The equilibrium H- and O-isotope fractionations can be approximated by the following equations which are based on experimental, empirical and/or theoretical data:

The equilibrium H-isotope fractionation factors vs. 106 × T−2 for kaolinite and probably smectite and illite are monotonic curves between 350-0°C. More complex curves, with a minimum fractionation near 200°C, are probably influenced by surface effects and/or disequilibrium fractionations among the different hydrogen sites. The H-isotope fractionations between smectite-water increase by ~70‰ from Fe-poor montmorillonite to nontronite at low temperatures. The pore-interlayer water in smectite H-isotope fractionation at low temperatures is ~20±10‰. The presence of organic matter can modify both the δD value of the clay analysis and its ‘water’ content. Clays — kaolinite, illite, smectite and probably halloysite — tend to retain their D/H and 18O/16O ratios unless subjected to more extreme diagenetic or metamorphic conditions or special local processes. Kinetic information is still only qualitative: for comparable grain sizes, hydrogen exchanges more rapidly than oxygen in the absence of recrystallization. Low-temperature diffusion coefficients cannot be calculated with sufficient precision from the higher temperature exchange data. The H- and O-isotope studies of clays can provide useful information about their conditions of formation.

In the Maláiguide Complex (Betic Cordilleras, Spain), dickite is widely developed in clastic Permo-Triassic sequences. The lateral extent stretches at least 300 km along the Betic range, whilst vertical extent is variable and appears limited to the lowest 20–150 m of these sequences. Textural, chemical and crystallochemical characteristics of the dickite, illite/mica and chlorite in dickite-bearing rocks and in the overlying (Permo-Triassic) and underlying (Carboniferous) rocks have been investigated to determine the approximate conditions in which dickite has developed. Using the chlorite geothermometer (based on A1IV contents), temperatures of 146±28°C and 169±12°C have been deduced for two Permo-Triassic members, and 305±12°C for Carboniferous. The Si content in illites has been used as a geobarometer, and pressures of 4.8±2 kbar have been estimated in Carboniferous rocks and tentative pressures of 2.7±3 and 2.1±2 kbar in Permo-Triassic members. Chemical evolution of phyllosilicates is accompanied by increasing illite crystallinity and % 2M1 polytype.

The uranium deposit (1350 Ma) of Cigar Lake (Canada) is surrounded by a late hydrothermal alteration halo (330 Ma) containing Fe-illites and kaolinites. Crystallochemical characterization of the kaolinites has been carried on the microscale using XRD, electron microscopy (SEM and TEM) coupled with EDX spectrometry and EPR. The large, well-crystallized particles show large amounts of Fe (0.9–1.8%) and V (0.3–0.5%). According to EPR measurements performed on both random powders and oriented samples, V occurs as the vanadyl ion VO2+, in substitution within the octahedral sheet of the kaolinite structure in the same way as Fe3+. Kaolinite growth proceeded through the hydrothermal alteration of anterior phyllosilicates devoid of V, induced by fluids which leached V-rich titano-magnetites in the surrounding sandstones.

The palygorskite-sepiolite group of clay minerals has a wide range of industrial applications derived mainly from its sorptive, rheological and catalytic properties which are based on the fabric, surface area, porosity, crystal morphology, structure and composition of these minerals. For assessing potential industrial uses, the mineralogical and chemical composition of the clay and its basic physical and physico-chemical parameters must be determined. Then some particular properties of commercial interest can be modified and improved by appropriate thermal, mechanical and acid treatments, surface active agents, organo-mineral derivatives formation, etc. In this paper, a revision of the principal characteristics of commercial palygorskite-sepiolite clays is presented, and potential uses are suggested according to these data. New products and applications are being investigated and those concerning environmental protection in particular, are noted. Finally, possible health effects of these elongate clay minerals are discussed.

