644 search hits
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Interactions between hydrology and biogeochemistry within riparian wetlands
(2013)
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Sven Frei
- Interactions between hydrology and biogeochemistry at various spatio-temporal scales are important control mechanisms within terrestrial and aquatic ecosystems and exist among different compartments and transition interfaces. Understanding the fundamental mechanistic couplings between hydrological and biogeochemical processes and how these couplings feed back into ecosystem services and functions is an interdisciplinary challenge that must be addressed especially in the context of humanly mediated climate change. Riparian wetlands, as a transition zone between terrestrial and aquatic ecosystems, occupy large fractions of terrestrial ecosystems and provide important ecohydrological services. Due to their anoxic environments, riparian wetlands are able to store significant amounts of carbon as peat and act as an effective nutrient sink e.g. for sulfur, phosphorous and nitrogen. Riparian wetlands are characterized by highly dynamical interactions between hydrologically controlled transport mechanisms and biogeochemically controlled substrate availability, which governs nutrient cycling as well as the sink and source functions of wetlands. Generally, these interactions and their potential implications on ecosystem functions are only poorly understood. The representation of the tight couplings between hydrology and biogeochemistry in mechanistic models is a very challenging task because they have revealed a complexity which is often beyond the capabilities of current models. The objective of this thesis is to investigate interactions between hydrology and biogeochemistry in riparian wetlands and to understand their potential implications for internal biogeochemical process distributions and solute mobilization. Additionally, one major focus of the thesis is the attempt to represent such fundamental couplings in a process-based, hydrological/biogeochemical modeling approach. To this end, this thesis uses a combination of field and virtual experiments, as well as catchment-scale numerical modeling, performed for the Lehstenbach catchment, which was exemplarily chosen as main study site.
Results from the virtual experiments show very complex small-scale hydrological dynamics within the riparian areas. Here, runoff generation processes are strongly influenced by the spatial structure of the wetland-typical micro-topography (hummocks and hollows). Surface flow is episodically generated by a highly dynamical, threshold-controlled process where extended surface flow networks drain large fractions of the wetland's area. During intensive rainstorm events these surface flow networks, which contribute to stream discharge due to a fill and spill mechanism, dominate runoff generation. These fast flow components are characterized by very low residence times (minutes to hours) and once they are activated, the surface flow networks are able to rapidly mobilize large amounts of solutes, like nitrate or dissolved organic carbon (DOC), out of the wetlands by bypassing deeper anoxic layers. The importance of fast flow components for the catchment-scale mobilization of DOC was further confirmed by field investigations and catchment-scale numerical modeling. High frequency measurements of DOC in runoff of the Lehstenbach catchment revealed that DOC export is subject to substantial short term variations at an hourly to daily timescale. During intense rainstorms, DOC concentrations are up to ten times higher (up to 40 mg/L) compared to low flow conditions (~3-5 mg/L). Short term variations together with the dramatic rise of DOC concentrations in runoff during rainstorms can be explained by the episodically activation of fast flow components in the wetland areas. At the catchment-scale, application of a hydraulic mixing-cell (HMC) methodology in combination with numerical modeling has revealed that fast flow components like saturated overland flow are exclusively generated in the wetland areas during intensive rainstorm events. On an annual basis, exemplarily for the hydrological year 2001, the HMC analysis quantified the relative contribution of saturated overland flow related to the total discharge with 19.5%, which highlights the importance of riparian wetlands for catchment-scale runoff generation.
Virtual experiments, additionally show that distinct shifts between surface and subsurface flow dominance, as a result of small-scale micro-topographic driven runoff generation in the wetlands, are responsible for very complex three-dimensional subsurface flow patterns showing a wide range of subsurface residence times. To investigate how these micro-topography induced subsurface flow patterns, together with the non-uniform hydrological and biogeogeochemical boundary conditions, affect the internal re-distribution and transformation of redox-sensitive species (like nitrate, sulfate or iron) a coupled hydrological/biogeogeochemical model was developed. In the model, wetland-typical biogeochemical processes are represented in a sequential stream tube approach where redox-sensitive processes are implemented as kinetic reactions. Simulations show the formation of local hot spots for redox-sensitive processes within the subsurface as a result of the complex subsurface flow paths and the transport-limited availability of electron acceptors and donors. Formation of hot spots was simulated for all key reduction processes including iron(III)-/sulfate reduction and denitrification as well as for the corresponding re-oxidation processes. These results offer a new perspective on hydrologically controlled biogeochemical transformation processes in riparian wetlands, which provides a dynamic framework to explain process heterogeneity in wetland soils and variability in process rates over space and time.
