SWy-2 (Wyoming), Sap-Ca saponite (California) and SAz-1 (Cheto, Arizona) were exchanged with different cations (Al, Ni, Mg, Ca and Na). The catalytic activity of these ionexchanged clays was measured directly using the isomerization of α-pinene at 80°C for 2 h to yield camphene, limonene and other minor products. The order of activity for the different cationexchanged forms was Al > Ni > Mg > Ca > Na, which correlated well with the known polarizing power of these cations and the resulting interlayer acidity. Catalysts derived from Sap-Ca were the most active followed by SWy-2, with SAz-1 the least active by a considerable margin. The greater activity of Sap-Ca over SWy-2 was attributed to the high tetrahedral charge in the former. Reduction of the layer charge of SAz-1 using Li fixation caused a significant improvement in the catalytic activity of the Al-exchanged reduced-charge SAz-1.

Metamorphic grade, palaeothermal history and the influence of tectonic strain on clay minerals and organic matter transformation were studied in the eastern part of the Teplá-Barrandian unit in the Czech Republic. The metamorphic grade of pelitic sediments ranges from the lower anchizone (IC ~0.30–0.36Δº2θ) to the lowermost epizone (IC ~0.24–0.26Δº2θ). Increase in metamorphic grade is paralleled by the development of anastomosing cleavage and lenticular quartz grains in the anchizone which give way to slaty cleavage and dynamically recrystallized ribbon quartz grains in the lower epizone. White mica in highly strained rocks generally has greater IC values whereas chlorite displays reduced values in deformed and cleaved samples. The organic matter dispersed in the sediments represents a complex assemblage of highly matured particles of uncertain origin, pyrobitumen and ‘transitional matter’. The reflectance of organic fragments generally varies from 3.1% to 7.7% of Rmax which suggests anthracite to meta-anthracite rank progrades to semigraphite in higher-grade samples, although the overall link between Rmax and IC values is weak, if present at all. Newly formed shear-induced graphite appears abruptly near the anchizone-epizone boundary and correlates with the onset of plastic deformation and dynamic recrystallization of quartz grains in the host sediments.

Maximum metamorphic temperatures within the Neoproterozoic sequence in the range of 250–350ºC were attained during the Cadomian (Pan-African) orogeny at 540–550 Ma. Apatite fission-track analysis reveals a subsequent decrease in rock temperature over the period 340–350 Ma that persisted throughout the late Palaeozoic. The most recent episode of accelerated cooling occurred between 20 and 40 Ma, corresponding with the regional uplift of the Bohemian Massif due to the Alpine orogeny.

The mineral phases and the distribution of major, minor and trace elements in the clays and bed rocks of two bore-holes at Adda and Chaubatta of the Birbhum area have revealed an intimate relationship of the kaolin-rich clays with the bed-rock of Adda. The possibility of a common origin for the clay deposits at Chaubatta, lying close to the Rajmahal trap formations, and at Adda, lying close to the Archaean boundary, has been inferred from trace element distribution and other factors. A genetic relationship of the clay deposit at Adda with the bed-rock, altered Archaean gneiss, has been established, but there is no significant relationship of the Chaubatta clay deposit with its bed-rock, the weathered basalt.

The lateritic cappings above the kaolin-rich clays of Adda and Chaubatta areas are explained as being formed from kaolinite in the weathering sequence as the end-product of intensive desilication under conditions of intensive leaching and increasing acidity near the surface.

Petrographic, mineralogical and geochemical core analysis of Palaeocene turbiditic sandstones in the Sleipner East gas-condensate reservoirs show the importance of diagenetic clay distribution on porosity, permeability, and water saturation. An observed ‘high resistivity zone’ (HRZ) corresponds to intervals with low water saturation, a more restricted distribution of diagenetic clay (mainly chlorite), and up to 5% quartz cement. The underlying ‘low resistivity zone’ (LRZ) corresponds to intervals with more widely distributed diagenetic clay, which have lower degrees of quartz cementation, higher porosity, and variably reduced permeability. Crosscutting relationships of the HRZ/LRZ with mapped sedimentary depositional units, as well as fluid inclusion analysis data, suggest that the distribution of diagenetic clay was affected by an earlier (late Miocene?) oil charge, and more extensive chlorite formation in a palaeo-water zone. Recent gas condensate charge and structuring of these sandstones resulted in LRZ reservoirs with substantially higher water saturations than those in the HRZ.

