Regional differences in clay mineralogy are found in British Lower Palaeozoic slate belts formed during Caledonian terrane amalgamation. Extensional basins in Wales, the northern Lake District and the Isle of Man are characterized by a greater diversity of species in clay mineral assemblages. Slates that evolved in these basins contain both the K- and Na-rich products of the 2:1 dioctahedral reaction series. Pyrophyllite, rectorite and corrensite are sporadically distributed but kaolinite is rarely recorded even in lowest-grade mudstones. In contrast, clay assemblages that evolved in the convergent basins of the Scottish Southern Uplands and northern England generally contain fewer mineral species, and Na-micas and pyrophyllite are rare or absent. Na-bearing clays may have been generated from low-temperature mixing of hydrothermal fluids and seawater in the extensional basins. Such fluids appear to have been unavailable in the convergent basins through lack of volcanic activity in the early stages of basin development.

Mixed-layer minerals with optical properties similar to metamorphic vermiculite were identified in rocks belonging to a Palaeozoic and a Triassic formation separated by an angular unconformity and exposed in the Coastal Range of central Chile. Both formations are affected by low-grade metamorphism. The mixed-layer minerals were studied by optical microscopy, X-ray diffraction (XRD), electron microprobe (EMPA), and transmission/ analytical electron microscopy (TEM/AEM). Two types of phyllosilicates were identified: chlorite-vermiculite and mica-chlorite, which are present in the Palaeozoic and Triassic rocks respectively. Chlorite-vermiculite mixed layers form packets with well-defined boundaries and mainly show 1:1 ordered sequences. On the contrary, mica-chlorite mixed layers show, in most cases, random sequences evolving laterally toward chlorite. The AEM data indicate compositions close to that of chlorite in the ternary Si-Al- (Fe+Mg+Mn) diagrams for both types of mixed-layer phyllosilicates. Relative to the coexisting chlorite, they have lower (Fe+Mg) contents, and a higher Si/Al ratio. They are interpreted as products of the transformation of chlorite, developed during prograde metamorphism, and probably represent intermediate, metastable phases, in the chlorite to biotite transformation.

Amorphous silicate sediments comprise most of the upper part of the sedimentary column of the Atlantis II Deep, whereas more crystalline phases are found in the lower part. The objective of this study was to focus on the newly-formed, metastable, hydrothermal phases, that eventually transform into clays or Fe oxides.

Short-range ordered Si-Fe phases (Si/Fe = 0.2 0.6) rounded to elliptical in shape, and amorphous Si-Fe platy phases (Si/Fe = 0.09 pure Si) comprise some of the amorphous sediments in Atlantis II Deep. The rounded particles have distinct electron-dense (thicker, relatively ordered) margins and a less crystalline inner core. They have rhombohedral symmetry with unit-cell parameters of a= 0.504 nm and c= 1.08 nm. They presumably transform into crystalline clay minerals in statunascendi(at the formative stage) in the sediments. Synthesis in NaCl brines designed to simulate crystallization of the rounded particles, was performed successfully. Similar rounded phases (Si/Fe = 0.26) were synthesized under saline, neutral, hydrothermal conditions (40°C, pH 7, 2 M NaCl) with initial Si/Fe = 1.5. We suggest that the metastable rounded particles precipitate from the hot brine created by the encounter between Red Sea Deep Water and the hydrothermal brine underneath. Within a few thousands years they disintegrate and transform into clay minerals, probably nontronite.

Spongolite from the State of Mato Grosso do Sul, Brazil, contains the remains of fossil sponges and hollow needles or microcapillaries with uniform surfaces. The central tunnels are ∼1/10 to 1/2 of the cylinder's diameter. The material is essentially X-ray amorphous though it contains small amounts of orthosilicic acids. The other main elements were Ti and Fe. Spongolite may have uses as a sorbent, as a bioavailable silicon source or, after blending with glass waste, it can be used in the fabrication of lightweight products having a closed-cell structure, potentially useful as an industrial insulator.

Dickite occurs over wide areas along the Italian Apennines strip throughout Italy, mainly in the allochtonous ‘varicoloured’ clay-shale formation. Morphological, fabric and crystallochemical features suggest an authigenic origin, from pore solutions. The nature of the solutions and the process of dickite formation, including hydrothermalism, diagenesis or supergene evolution have all been discussed. Stable isotope analysis (O, H) was performed to investigate these points. The δD values of dickite range between −63.7 and −79.1% (SMOW) and δ18O between +21% and +16.1‰ (SMOW), and are similar to those reported for kaolinites formed in equilibrium with meteoric waters. The data fall along the ‘Line of Meteoric Kaolinites’, supporting an origin involving meteoric waters and low temperatures. The isotopic compositions of the waters are within the range of Apennines meteoric water, and the temperatures derived are close to surface conditions. Contributions of diagenetic, hydrothermal or metamorphic waters must be discounted. The authigenic dickite from ‘varicoloured’ clays of the Italian Apennines formed by precipitation from flushing meteoric waters whose ingress was favoured by repeated surface erosion.

