A zeolite-montmorillonite (zeolite-Mt) nano-adsorbent was prepared by calcination at 600°C. The synthesized nano-adsorbent was tested for removal of a toxic and cationic dye (crystal violet) from water, and it was characterized by various techniques. The effects of variables such as pH, temperature, adsorbent dosage and initial dye concentration on the removal efficiency of the dye were investigated by response surface methodology (RSM). Experimental conditions were optimized by RSM to achieve the maximum dye removal efficiency. Optimum conditions for maximum removal of dye were obtained at pH 9, temperature of 25°C, adsorbent dosage of 2 g L−1 and initial dye concentration of 40 mg L−1. Under these conditions, the maximum removal efficiency obtained was 99.9%. Various isotherms were applied to study adsorption equilibrium, and of these, the Freundlich isotherm provided the best fit. In addition, the fractal-like integrated kinetic Langmuir model was the most appropriate among several kinetic models. The thermodynamic parameters were also determined. The zeolite-Mt prepared under optimum conditions displayed a greater adsorption capacity than activated carbon (manufactured by Merck) and than various other adsorbents.

The differences noticed in the porosity-permeability values and the clay mineralogy of the Brent and Statfjord reservoirs of two closely related wells from the Central Viking Graben appear to be due essentially to diagenesis. According to their type, nature and relationships, the diagenetic phases are organized into three distinct sequences, each induced by distinct hydrodynamic systems. These systems are related to three main episodes of the geological history of the reservoirs, which were: the compaction-lithilication phase, the Kimmerian to Lower Cretaceous emersive phase, and the hydrologic loading of the deep parts of the basins and/or fault panels. The late diagenetic sequence is expressed by quartz overgrowths, blocky kaolinite and illite authigenesis. With a probable ‘catalytic’ effect of temperature, this sequence is the most intensely developed and so greatly damages the porosity and permeability. In the oil-bearing reservoirs of Well 25/4-1, the stage of evolution of this third diagenetic sequence is not well advanced: illitization was rapidly stopped by the hydrocarbon charge so that permeabilities remained satisfactory (up to 500 mD). In the water-zone of Well 25/4-5, illitization is extensive and permeabilities considerably reduced (lower than 5 mD). K/Ar dating of authigenic illites provides evidence of a late Eocene phase (40–44 Ma) as the maximum age for the hydrocarbon entrapment in Well 25/4-1, whereas the last illite authigenesis from the water-zone of Well 25/4-5 gives an Oligocene phase (28 Ma in the Statfjord Formation). These data indicate that fluid circulation was effective until this time in the down-dip faulted panel of Well 25/4-5, and has therefore been responsible for the drastic permeability reduction.

The kinetics of clay formation in buried paleosols developed from late Quaternary rhyolitic tephra layers near Rotorua, New Zealand, can be described in terms of a combination of parabolic and linear kinetics, reflecting the hydration of glass, and the formation of clay minerals, respectively. Such a model is consistent with the formation of clay minerals showing an Arrhenian temperature dependence and suggests, on the basis of calculated activation energies, that the process of formation of Al-rich allophane (imogolite) is diffusion controlled, whereas the rate of formation of Si-rich allophane is controlled by the chemical processes at the site of reaction.

The work outlined in this paper was undertaken to show how, by a consideration of the energy changes involved, some insight may be gained into the reactions occurring when kaolin minerals are heated.

Activation energies have been determined experimentally for the dehydration of various kaolin minerals. The fireclay mineral is distinctive and it is suggested that it does not form part of a halloysitekaolinite series. It is further thought possible that there is a series of fireclay minerals.

From thermochemical and thermodynamic considerations the heat of formation of kaolinite has been calculated approximately and enthalpy and free energy changes have been estimated for the exothermic reaction at 980°C. These indicate that, if a compound is produced during dehydration, the most probable explanation of the exothermic reaction is the simultaneous production of mullite, γAl2O3 and SiO2. Finally the lattice energies of kaolinite and its thermal decomposition products have been calculated.

Organoclays are sorbent materials prepared from clays by exchanging inorganic with organic cations. Their properties depend on the loading and conformational structure of the organic cations, but little information is available about the surface structures of organoclays. In this work, X-ray photoelectron spectroscopy (XPS) and classical molecular dynamics (MD) simulations are combined to characterize the external interface of an organoclay prepared from hexadecylpyridinium (HDPy+) and bentonite. The XPS survey spectra show well the varying elemental composition of the surface with increasing amount of surfactant, showing a decreasing contribution of clay-derived elements with increasing organic coverage. The high-resolution C 1s XPS spectra depict sensitively the surface arrangement of the surfactant. In combination with MD simulations, the results implied a monolayer coating for low surfactant coverage and a disordered bilayer arrangement at high surfactant uptakes. Molecular dynamics simulations showed that for very high cation uptake a quasi-paraffin-like configuration is also possible. The combination of experimental and modelling methods yielded congruent information on the molecular-scale arrangement of organic cations at the organoclay surfaces and the controlling mechanisms.

