RESUMEN
The crystal structure of vanthoffite {hexa-sodium magnesium tetra-kis[sulfate-(VI)]}, Na6Mg(SO4)4, was solved in the year 1964 on a synthetic sample [Fischer & Hellner (1964 â¸). Acta Cryst. 17, 1613]. Here we report a redetermination of its crystal structure on a mineral sample with improved precision. It was refined in the space group P21/c from a crystal originating from Surtsey, Iceland. The unique Mg (site symmetry ) and the two S atoms are in usual, only slightly distorted octa-hedral and tetra-hedral coordinations, respectively. The three independent Na atoms are in a distorted octa-hedral coordination (1×) and distorted 7-coordinations inter-mediate between a 'split octa-hedron' and a penta-gonal bipyramid (2×). [MgO6] coordination polyhedra inter-change with one half of the sulfate tetra-hedra in <011> chains forming a (100) meshed layer, with dimers formed by edge-sharing [NaO7] polyhedra filling the inter-chain spaces. The other [NaO7] polyhedra are organized in a parallel layer formed by [010] and [001] chains united through edge sharing and bonds to the remaining half of sulfate groups and to [NaO6] octa-hedra. The two types of layers inter-connect through tight bonding, which explains the lack of morphological characteristics typical of layered structures.
RESUMEN
Glendonites have been found worldwide in marine sediments from the Neoproterozoic Era to the Quaternary Period. The precursor of glendonite, ikaite (CaCO3 · 6H2O), is metastable and has only been observed in nature at temperatures <7 °C. Therefore, glendonites in the sedimentary record are commonly used as paleotemperature indicators. However, several laboratory experiments have shown that the mineral can nucleate at temperatures>7 °C. Here we investigate the nucleation range for ikaite as a function of temperature and pH. We found that ikaite precipitated at temperatures of at least 35 °C at pH 9.3 -10.3 from a mixture of natural seawater and sodium carbonate rich solution. At pH 9.3, we observed pseudomorphic replacement of ikaite by porous calcite during the duration of the experiment (c. 5 hours). These results imply that ikaite can form at relatively high temperatures but will then be rapidly replaced by a calcite pseudomorph. This finding challenges the use of glendonites as paleotemperature indicators.
RESUMEN
A synthetic Cu-Al-SO4 layered double hydroxide (LDH), analogue to the mineral woodwardite [Cu1-xAlx(SO4)x/2(OH)2·nH2O], with x < 0.5 and n ≤ 3x/2, was synthesised by adding a solution of Cu and Al sulphates to a solution with NaOH. The pH values were kept constant at 8.0 and 10.0 by a continuous addition of NaOH. The material obtained had poor crystallinity, turbostratic structure, and consisted of nanoscopic crystallites. The analyses performed in order to characterise the obtained materials (X-ray diffraction (XRD), thermogravimetry (TG), and Fourier Transform Infra-Red (FTIR) spectroscopy) showed that the Cu-Al-SO4 LDH is very similar to woodwardite, although it has a smaller layer spacing, presumably due to a lesser water content than in natural samples. The synthesis was performed by adding light rare earth elements (LREEs) (La, Ce, and Nd) and heavy rare earth elements (HREEs) (Gd and Y) in order to test the affinity of the Cu-Al-SO4 LDH to the incorporation of REEs. The concentration of rare earth elements (REEs) in the solid fraction was in the range of 3.5-8 wt %. The results showed a good affinity for HREE and Nd, especially for materials synthesised at pH 10.0, whereas the affinities for Ce and La were much lower or non-existent. The thermal decomposition of the REE-doped materials generates a mixture of Cu, Al, and REE oxides, making them interesting as precursors in REE oxide synthesis.