Two sets of natural Al-substituted goethites from contrasting surface environments (24 tropical and subtropical soils vs. ten lake iron ores from Finland) were characterized by Mössbauer spectra obtained at room temperature and 4.2 K. A negative correlation between Bhf and Al substitution (R2 = 0.751) was found by combining the data of all the samples, which was slightly improved (R2 = 0.779) by taking the mean coherence length perpendicular to 111 (MCL111) into account. The effect of Al on lowering Bhf was, however, stronger for the tropical soil goethites than for those of the lake ores. This is parallelled by a corresponding difference in the unit-cell decrease per unit Al substitution. These differences are believed to result from the crystallization conditions in the two different environments.

The K-Ar dates and oxygen isotope data of illite-to-mica mineral phases in Permian to Triassic sandstones from Germany and Libya have been compared to previously published results of similar minerals of Liassic ages taken from lithologically similar rocks in several sites in western Europe and northern Africa. The widespread Liassic age for the micaceous mineral phases can be related to abnormal heat pulses induced by pre-rifting conditions. The temperatures in most cases appeared to be in the 150–220°C range. Some of these hydrothermal activities were responsible for both gas generation and U and Pb-Zn concentrations.

An approach combining K-Ar isotope dates and oxygen isotope signatures provides a framework for the characterization of the clay separates used in isotopic investigations and for depicting any crystallization conditions. The trend in decreases in δ18O values relative to increases in K-Ar dates, while the size of the clay fractions in a single sample increases, is indicative of detrital contamination. Varied trends in the δ18O values at constant K-Ar dates for clay fractions with increase in size might be indicative of changes in the pore volume of the host rocks.

Pore-lining chlorite is common in Rotliegend lake shoreline aeolian sandstones from northern Germany and preserves abnormally high primary intergranular porosity. In the north of the study area, in a basinward direction, the chlorites are Mg-rich while towards the south they become Fe-rich over a distance of about 15 km. All are unusually rich in Mn. Magnesium-rich examples tend to be more abundant than illite, while Fe-rich examples cover framework grains less continuously and are admixed with more abundant illite. Oxygen isotope analysis of 30 chlorites in the 2–6 µm fraction gave δ18O (SMOW) values of 7 to 12‰ (mean 9.8‰). These data show no obvious trend across the study area, nor in relation to changes in chlorite composition, or burial depth.

The honeycomb arrangement of chlorite crystals suggests chlorite formation via the sequence smectite-corrensite-chlorite. Chlorite distribution and the systematic changes in its composition suggest that formation of a precursor was related to lateral migration of Mg-rich fluids from basinal shales and/or evaporites during shallow burial. Interaction of these fluids with early formed oxyhydroxide coatings on the aeolian sand grains provided a source of Fe and the Mn. The isotope data suggest that the eventual formation of chlorite during deep burial occurred from waters with positive δ18O values, comparable to those present during the deep burial formation of illite.

Interpretation of K-Ar determinations of the apparent age of crystallization of diagenetic potassic layer silicates should take into account the current ideas concerning the smectite to illite conversion of clay minerals. These minerals are the major K-bearing neogenic phases in sedimentary rocks and, therefore, it is important to keep in mind their origin and the pathway of their evolution. Another important contributor to K and Ar content are detrital minerals which are not considered in detail in this paper. The radiogenic Ar retained by diagenetic illitic clay minerals (illite and illite-smectite interstratified minerals with a low smectite content) will be a function of: (1) the amount Ar lost through the destruction of mixed-layer and small grained illitic material dissolved to produce new, larger, illite-rich crystals; and (2) the amount of Ar produced and retained in the growing, stable illite mineral grains. Hence the K/Ar ratios in diagenetic illites depend on several variables. In samples where the detrital contribution is small, when the illite growth reaction is rapid, i. e. occurring over a short period of time, the accumulated radiogenic Ar can be used to date the geologic event which caused this crystal growth. However, if the process occurs over a significant period of time, as is usually the case in shales, the age deduced by radiogenic Ar content will indicate the changes in mineralogy and grain-sizes of the different participating phases. These changes will be the result of time and temperature variables of the sedimentation and burial of the samples studied. The radiogenic Ar accumulated will reflect a sequence of mineral changes over a period of time.

