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A hybrid fluorescent pigment composed of fluorescent yellow X-10GFF (FY-10G) and palygorskite (PLG) was prepared by semi-dry grinding. The effects of the physically adsorbed water content and grinding time on the environmental stability of FY-10G/PLG hybrid fluorescent pigments in terms of acid, ethanol and ultraviolet irradiation are discussed in detail. The incorporated FY-10 G molecules are mainly trapped on the external surface and the groove of PLG. Due to the host–guest interaction between PAL and FY-10G, the emission spectrum of the FY-10G/PLG hybrids shifts to a greater wavelength compared with that of FY-10G, but the physically adsorbed water content and grinding time have no effect on the position of the emission spectrum except for its intensity. A larger, physically adsorbed water content and appropriate grinding time may effectively prevent the aggregation and breakage of the bundles of PLG and facilitate FY-10 G molecules to enter into the groove of PAL. This increases the environmental stability of the as-prepared hybrid pigments.

Steam jet milling was applied for the first time to ultra-fine grind the filter cake (moisture content 23.80%) produced by a kaolin concentrator. The material was dehydrated and dried simultaneously during grinding, and the final ground sample met the moisture content requirement for powder products of

This work presents the results of the physical characterization of palygorskite and its adsorptive behaviour for three solvatochromic dyes (Nile blue chloride (NBC), methylene blue (MTB) and dithizone (DTZ)). Adsorption isotherms were used to determine the maximum adsorption of the solvatochromic dyes on the palygorskite. The characterization of palygorskite was carried out via mineralogical and chemical analysis with X-ray diffraction, X-ray fluorescence, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy, surface-charge measurement (ζ-potential), thermogravimetric analysis, textural analysis and cation-exchange capacity analysis. The material consists of palygorskite and quartz and its chemistry is dominated by SiO2, MgO and Fe2O3. The specific surface area and cation-exchange capacity of the palygorskite are 142 m2 g–1 and 41 cmol(+) kg–1, respectively. The SEM and TEM analyses showed a fibrous structure with fibres 20–100 nm long. The thermogravimetric analysis showed three endothermic events at 57.3°C, 171.8°C and 439.6°C. The adsorption capacities of the palygorskite for NBC (basic pH), MTB (basic pH) and DTZ (neutral pH) were 0.082, 0.013 and 0.102 g g–1, respectively. The adsorptions of NBC and MTB were fitted with the Langmuir isotherm model and the adsorption of DTZ was fitted with the Sips model.

Two novel adsorbents – montmorillonite (Mnt)-hyamine and Mnt-hyamine-sodium dodecyl sulfate (SDS) – were synthesized using Mnt nanoparticles. The modified Mnt and Mnt nanoparticles were used for the removal of crystal violet from water, and they were characterized using various techniques. The effects of pH, time, temperature, adsorbent dosage and initial dye concentration on the dye-removal efficiency were investigated using response surface methodology. The optimum conditions for maximum dye removal were obtained. The optimum conditions for crystal violet adsorption on Mnt-hyamine, Mnt-hyamine-SDS and Mnt nanoparticles are temperatures 25.00°C, 29.97°C and 27.28°C; pH values 9.00, 10.41 and 9.40; adsorbent dosages 1.00, 1.15 and 1.06 g L–1; and initial dye concentrations 30.00, 98.74 and 99.44 mg L–1, respectively. The adsorbent dosage is the most critical variable for dye removal. Temkin and Langmuir are the best isotherms for studying adsorption equilibria. In the kinetic study, the fractal-like integrated kinetic Langmuir model was the most appropriate model, and the thermodynamic parameters were also determined. The synthesized adsorbents could be easily separated from solution. The Mnt-hyamine-SDS adsorbent has a high adsorption capacity (690.69 mg g–1) for the removal of crystal violet.

Halloysite is a 1:1 dioctahedral clay mineral that has been studied widely for applications in nanotechnology and as a mineral exploration guide for recognizing regolith-hosted heavy rare earth element (HREE) deposits. In Brazil, pegmatites from the state of Rio de Janeiro have been catalogued, but their potential to host halloysite deposits has never been studied. After a mineral exploration programme, one pegmatite with considerable halloysite contents and economic potential was discovered. This study reports the mineralogical and chemical characterization of the halloysite of this pegmatite and evaluates the possibility of clay-adsorbedHREEdeposits, like that in the Zudong (China) regolith-hostedHREEdeposit. Seven samples were collected in horizontal channels. Bulk samples and clay fractions (2, 36.10 wt.% Al2O3, 14.62 wt.% loss on ignition and 1.04 wt.% Fe2O3, as well as technological properties close to those observed in world-class halloysite deposits such as Dragon Mine (USA) and Matauri Bay (New Zealand). The clay minerals did not present significantHREEcontents.

To produce an optimized matrix for the in situ crystallization of zeolite Y, a commercial kaolin chemically treated with NaOH solution at 97°C for 24 h and thermally transformed from 750 to 1100°C was studied. The kaolin calcined at 750°C has 20% more reactive tetrahedral aluminium species for the synthesis of zeolite Y than kaolin calcined at 865°C. The kaolin calcined at 1000°C has amorphous silica zones that may be extracted using caustic solution; this increases the surface area by a factor of 16 and generates mesopores ~5 nm in diameter. These structural changes in the calcined and treated kaolins were combined to prepare microspheres of the mesoporous matrix, upon which well-dispersed crystals of zeolite Y crystallized.