Chlorites from Cambrian basaltic vesicular lavas, characterized by relatively high Xc (0.81-0.98), gave temperatures of formation of 285 to 350°C (Cathelineau's empirical geothermometer). Both the Xc and temperature calculations gave results which were too high for the diagenetic conditions indicated by the interbedded shale mineralogy. The HRTEM and XRD studies indicate the absence of smectite layers in these chlorites; i.e. according to lattice images, the actual value of Xc is 1. The chlorite composition in these basaltic lavas must, therefore, be explained in relation to their whole-rock geochemistry, with which a good correlation has been found. The basaltic lavas are characterized by relatively high FeO/M ratios (3.28±1.66) and must be considered as an Fe-rich system, with similar chemical behaviour to pelitic rocks. In these cases, direct chlorite formation, without a previous smectite precursor, is a normal occurrence and the Xc calculation and empirical geothermometric calculations are inadequate.

An Fe-rich smectite from Ölberg (Germany) was characterized using X-ray diffraction, infrared spectroscopy and analytical electron microscopy. Progressive reduction of the octahedral charge was performed through the Hofmann & Klemen effect at increasing temperatures. The sample was heterogeneous, consisting of two smectite populations. One population, which comprises a minor portion of the sample, is an ‘Fe3+-montmorillonite’ with little or no tetrahedral charge and Fe3+ as the major octahedral cation. The other population, a major constituent of the sample, contains less Mg and more Al than the first one and exhibits some tetrahedral charge. This fraction may be considered as an inter-grade between nontronite (dominant tetrahedral charge) and Fe3+-montmorillonite (dominant octahedral charge). These two populations may occur as separate particles but also as interstratified layers.

Opaline silica residue accumulates on the surface and in the near surface of the Te Kopia, Tikitere and Rotokawa geothermal fields, where rhyolitic tuffs are attacked by steam condensate, made acid (pH 2–3) by sulphuric acid produced by oxidation of H2S that accompanies steam discharge. Silica residue is one product of this alteration process that also yields kaolinite, sulphur, sulphide and aluminous sulphates, including alunite and alunogen, as pH, Eh and available moisture fluctuate across the field surface. Coagulation of colloidal polymeric silica or, possibly, direct deposition of monomeric silica can occur from the acid solutions of the digested country rock, depending on pH, concentration, temperature and the presence and concentration of other species. As with silica sinter, the first-formed silica phase consists of disordered opal-A microspheroids, commonly 0.1–5 μm in diameter. These coalesce and become overgrown by further opaline silica to yield a mass resembling gelatinous ‘frog spawn’ that lines cavities and envelops surfaces. This mass is the principle component of botryoidal, transparent to translucent hyalite that comprises much residue. Following deposition, this juvenile residue may crystallize to opal-CT lepispheres, 1–3 μm across and, subsequently, to chalcedonic quartz. Both the opal-A and opal-CT of the New Zealand residues are more disordered than those occurring in typical moderate- to low-temperature sinters. The opaline silica of silica residues enjoys a reaction relationship with both kaolinite and aluminium sulphates, including alunite and alunogen. These phases and the silica precipitate continuously and undergo dissolution at the surface of all three localities. The precise pathway followed depends upon the prevailing surface conditions, including humidity, pH, Eh, and Al and K activities. As Al is flushed from the system, the ultimate stage of alteration that may result is the dissolution of the silica itself in acidified rainwater, fogdrip or further steam condensate.

A natural phengite-2M1 of composition (K0.95Na0.05)(Al0.76Fe0.14Mg0.10)2 (Si3.25Al0.75)O10(OH1.96F0.04) [a= 5.2173(1) Å, b= 9.0493(2) Å, c= 19.989 (1) Å and β = 95.734(4)°] was studied using in situ high-temperature FTIR. Correlations to structural changes were made using previously-reported neutron diffraction data from the same sample. Correlations have been made between the microscopic atomic displacements (arising from thermal effects) and analogous macroscopic properties, such as bond strain and ditrigonal distortions. Spectra were collected in the far-infrared region to study the behaviour of the interlayer (K+) cation and also in the mid-infrared region to distinguish the Si–O stretching modes. We found anisotropic thermal expansion of the interlayer site. The K O bond length is divided into K Oouter and K Oinner, and the K–Oinner bond length is correlated with the far-infrared spectra. The thermal dependence of the correlation between K–O bond length and corresponding far-infrared stretching frequency is different from the effect of the chemical composition. We also found that the K–O bond strain could be successfully resolved into the sum of inner strain and lattice strain. The Si–O stretching mode, obtained from the mid-infrared measurements, showed only weak changes. However, the neutron refinement data showed different thermal behaviour for distinct crystallographic T-sites.