A mineralogical and geochemical study of the Gabasa outcrop (Huesca, NE Spain) was undertaken. It consists of Early Oligocene marly and clayey fluvial and lacustrine (playa-lake) sediments. The phases detected were quartz, amorphous silica, calcite, dolomite, palygorskite, illite, interstratified illite-smectite, Al-smectite and Mg-smectite. The palygorskite expands with ethyleneglycol. Statistical analysis of the geochemical data shows that the rare earth elements and transition trace elements are basically associated with the detrital phyllosilicates, although a considerable amount of the latter is contained in the palygorskite (ΣREE = 60–70 ppm, Cr+Co+Ni+V+Zn+Cu = 120–150 ppm), in contrast to the normally low values for neoformed minerals. This fact, together with the significant presence of Al and Fe in the palygorskite, suggest genesis involving alteration by dissolution of the 2:1 structure of the illite and/or Al-smectite, followed by re-ordering in a fibrous structure.

Fine-grained sediments are a major parent material in Ebro Valley soils. During the 1960s, the area was transformed by irrigation and soils underwent serious degradation processes. The sediments have a fine texture, high CaCO3 contents and high salinity-sodicity levels, and contain illite as the most important phyllosilicate in the fine fractions. Two groups of finely laminated organization have been recognized in terms of layer thickness and grain-size distribution. Based on texture, the microstructure of the silty and clayey layers is different, irrespective of their mode of formation; porosity characteristics also differ between layers, leading exclusively to a capillary evaporation flow that results in salinization of the plough horizons. The sediments are formed by two different mechanisms, each layer resulting from uninterrupted sedimentation of a suspension or from deposition of suspended particles by water discharge.

Isomorphic substitution in goethites is common in nature and the properties of goethites generally change as a function of the degree of substitution (e.g. Al-goethites). In synthetic goethites, substitution by other elements such as Co is also known. Recent literature indicates that the influence of Al and Co on the unit-cell dimensions of goethite is similar. In contrast to Al-goethites, however, little is known about other properties of Co-goethites and in this study some properties of synthetic Co-goethites were investigated by XRD, IR, TEM, TGA and reductive dissolution techniques. Eight goethite samples (S1 to S8) with varying Co concentrations were synthesized from mixed alkaline solutions of Fe(III) nitrate and Co(II) nitrate, aged at 63°C and ambient pressure. The goethites contained up to 9.5 mol.% Co. Their redness increased with Co concentration, e.g. 0.5 Y 6.0/6.4 for S1 and 6.4 YR 3.3/3.2 for S8. Surface area ranged from 46 to 88 m2/g. Unit-cell parameters a, b, c and v all showed a negative linear dependency on the Co concentration of the goethites. Transmission and diffuse reflectance IR spectrometry showed the presence of strong bands which were interpreted as v-OH, δ-OH and γ-OH vibrations. The δ-OH and γ-OH band positions showed a positive linear dependency on the Co concentration of the samples. Dehydroxylation occurred between 280 and 315°C and dehydroxylation peak positions tended to decrease with increasing Co concentrations. As with Al-goethites, Co-goethite reductive dissolution rates decreased parabolically with increasing substitution. X-ray diffraction and IR analyses, TGA and congruent reductive dissolution suggest the existence of single phases, i.e. Co-goethites of varying degrees of isomorphic substitution.

