X-ray Absorption Linear Dichroism at the Ti K-edge of TiO2 anatase single crystal

Anatase TiO2 (a-TiO2) exhibits a strong X-ray absorption linear dichroism with the X-ray incidence angle in the pre-edge, the XANES and the EXAFS at the titanium K-edge. In the pre-edge region the behaviour of the A1-A3 and B peaks, originating from the 1s-3d transitions, is due to the strong $p$-orbital polarization and strong $p-d$ orbital mixing. An unambiguous assignment of the pre-edge peak transitions is made in the monoelectronic approximation with the support of ab initio finite difference method calculations and spherical tensor analysis in quantitative agreement with the experiment. It is found that A1 is mostly an on-site 3d-4p hybridized transition, while peaks A3 and B are non-local transitions, with A3 being mostly dipolar and influence by the 3d-4p intersite hybridization, while B is due to interactions at longer range. Finally, peak A2 which was previously assigned to a transition involving pentacoordinated titanium atoms exhibits a quadrupolar angular evolution with incidence angle. These results pave the way to the use of the pre-edge peaks at the K-edge of a-TiO2 to characterize the electronic structure of related materials and in the field of ultrafast XAS where the linear dichroism can be used to compare the photophysics along different axes.Comment: 43 pages, 19 figure

Integrated Fe- and S-isotope study of seafloor hydrothermal vents at East Pacific Rise 9–10°N

Author Posting. © Elsevier B.V., 2008. 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 Chemical Geology 252 (2008): 214-227, doi:10.1016/j.chemgeo.2008.03.009.In this study, we report on coupled Fe- and S-isotope systematics of hydrothermal fluids and sulfide deposits from the East Pacific Rise at 9-10°N to better constrain processes affecting Fe- isotope fractionation in hydrothermal environments. We aim to address three fundamental questions: (1) is there significant Fe isotope fractionation during sulfide precipitation? (2) Is there significant variability of Fe-isotope composition of the hydrothermal fluids reflecting sulfide precipitation in subsurface environments? (3) Are there any systematics between Fe- and S- isotopes in sulfide minerals? The results show that chalcopyrite, precipitating in the interior wall of a hydrothermal chimney displays a limited range of δ56Fe values and δ34S values, between –0.11 to –0.33‰ and 2.2 to 2.6‰ respectively. The δ56Fe values are, on average, slightly higher by 0.14‰ relative to coeval vent fluid composition while δ34S values suggest significant S-isotope fractionation (-0.6±0.2‰) during chalcopyrite precipitation. In contrast, systematically lower δ56Fe and δ34S values relative to hydrothermal fluids, by up to 0.91‰ and 2.0‰ respectively, are observed in pyrite and marcasite precipitating in the interior of active chimneys. These results suggest isotope disequilibrium in both Fe- and S-isotopes due to S-isotopic exchange between hydrothermal H2S and seawater SO42- followed by rapid formation of pyrite from FeS precursors, thus preserving the effects of a strong kinetic Fe-isotope fractionation during FeS precipitation. In contrast, δ56Fe and δ34S values of pyrite from inactive massive sulfides, which show evidence of extensive late-stage reworking, are essentially similar to the hydrothermal fluids. Multiple stages of remineralization of ancient chimney deposits at the seafloor appear to produce minimal Fe-isotope fractionation. Similar affects are indicated during subsurface sulfide precipitation as demonstrated by the lack of systematic differences between δ56Fe values in both high-temperature, Fe-rich black smokers and lower temperature, Fe-depleted vents.Support for W. Bach and K. Edwards was provided by NSF grant OCE-0241791 and support for O. Rouxel was provided by funding from the WHOI Deep Ocean Exploration Institute and NSF grant OCE-0622982 and OCE-0647948

Prevalence and characterization of Salmonella and Listeria monocytogenes in french raw pork meat at the distribution level

This study was undertaken in 2010 to estimate the occurrence of Listeria monocytogenes in raw pork meat at the distribution level in France

Glacial influence on the geochemistry of riverine iron fluxes to the Gulf of Alaska and effects of deglaciation

This paper is not subject to U.S. copyright. The definitive version was published in Geophysical Research Letters 38 (2011): L16605, doi:10.1029/2011GL048367.Riverine iron (Fe) derived from glacial weathering is a critical micronutrient source to ecosystems of the Gulf of Alaska (GoA). Here we demonstrate that the source and chemical nature of riverine Fe input to the GoA could change dramatically due to the widespread watershed deglaciation that is underway. We examine Fe size partitioning, speciation, and isotopic composition in tributaries of the Copper River which exemplify a long-term GoA watershed evolution from one strongly influenced by glacial weathering to a boreal-forested watershed. Iron fluxes from glacierized tributaries bear high suspended sediment and colloidal Fe loads of mixed valence silicate species, with low concentrations of dissolved Fe and dissolved organic carbon (DOC). Iron isotopic composition is indicative of mechanical weathering as the Fe source. Conversely, Fe fluxes from boreal-forested systems have higher dissolved Fe concentrations corresponding to higher DOC concentrations. Iron colloids and suspended sediment consist of Fe (hydr)oxides and organic complexes. These watersheds have an iron isotopic composition indicative of an internal chemical processing source. We predict that as the GoA watershed evolves due to deglaciation, so will the source, flux, and chemical nature of riverine Fe loads, which could have significant ramifications for Alaskan marine and freshwater ecosystems.We appreciate support from the USGS CMGP, NCCWSC, and the Mendenhall Postdoctoral Program

