Discrepancies between clay mineral and organic indicators of very low-grade metamorphism have been observed from the Southern Uplands of Scotland. In the Southern Belt, I-S expandability ranges from 18–5% and chitinozoan reflectance from 0·8–2·1% R0 mean; a clear correlation exists between I-S expandability and organic maturity. At Dob's Linn in the Central Belt, I-S expandabilities range from 18–10%, and chitinozoan reflectance from 3·6–4·8% R0 mean. The results from Dob's Linn show anomalously high I-S expandabilities with respect to maturity, both in comparison with the Southern Belt and with previous work from other regions. K-feldspar is present in variable amounts in the Southern Belt, but is not detectable by XRD at Dob's Linn. Low K+ activity is believed to have resulted in a slower reaction rate at Dob's Linn, and a consequent “lag” in I-S expandability with respect to the Southern Belt.

Zn-Al layered double hydroxides (LDH), before and after calcination, were tested for the removal of indigo carmine (IC) dye from solution. These LDH photocatalysts were characterized by powder x-ray diffraction (PXRD), Fourier transform infrared (FTIR) spectroscopy, thermogravimetry/differential thermogravimetry (TG/DTG), nitrogen physisorption at −196°C, scanning electron microscopy (SEM) and diffuse reflectance spectrophotometry (DRS). The different photocatalysts were supported on polyacrylonitrile (PAN) nanofibres, so that filtration was unnecessary.

The PXRD and FTIR analyses showed that the IC adsorption on c-Zn-Al-3-500 (LDH calcined at 500°C) was enhanced by construction of the hydrotalcite matrix intercalated with the dye. The intercalation was clearly evidenced by the appearance of a peak at low °2θ values. All of the materials prepared exhibited photocatalytic activity, which for the c-Zn-Al-3-500 was comparable to that of commercial PAN-supported ZnO nanoparticles (100% degradation after 180 min). Kinetic studies showed that the degradation of the IC followed a pseudo-first order rate. The high activity and the ease of both synthesis and separation processes rendered this photocatalyst a promising candidate for environmental remediation.

The chemical and structural stability of a Spanish sepiolite from Vallecas, Spain, was studied in 0.04 n NaOH (pH = 12.6), a saturated solution of Ca(OH)2 (pH = 12.6) and deionized/distilled water (pH = 7). The chemical stability was evaluated by determining the concentrations of Mg, Si and Ca in the solid residues during the kinetic test. The structural stability was studied by determining the changes in specific surface area and ‘crystallite’ size. The specific surface was determined by the BET method and the ‘crystallite’ size by the profile of the X-ray diffraction line. The main conclusion was that sepiolite is a material with high chemical stability in neutral and alkaline media, with no significant structural changes. However, in alkaline media, greater dissolution of silica was observed than in neutral media, the silica being derived from the most external tetrahedra attached to the OH− groups.

Adsorption of Cs on two samples of marl with different calcite, quartz and clay contents and surface areas of ∼10 m2/g was followed using the batch sorption technique. The experiments were carried out in an atmosphere of N2/1% CO2 using a synthetic groundwater of pH 7·3 and an ionic strength of 0·1 m. The initial Cs concentration ranged from 10−8 to 10−4m. Sorption of Cs was non-linear, fast and reversible. At equilibrium Cs concentrations <10−8m, an isotope exchange mechanism appeared to operate, whereas at higher concentrations, sorption involved ion exchange. The distribution coefficients ranged from 23–995 ml/g. They varied markedly with rock/water ratio; this variation could be explained in terms of the non-linear isotherm displayed by Cs. Although the two samples of marl differed in composition, uptake of Cs on both samples was very similar because the content of the principal sorbing component (illite) was the same in both samples.

The mechanism of colour reactions of clay minerals with amines, diphenylpicrylhydrazyl, tetracyanoethylene, and leuco bases are elucidated, and the results used as a guide to the reaction mechanism of polymerization reactions catalysed by clay surfaces.