The mineralogy, crystallochemistry and microfabric of clay minerals from acidic soils were studied using transmission electron microscopy (TEM) and analytical electron microscopy (AEM). Soil profiles, developed on saprolites, sampled in the main crystalline massifs of France represent different pedological environments. The study focused on the microsystem of mica weathering, which appeared to be the main source of secondary clay minerals, and involves microdivision, transformation and dissolution. Microdivision begins with the splitting of large particles along layer planes and their shearing normal to the layers. This induces the breakdown of particles of one hundred layers into particles having only a few layers. The transformation of micas follows two steps: they first transform into 1–1.4 nm mixed-layer minerals and then into hydroxy-Al interlayered vermiculite. The formation of hydroxy-Al interlayered vermiculite derived from micas is dominant in acidic soils; particles are generally small, consisting of only three to seven layers, and always have a dioctahedral composition, whatever the type of the original mica (trioctahedral or dioctahedral). Dissolution affects the surface layers or large domains of the core of the particles and leads to the formation of multi-elementary gels rich in Fe and Al.

Two smectites with different layer charge localization were used to characterize the chemical and structural aspects of minerals treated with 1.9 × 10−2m and 1 m heavy metal solutions (Zn2+ and Pb2+). Natural and treated smectites were analysed by: (1) X-ray powder diffraction first at 25°C and relative humidity of 60% and then at increasing temperature up to 400°C; (2) thermo-gravimetric and differential thermal analysis; (3) X-ray fluorescence; (4) atomic absorption and UV visible spectrophotometries. The sorption of both metals depends on 2:1 layer features and is enhanced when the total layer charge is mostly due to substitution in the octahedral sheet. The variability between Zn2+- and Pb2+-treated smectites in the interlayer water content depends both upon cation electrostatic features and upon smectite layer charge localization. The greatest water content was observed in [Zn2+]1 m-treated smectite showing charge imbalance in the octahedral sheet. In smectites treated with [Zn2+]1 m solutions, an additional thermal reaction occurs at a temperature of ∼380°C, and the d(001) spacing, which is 10 Å at a temperature of ∼200°C, gradually decreases in the temperature range 200–400°C. In smectites treated with 1 m [Pb2+] solutions this value is reached at a temperature of ∼150°C and remains quite constant up to 400°C.

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.

A series of reduced-charge montmorillonites (RCM), prepared from the same parent Li-montmorillonite (Jelšový Potok, Slovakia) by heating at various temperatures (105–210°C) for 24 h, was treated with 6 m HCl at 95°C for periods up to 30 h. Reaction solutions obtained were analysed for Al, Fe, Mg and Li and the solid reaction products were investigated by FTIR spectroscopy. Both analyses provided evidence that the extent of dissolution decreased with increased amounts of Li fixed within the montmorillonite structure, i.e. with increased heating temperature. Differences in the acid dissolution process were reflected in the structural changes which occurred within the RCM samples, due presumably to different positions of fixed Li. The ethylene glycol monoethyl ether (EGME) surface areas, and XRD and HRTEM analyses of the RCM series revealed an increased amount of non-swelling layers in the samples prepared at higher temperatures, which caused a substantially slower decomposition of M7 and M8 in HCl. The calculated XRD patterns of M6 and M7 confirmed the presence of 20% and 45% pyrophyllite-like layers, respectively, in these samples. Mixed-layer pyrophyllite-like-smectite and pyrophyllite-like crystals, containing only non-swelling layers, were found in sample M8. The results confirmed that the amount of swelling layers in RCM significantly affects their dissolution rate in HCl.

The phase changes that took place upon heating an Fe-rich illite (OECD #5) to 1300°C in an oxidizing atmosphere were studied by a variety of mineralogical techniques. Infrared spectra, showing the stepwise dehydroxylation of the illite, showed good agreement with variations in sample colour and Mössbauer spectra. Dehydroxylation did not lead to noticeable variations in X-ray powder diffraction patterns until the structural breakdown of illite and formation of new phases at about 900°C Mössbauer spectroscopy proved to be very sensitive to all changes induced by heating, showing the disappearance of Fe2+ at 250°C, the gradual dehydroxylation between about 350 and 900°C, and characteristic features of the products formed at higher temperatures, e.g. the formation of hematite as the illite structure breaks down and the subsequent disappearance of hematite due to the incorporation of Fe in glass above 1200°C. The formation of hematite in clusters large enough to order magnetically at room temperature was first observed in the sample heated to 900°C, whereas at 4.2 K, significant proportions of a magnetically ordered phase could already be identified in the sample heated to 650°C.

