Chemical Evolution of Calc-alkaline Magmas during the Ascent through Continental Crust: Constraints from Methana, Aegean Arc

M1 - egaa036Quaternary calc-alkaline andesitic to dacitic lavas effusively erupted on top of about 30 km thick accreted continental crust at Methana peninsula in the western Aegean arc. We present new data of major and trace element concentrations as well as of Sr-Nd-Pb isotope ratios along with mineral compositions of Methana lavas and their mafic enclaves. The enclaves imply a parental basaltic magma and fractional crystallization processes with relatively little crustal assimilation in the deep part of the Methana magma system. The composition of amphibole in some mafic enclaves and lavas indicates deeper crystallization at similar to 25km depth close to the Moho compared with the evolved lavas that formed atPeer reviewe

Effects of the Hydrous Domain in the Mantle Wedge on Magma Formation and Mixing at the Northeast Lau Spreading Center, SW Pacific

Abundant volcanic activity occurs in the back-arc region of the northern Tofua island arc where the Northeast Lau Spreading Center (NELSC) propagates southwards into older crust causing the formation of numerous seamounts at the propagating rift tip. An off-axis volcanic diagonal ridge (DR) occurs at the eastern flank of the NELSC, linking the large rear-arc volcano Niuatahi with the NELSC. New geochemical data from the NELSC, the southern propagator seamounts, and DR reveal that the NELSC lavas are tholeiitic basalts whereas the rear-arc volcanoes typically erupt lavas with boninitic composition. The sharp geochemical boundary probably reflects the viscosity contrast between off-axis hydrous harzburgitic mantle and dry fertile mantle beneath the NELSC. The new data do not indicate an inflow of Samoa plume mantle into the NELSC, confirming previously published He isotope data. The NELSC magmas form by mixing of an enriched and a depleted Indian Ocean-type upper mantle end-member implying a highly heterogeneous upper mantle composition in this area. Most NELSC lavas are little affected by a slab component implying that melting is adiabatic beneath the spreading center. The DR lavas show the influence of a component from the subducted Louisville Seamount Chain, which was previously thought to be restricted to the nearby arc volcanoes Niuatoputapu and Tafahi. This signature is rarely detected along the NELSC implying little mixing of melts from the low-viscosity hydrous portion of the mantle wedge beneath the rear-arc volcanoes into the melting region of the dry mantle beneath the NELSC.Peer reviewe

Protein Glycosylation in Helicobacter pylori: Beyond the Flagellins?

Glycosylation of flagellins by pseudaminic acid is required for virulence in Helicobacter pylori. We demonstrate that, in H. pylori, glycosylation extends to proteins other than flagellins and to sugars other than pseudaminic acid. Several candidate glycoproteins distinct from the flagellins were detected via ProQ-emerald staining and DIG- or biotin- hydrazide labeling of the soluble and outer membrane fractions of wild-type H. pylori, suggesting that protein glycosylation is not limited to the flagellins. DIG-hydrazide labeling of proteins from pseudaminic acid biosynthesis pathway mutants showed that the glycosylation of some glycoproteins is not dependent on the pseudaminic acid glycosylation pathway, indicating the existence of a novel glycosylation pathway. Fractions enriched in glycoprotein candidates by ion exchange chromatography were used to extract the sugars by acid hydrolysis. High performance anion exchange chromatography with pulsed amperometric detection revealed characteristic monosaccharide peaks in these extracts. The monosaccharides were then identified by LC-ESI-MS/MS. The spectra are consistent with sugars such as 5,7-diacetamido-3,5,7,9-tetradeoxy-L-glycero-L-manno-nonulosonic acid (Pse5Ac7Ac) previously described on flagellins, 5-acetamidino-7-acetamido-3,5,7,9-tetradeoxy-L-glycero-L-manno-nonulosonic acid (Pse5Am7Ac), bacillosamine derivatives and a potential legionaminic acid derivative (Leg5AmNMe7Ac) which were not previously identified in H. pylori. These data open the way to the study of the mechanism and role of protein glycosylation on protein function and virulence in H. pylori

Effects of the Hydrous Domain in the Mantle Wedge on Magma Formation and Mixing at the Northeast Lau Spreading Center, SW Pacific

