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Während es eine Vielzahl von Arbeiten zu der technologischen Entwicklung im Bereich der erneuerbaren Energien gibt, fehlt es jedoch bislang an einer mikroökonomischen Analyse
der Verhaltensmuster der Akteure im Umfeld von Anlagen nach dem EEG. Als Akteure kommen hier in erster Linie der Anlagenbetreiber selbst und der Staat in Betracht.
Im Hinblick auf Anlagenbetrieb und Vergütung der erzeugten Energie können beide mit unterschiedlichsten Interessen und Nutzenkalkülen aufeinander treffen. Diese Arbeit untersucht
mikroökonomische Aspekte des EEG-Förderungssystems. Im Mittelpunkt der Betrachtung stehen die Förderungsmechanismen für Biogasanlagen, die im Hinblick auf mögliche Prinzipal-Agenten-Konflikte einer Untersuchung unterzogen werden.
Nanoparticles are sensitive and robust systems; they are particularly reactive due to their large surface area and have properties that the bulk material does not have. At the same time, the production of nanoparticles is challenging, because even with the same parameters and conditions, the parameters can vary slightly from run to run. In order to avoid this, this work aims to develop a continuous synthesis in the microjet reactor for nanoceria. The aim is to obtain monodisperse nanoparticles that can be used in biosensors.
This work focuses on two precipitation syntheses with the intermediate steps of cerium carbonate and cerium hydroxide, as well as a microemulsion synthesis for the production of nanoceria. The cerium oxide nanoparticles are compared using different characterisation and application methods. The synthesised nanoparticles will be characterised with respect to their size, stability, chemical composition and catalytic capabilities, by electron microscopy, X-ray diffraction, Raman spectroscopy and photoelectron spectroscopy.
The biosensor systems to evaluate the nanoceria are designed to detect histamine and glucose or hydrogen peroxide, which are resulting from the oxidation of histamine and glucose. Hydrogen peroxide and glucose are detected by an electrochemical sensor and histamine by a colorimetric sensor system.
Die vorliegende Dissertation beschäftigt sich mit euroskeptischen Äußerungen in der Parteienkommunikation und der Medienberichterstattung im Vorfeld der Europawahl 2014. Die Arbeit verwendet ein akteurszentriertes Forschungsdesign, welches eine differenzierte Betrachtung der öffentlichen Debatte europäischer Themen erlaubt. Die Analyse deckt auf, welche nationalen Parteien euroskeptische Positionen vertreten und inwiefern diese Einzug in die mediale Berichterstattung finden. Auch die Positionierung der Medien selbst wird durch die Untersuchung meinungsbezogener Artikel berücksichtigt. Die den Studien zu Grunde liegende Konzeptualisierung des Euroskeptizismus-Begriff umfasst neben globalen und konkreten negativen Bewertungen der EU auch die Zuschreibung von Problemverantwortung als weitere Spielart euroskeptischer Äußerungen. Die Arbeit nimmt weiterhin eine international vergleichende Perspektive ein, um den Einfluss nationaler Kontextfaktoren auf die Verbreitung euroskeptischer Positionen aufzuzeigen.
Die Ergebnisse der Analyse decken zunächst auf, dass das Vorhandensein erstarkender euroskeptischer Oppositionsparteien nicht zwangsläufig zu einer Politisierung der europäischen Debatte führt, da sich die europhilen Mainstream-Parteien verschiedener Strategien zur Vermeidung einer solchen Kontroversen bedienen. Die Analysen ergeben weiterhin, dass europhile Regierungsparteien zwar mehrheitlich vor konkreten negativen Bewertungen der EU zurückschrecken, diese aber in Bezug auf die europäische Finanzkrise vorwiegend als Verursacher von Problemlagen skizzieren. Letztlich verdeutlichen die Ergebnisse, dass die mediale Berichterstattung zu Themen mit EU-Bezug eine starke Synchronizität zwischen Nachrichten- und Meinungsteil aufzeigt. Dies gilt sowohl in Bezug auf die geäußerten Bewertungen zur Europäischen Union als auch hinsichtlich der Darstellung von Verantwortlichkeit.
Die vorliegende Arbeit geht der Frage nach, wie sich Teilhabe und Inklusion von Menschen mit Lernschwierigkeiten in der allgemeinem Erwachsenenbildung realisieren lassen und was wesentliche Elemente und Rahmenbedingungen einer inklusiven Erwachsenenbildung mit Menschen mit Lernschwierigkeiten sind.
Menschen mit Lernschwierigkeiten haben ein gesetzlich verankertes Recht auf Teilhabe an inklusiver Erwachsenenbildung. Inklusive Erwachsenenbildung bezeichnet gemäß der UN-BRK die Teilnahme und Partizipation auch von Menschen mit Lernschwierigkeiten an allgemeiner Erwachsenenbildung, im Vordergrund steht das gemeinsame Lernen im regulären Programm allgemeiner Erwachsenenbildungseinrichtungen.
In der Aufarbeitung des theoretischen Diskurses und der praktischen Realisierung inklusiver Erwachsenenbildung zeigt sich allerdings, dass das Erwachsenenbildungsangebot für diese Personengruppe und die Möglichkeiten der Teilhabe am allgemeinen Erwachsenenbildungssystem in Deutschland eingeschränkt
sind. Umfassende Praxismodelle inklusiver Erwachsenenbildung sind erst in Ansätzen vorhanden, auch die Rahmenbedingungen gelingender inklusiver Erwachsenenbildung wurden kaum systematisch aufgearbeitet. Somit gilt es, für den Bereich der Erwachsenenbildung Konzepte zu entwickeln, die den Abbau von Barrieren und die Förderung von gleichberechtigter Teilhabe und Inklusion unterstützen. Es ist davon
auszugehen, dass die Kenntnis von wesentlichen Elementen und Rahmenbedingungen allgemeine Erwachsenenbildungseinrichtungen bei der Implementierung und Weiterentwicklung inklusiv gestalteter Erwachsenenbildung unterstützen und somit die Teilhabemöglichkeiten für Menschen mit Lernschwierigkeiten gezielt erweitern kann. Ziel dieser Arbeit ist deshalb die Erhebung und Beschreibung von wesentlichen Elementen und Rahmenbedingungen inklusiver Erwachsenenbildung.
Da es in Deutschland an Erfahrungswerten sowie der systematischen Ausarbeitung notwendiger Realisierungsbedingungen
inklusiver Erwachsenenbildung mangelt, richtet die vorliegende Arbeit ihren Blick in einem zweiten Schritt auf die ‚Inspiring Practice’ anderer Länder. In einer empirischen qualitativ-
explorativen Studie in elf Erwachsenenbildungseinrichtungen und -institutionen Englands werden mit Hilfe von 55 Leitfadeninterviews wesentliche Elemente und Rahmenbedingungen aus Sicht
der beteiligten Akteure erhoben und ausgewertet. Flankiert durch teilnehmende Beobachtungen, Dokumentenanalysen
und Gespräche liefern die Ergebnisse zugleich einen Einblick in die praktische Umsetzung inklusiver Erwachsenenbildung in England. Die Wahl fiel auf England, weil in diesem europäischen Land inklusive Erwachsenenbildung bereits seit den 1990er Jahren als fester Bestandteil
des Bildungssystems verankert ist und umfängliche Erfahrungen gesammelt werden konnten.
Aus der Analyse dieser Erfahrungswerte werden in der Diskussion und Zusammenschau mit theoretischen Überlegungen und praktischen Umsetzungen richtungsweisende Impulse für die Weiterentwicklung
der inklusiven Erwachsenenbildung in Deutschland abgeleitet und in einem Perspektivkonzept einer inklusiven Erwachsenenbildung zusammengefasst.
Over the past few decades, Single-Particle Analysis (SPA), in combination with cryo-transmission electron microscopy, has evolved into one of the leading technologies for structural analysis of biological macromolecules. It allows the investigation of biological structures in a close to native state at the molecular level. Within the last five years the achievable resolution of SPA surpassed 2°A and is now approaching atomic resolution, which so far has only been possible with Xray crystallography in a far from native environment. One remaining problem of Cryo-Electron Microscopy (cryo-EM) is the weak image contrast. Since the introduction of cryo-EM in the 1980s phase plates have been investigated as a potential tool to overcome these contrast limitations. Until now, technical problems and instrumental deficiencies have made the use of phase plates difficult; an automated workflow, crucial for the acquisition of 1000s of micrographs needed for SPA, was not possible. In this thesis, a new Zernike-type Phase Plate (PP) was developed and investigated. Freestanding metal films were used as a PP material to overcome the ageing and contamination problems of standard carbon-based PPs. Several experiments, evaluating and testing various metals, ended with iridium as the best-suited material. A thorough investigation of the properties of iridium PP followed in the second part of this thesis. One key outcome is a new operation mode, the rocking PP. By using this rocking-mode, fringing artifacts, another obstacle of Zernike PPs, could be solved. In the last part of this work, acquisition and reconstruction of SPA data of apoferritin was performed using the iridium PP in rocking-mode. A special semi-automated workflow for the acquisition of PP data was developed and tested. The recorded PP data was compared to an additional reference dataset without a PP, acquired following a conventional workflow.
Culture and violence
(2010)
The basic assumption of this study is that specific cultural conditions may lead to psychopathological reactions through which an increase in interpersonal violence may happen. The objective of this study was to define to what extent homicide rates across national cultures might be associated with the strength of their attitudes toward specific beliefs and values, and their scores in specific cultural dimensions. To answer this question, nine independent variables were defined six of which were related to the people- attitudes pertaining importance of religion (Religiosity), excessive feeling of choice and control (Omnipotence), clear-cut distinction between good and evil (Absolutism), proud of their nationality (Nationalism), approval of competition (Competitiveness), and high respect for authorities and emphasis on obedience (Authoritarianism). The data for these variables were collected from World Values Survey. For two cultural dimensions, Collectivism, and Power Distance, Hofstede- scores were used. The 9th variable was GNI per capita. After estimation of 7% missing values in the whole data through multiple imputation, a sample of 81 nations was used for further statistical analyses.
Results: Stepwise regression analysis indicated Omnipotence and GNI as the strongest predictors of homicide (β = .44 P = .000; β = -.27 P = .006 respectively). The 9 independent variables were loaded on two factors, socio-economic development (SED) and psycho-cultural factor (Psy-Cul), which were negatively correlated (-.47). The Psy-Cul was interpreted as an indicator of narcissism, and a mediator between SED and homicide. Hierarchical cluster analysis made a clear distinction among three main groups of Western, Developing, and post-Communist nations on the basis of the two factors.
Fungicide effects on the structure and functioning of leaf-associated aquatic fungal communities
(2022)
Aquatic hyphomycetes are a polyphyletic group of saprotrophic fungi growing abundantly on submerged leaf litter. In stream ecosystems shaped by allochthonous leaf litter inputs, they play a central functional role as decomposers and food source for other organisms. Fungicides pose a threat to aquatic hyphomycetes and their functions, since these substances are inherently toxic to fungi and contaminate surface waters around the world due to their widespread use in agricultural and urban landscapes. While fungicides’ potential to reduce fungal diversity are discerned, the extent of impacts on biodiversity-ecosystem functioning relationships (B EF) remains unclear. This is partly attributed to methodological constraints in the detection and quantification of single aquatic hyphomycete species within microbial leaf-associated communities. The primary aim of this thesis was, therefore, (1) to assess the ecotoxicological impacts of fungicides on B-EF relationships in aquatic hyphomycete communities. To facilitate this, subordinate aims were to (2) develop DNA-based biomolecular tools (i.e., qPCR assays) to detect and to quantify the biomass of different aquatic hyphomycete species in mixed cultures and (3) to investigate the mechanisms underlying B-EF relationships in the absence of chemical stressors.
