Halloysite clay minerals are ubiquitous in soils and weathered rocks where they occur in a variety of particle shapes and hydration states. Diversity also characterizes their chemical composition, cation exchange capacity and potassium selectivity. This review summarizes the extensive but scattered literature on halloysite, from its natural occurrence, through its crystal structure, chemical and morphological diversity, to its reactivity toward organic compounds, ions and salts, involving the various methods of differentiating halloysite from kaolinite. No unique test seems to be ideal to distinguish these 1:1 clay minerals, especially in soils. The occurrence of 2:1 phyllosilicate contaminants appears, so far, to provide the best explanation for the high charge and potassium selectivity of halloysite. Yet, hydration properties of the mineral probably play a major role in ion sorption. Clear trends seem to relate particle morphology and structural Fe. However, future work is required to understand the possible mechanisms linking chemical, morphological, hydration and charge properties of halloysite.

The relationships between the composition and the crystallization temperature of chlorites and illites have been investigated in different geothermal fields and in particular the Los Azufres system in Mexico, considered to be a natural analogue to experimental laboratories, as the main changes in physical and chemical conditions and mineralogy are related to progressively increasing temperature with depth. Temperature was estimated from combined geothermometric approaches, and especially from fluid inclusion studies on quartz coexisting with clays. The Al(IV) content in the tetrahedral site of chlorites, and the K content and total interlayer occupancy of illites increase with temperature. These chemical changes are mainly related to the marked decrease in the molar fraction of the Si(IV)-rich end-members (kaolinite for chlorites, and pyrophyllite for illites) which become negligible at ∼300°C. Other chemical changes, such as the variation in Fe and Mg contents, are partly influenced by temperature, but are strongly dependent on the geological environment, and consequently on the solution composition. The empirical relationships between chemical variables and temperature were calibrated from 150–300°C, but extrapolations at lower and higher temperatures seem possible for chlorites. Such geothermometers provide tools for estimating the crystallization temperature of the clays, and are important for the study of diagenetic, hydrothermal and low-T metamorphic processes.

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.

The transformations in the iron oxide-hydroxide system have been interpreted in a rational crystallochemical manner, some being characterized as topotactic and some as non-topotactic. Crystallographic measurements have been made on the more reactive or metastable phases, particularly on the “green rusts.” The oxyhydroxides β-FeOOH and δ-FeOOH have been examined more fully, but data on all the phases have been checked. New data on transformations, such as FeCO3 → FeO and Fe(OH)2 → FeO are reported.

Many problems—from soil research to ceramics—require a reliable characterization of the clay minerals involved. This can be done using four clay-organic reactions: (i) staining tests and dye adsorption; (ii) glycerol and glycol adsorption; (iii) intercalation; (iv) alkylammonium ion exchange. Dye adsorption (staining tests) and glycerol adsorption allow a preliminary identification of the clay mineral groups. Intercalation reactions indicate minute differences between kaolins which cannot be detected by XRD and DTA. Alkylammonium ion exchange provides the best method for characterizing smectites and is sensitive to changes in the layer charge.

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.

Coordinated visible/near-infrared reflectance/mid-infrared reflectance and emissivity spectra of four groups of phyllosilicates were undertaken to provide insights into the differences within and among groups of smectites, kaolinite-serpentines, chlorites and micas. Identification and characterization of phyllosilicates via remote sensing on Earth and Mars can be achieved using the OH combination bands in the 2.2–2.5 μm region and the tetrahedral SiO4 vibrations from ~8.8–12 μm (~1140–830 cm–1) and ~20–25 μm (500–400 cm–1). The sharp and well resolved OH combination bands in the 2.2–2.5 μm region provide unique fingerprints for specific minerals. Al-rich phyllosilicates exhibit OH combination bands near 2.2 μm, while these bands are observed near 2.29–2.31, 2.33–2.34 μm and near 2.35–2.37 μm for Fe3+-rich, Mg-rich and Fe2+-rich phyllosilicates, respectively. When a tetrahedral substitution of Al or Fe3+ for Si occurs, the position of the Si(Al,Fe)O4 stretching mode absorption shifts. Depending on the size of the cation, the Si(Al,Fe)O4 bending mode near 500 cm–1 is split into multiple bands that may be distinguished via hyperspectral remote sensing techniques. The tetrahedral SiO4 vibrations are also influenced by the octahedral cations, such that Al-rich, Fe-rich and Mg-rich phyllosilicates can be discriminated in reflectance and emissivity spectra based on diagnostic positions of the stretching and bending bands. Differences among formation conditions for these four groups of phyllosilicates are also discussed. Hyperspectral remote sensing can be used to identify specific phyllosilicates using electronic and vibrational features and thus provide constraints on the chemistry and formation conditions of soils.