Sorption of an acidic, amphoteric, sulphur containing and basic α-amino-acid (glutamic acid, glycine, methionine and lysine) by copper montmorillonite was studied by chemical and X-ray methods. With glutamic acid complex formation occurs only in solution but increasing basicity of the aminoacid favours complex formation in the clay interlayers.

The use of electron microscopy to study clay microfabrics in thin-sections is discussed. A technique is described to isolate undisturbed microparts of pedofeatures from thin-sections, which are subsequently used for TEM analysis. Re-embedding with a polyester resin of undisturbed, in situ, neoformed clay microfabrics, obtained by microdrilling and preparation of ultrathin sections by microtoming with a diamond knife are emphasized; these steps enable micromorphology, clay mineralogy, microchemical and HRTEM analysis to be performed on one unique microsample of clay fabrics, with conserved micro-organization. Two examples on clay neoformation are presented to demonstrate that this technique can successfully be applied to unravel the impact of mineral alteration and clay neoformation in undisturbed soil samples on a micro- and a nanometer scale.

The alteration of thirty-nine trioctahedral micas to vermiculite has been characterized by the K level, which is determined by repeated measurements of the stationary K concentration in the altering solution and provides a practical way of comparing the sensitivity to alteration. A calculated regression equation allows the K level of a sample to be predicted from its chemical composition. The model proposed for the alteration reaction outlines the physico-chemical meaning of the K level, with its experimental and theoretical limitations.

Veins of intimately associated fibrous and granular saponitic clay occur in a basalt quarry at Orrock, Fife, Scotland. Preliminary X-ray diffraction studies suggested that both fibrous and granular forms consisted of pure saponite but chemical and thermal studies showed the presence of subsidiary amounts of interstratified chlorite. The fibrous clay, which is strongly oriented around the a axis but with a uniform distribution of the b and c poles, consists mainly of highly-crystalline laths with minor amounts of turbostratically-ordered particles. The granular clay consists of turbostratically-ordered particles only. The swelling behaviour of both types of clay in water and in ethylene glycol is similar to that of pure saponite. With glycerol, only the granular clay swells completely but the fibrous clay behaves similarly if first subjected to grinding or chemical pre-treatment. These observations are accounted for on the basis that the fibrous clay has better order than the granular form, thus enabling the interlamellar constituents to participate more fully in layer-to-layer bonding.

Accessory green ferric clay occurs in fluvial litharenites of the Early Triassic Rewan Group. Although resembling glauconitic minerals in thin-section, electron microprobe analyses indicate that the green ferric clay is mainly ferric illite. The ferric illite may have formed in a small hypersaline lake or well drained, flood-plain soil, and its presence in the Rewan Group cannot be used to support a notion that the unit is partly marine influenced. Identification of the ferric illite by electron microprobe analysis shows that some green ferric clays, particularly those that resemble glauconitic minerals optically, may require precise quantitative elemental analysis before they can be used as a basis for environmental interpretation. Green ferric clay in the Rewan Group also includes detrital celadonite that most likely originated in a volcanic arc setting.

The general effect of grinding upon various minerals and the manner in which time of grinding affects cation-exchange capacity, etc., have been known for some time, but relatively little information is available upon the micas (Jackson and Truog, 1939; Kelley and Jenny, 1946; Parkert et al., 1950; Mackenzie and Milne, 1953). This, coupled with an observation made here on the pronounced effect of short-period grinding on muscovite, has led to a more detailed examination of the effects induced by such grinding upon some micas. Since the data for muscovite are completely discussed elsewhere (Mackenzie and Milne, 1953) only preliminary experiments upon biotite and vermiculite are recorded here.

The regional distribution, mineralogy, petrology and chemistry of the detrital and authigenic clay minerals associated with the Permo-Triassic strata (excluding the Rotliegend: see Ziegler, 2006; this volume), of the onshore and offshore regions of the British Isles are reviewed within their stratigraphical framework. The origin of these clay minerals is discussed in relation to current hypotheses on the developments of the Mg-rich clay mineral assemblages associated with the evaporitic red-bed Germanic facies of Europe and North Africa.