Time-series analysis of two hydrothermal plumes at 9°50′N East Pacific Rise reveals distinct, heterogeneous bacterial populations

Author Posting. © The Author(s), 2011. This is the author's version of the work. It is posted here by permission of John Wiley & Sons for personal use, not for redistribution. The definitive version was published in Geobiology 10 (2012): 178-192, doi:10.1111/j.1472-4669.2011.00315.xWe deployed sediment traps adjacent to two active hydrothermal vents at 9°50’N on the East Pacific Rise (EPR) to assess variability in bacterial community structure associated with plume particles on the time scale of weeks to months, to determine if an endemic population of plume microbes exists, and to establish ecological relationships between bacterial populations and vent chemistry. Automated rRNA intergenic spacer analysis (ARISA) indicated there are separate communities at the two different vents and temporal community variations between each vent. Correlation analysis between chemistry and microbiology indicated that shifts in the coarse particulate (>1 mm) Fe/(Fe+Mn+Al), Cu, V, Ca, Al, 232Th, and Ti as well as fine-grained particulate (<1 mm) Fe/(Fe+Mn+Al), Fe, Ca and Co are reflected in shifts in microbial populations. 16S rRNA clone libraries from each trap at three time points revealed a high percentage of Epsilonproteobacteria clones and hyperthermophilic Aquificae. There is a shift towards the end of the experiment to more Gammaproteobacteria and Alphaproteobacteria, many of whom likely participate in Fe and S cycling. The particle attached plume environment is genetically distinct from the surrounding seawater. While work to date in hydrothermal environments has focused on determining the microbial communities on hydrothermal chimneys and the basaltic lavas that form the surrounding seafloor, little comparable data exists on the plume environment that physically and chemically connects them. By employing sediment traps for a time series approach to sampling, we show that bacterial community composition on plume particles changes on time scales much shorter than previously known.This work was supported by the NSF Marine Geology and Geophysics program, the Science and Technology program, and the Gordon and Betty Moore Foundation

The neighbouring genes <i>AvrLm10A</i> and <i>AvrLm10B</i> are part of a large multigene family of cooperating effector genes conserved in Dothideomycetes and Sordariomycetes

Fungal effectors (small-secreted proteins) have long been considered as species or even subpopulation-specific. The increasing availability of high-quality fungal genomes and annotations has allowed the identification of trans-species or trans-genera families of effectors. Two avirulence effectors, AvrLm10A and AvrLm10B, of Leptosphaeria maculans, the fungus causing stem canker of oilseed rape, are members of such a large family of effectors. AvrLm10A and AvrLm10B are neighbouring genes, organized in divergent transcriptional orientation. Sequence searches within the L. maculans genome showed that AvrLm10A/AvrLm10B belong to a multigene family comprising five pairs of genes with a similar tail-to-tail organization. The two genes, in a pair, always had the same expression pattern and two expression profiles were distinguished, associated with the biotrophic colonization of cotyledons and/or petioles and stems. Of the two protein pairs further investigated, AvrLm10A_like1/AvrLm10B_like1 and AvrLm10A_like2/AvrLm10B_like2, the second one had the ability to physically interact, similarly to what was previously described for the AvrLm10A/AvrLm10B pair, and cross-interactions were also detected for two pairs. AvrLm10A homologues were identified in more than 30 Dothideomycete and Sordariomycete plant-pathogenic fungi. One of them, SIX5, is an effector from Fusarium oxysporum f. sp. lycopersici physically interacting with the avirulence effector Avr2. We found that AvrLm10A/SIX5 homologues were associated with at least eight distinct putative effector families, suggesting that AvrLm10A/SIX5 is able to cooperate with different effectors. These results point to a general role of the AvrLm10A/SIX5 proteins as “cooperating proteins”, able to interact with diverse families of effectors whose encoding gene is co-regulated with the neighbouring AvrLm10A homologue

A factorization of a super-conformal map

A super-conformal map and a minimal surface are factored into a product of two maps by modeling the Euclidean four-space and the complex Euclidean plane on the set of all quaternions. One of these two maps is a holomorphic map or a meromorphic map. These conformal maps adopt properties of a holomorphic function or a meromorphic function. Analogs of the Liouville theorem, the Schwarz lemma, the Schwarz-Pick theorem, the Weierstrass factorization theorem, the Abel-Jacobi theorem, and a relation between zeros of a minimal surface and branch points of a super-conformal map are obtained.Comment: 21 page