Lower Palaeozoic rocks crop out extensively in Wales, the Lake District of northern England and the Southern Uplands of Scotland; they also form the subcrop concealed beneath the English Midlands and East Anglia. These mainly marine sedimentary rocks were deposited in basins created during plate tectonic assembly of the various terranes that amalgamated to form the British Isles, 400-600 Ma ago. Final amalgamation occurred during the late Lower Devonian Acadian Orogeny when the basins were uplifted and deformed, producing belts of cleaved, low-grade metasediments, so-called slate belts, with a predominantly Caledonian (NE-SW) trend. The clay mineralogy of mudrock lithologies - including mudstone, shale and slate - found in these belts is reviewed. Using X-ray diffraction data from the <2 μm fractions of ~4500 mudrocks samples, clay mineral assemblages are summarized and discussed in terms of diagenetic and low-grade metamorphic reactions, and the metapelitic grade indicated by the Kübler index of illite crystallinity.

Two sequences of clay mineral assemblages, or regional assemblages, are recognized. Regional Assemblage A is characterized by a greater diversity of clay minerals in assemblages from all metapelitic grades. It includes K-rich, intermediate Na/K and Na-rich white micas, chlorite and minor amounts of pyrophyllite. Corrensite, rectorite and pyrophyllite are found in the clay assemblages of contact or hydrothermally altered mudstones. K-white micas are aluminous and phengite-poor, with b cell dimensions in the range 8.98-9.02 Å. Regional Assemblage B has fewer clay minerals in assemblages from a range of metapelitic grades. Phengite-rich K-mica is characteristic whereas Na- micas are rare, and absent in most assemblages; chlorite is present and minor corrensite occurs in mudrocks with mafic-rich detritus. Minor amounts of kaolinite are sporadically present, but dickite and nacrite are rare; pyrophyllite and rectorite are generally absent. The b cell dimensions of K-white mica in Regional Assemblage B are in the range 9.02-9.06 Å. The two regional assemblages are found in contrasting geotectonic settings. Regional Assemblage A is characteristic of the extensional basin settings of Wales, the northern Lake District and the Isle of Man. These basins have a history of early burial metamorphism associated with extension, and syn-burial or post-burial intrusive and extrusive volcanic activity. Intermediate Na/K mica probably developed from hydrothermal fluids generated around submarine volcanic centres. Deep diagenetic and low anchizonal clay mineral in these basins may develop a bedding-parallel microfabric. Chlorite-mica stacks also occur in the extensional basins and the stacking planes represent another type of bedding-parallel microfabric. Both types of microfabric are non-tectonic and developed by burial during the extensional phase of basin evolution. Regional Assemblage B is developed in the plate-convergent settings of the Southern Uplands and the southern Lake District. In the accretionary complex of the Southern Uplands the processes of burial diagenesis, metamorphism and tectonism were synchronous events. In both plate- convergent basins, low temperatures and tectonic fabric-formation had an important role in clay mineral reactions, whereas hydrothermal fluids played no part in clay genesis.

The thermal behaviour of sepiolite and palygorskite treated with butylamine was investigated by DTA, TG and EGA-MS under a flow of air and N2. It was shown that the amine was adsorbed by the clays, penetrating into the pores and replacing zeolitic and bound water. The presence of amine in the pores shifted the dehydroxylation peak to temperatures higher than for the untreated clays. Under N2 the thermal desorption of the amine from sepiolite was observed at 175, 275 and 525°C, and from palygorskite at 170 and 270°C. In addition to desorption, reactions of pyrolysis and condensation to charcoal were detected by the evolution of NH3, CH4 or H2, respectively. In air, oxidation of the organic matter led to the appearance of exothermic peaks, the temperatures of the most intense peaks being determined by the rate of C oxidation, but the shape of the DTA curves and the temperatures of exothermic shoulders were determined by the rate at which H from the organic molecules combined with O from the air.

Ferrihydrite transformed to crystalline Fe(III)-oxides in salt solutions but the degree of transformation generally decreased with increasing concentration (decreasing water activity) and haematite was favoured over goethite. More transformation occurred for chloride than for nitrate or sulphate and more for calcium than for magnesium or sodium. Calcium and magnesium favoured haematite over goethite. The results support the hypothesis that haematite not only can be formed but will be favoured over goethite in natural environments with low water activity, for instance dry or saline soils or sediments. The ionic environment modifies the general water activity effect.