Composite clay mineral successions are described for seven regions of the British Isles — the Western Approaches Trough; SW England; South Midlands; Central Midlands; the Cheshire Basin; NE Yorkshire; and the Central North Sea. The detrital clay mineral assemblages of the Early Permian strata are variable, consisting of mica, smectite, smectite-mica, kaolin and chlorite, whereas those of the Late Permian and the Trias are dominated by mica, usually in association with minor Fe-rich chlorite. The detrital mica consists of a mixture of penecontemporaneous ferric mica, probably of pedogenic origin, and recycled Pre-Permian mica. In the youngest Triassic strata (Rhaetian), the detrital clay assemblages may contain appreciable amounts of poorly defined collapsible minerals (irregular mixed-layer smectite-mica-vermiculite) and kaolin, giving them a Jurassic aspect. There are two types of authigenic clay mineral assemblages. Kaolin may occur as a late-stage diagenetic mineral where the original Permo-Triassic porewaters of the sediment have been replaced by meteoritic waters. A suite of early-stage diagenetic clay minerals, many of them Mg-rich, are linked to the evaporitic red-bed facies — these include sepiolite, palygorskite, smectite, irregular mixed- layer smectite-mica and smectite-chlorite, corrensite, chlorite and glauconite (sensu lato). The sandstones and mudstones of the onshore regions of the British Isles display little or no difference in their detrital and authigenic clay mineral assemblages. In contrast, the sandstones of the offshore regions (North Sea) show major differences with the presence of extensive chloritic cements containing Mg-rich and Al-rich chlorite, irregular mixed-layer serpentine-chlorite, and mica.

Polycyclic aromatic hydrocarbons are increasingly widespread pollutants introduced into the environment via oil spillage and incomplete anthropogenic combustion of fossil fuels. In this work, the capacity of stevensite and sepiolite to adsorb phenanthrene (PHE) has been evaluated experimentally by batch testing. Both clay minerals are distributed widely in the Madrid Basin, are of low cost and can be applied with minimal environmental impact. In the context of few previous studies, adsorption isotherms have been developed to understand the adsorption mechanisms and were fitted to the Freundlich and linear models with virtually the same results. Although stevensite showed greater adsorption capacity than sepiolite, the isotherms were constructed for equilibrium concentrations up to 0.8–1.0 mg/L due to the low solubility of PHE in water. When compared to other adsorbents the ability of stevensite to retain PAHs should be examined further in order to add and complement novel functions in reactive barriers.

The thermal dehydration of a series of smectites has been investigated by X-ray methods. It has been found that the rate of collapse of the layers is governed by the type of exchangeable ion present.

The high temperature changes of a new saponite have been investigated. The saponite dehydrates to talc and then to enstatite, the 5·2Å fibre axis remaining constant throughout.

Mixed-layered phyllosilicates with composition intermediate between mica and chlorite were identified in very low-grade metaclastites from the Malàguide Complex (Betic Cordilleras, Spain), and studied by X-ray diffraction, and transmission and analytical electron microscopy. They occur both as small grains in the rock matrix, and associated with muscovitechlorite stacks. Transmission electron microscope observations revealed a transition from chlorite to ordered 1:1 interstratifications through complex 1:2 and 1:3 interstratifications. Analytical electron microscopy data indicate a composition slightly different from the sum of discrete trioctahedral chlorite and dioctahedral mica. The types of layer transitions suggest that mixed-layer formation included two main processes: (1) the replacement of a brucite sheet by a cation sheet in the chlorite structure; and (2) the precipitation of mica-like layers between the chlorite layers. The strongest diffraction lines in oriented X-ray patterns are: 12.60 Å (002), 7.98 Å (003), 4.82 Å (005) and 3.48 Å (007).

