The unique properties of clays make them suitable for a large number of applications. Among the procedures that can be used to characterize clayey materials, the assessment of the abrasion and the abrasiveness index can be employed to predict the mechanical behaviour of clay samples. However, only a limited number of references to these testing procedures are available in the literature. Several Portuguese clayey samples were collected and the <63 μm fraction was analysed. The main clay minerals present are kaolinite, illite and smectite. The abrasiveness index depends on the granulometric and mineralogical compositions. A lower abrasiveness is induced by the presence of a high abundance of the <2 μm fraction, small mean particle size and a large phyllosilicate content . Kaolinite and illite show good correlation with the abrasiveness index, while smectite decreases abrasion.

Seven commercial cosmetic clays having different colour (white, green, pink and red) available in pharmacies and herbalists’ shops in the Greek market have been examined for their trace element concentrations (Ag, As, Ba, Be, Cd, Ce, Co, Cr, Cs, Cu, Ga, Hf, Hg, La, Mo, Ni, Pb, Rb, Sb, Sc, Se, Sr, Tl, V, Y, Zn and Zr). According to EC Regulation 1223/2009 the presence of As, Be, Cd, Cr, Hg, Ni, P, Pb, Sb, Se, Te, Tl, Zr and their compounds is prohibited in cosmetics. The most abundant trace elements in the white clays were P (330 μg/g), Pb (220 μg/g) and Zr (11 μg/g) and for the green clays were P (1250 μg/g), As (43 μg/g), Cr (31 μg/g), Pb (30 μg/g) and Ni (23 μg/g). Red and pink clays had lower concentrations of these elements than their white and green counterparts. The green clays are three times enriched in As and the kaolinite-rich white clays are nine times enriched in Pb compared to the Average Shale. The main mineral phase in the white clays is either kaolinite or calcite, in green clays smectite, in pink clay kaolinite and talc and in red clays it is vermiculite. The specific activities of 238U, 226Ra, 228Ra, 228Th and 40K were determined by γ-ray spectroscopy. The kaolinite-rich white clays are more enriched in 238U-series radionuclides (238U and 226Ra) than the smectitic green clays. In contrast, the green clays were more enriched in 232Th-series radionuclides (228Ra and 228Th) and 40K than the white clays.

This work describes the possible use of thick Early Cretaceous clay deposits, which occur in the southern sector of the Sierra de la Demanda range, as raw materials in the manufacture of ceramic articles. The global mineralogical composition is characterized by high proportions of phyllosilicates and quartz with variable quantities of feldspars, carbonates and hematite. The clay mineralogy differentiates two types of raw materials: illitic clay and kaolinitic-illitic clay. A granulometric distribution in the 2–60 µm fraction, good behaviour during the drying stage and acceptable results in firing tests confirmed that most samples can be utilized as raw material in the building ceramics industry. The range of suitable firing temperatures for these materials is 950–1000°C, a temperature which needs to be raised for samples with a high percentage of kaolinite and quartz. Moreover, other materials with abundant calcite (20–30%) are suitable for use as modifiers of some properties or colour.

The adsorption of DL-alanine at pH 4, 6 and 8 by a soil allophane has been determined. Two sets of experiments were carried out: (1) in which the allophane had been kept in a moist state throughout; and (2) in which the mineral had previously been dried at 50°C. In both instances, the adsorption isotherms showed three distinct regions as the concentration of alanine in solution was increased: (1) an initial, nearly linear, rise at low equilibrium concentrations; (2) a levelling off to a plateau at intermediate concentrations; and (3) a steep linear increase at high concentrations. For comparable concentrations of alanine in solution, adsorption decreased in the order pH 6 > pH 8 > pH 4. Irrespective of pH, however, more alanine was adsorbed by the ‘wet’ allophane than by its ‘dry’ counterpart. These observations are interpreted in terms of the morphology and aggregation of allophane unit particles together with the pH-dependent charge characteristics of allophane and alanine. The results are compared with published data on the adsorption of alanine by montmorillonite.