In the course of this thesis, qPCR assays were developed for detection and species-specific biomass quantification of ten common aquatic hyphomycete species and successfully validated for application in eco( toxico )logical microcosm experiments. Via a systematic manipulation of fungal diversity, these assays allow the examination of B-EF relationships by assessments of deviations between observed and (monoculture-based) predicted activities in fungal mixed cultures. Taking advantage of these tools in a microcosm experiment, it was uncovered that leaf decomposition results from the additive activity of community members, even though functionally distinct species were present. Colonization dynamics are characterized by complex interactions. Colonization success of aquatic hyphomycetes is higher if co-occurring species are genetically and functionally distinct (i.e., complementary interactions). However, the co-occurrence of aquatic hyphomycete species does not necessarily result in a greater colonization success compared to monocultures, unless bacteria are present. Accordingly, the presence of other microbial groups such as bacteria may induce new fungal diversity-based feedback loops, which ultimately enable coexistence of aquatic hyphomycete species in the environment. Exposure to fungicides revealed substantial differences in sensitivities among aquatic hyphomycetes. The most productive species were able to cope with extremely high fungicide concentrations up to the mg/L-range. In assemblages containing these species, leaf decomposition was maintained under fungicide exposure. Yet, already at environmentally relevant fungicide concentrations, tolerant species displaced more sensitive ones, potentially affecting leaves’ nutritional quality for consumers. This thesis thus indicates that fungicide exposure poses a risk to stream food webs rather than the microbial leaf decomposition process per se.
The implementation of physiological indicators reflecting the response of organisms to changes in their environment is assumed to provide potential benefits for ecological studies. By analysing the physiological condition of organisms in freshwater ecological studies rather than their ultimate effects, physiological indicators can contribute to a faster assessment of effects than using traditional ecological indicators, such as the evaluation of the benthic community structure or the determination of the reproductive success of organisms. This can increase the effectiveness of environmental health assessment and experimental ecology. In this respect the thesis focuses on physiological measures characterizing the energetic condition and energy consumption (the concentration of energy storage compounds, the adenylate energy charge, the energy consumption in vivo), as well as individual growth (RNA:DNA ratio) of organisms. Although these sub-individual indicators are commonly applied in marine ecology and more recently in ecotoxicology, they have been rarely applied in freshwater ecology to date. With respect to an increased use of physiological indicators in freshwater ecological studies, the objectives of the present thesis are twofold. First, it highlights the potential of assessing the individual fitness by means of physiological indicators in freshwater ecological studies. For that reason, Chapter 2 provides the basic assumptions as well as the theoretical and methodological fundamentals necessary for the application of physiological indicators within freshwater ecology and, furthermore, points out their applicability by several case studies. As second objective, the thesis addresses selected ecophysiological aspects of native and non-native freshwater amphipods, which are considered suitable candidates for the determination of physiological indicators in ecological studies due to their function as keystone species within aquatic habitats. The studies presented in Chapters 3−5 of the thesis provide information on (i) species- and sex-specific seasonal variations within the energetic condition of natural Gammarus populations (G. fossarum, G. pulex), (ii) differences in metabolic activity and behaviour between different amphipod species (G fossarum, G. roeselii and D. villosus), as well as (iii) the direct effects of ambient ammonia on the physiology and behaviour of D. villosus. The fundamental conclusions drawn from the conducted field and laboratory studies, as well as their relevance and general implications for the application of physiological indicators in freshwater ecological research are discussed in Chapter 6.
SUMMARY
Buildings and infrastructures characterize the appearance of our cultural landscapes and provide essential services for the human society. However, they inevitably impact the natural environment e.g. by the structural change of habitats. Additionally, they potentially cause further negative environmental impacts due to the release of chemical substances from construction materials. Galvanic anodes and organic coatings regularly used for corrosion protection of steel structures are building materials of particular importance for the transport infrastructure. In direct contact with a water body or indirectly via the runoff after rainfall, numerous chemicals can be released into the environment and pose a risk to aquatic organisms. Up to now, there is no uniform investigation and evaluation approach for the assessment of the environmental compatibility of building products. Furthermore, galvanic anodes and organic coatings pose particular challenges for their ecotoxicological characterization due to their composition. Therefore, the objective of the presented thesis was the ecotoxicological assessment of emissions from galvanic anodes and protective coatings as well as the development of standardized assessment procedures for these materials.
The possible environmental hazard posed by the use of anodes on offshore installations was investigated on three trophic levels. To ensure a realistic and reliable evaluation, the experiments were carried out in natural seawater and under natural pH conditions. Moreover, the anode material and its main components zinc and aluminum were exposed while simulating a worst-case scenario. The anode material examined caused a weak inhibition of algae growth; no acute toxicity was observed on the luminescent bacteria and amphipods. However, an increase of aluminum and indium levels in the crustacean species was found. On the basis of these results, no direct threat has been identified for marine organisms from the use of galvanic aluminum anodes. However, an accumulation of metals in crustaceans and a resulting entry into the marine food web cannot be excluded.
The environmental compatibility of organic coating systems was exemplarily evaluated using a selection of relevant products based on epoxy resins (EP) and polyurethanes. For this purpose, coated test plates were dynamically leached over 64 days. The eluates obtained were systematically analyzed for their ecotoxicological effects (acute toxicity to algae and luminescent bacteria, mutagenic and estrogenic effects) and their chemical composition. In particular, the EP-based coatings caused significant bacterial toxicity and estrogen-like effects. The continuously released 4-tert-butylphenol was identified as a main contributor to these effects and was quantified in concentrations exceeding the predicted no effect concentration for freshwater in all samples. Interestingly, the overall toxicity was not governed by the content of 4-tert-butylphenol in the products but rather by the release mechanism of this compound from the investigated polymers. This finding indicates that an optimization of the composition can result in the reduction of emissions and thus of environmental impacts - possibly due to a better polymerization of the compounds.
Coatings for corrosion protection are exposed to rain, changes in temperature and sun light leading to a weathering of the polymer. To determine the influence of light-induced aging on the ecotoxicity of top coatings, the emissions and associated adverse effects of UV-irradiated and untreated EP-based products were compared. To that end, the investigation of static leachates was focused on estrogenicity and bacterial toxicity, which were detected in the classic microtiter plate format and in combination with thin-layer plates. Both materials examined showed a significant decrease of the ecotoxicological effects after irradiation with a simultaneous reduction of the 4-tert-butylphenol emission. However, bisphenol A and various structural analogues were detected as photolytic degradation products of the polymers, which also contributed to the observed effects. In this context, the identification of bioactive compounds was supported by the successful combination of in-vitro bioassays with chemical analysis by means of an effect-directed analysis. The presented findings provide important information to assess the general suitability of top coatings based on epoxy resins.
Within the scope of the present study, an investigation concept was developed and successfully applied to a selection of relevant construction materials. The adaptation of single standard methods allowed an individual evaluation of these products. At the same time, the suitability of the ecotoxicological methods used for the investigation of materials of unknown and complex composition was confirmed and the basis for a systematic assessment of the environmental compatibility of corrosion protection products was created. Against the background of the European Construction Products Regulation, the chosen approach can facilitate the selection of environmentally friendly products and contributes to the optimization of individual formulations by the simple comparison of different building materials e.g. within a product group.
Many pharmaceuticals (e.g. antibiotics, contrast media, beta blockers) are excreted unmetabolized and enter wastewater treatment plants (WWTPs) through the domestic sewage system. Research has shown that many of them are not effectively removed by conventional wastewater treatment and therefore are detected in surface waters. Reverse osmosis (RO) is one of the most effective means for removing a wide range of micropollutants in water recycling. However, one significant disadvantage is the need to dispose the resultant RO concentrate. Due to the fact that there are elevated concentrations of micropollutants in the concentrate, a direct disposal to surface water could be hazardous to aquatic organisms. As a consequence, further treatment of the concentrate is necessary. In this study, ozonation was investigated as a possible treatment option for RO concentrates. Concentrate samples were obtained from a RO-membrane system which uses municipal WWTP effluents as feeding water to produce infiltration water for artificial groundwater recharge. In this study it could be shown that ozonation is efficient in the attenuation of selected pharmaceuticals, even in samples with high TOC levels (46 mg C/L). Tests with chlorinated and non-chlorinated WWTP effluent showed an increase of ozone stability, but a decrease of hydroxyl radical exposure in the samples after chlorination. This may shift the oxidation processes towards direct ozone reactions and favors the degradation of compounds with high apparent second order rate constants. Additionally it might inhibit an oxidation of compound predominantly reacting with OH radicals. Ozone reaction kinetics were investigated for beta blockers (acebutolol, atenolol, metoprolol and propranolol) which are permanently present in WWTP effluents. For beta blockers two moieties are common which are reactive towards ozone, a secondary amine group and an activated aromatic ring. The secondary amine is responsible for a pH dependence of the direct ozone reaction rate, since only the deprotonated amine reacts very quickly. At pH 7 acebutolol, atenolol and metoprolol reacted with ozone with an apparent second order rate constant of about 2000 M-1 s-1, whereas propranolol reacted at ~1.0 105 M-1 s-1. The rate constants for the reaction of the selected compounds with OH radicals were determined to be 0.5-1.0 x 1010 M-1 s-1. Oxidation products (OPs) formed during ozonation of metoprolol and propranolol were identified via liquid chromatography (LC) tandem mass spectrometry. Ozonation led to a high number of OPs being formed. Experiments were carried out in MilliQ-water at pH 3 and pH 8 as well as with and without the radical scavenger tertiary butanol (t-BuOH). This revealed the influence of pH and the OH radical exposure on OP formation. The OH radical exposure was determined by adding the probe compound para-chlorobenzoic acid (pCBA). Metoprolol: To define the impacts of the protonated and non protonated metoprolol species on OH radical formation, the measured pCBA attenuation was compared to modeled values obtained by a simplified kinetic model (Acuchem). A better agreement with the measured results was obtained, when the model was based on a stoichiometric formation of OH radical precursors (O2-) during the primary ozone reaction of metoprolol. However, for reaction of a deprotonated molecule (attack of the aromatic ring) a formation of O2- could be confirmed, but an assumed stoichiometric O2- formation over-estimated the formation of OH radicals in the system. Analysis of ozonated raw wastewater and municipal WWTP effluent spiked with 10 μM metoprolol exhibited a similar OP formation pattern as detected in the reaction system at pH 8 without adding radical scavenger. This indicated a significant impact of OH radical exposure on the formation of OPs in real wastewater matrices. Propranolol: The primary ozonation product of propranolol (OP-291) was formed by an ozone attack of the naphthalene ring, which resulted in a ring opening and two aldehyde moieties being formed. OP-291 was further oxidized to OP-307, presumably by an OH radical attack, which was then further oxidized to OP-281. Reaction pathways via ozone as well as OH radicals were proposed and confirmed by the chemical structures identified with MS2 and MS3 data. It can be concluded that ozonation of WWTP effluent results in the formation of a high number of OPs with an elevated toxic potential (i.e. formation of aldehydes).
Fate and effects of insecticides in vegetated agricultural drainage ditches and constructed wetlands
(2006)
Studies have shown that runoff and spray-drift are important sources of nonpoint-source pesticide pollution of surface waters. Owing to this, public concern over the presence of pesticides in surface and ground water has resulted in intensive scientific efforts to find economical, yet environmentally sound solutions to the problem. The primary objective of this research was to assess the effectiveness of vegetated aquatic systems in providing buffering between natural aquatic ecosystems and agricultural landscape following insecticide associated runoff and spray-drift events. The first set of studies were implemented using vegetated agricultural ditches, one in Mississippi, USA, using pyrethroids (bifenthrin, lambda-cyhalothrin) under simulated runoff conditions and the other in the Western Cape, South Africa using the organophosphate insecticide, azinphos-methyl (AZP), under natural runoff and spray-drift conditions. The second set of studies were implemented using constructed wetlands, one in the Western Cape using AZP under natural spray-drift conditions and the other in Mississippi, USA using the organophosphate MeP under simulated runoff conditions. Results from the Mississippi-ditch study indicated that ditch lengths of less than 300 m would be sufficient to mitigate bifenthrin and lambda-cyhalothrin. In addition, data from mass balance calculations determined that the ditch plants were the major sink (generally > 90%) and/or sorption site for the rapid dissipation of the above pyrethroids from the water column. Similarly, results from the ditch study in South Africa showed that a 180 m vegetated system was effective in mitigating AZP after natural spray drift and low flow runoff events. Analytical results from the first wetland study show that the vegetated wetland was more effective than the non-vegetated wetland in reducing loadings of MeP. Mass balance calculations indicated approximately 90% of MeP mass was associated with the plant compartment. Ninety-six hours after the contamination, a significant negative acute effect of contamination on abundances was found in 8 out of the 15 macroinvertebrate species in both wetland systems. Even with these toxic effects, the overall reaction of macroinvertebrates clearly demonstrated that the impact of MeP in the vegetated wetland was considerably lower than in the non-vegetated wetland. Results from the constructed wetland study in South Africa revealed that concentrations of AZP at the inlet of the 134 m wetland system were reduced by 90% at the outlet. Overall, results from all of the studies in this thesis indicate that the presence of the plant compartment was essential for the effective mitigation of insecticide contamination introduced after both simulated and natural runoff or spray-drift events. Finally, both the vegetated agricultural drainage ditch and vegetated constructed wetland systems studied would be effective in mitigating pesticide loadings introduced from either runoff or spray-drift, in turn lowering or eliminating potential pesticide associated toxic effects in receiving aquatic ecosystems. Data produced in this research provide important information to reduce insecticide risk in exposure assessment scenarios. It should be noted that incorporating these types of best management practices (BMPs) will decrease the risk of acute toxicity, but chronic exposure may still be an apparent overall risk.