Findings from this thesis clearly prove how useful interdisciplinary approaches are in understanding processes and mechanisms in ecosystems and how important functions of ecosystems are affected by couplings among those. However, a lot of knowledge gaps still exist in understanding the nature of dependency between water and nutrient cycles across scales and how these interacting cycles feed back into humanly-mediated climate change in ecosystems. Development of new interdisciplinary methodologies and frameworks as well as an integrated way of thinking across the boundaries of the different environmental disciplines is necessary to address the grand challenges associated with climate change.
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Über lasergeheizte kolloidale Goldnanopartikel in Polymerlösungen
(2013)
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Florian Schwaiger
- Im Rahmen dieser Arbeit wurden verschiedene Aspekte untersucht, die im Zusammenhang mit photothermischen Effekten durch absorbierende Goldkollide in binären Polymerlösungen stehen. Dabei kamen neben den experimentellen Untersuchungen durch Hellfeld- und Phasenkontrastmikroskopie in Verbindung mit lokalen Laserheizungen und Methoden der CCD-Einzelteilchenverfolgung auch numerische Verfahren zur Lösung von Differentialgleichungen zum Einsatz.
Das durch Absorption von Laserlicht erzeugte Temperaturfeld isolierter Goldnanopartikel wurde analytisch und die Abweichungen vom Idealfall eines unendlich ausgedehnten Mediums homogener Wärmeleitung mit Comsol für spezielle Geometrien und Grenzfälle berechnet.
Nach diesen Untersuchungen in isothermen Systemen wurde dann die Käfigbildung um geheizte Goldkolloide in Polymerlösungen untersucht. Zur theoretischen Beschreibung des System Polystyrol/Toluol wurde der Soret-Koeffizient als Funktion der Konzentration, Molmasse und Temperatur parametrisiert. Dabei wurden neben Literaturwerten für die Molmassenabhängigkeit auch eigene Messungen der Transportkoeffizienten für die Temperatur- und Konzentrationsabhängigkeit verwendet. Die Parametrisierung des Soret-Koeffizienten reproduziert in den essentiellen Grenzfällen großer und kleiner Konzentrationen die erwarteten Skalengesetze und das Verschwinden der Molmassenabhängigkeit. Das durch den Soret-Effekt hervorgerufene Konzentrationsfeld konnte dann durch die numerische Integration der erweiterten Diffusionsgleichung berechnet werden. Aufgrund der komplexen Temperatur-, Konzentrations- und Molmassenabhängigkeit dieses Prozesses stehen die Selbstverstärkung und Schwächung der Konzentrationsabreicherung im Wettbewerb. Die Konzentration in der nahen Umgebung der Heizquelle kann, in Abhängigkeit von der Gleichgewichtskonzentration und der Molmasse, stark reduziert oder sogar auf praktisch Null reduziert werden. Die Konzentration für verschiedene Parameter wie Abstand, Molmasse und Oberflächentemperatur wurden berechnet und visualisiert.
Der Soret-Koeffizient des Systems Pullulan/Wasser weist temperaturabhängig einen Nulldurchgang auf. Dadurch entstehen komplizierte Szenarien zur Strukturbildung. Das Konzentrationsfeld wurde numerisch berechnet und diskutiert. Im Gegensatz zum Konzentrationsfeld von PS/Toluol ist es für Pullulan/Wasser nicht mehr monoton, sondern zeigt neben eines starken Ausbleichens in der unmittelbaren Umgebung des Kolloids ein Konzentrationsmaximum oberhalb der Gleichgewichtskonzentration auf.
Da die Dynamik eingebetteter Goldkolloide von der lokalen Viskosität abhängt, wurden zwei Szenarien im System PS/Toluol diskutiert: bei hohen Polymerkonzentrationen, wo die Lösung in die Nähe des Glasübergangs kommt, sorgen sowohl die Abreicherung des Polymers als auch die dadurch bedingte Vergrößerung des Abstandes zur Glastemperatur für eine Abnahme der Viskosität. Dieser Effekt ist mit einer abschwächenden Rückkopplung verbunden und die Polymerkonzentration auf der Teilchenoberfläche bleibt endlich, unabhängig von der Molmasse im Hochpolymer-Regime. Das zweite Szenario beschreibt die Viskosität von Lösungen mit langen Ketten im halb-verdünnten Bereich. Dort findet man Selbstverstärkung aufgrund des zunehmenden Soret-Koeffizienten und das Polymer kann auch schon für moderate Temperaturerhöhungen vollständig von der Oberfläche verdrängt werden.
