Clay minerals are essential components of soil systems and understanding their role in soil structure and function is critical for soil environmental quality management and sustainable agricultural development. An in-depth study of clay minerals and the development of related materials is essential for a complete understanding and effective management of soil systems. This review is a detailed compilation of relevant studies over the past decade in this area, focusing on an overview of clay minerals and their modified materials and their regulation of soil structure and function. We focus on the direct influence of clay minerals on the physical, chemical and biological properties of soils, such as soil structure, soil fertility, plant growth, soil microbial activity and soil carbon sequestration. Finally, we concluded by summarizing the existing issues with clay mineral materials in soil improvement and by outlining potential future development trends and strategies.

Alkaline activation involves a reaction between aluminium silicates and compounds with alkalis or alkaline-earth elements in a caustic environment and under certain thermal and pressure conditions. It has been used in the production of non-structural building materials and in so-called ‘green’ concrete, as products display high mechanical strength, low chemical reactivity and high resistance to fire. Green concrete could be an eco-efficient alternative to concrete made using ordinary Portland cement (OPC), reducing CO2 emissions substantially. The main goal of this work is to test common clays, glass cullet and other industrial wastes as an alternative to the commonly used binders (metakaolin or fly ash) in geopolymers. Optimized formulations show interesting mechanical strength (approaching 20 MPa) after just 48 h of curing. The addition of F-sand as aggregate minimizes the shrinkage upon curing and the amount of activator required, and increases the density/degree of compaction of the bodies, thus improving their mechanical resistance within certain limits. Curing in ambient conditions also has a beneficial affect on the mechanical strength.

The Coalgate Bentonite deposit has been formed by the alteration of cryptocrystalline basaltic ash erupted in Upper Miocene to Pliocene times and deposited in a freshwater lake on a land surface of earlier tholeiitic flows. Physical and chemical analysis shows the bentonite to consist essentially of non-swelling (Ca2+ and Mg2+) ferriferous-beidellite with minor ferriferous montmorillonite. The process of montmorillonitization probably involved a crystal chemical structural reorganization without solution or precipitation and occurred in a mildly alkaline environment in which initial reducing conditions become oxidizing.

The extent to which the diagenesis of sedimentary sequences within the UK North Sea is influenced by the passage of meteoric water is subject of current debate. Petrographic (SEM, TEM, thinsection) observation and stable isotope ratios from authigenic illite separates are used to deduce the pore-fluid evolution of the Fulmar Formation within well 29/10-2 from the Central Graben, with emphasis on the past importance of meteoric water flushing.

Petrographic observation shows the illite to have two modes of occurrence (pore-filling and as pseudomorphs after feldspar). These can be equated with two authigenic crystal morphologies (plates and laths) observed by TEM within illite separates prepared for isotopic analysis. The laths are equated with late stage ‘hairy’ pore-filling illite, the plates with illite pseudomorphs after feldspar which are difficult to date petrographically.

The δD (−55 to −87‰ SMOW) and δ18O (12.4–14.6‰ SMOW) analyses can be interpreted in terms of a conventional hydrogen-oxygen cross-plot to indicate illite precipitation from pore-waters of meteoric origin at 50–60°C. However, these predicted precipitation temperatures are irreconcilable with the observed petrographic sequence. The hydrogen isotope compositions may have undergone resetting during burial. Consequently, only the δ18O data may be confidently interpreted in terms of the conditions of illite precipitation. This implies illite growth at temperatures above 80°C from waters with δ18O between −2.5 and +6‰ SMOW, leaving the case for meteoric water flushing of the sandstones unproven.

An intergradient 14 Å mineral showing X-ray diffraction features of “chloritized” vermiculite in a Korean Ultisol was studied. The structural formula of the whole 2:1 layer-silicate (14 Å mineral and mica) in the Na+-saturated 0·2–0·5 µm fraction was obtained by elemental, thermogravimetric and 29Si and 27Al nuclear magnetic resonance spectroscopic analyses in combination with extraction of the interlayer material from the 14 Å mineral by hot 1/3 m sodium citrate treatment. This formula showed: (1) the 2 : 1 layer contains nearly one Al3+ in four tetrahedral positions, and Al3+ is the dominant cation in the octahedral sheet; (2) K+, exchangeable Na+ and sodium citrate extractable 1 : 1 layer occupy the interlayer space of the 14 Å mineral in similar proportions. Very little interlayer K was replaced by Na+ during the citrate treatment. Possible schemes of alteration of the 2 : 1 layer to the 1 : 1 layer as its interlayer material are discussed.

