Authigenic clay minerals in the German Rotliegend formed mainly at burial depths >1.5 km. Illite is the dominant cement, although kaolinite, dickite and early radial chlorite are abundant locally. Illites contain more AI and late chlorites more AI and Fe in sequences showing extensive grain dissolution. This relationship between clay chemistry and grain dissolution suggests that clay cementation is linked to grain dissolution. Sequences at relatively shallow burial depths (<3-5 km) contain less clay cement. In the more deeply buried sections, increased illite and kandite cementation, together with extensive grain dissolution, is evident where the Rotliegend is juxtaposed against Carboniferous Coal Measures. Faults also acted as important conduits for acidic fluids. Illite and kandite growth occurred at similar depths and from waters of similar isotopic composition (618O = 1-6‰ SMOW) throughout most of the Southern Permian Basin. However, the timing of illite growth varied between areas and corresponded to periods to tectonic activity.

Samples of natural clinoptilolite modified by treatment with NH4Cl or HCl solutions, followed by thermal treatments, have been characterized, and their catalytic activity evaluated, in o-xylene isomerization and ethanol dehydration reactions. The substitution of the compensating cations by NH4+ does not produce structural changes in the original material, but it opens the channels and increases its acidity and thermal stability. The treatment with HCl increases both the acidity and the effective diameter of the channels and pores but it produces an important loss of zeolite phase. Calcination of the acidic forms above 973 K leads to the breakdown of the zeolite structure. Catalytic activity of the samples is related to the surface acidity. For the original and NH4Cl-treated samples, however, the conversion of o-xylene is limited by the access of the reactant inside the channels of the zeolite. A comparative study with modified sepiolite in dehydration of ethanol has also been performed.

A method has been developed to synthesize organo-hectorite clays directly from a Mg-silicate gel containing organic or organometallic molecules that are expected to be incorporated within the interlayer space. Complete crystallization occurs upon aqueous reflux for 48 h. The progress of clay layer formation was monitored by X-ray powder diffraction (XRD), differential thermal gravimetry (DTG), and infrared (IR) spectroscopy. Evidence of clay XRD peaks occurs after just 4 h of hydrothermal treatment, and Mg(OH)2 is no longer observable after 14 h. Observable changes in DTG and IR occur at about this time as well. Warren line-shape analysis of the 110 reflection indicates that when growth is complete the clay lamellae are on average ∼50% and 25% of the size of natural hectorites and montmorillonites, respectively. The N2 BET surface areas for all materials are also compared. Small angle neutron scattering shows that addition of tetraethyl ammonium (TEA) ions does not alter the structural integrity over that of the purely inorganic form of Li-hectorite, but that use of a cationic polymer does significantly alter the microstructure. The effect of temperature is critical, for at room temperature only the layered Mg hydroxide mineral brucite crystallizes unless very long time scales are used. The crystallizations carried out at room temperature show that clay will form after about 3 months, but that the presence of organics (at least TEA) acts to hinder this process greatly. The role of the organic molecules on silicate clay layer formation is compared with the role of organics in zeolite synthesis.

Textural, mineralogical and chemical parameters of clays belonging to the Upper Cretaceous ‘Argilas de Aveiro’ formation were determined and correlated, using geostatistical analysis, with some relevant geotechnical parameters. The data obtained made it possible to subdivide the region under study into distinctive sectors on the basis of geotechnical behaviour. Clay fraction content and composition control geotechnical parameters such as the expandability and the Atterberg plastic and liquid limits. A positive correlation was found between both expandability and the Atterberg plasticity index values and the total phyllosilicates, smectite, MgO and Al2O3. However, Atterberg plasticity index values were relatively independent of the diverse clay mineral assemblages.