Die laserinduzierte Plasmaspektroskopie (”Laser Induced Breakdown Spectroscopy”, im Folgenden auch ”LIBS” genannt) stellt eine schnelle und berührungslose Messmethode zur Elementanalyse von festen, flüssigen oder gasförmigen Stoffen unter normalen Umgebungsbedingungen ohne besondere Probenvorbereitung dar. Dazu wird ein gepulster Laser, dessen Intensität einen bestimmten Grenzwert überschreiten muss, auf eine Probe fokussiert. Das dort bestrahlte Material verdampft schlagartig und es bildet sich bei einer Temperatur von rund 10000 K ein Plasma aus. Die angeregten Atome und Ionen im Plasma strahlen bei der Rückkehr in energetisch niedrigere Zustände ein charakteristisches optisches Emissionsspektrum ab, welches über eine schnelle spektroskopische Analyse die Elementzusammensetzung des untersuchten Materials liefert. LIBS bietet in diesem Fall auch die Möglichkeit, ein unkompliziertes und bildgebendes Messverfahren aufzubauen, indem Elementverteilungen auf einer topographischen Oberfläche analysiert werden, um beispielsweise Materialübergänge, Einschlüsse oder Verschmutzungen sicher zu detektieren. Bei unebenen Oberflächen wird eine ständige Anpassung des Laserfokus an die Probenkontur benötigt, da die notwendige Intensität zur Erzeugung des Plasmas nur im Fokus aufgebracht werden kann. Als Grundlage dafür dient ein neu entwickelter Fokussieralgorithmus, der ohne jegliche Zusatzgeräte auskommt, und die Reproduzierbarkeit von LIBS-Messungen deutlich steigern kann, da die Messungen kontrolliert im Fokus stattfinden. Durch ihn ergeben sich neue Möglichkeiten des sogenannten „Element-Mappings", dem Erzeugen von Elementlandkarten, welche die Elementverteilungen in Falschfarben grafisch darstellen. Dabei ist das System nun nicht mehr auf eine ebene Oberfläche angewiesen, sondern kann beliebige Strukturen, auch mit scharfen Kanten und Löchern, sicher vermessen. Als Ergebnis erhält man ein flächiges Höhenprofil, welches zusätzlich die Elementinformationen für jeden Messpunkt beinhaltet. Dies erleichtert es dem Benutzer, gezielt Punkte von Interesse schnell wiederzufinden und zu analysieren. Die vorliegende Arbeit beschreibt die Entwicklung eines bildgebenden Low-Power-LIBSSystems mit niedriger Pulsenergie und hoher Pulsrate, welches sich mit dem dazugehörigen
Fokussieralgorithmus automatisiert an unebene Probenoberflächen anpassen kann. Als Ergebnisse werden die Analysen von ausgewählten metallhaltigen, geologischen, organischen und archäologischen Proben bzw. Fundstücken gezeigt.
The transport of pesticides from agricultural land into surface waters via diffuse entry pathways such as runoff is a major threat to aquatic ecosystems and their communities. Although certain risk mitigation measures are currently stipulated during pesticide product authorisation, further approaches might be needed to manage hot spots of pesticide exposure. Such a management is, for example, required by the European Union- directive for the sustainable use pesticides (2009/128/EC).
The need for mitigation measures was investigated within the present thesis at stream sites draining an arable and a vineyard region in Germany by characterising pesticide exposure following edge-of-field runoff and (expected) effects on the aquatic macroinvertebrates. The results of these field studies showed, that streams in both regions were exposed to pesticide concentrations suggesting effects on the macroinvertebrate community. In the arable region the observed toxicity was mainly attributed to the insecticides lambda-cyhalothrin (in the water-phase samples) and alpha-cypermethrin (in the suspended particle samples), whereas in the vineyard region fungicides were most important. Furthermore stream water and suspended particles sampled in the vineyard region showed critical copper concentrations, which might cause ecotoxicological effects in the field. In addition to pesticide exposure, in the arable region also the effects on aquatic macroinvertebrates were assessed in the field. Generally, invertebrate fauna was dominated by pesticide-tolerant species, which suggested a high pesticide exposure at almost all sites. The elevated levels of suspended particle contamination in terms of maximum toxic units per sample (logTUMax > -2) reflect also this result. At two sites that received high aqueous-phase entries of the insecticide lambda-cyhalothrin (logTUMax > -0.6), the abundance and number of sensitive species (indicated by the SPEcies At Risk index) decreased during the pesticide application period. In contrast, at sites characterised by low water-phase toxicity (logTUMax < -3.5), no acute significant negative effects on macroinvertebrates were observed. In conclusion these data showed that in both regions the implementation of risk mitigation measures is needed to protect the aquatic communities.
To mitigate runoff-related pesticide entries, riparian buffer strips are often recommended. However, the mitigating influence with increasing buffer strip width could not be demonstrated for riparian buffers which were already present in the arable and vineyard region. This result was attributed in the vineyard region to the high number of paved field paths associated with artificial erosion rills, which concentrate and rapidly transport receiving edge-of-field runoff in stream direction. Consequently the pesticide reduction efficiency of buffer strips is considerably reduced. We assumed that a similar process occurred in the arable region, due to a high number of erosion rills, which complicate a laminar sheet flow of edge-of-field runoff through the riparian buffer strip. Additionally also the presence of ephemeral drainage ditches, which led surface runoff from the agricultural fields to the streams may have contributed to observed pesticide entries despite wide buffers.
Effective risk mitigation measures should address these identified most important input pathways in the study areas. As possible measures the implementation of grassed field paths and vegetated ditches or wetlands were suggested. In general also the improvement of currently present riparian buffer strips regarding their efficiency to reduce pesticide runoff entries should be taken into account. In conclusion the results of the field studies underline the importance that risk mitigation measures are identified specifically for the respective pollution situation in stream catchments. To facilitate this process, a user guide was developed within the present thesis for identifying appropriate mitigation measures at high-risk sites. Based on a survey of exposure relevant landscape parameter a set of risk mitigation measures is suggested that focus on the specific pollution situation. Currently the guide includes 12 landscape- and six application-related measures and presents an overview of these measures" efficiency to reduce pesticide entries via runoff and spray drift, their feasibility and expected acceptability to farmers. Based on this information the user can finally choose the mitigation measures for implementation. The present guide promotes the practical implementation of appropriate risk mitigation measures in pesticide-polluted streams, and thus the protection of aquatic stream communities against pesticide entries.
In dieser Studie sollte hinsichtlich der Entwicklung eines faunistisch begründeten Monitoringkonzeptes für hydrologische Interaktionen untersucht werden, inwieweit die Meiofauna in Hyporheal und Grundwasser in der Lage ist, Oberflächenwasser-Grundwasser-Interaktionen zu reflektieren und die hydrologischen Verhältnisse einer Uferfiltrationsanlage aufzuzeigen. Dafür wurden hydrochemische und faunistische Analysen bezüglich ihrer Aussagekraft miteinander verglichen. Außerdem wurde die Anwendbarkeit des Grundwasser-Fauna-Index (GFI) zur Beurteilung der Stärke des Oberflächenwassereinflusses auf unterirdisches Wasser überprüft. Für die Untersuchung wurde die Uferfiltrationsanlage Flehe der Stadtwerke Düsseldorf ausgewählt, auf deren Gelände 70 vertikale Entnahmebrunnen über eine Strecke von 1,4 km eine Brunnengalerie bilden, die im Jahr insgesamt 11 Mio. m3 Wasser fördert. Am Untersuchungsstandort wurden insgesamt 15 Observationspegel von Februar 2005 bis Januar 2006 faunistisch und hydrochemisch beprobt. Die physikochemische Untersuchung ergab eine Aufteilung des Untersuchungsgebietes in vier Zonen. Neben dem Oberflächenwasser des Rheins [OW Rhein] konnten das Uferfiltrationswasser zwischen Rhein und den Entnahmebrunnen [Hyporheal], alluviales Grundwasser hinter der Brunnengalerie [Alluv. GW] und bei größerer Entfernung zum Rhein landseitiges Grundwasser [landseitiges GW] differenziert werden. Dabei wies der Rhein die typische Charakteristik eines Fließgewässers auf, gekennzeichnet durch eine große Temperaturamplitude mit einem Sommermaximum, hohen Sauerstoffkonzentrationen mit einem Wintermaximum und erhöhten AOX-, DOC- und SAK254nm-Werten. Am Uferfiltrat der Gruppe [Hyporheal] wurde die Wirksamkeit der mikrobiellen Abbauprozesse während der Uferfiltration mit deutlichen Reduzierungen der DOC- und SAK- und Sauerstoffkonzentrationen ersichtlich. Die Gruppe [Alluv. GW] und verstärkt das [landseitige GW] waren durch eine höhere elektrische Leitfähigkeit und erhöhten Bor- und Sulfatkonzentrationen sowie z. T. geringen Sauerstoffgehalten gekennzeichnet. Anhand dieser hydrochemischen Differenzen konnte die unterschiedliche Herkunft des Wassers im Untersuchungsgebiet ermittelt werden Die faunistischen Untersuchungen zeigten ein differenzierteres Bild von den hydrologischen Verhältnissen als die Hydrochemie. Insgesamt konnten fünf ökologische Gruppen ermittelt werden. Die Gruppe [Hyporheal 1] der A-Pegelreihe wies als einzige euryöke Arten auf, die einen stärkeren Oberflächenwassereinfluss anzeigten. Im [Hyporheal 2] der B-Pegelreihe konnte eine artenreiche ökotonale Fauna nachgewiesen werden, während die Proben des alluvialen Grundwassers der C-Pegelreihe [Alluv. GW (Pumpe)] den Einfluss der Entnahmebrunnen reflektierten. In den Pegeln des alluvialen Grundwassers [Alluv. GW] wurde aufgrund der geringeren Beeinflussung der Pumpen artenreichere Zoozönosen vorgefunden. Das [landseitige GW] wies schließlich eine arten- und abundanzarme Fauna auf, die charakteristisch ist für Grundwasser mit geringem Oberflächenwassereinfluss. Folglich konnte die Fauna nicht nur die Herkunft des Grundwassers anzeigen, sondern auch den Einfluss und die Intensität des Oberflächenwassers auf das Grundwasser sowie anthropogene Störungen wie eine verstärkte Kolmation bzw. die Effekte der Wasserentnahme durch die Brunnen. Die Meiofauna im Grundwasserleiter der Uferfiltrationsanlage dürfte somit als Indikator für hydrologische Verhältnisse gut geeignet sein. Der Grundwasser-Fauna-Index konnte als der wichtigste Faktor aller physikochemischen Parameter ermittelt werden, der die faunistischen Gruppen am stärksten beeinflusst. Außerdem war der GFI in der Lage, die Auswirkung und Intensität des Einflusses von Oberflächenwasser auf die einzelnen Probestandorte anzuzeigen. Die hier dargestellten Ergebnisse zeigen, dass die Grundwasserfauna und der GFI viel versprechende Methoden zur Bewertung der hydrologischen Verhältnisse, insbesondere des Einflusses von Oberflächenwasser auf das Grundwasser sind. Daher sind sie als Ergänzung zur hydrochemischen Analyse zu empfehlen und können auch einen wichtigen Beitrag für die Vulnerabilitätsabschätzung leisten.
