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Although the iron uptake and storage mechanisms of terrestrial/higher plants have been well studied, the corresponding systems in marine algae have received far less attention. Studies have shown that while some species of unicellular algae utilize unique mechanisms of iron uptake, many acquire iron through the same general mechanisms as higher plants. In contrast, the iron acquisition strategies of the multicellular macroalgae remain largely unknown. This is especially surprising since many of these organisms represent important ecological and evolutionary niches in the coastal marine environment. It has been well established in both laboratory and environmentally derived samples, that a large amount of iron can be 'non-specifically' adsorbed to the surface of marine algae. While this phenomenon is widely recognized and has prompted the development of experimental protocols to eliminate its contribution to iron uptake studies, its potential biological significance as a concentrated iron source for marine algae is only now being recognized. This study used an interdisciplinary array of techniques to explore the nature of the extensive and powerful iron binding on the surface of both laboratory and environmental samples of the marine brown alga Ectocarpus siliculosus and shows that some of this surface-bound iron is eventually internalized. It is proposed that the surface-binding properties of E. siliculosus allow it to function as a quasibiological metal ion 'buffer', allowing iron uptake under the widely varying external iron concentrations found in coastal marine environments.

The structures of two types of guanidine-quinoline copper complexes have been investigated by single-crystal X-ray crystallography, K-edge X-ray absorption spectroscopy (XAS), resonance Raman and UV/Vis spectroscopy, cyclic voltammetry, and density functional theory (DFT). Independ- ent of the oxidation state, the two structures, which are virtually identical for solids and complexes in solution, resemble each other strongly and are connected by a reversible electron transfer at 0.33 V. By resonant excitation of the two entatic copper complexes, the transition state of the electron transfer is accessible through vibrational modes, which are coupled to metal-ligand charge transfer (MLCT) and ligand-metal charge transfer (LMCT) states. Copper is one of the most important redox-active metals and plays a central role in many biological processes. (1) Blue copper electron-transfer proteins are natures workhorses for electron transfer (ET). They use copper as a one-electron relay that shuttles between the cuprous and cupric oxidation states. Their Cu II/I reduction potentials span a large window (E8' = 0.18 to > 1 V versus NHE (normal hydrogen elec- trode)), (2) which tailors these proteins to interact with a wide variety of ET partners. The inner coordination sphere most directly affects the redox properties of metal ions. (3) Hence, tuning the Cu II/I redox couple is central for electron transfer in nature and also important in synthetic complexes for catalytic applications. (4-6) There are multiple factors governing the redox potential, including the effects of the first coordination

Die Struktur von zwei Typen von Guanidin-Chinolin-Kupfer-Komplexen wurde mittels Einkristallrontgenstrukturanalyse, K-Kanten-Rontgenabsorptionsspektroskopie (XAS), Resonanz-Raman- und UV/Vis-Spektroskopie, Cyclovoltammetrie und Dichtefunktionaltheorie (DFT) untersucht. Unabhangig vom Oxidationszustand weisen beide Strukturen sowohl im Festkorper als auch in Losung nahezu die gleiche Struktur auf und konnen durch einen reversiblen Elektronentransfer bei 0.33 V ineinander uberfuhrt werden. Durch eine resonante Anregung der beiden entatischen Kupferkomplexe kann der Ubergangszustand des Elektronentransfers uber die Schwingungsmoden, die entweder den Metall-Ligand-Charge-Transfer-Zustand (MLCT) oder den Ligand-Metall-Charge-Transfer-Zustand (LMCT) verbinden, untersucht werden.

Methane seepage at south Hydrate Ridge (offshore Oregon, United States), one of the best-studied examples of gas venting through gas hydrates, is the seafloor expression of a vigorous fluid flow system at depth. The seeps host chemosynthetic ecosystems and release significant amounts of carbon into the ocean. With new three-dimensional seismic data, we image strata and structures beneath the ridge in unprecedented detail to determine the geological processes controlling the style of focused fluid flow. Numerical fluid flow simulations reveal the influence of free gas within a stratigraphic unit known as Horizon A, beneath the base of gas hydrate stability (BGHS). Free gas within Horizon A increases the total mobility of the composite water-gas fluid, resulting in high fluid flux that accumulates at the intersection between Horizon A and the BGHS. This intersection controls the development of fluid overpressure at the BGHS, and together with a well-defined network of faults, reveals the link between the gas hydrate system at depth and methane seepage at the surface.

When volcanic mountains slide into the sea, they trigger tsunamis. How big are these waves, and how far away can they do damage? Ritter Island provides some answers.

