Micropore distribution and effective size of the channels of natural sepiolite from Turkey were measured by the BET method. Before the BET measurement, the samples were treated under a water vapour atmosphere at various pressures to fill progressively the sepiolite micropores with water. The surface areas measured by means of N2 adsorption decreased with increased vapour pressures of water. The outer surface area was estimated by comparison of the surface area of the vacuum-dried sepiolite with that filled with adsorbed water. The total surface area was ∼290 m2/g, and the outer surface area was 170 m2/g, the difference being attributed to the structural micropores of the sepiolite. The ratio of the surface areas possessed by the channels and that of the outer surface suggest that the mean thickness of the sepiolite fibre was ∼12 nm. The effective size of the channels was estimated from the number of various-sized molecules sorbed by the sepiolite, the results showing that molecules larger than benzene could not migrate into the channels.

The Neogene volcanic region of Cabo de Gata, Almería, SE Spain, is dotted with many outcrops of bentonite, some of them of significant economic interest. The bentonites have their origin in the hydrothermal alteration of pyroclastic rocks (15-7 Ma). The deposits are usually associated with fractures. The major mineral is a dioctahedral Fe- and Mg-smectite (89-75%) and this is accompanied by minor amounts of feldspars, quartz, amphiboles, pyroxenes, biotite, zeolites, disordered tridymite, calcite, etc. This paper describes the geological background, the general characteristics of the bentonites and major aspects of their formation, e.g. type of low-temperature hydrothermal solutions, mass balance, chemical evolutions of the smectites and geochemistry of trace elements. Finally, the characteristics of three of the most important deposits are described.

Natural zeolites have traditionally been used as supplements in animal nutrition with positive effects in terms of either faster growth or reduced incidence of diseases and death. The discovery that natural zeolites may act as drugs or coadjutants in pharmaceutical preparations has greatly enlarged the field of their applications in many sectors of biology and medicine, opening unexpected horizons for either basic or applied research. This review updates the state of the art of research in this sector, focusing on clinoptilolite-rich materials, with two main purposes: (1) trying to rationalize this subject, which is extremely variable and heterogeneous, and (2) raising doubts about unsuitable uses of natural zeolites in the light of their known properties and expected behaviour.

The thermal decomposition of hydrotalcite (HT), with chemical composition Mg1-xAlx(OH)2(CO3)x/2.(1-3x/2)H2O, (0.20 < x ≤ 0.33), is a complex sequence of dehydration, dehydroxylation and decarbonization and leads to the formation of a series of metaphases: HT-D (dehydrated HT), HT-B (partially dehydroxylated HT) and MO (mixed oxides with periclase-like structure). The evolution of water and CO2 in natural and synthetic hydrotalcites (a Mg/Al ratio between 2:1and 3.7:1), heated to 800°C, was investigated by differential thermal analysis, thermogravimetry and evolved gas analysis. At least six endothermic and two exothermic effects were established by computer-aided resolving of the curves. The formation of each HT metaphase was related to the release of a discrete number of water molecules depending on the Al content in the samples and each appeared as a corresponding endothermic peak in the DTA curves. The exothermic processes associated with the crystallization of HT-B and MO metaphases were specified by decomposition of DTA curves. The evolution of CO2 during the thermal decomposition of the carbonate groups was found to be different for the samples studied. The preservation of CO3 even at high temperatures was established for synthetic samples with a high Al content. The release of volatile H2O and CO2 (which comprise ~40% of the sample mass) provokes fine cracking both along and across the layers.