Lernen in Citizen Science
(2021)
Unsere Welt und die technischen und naturwissenschaftlichen Erkenntnisse verändern sich aktuell sehr schnell. Dies betrifft auch die naturwissenschaftliche Forschung und erfordert vermehrten Einsatz der Wissenschaftskommunikation und der Bildung. Ein Instrument der Wissenschaftskommunikation und eine Erweiterung des schulischen Unterrichts kann die Beteiligung von Freiwilligen bei wissenschaftlichen Arbeiten sein, welches auch als Citizen Science (CS) bezeichnet wird. CS Projekte erfreuen sich einer wachsenden Beliebtheit, unter anderem von Schulen (Burger, 2016). Dabei werden unter anderem die Förderung des Kontextwissens, der Scientific Literacy, der Umwelteinstellung und des –verhaltens versprochen (Peter et al., 2019). Interventionsstudien zu den Bildungspotentialen kommen jedoch zu unterschiedlichen Ergebnissen (Gommermann & Monroe, 2012; Turrini et al., 2018). Diese inkonsistenten Ergebnisse der Studien können auf die unterschiedliche Gestaltung der einzelnen evaluierten CS Projekte zurückgeführt werden. Es wird angenommen, dass Teilnehmende, die in mehr Schritten des wissenschaftlichen Prozesses eingebunden werden, ein größeres Bildungspotential haben, als Teilnehmende, die nur in wenige Schritte eingebunden werden (Burger, 2016; Shirk & Bonney, 2018). Bonney, Ballard et al. (2009) haben dazu ein dreistufiges Modell entwickelt. Das Modell wird unter anderem auch von Shirk et al. (2012) und Jordan et al. (2015) unterstützt, ist jedoch bezüglich der Lernwirksamkeit nicht empirisch überprüft (Edwards et al., 2018; Jordan et al., 2015). Deswegen schließt die Forschungsfrage dieser Studie hier an: Unter welchem Partizipationsansatz sind die Lerneffekte in einem CS Projekt am größten für Schülerinnen und Schüler? Um diese Frage zu beantworten, wurde ein CS Projekt mit drei Experimentalgruppen geplant und durchgeführt. Insgesamt nahmen 199 Schülerinnen und Schüler an dem Projekt teil. Innerhalb der Interventionsstudie wurden die Schülerinnen und Schüler zu drei Testzeitpunkten zur Umwelteinstellung und -verhalten, Nature of Science, Einstellung zur Wissenschaft und dem Kontextwissen befragt. Die Analysen über die Messzeitpunkte zeigen keine statistisch signifikanten Einflüsse der Experimentalgruppen auf die abhängigen Variablen. Jedoch ist die Teststärke bei allen Tests zu gering, um abschließende Aussagen über die Annahmen zu treffen. Wird jedoch die generelle Wirkung der Intervention betrachtet, zeigen sich signifikante Effekte auf alle Schülerinnen und Schüler, unter anderem steigt das Verständnis über Nature of Science. Diese Ergebnisse stimmen mit früheren Schlussfolgerungen von Phillips (2017), Phillips et al. (2019) und Del Bianco (2018) überein, die ebenfalls Zweifel an dem Modell von Bonney, Ballard et al. (2009) äußerten. Innerhalb dieses CS Projektes konnte sich keiner der drei Partizipationsansätze bezüglich des Bildungspotential für Schülerinnen und Schüler hervorheben lassen. Jedoch ist diese Studie unter anderem durch die geringe Teststärke limitiert und endgültige Aussagen bedürfen weiterer systematischer Forschung.
Das Hauptziel der vorliegenden Arbeit ist die Absicherung der Qualität eines pharmazeutischen Produktionsprozesses durch die Überprüfung des Volumens mikroskopischer Polymerstäbchen mit einem hochgenauen 3D Messverfahren. Die Polymerstäbchen werden für pharmazeutische Anwendungen hergestellt. Aus Gründen der Qualitätssicherung muss das Istgewicht überprüft werden. Derzeit werden die Polymerstäbchen stichprobenartig mit einer hochpräzisen Waage gewogen. Für die nächste Generation von Polymeren wird angenommen, dass die Produktabmessungen weiter reduziert werden sollen und die Produktionstoleranzen auf 2,5% gesenkt werden. Die daraus resultierenden Genauigkeitsanforderungen übersteigen jedoch die Möglichkeiten der Wiegetechnik. Bei homogenen Materialien ist die Masse proportional zum Volumen. Aus diesem Grund kommt dessen Bestimmung als Alternative in Frage. Dies verschafft Zugang zu optischen Messverfahren und deren Flexibilität und Genauigkeitpotenzial. Für den Entwurf eines auf die Fragestellung angepassten Messkonzeptes sind weiterhin von Bedeutung, dass das Objekt kontaktlos, mit einer Taktzeit von maximal fünf Sekunden vermessen und das Volumen approximiert wird. Die Querschnitte der Polymerstäbchen sind etwa kreisförmig. Aufgrund der Herstellung der Fragmente kann nicht davon ausgegangen werden, dass die Anlageflächen orthogonal zur Symmetrieachse des Objektes sind. Daher muss analysiert werden, wie sich kleine Abweichungen von kreisförmigen Querschnitten sowie die nicht idealen Anlageflächen auswirken. Die maximale Standardabweichung für das Volumen, die nicht überschritten werden sollte, beträgt 2,5%. Dies entspricht einer maximalen Abweichung der Querschnittsfläche um 1106 µm² (Fehlerfortpfanzung). Als Bewertungskriterium wird der Korrelationskoeffzient zwischen den gemessenen Volumina und den Massen bestimmt. Ein ideales Ergebnis wäre 100%. Die Messung zielt auf einen Koeffzienten von 98% ab. Um dies zu erreichen, ist ein präzises Messverfahren für Volumen erforderlich. Basierend auf dem aktuellen Stand der Technik können die vorhandenen optischen Messverfahren nicht verwendet werden. Das Polymerstäbchen wird von einer Kamera im Durchlicht beobachtet. Daher sind der Durchmesser und die Länge sichtbar. Das Objekt wird mittels einer mechanischen Vorrichtung um die Längsachse gedreht. So können Bilder von allen Seiten aufgenommen werden. Der Durchmesser und die Länge werden mit der Bildverarbeitung berechnet. Das neue Konzept vereint die Vorteile der Verfahren: Es ist unempfindlich gegen Farb-/Helligkeitsänderungen und die Bilder können in beliebiger Anzahl aufgenommen werden. Außerdem sind die Erfassung und Auswertung wesentlich schneller. Es wird ein Entwurf und die Umsetzung einer Lösung zur hochpräzisen Volumenmessung von Polymerstäbchen mit optischer Messtechnik und Bildverarbeitung ausgearbeitet. Diese spezielle Prozesslösung in der Prozesslinie (inline) sollte eine 100%ige Qualitätskontrolle während der Produktion garantieren. Die Zykluszeiten des Systems sollte fünf Sekunden pro Polymerstäbchen nicht überschreiten. Die Rahmenbedienungen für den Prozess sind durch die Materialeigenschaften des Objekts, die geringe Objektgröße (Breite = 199 µm, Länge = 935 µm bis 1683 µm) und die undeffinierte Querschnittsform (durch den Trocknungsprozess) vorgegeben. Darüber hinaus sollten die Kosten für den Prozess nicht zu hoch sein. Der Messaufbau sollte klein sein und ohne Sicherheitsvorkehrungen oder Abschirmungen arbeiten. Das entstandene System nimmt die Objekte in verschiedenen Winkelschritten auf, wertet mit Hilfe der Bildverarbeitung die Aufnahmen aus und approximiert das Volumen. Der Korrelationskoffizient zwischen Volumen und Gewicht beträgt für 77 Polymerstäbchen mit einem Gewicht von 37 µg bis 80 µg 99; 87%. Mit Hilfe eines Referenzsystems kann die Genauigkeit der Messung bestimmt werden. Die Standardabweichung sollte maximal 2,5% betragen. Das entstandene System erzielt eine maximale Volumenabweichung von 1,7%. Die Volumenvermessung erfüllt alle Anforderungen und kann somit als Alternative für die Waage verwendet werden.
The biodegradable polymers polylactic acid (PLA) and polyhydroxybutyrate (PHB) produced from renewable raw materials were coated with hydrogenated amorphous carbon layers (a-C:H) at different deposition angles with various thicknesses as part of this thesis. Similar to conventional polymers, biopolymers often have unsuitable surface properties for industrial purposes, e.g. low hardness. For some applications, it is therefore necessary and advantageous to modify the surface properties of biopolymers while retaining the main properties of the substrate material. A suitable surface modification is the deposition of thin a-C:H layers. Their properties depend essentially on the sp² and sp³ hybridization ratio of the carbon atoms and the content of hydrogen atoms. The sp²/sp³ ratio was to be controlled in the present work by varying the coating geometry. Since coatings at 0°, directly in front of the plasma source, contain a higher percentage of sp³ and indirectly coated (180°) a higher amount of sp², it is shown in this work that it is possible to control the sp²/sp³ ratio. For this purpose, the samples are placed in front of the plasma source at angles of 0, 30, 60, 90, 120, 150 and 180° and coated for 2.5, 5.0, 7.5 and 10.0 minutes. For the angles 0°, the layer thicknesses were 25, 50, 75 and 100 nm. The a-C:H layers were all deposited using radio-frequency plasma-enhanced chemical vapor deposition and acetylene as C and H sources after being pretreated with an oxygen plasma for 10 minutes. Following the O₂ treatment and the a-C:H deposition, the surfaces are examined using macroscopic and microscopic measurement methods and the data is then analyzed. The surface morphology is recorded using scanning electron microscopy and atomic force microscopy. In addition, data on the stability of the layer and the surface roughness can be collected. Contact angle (CA) measurements are used to determine not only the wettability, but also the contact angle hysteresis by pumping the drop volume up and down. By measuring the CA with different liquids and comparing them, the surface free energy (SFE) and its polar and disperse components are determined. The changes in barrier properties are verified by water vapor transmission rate tests (WVTR). The chemical analysis of the surface is carried out on the one hand by Fourier transform infrared spectroscopy with specular reflection and on the other hand by synchrotron-supported techniques such as near-edge X-ray absorption fine structure and X-ray photoelectron spectroscopy. When analyzing the surfaces after the O₂ treatment, which was initially assumed to serve only to clean and activate the surface for the a-C:H coating, it was found that the changes were more drastic than originally assumed. For example, if PLA is treated at 0° for 10 minutes, the roughness increases fivefold. As the angle increases, it decreases again until it returns to the initial value at 180°. This can be recognized to a lesser extent with PHB at 30°. For both polymers, it can be shown that the polar fraction of the SFE increases. In the WVTR, a decrease in permeability can be observed for PLA and an increase in the initial value for PHB. The chemical surface analysis shows that the O₂ treatment has little effect on the surface bonds. Overall, it can be shown in this work that the O₂ treatment has an effect on the properties of the surface and cannot be regarded exclusively as a cleaning and activation process. With direct a-C:H coating (at 0°), a layer failure due to internal stress can be observed for both PLA and PHB. This also occurs with PHB at 30°, but to a lesser extent. Permeability of the polymers is reduced by 47% with a five-minute coating and the layer at 10.0 minutes continues to have this effect despite cracks appearing. The application of a-C:H layers shows a dominance of sp³ bonds for both polymer types with direct coating. This decreases with increasing angle and sp² bonds become dominant for indirect coatings. This result is similar for all coating thicknesses, only the angle at which the change of the dominant bond takes place is different. It is shown that it is possible to control the surface properties by an angle-dependent coating and thus to control the ratio sp²/sp³.
Introduction:
In March 2012 a secessionist-Islamist insurgency gained momentum in Mali and quickly took control of two-thirds of the state territory. Within weeks radical Islamists, drug smugglers and rebels suddenly ruled over a territory bigger than Germany. News of the abuse of the population and the introduction of harsh Sharia law spread soon, and word got out that the Malian Army had simply abandoned the land. The general echo of the IC was surprise, a reaction that was, as this research will show, as unfunded as it was unconstructive*. When Malian state structures collapsed, the world watched in shock, even though the developments couldhave been anticipated –and prevented. Ultimately, the situation had to be resolved by international forces (most notably French troops), who are still in Mali at the time of writing (Arieff 2013a: 5; Lohmann 2012: 3; Walther and Christopoulos 2015: 514f.; Shaw 2013: 204; Qantara, Interview, 2012;L’Express, Mali, 2015; Deutscher Bundestag, MINUSMA und EUTM Mali, 2016; UN, MUNISMA, 2016; Boeke and Schuurmann 2015: 801; Chivvis 2016: 93f.).