Vold's mathematical analysis of the d.t.a, curve has been applied to Murray's data on the dehydration of clays. Owing to experimental uncertainties, values for the heats of dehydration are lower than those determined by other methods. The first order law is obeyed and the activation energies of dehydration are of the same order as those derived from isothermal data; rates of dehydration are, however, higher. Furthermore, Smith's constant heat flow method has been used to determine specific heats and heats of dehydration of clays, and the effect of sample porosity upon the results has been determined. The thermal data has also been used to estimate the amount of clay mineral present. The kinetics of the dehydration process, evaluated from the apparent specific heat-temperature curves, follow a first order reaction curve. The activation energies obtained are, however, higher than those derived from other data.

Pisolites in the bauxitic laterites of Darling Range, Western Australia may contain up to 50% AI2O3, although no major Al-containing phases can be identified using standard X-ray diffraction techniques. These pisolites have been investigated using a range of techniques, and it has been demonstrated that Al is present in the form of x-alumina, a poorly crystalline form of A12O3. The x-alumina exhibits an indurating morphology and appears to have formed from a hydrated precursor.

The chemical composition of nine samples of Lower and Middle Chalk from the Givendale area of Yorkshire was determined; acetic acid residues were mechanically, chemically and mineralogically analysed. All nine chalk samples proved to be exceptionally pure calcium carbonate (96±1·5%), with only small amounts of MgO (1·03±0·53%), Al2O2 (0·33±0·28%) and Fe2O2 (0·20±0·14%). Insoluble residues ranged from 1·07 to 4·46%. Clay formed 56–88% of the insoluble residue. The non-clay fraction consisted of flint, quartz, collophane, limonite, feldspar, tourmaline and zircon. The clay fractions were dominated by montmorillonite (50%) with secondary illite (30%), apatite (3%), and quartz (8–30%). Kaolinite was detected by X-ray diffraction in the Lower Chalk.

The use of field emission electron microscopy for the study of clay mineral petrography in mudrocks and sandstones is discussed. The methodology including sample preparation is outlined and three examples of the application of the technique are described: the formation of authigenic illite in mudrocks, the multiple generation of authigenic illites in sandstones and the effects of KCl drilling muds on shale fabrics. In the study of authigenic illite formation in Palaeocene mudrocks from the North Sea, the FESEM analyses have demonstrated the formation of illites with increasing burial depth that conventional SEM and XRD analyses had failed to show. The FESEM analyses of the authigenic illites in Carboniferous sandstones from the southern North Sea revealed at least three different habits representing different generation episodes rather than one illite formation event.This has important repercussions with regard to the interpretation of stable isotope and dating data for the illites. Significant petrographic changes in shales after treatment with KCl drilling muds have been observed from FESEM analyses, suggesting reactivity between the shales and the KCl muds.

The localization and number of the different types of water in two Na-smectites (Laponite and hectorite) were studied as a function of the hydromechanical stresses applied. Water volume variation was obtained by macroscopic oedometric tests. Thermogravimetric analysis (TGA), X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) were used to study water-smectite interactions. The TGA results show that the bulk water content decreases while the adsorbed water content remains practically constant with increasing mechanical stress; hectorite adsorbs less water than Laponite at low hydraulic stress. The proportion of adsorbed water obtained by NMR confirms the TGA data. The interlamellar space and the equivalent water layers decrease with increasing mechanical stress and is always lower in hectorite than in Laponite. Hydromechanical effects on the water-Na-smectite system are in agreement with microtexture changes measured by porosimetry. Differences in the properties of the two clays can be attributed to the higher extension of the layers in hectorite compared with Laponite.

