A study was made of the extent to which the lateral surfaces contribute to the surface area of five kaolinites of different crystallinities. Methods used included the low-temperature adsorption of N2 and Ar as measured by a volumetric technique coupled with microcalorimetry, the interpretation of the adsorption isotherms of alkyldodecylammonium ions, particle-size distribution curves, and shadowed transmission electron microscopy. With the exception of surfactant adsorption and adsorption calorimetry using Ar, these methods gave different and debatable results. For instance, specific lateral surface area values expressed as a percentage of total specific surface area varied from 17·0 to 40·4% for the most crystalline sample and from 12·0 to 54·3% for the least crystalline. It is shown that the decrease in crystallinity of samples is accompanied by a reduction in crystallite size from 0·8 to 0·08 µm and a decrease in lateral surface area from 34·0 to 12·0%.

Authigenic illites and chlorites from clastic reservoirs, offshore Norway, have been studied by analytical transmission electron microscopy (ATEM). Present-day reservoir conditions range from 1600 m burial depth and 70°C to 4400 m and 160°C. The reservoir units have experienced continuous subsidence since early Cretaceous, and are presently at maximum burial. Textural and morphological evidence indicates that the authigenic illites and chlorites investigated are late diagenetic products, except for an early-formed berthierine in the shallowest reservoir. While the illites show very limited chemical variability at temperatures between 140° and 160°C the chlorites exhibit definite compositional trends with increasing temperatures. Tetrahedral Al increases substantially from 100°–160°C, and the octahedral vacancy decreases correspondingly. These observations indicate that continuous recrystallization of authigenic clays has taken place. This is also supported by the chemical composition of present-day porewaters, which are close to equilibrium with the clay mineral assemblage.

In this study, natural bentonite was modified with hexadecyltrimethylammonium (HDTMA) bromide to obtain organobentonite (HDTMA-bentonite). Bentonite and HDTMA-bentonite were then characterized using XRD, XRF, SEM, FT-IR, thermogravimetric (TG) analysis, elemental analysis and Brunauer-Emmett-Teller (BET) surface area techniques. The HDTMA+ cation was found to be located on the surface and enters the interlayer spaces of smectite according to the XRD and SEM results. FT-IR spectra indicated the existence of HDTMA functional groups on the bentonite surface. The BET surface area significantly decreased after the modification due to the coverage of the pores of natural bentonite. After the characterization, the adsorption of a textile dye, Reactive Blue 19 (RB19), onto bentonite and HDTMA-bentonite was investigated. The maximum adsorption capacity of HDTMA-bentonite for RB19 was 502 mg g-1 at 20°C. The adsorption process followed a pseudo-second-order kinetic model and it was exothermic and physical in nature.

Mössbauer spectroscopy is the technique of recoil-free resonant emission and absorption of gamma rays. It has the advantage of being oblivious to all elements except the one under survey. In the case of materials formed on the earth’s surface, such as soils and clays, the only propitious element is Fe. Iron is the fourth most abundant element in the Earth’s crust, it is essential for life, and almost all environmental materials contain at least some Fe. It is also fortuitous that 57Fe Mössbauer spectroscopy is among the most straightforward to operate. 57Fe Mössbauer spectroscopy thus allows the characterization of iron speciation, and thereby of environmental conditions, over a wide range of concentrations, making it an extremely effective environmental probe.

Straightforward as it may seem, Mössbauer spectroscopy nevertheless has many pitfalls. Besides problems arising from the basic physics, complications can arise among other causes from imperfect crystallinity (small particle size), non-stoichiometry, interparticle effects and isomorphous substitutions.

In this paper a succinct review of the basic principles of Mössbauer spectroscopy is presented, followed by examples of Mössbauer spectra of minerals that are common constituents of clays and soils, and by more complex cases of soils, clays and fired clays.

Palygorskite and associated clay minerals have been studied in a Pleistocene calcrete complex from the Negev desert (Sde Boqer, Israel). This complex is divided into five main parts: the chalky and marly bedrock overlain by its weathered product, a brecciated calcrete hardpan; the laminar crust; loess pockets trapped in the calcrete; and the overlying soft surficial soil. The distribution of clay minerals is directly dependent on the position of the sample in the calcrete complex. Smectite is inherited from the bedrock in the calcrete with an aeolian enrichment in loess pockets and upper soft soil. The source of kaolinite is mainly detrital, related to desert dust. Illite is partly inherited and partly neoformed in loess pockets and desert surficial soil. The origin of palygorskite is clearly related to precipitation processes from soil solutions, Si and Al ions being provided by the slope and detrital grains trapped in the calcrete, with Mg being provided by the parent rock, the slope and aeolian detrital dolomite. This neoformation occurs mainly around detrital grains such as quartz in the hardpan and along textural transitions in loess pockets and is associated with gypsum in the lower part of the toposequence where the evaporation fluxes are the most important. The existence as coatings around grains and the delicate structure of the fibres are incompatible with a detrital origin. Moreover, no evidence was found to support any transformation of smectite into palygorskite in the solid state. Palygorskite is the last step of the cycle of mobile silica and seems to be a product of late diagenesis in Sde Boqer calcrete.

