The present study examines the micro- and nano-texture and composition of ammonium-bearing and potassium micas in very-low grade metamorphic black Silurian shales from the SE Iberian Range (NE Spain). Two organic-rich shales were studied by X-ray diffraction (XRD), infrared spectroscopy (IR), transmission electron microscopy (TEM), analytical electron microscopy (AEM) and electron energy loss spectroscopy (EELS). The XRD showed the presence of two populations of micas: pure K micas with d001 = 9.98 Å and ammonium-bearing micas with larger d001 values (10.08 Å and 10.05 Å). The latter values indicate NH4 contents between 13 and 29% in the interlayer, which was confirmed by IR. Interstratifications of smectite and mica layers in the mica packets were not detected by XRD and TEM. Mica packets with sizes ranging from 100 to 250 Å show disordered polytypes and (001) lattice fringes that reflect the presence of K- and NH4-bearing layers (9.9–10.2 Å).

The combination of AEM and EELS analyses on powdered and lamellar samples indicates that micas have typical dioctahedral compositions with highly variable K contents. This variation in K is consistent with the presence of K and NH4 in the interlayers, even though the NH4 and K are not distributed homogeneously; rather they are segregated in nm-sized domains in the mica interlayer.

Radiometric dating of fault gouges has become a useful tool for regional tectonics studies and for exploring and understanding fault and earthquake processes. Methods to define the absolute age of faults achieved a solid scientific foundation almost 25 years ago when the development and application of illite age analysis for investigating sedimentary burial and thermal histories found a new potential application – defining the age of fold-and-thrust development. Since then, the methods have benefitted from further development and incorporation of the 40Ar/39Ar micro-encapsulation method and quantitative clay mineral evaluation to distinguish polytypes (Wildfire). These refinements to the methods have improved their application in fold-and-thrust terrains and have opened up applications in normal and strike-slip fault environments. Another important development is the use of absolute dating methods in retrograde clay gouges in which clays in a fault develop from igneous or metamorphic wall rocks that contain no clays. In addition, the method has also been shown to be useful at dating folds in fold-and-thrust belts. We think the method is now an established part of the geological toolkit, look forward to future fault structural and tectonic studies that incorporate fault ages and hope that researchers continue to probe and discover ways that the method can assist fault process studies, including earthquake fault studies.

The efficiency of two low-cost, abundant and natural clay minerals, palygorskite and vermiculite, in terms of reducing the concentation of Cu2+ and Ni2+ ions was evaluated here. Natural clay minerals were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), BET specific surface area and pore-diameter analysis. Batch-type experiments were performed and various parameters, i.e. pH, clay amount, contact time and initial metal concentration, that affect adsorption processes were investigated. The adsorption of Cu2+ and Ni2+ ions is pH-dependent, while minor clay quantities were sufficient to achieve high removal efficiencies. Adsorption equilibrium occurred in 60 min and the adsorption kinetics were better described by pseudo-second-order kinetics. Experimental results were analysed by the Langmuir, Freundlich, Dubinin–Radushkevich (D–R), Temkin and Halsey isotherm equations. The release of exchangeable cations (i.e. Ca2+, Mg2+, Na+ and K+) was examined to verify an ion-exchange mechanism.

In this contribution, a new raw material, Uşak clay (Usc), was investigated in order to assess its potential for the ceramic industry by comparing it with a world reference ceramic material, a Ukrainian clay (Ukc). Mineralogical characterization (X-ray diffraction [XRD], scanning electron microscopy [SEM] and Fourier-transform infrared [FTIR] spectroscopy), quantitative chemical analysis (X-ray fluorescence [XRF]) and the thermal properties of Ukc and Usc samples were investigated. Additionally, Atterberg limits, particle-size distribution and cation exchange capacity of both samples were determined. Various technological properties of Ukc and Usc were determined in the temperature range 800–1430°C. The bending and compressive strengths, total linear shrinkage, colour, water absorption and unit-volume mass values were measured. The findings from these analyses show that kaolinite-dominated Ukc and quartz-dominated Usc samples differ from each other not only mineralogically, but also in terms of their chemical, physical and technological properties. The firing colour of Usc was determined as 84% white, and so this can be considered as a light firing clay. In addition, due to its low plasticity, Usc may be utilized to reduce both the plasticity of the ceramic materials and the viscosity in slip-casting applied ceramics. Furthermore, the melting temperature of 1300°C suggests that Usc cannot be classified as refractory. However, this property does suggest an economic value for Usc in terms of developing technological characteristics at lower firing temperatures.