A review is given of the application of ESR spectroscopy to the study of hydrated transition metal ions and nitroxide spin probes in the interlamellar region of smectites and vermiculites. These investigations have not only provided information regarding the structure and mobility of the intracrystalline water-cation layers but have also demonstrated the reactivity and catalytic properties of certain transition metal exchange forms of smectites. Several novel coordination complexes and redox reactions between the exchange ions and a variety of simple organic molecules have been characterized.

The characterization of clay mineral assemblages in the diatomite-dominated Tripoli Formation (Lower Messinian, central Sicily) has resulted in delineation of suites dominated by generally well-crystallized dioctahedral smectite and illite of low crystallinity, with lesser amounts of kaolinite and chlorite. These minerals are thought to have a mainly detrital origin related to the calcareous and marly formations exposed in the margins of the depositional area. Vertical fluctuations of the montmorillonite/illite ratio and changes of the crystallinity and chemical composition of these phyllosilicates support environmental interpretations from isotopic data of associated carbonates, and point to a wide variability of depositional conditions ranging from evaporating to brackish. Early diagenesis of the clay minerals was controlled by the primary composition of the sediment which, in turn, affected the porewater chemistry.

The cation exchange capacity (CEC) of clay minerals has been determined by titration of aqueous suspension of clays with hexadecylpyridinium chloride, monitored using surface tension measurements. In order to make the method suitable for an accurate analysis of the CEC of the clays in drilling fluids or in soils, some parameters affecting the CEC determination (e.g. the presence of carboxymethylcellulose, mixing time and measurement device) have been investigated.

Precision intensity measurements were made on 27 00l reflexions using Mo Kα radiation. The interpretation of these results leads to the location of the Al and Si atoms of the tetrahedral layer in two different planes.

Les vermiculites magnésiennes chauffées durant plus de 24 h à une température de 700°C dans l'air, donnent une phase non gonflante qui est un biopyribole. Les diagrammes de diffraction X obtenus avec un monocristal montrent que ce matériau est constitué de deux phases: une enstatite en épitaxie sur le plan (010) d'un phyllosilicate. Le phyllosilicate a un empilement des feuillets semi-ordonné. Les rangées du plan (h0l) éant entièrement discrètes, la projection x0z a été étudiée par une analyse de Fourier classique à deux dimensions. Les autres rangéés du réseau réciproque sont plus ou moins diffuses dans la direction c*. Le désordre est creéé par une distribution aléatoire de trois translations entre les feuillets adjacents. Les relations structurales existant entre le phyllosilicate et l'enstatite expliquent l'absence de propriétés de gonflement de la phase phyllosilicate du biopyribole.

X-ray diffraction is one of the most effective tools for the characterization of the stacking defects which occur frequently in clay minerals. Modelling of the diffraction patterns of oriented mounts is often used for obtaining structural information about the nature of stacking order. Manual matching of calculated and observed patterns is time consuming and the results are user dependent and especially troublesome if a consistent model of the same mineral measured under different conditions needs to be obtained. It was shown recently that the Rietveld method could be applied successfully for the evaluation of the X-ray patterns of oriented mounts. Nevertheless, this automatic refinement procedure can also lead to inconsistent results if independent refinements are performed that describe the same sample measured under different conditions. One way to solve this problem is the application of parametric Rietveld refinement. For this approach a set of different measurements of the same sample was collected and fitted in one combined refinement by the connection of the structural models via external parameters. These conditions may involve different pre-treatments (e.g. different intercalations), different temperatures or relative humidities and/or different experimental setup (powder or oriented samples). All patterns were fitted in one overall refinement process by the BGMN software.

This approach was demonstrated on a mixture of two disordered reference materials and on a set of geological samples. Two different states for each sample were refined independently and parametrically and it was shown that this approach leads to consistent results, saves computation time and may even resolve small structural differences.