Bentonite samples from Choushan treated at various acid concentrations were studied using chemical analysis, XRD, 29Si and 27Al MAS NMR to investigate the microstructure of the activated montmorillonites. Two types of structural units were formed during the activation: (1) (SiO)3SiOH, in which up to 15% of Si is bound; (2) Q4(0Al), a major building unit when the acid concentration is >10%. A significant 27Al signal at 55.0 ppm was recorded for both untreated montmorillonite and (to a much greater extent) in acid-treated montmorillonites. This was interpreted as arising from four-fold coordinated Al located in the ‘bulk’ octahedral sheet of montmorillonite. In the course of activation, the removal of one of a pair of octahedral Al ions from montmorillonite removes two hydroxyl groups and leaves the other Al of the pair in four-fold coordination.

Hand-made bricks were manufactured from natural sediments by firing at 700°C and 800°C after which they were hydrothermally altered at 150°C in a high-pressure reactor for 1200 h. Sediments and fired pieces were studied by X-ray diffraction. The <2 μm size-fraction of fired and hydrolysed samples were also studied by X-ray diffraction and oxygen isotope analysis. The oxygen isotope composition of the samples became depleted in 18O by alteration. Our results are consistent with a process of hydration and hydroxylation of the partially destroyed clay minerals in the fired bricks. The work is relevant to understanding the origins and alteration processes in old ceramic materials.

Two soils, a haplic Podzol and a dystric Cambisol, developed from post-glacial tills, were studied with respect to their soil chemistry and clay mineralogy. Although the state factors (age, geology, topography, climate) of soil formation were almost identical, two different types developed. The E horizon of the Podzol contained more smectite, characterized by a montmorillonite-beidellitemixed phase. The neoformation of smectite could be traced back to the weathering of mica and chlorite. The Podzol had less hydroxy-interlayered smectite (HIS) in the surface horizons than the Cambisol. A larger amount of chelating compounds in the E horizon of the Podzol either transformed HIS into smectites or inhibited the formation of HIS and favoured the formation of smectites. The physical structure of the soil material is believed to be the most important factor in the different modes of soil evolution. The greater abundance of coarse pores in the topsoil at the Podzol site probably led to a faster eluviation of base cations, a different vegetation at ground level, and, consequently, to a faster soil evolution with the formation of spodic horizons.

Five vermiculite samples collected from Béni Bousera, Morocco and four from Palabora, South Africa were investigated by X-ray diffraction, chemical analysis, 57Fe Mössbauer spectroscopy, and 27Al magic angle spinning nuclear magnetic resonance. The X-ray diffraction studies indicate that all vermiculites have very similar crystallographic parameters. The chemical analyses and the NMR spectra indicate that the Béni Bousera vermiculites contain Al3+ cations in both octahedral and tetrahedral sheets and the Palabora vermiculites contain Al3+ in the tetrahedral sheet. The Mössbauer spectra indicate that the Béni Bousera vermiculites contain more Fe2+ cations than the Palabora vermiculites and do not contain tetrahedral Fe3+ cations. The different cation compositions and distribution in the two sets of vermiculites may result from different parent minerals, i.e. chlorite in the case of Béni Bousera and phlogopite in the case of Palabora, and different genetic processes, i.e. weathering in Béni Bousera and hydrothermal alteration in Palabora.

Mechanically-prepared binary mixtures of two dioctahedral smectites (of different chemical compositions) with two kaolinites (with different amounts of structural defects) were studied by infrared (IR) spectroscopy to verify the ability of IR spectroscopy to detect small amounts of individual components in the mixtures. The same samples were analysed by X-ray diffraction (XRD) in transmission and reflection geometries to compare the sensitivities of these techniques. Infrared spectroscopy is suitable for detecting small amounts of kaolinite in the smectite-rich samples but is not sensitive to small amounts of smectite in kaolinite-rich samples. The IR spectra of kaolinite/ smectite mixtures have a ‘strongly kaolinitic character’ even with only 30% kaolinite. The most characteristic band of kaolinite, near 3695 cm–1, gradually decreased in intensity with decreasing kaolinite content though the presence of this absorption allowed 0.5 mass % of both kaolinites to be detected in their mixtures with smectites. On the other hand, XRD powder techniques are much more adept at detecting low smectite contents in kaolinite-rich samples.

The purpose of this report is to describe the appropriate use of indices relating to crystallinity, such as the ‘crystallinity index’, the ‘Hinckley index’, the ‘Kü bler index’, and the ‘Árkai index’. A ‘crystalline’ solid is defined as a solid consisting of atoms, ions, or molecules packed together in a periodic arrangement. A ‘crystallinity index’ is purported to be a measure of crystallinity, although there is uncertainty about what this means (see below). This report discusses briefly the nature of order, disorder and crystallinity in phyllosilicates and discusses why the use of a ‘crystallinity index’ should be avoided. If possible, it is suggested that indices be referred to using the name of the author who originally described the parameter, as in ‘Hinckley index’ or ‘Kübler index’, or in honour of a researcher who investigated the importance of the parameter extensively, as in ‘Árkai index’.