H-bonding in lazulite: a single-crystal neutron diffraction study at 298 and 3 K

The crystal structure and crystal chemistry of a lazulite from Crosscut Creek (Kulan Camp area, Dawson mining district, Yukon, Canada) was investigated by electron microprobe analysis in wavelength-dispersive mode (EMPA) and single-crystal neutron diffraction at 298 and 3 K. Its empirical formula, based on EMPA data, is: (Mg0.871Fe0.127)\u3a30.998Al2.030(P1.985Ti0.008Si0.007O4)2(OH)2. The neutron diffraction experiments at room and low T proved that the H-free structural model of lazulite previously reported, on the basis of X-ray structure refinement, is correct: the building unit of the lazulite structure consists of a group of three face-sharing (Al-octahedron) + (Mg,Fe-octahedron) + (Aloctahedron), connected to the adjacent one via a corner-shared OH-group and two corner-shared oxygen sites of the P-tetrahedron, to form a dense 3D-edifice. Only one crystallographically independent H site occurs in the structure of lazulite, forming a hydroxyl group with the O5 oxygen, with O5\u2013H = 0.9997 \uc5 at room temperature (corrected for riding motion effect). The H-bonding scheme in the structure of lazulite is now well defined: a bifurcated bonding scheme occurs with the O4 and O2 oxygen sites as acceptors. The two H-bonds are energetically different, as shown by their bonding geometry: the H-bond with the O2 site as acceptor is energetically more favorable, being O5\u2013H\ub7\ub7\ub7O2 = 152.67(9)\ub0, O5\ub7\ub7\ub7O2 = 3.014(1) \uc5 and H\ub7\ub7\ub7O2 = 2.114(1) \uc5, whereas that with O4 as acceptor is energetically more costly, being O5\u2013H\ub7\ub7\ub7O4 = 135.73(8)\ub0, O5\ub7\ub7\ub7O4 = 3.156(1) \uc5 and H\ub7\ub7\ub7O4 = 2.383(1) \uc5, at room temperature. No T-induced phase transition occurs within the T-range investigated. At low temperature, the O5\u2013H\ub7\ub7\ub7O2 bond is virtually identical to the room-T one, whereas the effects of T on O5\u2013H\ub7\ub7\ub7O4 are more pronounced, with significant differences of the Odonor\ub7\ub7\ub7Oacceptor and H\ub7\ub7\ub7Oacceptor distances. The experimental findings of this study do not support the occurrence of HPO4 or H2PO4 units into the structure of lazulite, recently reported on the basis of infrared and Raman spectra

Metallogeny of Serpentinite-Hosted Magnetite Deposits : Hydrothermal Overgrowth on Chromite or Metamorphic Transformation of Chromite?

Peculiar and rare occurrences of serpentinite-hosted magnetite deposits with mineable sizes are found in the Mesozoic ophiolites of Greece (Skyros), Iran (Nain and Sabzevar) and Oman (Aniba). These deposits have diverse thickness (from a few centimeters up to 50 m) and length (2 to >500 m). Magnetite ores show variable textures, including massive, nodular and banded ores, veins, net and fine-grained disseminations in serpentinites. Intriguingly, the investigated magnetite deposits can be mistaken for chromitite pods. Serpentinite-hosted magnetite deposits show three modes of occurrences including: (i) boulders strewn across the serpentinites (i.e. Skyros Island) (ii) ore bodies along the nonconformity contacts between serpentinites and limestones (i.e. Aniba); (iii) irregular and discontinuous trails of massive and semi-massive ore bodies within highly sheared serpentinite masses (i.e. Nain; Sabzevar). In all of these magnetite ore bodies, relicts of chromian spinel grains are occasionally enclosed in magnetite crystals. The chemistry of Cr-spinel relics found in these magnetite bodies are comparable to those of accessory Cr-spinels in the surrounding serpentinized peridotites. BSE images and elemental mapping revealed that magnetite occurs as a nucleation on chromian spinels but not being involved in reaction either with chromite or ferritchromite. Low-grade metamorphic transformation of chromite into Fe-chromite is documented along the cracks and fractures of a few chromite grains. Generally, magnetite has typical hydrothermal compositions, characterized by low Cr, V and Ti and high Mg and Mn. It is crucial to note that a few magnetite grains with metamorphic origin are characterized by high Cr and low Ti and Ni. The potential source of iron is essentially the Fe-rich olivine, We believe that multi-episodic serpentinization of peridotite systems at high fluid-rock ratios is the main process responsible for precipitation of magnetite at ore levels whereas low-grade metamorphic transformation of chromite to magnetite has minor contribution. Cumulative factors in generation of these deposits are modal volume of mantle olivine, peridotite composition, fluid chemistry, fluid-rock ratio, mechanisms of transportation and precipitation, structural controls such as cracks and shear zones