This research will show that the developments in Mali in 2012 have been developing for a long time and could have been avoided. In doing so, it will also show why state security can never be analyzed or consolidated in an isolated manner. Instead, it is necessary to take into account regional dynamics and developments in order to find a comprehensive approach to security in individual states. Once state failure occurs, not only does the state itself fail, but the surrounding region equally failed to prevent the failure.
Weak states are a growing concern in many world regions, particularly in Africa. As international intervention often proves unsustainable for various reasons*, the author believes that states which cannot stabilize themselves need a regional agent to support them. This regional agent should be a Regional Security Complex (RSC) asdefined by Barry Buzan and Ole Waever (Buzan and Waever 2003). As the following analysis will show, Mali is a case in point. The hope is that this study will help avoid similar failures in the future by making a strong case for the establishment of RSC’s.
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This dissertation introduces a methodology for formal specification and verification of user interfaces under security aspects. The methodology allows to use formal methods pervasively in the specification and verification of human-computer interaction. This work consists of three parts. In the first part, a formal methodology for the description of human-computer interaction is developed. In the second part, existing definitions of computer security are adapted for human-computer interaction and formalized. A generic formal model of human-computer interaction is developed. In the third part, the methodology is applied to the specification and verification of a secure email client.
In the new epoch of Anthropocene, global freshwater resources are experiencing extensive degradation from a multitude of stressors. Consequently, freshwater ecosystems are threatened by a considerable loss of biodiversity as well as substantial decrease in adequate and secured freshwater supply for human usage, not only on local scales, but also on regional to global scales. Large scale assessments of human and ecological impacts of freshwater degradation enable an integrated freshwater management as well as complement small scale approaches. Geographic information systems (GIS) and spatial statistics (SS) have shown considerable potential in ecological and ecotoxicological research to quantify stressor impacts on humans and ecological entitles, and disentangle the relationships between drivers and ecological entities on large scales through an integrated spatial-ecological approach. However, integration of GIS and SS with ecological and ecotoxicological models are scarce and hence the large scale spatial picture of the extent and magnitude of freshwater stressors as well as their human and ecological impacts is still opaque. This Ph.D. thesis contributes novel GIS and SS tools as well as adapts and advances available spatial models and integrates them with ecological models to enable large scale human and ecological impacts identification from freshwater degradation. The main aim was to identify and quantify the effects of stressors, i.e climate change and trace metals, on the freshwater assemblage structure and trait composition, and human health, respectively, on large scales, i.e. European and Asian freshwater networks. The thesis starts with an introduction to the conceptual framework and objectives (chapter 1). It proceeds with outlining two novel open-source algorithms for quantification of the magnitude and effects of catchment scale stressors (chapter 2). The algorithms, i.e. jointly called ATRIC, automatically select an accumulation threshold for stream network extraction from digital elevation models (DEM) by assuring the highest concordance between DEM-derived and traditionally mapped stream networks. Moreover, they delineate catchments and upstream riparian corridors for given stream sampling points after snapping them to the DEM-derived stream network. ATRIC showed similar or better performance than the available comparable algorithms, and is capable of processing large scale datasets. It enables an integrated and transboundary management of freshwater resources by quantifying the magnitude of effects of catchment scale stressors. Spatially shifting temporal points (SSTP), outlined in chapter 3, estimates pooled within-time series (PTS) variograms by spatializing temporal data points and shifting them. Data were pooled by ensuring consistency of spatial structure and temporal stationarity within a time series, while pooling sufficient number of data points and increasing data density for a reliable variogram estimation. SSTP estimated PTS variograms showed higher precision than the available method. The method enables regional scale stressors quantification by filling spatial data gaps integrating temporal information in data scarce regions. In chapter 4, responses of the assumed climate-associated traits from six grouping features to 35 bioclimatic indices for five insect orders were compared, their potential for changing distribution pattern under future climate change was evaluated and the most influential climatic aspects were identified (chapter 4). Traits of temperature preference grouping feature and the insect order Ephemeroptera exhibited the strongest response to climate as well as the highest potential for changing distribution pattern, while seasonal radiation and moisture were the most influential climatic aspects that may drive a change in insect distribution pattern. The results contribute to the trait based freshwater monitoring and change prediction. In chapter 5, the concentrations of 10 trace metals in the drinking water sources were predicted and were compared with guideline values. In more than 53% of the total area of Pakistan, inhabited by more than 74 million people, the drinking water was predicted to be at risk from multiple trace metal contamination. The results inform freshwater management by identifying potential hot spots. The last chapter (6) synthesizes the results and provides a comprehensive discussion on the four studies and on their relevance for freshwater resources conservation and management.
Hintergrund: Veränderte gesetzliche Rahmenbedingungen in der stationären Altenhilfe, die demografische Entwicklung mit dem steigenden Bedarf an Pflegekräften einerseits und die Tatsache, dass immer weniger Menschen aufgrund des Images des Berufes und der Arbeitsbedingungen in der Pflege tätig sein wollen andererseits, machen es notwendig neue Wege zu suchen. Die Träger im Sozial- und Gesundheitswesen sind gefordert, Konzepte zu entwickeln, die ihre Wirtschaftlichkeit sichern, gleichzeitig aber auch den Belastungen und der Unzufriedenheit von Mitarbeitenden entgegenwirken. Es braucht Gestaltungsräume, um Lösungen im Konflikt zwischen Anspruch und Machbarkeit zu finden und so dem alltäglichen Stress, der Mitarbeiterfluktuation und dem drohenden Leistungsabfall entgegenzuwirken. Durch das Praxisprojekt eines sozial-karitativen Trägers zur Implementierung einer ´Konstruktiven Konfliktkultur´ in einer stationären Altenhilfeeinrichtung sollte eine Organisationskultur geschaffen werden, in der Konflikte offen angesprochen werden, eine Offenheit für Veränderungsprozesse entsteht, Belastungen reduziert und die Mitarbeitenden an die Organisation gebunden werden. Dazu wurden drei pädagogische Interventionen entwickelt, durch die die Mitarbeitenden und die Führungskräfte in ihrer Konfliktfähigkeit geschult werden sollten. Methode: Die wissenschaftliche Begleitung dieses Praxisprojektes fand als Evaluationsstudie statt. Zu drei Erhebungszeitpunkten wurde eine repräsentative Mitarbeitergruppe dieser Einrichtung zu den Themen Konflikterleben, Führungsverhalten, Macht/ Regeln und Veränderungen durch qualitative Leitfadeninterviews befragt. Die Auswertung und Analyse der Daten erfolgte im Sinne der qualitativen Inhaltsanalyse nach Mayring und floss ein in eine formative Prozessevaluation der einzelnen Interventionen und einer summativen Effektevaluation zu Bewertung der Zielerreichung des Projektes. Ergebnis: Die einzelnen Interventionen des Projektes konnten nicht dazu beitragen, dass eine ´Konstruktiven Konfliktkultur´ nachhaltig entwickelt werden konnte. Zwar gab es in der Bewusstseinsspanne des Projektes einen expliziten Wissensgewinn, jedoch mehr bei den Führungskräften als bei den Mitarbeitenden. Die Führungskräfte sahen im Projekt einen Gewinn, für einen Teil der Mitarbeitenden war es sogar Zeitverschwendung. Anhand der Ergebnisse lassen sich drei Merkmale herauskristallisieren, die kennzeichnend sind für die zugrundeliegenden Denk-, Urteils-, und Handlungsstrukturen in sozialen Organisationen im Umgang mit Konflikten: Konflikte sind nicht wahrnehmbare Konstrukte der Alltagswelt. Sie manifestieren sich aufgrund fehlender Legitimation in Überforderung und eine ´Konstruktiven Konfliktkultur´ kann nicht auf das Wissen Einzelner aufbauen, sondern benötigt verbindliche Handlungsstrukturen für alle Organisationsmitglieder gleichermaßen. Ergebnisinterpretation: Durch die Einbeziehung wissenssoziologischer und konfliktsoziologischer Theorien und deren Einordnung in Institutionen – und Organisationstheorien konnten die Ergebnisse diskutiert und neue Erkenntnisse über Konflikte in Organisationen, die sich in drei Spannungsfeldern zeigen, gewonnen werden. Die Spannungsfelder bewegen sich zwischen dem Konflikt als nicht-wahrnehmbarem Alltagsphänomen auf der einen Seite und einer manifestierten Belastung auf der anderen Seite, dem Gewohnheitswissen im alltäglichen Umgang einerseits und einem fehlenden Handlungswissen andererseits, einer funktional-positiven Sicht hier und einer dysfunktional-negativen Sicht dort. Anhand dieser Spannungsfelder kann die Konfliktmentalität und ihre Entstehung und auch die Möglichkeit ihrer Veränderbarkeit reflektiert und können Erfolgsfaktoren für die Implementierung einer ´Konstruktiven Konfliktkultur´ entwickelt werden.
Schlussfolgerung: Wissen, Legitimation und Institutionalisierung und die Stärkung der Wahrnehmungen sind der Schlüssel für die Veränderung der Konfliktmentalität in sozialen Organisationen. Nachhaltigkeit erhält die Thematik aber erst, wenn alle Organisationsmitglieder eine gewisse Handlungsnotwendigkeit für sich erkennen. Aktuell steht die Organisationsentwicklung für den expliziten Veränderungswillen von Management, der jedoch auf ein gewisses Beharrungsvermögen von Mitarbeitenden trifft.
The analysis of three-dimensional and complex motion sequences
of human gait and therefore the most important question
of kenesiology ”why are we falling?” is the essence of this
paper. The gerontology and its science of movement is currently
limited to simple and one-dimensional methods and models. An
extensive literature research shows the latest state of research of
the three common methods to determine the stability of human
gait. To assess the margin of stability, local stability and orbital
stability it is shown, how those methods are applicable to evaluate
the subject’s ability to recover from any disturbences of
the subject’s gait. Based on this assessment and the method’s
advantages and disadvantages a new method will be derived
that allows spatial analysis of dynamic instability of linear and
non-linear human gait. A motion capture system and the timed
up and go test serve as a basis for this new method and will be
explained. A numerical approximation to optimise the number
of markers within a marker-set of a motion capture analysis
and its maximum correlation with the full-body-marker-set will
be given. This simplification is very helpful for further clinical
or scientific research. To validate the new method a trial
with subjects will be shown and discussed. New appreciable
variables and snapshots of specific situations during the gait
offer new and different interpretations of the human gait. The
new method is the most applicable and appropriate assessment
of human gait and the individual development of the human
gait while aging, as well as to detect and prevent falling and
associated injuries. Especially directional change of a non-linear
gait become assessable with the new method.
The research described in this thesis was designed to yield information on the impact of particle-bound pesticides on organisms living in the interface between sediment and water column in a temporarily open estuary (TOCEs). It was hypothesized that natural variables such as salinity and temperature and anthropogenic stressors such as particle-bound pesticides contribute to the variability of the system. A multiple line of evidence approach is necessary due to the variability in sediment type, contaminant distribution and spatial and temporal variability within the ecosystem in particular within TOCEs. The first aim of this thesis was to identify which particle-bound pesticides are important to the contamination of the Lourens River estuary (Western Cape, South Africa), taking into account their environmental concentrations, physico-chemical and toxicological properties (Exposure assessment). The second aim was to identify spatial and temporal variations in particle bound pesticide contamination, natural environmental variables and benthic community structure (effect assessment). The third aim was to test the hypothesis: "does adaptation to fluctuating salinities lead to enhanced survival of the harpacticoid copepod Mesochra parva when exposed to a combination of particle associated chlorpyrifos exposure and hypo-osmotic stress during a 96 h sediment toxicity test?" The last aim was to identify the driving environmental variables (including natural and anthropogenic stressors) in a "natural" (Rooiels River) compared to a "disturbed" (Lourens River) estuary and to identify if and how these variables change the benthic community structure in both estuaries. Data produced in this research thus provide important information to understand the impact of pesticides and its interaction with natural variables in a temporarily open estuary. To summarise, this study indicated, by the use of the multi-evidence approach, that the pesticides endosulfan and chlorpyrifos posed a risk towards benthic organisms in a temporarily open estuary in particular during spring season. Furthermore an important link between pesticide exposure/ toxicity and salinity was identified, which has important implications for the management of temporarily open estuaries.