Abundant volcanic activity occurs in the back‐arc region of the northern Tofua island arc where the Northeast Lau Spreading Center (NELSC) propagates southwards into older crust causing the formation of numerous seamounts at the propagating rift tip. An off‐axis volcanic diagonal ridge (DR) occurs at the eastern flank of the NELSC, linking the large rear‐arc volcano Niuatahi with the NELSC. New geochemical data from the NELSC, the southern propagator seamounts, and DR reveal that the NELSC lavas are tholeiitic basalts whereas the rear‐arc volcanoes typically erupt lavas with boninitic composition. The sharp geochemical boundary probably reflects the viscosity contrast between off‐axis hydrous harzburgitic mantle and dry fertile mantle beneath the NELSC. The new data do not indicate an inflow of Samoa plume mantle into the NELSC, confirming previously published He isotope data. The NELSC magmas form by mixing of an enriched and a depleted Indian Ocean‐type upper mantle end‐member implying a highly heterogeneous upper mantle composition in this area. Most NELSC lavas are little affected by a slab component implying that melting is adiabatic beneath the spreading center. The DR lavas show the influence of a component from the subducted Louisville Seamount Chain, which was previously thought to be restricted to the nearby arc volcanoes Niuatoputapu and Tafahi. This signature is rarely detected along the NELSC implying little mixing of melts from the low‐viscosity hydrous portion of the mantle wedge beneath the rear‐arc volcanoes into the melting region of the dry mantle beneath the NELSC.Plain Language Summary: Volcanic activity is abundant at subduction zones and the chemical analysis of the erupted rocks allows to determine the material transport in the Earth's mantle. The Northeast Lau Spreading Center (NELSC) forms by extension and volcanism behind the northern Tofua island arc. Several large volcanic structures occur east of the NELSC and the lavas of these off‐axis volcanoes are chemically and isotopically distinct implying little mixing with the magmas of the NELSC. The differences suggest decompression melting of relatively dry mantle beneath the NELSC whereas the off‐axis volcanoes reflect melting of water‐rich mantle affected by fluids from the subducting Pacific Plate. The sharp geochemical boundary between the NELSC and off‐axis volcanoes is probably due to a large viscosity contrast between hydrous harzburgitic mantle and dry fertile mantle. Element and isotope ratios indicate that the NELSC magmas form by mixing of enriched and depleted portions of the upper mantle, and we do not find evidence for inflow of the Samoa deep mantle plume from the north. Some of the off‐axis lavas contain a component from a volcanic chain that was subducted some 4 million years ago and that was previously only known in two volcanoes of the Tofua island arc.Key Points: Variably enriched mantle sources melt beneath the Northeast Lau Spreading Center (NELSC) but there is no evidence for Samoa mantle plume inflow. Relatively dry fertile mantle beneath NELSC causes sharp geochemical boundary with hydrous harzburgitic North Tonga mantle wedge. Subducted Louisville Seamount Chain material affects rear‐arc volcanism.Bundesministerium für Bildung und Forschung (BMBF) http://dx.doi.org/10.13039/501100002347Deutsche Forschungsgemeinschaft (DFG) http://dx.doi.org/10.13039/50110000165

Effects of the hydrous domain in the mantle wedge on magma formation and mixing at the Northeast Lau Spreading Centre, SW Pacific

Major and trace element concentrations of young volcanic rocks from the Northeast Lau Basin in the SW Pacific Ocean, as well as Sr-Nd-Hf-Pb isotope compositions. Analyses were mainly carried out at the GeoZentrum Nordbayern, University of Erlangen, Germany, where major elements were determined by electrons microprobe on volcanic glasses and by XRF on whole rocks. Trace elements were analyzed by LA ICPMS on glass at the Macquarie University, Sydney, Australia, and by dissolution ICPMS at the GeoZentrum Nordbayern. Water concentrations on glasses were analyzed by SIMS at the Australian National University, Canberra, Australia. Isotope ratios were determined by TIMS and MC ICPMS at the GeoZentrum Nordbayern

Structural and functional characterization of PseC, an aminotransferase involved in the biosynthesis of pseudaminic acid, an essential flagellar modification in Helicobacter pylori