New data on Cu‑exchanged phillipsite: a multi‑methodological study

The cation exchange capacity of a natural phillipsite-rich sample from the Neapolitan Yellow Tuff, Southern Italy (treated in order to obtain a 95 wt% zeolite-rich sample composed mainly of phillipsite and minor chabazite) for Cu was evaluated using the batch exchange method. The sample had previously been exchanged into its monocationic form (Na), and then used for the equilibrium studies of the exchange reaction 2Na(+) a double dagger dagger Cu2+. Reversibility ion exchange tests were performed. The isotherm displays an evident hysteresis loop. Interestingly, the final Cu-exchanged polycrystalline material was green-bluish. Natural, Na- and Cu-exchanged forms were analyzed by X-ray powder diffraction, and the Cu-phillipsite was also investigated by transmission electron microscopy (TEM). Structure refinement of Cu-phillipsite was performed by the Rietveld method using synchrotron data, and it indicates a small, but significant, fraction of Cu sharing with Na two-three independent extra-framework sites. The TEM experiment shows sub-spherical nano-clusters of crystalline species (with average size of 5 nm) lying on the surfaces of zeolite crystals or dispersed in the amorphous fraction, with electron diffraction patterns corresponding to those of CuO (tenorite-like structure) and Cu(OH)(2) (spertiniite-like structure). X-ray and TEM investigations show that Cu is mainly concentrated in different species (crystalline or amorphous) within the sample, not only in phillipsite. The experimental findings based on X-ray and TEM investigations, along with the hysteresis loop of the ion exchange tests, are discussed and some general considerations about the mechanisms of exchange reactions involving divalent cations with high hydration energy are provided

A multi-methodological study of the (K,Ca)-variety of the zeolite merlinoite

A multi-methodological study of the (K,Ca)-variety of the zeolite merlinoite from Fosso Attici, Sacrofano, Italy was carried out on the basis of electron microprobe analysis in wavelength dispersive mode, singlecrystal X-ray diffraction (at 100 K), Raman and infrared spectroscopy. The chemical formula of the merlinoite from Fosso Attici is (Na0.37K5.69)\u3a3=6.06(Mg0.01Ca1.93Ba0.40)\u3a3=2.34(Fe3+0.02Al10.55Si21.38)\u3a3=31.9O64\u38719.6H2O, compatible with the ideal chemical formula K6Ca2[Al10Si22O64]\u38720H2O. Anisotropic structure refinements confirmed the symmetry and the framework model previously reported (space group Immm, a = 14.066(5),b = 14.111(5), c = 9.943(3) \uc5 at 100 K). Refinement converged with four cationic sites and sixH2Osites; refined bond distances of the framework tetrahedra suggest a highly disordered Si/ Al-distribution. The Raman spectrum of merlinoite (collected between 100 and 4000 cm 121) is dominated by a doublet of bands between 496\u2013422 cm 121, assigned to tetrahedral T\u2013O\u2013T symmetric bending modes. T\u2013O\u2013T antisymmetric stretching is also observed; stretching and bending modes of the H2O molecules are only clearly visiblewhen using a blue laser. The single-crystal near-infrared spectrum shows a very weak band at 6823 cm 121, assigned to the first overtone of the O\u2013H stretching mode, and a band at 5209 cm 121, due to the combination of H2O stretching and bendingmodes.Avery broad and convoluted absorption, extending from 3700 to 3000 cm 121 occurs in the H2O stretching region, while the \u3bd2 bending mode of H2O is found at 1649 cm 121. The powder midinfrared spectrum of merlinoite between 400\u20131300 cm 121 is dominated by tetrahedral T\u2013O\u2013T symmetric and antisymmetric stretches. Raman and Fourier-transform infrared spectroscopy spectra of merlinoite and phillipsite provide a quick identification tool for these zeolites, which are often confused due to their close similarity

Monoclinic La1-xBaxMnO3 (x=0.185) at 160 K

Single-crystal X-ray diffraction has shown that lanthanum barium manganese trioxide, La0.815Ba0.185MnO3, is monoclinic (I2/c) below a first-order phase transition at 187.1 (3) K. This result differs from the Pbnm symmetry usually assigned to colossal magnetoresistance oxides, A1-xA\u2032xMnO3 with x 43 0.2, which adopt a distorted perovskite-type crystal structure. The Mn atom lies on an inversion center, the disordered Li/Ba site is on a twofold axis and one of the two independent O atoms also lies on a twofold axis

