645 search hits
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Single-Particle Orbit Tracking - Setup, Characterisation and Application
(2013)
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Dominique Ernst
- In this thesis, the development and experimental realisation of an optical setup which records the 2-dimensional trajectories of single fluorescently labeled polystyrene beads, either 20nm or 50nm in diameter, with a high spatial and temporal resolution is introduced. Combining single molecule fluorescence techniques with a new method called single-particle orbit tracking the spatial position of the beads could be determined with an accuracy of less than 10nm at a time resolution of 4 ms. The idea is to manipulate the excitation light spatially and temporally to locate a particle. In order to do so, special optics which deflect a laser beam and guide it on a circular path were used. Subsequently, this rotating beam is projected by a microscope into the sample with the diffusing particles. Due to the spatially and periodically modulated excitation light, the emission signal of the bead is modulated with the frequency of the rotation of the laser focus. The amplitude of the modulated emission signal depends on the position of the particle within the excitation orbit. An ingeniously developed algorithm calculates the position of the particle with respect to the centre of the orbit by demodulating the emission signal and restores the particle back to the orbit centre. Applying this method successively, the trajectory of the diffusing bead can be reconstructed. Besides the experimental realisation, the characterisation of the setup in terms of the spatial and temporal accuracy as well as the experimental shortcomings that influences the measured trajectories and hence, the interpretation of the data, were also the main topics of this work. For this purpose a reference sample of 20nm sized beads in glycerol was used. The accuracies were studied mainly by computer simulations and the artifacts by experiments. The technical details of the setup and the characterisation results were published (publication P1).
The recorded trajectories were analysed with various methods, among which the commonly used mean squared displacement (MSD) yields the results with highest information. The diffusion coefficient as well as the diffusion behaviour could be quantified. With this method the obtainable accuracy in measuring the diffusion coefficient by the acquisition of single-particle trajectories was studied as a function of the length of the trajectories and as a function of the number of fitting points that were used for a linear fit to the experimentally determined MSD-curves. As expected, the relative error of the determined diffusion coefficient gets better for longer trajectories. Further, an optimal number of fitting points for the linear approximation to the MSD-curves was found, which yields the most exact values for the diffusion coefficients and which is independent of the trajectory length. For the first time, experimental results on that issue were compared with theoretical predictions, where a good agreement was found. These findings were published (publication P2). By the use of the Stokes-Einstein relation the diffusion coefficients could further be converted to particle radii. A closer examination of these radii emphasises the influence of the afore mentioned number of fitting points. For the optimal value, significantly precise radii could be determined.
Finally, an application of the new setup is presented. In cooperation with the chair of experimental physics I (group of Prof. Dr. M. Weiss) of the University of Bayreuth, the diffusion behaviour of single nanoparticles in a complex fluid was studied. Background hereto is the investigation of biochemical reactions in a biological cell, whose kinetic is given by the diffusion of the corresponding reaction partners. Due to the high crowding of the cell compartments the diffusion is hindered. The diffusion behaviour in these systems is called anomalous and more exactly subdiffusive. Several theoretical models have been developed to explain this phenomenon, but yet without experimental verifications. Here, the diffusion of 50nm sized polymer beads in the model system dextran (a highly branched biopolysaccaride) is investigated experimentally with high spatial and temporal resolution. The data were analysed in the group of the cooperation partner which yields a very good agreement with the model of “fractional Brownian motion”. These results were also published (publication P3).
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Mesostrukturierte Metalloxide und Polyoxometallate mittels Ionogener Diblockcopolymere - Synthese, Charakterisierung und Anwendung
(2013)
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Thomas Lunkenbein
- Das Ziel der vorliegenden Arbeit war es, Metalloxide und Polyoxometallate auf der Mesoebene mittels ionogener Diblockcopolymere zu strukturieren, zu charakterisieren und anwendungsspezifisch zu testen. Dabei wurden vor allem drei bisher bekannte Probleme, die mit der Mesostrukturierung von Metalloxiden einhergehen, umgangen.
Zum einen führt die schnelle Hydrolyse und Kondensation reaktiver Metallalkoxid-Precursoren zu unstrukturierbar großen Molekülen. Zum anderen ist oftmals ein direkter Zugang zu der gewünschten Morphologie aufgrund der mizellaren Dynamik des Templates, die von äußeren Einflüssen, wie pH-Wert, Konzentration oder Salzkonzentration abhängt, erschwert. Das dritte Problem ist die schlechte Anbindung des anorganischen Precursors an das organische Templat, was auf schwache, attraktive Wechselwirkungen zwischen beiden Materialien zurückzuführen ist. Generell müssen Hydrolyse, Kondensation und Hybridbildung zwingend synchron ablaufen, um eine Makrophasenseparation zuverlässig zu vermeiden.