Subduction Interface Processes Meeting (SIP), An International Conference Zooming On Subduction Zones, 19-21 April 2017, Barcelona, While releasing stress of the well-defined Northern Chile seismic gap, the 2014 Mw. 8.1 Iquique Earthquake only ruptured part of this gap, leaving large and possibly highly coupled areas untouched. These non-ruptured areas now may pose an elevated seismic hazard due to the transfer of stresses resulting from the 2014 rupture. Here we use multibeam bathymetric data, covering ~90% of the North Chilean marine forearc, in combination with seismic reflection images to derive a tectonic map of the marine forearc in the seismic gap. In the entire study area we find evidence for widespread normal faulting. On the upper continental slope, some of the normal faults dip towards the continent, defining N-S trending ridges that can be traced over tens of kilometers. Seaward dipping normal faults however displays segmentation in it distribution along the margin. In the unbroken southern segment of the seismic gap, seaward dipping normal faults cutting the forearc locally extend close to the slope toe and the deformation front at the deep-sea trench, under ~8 km of water. Similar normal faults cutting the lower slope are neither observed further north (2014 Iquique earthquake area) nor further south (2007 Tocopilla earthquake area). The spatial variation in lowermost-slope normal faulting does not correlate with obvious changes in the structural and tectonic setting of the subduction zone (e.g. plate convergence rate and direction, trench sediment thickness, subducting plate roughness). Thus, the changes in permanent deformation recorded by the spatial distribution of faults may hold crucial information about the long-term seismogenic behavior of the Northern Chile seismic gap over multiple earthquake cycles. Although the structural interpretations cannot directly be translated into seismic hazard, the tectonic map may hold key information to better understand deformation in the marine forearc related to the seismic cycle, historic seismicity, and spatial changes in plate-coupling

Reliable very deep shipborne SBE 911plus Conductivity Temperature Depth (CTD) data to within 60 m from the bottom and Kongsberg EM122 0.5° × 1° multibeam echosounder data are collected in the Challenger Deep, Mariana Trench. A new position and depth are given for the deepest point in the world's ocean. The data provide insight into the interplay between topography and internal waves in the ocean that lead to mixing of the lowermost water masses on Earth. Below 5000 m, the vertical density stratification is weak, with a minimum buoyancy frequency N = 1.0 ± 0.6 cpd, cycles per day, between 6500 and 8500 m. In that depth range, the average turbulence is coarsely estimated from Thorpe-overturning scales, with limited statistics to be ten times higher than the mean values of dissipation rate εT = 3 ± 2 × 10–11 m2 s−3 and eddy diffusivity KzT = 2 ± 1.5 × 10−4 m2 s−1 estimated for the depth range between 10,300 and 10,850 m, where N = 2.5 ± 0.6 cpd. Inertial and meridionally directed tidal inertio-gravity waves can propagate between the differently stratified layers. These waves are suggested to be responsible for the observed turbulence. The turbulence values are similar to those recently estimated from CTD and moored observations in the Puerto Rico Trench. Yet, in contrast to the Puerto Rico Trench, seafloor morphology in the Mariana Trench shows up to 500 m-high fault scarps on the incoming tectonic plate and a very narrow trench, suggesting that seafloor topography does not play a crucial role for mixing.

On March 13 1888, a large sector of the subaerial and submarine edifice of Ritter Island (Papua New Guinea) collapsed and slid into the Bismarck Sea, triggering a tsunami with run-up heights of more than 25 m on the neighboring islands. The tsunami traveled for more than 600 km and caused destruction in several settlements. German colonists described in detail the timing of the arriving waves. During research cruise SO252 onboard RV Sonne, we collected a comprehensive set of multibeam and sediment echosounder data, seafloor video footage, rock samples, 2D seismic profiles, and a 60 km2 high-resolution Pcable 3D seismic cube. This dataset, combined with the historic eyewitness accounts, allows detailed reconstruction of the large-scale volcanic sector collapse and the associated tsunami genesis. The 3D seismic cube reveals a change of emplacement dynamics during the collapse of the volcanic edifice. The initial failure occurred along a deep slide plane extending from the volcanic cone up to 300 m deep into the seafloor sediments adjacent to the volcanic edifice. Movement of large, intact sediment blocks and shortening characterize this deep-rooted mass-movement. In contrast to the well-preserved mobilization structures in the deep part of the volcanic edifice related to the initial phase of mass movement, there are hardly any deposits of the upper part of the volcanic cone comprising of well-stratified volcaniclastic layers. The 2 km3 cone was mobilized in the final stage of the sector collapse and its highly energetic slide mass eroded deeply into the previously emplaced slide deposits. The fast moving mass was channelized between two volcanic ridges, transported into the basin west of Sakar Island, and then deposited more than 30 km away from its source. We interpret the separation into two phases as the result of decoupling of the sliding mass of the cone from the deeper volcanic edifice. This process may be explained by gravitational acceleration of the sliding mass or a phreatomagmatic explosion due to the contact of the magmatic conduit with seawater.

