148 research outputs found

    Dissolved and particulate metals (Fe, Zn, Cu, Cd, Pb) in two habitats from an active hydrothermal field on the EPR at 13°N

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    Le texte intégral est accessible via Archimer: http://archimer.ifremer.fr/doc/2008/publication-3830.pdfInternational audienceThe distribution of Fe, Cu, Zn, Pb, Cd between the dissolved ( 2 μm) fractions was measured after in-situ filtration in two hydrothermal habitats. The total metal concentration ranges exhibit a clear enrichment compared with the seawater concentration, accounting for the hydrothermal input for all the metals considered. Iron is the predominant metal (5-50 μM) followed by Zn and Cu. Cd and Pb are present at the nM level. At the scale studied, the behavior of temperature, pH and dissolved iron is semi-conservative whereas the other dissolved and particulate metals are characterized by non-conservative patterns. The metal enrichment of the > 2 μm fraction results from the settlement and accumulation of particulate matter close to the organisms, acting as a secondary metal source. The enrichment observed in the dissolved fraction can be related to the dissolution or oxidation of particles (mainly polymetallic sulfide) or to the presence of small particles and large colloids not retained on the 2 μm frit. SEM observations indicate that the bulk particulate observed is characteristic of crystalline particles settling rapidly from the high temperature smoker (sphalerite, wurtzite and pyrite), amorphous structures and eroded particles formed in the external zone of the chimney. Precipitation of Zn, Cu, Cd and Pb with Fe as wurtzite, sphalerite and pyrite is the main process taking place within the area studied and is semi-quantitative. The distribution of the dominant observed fauna has been related to the gradient resulting from the dilution process, with the alvinellids worms colonizing the hotter and more variable part of the mixing zone, but also to the metallic load of the mixing zone. Dissolved and particulate metal concentrations are therefore necessary abiotic factors to be studied in a multiparametric approach to understand the faunal distribution in hydrothermal ecosystems

    DNA Origami Rotaxanes: Tailored Synthesis and Controlled Structure Switching

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    Mechanically interlocked supramolecular assemblies are appealing building blocks for creating functional nanodevices. Herein, we describe the multistep assembly of large DNA origami rotaxanes that are capable of programmable structural switching. We validated the topology and structural integrity of these rotaxanes by analyzing the intermediate and final products of various assembly routes by electrophoresis and electron microscopy. We further analyzed two structureâ switching behaviors of our rotaxanes, which are both mediated by DNA hybridization. In the first mechanism, the translational motion of the macrocycle can be triggered or halted at either terminus. In the second mechanism, the macrocycle can be elongated after completion of the rotaxane assembly, giving rise to a unique structure that is otherwise difficult to access.A new set of threads: Rotaxanes with a length of up to 200â nm were assembled by a DNA origami approach. The threaded macrocycles can be programmably docked at either dumbbell stopper, and the assemblies can be reconfigured to generate new, otherwise unfavorable rotaxane topologies.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/137326/1/anie201604621_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/137326/2/anie201604621-sup-0001-misc_information.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/137326/3/anie201604621.pd

    Simple and Rapid Voltammetric Method Using a Gold Microwire Electrode to Measure Inorganic Arsenic in Holopelagic <i>Sargassum</i> (Fucales, Phaeophyceae)

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    The valorization of massive strandings of holopelagic Sargassum spp. is strongly limited by high levels of inorganic arsenic (Asi) that are potentially above the limit of current regulations. Monitoring Asi in algal biomass is currently achieved using standard chromatographic separation followed by spectroscopic detection. Here, we propose an alternative simpler procedure based on the extraction of Asi from the freeze-dried algal powder in deionized water and the electroanalytical detection of the diluted extract at a gold-microwire electrode. The protocol was optimized both in terms of extraction (powder/water ratio, extraction time, temperature) and electrolyte used for the voltammetric detection. Two electrolytes were tested: one composed of citric acid, sulfamic acid and KCl (pH 2.0) and another composed of an acetate buffer (pH 4.7) and NaCl. We demonstrate here that Asi determination is possible with the first electrolyte but it is necessary to deal with a relative unstable signal. Measurement of Asi was best achieved with the second electrolyte (acetate buffer and NaCl) with the following optimized electrochemical conditions: deposition potential of −1.2 V, deposition time of 30 seconds and linear scan voltammetry. Voltammetric results were then compared to a reference method (HPLC-ICP-MS) using different morphotypes of holopelagic Sargassum spp. (S. natans VIII, S. natans I and S. fluitans III), using commercial extracts of brown seaweeds and using a Hijiki certified reference material. Very good agreement was obtained between our novel method and HPLC-ICP-MS. Both methods show that inorganic arsenic is almost entirely present as As(V) in Sargassum spp. extracts

    Assessing the drivers of dissolved organic matter export from two contrasting lowland catchments, U.K

