Lower Cretaceous (AJO and AJR) and Oligocene clays (AS) from northern Tunisia were analysed to evaluate their possible use in the production of earthenware tiles by dry processing and fast double-firing. The Cretaceous clays are carbonate-rich (AJO = 20%, AJR = 12%) while the Oligocene ones are carbonate-free. This led to noticeable differences in firing behaviour (shrinkage, sintering rate and loss on ignition) and consequently in functional properties (water absorption, mechanical strength, porosity). The AJO firing shrinkage is very small, which makes this clay suitable for rapid firing. The clays are illite-kaolinite-rich but the AS sample is mostly smectitic (44%) and so is used (10 wt.% maximum) only to adjust the consistency of the powder during pressing. The average agglomerate size ranges from 100 to 350 μm and the distribution is suitable for easy pressing of powders without any special need for further adjustments. Characterization of fired products confirms the high potential of these clays since all properties fall within the ceramic International Standards (ISO). For both technical and economic reasons dry processing is recommended for production of earthenware tiles, in particular for countries in sunnier climates, where solar energy can be exploited for clay drying.

The increasing presence of pesticides in natural ecosystems has stimulated research to look for improved adsorbent materials which can be used to remediate and prevent soil and water contamination by these compounds. Among the different materials that have been assayed as adsorbents of pesticides are natural clay minerals, particularly 2:1 phyllosilicates and their structurally complementary synthetic analogues layered double hydroxides (LDHs). The great interest in natural clays and LDHs as adsorbent materials is mainly related to the large specific surface areas associated with their layered structure, the ease with which they are obtained or synthesized, and the possibility of modifying their surfaces to increase their affinity for specific adsorbates. This review summarizes the adsorptive properties of natural clays and LDHs for pesticides and related organic compounds. Particular emphasis is given to the surface modification of clay minerals and LDHs with organic ions as a strategy to improve the efficiency of these materials as pesticide adsorbents. Potential applications of unmodified and modified clays and LDHs as adsorbents to prevent and remediate soil and water contamination by pesticides are also discussed.

The low-charge dioctahedral 2:1 phyllosilicates are an important group of clay minerals that have a low degree of cation substitution and very weak interlayer interatomic interactions which are difficult to reproduce with quantum mechanical calculations. In order to study the crystallographic properties of these compounds with density functional theory (DFT) quantum-mechanical methods, an optimization of norm-conserving pseudopotentials of Al, Si, O, H and Na atoms has been carried out, and an optimization of the cutoff radii of the basis sets has been accomplished. Crystallographic properties and vibrational stretching frequencies of the OH groups, ν(OH), have been calculated, being consistent with previous computational and experimental results. All frequencies can be related to the different molecular environment of the OH groups. The effect of octahedral Fe3+ substitution on the ν(OH) frequency is reproduced. Several configurations of cation substitutions and interlayer cation (IC) positions are studied in low-charge dioctahedral 2:1 phyllosilicates, such as Al4(Si7–xAlx)O20(OH)4Nax, with x = 0.25, 0.50 and 0.75, indicating that the IVAl3+ is highly dispersed and the IC tends to be in the substituted ditrigonal hole. For the Al4(Si7Al)O20(OH)4Na composition, the trans-vacant form is more stable than the cis-vacant one.

The formation of bentonites via alteration of volcanic glassy rocks is associated with apparently contradictory mineralogical, geological and geochemical characteristics, which remain poorly understood. This contribution attempts to answer some of the questions based on the work carried out in our laboratory over the past 15 y. The first question concerns the formation of opal-CT-free bentonites from acidic precursors. It is suggested that the formation of opal-CT-free bentonites is closely related to the mechanism of eruption and emplacement of parent volcanic rocks if the temperature of the parent glass after emplacement is high and/or the establishment of hydraulic gradients coupled with high permeability after deposition of volcanic glass (i.e. diagenetic alteration) if the temperature of the parent glass is low. The second question pertains to the behaviour of Fe during bentonite formation. Based on mineralogical and geological characteristics of different bentonite deposits, it is suggested that Fe is present mainly as Fe2+ and hence may be mobilized during alteration. Oxidation of Fe may take place when bentonites are exposed to more oxidizing conditions close to the surface. Assignment of Fe as Fe2+ increases the layer charge of smectites and decreases significantly the range of layer charge. Thus the smectites may have considerably different properties when formed compared with their counterparts on the surface. The third question considers the possible influence of parent-rock chemistry on the crystal chemistry of smectites. It is proposed that the parent rock may affect the chemistry of the neoformed smectites to some degree; therefore the smectite chemistry may provide indications about the geochemical affinities of the parent rock.