Efforts to reduce door-to-balloon (DTB) times for patients presenting with an ST-elevation myocardial infarction (STEMI) are widespread. Reductions in DTB times have been shown to reduce short-term mortality and decrease inpatient length of stay (LOS) in these high-risk patients. However, there is a limited literature examining the effect that these quality improvement (QI) initiatives have on patient care costs.A STEMI QI program (Cardiac Alert Team [CAT]) initiative was instituted in July 2006 at a single tertiary care medical center located in central Massachusetts. Information was collected on cost data and selected clinical outcomes for consecutively admitted patients with a STEMI. Differences in adjusted hospital costs were compared in three cohorts of patients hospitalized with a STEMI: one before the CAT initiative began (January 2005-June 2006) and two after (October 1, 2007-September 30, 2009, and October 1, 2009-September 30, 2011).Before the CAT initiative, the average direct inpatient costs related to the care of these patients was $14,634, which decreased to $13,308 (-9.1%) and $13,567 (-7.3%) in the two sequential periods of the study after the CAT initiative was well established. Mean DTB times were 91 minutes before the CAT initiative and were reduced to 55 and 61 minutes in the follow-up periods (p.001). There was a nonsignificant reduction in LOS from 4.4 days pre-CAT to 3.6 days in both of the post-CAT periods (p = .11).A QI program aimed at reducing DTB times for patients with a STEMI also led to a significant reduction in inpatient care costs. The greatest reduction in costs was related to cardiac catheterization, which was not expected and was likely a result of standardization of care and identification of practice inefficiencies.

Based on multichannel seismic, geoacoustic, and methane sensor data, four different areas along the Hikurangi Margin show multiple indications for seep activity including bright spots, transparent zones, vertical chimneys, and the occurrence and distribution of bottom simulating reflectors. Locations where these features reach the seafloor are characterised by high backscatter intensity on sidescan sonar images and transparent zones in sediment echosounder profiles, while methane sensors show episodic, elevated methane concentrations near the seep sites. Methane discharge is facilitated by reduced hydrostatic pressure during low tides. The greatest number of seeps at Opouawe Bank correlates with the highest methane activity along the Hikurangi Margin. High heat flow values on flanks of ridges and low heat flow values on anticlines reflect a topographic effect on subsurface temperatures. Elevated heat flow occurs in the vicinity of seeps on Opouawe Bank. We propose that there are two drivers behind methane seepage with respect to the migration pathways of methane through the gas hydrate stability zone (GHSZ) to the seafloor: (1) structurally controlled and (2) stratigraphically controlled. In the structural model, vertical chimneys are the major pathways for methane through the GHSZ. Part of the upwardly migrating methane forms gas hydrate within the chimney. In the stratigraphic model, methane migration is stratigraphically controlled beneath seeps that are located on bathymetric highs and/or where subsurface anticlines occur beneath seeps. The structurally controlled seeps produce higher methane escape at the seafloor than those that are stratigraphically controlled. A combination of both driving mechanisms results in the highest methane seepage rates at the Tui Seep on Opouawe Bank.

Objective: To analyze neonatal outcome after extreme preterm delivery before 27 weeks of gestation in early-onset preeclampsia, eclampsia and HELLP-Syndrome. Patients and methods: Maternal and neonatal outcome of 21 pregnancies complicated by preeclampsia (P), eclampsia (E) or/and HELLP-Syndrome (H) (Group P/E/H) were compared to the outcome of 45 normotensive women (control group, C) delivered between 23rd and 27th week of gestation at the Department of Obstetrics and Gynaecology, Medical University Graz. Exclusion criteria were premature rupture of membrane (PROM), intrauterine infection and twin pregnancy. Statistical analysis was performed by c2-Square Test and the P < 0.05 was accepted as significant. Results: The P/E/H-group included 9 women with preeclampsia, 1 woman with eclampsia and 11 women with HELLP-Syndrome. Two of the pregnancies were terminated after IUFD and 4 children died several days after delivery (3 ‰). In the C group, there were 6 cases of IUFD and 11 children died several days after delivery (4 ‰), ns. IUGR occurred in 20 women (95%) of the P/E/H-group compared to one pregnancy (2%) in the C-group (p < 0.001). All P/E/H women and 33 C women received betamethasone for lung maturation. Conclusion: Children from P/E/H suffer more frequently from growth restriction, asphyxia and cerebral palsy than children after extreme preterm delivery for other reasons. The higher incidence of cerebral palsy could be due to the higher frequency of intrauterine asphyxia. Otherwise, the decreased incidence of sepsis is associated with less PVL in P/E/H.

