Illite, the predominant component of the clay fraction of the Chinese loess, has been studied by X-ray diffraction (XRD) in 33 samples taken from the Holocene palaeosol (S0), the last glacial loess (L1) and the last interglacial palaeosol (S1) in the Louchuan loess section of the Loess Plateau in China. The XRD investigations indicate that it is mainly a 2M1 dioctahedral mineral with crystallinity values ranging from 0.23 to 0.36°Δ2θ (CIS Index). The 2M1 polytype illites with low IC values preclude a pedogenic formation of illites in the surface horizons of aridic and semi-aridic soils or deserts, and thus the clay mineral composition was largely determined by provenance. The illites are considered to be of detrital origin derived from pre-existing sediments and very low- to low-grade metamorphic rocks, eroded from the northern part of the Tibetan Plateau. The clay content of the loess and palaeosols was largely controlled by the strength of the winter monsoon, rather than by effects of in situ pedogenetic processes.

Changes in the molecular structure of a highly ordered kaolinite, intercalated with urea and potassium acetate, have been studied using Raman microscopy. A new Raman band, attributed to the inner surface hydroxyl groups strongly hydrogen bound to the acetate, is observed at 3605 cm-1 for the potassium acetate intercalate with the consequential loss of intensity in the bands at 3652, 3670, 3684 and 3693 cm-1. Remarkable changes in intensity of the Raman spectral bands of the low-frequency region of the kaolinite occurred upon intercalation. In particular, the 144 and 935 cm-1 bands increased by an order of magnitude and were found to be polarized. These spectroscopic changes provide evidence for the inner surface hydroxyl group-acetate bond being at an angle approaching 90° to the 001 face. Decreases in intensity of the bands at 243, 271 and 336 cm-1 were observed. The urea intercalate shows additional Raman bands at 3387, 3408 and 3500 cm-1 which are attributed to N-H vibrations after formation of the urea-kaolinite complex. Changes in the spectra of the inserting molecules were also observed.

A method is given for quantitative analysis of IR spectra of dioctahedral micas in the OH-stretching region, which involves spectral decomposition and correlation of octahedral cation contents with integrated optical densities of the corresponding bands. It provides a basis for the study of order-disorder in these minerals and has allowed revision of the crystallochemical formulae of some glauconites and celadonites.

Thermal transformations of kaolinite were studied by 29Si- and 27Al-MAS/NMR and ESR techniques. In metakaolin, Si is still dominantly in the Q3 state (three Si atoms bonded to an Si-O4 tetrahedron) and Al detectable by NMR is in both 4-coordination and 6-coordination. Coordination polyhedra around Al or Fe replacing Al are much distorted. Metakaolin crystallizes into γ-alumina and mullite exothermically at ∼980°C, this crystallization being preceded by a faint endothermic reaction. The latter is due to segregation of SiO2 and Al2O3, which results in an increase of Si in the Q4 state and an increase of 6-coordinated Al2O3.

The weathering of biotite in a sedentary soil profile developed on biotitehornblende- rock near Rehiran, Inverness-shire has been investigated by optical, X-ray, chemical, infrared and differential thermal methods. In the C horizon a direct transformation to hydrobiotite was observed. This involves oxidation of all the ferrous iron present and subsequent movement of ferric ions from the octahedral sheet. In the B horizon weathering proceeds to a fully expanded 14A phase and this was identified as interstratified vermiculite-chlorite in a 1:1 ratio. Chemical analysis indicates that this stage is accompanied by a substantial addition of magnesium, much of which goes to form the brucite-like interlayers. In the more acid surface horizon these interlayers tend to break down thus yielding a more vermiculitic product. The possible general implications of this type of biotite weathering are briefly discussed.

A sepiolite from Vallecas (Spain) was treated with solutions of HC1 (1.25, 2.5, 5.0, 10.0 and 20.0 wt%) at 25°C for 2, 6, 24 and 48 h, respectively. The resulting solids were characterized by XRD, FT-IR and thermal analyses, along with SEM, TEM and nitrogen adsorption isotherms at 77 K. The free silica was digested and determined in all samples. Several samples were seen to have specific surface areas up to 450 m2/g, with a maximum value of 549 m2/g in the sample treated with 1.25 wt% HCl for 48 h. A sudden decrease in specific surface areas was observed when free silica was digested.

