Purification processes performed on natural clays to select specific clay minerals are complex and expensive and can lead to over-exploitation of some deposits. The present study aimed to examine physicochemical (mineralogy, morphology, size, surface charge, chemical composition, cation exchange capacity [CEC], and pH) and hydration (swelling, wettability, water sorption, and rheological behavior) properties of three native clays from Italian deposits for potential pharmaceutical and cosmetic uses due to the presence of phyllosilicate minerals. Particular emphasis was placed on energy dispersive X-ray (EDX) microanalysis coupled with the ‘cesium method’ to assay clay elemental composition and CEC. One bentonite of volcanic origin (BNT) and two kaolins, one of hydrothermal origin (K-H) and another of lacustrine-fluvial origin (K-L), were evaluated in comparison with a commercial, purified bentonite. The CEC assay revealed the complete substitution of exchangeable cations (Na+ and Ca2+) by Cs+ in BNT samples and CEC values consistent with those of typical smectites (100.64 ± 7.33 meq/100 g). For kaolins, partial substitution of Na+ cations occurred only in the K-L samples because of the interstratified mineral component which has small CEC values (11.13 ± 5.46 meq/100 g for the K-H sample and 14.75 ± 6.58 meq/100 g for the K-L sample). The degree of isomorphous substitution of Al3+ by Mg2+ affected the hydration properties of BNT in terms of swelling, water sorption, and rheology, whereas both of the poorly expandable kaolins exhibited significant water-adsorption properties. The EDX microanalysis has proved to be of considerable interest in terms of providing more information about clay properties in comparison with other commonly used methods and to identify the role played by both chemical and mineralogical composition of natural clays for their appropriate use in pharmaceutical and cosmetic fields.

Hydrophobicity, swellability, and dispersion are important properties for organo-montmorillonites (OMnt) and have yet to be fully characterized for all OMnt configurations. The purpose of the present work was to examine the preparation of OMnt from the reaction of Ca2+-montmorillonite (Ca2+-Mnt) with a high concentration of surfactant and to reveal the relevant properties of hydrophobicity and dispersion of the resultant OMnt. A series of OMnt samples were prepared using a small amount of water and cetyltrimethylammonium bromide (CTAB) with a concentration more than the CTAB critical micelle concentration (CMC). The relationship between OMnt microstructure and the hydrophobicity and swellability properties was investigated in detail. The resulting OMnt samples were characterized using powder X-ray diffraction patterns (XRD), Fourier-transform infrared (FTIR) spectroscopy, thermogravimetric and differential thermogravimetry (TG-DTG), water contact angle tests, swelling indices, and transmission electron microscopy (TEM). The addition of CTAB and water in the OMnt preparation affected the OMnt microstructure and properties. An increase in CTAB concentration led to a more ordered arrangement of cetyltrimethylammonium (CTA+) cations in the interlayer space of the OMnt and a large amount of CTA+ cations on the outer surfaces of the OMnt. The swelling indices and the water contact angles of OMnt samples depended on the distribution of the CTAB surfactant on OMnt and the orientation of the surfactant hydrophilic groups on the inner and on the outer surfaces of OMnt. A maximum swelling index of 39 mL/g in xylene was achieved with an average water contact angle of 62.0° ± 2.0° when the amount of CTAB added was 2 times the cation exchange capacity (CEC) of Mnt and the lowest water to dry Mnt mass ratio was 3 during the preparation of OMnt samples. The platelets of OMnt aggregated together in xylene by electrostatic attraction and by hydrophobic interactions.

Burial-induced and hydrothermal-related illitization in bentonites and in sandstones can be modeled on the basis of isotopic studies of fundamental particles separated from mixed-layer illitesmectite. The model envisages different reaction rates and durations relative to the varied impacts of temperature, considering that the water:rock ratio also has an influence. The different pathways for illitization are suggested on the basis of the K-Ar, Rb-Sr and δ18O compositions of previously studied materials.

