CP (Cetylpyridinium)-exchanged smectite was manufactured by the cationic exchange reaction of Na-smectite with CP. The adsorption behaviour shows a typical L-type isotherm representing continuous and stable adsorption in excess of twice the cation exchange capacity of CP. CP-smectite shows a strong interlayer (d001) expansion to 40.2 Å when an amount of CP equivalent to 140% of the CEC is exchanged into smectite. CP-smectite is characterized by strong alkalinity (pH 9.3), low swelling (4.5 ml/2 g), low viscosity (3.9 mPa s), and strong and fast flocculation. These characteristics are in striking contrast to Na-smectite except for the alkalinity. CP-smectite shows no signs of desorption of the organic species under varying pH conditions (pH 2–12). Desorption is slight even when washed three times with DH2O (distilled water). Pyrolysis of CP-smectite begins at 250°C and ends at 400°C. These stable and persistent characteristics and the relatively low price of CP point to the likely increased use of CP-smectite as an organoclay.

An investigation was carried out on the bioavailability of kaolinite and the role it plays in remediating oil-polluted seawater, since kaolinite is known to enable hydrocarbon-degrading bacteria to grow well. Experimental results revealed that significant amounts of Al and Si dissolved from kaolinite were not observed ((P > 0.05) in comparison with a control sample which contained no kaolinite) in the aqueous phase during the ~24 day experimental period. Transmission electron microscope observations and energy-dispersive spectroscope data revealed that some altered kaolinite particles appeared, connected to intact kaolinite and bacterial cells. Bacterial cells were associated and encrusted with intact and/or altered kaolinite clay particles, where mixed (C, O, Na and Si)-precipitates of kaolinite clays were formed on the surface of hydrocarbon-degrading bacterial cells. However, the uptake of Si (from kaolinite) by bacterial cells appeared to be more prevalent than Al, and there were no significant changes in basal spacings of kaolinite due to these altered kaolinite particles. Separate studies showed that hydrocarbon-degrading bacteria have a high resistance to Si. Thus, the present data suggest that Si from kaolinite may facilitate hydrocarbon-degrading bacterial growth as shown in our previous study (Chaerun et al., 2005), and the C-O-Na-Si complexes on the surfaces of bacterial cell walls may be the stimulator for hydrocarbon-degrading bacterial growth in seawater contaminated with oil spill.

Mica-chlorite mixed-layering was identified by X-ray diffraction (XRD) as a major or subordinate constituent in several slates of the Puncoviscana Formation from Sierra de Mojotoro (Eastern Cordillera, NW Argentina). In order to determine the crystallochemical characteristics of these mixed-layered sequences and interpret their petrological meaning, anchizonal slate P90 was chosen for TEM observations. In this slate, dioctahedral mica and chlorite form interleaved phyllosilicate grains (IPG) or stacks, up to 110 um long, preferentially oriented with (001) planes at a high angle to the slaty cleavage but also oblique to S0.

In agreement with XRD results, the main phyllosilicates identified by transmission electron microscopy (TEM) were dioctahedral mica and random mixed-layer muscovite-chlorite, with chlorite in subordinate amounts and scarce smectite. In the lattice-fringe images of mixed-layer packets, a sequence of irregular stacking that produced apparent 24 Å (10 + 14) layers was observed, but it was frequently possible to distinguish the 10 Å layers from adjacent 14 Å layers. In nearly all packets, 14 Å layers prevail, exhibiting 14 Å:10 Å ratios between 1:1 and 3:1. Some elongated lenticular fissures which are probably a consequence of layer collapse caused by the TEM vacuum were identified in these packets. The straight, continuous appearance of lattice fringes plus the scarce evidence of collapsed layers identified suggest that these packets correspond principally to mixed-layer muscovite-chlorite, which is confirmed by analytical electron microscopy analyses. However, smectite-like layers are probably the third component of some of these mixed-layer sequences, which may account for their high Si and low (Fe + Mg) contents, their low interlayer charge in relation to theoretical interlayer muscovite-chlorite, and for the presence of Ca in the interlayer site.

Textural relationships between chlorite and muscovite packets in IPG along with the observed transformations from 14 Å to 10 Å along the layer, is compatible with a prograde metamorphic replacement of chlorite in stacks by dioctahedral mica layers, probably in the presence of an aqueous fluid.

