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The fertility of soils with respect to K+ and NH4+ is often difficult to measure, but is essential for achieving effective agronomic practices. This problem is especially important in the Vertisols of Thailand. The purpose of the study reported here was to characterize the composition and layer-charge behavior of Thai Vertisols in order to understand better their K+ and NH4+ fertility. Topsoil and subsoil clay of 12 representative highly smectitic Vertisols from Thailand were studied. Interlayer swelling of smectite with alkylammonium cations, cation exchange capacity (CEC), and chemical composition were determined. These data and the re-expansion on glycerol treatment of Li-saturated, heated smectite demonstrated that high-charge, Fe-rich beidellite is the major clay mineral in these soils. The beidellite has a heterogeneous layer-charge distribution as measured by the alkylammonium method, with mean values ranging from 0.43 to 0.62 charges per half unit cell. The layer charge determined by CEC and structural formula methods for some almost pure smectites is smaller (0.32–0.54) and greater (0.46–0.69), respectively, than determined by the alkylammonium method. The structural formulae of beidellite confirm that the layer charge originates mostly in the tetrahedral sheet.
The Markan Passion narrative alludes to Ps 22 (LXX Ps 21) in reverse, culminating with Jesus’ cry: ‘My God, my God, why have you forsaken me?’ (Mark 15.34; cf. Ps 22.1). I argue that this ‘extended inverted allusion’ was an admired literary technique. Through select examples of this technique in the writings of the Hebrew Bible and Greco-Roman literature, I demonstrate its various functions—it can be employed to reverse meaning, to dissociate causation or to create new narrative trajectories. Reading Mark 15 in light of the literary functions of inverted allusion reveals new interpretive possibilities. In the Septuagint, Psalm 21 suggests that the psalmist's suffering was merited because of transgressions, but the inverted allusions to this Psalm in Mark 15 reinforce that Jesus’ suffering is unmerited (cf. Mark 15.10, 14) by decoupling the suffering from the transgressions. Additionally, in LXX Ps 21, the psalmist moves from forsakenness on account of transgressions toward divine deliverance. By alluding to this Psalm in reverse, Jesus travels the psalmist's journey in reverse. Rather than move from forsakenness toward divine deliverance, Mark's Jesus moves toward forsakenness, precisely to bring about divine deliverance.
Marriage is an institution that varies from religion to religion. For Hindus, it is an indissoluble union; for Muslims, a civil contract; and for Christians, a holy union. However, individual autonomy has entered the forefront through the Indian Constitution and the revolution in Indian family law.
The Constitution of India specifies that the people can decide who they should marry, who they should not, and with whom they want and don't want to continue their marital bond. The remedy of the restitution of conjugal rights (RCR), available under personal law, applies to those who are legally married but withdraw from marital ties without a reasonable excuse.
This study found that RCR is one-sided and used against the other spouse's will. However, the Supreme Court of India has decided that individual autonomy is needed to protect individual liberty and promote national interest, but it has also upheld the validity of RCR, creating a genuine controversy. The object of this paper is twofold—to analyze the individual autonomy enshrined under article 21 of the Indian Constitution, which is contrary to the right to RCR, and to explore this topic through a comparative law technique.
Natural clay-sized glauconite has the same mineralogical composition as sand-sized glauconite pellets but occurs in <2 μm clay fractions. This particular glauconite habit has been described previously from soil environments resulting from pelletal weathering but is rarely reported in higher-energy sedimentary environments. In the present study, clay-sized glauconite was identified as a common constituent in transgressive Neogene glauconite pellet-rich deposits of the southern North Sea in Belgium. X-ray diffraction results revealed that the characteristics of the clay-sized glauconite are very similar to the associated glauconite pellets in sand deposits. Both glauconite types consisted of two glauconite-smectite R1 phases with generally small percentages of expandable layers (<30%) with d060 values ranging between 1.513 Å and 1.519 Å. Clay-sized glauconite was not neoformed but formed by the disintegration of sand-sized glauconite pellets which were abraded or broken up during short-distance transport within the sedimentary basin or over the hinterland. Even in an environment where authigenic glauconite pellets occur, minimal transport over transgressive surfaces is sufficient to produce clay-sized glauconite. Furthermore, clay-sized glauconite can be eroded from marine deposits and subsequently resedimented in estuarine deposits. Clay-sized glauconite is, therefore, a proxy for the transport intensity of pelletal glauconite in energetic depositional environments and, moreover, indicates reworking in such deposits which lack pelletal glauconite.