The zinc(II) coordination chemistry of the bioinspired bis(tetradentate) ligand 3,5-bis{bis[2-(1-methylimidazolyl)methyl]aminomethyl}pyrazole (L) was studied in detail both in solution and in the solid state. Six different species were determined in aqueous solution by means of potentiometry within the pH range 211, namely mononuclear [ZnH2L]4+, dinuclear [Zn2L]4+, [Zn2H1L]3+ and [Zn2H2L]2+, as well as tetranuclear [Zn4H5L2]3+ and [Zn4H6L2]2+. Complexes representing the protonation state of four of these species could be isolated and structurally characterized by X-ray diffraction, namely [ZnH2L(MeCN)](ClO4)4 (1), [Zn2H1L](SO3CF3)3 (4), [Zn2H1L(MeOHOMe)](ClO4)2 (5a), [Zn2H1L(OMe)](ClO4)2 (5b), and [(Zn2H1L)2(mu-O)(mu-OH)](ClO4)3 (6). In addition, a bis(pyrazolato)-bridged complex, [(ZnH1L)2](ClO4)2 (2), was obtained and structurally characterized, and it was found to exhibit ligand dynamics in solution. Both 5a and 5b are likely present in solution, which requires significant plasticity of the Zn...Zn distance (4.21 angstrom in 5a vs. 3.38 angstrom in 5b). Interconversion of 5a and 5b is proposed to be a facile process, supporting the idea that the ZnO2H3Zn moiety is a functionally relevant hydrolytic zincaqua structure in oligozinc metalloenzymes. The tetranuclear complex 6 that features two {Zn2H1L} subunits connected by a central mu-oxido-mu-hydroxido moiety is unprecedented in zinc(II) chemistry. Combining X-ray crystallography with potentiometry, ESI mass spectrometry, as well as NMR and EXAFS spectroscopy has provided a comprehensive picture of the multitude of species present in this rather complex system.

Tris(8-quinolinolato)gallium(III) (1, KP46) is a very promising investigational anticancer drug. Its interaction with serum proteins, elemental distribution, and coordination in tissue were investigated with X-ray absorption (XAS) methods. Model compounds with mixed O, N, and/or S donor atoms are reported. The coordination and structure of 1 in cell culture medium (minimum essential medium, MEM) and fetal calf serum (FCS) were probed by XANES and EXAFS. The interaction of 1 with the serum proteins apotransferrin (apoTf) and human serum albumin (HSA) was addressed as well. By application of micro-XAS to tissue samples from mice treated with 1, the gallium distribution pattern was analyzed and compared to those of physiological trace elements. The complex 1 turned out to be very stable under physiological conditions, in cell culture media and in tissue samples. The coordination environment of the metal center remains intact in the presence of apoTf and HSA. The gallium distribution pattern in tumor and liver tissue revealed high similarities to the distribution patterns of Zn and Fe, minor similarities to Cu and Ni, and no similarity to Ca.

The central Chilean subduction zone between 35°S and 37°S was investigated in order to identify, document and possibly understand fluid flow and fluid venting within the forearc region. Several areas were mapped using multibeam bathymetry and backscatter, high-resolution sidescan sonar, chirp subbottom profiling and reflection seismic data. On a subsequent cruise ground-truthing observations were made using a video sled. In general, this dataset shows surprisingly little evidence of fluid venting along the mid-slope region, in contrast to other subduction zones such as Central America and New Zealand. There were abundant indications of active and predominantly fossil fluid venting along the upper slope between 36.5°S and 36.8°S at the seaward margin of an intraslope basin. Here, backscatter anomalies suggest widespread authigenic carbonate deposits, likely the result of methane-rich fluid expulsion. There is unpublished evidence that these fluids are of biogenic origin and generated within the slope sediments, similar to other accretionary margins but in contrast to the erosional margin off Central America, where fluids have geochemical signals indicating an origin from the subducting plate.

Following the devastating 2004 tsunami that hit the southwestern coast of Thailand, the need for detailed bathymetric data of the Andaman Sea outer shelf became evident in order to better predict tsunami wave propagation and coastal impact. Bathymetric data and subbottom profiler records covering the outer shelf and upper slope of the Thai exclusive economic zone (EEZ) were collected onboard Thai RV Chakratong Tongyai in 2006 and 2007. The data cover an area of approximately 3000 km2 between 500 and 1600 m water depth. The soundings allowed generating a final bathymetric grid with 50 m grid cell spacing. The outer shelf is rather smooth and slightly inclined southward, while the upper slope is strongly dissected by gullies. Several previously unknown features are identified including mud-domes, pockmarks, three large plateaus surrounded by moats, gas-charged sediment on subbottom profiler records, and only few indications for small submarine landslides on the upper slope. The largest of these possibly translational submarine landslides involved 2.2×107 m3 of sediment. This slide would have generated a tsunami wave of less than 0.12 m wave height. Considering the entire data, there is no evidence that landslides have been the source of tsunami waves in recent geological time. Highlights