The effect of heating, to temperatures between 400 and 1200ºC, on the dehydroxylation of kaolin and the pozzolanic activity of the resulting amorphous material were determined by a variety of analytical techniques. Mixtures of concrete containing variable amounts of kaolin calcined at 700ºC were analysed and the results compared with those for concrete samples containing two different types of imported metakaolin. As shown in this work, Colombian kaolin can be used effectively as a raw material to obtain a highly active product (metakaolin). The optimum heating temperature for the kaolin is between 700 and 800ºC.

Clay minerals are ubiquitous constituents in soils on Earth, are occasionally found in meteorites, and may also occur on planetary surfaces in the presence of water. However, little is known about the fundamental Mössbauer parameters (the intrinsic isomer shift, δI, the characteristic Mössbauer temperature, θM, and the recoil-free fraction, f) that are characteristic of clay minerals and critical to the correct interpretation of the Fe3+/ΣFe ratios as well as the mineral modes. Spectra of well characterized single mineral samples at multiple temperatures may be used for the determinations of f. Hence, measurements of five-layer silicates with a range of layer types are presented here: nontronite, Fe-smectite, glauconite, annite and biotite. The spectra were fitted using three different software packages: WMOSS from Science, Engineering & Education Co. in Minnesota; Recoil, from the University of Ottawa in Canada; and two programs used at the University of Ghent in Belgium. Four different approaches to modelling line shapes were used: (1) Lorentzian; (2) pseudo-Voigt (convolution of Lorentzian and Gaussian curves); (3) quadrupole-splitting distributions (QSD); and (4) a technique that does not assume a particular line shape (subsequently referred to as ‘model-independent’). Values of δI, θM and f were determined using the method of De Grave & Van Alboom (1991).

Results show that multiple doublets are routinely required by all models to represent Fe-site occupancy, even when all the Fe atoms of the same valence are in the same site, as is the case for dioctahedral smectite, nontronite, mica and glauconite. Consistent values of centre shift (δ) and quadrupole splitting (Δ) were obtained for the two distributions of M2Fe3+ in the smectites. In glauconite, a single Fe2+ doublet was clearly resolved and gave systematic values for δ, Δ and area, but the two Fe3+ doublets were less defined. In annite, two Fe2+ and two Fe3+ doublets were modelled, while three Fe2+ and one Fe3+ doublet were used for biotite. Three different programs that use Lorentzian line shapes gave very similar results for δ, Δ and area. The two different implementations of QSD line shapes gave similar but sometimes slightly different results, and the pseudo-Voigt and model-independent fits usually fell between the ranges for Lorentzian and QSD results.

The value of δI is ~0.58 mm/s for Fe3+ and ~1.31 mm/s for Fe2+ across all models and line shapes, which is expected because the Fe3+ has an additional shielding 3d electron. Values for θM data are nearly identical for Fe3+ in nontronite and Fe-smectite (~450 K), somewhat varied for Fe3+ in glauconite and biotite (θM = ~730 K and ~615 K, respectively), and relatively distinct for Fe2+ (~350 K). Some values for θM and f could not be determined due to the non-monotonic behaviour of the fitted values for δ as a function of temperature. Values of f295 were 0.821–0.917 for Fe3+ and 0.662–0.743 for Fe2+, consistent with previous studies of the recoil-free fraction in micas and other silicates. Calculated scatter in δ, Δ, area and f values as a function of different line shapes and computer software was significantly reduced at lower temperatures. Sources of error in each of the calculated parameters are discussed.