The present study investigates the use of magnesium sulfate (MgSO4) instead of (NH4)2SO4 as a lixiviant in the recovery of rare earth elements (REEs) from clays. Experiments were carried out to investigate the influence of leaching conditions such as leaching time, lixiviant concentration and liquid:solid ratio on the leaching efficiency. The optimum leaching conditions, leading to 75.48% of total REE leaching efficiency, required a stirring speed of 500 rpm, a leaching time of 30 min, a lixiviant concentration of 3 wt.% and a liquid:solid ratio of 3:1. After extension of the leaching process by a second stage, the leaching efficiency may reach up to 96.19%, which is slightly higher than that obtained by (NH4)2SO4. Leaching varies from element to element, with Ce presenting the lowest leaching efficiency, and the partition in leaching solution is in agreement with that in raw ore other than for Ce. Based on these findings, MgSO4 lixiviant is an excellent alternative leaching agent for a sustainable REE industry because it reduces or eliminates NH4+–N pollution.

The stability of organoclays prepared from smectites and organic cations depends on the type of used cation, among other factors. This study provides a prediction of the structure, stability and dynamic properties of organoclays based on montmorillonite (Mt) intercalated with two types of organic cations – tetrabutylammonium (TBA) and tetrabutylphosphonium (TBP) – using first-principle density functional theory. The results obtained from simulations were also used in the interpretation of the experimental infrared spectrum of the TBP-Mt organoclay. Analysis of interatomic distances showed that weak C–O···H hydrogen bonds were important in the stabilization of both TBA- and TBP-Mt models, with slightly stronger hydrogen bonds for the TBP cation. Calculated intercalation and adsorption reaction energies (ΔEint//ΔEads*/ΔEads**) confirmed that TBP-Mt structures (–72.4//–32.8/–53.8 kJ/mol) were considerably more stable than TBA-Mt structures (–56.7//–22.6/–37.4 kJ/mol). The stronger interactions of the alkyl chains of the TBP cation with Mt basal surfaces in comparison to those of the TBA cation were also correlated with the positions of the calculated bands of the C–H stretching vibrations.

Two iron ore samples from Nigeria have been examined using TG, DTA, EGA, XRD, and optical and electron microscopy. Itakpe iron ore is hematite-rich, this mineral being intergrown with magnetite, and silica is the major impurity. Agbaja ore is an acidic oölite ore consisting of goethite and magnetite, with alumina, silica and phosphorus as major impurities. Itakpe is typical of a rich ore formed by magmatic segregation whilst Agbaja is a lean ore of sedimentary origin. Isothermal mass-change measurements in hydrogen and carbon monoxide in the range 800–1100°C show Agbaja to be less reducible than Itakpe; in particular, Agbaja is very irreducible at 1100°C because of sintering of the ore. Characterization and reducibility experiments were also carried out on Corby (Northamptonshire, UK) iron ore for comparison.

Ultramarine pigments were synthesized successfully from Na-A zeolite derived from kaolin waste. Na-A zeolite encapsulates the sulfur species formed and which act as chromophores, which circumvents their oxidation and the subsequent liberation of high levels of toxic gases during the reaction. Different Na-A zeolite matrices with various grain sizes (fine to coarse) were mixed with sulfur and sodium carbonate in various proportions to study the influence of these variables on the pigments’ colours and hues. After calcination at 500°C for 5 h, the products were characterized by X-ray diffraction, X-ray fluorescence and Raman spectroscopy and were classified by the Munsell system (colour and hue). Products with colour ranging from blue to green with various hues were obtained. Both colour and hue were affected by the amount of additives and by the particle size.

The Tamusu region in northwest China is a key candidate area for China's clay rock deep geological repositories (DGRs) for high-level radioactive waste (HLRW) as it is composed of a continuous layer of thick lacustrine mudstone. To evaluate this mudstone as a host rock, two special test boreholes were drilled to investigate its spatial distribution and mineralogical and hydraulic characteristics. The southwest boundary and depositional centre of the lake basin were well delineated by boreholes TZK-1 and TZK-2. The continuous single-layer thickness of the target mudstone formation was up to 300 m at a depth of 500–800 m. Three main mineral types were determined, namely carbonates (mainly dolomite and ankerite), analcime and albite, and their abundance was used to distinguish three different facies. Other mineral phases, such as clay minerals (mainly illite and kaolinite), pyrite, hematite, quartz and calcite, were present as admixtures. The presence of carbonates may increase the mechanical strength and analcime may enhance the radionuclide adsorption properties of the mudstone. The self-sealing properties, which may be affected by the small amount of clay minerals, remain to be investigated. The hydraulic conductivity of the mudstone determined via in situ pulse tests ranged from 10–13 to 10–10 m s–1, suggesting that the Tamusu mudstone has ultra-low permeability. The transmissivity of the Tamusu mudstone fluctuated in regions with varying lithologies, but remained relatively constant for consistent lithologies. In summary, these preliminarily results confirm the possible suitability of the target formation as a host rock for DGRs of China's HLRW.