The origin and formation of soil clay minerals, namely micas, vermiculites, smectites, chlorites and interlayered minerals, interstratified minerals and kaolin minerals, are broadly reviewed in the context of research over the past half century. In particular, the pioneer overviews of Millot, Pedro and Duchaufour in France and of Jackson in the USA, are considered in the light of selected examples from the huge volume of work that has since taken place on this topic. It is concluded that these early overviews may still be regarded as being generally valid, although it may be that too much emphasis has been placed upon transformation mechanisms and not enough upon neoformation processes. This review also highlights some of the many problems pertaining to the origin and formation of soil clays that remain to be resolved.

This paper describes the ways in which the major rock-forming primary minerals (olivine, pyroxenes, amphiboles, feldspars, micas and chlorites) break down during weathering, the products that develop during this breakdown and the rates at which this breakdown occurs. The perspective chosen to illustrate this vast topic is that of the residual soil weathering profile. Different physical and chemical conditions characterize the various parts of such a profile. Thus, in the slightly weathered rock at the base of the profile, mineral weathering will take place in microfissures and narrow solution channels and the capillary water in such spatially restricted volumes may be expected to be close to equilibrium with the primary mineral. In these circumstances, the weathering product formed may be closely related to the primary mineral both compositionally and structurally. The saprolite higher up in the weathering profile may or may not retain the fabric and structure of the original parent rock, but in either case the close relationship observed between primary mineral and weathering product in the slightly weathered rock may be lost. This part of the profile will usually be affected by freely flowing drainage waters, the composition of which will be far from equilibrium with specific primary minerals. Weathering products which do form are likely to reflect the interaction between bulk water and bulk parent material. In the soil profile, the situation will be further complicated by organic ligands derived from decomposing organic matter or from the direct activities of soil microbes or plant roots. Thus, biological weathering will assume a much greater significance in this part of the profile compared with the mainly inorganic processes dominating in the saprolite and the slightly weathered rock. The general nature of any particular weathering profile will reflect the interactions between climate, topography, parent material, soil biota and time and superimposed upon this complexity, when considering how individual primary minerals break down in detail, will be factors related to the nature of the mineral itself. Particularly important in this respect is the inherent susceptibility of the mineral to weathering, which is related to overall chemical composition and structure, as well as the distribution and density of defects, dislocations and exsolution features, which often control the progress of the weathering reaction.

Iron is the fourth most common element by mass in the Earth's crust and forms compounds in several oxidation states. Iron (hydr)oxides, some of which form inherently and exclusively in the nanometre-size range, are ubiquitous in nature and readily synthesized. These facts add up to render many Fe (hydr)oxides suitable as catalysts, and it is hardly surprising that numerous studies on the applications of Fe (hydr)oxides in catalysis have been published. Moreover, the abundant availability of a natural Fe source from rocks and soils at minimal cost makes the potential use of these as heterogeneous catalyst attractive.

Besides those Fe (hydr)oxides that are inherently nanocrystalline (ferrihydrite, Fe5HO8.4H2O, and feroxyhyte, δ’-FeOOH), magnetite (Fe3O4) is often used as a catalyst because it has a permanent magnetization and contains Fe in both the divalent and trivalent states. Hematite, goethite and lepidocrocite have also been used as catalysts in their pure forms, doped with other cations, and as composites with carbon, alumina and zeolites among others.

In this review we report on the use of synthetic and natural Fe (hydr)oxides as catalysts in environmental remediation procedures using an advanced oxidation process, more specifically the Fenton-like system, which is highly efficient in generating reactive species such as hydroxyl radicals, even at room temperature and under atmospheric pressure. The catalytic efficiency of Fe (hydr)oxides is strongly affected by factors such as the Fe oxidation state, surface area, isomorphic substitution of Fe by other cations, pH and temperature.