This study focuses on the characterization, thermal behaviour and firing properties of clays from Cap Bon Basin, Tunisia. Chemical (inductively coupled plasma atomic emission spectroscopy) and mineralogical (X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy) characterization of the clays was carried out. Physical properties were identified using particle-size distribution and Atterberg limits tests. Differential thermal analysis/thermogravimetry, dilatometry, XRD and FTIR analyses were conducted to assess the thermal behaviour, transformations and crystalline phase development during firing. The clays studied show large proportions of silt and clay fractions. They are rich in SiO2, Al2O3 and Fe2O3 and mostly consist of illite, kaolinite, smectite and minor mixed-layer illite-smectite. Associated minerals are mainly quartz, calcite and feldspar. To monitor the firing properties, three clay mixtures referred to as M1, M2 and M3 were prepared according to the physicochemical and mineralogical characteristics of the raw clays. These were sintered at 900°C, 1000°C and 1100°C and tested for firing shrinkage, flexural strength and water absorption. As a result, various mineralogical transformations occurred at 900–1100°C associated with the crystallization of new phases. The main transformations identified at >1000°C resulted in the formation of anorthite and mullite, causing significant densification of the fired ceramic materials. Sintering at 1100°C increased the densification and thus improved the flexural strength. At this temperature, the sintered ceramic tiles exhibited excellent properties, namely water absorption of 2–3% and flexural strength of 30–41 MPa, indicating that these studied clays might be used as raw materials for the production of stoneware tile ceramics.

The objective of this work was to use air-dried sepiolite granules as an additive in cigarette filter tips to increase the removal yield of tar and nicotine from mainstream smoke. Granules with a mass of 95 mg per cigarette filter and a mean particle size (D) of 0.05–0.41 mm were used to constrain the effects of the mean particle size and mass of sepiolite in the removal process. The granules were sandwiched in common cellulose acetate filter tips. Maximum removal yields of 90% were obtained when D ≤ 0.10 mm. Filters containing granules with a mean size of 0.10 mm and mass variations from 35 to 95 mg were tested, and increasing amounts of sepiolite added led to progressively greater yields of tar and nicotine from 20% to 90%. The sepiolite granules were examined using scanning electron microscopy with energy-dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy and X-ray diffraction techniques both before and after smoke experimentation. It is suggested that tar and nicotine were condensed both on the fibre clusters of the sepiolite granules and in the voids between them during the flow of the mainstream smoke.

Sepiolite powder was hydrothermally solidified into a cemented, designed to function both in humidity regulation and volatile organic compound (VOC) removal. The solidification process mimicked the cementation of sedimentary rocks. The formation of the calcium aluminium silicate hydrate (C-A-S-H) or Al-tobermorite enhanced the strength (maximum flexural strength >17 MPa) and improved the porosity of the solidified materials. Due to the low temperature of hydrothermal solidification (≤473.15 K), most sepiolite remained in the matrix of the solidified specimens. The cemented sepiolite aggregate shows outstanding humidity-regulating performance (moisture adsorption of 430 g m–2), and the synergistic effects of the residual sepiolite and neoformed Al-tobermorite exerted a positive influence on the humidity regulation performance of the material. Similarly to the behaviour of sepiolite, the solidified material also displayed good formaldehyde-removal capacity (60–68%). The pore dimensions controlled the humidity regulation and formaldehyde removal. The humidity regulation depends on the mesopores, which originate mainly from both the original sepiolite and the neoformed C-A-S-H phases and Al-tobermorite, while the formaldehyde removal depends on the micropores from the original sepiolite in the matrix. As such, the cemented sepiolite aggregate might be hydrothermally synthesized and might be used to improve the comfort and safety of indoor environments for human beings.

The interaction between a basic dye, rhodamine B, and a separated fine fraction from natural clay was studied. Chemical analysis, X-ray diffraction and Fourier-transform infrared spectroscopy confirmed the predominance of beidellite in the fine clay fraction. The interaction of rhodamine B with the fine clay fraction showed that sorption was fast and followed a pseudo-second-order kinetic model. The comparison between sorbed rhodamine B amounts as a function of the various experimental parameters such as pH, sorbent mass, dye concentration and the presence of competing ions suggests that: (1) the sorption process is largely pH-dependent; (2) significant competition is observed between the dye and the Ca2+ and Mg2+ ions; (3) the sorption proceeds, principally, by a cation-exchange mechanism; and (4) the sorption capacity of the fine fraction in the presence of competing cations such as Ca2+ is ~0.28 mmol g–1.

The influence of excess Al2O3 on 3:2 mullite produced from α-Al2O3 and pyrophyllite powder was examined. A mixture consisting of 28 wt.% dehydroxylated pyrophyllite and 72 wt.% α-Al2O3 was milled in an attrition mill. The milled powders were sintered by spark plasma sintering (SPS) at 1600°C for 10, 20 and 30 min. Subsequently, the samples were heated at 1350°C for 2 h to determine the influence of the excess Al2O3 on the microstructure. No glassy phase was detected in the sample containing 72 wt.% Al2O3 and sintered at 1600°C for 20 min. The sample with 72 wt.% Al2O3 had greater hardness and fracture toughness compared to 3:2 mullite. The greatest hardness and fracture toughness of 12.43 GPa and 2.71 MPa m–0.5, respectively, were obtained in the sample containing 72 wt.% Al2O3 sintered at 1600°C for 20 min.

The production of pottery in the traditional manner using local raw materials can provide insights into the provenance of ancient artefacts. This study uses mineralogical analysis to evaluate the raw clays and tempers used for pottery production in Zlakusa (western Serbia). Particle-size distribution, plasticity, X-ray fluorescence spectroscopy, X-ray powder diffraction, scanning electron microscopy/energy-dispersive X-ray spectrometry and differential thermal analysis techniques were applied. The mineral phases identified in the raw clay sample are kaolinite/halloysite, mica/illite, smectite, quartz, paragonite, feldspar, calcite and hematite. The clay body sample is a mixture of raw clay and crushed calcite in a ~50:50 ratio, which was confirmed using various techniques. We have also considered and investigated the technological potential of the sampled materials, taking into consideration their actual and potential applications. It was confirmed that the clay body may be used in the manufacture of bricks and pottery, but its industrial application is limited by the paste recipe.

Six clays from various deposits were studied for their use in the production of structural clay products. The clays were characterized using chemical (X-ray fluorescence), mineralogical (X-ray diffraction) and thermal (differential scanning calorimetry/thermogravimetry) analyses. Particle-size distribution was determined by laser diffraction, plasticity by the Pfefferkorn method and the residue by the sieve-size method. Next, specimens were formed by extrusion and characterized by their linear thermal shrinkage (on drying and firing), water absorption, bulk density, porosity and compressive strength. The clays were, in general, suitable for the manufacture of structural ceramics, mainly bricks. The clays from flooded pits (AV1 and AV2) were classified as floodplain clays and alluvial clays. The clays mined in mountainous regions (AM1 and AM2, as well as AV1) were characterized as siliceous clays due to the abundance of free SiO2phases.