Within the Variscan basement of Sardinia (Italy), two main Fe concentrations occur in the low-grade metamorphic tectonic units: (1) an uppermost-Ordovician oolitic ironstone of shallow anoxic water environment; and (2) a concentration of Fe oxyhydroxides lying on a palaeosurface. Two sets of samples were picked from the marine ironstone and from the continental Fe concentration following stratigraphic criteria. Chemical analysis, X-ray diffraction, scanning electron microscopy-energy dispersive X-ray analysis and thin-section studies were performed on 34 samples.

Marine ironstones formed under a highly reducing, anoxic, non-sulphidic methanic environment, and their Fe phases are chamosite, siderite and magnetite. Detrital chlorite and illite, produced during physical weathering, were chamosite precursors. Using the V/Cr proxy, an emergence stage that caused a transition to an oxic environment is documented. In contrast, continental ironstones formed under oxic conditions and the dominant Fe phase is goethite, which can adsorb Zn2+ and U6+. Unexpected negative Ce anomalies occur in this set of samples, suggesting that the oxyhydroxides originated from Ce-depleted solutions. Although the ironstones of Sardinia formed in different environments (marine vs. continental) and under contrasting climatic conditions (sub-glacial vs. tropical) they share similar geochemical features. These dramatic palaeoenvironmental differences did not result in large differences between the geochemistry of the chemical sediments.

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 thermal history of the Buntsandstein (Lower Triassic) sedimentary rocks that crop out in the Vosges Mountains, or are deeply buried in the Rhine Graben, was evaluated on the basis of a combined mineralogical, morphological, oxygen isotope and K-Ar-dating study of illite separates from five locations over a limited 120 km2 area. The results indicate a complex pre-rift evolution characterized by the following features: (1) in the northern Vosges, no record of diagenetic illite formation could be detected; (2) in the nearby Saverne rifting fracture-field, tectonic activity favoured the formation of faults in the crystalline basement ~210 Ma ago. This induced fluid migrations into the porous sandstone cover with illite precipitation occurring either repetitively over a period of ~25 Ma or as two separate events, the latter at ~185 Ma, affecting rocks to the east in the deeper part of the post-Eocene Upper Rhine Graben system; this latter stage of tectonic activity and fluid migration continued until 160 Ma, unless overprinted by another tectonic pulse at that time; (3) afterwards, the main tectonic activity moved to the Soultz-sous-Forêts area where two episodes could be identified at ~95 and 70 Ma by dating mineral crystallization; the latter illite age was also detected in more deeply buried Buntsandstein lithologies of the rift basin, west of Strasbourg, reflecting diverse crystallization under different physical and/or chemical conditions; (4) further illitization which at present is poorly constrained may have restarted ~55 My ago in the same deep part of the rift graben.

The youngest detected illitization age is clearly older than the main Miocene rifting episode of the Rhine Graben, suggesting that no illite crystallization occurred in the Buntsandstein sandstones during this tectonic event. This is explained by the fact that these rocks, as well as most of the underlying crystalline basement, were already sealed by fluid migration and mineralization during late Mesozoic rifting, and were therefore almost impermeable to the circulation of Tertiary fluids. The overall evolution of the region between the Vosges Mountains and the central Rhine Graben appears to be more complex than that of equivalent rock lithologies elsewhere in Western Europe. Several episodes identified here have been detected in other regions, but no single location exists which was affected by all events.

The purpose of this study was to investigate the clay mineral phases in a Rhodic Acrisol soil and to discuss their evolution in subtropical conditions. Prairie and forest soil profiles were sampled and clay fractions of the parent material and soil horizons analysed by X-ray diffraction (XRD) at the Federal University of Santa Maria, Rio Grande do Sul-Brazil. The XRD results show the presence of interstratified kaolinite-smectite and illite-smectite as well as illite in the parent material. These minerals were also found in the soil samples but with two new phases: hydroxy-aluminium interlayered vermiculite (HIV), which showed incomplete collapse with treatment at 550ºC, and a newly formed kaolinite (d = 7.17 Å). Under a subtropical climate and a sandy lithology, HIV and kaolinite appear to be a result of a specific pedogenic clay formation, related to the natural vegetation. Originally, under the prairie area, the intensity of the weathering processes was weak (within 2:1 clay minerals), as only small quantities of kaolinite and Fe oxides, and no evidence of gibbsite, were found.