Abdriftbedingte Pflanzenschutzmittelrückstände in unbehandelten Kulturen auf angrenzenden Flächen
(2020)
Die vorliegende Arbeit beschäftigt sich mit der Abdrift von Pflanzenschutzmitteln (PSM), die auf Lebensmittelkulturen in angrenzenden Flächen, insbesondere in benachbarte Haus- und Kleingärten, gelangt. In einer Reihe von Windtunnelversuchen wurde die Abdrift von PSM aus Flächen- und Raumkulturen während der Applikation mit zwei verschiedenen Testsystemen nachgestellt. Das Testsystem Flächenkultur simuliert die Applikation auf Flächenkulturen, das Testsystem Raumkultur die auf Raumkulturen. Auf der Nicht-Zielfläche wurden die auf Grund von Abdrift entstandenen Rückstände des verwendeten Tracers Pyranin nach der Applikation entfernungsabhängig auf den Lebensmittelkulturen Kopfsalat, Erdbeeren und Tomaten gemessen. Durch die gleichzeitige Messung der Bodendeposition konnten die Messwerte mit Hilfe von Regressionsgleichungen (R² = 0,88 bis 0,97) in Bezug zu den Abdrifteckwerten (AEW) gebracht werden. Dadurch war es möglich, erste Abschätzungen der Höhe von Rückständen vorzunehmen, die über Abdrift von landwirtschaftlichen Flächen auf benachbarte Lebensmittelkulturen im Freiland gelangen können. Diese Abschätzung ist zunächst limitiert auf die drei Versuchspflanzen. Die Versuche zeigen, dass sich die meisten durch Abdrift entstehenden Rückstände auf Salatköpfen wieder finden, gefolgt von Erdbeeren und Tomaten.
Neben dem experimentellen Teil wurden Analysen mit Geoinformationssystemen (GIS) durchgeführt, um die Nachbarschaftsverhältnisse zwischen landwirtschaftlich genutzten Flächen und Gartenflächen für ganz Deutschland und speziell für Rheinland-Pfalz (RLP) zu analysieren. Dazu wurden für die deutschlandweiten Berechnungen die Daten des amtlichen topographisch-kartographischen Informationssystems (ATKIS) und für die RLP-weiten Berechnungen die Daten des amtlichen Liegenschaftskatasterinformationssystem (ALKIS) verwendet. Beachtet werden muss, dass auf Grund der Datenbeschaffenheit eine Abgrenzung der Gartenflächen zu Wohnflächen nicht möglich ist. Deutschlandweit liegen etwa 1,1 % aller potentiellen Gartenflächen innerhalb eines 5 m Pufferbereichs um Raumkulturen bzw. innerhalb eines 2 m Pufferbereichs um Flächenkulturen. Für RLP sind es 0,75 %. Mit Hilfe eines Landbedeckungsdatensatzes der Fa. RLP AgroScience GmbH und den ALKIS-Daten konnte jedoch die exakte Gartenfläche für RLP auf 47.437 ha bestimmt werden. Basierend auf dieser Datengrundlage liegen 1,2 % der Gartenfläche von RLP innerhalb der genannten Pufferbereiche. Des Weiteren ergaben Berechnungen, dass 3 % der Gärten in RLP direkt angrenzend zu landwirtschaftlich genutzten Flächen liegen.
Im Rahmen dieser Arbeit wurden nicht nur Gärten betrachtet, die an landwirtschaftliche Flächen grenzen, sondern auch Nachbarschaftsverhältnisse zwischen ökologisch und konventionell bewirtschafteten Flächen untersucht. Diese Berechnungen erfolgten mit den Daten des Integrierten Verwaltungs- und Kontrollsystems (InVeKoS). Insgesamt grenzen in RLP 47,1 % aller ökologisch bewirtschafteten Flächen unmittelbar an konventionell bewirtschaftete Flächen an.
Studien zeigen einen hohen Anteil an gut ausgebildeten Frauen, auch weisen Untersuchungen über die Führungskompetenz mehr führungsstarke Frauen (jede 12.) als Männer (jeder 17.) auf. Diese Ergebnisse spiegeln sich jedoch nicht in der nur geringen Anzahl von Frauen in höheren Führungspositionen wieder, mit der Folge, dass diese Ressource damit ungenutzt bleibt. Wenn Mitarbeitende aber als bedeutsam für den Unternehmenserfolg angesehen werden, dann sollten ein optimaler Einsatz und eine bestmögliche Entwicklung selbstverständlich sein. Dieser Aspekt findet sich auch in der Politik zur Gleichbehandlung der Geschlechter wieder. Organisationen vernachlässigen Potential, wenn sie Frauen, die gut ausgebildet sind, nicht die Möglichkeiten geben, beruflich aufzusteigen. Gerade in der Sozialen Arbeit ist der Anteil der Frauen sehr hoch, dennoch kehrt sich diese Verhältnismäßigkeit, vor allem bei den höheren Führungspositionen wie Vorstände, Geschäftsführungen, Aufsichtsgremien, um. Im Rahmen der vorliegenden Dissertation werden förderliche und hemmende Faktoren im Erreichen einer Leitungsposition von Frauen analysiert. Der besondere Fokus ist dabei auf die obere Führungsebene in Organisationen der Sozialen Arbeit gerichtet, im Besonderen auf die Freie Wohlfahrtspflege. Ziel ist darüber hinaus die Darstellung von Handlungsimplikationen zur Förderung weiblicher Karrieren in der Sozialen Arbeit, als Beitrag zur besseren Nutzung weiblichen Know-Hows. Die Arbeit berücksichtigt dabei sowohl die Sicht von Frauen in Führungspositionen, als auch die Sicht von Personalentscheiderinnen und -entscheidern und leistet einen Beitrag dazu, wie Frauen in Verbänden und Organisationen der Freien Wohlfahrtspflege der Zugang zu Führungspositionen ermöglicht werden kann. Die hieraus resultierenden Leitfragen sind: Welche biografischen und institutionellen Faktoren fördern und hemmen den Aufstieg weiblicher Führungskräfte in die obere Führungsebene? Welche Faktoren zeigen sich aus Sicht der Frauen, welche aus Sicht der Personalentscheiderinnen und -entscheider? Welche Lösungswege ergeben sich zur Anhebung des Frauenanteils in der oberen Führungsebene? In der theoretischen Ausarbeitung werden zunächst im Rahmen des ersten Themenkomplexes Frauen und Führung bspw. geschlechtsspezifische Aspekte von Führungsverhalten besprochen, Bezug nehmende Ergebnisse der Führungsforschung sowie der Frauen- und Geschlechterforschung aufgezeigt und berufliche Situationen und Karrieren von Frauen dargestellt. Einfluss- und Erfolgsfaktoren weiblicher Karrieren, mögliche Aufstiegsbarrieren (biografisch konstruiert, gesellschaftlich sozialisiert, organisationsstrukturell) und Strategien zur Realisierung von Chancengleichheit im Aufstieg werden beschrieben. Der erste Themenkomplex endet mit der analytischen Betrachtung des Nutzens dieser Chancengleichheit. Der zweite Themenkomplex geht konkret auf den Bereich Soziale Arbeit ein, beleuchtet den Begriff Frauenberuf, die berufliche Situation von Frauen in der Sozialen Arbeit, die Freie Wohlfahrtspflege, das hier vorherrschende Verständnis von Führung und geht im Abschluss auf Frauen in Führungspositionen in der Sozialen Arbeit ein. Neben Faktoren, die Frauen möglicherweise einen Führungsaufstieg erschweren, werden auch Möglichkeiten von Organisationen bei der Unterstützung von Karrieren der Frauen beleuchtet. Die Untersuchung legt ihren Schwerpunkt auf die Organisationen der Sozialen Arbeit und die Führungspositionen des oberen Managements. Im sich anschließenden empirischen Teil erfolgt daher die Darstellung des Forschungsprojekts und des Forschungssettings, der Forschungsergebnisse, als auch der daraus abgeleiteten Schlussfolgerungen.
Method development for the quantification of pharmaceuticals in aqueous environmental matrices
(2021)
As a consequence of the world population increase and the resulting water scarcity, water quality is the object of growing attention. In that context, organic anthropogenic molecules — often defined as micropollutants— represent a threat for water resources. Among them, pharmaceuticals are the object of particular concerns due to their permanent discharge, their increasing consumption and their effect-based structures. Pharmaceuticals are mainly introduced in the environment via wastewater treatment plants (WWTPs), along with their metabolites and the on-site formed transformation products (TPs). Once in the aquatic environment, they partition between the different environmental compartments in particular the aqueous phase, suspended particulate matter(SPM) and biota. In the last decades, pharmaceuticals have been widely investigated in the water phase. However, extreme polar pharmaceuticals have rarely been monitored due to the lack of robust analytical methods. Moreover, metabolites and TPs have seldom been included in routine analysis methods although their environmental relevance is proven. Furthermore, pharmaceuticals have been only sporadically investigated in SPM and biota and adequate multi-residue methods are lacking to obtain comprehensive results about their occurrence in these matrices. This thesis endeavors to cover these gaps of knowledge by the development of generic multi-residue methods for pharmaceuticals determination in the water phase, SPM and biota and to evaluate the occurrence and partition of pharmaceuticals into these compartments. For a complete overview, a particular focus was laid on extreme polar pharmaceuticals, pharmaceutical metabolites and TPs. In total, three innovative multi-residue methods were developed, they include analytes covering a broad range of physico-chemical properties. First, a reliable multi-residue method was developed for the analysis of extreme polar pharmaceuticals, metabolites and TPs dissolved in water. The selected analytes covered a significant range of elevated polarity and the method would be easily expendable to further analytes. This versatility could be achieved by the utilization of freeze-drying as sample preparation and zwitterionic hydrophilic interaction liquid chromatography (HILIC) in gradient elution mode. The suitability of HILIC chromatography to simultaneously quantify a large range of micropollutants in aqueous environmental samples was thoroughly studied. Several limitations were pointed out: a very complex and time-consuming method development, a very high sensitivity with regards to modification of the acetonitrile to water ratio in the eluent or the diluent and high positive matrix effects for certain analytes. However, these limitations can be overcome by the utilization of a precise protocol and appropriate labeled internal standards. They are overmatched by the benefits of HILIC which permits the chromatographic separation of extreme polar micropollutants. Investigation of environmental samples showed elevated concentrations of the analytes in the water phase. In particular, gabapentin, metformin, guanylurea and oxypurinol were measured at concentrations in the µg/L range in surface water. Subsequently, a reliable multi-residue method was established for the determination of 57 pharmaceuticals, 47 metabolites and TPs sorbed to SPM down to the low ng/g range. This method was conceived to cover a large range of polarity in particular with the inclusion of extreme polar pharmaceuticals. The extraction procedure was based on pressurized liquid extraction (PLE) followed by a clean-up via solvent exchange and detection via direct injection-reversed-phase LC-MS/MS and freeze-drying HILIC-MS/MS. Pharmaceutical sorption was examined using laboratory experiments. Derived distribution coefficients Kd varied by five orders of magnitude among the analytes and confirmed a high sorption potential for positively charged and nonpolar pharmaceuticals. The occurrence of pharmaceuticals in German rivers SPM was evaluated by the investigation of annual composite SPM samples taken at four sites at the river Rhine and one site at the river Saar between the years 2005 and 2015. It revealed the ubiquitous presence of pharmaceuticals sorbed to SPM in these rivers. In particular, positively charged analytes, even very polar and nonpolar pharmaceuticals showed appreciable concentrations. For many pharmaceuticals, a distinct correlation was observed between the annual quantities consumed in Germany and the concentrations measured in SPM. Studies of composite SPM spatial distribution permitted to get hints about specific industrial discharge by comparing the pollution pattern along the river. For the first time, these results showed the potential of SPM for the monitoring of positively charged and nonpolar pharmaceuticals in surface water. Finally, a reliable and generic multi residue method was developed to investigate 35 pharmaceuticals and 28 metabolites and TPs in fish plasma, fish liver and fish fillet. For this matrix, it was very challenging to develop an adequate clean-up allowing for the sufficient separation of the matrix disturbances from the analytes. In the final method, fish tissue extraction was performed by cell disruption followed by a non-discriminating clean-up based on silica gel solid-phase extraction(SPE) and restrictive access media (RAM) chromatography. Application of the developed method to the measurement of bream and carp tissues from German rivers revealed that even polar micropollutants such as pharmaceuticals are ubiquitously present in fish tissues. In total, 17 analytes were detected for the first time in fish tissues, including 10 metabolites/TPs. The importance of monitoring metabolites and TPs in fish tissues was confirmed with their detection at similar concentrations as their parents. Liver and fillet were shown to be appropriate for the monitoring of pharmaceuticals in fish, whereas plasma is more inconvenient due to very low concentrations and collection difficulties. Elevated concentrations of certain metabolites suggest possible formation of human metabolites in fish. Measured concentrations indicate a low bioaccumulation potential for pharmaceuticals in fish tissues.
