∼25 at.% Al without the formation of multi-phasic Al and Fe oxyhydroxides. Using basic chemistry and crystal-chemical relationships we propose here that the saturation limit of Al substitution in the structure of Fe oxyhydroxides is controlled by Al – Al avoidance in a manner that conforms to Pauling's distortion rule. Employing this hypothesis, we show that the predicted miscibility limit for Al incorporation is 25 at.% in ferrihydrite and 33 at.% in goethite, in agreement with previous observations. These results indicate that the classical f-phase model for ferrihydrite best represents observations. Incorrect assignment of Fe site occupancy and other shortcomings of the akdalaite/tohdite model for ferrihydrite are also discussed.

The characterization, pillaring ability and some catalytic properties of a saponite from the Vicálvaro deposit of Tolsa, located in Madrid have been studied. This mineral is associated with sepiolite in the same lacustrine environment. The raw saponite presents, as special characteristics, high specific surface area (>200 m2/g) and a high percentage of tetrahedral Al (90% of the total Al in the sample). Natural saponite gives rise to high conversions when used as a catalyst in the reaction of alkylation of benzene with 1-dodecene. Increased catalytic performances are obtained over the alumina-pillared saponite derivatives. These materials have also been tested in the cracking of gas-oil (microactivity test), giving good conversions and high selectivity towards the gasoline fraction, especially the pillared forms.

A new set of clay mineral ‘Crystallinity’ Index Standards (CIS) is available for improved calibration of the half-peak-width values of the X-ray diffraction 001 illite reflection (the Kübler index) and the 002 chlorite reflection (the Árkai index), two widely used indices for determining the state of prograde diagenesis and low-temperature metamorphism. Calibration using mudrock standards removes the numerical differences between laboratories caused by variations in sample preparation, machine settings and measurement methods, thus avoiding erroneous grade determinations. The number of standards available has been increased to nine. These can be used to obtain Kübler index values for each CIS sample and Árkai index values for upper anchizonal and epizonal samples. The diagenetic and lower anchizonal mudrocks are not suitable for Árkai index measurements due to the absence of chlorite or overlap by the 001 kaolinite reflection. Applying the new Kübler-equivalent upper and lower boundary limits of the anchizone placed at 0.32°2θ and 0.52°2θ, respectively (Warr & Ferreiro Mählmann, 2015), the nine standards from the Palaeozoic mudrocks of southwest England now comprise two diagenetic, two lower anchizonal, three upper anchizonal and two epizonal grade samples. These range from weakly cleaved mudstones to strongly foliated slates.

The reaction of a Wyoming-type bentonite with pH 13.5 solutions was investigated experimentally at 35 and 60°C for periods of 1 to 730 days. Some crystal properties of the starting montmorillonitic clay remain unchanged, i.e. stability of the octahedral sheet, total cation exchange capacity (CEC) and CEC after neutralization of the octahedral charge, full expandability in the Casaturated state, and size distribution. Other properties are changed, e.g. there is an increase in the expandability after octahedral charge neutralization; a slight increase in the average layer charge; a decrease of the total surface area; and a particle morphological change from flakes to hexagonal shape.

The composition and the structure of the smectite layers did not change significantly during the reaction. The increasing number of expandable layers after octahedral charge neutralization is attributed to modifications in the stacking sequence. The number of interlayers surrounded by two charged tetrahedral sheets increases with reaction time.

The anion adsorption capability of clays can be improved significantly by modification with certain organic cations. However, surface properties and the microstructure of the clay might change and limit the use of organo-clays in barrier systems. In this study an experimental setup is introduced which allows the rapid determination of effective diffusion coefficients (Deff) for H2O in clay samples. H2O→D2O exchange experiments on hexadecyl-pyridinium (HDPy)-montmorillonite samples were performed in a diffusion cell attached to the ATR unit of a Fourier-transform infrared spectrometer. The mean Deff for H2O in a D2O-saturated original montmorillonite is 2.44 × 10–11 m2/s in the bulk density range of 1.1–1.8 g/cm3. Hydrophobic surfaces increase the diffusivity only at high bulk densities in the saturated state. The mean Deff is lower when HDPy is applied in amounts ⩾80% of the cation exchange capacity in comparison with the original sample. At a saturation degree of the pores of 40%, Deff for all samples is one order of magnitude less than in the saturated state. Results on Deff obtained by ATR-FTIR spectroscopy are in good agreement with through-diffusion studies.

The Devonian-Carboniferous reservoir of the Clair Field contains a complex and variably abundant clay mineral assemblage. An abrupt vertical change in clay mineralogy has been observed in both wells studied (UKCS 206/8-7 and 206/8-8) from being rich in Mg-chlorite, chlorite- smectite (including dioctahedral corrensite), illite, illite-smectite and Fe-chlorite, to being smectite- rich. This change broadly coincides with the unconformable boundary between the Lower Clair Group and Upper Clair Group of the reservoir which possibly defines the Devonian-Carboniferous boundary. The clay minerals present reflect interaction between: (1) tectonic stability and climate that controlled the detrital composition of the sediment; (2) the pore-waters that developed; and (3) the result of diagenetic modification.