In the eastern Black Sea, we determined methane (CH4) concentrations, gas hydrate volumes, and their vertical distribution from combined gas and chloride (Cl−) measurements within pressurized sediment cores. The total gas volume collected from the cores corresponded to concentrations of 1.2–1.4 mol CH4 kg−1 porewater at in-situ pressure, which is equivalent to a gas hydrate saturation of 15–18% of pore volume and amongst the highest values detected in shallow seep sediments. At the central seep site, a high-resolution Cl− profile resolved the upper boundary of gas hydrate occurrence and a continuous layer of hydrates in a sediment column of 120 cm thickness. Including this information, a more precise gas hydrate saturation of 22–24% pore volume could be calculated. This volume was higher in comparison to a saturation calculated from the Cl− profile alone, resulting in only 14.4%. The likely explanation is an active gas hydrate formation from CH4 gas ebullition. The hydrocarbons at Batumi Seep are of shallow biogenic origin (CH4 > 99.6%), at Pechori Mound they originate from deeper thermocatalytic processes as indicated by the lower ratios of C1 to C2–C3 and the presence of C5.

TcHMA4 (GenBank no. AJ567384 ), a Cd/Zn transporting ATPase of the P 1B -type (= CPx-type) was isolated and purified from roots of the Cd/Zn hyperaccumulator Thlaspi caerulescens . Optimisation of the purification protocol, based on binding of the natural C-terminal His-tag of the protein to a Ni-IDA metal affinity column, yielded pure, active TcHMA4 in quantities sufficient for its biochemical and biophysical characterisation with various techniques. TcHMA4 showed activity with Cu(2+), Zn(2+) and Cd(2+) under various concentrations (tested from 30 nM to 10 μM), and all three metal ions activated the ATPase at a concentration of 0.3 μM. Notably, the enzyme worked best at rather high temperatures, with an activity optimum at 42 °C. Arrhenius plots yielded interesting differences in activation energy. In the presence of zinc it remained constant ( E A = 38 kJ⋅mol −1 ) over the whole concentration range while it increased from 17 to 42 kJ⋅mol −1 with rising copper concentration and decreased from 39 to 23 kJ⋅mol −1 with rising cadmium concentration. According to EXAFS the TcHMA4 appeared to bind Cd(2+) mainly by thiolate sulphur from cysteine, and not by imidazole nitrogen from histidine.

Oxidation of methionine to methionine sulphoxide (MetSO) may lead to loss of molecular integrity and function. This oxidation can be 'repaired' by methionine sulphoxide reductases (MSRs), which reduce MetSO back to methionine. Two structurally unrelated classes of MSRs, MSRA and MSRB, show stereoselectivity towards the S and the R enantiomer of the sulphoxide respectively. Interestingly, these enzymes were even maintained throughout evolution in anaerobic organisms. Here, the activity and the nuclear magnetic resonance (NMR) structure of MTH711, a zinc containing MSRB from the thermophilic, methanogenic archaebacterium Methanothermobacter thermoautotrophicus, are described. The structure appears more rigid as compared with similar MSRBs from aerobic and mesophilic organisms. No significant structural differences between the oxidized and the reduced MTH711 state can be deduced from our NMR data. A stable sulphenic acid is formed at the catalytic Cys residue upon oxidation of the enzyme with MetSO. The two non-zinc-binding cysteines outside the catalytic centre are not necessary for activity of MTH711 and are not situated close enough to the active-site cysteine to serve in regenerating the active centre via the formation of an intramolecular disulphide bond. These findings imply a reaction cycle that differs from that observed for other MSRBs.

Phosphine-modified thioester derivatives are shown to serve as efficient precursors to phosphine-stabilized ferrous acyl thiolato carbonyls, which replicate key structural features of the active site of the hydrogenase Hmd. The reaction of Ph(2)PC(6)H(4)C(O)SPh and sources of Fe(0) generates both Fe(SPh)(Ph(2)PC(6)H(4)CO)(CO)(3) (1) and the diferrous diacyl Fe(2)(SPh)(2)(CO)(3)(Ph(2)PC(6)H(4)CO)(2), which carbonylates to give 1. For the extremely bulky arylthioester Ph(2)PC(6)H(4)C(O)SC(6)H(3)-2,6-(2,4,6-trimethylphenyl)(2), oxidative addition is arrested and the Fe(0) adduct of the phosphine is obtained. Complex 1 reacts with cyanide to give Et(4)N[Fe(SPh)(Ph(2)PC(6)H(4)CO)(CN)(CO)(2)] (Et(4)N[2]). (13)C and (31)P NMR spectra indicate that substitution is stereospecific and cis to P. The IR spectrum of [2](-) in ν(CN) and ν(CO) regions very closely matches that for Hmd(CN). XANES and EXAFS measurements also indicate close structural and electronic similarity of Et(4)N[2] to the active site of wild-type Hmd. Complex 1 also stereospecifically forms a derivative with TsCH(2)NC, but the adduct is more labile than Et(4)N[2]. Tricarbonyl 1 was found to reversibly protonate to give a thermally labile derivative, IR measurements of which indicate that the acyl and thiolate ligands are probably not protonated in Hmd.