The redox potential and pH of aerated suspensions of iron(II) hydroxide in sulphate–containing aqueous solutions are measured during the oxidation process. Plateaux corresponding to the equilibrium conditions between Fe(OH)2(s) and Fe(II)-Fe(III) hydroxysulphate GR2(SO2-4)(s) on the one hand, and between GR2(SO2-4)(s) and FeOOH(s) on the other hand, are displayed. Potentiometry, voltammetry, pH-metry and Mössbauer spectroscopy are applied to follow all reactions. The thermodynamic meaning of the measured potential of the first plateau which corresponds to the GR2(SO2-4)(s)/Fe(OH)2(s) equilibrium is demonstrated. The chemical composition of GR2(SO2-4)(s) is found to be FeII4 FeIII2(OH)12SO4·nH2O all along the oxidation process, implying that this compound must be considered as a pure phase with a well-defined composition. The Gibbs standard free energy of formation or chemical potential μ°[GR2(SO2-4)(s)] in ‘anhydrous form’ (n = 0) is determined at −3790±10 kJ mol-1. A consistent value of μ°[Fe(OH)2(s)] at −490±1 kJ mol-1 is obtained.

Odinite is a Fe3+-rich green clay that is widespread in the form of infillings or replacements of microtests, bioclasts, faecal pellets, or mineral debris on shallow marine shelfs and reef lagoonal areas in tropical latitudes. The structure is based on a 1 : 1 serpentine-type layer that is intermediate between dioctahedral and trioctahedral. Octahedral cation totals range from 2·30 to 2·54 cations per 3·0 sites for 10 samples. The structural formula for the purest sample is Both monoclinic and trigonal polytypes are present in most samples, with 1M more abundant than 1T. Unit-cell dimensions are 1M: a = 5·373(3), b = 9·326(7), c = 7·363(6) Å, β = 104·0(1)°; 1T: a = 5·366(5), b = 9·334(9), c = 7·161(8), β = 90° (on orthohexagonal axes). The name is for Dr. Gilles Serge Odin, Département de Géologie Dynamique, Université Pierre et Marie Curie, Paris, who has done most of the pioneering work on this new mineral.

Mixed-layer illite-smectite samples from the Ordovician and Silurian K-bentonites of the Baltic Basin and the Baltic Shield (Norway, Sweden, Denmark, Poland and Estonia) were dated by K-Ar on several grain fractions and were studied by X-ray diffraction (XRD), both on oriented and random preparations, in order to reveal the conditions of smectite illitization in the area. Authigenic K-feldspar was also dated. The geographic pattern of the degree of illitization (% smectite in illite-smectite measured by XRD) is consistent with other indicators of palaeotemperatures (acritarchs, conodont alteration index, vitrinite reflectance, apatite fission track ages). It reveals the highest maximum palaeotemperatures (up to at least 200ºC) along the Norwegian and the German-Polish branches of the Caledonides and the lowest palaeotemperatures (120ºC) in the central part of the studied area. The distribution of K-Ar ages is not well correlated with this pattern, revealing a zone of older ages (Lower Devonian-Lower Carboniferous) between Denmark and Estonia, and areas of younger ages (Upper Devonian to Carboniferous/Permian boundary) to the north and south of this zone. The zone of older ages is interpreted as the result of illitization induced by a thermal event in front of the Caledonian orogenic belt (migration of hot metamorphic fluids?). The areas of younger ages are considered as representing deep burial illitization under a thick Silurian-Carboniferous sedimentary cover, perhaps augmented by a tectonic load. The K-Ar dates invalidate the hypothesis of a long-lasting low-temperature illitization as the mechanism of formation of the Estonian Palaeozoic illite-smectite. The ammonium content of illite-smectite from the Baltic K-bentonites reflects the proximity of organic-rich source rocks that underwent thermal alteration at the time of illite crystallization.