Hydroxy-aluminium beidellites are prepared by treating Na-saturated beidellites from Taiwan, with compositions intermediate between end-member beidellite and end-member montmorillonite, with hydroxy-aluminium solutions having OH/Al ratios mainly between 2·00 and 2·50. Chemical analyses show that hydroxy-aluminium ions have compositions near Al6(OH,O)16 and charges near 1·0 in two cases, and near 2·2 in a third case. The basal spacing of the prepared clays is near 17 Å and remains without collapse up to 500°C. Argon adsorption measurements at liquid nitrogen temperatures, after heat-treatment up to 325°C in vacuo overnight, give surface areas near 500 m2/g when the exchangeable Na ions are about one-third replaced by hydroxy-aluminium, but near 200 m2/g when wholly replaced by hydroxy-aluminium. In the latter case the hydroxy-aluminium covers the internal surfaces of the clay almost completely prior to the heat-treatment.

Olique-texture electron diffraction examination of K-saturated dioctahedral smectites after 70–100 wetting-drying cycles allows the determination of cation distribution between trans and cis octahedra of the 2:1 layers. Studies of smectites with different compositions has revealed a wide variety of occupancies of the available octahedral sites.

X-ray diffraction is used widely for quantitative analysis of geological samples but studies which document the accuracy of the methods employed are not numerous. Synthetic sandstones of known composition are used to compare a ‘routine application’ of a Rietveld and a reference intensity ratio (RIR) method of quantitative phase analysis. Both methods give similar results accurate to within ~±3 wt.% at the 95% confidence level. The high degree of accuracy obtained is believed to depend to a large extent on the spray-drying method of sample preparation used to eliminate preferred orientation.

The clay minerals kaolin, smectite and palygorskite-sepiolite are among the world's most important and useful industrial minerals. Clay minerals are important in a number of geological applications such as stratigraphic correlations, indicators of environments of deposition and temperature for generation of hydrocarbons. In agriculture, the clay minerals are a major component of soils and determinant of soil properties. The clay minerals are important in construction where they are a major constituent in brick and tile. The physical and chemical properties of the clay minerals determine their utilization in the process industries.

What about tomorrow? Processing techniques will be improved and new equipment will be available so that improved clay mineral products will be available. Pillared clays and nanocomposites will become important. Further developments in organoclay technology and surface treatments will provide new usages for these special clays. Tomorrow will see further growth and utilization of the clay minerals.

The structure of 6-line and 2-line ferrihydrite (Fh) has been reconsidered. X-ray diffraction (XRD) curves were first simulated for the different structural models so far proposed, and it is shown that neither of these corresponds to the actual structure of ferrihydrite. On the basis of agreement between experimental and simulated XRD curves it is shown that Fh is a mixture of three components: (i) Defect-free Fh consisting of anionic ABACA . . . close packing in which Fe atoms occupy only octahedral sites with 50% probability; the hexagonal unit-cell parameters are a = 2-96 Å and c = 9-40 Å, and the space group is P1c. (ii) Defective Fh in which Ac1Bc2A and Ab1Cb2A structural fragments occur with equal probability and alternate completely at random; Fe atoms within each of these fragments have identical ordered distribution with in the hexagonal super-cell with a = 5.26 Å. (iii) Ultradispersed hematite with mean dimension of coherent scattering domains (CSD) of 10-20 Å. The main structural difference between 6-line and 2-line Fh is the size of their CSD which is extremely small for the latter structure. Nearest Fe-Fe distances calculated for this new structural model are very close to those determined by EXAFS spectroscopy on the same samples.

The diagenetic evolution of kaolin and illitic minerals in sandstones is described here. The structural characterization of these minerals, the possible reaction pathways leading to their crystallization, and the origin of the fluids involved are discussed specifically.

While early precipitation of kaolinite is in general related to flushing by meteoric waters, subsequent diagenetic kaolinite-to-dickite transformation probably results from invasion by acidic fluids of organic origin. Dickite is the stable polytype in most sandstone formations and the kaoliniteto- dickite conversion is kinetically controlled.

The conventional model of kaolin illitization, assuming a thermodynamic control in a closed system, is discussed and compared to an alternative model in which illitization of kaolin is not coupled to dissolution of K-feldspar (Berger et al., 1997). In the latter model, illite crystallization at the expense of kaolin implies that an energy barrier is overcome either by an increased K+/H+ activity ratio in solution or by a considerable temperature increase.