Methods are described for estimating a valuable absorption coefficient for OH stretching bands of micas: the integrated parallel absorption coefficient K.

From a correlation between this coefficient and the OH content of biotites and phlogopites, it was found that the parallel absorption coefficient per hydroxyl group in these trioctahedral micas is not appreciably influenced by the chemical composition and the direction of the OH bond. A clear deviation was observed for the low frequency band of a biotite characterized by a well-ordered orientation distribution for the corresponding hydroxyl groups.

The integrated parallel absorption coefficient of muscovite is proportionally 2·5 to 3 times larger than that of trioctahedral micas.

In the Maláiguide Complex (Betic Cordilleras, Spain), dickite is widely developed in clastic Permo-Triassic sequences. The lateral extent stretches at least 300 km along the Betic range, whilst vertical extent is variable and appears limited to the lowest 20–150 m of these sequences. Textural, chemical and crystallochemical characteristics of the dickite, illite/mica and chlorite in dickite-bearing rocks and in the overlying (Permo-Triassic) and underlying (Carboniferous) rocks have been investigated to determine the approximate conditions in which dickite has developed. Using the chlorite geothermometer (based on A1IV contents), temperatures of 146±28°C and 169±12°C have been deduced for two Permo-Triassic members, and 305±12°C for Carboniferous. The Si content in illites has been used as a geobarometer, and pressures of 4.8±2 kbar have been estimated in Carboniferous rocks and tentative pressures of 2.7±3 and 2.1±2 kbar in Permo-Triassic members. Chemical evolution of phyllosilicates is accompanied by increasing illite crystallinity and % 2M1 polytype.

K-Ar ages of Eocene glauconite pellets from the Isle of Wight are related to quantified amounts of older glauconite pellets and to occurrences of detrital mica/illite particles that might have been added to synsedimentary pellets during reworking processes. Addition of older glauconite did not significantly bias the K-Ar dates, as the results most often provide the expected stratigraphic reference ages or even significantly lower ages. Alternatively, K-Ar dates significantly greater than those suggested by the stratigraphy appear to result from non-glauconized detrital mica in the pellets which is not always removable, even by high-gradient magnetic separation.

Unexpected ‘old’ K-Ar glauconite ages do not result from misapplication of the method, but from inability to systematically identify and remove the `contaminant' particles from glauconite splits. Analysis of highly evolved glauconite separates is definitely appropriate for reliable isotopic age determinations, but it might not be enough for the final selection, as long-lasting diagenesis might have taken over the synsedimentary process. Much if not all depends on the separation and characterization of the separates, but also on the completion of the glauconitization process which effects cannot always be anticipated.

The removal of the alkali-soluble fraction from soil clays has been found to influence markedly the efficiency with which iron oxides can be removed from such clays. In clays pretreated with 5% Na2CO3, up to 40% more iron oxide was extracted by dithionite (Na2S2O4) than from soil clays treated with this reagent alone. Chemical analysis, electron microscopy, X-ray and differential thermal examination, and specific surface area and cation-exchange capacity measurements indicated an improved dispersion brought about by the removal of aluminosilicate binding material by Na2CO3. The electron-optical studies also showed that the dithionite-soluble iron was principally in the form of small granules. These were amorphous to X-rays and electrons and chemical analysis of the dithionite-soluble fraction suggested that they were ferruginous complexes containing considerable quantities of silica and alumina.

IR spectra of antigorite and sepiolite show an absorption band at ∼ 1200 cm−1. Spectra of palygorskite show several small absorptions between 1140–1200 cm−1. Since these three minerals are the only layer-silicates which show this absorption this band was assigned to Si-O-Si groups which serve as bridges between alternating alumino-Mg-silicate ribbons. By comparing the location of this band to bands observed in the spectra of P=O groups it was concluded that the contribution of π bonding in the bridging Si-O-Si group is of a high order. Similar conclusions were drawn after comparing the spectra of antigorite, sepiolite and palygorskite with those of various pyrosilicates. An inversion of the tetrahedral sheet requires an Si-O-Si angle of 180° which can be stabilized by dπ-pπ bonding in the Si-O-Si group. Due to the inductive effect of the octahedral sheet this type of bonding may occur in trioctahedral clay silicates, but is not to be expected in dioctahedral clay silicates.