Transmission electron microscope-analytical electron microscope analyses have been carried out on secondary minerals from pillow basalts with various degrees of alteration from the Juan de Fuca Ridge (ODP Leg 168). The electron microscopic data indicate that the alteration products consist mainly of phyllosilicate mixtures. The least altered sample shows poorly crystalline phyllosilicates occurrring as flakes with 10 Å -spaced lattice fringes. They have compositions of celadonite mixed with smectite and/or Fe oxyhydroxides and Mg-rich smectite. Proceeding towards older, more altered basalts, the alteration products consist of: (1) poorly crystalline celadonite mixtures and Mg-rich smectite; and (2) phyllosilicates with a higher degree of crystallinity, showing lattice fringes with 9.1 Å -spacing and with a talc-like composition. Changes in phyllosilicate association occur as the type of alteration changes from an oxidizing, water-dominated system (occurrence of celadonite mixtures with Fe hydroxides) to a reducing, rock-dominated system (occurrence of Fe-smectite and talc-like mixtures).

L'étude de l'adsorption des acides fulviques, des acides humiques ou de leur mélange par la montmorillonite saturée avec du calcium ou de l'aluminium permet de: (i) définir les mécanismes de fixation des substances humiques en phase aqueuse; (ii) préciser une orientation différente des moécules adsorbées selon leur nature; acides fulviques ou acides humiques; (iii) caractériser une forte sélectivité d'adsorption pour les molécules les moins polymérisées.

A partir de ces résultats, il est montré que, d'une part, la flexibilité des molécules est un paramètre important pour les propriétés de sélectivité et, d'autre part, les acides humiques ne peuvent pas être considérés en équilibre avec les acides fulviques.

Commercial bentonite from the Kopernica deposit, Slovakia, is currently mined by the CERTECH Company, Poland, to produce materials intended for animal-care applications and other industrial purposes. The present study aimed to assess the mineralogical, petrographic and physicochemical characteristics of three bentonite varieties from Kopernica used by the company. The X-ray diffraction, optical microscopy, field emission scanning electron microscopy (FESEM), nuclear magnetic resonance, thermal analysis, infrared spectroscopy and chemical analyses showed that the main component of the rocks is montmorillonite with the average structural formula Ca0.31K0.08Na0.04(Al3.23Mg0.54Fe0.23)[(Si7.80Al0.20)O20](OH)4. In addition, opal-C/CT, biotite, potassium feldspar and plagioclase, quartz, clinoptilolite and kaolinite are present. Key information about the textural relationships between the mineral components identified was obtained from detailed thin-section petrography and FESEM studies. The rocks studied have fragmented, eutaxitic texture. They are composed of pumice fragments collapsed into lenticular masses (fiamme) which were strongly deformed and altered, though the shard structures were retained. The compressed glass shards were moulded around pyroclastic grains such as crystal fragments of quartz, biotite and zoned plagioclases, and clasts of volcanic rocks. Observations by FESEM showed that the axes of shards and the walls of the flattened vacuoles are outlined by the inward-growing microlites of silica (axiolitic texture), whilst the interiors of shards are altered to clay. Grain-size distribution, textural properties and microscope observations of grain-size fractions reveal that the Kopernica bentonite contains montmorillonite-opal aggregates difficult to disperse in water.

The term ferrihydrite, originally defined as a poorly ordered hydrous ferric oxide exhibiting five or more distinctive X-ray diffraction maxima, has come to be extended to include species that exhibit only 4, 3 or 2 of these maxima. It is pointed out here that hisingerites may exhibit a similar 2-line diffraction pattern. The laboratory synthesis of hisingerites show that they can form under soil conditions. Acid oxalate buffer of pH 3, a reagent considered a fairly specific solvent for ferrihydrite, extracts the iron content of these synthetic hisingerites quantitatively.

From this investigation it was hoped to obtain information about the position of the exchangeable cations. That they take up a position between the layers of the mineral seems obvious from the varying c spacing of dried montmorillonite saturated with different ions, but in the complexes with water and organic liquids it was not known whether the ions remained close to the layers or were removed from them. It was also hoped that the Fourier syntheses would give some information about the actual layer structure of the mineral (montmorillonite) and thereby lend support to one of the two suggested structures, those of Hofmann, EndeU and Wilm on the one hand and of Edelman and Favejee on the other.

The montmorillonite used was a sample of Wyoming bentonite separated on the Sharples supercentrifuge. In order to get as large a contrast as possible between the two syntheses it was decided to use Li+-saturated montmorillonite and Ti+-saturated montmorillonite.