The stable isotopic compositions of diagenetic minerals can provide valuable constraints on the sources, precipitation temperatures and relative timing of cements in reservoir rocks. This type of information is essential when trying to understand and predict the distribution of cements in the subsurface, and their impact on reservoir quality. Conventional isotope methods contribute to answers to many diagenetic problems, but where core or time are scarce, or where good mineral separation is unobtainable, laser-based stable isotope methods offer several advantages. These include the ability to analyse carbonates, sulphides and anhydrite in situ with 50–100 μm resolution, simple and clear sample and analysis viewing optics, savings on sample preparation time and greatly reduced sample size requirements.

Diagenetic silicates such as quartz and clay cements cannot be analysed in situ by laser but, where in situ analysis of quartz δ18O is demanded, ion microprobe analysis can provide very high resolution (20–30 μm) capability with a precision of ±1%.

Diagenetic kaolinite in reservoir sandstones of the Brent Group precipitated following the dissolution of detrial feldspar. Two distinct morphologies of kaolinite occur: (1) early diagenetic vermiform kaolinite which is often associated with expanded detrital micas; (2) later diagenetic ‘blocky’ kaolinite. Combined hydrogen and oxygen isotopic studies suggest that vermiform kaolinite precipitated at 25–50°C, and blocky kaolinite at 50–80°C, from pore-waters of a similar isotopic composition (δ18O = −6.5 to −3.5‰). These pore-waters are interpreted to be either a mixture of meteoric and compactional waters, or alternatively a meteoric water that had evolved isotopically due to water-rock interaction. Kaolinite precipitation occurred predominantly during the late Cretaceous to early Eocene. Influx of meteoric water into the Brent Group, probably occurred during the Palaeocene. Fluid flow across the entire basin was driven by a hydrostatic head on the East Shetland Platform palaeo-landmass to the west. The development of the two kaolinite morphologies is possibly related to the degree of supersaturation at the time of precipitation. At low degrees of supersaturation, vermiform kaolinite precipitated slowly upon detrital mica surfaces. Blocky kaolinite precipitated more rapidly into open pore-space at higher degrees of supersaturation. Precipitation of blocky kaolinite was perhaps triggered by the decay of oxalate.

The evidence is reviewed for the various hypotheses put forward to explain the origin of the Chalk montmorillonite.

Recent X-ray investigation of the mineralogy of the acid-insoluble clay fractions (buffered 2 N acetic acid at pH 3; <2 µ e.s.d.) of the Lower Chalk of England sheds light on the origin of the montmorillonite. The relations between the qualitative and semi-quantitative mineralogy of the clay fractions and the facies and stratigraphy in this formation have been studied in detail. Montmorillonite, illite, kaolinite, chlorite, vermiculite, pyrophyllite, mixed-layer minerals, quartz, low-temperature cristobalite and apatite have been identified; their semi-quantitative distribution reveals that two main antipathetic assemblages are present, between which all gradations occur. The first is characterized by montmorillonite, illite, quartz and by montmorillonite/illite (M/I) values of 0·7 and above; and the second by illite, kaolinite, chlorite, vermiculite and by M/I values of below 0·2. The distribution of these assemblages or of any particular mineral does not show obvious relations to the facies or stratigraphy.

There is strong evidence that the second of these assemblages is of detrital origin, introduced into the Lower Chalk seas by currents flowing mainly from areas to the east and south-east of England. There is no evidence to suggest that the montmorillonite and the illite of the first assemblage are of detrital or volcanic origin, and their distribution in the Lower Chalk is best explained by their neoformation in the sediment on the sea floor by precipitation from the porewaters. By extrapolation it is thought that most of the Chalk montmorillonite of clay-grade is of neoformational origin. Some from the Campanian and younger Chalks may be detrital. Locally in N.W. Germany and possibly Poland minor amounts may have been derived from the decomposition of volcanic glass in the Chalk seas.

X-ray powder diffraction patterns of halloysite (7 Å) are characteristically altered following solvation with ethylene glycol. Some effect was first noted in the classic work of MacEwan but its value in the unequivocal identification of halloysite (7 Å ) seems to have been overlooked subsequently. The response to ethylene glycol solvation involves a decrease in the intensity (peak height) of the peak at ∼7.2 Å and an increase in the intensity (peak height) of the peak at ∼3.58 Å thus narrowing the 7.2 Å /3.58 Å peak height intensity ratio. For pure samples of halloysite, this ratio is narrowed by an average of ∼50%. This distinctive change is related to the interstratified nature of halloysite (7 Å), specifically the presence of ‘residual’ interlayer water, i.e. halloysite (10 Å), which can be replaced with ethylene glycol so forming 10.9 Å layers, a spacing that is almost exactly one and a half times the thickness of dehydrated (7.2 Å) layers which do not imbibe ethylene glycol. Thus the separation between the 001 peaks in the 7.2 Å /10.9 Å interstratification is increased and the 0027.2 (3.58 Å) and 00310.9 (3.63 Å) peaks become more or less coincident, compared to the 7.2 Å /10 Å interstratification, i.e. the partially hydrated state. The widespread use of ethylene glycol solvation in clay mineral studies makes it a particularly useful and simple test to determine the presence of halloysite. Pure halloysites should be readily identifiable and experiments indicate a ‘routine’ sensitivity of ∼20% halloysite in mixtures with kaolinite, although this will depend on factors such as ‘crystallinity’ and could be improved with careful attention to intensity measurements. It is proposed to call this phenomenon the ‘MacEwan effect’ in honour of its discoverer Douglas Maclean Clark MacEwan.