Clay minerals occur as replacements of olivine, pyroxenes, plagioclase and interstitial materials, and as vesicle fillings, in altered basalts from the Middle Atlas (Morocco). Phyllosilicates are the main components of this alteration process. They have been characterized here by optical microscopy, X-ray diffraction, scanning electron microscopy and high-resolution transmission electron microscopy as saponite, talc, corrensite and chlorite. The homogeneity of the chemical compositions of these phyllosilicates, in different alteration environments, probably means that they are controlled by the composition of the hydrothermal fluid. Talc-saponite-corrensite (with dominant saponite) is the clay mineral association most frequently observed (corrensite being more abundant in the vesicular levels of the basalts). Such an association, with no evidence of albite and zeolite, suggests that these basalts have suffered minimal alteration at relatively low temperatures. Another association, chlorite-corrensite, was detected in a deeper (vesicular) sample, probably resulting from a slightly higher temperature. Lastly, only discrete phyllosilicates (i.e. no random mixed-layer minerals) were observed. This suggests that near-equilibrium conditions prevailed during this alteration stage and that a dissolution-crystallization process was the main mechanism of transformation.

Two different approaches used to express the tortuosity of water pathways in a solid clay body are known: (1) a static approach based on microscopic measurement in thin sections; and (2) a dynamic approach based on ‘imbibition’ speed. Each is expressed by a corresponding equation. The second method has the following advantages over the first: (a) it enables the testing of a much larger volume than that observed in a common thin section; (b) it measures the effects of all particles, including the finest fragments barely visible under optical microscope which also have influence on hydraulic conductivity or the imbibition speed of water; (c) in the case of expansible clays, the magnitude of k (tortuosity of pathways including the shape of particles) can be compared with k for non-expansible clays using a non-polar liquid, e.g. tetraline; (d) the measurement of the imbibition speed into the clay aggregate through a constant area is automated. Specific properties and processes important for sealing clays are discussed in the connection with the dynamic approach.

Variations in clay mineral assemblages, changes in Kübler index (KI), and the chemical composition of chlorites are used to identify source areas in the lacustrine materials in the Lower Cretaceous Leza Limestone Formation of the Cameros Basin, northern Spain. This formation has fairly homogeneous lithological characteristics and facies associations which do not allow for identification and characterization of local source areas. The Arnedillo lithosome of the Leza Limestone Formation contains a clay mineral association (Mg-chlorite, illite and smectite) indicative of its provenance. Chlorite composition and illite KI values indicate that these minerals were formed at temperatures higher than those reached by the Leza Formation which indicates its detrital origin. The similarity in the Mg-chlorite composition between the Arnedillo lithosome and the Keuper sediments of the area indicates that these materials acted as a local source area. This implies that Triassic sediments were exposed, at least locally, at the time of deposition of the Leza Formation. The presence of smectite in the Leza Formation is related to a retrograde diagenesis event that altered the Mg-chlorites in some samples.

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.

The adsorption of the large cationic alkaloid berberine by montmorillonite in aqueous suspensions was investigated. An adsorption isotherm of berberine and desorption isotherms of exchangeable Na+, K+, Mg2+ and Ca2+ were determined by chemical analysis of the non-adsorbed berberine and the released cations in the supernatants. The isotherms suggest that the adsorption of berberine takes place in two different types of reaction mechanism: (1) cation exchange, and (2) a secondary organophyllic adsorption. The cation exchange occurring first is followed by the secondary adsorption which is accompanied by Cl- adsorption. Monovalent cations are exchanged before the divalent cations.

