Fuller's earth from near Dry Branch, Georgia, is shown by X-ray analysis to contain comparable amounts of montmorillonite and cristobalite, and only minor amounts of other minerals. The cristobalite resembles the high form, but may be a very disordered low form. Electron micrographs show the montmorillonite to be lath-like, and the cristobalite globular in form.

Triassic sequences from 'intermediate units' between the Alpujárride and the Malâguide complexes (Betic Cordilleras, Spain) of the westernmost part of the Cordilleras (Casares area) occur as four superimposed tectonic units; the uppermost unit shows lithological characteristics similar to those of the Malâguide complex, changing progressively at increasing depth, towards lithologies typical of the Alpujárride complex. The units studied, with a maximum thickness of ~400 m, record important variations in metamorphic pressures, according to the b parameter of white micas: from low-pressure metamorphism (in the unper unit) to high-pressure faciès series (in the deepest one). The mean b values range from 8.988 Å in the uppermost unit (Crestellina) to 9.042 Å in the lowermost one (Jubrique). The lowest metamorphic grade is represented by mineral assemblages consisting of phengite + intermediate Na-K white mica ± Fe-chlorite ± sudoite ± pyrophyllite, which record temperatures of ~300°C and pressures of 1.5—3 kbar. At increasing tectonic depth, intermediate Na-K mica and pyrophyllite disappear and the metamorphic assemblages consist of phengite ± paragonite ± margarite + Mg-chlorite ± sudoite, which record minimum pressures of ~7 kbar and temperatures in the order of 400—450°C. These mineral assemblages provide evidence of the passage from collisional to extensional geotectonic settings. The units showing different metamorphic patterns were juxtaposed tectonically, after the development of metamorphic mineral assemblages.

The idea is tested that the evolution of the Chalk’s clay mineral assemblage during diagenesis can be deduced by examining the relationships between its clay mineralogy, particle size distribution pattern, and the timing and trace element chemistry of the calcite cement. The preliminary results from five different examples of cementation developed at different stages of diagenesis in chalks with smectite-dominated clay assemblages suggest that this is a promising line of investigation. Soft chalks with minor amount of anoxic series calcite cement poor in Mg, Fe and Mn are associated with neoformed trioctahedral smectite and/or dioctahedral nontronite and talc. Hard ground chalk with extensive anoxic series calcite cement enriched in Mg and relatively high Fe, Mn and Sr are associated with neoformed glauconite sensu lato, berthierine and dioctahedral smectite, possibly enriched in Fe. The chalk associated with large ammonites shows extensive suboxic series calcite cement enriched in Mg, Mn and Fe that show no obvious correlation with its clay mineralogy. Nodular chalks with patchy suboxic series calcite cement enriched in Fe are associated with neoformed dioctahedral smectite, possibly enriched in Al, and berthierine. Regionally hardened chalk with extensive suboxic calcite cement and relatively high trace element contents contain pressure dissolution seams enriched in kaolin and berthierine. Laser-based particle-size distribution patterns suggest that each type of lithification has a typical complex clay mineral population, indicating that subtleties in mineralogy are not being identified and that there could be some control on the size and shape of the clay crystals by the different types of cementation.

Development of the Polish ceramic industry over the last ten years has resulted in a sharp increase in demand for basic raw materials, especially for ceramic clays – both white- and light-firing as well as red-firing varieties. Polish sources of white-firing clays are rather scarce. Their production is based on Santonian sandy-clayey sediments of the North-Sudetic Trough (Lower Silesia, SW Poland). Light-firing varieties occur mainly in Lower Jurassic sediments on the northern margin of the Holy Cross Mountains (central Poland). Red-firing well-sintering clays of Triassic age are known in the northern margin of the Holy Cross Mountains as well as in the Cracow-Silesian Monocline.

The white-firing Santonian clays contain mainly highly-ordered kaolinite (~50%) and quartz (~30%) with minor amounts of illite. Their grain-size median ranges between 1.9 and 2.5 μm. They show moderate plasticity (bending strength after drying at 1.7–1.9 MPa) and weak sinterability (water absorption after firing ~12%), but greater lightness after firing (L parameter ~86%). The light-firing Jurassic clays are kaolinitic-illitic in character, with a variable content of quartz. Kaolinite is represented by the low-ordered variety. The grain-size median is also variable, ranging between 1.1 and 3.4 μm. They show good plasticity (bending strength after drying 2.6–2.8 MPa), good or very good sinterability (water absorption after firing <6%) but moderate lightness (L ~79%).

Triassic red clays are highly polymineralic, with illite, kaolinite, smectite, chlorite and mixed-layered minerals occurring in variable amounts. Their specific features are: large hematite content (5–12%), commonly small CaO content (<0.5 wt.%) and an extremely small organic matter content (⩽0.1 wt.%). Their grain-size median usually varies between 2 and 3 mm. Using such clays, sintered ceramics (e.g. stoneware tiles) are obtained after firing in the temperature range 1150–1200ºC.

