Dieser Fortsetzungsantrag eines bestehenden Forschungsprojekts innerhalb der Forschergruppe INUIT (Ice Nuclei Research UnIT) hat zum Ziel, die physikalischen und chemischen Eigenschaften von atmosphärischen Eiskeimen (ice nucleating particles, INP) und Eispartikelresiduen (ice particle residuals, IPR) zu untersuchen. Es werden hauptsächlich zwei Messtechniken eingesetzt: virtueller Gegenstromimpaktor und Laserablationsmassenspektrometrie. Eiskeime (INP) aus atmosphärischem Aerosol werden erst in einem Eiskeimzähler aktiviert, so dass sich Eiskristalle bilden, die dann mit einem bepumpten Gegenstromimpaktor aufgrund ihrer Größe extrahiert und verdunstet werden können. Die freigesetzten INP können wiederum mit dem Massenspektrometer oder anderen Messtechniken untersucht werden. Dieses Experiment wird während einer Feldmesskampagne in der Nähe der Quellen von potentiell guten Eiskeimen (Mineralstaub, Biopartikel, anthropogene Partikel) durchgeführt. Ein geeigneter Kampagnenort hierfür ist die Mittelmeerregion, z.B. Südspanien. Die Eispartikelresiduen werden direkt aus unterkühlten Mischphasenwolken gesammelt. Hierzu wird ein spezieller Eis-Gegenstromimpaktor eingesetzt, der nur Eiskristalle sammelt und von den unterkühlten Wolkentröpfchen trennt. Nach der Sammlung wird das Eis der Eiskristalle verdunstet, so dass die Eisresidualpartikel freigesetzt werden und mittels des Laser- Ablationsmassenspektrometers analysiert werden können. Dieses Experiment wird auf einer Bergstation (Jungfraujoch) durchgeführt. Die Kombination aus Eiskeimzähler, bepumptem Gegenstromimpaktor und Massenspektrometer wird auch unter Laborbedingen zur Bestimmung der Eiskeimfähigkeit von internen und externen Partikelmischungen (z.B. biologisch/mineralisch) betrieben. Das Laserablationsmassenspektrometer in seiner Eigenschaft als Einzelpartikel-Analysegerät wird ebenfalls dazu eingesetzt, um den Mischungszustand der erzeugten Mischpartikel zu charakterisieren.
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).
Comprehension of belowground competition between plant species is a central part in understanding the complex interactions in intercropped agricultural systems, between crops and weeds as well as in natural ecosystems. So far, no simple and rapid method for species discrimination of roots in the soil exists. We will be developing a method for root discrimination of various species based on Fourier Transform Infrared (FTIR)-Attenuated Total Reflexion (ATR) Spectroscopy and expanding its application to the field. The absorbance patterns of FTIR-ATR spectra represent the chemical sample composition like an individual fingerprint. By means of multivariate methods, spectra will be grouped according to spectral and chemical similarity in order to achieve species discrimination. We will investigate pea and oat roots as well as maize and barnyard grass roots using various cultivars/proveniences grown in the greenhouse. Pea and oat are recommendable species for intercropping to achieve superior grain and protein yields in an environmentally sustainable manner. To evaluate the effects of intercropping on root distribution in the field, root segments will be measured directly at the soil profile wall using a mobile FTIR spectrometer. By extracting the main root compounds (lipids, proteins, carbohydrates) and recording their FTIR-ATR spectra as references, we will elucidate the chemical basis of species-specific differences.
Water is an intrinsic component of ecosystems acting as a key agent of lateral transport for particulate and dissolved nutrients, forcing energy transfers, triggering erosion, and driving biodiversity patterns. Given the drastic impact of land use and climate change on any of these components and the vulnerability of Ecuadorian ecosystems with regard to this global change, indicators are required that not merely describe the structural condition of ecosystems, but rather capture the functional relations and processes. This project aims at investigating a set of such functional indicators from the fields of hydrology and biogeochemistry. In particular we will investigate (1) flow regime and timing, (2) nutrient cycling and flux rates, and (3) sediment fluxes as likely indicators. For assessing flow regime and timing we will concentrate on studying stable water isotopes to estimate mean transit time distributions that are likely to be impacted by changes in rainfall patterns and land use. Hysteresis loops of nitrate concentrations and calculated flux rates will be used as functional indicators for nutrient fluxes, most likely to be altered by changes in temperature as well as by land use and management. Finally, sediment fluxes will be measured to indicate surface runoff contribution to total discharge, mainly influenced by intensity of rainfall as well as land use. Monitoring of (1) will be based on intensive sampling campaigns of stable water isotopes in stream water and precipitation, while for (2) and (3) we plan to install automatic, high temporal-resolution field analytical instruments. Based on the data obtained by this intensive, bust cost effective monitoring, we will develop the functional indicators. This also provides a solid database for process-based model development. Models that are able to simulate these indicators are needed to enable projections into the future and to investigate the resilience of Ecuadorian landscape to global change. For the intended model set up we will couple the Catchment Modeling Framework, the biogeochemical LandscapeDNDC model and semi-empirical models for aquatic diversity. Global change scenarios will then be analyzed to capture the likely reaction of functional indicators. Finally, we will contribute to the written guidelines for developing a comprehensive monitoring program for biodiversity and ecosystem functions. Right from the beginning we will cooperate with four SENESCYT companion projects and three local non-university partners to ensure that the developed monitoring program will be appreciated by locals and stakeholders. Monitoring and modelling will focus on all three research areas in the Páramo (Cajas National Park), the dry forest (Reserva Laipuna) and the tropical montane cloud forest (Reserva Biologica San Francisco).