Schrift ist in ihrer Besonderheit verkannt, versteht man sie allein als Mittel zur Stillstellung gesprochener Sprache. Phänomene wie Schriftbildlichkeit, Operativität und die Physiognomie des Schriftbildes machen Schrift zu einem Medium. In der Entwicklung und in der Verwendung von Schriftgebrauchsformen in unterschiedlichen Kontexten werden sowohl die Eigenschaften, die Schriftzeichen mit verbalen Zeichen gemeinsam haben, als auch die Potentiale, die sie mit pikturalen Zeichen gemeinsam haben, genutzt. Daher werden in der vorliegenden Arbeit die Funktionalisierungsmöglichkeiten von Schriftgebrauchsformen vor dem Hintergrund der Symboltheorie Nelson Goodmans vorgestellt. Eine an die ästhetische Theorie angelehnte Herangehensweise ermöglicht es, gerade die bildlichen Aspekte von Schriftformen – die bislang in schrifttheoretischen Arbeiten meist als irrelevant ausgeblendet werden – zu berücksichtigen. Es wird ein dynamischer Kompetenzbegriff in Anlehnung an J.G. Schneider entwickelt, der alle Fähigkeiten umfasst, die benötigt werden, um Schriftgebrauchsformen erfolgversprechend verwenden zu können. Zu diesen Fähigkeiten gehören nicht nur grammatische und orthographische Kompetenz, sondern ebenso Geschmack und die Fähigkeit zur Analogiebildung. An Beispielen verschiedener Schriftverwendungen wird gezeigt, wie unterschiedlich Schriftgebrauchsformen eingesetzt werden können. So wird Schrift als Kulturtechnik darstellbar und mithin verdeutlicht, dass die Art und Weise, wie Menschen ihre Kultur, ihre Welt, aber auch ihre spezifische Umgebung und eigene Identität modellieren, von Schriftverwendungen geprägt und verändert wird.
Gel effect induced by mucilage in the pore space and consequences on soil physical properties
(2020)
Water uptake, respiration and exudation are some of the biological functions fulfilled by plant roots. They drive plant growth and alter the biogeochemical parameters of soil in the vicinity of roots, the rhizosphere. As a result, soil processes such as water fluxes, carbon and nitrogen exchanges or microbial activity are enhanced in the rhizosphere in comparison to the bulk soil. In particularly, the exudation of mucilage as a gel-like substance by plant roots seems to be a strategy for plants to overcome drought stress by increasing soil water content and soil unsaturated hydraulic conductivity at negative water potentials. Although the variations of soil properties due to mucilage are increasingly understood, a comprehensive understanding of the mechanisms in the pore space leading to such variations is lacking.
The aim of this work was to elucidate the gel properties of mucilage in the pore space, i.e. interparticulate mucilage, in order to link changes of the physico-chemical properties in the rhizosphere to mucilage. The fulfilment of this goal was confronted to the three following challenges: The lack of methods for in situ detection of mucilage in soil; The lack of knowledge concerning the properties of interparticulate mucilage; The unknown relationship between the composition and the properties of model substances and root mucilage produced by various species. These challenges are addressed in several chapters.
In a first instance, a literature review picked information from various scientific fields about methods enabling the characterization of gels and gel phases in soil. The variation of soil properties resulting from biohydrogel swelling in soil was named the gel effect. The combined study of water entrapment of gels and gel phases in soil and soil structural properties in terms of mechanical stability or visual structures proved promising to disentangle the gel effect in soil.
The acquired methodical knowledge was used in the next experiments to detect and characterize the properties of interparticulate gel. 1H NMR relaxometry allows the non-invasive measure of water mobility in porous media. A conceptual model based on the equations describing the relaxation of water protons in porous media was developed to integrate the several gel effects into the NMR parameters and quantify the influence of mucilage on proton relaxation. Rheometry was additionally used to assess mucilage viscosity and soil microstructural stability and ESEM images to visualize the network of interparticulate gel. Combination of the results enabled to identify three main interparticulate gel properties: The spider-web effect restricts the elongation of the polymer chains due to the grip of the polymer network to the surface of soil particles. The polymer network effect illustrates the organization of the polymer network in the pore space according to the environment. The microviscosity effect describes the increased viscosity of interparticulate gel in contrast to free gel. The impact of these properties on soil water mobility and microstructural stability were investigated. Consequences on soil hydraulic and soil mechanical properties found in the literature are further discussed.
The influence of the chemical properties of polymers on gel formation mechanism and gel properties was also investigated. For this, model substances with various uronic acid content, degree of esterification and amount of calcium were tested and their amount of high molecular weight substances was measured. The substances investigated included pectic polysaccharides and chia seed mucilage as model polymers and wheat and maize root mucilage. Polygalacturonic acid and low-methoxy pectin proved as non-suitable model polymers for seed and root mucilage as ionic interactions with calcium control their properties. Mucilage properties rather seem to be governed by weak electrostatic interactions between the entangled polymer chains. The amount of high molecular weight material varies considerably depending on mucilage´s origin and seems to be a straight factor for mucilage’s gel effect in soil. Additionally to the chemical characterization of the high molecular weight compounds, determination of their molecular weight and of their conformation in several mucilages types is needed to draw composition-property profiles. The variations measured between the various mucilages also highlight the necessity to study how the specific properties of the various mucilages fulfill the needs of the plant from which they are exuded.
Finally, the integration of molecular interactions in gel and interparticulate gel properties to explain the physical properties of the rhizosphere was discussed. This approach offers numerous perspectives to clarify for example how water content or hydraulic conductivity in the rhizosphere vary according to the properties of the exuded mucilage. The hypothesis that the gel effect is general for all soil-born exudates showing gel properties was considered. As a result, a classification of soil-born gel phases including roots, seeds, bacteria, hyphae and earthworm’s exuded gel-like material according to their common gel physico-chemical properties is recommended for future research. An outcome could be that the physico-chemical properties of such gels are linked with the extent of the gel effect, with their impact on soil properties and with the functions of the gels in soil.
Im Zentrum der Arbeit steht die Frage, inwiefern erwachsenenpädagogische Professionalität und Qualitätsmanagement als je eigene Zugänge der Qualitätssicherung im Kontext der Weiterbildung miteinander kompatibel sind.
Diese Frage wird seit den 1990er Jahren diskutiert und stellt sich gegenwärtig neu, u.a. angesichts branchenspezifischer Ansätze wie der Lernerorientierten Qualitätstestierung in der Weiterbildung (LQW).
Zur Beantwortung werden einschlägige Vertreter des Professionalitäts- und Qualitätsmanagementzugangs aus einer handlungstheoretischen Perspektive vergleichend im Hinblick auf ihre Handlungsordnungen gegenübergestellt. Grundlage bildet eine kategoriengeleitete, heuristisch angelegte Dokumentenanalyse sowohl von Grundlagentexten als auch von Normen- und Anforderungskatalogen.
Die Untersuchung zeigt, dass die Passung differenziert und jenseits dichotomisierender Gegenüberstellungen von Pädagogik bzw. Profession und Organisation oder von Pädagogik und Ökonomie zu beurteilen ist:
Zum einen wird die Heterogenität der Einzelansätze deutlich, welche sich in unterschiedlichem Umfang als kompatibel zueinander erweisen. Zum anderen werden entlang einzelner Handlungsdimensionen sowohl Anschluss- als auch Bruchstellen sichtbar.
Als ein weiterer zentraler Befund lässt sich festhalten, dass auch die Art der Spannungsverhältnisse zwischen erwachsenenpädagogischer Professionalität und Qualitätsmanagement unterschieden werden muss:
Während die Spannungen zwischen den gegensätzlichen methodischen Strategien (z.B. zwischen professionellem Fallbezug und organisationaler Standardisierung) gradueller Natur sind und „bearbeitet“ werden können, zeigen sich zwischen den programmatischen Zweck- und Aufgabenbestimmungen kategoriale Unterschiede und antinomische Konstellationen.
So verweisen das professionelle Leitprinzip der Teilnehmerorientierung sowie die für die Qualitätsmanagement-Ansätze maßgebliche Kunden- bzw. Lernerorientierung auf jeweils eigene sowie voneinander abweichende Vermittlungskonzepte, die nicht widerspruchsfrei zusammengeführt werden können.
Non-Consumptive Effects of Spiders and Ants: Does Fear Matter in Terrestrial Interaction Webs?
(2014)
Most animals suffer from predators. Besides killing prey, predators can affect prey physiology, morphology and behaviour. Spiders are among the most diverse and frequent predators in terrestrial ecosystems. Our behavioural arena experiments revealed that behavioural changes under spider predation risk are relatively scarce among arthropods. Wood crickets (Nemobius sylvestris), in particular, changed their behaviour in response to cues of various spider species. Thereby, more common and relatively larger spider species induced stronger antipredator behaviour in crickets.
Behavioural changes under predation risk are expected to enhance predator avoidance, but they come at a cost. Crickets previously confronted with cues of the nursery web spider (Pisaura mirabilis) were indeed more successful in avoiding predation. Surprisingly, crickets slightly increased food uptake and lost less weight under predation risk, indicating that crickets are able to compensate for short-term cost under predation risk. In a following plant choice experiment, crickets strongly avoided plants bearing spider cues, which in turn reduced the herbivory on the respective plants.
Similar to spiders, ants are ubiquitous predators and can have a strong impact on herbivores, but also on other predators. Juvenile spiders increased their propensity for long-distance dispersal if exposed to ant cues. Thus, spiders use this passive dispersal through the air (ballooning) to avoid ants and colonise new habitats.
In a field experiment, we compared arthropod colonisation between plants bearing cues of the nursery web spider and cue-free plants. We followed herbivory during the experimental period and sampled the arthropod community on the plants. In accordance with the plant choice experiment, herbivory was reduced on plants bearing spider cues. In addition, spider cues led to changes in the arthropod community: smaller spiders and black garden ants (Lasius niger) avoided plants bearing spider cues. In contrast, common red ants (Myrmica rubra) increased the recruitment of workers, possibly to protect their aphids.
Although behavioural changes were relatively rare on filter papers bearing spider cues, more natural experimental setups revealed strong and far-reaching effects of predation risk. We further suggest that risk effects influence the spatial distribution of herbivory, rather than reduce overall herbivory that is expected if predators kill herbivores. Consequently, the relative importance of predation and risk effects is crucial for the way predators affect lower trophic levels.
Organic substances play an essential role for the formation of stable soil structures. In this context, their physico-chemical properties, interactions with mineral soil constituents and soil-water interactions are particu-larly important. However, the underlying mechanisms contributing to soil particle cementation by swollen or-ganic substances (hydrogels) remains unclear. Up to now, no mechanistic model is available which explains the mechanisms of interparticulate hydrogel swelling and its contribution to soil-water interactions and soil structur-al stability. This mainly results from the lack of appropriate testing methods to study hydrogel swelling in soil as well as from the difficulties of adapting available methods to the system soil/hydrogel.
In this thesis, 1H proton nuclear magnetic resonance (NMR) relaxometry was combined with various soil micro- and macrostructural stability testing methods in order to identify the contribution of hydrogel swelling-induced soil-water interactions to the structural stability of water-saturated and unsaturated soils. In the first part, the potentials and limitations of 1H NMR relaxometry to enlighten soil structural stabilization mechanism and vari-ous water populations were investigated. In the second part, 1H-NMR relaxometry was combined with rheologi-cal measurements of soil to assess the contribution of interparticulate hydrogel swelling and various polymer-clay interactions on soil-water interactions and soil structural stability in an isolated manner. Finally, the effects of various organic and mineral soil fractions on soil-water interactions and soil structural stability was assessed in more detail for a natural, agriculturally cultivated soil by soil density fractionation and on the basis of the experiences gained from the previous experiments.
