For a series of mixed-layer illite-smectite (I-S) minerals from a drillhole near the Kakkonda geothermal field, one-dimensional structure analysis by X-ray diffraction (XRD) was performed using Casaturated specimens in both air-dried and ethylene glycol-solvated states. The expandability characteristics of component layers were also examined by means of alkylammonium exchange and Li saturation. The K content in the illite layers was 1.5–1.7/O20(OH)4 in the I-S series from 3 to 85% of I-layer content (% I). The layer charge of the smectite layer varied slightly within the range of 0.3–0.5/O10(OH)2 by alkylammonium exchange experiments and the expandability was independent of the beidellite content within a range of 0–0.5 by the Li-saturation test. The degree of long-range ordering represented by Reichweite (R) parameters varied from R0 to R3 via R1 and R2 with increase in % I. The I-S samples contained <10% vermiculite as the third component and the vermiculite content tended to decrease with progressive illitization.

In contrast to the smectitic R0 samples (<10% I), more illitic R0 (e.g. 35% I) and >R1 I-S samples showed complicated expandability with alkylammonium exchange. The XRD patterns of dodecylammonium-exchanged I-S samples can be interpreted by random interstratification of several types of sub-units such as layer-doublets, layer-triplets and layer-quartets present in the crystallites. This interpretation is consistent with the variation in the occurrence probabilities of layer-multiplets calculated from the junction probabilities and the proportions of layers. Because the interpretation indicates that I-S is a stack of various types of the sub-units, the smectite illitization can be described by a systematic change in the type and proportion of the sub-units constituting crystallites.

Smectite illitization was investigated in felsic volcaniclastic rocks from a drill core near the Kakkonda active geothermal system, Japan, using high-resolution transmission electron microscopy (HRTEM) that provided one-dimensional structure images of mixed-layer illite-smectite (I-S) minerals normal to [M0]. Simulated images of a rectorite-like structure revealed that smectite can be distinguished from illite in mixed-layer I-S by HRTEM if the basal spacing of smectite is larger than that of illite. The larger basal spacing of smectite, 1.3 nm under HRTEM, was obtained by intercalation of dodecylammonium ions into smectitic interlayers. In simulated and observed images normal to [hk0], tetrahedral (T) and octahedral (O) cation planes are imaged as dark lines, an illitic interlayer as a bright line, and a smectitic interlayer as a dark line sandwiched between two bright lines.

The samples are from depths of 435 m (5% I; R0), 635 m (35% I; R0), 656 m (62% I; R1), and 756 m (85% I; R3) where % I is the percentage of illite layers in a sample and R is the Reichweite parameter. Sample 435 consisted mostly of smectite, and illite layers occurred, though small in amount, as M1 units (module of type 1, defined as consisting of two polar T-O-T silicate layers with one central illitic interlayer and two, half smectitic interlayers at the outermost surface; the number corresponds to that of central illitic interlayers). The M1 units were dominant and isolated and consecutive smectite layers (>2) were present in sample 635. Sample 656 consisted mostly of packets of M1 units of 1 to 5 layers containing M2 to M5 units occasionally. Isolated or consecutive smectite layers (>2) were not present in 656. Illite layers occurred almost entirely as M1 units in samples 435, 635 and 656, and the number of M1 units increased with increase in % I. Sample 756 was characterized by the presence of M2 to M10 units accompanied by smectitic interlayers at the external surface and the absence of M1 units and isolated smectite layers. The HRTEM data strongly suggest that illitization in a hydrothermal system occurs by precipitation of M1 units for mixed-layer I-S minerals up to 60% I. This does not require the presence of precursor smectite. Illitization of I-S minerals with >60% I proceeds by precipitation of various types of Mn (n ⩾ 2) units. Illite occurs only as Mn (n ⩾ 1) units throughout illitization.

Millimetric to centimetric green grains widespread in pelagic calcareous sediments recovered at a water depth of3000 m near the Costa Rica margin were studied by X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy. Samples were collected, during the Ticoflux II expedition, from the upper bioturbated part of four sedimentary cores (0.13–3.75 m below seafloor). The sediments are calcareous and siliceous nanofossil oozes (coccoliths, diatoms, radiolarians, etc.).

Green grains show generally a concentric zoning with a green rim in which smectite largely predominates over pyrite and a black core in which pyrite is prevalent. Observations by SEM indicate that this zoning results from a progressive inward alteration and replacement of the accumulations of pyrites by smectites. The high-resolution TEM observations of the smectite-pyrite interfaces suggest that the replacement of pyrites by smectite occurs through a dissolution-precipitation process with the formation of a gel. The pyrite matrix is composed of a huge number of very small (0.5–22 µm) pyrite octahedra, a typical texture resulting from the pyritization of organic material in early diagenetic environments.