The aim of P2 within the Research Unit 'The Forgotten Part of Carbon Cycling: Organic Matter Storage and Turnover in Subsoils (SUBSOM)' is to contribute to the understanding of the different sources and stabilization processes of subsoil organic matter. This will be achieved by the analysis of the soil organic matter composition in topsoil versus subsoil by 13C NMR spectroscopy in bulk soils as well as organo-mineral associations. This will be done on a number of soil profiles differing in parent material and mineralogy and therefore also in the relevance of organo-mineral associations for subsoil C stabilization. In addition, a specific sampling approach will allow to differentiate three zones associated with the dominating effect of (1) leaching of DOC (the 'bulk soil' between trees), (2) root litter decomposition (the 'root-affected zone'), and (3) direct rhizodeposition of root exudates (the 'rhizosphere' sensu strictu). The contribution of above-ground versus below-ground litter is differentiated by the analysis of cutin and suberin biomarkers. Organic matter derived from microbial sources will be identified by the microbial signature of polysaccharides in the subsoil through the analysis of neutral sugars and amino sugars. Organo-mineral associations will be further characterized by N2-BET analyses to delineate the coverage of the mineral phase with organic matter. With these analyses and our specific analytical expertise at the submicron scale (nanoSIMS) we will participate in selected joint experiments of the research unit.
In my project I aim at a better understanding of the evolution of malacostracan crustaceans, which includes very different groups such as mantis shrimps, krill and lobsters. Previous studies on Malacostraca, on extant as well as on fossil representatives, focussed on adult morphology.In contrast to such approaches, I will apply a Palaeo-Evo-Devo approach to shed new light on the evolution of Malacostraca. Palaeo-Evo-Devo uses data of different developmental stages of fossil malacostracan crustaceans, such as larval and juvenile stages. With this approach I aim at bridging morphological gaps between the different diverse lineages of modern malacostracans by providing new insights into the character evolution in these lineages.An extensive number of larval and juvenile malacostracans is present in the fossil record, but which have only scarcely been studied. The backbone of this project will be on malacostracans from the Solnhofen Lithographic Limestones (ca. 150 million years old), which are especially well preserved and exhibit minute details. During previous studies, I developed new documentation methods for tiny fossils from these deposits, e.g., fluorescence composite microscopy, and also discovered the first fossil mantis shrimp larvae. For malcostracan groups that do not occur in Solnhofen, I will investigate fossils from other lagerstätten, e.g., Mazon Creek and Bear Gulch (USA), or Montceaules- Mines and La-Voulte-sur-Rhône (France). The main groups in focus are mantis shrimps and certain other shrimps (e.g., mysids, caridoids), as well as the bottom-living ten-footed crustaceans (reptantians). Examples for studied structures are leg details, including the feeding apparatus, but also eyes. The results will contribute to the reconstruction of 3D computer models.The data collected in this project will be used for evaluating the relationships within Malacostraca, but mainly for providing plausible evolutionary scenarios, how the modern malacostracan diversity evolved. With the Palaeo-Evo-Devo approach, I am also able to detect shifts in developmental timing, called heterochrony, which is interpreted as one of the major driving forces of evolution. Finally, the reconstructed evolutionary patterns can be compared between the different lineages for convergencies. These comparisons might help to explain the convergent adaptation to similar ecological niches in different malacostracan groups, e.g., life in the deep sea, life on the sea bottom, evolution of metamorphosis or of predatory larvae.As the project requires the investigation of a large number of specimens in different groups, I will assign distinct sub-projects to three doctoral researchers. The results of this project will not only be published in peer-reviewed journals, but will also be presented to the non-scientific public, e.g., during fossil fairs or museum exhibitions with 3D models engraved in glass blocks.