The aim of this study was to help drive the Tunisian construction industry towards a more sustainable approach given the existence of abundant local raw material deposits that could be exploited for the production of low-CO2 binders. Various clay sediments from the Kebili region (southern Tunisia) were characterized by chemical analysis, X-ray diffraction, thermal analysis and geotechnical tests to determine their suitability for the preparation of geopolymer binders. The clays consist of illite and kaolinite with other accessory minerals. To test the possibility of using these materials as precursors for the production of low-CO2 and low-cost geopolymers, the raw samples were calcined and activated by addition of solid sodium silicate. Compressive strength tests performed on four alkali-activated clays show that promising mechanical performance may be achieved, with mechanical strength values as high as 25 MPa after 7 days, depending on the clay composition. The mechanical strength is related to the SiO2:Al2O3 and Al2O3:(NaO2 + K2O) ratios. Careful selection of the raw materials is, therefore, an essential step in the exploitation of clay deposits to be used for the production of ecological materials such as geopolymers.

Drilling fluids are essential for the operation and productivity of petroleum wells. This study compares the efficiency of a salted water-based mud for which the viscosity has been enhanced with polymeric compounds with that of a new salted water-based mud containing palygorskite clay, which mainly functions as a viscosity enhancer. The experiment measured the density, apparent viscosity, plastic viscosity, yield point, American Petroleum Institute filtrate and pH of the samples. The results indicate that the rheological properties of the fluids containing greater amounts of palygorskite were not affected significantly by the addition of salt. However, when the concentration of palygorskite was low, the rheological behaviour of the samples was appropriate to the drilling operation only with lesser amounts of salt. In addition to its good rheological properties, the filtrate volume obtained for samples containing greater concentrations of palygorskite was lower, which suggests that the filtration properties at the bottoms of the wells were controlled appropriately.

The kinetic parameters of the thermal degradation of sepiolite were evaluated with a new method based on thermal analysis data. Thermogravimetric/differential thermal analysis curves were recorded for the natural and preheated sepiolite samples in the temperature range 25–800°C for 4 h. The temperature-dependent height of the exothermic heat flow peak for the thermal decomposition of sepiolite located at ~850°C on the differential thermal analysis curve was taken as a kinetic variable for the thermal degradation. A thermal change coefficient was defined depending on this variable because this coefficient fit to the Arrhenius equation was assumed as a rate constant for the thermal degradation. The Arrhenius plot showed that the degradation occurs in three steps. Two of these are due to stepwise dehydration and the third originated from dehydroxylation of sepiolite. Three activation energies were obtained that increase with the increasing temperature interval of the steps.

Sodium smectite clays were enriched with ferric ions (Argel-Fe and Volclay-Fe) to convert the surface charge of the clays from negative to positive and to use the clays in the discolouration of a synthetic effluent composed of seven anionic dyes (mixed from tartrazine, Brilliant Blue FCF and amaranth). The iron content increased from 5.99% to 11.02% for Argel-Fe and from 5.39% to 10.54% for Volclay-Fe. The efficiency of the discolouration of the anion dye mixture was evaluated by measuring the absorbance of the mixture at 562 nm, where the band with the greatest intensity was found. The contact time required for the system to reach equilibrium was ~5 min for both adsorbents. The kinetic adsorption data supported a pseudo-second-order kinetic model. The experimental data support the dual-site Langmuir–Freundlich isotherm model. The maximum adsorption capacities were 88.68 mg g–1for Argel-Fe and 392.21 mg g–1for Volclay-Fe. The enrichment of clays with Fe(III) added functionality to the clays and generated adsorbents with rapid adsorption abilities and high discolouration capacities.

Hydrotalcites with heterogeneous distributions of anions between their layers were synthesized. Some synthesis parameters were studied to verify their influence on the anionic segregation properties of the hydrotalcites. The nature of the divalent cation and the crystallization method were most relevant. Zinc, in contrast to magnesium, assisted in discriminating carbonates and attracting nitrates to form hydrotalcites with heterogeneous distributions using microwave irradiation. Furthermore, the identification of this kind of hydrotalcite could be easily verified by determining the presence of a double reflection in the 003 X-ray diffraction (XRD) maximum, which definitively characterized a heterogeneous anion distribution. Finally, the reason as to why in some cases the hydrotalcite presented two reflections in the 003 XRD peak was elucidated.

An effective method that combines solvent extraction with ultrasonic irradiation was developed to recycle spent bleaching clay (SBC) from modern oil refinery plants. The principle of ‘waste to treasure’ was used to achieve the regenerated SBC. Various characterization techniques were applied to analyse and compare regenerated SBC and commercial bleaching clay (CBC). The structure of the regenerated SBC did not show any obvious change compared with that of CBC, but the Brunauer–Emmett–Teller-specific surface area (SBET) and pore-volume values of the regenerated SBC increased. At the same time, the parameters of the regenerated SBC reached national standards. In addition, the samples were used as low-cost adsorbents for the adsorption of methylene blue (MB) from water. The regenerated SBC had greater adsorption efficiency and cycle performance for MB than CBC. Hence, the SBC may be treated by ultrasonic radiation combined with extraction, and the regenerated SBC has better properties than CBC. This work opens up a new approach to the regeneration and utilization of SBC and raises the potential of ultrasonic irradiation as an environmentally friendly method to be applied to various regeneration systems.

In a high-level radioactive waste repository, bentonite may react with the alkaline solution produced by cement degradation. In this study, bentonite was mixed with alkaline solution in a closed system and reacted for 3–24 months. Furthermore, swelling tests were conducted on the alkaline-dissolved bentonite immersed in distilled water. The swelling deformation decreased significantly with increases in the concentration of NaOH solution and reaction time, and this was mainly due to montmorillonite dissolution. The fractal e–p relationship (e is the void ratio and p is the vertical pressure) with two calculation coefficients (the swelling coefficient and the fractal dimension) was employed to determine the swelling of alkaline-dissolved bentonite. The fractal dimension increased slightly with increasing reaction time or concentration of NaOH solution, as the dissolution traces caused by the alkaline solution favoured an increase in the irregularity and fractality of the bentonite surface. The swelling coefficient decreased linearly with decreasing montmorillonite content. In addition, the swelling coefficient and the fractal dimension were related exponentially to the reaction time in alkaline solution. A relationship between the swelling of alkaline-dissolved samples and the reaction time was proposed, which might be used to assess the swelling properties of bentonite barriers that would be affected by long-term dissolution of the alkaline solution in a closed repository.