In order to provide a theoretical foundation for the utilization of tailings as supplementary cementitious materials, the pozzolanic activity of muscovite—a typical mineral phase in tailings—before and after mechanical activation was investigated. In this study, significant pozzolanic activity of muscovite was obtained as a result of the structural and morphological changes that were induced by mechanical activation. The activated muscovite that was obtained after mechanical activation for 160 min satisfies the requirements for use as an active supplementary cementitious material, and the main characteristics of the pozzolana were as follows: median particle size (D50) of 11.7 μm, BET specific surface area of 28.82 m2 g−1, relative crystallinity of 14.99%, and pozzolanic activity index of 94.36%. Continuous grinding led to a gradual reduction in the relative crystallinity and an increase in the pozzolanic activity index due to the dehydroxylation reaction induced by mechanical activation, which occurred despite the fact that the specific surface area showed a decreasing trend when the grinding time was prolonged. Mechanically activated muscovite exhibited the capacity to react with calcium hydroxide to form calcium silicate hydrate, which is a typical characteristic of pozzolana. This experimental study provided a theoretical basis for evaluating the pozzolanic activity of muscovite using mechanical activation.
The relationship between vacant Mn structural sites in birnessites and heavy-metal adsorption is a current and important research topic. In this study, two series of birnessites with different average oxidation states (AOS) of Mn were synthesized. One birnessite series was prepared in acidic media (49.6–53.6 wt.% Mn) and the other in alkaline media (50.0–56.2 wt.% Mn). Correlations between the Pb2+ adsorption capacity and the d110 interlayer spacing, the AOS by titration, and the release of Mn2+, H+, and K+ during adsorption of Pb2+ were investigated. The maximum Pb2+ adsorption by the birnessites synthesized in acidic media ranged from 1320 to 2457 mmol/kg with AOS values that ranged from 3.67 to 3.92. For birnessites synthesized in alkaline media, the maximum Pb2+ adsorption ranged from 524 to 1814 mmol/kg, with AOS values between 3.49 and 3.89. Birnessite AOS values and Pb2+ adsorption increased as the Mn content decreased. The maximum Pb2+ adsorption to the synthetic birnessites calculated from a Langmuir fit of the Pb adsorption data was linearly related to AOS. Birnessite AOS was positively correlated to Pb2+ adsorption, but negatively correlated to the d110 spacing. Vacant Mn structural sites in birnessite increased with AOS and resulted in greater Pb2+ adsorption. Birnessite AOS values apparently reflect the quantity of vacant sites which largely account for Pb2+ adsorption. Therefore, the Pb2+ adsorption capacity of birnessite is mostly determined by the Mn site vacancies, from which Mn2+, H+, and K+ released during adsorption were derived.