Physical alteration of magnetite-bearing antigorite grains is investigated in this study using Mössbauer, visible/near-infrared (VNIR) and mid-IR spectroscopy coupled with scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) analyses. An expected decrease in grain size with grinding is observed using SEM. The HRTEM images illustrate that the nanophase-sized grains which adhere to larger grains have 7 Å antigorite patterns. Mössbauer spectroscopy shows the presence of antigorite, magnetite and an amorphous phase. Visible/near infrared spectra exhibit features common in serpentine. These spectra also show an increasing continuum slope with grinding, an effect which is characteristic of thin coatings or tiny grains on surfaces. Mid-IR spectra indicate the formation of fine-grained Si-OH and carbonate in these samples with grinding.

Eleven Oxisols with high clay contents, 2.6–59.7 wt.% Fe2O3, and containing hematite, goethite, magnetite and maghemite, from São Paulo, Minas Gerais and Goiás, Brazil, were studied for the purpose of microwave remote sensing applications in the 0.3 to 300 GHz range. Of special interest are: the pseudosand effect caused by Fe-oxide cementation of clusters of soil particles; the mineralogy; and whether the soil magnetic susceptibility affected by ferromagnetic magnetite and maghemite interferes with microwave propagation. Quantitative mineralogical analyses were conducted using X-ray diffraction with Rietveld refinement. Visible, near infrared and short wave infrared spectroscopic analyses were used to characterize the samples qualitatively for comparison with published spectral radiometry results. Quartz (3–88%), hematite (2–36%) and gibbsite (1–40%) occurred in all soils, whereas kaolinite (2–70%) and anatase (2–13%) occurred in nine samples. Ilmenite (1–8%) was found in eight soils and goethite (2–39%) in seven. Of the ferromagnetic minerals, maghemite occurred in seven soils (1–13%) and three contained magnetite (<2%). These results will be applied to the interpretation of the effect of Fe oxides, particularly the ferromagnetic oxides, on microwave interaction with high-Fe soils, with ultimate application to the monitoring of soil water content by microwave remote sensing.

Desorption experiments performed on four Cu-adsorbed palygorskites suggest that the leached Cu2+ ion originates at the surface and/or net-like interstice of the palygorskite fibres. The leached fraction, calculated from the quantities of adsorbed Cu2+ before and after desorption, is <1%. This may indicate that the majority of Cu is in inaccessible structural sites. X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared (FTIR) spectroscopy and electron spin resonance (ESR) were used to determine the mineralogical character of the Cu-adsorbed palygorskite. Two photoelectron lines at 932.5 and/or 933.7 eV in the narrow scan Cu 2p3/2 spectra show that Cu adsorbed on the surface of palygorskite is in the Cu+ and Cu2+ state. The stretching vibrations of the octahedral cation shift ~3–5 cm–1 towards a greater wavenumber in the FTIR spectra of Cu-adsorbed palygorskite. It can be deduced that the Cu2+ is trapped in the channel of the palygorskite structure. The ESR spectra of the palygorskite give g values of 2.34, 2.12, 2.08 and 2.05, suggesting that some Cu ions cannot be reached by H+. These results confirm that Cu is adsorbed by palygorskite via three possible mechanisms: (1) the Cu is adsorbed onto the surface or in a net-like interstice, and its oxidation states are +1 and +2; (2) Cu forms a complex ion – [Cu(H2O)4]2+ or [Cu(H2O)6]2+, and is trapped in the channel; or (3) Cu enters into the hexagonal channel of the tetrahedral sites or the unoccupied octahedral sites of palygorskite.