New information is provided on why fundamental particles separated from mixed-layer illite-smectite in shales yield K-Ar age data that are systematically greater than the ages of the fundamental particles from associated bentonites and/or sandstones, and greater than the reported stratigraphic ages. The study of pure authigenic, recent to present-day smectite from Pacific sediments shows that (1) those collected from active hydrothermal vents have 40Ar/36Ar ratios identical to that of the atmosphere, and (2) those of mud sediments have 40Ar/36Ar ratios above the atmospheric value, indicating addition of 40Ar not generated in situ by radioactive decay. A preliminary but detailed analysis of the noble-gas (Ar, Xe, Kr) contents of authigenic smectite-rich size fractions from Pacific deep-sea red clays suggests trapping of these gases by smectite. Therefore, the results point to the fact that fundamental particles can incorporate excess 40Ar into their structure when nucleating in restricted to closed systems, such as shales. This excess 40Ar, which represents radiogenic 40Ar released from nearby altered silicates, might be temporarily adsorbed at the surface of the rock pore spaces and is therefore available for incorporation in nucleating and growing particles.

The thermal maturity of samples of the Posidonia Shale collected from the Hils Syncline, northern Germany, varies significantly as a function of location indicating variations in local history. Synchrotron X-ray diffraction was used to document the composition and the preferred orientation of four samples of the Posidonia Shale with different degrees of maturity (0.68–1.45%, Ro) to determine possible effects on diagenesis and preferred orientation. Overall, the degree of preferred orientation of all clay minerals (illite-smectite, illite-mica, and kaolinite) and in all samples is similar, with (001) pole figure maxima ranging from 3.7 to 6.3 multiples of a random distribution (m.r.d.). Calcite displays weak preferred orientation, with c axes perpendicular to the bedding plane (1.1–1.3 m.r.d.). Other constituent phases such as quartz, feldspars, and pyrite have a random orientation distribution. The difference in thermal history, which causes significant changes in the maturity of organic matter, influenced the preferred orientation of clay minerals only marginally as most of the alignment seems to have evolved early in their history. Synchrotron X-ray microtomography was used to characterize the three-dimensional microstructure of a high-maturity sample. Low-density features, including porosity, fractures, and kerogen, were observed to be elongated and aligned roughly parallel to the bedding plane. The volume of low-density features was estimated to be ~7 vol.%, consistent with previous petrophysical measurements of porosity of 8–10 vol.%. Transmission electron microscopy analysis of samples with different degrees of maturity (0.74%Ro and 1.45%Ro) was used to document microstructures at the nanoscale as well as the presence of kerogen. In the high-maturity sample, pores were less abundant while minerals were more deformed as shown by fractured calcite and by kinked and folded illite. Some of the porosity was aligned with clay platelets.

In deep geological repositories for high-level nuclear wastes, interactions between steel canisters and clay-rich materials may lead to mineralogical transformations with a loss of the confining properties of the clays. Experiments simulating the conversion of smectite to Fe-rich clay phases in contact with Fe metal have been carried out to evaluate such a possibility by taking into account the effects of a series of critical parameters, including temperature, pH, and Fe/clay (Fe/C) and liquid/clay (L/C) ratios. The mineralogical and chemical transformations observed in these experiments have been compared with data from the literature, and subsequently used to propose a conceptual model for the main mineralogical transformations which can be expected in clay formations surrounding high-level nuclear waste repositories. In the presence of Fe metal and under low oxygen fugacity (<-40) the main mineralogical sequences are as follows:

1. (1) up to 150°C, under neutral pH, and L/C > 5: dioctahedral smectite (di-sm) → 7 Å Fe-rich phase (berthierine, odinite-cronstedtite) for large Fe/C ratios (>0.5), or di-sm → Fe-rich di-sm + Fe-rich trioctahedral smectite (tri-sm) for small Fe/C ratios (0.1)

2. (2) up to 150°C, under alkaline pH (10–12), and L/C > 5: di-sm → Fe di-sm (±palygorskite) for a small Fe/C ratio (0.1)

3. (3) at 300°C, Fe/C = 0.1, and L/C > 5: di-sm → Fe-rich saponite → trioctahedral chlorite + feldspar + zeolite (near-neutral pH); di-sm → Fe-rich vermiculite + mordenite (pH 10–12).

Low temperatures (<150°C) and large L/C and Fe/C ratios seem to favor the crystallization of the serpentine group minerals instead of Fe-rich trioctahedral smectites or chlorites, the latter being favored by higher temperatures. The role of L/C and Fe/C ratios and the competition between them at different temperatures is a crucial point in understanding the transformation of smectite in contact with Fe metal.