Um diese Makrophasenseparation zu vermeiden, wurde am Lehrstuhl AC I ein neuartiges Konzept entwickelt, in dem alle drei Probleme adressiert und gelöst werden konnten. Diese Lösungsansätze werden nachfolgend entsprechend ihrer oben aufgeführten Reihenfolge erklärt. Zunächst wurden anionische oligomere Cluster oder pre-synthetisierte Kolloide als anorganische Precursoren verwendet, anstelle schnell hydrolyisierender und kondensierender Metallalkoxide. Die Cluster besetzen energetische Minima auf dem Weg zu ausgedehnten Oxidstrukturen und neigen somit nicht zur Kondensation. Weiterhin konnte mit 1-dimensionalen kernquervernetzten Polymerbürsten die mizellare Dynamik umgangen werden, da die rigiden zylindrischen Polymerbürsten invariant gegenüber äußeren Einflüssen sind. Außerdem besitzen diese 1-dimensionalen Nanoobjekte ionisierbare Seitenarme, welche einfach protoniert werden können und somit über starke Coulomb-Wechselwirkungen eine stabile Anbindung der anorganischen Oxide an das organische Templat gewährleisten.
Dieses Konzept der ladungsinduzierten Mesostrukturierung mittels molekularer oxidischer Precursoren wurde innerhalb dieser Doktorarbeit weitergeführt, deren Ergebnisse nachfolgend kurz dargestellt werden.
Zuerst wurde am Beispiel von pre-synthetisierten Rutil- und Anatas-Kolloiden gezeigt, dass nicht nur anionische oligomere Cluster, sondern auch Kolloide in 1-dimensionale Poylmerstrukturen eingelagert werden können. Die Kristallstruktur von Rutil und Anatas konnte durch Verwendung unterschiedlicher Säuren (HCl: Rutil; Essigsäure: Anatas) bei der Hydrolyse des Titanalkoxid-Precursors gezielt eingestellt werden. Diese TiO2-Polymorphe besitzen bei niedrigen pH-Werten eine positive Oberflächenladung. Polystyrolsulfonsäure-block-polyallylmethacrylat (PSS-b-PAMA) wurde in Zusammenarbeit mit dem Lehrstuhl MCII als zylindrischer anionischer Antagonist synthetisiert. Die PSS-Seitenarme sind selbst bei niedrigen pH-Werten noch negativ geladen. Die resultierenden 1-dimensionalen Hybridmaterialien besaßen dieselbe Kristallstruktur wie der Precursor, eine homogene Verteilung der Nanopartikel in der Polymermatrix und nach Trocknung eine verschlaufte, sphaghetti-ähnliche Mikrostruktur mit relativ hoher spezifischer Oberfläche.
In einer detaillierteren Studie wurde zusätzlich der Einfluss der Länge der zylindrischen Template auf die Packung der 1-dimensionalen Nanoobjekte und auf die daraus resultierende spezifische Oberfläche untersucht. Dabei wurden zylindrische Hybridmaterialien aus Heteropolysäuren des Keggin-Typ Polyoxometallates (Keggin POM), die in 1-dimensionale Polybutadien-block-poly(2-vinylpyridin) (PB-b-P2VP) Polymerbürsten eingelagert wurden, verwendet. Hierbei zeigte sich insbesondere, dass eine kurze Ultraschallbehandlungsdauer das Aspektverhältnis der 1-dimensionalen Strukturen nur gering verändert, die Dispersion der anisotropen Hybridmaterialien perfektioniert und die interpartikulären Kontaktpunkte innerhalb der Mikrostruktur minimiert. Als Ergebnis wurde hierfür die maximal zugängliche spezifische Oberfläche erhalten. Eine Ausweitung dieses Syntheseprotokolls auf Keggin POMs mit unterschiedlicher Ladung, Heteroatomen und Metallkationen konnte auch erfolgreich durchgeführt werden. Katalysetests dieser Hybridzylinder offenbarten dabei Unterschiede in der Aktivität dieser Nanostäbchen in der sauer katalysierten Zersetzung von Isopropanol.
