The swelling behaviour and hydraulic conductivity of Na-bentonite powder and bentonite-sand mixtures (10 and 20% of bentonite by dry weight) have been measured with distilled water and various salt solutions (0.01, 0.1 and 1 mol/l concentrations), It was found that in dilute solutions, the bentonite in mixtures subjected to small confining stresses swells sufficiently to separate the sand particles and reach a clay void ratio similar to that achieved by bentonite alone. At high stresses, or in strong solutions, the bentonite in a mixture has insufficient swelling capacity to force the sand particles apart and swelling is limited by the sand pore volume. The hydraulic conductivity of a mixture depends on the bentonite void ratio, and the porosity and tortuosity of the sand matrix. A design model is proposed to predict the engineering properties of a mixture over a range of confining stresses from the properties of its constituents and the permeant.

Isotherms were obtained for nitrogen adsorption and desorption on seven halloysite-rich samples from New Zealand and Western Australia. Calculations from these isotherms indicate that halloysites with mainly small particles (< c. 0.08 μm in width) had abundant cylindrical pores with narrow size distributions in the 5-15 nm range. They also indicate that halloysites with mainly large particles (> c. 0.1 μm in width) had few if any pores in the mesopore range (2–50 nm). Transmission electron microscopy (TEM) shows that cylindrical pores originate from the central holes in tubular particles. The TEM also suggests that slit-shaped pores can originate from the shrinkage of blocks of layers upon dehydration of halloysite.

According to XRD, DTA, geochemistry and electron microscopy data of a few selected samples, three categories of smectitic clay minerals occur in the Cenomanian and Turonian chalks sampled in several sections of northern France. The first one corresponds to detrital illitesmectite mixed-layers reworked from pedogenic blankets. The second category, characterized by crystalline overgrowths around detrital particles, is especially well-developed in slowly deposited sediments. The third category, located in thin marly horizons, corresponds to Cheto-montmorillonite derived from the submarine alteration of volcanic glass. Smectitic minerals having distinct origins may therefore occur at different levels of a given formation. From these examples, the smectite-rich clay sedimentation of the Late Cretaceous is tentatively explained by the combination of favourable factors induced mainly by highstand of the sea-level. The climatic conditions, the reduction of continental areas, the development of carbonate platforms and the decrease in sedimentation rates constitute the most relevant of these factors.

A new conceptual model for interstratified clays is proposed, based on complementary use of the transmission electron microscope (TEM) and X-ray diffraction (XRD). Clays yielding interstratified XRD patterns are shown to be composed of aggregates of fundamental particles (here defined as an individual or free particle which yields a single crystal pattern by electron diffraction) whose interfaces are capable of adsorbing water and organic molecules. In these circumstances, the interstratified XRD character results from an interparticle diffraction phenomenon. Smectites are shown to be primarily composed of particles 10 Å thick corresponding to elementary 2:1 silicate layers. Nearest-neighbour regularly interstratified illitesmectite (K-rectorite) is composed of particles of elementary ‘illite’ 20 Å. thick, corresponding to two silicate layers coordinated by a single plane of potassium ions. Regularly interstratified chlorite-smectite (corrensite) consists of particles 24 Å thick corresponding to two silicate layers coordinated by a single brucitic sheet. The layer sequence examined by XRD is determined by the types and proportions of particles present within the clay material. Thus a sedimented aggregate of 20 Å elementary ‘illite’ particles appears to be a regularly alternating sequence of illite and smectite layers by XRD. Randomly interstratified itlite-smectite and chlorite-smectite can be synthesised by making mixed suspensions of the <0·1 µm fractions of smectite with those of K-rectorite and corrensite respectively, providing experimental confirmation of the proposed model. Unusual associations, such as three-component illite-chlorite-smectite interstratified systems can be synthesised by making mixed suspensions of K-rectorite and corrensite. Long range regularly interstratified illite-smectite of the IIS and IIIS types are composed primarily of fundamental ‘illite’ particles 20–50 Å thick. Conventional illite is composed primarily of particles > 50 Å thick. This conceptual model has implications for the chemistry, behaviour and genesis of interstratified clays which are common constituents of soils and sediments.

The fine silt (2–5 μm) and fine clay (<0.1 μm) fractions from four acid soils developed from moraines of increasing age (80, 400, 3,000 and 6,500 years old) in Switzerland, were studied by X-ray diffraction and chemical analyses. The soil parent material is homogeneous at the four sites and the soils can be considered as forming a chronosequence of soil development leading to the formation of Podzols. Mineralogical evolution of silt-sized phyllosilicates and fine clay fractions follows different pathways according to their composition and the soil horizon in which they are located. Dioctahedral and trioctahedral minerals in the soil parent material were both weathered in the Bw and Bs horizons but the trioctahedral phase more strongly and faster than the dioctahedral one. Weathering products are mica-vermiculite mixed-layers, vermiculite and finally gibbsite and Fe oxy-hydroxides. Weathering of the trioctahedral fraction was faster in the eluvial A or E horizons than in the B horizons, being almost complete after 3,000 years of soil development. Appreciable weathering of the dioctahedral fraction occurs only in the eluvial horizons leading to the formation of mica-smectite mixed-layers and smectite. Although smectite has been reported in the E horizon of Podzols in different environments, the significant finding in this work is the presence of this mineral in soils developed from the same parent material. This supports the fact that smectite is the end- product of mica alteration in strongly leached and acidified E horizons of Podzols.

A method for estimating Gibbs free energies and stabilities of clay minerals is proposed for use with computer programs aimed at calculating the chemical evolution of natural water-rock systems. This is based on (i) a model for ideal solid solutions of a large number of end-member compositions and (ii) a data set of estimated solubility products from 36 end-members. The application of the method to the production of experimental or natural clay stabilities is discussed.

A structural scheme is proposed for the synthetic Mg-Al hydroxycarbonates described in Part I (Gastuche, Brown & Mortland, 1967) based on chemical and X-ray powder data. The structure consists of positively-charged brucite-like layers in which Al replaces Mg up to a maximum of about one in three sites. The positive charge is balanced by an interlayer sheet containing carbonate groups and water molecules. The idealized structural formula for the Al-rich material is:

[Mg4Al2(OH)12]2+ [CO3.3H2O]2−.

A similar structural scheme seems to apply to many other materials including the minerals of the pyroaurite group, the compound 4CaO.Al2O3.13H2O and the related mineral hydrocalumite, a nickeliferous magnesium hydroxide mineral described recently and to many synthetic products that have been referred to as double sheet structures.

Electron spin resonance (ESR) spectroscopy has contributed significantly to the identification and characterization of paramagnetic impurities associated with clays. Following a brief discussion of the general principles of the technique, a review is given of the application of ESR to the study of those paramagnetic species (chiefly iron and radiation-induced lattice defects) located either within the aluminosilicate structure or present as an external impurity phase.

Kaolin has been used as an alternative cheap raw material for the synthesis of zeolite 4A. Two steps are involved in the reaction: (1) dehydroxylation of kaolin at 550–900°C to form an activated X-ray amorphous material called metakaolin; (2) hydrothermal treatment of metakaolin with aqueous alkali to form the zeolite. The inherent colouring impurities in kaolin, especially the Fe minerals, affect the brightness of metakaolin and the resultant zeolite. The dehydroxylation temperature is found to have a significant influence on the kinetics of zeolite formation as well as on the brightness of zeolite. The present investigation deals with the preparation of metakaolins from a good quality kaolin at different temperatures and their characterization by XRD, IR, TGA, MAS NMR and brightness measurements. Hydrothermal reactions of these metakaolins with aqueous alkali have been conducted. The residual Fe in the mother liquor has been estimated. The improvement in brightness and change in reactivity of the metakaolin, difference in the kinetics of its conversion to zeolites and dissolution of Fe during zeolite formation have been correlated with the calcination temperature. A calcination temperature of 900°C (1 hr) is the optimum for this clay to change into a reactive metakaolin which gives detergent grade zeolite 4A of high crystallinity and maximum brightness.

Clay mineral abundances and illite-smectite (I/S) compositions have been determined by X-ray diffraction (XRD) in shales of Permo-Triassic to Quaternary age from seven wells in the Viking Graben and Moray Firth. Chemical analyses of size fractions provide evidence that diagenetic illitization of smectite has occurred during burial by uptake of Al and K, and release of Si. K-feldspar was probably the main source of K for illitization. The depth at which random I/S disappears occurs at similar temperatures (mean 93°C) in each well for which reliable measurements are available. Vitrinite reflectance measurements at this depth are also similar (mean 0·64% R0) and correspond to early oil generation. I/S diagenetic levels may have been imprinted by a Tertiary heating event.