As self-appointed guardians of light who performed many of their activities between sunset and sunrise, medieval monks and nuns had a special relationship with fire, light, and darkness. While medieval monastic authors wrote copiously about light, however, modern scholars have shown comparatively little interest in this topic. Using the concept of lightscape, this essay recreates the unique Latin monastic culture of light of the tenth to thirteenth centuries, considering how religious communities used natural and artificial light as well as darkness to reinforce spiritual lessons, heighten the sensory experience of liturgical life, and signal distinctions between orders in a reform-minded age. Evidence from material culture as well as several textual genres demonstrates that monastic uses of candles, oil lamps, and lanterns reflected the commitment to a strictly regulated life which foregrounded bonds of community and encouraged constant spiritual and physical vigilance. Contemporary understandings of fire and light as heavenly matter also conditioned religious to see everyday light-sources as ready conduits for the miraculous, as well as technologies by which earthly spaces could be made to approximate heavenly ones.

A Parisian public library specializing in decorative arts, the Bibliothèque Forney is considered one of the first public lending art libraries in France. From the library's opening in the nineteenth century to the year 2000, readers could borrow art images to use as models or sources of inspiration. Today a selection of art plates are still freely accessible. The history of this unique service highlights the librarians’ efforts to meet the evolving needs of researchers looking for easily accessible art; their work to keep up with modernity; and their efforts to add value for their users.

Np and Pu are two important actinides of concern for the safe long-term disposal of nuclear waste. Both actinides are, in addition, constituents of global nuclear fallout. Investigation of their environmental behavior requires ultra-sensitive analytical methods, but current methods for a concurrent determination in clay minerals are lacking. In the present study, a Pu isotope was investigated for use as a non-isotopic yield tracer for Np in extraction, purification, and mass spectrometric determination of Np and Pu isotopes in clay materials. Inductively coupled plasma mass spectrometry was used in this developmental study, but the method is intended for future ultra-trace analysis of global-fallout Np and Pu in clay-rich soil materials by the more sensitive accelerator mass spectrometry. Another field of application may be the investigation of diffusion patterns of actinides in compacted clay liners and potential host rocks for radioactive waste disposal. The analytical procedure includes the following steps: (1) extraction of Np and Pu from clay samples; (2) adjustment of Np and Pu to Np(IV) and Pu(III); (3) pre-concentration of Np and Pu by co-precipitation with iron hydroxide; (4) adjustment of Pu to Pu(IV); (5) extraction chromatographic separation of Pu and Np from iron and matrix elements; and (6) determination of Np and Pu by mass spectrometry. The analytical procedure was applied successfully to spiked montmorillonite and illite test portions of up to 1 g. High chemical yields near 90% were obtained for both Np and Pu. The suitability of Pu as a non-isotopic tracer for Np was indicated by Np/Pu chemical yield ratios close to unity. Accurate pH adjustment during the reductive co-precipitation and short processing times are vital to obtain high chemical yields and Np/Pu yield ratios close to unity.

Numerous occurrences of asbestos minerals, notably chrysotile and tremolite, are to be found on fracture surfaces in thrust fault deformation zones of Cretaceous dunite-harzburgite and pyroxenite in the Çankırı and Ankara regions, central Anatolia, Turkey. Consequently, potential exists for the development of regional malignant mesothelioma. The means of serpentinization, such as reaction of seawater during accretion of the upper ophiolitic mantle crust in a subduction zone and/or following uplift of ophiolitic units and the influence of hydrothermal/meteoric fluids along fractures, were investigated. Cretaceous dunite-harzburgite and localized pyroxenite rocks are mainly composed of serpentinized olivine and pyroxene associated with opaque minerals and Fe-(oxyhydr)oxide phases. Smectite, chlorite, illite, kaolinite, hydromagnesite, goethite, quartz, and opal-CT are also present. Chrysotile and localized tremolite occur either as a mesh, a suboriented to oriented long-fiber bundle, or as fiber-filling millimetric micro-vein textures on relicts of olivine and pyroxene (enstatite, augite). The chrysotile and tremolite have non-pseudomorphic textures developed under high pressure and temperature. The textures suggest authigenic formation of chrysotile and tremolite via a dissolution and precipitation mechanism. Additionally, spherical structures of opal-CT and locally platy hydromagnesite crystals either enclose or are developed within chrysotile/tremolite fiber bundles. The leaching of MgO, Fe2O3, Al2O3, Ni, Cr, and Nb, an increase in the LREE/HREE ratio, and negative Eu anomalies in the dunite-harzburgite and pyroxenite, and asbestos samples suggest that the chrysotile and tremolite were derived from the serpentinization of olivine and pyroxene. The chrysotile and tremolite were developed along fractures by hydrothermal fluid alteration during accretion and/or following the uplift of ophiolitic units of the region under high pressure and temperature conditions. This interpretation is also supported by isotope data and the calculated formation temperature of 170–555°C for chrysotile and tremolite. The average structural formulae for chrysotile and tremolite are (NanK0.03)(Mg5.54Fe0.09Al0.05Ca0.01Mn0.001) (Si3.96Al0.03)O10(OH)8 and (Na0.17K0.07)(Ca1.59Mg0.19Mn0.002)(Mg4.72Fe0.28)(Si7.86Al0.1Fe0.06)O22(OH)2, respectively.