The Morrón de Mateo bentonite deposit has been studied as a natural analogue of the thermal effect on the bentonite barrier of a geological radioactive waste repository. This deposit was intruded by a volcanic dome that induced hydrothermal activity affecting the smectite clay minerals close to the dome. Previous studies of proximal bentonites indicated that Al-montmorillonites were transformed into Fe-rich smectites with intermediate composition between beidellite and saponite through gradual steps formed by smectites increasingly rich in Mg and Fe. In order to confirm the suggested transformation and the Fe distribution into the smectites, infrared and Mössbauer spectroscopy studies were performed. Infrared spectra of samples away from the dome show typical bands for montmorillonite type with prevailing Al in octahedral positions, while proximal samples also show bands of Fe-rich smectites. Mössbauer data confirm that Fe present in the fine fraction of bentonites is fundamentally located in the smectites structure, mainly as octahedrally coordinated Fe(III). Proximal smectites have a considerably more distorted octahedral environment for Fe(III) which probably stemmed from a significant degree of substitution of Al by Fe(III). These results confirm that an alteration process occurred related to the volcanic intrusion which produced an increase in temperature and Fe-rich solutions responsible for the transformation of Al-montmorillonites.

A kaolin deposit from Mankon (northwest Cameroon) was prospected and studied for potential applications in ceramics. Six samples were investigated with X-ray diffraction (XRD), infrared (IR) spectroscopy and scanning electron microscopy (SEM) to determine the mineralogical composition and with X-ray fluorescence (XRF) to determine the chemical composition and properties for ceramic applications. The main minerals in the clays are kaolinite/halloysite and anatase associated with alunite, illite, gibbsite and maghemite. The kaolin samples have abundant organic matter (4–10%) and low absorption of methylene blue (0.2–2.5 meq/100 g), while SiO2 (33.28–56.31%) and Al2O3 (19.26–35.87%) are major oxides. The particle-size distribution derived from sieving and the hydrometer method indicates that 12–38% of the samples are in the <2 μm clay fraction. The clays have low to moderate plasticity (7–21%). One sample with K-feldspar and plagioclase displays the necessary properties for red ceramic products. SEM confirmed the occurence of halloysite in sample M9. The high kaolinite/halloysite content (64–97%), associated with low Fe2O3 content (0.5–1.4%) demonstrates that five samples are suitable raw materials for white firing industrial kaolin.

The occurrence of smectite-illite and smectite-chlorite minerals series was studied along a thick clay cap (~300 m) drilled in the Cerro Pabellón geothermal field (northern Andes, Chile). X-ray diffraction (XRD) and scanning electronic microscopy (SEM) were used to characterize the alteration mineralogy and clay mineral assemblages and their changes with depth. Cerro Pabellón is a high-enthalpy blind geothermal system, with a reservoir zone from ~500 m to 2000 m depth, with temperatures of 200–250°C. Three main hydrothermal alteration zones were identified: (1) argillic; (2) sub-propylitic, and (3) propylitic, with variable amounts of smectite, illite-smectite, chlorite-smectite, mixed-layer chlorite-corrensite, illite and chlorite appearing in the groundmass and filling amygdales and veinlets. Chemical and XRD data of smectites, I-S and illites show, with some exceptions, a progressive illitization with depth. The evolution of I-S with depth, shows a sigmoidal variation in the percentage of illite layers, with the conversion of smectite to R1 I-S at ~180–185°C. These temperatures are greater than those reported for other similar geothermal fields and might indicate, at least in part, the efficiency of the clay cap in terms of restricting the circulation of hydrothermal fluids in low-permeability rocks. Our results highlight the importance of a better understanding of clay-mineral evolution in active geothermal systems, not only as a direct (or indirect) way to control temperature evolution, but also as a control on permeability/porosity efficiency of the clay cap.