The chemical and biological methods employed to date in the removal of free cyanide (CN−) and metal-cyanide complexes from aqueous fluids have proved expensive and problematic. A simpler and more economical approach was attempted in the present study using zeolite and sepiolite. The effectiveness of zeolite from Manisa-Gördes (Turkey) and of sepiolite Eskişehir-Sivrihisar (Turkey) at removing free and Cu-complexed cyanide, [Cu(CN)3]2− was investigated. For removal of CN−, the system performance was examined in terms of concentration, particle size, and retention time. Material with smaller particle sizes (<0.106 mm) performed better, particularly in the case of sepiolite. The maximum CN− removal capacities of zeolite and sepiolite were calculated as 571 and 695 meq/100 g for free CN adsorption, and 455 and 435 meq/100 g for Cu-complexed CN adsorption, respectively. The time to reach equilibrium was calculated as 1050 min. Acid activation, a simple cation adsorption removal method, did not improve the process, instead leading to reduced CN adsorption. Hydroxylated surfaces of metal oxides at the edges of zeolite develop charges and exchange with anions in water. Mg2+ ions located at the edges of the octahedral sheet can create complexes with CN− anions. Moreover, hydrogen bonding with anions (CN− in this case) and H+ of zeolitic water bonded to coordinated water molecules can also create complexes. These two complexes are considered to be effective mechanisms for sepiolite. The effects of both acid activation and CN adsorption were clearly observed in the Fourier-transform infrared spectra. Removal of CN was characterized by the Langmuir isotherm, indicating monolayer coverage with chemical bonding to the surface, which deteriorated during acid activation. The study indicated that zeolite and sepiolite can be used efficiently and easily for removal of free and Cu-complexed CN.
Naturally deformed biotite in contact-metamorphosed slates affected by a shear zone of the Southern Iberian Massif near Jaén (SE Spain) were studied by X-ray diffraction, optical microscopy, scanning electron microscopy, electron probe microanalysis and high-resolution transmission and analytical electron microscopy. Biotite is found in the contact metamorphism aureole produced by the intrusion of a granodioritic stock, but shear strain caused its deformation. The southern part of the shear band is strongly deformed, containing thick clay gouge zones. The northern part is less deformed and develops weaker planar-linear fabrics. X-ray diffraction data reveal the predominance of the 2M1 biotite in the undeformed samples whereas the 1M polytype is predominant in the sheared samples. Chemical data and electron images of the biotite from unsheared slates do not show the presence of intercalated phases. This biotite is almost defect-free and electron diffraction patterns have sharp reflections indicating a two-layer polytype (probably 2M1). Back-scattered electron images from the deformed biotite in the moderate deformation part of the shear zone do not reveal intergrown minerals, but the electron microprobe analyses show some Fe- and Mg-enriched compositions. Transmission electron microscopy indicates that disordered polytype packets are predominant (probably 1Md). Their electron diffraction patterns have diffuse streaking along c*. These packets have high dislocation densities, microcavities with ∼5 Å latticefringe regions (probably brucite-like sheets) and interlayering of chlorite-berthierine. Kaolinized biotite can be observed in the clay gouges from the strongly deformed south part of the shear zone. The degree of streaking, as an indication of the intensity of deformation, revealed that the disordered polytype packets are more deformed than the two-layer polytype packets. The microcavities of the disordered polytype packets could act as potential channels for transport of fluids during the shearing stage and serve as sites for chloritization of biotite, producing chlorite-berthierine domains within biotite. Berthierine is an intermediate metastable phase replaced by chlorite with along-layer transitions.
Understanding clay-mineral assemblages forming in saline lakes aids in reconstructing paleoenvironments on Earth and other terrestrial planets; this is because authigenic phyllosilicates are sensitive to the prevailing geochemical conditions present during formation. In most geochemical models, evaporative concentration favors sepiolite with increasing silica and Mg2+ concentrations without considering the role of the biogenic removal of silica from solution by diatoms. In the present study, phyllosilicates occurring in the mudflats of Bolivian salars were investigated to aid in understanding the geochemical factors that control mineral assemblages forming in (SO42–)- and (Cl–)-rich environments in relation to dissolved silica. From transects across the mudflats, the physical, chemical, and mineralogical characteristics of the bulk sediment and the <2 μm fraction of each sedimentary layer were analyzed. From these analyses, three types of sediments were identified: (1) regolith sediments dominated by Al-dioctahedral smectite, illite, and chlorite; (2) detritus-rich mudflat sediments with Mg-trioctahedral smectite and Al-dioctahedral smectite along with illite and chlorite; and (3) authigenic mudflat sediments dominated by poorly formed Mg-trioctahedral smectite, kerolite, and biogenic silica. The absence of sepiolite-palygorskite in the salars is the result of excessively high Mg:Si ratios within the waters. In the surface water Mg becomes enriched relative to Si as diatoms remove dissolved Si from solution through biologically mediated uptake. The geochemical conditions present within the salars that act to preserve the diatom frustules and prevent their dissolution include: neutral–slightly alkaline pH solutions, cold temperatures, shallow water, and high salinity. Under these conditions the formation of sepiolite is restricted by the small amount of dissolved silica, despite the silica-rich environment. The formation of Mg-smectite and kerolite is favored under these conditions.