Syntheses of ferric smectites were performed at low temperature (75° C by aging coprecipitated gels of silica and Fe2+-sulphate under initially reducing then oxidizing conditions. Under strictly reducing conditions only nuclei of a trioctahedral ferrous stevensite were observed and crystal growth did not take place. When a spontaneous oxidization, in contact with air, was effected, the ferrous smectite nuclei transformed rapidly into a ferric, nontronite-like, smectite. Crystallogenesis of the ferric smectite was studied by XRD, IR, DTA, Mössbauer and EPR spectroscopies. The end-synthesis smectite contained only Fe3+ ions, all located in the octahedral sheet. This clay was mixed with a cryptocrystalline iron oxide phase containing one-third of the iron atoms and undetectable by XRD.

The Biga Peninsula of NW Turkey is host to six major halloysite deposits in the Go¨nen, Yenice and Balya districts. Mineralization took place in areas of Permian limestone blocks where the Triassic Karakaya Complex is in contact with early Miocene calc-alkaline volcanic rocks. Hypogene halloysite mineralization was controlled by the intersection of minor faults in the vicinity of clay deposits. During the Pleistocene, activity of the North Anatolian Fault (NAF) brought ascending geothermal solutions through the fault zones to the surface, which led to hydrothermal alteration and halloysite formation. N-MORB normalized element values for each halloysite deposit and the volcanic rocks suggest genetic links. Alunite and halloysite were formed in the Turplu area where upwelling hydrothermal waters contained major H2S and SO2 acids. Only halloysite mineralization occurred in outflow areas of the same fossil geothermal field.

Pyrite and alunite samples from the Turplu deposits have δ34S values of 0.6–1.8% and 4.8–7.9%, respectively, with values for gypsum of 3.1–3.5%. The δ34S values of pyrite suggest that local meteoric waters had partially mixed with the dominant fluid during the closure stage of fossil hydrothermal activities. The range of δD values of halloysite samples from Turplu is –58.4 to –68.6%. The δ18O values for halloysite are in the range 16.7–18.1%. All halloysite deposits in the study areas are either overlying or adjacent to limestone blocks, and these provide excellent drainage for the discharging geothermal waters. Subsurface drainage systems in the karstic environment and the SO2-bearing thermal waters indicate the importance of acidic waters and the continuous leaching of elements in forming relatively pure hydrated halloysite. A steam-heated dissolution-precipitation model is proposed for the occurrence of all halloysite and alunite deposits. Sulphur gases (H2S-SO2) of hypogene origin rose from deep in the fault zone to the surface where they encountered oxygenated groundwater at the water table. The occurrence of H2SO4 in this hydrothermal system enhanced the acidity of geothermal waters provoking advanced argillic alteration. Hypogene alunite deposits also have large P2O5 contents, suggesting a parent material with a magmatic origin deeper than the alkaline tuffs. Halloysite is a fast-forming metastable precursor to kaolinite.

A preliminary set of ‘rules’ for acid-catalysis by ion-exchanged montmorillonites has been derived from the reaction of alkenes, alcohols and alicyclic acids over such catalysts. It has been shown that: 1. Cr(III) and Fe(III) are the most active interlayer cations. Although Al is also active, the exact procedures used for the ion-exchange and washing steps appear to be critical for giving catalysts of reproducible activity. 2. Below 100°C, the reactions proceed provided they involve tertiary or allylic carbocation intermediates, whereas at 150–180°C reactions involving primary and secondary carbocations are possible. 3. Reactions of carbocations with unsaturated hydrocarbons take place overwhelmingly in the interlayer region of the clay, where the hydrocarbon double bond can be effectively polarized. Reactions of carbocations with polar, oxygenated, species can take place on the surface of the clay particles as well as in the interlayer space. 4. When the acid-catalysed reactions are performed in the liquid phase and involve tertiary carbocations, the most suitable solvents are those which provide miscibility; 1,4-dioxan is especially good. However, when more acid conditions are required for the formation of primary and secondary carbocations a non-polar solvent is more efficacious.