Celadonite, glauconite and Fe-illite samples were studied by XRD, EXAFS, IR and Mössbauer spectroscopy. The samples were monomineralic and corresponded to 1M polytype. In the OH-stretching region of the IR spectra the content of each definite pair of cations bonded to OH groups was determined. The number of heavy (Fe) and light (Al, Mg) octahedral cations nearest to Fe was found by the EXAFS technique. The predicted quadrupole splitting values for each definite arrangement of cations nearest to Fe3+ were used to interpret the Mössbauer spectra. After the fitting procedure, the intensity of each doublet corresponded to a definite set of local cation arrangements around Fe3+ and to a definite occurrence probability of these arrangements. Computer simulation and the experimental data obtained were used to reconstruct the distribution of isomorphous octahedral cations in the 2:1 layers. For all samples, R2+ cations prefer to occupy one of the two symmetrically independent cis-sites and R2+-R2+ and/or Al-Fe3+ were prohibited in the directions forming ± 120° with the b axis. Therefore, octahedral sheets of the samples revealed domain structure, in which domains differ in size, in the nature of predominant cation and/or by cation ordering.

The most abundant silicates formed under the Earth's 'normal' surface conditions, i.e. clay minerals, are always of small grain size. Under the same conditions, other mineral species such as carbonates, sulphates and oxides may form much bigger crystals. The reason why phyllosilicates formed in soils or in weathered rocks are always of small grain size is not related to the low-temperature-pressure conditions but rather to particular aspects of their crystal structure. Many recently published works describe the order-disorder cation distribution in the tetrahedral and octahedral sheets and the crystal defects in the layer stacks. Related to the Periodic Bond Chains (PBCs) theory, these data suggest that the size and the shape of clay crystallites could depend on the amount of crystal defects in the three axes of symmetry [100], [10] and [0]. The accumulation of crystal defects poisons the crystal growth along one, two or three PBCs. Then, nucleation becomes less energy-consuming than crystal growth and favours the formation of numerous smaller crystals rather than fewer bigger ones.

Three principal modes of formation are apparent for authigenic smectites in Recent marine sediments: alteration of volcanic rocks and glass, low-temperature combination of biogenic silica and Fe-oxyhydroxides, and direct precipitation from hydrothermal fluids. The latter two mechanisms are discussed with reference to new evidence from studies of sediments from the Bauer Deep of the equatorial eastern Pacific and the Atlantis II Deep in the Red Sea. In the Atlantis II Deep sediments, three sub-environments of smectite formation from hydrothermal fluids are recognized. In two of them nontronites are formed, whilst in the third an Fe-poor smectite, intermediate in composition between beidellite and montmorillonite, occurs.

Examination of the infrared spectra of synthetic kaolinites, with various degrees of substitution of hydroxyls by OD groups, allows a more detailed attribution of the stretching bands due to inner-surface hydroxyls of kaolinite. Among the three innersurface OH groups of the unit cell, two are nearly perpendicular to the sheet and give coupled vibrations which are responsible for the bands around 3695 and 3670 cm−1; the band near 3655 cm−1 is due to the other hydroxyl, which is lying close to the sheet.

Synthetic kaolinites of varying crystallinity, and in some instances with ideal morphology, have been produced by hydrothermal reaction of aluminiosilicate gels. Synthetic kaolinites doped with Mg2+ and Fe3+ were also obtained.

Synthetic kaolinite doped with Fe3+ produced an ESR spectrum at g = 4 identical to spectra observed in natural kaolinites. Following X-irradiation and annealing at ~200°C, synthetic kaolinite doped with Mg2+ exhibited an ESR signal at g = 2·0 identical to a resonance observed in natural kaolinites. It is concluded that the g = 2·0 signal in kaolinite is due to a defect centre stabilized by Mg2+ substitution.

All synthetic and natural kaolinites exhibit an additional resonance at g = 2·0 following X-irradiation which can be repeatedly created and destroyed by irradiation and annealing. This resonance is attributed to defects possibly associated either with the substitution of Al3+ for Si4+ in kaolinite or with lattice vacancies.

