A series of samples of “metabentonites,” here referred to as K-bentonite, and related limestones were collected from the Upper Black River and Lower Trenton formations of the Ordovician System in Central Pennsylvania. The K-bentonite occurs in yellow and gray beds which range from half an inch to ten inches in width.

X-ray diffraction patterns of the 22 K-bentonite samples are similar to those for illite and have the (060) reflection at 1·50Å indicating that the clay mineral is of the dioctahedral variety. However, the value of the (001) reflection ranges from 10·2 to 10·6Å, suggesting that the material is a mixed layer clay composed of expanded and non-expanded layers of hydrous mica (montmorillonite and illite). This possibility was tested by saturating the clay with H, Ca, Na, K, NH4, and ethylene glycol and noting the effect of the treatment on the position of the (00l) spacings in the X-ray diffraction patterns. Using the curves published by Brown and MacEwan (1950) for the analysis of mixed layer complexes, it was found that approximately 20% of the layers are expanded and 80% are not. This ratio is supported by chemical analyses which show that of the exchangeable cations 20% are calcium, sodium, and magnesium and the remaining 80% is potassium.

Adsorption of cis-2-butene and trans-2-butene on clinoptilolite-rich tuff and ion-exchanged forms was investigated. Clinoptilolite samples were characterized by X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, chemical analysis and nitrogen adsorption techniques. Adsorption isotherms for cis and trans 2-butene on purified clinoptilolite (Cp) and modified forms (Na-Cp, K-Cp, Ca-Cp and Mg-Cp) were obtained at pressures up to 2.7 atm. and at 25ºC. The results show that natural clinoptilolite has a considerable potential for separation of the two hydrocarbons. Mg-Cp samples showed maximal uptake of both cis-2-butene and trans-2-butene.

Mineralogical and chemical compositions of residual and sedimentary clays (bulk and <2 μm fraction) from the Nelas region (schist, aplite-pegmatites, granites and Tertiary sediments from both Mondego River margins), Portugal, were studied, aiming to establish indicators for raw materials in ancient ceramic provenance studies. The mineralogy of bulk material does not provide a clear distinction between samples. Among clay minerals, kaolinite dominates, except in the aplite-pegmatites where illite prevails. Smectite was only found in sediments of the left river bank.

A more successful result was the geochemical differentiation of clay types. The weathered schist presents greater enrichment in Cr, whereas the clay fraction of aplite-pegmatites shows enrichment in all the chemical elements studied. The sediments and weathered granites are not easy to differentiate; the best geochemical indicators are U (lower contents in clay-size fraction of sediments) and REE patterns in both bulk and clay-size fraction.

Two well-characterized soils containing substantial amounts of interstratified mica-smectite have been examined by a combination of techniques in an attempt to correlate the characteristics of the interlamellar surfaces with other properties. The techniques used included XRD and chemical analyses, determination of surface area by nitrogen sorption and by desorption of water and ethylene glycol monoethyl ether vapour, and determination of cation exchange capacity. Reasonable agreement was found between the results obtained for the proportion of expanding or smectite-like surfaces, although estimates by XRD, especially when coarser material (> 2/µm) was included, were generally lower than those obtained by the other methods. The mean density of charge on the surfaces of the soil clays appeared to be similar to that of smectite. The decrease in porosity observed for both soils dried by the critical point method was largely accounted for by the decrease in volume associated with the loss of interlamellar water from the smectite-like interlamellar surfaces included within the clay fraction.

Des kaolinites sont exploitées dans les sédiments du Tertiaire inférieur des Charentes, constitués d'argiles, de lignites, de sables noirs à gros bois et pyrite et de sables roux. Deux niveaux de kaolinite sont exploités: (i) des kaolinites ordonnées accompagnées de muscovite, (ii) des kaolinites désordonnées toujours accompagnées d'anatase. Ces deux niveaux correspondent à deux épisodes sédimentaires successifs, datés du Sparnacien et du Cuisien par la palynologie. Le premier épisode est vraisemblablement issu de la reprise d'altérations éablies sur le socle cristallin du Massif Central, alors que le second reprendrait des matériaux issus de l'altération des roches sédimentaires des bordures du bassin. Des kaolinites très bien ordonnées et de la gibbsite résultent de transformations géochimiques au sein des dépôts. Elles sont liées aux milieux acides des dépôts ligniteux et à l'oxydation des pyrites qui amènent la mobilisation de l'aluminium.