Es konnte weiterhin gezeigt werden, dass sich Goldnanopartikel als Markierungen eignen, um über ein einzelnes, geheiztes Kolloid thermooptisch induzierte Netzwerkdeformationen mittels Lichtmikroskopie sichtbar zu machen. Auf Zeitskalen des Experiments, in denen das verschlaufte, transiente Polymernetzwerk bestehen bleibt und die Kolloide daher in den Netzwerkmaschen praktisch immobil sind, kann durch Einzelteilchenverfolgung die Verschiebung der Kolloide mit dem Deformationsfeld des Netzwerkes korreliert werden. In realistischen Geometrien nimmt die Verschiebung aufgrund der Randbedingungen mit steigendem Abstand zwar (in erster Näherung linear) ab, bleibt aber langreichweitig. Die Modellierung dieser Geometrie erfolgte über die Vorstellung zweier impermeabler konzentrischer Kugeln. Trotz dieses recht einfachen Modells konnte eine gute Übereinstimmung zwischen Messung und numerisch berechneten Verschiebungen gefunden werden.
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The Re-implementation of Sharia in Northern Nigeria and the Education of Muslim Women 1999-2007
(2013)
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Chikas Danfulani
- This study investigates the impact of the re-implementation of Sharia on the education of Muslim women between 1999 and 2007, in four states in northern Nigeria namely, Zamfara, Kano, Bauchi and Kaduna. The study fills the research gap in the description of the status of women with respect to education under the Sharia dispensation re-introduced in 1999. Before this era, scholarly works have documented the state of female education in northern Nigeria; however, none deals directly with post re-implementation and its impact on Muslim women’s education. This period is particularly interesting because it coincides with the return of the country to democratic rule after a string of military rules. Using interviews with Sharia proponents, school administrators, women and reports from Sharia Commissions in these states, the work establishes that while Zamfara and Kano States underwent transformations in the educational sector as a result of the programs introduced by the Sharia governments, the changes in the educational domain in Bauchi and Kaduna were exceedingly triggered by the return of democracy in Nigeria after decades of military rule. The results arrived at in this study reveal interesting facets of the relationship between Sharia and the education of Muslim women. The research shows that proponents of Sharia used the premise (also supported by verses from the Qur’an and Prophet Mohammed’s teachings) that education is an important part of Islam to which both males and females have equal rights, to sell the Islamic-based educational programs introduced by the Sharia regime. Using religion to promote these programs, the predominantly male Sharia bodies, mitigate the often tough cultural practices and religious dogmas that have prevented women from having full access to formal, western education. However, the type of education offered to women under these Sharia programs is a hybrid of formal education and Islamic education which pays strict attention to such cultural and religious practices like the wearing of the hijab, the separation of males and females in schools, the teaching of practical, home craft skills such as knitting and baking to the women. So, instead of the education taking women out of the home domain in which they have been restricted in the past, it rather further maintains them while providing them access to formal education which they will hardly use in any public career.
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Crystalline-core micelles based on triblock terpolymers with polyethylene middle blocks
(2012)
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Joachim Schmelz
- This thesis is focused on the crystallization-induced structure formation of polyethylene containing triblock terpolymers in organic solvents to surface-compartmentalized worm-like crystalline-core micelles (wCCMs). Obtaining profound knowledge of the parameters controlling the self-assembly process allowed the production of a variety of complex one-dimensional micellar architectures with many potential applications, such as adaptive surfactants.
At first, the basic parameters that control the crystallization-induced self-assembly were explored using symmetric polystyrene-block-polyethylene-block-poly(methyl methacrylate) (PS-b-PE-b-PMMA) triblock terpolymers and a PS-b-PE-b-PS triblock copolymer. In good solvents for the PE block, e.g. THF and toluene, the selective formation of wCCMs was observed over a wide range of concentration, applied crystallization temperature and polymer composition. Whereas wCCMs produced by PS-b-PE-b-PS showed a homogeneous PS corona, a patch-like compartmentalization of the corona was observed if the micelles were formed by PS-b-PE-b-PMMA. As THF shows equal solvent quality for both corona blocks, wCCMs with almost alternating PS and PMMA compartments of about 15 nm were observed in this solvent. However, if structure formation was conducted in bad solvents for PE, such as dioxane or dimethylacetamide, spherical micelles with amorphous PE cores were formed already before crystallization. Hence, the subsequent crystallization of PE resulted in spherical CCMs with a patchy or a homogeneous corona depending on the used triblock. These findings allow the highly selective production of stable spherical or worm-like CCMs from the same polymer.
As the corona structure of the patchy micelles self-assembled from triblock terpolymers was mainly deduced from transmission electron microscopy (TEM) performed on dried samples, a small-angle neutron scattering (SANS) study was performed in order to elucidate the morphology in solution. Therefore a partly deuterated triblock terpolymer was synthesized and measured at different contrasts to allow the selective detection of the different corona compartments. The resulting SANS curves could be interpreted using a form factor model for core-shell cylinders with alternating PS and PMMA hemishells including interparticle interactions, thus validating the TEM observations. Notably, Janus-type and patchy cylinders can be clearly distinguished using the applied form factor model.