Infrared spectroscopy in the mid-IR region was used to follow the structural changes occurring in five Li-saturated dioctahedral smectites upon heating. The smectites included three montmorillonites, an Fe-beidellite and a ferruginous smectite. Fixation of Li+ ions in the structure even upon heating at 120°C caused the appearance of an AlMgLiOH-stretching band near 3670 cm–1 in the spectra of all three montmorillonites. This band confirmed the presence of Li(I) in the previously vacant octahedral positions in montmorillonites. No similar band was observed in the spectra of ferruginous heated smectites with prevailing tetrahedral charge. A gradual upward frequency shift and decrease in intensity of the AlAlOH-bending band showed that Li(I) present in the hexagonal cavities causes pronouncedperturbation of this OH-bending mode. The Li(I) present in the octahedral sheets causes small perturbations of the OH-bending mode near 850 cm–1 and activation of a new OH-bending mode near 803 cm–1. Reversible changes in the positions of the stretching Si–O and bending OH bands in the spectra of Fe-beidellite and a ferruginous smectite proved that Li was present in these minerals primarily in the hexagonal holes of the tetrahedral sheets.

Mixed-layer clay minerals of illite-smectite, having smectite contents ∼25% and IS ordering, kaolinite-smectite, and a three-component variety with kaolinite-smectite-chlorite-like material are described from a Carboniferous paleosol in South Wales. The clays, which are restricted to particular horizons, are unusual occurrences in a pedogenic sediment and pose particular problems as to their genesis. Positive geological evidence, principally in the form of mineralogical and organic thermal maturation data, demonstrates that the rocks of the region cannot have reached diagenetic temperatures > 100°C. This would appear to suggest a pedogenic rather than a diagenetic origin for these clays. In these sediments the only plausible mechanism of illitization to produce the illite-smectite would be by repeated wetting and drying cycles causing irreversible K fixation. Such cycles would be entirely realistic for a vertisol-like paleosol formed on overbank deposits in a floodplain environment subject to strong seasonal moisture contrasts. If this interpretation is correct, this illite-smectite represents the most illitic yet recorded from a non-burial or non-hydrothermal environment.

A survey of the clay fraction at the surface of 86 loam and silt loam agricultural soils from the Central United States was undertaken to observe the possible influences of climate and parent material (dominantly phyllosilicates in this study) on the clay mineralogy of the upper portions of the soils, for the most part in Mollisol–Alfisol order soils.

Decomposed X-ray diffraction spectra show that the most abundant clay minerals are two disordered illite-smectite (I-S) minerals, one with ∼50% smectite layers and another, less abundant, disordered I-S phase with 20% smectite. These minerals usually co-exist in the same samples. The charge site in both of these I-S minerals is both beidellitic and montmorillonitic in the expanding layers. A relatively large proportion of these smectite layers (up to 20%) are of high charge.

There seems to be a convergence in mineralogy towards mixed-layer phases formed under a range of mid-Continent climates from a range of phyllosilicate parent materials.

Experiments carried out in the author's laboratory on the artificial weathering, in an open system, of potash felspar, albite, leucite, tremolite, olivine, sideromelane, muscovite, and clay minerals are reviewed. The results are assessed, and eventually compared on the basis of the amount of SiO2 removed after leaching with 4 1 solvent.

Seven samples, representative of all zones of the Upper Chalk in the Arundel area of Sussex, were treated with acetic acid and the residues analysed to determine their mechanical and mineralogical compositions. The sand and silt fractions of the residues consist mainly of flint and opaline silica, collophane, limonite, and quartz, and the clay fractions consist of montmorillonite, mica, quartz, and apatite. Authigenic apatite and quartz occur in the clay and silt and authigenic alkali feldspar in the silt. The montmorillonite may also be authigenic.

The amounts of potassium retained, after exchange with normal ammonium acetate solution at pH 7, were measured with six montmorillonite-beidellite minerals, whose interlayer charge ranged 0·72-1·00 M+/Si8O22 and where tetrahedral substitution of Al for Si ranged 0·14-0·93 M+/Si8O22. The amount of potassium retained increased with increasing interlayer charge, but there was no correlation between the amount of potassium retained and the tetrahedral charge.

The nickel arsenate KNiAsO4 has a mica-like layer structure with surface charge densities similar to brittle micas. In contrast to micas it easily exchanges alkylammonium ions. The interlayers have paraffin-type chain arrangements, as in alkylammonium vermiculites and alkylamine smectites and vermiculites, but the very regular chain packing causes a marked odd/even alternation of the basal spacings. The reactions of KNiAsO4 throw light on the exchange behaviour of micas.