A synthetic phyllomanganate saturated with a series of primary alkylammonium cations has been examined using XRD, chemical analysis and X-ray photoelectron spectroscopy. A linear relationship exists between the basal spacing of the saturated alkylammonium-manganate and the hydrocarbon chain length in the interlayer, and from the gradient it is concluded that the alkyl chains are perpendicular to the manganate sheet. This orientation is a function of both the charge density and the presence of a layer of water molecules immediately adjacent to the manganate basal surfaces. Evacuation results in the loss of this interlayer water and the structure of the organo-manganate is considerably disrupted. The extent to which the interlayer arrangement can be reinstated by rehydration is dependent on the chain length of the saturating organo-cation. For cations of chain length > C6 the C contents suggest that cation in excess of the exchange capacity is present in the interlayer, but the absence of any compensating anion and the release of amine on evacuation suggests that the excess C arises from the presence of free amine.

A new method for determining the cation exchange capacity (CEC) of clays is proposed. The method is based on X-ray fluorescence analysis of natural and Ba-exchanged clays following the analytical procedure suggested by Franzini et al. (1975). This procedure, which utilizes powder pellets and is based on a full matrix correction method, is frequently applied in Earth Sciences laboratories for the routine analysis of minerals and rocks. For the analysis of Ba-exchanged clays, Franzini's procedure has been modified slightly to account for the contribution of Ba to matrix effects.

The new method, which furnishes both the CEC and the chemical compositions of the whole natural clay samples, has been tested on the eight ‘Source Clays’ of The Clay Minerals Society. The results compare well with data reported in the literature and confirm the accuracy and precision of the method and make it a valid alternative to techniques based on wet chemistry, execution of which is usually more time-consuming and which often requires greater analytical skill.

Experimental illitization of smectite has been simulated by means of hydrous pyrolysis, using a smectite-rich starting material from a Lower Tertiary claystone from the Oseberg field, North Sea. The <2 µm fraction was subjected to hydrous pyrolysis using KCL solutions at concentrations of 1.0 and 0.01 N, temperatures from 180-350°C and reaction times from 24-72 h. The conversion of smectite into illite has been identified by XRD analysis of the pyrolysed products. It was clearly demonslrated that the K+ concentration ([K+]) and temperature are the major factors controlling the rate and extent of illitization. The distributions of activation energies around 33 kcal/mol and frequency factors in the range of 10+8 to 10+9 S-1 have been calculated by applying a parallel reaction model. However, geological modelling and comparison with buried smectite clays indicates that both 1.0 n and 0.01 N KCL are too high in K+ content compared to the pore-water. The results suggest that dilute KCL solution close to pore-water should be used in hydrous pyrolysis to obtain proper kinetic models.

This paper reports a novel approach in the study of trace-element mobility during the argillization of volcanic glass that is based on in situ laser ablation inductively coupled plasma mass spectrometry glass analyses and that of spatially related illite-smectite collected in the form of fraction separates. The material studied originates from lacustrine sediments of the Dinaride Lake System that bear evidence of intensive weathering of distal tephra during the Miocene climatic optimum. Yttrium and HREE were probably mobilized from decomposing glass in the form of carbonate complexes and were consequently depleted significantly in the clays studied. On the other hand, the Mg-rich illite-smectite demonstrates an elevated adsorption potential of solvated LREE complexes. This may be explained through clay surface geochemistry controlled largely by Mg for Al octahedral substitution. This paper highlights the role of eogenetic 2:1 clay aluminosilicates that, under favourable geological conditions, may be conducive to secondary REE enrichment and the formation of potential ion adsorption-type deposits.