Most dioctahedral 2:1 swelling clays in natural systems contain ferric iron, Fe(III), which can be located in both the tetrahedral and the octahedral sheets. The distribution of Fe(III) between octahedral and tetrahedral sites in nontronite depends on the Fe and Si speciation during nontronite synthesis. The role played by the chemical properties of solutions in the Fe(III) distribution between structural sites was studied through nontronite syntheses. A chemical series of Fe(III)-nontronites with variable tetrahedral [4]Fe(III) content (x) ([Si4-xFe(III)x]Fe(III)2O10(OH)2Nax) was synthesized at 150°C across a range of initial aqueous pH values between 11 and 14. The permanent layer charge, due to Fe(III)-for-Si(IV) tetrahedral substitutions only, ranged from 0.43 to as high as 1.54 per half-unit cell. A d063̄3 value of 1.562 Å was measured by X-ray diffraction (XRD) for the highest charged nontronite (x = 1.54). This high d063̄3 value has not been reported in the literature for a dioctahedral smectite until now. The [4]Fe(III) content (x) of the synthetic nontronites, estimated using Fourier-transform infrared spectroscopy (FTIR) through the wavenumber of the main stretching vSi-O band, was correlated with synthesis pH and its influence on calculated aqueous Si speciation. The increase in synthesis pH induced the increase in anionic aqueous Si species ratios (i.e. H3Si4(aq)− and H2Si4(aq)−), and favored the incorporation of Fe(III) in tetrahedral sites of synthesized nontronites. During nontronite formation in natural systems, the level of tetrahedral Fe(III)-for-Si(IV) substitutions may, therefore, be partly linked to the aqueous Si speciation and thus strongly dependent on the pH of the crystallization fluids.

To apply hydrotalcites more effectively to the problem of dye wastewater, the effects of divalent metal ions on the structure and stability of hydrotalcites, especially on their photocatalytic activity, were compared. In the present study, M/Cr hydrotalcites (M3Cr-CO3-LDHs) (in which M = Mg, Co, Ni, Cu, Zn), where the M/Cr molar ratio was 3, were prepared by the co-precipitation method. The structures and properties were characterized using powder X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric-differential thermal analysis (TG-DTA), and UV-Visible diffuse reflectance spectroscopy (UV-Vis DRS). The results showed that five kinds of M3Cr-CO3-LDHs were synthesized successfully, and the layered structure of the samples obtained was regular and the crystal phase was single. When methylene blue (MB) solution was exposed to ZnCr-CO3-LDHs, H2O2, and visible light irradiation, more than 90.67% of the methylene blue (MB) was removed after 140 min. The photocatalytic activity of the samples was in the order: Co3Cr-CO3-LDHs > Mg3Cr-CO3-LDHs > Cu3Cr-CO3-LDHs > Zn3Cr-CO3-LDHs > Ni3Cr-CO3-LDHs. The results of a catalytic mechanism study showed that photocatalytic degradation of MB involved a demethylation reaction, with the reactive species containing •O2-, •OH, and h+.

Carbonate-intercalated layered double hydroxides of Co(II) and Ni(II) with Fe(III) and Al(III) were precipitated under different conditions (pH = 8–12; T= 25–80°C). All the samples are replete with stacking faults which are not eliminated by post-precipitation hydrothermal treatment (80–180°C, 18 h). DIFFaX simulations show that the layer stacking sequence of the disordered samples can be generated by a mixture of motifs corresponding to the 3R1 and 2H1 polytypes. These specific sequences are selected in preference to others because of the need for hydrogen bonding between the intercalated carbonates and hydroxide sheets. Thermodynamic considerations show that faulted crystals have greater stability than ordered crystals. Stacking faults arising from a mixture of 3R1 and 2H1 motifs, while having the same enthalpy as that of the ordered crystal, nevertheless contribute to thermodynamic stability by enhancing disorder.