Angliedernd an die ladungsinduzierten Mesostrukturierung wurde ein neues Synthesekonzept zu invers hexagonal geordneten Polymer/ Keggin POM Mesostrukturen erarbeitet. Als organisches Templat wurde Polybutadien-block-poly(2-dimethylaminoethylmethacrylat) (PB-b-PDMAEMA) mit einem hohen Polymerisations-grad des PB-Blockes synthetisiert. Als weitere Schlüsselfaktoren erwiesen sich neben diesem hohen Polymerisationsgrad des PB-Blockes die Wahl des Lösungsmittel und der Keggin POM-Anteil. Um dieses Material auch für Anwendungen wie der Katalyse ansprechend zu machen, muss das polymere Templat am besten vollständig entfernt werden, um eine möglichst hohe Zugänglichkeit der aktiven Zentren zu gewährleisten. Dies wurde sowohl thermisch als auch mit aggressiveren Methoden versucht. Zum einen wurde durch systematische Studien zur thermischen Entfernung des Templates gezeigt, dass die Mesostruktur kollabiert bevor der Kohlenstoff komplett entfernt werden kann. Zum anderen wurde durch aggressivere Methoden, wie Plasmaätzen, erfolgreich der Zugang zu den Mesoporen an Ultradünnschnitten (<50 nm) realisiert. An die thermische Behandlung reihte sich auch die Umwandlung der geordneten Mesophasen in geordnete Carbid/ Kohlenstoff-Nanokomposite an. Letztere sind für Katalyse oder Ladungsspeicherung auch wissenschaftlich interessant. Für die Umwandlung der geordneten oxidischen Mesophasen in Carbid/ Kohlenstoff Nanokomposite wurde nicht versucht das polymere Templat in den Poren zu entfernen, sondern es wurde zum ersten Mal als Kohlenstoffquelle in der Carbidisierungsreaktion verwendet. Folglich lieferten die hergestellten geordneten Mesophasen einen direkten und einfachen Zugang zu porösen Carbid/ Kohlenstoff Nanokompositen und zeigten katalytische Aktivität in der Zersetzung von Ammoniak.
Diese Arbeit ist eine kumulative Dissertation. Die detaillierten Ergebnisse werden in den angehängten Publikationen beschrieben.
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Polyelectrolyte Coatings with Internal Hierarchy
(2013)
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Julia Gensel
- The results presented in this thesis are focused on the surface modification by polyelectrolytes and polyelectrolyte copolymers. The internal structural hierarchy originate thereby from the self-assembly processes at different length scales. To generate different levels of hierarchy, the coatings were constructed by using either the layer-by-layer (LbL) deposition method (lateral chemical structure), the adsorption of supramolecular aggregates (lateral topographycal structure), or the combination of both. Using these techniques, one can control the properties of the coatings by varying the chemical structure of the polyelectrolytes, for instance, their charge density, thus providing a convenient way for their functionalization and the ability to tune properties of the surface. Therefore, we were working with systems which have variable charge densities. With this approach, we were able to produce thin and ultrathin nanostructured films with tunable properties and functionality.
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Charge and excitation-energy transfer in time-dependent density functional theory
(2013)
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Dirk Hofmann-Mees
- Learning about and understanding the mechanisms and pathways of charge and excitation-energy transfer of natural molecular complexes is a promising approach for the tailored design of new artificial energy-converting materials. Therefore, next to extensive experimental investigations, a theoretical method that is able to reliably describe and predict these phenomena from first principles is of practical relevance. In principle, density functional theory (DFT) and time-dependent density functional theory (TDDFT) appear as natural choices to study the relevant sizable molecules on a first-principles scale at bearable computational cost. However, the application of standard local and semilocal density functional approximations suffers from well-known deficiencies, in particular, as far as the simulation of charge-transfer phenomena is concerned. The present thesis approaches charge and excitation-energy transfer with the objective of improving the predictive power and extending the range of applicability of (TD)DFT.
The deficiencies of standard density functional approximations have been related to self-interaction. Hence, one major aspect of this work is the extension of the self-interaction correction in Kohn-Sham DFT that is based on the generalized optimized effective potential to TDDFT using a real-time propagation approach. The multiplicative Kohn-Sham potential allows for a transparent analysis of the exchange-correlation potential during time evolution. It reveals frequency-dependent field-counteracting behavior and step structures that appear in dynamic charge-transfer situations. The latter are important for the proper description of charge transfer. Self-interaction correction allows to access many cases that are difficult for standard TDDFT ranging from chain-like systems over excitonic excitations in semiconductor nanoclusters to short- and long-range charge-transfer excitations. At the same time, it does not spoil the reasonable accuracy that already (semi)local functionals exhibit for local excitations. Moreover, the TDDFT perspective on self-interaction correction sheds new light also on the ground-state formalism. Complex degrees of freedom in the energy-minimizing transformation of the generalized optimized effective potential approach yield smoother orbital densities that appear more reasonable when inserted into approximate functionals in the self-interaction correction formalism. This work provides new insight into the use of different functional approximations. Last but not least, the influence of spin-symmetry breaking and step structures of the potential on the preference to transfer integer units of the elementary electric charge between largely separated donor and acceptor moieties is illustrated when static external electric fields are applied. This work has been reported in three publications and one submitted manuscript.