Weathering profiles developed on the top surface of a bentonite (containing Al-Mg montmorillonite) and a K-bentonite (containing mixed-layer illite-smectite (I-S)) under Central European temperate conditions were studied by XRD, HRTEM, FTIR, K-Ar and chemical analyses. Weathering of montmorillonite results in the decrease of cation exchange capacity (CEC), total surface area and Mg content. The process is interpreted as montmorillonite dissolution and precipitation of amorphous SiO2. Weathering of I-S produces an increase in CEC and total surface area. The XRD data suggest dissolution of I-S and appearance of smectite as a separate phase at intermediate depths. The fixation of ammonium is documented in the topmost sample. In both profiles, abundant aeolian contaminants, including mica, were identified and their migration was traced using K-Ar dating.

An investigation of the acid-leaching of a calcined kaolin was made to compare the reaction kinetics of hydrochloric, nitric, and sulphuric acids. The acid concentrations used were 5·9 and 8·6 normal. Reaction temperatures used were 95°, 80° and 60° C.

Particular attention was given to finding a reaction equation which would mathematically represent the kinetic data. A nucleation rate equation of the general form, was found to represent these data. Values of m varied from 1·10 to 1·55 depending on the experimental conditions.

Under the conditions employed the rate of alumina leaching is fastest with hydrochloric acid, slower with sulphuric acid, and slowest with nitric acid. The rate controlling steps are proposed from the experimental evidence.

Diagenesis in the Podhale and Orava Paleogene flysch basins and in the underlying Mesozoic structural units was studied by XRD measurement of the percent smectite in the mixedlayer illite-smectite from shales and K-Ar dating of the illite-smectite from bentonites, supported by XRD quantitative mineral analysis, grain density, and porosity measurements of the bulk shales. The diagenetic mineral reactions identified in the flysch shales include illitization of smectite (>60 to <5%S), dissolution of K-feldspar and kaolinite, crystallization of quartz, albite and chlorite. An unusually large amount of basin history information was obtained by combining the illite-smectite data from wells and from the present erosional surface of the basin.

The rocks underwent burial diagenesis at a stable geothermal gradient similar to the present-day value of 21±2°C/km. The maximum burial temperatures were reached very quickly (high sedimentation rate) close to the basin inversion time, at ∼17 Ma in the western part and 18 Ma in the eastern part.

The basin floor, which included the present-day Tatra Mts., was inclined towards the East. The thickness of the sedimentary filling of the basin ranged from 3.5–4.5 km in the western Tatra (removed entirely), to 5–6 km in the western Podhale (<3–4 km removed), to 6.5–7.5 km in the eastern Podhale (>4–5 km removed), and even more in the eastern Tatra and Spisská Magura close to the Ružbachy Fault. These data imply a major subsidence followed by uplift of the Podhale plus Tatra block along the Ružbachy Fault and the deposition of a thick sequence of Lower Miocene sediments over the entire area (latter removed by erosion).

The Mesozoic rocks of all the structural units underlying the flysch basin underwent advanced diagenesis (maximum palaeotemperatures of 160–270°C) during an Upper Cretaceous tectonic burial event at ∼80–90 Ma. The tectonic overload was removed before the Eocene transgression (49–42 Ma).

Low crystallinity of unsubstituted goethites is characterized by a small coherently diffracting domain, which may be accompanied by another type of disorder revealed by broader IR half-absorbance band widths. Inside the unit cell, the H-bond is weaker, which increases the OH stretching frequency and lowers the bending frequencies. Also, an increase in parameter a and a change in Fe-O bonds, which might correspond to a minor tilting of octahedra, occur along with a lowering of the frequency of the 630 cm−1 band.

Powdered 2:1 Mg-clay samples were rehydrated up to the maximum hydration. Both scanning and transmission electron microscopy were used to characterize their structural organization i.e. particle arrangement, texture and crystal structure. Low-angle X-ray scattering experiments were carried out to quantify the microstructure of the system. The results showed that sample water contents reached at saturation are not directly related to changes in layer distance. The hydration mechanism is rather correlated to particle size and particle aggregate size. It is also shown that the a, b plane extension of the layers influences particle size and shape. Finally, it appears that for a better understanding of clay swelling mechanisms, at high water contents, it is necessary to take into account all organization levels and that the contribution of interlayer space to the total water content, for Mg-smectites, is small.

