In the Czechoslovak part of the Upper Silesian Coal Basin (Ostrava-Karvina Coal Basin), only part of the Upper Carboniferous (Namurian A, B, C and Westphalian A) is well developed, and tonsteins, which are clayey rocks or claystones, occur as thin, clayey interlayers in the coal seams. Two types of primary volcanic mineral assemblages were identified in four tonstein samples from different coal seams; the first type is characterized by the presence of biotite and sanidine, and the second by the presence of biotite, bytownite and Ca-amphibole. All tonsteins studied contained kaolinite minerals, volcanic quartz grains, crystals of zircon and apatite. Separated biotite flakes with an admixture of kaolinite layers were identified as 1M polytype. The flakes without kaolinite minerals were identified as epitactic overgrowth of 1M and complex polytypes, and twinned crystals of 2M1 polytype. Kaolinization of biotite flakes was observed in all tonstein samples studied. Kaolinite single layers (7 Å) as well as two-layer polytype of kaolinite minerals (14 Å) sandwiched between biotite layers (10 Å) were identified by HRTEM imaging.

Mixed-layer illite-smectites (I-S) have a stable charge on the illite interlayer equal to 0·89/O10(OH)2, as shown by electron microscope measurements of mean fundamental particle thickness, using both Pt-shadowing and high-resolution techniques. This has been verified by independent measurements of total surface area and CEC. Typically, the smectite interlayer charge is close to 0·4/O10(OH)2 but clays evolving in K-deficient environments may exhibit higher values. In the course of illitization, the silicate layer composition becomes more restricted than the smectite composition, AlIV and AlVI increasing while Fe and Mg decrease. These substitutions lead to the composition of non-expandable illite differing distinctly from that of muscovite and phengite, close to FIX0·89Al1·85Fe0·05Mg0·10Si3·20Al0·80. HRTEM data show that XRD systematically underestimates %S layers in I-S due to the small size of coherent scattering domains. An experimental curve is proposed for correcting XRD data. The above results were obtained for I-S formed from volcanic materials in different diagenetic and hydrothermal environments. The illite interlayer charge value close to 0·9 reconciles well the available data on I-S produced by wetting and drying of K-smectites.

Synthetic 2-line and 6-line ferrihydrites were heated to 400 K, 500 K and 600 K, under dry conditions. Heating to 400 K lowered the ratios of structural OH to Fe2O3 without a phase transformation. The lowest ratios observed at 400 K were 1·23 (2-line) and 0·85 (6-line ferrihydrite) after 1150 h. For 6-line ferrihydrites heated to 400 K, the solubility in oxalate and the BET surface areas decreased with increasing heating time, whereas the unit-cell parameters, the relative peak intensities and the mean coherence lengths did not change significantly. Heating the 2-line ferrihydrites to 400 K produced microporosity.

The clay mineralogy of K-fixing soils from southern Germany was investigated using the alkylammonium method. Conventional X-ray diffraction chart recordings of glycerol-saturated <0·1 µm samples showed peaks at 18 Å that were initially interpreted as smectites. However, step-scanning combined with the Lorentz- and polarization-correction and curve-fitting, revealed the presence of low- and high-charge smectites and of low- and high-charge vermiculites. The severe overlap of the 001 basal reflections of the high-charge vermiculites with the broad and intensive peaks of smectites sensu stricto prevented visual evaluation at the alkylchains nc = 5–9, but this problem was overcome by curve-fitting. The 002 peaks of high-charge vermiculites (nc = 8 and nc = 10) in the fraction 0·1–0·2 µm could furthermore be clearly resolved from the 001 peaks of illite by curve-fitting. In one example, 003 (at nc = 17) could be resolved from 001 of illite.

The surface composition of some halloysites with different particle morphology has been investigated by X-ray photoelectron spectroscopy (XPS) before and after removal of external Fe. The Fe(III) 2p3/2 binding energy of external Fe is appreciably smaller than that of structural Fe. Particle morphology is influenced by structural Fe content. The long-tubular halloysite has very little surface Fe, and its concentration tends to increase with the proportion of non-tubular particles in the samples. The spheroidal sample contains the most structural Fe which, however, does not appear to influence particle shape directly. Study by XPS indicates that Fe substitutes for Al in octahedral positions in approximately 1 : 2 proportion. As a result, an increase in octahedral vacancies and cation exchange capacity would be predicted. Further, halloysite layers within a crystal are generally inhomogeneous in composition. Built up like “onion skins”, the surface layers would either be enriched or depleted in Fe depending on the chemical environment in which crystal growth occurs.