In the field of excitation-energy transfer, recent discoveries of quantum coherence effects shed new light on the mechanisms behind energy-transfer rates. The latter are affected by a number of different properties of the isolated molecules, but involve also effects due to the environment of the system. This thesis addresses excitation-energy transfer phenomena from two perspectives. First, I use real-time propagation TDDFT to investigate the intermolecular coupling strength and the coupling mechanism between single fragments of supermolecular setups. These investigations base on standard closed quantum system TDDFT and exploit the coherent oscillation of excitation energy between separated molecules after the initial excitation process. Second, I use open quantum system ideas in the framework of TDDFT to study the influence of the system’s environment on the energy-transfer time scales and pathways in a circular arrangement of molecules using an effective energy-dissipation mechanism. The first part of these results is published. The second part is presented in this thesis and includes work in progress.
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Intuitive Human-Robot Interaction by Intention Recognition
(2013)
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Muhammad Awais
- For two humans to interact with each other to perform a common task, they need to know the expectation of each other during interaction. For example if we consider an example of a waiter and a guest. If the waiter tilts the bottle to offer a drink to the guest then he may expect two actions from the guest, i.e., either the guest will forward his glass to get it filled or he will take his glass backward for not accepting the drink. If the guest forwards his glass then the waiter expects that the guest will keep his glass at a certain point until he pours the liquid into the glass. Similarly if the guest takes its glass backward then he expects from the waiter not to pour the liquid into his glass. In any case of misunderstanding an accident can occur. It applies to almost all the instances of human-human interaction. The recognition of the intention plays a key role in human-human interaction. It is equally important in human-robot interaction.
With the increase of research in the field of robotics, the robots are and will be becoming more and more part of human life. For the robots to be the effective part of the human life they should be helpful to the human. For a robot to be helpful to the human he should act according to the human. In case if the robot tries to help the human without knowing the intention of the interacting human then the robot can be itself a problem rather than a solution to the problems. Therefore it is necessary for a robot to know the intention of the human with whom the robot is supposed to interact to facilitate him.
The aim of this work is to propose a solution to make the human robot interaction intuitive. For making the human-robot interaction intuitive the intention of the human should be known to the interacting robot. A probabilistic approach is introduced to recognize the human intention. The approach uses the finite state machines. Each finite state machine representing a unique human intention carries a probabilistic value that is called the weight of the finite state machine. That weight tells the robot about the current human intention.
Since it is not possible to embed all the possible intentions into the robot that the robot may need to recognize. Thus, there should be a measure that the robot can learn new human intentions. An approach is discussed for this purpose.
For the human-robot interaction to be intelligent the robot should be quick in his response towards the human intention. An approach is described that addresses the issue of quick (proactive) response of the robot. The proposed approach also discusses the scenario concerning the ambiguous human intention. An ambiguous intention is a human intention that apparently corresponds to more than one human intention.
There may be a scenario in which the human has a totally new intention that the robot does not know already and also has not learned that intention. In this case, apparently there is no human- robot interaction. In order to cope with this problem an approach is discussed that enables the robot to select an appropriate action to interact with the human.
An approach concerning the generalization of the human intention is also discussed. By generalizing the human intention, the robot can extend its response according to the human intention. The extension of the response means that the robot takes those actions that were not instructed to him to be taken concerning the human intention.
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Comparisons of N2O and CH4 fluxes as affected by land use systems and climate in small catchments in Korea
(2013)
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Sina Berger
- In the course of global and climate change humankind has to face extreme weather events with increased intensity and frequency and it has to deal with feeding an increasing number of people which is accompanied by shortage of resources such as water. Since half of humankind directly depends on freshwater and other ecosystem services provided by mountainous areas, it is essential to study such complex terrains and how natural as well as agricultural systems react to climatic and other anthropogenic changes.
Emissions of greenhouse gases like Nitrous oxide (N2O) and Methane (CH4) are of global concern, too, because they are involved in global warming and therewith: climate change. Major sources of N2O are agriculturally managed soils, and very important sources of CH4 are rice paddies. Thus, it is of great importance to study intensively managed agricultural systems and the effects of the management practices on greenhouse gas emissions.
The major focus of this thesis is to quantify dry crop fields’ and forests’ N2O emissions as well as rice paddies’ N2O and CH4 emissions and to identify climatic as well as management related factors and underlying processes which are driving the N2O fluxes in a complex terrain.
A prolonged early summer drought in 2010 led to significant N2O consumption in soil of three different forest sites. The following above-average monsoon rainfall period indeed turned the N2O consumption into emission but could not turn the N2O balance of a forest on sandy-loam substrate from negative into a positive one, which means that for the first time a negative N2O balance was observed for a forest soil during the growing season. The N2O emissions of those forest sites were clearly driven by soil moisture and temperature and there appeared to be an effect of the substrate on N2O emissions as well, as it is increasingly often observed that sandy-loam soils show significant N2O consumption.
Plastic mulching – a worldwide used method in agriculture to increase crop production by enhancing soil temperature, creating more stable soil moisture conditions and restricting arable weed growth – turned out to have a mitigating effect on N2O emissions. DNDC (Denitrification and Decomposition) modeling results matched best with the measurement results when the maximum daily soil temperature and half of the daily precipitation was assumed to occur as dominating climate conditions underneath the impervious polyethylene (PE) film, suggesting that N2O production underneath the plastic cover was driven by soil moisture and temperature. N2O emissions from a non-fertilized soy bean field, which has Nitrogen fixation as an additional Nitrogen source, were similar to the N2O emissions from a radish field after application of an intermediate amount of N fertilizer of 200 kg ha-1.
Comparing N2O and CH4 emissions from rice paddies under different water management practices showed that intermittent irrigation (II) (no continuous flooding, no water logging)
had the least global warming potential (GWP) which was only 30% of the global warming potential (GWP) of a traditionally irrigated (TI) paddy (continuous flooding and water logging). Another practice of 2.5 months of continuous flooding, followed by midseason drainage and reflooding which created moist but non-water logged conditions (FDFM) lead to 66% of the traditionally irrigated paddies combined CH4 and N2O emissions. These results suggest that a trend towards less flooding has a great potential to mitigate greenhouse gas emissions from a sandy or sandy-loam substrate, respectively. Studying the three paddies’ subsoil conditions revealed that N2O production and consumption processes had mainly taken place between 25 and 50 cm soil depth judging by N2O concentrations and δ15N-N2O values along the soil profiles of all the investigated paddies as well as gene abundances of denitrifying and nitrifying bacteria of the FDFM paddy.
Apart from these important findings on N2O flux dynamics of three different land use systems, it is noticeable that the N2O emissions of the study region are in general very low which is very pleasing and implies that the area deals with global change challenges and associated intensive agriculture in a way that comparatively only small amounts of N2O degas. But this raises the question after the “why?” considering that large amounts of fertilizer are applied on the fields. This thesis does not have a final answer to that question but it discusses whether the sandy substrate may play a major role for the N dynamics of the whole area. There is evidence that NO3- - as the substrate for denitrification - leaches easily due to the soil conditions. To finally figure out why the N2O emissions are that low a more detailed investigation on the fate of NO3- would be desirable.
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Rhizodeposition and its effects on C fluxes in the soil
(2013)
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Johanna Pausch
- Organic compounds released from living roots (rhizodeposits) are easily available sources of energy for microorganisms strongly affecting soil organic matter (SOM) dynamics. Although, rhizodeposition is a key driver of microbially mediated processes in the soils, it still remains the most uncertain component of the terrestrial carbon (C) cycle.
The input of C through rhizodeposition occurs in temporal and spatial hotspots. The objective of Study 1 was to determine the dynamics of hotspots of recently assimilated C in ryegrass roots. Shoots were 14CO2 pulse labeled and the allocation patterns at increasing time intervals were visualized by phosphor imaging. We could show a quick translocation of assimilated C to the roots. 14C hotspots were detected at the root tips already 6 hours after labeling. The hotspots remained active for at least 2 days. Eleven days after assimilation the hotspots at the tips had disappeared, and the 14C distribution was much more even than after 6 hours and 2 days.
Through the availability of rhizodeposits, hotspots create preferred habitats for microbes. Rhizodeposits are an important source of C and energy for microorganisms stimulating their growth and activity. Thereby, roots can influence the rate of native SOM decomposition in the rhizosphere. This rhizosphere priming effect (RPE) was reported to be plant-species specific. Therefore, we hypothesized that also plant inter-species interactions affect the RPE.
In Study 2, we used continuous 13CO2 labeling to investigate the RPE of monocultures and mixtures of typical agricultural crops. The RPE was consistently positive for all cultures with an increase of 43% - 136% above the unplanted soil. Of particular interest was the result that plant inter-species interactions between sunflower and wheat significantly reduced the RPE in contrast to mixtures which included soybean as a legume. It was argued that the RPE of the sunflower-wheat mixture was reduced through a more severe competition for nitrogen (N), whereas, due to the N-rich rhizodeposits of the legume and its lower demand for soil mineral N the RPE of the legume containing mixtures remained unaffected.
Besides potential plant-specific differences in the quality and quantity of rhizodeposits, also photosynthesis could control root exudation because of the fast transport of recently assimilated C to belowground pools. Taking both factors into account, in Studies 3 and 4 the effect of limited photosynthesis on the distribution of recently assimilated C, of stored C and of N was investigated. Based on 13C, 14C and 15N labeling of a legume and a non-legume we could demonstrate that high C and N demands of regrowing shoots after clipping led to a remobilization of stored C and N to the shoots. Additionally, recently assimilated C was retained in the regrowing shoots.
Shading, in contrast, did not induce a remobilization of stored C, since recently assimilated C obviously covered the demand of the shoots with lower growth rates. For both treatments lower amounts of recently assimilated C were observed in the belowground pools emphasizing the importance of the tight coupling of assimilation and belowground processes. Furthermore, different responses of clipping and shading of the legume and the non-legume could be detected for root-derived CO2.
The quantitative importance of rhizodeposition at field scale was determined in Study 5. We proposed a new approach for an improved quantification of rhizodeposition under field conditions taking into account the decomposed fraction of rhizodeposits. Based on a 14CO2 pulse labeling experiment under controlled conditions a rhizodeposition-to-root ratio was calculated and was applied to the root biomass of the field. The root biomass C of maize, sampled in July 2009, was 298±64 kg C ha-1. Gross rhizodeposition was 166±53 kg C ha-1.
With aging of SOM, the availability of C for microbial decomposition declines. In Study 6 the availability of younger relative to older C sources was assessed. The natural isotope abundances of 13C and 12C of SOM and CO2 were analyzed after a C3 to C4 vegetation change. The contribution of younger C, originating from the belowground C input by maize in the previous year, and that of older C sources, derived from the former C3 vegetation, to SOM and CO2 was determined. Comparing the proportions of younger and older C in SOM with that in CO2, we found that younger C was 7 times more available for microbial decomposition than older C pools.
In summary, this thesis extends the understanding of factors affecting rhizodeposition and of processes occurring at the soil-root interface. Furthermore, it presents a new method to quantify gross rhizodeposition at field scale. Although, we could gain insight in temporal changes of the availability of C pools for microbes, the ecological importance of C fluxes in the rhizosphere requires future research on this topic with regard to spatial and temporal predictions.
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Kinetische Untersuchungen der Halogen-Aktivierung einer simulierten Salzpfanne in einer Smogkammer
(2013)
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Natalja Balzer
- Reaktive Halogenverbindungen, insbesondere solche von Br und Cl, spielen eine wichtige Rolle beim atmosphärischen Abbau von Ozon und Kohlenwasserstoffen. Auch beeinflussen sie die Radikalzusammensetzung in der Troposphäre und haben somit eine Auswirkung auf klimarelevante Prozesse. Ziel dieser Arbeit war die Untersuchung der Halogenfreisetzung aus einer künstlichen Salzpfanne bei unterschiedlichen umweltrelevanten Bedingungen, wie relative Feuchte (RF) und Konzentrationen von Stickoxiden und Kohlenwasserstoffen, in einer Smogkammer. Diese Methode wurde in Rahmen dieser Arbeit entwickelt, um diese bislang wenig untersuchte Quelle von Halogenen zu untersuchen. Als Modell für die Salzpfanne wurde eine umweltrelevante Mischung von NaCl mit NaBr verwendet. Kinetische Berechnungen lieferten die zeitlichen Verläufe der Cl-Atome und OH-Radikale aus dem Verbrauch der zugesetzten Kohlenwasserstoffe und der Br-Atome aus dem Ozonverbrauch und UV-Absorptionsmessungen die Verläufe der BrO-Radikale. Während Salzpfannen-Experimenten bei einer mittleren RF von 37 % erreichte die Cl-Konzentration ein Maximum von 5 x104 cm-3. Ein rascherer Ozonabbau wurde bei größerer RF und zugleich höherer BrO-Konzentration beobachtet. Bei den Experimenten in Anwesenheit von sekundären organischen Aerosolen (SOA) verlangsamte sich der Ozonabbau um einen Faktor 16. Das BrO-Mischungsverhältnis erreichte in diesem Fall maximal 0.15 ppb im Vergleich zu Experimenten ohne SOA, bei denen das BrO Mischungsverhältnis 6 ppb erreichte. Nach Einwirkung der aus der Salzpfanne freigesetzten Halogene auf das SOA wurde ein erneutes Partikelwachstum beobachtet. Dies könnte eine Hauptsenke für Halogene in der Atmosphäre darstellen und einen neuen Weg zur Partikelbildung.