Expanding and non-expanding layers of interstratified clay minerals have been examined by high-resolution transmission electron microscopy. Permanent expansion of swelling layers under the electron beam was achieved by intercalation of n-alkylammonium ions, especially the octadecylammonium ion. Oriented flakes of clay minerals were prepared by embedding the expanded or non-expanded clay minerals in epoxy resin, followed by centrifugation before hardening of the resin. The minerals were then cut perpendicular to 001 using an ultramicrotome. Crystals of macroscopic trioctahedral vermiculites show homogeneous interplanar distances of 24 Å after intercalation of octadecylammonium ions. Crystals of dioctahedral soil vermiculites often show a central zone with non-expanding 10 Å layers; the outer zone shows a disturbed layer sequence extensively expanded by n-alkylammonium ions. After embedding in epoxy resin, vermiculites show stable 9·2 Å interplanar spacings but smectites expand to 13 Å. Montmorillonites of the Wyoming type show curved stacks of layers. Most of the layer stacks of montmorillonites of the Cheto type are split and disordered aggregates of single layers are formed. Crystals of illites and glauconites are built up of aggregated small stacks of 10 Å layers, the layer stacks consisting of 10 layers. Mostly the boundaries of the layer stacks are parallel to their 001 planes; sometimes low-angle boundaries are found. The dimensions of the layer stacks, ∼ 100 Å thick and some hundreds of Å in plane, are equal to the dimensions of the domains of coherent scattering of X-rays. The border layers between the layer stacks are identical with those 5 to 10% of layers which swell with glycerol or ethylene glycol during X-ray analysis. Some of the layer stacks of illite and glauconite crystals are expanded by octadecylammonium ions within a fortnight. The other stacks show unchanged 10 Å spacings. The different expanding behaviour of different layer stacks reflects the heterogeneity of the layer-charge distribution in the mica clay minerals. K-bentonites show the same expanding behaviour as illites and glauconites but the number of layers expanding with octadecylammonium ions is greater in K-bentonites than in illite crystals. Expanded mixed-layered minerals of the illite-smectite type show a different layer stacking sequence from illites. Random irregular stacking of mica layers with expanded layers are recognized rather than coherent stacks of mica layers. The crystals have a stepped morphology, perhaps effected by translations along the 001 plane. After reaction of the rectorite from Garland County with octadecylammonium ions, the non-expanded mica layers and the expanded smectite-like layers can be distinguished. The heterogeneity of the interlayer charges of the smectite layers is documented by the formation of alkyl double-layers with 17 Å spacings and alkyl triple-layers with 21 Å spaces in irregular sequence. The ‘rectorite’ from the Goto Mine expands nearly homogeneously in comparison with the rectorite from Garland County. After reaction with octadecylammonium ions, interplanar spacings of mostly 31 Å are observed but rarely spacings of 27 Å. The smectite layers of the corrensite from Kaubenheim are expanded by tetradecyl-ammonium ions to 18 Å spacings by formation of alkyl double-layers. A regular 1 : 1 layer structure of 14 Å chlorite layers and expanded 18 Å smectite layers with total spacing of 32 Å can be observed. Muscovite and pyrophyllite are not expandable by n-alkyl-ammonium ions within a fortnight. However, sporadic layers of celadonite crystals are expanded. Generally the 10 Å or 9·2 Å layers extend over the whole crystals of the three minerals. In celadonite crystals, disorder is caused sporadically by interrupted layers or slightly enlarged layer spacings.

The pzc of H+-kaolins determined by titration method is nearly pH = 3. The pzc of SiO2 + Al2O3 mixtures is not additive, and depends principally on Al2O3 content in mixture. The curve pzc—t°C (t°C = temperature of treatment of kaolins) has two maxima: 4·7 after treatment at 800-900°C, and 5 after treatment at 1300°C.

Brindley et al. (1951) reported the earliest efforts to obtain international collaboration on nomenclature and classification of clay minerals, initiated at the International Soil Congress in Amsterdam in 1950. Since then, national clay groups were formed, and they proposed various changes in nomenclature at group meetings of the International Clay Conferences. Most of the national clay groups have representation on the Nomenclature Committee of the Association Internationale pour l'Etude des Argiles (AIPEA, International Association for the Study of Clays), which was established in 1966. The precursor committee to the AIPEA Nomenclature Committee was the Nomenclature Subcommittee of the Comité International pour l'Etude des Argiles (OPEA, International Committee for the Study of Clays).