Dry grinding of pyrophyllite (Hillsboro, USA) has been studied by X-ray diffraction (XRD), specific surface area measurements (BET) and scanning electron microscopy (SEM). At the beginning of the grinding process, some effects such as delamination, gliding and folding of the layers, and decrease in particle size were detected by SEM and XRD, resulting in a large increase in specific surface area, up to a maximum of ∼60 m2·g−1. Marked changes in the structure take place between 30 and 32 mins grinding. Longer grinding times increase the degree of disorder and SEM and specific surface area data suggest that aggregation occurs. XRD results indicate that some residual order persists in the degraded structure.

The definition of ‘clay’ was first formalized in 1546 by Agricola. It has been revised many times since, although the fundamentals involving plasticity, particle size, and hardening on firing were retained by most. For an exhaustive account of the history of the definition to 1963, the reader is referred to Mackenzie (1963). More recent developments may be found in Weaver (1989).

The definition of clay raises the important issue of clay constituents and, implicitly, the definition of ‘clay mineral'. Mackenzie (1963, p. 15) noted the inappropriateness of defining clay mineral as “any mineral which occurs in clay” since, among several reasons, it would include many accessory minerals that are not characteristic of clay.

The controversy on the origin of the English Mesozoic fuller's earths is reviewed. Findings of (1) unaltered, devitrified, zeolitized and argillized glass, (2) fragments of holocrystalline and hypocrystalline igneous rocks, and (3) high temperature feldspar and sphene, conclusively demonstrate their volcanic origin. The bulk chemistries of the Bathonian and Lower Cretaceous earths are similar and suggest derivation from ash of trachytic composition. The two earths can be differentiated mineralogically and petrographically by: (a) the presence of sphene, and zeolites replacing glass in the Lower Cretaceous earths; (b) the presence of minor amounts of basaltic glass in the Bathonian earths.

K/Ar radioisotope dating on high-temperature alkali feldspar gives (1) 152–159 Ma for the Bathonian fuller's earth, and (2) 118–125 Ma and 142–148 Ma for the Lower Cretaceous fuller's earths. The distribution of the Mesozoic fuller's earths and the origin of their parent ash is discussed.

Fine clay, coarse clay, and silt fractions of four Bangladesh soils were studied using XRD, ion exchange, and selective dissolution techniques. Constants for the XRD intensity-weight proportion relationships were derived using these techniques. Smectite and mica were found to be dominant in Batra and Ghior soils, whereas kaolinite and mica were dominant in the Naraibag and Ghatail soils. Other minerals present were vermiculite, vermiculite with hydroxyaluminium interlayers, chlorite, randomly interstratified chlorite-mica, feldspar, quartz, and trace amounts of amphibole. The amorphous material content varied between 1 and 11% and decreased with increasing particle size. No crystalline iron oxides were detected in untreated clay fractions.

A statistical comparison has been made of chemical data for terra rossa and carbonate-free residues of Cretaceous limestones and dolostones in Apulia in order to evaluate the hypothesis that the terra rossa is a product of weathering of the underlying carbonate rocks. It has been shown that the differences in chemical composition between the residue of the carbonate rocks and the terra rossa are consistent with the former being the parent material of the latter. The transformation from carbonate rock residue to terra rossa was governed mainly by chemical weathering which produced a marked decrease in the K2O/Al2O3 (i.e. illite/kaolinite) ratio. The geochemical pattern of the Apulian terra rossa has been influenced by sedimentary processes which have led to a characteristic distribution of mineralogical components and a moderate contamination by biogenic silica.

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.

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.

The present study investigated the removal of methylene blue (MB) and orange II (OII) dyes from synthetic wastewater by means of adsorption and photocatalysis using natural kaolins. ForMB adsorption, the raw kaolinite-rich samples showed the greatest adsorption capacity, with rapid uptake (90% after 20 min). The experimental results were fitted better using the Langmuir isotherm model parameters compared to the Freundlich model, suggesting that the adsorption corresponds to monolayer coverage of MB molecules over the kaolinite surface. For OII, neither the Langmuir nor the Freundlich model gave reliable results, because the adsorption of anionic dye molecules by the clayey particles is not favoured.