Helicobacter pylori flagellin is heavily glycosylated with the novel sialic acid-like nonulosonate, pseudaminic acid (Pse). The glycosylation process is essential for assembly of functional flagellar filaments and consequent bacterial motility. Because motility is a key virulence factor for this and other important pathogens, the Pse biosynthetic pathway offers potential for novel therapeutic targets. From recent NMR analyses, we determined that the conversion of UDP-alpha-d-Glc-NAc to the central intermediate in the pathway, UDP-4-amino-4,6-dideoxy-beta-l-AltNAc, proceeds by formation of UDP-2-acetamido -2,6-dideoxy-beta-l-arabino-4-hexulose by the dehydratase/epimerase PseB (HP0840) followed with amino transfer by the aminotransferase, PseC (HP0366). The central role of PseC in the H. pylori Pse biosynthetic pathway prompted us to determine crystal structures of the native protein, its complexes with pyridoxal phosphate alone and in combination with the UDP-4-amino-4,6-dideoxy -beta-l-AltNAc product, the latter being converted to the external aldimine form in the active site of the enzyme. In the binding site, the AltNAc sugar ring adopts a (4)C(1) chair conformation, which is different from the predominant (1)C(4) form found in solution. The enzyme forms a homodimer where each monomer contributes to the active site, and these structures have permitted the identification of key residues involved in stabilization, and possibly catalysis, of the beta-l-arabino intermediate during the amino transfer reaction. The essential role of Lys(183) in the catalytic event was confirmed by site-directed mutagenesis. This work presents for the first time a nucleotide-sugar aminotransferase co-crystallized with its natural ligand, and, in conjunction with the recent functional characterization of this enzyme, these results will assist in elucidating the aminotransferase reaction mechanism within the Pse biosynthetic pathwayNRC publication: Ye

O pantanal como fonte ou sumidouro de vapor d'agua e calor sensivel

O objetivo deste trabalho é avaliar e quantificar quando o Pantanal age como fonte ou sumidouro de vapor d’água e calor sensível, através da análise dos fluxos de superfície. Para isto, foram usados os dados coletados durante o experimento IPE (Experimento Interdisciplinar do Pantanal) da época seca (IPE 2) e da época inundada (IPE 3). Para as estimativas dos fluxos de calor latente e sensível foi aplicado o método de Penman-Monteith. Considerando o sítio experimental representativo de toda a área do Pantanal, os resultados de fluxo de calor latente foram comparados com os dados de precipitação. Isto mostrou que a região do Pantanal é uma fonte fraca de vapor d’água na estação seca e um forte sumidouro na estação úmida. Uma explicação para a diferença entre a precipitação e os fluxos de calor latente é a atuação de fontes externas de umidade, principalmente a Amazônia. Desta forma, também foi analisada heuristicamente a influência do Jato de Baixos Níveis na convergência de umidade sobre o Pantanal

Elucidating the Formation of 6-Deoxyheptose: Biochemical Characterization of the GDP-d-glycero-d-manno-heptose C6 Dehydratase, DmhA, and Its Associated C4 Reductase, DmhB

6-Deoxyheptose is found within the surface polysaccharides of several bacterial pathogens. In Yersinia pseudotuberculosis, it is important for the barrier function of the O-antigen in vitro and for bacterial dissemination in vivo. The putative C6 dehydratase DmhA and C4 reductase DmhB, that were identified as responsible for 6-deoxyheptose synthesis based on genetics data, represent potential therapeutical targets. Their detailed biochemical characterization is presented herein. The substrate, GDP-D-glycero-D-manno-heptose, was synthesized enzymatically from sedoheptulose 7-phosphate using overexpressed and purified GmhA/B/C/D enzymes from Aneurinibacillus thermoaerophilus. Overexpressed and purified DmhA used this substrate with high efficiency, as indicated by its K(m) of 0.23 mM and k(cat) of 1.1 s(-1). The mass spectrometry (MS) analysis of the reaction product was consistent with a C6 dehydration reaction. DmhB could readily reduce this compound in the presence of NAD(P)H to produce GDP-6-deoxy-D-manno-heptose, as indicated by MS and NMR analyses. DmhA also used GDP-mannose as a substrate with a K(m) of 0.32 mM and a k(cat) of 0.25 min(-1). This kinetic analysis indicates that although the K(m) values for GDP-mannose and GDP-manno-heptose were similar, the genuine substrate for DmhA is GDP-manno-heptose. DmhB was also able to reduce the GDP-4-keto-6-deoxymannose produced by DmhA, although with poor efficiency and exclusively in the presence of NADPH. This study is the first complete biochemical characterization of the 6-deoxyheptose biosynthesis pathway. Also, it allows the screening for inhibitors, the elucidation of substrate specificity determinants, and the synthesis of carbohydrate antigens of therapeutic relevance