Intercalated compounds of montmorillonite and poly-6-amide were prepared by heating mixtures of ɛ-caprolactam and 5, 10, 15 and 30 wt% of montmorillonite, cation-exchanged with NH3+(CH2)11COOH, at 250°C in a nitrogen atmosphere, and examined by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), gel permeation chromatography (GPC) and elemental analysis. ɛ-caprolactam was polymerized to poly-6-amide by the heat treatment. The mean number-average molecular weight decreased from 3·6 × 104 to 0·8 × 104 with increasing montmorillonite content. TEM showed that considerable swelling had taken place subsequent to polymerization and that the clay layers were uniformly distributed in the final clay/poly-6-amide products. Both XRD and TEM showed that the basal spacing of the compound increased from 51 Å to 210 Å with increasing polyamide content. The driving force for the swelling was considered to be a combination of the polymerization energy of ɛ-caprolactam and the attractive interaction between the interlayer cation and ɛ-caprolactam.

Mineralogical and geotechnical investigations on the possible use of compacted bentonite as a buffer material in nuclear waste repositories are reported. The swelling capacity is highly dependent on the density of the compacted bentonite. Swelling pressures >30 MPa were measured for dry densities of ~2.0 g/cm3. Added iron or magnetite powder up to 20 wt% had no influence on the swelling capacity. Compacted mixtures of 20 wt% ground set cement and bentonite showed higher swelling pressures but lower swelling strain capability than compacted bentonite alone. Steam lowered the swelling pressure of compacted bentonite to ~60% of the original value. The influence was, however, reversible by ultrasonic treatment. The thermal conductivity of saturated compacted bentonite at a density of 2.0-2.1 g/cm3 is ~1.35-1.45 W/m°K The volumetric heat capacity ranges from 3.1 x 106 to 3.4 x 106 j/m3°C The saturated hydraulic conductivity of the compacted bentonite is <10-12 m/s. The apparent diffusion coefficients for various ions in compacted bentonite for water contents in the range of 20 to 25 wt% are: K+: 5 x 10-11, Cs+: 6 x 10-12, Sr2+: 3 x 10-11, UO22+: <10-13, Th4+: <10-13, Fe2+: 4 x 10-11, Fe3+: 4 x 10-11, Cl-: 1 x 10-10 and I- : 1 x 10-10 m2/s. The 'breakthrough time' for an apparent diffusion coefficient of 10-11 m2/s in compacted bentonite 1 m thick was estimated to be ~3000 years. The mineralogical longevity was investigated on natural K-bentonites from Kinnekulle, Sweden, and Montana, USA. Although these materials have undergone considerable changes during diagenesis and contain various amounts of mixed-layer illite-smectite, they still have a substantial swelling and adsorption capacity. The investigations demonstrate that although the properties of bentonite are negatively influenced to a certain extent by heat, hot steam, iron and cement, compacted bentonite is still the best choice to act as a buffer material in a nuclear waste repository.

Fifty-seven goethites, synthesized by a variety of procedures and with Al substitutions of 0–33 mole%, were characterized by XRD, IR, DTA, TEM and chemical techniques. Most of the properties measured showed significant intercorrelations. Mole% Al substitution (measured chemically) did not explain all the relationships among variables, but the inclusion of Δa, defined as the observed a dimension minus the a dimension predicted by the Vegard rule, explained much of the variation not explained by Al substitution. OH stretching frequency, in particular, was better correlated with Δa than the Al substitution or other properties. The properties of the goethites could best be explained by a combination of Al substitution and structural defects, with Δa being a measure of the defects. In general, the effect of structural defects was opposite to that of Al substitution. Increase in Al substitution led to a decrease in all three unit-cell dimensions and OH stretching frequency and to an increase in the distance between the two OH bending vibrations (δOH-γOH) and the temperature of dehydroxylation. Increase in structural defects, on the other hand, caused the a dimension, Δa, and OH stretching frequency to increase and δOH-γOH and the average temperature of dehydroxylation to decrease. Crystal size tended to decrease with increases in both Al substitution and structural defects. Surface area was significantly correlated with the reciprocal of the mean crystal thickness in the a direction. Comparison of XRD and TEM data showed that many samples consisted of crystals with several coherently scattering domains. The nature of the defects, i.e. whether they occur primarily in the interdomain areas or whether they are also distributed throughout the coherently diffracting domains, could not be determined.

A detailed study of the IR spectrum of goethite is given with the aim of relating variations to crystalline order and particle size. The OH stretching vibrations are split into two active components at high frequency, plus two inactive ones at low frequency. Two different bending modes exist from site group splitting. Their active modes from factor group splitting are at lower frequencies than the uncoupled ones. The lattice bands at 630 and 400 cm−1 correspond to Fe-O or Fe-OH stretching, approximately parallel to a and c, and thus respectively sensitive and not sensitive to the particle shape, as long as it remains elongated along c.