In the production of alumina (Al2O3) from clays by acid leaching, thermal activation by calcination is applied widely as a pre-treatment to improve the dissolution of aluminum. Previous studies have focused only on the thermal behavior of high-purity kaolinite and pyrophyllite, individually. However, thermal activation of complex clay ores containing several silicate minerals and their effect on aluminum extraction have not been studied. The purpose of the present study was to characterize the thermal behavior of a clay ore containing mainly pyrophyllite (Al2Si4O10(OH)2), kaolinite (Al2Si2O5(OH)4), muscovite (KAl2(AlSi3O10)(OH)2), quartz (SiO2), and kyanite (Al2SiO5) from the Pütürge clay deposits (Malatya, Turkey) for possible use in alumina (Al2O3) production by acid leaching. The ore and its calcination products obtained at various temperatures were characterized with respect to their mineral paragenesis, crystal structure, surface morphology, and thermal, calorimetric, and aluminum dissolution properties in order to understand the changes that occurred. Aluminum recovery in the leach solution increased in direct proportion to the dehydroxylation degree (Dtg) of the ore as the calcination temperature increased to 900°C. A maximum aluminum extraction of 90.57% was achieved by leaching of the product from calcination at 900°C. Aluminum extraction decreased sharply above that temperature, even though Dtg increased a little. By increasing the calcination temperature; the structures of pyrophyllite, kaolinite, and muscovite were destroyed by dehydroxylation, resulting in the exfoliation of the mineral layers, thus, a mixture of dehydroxylated phases formed. Depending mainly on the temperature range at which each of the dehydroxylated phases is durable, aluminum could be leached to some extent. The sharp decrease in the extraction of aluminum, iron, and potassium at higher temperatures was attributed to compaction of previously exfoliated layers of the minerals through re-crystallization to form mullite-like structures which seemed insensitive to acid attack during the leaching.

The Bursa-Orhaneli and Keles-Harmanalan coal deposits were developed in swampy and fluvial-lacustrine environments in western Anatolia under the E–W-trending graben zone during the Neogene. The present study aimed to determine the mineralogical and geochemical properties of clays interlayering the coal seams to define the origin of clay minerals, in particular, smectite. These deposits, comprising argillaceous sediment, marl, coal seam, mudstone, organic-rich shale, and sandstone, were deposited in a lacustrine environment accompanied by volcanogenic materials. The characteristics of sediments and their parent rocks were examined using X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, palynology, and chemical analyses. The association of abundant smectite with quartz, amphibole, accessory chlorite, and a decrease in feldspar in fluvial-lacustrine sediments compared to those in the smectite accompanied by feldspar and volcanic glass and the absence of quartz and amphibole in the pyroclastic units suggest that smectite had detrital and authigenic origins. Flaky smectite shows either detrital, irregularly outlined coating and filling pores of terrigenous sediments or in situ precipitation edging resorbed feldspar and devitrified volcanic glass. Chemical analyses of the smectite-rich fraction show montmorillonite compositions with an average structural formula of: (Ca0.42Na0.25K0.08)(Al2.76Fe0.47Mg0.59Ti0.07Mn0.002)(Si7.65Al0.35)O20(OH)4.

The positive correlation of Al2O3 vs. TiO2 and K2O vs. Rb may be related to the abundant detrital input. Feldspar and biotite were replaced by illite during diagenesis.

An increase in the Ni/Co and V/(V + Ni) ratios in the altered units also suggest oxic, suboxic to anoxic conditions, under the control of a dry, warm to subtropical climate in fresh water and lakes during the Late Eocene to Middle Miocene. The slight enrichment of light rare earth elements (LREE) compared to heavy rare earth elements (HREE) with positive Eu and positive/negative Ce anomalies reflect fractional crystallization of feldspar. The δ18O and δD values of smectite and illite fractions and the wide range of δ34S isotope values (–1.5 to 15‰) for pyrite and chalcopyrite associated with coal indicate a signature of both diagenetic and partial hydrothermal origin.