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  • 1
    Publication Date: 2016-12-19
    Description: A shipboard-deployable, flow-injection (FI) based instrument for monitoring iron(II) in surface marine waters is described. It incorporates a miniature, low-power photon-counting head for measuring the light emitted from the iron-(II)-catalyzed chemiluminescence (CL) luminol reaction. System control, signal acquisition, and data processing are performed in a graphical programming environment. The limit of detection for iron(II) is in the range 8-12 pmol L-1 (based on 3s of the blank), and the precision over the range 8-1000 pmol L-1 varies between 0.9 and 7.6 (n = 4). Results from a day-night deployment during a north-to-south transect of the Atlantic Ocean and a daytime transect in the Sub-Antarctic Front are presented together with ancillary temperature, salinity, and irradiance data. The generic nature of the components used to assemble the instrument make the technology readily transferable to other laboratories and the modular construction makes it easy to adapt the system for use with other CL chemistries.
    Type: Article , PeerReviewed
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  • 2
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    American Chemistry Society
    In:  Environmental Science and Technology, 36 (5). pp. 914-920.
    Publication Date: 2016-12-19
    Description: Using high specific activity 64Cu 2+ as radiotracer, the distribution kinetics among Cu species were established in natural organic-rich freshwaters under steady-state conditions, i.e., with minimal disturbance of existing equilibria. Study sites with contrasting suspended particulate matter (SPM) characteristics were investigated. Our analytical protocol allowed the differentiation between the following Cu species: SPM associated Cu, dissolved reactive (free and labile) Cu, and organically complexed Cu. The data obtained were successfully evaluated by compartmental analysis, which showed the importance of organically complexed Cu in freshwaters, and the dominant role of the interactions between organically complexed Cu and SPM in a SPM-rich water. The kinetic 64Cu measurements indicated that the attainment of equilibrium between dissolved reactive and organically complexed Cu took ca. 〈1-2 h, and 4-15 h for the interaction between dissolved organically complexed and SPM associated Cu. The kinetic study was augmented by voltammetric measurements of the dissolved (stable) Cu equilibrium speciation conditions in the natural waters. These measurements showed that the waters contained very low cupric ion concentrations (10 -12-10 -15 M), with more than 99.9 of the dissolved Cu complexed by strong organic ligands (conditional stability constants: 10 13.4- 10 15.4.
    Type: Article , PeerReviewed
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  • 3
    Publication Date: 2017-10-24
    Description: Siderophores are chelates produced by bacteria as part of a highly specific iron uptake mechanism. They are thought to be important in the bacterial acquisition of iron in seawater and to influence iron biogeochemistry in the ocean. We have identified and quantified two types of siderophores in seawater samples collected from the Atlantic Ocean. These siderophores were identified as hydroxamate siderophores, both ferrioxamine species representative of the more soluble marine siderophores characterized to date. Ferrioxamine G was widely distributed in surface waters throughout the Atlantic Ocean, while ferrioxamine E had a more varied distribution. Total concentrations of the two siderophores were between 3 and 20 pM in the euphotic zone. If these compounds are fully complexed in seawater, they represent approximately 0.2-4.6 of the 〈0.2 μm iron pool. Our data confirm that siderophore-mediated iron acquisition is important for marine heterotrophic bacteria and indicate that siderophores play an important role in the oceanic biogeochemical cycling of iron. © 2008 American Chemical Society.
    Type: Article , PeerReviewed
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  • 4
    Publication Date: 2017-10-24
    Description: Four surveys of the Huelva Estuary in southwest Spain and its sources, the Tinto and the Odiel Rivers, were carried out between 1996 and 1998. The surveys investigated the impact of metalliferous mining of sulfide-rich ores in the catchment area on metal speciation, metal concentrations in a macrophyte, and phytoplankton diversity and abundance. Chemical speciation measurements in the lower Tinto Estuary showed that metals were predominantly electrochemically labile (>99 of total dissolved Cu, Co, and Ni at 10 μM Cu, 424 nM Co, and 500 nM Ni, S = 28). Concentrations of Cu complexing ligands and free cupric ions Cu2+ in the Gulf of Cádiz ranged between 5.3 and 38 nM and 0.2-7.9 pM, respectively, with conditional stability constants of the ligands of log K′CuL = 11.7-12.6. At enhanced dissolved Cu concentrations in the lower Huelva Estuary, Cu complexing ligands were saturated with Cu, resulting in nanomolar Cu2+, which increased upstream. Metal tissue concentrations of the macrophyte Blindingia marginata were high, and a clear relationship between dissolved labile Cu and macrophyte tissue Cu concentrations was observed. A low biodiversity was observed in the Huelva system (Shannon-Wiener indices (H) typically 〈0.2). Nevertheless, the maximum biomass was observed in the lower Tinto Estuary, which showed high labile metal and nutrient concentrations and a low biodiversity (H 〈 0.02), thereby suggesting adaptation through evolutionary processes of the phytoplankton community to the harsh conditions. © 2007 American Chemical Society.
    Type: Article , PeerReviewed
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