The present work deals with the hydrothermal synthesis of Na zeolites (Na-A, Na-X and Na-P) and hydroxysodalite using kaolinite calcined at 650°C as starting material. The focus was on definition of the most favourable conditions for the synthesis of zeolite Na-A and Na-X from metakaolin in order to economize on both energy (i.e. synthesis temperatures) and reaction time and to enlarge the field of pure and isolated synthesized phases. Metakaolin was mixed with calculated amounts of NaOH solution and sodium silicate and five sets of experiments were carried out at ambient pressure and 68±0.1°C varying the SiO2/Al2O3 ratio from 2.2 to 7. Optimal conditions for crystallization of Na-A zeolite from kaolinite were reached with a SiO2/Al2O3 ratio of 2.2 plus 4 M NaOH without adding sodium silicate; transformation into hydroxysodalite develops after ∼8 h. For SiO2/Al2O3 ratios between 4 and 7, crystallization of the separate Na-X zeolite phase could be achieved and transformation into Na-P and hydroxysodalite occurred after 382 h and 190 h, respectively. For SiO2/Al2O3 ratios between 5 and 6, transformation of metakaolin into Na-X plus Na-A, hydroxysodalite and Na-P occurred, and the field within which Na-A and Na-X zeolite exists overlapped that of the other zeolites.

The products of synthesis were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma optical emission spectrometry (ICP-OES), infrared spectroscopy (IR) and thermal analyses (TG-DTG-DTA).

Obtaining pure Na-A and Na-X zeolite from kaolinite treated at low metakaolinitization temperature (650°C) and low hydrothermal synthesis temperature (68°C) represents a considerable economic advantage in terms of both energy and time.

This paper focuses on the clay mineralogy (using XRD, SEM and TEM methods) of the lacustrine “Calizas de Torrente de Cinca” unit that represents the Oligocene-Miocene transition in the central part of the Ebro Basin (NE Spain). Phyllosilicates are mainly detrital although Mgsmectites could have been generated in the lake.Although a temperate, relatively humid climate dominated the source area during the Oligocene-Miocene transition (Chattian-Aquitanian), as deduced by detrital phyllosilicates assemblage, mineralogical vertical trends along with sedimentological studies indicate some changes.Relatively warmer and more humid conditions during the late Chattian, that favoured increasing chemical weathering, were replaced during the early Aquitanian by drier conditions coinciding with the Mi-1 glaciation effects; this change is coeval with a transition from deeper to shallower lacustrine facies.Phyllosilicate association analysis has also permitted an improvement in the palaeogeographical sketch and infers that the Pyrenees are the main source area for the lacustrine system.

An unusual occurrence of palygorskite was found near Montestrutto, lower Val d'Aosta (Italy), within an eclogite-facies leucogneiss of the Sesia-Lanzo zone. Under the optical microscope the mineral appears as a felt of fibres hundreds of μm long and a few μm thick. SEM observation proved each filament to be a bundle of smaller but remarkably long fibres (length mostly 15–20 μm and thickness <1 μm). EDS and TGA showed a water content [zeolitic H2O ( ≅ 6%) + structural OH2 (≅8%) + framework OH (≅2%) ≅l6 wt.%] lower than average (≅20 wt.%). Structure refinement by the Rietveld method confirmed the clay dioctahedral character and coexistence of two polymorphs, monoclinic [77.4(4)%] and orthorhombic [22.6(6)%], the latter showing anomalous variations of some cell parameters [c shortens to 5.138(3) and a lengthens to 12.903(7) Å]. The high crystallinity of this palygorskite suggests that it formed under low-T hydrothermal conditions due to interaction between Mg-rich hydrous fluids, derived from mantle ultramafics, and Al-rich continental rocks. Predominance of unusually long fibres (>5 μm) causes the Montestrutto palygorskite to be potentially carcinogenic.