Position paper of the European Academy of Allergy and Clinical Immunology

Rhinitis is a common problem in childhood and adolescence and impacts negatively on physical, social and psychological well-being. This position paper, prepared by the European Academy of Allergy and Clinical Immunology Taskforce on Rhinitis in Children, aims to provide evidence-based recommendations for the diagnosis and therapy of paediatric rhinitis. Rhinitis is characterized by at least two nasal symptoms: rhinorrhoea, blockage, sneezing or itching. It is classified as allergic rhinitis, infectious rhinitis and nonallergic, noninfectious rhinitis. Similar symptoms may occur with other conditions such as adenoidal hypertrophy, septal deviation and nasal polyps. Examination by anterior rhinoscopy and allergy tests may help to substantiate a diagnosis of allergic rhinitis. Avoidance of relevant allergens may be helpful for allergic rhinitis (AR). Oral and intranasal antihistamines and nasal corticosteroids are both appropriate for first-line AR treatment although the latter are more effective. Once-daily forms of corticosteroids are preferred given their improved safety profile. Potentially useful add-on therapies for AR include oral leukotriene receptor antagonists, short bursts of a nasal decongestant, saline douches and nasal anticholinergics. Allergen-specific immunotherapy is helpful in IgE-mediated AR and may prevent the progression of allergic disease. There are still a number of areas that need to be clarified in the management of rhinitis in children and adolescents.publishersversionpublishe

Cancrinite-group minerals at non-ambient conditions: a model of the thermo-elastic and structure behavior

The cancrinite-group of minerals comprises more than ten species sharing the [CAN]-topology of the tetrahedral framework. Their microporous structure has wide 12-ring channels, bound by columns of cages (can units). Besides the aluminosilicate composition of the framework (with the only exception of tiptopite, having instead Be and P), the minerals of the cancrinite group show a remarkable chemical variability concerning the extraframework population. Two subgroups can be identified according to the content of the can units: the first with Na-H2O (cancrinite and vishnevite) and the second with Ca-Cl chains (balliranoite and davyne). The channels are stuffed by cations, anions and molecules. In Nature, cancrinite-group minerals occur in the late/hydrothermal stages of alkaline (SiO2)-undersaturated magmatism and in related effusive or contact rocks. On the technological front, cancrinite-group compounds have been proposed as stable storage form for alkaline waste solutions, of which are common precipitation products. We aimed to model the thermo-elastic behavior and the mechanisms of (P,T)-induced structure evolution of cancrinite-group minerals, focusing to the role played by the extraframework population. The study was restricted to the following (CO3)-rich and (SO4)-rich end-members: cancrinite {[(Na,Ca)6(CO3)1.2-1.7][Na2(H2O)2][Al6Si6O24]}, vishnevite {[(Na,Ca,K)6(SO4)][Na2(H2O)2][Al6Si6O24]}, balliranoite {[(Na,Ca)6(CO3)1.2-1.7][Ca2Cl2][Al6Si6O24]} and davyne {[(Na,Ca,K)6((SO4),Cl)][Ca2Cl2][Al6Si6O24]}. Their high-P and low-T (T < 293 K) behavior was investigated by in situ single crystal X-ray diffraction, using diamond-anvil cells and (N2)-cryo-devices, respectively. Though sharing a similar volume compressibility [i.e., ~ 0.021 GPa-1, KV0 ~ 47 GPa] and thermal expansivity [i.e., ~ 4.0-4.5\ub710-5 K-1], these minerals show a different anisotropic pattern, more pronounced in cancrinite and vishnevite. This behavior is governed by different deformation mechanisms, which reflect the different coordination environments of the cage population between the minerals of the two subgroups. In vishnevite, a P-induced re-organization of the channel population took place at P >= 3.5 GPa, suggesting that also the channel-constituents (and not only the cage one) can play an active role on the structure response at non-ambient conditions. In addition, the high-T behavior of cancrinite was studied up to 823 K, by in situ single-crystal X-ray diffraction. At 748 K, a slow dehydration process takes place towards a (quasi)-anhydrous structure. These are the first experimental findings aimed to provide a comparative thermo-elastic analysis of the CAN-group compounds, expanding the knowledge about the P/T-behavior of isotypic materials with open-framework structures

Spike-in SILAC proteomic approach reveals the vitronectin as an early molecular signature of liver fibrosis in hepatitis C infections with hepatic iron overload

Hepatitis C virus (HCV)-induced iron overload has been shown to promote liver fibrosis, steatosis, and hepatocellular carcinoma. The zonal-restricted histological distribution of pathological iron deposits has hampered the attempt to perform large-scale in vivo molecular investigations on the comorbidity between iron and HCV. Diagnostic and prognostic markers are not yet available to assess iron overload-induced liver fibrogenesis and progression in HCV infections. Here, by means of Spike-in SILAC proteomic approach, we first unveiled a specific membrane protein expression signature of HCV cell cultures in the presence of iron overload. Computational analysis of proteomic dataset highlighted the hepatocytic vitronectin expression as the most promising specific biomarker for iron-associated fibrogenesis in HCV infections. Next, the robustness of our in vitro findings was challenged in human liver biopsies by immunohistochemistry and yielded two major results: (i) hepatocytic vitronectin expression is associated to liver fibrogenesis in HCV-infected patients with iron overload; (ii) hepatic vitronectin expression was found to discriminate also the transition between mild to moderate fibrosis in HCV-infected patients without iron overload. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim