Stable isotope and chemical compositions of vesicle- and fissure-filling smectites (i.e. montmorillonite and saponite) in Penghu subaerial basalts were analysed to establish their possible formation conditions. The results show that montmorillonites have higher Fe contents (as FeOtotal), as well as higher O-isotope and H-isotope compositions than saponites. These differences may largely reflect dissimilar formation conditions and/or fluid compositions. It is suggested that saponites probably precipitated from fluids dominated by meteoric groundwaters at 40–50°C, whereas montmorillonites were probably formed at 20–40°C from mixtures of groundwaters and seawater. Considering all the possible uncertainties, the above estimated temperature conditions are suggested as reasonable lower limits.

It is established that the associated calcite is not in O-isotope equilibrium with the montmorillonite. The calcite might have been formed in environments with ambient fluid dominated by meteoric groundwaters at temperatures lower than those for montmorillonite.

Photochemical isomerization of azobenzene intercalated in the hydrophobic, interlayer spaces of swelling fluor-tetrasilicic micas exchanged with dialkyldimethylammonium ions, with the alkyl chain length from 10 to 18, was investigated. Thin films of the organoammonium-mica-azobenzene intercalation compounds were obtained by depositing a suspension of the organoammonium-micas (prepared using a toluene/methanol solution of azobenzene) on quartz substrates. The intercalated azobenzene showed reversible photochromic reactions induced by UV and visible light irradiation. The fraction of the photochemically formed cis-isomer in the photostationary states decreased with a decrease in temperature. The observed change in the photochemical reactions is thought to reflect changes in the states of the dialkyldimethylammonium ions in the interlayer space of the swelling fluor-tetrasilicic mica.

Illite, the predominant component of the clay fraction of the Chinese loess, has been studied by X-ray diffraction (XRD) in 33 samples taken from the Holocene palaeosol (S0), the last glacial loess (L1) and the last interglacial palaeosol (S1) in the Louchuan loess section of the Loess Plateau in China. The XRD investigations indicate that it is mainly a 2M1 dioctahedral mineral with crystallinity values ranging from 0.23 to 0.36°Δ2θ (CIS Index). The 2M1 polytype illites with low IC values preclude a pedogenic formation of illites in the surface horizons of aridic and semi-aridic soils or deserts, and thus the clay mineral composition was largely determined by provenance. The illites are considered to be of detrital origin derived from pre-existing sediments and very low- to low-grade metamorphic rocks, eroded from the northern part of the Tibetan Plateau. The clay content of the loess and palaeosols was largely controlled by the strength of the winter monsoon, rather than by effects of in situ pedogenetic processes.

The composition, texture and genetic evolution of kerolite and related Mg clays belonging to the Intermediate Unit of the Miocene from the Madrid Basin have been studied. About 400 samples from the Esquivias deposit were analysed by several mineralogical and/or chemical techniques. Two genetic pathways for the development of Mg clays during early diagenesis have been observed: (1) mudflat environment: Al-smectite (beidellite) → Mg-smectite (saponite); and (2) palustrine environment: Si-Mg gel → kerolite → kerolite-stevensite → stevensite.

In the mudflat deposit the transformation processes predominate, whilst in the palustrine environment, kerolite is neoformed, probably from a gel-like medium. Stevensite seems to have originated from the transformation of mixed-layer kerolite-Mg-smectite, but also through neoformation at a later stage.

The textural features, isotopic data and sedimentary evolution within each lithofacies are indicative of shallowing-upward sequences with development of palaeosols. A post-sedimentary origin for sepiolite, calcite, authigenic quartz, zeolites and baryte is inferred.

Well crystallized chlorite has been detected in a Typic Hapludult developed on quartz porphyry at Ulsan, Korea, after treatment of the <0.2 µm fraction with a high-gradient magnetic separation (HGMS) technique. The X-ray diffraction (XRD) characteristics of the chlorite suggest that it is an Fe-rich variety and this was confirmed by energy dispersive spectroscopy (EDS) analysis. The chlorite could not be detected with certainty in the <0.2 µm fraction but is clearly present throughout the soil profile in the <0.2 µm fraction. It is suggested that this chlorite is residual inherited chlorite, the rest of which has dissolved in the acidic environment (pH 4—5).

A progressive decrease in cation exchange capcity (CEC) values was observed by treating Ca-montmorillonite with sulphuric acid solutions and this can be understood in terms of the layered structure of the clay. Elemental analysis showed that moderate activation occurred and only 25–30% of the octahedral cations were removed. At the same time the total surface area and the clay acidity increase. X-ray and FTIR data confirmed that acid activation affects both the octahedral and the tetrahedral sheets. The efficiency of acid-activated montmorillonite for the bleaching of cottonseed oil was investigated. The differences in bleaching efficiency appeared to be due to differences in the physical and chemical properties of the bleaching media. The oil acid value was not affected by the bleaching procedure but a slight shift in the absorption maximum of the bleached cottonseed oil was observed. Medium activation of the clay (treatment of Ca-montmorillonite with 4 N H2SO4) was the most effective in bleaching the cottonseed oil, resulting in the best colour index and the lowest peroxide value. A linear dependence of the bleaching efficiency on the clay surface area and acidity was observed. The role of the increased Bronsted acidity is also discussed.