Based on multibeam bathymetry, high-resolution deep-towed sidescan sonar and Chirp subbottom profiling 32 cold seep sites, already identified in Sahling et al. (2008a), have been studied in an approximately 1000 km2 large area ranging from 800 to 2600 m water depth along the middle slope of the active continental margin offshore Nicaragua. Ground truthing is available from towed camera surveys and coring on seven of the structures. The seeps occur in different settings on the slope: upslope and along the headwall of large submarine slides, as isolated eroded massifs, and forming linear ridges between deeply incised canyons. The seep sites show a wide range regarding their size and morphology, their backscatter intensity patterns, their structure in subbottom profiles, and their fluid venting activity inferred from seafloor observations. Surface extension of the seep sites ranges from less than 200 to more than 1500 m in diameter, and relief height varies between no relief and 180 m. Indications of extruded materials such as mud flows are not observed in the area of the seep sites. Instead the seeps are characterized by high proportions of authigenic carbonates. The carbonates occur as crusts, detritus, or single layers embedded in the seafloor sediments. They appear as high backscatter intensities on sidescan sonar images. On some seep sites living vent fauna indicative of active seepage is observed, but gas bubbles have not been observed. To explain the high morphological variability of the features, we propose a generic model including the interaction of several processes: (1) episodic fluid venting and associated authigenic carbonate formation; (2) background sedimentation and subsidence; (3) linear erosion along canyons and denudation on the slope surface.

Fluid escape structures on the Nile Deep Sea Fan were investigated during the MEDIFLUX MIMES expedition in 2004. Mud volcanoes, pockmarks and authigenic carbonate structures were surveyed for the first time with a high-resolution deep-towed 75 kHz sidescan sonar and a 2-8 kHz Chirp sediment echosounder. In combination with existing multibeam bathymetry and detailed seafloor in situ geological observations, these new data allowed detailed seep analyses. About 60 gas flares were detected acoustically in the water column from the sidescan sonar raw data at water depths from 770 to 1700 m. These gas flares coincide at the seabed with 1) the centres of the mud volcanoes where mud is also extruded, 2) the borders of the mud volcanoes where the emitted gases contribute to the precipitation of authigenic carbonates, and 3) to the edges of broad sheets of authigenic carbonates. Subsurface sediments are commonly disturbed by ascending fluids throughout the delta, with an abundance of seep-related carbonate structures on the seafloor. The feeder channels below mud volcanoes, similar to the gas conduits below the widespread carbonate crust structures and pockmarks, are relatively narrow and, for the vast majority of them, do not exceed a few metres in diameter. The seeps on the Nile Deep Sea Fan clearly follow lineations on the seafloor that we can relate to faults. (C) 2010 Elsevier B.V. All rights reserved.

The influence of sulfur versus selenium coordination to molybdenum on the oxo transfer reaction mechanisms of functional models for oxidoreductases has been studied. The solution structure of the dimeric molybdenum compound with tridentate bis-anionic ligands containing a thioether function (−O(CH2)3S(CH2)3O−) has been determined using EXAFS spectroscopy to be able to compare a feature of its solution structure to that of its selenoether analogue. A significant difference is found for the solution structures of the two compounds. The thioether group remains coordinated in solution, whereas the selenoether does not. The influence of this difference on the catalytic oxo transfer has been investigated in detail by following the catalytic transition of PPh3 to OPPh3 with DMSO as oxygen donor with variation of both substrate concentrations.

The non-proteinogenic amino acid nicotianamine (NA) is a major player in plant metal homeostasis. It is known to form complexes with different transition metals in vitro. Available evidence associates NA with translocation of Fe, and possibly other micronutrients, to and between different plant cells and tissues. To date, however, it is still extremely challenging to detect metal-ligand complexes in vivo because tissue disruption immediately changes the chemical environment and thereby the availability of binding partners. In order to overcome this limitation we used various Schizosaccharomyces pombe strains expressing a plant NAS gene to study formation of metal-NA complexes in vivo. Tolerance, accumulation and competition data clearly indicated formation of Zn(ii)-NA but not of Cu(ii)-NA complexes. Zn(ii)-NA was then identified by X-ray absorption spectroscopy (XAS). About half of the cellular Zn was found to be bound by NA in NAS-expressing cells while no NA-like ligands were detected by XAS in control cells not expressing NAS. Given the high conservation of eukaryotic metal homeostasis components, these results strongly suggest the possible existence of Zn(ii)-NA complexes also in planta. Reported observations implicating NA in plant Zn homeostasis would then indeed be attributable to direct interaction of Zn(ii) with NA rather than only indirectly to perturbations in Fe metabolism. Re-evaluation of extended X-ray absorption fine structure (EXAFS) spectra for the Zn hyperaccumulator Thlaspi caerulescens showed that NA is as expected not a major storage ligand for Zn. Instead it is hypothesized to be involved in efficient translocation of Zn to above-ground tissues in hyperaccumulators.