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Sozialphilosophie und Geldpolitik bei Friedrich August von Hayek, Walter Eucken, Joseph Alois Schumpeter, Milton Friedman und John Maynard Keynes
(2013)
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Stephan Balling
- Die globale Finanzkrise, die im Frühjahr 2007 begann und im September 2008 durch den
Zusammenbruch der Investmentbank Lehman Brothers eskalierte, begann im vierten Quartal
2008 weltweit auf die Realwirtschaft durchzuschlagen. Die deutsche Bundesregierung
rechnete damit, dass im Jahr 2009 das Bruttoinlandsprodukt (BIP) um 6 Prozent einbrechen
werde – so stark wie nie seit dem Zweiten Weltkrieg. Es kam mit einem BIP-Rückgang von
4,9 Prozent dann zwar nicht ganz so schlimm, aber auch diese Rezession war die stärkste
seit 1945. Für diese dramatischen Entwicklungen lieferten Ökonomen im Wesentlichen zwei
Erklärungsmuster: Die einen gaben den Zentralbanken die Schuld, sie hätten in den zwei
Jahrzehnten vor der Krise zu viel Liquidität geschaffen, die dann zu Preisblasen etwa auf
dem amerikanischen Immobilienmarkt führte. Andere machten eine zu schlaffe Regulierung
und die Liberalisierung der Finanzmärkte für die Entwicklungen verantwortlich.
Vor dem Hintergrund dieser Ereignisse entstand die Idee, nicht nur eine technische Analyse
durchzuführen um zu erkennen, welches Erklärungsmuster plausibler sei. Stattdessen sollte
analysiert werden, wie sich diese diametral wiedersprechenden Aussagen von Ökonomen
ideengeschichtlich erklären lassen. Es erschien nötig, sich ideengeschichtlich mit
Sozialphilosophie, der Rolle des Staates in der Wirtschaft sowie dem Wesen des Geldes und
des Zinses in den wichtigsten ökonomischen Schriften des 20. Jahrhunderts zu
beschäftigen. Dabei sollte es um die Frage gehen, ob bei Ökonomen und Sozialphilosophen
zwischen den generellen gesellschafts- und wirtschaftspolitischen Vorstellungen einerseits
und den geldpolitischen Vorstellungen andererseits ein Zusammenhang besteht. Diese
Frage sollte durch einen Literaturvergleich verschiedener Staats- und Geldtheoretiker geklärt
werden, die – bei allen Unterschieden im Detail – für sich das Attribut „liberal“ reklamieren.
Die vorliegende Arbeit analysiert folglich die Werke von fünf großen Wirtschafts- und
Sozialphilosophen, nämlich von Friedrich August von Hayek als Repräsentant der
Österreichischen Schule der Nationalökonomie, Walter Eucken als Vertreter der Freiburger
Schule der Ordnungsökonomik, Joseph A. Schumpeter als Vertreter einer
Unternehmertheorie, Milton Friedman als Begründer des Monetarismus und John Maynard
Keynes als Vertreter einer expansiven Geld- und Fiskalpolitik. Dabei wird ein
Zusammenhang des Denkens in Bezug auf allgemeine staatsphilosophische Vorstellungen,
wirtschaftspolitische Ziele und die Aufgabe sowie den Instrumentenkasten der Geldpolitik
hergestellt.
Dabei zeigt sich: Individualistische Vorstellungen über die Gesellschaft gehen mit
Präferenzen für eine geringe Tätigkeit des Staates in der Wirtschaft sowie einer
weitgehenden, teils sogar völligen Entkopplung der Geldpolitik von politischer Einflussnahme
einher. Umgekehrt gehen Vorstellungen, die weniger einem negativen als einem positiven
Freiheitsbegriff folgen und dem wirtschaftlichen Erfolg des Kollektivs den Vorzug vor der
Freiheit des Einzelnen geben, mit einer stärkeren Rolle des Staates im wirtschaftlichen
Koordinations- und Allokationsprozess einher und fordern zugleich eine aktive Rolle der
Geldpolitik bei der Steuerung des wirtschaftlichen Prozesses. Daraus ist wiederum zu
schließen: Die Forderung nach einer expansiv ausgerichteten Geldpolitik zur Stimulierung
von Konjunktur und Wachstum beruht ideengeschichtlich nicht nur auf technischen
Überlegungen zur Effizienz, sondern stammt von einer grundsätzlich kollektivistischer – teils
sozialistischer – ausgerichteten Grundüberzeugung. Die Argumentation zum Beispiel für
oder gegen eine konjunkturstützende Geldpolitik leitet sich nicht nur aus theoretischen
ökonomischen Modellen ab, deren Richtigkeit etwa durch empirische Methoden überprüft
werden kann. Sie leitet sich auch aus grundsätzlichen Überzeugungen zum Beispiel über
den Wert der individuellen Freiheit oder des Schutzes von Eigentumsrechten ab. In der
politischen wie in der wissenschaftlich-ökonomischen Diskussion kommt dieser Aspekt
allerdings zu kurz.
