The biogeochemical interface (BGI) in this project is defined as the organo-mineral surface of soil particles colonized by microorganisms. In the preceding project it was demonstrated that the different soil particle size fractions were associated with specifically structured microbial communities, a characteristic amount of soil organic carbon, and a specific capacity for adsorption of the organic chemicals phenol and 2,4-dichlorophenol, respectively. While the diversity of the microbial community was responsive to fertilization-determined additional organic soil carbon in the larger particle size fractions, it was unaffected in clay. Stable isotope probing with 13C-labelled phenol and 2,4-dichlorophenol revealed that the soil organic carbon in the BGIs also affected the diversity of microorganisms involved in the degradation of these chemicals. All these results are yet only based on studying one soil with three organic carbon variants (Bad Lauchstädt) and only two organic compounds. The objective of this 2nd phase project is to apply the innovative technology developed in the 1st phase for studying the BGI processes with soil organic carbon variants from another soil (Ultuna, SPP 1315 site) and with the chiralic anilide Fungicide metalaxyl as an additional compound. This 2nd phase SPP 1315 project will also, in a collaborative effort with two other SPP 1315 partners, investigate (1) the importance of BGIs for the entantio-selective degradation of metalaxyl and (2) the role of soil microorganisms in the formation of bound residues, respectively. Furthermore, the project will utilize stable isotope probing and next-generation DNA sequencing to link the structural and functional diversity of the microbial communities responsible for metabolism of organic chemicals in the different BGIs determined by particle size fractions and soil organic carbon variants.
Changes in agroecosystem management (e.g. landscape diversity, management intensity) affect the natural control of pests. The effects of agricultural change on this ecosystem service, however, are not universal and the mechanisms affecting it remain to be understood. As biological control is effectively the product of networks of interactions between pests and their natural enemies, food web analysis provides a versatile tool to address this gap of knowledge. The proposed project will utilize a molecular food web approach and examine, for the first time, how changes in plant fertilisation and landscape complexity affect quantitative aphid-parasitoid-hyperparasitoid food webs on a species-specific level to unravel how changes in food web interactions affect parasitoid aphid control. Based on the fieldderived data, cage experiments will be conducted to assess how parasitoid diversity and identity affect parasitoid interactions and pest control, complementing the field results. The work proposed here will take research on parasitoid aphid control one step further, as it will provide a clearer understanding of how plant fertilization affects whole aphid-parasitoid food webs in both simple and complex landscapes, allowing for further improvements in natural pest control.
Sandy soils of the arid/semiarid dune fields of the Palestinian Gaza Strip and the Israeli western Negev are extensively covered by biological soil crusts (BSC), which stabilize the surface and prevent desertification. Political discussions in Israel suggest transferring a large part of this sand belt to the Gaza Strip within a final peace accord. Inappropriate land uses may lead to destruction of the BSC and initiate desertification, as already occurring in parts of the Gaza Strip. In this interdisciplinary project the influence of environmental factors on the vitality, stability and the recovery potential of the BSC will be investigated in order to evaluate the carrying capacity of this fragile landscape, in relation to rainfall, soil and relief conditions. A transect stretching from the Mediterranean coast in the Palestinian Gaza Strip (370 mm rainfall) to 65 km southwards in Israel ( Nizzana , less than 100 mm rainfall) has been selected. The interactions of molecular biological, physiological, physical and soil chemical processes, expressed in specific characteristics of the BSC and the underlying soil, will be assessed from the molecular to the landscape scale.
Subproject 3 will investigate the effect of shifting from continuously flooded rice cropping to crop rotation (including non-flooded systems) and diversified crops on the soil fauna communities and associated ecosystem functions. In both flooded and non-flooded systems, functional groups with a major impact on soil functions will be identified and their response to changing management regimes as well as their re-colonization capability after crop rotation will be quantified. Soil functions corresponding to specific functional groups, i.e. biogenic structural damage of the puddle layer, water loss and nutrient leaching, will be determined by correlating soil fauna data with soil service data of SP4, SP5 and SP7 and with data collected within this subproject (SP3). In addition to the field data acquired directly at the IRRI, microcosm experiments covering the broader range of environmental conditions expected under future climate conditions will be set up to determine the compositional and functional robustness of major components of the local soil fauna. Food webs will be modeled based on the soil animal data available to gain a thorough understanding of i) the factors shaping biological communities in rice cropping systems, and ii) C- and N-flow mediated by soil communities in rice fields. Advanced statistical modeling for quantification of species - environment relationships integrating all data subsets will specify the impact of crop diversification in rice agro-ecosystems on soil biota and on the related ecosystem services.