RESUMEN
Metal-polluted mine waters represent a major threat to the quality of waters and sediments in a downstream basin. At the confluence between acidic mine waters and the unpolluted waters of the Gromolo Torrent (Liguria, North-West Italy), the massive formation of an ochreous amorphous precipitate takes place. This precipitate forms a soft blanket that covers the torrent bed and can be observed down to its mouth in the sea. The aim of this work is to evaluate the dispersion of metals in the Gromolo Torrent basin from the abandoned Cu-Fe sulphide mine of Libiola to the Ligurian Sea and to assess the metal remobilisation from the amorphous precipitates. The mineralogy of the superficial sediments collected in the torrent bed and the concentrations of different elements of environmental concern (Cu, Zn, Cd, Co, Cr, Mn, Ni, Pb, As, and Sb) were therefore analysed. The results showed that the precipitates contain high concentration of Fe, Al, Cu, and Zn, significantly modifying the bulk chemistry of the Gromolo Torrent sediments. In order to evaluate the possible remobilisation of ecotoxic elements from the amorphous precipitates, bulk leaching tests were performed with both deionised and seawater. Bulk leaching tests with deionised water mobilised primarily high Pb amounts, but also relatively high concentrations of Fe, Al, Cu, and Zn are released in the leachate. In seawater tests, Fe, Al, Cu, and Zn were released in smaller amounts, while other elements like Mn, Cd, Co, and Ni increased in the released fraction. Pb was still strongly released as in deionised water experiments. The results show that the interaction of precipitates and seawater can remobilise high concentrations of metals, thus affecting the surrounding environment.
Asunto(s)
Monitoreo del Ambiente , Metales Pesados/análisis , Contaminantes Químicos del Agua/análisis , Sedimentos Geológicos , Italia , Metales , Metales Pesados/química , Minería , Contaminantes Químicos del Agua/químicaRESUMEN
Stable isotope ratios of H, C, and O are powerful indicators of a wide variety of planetary geophysical processes, and for Mars they reveal the record of loss of its atmosphere and subsequent interactions with its surface such as carbonate formation. We report in situ measurements of the isotopic ratios of D/H and (18)O/(16)O in water and (13)C/(12)C, (18)O/(16)O, (17)O/(16)O, and (13)C(18)O/(12)C(16)O in carbon dioxide, made in the martian atmosphere at Gale Crater from the Curiosity rover using the Sample Analysis at Mars (SAM)'s tunable laser spectrometer (TLS). Comparison between our measurements in the modern atmosphere and those of martian meteorites such as ALH 84001 implies that the martian reservoirs of CO2 and H2O were largely established ~4 billion years ago, but that atmospheric loss or surface interaction may be still ongoing.
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A direct comparison between two complete intensity datasets, collected on the same sample loaded in two identical diamond-anvil pressure cells equipped, respectively, with beryllium and diamond-backing plates was performed. The results clearly demonstrate that the use of diamond-backing plates significantly improves the quality of crystal structure data. There is a decrease in the internal R factor for averaging, structure refinement agreement factors, and in the errors and uncertainties of the atomic coordinates, atomic displacement parameters, and individual bond lengths.
RESUMEN
An increasing number of engineered particles, including nanoparticles, are being manufactured, increasing the need for simple low-dose toxicological screening methods. This study aimed to investigate the kinetics of biomarkers related to acute and sub-chronic particle-induced lung inflammation of quartz. Mice were intratracheal instilled with 50 µg of microsized or nanosized quartz. Acute inflammation was assessed 1, 2, 4, 8, 16 or 48 hours post exposure, whereas sub-chronic inflammation was investigated 3 months after exposure. Markers of acute inflammation in the bronchoalveolar lavage fluid (BALF) were neutrophils (PMN), tumor necrosis factor-alpha (TNF-α), interleukin (IL)-1ß, macrophage inflammatory protein-2 (MIP-2), keratinocyte derived chemokine (KC) and total protein, which were all close to maximum 16 hours post instillation. No major differences were seen in the time-response profiles of nano- and micro-sized particles. The potency of the two samples cannot be compared; during the milling process, a substantial part of the quartz was converted to amorphous silica and contaminated with corundum. For screening, BALF PMN, either TNF-α or IL-1ß at 16 hours post instillation may be useful. At 3 months post instillation, KC, PMN and macrophages were elevated. Histology showed no interstitial inflammation three months post instillation. For screening of sub-chronic effects, KC, PMN, macrophages and histopathology is considered sufficient.