The weathering of montmorillonite in the acid clay deposit at Itoigawa, Japan has been investigated by X-ray diffraction (XRD), infrared spectroscopy (IR) and scanning electron microscopy (SEM). In the lower, least weathered part of the deposit, weathering has occurred by the formation of minor amounts of halloysite with concomitant precipitation of a silica phase identified as opal C-T. A relatively rapid transition occurs to the most weathered, upper part of the deposit where the mineralogy is dominated by interstratified halloysite-smectite. Computer simulations of XRD profiles indicate that the interstratified arrangement is random with a probable composition of 70% halloysite and 30% smectite, a composition supported by the 75–85% and 15–25% of the phases, respectively, calculated from the IR spectra.

Sudoite occurs as a cryptocrystalline clay in some Visean K-bentonites from Belgium. Usually associated with illite-smectite mixed-layers, this chlorite has been found locally as a monomineralic clay component of a K-bentonite bed. The mineral has a composition close to (Al3Mg2)(Si3Al)O10(OH)8. The cell parameters have been calculated from the diffractogram using the space group C2/m (a = 5·228, b = 9·056, c = 14·326 Å, β = 97°00′, d(060) = 1·509 Å). The polytype corresponds to a IIb structure. Some hypotheses are proposed for the origin of this chlorite. The coexistence of sudoite and pyrite could explain why the chlorite present in Visean K-bentonites is not a Fe-rich species typical of diagenetic conditions, but a Fe-poor one.

Structural differences which occur on heating La-montmorillonite have been studied and compared with those for montmorillonite saturated with Na(I) and Li(I). Rehydration experiments show that La-montmorillonite swells after preheating up to 500°C. However, FT-IR spectra suggest partial migration of the La(III) cations from the interlamellar region to the structural sheets and(or) deprotonation of hydrated La(III) cations, followed by migration of the resulting protons to vacant octahedral sites. Additional measurements of X-ray absorption spectra (EXAFS, XANES) and heating to 700°C suggest that interlamellar hydrated La(III) partially deprotonates producing polyoxocations.

The weathering of biotite in Quaternary lahars from Monti Ernici (Central Italy) via interstratification stages has been studied by X-ray diffraction of both the interstratified minerals and the initial (biotite) and final (vermiculite) end-members. The structure of the biotite and vermiculite is described by means of monodimensional Fourier series. The interstratified phases have been studied using the INTER program which permits an analysis of two interstratified components by Fourier transform methods. It is shown that in the alteration range for biotite to vermiculite even small samples have different spatial concentrations of biotite, vermiculite and an intermediate biotite-vermiculite-type phase. Hydrobiotite and a rare biotite-hydrobiotite with a tendency to regularity have also been documented. Chemically, the process involves considerable oxidation of Fe2+ and the removal of most of the elements, corresponding to a 34% loss in matter. The sequence of the element losses is: K+ > Fe2+ > F− > Mn2+ > Si4+ > Mg2+ > Al3+ > Ti4+. There are also some gains in the order: H+ > Ca2+ > Fe3+ > Na+.

Chemical and mineralogical analyses of fossil caliche profiles developed on top of Lower Pleistocene alluvial formations in the East-central sector of the Ebro basin indicate that they have high content of carbonate (average 84%) and high Ca/Mg ratios (average 136). The clay mineral assemblages vary slightly depending on the host material, and, therefore, on the alluvial formation in the source area. Inherited detrital minerals (illite, kaolinite and chlorite), transformed components (from chlorite to mixed-layers of chlorite-vermiculite, and from smectite to palygorskite) and a neoformed phase (palygorskite) have been observed. The contents of carbonate and magnesian clay minerals (smectite and palygorskite) increase from the bottom to the top of the profiles, in relation to hardpan laminated caliche facies. The amount of palygorskite is controlled by the concentration of Mg2+ which in turn depends on the absolute content of Mg2+ in the host material and on its relative concentration by processes of evaporation linked to decreasing permeability in the profile during the biogenic-pedogenetic carbonate accumulation stages. These processes form part of the development of caliche profiles in a semi-arid environment.

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.

Modification of clay minerals by exchange, intercalation, calcination and imbibition of organics followed by their polymerization and carbonization was studied. The surface properties of the clays were investigated by inverse gas chromatography at infinite dilution employing alkanes and alkenes as probes; the structural properties were measured directly by X-ray diffraction and inferred from the results of high pressure hydrogen adsorption. Calcination of pillared smectites prior to polymerization and carbonization of organic material in the interlayer space leads to a microporous “activated carbon” that demonstrates unique properties as an adsorbent for hydrogen, significantly different from clays that have not been calcined.

The allophane studied occurs in the weathered zones of the barite-sulphide-bearing dolomitic levels, interbedded in the barite ore deposits of Vide de Alba and San Bias (Province of Zamora). These ore deposits are interstratified in the Silurian-Devonian sulphide bearing volcano sedimentary materials of the Alcañices Synform. The allophanic samples have been studied by polarizing microscopy, SEM, XRD, DTA, TG, IRS, EMA and chemical analyses, the last after dissolving the samples by acid (HF + HNO3 + 3HCl + H3BO3) and alkaline digestion (0·5 m NaOH). It is suggested that allophane originates from the reaction of acid solutions released during the weathering of sulphides with acid volcanoclastic rocks. Silica-alumina gels were deposited in holes formed during earlier dissolution of the dolomite associated with the barite ores. Later processes of desilication partially transform allophane to gibbsite.