Mine-drainage waters and associated precipitates from several active and abandoned lignite mines and mine dumps in the Sokolov Basin, northwestern Czech Republic, were sampled and analysed. The data showed considerable variations of effluent composition and pH that can generally be related to differences in the local microenvironments. Temporal changes such as seasonal fluctuations of precipitation, leading to variations of water infiltration through and runoff over mines and mine dumps, were also observed to noticeably affect effluent composition. These variations have led to a wide range of precipitates, the principal constituents of which are generally one or several of the ferric minerals jarosite, schwertmannite, goethite, ferrihydrite and lepidocrocite.

The present paper consists of two parts: a short review of the genesis and properties of the named minerals, and a study of mine-drainage precipitates formed under different local conditions in various lignite mines and mine dumps of the Sokolov mining district. We show that variations in mine-drainage precipitate mineralogy, such as the presence or absence of specific ‘key’ minerals, can serve as indicators for factors such as the pH and sulphate concentration, and thus — with certain limitations — for the genetic environment during precipitate formation. Such variations in composition are reflected, among other properties, in the precipitate colour, which can therefore be used for a rapid identification and classification — both in the field and by remote sensing — of regions that are potentially prone to acid mine drainage.

Analysis of the distribution of gibbsite in soils and saprolites of Galicia, NW Spain, leads to the conclusion that this mineral is mostly formed by inorganic mechanisms in open, well-drained and desaturated systems in the initial stages of weathering of various aluminosilicates, especially plagioclases. No evidence has been found to support the hypothesis that it is a feature inherited from hotter climates, as it has not been identified to date either in ancient sediments or in the most evolved and weathered soils. The role of organic matter and the possibility ofa biogeochemical origin is also discussed: it is considered that this mechanism is only important during podsolic soil development.

Changes which occur during the natural weathering of biotite in granite gneiss and associated soils are measured by microanalysis and illustrated by SEM. Biotite weathers through a series of interstratified minerals to vermiculite and/or smectite phases which decompose rapidly to kaolinite. Both vermiculite and smectite phases appear to be dioctahedral, on the basis of chemical compositions derived from microprobe data. Weathering products are first apparent on the edges of laminae, where interstratified minerals are formed at right angles to both the edge face and the cleavage. Weathering soon develops along cleavage planes, initially most strongly near the edges of flakes, but then permeating extensively into the body of flakes and subdivided segments. The orientation of interstratified minerals and kaolinite within cleavages is parallel to the cleavage.

The weathering of a trachytic pumice within a pyroclastic flow underlying an andic-brown soil on the volcano Vico has been studied. The main mineral formed is a spherical 10 Å halloysite which has been shown by SEM and in situ microprobe analysis to have formed directly from the glass. The major mineralogical characteristics as determined by XRD, IR, DTA, TEM and microdiffraction are typical of 10 Å halloysite. However, some minor mineralogical properties and the high Fe and K contents, suggest that it is an interstratification of 74% halloysite and 26% illite-smectite. The calculated formula of the hypothetical 2:1 minerals reveals an Fe- and K-rich clay, with high tetrahedral substitution, like an Fe-rich vermiculite, but the detailed structure of this mineral remains uncertain.

Cationic dye, methylene blue (MB), was intercalated into films of expandable clay minerals with low, moderate and high layer charges (saponite, montmorillonite and synthetic expandable mica-fluorohectorite, respectively) . Tilted orientation of the dye cations on the silicate surface was observed by polarized ultraviolet-visible (UV-Vis) transmission spectroscopy. The tilting angle of the dye cations increased with the formation of high-order H-aggregates that absorb light at 525 nm. These dye species were formed only on the surface of fluorohectorite, which has the highest layer charge, and exhibited dichroism. Models for the orientation of MB cations on a clay surface were proposed based on MB orientation models previously reported, and compared with the basal spacings determined by X-ray diffraction.