On a étudié les transformations minéralogiques des argiles et des biotites isolées d'un sol cryptopodzolique humifère du Plateau de Millevaches, France. Pour les argiles, la diffraction de rayons X fait apparaître un comportement intergrade de plus en plus prononcé de l'horizon C vers l'horizon A1. La nature des éléments extraits par les traitements citratedithionite et Tamura indique que ce comportement est lié à la présence d'aluminium interfoliaire pour les argiles de l'horizon A1Bh, mais également à des résidus de chlorite altérée pour celles de l'horizon A1. Pour les biotites, on observe un comportement aux RX très voisin de celui de la fraction argileuse. On peut mettre en évidence dans l'espace interfoliaire des biotites altérées la présence d'ions alumineux et de composés organiques.

Nine muscovite samples from different localities were analysed for all major chemical elements and examined by infrared spectroscopy in the range of 4000–250 cm−1. Iron in the octahedral positions was found to cause an intensity decrease and shifting of some absorption bands. Other structural cations were found not to be effective in producing intensity and frequency changes due to the narrow variations in their amounts. Heating studies indicated that at about 800°C muscovite transforms into a dehydroxylated phase which is stable at least up to 1000°C. Particle size studies showed that 5 µm is the upper size limit for a representative spectrum.

The synthesis of clay composites modified with magnetite and Co ferrite magnetic nanoparticles is described. The synthetic method relies on the adsorption of colloidal magnetite or Co ferrite particles onto the external surfaces of a Na-saturated clay mineral to give magnetic clay composites that can be converted easily, through ion exchange reactions, to valuable clay derivatives, e.g. organoclays, which maintain the magnetic properties of the parent composite. The magnetic solids were characterized by XRD, EPR, Mössbauer, magnetic measurement and TEM techniques.

A theoretical mechanism for the oxidation of ferrous iron in hydroxylated silicates is described. The reaction is represented by the general equation 4Fe2+ + 2nOH− + O2→4Fe3+ + (n + 2)O2− + nH2O, where n can vary. Oxidation occurs only at the surface of the mineral and is sustained by the migration of protons and electrons through the crystal. Non-oxidizable ions, such as Mg2+, and water formed during oxidation inhibit the reaction. The experimental evidence for the theory is derived, from a study of the oxidation of amphiboles.

L-cysteine (Cys) was adsorbed by bentonite (Ben) from aqueous solutions of variable concentrations and pHs. The raw materials and the adsorbed molecules (Ben-Cys) were characterized using X-ray diffraction (XRD), infrared spectroscopy (IR), thermal analysis methods (TG, DTG and DSC). The results indicated that the adsorption process depended strongly on pH, temperature and concentration of amino acid. Cysteine is specifically adsorbed on bentonite surface sites, probably through its NH3+ moiety. The pH dependence suggests that these sites may be silanolate groups (≡Si-O–). It is presumed that ion exchange interaction governs the adsorption process. The experimental data of adsorption isotherms obtained and analysed with the Langmuir model showed that this model fitted the adsorption data. Calculated thermodynamic parameters (ΔHº, ΔSº, and ΔGº) indicate that the adsorption processes were exothermic.

The chemisorption of methylene blue by kaolinite crystals increased as the aqueous suspensions changed from acid to alkaline because, at high pH values, not only the basal pinacoids but the edge-faces were negatively charged. The inability to calculate acceptable specific surfaces or cation exchange capacities from the chemisorption data is discussed, with special reference to the orientation of adsorbed dye cations, the covering of more than one exchange site by a monomer or polymer, the different concentrations of exchange sites on the basal pinacoids and edge-faces respectively, the possibility that such sites occur on the tetrahedral rather than on the octahedral basal pinacoid, and the incomplete replacement of inorganic cations.