The Numidian Aquitano-Burdigalian nappe from the Jijel region (northeast Algeria) shows an important clay-rich basal series. In this study, seven representative clay samples were collected from the Djimla and El-Milia areas of this region in order to analyse their mineralogy using X-ray diffraction and Fourier-transform infrared spectroscopy, chemical composition by X-ray fluorescence, particle size, plasticity, morphology by scanning electron microscopy and their ceramic properties. Samples were prepared by pressing the clays and firing them at 800–1100°C, and bulk density, water absorption, linear firing shrinkage, weight loss and bending strength values were determined on the fired samples. The clays are mainly composed of kaolinite and illite, with a small amount of 10–14 Å interstratified clay minerals and chlorite, associated with quartz and feldspars. The main oxides in the samples were SiO2, Al2O3and Fe2O3. The clays may be classified as moderately plastic according to their Atterberg limits. Ceramic tiles have been produced by dry pressing. At all tested firing temperatures, the clays present the required standard values for linear firing shrinkage, weight loss, bulk density, water absorption and bending strength, and they are defect-free. The main transformations were observed at 1000°C with the appearance of new crystalline phases. The measured technological properties of the investigated deposits confirm that the Numidian clays from the Djimla and El-Milia regions are suitable materials for the production of high-quality structural ceramics.

The Neogene marls from the lower Kert area (northeast Morocco) were characterized to evaluate their suitability for the ceramics industry. Two cross-sections involving all of the Neogene facies were studied on both banks of the Kert River. Grey and green marls occurring between sandstone and tuffs were characterized by mineralogical (X-ray diffraction) and physicochemical (grain size, Atterberg limits, X-ray fluorescence and specific surface area) analyses. The Neogene clays studied are mainly calcareous silty marls containing 13–20 wt.% calcite. They consist of quartz, calcite, feldspars, dolomite, illite, kaolinite, chlorite and 10–14 Å illite-vermiculite mixed layers. Cristobalite was detected only in the uppermost level of the green marls, and it originates from a volcanic ash of Messinian age. Trace amounts of siderite and rhodochrosite indicate reducing or locally oxidizing conditions during sedimentation or shortly thereafter. The marls have medium to high plasticity, making them optimal for extrusion. Raw Neogene marls are suitable for manufacturing structural clay products. More specific uses, such as hollow products, roofing tiles and masonry bricks, were supported by the geochemical results and grain-size distribution.

The zeta potential and yield-stress behaviour of gels prepared from as-received SHCa-1 hectorite (Ht) containing 50 wt.% impurities, mainly of calcite, dolomite and quartz, were characterized. The zeta potential is negative in the pH range 4–12. At pH 3 producing CO2 and Ca2+ increased the solution conductivity significantly and reduced the zeta potential. The buffering effect due to this chemical reaction was also observed in the yield stress–pH characterization below pH 8. Low yield stress was observed below pH 6 and above pH 12. The yield stress peaked at pH ~8, where Ht displayed a zeta potential of –20 mV. The relationship between maximum yield stress and Ht content (wt.%) was linear and was not affected by impurities. The ageing behaviour was characterized by an initial phase of rapid yield-stress increase and then by a phase of gradual increase. The Leong model performed better than the two-parameter glassy polymer ageing model in describing this ageing behaviour. However, the empirical power law model was more accurate. The timescale of the ageing process is long, lasting several days. An open cellular microstructure was observed to form in the gels. Impurities appeared not to interact with or bind to the Ht platelets.

There is growing interest in the use of natural materials as alternatives to medicinal products composed of chemicals. For this reason, it is important to study materials which fill this need (e.g. the formulation of peloids). Historically, the Azores archipelago has long been visited for its mud baths, mainly on São Miguel Island, where volcanic muds demonstrate beneficial properties. The volcanic muds are scarce, however. Thus, residual clay materials of Santa Maria Island were studied to assess their suitability for the formulation of peloids. The results of tests from 20 samples, collected from all over the island, presented evidence that they are very favourable for peloid formulations, due to their mineralogical, chemical and technological properties. The materials showed good potential for blending with the São Miguel volcanic muds. The deposits studied show extensive outcrops.

Portuguese gypsum deposits utilized by the cement industry were characterized mineralogically, chemically and technologically for possible application in dermocosmetics. The deposits studied (Loulé, Óbidos and Soure) correspond to small outcrops in diapiric anticline areas. In principle, they represent gypsites which are white, and generally of higher quality for traditional applications (e.g.white cement), or greyish, and generally not adequate for cements and mortars. The analytical methods used to characterize the materials were wet sieving and X-ray sedimentation, X-ray diffraction, X-ray fluorescence spectrometry and assessment of abrasiveness, plasticity, texturometrics (adhesivity and firmness), oil absorption and cooling rate. The Óbidos gypsum displayed greater mineralogical and chemical quality (almost pure calcium sulfate) and had a finer grain size (

Early Copper Age pottery sherds discovered in a cave within the crystalline dolomites of the Southern Carpathians (Romania) were investigated by polarized light optical microscopy (OM), X-ray powder diffraction (XRPD) and electron microprobe analysis (EMPA) to obtain information on the pottery production in the Copper Age in the territory of present-day Romania. Microscopically, the clayey matrix of the ceramic body is highly birefringent or consists of low-birefringent and isotropic parts mixed together, containing fragments of quartz, muscovite, alkali feldspar, plagioclase, biotite, chlorite, heavy minerals and metamorphic and magmatic rocks, as well as an opaque material. The EMPA data revealed an Fe-rich illite-like matrix and helped to identify the mineral nature of the inclusions. Local pottery production in bonfires or surface clamps is envisaged. Miocene illitic clays may have been used as raw materials, mixed with a small amount of sandy temper. The thermal changes revealed by OM, the modification of the XRPD peaks and the EMPA data suggest firing temperatures of between 800 and 850°C.