Samples loaded with increasing amounts of berberine were examined by X-ray diffraction at room temperature, and after gradual heating up to 420°C. The basal spacing of the loaded samples after the thermal treatment became 1.28 nm, indicating the formation of carbon in the interlayer, thus proving that the adsorbed berberine was located in the interlayer space. At room temperature the basal spacing of samples loaded with 8 and 15 mmol of berberine per 100 g of clay was 1.28–1.30 nm indicating that in the interlayer space berberine cations were lying parallel to the alumino-silicate layers. The basal spacing of a sample with 36 mmol of berberine per 100 g of clay was 1.48 nm. This spacing does not give conclusive information on the arrangement of berberine in the interlayer. The spacing of samples with 57–147 mmol of berberine per 100 g of clay was 1.59 nm, suggesting the presence of bilayers of berberine in the interlayers. During thermal dehydration, the spacing of samples with 36–73 mmol of berberine per 100 g of clay decreased, but that of samples with 105–147 mmol of berberine per 100 g of clay increased to 1.66 nm. These samples contain organophilic adsorbed berberine and it is suggested that due to the thermal treatment berberine was tilted relative to the TOT lamellae, with anhydrous Cl- between the berberine cations.

The intercalation of the cationic surfactant cetyltrimethylammonium (C16TMA) into the interlayer of an acid-activated clay in the presence of different anions has been studied in detail. When Br or OH anions were used, the basal spacing increased significantly, the increase being related to the loading concentration of the surfactant solution. For intercalated compounds prepared from the hydroxide form, the basal spacing at room temperature varied from 1.6 to 3.8 nm. However, for organoclays prepared from the surfactant bromide, the basal spacing is almost loading- independent (1.9 nm). The use of hydroxide and bromide at higher pH is crucial to intercalating larger amounts of C16TMA cations and, hence, to improving the exfoliation of the silicate sheets. Magic-angle spinning 13C nuclear magnetic resonance spectroscopy indicates that the intercalated surfactants exhibit a significant degree of gauche conformation. According to in situ powder X-ray diffraction, an increase of the basal spacing to 4.08 nm is observed at intermediate temperatures of 50 to 150°C for organoclay with an initial basal spacing of 3.7 nm. At higher temperatures, decomposition of the surfactant occurs and the basal spacing decreases to ~1.4 nm.

Pelitic and basic rocks occurring within prograde sequences in Portugal, Spain and Hungary have been studied by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The minerals formed in typical prograde reactions define the general sequences, but smectite, chlorite-smectite (corrensite) and/or berthierine were found to have replaced chlorite, whereas kaolinite and mixed-layer illite-smectite replaced illite-muscovite. Alteration occurred under conditions normally associated with diagenesis, subsequent to regional metamorphism, and we therefore refer to such processes with the term “retrograde diagenesis”. In the cases studied and in other cited examples, reactions occurred on a regional basis via pervasive fluids under open-system conditions inferred to be related to tectonic stress. The observed alterations could generally not be inferred from XRD data, although the presence of pure smectite in sediments other than bentonite is suggestive of retrograde relations, especially where other minerals are consistent with a higher grade of diagenesis. Retrograde diagenesis is readily observed through imaging of textures by TEM, however. Textural features show that retrograde reactions are more common than generally assumed, and that care should be used in interpreting geological events where appropriate textural relations are not seen.

α-amylase was immobilized on acid-activated montmorillonite K-10 via adsorption and covalent linkage. The immobilized enzymes were characterized by X-ray diffraction (XRD), surface area measurements, 27Al nuclear magnetic resonance (NMR) and scanning electron microscopy (SEM). Surface area measurements indicate pore blockage due to linking of the enzyme in the vicinity of the pore mouth. The XRD demonstrates intercalation of enzyme upon immobilization. The NMR studies indicate that, during adsorption, tetrahedral Al sites are involved, while covalent binding occurs exclusively on the octahedral Al sites. The SEM images depict the changed morphology of the clay surface due to immobilization. The efficiency of immobilized enzymes for starch hydrolysis was tested in a batch and a fixed-bed reactor and the performances were compared. The immobilized α-amylase showed a broad pH profile and improved stability characteristics in both reactor types when compared to the free enzyme. The effectiveness factor increased in the fixed-bed reactor, implying that diffusional restrictions to mass transfer operate in the heterogeneous reaction and the use of a fixed-bed reactor leads to a reduction in these diffusional resistances. In the continuous run, 100% initial activity was maintained for 72 h, and after 96 h, >80% activity was retained.

