Chemical diffusion of fluorine in melts in the system Na2OAl2O3SiO2

The volatilization of fluorine from three melts in the system Na2OAl2O3SiO2 has been investigated at 1 atm pressure and 1200–1400°C. The melts chosen have base compositions corresponding to albite, jadeite and a peraluminous melt with 75 mole % SiO2. Melt spheres were suspended from platinum loops in a vertical tube furnace in a flow of oxygen gas, then quenched, sectioned and analysed by electron microprobe. The microprobe scans indicate that transport of fluorine to the melt-vapor interface is by binary, concentration-independent interdiffusion of fluorine and oxygen. FO interdiffusivity increases in the order albite < peraluminous < jadeite. There is no simple reciprocal relationship between FO interdiffusivity and melt viscosity. Comparison with data on high-pressure interdiffusivity of fluorine and oxygen in jadeite melt indicates that FO interdiffusivity increases with pressure from 0.001 to 10 kbar while the activation energy remains unchanged. Fluorine chemical diffusivity in albite melt is substantially lower than H2O chemical diffusivity in obsidian melts suggesting that different diffusive mechanisms are responsible for the transport of F and H2O in igneous melts. Fluorine diffuses in albite melt via an anionic exchange with oxygen whereas water probably diffuses in obsidian melt via an alkali exchange mechanism

PocketMatch: A new algorithm to compare binding sites in protein structures

Background: Recognizing similarities and deriving relationships among protein molecules is a fundamental&#xd;&#xa;requirement in present-day biology. Similarities can be present at various levels which can be detected through comparison of protein sequences or their structural folds. In some cases similarities obscure at these levels could be present merely in the substructures at their binding sites. Inferring functional similarities between protein molecules by comparing their binding sites is still largely exploratory and not as yet a routine protocol. One of&#xd;&#xa;the main reasons for this is the limitation in the choice of appropriate analytical tools that can compare binding sites with high sensitivity. To benefit from the enormous amount of structural data that is being rapidly accumulated, it is essential to have high throughput tools that enable large scale binding site comparison.&#xd;&#xa;&#xd;&#xa;Results: Here we present a new algorithm PocketMatch for comparison of binding sites in a frame invariant&#xd;&#xa;manner. Each binding site is represented by 90 lists of sorted distances capturing shape and chemical nature of the site. The sorted arrays are then aligned using an incremental alignment method and scored to obtain PMScores for pairs of sites. A comprehensive sensitivity analysis and an extensive validation of the algorithm have been carried out. Perturbation studies where the geometry of a given site was retained but the residue types were changed randomly, indicated that chance similarities were virtually non-existent. Our analysis also demonstrates that shape information alone is insufficient to discriminate between diverse binding sites, unless&#xd;&#xa;combined with chemical nature of amino acids.&#xd;&#xa;&#xd;&#xa;Conclusions: A new algorithm has been developed to compare binding sites in accurate, efficient and&#xd;&#xa;high-throughput manner. Though the representation used is conceptually simplistic, we demonstrate that along&#xd;&#xa;with the new alignment strategy used, it is sufficient to enable binding comparison with high sensitivity. Novel methodology has also been presented for validating the algorithm for accuracy and sensitivity with respect to geometry and chemical nature of the site. The method is also fast and takes about 1/250th second for one comparison on a single processor. A parallel version on BlueGene has also been implemented

Lavoisier: A Low Altitude Balloon Network for Probing the Deep Atmosphere and Surface of Venus

The in-situ exploration of the low atmosphere and surface of Venus is clearly the next step of Venus exploration. Understanding the geochemistry of the low atmosphere, interacting with rocks, and the way the integrated Venus system evolved, under the combined effects of inner planet cooling and intense atmospheric greenhouse, is a major challenge of modern planetology. Due to the dense atmosphere (95 bars at the surface), balloon platforms offer an interesting means to transport and land in-situ measurement instruments. Due to the large Archimede force, a 2 cubic meter He-pressurized balloon floating at 10 km altitude may carry up to 60 kg of payload. LAVOISIER is a project submitted to ESA in 2000, in the follow up and spirit of the balloon deployed at cloud level by the Russian Vega mission in 1986. It is composed of a descent probe, for detailed noble gas and atmosphere composition analysis, and of a network of 3 balloons for geochemical and geophysical investigations at local, regional and global scales

