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Herkunft von Schelfwasser und Pazifischem Wasser in der arktischen Salzgehaltsschichtung abgeleitet von stabilen Sauerstoffisotopen

Ziel des Projektes ist eine Bestandsaufnahme der Wassermassenverteilung und der Zirkulation im Arktischen Ozean. Stabile Sauerstoffisotopen (delta18O) des Wassers ist ein konservativer Tracer und werden zusammen mit hydrochemischen Daten dazu verwendet das vom Schelf stammende Süßwasser (Flusswasser und Meereis-Schmelze oder Bildung) und die aus dem Pazifik stammende Komponente zu untersuchen. Auf diese Weise wird der Einfluss dieser Wassermassen in der arktischen Salzgehaltsschichtung (Halokline), dem Atlantischen Zwischenwasser und dem Tiefen- und Bodenwasser des Arktischen Ozeans quantifiziert werden. Es ist bekannt, dass die Verteilung der Pazifischen Komponente starken Veränderungen auf dekadischen Zeitskalen unterliegt aber auch in den Süßwasserverteilungen im Transpolaren Drift Strom wurden 2007 starke Variationen beobachtet welche somit auf zusätzliche jährliche Variationen hinweisen. Es ist nicht bekannt ob die 2007 beobachteten Variationen ein permanentes Phänomen sind und ob diese mit dem weitgehenden Fehlen des Pazifischen Wassers in diesem Zeitraum zusammenhängen. Die geplante flächendeckende und quantitative Erfassung der Süßwasserverteilung und des Pazifischen Wassers werden daher dazu beitragen, den Einfluss und die möglichen Rückkopplungsmechanismen der arktischen Hydrographie auf den arktischen und globalen Klimawandel weitergehend zu verstehen.

Forschergruppe (FOR) 1525: INUIT - Ice Nuclei research UnIT, Screening und Charakterisierung biologischer Eiskeime und Untersuchung deren Einflusses auf die Eiskeimaktivität von Boden-und Mineralstaub

Mikroorganismen sind im Boden, in kryptogamen Gemeinschaften und in der Atmosphäre von zentraler Bedeutung. Verschiedene Spezies von Bakterien, Pilzen, Flechten und Pollen wurden bereits als Eiskeime, welche eine Eisbildung bei relativ hohen Temperaturen initiieren können, identifiziert, und besonders biologische Bestandteile aus dem Boden sind eine vermutlich bedeutsame Quelle atmosphärischer Eiskeime. Die genauen Quellen biologischer Eiskeime in der Atmosphäre sind jedoch kaum bekannt, obwohl ein potentieller Beitrag dieser, zur Eis- und Niederschlagsbildung mittlerweile von verschiedenen Studien untermauert wird. Aktuelle Untersuchungen verschiedener Boden- und Luftproben zeigen Hinweise, dass verschiedene eisaktive Pilze unterschiedlicher Phyla nicht nur im Boden und in der Luft vorhanden sind, sondern auch häufig in der kultivierbaren Fraktion vorkommen können. Aus diesem Grund befasst sich das vorgeschlagene Projekt mit der Suche nach weiteren bisher unbekannten eisaktiven Mikroorganismen und Bestandteilen aus dem Boden, von Pflanzen und kryptogamen Gemeinschaften und mit der Erforschung ihres Einflusses auf die Eiskeimaktivität des Bodens. Die nötigen Methoden für ein Screening verschiedenster Kulturen z.B. von Cyanobakterien sind in unserem Labor gut etabliert. Zudem sollen die jeweiligen Eiskeime der neu gefundenen eisaktiven Organismen auf molekularer Ebene charakterisiert werden.

Soil colour spectra of prehistoric pit fillings as a new analytical tool to measure changing soil characteristics over time on a regional scale

Prehistoric pits are filled with ancient topsoil material, which has been preserved there over millennia. A characteristic of these pit fillings is that their colour is different depending on the time the soil material was relocated. Soil colour is the result of soil forming processes and soil properties, and it could therefore indicate the soil characteristics present during that specific period. To the best of our knowledge, no investigation analysed and explained the reasons for these soil colour changes over time. The proposed project will investigate soil parameters from pit fillings of different archaeological periods in the loess area of the Lower Rhine Basin (NW-Germany). It aims to implement the measurement of colour spectra as a novel analytical tool for the rapid analyses of a high number of soil samples: the main goal is to relate highresolution colour data measured by a spectrophotometer to soil parameters that were analysed by conventional pedogenic methods and by mid infrared spectroscopy (MIRS), with a main focus on charred organic matter (BPCAs). This tool would enable us to quantify the variation of soil properties over a timescale of several millennia, during different prehistoric periods at regional scale and for loess soils in general. Detailed information concerning changing soil properties on a regional scale is necessary to determine past soil quality and it helps to increase our understanding of prehistoric soil cultivation practices. Furthermore, these information could also help to increase our understanding about agricultural systems in different archaeological periods.