Bernard Kübler measured illite ‘crystallinity’, the half-height width or full width at half maximum (FWHM) of the X-ray diffraction line of illite/mica at 10 Å, directly on the diffraction traces; this procedure has since been followed by the vast majority of workers. However, some workers have recently measured the FWHM of the fitted Pearson VII function rather than on the diffraction traces. The FWHM of this function for low-angle phyllosilicate diffraction peaks (FWHM*PVII) is almost consistently ‘broader’ than those measured directly on the diffraction trace profiles (FWHMtrace) by up to 0.08°Δ2θ for the broader peaks. The Pearson VII function shows gentle curvature (‘smoothing’) at its tops and fast fading of the tails relative to virtually all 10 Å diffraction traces. The broad FWHM*PVII results from the consequent lowering/’under-fitting’ of the peak tops and the upper tails and compensatory broadening/’over-fitting’ of the intermediate peak flanks. FWHM*PVII ‘contraction’ with respect to FWHMtrace and enhancement of the peak maximum is found on traces of muscovite strips. The fitting reliabilities of the Cauchy function are almost invariably better than those of the Pearson VII function. Their FWHM*Cauchy values are narrower for both the illite/mica 10 Å and the chlorite 7 Å reflections; although they still differ somewhat from the FWHMtrace, they are much closer, usually within 0.02°Δ2θ. This markedly lesser broadening of FWHM* of the Cauchy of the Pearson VII function is the result of its stronger top curvature and notably faster tail fading (less ‘smoothening’). For higher-angle mica peaks, the FWHM* values of the Pearson VII and Cauchy functions converge, usually differing only by 0.01–0.03°Δ2θ for the 5 Å peak, and even less for the 3.3 Å peak. It is therefore strongly recommended that FWHM values of the illite/mica 10 Å reflections be measured on the diffraction traces rather than on fitted functions. Where peak fitting is unavoidable (e.g. in order to separate the contributions of adjoining, partly resolved or unresolved reflections on broadened 10 Å reflections), Cauchy rather than Pearson VII functions should be used.

Clay minerals and organic matter occur frequently in fault zones. Their structural characteristics and their textural evolution are driven by several formation processes: (1) reaction by metasomatism from circulating fluids; (2) in situ evolution by diagenesis; and (3) neoformation due to deformation catalysis. Clay-mineral chemistry and precipitated solid organic matter may be used as indicators of fluid circulation in fault zones and to determine the maximum temperatures in these zones. In the present study, clay-mineral and organic-matter analyses of two major fault zones – the Adams-Tinui and Whakataki faults, Wairarapa, North Island, New Zealand – were investigated. The two faults analysed correspond to the soles of large imbricated thrust sheets formed during the onset of subduction beneath the North Island of New Zealand. The mineralogy of both fault zones is composed mainly of quartz, feldspars, calcite, chabazite and clay minerals such as illite-muscovite, kaolinite, chlorite and mixed-layer minerals such as chlorite-smectite and illite-smectite. The diagenesis and very-low-grade metamorphism of the sedimentary rock is determined by gradual changes of clay mineral ‘crystallinity’ (illite, chlorite, kaolinite), the use of a chlorite geothermometer and the reflectance of organic matter. It is concluded here that: (1) the established thermal grade is diagenesis; (2) tectonic strains affect the clay mineral ‘crystallinity’ in the fault zone; (3) there is a strong correlation between temperature determined by chlorite geothermometry and organic-matter reflectance; and (4) the duration and depth of burial as well as the pore-fluid chemistry are important factors affecting clay-mineral formation.

A new set of clay mineral ‘Crystallinity’ Index Standards (CIS) is available for improved calibration of the half-peak-width values of the X-ray diffraction 001 illite reflection (the Kübler index) and the 002 chlorite reflection (the Árkai index), two widely used indices for determining the state of prograde diagenesis and low-temperature metamorphism. Calibration using mudrock standards removes the numerical differences between laboratories caused by variations in sample preparation, machine settings and measurement methods, thus avoiding erroneous grade determinations. The number of standards available has been increased to nine. These can be used to obtain Kübler index values for each CIS sample and Árkai index values for upper anchizonal and epizonal samples. The diagenetic and lower anchizonal mudrocks are not suitable for Árkai index measurements due to the absence of chlorite or overlap by the 001 kaolinite reflection. Applying the new Kübler-equivalent upper and lower boundary limits of the anchizone placed at 0.32°2θ and 0.52°2θ, respectively (Warr & Ferreiro Mählmann, 2015), the nine standards from the Palaeozoic mudrocks of southwest England now comprise two diagenetic, two lower anchizonal, three upper anchizonal and two epizonal grade samples. These range from weakly cleaved mudstones to strongly foliated slates.