Laboratory measurements of electrical conductivities of hydrous and dry Mt. Vesuvius melts under pressure

International audienceQuantitative interpretation of MT anomalies in volcanic regions requires laboratory measurements of electrical conductivities of natural magma compositions. The electrical conductivities of three lava compositions from Mt. Vesuvius (Italy) have been measured using an impedance spectrometer. Experiments were conducted on both glasses and melts between 400 and 1300°C, and both at ambient pressure in air and at high pressures (up to 400 MPa). Both dry and hydrous (up to 5.6 wt% H2O) melt compositions were investigated. A change of the conduction mechanism corresponding to the glass transition was systematically observed. The conductivity data were fitted by sample-specific Arrhenius laws on either side of Tg. The electrical conductivity increases with temperature and is higher in the order tephrite, phonotephrite to phonolite. For the three compositions investigated, increasing pressure decreases the conductivity, although the effect of pressure is relatively small. The three compositions investigated have similar activation volumes (ΔV=16-24 cm3/mol). Increasing the water content of the melt increases the conductivity. Comparison of activation energies (Ea) from conductivity and sodium diffusion, and use of the Nernst-Einstein relation allow sodium to be identified as the main charge carrier in our melts and presumably also in the corresponding glasses. Our data and those of previous studies highlight the correlation between the Arrhenius parameters Ea and σ0. A semi-empirical method allowing the determination of the electrical conductivity of natural magmatic liquids is proposed, in which the activation energy is modelled on the basis of the Anderson-Stuart model, σ0 being obtained from the compensation law and ΔV fitted from our experimental data. The model enables the electrical conductivity to be calculated for the entire range of melt compositions at Mt. Vesuvius and also predicts satisfactorily the electrical response of other melt compositions. Electrical conductivity data for Mt. Vesuvius melts and magmas are slightly lower than the electrical anomaly revealed by MT studies

Catalytic residues in hydrolases: analysis of methods designed for ligand-binding site prediction

The comparison of eight tools applicable to ligand-binding site prediction is presented. The methods examined cover three types of approaches: the geometrical (CASTp, PASS, Pocket-Finder), the physicochemical (Q-SiteFinder, FOD) and the knowledge-based (ConSurf, SuMo, WebFEATURE). The accuracy of predictions was measured in reference to the catalytic residues documented in the Catalytic Site Atlas. The test was performed on a set comprising selected chains of hydrolases. The results were analysed with regard to size, polarity, secondary structure, accessible solvent area of predicted sites as well as parameters commonly used in machine learning (F-measure, MCC). The relative accuracies of predictions are presented in the ROC space, allowing determination of the optimal methods by means of the ROC convex hull. Additionally the minimum expected cost analysis was performed. Both advantages and disadvantages of the eight methods are presented. Characterization of protein chains in respect to the level of difficulty in the active site prediction is introduced. The main reasons for failures are discussed. Overall, the best performance offers SuMo followed by FOD, while Pocket-Finder is the best method among the geometrical approaches

Determinants of Unlawful File Sharing: A Scoping Review

We employ a scoping review methodology to consider and assess the existing evidence on the determinants of unlawful file sharing (UFS) transparently and systematically. Based on the evidence, we build a simple conceptual framework to model the psychological decision to engage in UFS, purchase legally or do nothing. We identify social, moral, experiential, technical, legal and financial utility sources of the decision to purchase or to file share. They interact in complex ways. We consider the strength of evidence within these areas and note patterns of results. There is good evidence for influences on UFS within each of the identified determinants, particularly for self-reported measures, with more behavioral research needed. There are also indications that the reasons for UFS differ across media; more studies exploring media other than music are required