Porewater composition is the main control on diagenetic reactions in sandstones. Porewater has two possible contrasting primary sources: (i) fresh meteoric water, which is dilute and acidic, (ii) sea-water, which is alkaline and more concentrated than meteoric water. During burial, unstable minerals equilibrate with these porewaters, thus increasing the concentrations of dissolved species. A simple manometer model is used to describe the diagenesis of interconnected (fluvial or deltaic) sandstones. This model illustrates the following geological relationships: (a) a hydraulic head causes meteoric waters to penetrate deep into sedimentary basins, typically generating authigenic kaolinite; (b) decrease of the hydraulic head (by lowering the land level or by raising sea level) causes concentrated brines to rise within the basin, typically forming illitic cements; (c) enclosed sandstones (marine facies) are isolated from meteoric water flux and only receive fluxes when fault-induced or when uplifted. Kaolinite morphology and distribution are identified as being flux- or diffusion-controlled.

Interstratified kaolinite-smectite minerals form the major part of a pedon transitional between ‘red’ kaolinitic and black smectitic soils in a soil toposequence derived from basalt in Burundi, Central Africa. These interstratified kaolinite-smectites have many X-ray, morphological and chemical features in common with ‘tabular halloysite’. Modifications to the 00l spacings of these minerals brought about by thermal and chemical treatments, however, show that they are not halloysite but consist of a mixture of ∼70% kaolinite and 30% smectite randomly interstratified. Field evidence indicates that these clays can be considered as a transient stage in the overall reaction smectite→kaolinite + iron oxides, which takes place in this landscape whenever the slope gradients give rise to better drainage conditions.

The purpose of this report is to describe the appropriate use of indices relating to crystallinity, such as the ‘crystallinity index’, the ‘Hinckley index’, the ‘Kü bler index’, and the ‘Árkai index’. A ‘crystalline’ solid is defined as a solid consisting of atoms, ions, or molecules packed together in a periodic arrangement. A ‘crystallinity index’ is purported to be a measure of crystallinity, although there is uncertainty about what this means (see below). This report discusses briefly the nature of order, disorder and crystallinity in phyllosilicates and discusses why the use of a ‘crystallinity index’ should be avoided. If possible, it is suggested that indices be referred to using the name of the author who originally described the parameter, as in ‘Hinckley index’ or ‘Kübler index’, or in honour of a researcher who investigated the importance of the parameter extensively, as in ‘Árkai index’.

It is shown from studies of synthetic kaolinites doped with Fe3+ that the ESR spectrum of kaolinite at g = 4 consists of two components attributed to Fe3+ ions occupying two distinct substitutional sites (Centres I and II). The relative intensity of the two components can be correlated with the X-ray crystallinity of the samples. The ESR spectrum is influenced by artificial changes in crystallinity produced by subjecting samples to high stresses or by intercalation. It is concluded that Centre II is due to Fe3+ replacing Al3+ in the octahedral layer in a region of high crystallinity. Centre I is assigned to Fe3+ occupying Al3+ sites distorted by changes in the hydroxyl orientations associated with layer stacking disorder or disruption of interlayer bonding.

A stable defect centre in kaolinite which produces an ESR spectrum at g = 2·0 is attributed to either a hole centre located on an Si—O bond adjacent to an Mg2+ octahedral impurity or to an O2− ion trapped within the lattice.

In order to study Al-Fe substitution, Fe-kaolinites were synthesized at 200°C from glasses (Si/(Al + Fe) = 1) with varying Fe content. XRD and IR spectroscopy showed that kaolinites with increasing Fe contents could be synthesized, and Mössbauer spectroscopy indicated that the iron is strictly ferric. Chemical analyses (STEM) of kaolinite particles determined up to almost 7% Fe2O3, which probably does not represent a structural limit. The effect of Fe3+ content is evident on growth kinetics and particle size of kaolinites, both decreasing with % Fe2O3. However, it is not possible to establish a general correlation between Fe content and percentage of structural defects. Acccording to IR spectroscopy, some synthesized Fe-rich kaolinites can have relatively good crystallinity.

The value of peak width at half-height for the illite 001 XRD reflection is known as the Kubler index or the illite ‘crystallinity’ index. This measurement, which has been related to the degree of metamorphism of very low-grade, pelitic rocks, is a function of at least two crystal-chemical factors: (1) illite X-ray scattering domain size; and (2) illite structural distortions (especially swelling). Reynolds' NEWMOD computer program is used to construct a grid with which these two contributions to illite peak width can be determined independently from measurements of the 001 peak width at half-height and the Środoń intensity ratio. This method yields more information about changes undergone by illite during metamorphism than application of the Kubler index method alone.

Proportions of the component layers in randomly interstratified illite-smectites can be determined precisely in the presence of discrete illite if two reflections (at 15–16 and 31–32°2θ Cu Kα) are strong enough to be measured accurately. The method takes into account the variable thickness of the smectite-ethylene glycol complex and involves a correction for the interference from illite reflections.