The stability of a shale containing smectite with different exchangeable cations (Na+, Ca2+) was improved using optimum solutions containing polyether amine (PA), poly-alcohol (PO) or KCl. Two types of shale samples with Na+ and Ca2+ as the main exchangeable cations, respectively, were used and the optimized solutions were determined using X-ray diffraction (XRD), an adsorption test, an oedometer swelling test, and an immersion test. The use of KCl prevented intercalation of PA or PO and maintained the stability of the Na-smectite-bearing shale. PA or PO adsorption reduced water adsorption sites on the clay layer, and K+ reduced hydration of exchangeable Na+, resulting in good shale stability in mixed solutions of KCl+PA, and KCl+PO. More stable shale was achieved in KCl+ PA mixed solution, whereas in the KCl+ PO solution the transport of water or solute molecules in the shale was reduced. In the shale containing mainly Ca-smectite, PA, PO and KCl maintained shale stability when applied separately or in common, as PA or PO cannot exchange Ca2+ in the smectite interlayer. As a result, PA or PO should be used together with KCl during drilling in shale formations containing Na-smectite, whereas in shales with Ca-smectite, PA, PO or KCl may be used separately.

Diverse applications of chlorite thermometry have been considered for better understanding the formation process in nature. Here, an approach which combined a semi-empirical thermometer (Inoue et al., 2009) with the method of Walshe (1986) was tested to estimate the redox conditions (log fO2) and the formation temperature, using the literature data from Niger, Rouez and St Martin and new data for chlorite which coexists with pink-coloured epidote in the Noboribetsu geothermal field. The log fO2 predicted for the former data sets were compatible with those estimated by Vidal et al. (2016), suggesting that the present approach is valid for quantifying the variations in log fO2. The Noboribetsu chlorites have lower Fe/(Fe + Mn + Mg) and greater Fe3+/ΣFe ratios than those observed in adjacent propylite rocks. The peculiar mineral assemblage and chemical composition are attributed to the formation under higher fO2 conditions and possibly low Fe concentration in the alteration fluids.

Chemical modification of kraft lignin from Pinus caribaea (Sénécl.) W.H.G. was performed with cyclic anhydrides (succinic, maleic and glutaric) assisted by microwave radiation. Esterification of the lignin was proven by the mass increase and Fourier Transform Infrared (FTIR) spectroscopy. Aqueous suspensions of bentonite were prepared using unmodified lignin and the corresponding derivatives as dispersants. Suspensions were evaluated in term of stability, viscosity and dispersibility. The esterified derivatives showed better dispersing properties than the neat lignin because the derivatives-based suspensions were less viscous. The dispersing properties of lignin and the esterified derivatives were compared with those of a high-molecular-weight lignin fraction obtained by ultrafiltration. In addition, two commercial lignosulfonate dispersants commonly used for drilling muds were used as references. The high-molecular-weight esterified derivatives proved to be better dispersants than their unfractionated counterparts. In general, the esterified derivatives showed similar properties to those obtained with the commercial dispersants. Modified lignin based on succinic-, maleic- and glutaric-anhydride is expected to play a key role in the design of novel bio-based dispersants for drilling-mud applications.