The reactivity of soils and sediments is often described by parameters such as the specific surface area (SSA) and the cation exchange capacity (CEC). Both, however, are bulk values controlled by the presence and crystallinity of different phases, e.g. clay minerals and iron oxides. Amongst the latter, ferrihydrite and goethite are the most abundant minerals. Goethite gradually forms from a ferrihydrite precursor, a process involving a decrease in surface area. Today the BET gas adsorption technique is the most common method to measure SSA. In this study, BET surface areas of synthetic and natural ferrihydrite and goethite of variable crystallinity were compared to (a) mineral-specific measurements, including infrared analysis (IR), differential thermal analysis (DTA), and (b) bulk methods, such as cation exchange capacity and oxalate-soluble iron. Correlations showed that the SSA can be indirectly inferred from all methods. There is no general correlation between IR and BET measurements due to the variability of adsorbed water, which depends on drying and ambient conditions. DTA, particularly using the dehydroxylation peak at 300°C, allows quantification of the goethite content, and hence the SSA, because adsorbed water does not affect this peak. The data set of the present study enabled us to estimate either SSA and/or the content of iron oxides, even in natural mixtures, e.g. those in which smectites determine the SSA.

The Yaylayolu kaolin deposit is situated in the vicinity of Tavşanlı, Kütahya, western Turkey. Mineral identification and characterization studies were conducted using powder X-ray diffraction (XRD), differential thermal analyses (DTA), scanning electron microscopy with an energy dispersive X-ray spectrometer (SEM-EDX), X-ray fluorescence (XRF) and Fourier transform infrared spectroscopy (FTIR) techniques. The degree of crystallinity, Hinckley's index (HI) and the Stoch index (SI) values were determined for kaolinite from the deposit.

Five representative samples from the kaolin deposit were used for ceramic technological tests. Particle size distribution, pH value, loss on ignition, A12O3, Fe2O3 and TiO2 contents were determined, drying shrinkage, firing shrinkage, dry bend strength, fired bend strength, water absorption, pfefferkorn plasticity index, whiteness of the fired and unfired samples (L* value) and bulk density were measured. The kaolin was found to be suitable for making white cement and wall tiles, floor tiles, and tableware items which are shaped by dry pressing and extrusion.

The Cu-triethylenetetramine-complex (Cutrien) is one of the commonly used index cations for CEC determination in clay science. Cutrien-exchanged smectites show basal spacings between 13.0 and 13.5 Å after correction for the Lorentz and polarization factors. The full width at half maximum (FWHM) of the d001 reflection is today related to the percentage of tetrahedral charge (beidellitic character) and/or to the Fe content of the smectites. The structural Fe content and the tetrahedral charge correlate, so their individual influence on d001 cannot be resolved. Nevertheless, the FWHM of Cutrien smectites should depend on the charge distribution rather than the Fe content.

X-ray diffraction (XRD) and water uptake capacity measurements showed that the interlayer of Cutrien-exchanged smectites does not swell any more, but can take up a few water molecules. Accordingly, the water uptake capacity of the external surface area can be determined independently from the interlayer water uptake capacity. Adjusting the pH of Cutrien-bentonite dispersion to different values allows for the determination of the variable charge.

In conclusion, Cutrien exchange of smectites appears to be suitable for the study of external surfaces area related phenomena (e.g. edge adsorption processes) without any influence of the interlayer region.