Intercalation of cationic surfactants hexadecylpyridinium (HDPy+) and hexadecyltrimethylammonium (HDTMA+) into the interlayer space of homoionic (Na-, Ca- and Zn-) smectites by solid-solid reactions was investigated. These reactions were complete within 15 min. Changes in the surface and structure of the smectites modified with different surfactants were characterized using XRD, FTIR and DSC. The intercalation of surfactant is controlled by the exchangeable cation of smectite and monofunctional ammonium cation type. HDPy+ and HDTMA+ surfactants were retained by Zn-exchanged smectite, suggesting important surface properties (CEC = 80 meq/100 g clay, SBET = 116.5 m2/g) and acid-base properties (point of zero proton charge PZC, density charge σH). HDPy cation loading was effective, suggesting that the aromatic polar group is favoured for intercalation. Comparing with original clay, modification with surfactants increased the basal spacings d001. Based on the d001 spacing of modified smectites, different configurations of surfactants within smectite interlayer were proposed as a function of surfactant concentration, which were examined by FTIR and DSC.

The removal of enrofloxacin, a fluoroquinolone antibiotic, from aqueous solution by adsorption onto bentonite was investigated in this study. The effects of initial concentrations, contact time and temperature on the adsorption of enrofloxacin were studied via batch experiments. The adsorption equilibrium was achieved within 60 min for all studied concentrations. The adsorption capacity increased with the increase of initial concentration within a concentration range. Higher temperatures were favourable for the adsorption. The change of Gibbs free energy (ΔG°), change of enthalpy (ΔH°) and change of entropy (ΔS°) were evaluated and the results indicate that the adsorption should be an endothermic and spontaneous process. The Langmuir isotherm model fitted to the experimental data better than the Freundlich model. The adsorption follows the pseudo-second order kinetic model.

Three organic reactions which affect individual compounds present in most organic-rich sedimentary rocks have been identified—configurational isomerization and aromatization of steroid hydrocarbons, and configurational isomerization of hopanes. The extents to which these reactions have occurred can be assessed by gas chromatographic-mass spectrometric analysis of the organic extracts of the sediment samples; they provide sensitive indicators of thermal maturation. When combined with the model of sedimentary basin formation by extension of the lithosphere, this molecular approach to the maturation of organic material can be used to constrain the temperature-time histories of sedimentary sequences. This temperature history may be used to integrate the relevant Arrhenius’ and rate equations governing the reaction rates. Each rate equation has three constants—the activation energy, frequency factor and the ratio of forward reaction to backward reaction. These have been estimated using analyses of samples whose temperature-time history is well constrained. The resulting estimates can then be used to reconstruct the temperature-time histories of other samples from organic geochemical data, e.g. calculation of the amount and timing of uplift.

Two sedimentary profiles, at 18 km and at 125 km from the Rhône River mouth were selected to study the steps of glauconitization inside green (glaucony) grains, in a temperate marine environment. The proximal site is characterized by a greater content of alpine minerals (chlorite, illite) than the distal one. In the proximal site, pellets at a younger level demonstrate a largely inherited mineral composition. In the older level, representing the most advanced stage of glauconitization, there is a mixed-layer glauconite-nontronite (G-N) phase with 20% glauconite-80% nontronite in dark green grains. In the distal site, more evolved glaucony has up to 92% glauconite in the G-N. In spite of this difference, the glauconitization process developed similarly in the two sites. The relatively low Fe content in the mud-matrix does not reflect the concentration of this element inside the grains. During diagenesis, most of the inherited minerals disappear, making way for neoformed mixed-layer glauconite-nontronite.

Mixed hydroxy Al-Fe-montmorillonite complexes (5 mmol of Al+Fe per g of clay) were prepared at pH 5.0 by mixing different amounts of Al(NO3)3 and Fe(NO3)3 to give initial Fe/Al molar ratios (R) of 0, 0.1, 0.25, 0.5, 1.0, 4.0, 10.0 or ∞. The effect of ageing on the interlayering, mineralogy, chemical composition, CEC and external surface area of the complexes was studied. The degree of interlayering of freshly prepared and aged complexes (up to 120 days at 50°C) was always greater in the samples with R ranging from 0.5 to 4. Gibbsite and hematite (with traces of goethite) formed in the samples with R ⩽ 1 and R∞, respectively. No crystalline Fe oxide was detected by XRD analyses in the complexes with R ranging from 0.1 to 10, whereas no crystalline Al and Fe oxides were formed in the complexes at R = 4–10. However, some evidence suggests the possible formation of a microcrystalline Fe oxide/oxyhydroxide undetectable by XRD analyses in the complexes richer in Fe. The CEC and the surface area of the freshly prepared mixed hydroxy Al-Fe-montmorillonite complexes increased with increasing R. Large quantities of Al+Fe were solubilized by oxalate in the complexes with R ⩾ 0.5, even after ageing for 120 days at 50°C, indicating that interlayering of Al-Fe species at certain Fe/Al molar ratios was particularly stable.