In the post-closure period of a geological disposal facility for radioactive waste, leaching of cement components is likely to give rise to an alkaline plume which will be in chemical disequilibrium with the host rock (which is clay in some concepts) and other engineered barrier system materials used in the facility, such as bentonite. An industrial analogue for cement-clay interaction can be found at Tournemire, southern France, where boreholes filled with concrete and cement remained in contact with the natural mudstone for 15–20 years. The boreholes have been overcored, extracted and mineralogical characterization has been performed. In this study, a reactive-transport model of the Tournemire system has been set up using the general-purpose modelling tool QPAC. Previous modelling work has been built upon by using the most up-to-date data and modelling techniques, and by adding both ion exchange and surface complexation processes in the mudstone. The main features observed at Tournemire were replicated by the model, including porosity variations and precipitation of carbonates, K-feldspar, ettringite and calcite. It was found that ion exchange needed to be included in order for C-S-H minerals to precipitate in the mudstone, providing a better match with the mineralogical characterization. The additional inclusion of surface complexation, however, led to limited calcite growth at the concrete-mudstone interface unlike samples taken from the Tournemire site that have a visible line of crusty carbonates along the interface.

Bentonite colloids generated from the backfill barrier in nuclear waste repositories may act as radionuclide carriers, if they are stable and mobile. Repository scenarios with highly saline groundwater inhibit colloid stability as particles tend to aggregate but, in the time frame of repositories, groundwater conditions may evolve, promoting particle disaggregation and stabilization. The disaggregation of FEBEX bentonite colloids by fast dilution to lower ionic strength was analysed in this study. Time-resolved dynamic light-scattering experiments were carried out to evaluate the kinetics of bentonite colloid aggregation and disaggregation processes in Na+ and Na+-Ca2+ mixed electrolytes of low ionic strength. Attachment and detachment efficiencies were determined.

Aggregation is promoted by increasing ionic strength, being more efficient in the presence of divalent cations. Once bentonite colloids are aggregated, a decrease in ionic strength facilitates disaggregation, but the process is not fully reversible as the initial size of the stable bentonite colloids at low ionic strength is not fully recovered. Particle-size distribution and concentration in suspension were analysed on disaggregated samples by single particle-counting measurements. Small colloids were measured in the disaggregated samples but their population was smaller than in the initial stable sample, especially in the presence of Ca2+.

Water vapour atmospheres are known to raise the temperature of the endothermic reaction of clay minerals in differential thermal analyses. In isothermal kinetic studies of dehydroxylation, it is shown that a stationary state is attained depending on the operating temperature. The rate of dehydroxylation is a function of specimen size and shape, which suggests a controlling influence by entrapped water vapour. Even at constant reaction temperatures, the rate of dehydroxylation varies greatly between the interior and the exterior of a specimen. The bearing of these results on thermal analyses and on kinetic studies generally is discussed.

The surface properties of various synthetic layered silicates, Na-kanemite, Nakenyaite and magadiite, exchanged with H, K and Ca, were examined using high-resolution nitrogen and argon adsorption and the data were treated using the Derivative Isotherm Summation method. Using argon as an adsorbate, the aspect ratio of platelets can be determined. In the case of magadiite exchanged with various cations, the stacking of particles is influenced by the nature of the exchangeable cations, thicker platelets being observed for ions with low polarizability. Highresolution argon adsorption data also confirm some structural information previously deduced from Raman spectroscopy experiments concerning the existence of rather open six-membered rings at the surfaces of both magadiite and kenyaite. Furthermore, in the low-energy domain of the isotherms, argon forms a very organized film on basal planes, suggesting a commensurate relationship between silica framework and argon atoms for both magadiite and kenyaite, contrary to what is observed for kanemite. Nitrogen adsorption results reveal the presence of polar sites on the surface of all the investigated minerals but does not allow us to propose an unequivocal assignment for such sites.