Moreover, the controlled formation of wCCMs with tunable corona composition and structure was achieved using the cocrystallization of different triblock copolymers. Via random cocrystallization of PS-b-PE-b-PMMA and PS-b-PE-b-PS the corona morphology could be tuned continuously from a mixed corona at low PMMA content over spherical PMMA patches of increasing number and size to alternating PS and PMMA patches. This approach allows to manufacture wCCMs with predefined corona structure omitting the need to synthesize a new tailor-made triblock terpolymer for every desired morphology.
By establishing the controlled crystallization-driven self-assembly of triblock terpolymers with PE middle blocks, it was further possible to prepare wCCMs with predefined average lengths up to 500 nm and length polydispersities as low as Lw/Ln = 1.1. Here, self-assembled spherical CCMs of PS-b-PE-b-PS were used as seeds for the controlled growth of PS-b-PE-b-PS unimers. Upon further addition of PS-b-PE-b-PMMA unimers these grew epitaxially onto the preexisting wCCMs, resulting in triblock co-micelles that consisted of middle blocks with a homogeneous PS corona and outer blocks with alternating PS/PMMA compartments. These structures represent not only the first block co-micelles including blocks with a patchy corona, but also the first ones produced from purely organic block copolymers.
In view of application, the ability of patchy wCCMs formed by PS-b-PE-b-PMMA to stabilize interfaces was investigated using pendant-drop tensiometry. The observed reduction of the interfacial tension at the toluene/water interface was significantly higher than that of comparable triblock terpolymer single chains and that of wCCMs with a homogeneous PS corona. Interestingly, the obtained equilibrium interfacial tension equaled that of Janus cylinders with similar dimensions. To explain this unexpected finding the corona chains were proposed to adapt to the interface via selective collapse and shielding of the incompatible part of the corona chains. Studying wCCMs formed by several triblock terpolymers with different compositions, the interfacial activity was found to increase with increasing overall length of the corona chains, and to a certain extent with the molar fraction of PS units in the corona.
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Applicability of weight-shift microlight aircraft for measuring the turbulent exchange above complex terrain
(2013)
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Stefan Metzger
- The possibility to reliably observe the exchange of heat and moisture between the land surface and the atmosphere is vital to our understanding of the regional and global cycling of energy and water. While ground-based flux measurements can be made continuously for long periods, they only represent a small landscape unit. On the other hand, aircraft-based measurements have the ability to directly measure the exchange over large areas. Especially over heterogeneous landscapes the spatio-temporal characteristics of both approaches complement each other. However, complex terrestrial ecosystems are sparsely investigated to date, in particular over topographically structured terrain. This can be attributed to; (i) limitations in the description of boundary layer processes over non-homogenous terrain, and (ii) a lack of applicable measurement platforms and techniques to study these processes. In pursue of a resolution strategy, this dissertation investigates the applicability of weight-shift microlight aircraft (WSMA) to gain new insights in the spatial variability of heat and moisture exchange over complex terrain.
WSMA are comparatively cheap in procurement and maintenance, and their unique structure provides exceptional transportability and climb rate. These structural features qualify the WSMA for terrain-following flight over complex and inaccessible terrain, but potentially influence measurements aboard the aircraft. In this dissertation a WSMA with a scientific payload enabling fast measurements of the 3D wind, temperature, water vapor concentration, position, and the radiative flux is used to;
(i) Quantify the WSMA wind measurement uncertainty. A novel time-domain procedure is developed, which improves the accuracy of the WSMA wind measurement by 63% for the horizontal- and 72% for the vertical wind components. The resulting precisions are ±0.09 m s−1 and ±0.04 m s−1, and the agreement with ground-based measurements is in the order of ±0.4 m s−1 and ±0.3 m s−1 (root mean square deviation), respectively.
(ii) Quantify the WSMA eddy-covariance flux measurement uncertainty. From uncertainty propagation the smallest resolvable changes in friction velocity (0.02 m s−1), and sensible- (5 W m−2) and latent (3 W m−2) heat flux are estimated. In comparison to tower measurements, the WSMA observes higher fluxes (17–21%). The differences are not statistically significant, and can be explained by the tower setup and non-propagating eddies.
(iii) Spatially resolve and regionalize the heat and moisture exchange above a complex landscape. Wavelet decomposition of the turbulence data is used to yield a flux observation each 90 m along the flight path. For each flux observation the biophysical surface properties in the flux footprint are determined. An environmental response function between the flux observations and biophysical and meteorological drivers is then inferred using a machine learning technique. This function is used to produce regional maps of the heat and moisture exchange to an accuracy of ≤18% and a precision of ≤5% for individual land covers.
Hence this dissertation provides the necessary basis for using WSMA to investigate the mechanisms of turbulent exchange over heterogeneous and topographically structured terrain. Moreover, the developed algorithms are generally applicable to (i) partitioning flux uncertainty and environmental variability, (ii) extrapolating flux measurements, (iii) assessing the spatial representativeness of long-term tower flux measurements, and (iv) designing, constraining and evaluating flux algorithms for remote sensing and numerical modeling applications.
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Effects of copper on calcium metabolism and detoxification mechanisms in freshwater bivalve species of Anodonta
(2013)
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Olivier Santini
- Copper (Cu) is one of the metals contaminating European fresh water ecosystems. Filter feeding bivalves have high bioaccumulation potential for transition metals as Cu. While copper is an essential micronutrient for living organisms, it causes serious metabolic and physiological impairments when in excess.
The objectives of this thesis are to get knowledge on toxic effects and detoxification mechanisms of copper in Anodonta cygnea and Anodonta anatina, two mussel species widely distributed in continental waters. Because Ca plays a fundamental role in shell formation and in numerous biological processes, Cu2+ effects on cellular plasma membrane calcium transport were studied first. In the second step, the investigations focused on Cu2+ detoxification mechanism involving cysteine (Cys) rich compounds known to play a major role in homeostasis of essential trace metals and in cellular metal detoxification.
Under our experimental conditions, copper inhibition of Ca2+-ATPase activity was observed in the gills and the kidneys, and inhibition of Na+/K+-ATPase in the gills and the digestive gland (DG) upon 4 d of exposure to 0.35 micro mol/L Cu2+. At day 7 of exposure to environmental Cu2+ concentrations total recoveries was observed in the kidneys and the gills for Ca2+-ATPase activity, and in the DG for Na+/K+-ATPase, but not at high doses. Ca and Na transport inhibition may entail disturbance of osmo-regulation and lead to continuous under-supply of Ca. Recoveries of Na+/K+-ATPase and Ca2+-ATPase enzymes function suggest that metal-detoxification is induced.
Phytochelatins (PC) are Cys-rich oligopeptides synthesised by phytochelatin synthase from glutathione in plants and fungi. Phytochelatin synthase genes have recently been identified in invertebrates; this allows us to hypothesize a role of PC in metal detoxification in animals.
In the second part of this work, PC and their precursors as well as metallothionein were analyzed in the gills and in the DG of Anodonta cygnea exposed to Cu2+. Our results showed for the first time the presence of PC2-4 in invertebrates. PC were detected in control mussels not exposed to metal, suggesting a role in essential metal homeostasis. Compared to control, PC2 induction was observed during the first 12 h of Cu2+ exposure. Those results confirm the role of PC as a first line detoxification mechanism in A. cygnea.
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Effektivität von Umweltbildung zum Thema Wasser – Empirische Studie zu Naturverbundenheit, Umwelteinstellungen und Umweltwissen
(2013)
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Anne K. Liefländer
- Die Stärkung des Umweltbewusstseins in der Bevölkerung ist heute notwendiger denn je. Um Umweltprobleme zu lösen und vorzubeugen, soll adäquate Umweltbildung unter anderem darauf abzielen, Motivation, Einstellungen und Wissen für den Schutz und Erhalt der natürlichen Umwelt zu fördern (IUCN, UNEP & WWF, 1991; Potter, 2010). Naturverbundenheit stellt eine wichtige Motivation für den Umweltschutz dar und wird durch direktes, affektives Naturerleben gestärkt (z.B. Kaiser, Roczen & Bogner, 2008; Davis, Green & Reed, 2009). Diese Verbundenheit kann sich, ebenso wie Umwelteinstellungen, im Laufe des Lebens verändern, was sich wahrscheinlich auf die Effizienz von Umweltbildung bezüglich der unterschiedlichen Altersgruppen auswirkt (Bruni & Schultz, 2010; Ernst & Theimer, 2011). Frick und Kollegen (2004) gehen von drei kognitiven Wissensarten aus, die für ökologisch-nachhaltiges Handeln essentiell sind: System-, Handlungs- und Wirksamkeitswissen, welche bewusst in Bildungsaktionen integriert werden sollten.
Bis heute ist nicht genau untersucht, wie sich Schüler/innen ungleichen Alters hinsichtlich ihrer Naturverbundenheitswerte und Umwelteinstellungen unterscheiden. Es ist ebenfalls unklar, ob Kinder und vorpubertäre Jugendliche durch Umweltbildung in den genannten Aspekten unterschiedlich beeinflusst werden, und ob ein erzielter Effekt über einen längeren Zeitraum nach einer Intervention bestehen bleibt. Eine systematische Integration der drei Umweltwissensarten in ein Umweltbildungsprojekt stellt eine zusätzliche Herausforderung dar, durch die eine Zunahme der spezifischen Umweltwissensarten und deren Konvergenz nachgewiesen werden kann. Aus diesem Grund befasst sich die vorliegende Studie zunächst mit dem Ist-Zustand der Naturverbundenheit und den Umwelteinstellungen von 9 bis 13-Jährigen. Anschließend wird der Effekt eines umfassenden viertägigen Umweltbildungsprogramms auf Naturverbundenheit, Umwelteinstellungen und Umweltwissen untersucht.
Am Schullandheim-Projekt zum Thema „Wasser im Leben - Leben im Wasser“ nahmen rund 200 Schüler/innen teil. Die Naturverbundenheit wurde mit der INS-Skala ermittelt (Inclusion of Nature in Self; Schultz, 2002), die Umwelteinstellungen mit den Subskalen preservation und utilisation nach dem 2-MEV-Modell (Two Major Environmental Values; z.B. Bogner & Wiseman 2006) und die Wissensarten mit drei neu entwickelten Skalen. Alle Skalen waren in einem Fragebogen eingebettet, welcher als Vor-, Nach- und Behaltenstest eingesetzt wurde. Eine externe Kontrollgruppe, die nicht am Projekt teilnahm, füllte ausschließlich die Fragebögen aus.
Die Ergebnisse zeigen für 9 bis 10-Jährige (Klasse 4) eine stärkere Naturverbundenheit und bessere Umwelteinstellungen als für 11 bis 13-Jährige (Klasse 6). Der Effekt des Umweltbildungsprojekts auf die Naturverbundenheit und Umwelteinstellungen ist bei den jüngeren Schüler/innen größer als bei den älteren. Beide Altersgruppen zeigen direkt nach der Teilnahme eine größere Naturverbundenheit, die jedoch nur bei den jüngeren Teilnehmer/innen auch über vier Wochen nach dem Projekt bestehen bleibt. Ein ähnliches Bild zeigt sich bezüglich der Umwelteinstellungen: Beide Einstellungen der jüngeren Schüler/innen verbessern sich durch die Programmteilnahme, jedoch bleibt nur preservation auch nach dem Projekt verbessert. Im Vergleich dazu zeigt die preservation-Einstellung der älteren Schüler/innen nur eine kurzfristige Verbesserung, die utilisation-Einstellung wurde nicht beeinflusst. Der Beginn der Pubertät bei den älteren Schüler/innen könnte der Grund für die geringere Naturverbun¬denheit und die ungünstigeren Umwelteinstellungen sein. Aufgrund ihres Alters streben die vorpubertären Schüler/innen wahrscheinlich bereits nach Unabhängigkeit und erleben emotionale Distanz zu anderen (Parra & Oliva, 2009; Steinberg & Silverberg, 1986) und möglicherweise auch zur Natur. Die neuen Skalen zur Messung der Umweltwissensarten erwiesen sich als reliabel und homogen. Das Umweltwissensniveau und die Wissenskonvergenz der Schüler/innen nehmen durch die Projektteilnahme zu und beide bleiben größtenteils über den Zeitraum von vier Wochen nach dem Projekt erhalten. Wirksamkeitswissen zeigt den geringsten Wissenszuwachs, was durch die hierarchische Abhängigkeit der Umweltwissensarten erklärt werden kann. Zusammenfassend war das viertägige Umweltbildungsprojekt bezüglich Naturverbundenheit, Umwelteinstellungen und Umweltwissen vor allem bei den 9 bis 10-jährigen Schüler/innen erfolgreich. Die Befunde werden abschließend bezüglich ihrer Herausforderungen für die Bildungsforschung und ihrer Konsequenzen für die schulische Umweltbildung beleuchtet.
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Light Harvesting using Metal-Organic and Organic Sensitizers in Hybrid Solar Cells: Synthesis, Characterisation and Application
(2012)
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Katja Gräf
- This thesis addresses the question how to improve light harvesting with novel tailor-made metal-organic and organic sensitizers for solid-state hybrid solar cell applications. Two approaches are in the focus: 1) the design and synthesis of sensitizers featuring high extinction coefficients over a broad wavelength range and 2) modern device concepts to further enhance or extend the absorption by the combination of two sensitizers. In short: The primary goal was to broaden and boost the optical density of hybrid solar cells. To reach this, novel sensitizer with extended conjugated π-system providing excellent optical properties had to be designed and synthesised in complex multi-step reaction sequences. For ideal sensitizers, further aspects had to be taken into account such as structural demands, electronic properties, and the tendency towards aggregation.
The first part of this thesis deals with the synthesis, characterisation and application of a series of metal-organic ruthenium(II) donor-antenna complexes. In addition to the typically broad absorption of Ru(II)bis(bipyridyl)(NCS)2 complexes in the blue-green region arising from MLCT, these dyes feature much higher extinction coefficients in comparison to a commercially available reference dye lacking any donor-antenna groups. By the application of these Ru(II) complexes in solid-state dye-sensitized solar cells, we found a clear structure-property relationship. The performance - especially the photocurrent density - was significantly improved with increasing extension of the delocalized system of the donor-antenna groups.
To further boost the optical density in hybrid solar cells sensitized with a donor-antenna ruthenium dye (Ru-TPA-NCS), we developed an innovative and technically relevant concept for multichromophore sensitization involving a second sensitizer (TPD-dye). The latter absorbs in a region where Ru-TPA-NCS absorbs weakly. The solar cells were fabricated according to a novel method developed by us. However, the power conversion efficiencies of multichromophore hybrid blend solar cells were initially low due the weak interconnectivity of the TiO2 particles. This issue was addressed by an optimization of the TiO2:spiro-OMeTAD ratio and the addition of PCBM
A further concept dealing with the combination of two sensitizers in solid-state dye-sensitized solar cell was accomplished by co-sensitization of a triphenyldiamine-based dye (TPD-dye) absorbing in the blue region and squaraine dye (SQ-dye) mainly absorbing the red part of the visible spectrum. In this way, the optical response of the device was extended up to 700 nm. Under optimized conditions, a conversion efficiency of 2.41 % could be reached.
To accomplish the desired panchromaticity or even an extension of the absorption up to the NIR region with a single sensitizer, novel BODIPY dyes with excellent optical properties were designed and synthesised. We prepared BODIPYs with donor-groups to extend the delocalized system and integrated a meso-ethynyl bridge between the BODIPY core and the anchoring group to improve the electronic connection between them. For comparison, we synthesised the corresponding BODIPYs without donor-moieties and without ethynyl bridge. The multi-step synthetic routes were optimized, the mechanism of the donor-attachment was clarified and the introduction of the ethynylphenyl group in the meso-position was accomplished for the first time. The optical characterisation of the compounds disclosed an impressively broad and intensive spectral response, especially for a meso-ethynylphenyl BODIPY with donor-groups. This dye absorbs up to 1030 nm with high extinction coefficients. This makes suitable functionalised BODIPYs promising candidates for solar cell applications.
The next part took advantage of the excellent optical properties of BODIPYs and expanded the topic towards the concept of energy transfer. Here, an unattached energy donor dye provides additional adsorption and transfers the energy to a sensitizing acceptor dye. Indeed, for appropriate combinations an additional contribution to the external quantum efficiency was found in the absorption region of the energy donor dye.
Furthermore, a review chapter covering all aspects of dye-sensitized solar cells and the sensitizers is added as appendix.
In summary, this thesis presents the successful design, synthesis and characterisation of both metal-organic and organic sensitizers including ruthenium complexes, triphenyldiamine-based dyes, a squaraine sensitizer and BODIPY dyes. The sensitizers (either individually or in combination with complementary sensitizers) provide excellent optical properties for the application in solar cells. The applicability of these sensitizers was successfully demonstrated in standard solid-state dye-sensitized solar cells, in newly developed multichromophore hybrid blend solar cells, co-sensitized solar cells and in solid-state dye-sensitized solar cells taking advantage of energy transfer.
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Über eine Erweiterung der Methode von Soshnikov zur Untersuchung des größten Eigenwerts auf unsymmetrische Verteilungen
(2013)
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Felix Grimme
- Seit der Entdeckung des Halbkreisgesetzes durch Wigner werden reell-symmetrische Zufallsmatrix-Ensembles untersucht. Soshnikov hat in einer bahnbrechenden Arbeit gezeigt, dass für Wigner-Ensembles $A_n=(\xi_\ij)_{1\le i\le j\le n}$ mit symmetrisch verteilten Einträgen die Verteilung des größten Eigenwerts in einer geeigneten Skalierung für $n\to\infty$ universelles Verhalten zeigt und schwach gegen die Tracy-Widom-Verteilung, die Verteilung des Gauß'schen orthogonalen Ensembles, konvergiert. Für den Beweis nutzt Soshnikov die Momentenmethode. Hierbei wird die Analyse der Verteilungsfunktion des größten Eigenwerts auf die Analyse von Erwartungswerten von Spuren hoher Matrixpotenzen zurückgeführt (die Exponenten wachsen mit $n^{2/3}$). Die Spuren werden via $\tr A_n^{p_n}=\sum_{(i_0,\ldots,i_{p-1})\in[n]^p}\xi_{i_0,i_1}\xi_{i_1,i_2}\ldots\xi_{i_{p-1},i_0}$ als Summe über geschlossene Pfade kombinatorisch interpretiert. In der Analyse gilt es herauszufinden, welche Klassen von Pfaden (die mit den Momenten der Matrixeinträge in Verbindung stehen) die Spuren in der Asymptotik $n\to\infty$ dominieren. Es stellt sich heraus das dies Pfade sind, die jede ihrer Kanten genau zweimal durchlaufen. Das bedeutet, dass die Spuren asymptotisch nur von den für alle Matrixeinträge gleichen zweiten Momenten abhängen, sie sind also asymptotisch für alle betrachteten Ensembles universell.