This paper deals with the adsorption of an essential oil (EO) on a kaolinite-rich clay and a smectite-rich clay. The two clays were modified with a quaternary alkyl ammonium surfactant to create a lipophilic environment for better adsorption of the EO. The preparation of the clay/EO hybrids avoided the use of a slurry and organic solvent. The selected EO was that of Lippia multiflora. This EO has insecticidal properties. The surfactant was trioctyl methylammonium (TOMA). The modified clays were characterized by X-ray diffraction (XRD) and infrared (IR) spectroscopy. The smectite-rich clay displayed greater adsorption of the L. multiflora EO compared to the kaolinite-rich clay. The interlayer space of the kaolinite-rich clay was not affected by the adsorption of the TOMA and/or EO molecules, which suggests that the adsorption in this clay took place on the external surface. By contrast, a significant increase in the interlayer space of the smectite-rich clay was observed, suggesting that the adsorption process of TOMA and/or EO took place on both the external and internal surfaces. The IR analysis showed that the surfactant loading in the interlayer space of the smectite-rich clay introduces a gauche conformation in the alkyl chains. A formulation mixing this local smectite-rich clay and the L. multiflora EO has potential for the manufacture of new biopesticides.

Calcigel bentonite-polyacrylamide (PAA) composites were investigated for their formation characteristics and their macroscopic hydro-mechanical and microscopic structural properties. The composites prepared were different in terms of the polymer charge, i.e. cationic (PAA+), anionic (PAA−), non-ionic (PAA°) and in terms of the polymer-to-clay ratio. The latter varied according to the individual maximum sorption capacity established from adsorption isotherms. Oedometer and waterretention testswere conducted on composites prepared under initial slurry conditions. The microstructure of the composites was investigated using environmental scanning electron microscopy (ESEM). At low stress, distinctly increased void ratios were found for all types of the composites, whereas under highstress conditions only the PAA+-composite prepared at 100% of the maximum sorption capacity showed an increase in void ratio. Analyses by ESEM on this composite indicated structural changes related to the preferential face-to-face aggregation, which help to explain the macroscopic behaviour and also account for the increased hydraulic permeabilities observed.

In situ measurements were carried out to quantify montmorillonite dissolution rates at a compaction pressure ranging from 0.04 to 10.00 MPa and temperature of 70°C in 0.3 M NaOH solution (pH 12.1 at 70°C) using vertical scanning interferometry (VSI) and an auto-compaction cell. Ex situ measurements of the reacted samples using atomic force microscopy (AFM) were performed to quantify the ratio of edge surface area (ESA) to total surface area (TSA) (XESA = ESA/TSA). Accordingly, the actual ESA for the montmorillonite examined by in situ VSI could be estimated. The XESA value increases as a function of run duration or compaction pressure. At atmospheric pressure, XESA is approximately 0.0054 and converges to ∼0.0107 at 10 MPa, An expression that relates reactive surface area and montmorillonite compaction (XESA/XESA initial = kXESA, k: variable factor) is kXESA = 1.0 + 0.64628 P0.1527 where P is in MPa. Using the calculated XESA, dissolution rates from the in situ VSI measurements are obtained. The early dissolution (<1500 min) at less compaction pressure tends to show faster rates (>1.0 × 10-11 mol/m2/s) than that at higher compaction pressure. The rates after >1500 min are slower, with values of less than 3×6 10-12 mol/m2/s, but there is no significant dependency on the density in the range from 1.0 to 1.7 Mg/m3. These observed rates for compacted montmorillonite are two-orders of magnitude slower (2.63×10-13 mol/m2/s) than dissolution rates in the suspended state.

Compacted bentonite is to be used as a buffer material between waste canisters and the bedrock in the deep geological disposal of high-level nuclear waste in several countries. In spite of the fact that such large bentonite systems have long equilibration times, estimation of the material properties and performance in repository conditions is often based on short-term, laboratory-scale experiments. Sample-preparation procedures in these experiments may differ from the natural evolution of the bentonite in the repository, however, affecting the bentonite properties. The present study reports the influence on the structure of clay tactoids of four different preparation procedures of water-saturated, compacted MX-80 bentonite samples using four target dry bulk densities. Small-angle X-ray scattering was used to illustrate the differences between the samples. The different treatments of the bentonite samples may lead to different structural features. Clear differences between low-density samples prepared using different procedures were observed. The influence of the preparation methods was less, but still noticeable, for the high-density samples.