Iranian montmorillonite (MMT) was modified with hexadecyltrimethylammonium bromide (HDTB) and used as a nano-additive for the enhancement of the mechanical and anticorrosion properties of an epoxy coating. Infrared (IR) spectroscopy, thermo-gravimetric analysis (TGA), transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis indicated that HDTB reacted with MMT (with 97% yield) and increased the d001 spacing of MMT from 1.27 to 3.92 nm. Some 1, 3 and 5 wt.% of organically modified montmorillonite (OMMT) were added to the epoxy coating formulation. XRD and TEM/image processing analysis showed that the extent of intercalation/exfoliation of OMMT was substantially greater than that of MMT. Dynamic mechanical analysis showed that the glass transition temperature and storage modulus increased significantly with the addition of OMMT. Electrochemical impedance spectroscopy (EIS) and salt spray/image processing results revealed that addition of OMMT to the epoxy coating significantly increased the corrosion resistance of the coating compared to neat and MMT-containing epoxy coatings. The optimum concentration of OMMT was 3 wt.%. At this concentration, the mechanical and anticorrosion properties were greatly superior to those of neat and MMT-containing epoxy coatings.

The [MnO|SiO2,Al2O3,FeO,MgO] balanced ratio (i.e. the isometric log-ratio of the MnO concentration relative to the concentration of SiO2, Al2O3, FeO and MgO) of chlorite and of whole-rock composition is an effective discriminant between Mesozoic stratigraphic formations in the Magallanes Basin (Chile). The MnO content in chlorite is only controlled by the host rock chemistry and is dependent on the geological environment. The MnO content in chlorite remains unchanged at low-grade metamorphic conditions. Single-grain chlorite analysis (n = 1042, electron microprobe) and whole-rock analysis (n = 40, X-ray fluorescence) were used to discriminate stratigraphic formations and to decipher differences in the depositional environment in the Magallanes Basin. The samples are from one Upper Jurassic and three Cretaceous sedimentary units that were affected either by low-grade regional metamorphism or by Miocene contact metamorphism. The highest [MnO|SiO2,Al2O3,FeO,MgO] values are recorded in the upper Zapata Formation. The Punta Barrosa, Cerro Toro and Tobífera Formations show slightly lower [MnO|SiO2,Al2O3,FeO,MgO] values. Elevated [MnO|SiO2,Al2O3,FeO,MgO] values at the transition between Zapata and Punta Barrosa Formations record an oxygenated shallow marine environment that can be linked to the closure of the Rocas Verdes Basin and the onset of fold-and-thrust belt formation. Decreasing [MnO|SiO2,Al2O3,FeO,MgO] values from the Punta Barrosa towards the Cerro Toro Formation indicate gradually increasing water depths during the Upper Cretaceous that correlate well with the global sea level.

Purified and surfactant-modified Tunisian clays were investigated for their capacity to remove cationic and anionic dyes (crystal violet, CV and methyl orange, MO) from aqueous solution. The samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and potentiometric acid-base titration. Batch-sorption experiments were carried out to evaluate the influence of pH, contact time, initial dye concentration and temperature on the adsorption of dyes. Pseudo-first order, pseudo-second order, intra-particle diffusion and Elovich kinetic models were considered to evaluate the kinetic parameters. To understand the interaction of the dye with the adsorbent, Langmuir, Freundlich, Temkin and Dubinin-Radushkevish isotherms were applied. Thermodynamics studies were conducted to calculate the changes in free energy (Δ°G), enthalpy (Δ°H) and entropy (Δ°S). A difference in the maximum adsorption capacity was observed, suggesting that the retention of dyes was influenced by structure, functional groups of dyes and surface properties of the adsorbents. Moreover, different mechanisms may control the removal of dyes. The purified Tunisian clays are excellent adsorbents for removal of the cationic dye CV and its modified form is suitable for removal of the anionic dye, MO, from aqueous solution.

Second-century CE (common era) household pottery sherds found in the city of Napoca (present day Cluj-Napoca, Romania) in Roman Dacia were investigated by polarized light optical microscopy, X-ray powder diffraction, Fourier-transform infrared spectroscopy and cold field emission scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy to obtain information on technology, raw materials and site of production. Compositionally, all samples are similar with comparable fine and semi-fine microstructures and oriented microtextures. Optically, there is a gradual transition from microcrystalline to an amorphous illitic-muscovitic matrix. The small aplastic inclusions are mostly quartz and feldspar. Fine-grained carbonate aggregates are distributed inhomogeneously in the ceramic body. Well-preserved Middle Miocene foraminifera tests are characteristic of the ceramics. The gradual thermal changes of the matrix and the newly formed phases upon firing, such as ‘ceramic melilite’, Fe-gehlenite, clinopyroxene, glass, hematite and some maghemite support inferences regarding the technological constraints in producing the pottery. The firing took place in a mostly oxidizing atmosphere and the temperature extended from at least 850°C to >900°C. The Middle Miocene marly clay from the area surrounding the site shows similar mineralogical and micropalaeontological contents to those of the ceramic specimens and is the best candidate for the raw material used for local production of the Roman pottery.