Matrix porosity and permeability is severely restricted where the pore-lining clays are abundant (>15%) and where the clays bridge or fill pores. The type of clay mineral species appears to have a minor influence on reservoir quality, although they may be extremely important during production. The best reservoir quality occurs in mature aeolian sediments with a thin illite and illite-smectite clay coating.

X-ray diffraction was used to analyse the distribution of clay minerals in the <2 µm fraction of the lutitic and marly facies from the centre of the Basque-Cantabrian Basin (Basque Arc), where the sedimentary section is 2000 to 10,000 m thick. Most of the deposits were laid down during the Cretaceous and Paleogene and were related to the opening and closing of the Bay of Biscay. The most noteworthy variations are in kaolinite, smectite and mixed-layered (R = 0, R = 1 and R ≥ 3) illite-smectite, which can be ascribed both to provenance and to diagenesis. A general diminution in expandability is related to the gradual transformation of smectite to illite from south to north, and with depth. Temperature, residence time and chemical activity during diagenesis are the factors that had greatest influence on the changes in the original mineral assemblages inherited from the source area. On the basis of the clay minerals and the Kübler index, a general scheme is proposed for the diagenetic evolution of the area from the initial stages to anchimetamorphism.

The physicochemical properties of clays can be modified by acid treatment with inorganic acids. This treatment is usually referred to as ‘acid activation’, because it increases the specific surface area and the number of active sites of the solids. In the present study, the acid activation of saponite from Cerro del Aguila (Madrid, Spain) with HCl solutions was measured. Illite, quartz and small amounts of feldspar were found as impurities in the raw saponite.

Acid treatments were carried out with different concentrations of HCl solutions. The samples obtained were characterized by mineralogical and chemical analyses, XRD, FT-IR spectroscopy, N2 adsorption-desorption isotherms and TEM. The acid attack, under the conditions employed, produced a progressive destruction of the structure of saponite by partial dissolution of the octahedral Mg(II) cations. Amorphous silica coming from the tetrahedral sheet of saponite was generated. The specific surface area of the most intensely treated sample (2.5% for 24 h) was doubled with respect to that of natural saponite. This increase in the surface area is due to the increase in both the external and internal surface areas.

The thermal decomposition of stearic acid in the presence of various clay minerals was studied in an open, inert system under isothermal (250°C) conditions. The distribution of hydrocarbons and the amount of CO2 evolved were determined. The degree of decarboxylation depended on the composition of the octahedral sheets of the clays. It was greater with trioctahedral than with dioctahedral minerals. The presence of dioctahedral minerals tended to reduce the amount of CO2 produced below that obtained with the neat acid. The nature of the hydrocarbons formed depended on the structure of the minerals. Different products were obtained with minerals that have accessible interlayers and channels (smectites, palygorskitesepiolite) than with the 1:1 clays and pyrophyllite or talc. Some minerals caused cracking to light-weight hydrocarbons. Higher surface acidity of the clay interlayers enhanced this process but was not the only decisive factor. In the systems studied, evolution of CO2 did not necessarily precede the formation of light- or medium-weight hydrocarbons from the parent acid.

57Fe Mössbauer spectra of the Na+- and Ca2+-saturated forms of four ferruginous smectites,displaying a range of compositions, have been fitted with Voigtian profiles to represent (principally) two correlated distributions of isomer shifts and quadrupole splittings for the Fe3+ sites. Correlating the areas and hyperfine parameters of these distributions with simulations of the octahedral array of cations based on chemical analyses and infrared spectroscopy has enabled identification of the Fe3+ ions that contribute to the outer quadrupole doublet. The octahedral Fe3+ sites are characterized as having at least one Mg2+ nearest-cation neighbour and probably a cisconfiguration with respect to the OH– ions.

Mössbauer spectra of several smectites demonstrate the existence of at least three phases with distinct Fe populations: (i) a component with very low Fe content (< 1%), which shows slowly-relaxing paramagnetic hyperfine structure at both 4·2 K and 77 K; (ii) a component with intermediate Fe content (∼ 1–10%) which is seen as doublets in the spectra at 4·2 K, 77 K and ambient temperature; (iii) an Fe-rich phase (> 30% Fe), which shows magnetic ordering at 4·2 K and 77 K. These data are consistent with components (i) and (ii) corresponding to Fe incorporated in aluminosilicate structures from distinct phases, whereas (iii) is characteristic of an iron oxide phase, probably goethite in most cases. These conclusions are supported by EPR measurements which show magnetically-dilute Fe in more than one type of structural environment plus an additional component with magnetically-interacting ions.

In the last 10 years or so much work has been done to determine the crystal structures of layer silicates more precisely than previously and, as a result, ideas about these structures have had to be revised.

Around 1930 the classical studies of Bragg and his collaborators, and of Pauling, established the general geometrical features of layer silicate structures. The basic building units were found to be layers of linked tetrahedra articulated, by sharing oxygens, with layers of octahedra. In the 1 : 1, kaolinite type materials, with layer thicknesses about 7 Å, the composite layer unit was made up of one tetrahedral layer and one octahedral layer; in the mica and chlorite minerals the silicate layer was formed by joining two tetrahedral layers, one on either side, to an octahedral layer.