The risk of overfitting pair distribution function (PDF) data for highly defective material (Farrow et al., 2007) is illuminated with the example of the nanocrystalline hydrous ferric oxyhydroxide, ferrihydrite. Two structural models have been published by Michel et al. (2007, 2010) using this method, both of which contradict the standard ‘ferrihydrits’ model established by X-ray diffraction (Drits et al., 1993), and confirmed by single-crystal electron nanodiffraction (Janney et al., 2001) and neutron diffraction (Jansen et al., 2002). Although PDF data are reproduced equally well with the two regression models, neither model is realistic: the first (fhyd6) violates Pauling's 2nd rule, and the second (ferrifh), Pauling's 3rd rule.

The mineralogical and geochemical characteristics of the Tirschenreuth and Kohdachi kaolin deposits, which both occur in granite, are compared and the genesis of the deposits discussed. The Tirschenreuth deposit (Rappauf pit) is considered to have formed by weathering because: (i) the kaolinite has formed by the alteration of plagioclase and biotite, whereas microcline and muscovite are unaltered; (ii) the kaolin body has a very homogeneous composition and alteration zones cannot be recognized; (iii) there has been no addition of trace elements from sources other than plagioclase and biotite in the parent rock; (iv) particle-size distribution shows that the kaolinite crystals grew under uniform physical conditions; (v) quartz grains have smooth surfaces.

The Kohdachi deposit contains many clay veins and three alteration zones: (i) halloysite with weak silicification; (ii) halloysite-kaolinite; (iii) kaolinite. Many large dissolution pits were observed by SEM on the surface of quartz crystals from the kaolin zone. Silicification, precipitation of goethite at the border of zones (ii) and (iii), and dissolution of quartz in different areas of the deposit indicate a variable pH within a distance of <100 m. The Cu and Li contents in the <2 µm fractions of the Kohdachi kaolin samples are markedly higher than those at Tirschenreuth. From hydrogen isotopic analysis, the formation temperature of the Kohdachi kaolinite may be roughly estimated at 70–150°C. It is suggested that the Kohdachi deposit formed by hydrothermal alteration.

A new method is proposed for modelling complex X-ray diffraction patterns effectively. The method is based on the calculation of the interference function of the onedimensional disordered crystals with finite thickness. First, we calculated the diffraction effects from structures of individual mineral phases with different layer defects modelled according to the Reynolds’ algorithm. To fit the theoretical to the observed XRD patterns more accurately, we then used a specially developed optimization procedure. This iterative procedure selects the optimal set of chemical and structural parameters (probability and domain size) and yields consistent solutions.

The composition of the clay component in bottom sediments of Lake Baikal relates strongly to glacial/interglacial climate cyclicity. Besides changes in the relative abundance of illite and illite/ smectites between glacial and interglacial periods, significant differences are observed in the crystal chemistries and structures of layered minerals. A change from chlorite during glacial periods to chlorite-smectite during interglacials is probably indicative of the weathering processes in the watershed. Changes in the degree of ordering, in domain size and grain-size distribution of illitesmectites imply differences in genesis of this mineral phase in different palaeoenvironments. These findings further strengthen the case for using clay minerals in the sedimentary record of Lake Baikal as palaeoclimate indicators.

One of our findings was that none of the fractions separated by Stokes’ settling is representative of the bulk sample for either the glacial or interglacial intervals. For the interglacial sample, illitesmectite was concentrated in the <2 μm fraction whereas, for the glacial sample, most of illitesmectite is contained in the <1 μm fraction. The selective use of one fraction is yet another potential source of uncontrolled errors that has to be avoided. We suggest using X-ray patterns of bulk samples as a preferred method of analysis of Lake Baikal (and other) sediments.

De-intercalation of DMSO from well-crystallised kaolinites induced disorder. SEM, XRD and low-temperature IR were used to probe changes in morphology, layer stacking, and the environment of OH groups, respectively. The degree and type of disorder depended on the starting material and on the method of removing the intercalate. Rapid removal by heating at 250°C caused smaller changes than more prolonged heating at lower temperature, or washing with water.

A three-fold zonation can be imaged within authigenic siderite from sandstones of the Brent Group using back-scatter SEM techniques. We interpret this zonation in terms of the biogeochemical zonation of shallow buried sediment. The innermost siderite crystal zone is very Fe rich (95.0±0.5 mol.% FeCO3), with high Mn levels relative to Ca and Mg. This is interpreted as forming within the Fe reduction zone, with Mn from the closely associated Mn reduction zone. The second siderite crystal zone is frequently represented either by an episode of dissolution, or is impure (80±1 mol.% FeCO3), and this corresponds to the sulphate reduction zone. The outer crystal zone is intermediate in composition, and is equated with the zone of methanogenesis (88±1 mol.% FeCO3). Isotopic values cannot be assigned to individual crystal zones. Bulk δ18O values (−2.7 to −13.0‰ V-PDB) are not consistent with precipitation from seawater at low temperatures, but suggest meteoric pore-waters. δ13C data (−4.3 to −15.7‰ V-PDB) are consistent with microbially-mediated precipitation.

Pyrite and siderite are usually mutually exclusive within a single sample. Sedimentary conditions which favour the development of a strong sulphate reduction zone, and hence the formation of pyrite, do not favour the formation of a strong sub-oxic zone, where siderite is preferentially precipitated, and vice versa. There is a strong facies control upon siderite formation, with ripple cross-laminated sands being most strongly siderite cemented.

The influence of sorbed cations and hydration on the a and b dimensions of montmorillonite, has been established by the selected area diffraction technique (S.A.D.) and by X-ray diffraction analysis. Concepts on the bonds and interaction mechanism of aluminosilicate layers with sorbed cations and water molecules (which form hydrate-ionic layers) are discussed. These concepts also indicate the basic stages of the sorption process and the formation of the montmorillonite structure. Assuming that aluminosilicate and hydrate-ionic layers represent a single crystal-chemical structure, the change of configuration of the aluminosilicate layers and dimensions of the montmorillonite lattice are explained.

Les analyses thermiques (A.T.P. et A.T.D.) de la palygorskite ont été réalisées entre 20 et 900° La palygorskite contient trois types d'eau nettement différenciés par leur rôle dans la structure. Cependant, les analyses thermiques indiquent un chevauchement des domaines de température où ces diverses molécules d'eau sont éliminées. L'interprétation des enregistrements à partir de la zone de plus haute température (qui correspond aux plus fortes énergies de liaison des molécules d'eau éliminées) permet d'obtenir un bon accord entre les résultats expérimentaux et ceux calculés à partir du modèle dioctaédrique du minéral.

The finest fractions of Upper Jurassic shales from the North Sea and onshore Denmark contain 80–90% of an illite-smectite-vermiculite (I-S-V) mixed-layer mineral and, in addition a phase which has X-ray diffraction (XRD) peaks at 7.20–7.26 Å and 3.56–3.58 Å in air- dried and glycolated specimens. This phase may be a fine kaolinite with a small thickness of coherent scattering domains (CSDs) or alternatively a mixed-layer mineral which has kaolinite as the dominant component. For one sample from the Norwegian well 9/4-3, these alternatives are investigated using the multi-specimen method by which agreement between the experimental pattern and the pattern calculated for one and the same structure is obtained for each of several specimens saturated with different cations and with/without glycolation. It is demonstrated that the modelled XRD patterns for a kaolinite-illite-vermiculite (K-I-V) structure having 0.94 kaolinite, 0.03 illite and 0.03 vermiculite layers and random alternation fit the experimental patterns.

The very fine (<0·04 µm) clay fraction of a Denchworth series subsoil in weathered Oxford Clay has been investigated in detail. It contains a layer silicate mineral, almost free from impurities, that is a randomly interstratified mixture of approximately 45% expanding and 55% non-expanding interlayers with the following unit formula: Na0.33K0.29(Al1.41Fe0.34Mg0.26)(Si3.60Al0.40)O11. Computer-simulated diffraction patterns showed that experimental patterns are best matched when an average diffracting packet consists of between 4 and 5 2:1 layer silicate units. Correction of the chemical composition for external exchangeable ions associated with such small packets gives non-expanding interlayers a charge density of 0·69K/Si4O11 and expanding interlayers one of 0·57M+/Si4O11. The relationship between these values and those of mica and regularly expanding minerals is briefly discussed.

Millimetre-sized flakes of a homogeneous, high layer charge vermiculite from S. Olalla (Spain) saturated with l'ornithine cations were made to swell in l'ornithine hydrochloride solutions of various concentrations, and the gel-like structures formed were subjected to uniaxial loads up to 150 g/cm2. Small-angle X-ray diffraction measurements from the swollen flakes show well-modulated intensity patterns from which the equilibrium interlayer distances were obtained for the various swelling conditions. The interlayer spacings can be adequately expressed as normal-logarithmic distribution functions of probability density. The gel texture is described in terms of the average number of elementary layers, all in parallel orientation, constituting independent coherent domains within the swollen flake. Changes in structure and in texture taking place as the gel volume increases, or as water is expelled from the interlayer volume under mechanical compression, are followed by the variation of the corresponding parameters of order.

The removal of Cr(VI) from aqueous solutions under various conditions was investigated using a natural clinoptilolite and a synthetic zeolite derived from fly-ash (Na-P1), modified either with hexadecyltrimethylammonium bromide (HDTMA) or octadecyltrimethylammonium bromide (ODTMA). The study was focused mainly on the impact of the properties of the zeolite on the sorption capacity, the sorption mechanism, the influence of pH and the durability of the immobilization. The zeolites were modified with HDTMA and ODTMA surfactants up to 100% and 120% of their external cation exchange capacity. Batch and column studies were conducted to evaluate the influence of pH and the initial Cr(VI) concentration on their efficiencies for removing chromates. The organo-zeolites show a significant ability to remove Cr(VI) from aqueous solutions. The amount of Cr(VI) removed by organo-clinoptilolite and organo-zeolite Na-P1 is greater at low pH values, whereas the sorption efficiency decreased with increasing pH. Sorption of Cr(VI) was more efficient with the HDTMA-modified organo-clinoptilolite (150 mmol Cr(VI)/kg) than the ODTMA-modified clinoptilolite (132 mmol Cr(VI)/kg). The maximum sorption capacity was obtained with the 1.2 × ECEC ODTMA-modified clinoptilolite (237 mmol Cr(VI)/kg). The organozeolites Na-P1 adsorbed Cr(VI) from aqueous solutions more effectively and were much more durable than the organo-clinoptilolites.

XRD, DTA and IR patterns showed clay veins filling fissures in a granite of the Bayerischer Wald (eastern Bavaria) to consist mainly of hydrated halloysite of low crystallinity with traces of gibbsite, 2:1 (mixed layer) clay minerals and iron oxides. The halloysite forms thin plates which exhibit varying degrees and types of enrolment, resulting in platy, tubular and spheroidal crystals within the same sample. Concentrations of the trace elements Rb, Sr, Ba, Zr, Y, Ce, Pb, Zn and Cu indicate halloysite formation to have taken place via an aqueous phase under the influence of vadose waters circulating in fissures.

Observations of natural minerals and experimental run products show that I-S (illitesmectite mixed-layer minerals) with a high illite content as well as pure mica-illite crystallites can have a lath shape (aspect ratio >3). This shape is common to the I-S minerals under a variety of conditions of formation. The experiments presented indicate that the occurrence of lath-shaped micaillite is due to a slow growth rate from supersaturated solutions. This lath-shaped crystallite is metastable as the ultimate stable shape is hexagonal. A longer period of crystal growth will replace the mica-illite laths with crystallites of a hexagonal form. Thus the presence of lath-shaped micaillite indicates the existence of a metastable crystal form for this mineral.

An homogenous 8.4 Å hydrate was obtained after washing intercalated KAc- nacrite. X-ray diffraction analysis based on comparison of the experimental and calculated profiles enabled the amount of water (one molecule per Si2Al2O5(OH)4) and the z coordinate along c* (6.5 Å) to be determined. The hydration state was accompanied by a decrease in the coherent domain along c* in the order nacrite > KAc-nacrite > H2O-nacrite. The IR spectrum of the hydrated nacrite showed an evolution of the structure with a shift of ν(OH) from 3702, 3649 and 3630 cm−1 to 3690, 3641 and 3620 cm−1, respectively for the nacrite hydroxyls. The ν(OH) stretching bands of the interlayer water appeared at 3602 and 3545 cm−1 and their bending band at 1655 cm−1. The TGA/DTG analysis of the air-dry hydrated nacrite showed a loss of water at 245°C the weight loss (1 molecule per Si2Al2O5(OH)4) corresponding to the interlamellar water, in agreement with that determined by XRD.

The relation between counter ion distribution, ion mobility and degree of contraction has been studied on hydrobiotite (2–5 µ size), equilibrated with mixed RbCl-SrCl2 solutions. From X-ray data, isotopic exchange and chemical extraction, it appears that the counter ions of the contracted portions of the interlayers are not in equilibrium with the solution phase. The distribution of counter ions in the interlayer space follows a gradient from the margin of the mineral to the centre. This distribution is the result of the interruption of a diffusion process, caused by the contraction of layers during exchange. Isotopic exchange is rapid on the external surfaces and in the expanded portions of the interlayers, but very slow in the contracted part, where the rate of exchange amounts to only 0.002–0.02 m-eq/100 g/day, and decreases with time. On exchange with MgCl2 solutions, secondary expansion of the interlayer space occurs and some of the counter ions trapped in the contracted regions are released.

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.

This paper presents detailed mineralogical analyses of the non-carbonate material obtained from four cored boreholes in the Chalk of Berkshire and Oxfordshire, England. Consideration is given to the relationship between the non-carbonate material and the interstitial water chemistry.

Sample preparation was by means of acid digestion followed by vacuum sedimentation. Analyses were carried out using X-ray diffraction techniques.

Results are presented in a semi-quantitative form based upon integrated peak intensities and are compared to those of previous studies on the Chalk of southern England. It is concluded that the zones of occurrence of the major clay minerals as demonstrated in this study are in general agreement with those established by other authors. The non-carbonate content of the Chalk increases from the concealed beds at the Fair Cross site towards the outcrop Chalk of Lambourn and Harwell. The variation in mineralogy and purity is ascribed to changing conditions of deposition and to diagenesis related to groundwater circulation.

Initial stages of the gel-to-kaolinite transformation were studied using HRTEM. Spherical aggregates of kaolinite crystals were produced during the synthesis of kaolinite by hydrothermal treatment of Si-Al amorphous gels. Prior to sphere formation, gels transform into pseudospherical domains that have a Si/Al ratio of one and display no SAED pattern. The spherical particles consist of radially arranged sectors of stacks of planar crystallites. Crystals display nonbasal spacings of 4.5, 4.2 and 3.8 Å and a basal spacing of 7.1 Å , the c* axis following the radius of the sphere.

Interpretation of the 3D nanostructure of the spheres is difficult. The c* axis exhibits a radial disposition, but the relative orientation of the a* and b* axes in neighbouring crystallites may produce bent layers or incoherent contacts. In addition, curved layers with a d spacing of 7.4 Å may be attributed to halloysite layers collapsed under microscopy conditions. The disappearance of the spheres during the hydrothermal treatment is probably due to preferential dissolution of either highstress areas near bent layers or non-crystalline material filling crystal boundaries. Dissolution leads to sphere disaggregation and allows the component columnar crystals to continue to grow. Observations of the gel matrix suggest that under our experimental conditions kaolinite crystallizes via an in situ transformation of the gel.

Mineralogical and chemical variations were studied in the upper half of a 1 m thick discontinuous bentonite bed interlaminated in the Lower Cenomanian sedimentary formations of the northern Aquitaine basin (France). X-ray diffraction patterns obtained from the <2 mm fraction in the Ca and K-saturated states were decomposed and compared to those calculated from decomposition parameters. They revealed the presence of two highly expandable illite-expandable (I-Exp) mixedlayer minerals (MLMs). The relative proportions of the two MLMs evolve steadily with depth leading to the decrease of the cation exchange capacity and of the (Na + Ca) content towards the centre of the bentonite bed. However, the system is essentially isochemical and Mg, Al, Si, K and Fe are roughly constant in the bulk samples. It is thought that the mineralogical zonation results from the initial stages of the smectite formation in an ash layer.

In the Ca-saturated state, the expandable component of these MLMs was for the most part homogeneous with the presence of 2 sheets of ethylene glycol molecules in the interlayer. However, the heterogeneous hydration behaviour of these expandable layers was enhanced by the K-saturation test. From this test, the presence of three layer types with contrasting layer charge was evidenced from their contrasting swelling abilities. The C12-alkylammonium saturation test applied to samples in which the octahedral charge had previously been neutralized (Hofmann-Klemen treatment) showed that the tetrahedral charge is located on specific layers. These layers are responsible for the heterogeneous hydration behaviour. Low-charge smectite layers are mostly octahedrally substituted, whereas for intermediate- and high-charge layers this montmorillonitic charge is complemented by additional tetrahedral substitutions (0.30 and 0.35–0.40 charge per O10(OH)2, respectively).

A variety of stevensite was collected at the Obori mine, Yamagata Prefecture, Japan. Analysis shows close agreement with published data for stevensite. Chemical composition: SiO2 52·76%; A1203 trace; Fe203 0·38%; MgO 23·67%; MnO 1·57%; CaO 2·19%; Na2O 0·37%; K2O 0·00%; H2O+ 6·52%; H2O− 12·38%; Total 99·84%. The structural formula is (Fe0·04 Mg5·31 Mn0·02) Si80·1 020·00 (OH)4·00·Ca0·36, Na0·10.

This specimen shows an interstratified structure of dehydrated and hydrated layers, the former caused by dehydration of the interlayer water, although stevensite essentially contains a non-swelling layer and shows interstratification. The intensities and spacings of the 00l reflections change successively with changes in humidity. When treated with water and glycerol, the 00l reflections are similar to those of montmorillonite. The DTA and TG curves are similar to those of stevensite and an interstratified mineral of talc and saponite.