In this study, a clinoptilolite modified with apolaccase was used to adsorb Reactive Black 5 (RB5) dye from aqueous solution using the batch procedure. The influences of pH, contact time, temperature and absorbent dosage on the adsorption were investigated. The optimum adsorption was obtained at pH = 6, contact time = 60 min, temperature = 25ºC and adsorbent dosages of 1.62 and 1.59 mg/50 mL per gram of clinoptilolite and of apolaccase-modified clinoptilolite (LMC), respectively). The adsorption experimental data fitted both the Langmuir and Freundlich isotherm models well. In addition, pseudo-first-order and pseudo-second-order kinetics were used to study the kinetics of RB5 dye adsorption onto natural clinoptilolite and LMC. Adsorption appears to follow pseudo-second-order kinetics with a high correlation coefficient. Thermodynamic parameters such as changes in the free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) of adsorption were calculated. The thermodynamic parameters indicate that the adsorption of RB5 dye onto LMC was less spontaneous, feasible and endothermic. The LMC can be used as an alternative low-cost adsorbent for the dye removal from aqueous solutions.

Purified and surfactant-modified Tunisian clays were investigated for their capacity to remove cationic and anionic dyes (crystal violet, CV and methyl orange, MO) from aqueous solution. The samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and potentiometric acid-base titration. Batch-sorption experiments were carried out to evaluate the influence of pH, contact time, initial dye concentration and temperature on the adsorption of dyes. Pseudo-first order, pseudo-second order, intra-particle diffusion and Elovich kinetic models were considered to evaluate the kinetic parameters. To understand the interaction of the dye with the adsorbent, Langmuir, Freundlich, Temkin and Dubinin-Radushkevish isotherms were applied. Thermodynamics studies were conducted to calculate the changes in free energy (Δ°G), enthalpy (Δ°H) and entropy (Δ°S). A difference in the maximum adsorption capacity was observed, suggesting that the retention of dyes was influenced by structure, functional groups of dyes and surface properties of the adsorbents. Moreover, different mechanisms may control the removal of dyes. The purified Tunisian clays are excellent adsorbents for removal of the cationic dye CV and its modified form is suitable for removal of the anionic dye, MO, from aqueous solution.

Sepiolite powder was hydrothermally solidified into a cemented, designed to function both in humidity regulation and volatile organic compound (VOC) removal. The solidification process mimicked the cementation of sedimentary rocks. The formation of the calcium aluminium silicate hydrate (C-A-S-H) or Al-tobermorite enhanced the strength (maximum flexural strength >17 MPa) and improved the porosity of the solidified materials. Due to the low temperature of hydrothermal solidification (≤473.15 K), most sepiolite remained in the matrix of the solidified specimens. The cemented sepiolite aggregate shows outstanding humidity-regulating performance (moisture adsorption of 430 g m–2), and the synergistic effects of the residual sepiolite and neoformed Al-tobermorite exerted a positive influence on the humidity regulation performance of the material. Similarly to the behaviour of sepiolite, the solidified material also displayed good formaldehyde-removal capacity (60–68%). The pore dimensions controlled the humidity regulation and formaldehyde removal. The humidity regulation depends on the mesopores, which originate mainly from both the original sepiolite and the neoformed C-A-S-H phases and Al-tobermorite, while the formaldehyde removal depends on the micropores from the original sepiolite in the matrix. As such, the cemented sepiolite aggregate might be hydrothermally synthesized and might be used to improve the comfort and safety of indoor environments for human beings.