The accurate mineralogical and crystal chemical characterization of the smectites indicate that they are Fe3+-montmorillonites (Fe3+-rich smectite with a dominant octahedral charge, rarely recorded in the literature). The formation of such Fe3+-montmorillonites forming green grains could be explained by two successive diagenetic redox stages: (1) reducing stage: early pyritization of the organic matter by microbial reduction within reducing micro-environments; (2) oxidizing stage: Fe3+-montmorillonite crystallized in space liberated after dissolution of pyrite connected with the rebalancing of the redox conditions of the micro-environments with the oxidizing surrounding sediments.

Chlorites formed as a replacement of phenocrysts in metabasites from the pumpellyite-actinolite to lower-greenschist facies Mikabu and North Chichibu belts in southwest Japan were studied by X-ray powder diffraction, electron microprobe analysis (EMPA) and high-resolution transmission electron microscopy (HRTEM). The metabasites contain a small quantity of fine-grained smectite and corrensite in the <1 μm size fraction. The chlorite also contains trace amounts of Ca, Na and K, which generally appear to be associated with smectite stacked in chlorite packets. The smectite layers comprise up to 13% of the chlorite domains. Theoretical estimates of the smectite ratio by the Wise method using EMPA data coincide well with the ratio determined based on HRTEM observations in most chlorites. However, in some chlorites with high proportions of Ca, Na and K, the cations cannot be reasonably attributed to smectite alone. Based on the present analyses, Ca, Na and K cations are also hosted in discrete interstitial phases of fine-grained smectite and corrensite as possible retrograde metamorphic products. These findings suggest that care should be taken in application of the Wise method to estimate the smectite ratio, and that the whole-rock chlorite composition may not be suitable as a geothermometer.

Eighteen purified kaolin samples from Thai Ultisols were studied by X-ray diffraction, X-ray fluorescence, transmission electron microscopy and BET methods. Minor amounts of inhibited vermiculite, quartz and anatase were general contaminants of the kaolins which had an average chemical composition of 403 g kg−1 Al2O3, 550 g kg−1 SiO2, 25.3 g kg−1 Fe2O3, 15.6 g kg−1 TiO2 and 4.65 g kg−1 K2O on an ignited basis. Appreciable concentrations of Mn, Co, Ni, Cu, Zn, As and Pb were present and most of the Ni, Cu and Zn in the original clay fraction was retained in the deferrated kaolin concentrate. It was not possible to determine if these elements are present as structural ions in kaolin crystals.

The kaolins exhibited a variety of crystal morphologies ranging from sub-micron, euhedral, hexagonal plates to anhedral plates and tubes. Their specific surface areas ranged from 15.9 to 61.4 m2g−1 (mean 44.9 m2g−1) and surface area increased with decrease in crystal size. The cation exchange capacity of the kaolins ranged from 7.2 to 23.4 cmolc kg−1 and surface charge density from 0.16 to 0.99 C m−2 but these values are sensitive to the presence of contaminants. Structural iron ranged from 12.4 to 44.8 g kg−1 Fe2O3 and there was an increase in structural defects towards the soil surface associated with an increase in the amount of structural iron.

Most detrital ilmenite grains in sandstones of the Chaswood Formation are completely altered to pseudorutile, leucoxene and rutile. The textural, chemical and mineralogical changes involved in alteration were tracked using electron microprobe analyses, backscattered electron images, and elemental maps. Ilmenite grains (Ti/(Ti+Fe) ≈ 0.48) alter patchily to pseudorutile (Ti/(Ti+Fe) 0.5–0.7) with volume loss, forming a porous structure and this process continues with the development of leucoxene (Ti/(Ti+Fe) 0.7–0.9). Within the pseudorutile and leucoxene, stubby prismatic rutile crystals have been precipitated. Si and A1 occur in the altered ilmenite, either (1) inherited from original quartz and muscovite inclusions in the parent crystal or (2) as kaolinite altered from muscovite inclusions or precipitated in the pore space, under pedogenic or early diagenetic conditions. Distribution of alteration phases has been related to facies and diagenetic variations. With increasing amounts of leaching in different types of paleosols, there was increasing alteration of pseudorutile to leucoxene. In light gray mudstones and interbedded sandstones with diagenetic kaolinite that formed beneath the water table from percolating meteoric water, most leucoxene was converted to rutile. Burial diagenesis (to vitrinite reflectance values >0.4%) also promoted the change from leucoxene to rutile. The alteration of ilmenite is an important source of Fe for diagenetic minerals in the Chaswood Formation and correlative offshore deltaic and marine facies of the Scotian basin.