In structured soils, the interaction of percolating water and reactive solutes with the soil matrix is mostly restricted to the surfaces of preferential flow paths. Flow paths, i.e., macropores, are formed by worm burrows, decayed root channels, cracks, and inter-aggregate spaces. While biopores are covered by earthworm casts and mucilage or by root residues, aggregates and cracks are often coated by soil organic matter (SOM), oxides, and clay minerals especially in the clay illuviation horizons of Luvisols. The SOM as well as the clay mineral composition and concentration strongly determine the wettability and sorption capacity of the coatings and thus control water and solute movement as well as the mass exchange between the preferential flow paths and the soil matrix. The objective of this proposal is the quantitative description of the small-scale distribution of physicochemical properties of intact structural surfaces and flow path surfaces and of their distribution in the soil volume. Samples of Bt horizons of Luvisols from Loess will be compared with those from glacial till. At intact structural surfaces prepared from soil clods, the spatial distribution (mm-scale) of SOM and clay mineral composition will be characterized with DRIFT (Diffuse reflectance infrared Fourier transform) spectroscopy using a self-developed mapping technique. For samples manually separated from coated surfaces and biopore walls, the contents of organic carbon (Corg) and the cation exchange capacity (CEC) will be analyzed and related to the intensities of specific signals in DRIFT spectra using Partial Least Square Regression (PLSR) analysis. The signal intensities of the DRIFT mapping spectra will be used to quantify the spatial distribution of Corg and CEC at these structural surfaces. The DRIFT mapping data will also be used for qualitatively characterizing the small scale distribution of the recalcitrance, humification, and microbial activity of the SOM from structural surfaces. The clay mineral composition of defined surface regions will be characterized by combining DRIFT spectroscopic with X-ray diffractometric analysis of manually separated samples. Subsequently, the spatial distribution of the clay mineral composition at structural surfaces will be determined from the intensities of clay mineral-specific signals in the DRIFT mapping spectra and exemplarily compared to scanning electron microscopic and infrared microscopic analysis of thin sections and thin polished micro-sections. The three-dimensional spatial distribution of the total structural surfaces in the volume of the Bt horizons will be quantified using X-ray computed tomography (CT) analysis of soil cores. The active preferential flow paths will be visualized and quantified by field tracer experiments. These CT and tracer data will be used to transfer the properties of the structural surfaces characterized by DRIFT mapping onto the active preferential flow paths in the Bt horizons.
Organotin and especially butyltin compounds are used for a variety of applications, e.g. as biocides, stabilizers, catalysts and intermediates in chemical syntheses. Tributyltin (TBT) compounds exhibit the greatest toxicity of all organotins and have even been characterized as one of the most toxic groups of xenobiotics ever produced and deliberately introduced into the environment. TBT is not only used as an active biocidal compound in antifouling paints, which are designed to prevent marine and freshwater biota from settlement on ship hulls, harbour and offshore installations, but also as a biocide in wood preservatives, textiles, dispersion paints and agricultural pesticides. Additionally, it occurs as a by-product of mono- (MBT) and dibutyltin (DBT) compounds, which are used as UV stabilizer in many plastics and for other applications. Triphenyltin (TPT) compounds are also used as the active biocide in antifouling paints outside Europe and furthermore as an agricultural fungicide since the early 1960s to combat a range of fungal diseases in various crops, particularly potato blight, leaf spot and powdery mildew on sugar beet, peanuts and celery, other fungi on hop, brown rust on beans, grey moulds on onions, rice blast and coffee leaf rust. Although the use of TBT and TPT was regulated in many countries world-wide from restrictions for certain applications to a total ban, these compounds are still present in the environment. In the early 1970s the impact of TBT on nontarget organisms became apparent. Among the broad variety of malformations caused by TBT in aquatic animals, molluscs have been found to be an extremely sensitive group of invertebrates and no other pathological condition produced by TBT at relative low concentrations rivals that of the imposex phenomenon in prosobranch gastropods speaking in terms of sensitivity. TBT induces imposex in marine prosobranchs at concentrations as low as 0,5 ng TBT-Sn/L. Since 1993, for the littorinid snail Littorina littorea a second virilisation phenomenon, termed intersex, is known. In female specimens affected by intersex the pallial oviduct is transformed of towards a male morphology with a final supplanting of female organs by the corresponding male formations. Imposex and intersex are morphological alterations caused by a chronic exposure to ultra-trace concentrations of TBT. A biological effect monitoring offers the possibility to determine the degree of contamination with organotin compounds in the aquatic environment and especially in coastal waters without using any expensive analytical methods. Furthermore, the biological effect monitoring allows an assessment of the existing TBT pollution on the basis of biological effects. Such results are normally more relevant for the ecosystem than pure analytical data. usw.