Variations of Li and Mg isotope ratios in bulk chondrites and mantle xenoliths

Author Posting. © The Author(s), 2011. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 75 (2011): 5247-5268, doi:10.1016/j.gca.2011.06.026.We present whole rock Li and Mg isotope analyses of 33 ultramafic xenoliths from the terrestrial mantle, which we compare with analyses of 30 (mostly chondritic) meteorites. The accuracy of our new Mg isotope ratio measurement protocol is substantiated by a combination of standard addition experiments, the absence of mass independent effects in terrestrial samples and our obtaining identical values for rock standards using 2 different separation chemistries and 3 different mass-spectrometric introduction systems. Carbonaceous, ordinary and enstatite chondrites have irresolvable mean stable Mg isotopic compositions (δ25Mg = -0.14 ± 0.06; δ26Mg = - 0.27 ± 0.12‰, 2sd), but our enstatite chondrite samples have lighter δ7Li (by up to ~3‰) than our mean carbonaceous and ordinary chondrites (3.0 ± 1.5‰, 2sd), possibly as a result of spallation in the early solar system. Measurements of equilibrated, fertile peridotites give mean values of δ7Li = 3.5 ± 0.5‰, δ25Mg = -0.10 ± 0.03‰ and δ26Mg = -0.21 ± 0.07‰. We believe these values provide a useful estimate of the primitive mantle and they are within error of our average of bulk carbonaceous and ordinary chondrites. A fuller range of fresh, terrestrial, ultramafic samples, covering a variety of geological histories, show a broad positive correlation between bulk δ7Li and δ26Mg, which vary from -3.7 to +14.5‰, and -0.36 to +0.06‰, respectively. Values of δ7Li and δ26Mg lower than our estimate of primitive mantle are strongly linked to kinetic isotope fractionation, occurring during transport of the mantle xenoliths. We suggest Mg and Li diffusion into the xenoliths is coupled to H loss from nominally anhydrous minerals following degassing. Diffusion models suggest that the co-variation of Mg and Li isotopes requires comparable diffusivities of Li and Mg in olivine. The isotopically lightest samples require ~5-10 years of diffusive ingress, which we interpret as a time since volatile loss in the host magma. Xenoliths erupted in pyroclastic flows appear to have retained their mantle isotope ratios, likely as a result of little prior degassing in these explosive events. High δ7Li, coupled with high [Li], in rapidly cooled arc peridotites may indicate that these samples represent fragments of mantle wedge that has been metasomatised by heavy, slab-derived fluids. If such material is typically stirred back into the convecting mantle, it may account for the heavy δ7Li seen in some oceanic basalts.PPvS was supported by NERC grant NER/C510983/

The lithophile trace elements in enstatite chondrites

International audienceWe report on the abundances of a selected set of lithophile trace elements (namely REEs, Y, Rb, Ba, Sr, Zr, Hf, Nb, Th, U) in a comprehensive suite of enstatite chondrites (EC - 13 EH and 11 EL). EH3 and EL3 display only minor deviations from chondritic distributions for these elements. In most metamorphosed EC, a wide range of compositions is observed and suggests a mobility of many of the elements studied during the history of these rocks. For example, EL6 chondrites exhibit light-REE and Nb depletions, negative Eu anomalies, and positive Y anomalies. More important trace element fractionations are observed in metamorphosed EH like St Marks (Rb depletion), LAP 02225 (Rb, Nb, Zr, Eu, light REE depletions) and Galim (b), which displays large Ba, Sr, Eu, Nb and light REE depletions. Leaching experiments were undertaken to investigate the contributions of sulfides in the whole rock budgets. These phases control not only the REE budget, but also important fractions of the other elements we studied. These fractions strongly depend on the type of the rock (EH or EL, and metamorphic grade). For many elements, the sulfide contributions increase with the metamorphic grades. The trace element abundances of silicate residues are extremely variable. Negative Sm and Yb anomalies are observed in EL3 and EH3 residues, and are certainly the results of early nebular processes. Such anomalies are lacking in residues obtained with most metamorphosed EC, underlining the importance of trace element redistributions during metamorphism. In addition, EL6 residues display distinctive positive Y anomalies that could be potentially ascribed to a less chalcophile behavior than Ho in the conditions that prevailed during EL metamorphism