The thermal transformations of kaolinite have been studied using 27Al and 29Si magic angle spinning nuclear magnetic resonance (MAS NMR), X-ray diffraction (XRD), differential thermal analysis (DTA) and thermogravimetric analysis (TG). The experimental results show that this sample is a pure kaolinite which contains ∼3% carbonaceous material as impurity. 27Al and 29Si MAS NMR spectra show that the microstructural evolution of the thermal transformation of kaolinite at 450 –1050ºC is similar to that of the kaolinite– mullite reaction series previously published by many authors. 29Si MAS NMR spectra of mullite at 1190 and 1250ºC display two resonances at ∼ – 87 and –92 ppm, corresponding to sillimanite-type geometry around Si and the typical Si environment of mullite, respectively. At 1350ºC, the splitting of (hk0) and (kh0) of mullite occurs, indicating that the primary mullite transforms into orthorhombic mullite. Simultaneously, the resonance at ∼ – 92 ppm splits into two signals at ∼ –90 and –94 ppm. 27Al MAS NMR spectra of the mullite consist of three signals centred at ∼ –4, 45 and 60 ppm, corresponding to octahedral, distorted tetrahedral and tetrahedral Al sites, respectively.

This study focuses on the mineralogical and geotechnical characterization of northern Moroccan clays from the Tangier and Tetouan areas and compares them with the main clay deposits used in the Moroccan ceramic industry (from Meknes, Fes, Salé and Safi regions). Sampled clays were analysed by X-ray diffraction on bulk and clay (<2 μm) fractions to identify the mineralogical assemblages of the clay outcrops. Further analyses were conducted to determine the particle size distribution (laser diffraction particle analyser), the total organic matter content (Loss- On-Ignition measurements) and the Atterberg limits of the raw clays. The study aims at investigating the spatial variability of the clay samples and at evaluating their potential application as raw materials in the ceramic industry.

Tetouan and Tangier clays are characterized by diversified mineralogical assemblages (in particular a variable proportion of clay, quartz and calcite) compared with the Meknes, Fes, Salé and Safi clays (high clay content, quartz and calcite). The clay fraction of the Tetouan and Tangier samples is dominated by illite and kaolinite with variable amounts of chlorite, smectite and/or vermiculite. Illite is the dominant phase in the Meknes, Fes, Safi and Salé clays, but is associated with kaolinite. No direct relationship between the mineral assemblage composition and the lithology of the series was found.

The clays materials studied consist generally of fine particles with medium to high plasticity and low organic matter content. Due to their mineralogy, grain-size distribution and plasticity the clays appear to be suitable as raw material for the growing Morocco ceramic industry.

Aluminium substituted goethites (Fe, Al)OOH were synthesized from Fe(III), Al systems (ferrihydrites) in m KOH at room temperature. A linear correlation existed between degree of Al substitution and log[Al] in solution. Incorporation of up to 12 mole % Al was obtained. The rate of conversion of ferrihydrite to goethite decreased as [Al] increased. The goethite consisted of thin elongated plates approximately 0·1 µm long with serrated edges and reduced growth in the crystallographic X-direction. The presence of salts and the nature of the starting material either an Al-ferrihydrite or a ferrihydrite in aluminate solution did not influence the degree of substitution, but only the rate of formation of the goethite.

The nature, distribution and origin of clay minerals in the hydrocarbon-bearing Permian Rotliegend sandstones of the North Sea and the adjacent areas of the Netherlands and Germany are reviewed. The clay minerals occur as detrital coatings of smectite and smectite-illite on the surfaces of sandgrains, and as later diagenetic cements of kaolinite, chlorite (two varieties), and illite in the pore spaces of those sandstones. Two diagenetic clay mineral assemblages are predominant in the Rotliegend of the North Sea. The kaolinite-illite assemblage is restricted to the Rotliegend of shelf areas which underwent shallow burial followed by strong Jurassic/Cretaceous (Late Cimmerian) structural inversions, whereas the illite-chlorite assemblage is associated with basinal areas that underwent deep and rapid burial throughout the Mesozoic.