Photocatalytic degradation of polluted water by means of minerals, such as clays and oxides, which have surfaces that exhibit catalytic properties, has been suggested to be a useful new strategy to promote both organic and inorganic pollutant degradation. Nevertheless, much still remains to be studied about the capability of mixed metal oxides derived from lanthanum-containing layered double hydroxides to promote pollutant removal by means of photocatalytic degradation with the mineral surfaces. The objective of the present study was to investigate the synthesis of ternary MgAlLa mixed-metal oxides (MgAlLa-M) with various Mg/Al/La molar ratios through a hydrotalcite-like precursor route by co-precipitation of appropriate amounts of metal salts from homogeneous solution, followed by calcination at 600°C. The crystal structure, surface morphology, and optical properties of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), and UV-Vis diffuse reflectance spectroscopy (DRS). Analysis by XRD showed that MgO, La2O3, MgAl2O4, and La10Al4O21 phases coexisted in calcined samples as MgAlLa-M. The samples showed a small band gap of 3.11–3.35 eV according to DRS. The photocatalytic activities of the samples were evaluated by degradation of methylene blue (MB) under visible light irradiation. MgAlLa-M had better photocatalytic properties than hydrotalcite precursors, and the MgAlLa-0.5-M possessed the best photocatalytic activity. The photocatalytic degradation efficiency of MB dye with MgAlLa-0.5-M under visible light irradiation for 1 h was 99.89% in the presence of H2O2, which exceeded the binary MgAl-M (84.06%) under the same conditions. The high photocatalytic activity of the sample was attributed to the addition of La(III). In addition, the possible mechanism of photocatalytic degradation of MB by MgAlLa-M was discussed. The results showed that •O2– plays a major role in the MgAlLa-0.5-M/H2O2 system.
Air-dried and high-pressure frozen/freeze-etched samples of clinopyroxene and smectite in a saprolitized clinopyroxenite from Koua Bocca, Ivory Coast, West Africa, were compared to characterize textures developed during natural weathering of chain silicates. Comparison with air-dried material allowed evaluation of high-pressure cryofixation as a technique for preserving textures of hydrated clay minerals. Air-dried pyroxene surfaces appear very smooth. Small, flat lamellae, oriented parallel to the c axis, lend a distinct splintery appearance to pyroxene surfaces in fully hydrated samples. These lamellae often display a combination of straight (110) pyroxene edges and a crinkled border, suggestive of smectite. Narrow lenticular (110) open cleavages occur in both preparations and are not a pressurization artifact. Most often these openings contain no secondary minerals. Spaces between pyroxene denticles, lined with collapsed smectite in air-dried samples, are filled with thin packets of anhedral smectite crystallites oriented face to face when hydrated. Smectite microboxwork preserves original topotactic textures developed during isovolumetric pyroxene transformation, and smaller nanoporosity appears in hydrated cryofixed examples. Occasional regions of edge-to-face ‘house of cards’ texture also occur. Elimination of sample preparation artifacts induced by surface tension during air drying demonstrates that pores actually present during a hydration reaction-driven weathering episode are smaller and more numerous than would be inferred from examining air-dried materials.