Vodyanitskii mud volcano is located at a depth of about 2070 m in the Sorokin Trough, Black sea. It is a 500-m wide and 20-m high cone surrounded by a depression, which is typical of many mud volcanoes in the Black Sea. 75 kHz sidescan sonar show different generations of mud flows that include mud breccia, authigenic carbonates, and gas hydrates that were sampled by gravity coring. The fluids that flow through or erupt with the mud are enriched in chloride (up to similar to 650 mmol L-1 at similar to 150-cm sediment depth) suggesting a deep source, which is similar to the fluids of the close-by Dvurechenskii mud volcano. Direct observation with the remotely operated vehicle QUEST revealed gas bubbles emanating at two distinct sites at the crest of the mud volcano, which confirms earlier observations of bubble-induced hydroacoustic anomalies in echosounder records. The sediments at the main bubble emission site show a thermal anomaly with temperatures at similar to 60 cm sediment depth that were 0.9 degrees C warmer than the bottom water. Chemical and isotopic analyses of the emanated gas revealed that it consisted primarily of methane (99.8%) and was of microbial origin (delta D-CH4 = -170.8 parts per thousand (SMOW), delta C-13-CH4 = -61.0 parts per thousand (V-PDB), delta C-13-C2H6 = -44.0 parts per thousand (V-PDB)). The gas flux was estimated using the video observations of the ROV. Assuming that the flux is constant with time, about 0.9 +/- 0.5 x 106 mol of methane is released every year. This value is of the same order-of-magnitude as reported fluxes of dissolved methane released with pore water at other mud volcanoes. This suggests that bubble emanation is a significant pathway transporting methane from the sediments into the water column. (C) 2009 Elsevier Ltd. All rights reserved.

The cadmium/zinc hyperaccumulator Thlaspi caerulescens is sensitive toward copper (Cu) toxicity, which is a problem for phytoremediation of soils with mixed contamination. Cu levels in T. caerulescens grown with 10 μ m Cu2+ remained in the nonaccumulator range (

Salt tectonics and mud volcanism in the Latakia and Cyprus Basin, eastern Mediterranean, is investigated by means of swath sounding, reflection seismics and side-scan data as well as by camera and video sledge observations. Both basins are located east of Cyprus and are associated with the collision front between the African and Anatolian plate. The Pliocene–Quaternary sediment succession is underlain by up to 1 km thick Messinian evaporites. Both thick-skinned plate tectonic and thin-skinned salt tectonic control fluid dynamics and associated mud volcanism in the Latakia and Cyprus Basin as well as at the Troodos Latacia Culmination, which separates both basins. An end-member model is proposed which explains the presence of elongated topographic highs and trenches along the Troodos Larnaca Culmination and south of it by gravity gliding of the Messinian evaporites and associated fluid migration. Thin-skinned extension in the Troodos Larnaca Culmination and boudinage, respectively, facilitate fluid flow through and out of the evaporites. The fluid or mud flow dissolutes the salt layer and creates elongated trenches. Mud intrudes into the Pliocene–Quaternary sediments above the trenches. Consequently, the overburden is thickened and forms morphological ridges. South of the culmination the evaporites and overburden are folded due to thin-skinned shortening of the evaporites. In one instance fluid extrusion out of the evaporites is inferred from seismic data interpretation. The outflow caused a volume reduction and collapse of the evaporites. Mud volcanoes and fold anticlines align above deep-rooted transpressional fault systems which are associated with the African–Anatolian collision zone. The faults may act as conduits for rising fluids. In the western part of the survey area, where the Cyprus Arc strikes almost West–East and the collision occurred more frontal and stress was highest, mud volcanoes emerged. Further to the east, where the Cyprus Arc runs SW–NE and sinistral strike-slip has been proposed, fold anticlines evolved. Particular mud volcanoes and folds emerged prior to the deposition of the Messinian evaporites. The undisturbed upper Pleistocene sequences as well as the absence of significant mud outflow on the seafloor strongly suggest that the main fluid dynamic ceased.

Zinc serves regulatory functions in cells and thus, several mechanisms exist for tight control of its homeostasis. One mechanism is storage in and retrieval from vesicles, so-called zincosomes, but the chemical speciation of zincosomal zinc has remained enigmatic. Here, we determine the intravesicular zinc-coordination in isolated zincosomes in comparison to intact RAW264.7 murine macrophage cells. In elemental maps of a cell monolayer, generated by microbeam X-ray fluorescence, zincosomes were identified as spots of high zinc accumulation. A fingerprint for the binding motif obtained by μXANES (X-ray absorption near edge structure) matches the XANES from isolated vesicles; zinc is not free, but present as a complexed form (average coordination; 1.0 sulfur, 2,5 histidines 30 and 1.0 oxygen), resembling regulatory or catalytic zinc sites in proteins. Such coordination enables reversible binding, acting as a ‘zinc sink’, facilitating the accumulation of high amounts of zinc against a concentration gradient.