Three samples of bulk smectite clay from the Pilori and Velanida bentonite deposits of the Ventzia basin, western Macedonia, Greece, were characterized in detail. Chemical analyses and X-ray diffraction (XRD; Rietveld method) showed that the samples are rich in Fe and Mg (8–13 mass% and 6–10 mass% as oxides, respectively) and contain ~60–65 mass% smectite. The high Fe and Mg content as well as the high Cr (0.3–0.5 mass%) and Ni content (0.1–0.3 mass%) are consistent with the formation of these clays from ultramafic precursor sediments of the Vourinos ophiolite complex. Both XRD and infrared spectroscopy indicate the presence of other clay minerals besides smectite, such as minor amounts of kaolinite, trioctahedral-rich palygorskite, serpentine and talc (depending on the sample). The position of the d060 reflection (1.51–1.52 Å) is compatible with either high Fe content or partial trioctahedral character, or probably both. The predominance of ferruginous smectite or nontronite was confirmed by infrared spectroscopy, but the minor presence of a trioctahedral magnesian smectite in some of the samples cannot be excluded. Layer charge densities, determined by the νO-D (oxygen-deuterium IR-stretching) method calibrated against the structural formula method, are in the 0.48–0.52 eq/FU range. Various methods point to the existence of a significant amount of tetrahedral charge, which is typical of ferruginous smectites. The major exchangeable cation is Mg2+ (73–90%), which represents a special property of these materials compared with other bentonites.

The modification of halloysite nanotubes (HNTs) as fillers is very effective at improving the performance of polymers. A novel modification of HNTs through grafting dodecylamine onto their surfaces was conducted here. Owing to the improvement in dispersibility of HNTs in polytetrafluoroethylene (PTFE), the mechanical properties and wear resistance (in particular) of the dodecylamine-modified HNT-filled PTFE composite were enhanced significantly.

Textural, mineralogical and chemical characterization of archaeological ceramics (zellige) from El Badi Palace (Marrakech, Morocco), the main Islamic monument from the Saadian period (sixteenth century), has been performed to enhance restoration and to determine the technology of manufacturing. A multi-analytical approach based on optical and scanning electron microscopy, cathodoluminescence, X-ray fluorescence and X-ray diffraction was used. Re-firing tests on ceramic supports were also performed to determine the firing temperatures used by the Saadian artisans. A calcareous clay raw material was used to manufacture these decorative ceramics. The sherds were fired at a maximum temperature of 800°C in oxidizing atmosphere. The low firing temperature for ‘zellige’ facilitates cutting of the pieces, but also causes fragility in these materials due to the absence of vitreous phases.

We have carried out optical microscopy, X-ray diffraction (XRD) and scanning and transmission electron microscopy (SEM and TEM) studies of phyllosilicates from black slates of very low to low-grade metamorphism. Such slates belong to a Middle/Late Devonian basin and an Early Carboniferous basin associated with the Porto–Tomar–Ferreira do Alentejo strike-slip shear zone (Ossa-Morena Zone, Portuguese Iberian Variscan Massif). These black slates are imbricated in an Upper Proterozoic substratum of higher metamorphic grade. Kübler Index values of white micas and mineral assemblages deduced from the XRD, SEM and TEM data (muscovite, chlorite and pyrophyllite) indicate high anchizonal and epizonal metamorphic conditions for slates from these basins. The b parameter and the phengitic contents of mica suggest the occurrence of low pressures (1–2 kbar) related to an extensional geotectonic setting. The dense fracture network shown by SEM images and the high density of crystal defects revealed by the TEM study in the eastern basin, adjacent to faults produced by shearing, suggest that their epizonal phyllosilicates were more affected during deformation than those belonging to the western basin, favouring the development of a retrograde association (siderite, kaolin group minerals and Al-smectite) on the epizonal paragenesis. Microcavities formed along phyllosilicate cleavage acted as channels for fluid transport favouring alteration under low-temperature conditions.

A Quaternary or Recent tuff or pumice has weathered to an allophanic soil reminiscent of some described by Sudo. The soil has interesting engineering properties. Electronmicrographs show the apparent coalescence of alophane ribbons into a thin platy mineral, probably an early form of hydrated halloysite. The formation of crystals by the coalescence of mosaic crystallites is discussed.

Studies of the thermal stability of organic compounds adsorbed on clay minerals are of interest from several points of view, e.g. the type and strength of bonding forces between the organics and the clay surfaces (Chou & McAtee, 1969; Yariv et al., 1971; Lacher et al., 1981), and the effect of the clay surface on stability or degradation mechanism of the organic compounds adsorbed on clays (Bodenheimer et al., 1966; Yariv et al., 1971; Durand et al., 1972).