Swelling deformation tests of Kunigel bentonite and its sand mixtures were performed in distilled water and NaCl solution. The salinity of NaCl solution has a significant impact on the swelling properties of bentonite, but not on its surface structure. The surface structure was characterized using the fractal dimension Ds. Based on the fractal dimension, a unique curve of the em–pe relationship (em is the void ratio of montmorillonite and pe is the effective stress) at full saturation was introduced to express the swelling deformation of bentonite–sand mixtures. In mixtures with a large bentonite content, the swelling deformation always followed the em–pe relationship. In mixtures with a small bentonite content, when the effective stress reached a threshold, the void ratio of montmorillonite em deviated from the unique em–pe curve due to the appearance of a sand skeleton. The threshold of vertical pressure for mixtures in different solutions and the maximum swelling strains were estimated using the em–pe relationship. The good agreement between estimates and experimental data suggest that the em–pe relationship might be an alternative method for predicting the swelling deformation of bentonite–sand mixtures in salt solution.

To reveal the factors that determine the different ranges of compositional variations in high- and low-temperature Al-rich K-dioctahedral micas, relationships between structural parameters and cation composition were analysed for: (1) a series of synthetic 2M1 muscovite–phengite–aluminoceladonite samples; and (2) Al-rich, K-dioctahedral 2M1 micas with previously published refined structural data. The dependences of the unit-cell parameters on cation composition and the variations in tetrahedral and octahedral lateral dimensions and sheet thicknesses, interlayer distances and tetrahedral rotation angles were analysed and compared with those found previously for the series 1M trans-vacant (tv) illite–1M aluminoceladonite. The similarities in the variations of unit-cell parameters with cation composition observed in 2M1 and 1M natural and synthetic K-dioctahedral micas imply that these variations are controlled by similar – albeit not identical – structural factors. A major structural factor is the readjustment of the differently sized tetrahedral and octahedral sheets, which is realized in a different manner in micas formed under different pressure and temperature conditions.

Temporary excavations during the construction of the Glendoe Hydro Scheme above Loch Ness in the Highlands of Scotland exposed a clay-rich fault gouge in Dalradian Supergroup psammite. The gouge coincides with the mapped trace of the subvertical Sronlairig Fault, a feature related in part to the Great Glen and Ericht–Laidon faults, which had been interpreted to result from brittle deformation during the Caledonian orogeny (c. 420–390 Ma). Exposure of this mica-rich gouge represented an exceptional opportunity to constrain the timing of the gouge-producing movement on the Sronlairig Fault using isotopic analysis to date the growth of authigenic (essentially synkinematic) clay mineralization. A series of fine-size separates was isolated prior to K–Ar analysis. Novel, capillary-encapsulated X-ray diffraction analysis was employed to ensure nearly perfect, random orientation and to facilitate the identification and quantification of mica polytypes. Coarser size fractions are composed of greater proportions of the 2M1 illite polytype. Finer size fractions show increasing proportions of the 1M illite polytype, with no evidence of 2M1 illite in the finest fractions. A series of Illite Age Analysis plots produced excellent R2 values with calculated mean ages of 296 ± 7 Ma (Late Carboniferous–Early Permian) for the oldest (2M1) illite and 145 ± 7 Ma (Late Jurassic–Early Cretaceous) for the youngest (1M) illite. The Late Carboniferous–Early Permian (Faulting event 1) age may represent resetting of earlier-formed micas or authigenesis during dextral displacement of the Great Glen Fault Zone (GGFZ). Contemporaneous WNW(NW)–ESE(SE) extension was important for basin development and hydrocarbon migration in the Pentland Firth and Moray Firth regions. The Late Jurassic–Early Cretaceous (Faulting event 2) age corresponds with Moray Firth Basin development and indicates that the GGFZ and related structures may have acted to partition the active extension in the Moray Firth region from relative inactivity in the Pentland Firth area at this time. These new age dates demonstrate the long-lived geological activity on the GGFZ, particularly so in post-Caledonian times where other isotopic evidence for younger tectonic overprints is lacking.

The present work describes the removal of Direct Red 81, Methyl Orange, Methylene Blue and Crystal Violet from aqueous solution using halloysite nanotubes. The clay mineral was physicochemically characterized using various methods. The influences of pH, interaction time, initial dye concentration, adsorbent amount and temperature on adsorption were monitored and interpreted. Although previous work has shown that acidic pH conditions favour the adsorption of pollutants from aqueous systems by clay materials, in this study maximum removal was possible over a wide range of pH conditions (pH ≥2–12). Adsorption was very rapid, and equilibrium was attained within 30 min. For all four dyes studied, chemical reaction seemed significant in the rate-controlling step, and the pseudo-second-order chemical reaction kinetics provided the best correlation of the experimental data. Thermodynamically, the process was spontaneous, with Gibbs energy decreasing with increasing temperature. Halloysite would be suitable for removing dyes from aqueous solution. This was further tested by using the halloysite nanotubes for the removal of complex dyes from printing and ink industry effluents.