The factors controlling mineralogy, crystal chemistry and morphology of those diagenetic clay minerals, as well as their regional distribution and origin, are numerous, complicated, and inter- related. Evidence suggests that the following aspects were important parameters: (1) variations in the original depositional arid desert environment; (2) the chemistry and flow patterns of the porewaters; (3) temperature and timing of clay mineral formation; (4) local burial history; (5) the presence or absence of meteoric water; and (6) the structural setting of the Rotliegend sandstones.

Oxygen isotope data indicate that the illite cements formed over a wide range of temperatures (24–140°C) that is consistent with the deep burial conditions prevailing in the palaeo-basins. In contrast, oxygen isotopes indicate that kaolinite cements formed over a more restricted temperature range (40–80°C) and under the influence of meteoric water penetrating the sandstones of the shelf areas as a result of their Late Cimmerian uplift and associated erosion. Hypotheses suggesting that the absence of kaolinite cement from the deeply buried Rotliegend sandstones is caused by its illitization during burial, and that the chlorite cements have formed by the alteration of earlier smectite, smectite-chlorite and corrensite cements, are not supported by evidence.

Authigenic kaolin is a major occluder of porosity at all depths in the Hutton-NW Hutton Brent Group reservoirs. Two polytypes, kaolinite and dickite, are present. Kaolinite occurs to a depth of ∼10,600 ft and is interpreted to be eogenetic. Dickite increases in abundance with burial depth, concomitant with increasing K-feldspar dissolution. Kaolin petrography indicates that kaolinite transforms to dickite via dissolution-reprecipitation at depths of ∼11,000 ft. Dickite has δ18O values characteristic of modified meteoric water for growth at temperatures of contemporaneous quartz authigenesis.

Palaeohydrodynamic models involving meteoric water penetration down to 2 km through faults or Palaeozoic rocks of the East Shetland Platform are unlikely to provide the vigorous fluid throughput required for kaolin precipitation. Reverse post-rift modelling indicates that the crest of the Hutton-NW Hutton fault block was not sub-aerially exposed, precluding meteoric water ingress via this route. Eogenetic kaolinite formed in a meteoric water flush driven by topographic head on the Brent Delta. Dickite is, in part, derived from kaolinite dissolution, with additional sourcing from K-feldspar dissolution and Si-Al in pore-waters expelled from mudstones during burial. This model precludes the need for extensive fluid-flushing at intermediate burial depths.

A trioctahedral, ferrous smectite has been located in the uppermost deposits of Atlantis II Deep, SW basin, Red Sea. This clay is very unstable when removed from its environment of formation and, for example, oxidizes during desiccation under laboratory conditions. Only X-ray transmission diffraction study of the mud itself demonstrates the trioctahedral character of the clay. Electron-optical investigation shows that oxidation within the octahedral sheet creates a juxtaposition of dioctahedral and trioctahedral sub-lattices in the same particle. Ferrous smectite authigenesis is located near the hydrothermal spring outlets of the Atlantis II Deep.

Oedometer swelling and compaction tests up to a maximum pressure of 32 bars were made on the Wyoming montmorillonite SWy-1 with a range of mixed (Na,K) exchange ion compositions. The permeabilities and water diffusivities of the compacted clays were calculated using soil physics theory. Significant inhibition of swelling from that of the Na-montmorillonite is developed for K fractions in the range 0·30 < K+ < 0·56. However, the water diffusivity increases by a factor of approximately six as the K exchange fraction increases from 0 to 0·7. Permeabilities to water flow show a power-law dependence on the void ratio e.

XRD measurements at controlled humidity yield equilibrium interlayer spacings which in general increase with both increasing relative humidity and increasing Na exchange fraction. The extent of swelling is strongly inhibited in clays having Na exchange fractions of 0·44 or less, in good agreement with the oedometer studies.