Chemical modification of kraft lignin from Pinus caribaea (Sénécl.) W.H.G. was performed with cyclic anhydrides (succinic, maleic and glutaric) assisted by microwave radiation. Esterification of the lignin was proven by the mass increase and Fourier Transform Infrared (FTIR) spectroscopy. Aqueous suspensions of bentonite were prepared using unmodified lignin and the corresponding derivatives as dispersants. Suspensions were evaluated in term of stability, viscosity and dispersibility. The esterified derivatives showed better dispersing properties than the neat lignin because the derivatives-based suspensions were less viscous. The dispersing properties of lignin and the esterified derivatives were compared with those of a high-molecular-weight lignin fraction obtained by ultrafiltration. In addition, two commercial lignosulfonate dispersants commonly used for drilling muds were used as references. The high-molecular-weight esterified derivatives proved to be better dispersants than their unfractionated counterparts. In general, the esterified derivatives showed similar properties to those obtained with the commercial dispersants. Modified lignin based on succinic-, maleic- and glutaric-anhydride is expected to play a key role in the design of novel bio-based dispersants for drilling-mud applications.

The solvent-casting method was used to synthesize a silver–zeolite–chitosan (AgZ-Ch) composite from Philippine natural zeolites. X-ray diffraction, ultraviolet–visible (UV-Vis) spectroscopy, optical emission spectroscopy (OES), thermogravimetric analysis (TGA) and differential thermogravimetry (DTG) were used to investigate the different properties of the composite before and after plasma treatment. The major phase of the zeolite is Na-clinoptilolite with trace amounts of mordenite, feldspar and quartz. UV-Vis and OES analyses confirmed the presence of Ag and zeolite on the chitosan matrix. The decrease in the transmittance signal at 290 nm and the emission spectra of the discharge showed the presence of Ag I, Al I and Si I signals at 705–852 nm. The TGA and DTG curves revealed the thermal stability of the natural zeolites after ion exchange and after incorporation in the chitosan matrix, where the onset of degradation was observed to occur above ~37°C, the human body temperature. Bacterial count showed minimal growth of colonies on all samples, both pristine and plasma-treated, suggesting that the surface of the composites does not influence bacterial habitation. The fabricated composites meet the minimum requirements for biomedical application such as thermal stability with respect to the average human body temperature and absence of bacteria.

The adsorption capacities of nano-sized organoclays composed of a stevensite-rich clay (R), phosphorus dendrimers (GC1 and GC2) and Na+-saturated clay were evaluated for their capacity to adsorb chromate and methylene blue (MB) in the range of 298–318 K. The adsorption kinetics and the isotherms were analysed based on kinetic equations and isotherm models and by adopting a non-linear regression procedure. In addition, the organoclays and the Na+-saturated clays were characterized principally by solid-state nuclear magnetic resonance spectroscopy. The pseudo-second-order rate equation described kinetics data well, and the adsorption rates were not limited by the intraparticle diffusion or by the liquid film diffusion. Both chemical species were adsorbed spontaneously (–31 < ΔG°T< –10 kJ/mol), but the adsorbents had a high affinity for MB species. The adsorption isotherms of chromate were fitted better by the Freundlich model, while those of MB followed the Langmuir model. Chromate adsorption took place at the edges and the free surfaces of stevensite, particularly at the protonated aluminols. MB was adsorbed as MBH2+ and MB+. The MB protonation occurred at the clay surfaces, and MB+ ions were located at the planar surfaces of stevensite as well as at the external surfaces of aggregates. Moreover, the tetrahedral sheet of stevensite involved in the formation of GC1-based organoclays was the subject of a partial chemical modification.

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.

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.

Ammonium illite and ammonium illite-smectite mixed layers, together with potassium illite, smectite and minute amounts of kaolinite were identified in hydrothermally altered andesite rocks from the Harghita Bãi area of the Eastern Carpathians, Romania. K-Ar dating and oxygen isotope tracing, as well as rare-earth elemental analyses were made to provide new information on the timing and crystal-chemical processes characterizing the crystallization and further evolution of these illite-type mineral phases.

The combined results suggest the occurrence of hydrothermal activity in two distinct episodes with nucleation of two generations of illite-type particles of different chemistry and morphology. About 9.5 Ma ago, potassium illite crystallized in alteration halos of the porphyry Cu system, probably at a temperature of ~270ºC from fluids having a δ18O of ~2.9% (V-SMOW). Associated smectite seems to have precipitated slightly later in external alteration halos at a similar temperature, but from fluids depleted in alkalis and with a different δ18O. Alternately, ammonium-rich illite-smectite mixed layers formed very recently, less than ~1 million years ago at a temperature of ~90ºC from fluids of probable meteoric origin that altered the previously crystallized potassium illite, resulting in the crystallization of a new generation of ammonium illite-smectite mixed layers. Evidence of this dissolution-precipitation process is provided by a significant increase in the δ18O of the mixed-layer structures and by a significant change in their REE contents and distribution patterns. Occurrence of potassium in the ammonium-rich mixed layers probably relates to the progressive alteration of the first-generation potassium illite and a discrete concomitant take up of released K by the new NH4-rich interlayers of the ammonium mixed layered sequence.

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.

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.