The smectite-bearing red bed series of the Palaeogene Ergeliin zoo Formation in Mongolia is part of an alluvial-fluvial fan prograding over prodelta/mudflat deposits. The series was investigated in the field (mapping and portable infrared (IR) spectrometry in the short wavelength (SW) range) and samples were analysed in the laboratory using thin sections, X-ray diffraction, X-ray fluorescence, cation exchange capacity and Fourier transform infrared spectrometry in the mid-IR range. Two reference sections are treated in more detail as to the environment of deposition and concentration of smectite. The deposits at Ulaan uul are representative of a distal fan section with prevalent mudflats, whereas Ulaan buur offers insight into a braided river drainage system. Metabasic rocks in the hinterland delivered mica and chlorite from which smectite originated during diagenesis under semi-arid climatic and surface-near conditions. Towards the basin edge, smectite is replaced by kaolinite. The prime area in which we were interested in the smectite is the most distal part of the alluvial-fluvial fan, which was the subject of a field-based IR survey. This exploration method is a valuable tool to obtain a quick overview of the mineral composition and reduce the number of samples in the field for follow-up analyses. Its weak and strong points are discussed.

Syntheses of Na-magadiite were performed under hydrothermal conditions in a water/alcohol medium. It is only possible to obtain a pure and well crystallized magadiite sample using a water/ethanol medium at a water/ethanol molar ratio of ∼0.12. As shown by thermal analysis and 1H liquid nuclear magnetic resonance spectroscopy, ethanol is not incorporated into the magadiite. Intercalation of dodecyl- and hexadecyltrimethylammonium cations in the interlayer space of Na-magadiite at different theoretical ion-exchange rates shows that the experimental ion-exchange rates are in good agreement with the theoretical ones. However, scanning electron micrographs of the sample having a theoretical ion exchange rate of 25–75% shows that the exchanges are not homogeneous (both thin and thick platelets are present). Attempts to obtain a Si-pillared compound starting from C16TMA-magadiite as the host material leads to a microporous compound having a BET surface area of 778 m2g-1.

This study focused on whether the presence of clay minerals (montmorillonite and kaolinite) in marine or coastal environments contaminated with high concentrations of heavy-oil spills were able to support the growth of hydrocarbon degraders to enable bioremediation. The bacterial growth experiment utilizing ~150 g/l of heavy oil (from the Nakhodka oil spill) was conducted with 1500 mg/l of montmorillonite or kaolinite. Bacterial strain Pseudomonas aeruginosa (isolated from Atake seashore, Ishikawa Prefecture, Japan), capable of degrading heavy oil, was employed in combination with other hydrocarbon degraders inhabiting the heavy oil and seawater (collected from the Sea of Japan). The interactions among microbial cells, clay minerals and heavy oil were studied. Both clays were capable of promoting microbial growth and allowed microorganisms to proliferate (to a greater degree than in a control sample which contained no clay) in an extremely high concentration of heavy oil. Observation by transmission electron microscopy of the clay-oil-cell complexes showed that microbial cells tended to be bound primarily on the edges of the clays. X-ray diffraction analysis showed that the clay-oil and clay-oil-cell complexes involved the adsorption of microbial cells and/or heavy oil on the external surfaces of the clays. How do the interactions among clay minerals, microbial cells and heavy oil contribute to environmental factors influencing the bioremediation process? To our knowledge, there are no previous reports on the use of clay minerals in the bioremediation of the Nakhodka oil spill in combination with biofilm formation.

In a study of wall-rock alteration in the 1.4 km long Würmtal adit at the Käfersteige hydrothermal vein deposit (northern Black Forest, Germany) illite was found to be the only clay mineral within the Bunter sandstone and intercalated claystone. Illite occurs mainly as a detrital mineral in the claystone, whereas it is hydrothermally neoformed in the sandstone, either in the pores or as an alteration product of K-feldspar. The extensive occurrence of authigenic illite along the entire 1.4 km long profile confirms that the fluids migrated far into the sandstone.

The authigenic illite formed during a first pulse of high-temperature fluids (Th of ~220°C) with a low salinity (~1 wt.% NaCleq). These fluids also dissolved Sr and Rb from detrital illite of the claystones at the vein. A later hydrothermal pulse with a lower temperature (~70–150°C) and higher salinity (21–28 wt.% NaCleq) silicified the sandstone adjacent to the vein and caused partial substitution of OH- by F- in the structure of the detrital and neoformed illite along the profile.