Turkey has a long tradition (starting with prehistoric civilizations) and experience in exploring for raw clay materials and processing them into ceramic products. Many of these products, such as tiles and sanitary ware, are manufactured for domestic and export markets. Kaolin is one of the raw materials of major importance for the ceramic and paper industry, as well as for a number of auxiliary applications. There is ongoing interest in applying kaolin in the construction industry as a raw material in the production of white cement clinker and as an artificial pozzolanic additive for concrete (in the form of metakaolin). This report presents results related to search, assessment and evaluation of available resources for advanced cement and concrete additives.

Pour les hydrates à ‘deux couches’ des vermiculites issues des phlogopites 1 M, saturées par Li, Na, Ca, Mg ou Ba, nous avons rencontré quatre modes d'empilement des feuillets. Un seul (VIII) présente une structure ordonnée tridimensionnellement. Les trois autres (VI, VV et VVII) sont des structures semi-ordonnées.

Nous avons défini les translations entre feuillets pour chaque empilement ainsi que les domaines d'existence en fonction du cation et de l'humidité relative.

Pour l'édifice ordonné VIII calcique la structure de la couche interfoliaire est décrite (deux types de polyèdres d'eau plus de l'eau de liaison entre polyèdres).

Les diffèrents facteurs conditionnant, pour une vermiculite donnée, le ‘choix’ d'un mode d'empilement sont discutés : facteurs propres à la couche interfoliaire (nature des cations et degré d'hydratation); facteurs propres au feuillet (densité et localisation des charges, disposition des oxygènes de surface); facteurs liés à la texture.

Rhaetian (Upper Triassic) sandy horizons were sampled from the Paris Basin from SW to NE, crosscutting the Rhaetian at different depths from outcrop in the NE to 2700 m in the centre of the basin. The smallest day sub-fractions (<0·2 μm) from the deepest samples consist mainly of illite and chlorite having a K-Ar age of 〜190 Ma. Both minerals probably formed under specific hydrothermal conditions at high temperature, but at a burial depth of only 500 m. This thermal event could represent an echo of the "crustal" breakdown of the Northwestern European craton during the opening of the North Atlantic Ocean. Two other generations of illite-smectite mixed-layers formed in the same Rhaetian horizons at somewhat lower temperatures about 150 and 80 Ma ago. The three generations of clay minerals could be characterized and dated because of combined mineralogical, crystallographical and morphological data supporting the dating attempts.

Calculated diffraction profiles for interstratified kaolinite and montmorillonite have been used to determine the composition of clays reported from Poland, Japan and Mexico. The predicted layer proportions determined from the curves and by other methods are in close agreement for the first two but a higher kaolinite content than that originally proposed is obtained for the Mexican clays.

The adsorption of Cd and Zn on a standard montmorillonite (SAZ-1) in the presence of the cationic pesticide chlordimeform, both in solution (simultaneous adsorption) and when the pesticide is previously adsorbed on the clay (successive adsorption) has been studied. The adsorption of Zn decreases when the chlordimeform concentration increases in both simultaneous and successive adsorptions, following the sequence: chlordimeform-free solutions > successive > simultaneous. In the adsorption of Cd the sequence is different: successive > chlordimeform-free solutions > simultaneous, indicating that a small amount of pesticide adsorbed favours Cd adsorption. In all cases, the apparent affinity of the metal for adsorption on montmorillonite, on the basis of distribution coefficients, KD, is higher for lower metal surface coverage, and decreases largely with the amount of the metal adsorbed. This indicates the existence of high affinity sites on the clay, probably those of variable charge edge regions. The contribution of edge and interlamellar positions to adsorption of Zn and Cd on SAZ-1 has been studied.

Analytical transmission electron microscopy (ATEM) was used to obtain chemical analyses of single illite crystals from Upper Carboniferous reservoir sandstones of the Bothamsall Oilfield, East Midlands, UK, and from Rotliegendes (Permian) sandstones of the North Sea. All samples were found to be highly aluminous, with only minor Mg and Fe, and to have near-ideal dioctahedral sheet totals. No significant variation in chemical composition of illite was found within the Bothamsall reservoir rocks, irrespective of paragenesis or stratigraphic horizon. Similar results were obtained from the Rotliegendes samples. Variation was found, however, between Bothamsall and Rotliegendes analyses populations. The Rotliegendes illites were distinctly more K-rich, which is the result of greater charge deficiency in the octahedral sheet. These results indicate that all the illite in both reservoirs precipitated in equilibrium with the reservoir pore-fluid. Furthermore, they imply that the physico-chemical composition of the pore-fluid did not evolve significantly between the different illite generations in the Bothamsall samples. These data, when compared with published analyses of authigenic illite, indicate that the compositional field for illite in sandstones is restricted in comparison with that of illite in mudrocks.