Clay mineral ‘Crystallinity Index Standards’ (CIS) composed of Palaeozoic mudrocks from southwest England were investigated systematically in five sub-fractions per sample for the first time. X-ray diffraction was used to determine mineral assemblages, calibrated 001 illite full-width-at-half-maximum (FWHM) values and illite polytype compositions, in addition to K–Ar isotopic analyses of all fine fractions. The FWHM results of the M+ 1Mdillite and detrital 2M1white mica polytypes suitable for illite age analysis. The estimated end-member ages of the Bude (SW1-1992) and younger Crackington (SW3-2000) mudstones yield detrital ages of Late Cambrian to Middle Ordovician (493–457 Ma) and a broad range of 1M+ 1Mdillite ages between Middle Permian and Early Jurassic (271–190 Ma). The detrital age of the stratigraphically older Crackington Formation mudrock (SW2-1992) is Late Devonian (384–364 Ma) with 1M+ 1Mdillite ages between Late Triassic and Early Jurassic (219–176 Ma). The origin of Mesozoic 1M+ 1Mdillite ages may represent neocrystallized illite associated with Mesozoic hydrothermal events or similar events that thermally reset older authigenic illite with partial loss of radiogenic argon and no renewed crystal growth. In contrast, upper anchizonal and epizonal Devonian slates (SW3-2012, SW4-1992, SW6-1992 and SW7-2012) contain only the 2M1polytype, with K–Ar ages younger than the stratigraphic age. The three finest fractions of SW4-1992 yield consistent Late Carboniferous ages (331–304 ± 7 Ma) that are considered to date the neocrystallized 2M1mica. Most fractions of epizonal slate (SW6-1992, SW7-2012) yield Early Permian ages (293.6–273 Ma) corresponding to published cooling ages of the Tintagel High-Strain Zone and the intrusion of the Bodmin granite (291.4 ± 0.8 Ma). These first K–Ar age constraints for the fine fractions of the CIS should provide useful reference values for testing analytical procedures of illite age analysis.

An iron catalyst supported on the modified Tamazert kaolin has been prepared and tested in catalytic wet peroxide oxidation using phenol and 4-chlorophenol (4-CP) as target compounds (100 mg/L initial concentration). Kaolin is not usually employed as a catalytic support due to its low developed porous structure, but its textural properties may be improved upon calcination and acid and basic treatment. The catalyst was characterized by N2 adsorption–desorption and chemical analysis by total-reflection X-ray fluorescence spectroscopy. The catalytic tests were carried out in a batch reactor with a stoichiometric amount of H2O2. The catalytic efficiency was studied within the temperature range of 25–55°C at an initial pH of 3.3 and 1 g/L catalyst. Complete phenol and 4-CP removal was achieved with no significant differences in phenol and 4-CP conversions within the temperature range tested. Meanwhile, total organic carbon (TOC) reduction was greatly favoured by increasing the temperature, which may be partially attributed to a probable contribution of a homogeneous reaction associated with iron leaching. However, this effect might be of limited significance because the highest concentrations of iron in the liquid phase were below 4.5 and 8.5 mg/L in the experiments with phenol and 4-CP, respectively. At 55°C, TOC was reduced by ~70% after 4 h reaction time, with the remaining by-products corresponding almost completely to low-molecular-weight carboxylic acids of very low ecotoxicity.

Systems consisting of layered structures and photoactive molecules have been studied extensively. The structures of resulting complexes may be controlled by UV–Vis radiation, which subsequently affects their materials properties. This study describes a synthesis route for obtaining a photoresponsive kaolinite intercalation compound. The material was prepared by co-intercalating azobenzene and benzylalkylammonium chlorides into a methoxy form of kaolinite. The resultant materials possessed large basal spacing values in the range of 45–55 Å. The UV–Vis and Fourier-transform infrared spectroscopy analyses confirmed the reversible photoisomerization of azobenzene upon exposure to UV and Vis radiation. This phenomenon was significantly influenced by the type and amount of co-intercalated molecules. Upon multiple trans–cis conversions, the azobenzene partially evaporated. For the first time, a kaolinite-based material was prepared that exhibited photochromic behaviour upon UV and Vis irradiation.

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.

Nitrogen influx was identified in the Harghita Bãi area, where the mechanism of NH4+-fixation in illitic clays is relevant for the N-input budget estimation. The nanotextural features of K-illite (K-I), NH4,K-I and NH4-illite-smectite (NH4-I-S) mixed layers observed in argillic-altered andesitic rocks from the hydrothermal area of Harghita Bãi (East Carpathians) were studied by X-ray diffraction, infrared spectroscopy and transmission and analytical electron microscopy (TEM-AEM). The texture of undisturbed argillic-altered andesite rocks exhibits chaotic intergrowths of randomly oriented and curved illitic packets with abundant pore spaces and high porosity between packets. The TEM images of K-I and NH4,K-I intergrowths show subparallel packets with clear contacts, exhibiting a diffuse contrast across layers. The thicknesses of K-I and NH4,K-I packets range from 150 to 500 Å, and 1Md and 1M polytypes were identified by selected area electron diffraction patterns. Crystal chemistry of K-I, NH4,K-I and NH4-I-S was carried out by AEM. A third interlayer cation Na+ beside K+ was detected in several NH4,K-I packets. The NH4,Na,K-I packets interleaved with NH4,K-I or NH4-I-S (12% smectite layers) packets were also identified by TEM. The thicknesses of NH4,Na,K-I packets range from 300 to 1200 Å, with abundant lenses and lenticular layer separation along the boundaries between them. The 1Md polytype dominates the NH4,Na,K-I packets. Straight and parallel packets, continuous 00l layers and collapsed swelling layers at the boundary of individual NH4-I (5% smectite layers) packets with thicknesses ranging from 20 to 95 Å were observed. The nanotextural observations indicate direct crystallization of NH4-I crystals within a NH4-I-S series from a pore fluid, where NH4-I packets occupy void spaces previously occupied by fluids.

Bentonite clay is often included as a buffer, backfill and/or sealing material in designs for deep geological repositories for radioactive wastes. It is expected that bentonite materials may undergo some mineralogical alteration as they interact with in situ groundwaters over long timescales on the order of thousands to millions of years. Long-term modelling of these materials is therefore important in order to demonstrate confidence that the engineered designs will continue to perform as required over their intended lifetimes (required assessment timescales can be up to 1 million years). The key geochemical processes that must be considered in such modelling are mineral dissolution and precipitation and cation exchange. These processes are expected to occur simultaneously and so modelling of their coupled effects and their rates (kinetics) is necessary. Illustrative reactive-transport models of the geochemical alteration of montmorillonite (the primary mineral in bentonite exhibiting cation exchange) are presented which demonstrate that one possible approach to fully coupling cation exchange and clay mineral dissolution kinetics, referred to here as the ‘all-component coupling’ approach, may lead to unrealistic behaviour due to feedback that may occur in the formulation. This feedback can be avoided if a ‘common-component’ conceptual model for the dissolution of exchanger end members is adopted, where only the saturation of the exchanger ‘structural unit’ is considered when evaluating the potential for dissolution of the mineral. Such considerations have been proposed historically in stability analyses for montmorillonite, but have not been explored widely in the modelling literature.