Silica-indurated subsurface horizons of an in situ lateritic profile in semi-arid western Australia were investigated using a range of electron-optical and X-ray diffraction (XRD) techniques. These indurated materials were compared with underlying non-indurated pallid zone material. The secondary silica content of the indurated horizons, as determined by electron microprobe analysis, varied from 8 to 33%. Quantitative digital images for secondary silica, generated by mathematical manipulation of digital Si and AI-Kα: images, showed that kaolinite pseudomorphs after mica contained the lowest amounts of secondary silica, with the highest amounts being present in the inter-pseudomorph clay matrix. Variations in the amount of silica in the matrix are considered to reflect variations in the initial porosity of the clay matrix. Such variations may arise from differences in the Al/Si ratio of parent minerals. Transmission electron microscopy (TEM) showed that amorphous silica adhered to the (001) face of kaolinite crystals. The secondary silica could not be detected by either standard or differential XRD procedures.

The Permo-Triassic red bed sequence penetrated in BNOC Well 72/10-1A, located in the Western Approaches, is divided into eight clay mineral zones. The zones are defined by variations in the clay assemblage in which iron- and magnesium-rich chlorite, corrensite and mica occur. This zonal sequence is matched mineralogically and stratigraphically with the pattern of clay mineral variation recorded from the Permo-Triassic sediments of the south Devon coast, some 500 km distant.

This paper presents results from comparative thermogravimetric, calorimetric and pozzolanic activity analyses of five natural zeolite samples from Bulgaria, Slovakia, Philippines, USA and North Korea. The zeolites actively participate in the hydration processes of cement. Their activity in the early stage of hydration is based mainly on the large surface area of the particles while, in the later stages of activation, chemical reactions occur between the products of the hydration of cement and the soluble SiO2 that is present in the bulk of the zeolites. It has been shown that in all cement pastes which contain zeolite additives, the quantity of portlandite is lower than that in pure cement paste or is even totally absent. The amounts of hydration products are greater when 30% zeolite is used than when 10% zeolite is added (excluding the sample with chabazite). The lowest pozzolanic activity is shown by chabazite, which possessed the lowest SiO2/Al2O2 ratio.

Structural iron in smectites correlates with the cell edge length b and increases the refractive index. The cell edge length b is usually obtained from the position of the (060) reflection, but in this work we show that such b values differ from the values obtained from Rietveld fits because contributions from (hkl) reflections shift the position of the (060) reflection. The correlation between Fe and cell edge length b was significant (r2 > 0.99); the relationship is b [Å] = 8.9977(0.0035) + 0.1117(0.0032) × Fetot. Furthermore, we present for the first time measurements of the refractive index n of Fe-bearing smectites, applying a recently published turbidity method (Weidler & Friedrich, 2007). The refractive index correlates both with structural iron (r2 = 0.64) and with b (r2 = 0.94).

Metakaolins formed by total dehydroxylation of kaolinite, dickite and nacrite were hydrothermally treated at 240°C, for 2, 21 or 182 days, at initial pH = 5– 6 or 1. Kaolinite was the only mineral of the kaolin subgroup crystallized in these treatments. Kaolinite is less ordered for pH = 4– 6 than for pH = 1. This can be attributed to the influence of specific chemical, morphological, and/or crystalline properties of the metakaolins. Two different processes of kaolinite formation and crystal growth must be involved depending on the pH and metakaolin. The first process implies the dissolution of the metakaolin and crystallization of thin prismatic or dendritic kaolinite particles which curl, probably due to surface tension. The second process implies the rapid formation of small pseudohexagonal kaolinite particles which would aggregate and coalesce to form bigger particles.

Fluvial and aeolian sandstones of the Sergi Formation are the most important reservoirs of the Recôncavo Basin, Brazil. Optical and scanning electron microscopy, X-ray diffraction and infrared spectroscopy revealed the occurrence of dickite, a clay mineral indicative of deep burial conditions (T >100ºC), in the shallow Buracica (630–870 m) and Água Grande (1300–1530 m) oilfields. Vermicular dickite replaces K-feldspar and plagioclase grains, and fills intra- and inter-granular pores. Its vermicular habit is a product of pseudomorphic kaolinite transformation during burial. The presence of dickite is in accordance with the intensity of compaction, post-compactional quartz cementation and δ18O values of calcite cements (T up to 109ºC). These petrological features of deep burial, as well as apatite fission-track analyses, indicate that uplift and erosion of at least 1 km, and probably >1500 m, affected the central part of the Recôncavo Basin and possibly the entire region. This uplift has not been detected previously by conventional structural and stratigraphic models.