Ecological-physical linkages in fluvial eco-hydromorphology

Recent discussions on the path eco-hydromorphic research has followed in the past decades highlight the need for greater ecological input into this field. Traditional approaches have been criticized for being largely correlation-based (Vaughan et al., 2009) ecological black boxes (Leclerc, 2005) and strongly relying on weak, disproven and/or outdated assumptions about the dynamics of stream biota (Lancaster & Downes, 2010). In recognition of this, process-oriented research aiming at elucidating and quantifying causal mechanisms has been proposed as a promising approach, though challenging, to study the relations between flow, morphodynamics and biological populations in running waters. In terms of levels of biological organization, it has been recognized that processes determining the response of aquatic biota to hydromorphological alteration occur mainly at the population level. In this sense, relating demographic rates to flow and morphology seems to offer great potential for progress (Lancaster & Downes, 2010). Thus, tapping into existing ecological knowledge (e.g., key patch approach for habitat networks, Verboom et al. 2001; metapopulation theory, Levins 1970; Hanski & Gaggiotti 2004, landscape-scale estimations of habitat suitability and carrying capacity, Reijnen et al. 1995; Duel et al. 1995 2003; population-level viability estimations; Akçakaya 2001; resource utilization scales, ONeill et al. 1988; habitat-use patterns, Milne et al. 1989) in order to link ecology to hydromorphology at a more fundamental level constitutes an important path towards better science and management.

Diffusion and advection with sorption of anions, cations and non-polar molecules in organo-clays at varying thermo-chemical conditions - validation by analytical methods and molecular simulation

The sorption of anions in geotechnical multibarrier systems of planned high level waste repositories (HLWR) and of non-ionic and organic pollutants in conventional waste disposals are in the center of recent research. In aquatic systems, persistent radionuclides such as 79Se, 99Tc, 129I exist in a form of anions. There is strongly increasing need to find materials with high sorption capacities for such pollutants. Specific requirements on barrier materials are long-term stability of adsorbent under various conditions such as T > 100 C, varying hydrostatic pressure, and the presence of competing ions. Organo-clays are capable to sorb high amounts of cations, anions and non-polar molecules simultaneously having selectivity for certain ions. This project is proposed to improve the understanding of sorption and desorption processes in organo-clays. Additionally, the modification of material properties under varying chemical and thermal conditions will be determined by performing diffusion and advection experiments. Changes by sorption and diffusion will be analyzed by determining surface charge and contact angles. Molecular simulations on models of organo-clays will be conducted in an accord with experiments with aim to understand and analyze experimental results. The computational part of the project will profit from the collaboration of German partner with the group in Vienna, which has a long standing experience in a modeling of clay minerals.

International Collaboration in Chemistry: First Principles Multi-Lattice Kinetic Monte Carlo Simulations of NOx Storage Reduction Catalysts

The broad objective of the research is to gain a fundamental understanding of the surface reaction chemistry of exhaust catalysts operating under cycling conditions. Using an integrated theoretical approach we specifically target NOx abatement, with particular emphasis on the appearance and destruction of surface oxide phases as the reactor conditions cycle from oxidative to reductive during the operation of the NOx Storage Reduction (NSR) catalyst system. Methodologically this requires material-specific, quantitative and explicitly time-dependent simulation tools that can follow the evolution of the system over the macroscopic time-scales of NSR cycles, while simultaneously accounting for the atomic-scale site heterogeneity and spatial distributions at the evolving surface. To meet these challenging demands we will develop a novel multi-scale methodology relying on a multi-lattice first-principles kinetic Monte Carlo (kMC) approach. As representative example the simulations will be carried out on a PdO(101)/Pd(100) surface oxide model, but care will be taken to ensure a generalization of the multi-lattice first-principles kMC approach to other systems in which phase transformations may occur and result in a change in the surface lattice structure depending upon environmental variables.

Effect of diffusive/dispersive processes on stable isotope ratios of organic contaminants in aquifer systems

Groundwater contamination by organic compounds represents a widespread environmental problem. The heterogeneity of geological formations and the complexity of physical and biogeochemical subsurface processes, often hamper a quantitative characterization of contaminated aquifers. Compound specific stable isotope analysis (CSIA) has emerged as a novel approach to investigate contaminant transformation and to relate contaminant sources to downgradient contamination. This method generally assumes that only (bio)chemical transformations are associated with isotope effects. However, recent studies have revealed isotope fractionation of organic contaminants by physical processes, therefore pointing to the need of further research to determine the influence of both transport and reactive processes on the observed overall isotope fractionation. While the effect of gasphase diffusion on isotope ratios has been studied in detail, possible effects of aqueous phase diffusion and dispersion have received little attention so far.The goals of this study are to quantify carbon (13C/12C) and, for chlorinated compounds, chlorine (37Cl/35Cl) isotope fractionation during diffusive/dispersive transport of organic contaminants in groundwater and to determine its consequences for source allocation and assessment of reactive processes using isotopes. The proposed research is based on the combination of high-resolution experimental studies, both at the laboratory (i.e. zero-, one- and two-dimensional systems) and at the field scales, and solute transport modeling. The project combines the expertise in the field of contaminant transport with the expertise on isotope methods in contaminant hydrogeology.