The adsorption by different silicate minerals of some heavy metals, present in industrial waste water, has been studied. These adsorbents (mainly clay minerals) are readily available, inexpensive materials and offer a cost-effective alternative to conventional treatment of wastes from the metal finishing industry. The results show that some mineral species are suitable for the purification of such residual waters down to the limits prescribed by current legislation concerning industrial wastes. The Langmuir model was found to describe such adsorption processes best. Sepiolite (Orera, Spain) has an adsorption capacity of 8.26 mg g-1 for Cd2+, the capacities depending on the metal adsorbed in the order: Cd2+ > Cu2+ > Zn2+ > Ni2+. This mineral shows the highest sorption capacity relative to the other minerals studied. Factors in the reaction medium such as pH and ionic strength influenced the adsorption process.

Mössbauer spectra of three natural ferrihydrites of different crystallinities were collected between 295 and 4·2 K. Optimal fits of the room-temperature spectra were obtained using distributions of quadrupole-split doublets; half-widths of the distributions (0·71–0·86 mm/s) increased, and maxima (at 0·62–0·78 mm/s) shifted to higher quadrupole splittings with decreasing crystallinity. Rather poorly-defined magnetically-ordered spectral components appeared and gradually replaced the superparamagnetic doublets as temperatures were reduced. Blocking temperatures between 115 and 28 K, derived from the relative areas under the doublets and magnetic sextets, indicated average particle sizes between ∼ 5 and 3 nm. The sextets were relatively broad and could be fitted with distributions of hyperfine fields. These distributions narrowed and their maxima shifted to higher fields as temperatures decreased; the influence of superparamagnetism was no longer apparent at 4·2 K.

Due to its channels of molecular dimensions and a high specific surface area, sepiolite has many industrial applications which require high resistance to thermal effects in addition to a large surface area. On heating, sorbed water molecules are removed causing changes in the pore size distribution. In this study, the effects of thermal treatment on the pore structure of sepiolite and the acid-treated sepiolite samples were investigated. The solid density of sepiolite, measured by a He displacement technique, was 2.08 g cm-3 and total porosity was ~0.58. Both of these values showed an increase at 100°C, then decreased with further temperature increase due to crystal deformation and channel plugging which occurred at elevated temperatures. The BET surface area of the original sepiolite was 148 m2 g-1, and increased to 263 m2 g-1 at 100°C and then started to decrease. Approximately 16% of the total volume was in the micropores at 100°C. The acid pre-activation caused restrictions in possible crystal deformation during thermal treatment. The micropore volume increased to 20% and BET surface area reached values >500 m2 g-1 for the acid-treated samples.

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.

Following a round-table discussion at the Mid-European Clay Conference in Dresden 2014, new recommendations for illite ‘crystallinity’ Kübler index standardization have been agreed upon. The use of Crystallinity Index standards in the form of rock-fragment samples will be continued, along with the same numerical scale of measurement presented by Warr & Rice (1994). However, in order to be compatible with the original working definition of Kübler's (1967) anchizone, the upper and lower boundary limits of the Crystallinity Index Standard (CIS) scale are adjusted appropriately from 0.25°2θ and 0.42°2θ to 0.32°2θ and 0.52°2θ. This adjustment is based on an inter-laboratory correlation between the laboratories of Basel, Neuchâtel and the CIS scale. The details of this correction are presented in this first note, as discussed at the round-table meeting and will be further substantiated by a correlation program between CIS and former Kübler–Frey–Kisch standards.

Three bentonites, from Bavaria, Wyoming and Brazil, were separated into various fractions. The layer charge was determined by alkylammonium ion exchange and increases with particle size from 0·25 Eq/(Si, Al)4O10 (<0·06 µm) to 0·28 Eq/(Si, Al)4O10 (1–10 µm). The charge density corresponds to an interlayer cation density of 0·75–0·80 mEq/g silicate. Total amounts of 0·90–1·0 mEq of different surfactant cations (dimethyl dioctadecylammonium, trimethyl tetradecylammonium, alkylammonium ions) are bound per gram silicate. The difference between the total and the interlayer amount of surfactant ions decreases with increasing particle size. The amounts exceeding the interlayer CEC are bound at the edges. Tetramethylammonium (TM) ions restrict the interlayer adsorption of long-chain quaternary alkylammonium ions such as trimethyl tetradecylammonium (TMTD) ions, and only monolayers of flat-lying surfactants are formed. A ratio of TMTD and TM is attained which leads to densely packed monolayers of organic ions. The collapsing effect is smaller for tetraethylammonium ions so that considerable amounts of TMTD ions are adsorbed in bilayers. When bentonites are reacted with quaternary alkylammonium ions of technical quality some selectivity is observed according to particle size and layer charge. Smaller particles with lower charge density preferentially bind the longer chain compounds, whereas large particles with higher charge density select smaller sized surfactants.