Study of sandstone diagenesis provides information about the origin, texture, distribution and composition of clay minerals, which in turn is used in reservoir description. Three examples of the use of clay mineralogy in reservoir description are given. (1) Kaolinite commonly forms pore-filling cements which are pervasive in specific sandstone intervals. It is shown that water-zone kaolinization homogenizes and lowers the porosity and permeability relative to the oil zone; in a reservoir model different Ø/K relationships are defined above and below the oil-water contact. (2) An occurrence of chlorite in dish-structured horizons is shown to increase horizontal permeability and decrease formation resistivity. The sensitivity of the neutron porosity log to the chlorite cement reduces the usefulness of the log for porosity evaluation. Uncritical application of wireline logs to define reservoir parameters can give pessimistic reservoir evaluation. (3) Sand production can be related to wettability, which in turn is strongly influenced by clay mineralogy. A perforation strategy to minimize sand production may then be based on knowledge of the clay mineralogy of a reservoir.

An understanding of the behaviour of contaminants in compacted clays is important in assessing the effectiveness of clay-based barrier materials used in many waste containment strategies. Here the diffusion and sorption behaviour of I− with selected compacted clays is examined (129I is a relatively long-lived radioisotope present in high-level nuclear fuel waste.) Diffusion coefficients, D, and distribution coefficients, Kd, were measured for I− with four clays: bentonite, Lake Agassiz clay (a glacial lake clay composed mainly of smectite, illite, kaolinite, and quartz), interstratified illite-smectite, and kaolinite. For the diffusion experiments the clays were compacted to a dry bulk density, ρ, of ∼1.2 Mg m−3. The mean measured D values, Dm, were as follows: bentonite, 310 µm2 s−1; Lake Agassiz clay, 0.62 µm2 s−1; illitesmectite, 190µm2s−1; and kaolinite, 74µm2s−1. The measured values were compared with those calculated, Dc, from the following model: D=Doτan/(n + ρKd), where Do is the diffusion coefficient in pure bulk water, τa the apparent tortuosity factor, and n the solution-filled porosity of the clay. Except for the Lake Agassiz clay, where Dm was about an order of magnitude lower than Dc, the Dm and Dc values agreed within a factor of about two. The Lake Agassiz clay has a markedly higher organic carbon content than the other three clays, and this could affect τa, which may be overestimated in the model.

Few reports exist on the use of Diffuse Reflectance Infrared Fourier Transform Spectrometry coupled with Mass Spectrometry (DRIFTS-MS) in situ to monitor the dehydroxylation of kaolinitic clays. The use of DRIFTS-MS in situ allows study of the effect of heat treatment on the dehydroxylation, identifying intensities and temperatures at which the hydroxyl groups are released, forming metakaolinite and meta-alunite. The effluent gases from the infrared cell were analysed by mass spectrometry. The decrease in intensity of the bands at 3694, 3669, 3650 and 3621 cm−1 associated with the −OH stretching vibration modes of AlVI−OH−AlVI of kaolinite began at 450°C. Two additional bands at 3513 and 3485 cm−1 are associated with the vibration of AlVI−OH of alunite that also began to disappear during thermal treatment. Monitoring of the fractions m/e 17 and 18 using a mass spectrometer revealed that the intensity of these fractions increased starting at 450°C. Therefore, it is possible to study the dehydroxylation process of clays during thermal treatment.Chemical and mineralogical characterization of a kaolinitic clay (KN) fromMexico showed that the clay consists of 64.8% kaolinite, 11.0% alunite and 24.4% quartz based on PXRD, EDS, TG/DTA, TEM and FTIR results, and suggested that the material might have potential for use in the manufacture of ceramics, refractory bricks or geopolymers.

Back-scattered electron imaging was used in conjunction with energy-dispersive spectral analysis to study phyllosilicate minerals in polished thin-sections of Carboniferous (Westphalian) sandstones and associated mudstones from the East Midlands and from the diagenetically higher grade area of Abernant in the South Wales coalfield. Chemical diagenesis proceeded more rapidly in the sandstones than in the mudstones. In the East Midlands, greater flow of freshwater through the sandstones than the mudstones produced a higher degree of alteration of muscovite to kaolinite in the sandstones. Chlorite is present in the Well 1 and Well 2 East Midlands sandstones but not the mudstones nor any Well 3 samples. The chlorite may be an early diagenetic replacement of biotite. Much chlorite has been replaced by kaolinite. In the Abernant samples chlorite is present in both the sandstones and mudstones. In the former it appears to have replaced detrital biotite. In the latter the chlorite is too fine-grained to discern whether it is detrital or authigenic. The chlorite may have formed during the Hercynian orogeny. Much of the mica and chlorite in the Abernant sandstones has been replaced by illite, possibly in the post-orogenic period. The scarcity of kaolinite in the Abernant samples reflects the lack of freshwater leaching.