The thermal stability of surfactant-modified clays plays a key role in the synthesis and processing of organoclay-based nanocomposites. Differential thermal analysis (DTA), thermogravimetric measurement and differential scanning calorimetry (DSC) were used in this study to characterize the thermal stability of hexadecyltrimethylammonium bromide-modified montmorillonites prepared at different surfactant concentrations. Analysis by DSC shows that the molecular environment of the surfactant within the montmorillonite galleries is different from that in the bulk state. The endothermic peak at 70–100°C in the DTA curves of the modified montmorillonites is attributed to both the surfactant phase transformation and the loss of free and interlayer water. With an increase of surfactant-packing density, the amount of water residing in the modified montmorillonite decreases gradually, reflecting the improvement of the hydrophobic property for the organoclay. However, the increase in the surfactant packing density within the galleries leads to a decrease in the thermal stability of the organoclays.
With an increase of initial surfactant concentration for the preparation of organoclays, the surfactant- packing density increases gradually to a ‘saturated’ state. It was found that the cationic surfactant was introduced into the montmorillonite interlayer not only by cation exchange but also by physical adsorption.
This study presents a mathematical formalism describing diffraction effects from periodic and mixed-layer minerals in which the outer surface layers of crystals possibly differ from layers forming the core of the crystals. The X-ray diffraction (XRD) patterns calculated for structure models of chlorite and irregular chlorite-smectites terminated on both sides of the crystals by either brucite-like sheets or 2:1 layers show the strong influence that different outer surface layers have on the distribution of basal reflection intensities. Simulation of the experimental XRD patterns from two chlorite samples having different Fe contents shows that in these two samples the chlorite crystals were terminated by brucite-like sheets on both sides. In contrast, crystals in a corrensite sample were terminated by water molecules and exchangeable cations. The nature of diffraction effects due to outer surface layers is discussed.
Dilute aqueous smectite suspensions are well suited to convert into functional nanofilms. The functionalization is performed by ion exchange of amphiphilic molecules carrying the desired functionality. A functionalized clay mineral nanofilm is obtained by the organization of the molecules at the clay surface and by the organization of the elementary clay platelets in the film. Two techniques are presented: self-assembling and Langmuir-Blodgett (LB). Self-assembling is a very simple experiment, but the organizational order of the clay mineral particles is low. Nevertheless, films with nonlinear optical properties which are able to generate frequency-doubled light have been produced. The drawback of disorder of the clay platelets in the film can be largely overcome with the LB technique. Well organized films are obtained. In the presence of amphiphilic ruthenium(II)-bipyridine complexes, nonlinear optical properties are measured. In the presence of two dyes, oxacarbocyanine and rhodamine B, simultaneously adsorbed, efficient energy transfer between the donor (oxacarbocyanine) and the acceptor (rhodamine B) is measured. Fundamental research into the organization of molecules at clay mineral platelets is necessary to optimize the materials for specific applications.
In recent decades, the Turkish government has adopted a proactive policy of pursuing the restitution of cultural objects it believes were illegally removed from its territory. Utilising open-access sale data, the following article examines the impact of this formal restitution policy upon antiquity market sales in Anatolian figurines between 1999 and 2022 across three major international auction houses and the internet market. By casting a forensic gaze upon seemingly decreasing sale rates and ostensibly improving standards of provenance, this study suggests that apparent improvements in the market for Anatolian figurines should not be attributed to the Turkish government restitution policy. Instead, it argues that salient commercial dynamics and the profit-oriented business strategies of individual auction houses are the operative factors in shaping antiquity market data. In doing so, it provides the first quantitative market analysis of auction house sales in Anatolian figurines, widens the applicability of existing methodologies for navigating the duplicitous nature of antiquity market data, and offers much needed empirical insights into the illicit antiquities trade.