Release of hexavalent chromium from ore processing residues and the potential of biochar for chromium immobilization in polluted soils

Chromium (Cr) is introduced into the environment by several anthropogenic activities. A striking ex-ample is the area around Kanpur in the Indian state of Uttar Pradesh, where large amounts of Cr-containing wastes have been recently illegally deposited. Hexavalent Cr, a highly toxic and mobile contaminant, is present in significant amounts in these wastes, severely affecting the quality of sur-roundings soils, sediments, and ground waters. The first major goal of this study is to clarify the solid phase speciation of Cr in these wastes and to examine its leaching behavior. X-ray diffraction and synchrotron-based X-ray absorption spectroscopy techniques will be employed for quantitative solid phase speciation of Cr. Its leaching behavior will be studied in column experiments performed at un-saturated moisture conditions with flow interruptions simulating monsoon rain events. Combined with geochemical modeling, the results will allow the evaluation of the leaching potential and release kinetics of Cr from the waste materials. The second major goal is to investigate the spatial distribution, speciation, and solubility of Cr in the rooting zone of chromate-contaminated soils surrounding the landfills, and to study the suitability of biochar as novel soil amendment for mitigating the deleterious effects of chromate pollution. Detailed field samplings and laboratory soil incubation studies will be carried out with two agricultural soils and biochar from the Kanpur region.

Der Einfluss der SML auf die Spurengasbiogeochemie und den Ozean-Atmosphäre-Gasaustausch

Labor- und Feldstudien zeigen, dass die Oberflächengrenzschicht des Ozeans (â€Ìsurface microlayerâ€Ì, kurz SML) die biogeochemischen Kreisläufe von klimaaktiven und atmosphärisch wichtigen Spurengasen wie Kohlenstoffdioxid (CO2), Kohlenstoffmonoxid (CO), Methan (CH4), Lachgas (N2O) und Dimethylsulfid (DMS) stark beeinflusst: (i) Jüngste Studien aus den PASSME- und SOPRAN-Projekten haben hervorgehoben, dass Anreicherungen von oberflächenaktiven Substanzen (d.h. Tensiden) einen starken (dämpfenden) Effekt sowohl auf die CO2- als auch auf die N2O-Flüsse über die SML/Atmosphären-Grenzfläche hinweg haben und (ii) Spurengase können durch (mikro)biologische oder (photo)chemische Prozesse in der SML produziert und verbraucht werden. Daher kann der oberste Teil des Ozeans, einschließlich der SML, verglichen mit dem Wasser, das in der Mischungsschicht unterhalb der SML zu finden ist, eine bedeutende Quelle oder Senke für diese Gase sein, was von sehr großer Relevanz für die Forschungseinheit BASS ist. Die Konzentrationen von CO2, N2O und anderen gelösten Gasen in der SML (oder den oberen Zentimetern des Ozeans) unterscheiden sich nachweislich von ihren Konzentrationen unterhalb der SML. Typischerweise werden die Nettoquellen und -senken wichtiger atmosphärischer Spurengase mit Konzentrationen berechnet, die in der Mischungsschicht gemessen wurden und mit Gasaustauschgeschwindigkeiten, die die SML nicht berücksichtigen. Diese Diskrepanzen führen zu falsch berechneten Austauschflüssen, die in der Folge zu großen Unsicherheiten in den Berechnungen der Klima-Antrieben und der Luftqualität in Erdsystemmodellen führen können. Durch die Verknüpfung unserer Spurengasmessungen mit Messungen von (i) der Dynamik und den molekularen Eigenschaften der organischen Materie und speziell des organischen Kohlenstoffs (SP1.1; SP1.5), (ii) der biologischen Diversität und der Stoffwechselaktivität (SP1.2), (iii) den optischen Eigenschaften der organischen Materie (SP1.3), (iv) der photochemischen Umwandlung der organischen Materie (SP1.4) und (v) den physikalischen Transportprozessen (SP2.3) werden wir ein umfassendes Verständnis darüber erlangen, wie die SML die Variabilität der Spurengasflüsse beeinflusst.

The importance of peripheral oceanic processes in the Labrador Sea for the Atlantic meridional overturning circulation

The Labrador Sea is one of the few places in the world ocean, where deep water formation takes place. This water is exported from the Labrador Sea to become part of the southward branch of the meridional overturning circulation. Previous observational work has largely focused on the role of deep convection in the interior of the Labrador Sea. Recent evidence from observations and numerical ocean models specifically indicate that processes near the ocean boundaries might be most relevant for both Eulerian downwelling of waters in the Labrador Sea and the fast export of newly transformed waters. We propose to analyze mooring based observations at the western margin of the Labrador Sea together with high resolution numerical model simulations to understand the role both processes play for the meridional overturning circulation in the subpolar North Atlantic. Specifically, we want to test (i) if (and where) downwelling occurs along the margins of the Labrador Sea, (ii) how downwelling relates to the seasonal evolution of convection and eddy activity, (iii) how fast waters newly transformed near the western margin of the Labrador Sea are exported, and (iv) how the two processes (downwelling, fast export) affect the temporal variability of the Atlantic meridional overturning circulation.

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