Chlorinated ethylenes are prevalent groundwater contaminants. Numerous studies have addressed the mechanism of their reductive dehalogenation during biodegradation and reaction with zero-valent iron. However, despite insight with purified enzymes and well-characterized chemical model systems, conclusive evidence has been missing that the same mechanisms do indeed prevail in real-world transformations. While dual kinetic isotope effect measurements can provide such lines of evidence, until now this approach has not been possible for chlorinated ethylenes because an adequate method for continuous flow compound specific chlorine isotope analysis has been missing. This study attempts to close this prevalent research gap by a combination of two complementary approaches. (1) A novel analytical method to measure isotope effects for carbon and chlorine. (2) A carefully chosen set of well-defined model reactants representing distinct dehalogenation mechanisms believed to be important in real-world systems. Isotope trends observed in biotic and abiotic environmental dehalogenation will be compared to these model reactions, and the respective mechanistic hypotheses will be confirmed or discarded. With this hypothesis-driven approach it is our goal to elucidate for the first timdehalogenation reactions.
Über dem Nordatlantik und Europa wird die Variabilität der großräumigen Wetterbedingungen von quasistationären, langandauernden und immer wiederkehrenden Strömungsmustern â€Ì sogenannten Wetterregimen â€Ì geprägt. Diese zeichnen sich durch das Auftreten von Hoch- und Tiefdruckgebieten in bestimmten Regionen aus. Verlässliche Wettervorhersagen auf Zeitskalen von einigen Tagen bis zu einigen Monaten im Voraus hängen von einer korrekten Darstellung der Lebenszyklen dieser Strömungsregime in Computermodellen ab. Um das zu erreichen müssen insbesondere Prozesse, die günstige Bedingungen zur Intensivierung von Tiefdruckgebieten aufrecht erhalten, und Prozesse, die den Aufbau von stationären Hochdruckgebieten (blockierende Hochs) begünstigen, richtig wiedergegeben werden. Aktuelle Forschung deutet stark darauf hin, dass Atmosphäre-Ozean Wechselwirkungen, insbesondere entlang des Golfstroms, latente Wärmefreisetzung in Tiefs, und Kaltluftausbrüche aus der Arktis dabei eine entscheidende Rolle spielen. Dennoch mangelt es an grundlegendem Verständnis wie solche Luftmassentransformationen über dem Ozean die großskalige Höhenströmung beeinflussen. Darüber hinaus ist die Relevanz solcher Prozesse für Lebenszyklen von Wetterregimen unerforscht. In dieser anspruchsvollen drei-jährigen Kollaboration zwischen KIT und ETH Zürich streben wir an ein ganzheitliches Verständnis zu entwickeln, wie Wärmeaustausch zwischen Ozean und Atmosphäre und diabatische Prozesse in der Golfstromregion die Variabilität der großräumigen Strömung über dem Nordatlantik und Europa prägen. Zu diesem Zweck werden wir ausgefeilte Diagnostiken zur Charakterisierung von Luftmassen mit neuartigen Diagnostiken zur Bestimmung des atmosphärischen Energiehaushaltes verbinden und damit den Ablauf von Wetterregimen und Regimewechseln in aktuellen hochaufgelösten numerischen Modelldatensätzen und mit Hilfe von eigenen Sensitivitätsstudien untersuchen. Dazu werden wir unsere Expertise in größräumiger Dynamik und Wettersystemen, sowie Atmosphäre-Ozean Wechselwirkungen â€Ì insbesondere während arktischen Kaltluftausbrüchen â€Ì und der Lagrangeâ€Ìschen Untersuchung atmosphärischer Prozesse nutzen. Im Detail werden wir (i) ein dynamisches Verständnis entwickeln, wie Luftmassentransformationen entlang des Golfstroms die Höhenströmung über Europa beeinflussen, mit Fokus auf blockierenden Hochdruckgebieten, (ii) die Bedeutung von Luftmassentransformationen und diabatischer Prozesse für den Erhalt von Bedingungen, die die Intensivierung von Tiefdruckgebieten während bestimmter Wetterregimelebenszyklen bestimmen, untersuchen, (iii) diese Erkenntnisse in ein einheitliches und quantitatives Bild vereinen, welches die Prozesse, die den Einfluss des Golfstroms auf die großräumige Wettervariabilität prägen, zusammenfasst und (iv) die Güte dieser Prozesse in aktuellen numerischen Vorhersagesystemen bewerten. Diese Grundlagenforschung wird wichtige Erkenntnisse zur Verbesserung von Wettervorhersagemodellen liefern.
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.