The Hallaçlar kaolinite deposit of the Uşak Province (western Turkey) is hosted by dacite, andesite and siliceous materials of the Miocene Karaboldere volcanites. Mineralogical zonation, such as the prevalence of kaolinite at the centre of the deposit, coexisting with silica polymorphs such as quartz and cristobalite along with feldspar and hornblende, and a relative increase of smectite, illite, chlorite, and Fe-oxide/-hydroxide phases outward and upward, demonstrate that hydrothermal-alteration processes resulted in kaolinization. Micromorphologically, kaolinite occurs as pseudohexagonal blocky kaolinite with coarse-grained quartz in microfractures, and the presence of relatively fine-grained vermiform kaolinite that edges volcanic materials indicates that kaolinite developed in several phases coexisting with goethite, lepidocrocite, hematite, pyrite, jarosite, alunite, and gypsum/anhydrite with smectite in fractures. The highly crystallized Hallaçlar kaolinite is identified by: (1) sharp reflections at 7.23 and 3.57 Å, with triplet and doublet non-basal reflections; (2) sharp infrared spectral bands at 3687, 3651 and 3620 cm-1; (3) well defined, pseudohexagonal and hexagonal kaolinite crystal growth; (4) a chemical index of weathering of 98.6-100; and (5) SiO2/Al2O3 ratios between 1.04 and 1.45. Enrichment of Sr and depletion of Rb+Ba, Ti, and HREE relative to LREE, with a distinct negative Eu anomaly, are responses to the fractionation of feldspar and hornblende by the hydrothermal fluid; these results are also supported by the O- and H-isotopic character and formation temperatures of the Hallaçlar kaolinite and smectite; namely, 134.1-183.4°C and 65.6°C, respectively. The negative δ34S (-20.7‰) value of gypsum/anhydrite reflects its formation from geothermal-water-derived sulphur. Under the influence of a tectonically controlled hydrothermal process, feldspar, hornblende and volcanic glass were altered, resulting in the conservation of Al and depletion of Si, Na, Ca, K, Mg and Fe in an open hydrological system such that formation of kaolinite in the central part of the deposit under acidic conditions and development of smectite and illite upward and outward under basic conditions were favoured.

Bentonite mixed with varying quantities of sand is currently of widespread interest as engineering liners for water containment and waste disposal. However, the alternative use of pumice, widespread in many volcanic regions, has been less studied and requires further characterization of geotechnical properties and performance prior to its extensive use. The objective of this study was to determine and compare the compaction and swelling characteristics of sandbentonite and pumice-bentonite mixtures using available geo-materials from Turkey. Standard Proctor compaction tests and constant volume swell tests were carried out using mixtures with four different bentonite contents (15, 20, 25, 30%) and three different sand and pumice grain size ranges (2.00–1.00; 1.00–0.50; 0.50–0.25 mm). The results indicate that pumice-bentonite mixtures have lower maximum dry unit weights, higher optimum moisture contents and greater swelling potentials than equivalent sand-bentonite mixtures. Important differences occur in the swelling potentials of the sand and pumice mixtures with respect to grain size whereby sand-bentonite mixtures show increased swelling with coarsening grain size, in contrast to the pumice–bentonite mixtures which showed a decrease. These differences are attributed to the amount of grain-size-dependent connected pore space that can be filled during bentonite expansion and the presence of dissolvable salts in the pumice. It is concluded that locally available pumice material could be used to replace sand in engineering bentonite seals, despite some differences in their geotechnical properties.

The adsorption of methylene blue (MB) on montmorillonite from acid solutions has not yet been studied in detail. In this paper the adsorption of this dye on Ca/SAz montmorillonite from 0.32, 0.80 and 1.60 M HCl solutions at ambient temperature and after 2 hours leaching was carefully studied and evaluated. Under the above conditions the MB/SAz intercalates formed are practically insoluble. In contrast to the adsorption of methylene blue on montmorillonite from aqueous solutions, the adsorption from acid solutions consists of two adsorption waves. The intercalated samples from the first and second waves were studied using X-ray powder diffraction (XRD), FTIR, Vis spectroscopy, and scanning electron microscopy (SEM) equipped with a microprobe system. The adsorption of MB in the first wave is attributed to ion exchange of the dye cationic species (MB+, MB22+, H-aggregates, MBH2+ and H+) for the original interlayer cations of montmorillonite. The percentages of MBH2+ and H+ based on total adsorbed MB were estimated for varying HCl concentrations. The second adsorption wave is linked to the precipitation of MB species on the outer MB/SAz surface.