The Kawasaki and Dobuyama bentonite deposits in northeastern Japan show contrasting properties even though they are only 5 km apart in a sequence of Neogene sedimentary and pyroclastic rocks. The Kawasaki deposit consists of stratiform bentonite layers up to >50 m thick, and its wall rocks are unaltered shallow marine sedimentary rocks. In contrast, the Dobuyama deposit consists of a funnel-shaped ore body 200 m across, and its wall rocks are hydrothermally altered terrestrial rhyolitic pyroclastic rocks. The Kawasaki and Dobuyama bentonites mainly consist of Na-Ca smectite and Ca smectite, respectively, with subordinate opal-CT, quartz and zeolite. The geological occurrences of the deposits and wall-rock properties suggest that the Kawasaki and Dobuyama deposits were probably formed by diagenesis and low-temperature hydrothermal alteration, respectively. The difference in exchangeable cation ratios of the smectite between the two deposits is attributable to the difference in their sedimentary environments and/or burial depth.

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.

From their isothermal experiments, Murray and White drew the conclusion that the dehydration reactions of clays are first-order with a rate factor of Arrhenius form. The object of this paper is to discuss whether differential thermal analysis can be used to confirm or refute this hypothesis. The problem, previously considered by Murray and White, of a sample heated at a constant rate throughout is recalled. Particular attention is drawn to the effect of heating rate on the temperature at which the maximum rate of reaction occurs.

To apply to differential thermal analysis, the treatment must be extended to take account of thermal gradients; as the mathematics involved is cumbersome, only results are considered. The most important result concerns the effects of sample size and dilution on the position of the turning-point. A disagreement with the results of experiments on kaolinite is pointed out; it is argued that only a small part of this disagreement is due to simplifications made in developing the theory, and it is concluded that the hypothesis that the clay reactions are first-order, with a rate factor of Arrhenius form, is only approximate.

The industrial applications of Fullers' Earth are discussed including those of the clay in its natural form, calcium montmorillonite, and after modification by acid activation or sodium exchange. Special consideration is given to uses in oil refining, foundry bonding, civil engineering, and agriculture.

Low molecular weight polycyclic aromatic hydrocarbons can intercalate from the solid phase into montmorillonite (Mt) saturated with quaternary alkylammonium ions. However, the interaction and relationship between guest and host organic molecules in the interlayer space of the clay are not well understood. We have intercalated phenanthrene into tetradecyltrimethylammonium (TDTMA)-montmorillonite by a solid-solid reaction. The basal spacing of the original TDTMA-Mt complex is close to 1.8 nm, indicating the presence in the interlayer space of a double layer of TDTMA ions with the alkyl (polymethylene) chains lying parallel to the silicate layers, and the carbon zig-zags adopting an all-trans conformation. After intercalation of phenanthrene the basal spacing increases to about 3.4 nm, indicating a change in orientation of the alkyl chains with respect to the silicate layers. 13C-NMR spectroscopy shows that adding phenanthrene to TDTMA-Mt leads to a displacement by -3 ppm of the -(CH2)n- signal for TDTMA. This signal and that for interlayer phenantbrene are also broadened relative to the respective pure compounds. These observations, together with measurements of nuclear spin relaxation time constants, strongly suggest that in the complex with phenanthrene the polymethylene chains of TDTMA extend away from the silicate layers, and no longer assume a rigid all-trans carbon zig-zag conformation. Rather, the TDTMA chains become relatively disordered and intimately mixed with phenanthrene.

Two-line ferrihydrite samples were synthesized following conventional procedure. Detailed characterizations of freeze-dried and untreated samples – prepared from direct inclusion of the fresh precipitates in hydrophilic resin – were made by high resolution transmission electron microscopy to investigate in detail their structural organization and to compare the two types of preparations.

Only highly disordered chain-like aggregates of 2 5 nm diameter size nano-particles were revealed within the untreated samples. Conversely, in freeze-dried samples, domains with different degrees of order were recognized, from poorly ordered 2-line ferrihydrite to 3-line ferrihydrite particle aggregates that revealed lattice fringes. Associated with these aggregates, a goethite phase with a modified crystal morphology was also observed.

These HRTEM observations revealed that freeze-drying techniques induce artifacts by disturbing ferrihydrite aggregates while direct inclusion in hydrophilic resin preserves the primary organization of such poorly ordered phases.