Kaolin mined from the Ipixuna deposit of Pará Pigmentos S.A. in the Capim river area of northern Brazil has been studied at various stages of beneficiation to determine the behaviour of Fe- and Ti-bearing minerals which can reduce the brightness of the product. X-ray diffraction and Mössbauer spectroscopy showed the principal pigmenting minerals to be hematite and goethite, with chemical analyses showing a distinct decrease of both the total Fe and Ti contents in the course of processing. The Ti contents were primarily reduced due to the removal of anatase during particle size fractionation and dithionite reduction. While the Fe content of the final product is structurally bound in kaolinite, Raman spectroscopy indicates the remnant Ti to be bound both structurally in kaolinite and in remnant anatase.

A profile within the Upper Freshwater Molasse (OSM) of eastern Switzerland was sampled. Particle-size analyses, bulk chemical analyses, cation exchange capacities and Fe fractions (oxalate- and dithionite-citrate-bicarbonate-soluble Fe, total Fe) were measured. The mineralogical composition was determined by X-ray diffraction and quantified with Rietveld analysis. The layer charge of selected fine-clay samples was determined with the alkylammonium method using chain nc = 12. The profile could be divided into a lower sequence (I) and an upper sequence (II) by a hiatus. Chemical data, particle-size distributions and calcite contents indicated that soil formation was essentially restricted to wetting-drying cycles associated with redox cycles evident from Feo/Fed and Fed/Fet ratios. A significant correlation between the d060 values of the dioctahedral smectite-illite mixed-layer phases and Feo/Fed was interpreted as the influence of microbial Fe3+ reduction, which affected both the Fe oxides and Fe-rich clay minerals. This is the first evidence that the Fe dynamics of both mineral groups may be linked. The amount of illitization also correlated with Feo/Fed, but only in the upper part of the profile. This indicates that wetting-drying cycles were necessary for the illitization process.

The mafic rocks from boreholes studied here contain the assemblage typical for upper-subgreenschist to lower-greenschist facies (albite, chlorite, illite, titanite, quartz, Ti-oxide ± actinolite) as well as relict clinopyroxene.Metapelites underlying a metabasic rock sequence also record metamorphic alteration as demonstrated by the chlorite and illite crystallinities. Chlorite crystallinity suggests formation in conditions close to the subgreenschist/greenschist facies boundary, but this mineral is partly decomposed during metamorphic retrogression.

Synthetic hectorites and the corresponding surfactant-exchanged clays have been characterized by X-ray diffraction and 1H, 7Li, 13C, 23Na and 29Si solid-state nuclear magnetic resonance (NMR) spectroscopy. The low-charge clays retain water more efficiently, forming aggregates without extensive drying. The hydroxylated hectorite exhibits two 1H NMR signals near 0 ppm whereas the fluorohectorites are characterized by a single peak in the same region. The 23Na 2D 3Q magic angle spinning (MAS) spectra of the low-charge hectorites show a single peak. The 29Si NMR shift depends on the interlayer charge. Tactoids formed by the low-charge hectorites reduce the rate of surfactant incorporation. The population of the all-trans conformer of the hydrocarbon chain, determined by 13C MASNMR, varies with the surfactant content. 13C NMR relaxation data show an increase in mobility with the surfactant loading and along the long alkyl chain, from the polar head to the terminal group. Complexity of the motional behaviour precludes any detailed analysis. These modified clays are not useful in preparing poly(ε-caprolactone) nanocomposites by in situ polymerization.

The composition of Rhassoul clay is controversial regarding the nature of the pure-mineral clay fraction which is claimed to be stevensite rather than saponite. In this study, the raw and mineral fractions were characterized using various techniques including Fourier transform infrared spectroscopy and magic angle spinning nuclear magnetic resonance (MAS NMR). The isolated fine clay mineral fraction contained a larger amount of Al (>1 wt.%) than that reported for other stevensite occurrences. The 27Al MAS NMR technique confirmed that the mineral is stevensite in which the Al is equally split between the tetrahedral and octahedral coordination sites. The 29Si NMR spectrum showed a single unresolved resonance indicating little or no short-range ordering of silicon. The chemical composition of the stevensite from Jbel Rhassoul was determined to be ((Na0.25K0.20)(Mg5.04Al0.37Fe0.20☐0.21)5.61(Si7.76Al0.24)8O20(OH)4). This formula differs from previous compositions described from this locality and shows it to be an Al-bearing lacustrine clay mineral.