The influence of clay preparation procedure on sorption and hydrolysis of carbaryl (1-naphthyl, A-methyl carbamate) by the reference smectite SWy-2 was examined. For research purposes, reference clays are sometimes used without purification, or more commonly, the <2 μm size fraction is obtained by gravity sedimentation or low-speed centrifugation. We determined that these common methods did not remove all the inorganic carbonate impurities present in SWy-2, and that these impurities caused alkaline conditions in aqueous clay suspensions leading to the alkaline hydrolysis of carbaryl to 1-naphthol. The hydrolytic activity of homoionic K-SWy-2 disappeared once carbonates were eliminated. Two methods were evaluated for preparing K-SWy-2 devoid of inorganic carbonates. In Method A, inorganic carbonates were first removed by incremental additions of a 0.5 M sodium acetate buffer (pH 5.0) until the clay suspension reached pH 6.8, followed by low-speed centrifugation to obtain the <2 μm size fraction; in Method B, the order of these steps was reversed. Carbaryl hydrolysis was used as a probe to determine the effectiveness of the two methods in terms of the removal of carbonate accessory minerals. Homoionic K-SWy-2 obtained by Methods A and B produced near neutral pH when suspended in water and hydrolysis of carbaryl in these suspensions was not evident. In this regard, both clay preparation methods were acceptable. However, there were procedural advantages with Method B, which is therefore recommended for the partial purification of reference clays, as detailed in this paper.

Carbonate-intercalated layered double hydroxides of Co(II) and Ni(II) with Fe(III) and Al(III) were precipitated under different conditions (pH = 8–12; T= 25–80°C). All the samples are replete with stacking faults which are not eliminated by post-precipitation hydrothermal treatment (80–180°C, 18 h). DIFFaX simulations show that the layer stacking sequence of the disordered samples can be generated by a mixture of motifs corresponding to the 3R1 and 2H1 polytypes. These specific sequences are selected in preference to others because of the need for hydrogen bonding between the intercalated carbonates and hydroxide sheets. Thermodynamic considerations show that faulted crystals have greater stability than ordered crystals. Stacking faults arising from a mixture of 3R1 and 2H1 motifs, while having the same enthalpy as that of the ordered crystal, nevertheless contribute to thermodynamic stability by enhancing disorder.

Of all the known pillared layered clays (PILC), Al-PILC is the most studied. In spite of that, its use on a commercial scale is not yet possible due to the large amount of water required for its synthesis. The aim of the present work was to take advantage of the beneficial effects of ultrasound radiation for reducing intercalation time, and to optimize the synthesis parameters in order to find a viable industrial means of preparing Al-PILC.

A comprehensive study of the effect of ultrasonic radiation on the parameters which have a direct effect on the amount of water used in the synthesis was conducted, specifically on the effects of: (1) mmol of Al/g of clay ratio (R) by decreasing the volume of A1 solution and keeping the amount of clay constant, (2) the concentration of clay in the initial suspension (or not suspending the clay at all), and (3) the concentration of the A1 precursor solution. The use of ultrasonic radiation produced the expected reduction in exchange time which was attributed to a decrease of the clay-particle size. This decrease of particle size gave rise to an improvement in the diffusion of the A1 precursor towards the core of the clay grain leading to solids with increased surface areas, basal spacing and X-ray diffraction peak definition. By optimizing the synthesis parameters directly involved in the consumption of water, it was possible to decrease the amount used by >60%.

Calcium-sodium exchange on Wyoming bentonite in methanol, ethanol and acetone-water systems were investigated at 0.03 N Cl and at room temperature. Calcium-sodium exchange isotherms were plotted at cosolvent concentrations ranging from 0 to 70% wt./wt. using Ca and Na ionic activities before and after correction for CaCl+ formation. In both cases and in all treatments, a greater selectivity of bentonite surfaces for Ca ions was observed. When compared to water, different trends were observed among and within cosolvents. These trends varied depending on whether or not CaCl+ formation was accounted for. Ignoring the formation of CaCl+, the preference of bentonite for Ca increased in methanolwater systems with increased percent methanol at low equivalent Ca fraction (<0.2). At higher Ca fractions, this preference matched that of water. In ethanol-water, no increased preference of the surface for Ca was observed. In acetone-water, increasing cosolvent concentration decreased the preference of the surface for Ca. The magnitude of this decrease was larger at low equivalent Ca fraction (<0.2). After correction for CaCl+, both in solution and on the surface, the preference of bentonite for Ca2+ was larger in methanol- and ethanol-water systems. In acetone-water, increased surface preference for Ca was only apparent at low acetone fractions (<50%). At higher acetone fractions, there was evidence of increased Na loading but no increase in Ca2+ selectivity. Clearly, ion-pair formation and its effects on Ca-Na exchange reactions cannot be ignored in mixtures of aqueous-organic solvents. After accounting for this effect, Ca-Na exchange in the studied solvents appears to be more of a surface- than a solution-controlled phenomenon that involves both electrostatic and specific solvent-surface types of interactions that have not been elucidated.