Within analytical error, the K-Ar dates for the neoformed illite of the <2 µm fraction are the same along the profile (~150 Ma). During this hydrothermal process, the age of the detrital illite within the claystone was reset from 310 to 190 Ma. The illite-rich <0.2 µm fractions yield ages of ~142 Ma (sandstone) indicating a Jurassic origin. The uniform age data for illite in the sandstone and in the claystone are probably due to extensive migration of hot fluids through the wall rocks.

The hydrothermal fluids are attributed to recycled meteoric water and brines that ascended from the basement into the cover rocks during the opening of the North Atlantic and/or the nearby Tethys area.

SWy-1 and SAz-1 smectites and an Italian bentonite from Sardinia were mechanically deformed via high-energy ball milling for 20 h, in a controlled thermodynamic environment at constant temperature (25°C) under vacuum. The deformed smectites have a lower cation exchange capacity (CEC) and form thicker particles than the original ones, due to agglomeration of smectite crystallites. The 001 diffraction maximum shifted to lower d spacings, the intensity of the 060 reflection decreased and the background at 20-30°2θ increased, suggesting partial amorphization of the smectite. Moreover, the layer charge of the smectites decreased. The intensity of the complex stretching band at 3625 cm-1, and the AlAlOH, and AlFe3+OH bending bands at 916 cm-1 and 886 cm-1, respectively, decreased, while the band at AlMgOH bending at 849 cm-1, disappeared. Deformation mainly disrupted the octahedral sheet and preferentially destroyed those sites occupied by Mg cations, thus explaining the observed decrease in layer charge. Octahedral sites occupied by Fe were least affected. The disruption of the octahedral sheet is substantiated further by the almost total disappearance of the dehydroxylation peak, which is more pronounced in the Mg-rich SAz-1 smectite.

The colloidal state (sol, flocs, gels) of Na-montmorillonite dispersions (from bentonite from Bavaria, Germany) was adjusted by the addition of poly(ethylene oxides) with terminal trimethylammonium groups. The colloidal state of the dispersions changed with the molar mass of these end-capped poly(ethylene oxides). The sol-gel diagrams (up to 4.5% (w/w) montmorillonite) in the presence of TMA-PEO 1500 and TMA-PEO 4000 (up to 40 g/l) were characterized by large fields of gel whereas TMA-PEO 20000 and TMA-PEO 35000 caused peptization by steric stabilization. Even dispersions with the highest montmorillonite content (4.5%) were peptized by >0.2 g/l TMA-PEO 35000. The critical coagulation concentration of NaCl was increased by the polymer addition, but the increase was modest (from 8-12 mmol/l to 50 mmol/l). The changes of the colloidal state, the flow behaviour and the salt coagulation reveal the sensitive interplay between stabilization mechanisms (electrostatic, steric) and destabilization effects (bridging, charge compensation, depletion flocculation).

The origin of the regional and stratigraphical variation in the Triassic authigenic clay assemblages of England is discussed in relation to new estimates of the palaeotemperatures experienced by their host sediments and a preliminary study by transmission electron microscopy of their microtextural features. Spore colour index measurements, based on the spore type Deltoidospora s.l. occurring in the sediments (Penarth Group) at the very top of the Triassic sequence, give estimated palaeotemperatures ranging from 60–74°C (south Devon) to 89–97°C (northeast Yorkshire). Calculated palaeotemperatures, based on a gradient of 25°C/km, for the main zone of authigenic clay minerals range from 63–77°C to 89–97°C for the top to 71–85°C to 94–104°C for the base. Irregular mixed-layer smectite-chlorite, corrensite and Mg-rich chlorite are associated with calculated palaeotemperatures of 66–86°C, 66–104°C and 75–104°C respectively. The suggestion that elsewhere in the UK corrensite and Mg-rich chlorite were formed at temperatures in excess of 100°C finds no support. Geothermal gradients would have to have been of the order of at least 100–300°C/km to obtain these temperatures within the Triassic sediments; such values are associated typically with high-level magmatic intrusions or geothermal systems of which there is no geological evidence. The balance of evidence suggests that the Triassic authigenic clay assemblages formed by neoformation during the early stages of sediment diagenesis under the influence of variation in the alkalinity of the depositional environments.