Local chemotherapy with biocompatible drug-delivery systems prolongs survival in patients. Due to the biocompatibility and high loading capacity, bentonite nanoclay is a good candidate for the fabrication of drug-delivery vehicles. In this study, doxorubicin-bentonite nanoclay complex (DOX-Bent complex) was prepared for the first time as a sustained-release drug-delivery system for intratumoural chemotherapy of melanoma. An efficient loading of DOX on 1 mg of bentonite nanoclay as high as 994.45 ± 4.9 µg was obtained at a 30:1 DOX:bentonite nanoclay mass ratio. The DOX-Bent complex showed a low initial burst release of DOX in the first 24 h of release, followed by a sustained-release pattern for 21 days. The cumulative in vitro release of DOX from the DOX-Bent complex at pHs 6.5 and 7.4 revealed that the DOX-Bent complex can distinguish between tumour and normal tissues and express specific drug release at the tumour site. The results of cytotoxicity experiments indicated that the release pattern of DOX can supply sufficient DOX to inhibit growth of the melanoma cancer cell with an IC50 of 0.29 ± 0.07 µg/mL. It is thus suggested that the DOX-Bent complex be introduced as a drug-delivery system for effective local cancer therapy.

The retention mechanisms of metal ions during interaction of clay with metal-rich aqueous solutions is usually investigated by sorption isotherms. Although classical isotherm models may provide sufficient information about the characteristics of the solid–liquid system, they do not distinguish among the various retention mechanisms. This study presents a methodological approach of combining batch experiment data and geochemical modelling for the characterization of the interaction of Mg-Fe-rich clay materials with monometallic solutions of Pb and Cu. For this purpose, a palygorskite clay (PCM), an Fe-smectite clay (SCM) and a natural palygorskite-Fe-smectite mixed clay (MCM) were assessed for their effectiveness as metal ion sorbents. The sorption capacity of the materials follows the order MCM > SCM > PCM and ranges between 27.6–52.1 mg g–1 for Pb and 7.7–17.6 mg g–1 for Cu. Based on the experimental results that allowed the speciation calculations, fitting of sorption isotherms and the investigation of relationships between protons, Mg and the metals studied we suggest that a combination of sorption mechanisms occurs during the interaction of clay materials with metal solutions. These involve surface complexation, ion exchange and precipitation of solid compounds onto the solid surface. A three-term isotherm model was employed to quantify the role of each of the above mechanisms in the overall retention process. The superior performance of mixed clay among the materials tested is attributed to the synergetic effect of exchange in the interlayer and specific sorption on the clay edges.

The layered uranyl silicate clay-like mineral, uranophane-α, Ca(UO2)2(SiO3OH)2·5H2O, was studied by first-principles calculations based on the density functional theory method. The structure, observed in nature in a wide variety of compounds having the uranophane sheet anion topology, is confirmed here for the first time by means of rigorous theoretical solid-state calculations. The computed lattice parameters, bond lengths and bond angles were in very good agreement with the experimental ones, and the calculated X-ray powder trace accurately reproduced its experimental counterpart. The mechanical properties of uranophane-α, for which there are no experimental data for terms of comparison, were determined, and the satisfaction of the mechanical stability Born conditions of the structure was demonstrated by calculations of the elasticity tensor. The Raman spectrum was computed by the density functional perturbation theory and compared with the experimental spectrum. The vibrational properties of this mineral were well characterized, showing a good performance in all of the studied spectral range. Theoretical methods allowed assignment of the Raman bands to vibrations localized in different fragments within the crystal unit cell. Finally, the possibility of incorporation of strontium inside the uranophane structure was studied. The computed structure, X-ray powder trace and Raman spectrum of Sr-exchanged uranophane were very close to those of the ordinary Ca-uranophane.