The origin and formation of soil clay minerals, namely micas, vermiculites, smectites, chlorites and interlayered minerals, interstratified minerals and kaolin minerals, are broadly reviewed in the context of research over the past half century. In particular, the pioneer overviews of Millot, Pedro and Duchaufour in France and of Jackson in the USA, are considered in the light of selected examples from the huge volume of work that has since taken place on this topic. It is concluded that these early overviews may still be regarded as being generally valid, although it may be that too much emphasis has been placed upon transformation mechanisms and not enough upon neoformation processes. This review also highlights some of the many problems pertaining to the origin and formation of soil clays that remain to be resolved.

Detrital smectite in a sandy claystone and a phosphorite, and authigenic palygorskite in a dolomitic marl and a porcellanite from Cretaceous-Tertiary phosphorite deposits of the Ganntour Basin (Morocco) were purified using cation exchange resin, leached with dilute acid, and analysed for the contents and distribution patterns of their REE before and after acid treatment. The normalized patterns confirm a detrital origin for the smectite in the sandy claystone, whereas the origin of the smectite from the phosphorite is obscured by the addition of REE from the phosphogenic environment. The normalized REE patterns of the palygorskite suggest formation in non-oxidizing restricted environments. The Al2O3/ΣREE ratio of the two clay types suggests formation of diagenetic palygorskite (and mixed-layer illite-smectite) from Al-bearing detrital smectite by a dissolution-crystallization process.

The IR spectra of -saturated smectites were examined in terms of their charge characteristics. The υ4 band near 1440 cm-1, observed in the DRIFTS spectra (obtained without use of a KBr matrix), was assigned to the vibrations of ions compensating the negative charge of the clays. When KBr was used as a diluting matrix, the υ4 band was located at 1400 and/or 1440 cm-1. The band at 1400 cm-1, related to NH4Br, originated from the replacement of in the clay by K+ from the KBr. For swelling clay minerals this band indicates that layers have permanent low charge density and/or variable charge. For non-swelling clay minerals, the 1400 cm-1 band characterizes the presence of variable charges only. The υ4 band at 1440 cm-1 suggests that in the clay was not replaced by K+ from KBr and remains in the interlayer space of the clay minerals. This absorption is due to compensating only permanent charge in the interlayers, or part of the interlayers with a high charge density. The presence of both bands at 1400 cm-1 and 1440 cm-1 in the IR spectrum suggests that the clays studied have a heterogeneous interlayer charge.

The adsorption of DL-alanine at pH 4, 6 and 8 by a soil allophane has been determined. Two sets of experiments were carried out: (1) in which the allophane had been kept in a moist state throughout; and (2) in which the mineral had previously been dried at 50°C. In both instances, the adsorption isotherms showed three distinct regions as the concentration of alanine in solution was increased: (1) an initial, nearly linear, rise at low equilibrium concentrations; (2) a levelling off to a plateau at intermediate concentrations; and (3) a steep linear increase at high concentrations. For comparable concentrations of alanine in solution, adsorption decreased in the order pH 6 > pH 8 > pH 4. Irrespective of pH, however, more alanine was adsorbed by the ‘wet’ allophane than by its ‘dry’ counterpart. These observations are interpreted in terms of the morphology and aggregation of allophane unit particles together with the pH-dependent charge characteristics of allophane and alanine. The results are compared with published data on the adsorption of alanine by montmorillonite.

This article reviews that clay literature from the last ten years, which is devoted to the applications of clay minerals in the interpretation of geological processes in sedimentary basins. The results, selected by the author as being of particular interest, are presented, arranged according to the successive phases of the rock cycle.

Infrared reflectance spectra of Li-, Na-, K-, Rb- and Cs-saturated samples of montmorillonite Zenith-N (Milos, Greece) have been measured in the 400–1300 cm-1 region in an attempt to elucidate the behaviour and migration properties of alkali cations after heating the montmorillonites at 300°C for 24 h. Deconvolution of the complex Si–O stretching band reveals that the component band that arises from the asymmetric stretching vibrations of the silicon-apical oxygen units exhibits the biggest change upon heating the montmorillonites. The normalized absorption area of this band has been correlated with the decrease in the layer charge due to the cation migration. Analysis of the IR data for each alkali-saturated montmorillonite has shown that only Li+ migrates near, or to, vacant octahedral sites.