In deep geological repositories, compacted bentonites have been proposed for use as barrier materials for isolating nuclear waste. The prevailing thermo-hydro-mechanical boundary conditions in the repositories may affect the swelling capacity and permeability of the compacted bentonites. In this study, the effect of preliminary desiccation on the subsequent hydro-mechanical behaviour (swelling pressure and hydraulic conductivity) of compacted Calcigel bentonite was investigated experimentally at 22°C and 80°C. In the first stage of the test, the compacted specimens were subjected to suction-controlled desiccation at 22°C and 80°C using the vapour-equilibrium technique. After the water content reached equilibrium at a given suction, the axial, radial and volumetric shrinkage strains were measured. Afterwards, constant-volume swelling-pressure tests were performed on the desiccated specimens (second test stage) by saturating the dried specimens with deionized water at 22°C and 80°C. At the end of the swelling-pressure test, the hydraulic conductivities of four saturated specimens were measured at each temperature. The volumetric shrinkage strain of the compacted bentonite during desiccation is controlled by suction instead of temperature. In addition, the preliminary desiccation increases both the swelling pressure and hydraulic conductivity of compacted bentonite, particularly if compacted bentonite undergoes extreme desiccation at an applied suction of >700 MPa.

Clay-mineral type and content, bulk mineralogical composition and alteration of bentonite are very important factors for the ultra-long-term stabilization of barriers and backfills in radioactive waste disposal. This study investigates the effects of clay-mineral type and content on the swelling characteristics and permeability of bentonite–sand mixtures with clay minerals using one-dimensional swelling-pressure and constant-pressure permeability tests. The hydraulic conductivity of bentonite–sand–clay mineral mixtures increased with increasing content of non-swelling alteration products of montmorillonite. Furthermore, hydraulic conductivity was comparable to that determined with the Kozeny–Carman equation for a specific surface area, suggesting that hydraulic conductivity may be estimated based on the abundance of expected alteration products of montmorillonite. This study provides a basis for evaluation of the hydraulic conductivity of bentonite–sand mixtures with known quantities of expected alteration products of montmorillonite., This paper was presented during the ‘7th International Conference on Clays in Natural and Engineered Barriers for Radioactive Waste Confinement’, September 2017.

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 FEBEX experiment, a full-scale, high-level radioactive waste repository test, ran for ~18 years and hence is the longest-running disposal test to date. The test consisted of a heater emplaced in an envelope of compacted bentonite at the Grimsel test site, Switzerland. The water content of the bentonite was somewhat lower near the heater and increased towards the granite. This phenomenon probably led to gradients in the exchangeable cation population at various locations within the bentonite buffer. The cement (shotcrete) bentonite interface of one block was characterized by a thin (0.1–1.0 mm) reaction zone in which bentonite constituents, carbonates and sulfates occurred. Cation exchange and a slight decrease of the cation exchange capacity were observed near the heater. Oxic corrosion was observed predominantly at the bentonite/steel liner interfaces, pointing towards a role of air entrapped between the liner and heater during emplacement. At the liner surface, intimate intergrowth of bentonite constituents, metal and corrosion products was observed. At the face of the heater, the bentonite blocks were in direct contact with the heater surface without any signs of metal corrosion. Instead, a significant increase in the Mg content was recorded, which is in agreement with previous large-scale disposal tests. The FEBEX experiment proved that the Mg increase and corrosion were independent processes. The increase in Mg may be explained by the formation of trioctahedral domains or the precipitation of neoformed silicates. For the first time, however, brucite was identified as an additional phase that formed at the metal/bentonite interface, pointing towards a special role for Mg mobility in the bentonite barrier.

Despite many reviews and original articles, the actual crystal structure of tubular halloysites remains unclear. Analysis of the structural features of defect-free kaolinite, refined by Bish & von Dreele (1989), shows that the ordered 1Tc kaolinite structure can be described equally well by the orthogonal layer cell {a0, b0, γ0} (γ0 = 90°) or by two enantiomorphic oblique layer cells {a1, b1, γ1} and {a2, b2, γ2}, related to each other by a mirror plane. To simulate diffraction effects for tubular halloysite, the parameters and atomic coordinates of the orthogonal layer unit cell and the layer-displacement vectors t1 and t2 responsible for formation of the kaolinite enantiomorphs were deduced by transformation of the parameters of the defect-free kaolinite refined by Bish & von Dreele (1989). Modelling X-ray diffraction patterns show that the samples consist of either single, two or three phases, with the number and their structural features depending on the morphology of the particles. Samples formed of prismatic particles consist of halloysite-like structure (HLS), kaolinite-like structure (KLS) and halloysite cylindrical structure (HCS) phases occurring in various proportions. Samples of proper cylindrical tubes consist of a single HCS phase, whilst samples formed by particles having morphologies intermediate between proper cylindrical and well-developed prismatic forms consist of the KLS and HCS phases. The KLS phase is comparable to low-ordered platy kaolinite with identical unit-cell parameters, layer-displacement vectors and arbitrary stacking faults, except that the layer displacements are not random as in kaolinite, but are distributed at R = 1 such that t1 and t2 displacements have a strong tendency to be segregated. Structural parameters describing the HLS and KLS phases are identical, but in the HLS phase there is a strong tendency to the regular alternation of the t1 and t2 displacements, and the HLS phases do not contain arbitrary stacking faults. A characteristic feature of the three-phase prismatic samples is that the stacking of the layers along the c* axis is periodic and the layer thicknesses are similar to those of platy kaolinite. In contrast, in the KLS phase formed in samples with particles of intermediate morphologies, the hydrated 10 and 7.25 Å layers are interstratified. The relationship between the structural and morphological features of the coexisting phases suggests a sequence of phase formation from the centre to the surface of halloysite tubes that progresses from the HCS to the HLS via the KLS phase. The results of this study demonstrate that all kaolinite and halloysite (7 Å) varieties are built by the same fundamental structural units.

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.