Asunto(s)
Exposición por Inhalación/efectos adversos , Nanopartículas/toxicidad , Neumonía/inducido químicamente , Cuarzo/toxicidad , Animales , Líquido del Lavado Bronquioalveolar/citología , Líquido del Lavado Bronquioalveolar/inmunología , Citocinas/inmunología , Relación Dosis-Respuesta a Droga , Femenino , Ratones , Ratones Endogámicos BALB C , Microscopía Electrónica de Transmisión , Neutrófilos/citología , Neutrófilos/efectos de los fármacos , Tamaño de la Partícula , Neumonía/inmunología , Difracción de Polvo , Propiedades de Superficie , Factores de Tiempo , Pruebas de Toxicidad , Difracción de Rayos XRESUMEN
Raman microspectroscopy was first used to determine the composition of a calcified plaque located at the pterygium-excision site of a 51-year-old female patient's left nasal sclera after surgery. It was unexpectedly found that the Raman spectrum of the calcified sample at 1149, 1108, 1049, 756, 517, 376 and 352/cm was similar to the Raman spectrum of monoclinic form of calcium pyrophosphate dihydrate (CPPD) crystal, but differed from the Raman spectrum of triclinic form of CPPD. An additional peak at 958/cm was also observed in the Raman spectrum of the calcified plaque, which was identical to the characteristic peak at 958/cm of hydroxyapatite (HA). This is the first study to report the spectral biodiagnosis of both monoclinic CPPD and HA co-deposited in the calcified plaque of a patient with sclera dystrophic calcification using Raman microspectroscopy.
Asunto(s)
Calcinosis/metabolismo , Pirofosfato de Calcio/análisis , Durapatita/análisis , Enfermedades de la Esclerótica/metabolismo , Calcinosis/diagnóstico , Calcinosis/patología , Femenino , Humanos , Persona de Mediana Edad , Enfermedades de la Esclerótica/diagnóstico , Enfermedades de la Esclerótica/patología , Espectrometría Raman/métodosRESUMEN
The use of the superspace formalism is extended to the description and refinement of the homologous series of modular structures with two symmetry-related modules with different orientations. The lillianite homologous series has been taken as a study case. Starting from a commensurate modulated composite description with two basic subsystems corresponding to the two different modules, it is shown how a more efficient description can be achieved using so-called zigzag modulation functions. These linear zigzag modulations, newly implemented in the program JANA2006, have very large fixed amplitudes and introduce in the starting model the two orientations of the underlying module sublattices. We show that a composite approach with this type of function, which treats the cations and anions as two separate subsystems forming a misfit compound, is the most appropriate and robust method for the refinements.
RESUMEN
The compound Pb 3Bi 2S 6 is investigated by X-ray diffraction on single crystals in a diamond-anvil cell between 0.0001 and 10.5 GPa. It undergoes a first-order phase transition at hydrostatic pressure between 3.7 and 4.9 GPa. The space group symmetry changes from Bbmm to Pbnm, and the unit-cell volume decreases by 4%. The transition is strongly anisotropic, with a contraction along one of the crystal axes by 16% and expansion along another one by 14%. This is a piezoplastic phase transition, a displacive pressure-induced phase transition with systematic shearing of atomic planes and a migration of chemical bonds in the structure. In the case of Pb 3Bi 2S 6 the transition is achieved by the change of the archetypal architecture of the structure-building modules from a PbS-like to a SnS-like arrangement and a loss of mirror planes on the contact surfaces of modules. The phase transition is reversible with a preservation of the single crystal, which is a result of the stereochemical influence and migration of the s (2) lone electron pairs of Pb (II) and Bi (III).
RESUMEN
Cu(3)Bi(2)S(3)I(3) was crystallized during an attempt to synthesize Cu-Pb-Bi sulfosalts with iodine as the transport medium. The crystal structure was solved from a black needle-like crystal on a four-circle diffractometer with a CCD detector. The solution was obtained by direct methods and subsequent difference-Fourier syntheses. S and I atoms are arranged in a systematically distorted cubic eutaxy (close packing). Bi atoms have monocapped trigonal prismatic coordinations, while Cu atoms occupy coordination sites which vary from trigonal planar to distorted tetrahedral. A prominent feature is the distribution of Cu atoms over many closely spaced sites in the structure, the majority of them being only partly occupied, which strengthens the case for mobile Cu atoms during crystal growth at elevated temperatures. In this respect, Cu(3)Bi(2)S(3)I(3) represents an extreme example of a statistical distribution of Cu in the structure; a frequently observed property of this element in sulfosalts.