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

Overlapping redox zones control arsenic pollution in Pleistocene multi-layer aquifers, the Po Plain (Italy)

Understanding the factors that control As concentrations in groundwater is vital for supplying safe groundwater in regions with As-polluted aquifers. Despite much research, mainly addressing Holocene aquifers hosting young (12,000 yrs) groundwaters are not yet fully understood and so are assessed here through an evaluation of the redox properties of the system in a type locality, the Po Plain (Italy). Analyses of redox-sensitive species and major ions on 22 groundwater samples from the Pleistocene arsenic-affected aquifer in the Po Plain shows that groundwater concentrations of As are controlled by the simultaneous operation of several terminal electron accepters. Organic matter, present as peat, is abundant in the aquifer, allowing groundwater to reach a quasi-steady-state of highly reducing conditions close to thermodynamic equilibrium. In this system, simultaneous reduction of Fe-oxide and sulfate results in low concentrations of As (median 7 μg/L) whereas As reaches higher concentrations (median of 82 μg/L) during simultaneous methanogenesis and Fe-reduction. The position of well-screens is an additional controlling factor on groundwater As: short screens that overlap confining aquitards generate higher As concentrations than long screens placed away from them. A conceptual model for groundwater As, applicable worldwide in other Pleistocene aquifers with reducible Fe-oxides and abundant organic matter is proposed: As may have two concentration peaks, the first after prolonged Fe-oxide reduction and until sulfate reduction takes place, the second during simultaneous Fe-reduction and methanogenesis

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

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. \uc2\ua9 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Local distortion and octahedral tilting in BaCexTi1−xO3perovskite

Ceramics with perovskite structure and composition BaCexTi1 12xO3(x = 0.02\u20130.30) show a progressive evolution with increasing x, from the long-range polar order of ferroelectric BaTiO3to the short-range polar order typical of relaxors. The ionic size mismatch between Ti4+and Ce4+determines strong local strains which have a significant impact on dielectric properties and phase transitions. The pair distribution function, coupled with transmission electron microscopy analysis, was applied to study the local structure. Because of the inner B-cation sizes, the superposition of rigid B\u2014O octahedra with different volumes is not compatible with the construction of an ideal perovskite structure. In this light, local structure can be described by an original model which allows (i) different Ti\u2014O and Ce\u2014O distances and (ii) the typical distortions of the two end members: off-center displacement of Ti occurring in BaTiO3and octahedral tilt in BaCeO3. The results show a clear difference, in terms of volumes, between oxygen octahedra with titanium and those related to cerium. In addition, the inclusion of cerium causes a tilt of its oxygen cage, as occurs in pure BaCeO3, creating contra-rotations and distortions of the octahedra containing titanium. This complex arrangement entails a substantial distortion, increasing as a function of cerium amount, which strongly influences the directions of titanium displacements, their local correlation and consequently their long-range cooperative effects

The effects of irrigation on groundwater quality and quantity in a human-modified hydro-system: The Oglio River basin, Po Plain, northern Italy

For several hundred years, farming in the Po Plain of Italy (46,000 km2, 20 million inhabitants) has been supported by intensive surface irrigation with lake and river water. Despite the longevity of irrigation, its effects on the quality and quantity of groundwater is poorly known and so is investigated here through seasonal measurements of hydraulic heads and water quality in groundwaters, rivers, lake, springs and rainwaters. In the north of the study region, an unconfined coarse-grained alluvial aquifer, infiltration of surface irrigation water, sourced from the Oglio River and low in NO3, contributes much to aquifer recharge (up to 88%, as evidenced by a δ2H-Cl/Br mixing model) and has positive effects on groundwater quality by diluting high concentrations of NO3 (decrease by 17% between June and September). This recharge also helps to maintain numerous local springs that form important local micro-environments. Any increase in water-use efficiency in irrigation will reduce this recharge, imperil the spring environments, and lessen the dilution of NO3 leading to increasing NO3 concentrations in groundwater. These findings can be extended by analogy to the entire Po Plain region and other surface-water-irrigated systems worldwide where inefficient irrigation methods are used and similar hydrogeological features occur

Erratum to: Allergen immunotherapy for allergic rhinoconjunctivitis: protocol for a systematic review.

[This corrects the article DOI: 10.1186/s13601-016-0099-6.]