A new structural model for ferrihydrite that challenges the standard ferrihydrite model established by X-ray diffraction and confirmed by neutron diffraction and single-crystal electron nanodiffraction was recently proposed by Michel et al. (2007a) from the simulation of the pair distribution function obtained by Fourier transformation of diffraction data measured at λ = 0.137 Å. The new ferrihydrite model is isostructural to akdalaite (Al10O14(OH)2), a mineral having the Baker-Figgis δ-isomer of the Al13-Keggin structure as its structural motif. The new model is unrealistic because: (1) it is completely periodic (i.e. defect-free); (2), it has 20% tetravalent octahedral iron (VIFe4+), 20% divalent tetrahedral iron (IVFe2+), and some IVFe–O distances equal to or larger than the VIFe3+–O distances, thus violating Pauling's 2nd rule; (3) it does not describe X-ray diffraction and EXAFS spectroscopic data; and, (4) it is inconsistent with electron microscopy results and contradicts previous X-ray scattering studies.

Grain-size distribution, specific surface, thermal analysis, electron microscopy and X-ray diffraction were used to study the effect of dry grinding on the structure and properties of two kaolins of different degree of crystallinity. Grinding caused particles to fragment and resulted in the formation of stable large spheroidal aggregates of fine particles. These two processes were not clearly separated by a specific grinding time, but occurred in parallel shortly after grinding was started, although aggregate formation persisted at longer grinding times. The variation in the specific surface area during grinding was found to be dependent on these two processes and on the particle size and crystallinity of the initial kaolin. DTA and XRD data and the amount of water released at different temperatures revealed grinding to gradually destroy the kaolinite structure and cause the loss of hydroxyl ions and the formation of others that were subsequently removed at low and medium temperatures. An explanation for the process whereby the new hydroxyl ions are formed is provided.

The crystal-chemical basis of the relationship between hydrated calcium silicate and clay minerals is discussed, and a review is given of recent work on the tobermorite minerals, the group of hydrated calcium silicates which most nearly resembles the clay minerals. New data are presented for the specific gravities, refractive indices, basal spacings, and dehydration isobars of synthetic tobermorite minerals, and a tentative explanation is proposed for the variability of Ca : Si ratio in these substances.

Mineralogical compositions have been calculated from a number of average analyses of shales and clays using the scheme of Imbrie and Poldervaart (1959). The average shale comprises 59 per cent. clay minerals, 20 per cent. quartz and chert, 8 per cent. felspars, 7 per cent. carbonates, 3 per cent. iron oxide minerals, 1 per cent. organic matter and 2 per cent. other minerals. Illite predominates among the clay minerals.

The acidity of Ni2+- and Co2+-exchanged montmorillonite has been probed using the diagnostic bases n-butylamine, cyclohexylamine and pyridine. Derivative thermograms for the desorption of pyridine from Ni2+- and Co2+-exchanged montmorillonite exhibited strong maxima at 40°, 90° and 360°C together with a weak maximum near 170°C The desorption maximum at 360°C is usually attributed to desorption of base from Bronsted acid sites. However, IR spectra of pyridine adsorbed on Ni2+- and Co2+-exchanged montmorillonite, at 250°C were dominated by intense bands near 1450 and 1607 cm−1 which are diagnostic of Lewis-bound pyridine. Consequently, the desorption maximum at 360°C must, in this instance, be attributed to desorption of pyridine from Lewis acid centres. Other bases, including cyclohexylamine and butylamine, also desorb at temperatures which have previously been attributed to the desorption of protonated base. Ni2+- and Co2+-exchanged clay contained predominatly Lewis acid or electron accepting sites, which is in marked contrast to the behaviour of trivalent cation exchanged clays.

The dehydroxylation of kaolinite has been investigated by isothermal thermogravimetry. Kinetic analysis using the Avrami equation shows that a combination of atomic mechanisms operates throughout the temperature range 734 K to 890 K. An empirical activation energy of 222 kJ mol-1 was calculated from the Arrhenius relationship using rate constants based on diffusion and homogeneous models. The activation energy (Ea) was calculated for a series of degrees of dehydroxylation by the time to a given fraction method, showing an increase in Ea during the early stages of the reaction. The isothermal plots indicate that OH is retained in the final stages of the reaction. The observations are explained in terms of a reaction mechanism in which kaolinite grains dehydroxylate from the edges inwards, parallel to (001).

The vertical clay mineral distribution pattern in two sediment cores taken from two East African lakes has been studied in detail. In the core from Lake Albert (Mobutu Sese Seko) a clay assemblage consisting principally of smectite with some illite and kaolinite in the uppermost segment of the core changed with depth into first a mixed-layer illite-smectite dominated clay and then at 6·60 m into an iltite dominated clay. Lower in the core there was again a transition towards interlayer mixtures, and in the bottom segment towards smectite. These changes are interpreted as a diagenetic transformation of smectite into illite, effected by saline palaeo-lake water with an unusually high K/Na ratio. Three smectite→illite-smectite→illite transition cycles were recognized in a 56 m deep sediment core from Lake Manyara. The sections in which illite dominated contained silt-sized analcime, while those with interlayer mixtures contained alkaline zeolites. The diagenetic illitization of smectite appeared to parallel the process of analcime formation, the K necessary for illitization being released during K,Na-zeolite→analcime transformation. These occurrences suggest that high temperature and pressure may not constitute absolute prerequisites for the diagenetic illitization of smectite.

The alteration and transformation behaviour of montmorillonite (bentonite from Wyoming, MX-80) in low-salinity solutions (NaCl, CaCl2) in the presence of metallic Fe (powder and 86461 mm plate) and magnetite powder was studied in batch experiments at 300ºC to simulate the mineralogical and chemical reactions of clays in contact with steel in a nuclear waste repository. The evolutions of pH and solution concentrations were measured over a period of 9 months. The mineralogical and chemical evolution of the clays was studied by XRD, SEM, Transmission Mössbauer Spectroscopy and TEM (EDS, HR imaging and EELS). Dissolution of the di-octahedral smectite of the starting bentonite was observed, in favour of newly formed clays (chlorite and saponite), quartz, feldspars and zeolite. The formation of Fe-chlorite was triggered by contact with the metallic Fe plate and Fe-Mg-chlorite at distance from the Fe plate (>2 mm).

The fibrous aluminosilicate imogolite has been studied by electronoptical and infrared absorption methods. Electron diffraction patterns are interpreted in terms of repeat units of 8·4 Å parallel and 23 Å perpendicular to the fibre axis. These spacings can not be reconciled with a continuous silicate chain structure and this conclusion is supported by an Si-O vibration near 930 cm−1. A structure is postulated in which distorted chains of Al-O octahedra are cross-linked through isolated Si2O7 groups.

Multiple OH stretching vibrations indicate different types of OH group in the imogolite structure. Absorption bands near 1000, 700 and 600 cm−1 are sensitive to sample orientation. This is attributed to the morphology and dimensions of the imogolite fibres.

Although natural Na-bentonite has little catalytic activity, various cation-exchanged bentonites have proved to be effective catalysts for a wide variety of organic reactions. In the presence of these catalysts alkenes can be induced to add (a) water, to yield branched-chain symmetrical ethers; (b) alcohols, to give a variety of ethers; (c) thiols, to yield thio-ethers; (d) carboxylic acids, to give esters. The number of products obtained in each reaction depends on the ease of rearrangement of the carbocation intermediates. High yields are obtained where a single carbocation intermediate is formed, A variety of elimination reactions is also catalysed by these sheet silicates. Water is eliminated from alcohols to produce ethers, ammonia is eliminated from amines to make secondary amines, and hydrogen sulphide is eliminated from thiols to give dialkyl sulphides. In most cases the ion-exchanged bentonites react as acidic heterogeneous catalysts.