Virtually all 2:1 clay minerals contain some Fe in their crystal structure, which may undergo redox reaction with surrounding redox-active species causing potentially significant changes in the chemical and physical properties of the clay mineral and its surrounding matrix. This phenomenon was originally of interest mostly as a laboratory experiment using strong inorganic reduction agents, but the discovery that the structural Fe could be reduced by microorganisms in natural soils and sediments opened the way for this to become a practical method for altering the chemical and physical properties of soils and sediments in situ. The purpose of this report was to review the body of literature that has been published since the inception of this field of inquiry and to complement, update, and complete three other reviews that have been published during the intervening years. Studies of microbial reduction of structural Fe in smectites have revealed the extent of reduction, effects on chemical and physical properties, reversibility (or lack thereof) of microbial reduction, stoichiometry, possible reaction mechanism, and types of organisms involved. Some organisms are also capable of oxidizing structural Fe, such as in biotite or reduced smectite, while one appears to be able to do both. Illitic layers resist reduction by microorganisms, but this can be partially overcome by the presence of an electron shuttle compound such as anthraquinone-2,6-disulfonate, which also enhances the extent of reduction in smectites. Microorganisms may be employed as an in situ reducing agent to drive redox cycles for structural Fe in constituent clay minerals of soils and sediments, which in turn can serve as an abiotic source for redox-mediated remediation of environmental contaminants.

Investigation of the clay mineralogy of forty-seven samples of sediments from boreholes in the western Nile Delta, an area little studied hitherto, and from surface sites on the mouth of the Nile and adjacent coast shows that the clay fractions consist of dominant iron-rich, dioctahedral, randomly interstratified smectite-illitcs together with kaolinite, illite and chlorite.

Amounts of the constituent minerals of the clay fractions are estimated from their X-ray diffraction intensities, supported by selective dissolution chemical data, and a new method is used to estimate the proportion of expanding layers in randomly interstratified smectite-illite. The results, which confirm and extend the work of previous investigators, also show that there is little correlation between the clay mineral composition and texture of the sediments, only kaolinite being weakly linearly correlated with clay content. Transformation of 2:1 layer silicate minerals occurs within the buried sediments ; chlorite is transformed and smectite and illite interlayers redistributed within randomly interstratified smectite-illites.

The adsorption and desorption of water, the layer spacing of the montmorillonite with increasing water content and the heat of immersion with water have been measured for a Na-bentonite and two Ca-bentonites. The bentonite-water system is treated in terms of a micropore-filling process. Uptake of water occurs in discrete stages as the montmorillonite structure expands and the internal surface is calculated from these discrete stages of water adsorption.

Swelling, shrinking and physical breakdown processes are reviewed with reference to well-known mudrock and overconsolidated clay formations in the UK and USA. Swelling results from two processes: the equilibration of depressed porewater pressures following stress relief, and the physico-chemical (osmotic) response of component clay minerals. Expansion in Na-smectite, and to a lesser extent Ca-smectite, clays is governed by double-layer swelling, whereas in kaolinites it is purely a mechanical unloading phenomenon; illites show an intermediate response. Intraparticle swelling in mudrocks older than the Silurian in the UK, or Upper Mississippian in the USA, can be expected to be reduced because of the removal of expandable layers by burial diagenesis. Shrinkage, like mudrock breakdown, is restricted to the partly saturated zone. Suction pressure-moisture content curves of indurated mudrocks are shown to be different from mudrocks and clays with high proportions of expandable clay minerals. Classification of expansion potential based on activity ratio poses problems with indurated types, but with some modification of method reasonable predictions can be made. Controls on physical disintegration are identified as: (i) incidence of sedimentary structures and discontinuities, (ii) slaking (air breakage), (iii) expandable clay mineral content, especially smectite, and (iv) clay mineral fabric orientation. Exceptionally high exchangeable sodium percentages have been measured in Coal Measures rocks susceptible to breakdown.