We are currently facing the urgent need to improve our understanding of carbon cycling in subsoils, because the organic carbon pool below 30 cm depth is considerably larger than that in the topsoil and a substantial part of the subsoil C pool appears to be much less recalcitrant than expected over the last decades. Therefore, small changes in environmental conditions could change not only carbon cycling in topsoils, but also in subsoils. While organic matter stabilization mechanisms and factors controlling its turnover are well understood in topsoils, the underlying mechanisms are not valid in subsoils due to depth dependent differences regarding (1) amounts and composition of C-pools and C-inputs, (2) aeration, moisture and temperature regimes, (3) relevance of specific soil organic carbon (SOC) stabilisation mechanisms and (4) spatial heterogeneity of physico-chemical and biological parameters. Due to very low C concentrations and high spatio-temporal variability of properties and processes, the investigation of subsoil phenomena and processes poses major methodological, instrumental and analytical challenges. This project will face these challenges with a transdisciplinary team of soil scientists applying innovative approaches and considering the magnitude, chemical and isotopic composition and 14C-content of all relevant C-flux components and C-fractions. Taking also the spatial and temporal variability into account, will allow us to understand the four-dimensional changes of C-cycling in this environment. The nine closely interlinked subprojects coordinated by the central project will combine field C-flux measurements with detailed analyses of subsoil properties and in-situ experiments at a central field site on a sandy soil near Hannover. The field measurements are supplemented by laboratory studies for the determination of factors controlling C stabilization and C turnover. Ultimately, the results generated by the subprojects and the data synthesized in the coordinating project will greatly enhance our knowledge and conceptual understanding of the processes and controlling factors of subsoil carbon turnover as a prerequisite for numerical modelling of C-dynamics in subsoils.
Die Grenzfläche zwischen Ozean und Atmosphäre ist durch einen allgegenwärtigen, < 1 mm dicken marinen Oberflächenfilm, den sogenannten sea-surface microlayer (SML), charakterisiert. Der SML ist nicht nur direkter UV-Strahlung und atmosphärischen Oxidantien ausgesetzt, sondern zeichnet sich im Vergleich zum unterliegenden Wasser auch durch höhere Konzentrationen an organischen Stoffen aus. Bisher ist unklar, welche Bedeutung die dadurch bedingten SML-spezifischen abiotischen Prozesse für die Umsetzung und die Emission organischer Stoffe insgesamt haben und wie man diese Prozesse parametrisieren kann. In diesem Projekt, das eng mit anderen Projekten der interdisziplinären Forschungsgruppe â€ÌBiogeochemische Prozesse und Ozean/Atmosphäre- Austauschprozesse in marinen Oberflächenfilmen (BASS)â€Ì verbunden ist, sollen daher molekulare Details SML-spezifischer Reaktionen (Photochemie, heterogene Oxidation, Radikalchemie) genauer untersucht werden. Ziel ist es, Reaktionsprodukte und -geschwindigkeiten quantitativ zu erfassen und Unterschiede zwischen Reaktionen im SML und in der freien Wassersäule herauszuarbeiten. Basierend auf der Expertise der drei beteiligten Arbeitsgruppen im Bereich Photochemie, Reaktionskinetik, Laserspektroskopie, Analytik und theoretischer Modellierung, soll ein molekulares Verständnis ausgewählter Reaktionen und des Einflusses der komplexen SML-Reaktionsumgebung erreicht werden. Dazu sollen experimentelle Verfahren wie Schwingungs-Summenfrequenzerzeugung, hochempfindliche Chromatographie-Massenspektrometrie und gepulste Laserphotolyse-Langwegabsorption mit Methoden der Quantenchemie und Molekulardynamik kombiniert werden. Arbeitsschwerpunkte bilden die Oxidationskinetik von Halogen- bzw. Hydroxyl-Radikalreaktionen in der flüssigen Phase, die Ozonolyse von Fettsäure-Monoschichten und die durch Photosensibilisatoren verstärkte Bildung von reaktiven Radikalen bzw. Zersetzung von organischen Schichten. Neben wohldefinierten Labor-Modellsystemen werden auch natürliche Proben analysiert werden. Dabei stellt sich z.B. die Frage nach den Einflussfaktoren der während einer Algenblüte zunehmenden Bildung von oberflächenaktiven Stoffen im SML und der Bedeutung der durch die Sonne bedingten Photolyse auf die abiotische Umsetzung organischer Stoffe. Flankierend werden im Projekt auch die eingesetzten Untersuchungsmethoden weiterentwickelt; das beinhaltet sowohl die Ausarbeitung von Messprotokollen zur Quantifizierung bestimmter organischen Substanzklassen (z.B. Carbonyle und Kohlenhydrate) im SML, die Synthese und Charakterisierung von neuartigen oberflächenaktiven Photosensibilisatoren (z.B. Benzoyl-Benzoesäure-funktionalisierte Lipide) sowie die Entwicklung und Erprobung mehrstufiger Modellierungsverfahren zur theoretischen Beschreibung von Struktur-Reaktivitätsbeziehungen der Fettsäure-Ozonolyse (z.B. Beschreibung des Einflusses sterischer und elektronischer Effekte der organischen Matrix).
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.
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