The adsorption of Cd and Zn on a standard montmorillonite (SAZ-1) in the presence of the cationic pesticide chlordimeform, both in solution (simultaneous adsorption) and when the pesticide is previously adsorbed on the clay (successive adsorption) has been studied. The adsorption of Zn decreases when the chlordimeform concentration increases in both simultaneous and successive adsorptions, following the sequence: chlordimeform-free solutions > successive > simultaneous. In the adsorption of Cd the sequence is different: successive > chlordimeform-free solutions > simultaneous, indicating that a small amount of pesticide adsorbed favours Cd adsorption. In all cases, the apparent affinity of the metal for adsorption on montmorillonite, on the basis of distribution coefficients, KD, is higher for lower metal surface coverage, and decreases largely with the amount of the metal adsorbed. This indicates the existence of high affinity sites on the clay, probably those of variable charge edge regions. The contribution of edge and interlamellar positions to adsorption of Zn and Cd on SAZ-1 has been studied.

An organo-clay composite was prepared by contacting Na-montmorillonite and humic acid in aqueous solution which was of variable pH. After freeze-drying the precipitate of the solution, the detailed structure of the humic acid-montmorillonite composite was observed. Transmission electron micrographs and electron diffraction patterns indicate that the composite which was formed under acidic conditions has a characteristic microstructure. Humic acid, a large organic molecule, is combined with bent or curled thin foils of montmorillonite to form a spherical aggregate. The X-ray diffraction pattern supports this observation and suggests that the montmorillonite is cleaved into thin flakes as a silicate layer. The composite formed under alkaline conditions was in the form of a thin plate or lath and had a similar morphology to that of montmorillonite. The difference in the microstructure of the composite is reasonably attributed to the chemical flexibility of humic acid, i.e., conformation changes depending on the pH of the solution.

A highly illitic phase containing <5–10% interstratified smectite was described by Mossmann et al. (1992) and, more recently, by Clauer et al. (1995) from Upper Triassic sandstones of the Paris Basin (France). This phase is present in all size-fractions of all samples and was interpreted as authigenic. The K/Ar model ages of this illite range from 189–200 Ma and, combined with oxygen isotope data, were cited as evidence of high-temperature (220–250°C hydrothermal precipitation from highly 18O-enriched fluids at burial depths of only 500 m.

We suggest that this type of illite is more likely to be diagenetically altered detrital illitic material and unlike authigenic illite-smectite which is also present in many of their samples. This reassessment of their petrographic observations leads to a much more realistic diagenetic interpretation consistent with previous studies of the basin and avoids the need to invoke basin-wide hydrothermal activity during shallow burial.

Stichtite is the layered Mg-Cr(III) hydroxide carbonate of the pyroaurite group. The possibility of describing Cr(III) short range order (SRO) in stichtite by use of ion chromatography of the Cr(III)-hydroxo species following acid dissolution of the compound is described. Two synthetic stichtites of similar composition (average Mg5.73Cr(III)2.27(OH)15.93(O)0.07(CO3)1.10·xH2O) prepared in the absence or presence of hydroxy-bridged Cr(III) dimers and a sample from Dundas, Tasmania, Mg6.29Ni(II)0.02Cr(III)0.90Al0.65Fe(III)0.15(OH)15.26(OH2)0.74(CO3)1.23·xH2O have been examined. Ion chromatography showed the highest degree of SRO for the Dundas stichtite. For the synthetic stichtites the sample synthesized from Cr(III) dimers had the highest SRO. No information on cation ordering could be extracted from powder X-ray diffraction data. Visible spectroscopy indicates that for constant Mg:Cr(III) ratio the crystal field splitting increases with increasing SRO. Two different OH-stretching IR absorption bands (3585 and 3472 cm−1) are assigned to OH coordinated to 3Mg and OH coordinated to 2MgCr or Mg2Cr, respectively.