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    AbstractTwo lowland catchments in the U.K. were sampled throughout 2010–11 to investigate the dominant controls on dissolved organic matter quantity and composition. The catchments had marked differences in terms of nutrient status, land cover and contrasting lithologies resulting in differences in the dominant flow pathways (groundwater vs. surface water dominated). The Upper Wylye is a chalk stream with a baseflow index of 0.98, draining a catchment dominated by intensive agricultural production. Millersford Brook is a lowland peat catchment with a baseflow index of 0.43, draining a semi-natural catchment with heather moorland and coniferous forest. Samples were collected weekly between October 2010 and September 2011 from eleven sampling locations. Samples were analysed to determine dissolved organic carbon, nitrogen and phosphorus fractions with DOM composition evaluated via the DOC:DON ratio, DOC:DOP ratio, specific UV absorption at 254nm, absorbance ratio (a250:a365) and the spectral slope parameter between 350 and 400nm (S350–400). Significant differences were observed in all determinands between the catchments, over time, and spatially along nutrient enrichment and geoclimatic gradients. Seasonal variation in preferential flow pathways mobilising groundwater-derived DOM were identified as likely controls on the delivery of DOM in the permeable chalk dominated catchment. Steeper S350–400 values and elevated a250:a365 ratios in this catchment suggest material of a lower bulk aromatic C content and molecular weight delivered during the winter months when compared to the summer. DOC:DON ratios were markedly lower in the chalk catchment than the peatland catchment, reflecting the paucity of organic matter within the mineral soils of the chalk landscape, and higher fertiliser application rates. This manuscript highlights that DOM composition varies according to catchment landscape character and hydrological function

    Bedform migration in a mixed sand and cohesive clay intertidal environment and implications for bed material transport predictions

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    Many coastal and estuarine environments are dominated by mixtures of non-cohesive sand and cohesive mud. The migration rate of bedforms, such as ripples and dunes, in these environments is important in determining bed material transport rates to inform and assess numerical models of sediment transport and geomorphology. However, these models tend to ignore parameters describing the physical and biological cohesion (resulting from clay and extracellular polymeric substances, EPS) in natural mixed sediment, largely because of a scarcity of relevant laboratory and field data. To address this gap in knowledge, data were collected on intertidal flats over a spring-neap cycle to determine the bed material transport rates of bedforms in biologically-active mixed sand-mud. Bed cohesive composition changed from below 2 vol% up to 5.4 vol% cohesive clay, as the tide progressed from spring towards neap. The amount of EPS in the bed sediment was found to vary linearly with the clay content. Using multiple linear regression, the transport rate was found to depend on the Shields stress parameter and the bed cohesive clay content. The transport rates decreased with increasing cohesive clay and EPS content, when these contents were below 2.8 vol% and 0.05 wt%, respectively. Above these limits, bedform migration and bed material transport was not detectable by the instruments in the study area. These limits are consistent with recently conducted sand-clay and sand-EPS laboratory experiments on bedform development. This work has important implications for the circumstances under which existing sand-only bedform migration transport formulae may be applied in a mixed sand-clay environment, particularly as 2.8 vol% cohesive clay is well within the commonly adopted definition of “clean sand”

    Electrochemical methods for speciation of trace elements in marine waters. Dynamic aspects

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    The contribution of electrochemical methods to the knowledge of dynamic speciation of toxic trace elements in marine waters is critically reviewed. Due to the importance of dynamic considerations in the interpretation of the electrochemical signal, the principles and recent developments of kinetic features in the interconversion of metal complex species will be presented. As dynamic electrochemical methods, only stripping techniques (anodic stripping voltammetry and stripping chronopotentiometry) will be used because they are the most important for the determination of trace elements. Competitive ligand ex- change-adsorptive cathodic stripping voltammetry, which should be considered an equilibrium technique rather than a dynamic method, will be also discussed because the complexing parameters may be affected by some kinetic limitations if equilibrium before analysis is not attained and/or the flux of the adsorbed complex is in fluenced by the lability of the natural complexes in the water sample. For a correct data interpretation and system characterization the comparison of results obtained from different techniques seems essential in the articulation of a serious discussion of their meaning

    Metal size distribution in rainfall and snowmelt-induced runoff from three urban catchments

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    The size distribution of metals transported by urban runoff has implications for treatment type and design, predicting their mobility and evaluating their potential impact on receiving waters. There is an urgent need to better understand the distribution of metals between fractions, particularly those in the sub-dissolved fractions. As a contribution to addressing this need, this study characterises the size distribution of Cd, Cr, Cu, Ni, V and Zn using conventional and novel techniques. Data is presented as event mean concentrations (EMC) of a total of 18 rainfall and snowmelt events at three urban sites. For all studied metals in all events and at all sites, the contribution of the truly dissolved fraction made a greater contribution to the total concentrations than the colloidal fraction. Truly dissolved Cd and Zn concentrations contributed (on average) 26% and 28% respectively, of the total EMCs with truly dissolved Cu and Ni contributing (on average) 18%. In contrast, only 1% (V) and 3% (Cr) were identified in the truly dissolved fraction. The greatest contribution of truly dissolved Cd, Cu and Zn concentrations (relative to total oncentrations) were reported during rainfall events. However, no seasonal differences were identified and differences between the sites regarding the EMCs distribution by fractions were not at a statistically significant level (p N 0.05) for any metal or event. The loads of truly dissolved and colloidal metals did not follow the patterns of particulate metal loads indicating particulates are not the main source of subdissolved metals. The data suggests that ultrafiltration as a treatment technique would not efficiently mitigate the risks posed by metals to receiving water cologie
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