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Soil erosion and conservation potential of row crop farming in mountainous landscapes of South Korea
(2013)
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Sebastian Arnhold
- Soils play an essential role for mankind because they provide fundamental ecosystem services required for human life, primarily for the production of food by providing the environment for plant growth. However, soils worldwide became highly threatened by human induced degradation, especially as a consequence of accelerated erosion by water during recent decades. In consideration of climate change and an increasing food demand of a rising population, there is an urgent need to conserve the soil resources by implementing effective erosion control measures for agricultural production. The effective implementation of those measures strongly depends on the specific conditions of particular regions and requires the analysis of the existing farming systems and their capability for erosion control.
Objective of this thesis is the analysis of the major agricultural practices applied for row crop cultivation in mountainous watersheds of South Korea with respect to water erosion and the identification of their conservation potential. Our first two studies analyze the subsurface flow processes, the runoff patterns, and the associated erosion rates of the widely applied plastic covered ridge-furrow system (plastic mulch), and our third study investigates the impact of herbicide applications on erosion associated with conventional and organic farming. To analyze the flow processes induced by the plastic mulch cultivation, we conducted four irrigation experiments on potato fields that represent a smooth surface, uncovered ridges, and plastic covered ridges with and without a developed crop canopy. With an automatic sprinkler, we irrigated small plots with a dye tracer solution of Brilliant Blue and potassium iodide, collected surface runoff, and excavated soil profiles to visualize the subsurface flow patterns, which were subsequently analyzed by image index functions. We found that the ridge-furrow system, especially when ridges are covered with plastic, decreased infiltration and generated high amounts of surface runoff, whereas a developed crop canopy increased infiltration due to interception and stem flow. The analyses of the subsurface flow patterns show that the plastic covered ridge-furrow system induces preferential infiltration in furrows and planting holes due to its topography and the impermeable covers, but that the impact on flow processes in the soils is relatively small compared to the impact on runoff generation. To identify the patterns of overland flow and the erosion rates associated with the plastic mulch system, we installed runoff collectors to monitor runoff and sediment transport of two potato fields with concave and convex topographies, and we applied the EROSION 3D model to compare the plastic covered ridge-furrow system to uncovered ridges and a smooth surface. We found that plastic mulch cultivation considerably increases soil erosion compared to uncovered ridges as a consequence of high amounts of surface runoff. Our results show that the ridge-furrow system concentrated overland flow on the concave field, resulting in severe gully erosion, but prevented flow accumulation and reduced erosion on the convex field, which demonstrates that the effect of this cultivation strategy is primarily controlled by the field topography and its orientation. To analyze the effects of conventional and organic farming on water erosion, we measured multiple vegetation parameters of crops and weeds of conventional and organic farms cultivating bean, potato, radish, and cabbage, and we simulated long-term soil loss rates with the Revised Universal Soil Loss Equation (RUSLE). We found that organic farming reduced erosion for radish, as a result of an increased weed biomass due to the absence of herbicides, but that it increased erosion for potato due to lower crop coverage, presumably as a consequence of crop-weed competition or herbivory associated with the absence of agricultural chemicals. Although we demonstrated that a developed weed cover in the furrows can potentially decrease the erosion risk for row crops, our results show that the average annual erosion rates of both farming systems exceed by far any tolerable soil loss.
In consideration of the generally high soil loss found in our studies, we conclude that the applied farming practices are not capable for effective erosion control and soil conservation in this region. However, based on our findings, we could identify possible modifications of those practices that can help to reduce the risk of erosion in the future. We recommend perforated plastic covers for ridges to reduce runoff generation, and the orientation of the ridge-furrow system along the contours or towards field edges to prevent flow accumulation and gully formation. Additionally, we suggest residue mulching of furrows to protect the soil surface from overland flow, and the cultivation of winter cover crops after harvest to maintain a better soil cover throughout the year.