The high frequency OH-stretching band in micro-Raman spectra of kaolinites consistently exhibits two partly overlapping components with varying relative intensities. These bands, labelled A and Z, are located at ~3700–3690 and 3690–3680 cm-1, respectively. Band Z displays greater intensity in Raman spectra of highly crystallized kaolinites which have large coherent domains. Both components are also observed in the curve fitted infrared (IR) spectra of kaolinites; band Z is stronger in IR spectra of highly crystallized samples. Data for kaolinites with different particle size support the idea that bands A and Z are the longitudinal optic and transverse optic modes of the high frequency OH-stretching band.

The adsorption of the silane coupling agents N-(2-amino-ethyl)-3-aminopropyl- trimethoxysilane (Z-6020), N-(2-(vinylbenzyl-amino)-ethyl)-3-amino-propyl-trimethoxysilane (Z-6032) and 3-glycidoxy-propyl-trimethoxysilane (Z-6040) onto the surface of kaolinite has been studied using the solvents water and ethanol. The adsorbed silanes were analysed using diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy and FT-Raman spectroscopy. When the silane coupling agents are dissolved in water, silanol groups are formed. Raman spectra of aqueous solutions of the silanes show that condensation of the silanols into oligomers occurred. The peak at 1000 cm-1 assigned to Si–O–Si vibrations indicates that polymerization has occurred. A similar behaviour is observed when the silanes are dissolved in ethanol. The DRIFT spectra show that the silane coupling agents adsorb onto the surface of kaolinite. It is proposed that the oligomers are bonded to the kaolinite surface only by hydrogen bondings with no covalent bonds formed.

The intercalation complex of kaolinite and potassium acetate (KAc) was studied by HTXRD, IR spectroscopy and DTA-TG. The HTXRD patterns indicate that the 14.06 Å basal spacing of the complex contracts to 11.77 Å and 9.35 Å after heating at 60°C. The DTA-TG data indicate that water is present in these new complexes, the decomposition of which occurs between 290°C and 400°C. Modifications observed in the high-frequency region of the spectra obtained after heating suggest that K ions occupy the ditrigonal holes in the OH surface of the kaolinite layers, whereas water is probably located between the KAc layer and the OH surface of the kaolinite. This structural arrangement would favour the H-bonding between inner-surface OH groups and water and justifies the presence of new bands at lower frequencies. Electrostatic interactions between the keyed K ions and O of the inner OH groups would justify the modifications of the 3619 cm-1 OH-stretching band.

In order to assess the influence of tetrahedral sheet charge on the hydroxyl-stretching vibration in clay minerals, a series of synthetic Na-saponites, with increasing layer charge, was studied by infrared (IR) spectroscopy. When recorded after KBr dilution either in transmission or diffuse reflectance, the IR spectra exhibit a component at ~3710 cm-1, the intensity of which increases linearly with increasing layer charge. When experiments are carried out without any dilution of the samples, this component is not observed, suggesting a Na+/K+ exchange upon mixing of the sample with KBr. The spectra obtained for K-saponite confirm this exchange. This shows that the dilution procedure can lead to serious misinterpretations of IR spectra in the OH-stretching region.

The clay minerals kaolin, smectite and palygorskite-sepiolite are among the world's most important and useful industrial minerals. Clay minerals are important in a number of geological applications such as stratigraphic correlations, indicators of environments of deposition and temperature for generation of hydrocarbons. In agriculture, the clay minerals are a major component of soils and determinant of soil properties. The clay minerals are important in construction where they are a major constituent in brick and tile. The physical and chemical properties of the clay minerals determine their utilization in the process industries.

What about tomorrow? Processing techniques will be improved and new equipment will be available so that improved clay mineral products will be available. Pillared clays and nanocomposites will become important. Further developments in organoclay technology and surface treatments will provide new usages for these special clays. Tomorrow will see further growth and utilization of the clay minerals.

The use of disodium peroxodisulphate combined with a neutral buffer is a new method for the efficient removal of organic matter from clay-bearing sediments. The effects of this oxidation procedure on mineral structure were investigated by treatment of different standard clay minerals (kaolinite ‘china clay’, illite ‘Le Puy’, montmorillonite SWy-1). The materials were characterized by means of XRD, FTIR, SEM and TEM before and after leaching with disodium peroxodisulphate. Systematic experiments were conducted to determine the effects of leaching on the chemical and isotopic composition of oxygen, hydrogen and K-Ar in these samples. Effects on the physicochemical properties of the clays such as BET external surface area, cation exchange capacity (CEC) and expandability with ethylene glycol were also investigated. The results show that structure, chemical composition, oxygen and hydrogen isotope ratios, as well as the K-Ar system remain unaffected by leaching with disodium peroxodisulphate. The CEC and expandability remain unchanged, whereas changes in BET area can be attributed to mechanical dispersion by ultrasonic treatment.