The expandability of K-depleted biotite and natural vermiculite was studied using transmission electron microscopy (TEM) and X-ray diffraction (XRD). K-depletion in layer-silicates was achieved by treating ultrathin sections with 0·1 m CaCl2 and BaCl2 solutions. The natural sample of biotite, which by XRD revealed no expandability on ethylene glycol or glycerol solvation, displayed 10–15% expanded layers when viewed by TEM after alkylammonium intercalation. The proportion of expanded layers increased after CaCl2 treatment. XRD of vermiculite samples revealed two sets of expandable interlayers after alkylammonium treatment, corresponding to two types of particles with different layer structures observed by TEM. Identification of vermiculite by TEM based on basal spacings is reliable with alkylammonium treatment. Intercalation of alkylammonium ions into the interlayers of vermiculite improved the degree of stacking order of the 2:1 layers.

The soils developed from crystalline and metamorphic rocks in Galicia (NW Spain), are characterized by high concentrations of 1 : 1 phyllosilicates and gels. Thermal analyses, X-ray diffraction after formamide treatment, and IR spectroscopy in the OH vibration range have been performed on the clay fractions, but do not discriminate clearly between the different associated mineralogical phases. HRTEM studies linked with microdiffraction and microanalyses have led to the identification of several types of gel which transform into goethite, gibbsite, clay precursors, and/ or halloysite according to their composition (Fe, Al or Si-Al). Halloysite-like minerals are the main constituents and they have a great variety of morphologies: lamellar, spheroidal, tubular, platy or poikilitic. In general, halloysite and gel formation on crystalline rocks is related to the bioclimatic conditions, involving high hydrolysis in the presence of organic matter. This halloysite seems to be a metastable mineral which would evolve into kaolinite with increasing weathering time.

Solutions obtained from soils in the Galicia Region of NW Spain had considerably lower activities of Al3+ when obtained by a speciation procedure (fractionation with an ionic column and application of specific software) than when obtained from concentrations of reactive Al (colorimetry with pyrocatechol violet) by a calculation that only considers simple hydroxylated species. Using the speciation method, many of the solutions obtained from surface horizons are unsaturated for most minerals, especially in granitic areas.

Complexes of SnCl2/montmorillonite have been prepared from solutions which contained 10, 20, 40 and 200 times the cation exchange capacity of the clay, resulting in complexes which contained 1·7, 1·6, 2·8 and 4·6 wt% of tin. Detailed thermogravimetric and variable temperature 119Sn Mössbauer spectroscopic studies of these complexes, both as prepared and following back exchange with Ca2+-ions, have shown that (i) the complexes are quite acidic in nature, and (ii) the majority of the Sn forms an oxy/hydroxy coating over the montmorillonite surface in which the vibrational freedom of Sn depends upon both the Sn content and the state of hydration of the coating.

An XRD method for measurement of quartz content using ZnO as the internal standard was tested on different particle sizes between 0 and 20 µm. Calibration curves showed a good correlation coefficient for particle-size fractions up to 20 µm; the slope increased for the fractions from 0·7 to 5 µm and was relatively constant for coarser particle sizes. Fine quartz fractions were etched with hydrofluoric acid to remove the surface layer damaged during dry grinding. The use of such etched quartz increased the slopes of the calibration curves for small particle-size fractions and approximated the natural fine quartz fraction much better than the original dry-ground material. The mean of six measurements gave good accuracy provided that the slope of the calibration curve was adjusted for the particular particle-size fraction. This method was used on 0–2 µm, 0–0·2µm and 0·2–2 µm fractions of French silty soils and the results are in agreement with the data from chemical analysis and with the mineralogical interpretation.

Understanding the chemical variability of clay minerals depends on the analytical reliability of the techniques used. Uncertainties in clay mineral compositions were computed for common sources of analytical error such as those that arise from contaminant phases present in clay size-fractions in concentrations below the detection limit of routine XRD screening techniques, and the analytical limits of precision for TEM/AEM analysis. When plotted on standard diagrams used to represent clay mineral compositions, the calculated error envelopes were found to be of significant size, such that analyses of pure illites and pure smectites straddled the field for mixed-layered illite-smectites. In addition, on some diagrams random analytical errors resulted in linear trends identical to those caused by mixtures of two or more clay minerals. It follows that variations in the compositions of clay minerals reported in the literaure do not always necessarily represent the actual chemical variation of the minerals. As a result, current interpretations of clay compositional variations may not be as definitive as hoped.