[Fe]-hydrogenase is one of three types of enzymes known to activate H2. Crystal structure analysis recently revealed that its active site iron is ligated square-pyramidally by Cys176-sulfur, two CO, an “unknown” ligand and the sp2-hybridized nitrogen of a unique iron–guanylylpyridinol-cofactor. We report here on the structure of the C176A mutated enzyme crystallized in the presence of dithiothreitol (DTT). It suggests an iron center octahedrally coordinated by one DTT-sulfur and one DTT-oxygen, two CO, the 2-pyridinol’s nitrogen and the 2-pyridinol’s 6-formylmethyl group in an acyl-iron ligation. This result led to a re-interpretation of the iron ligation in the wild-type.

A full quantitative analysis of Fe K-edge X-ray absorption spectra has been performed for hemes in two porphynato complexes, that is, iron(III) tetraphenylporphyrin chloride (Fe(III)TPPCl) and iron(III) tetraphenylporphyrin bis(imidazole) (Fe(III)TPP(Imid)2), in two protein complexes whose X-ray structure is known at atomic resolution (1.0 A), that is, ferrous deoxy-myoglobin (Fe(II)Mb) and ferric aquo-myoglobin (Fe(III)MbH2O), and in ferric cyano-myoglobin (Fe(III)MbCN), whose X-ray structure is known at lower resolution (1.4 A). The analysis has been performed via the multiple scattering approach, starting from a muffin tin approximation of the molecular potential. The Fe-heme structure has been obtained by analyzing independently the Extended X-ray Absorption Fine Structure (EXAFS) region and the X-ray Absorption Near Edge Structure (XANES) region. The EXAFS structural results are in full agreement with the crystallographic values of the models, with an accuracy of +/- 0.02 A for Fe-ligand distances, and +/-6 degrees for angular parameters. All the XANES features above the theoretical zero energy (in the lower rising edge) are well accounted for by single-channel calculations, for both Fe(II) and Fe(III) hemes, and the Fe-N p distance is determined with the same accuracy as EXAFS. XANES evaluations of Fe-5th and Fe-6th ligand distances are determined with 0.04-0.07 A accuracy; a small discrepancy with EXAFS (0.01 to 0.05 A beyond the statistical error), is found for protein compounds. Concerns from statistical correlation among parameters and multiple minima in the parameter space are discussed. As expected, the XANES accuracy is slightly lower than what was found for polarized XANES on Fe(III)MbCN single crystal (0.03-0.04 A), and states the actual state-of-the-art of XANES analysis when used to extract heme-normal parameters in a solution spectrum dominated by heme-plane scattering.

Flow parameters (velocity and density) for turbidity currents in the Northwest Atlantic Mid-Ocean Channel (NAMOC) have been determined based on two different approaches, channel geometry and grain-size distributions of turbidites. Channel geometry has been obtained by a quantitative morphological analysis of the NAMOC which shows three genetically different segments in the upper 2000 km: (1) an upper 350 km-long ‘equilibrium channel’, (2) a middle 700 km-long ‘modified equilibrium channel’and (3) a lower ‘basement-controlled channel’which is more than 1000 km-long. In contrast to other meandering submarine channels the NAMOC has very low sinuosities and gradients. A consistently higher right-hand levee limits mean flow velocities to 3ms−1 and channel geometry indicates mean flow velocities of 0·86 m s−1 that decrease within the equilibrium channel to 0·05 m s−1. Grain-size distributions on the levees and in the channel suggest strong vertical velocity and density gradients for bank-full flows with velocities of up to 8 m s−1 and excess densities up to 87 kg m−3 at the base, and 0·45 m s−1 and 4 kg m−3 at the top. The internal shear produced by these strong vertical gradients results in a decoupling of the current head and body. Channel geometry appears to be mainly the result of the slowly moving dilute body of the current.

There are more than six million people with atrial fibrillation (AF) in the United States, and approximately 1.6 million new cases occur annually. Many such patients present to the emergency department (ED) and require management of symptoms or an unfavorable hemodynamic profile. Whereas heart rate control has historically been the focus of ED management, attempts to cardiovert selected patients to sinus rhythm have been shown to be a safe and cost-effective strategy that can negate the need for hospital admission for many patients. The decision to pursue an early rhythm control strategy depends on a variety of factors, including patient stability, age, precipitants, coinciding heart failure, duration of the AF episode, and more. However, there is tremendous variation across providers, hospital systems, and even regions with regard to how new-onset AF is managed in acute setting. The goal of this review is to outline indications and techniques for cardioversion of new-onset AF – both pharmacologic cardioversion (PC) and electrical cardioversion (EC) – in the first 24–48 h after a patient arrives to the hospital/ED. One of the central tenets of cardioversion should be considered when reading this review – namely, that symptomatic patients benefit from cardioversion whereas asymptomatic patients may not.