Diese Methode wird in der vorliegenden Arbeit auf Wigner-Ensembles mit nicht notwendig symmetrischen Verteilungen der Einträge erweitert. Die Kombinatorik ist in diesem Fall komplexer. Resultat der Arbeit ist, dass die Methode von Soshnikov funktioniert, wenn folgende Bedingungen erfüllt sind:
die ersten und dritten Momente der Einträge sind~0
für die 97.\ Momente existiert eine in~$n$ gleichmäßige Schranke.
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Heterogeneous chemistry of HONO and surface exchange
(2013)
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Matthias Sörgel
- Nitrous acid (HONO) is an important precursor of OH radicals, which are the key oxidizing species in the atmosphere and are therefore called the detergent of the atmosphere. Despite the importance of HONO for atmospheric chemistry and about 30 years of detailed research the exact formation mechanisms of both day- and night-time formation remain unclear. The main formation pathways discussed to date are heterogeneous reactions with nitrogen dioxide as the HONO precursor or microbiological activity in soil. As the ground surface is a major source of HONO, the vertical distribution of HONO is very sensitive to the extent of vertical mixing. Additionally, some uncertainty in comparing laboratory and field measurements might be caused by the not yet clarified role of relative humidity and surface wetness on HONO formation and deposition, respectively. These influences have been investigated in field measurements in the present study. For HONO measurements, LOng Path Absorption Photometers (LOPAPs) have been deployed.
During the Diel Oxidant Mechanism In relation to Nitrogen Oxides (DOMINO) campaign, HONO and other reactive trace gases were measured above a pine forest in south west Spain. In line with all recently published work, this study also found a substantial daytime formation of HONO. This so-called additional daytime source or unknown source was found to be slightly correlated (r² = 0.16) with actinic flux. Normalizing this unknown source to nitrogen dioxide mixing ratios improved the correlation (r² = 0.38), which indicates an influence of nitrogen dioxide availability. The coefficient of determination improved further to 0.47 by restricting the data to clear days and rejecting data from advection events. Thus, a fraction of the unknown source might be explained by light-induced nitrogen dioxide conversion but other factors have to be taken into account. Two processes of light-induced nitrogen dioxide conversion, proposed by recent laboratory studies, were shown to be negligible for the semirural conditions during our study. HONO photolysis was found to be the most important primary OH-radical source during DOMINO, contributing 20 % more OH than ozone photolysis integrated over the day.
Vertical exchange of HONO was studied at the “Waldstein-Weidenbrunnen” field site of the University of Bayreuth in the Fichtelgebirge Mountains in south east Germany. The simultaneous HONO measurements in and above a forest canopy highlighted the importance of turbulent exchange for the vertical distribution of HONO mixing ratios. The so-called coupling regimes of the forest (with the air layers above) were found to be a very useful micrometeorological concept to study vertical differences of mixing ratios in a forest. They denote which parts of the forest are coupled to the air layer above the canopy and thus take part in turbulent exchange of energy and matter. With this coupling tool it was possible to explain vertical mixing ratio differences by different sources and sinks and the magnitude of the difference by the intensity of vertical exchange. Studying the vertical mixing ratio differences of HONO, an unexpected result was that during late morning and around noon they were close to zero. As the lifetime of HONO below canopy of about 250 to 300 min was a factor of 25 to 30 longer than that above canopy of about 10 min, large mixing ratio differences would have been expected. The lack of these differences could be explained by efficient vertical mixing, which was indicated by a full coupling of the forest or a coupling by sweeps and only intermittent decoupling of the subcanopy during these periods. Around sunset, the whole forest became decoupled from the air layers above. This caused a steep increase in mixing ratio differences up to about 170 ppt due to a faster increase below canopy, indicating local formation below the canopy.
HONO and RH are correlated due to their diurnal cycles which are mainly caused by radiation. This diurnal contribution has to be removed from the respective signals in order to extract correlations on other timescales. Singular System Analysis, a tool for time series analysis, has been applied successfully to remove diurnal variations and long-term trends from the HONO and RH time series. Correlations of the higher frequency contributions of the remaining signals were poor but slightly positive. The HONO mixing ratios increase exponentially with RH from about 25 % RH to about 70 % RH. No clear correlation was found between around 70 and 95 % RH. Above 95 % RH, HONO mixing ratios decreased due to HONO uptake in droplets and liquid films. These features are in line with previously proposed mechanisms for interactions of water and HONO on surfaces.
The study highlighted the need to assess turbulent transport and surface properties in addition to chemistry for understanding the heterogeneous reactions and processes forming HONO.