Die Bildung der Eis Phase in der Troposphäre stellt einen wichtigen Fokus der aktuellen Atmosphärenforschung dar. Durch heterogene Nukleation entstehen bei Temperaturen oberhalb von -37°C primäre Eiskristalle an sogenannten eiskeimbildenden Partikeln (INP, engl, ice nucleating particles). Die räumliche Verteilung der INP und deren Quellen variieren stark. In der Atmosphäre finden sich INP nur in sehr geringer Anzahlkonzentration, oft weniger als ein Partikel pro Liter, und sie stellen nur eine kleine Untergruppe des gesamten atmosphärischen Aerosols dar. Ziel dieses Antrages ist es die Anzahlkonzentrationen von eiskeimbildenden Partikeln und deren Variabilität in der Atmosphäre zu messen. Außerdem sind Laborstudien geplant, in denen unser Verständnis über die chemischen und biologischen Eigenschaften der Partikel, die die Eisbildung initiieren, verbessert werden soll. Mit dem von unserer Arbeitsgruppe entwickelten Eiskeimzahler FINCH (Fast Ice Nucleaus CHamber) sollen die atmosphärischen Anzahlkonzentrationen von INP bei verschiedenen Gefriertemperaturen und Übersättigungen an mehreren Standorten gemessen werden. Die Kopplung von FINCH mit einem virtuellen Gegenstromimpaktor (CVI, engl, counter-flow virtual impactor, Kooperation mit RP2), die während lNUIT-1 entwickelt und getestet wurde, soll nun weiter charakterisiert und Messungen damit fortgesetzt werden. Bei dieser Methode werden die Eispartikel, die in FINCH gebildet werden, von den unterkühlten Tröpfchen und inaktivierten Partikeln separiert und mit weiteren Messmethoden untersucht. In Kooperation mit RP2 und RP8 planen wir hierbei die Charakterisierung der INP mittels Größen- und Aerosolmassenspektrometer sowie die Sammlung der INP auf Filtern oder Impaktorplatten zur anschließenden Analyse mit einem Elektronenmikroskop (ESEM, engl. DFG fomi 54.011 -04/14 page 3 of 6 Environmental Scanning Electron Microscopy). Die Feldmessdaten werden von umfangreichen Laborstudien an den Forschungseinrichtungen AIDA (RP6) und LACIS (RP7) ergänzt. Dort soll das Immersionsgefrieren von verschiedenen Testpartikeln aus biologischem Material (z.B. Zellulose), porösem Material (z.B. Zeolith) und Mineralstaub mit geringem organischem Anteil im Detail untersucht werden. Des Weiteren planen wir Labormessungen, bei denen eine verbesserte Charakterisierung der Messunsicherheiten von FINCH erarbeitet werden soll. Außerdem werden regelmäßige Tests und Kalibrierungen mit FINCH durchgeführt, für die Standardroutinen festgelegt werden sollen. Um die Rolle der INP bei der Wolken- und Niederschlagsbildung sowie bei den Wolkeneigenschaften abzuschätzen, werden die gewonnenen Messergebnisse am Ende als Eingabeparameter für erweiterte Wolkenmodelle (Kooperation mit WP-M) dienen.
Forests play a relevant role in mitigation of climate change. A major issue, however, is the scientifically well founded, transparent and verifyable monitoring of achievements in forest carbon sequestration through reduction of deforestation and forest degradation, and through fostering sustainable forest management. Monitoring is particularly difficult in diverse and inaccessible humid tropical forest areas. The proposed research will contribute to the improvement of forest carbon monitoring under the challenging conditions of humid tropical forests. Sample based field observations and model based biomass predictions will be linked to area-wide satellite remote sensing imagery (RapidEye) and to strip samples of LiDAR imagery. Techniques of linking these data sources will be further developed and analysed with respect to (1) precision of carbon estimation and (2) accuracy of carbon regionalization. The proposed project implies research on methodological improvements of both sample based forest inventories (resampling techniques for biomass, imputation of non-response) and remote sensing application to forest monitoring (regionalization, sample based application of LiDAR data). At the core of this research is the analysis of the error variance components that each data source brings into the system. Such error analysis will allow identifying optimal resource allocation for the efficient improvement of forest carbon monitoring systems.
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