The Alto dos Quintos Mine, Rio Grande do Norte, northeast region of Brazil, is one of the few mines where a LCT (Li-Cs-Ta-enriched) pegmatite is exploited for the deep blue gemstone called “Paraiba Tourmaline (PT)”. Blue cuprian elbaite, a fault-bound pink montmorillonite bearing some relict apatite and newly-formed Ca-Al-phosphate of the Al-P-sulphate group (APS minerals) also occur in the underground mine. The montmorillonite was studied using extended clay mineralogical tools (XRD, IR spectroscopy, XRF, SEM-EDX, cation exchange capacity (CEC), DTA). The structural formula method for calculation of the smectite formula based on EDX data yielded an extremely Fe-poor montmorillonite: (Ca0.22+)(Al1.7Fe0.0Mg0.4)(Si3.8Al0.2). The charge on the tetrahedral sheets accounts for approximately 30% of the total permanent negative charge. However, based on the more precise Hofmann & Klemen test, tetrahedral charge values of 11% to 13% were calculated. This is indicative of the dominance of montmorillonite rather than beidellite among the smectite minerals, which is independently proved by a pronounced IR band at 630 cm-1. The formation of pink montmorillonite is not directly related to the emplacement of the Li-bearing PT pegmatite. The sheet silicate developed after a considerable hiatus (Mesozoic?), when the Neoproterozoic pegmatites had already undergone different stages of hypogene (cookeite) and supergene (illite, kaolinite) alteration, during which Li was flushed out to a degree that formation conditions of expandable Li-bearing phyllosilicates were no longer favoured. The nature of the pinkish tint is not yet clarified. The montmorillonite formed in a temperature regime close to 250°C, when apatite was transformed into Ca-bearing APS minerals under acidic conditions. Cainozoic volcanic activity and the reactivation of deep-seated fault zones are considered to be responsible for the formation of this pink P-bearing montmorillonitic clay.

Fluorescence and phase transitions of a new Mg-Al-Eu ternary layered double hydroxide (LDH) and their dependence on thermal treatment were studied for the first time. Phase transitions occurred as the temperature increased from 400 to 1100°C. The process of phase transition is discussed in detail. The emissions of Eu3+ ions described by the 5D0–7FJ transition (J = 1,2,3,4), and especially for the 5D0–7FJ transition (J = 1,2) varied markedly with phase transformations from LDH, MgO, to mixtures of MgO and MgAl2O4. Moreover,strong emissions of Eu3+ ions are present in these new host materials. These results indicate that Mg-Al-Eu ternary LDH may be a potential candidate for materials applied in fluorescent devices.

Hydrothermal alteration of Proterozoic granitic rocks in the Äspö underground laboratory, southestern Sweden, resulted in the formation of chlorite with large variations in textural and chemical characteristics, which reflect differences in formation temperatures, fluid composition, and reaction mechanisms. The mineral assemblage associated with chlorite, including Ca-Al silicates (prehnite, pumpellyite, epidote, and titanite), Fe-oxides, calcite, albite and K-feldspar, suggests that chloritization occurred at temperatures of between 200–350°C during various hydrothermal events primarily linked to magmatism and rock deformation. Petrographic and electron microprobe analyses revealed that chlorite replaced biotite, amphibole and magnetite, and hydrothermal chlorite phases filled fractures and vugs in the granitic rocks. While fracture-filling chlorite reduces fracture permeability, chloritization reactions in the host granite resulted in the formation of new localized microporosity that should thus be taken into consideration when evaluating the safety of the granitic basement rocks as a repository for nuclear waste. It is also important to take into account that similar alteration reactions may occur at the site of stored nuclear waste where temperatures in excess of 100°C might be encountered.

The objective of this study was to build an automated size fractionator to process up to 16 samples at one time. Most parts used in the apparatus are inexpensive items, available from lawn irrigation, household appliance and aquatic pet supply stores. The device can be used to extract different silt and clay fractions by changing sedimentation time. A bentonite, a kaolin and an ironoxide-rich Oxisol were fractionated by this instrument to sequentially extract particles that have sizes equivalent to <2 µm, <5 µm, <10 µm and <20 µm quartz spheres. A laser diffraction particle size analyser revealed size differences in the different fractions and also showed that the silt fractions contained particles having slightly larger sizes than the assumed diameters of spherical quartz. Scanning electron microscope examination suggested that the greater particle size was mainly due to the non-spherical shapes of the particles and a reduced bulk density of the porous aggregates.