Pelitic and basic rocks occurring within prograde sequences in Portugal, Spain and Hungary have been studied by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The minerals formed in typical prograde reactions define the general sequences, but smectite, chlorite-smectite (corrensite) and/or berthierine were found to have replaced chlorite, whereas kaolinite and mixed-layer illite-smectite replaced illite-muscovite. Alteration occurred under conditions normally associated with diagenesis, subsequent to regional metamorphism, and we therefore refer to such processes with the term “retrograde diagenesis”. In the cases studied and in other cited examples, reactions occurred on a regional basis via pervasive fluids under open-system conditions inferred to be related to tectonic stress. The observed alterations could generally not be inferred from XRD data, although the presence of pure smectite in sediments other than bentonite is suggestive of retrograde relations, especially where other minerals are consistent with a higher grade of diagenesis. Retrograde diagenesis is readily observed through imaging of textures by TEM, however. Textural features show that retrograde reactions are more common than generally assumed, and that care should be used in interpreting geological events where appropriate textural relations are not seen.

There is increasing research interest in potential applications of halloysite as fillers for polymer composites, controlled drug delivery, carriers for the supply and sustained release of active agents for anticorrosion coatings, in nanoreactors or nanotemplates, and for the uptake of contaminants or pollutants and support for catalysts. In this review, recent findings in terms of the prospects and challenges of using halloysite nanotubes (HNTs) in different polymeric matrices targeting a range of old and new applications are discussed and evaluated. The compositions include chitosan/halloysite membranes as bone-tissue scaffolds, polylactic acid (PLA)/halloysite membranes for food-packaging applications and their antimicrobial activities, instrumented impact properties of epoxy/halloysite nanocomposites and the role of halloysite in the self-healing of epoxy composites, polyacryronitrile (PAN)/halloysite membranes for use in water filtration as well as a review of some recent applications of halloysite/alginate beads in the adsorption of contaminants such as lead.

Six clays from volcanic ash soils at different stages of weathering differ in their relative halloysite content with respect to kaolinite and several surface properties, namely CEC, and exchange selectivity for K+. These three parameters are related to each other in that they all decrease with increasing soil weathering stage. XRD data show that the hydrated 1:1 layer-silicates in these clays combine with smectite to form interstratified H/Sm clay minerals. In these mixed-layers, the content and layer charge of smectitic units decrease as the relative halloysite content in the clay decreases. These clays thus depict a weathering sequence that is parallel to the weathering sequence of the soils from which they originate. It is also shown that the smectites in the H/Sm minerals have the distinctive composition and ESR spectrum of Fe-rich 2:1 clay minerals belonging to the beidellite-nontronite series. The information obtained explains why these clays have high CEC and distinct affinities for K+. It is hoped that this study will help to clarify the controversy concerning the CEC and related surface properties attributed to hydrated halloysite.

The impact of diagenetic processes on petroleum entrapment and recovery efficiency has focused the vast majority of the world's conventional oil and gas resources into relatively narrow thermal intervals, which we call Earth's energy “Golden Zone”. Two key mineralogical research breakthroughs, mainly from the North Sea, underpinned this discovery. The first is the fundamental particle theory of clay mineralogy, which showed the importance of dissolution/precipitation mechanisms in the formation of diagenetic illitic clays with increasing depth and temperature. The second is the surface area precipitation-rate-controlled models for the formation of diagenetic cements, primarily quartz, in reservoirs. Understanding the impacts of these geological processes on permeability evolution, porosity loss, overpressure development, and fluid migration in the subsurface, lead to the realization that exploration and production risks are exponential functions of reservoir temperature. Global compilations of oil/gas reserves relative to reservoir temperature, including the US Gulf Coast, have verified the “Golden Zone” concept, as well as stimulated further research to determine in greater detail the geological/mineralogical controls on petroleum migration and entrapment efficiency within the Earth's sedimentary basins.