Mixtures of kaolinite/Degussa TiO2 were also prepared, and their photocatalytic properties under UVlight exposure were investigated. Decolourization of MB solutions was observed, even in a mixture with low TiO2 content. This is related to the combined effect of adsorption and photocatalysis and, unlike the pure clay samples, the efficiency of such mixtures against OII was only slightly weaker (80–94%).

For TiO2-impregnated clays, with the kaolinite layers separated by sol-gel TiO2 particles, the MB removal was slow and effective only after >24 h due to the complexity of the bonding of MB molecules. On the other hand, the removal performance against OII solutions was very efficient (nearly 100%) within only 2 h. This excellent performance was attributed to morphological changes in clay particles.

The mineralogy and geochemistry of the clay fraction of Victoria Land Basin (Ross Sea, Antarctica) sediments was investigated, to determine the origin of clay minerals and the features of authigenic smectite. The investigated core (CRP-3) is ~800 m long, mostly of Oligocene age. The clay fraction of the upper sequence consists of mica, chlorite and detrital smectite, while that of the central and lower part is largely made up of authigenic smectite. Authigenic smectites are ditrioctahedral, with a composition close to saponite, while detrital smectites such as Al-Fe beidellites are dioctahedral. Authigenic smectites have no illite mixed layers, show a higher degree of crystallization, higher MgO, Fe2O3, V, Cr, Co, Ni and Sc contents and lower SiO2, Al2O3, K2O, TiO2, Ba, Rb and Zr contents with respect to detrital clay minerals, and a clear depletion of LREE with respect to HREE. Authigenic smectite formed from the alteration of volcanic materials and clay minerals.

A natural saponite was acid activated at room temperature or 90°C with different acid/clay ratios and the products were characterized by powder X-ray diffraction, infrared spectroscopy and thermogravimetry. The leaching of Mg from the octahedral sheets is enhanced by an increase in the acid/clay ratio and by an increase in temperature of activation. Textural properties are reported, and it appears that they are strongly correlated to the presence of a noncrystalline silica phase which is formed during the acid activation process. The desorption of cyclohexylamine indicates that for samples activated at 90°C the number of acid sites in the acidactivated saponites decreases following severe acid treatment. Infrared spectroscopy of adsorbed pyridine on samples after calcination at 500°C suggests that acid activation at 90°C produces a single type of Bronsted site but two types of Lewis sites whereas activation at room temperature results in only one type of Lewis site in addition to a Brønsted site. The two Lewis sites are suggested to originate from residual Al in the clay structure and to AI exsolved from the layers during activation. The dehydration of pentan-1-ol has been used as a further probe to measure acidity by monitoring the degree of conversion and selectivity for the different samples.

A selective chemical dissolution method has been worked out in order to characterize quantitatively amorphous Al, Fe and Si oxides simultaneously in soils. Based on theoretical considerations an alkaline Tiron solution was tried out. Experiments on well-characterized synthetic and natural substrates were carried out in order to find the optimum set of conditions of pH, temperature and reaction time. These are: an alkaline medium consisting of 0·1 m Tiron and buffered at pH 10·5, an extraction temperature of 80°C and an extraction time of 1 h.

Chemical and X-ray analysis of eight samples of nontronite are consistent with the Hofmann et al. montmorillonite structure. The finest fraction of some fully hydrated (15·3 Å) samples is composed of crystals all about 6 or 7 unit cells thick, and having 12 H2O per 8 Si, arranged at three levels in the interlayer, possibly as upright octahedra. During dehydration, non-integral 00l sequences, and variations in d001 result from a range of layer thickness in one crystal, caused by loss of water from the crystal periphery with consequent margin collapse. At about 50% relative humidity, the H2O content of nontronite is determined by the tetrahedral aluminium, probably because Aliv controls maximum crystal size.

The clay-mineralogical assemblages of Purbeckian carbonate sediments of the Swiss and French Jura Mountains are often composed of illite and interstratified illite-smectite. These illitic minerals occur mainly in thin layers of green marls which show evidence of subaerial exposure and mark the top of shallowing-upward sequences. X-ray diffraction, chemical and thermal analyses coupled with transmission electron microscopy suggest that the Purbeckian illitic minerals replaced smectite in intermediate continental-marine environments. The transition from smectite to illite and interstratified illite-smectite probably resulted from repeated cycles of wetting by marine waters and subsequent drying in hypersaline environments, under a hot Purbeckian climate.

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.

The sorption of boron by clay minerals from natural waters has been studied experimentally. The quantity of boron sorbed per unit weight of clay mineral is dependent on both the salinity and the boron content of the solution. Previous work has shown that illite is the best clay mineral sorbent, though kaolinite and montmorillonite do sorb some boron and this is confirmed by the present work. The new experimental results demonstrate that the amount of boron sorbed by illite is not affected by the original boron content of the mineral and suggest that the process of incorporation of boron into the lattice proceeds in two stages. The bearing of these experimental results on the use of boron as a palaeosalinity indicator in sedimentary rocks is discussed and this leads to the conclusion that the rate of sedimentation may also influence the boron content of such rocks.

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.