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 2O3 content (0.5–1.4%) demonstrates that five samples are suitable raw materials for white firing industrial kaolin.

Five clay deposits in Foumban, west Cameroon, were studied for their morphological, mineralogical and geochemical properties to determine their suitability for ceramics. The clays were examined with X-ray diffraction, X-ray fluorescence, thermal gravimetric analysis and Fourier-transform infrared spectroscopy. Field studies showed that a homogeneous clayey layer occurs at the upper part of the laterite cover of the interfluves, while the valleys are occupied by a clayey heterogeneous hydromorphic material. The clays are composed of kaolinite, illite, smectite and chlorite, associated with quartz, K-feldspars, plagioclase, goethite, traces of rutile and hematite. Geochemical analyses of these samples show a relatively large amount of SiO2(45–71%), Al2O3(14–31%) and relatively little Fe2O3(up to 11%), suggesting weathering of mainly granitic and rhyolitic parent rocks. The majority of these clays may be used in the production of structural ceramics such as bricks (refractory or not) and tiles. The relatively high proportion of the alkalis (K2O + Na2O; 6–8%) in some samples from Marom and Njindare areas might be responsible for the low firing temperatures. The abundance of smectite limits the application of some Koutaba and Marom clays for structural ceramics, while the high Fe2O3contents (>8%) in some Bangourain clays indicate that some pre-treatment might be necessary prior to use.

Textural, mineralogical and chemical characterization of archaeological ceramics (zellige) from El Badi Palace (Marrakech, Morocco), the main Islamic monument from the Saadian period (sixteenth century), has been performed to enhance restoration and to determine the technology of manufacturing. A multi-analytical approach based on optical and scanning electron microscopy, cathodoluminescence, X-ray fluorescence and X-ray diffraction was used. Re-firing tests on ceramic supports were also performed to determine the firing temperatures used by the Saadian artisans. A calcareous clay raw material was used to manufacture these decorative ceramics. The sherds were fired at a maximum temperature of 800°C in oxidizing atmosphere. The low firing temperature for ‘zellige’ facilitates cutting of the pieces, but also causes fragility in these materials due to the absence of vitreous phases.

Three clayey materials named MY3, KK and KG originating from the Foumban region (west Cameroon) were analysed to determine their granulometry, plasticity, major-element chemistry and mineralogy. Dilatometric and ceramic behaviour were also investigated. Clays were shaped by uniaxial pressing in a steel mould. Shaped samples were heated at 1300, 1400 and 1500°C. The end products were characterized in terms of their density, porosity and compressive strength. Raw materials differ in terms of their mineralogical composition, grain-size distribution, Al2O3 content and the nature and abundance of impurities inducing specific thermal behaviour during dilatometric analysis and sintering tests. The final material properties may be related to the main features of the raw materials used.

The recent discovery of a Roman ceramics manufacturing workshop at Montelabate (Perugia, Italy), in use from the first century BC until the late-fourth to fifth centuries AD, offers a unique opportunity to study the technical processes for producing Roman amphorae. Ancient and modern clays were sampled and analysed; they do not differ significantly, supporting the hypothesis of the exploitation of the rich local clay source that allowed a continuity of production. Characterization of the clays was performed using geotechnical methods (Atterberg limits and size distribution) and by thermogravimetric and differential thermogravimetric analysis, Fourier-transform infrared spectroscopy, X-ray diffraction and X-ray fluorescence analyses. The material was suitable for pottery making with the addition of calcite and quartz sand temper. Production waste and discarded materials as well as good-quality products were also analysed with the same methodology. It is therefore possible to reconstruct the ancient technology by defining the recipe for the production of the amphorae and their firing temperature on the basis of the decomposition of clay materials and the presence of newly formed minerals.

The use of natural clays for the removal of dyes from wastewater, an important part of environmental remediation, is desirable due, not least, to their low cost. Palygorskite (PAL), a rigid-structure clay, is a good candidate for use in the elimination of industrial effluents, based on its exceptional adsorptive properties. Recently, a new palygorskite deposit has been discovered in Cuba and its use in the adsorption of dyes has not yet been explored in detail. In the present study, the use of unmodified natural Cuban palygorskite as a host for dyes was evaluated. Congo red (CR) and methylene blue (MB) were the anionic and cationic dyes tested, respectively, because of their wide use and toxicity to the environment. Several physical-chemical parameters were studied in order to establish the best experimental conditions under which to achieve the greatest dye load per gram of clay. Natural mixtures with different percentages of montmorillonite were also tested to evaluate their effect on the adsorption of the dyes. The results indicated that at pH values of ~7–9 and an initial dye concentration of 0.1 mg mL–1, the process was efficient. X-ray diffraction (XRD) analysis proved the surface adsorption of both dyes on the clays. The main interactions involved in the clay-dye system were electrostatic forces and H-bonds. Adsorption of CR seemed to be controlled fundamentally by the palygorskite phase. Such results support the use of this natural clay as an efficient host for the removal of MB and CR from wastewater.

Earthquake-induced rock shear through a bentonite-filled deposition hole in a repository for spent nuclear fuel is an important scenario for the safety analysis because it may cause substantial damage to the canister hosting the spent fuel. Appropriate tools to investigate the effects on the buffer and the canister are required.The study described here explored the laboratory tests conducted to develop a material model of the bentonite buffer to be used in the simulations, the material models that these tests have provided and finite element (FE) simulations of three scale tests of a rock shear for comparison between modelled and measured results. The results were used for validation of the material models and the calculation technique that was used for modelling different rock-shear cases.The laboratory study consisted of swelling-pressure tests and tests to determine shear strength and stress-strain properties. The material model is elastic-plastic with a nonlinear stress-strain relation which depends on the density of the bentonite buffer and is a function of the strain rate. The three scale tests were modelled using theAbaqusfinite element code. Good agreement between modelled and measured results was observed, in spite of the complexity of the models and the difficulties associated with measuring stresses and strains under the very fast shear.The modelling results thus validate the modelling of the SR-Site. The modelling technique, the element mesh and the material models used in these analyses are well fitted and useful for this type of modelling.

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–1for Pb and 7.7–17.6 mg g–1for 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.