The increased experiment complexity in the course of this thesis enabled to link physico-chemical properties of interparticulate hydrogel structures with soil structural stability on various scales. The established mechanistic model explains the contribution of interparticulate hydrogels to the structural stability of water-saturated and unsaturated soils: While swollen clay particles reduce soil structural stability by acting as lubricant between soil particles, interparticulate hydrogel structures increase soil structural stability by forming a flexible polymeric network which interconnects mineral particles more effectively than soil pore- or capillary water. It was appar-ent that soil structural stability increases with increasing viscosity of the interparticluate hydrogel in dependence on incubation time, soil texture, soil solution composition and external factors in terms of moisture dynamics and agricultural management practices. The stabilizing effect of interparticulate hydrogel structures further in-crease in the presence of clay particles which is attributed to additional polymer-clay interactions and the incor-poration of clay particles into the three-dimensional interparticulate hydrogel network. Furthermore, the simul-taneous swelling of clay particles and hydrogel structures results in the competition for water and thus in a mu-tual restriction of their swelling in the interparticle space. Thus, polymer-clay interactions not only increase the viscosity of the interparticulate hydrogel and thus its ability to stabilize soil structures but further reduce the swelling of clay particles and consequently their negative effects on soil structural stability. The knowledge on these underlying mechanisms enhance the knowledge on the formation of stable soil structures and enable to take appropriate management practices in order to maintain a sustainable soil structure. The additionally out-lined limitations and challenges of the mechanistic model should provide information on areas with optimization and research potential, respectively.
Studies have shown that wastewater treatment plant (WWTP) effluents are the major pathways of organic and inorganic chemicals of anthropogenic use (=micropollutants) into aquatic environments. There, micropollutants can be transferred to ground water bodies - and may finally end up in drinking water - or cause various effects in aquatic organisms like multiple resistances of bacteria. Hence, the upgrading of WWTPs with the aim to reduce the load of those micropollutants is currently under discussion.
Therefore, the primary objective of this thesis was to assess ecotoxicological effects of wastewater ozonation, a tertiary treatment method, using specifically developed toxicity tests with Gammarus fossarum (Koch) at various levels of ecological complexity. Several studies were designed in the laboratory and under semi-field conditions to cope with this primary objective. Prior to the investigations with ozone treated wastewater, the ecotoxicity of secondary treated (=non-ozone treated) wastewater from WWTP Wüeri, Switzerland, for the test species was assessed by a four-week experiment. This experiment displayed statistically significant impairments in feeding, assimilation and physiological endpoints related to population development and reproduction. The first experiment investigating ecotoxicological implications of ozone application in wastewater from the same WWTP displayed a preference of G. fossarum for leaf discs conditioned in ozone treated wastewater when offered together with leaf discs conditioned in non-ozone treated wastewater. This effect seems to be mainly driven by an alteration in the leaf associated microbial community. Another series of laboratory experiments conducted also with wastewater from WWTP Wüeri treated with ozone at the lab- or full-scale, revealed significantly increased feeding rates of G. fossarum exposed to ozone treated wastewater compared to non-ozone treated wastewater. These laboratory experiments also indicated that any alteration in the organic matrix potentially caused by ozone treatment is not related to the effects in feeding as this endpoint showed only negligible deviation in secondary treated wastewater, which contained hardly any (micro)pollutants (i.e. pharmaceuticals), from the same wastewater additionally treated with ozone. Moreover, it was shown that shifts in the dissolved organic carbon (DOC) profile do not affect the feeding rate of gammarids. In situ bioassays conducted in the receiving stream of the WWTP Wüeri confirmed the results of the laboratory experiments by displaying significantly reduced feeding rates of G. fossarum exposed below the WWTP effluent if non-ozone treated wastewater was released. However, at the time the ozonation was operating, no adverse effects in feeding rates were observed below the effluent compared to the unaffected upstream sites. Also population studies in on-site flow-through stream microcosms displayed an increased feeding and a statistically significantly higher population size after ten weeks when exposed to ozone treated wastewater compared to non-ozone treated wastewater.
In conclusion, the present thesis documents that ozonation might be a suitable tool to reduce both the load of micropollutants as well as the ecotoxicity of wastewaters. Thus, this technology may help to meet the requirements of the Water Framework Directive also under predicted climate change scenarios, which may lead to elevated proportions of wastewater in the receiving stream during summer discharge. However, as ozone application may also produce by-products with a higher toxicity than their parent compounds, the implementation of this technique should be assessed further both via chemical analysis and ecotoxicological bioassays.
The adoption of the EU Water Framework Directive (WFD) in 2000 marked the beginning of a new era of European water policy. However, more than a decade later, the majority of European rivers are still failing to meet one of the main objectives of the WFD: the good ecological status. Pesticides are a major stressor for stream ecosystems. This PhD thesis emphasises the need for WFD managers to consider all main agricultural pesticide sources and influencing landscape parameters when setting up River Basin Management Plans and Programmes of Measures. The findings and recommendations of this thesis can help to successfully tackle the risk of pesticide contamination to achieve the WFD objectives.
A total of 663 sites that were situated in the German Federal States of Saxony, Saxony-Anhalt, Thuringia and Hesse were studied (Chapter 3 and 4). In addition to an analysis of the macroinvertebrate data of the governmental WFD monitoring network, a detailed GIS analysis of the main agricultural pesticide sources (arable land and garden allotments as well as wastewater treatment plants (WWTPs)) and landscape elements (riparian buffer strips and forested upstream reaches) was conducted. Based on the results, a screening approach was developed that allows an initial rapid and cost-effective identification of those sites that are potentially affected by pesticide contamination. By using the trait-based bioindicator SPEARpesticides, the insecticidal long-term effects of the WWTP effluents on the structure of the macroinvertebrate community were identified up to at least 1.5 km downstream (in some cases even 3 km) of the WWTPs. The results of the German Saprobic Index revealed that the WWTPs can still be important sources of oxygen-depleting substances. Furthermore, the results indicate that forested upstream reaches and riparian buffer strips at least 5 m in width can be appropriate measures in mitigating the effects and exposure of pesticides.
There are concerns that the future expansion of energy crop cultivation will lead to an increased pesticide contamination of ecosystems in agricultural landscapes. Therefore, the potential of energy crops for pesticide contamination was examined based on an analysis of the development of energy crop cultivation in Germany and a literature search on perennial energy crops (Chapter 5). The results indicate that the future large-scale expansion of energy crop cultivation will not necessarily cause an increase or decrease in the amounts of pesticides that are released into the environment. The potential effects will depend on the future design of the agricultural systems. Instead of creating energy monocultures, annual energy crops should be integrated into the existing food production systems. Financial incentives and further education are needed to encourage the use of sustainable crop rotations, innovative cropping systems and perennial energy crops, which may contribute to crop diversity and generate lower pesticide demands than do intensive farming systems.
Bislang mangelt es an Forschung zur Führung durch Selbstführung, ein laut Manz und Sims (2007) für die modernen Arbeitsbedingungen des 21. Jahrhunderts adäquater Führungsansatz. Zudem findet dieses Führungsverhalten in der Praxis bisher noch wenig Verbreitung (vgl. Butzmann, 2008; Jilg, 2010). Dies verdeutlicht, dass ein erheblicher Bedarf an Förderung und Training von Führung durch Selbstführung besteht. In diesem Zusammenhang wären zum einen Kenntnisse darüber von Vorteil, welche Eigenschaften und Kompetenzen für den Erwerb dieses Führungsverhalten prädisponieren. Zum anderen wäre eine empirische Fundierung der Erfolgsrelevanz von Führung durch Selbstführung interessant.
Anliegen vorliegender Arbeit ist, hierzu einen Beitrag zu leisten. Auf eignungsspezifischer Seite wurden das unternehmerische Eignungspotential sowie die individuelle Selbstführungskompetenz untersucht. Auf erfolgsspezifischer Seite wurde Führung durch Selbstführung sowohl mit dem objektiven Unternehmenserfolg als auch mit der Arbeitszufriedenheit und dem Wohlbefinden, als Indikatoren des subjektiven Unternehmenserfolgs, in Beziehung gesetzt. Die Untersuchung erfolgte an einer Stichprobe von N = 102 beruflich selbstständige Personen. Aufgrund der sehr homogenen Stichprobenzusammensetzung in Bezug auf das unternehmerische Eignungspotential sowie einer eingeschränkten Messqualität einer der Skalen zur Erfassung von Führung durch Selbstführung konnten einige der aufgestellten Hypothesen nicht bestätigt werden. Ein explorativ getestetes Modell, aus welchem diese kritischen Skalen bzw. Variablen entfernt wurden, weist allerdings einen sehr guten ModellFit auf und bestätigt weitestgehend die postulierten Zusammenhänge zwischen der individuellen Selbstführungskompetenz, Führung durch Selbstführung sowie den subjektiven und objektiven Erfolgsindikatoren. Zu beachten ist, dass dieses Modell aufgrund seines explorativen Charakters erst nach seiner erfolgreichen Replizierung als bestätigt angesehen werden darf, wobei die gefundenen Ergebnisse zu weiterführenden Untersuchungen im Bereich der Führung-durch-Selbstführungsforschung ermutigen.
Die vorliegende Doktorarbeit verfolgt das Ziel, die Bevölkerungsentwicklung im Westerwaldkreis im Zeitraum von 1974 bis 2008 auf Kreis-, Verbandsgemeinde- und Gemeindeebene detailliert zu untersuchen und im Rahmen eines Handlungskonzeptes für ausgewählte Gemeinden geeignete Maßnahmen zur konkreten Gestaltung des Demographischen Wandels aufzuzeigen. Dies geschieht zunächst anhand einer umfassenden Analyse der Bevölkerungsdaten. Dazu zählt eine Einteilung des Untersuchungszeitraums in spezielle Phasen der Bevölkerungsentwicklung, welche durch die jährlichen Veränderungsraten des Bevölkerungsstandes des Westerwaldkreises charakterisiert werden. Anschließend wird ausführlicher auf wichtige Kennzahlen der Bevölkerungsentwicklung aus den Bereichen der natürlichen Bevölkerungsbewegung, der Bevölkerungsstruktur und der Wanderungen eingegangen mit der Intention, einerseits detaillierte Ergebnisse hervorzubringen, die im Rahmen bisheriger Untersuchungen nicht vorliegen und andererseits Grundlagen für die Ursachenforschung zu schaffen, die der Analyse der Bevölkerungsdaten folgt. Für diese Ursachenforschung werden fünf Gemeinden exemplarisch ausgewählt, die eine besonders positive bzw. negative Bevölkerungsentwicklung im Untersuchungszeitraum aufweisen. Integrale Bestandteile dieser Ursachenforschung sind, neben einer ausführlichen Darstellung der Bevölkerungsentwicklung der Gemeinden, Experteninterviews und eigene humangeographische Beobachtungen. Des Weiteren wird speziell für die drei ausgewählten Gemeinden mit negativer Bevölkerungsentwicklung eine Online-Umfrage unter Jugendlichen durchgeführt, um weitere Ursachen herauszufinden und erste zentrale Ansatzpunkte für das abschließende Handlungskonzept zu finden. Dieses Konzept verfolgt primär die Intention, den Demographischen Wandel in den drei Gemeinden in der Art und Weise zukünftig zu gestalten, dass seine negativen Folgen vermieden bzw. zumindest abgemildert werden. Dazu ist es notwendig, auf die spezifischen Situationen vor Ort einzugehen und die praktische Umsetzbarkeit möglicher Handlungsempfehlungen zu berücksichtigen, damit das Konzept Eingang in die kommunalpolitische Planung findet und somit nicht nur einen Beitrag zur bevölkerungsgeographischen Forschung darstellt, sondern auch einen Nutzen für die kommunale Handlungspraxis stiftet.
Software systems have an increasing impact on our daily lives. Many systems process sensitive data or control critical infrastructure. Providing secure software is therefore inevitable. Such systems are rarely being renewed regularly due to the high costs and effort. Oftentimes, systems that were planned and implemented to be secure, become insecure because their context evolves. These systems are connected to the Internet and therefore also constantly subject to new types of attacks. The security requirements of these systems remain unchanged, while, for example, discovery of a vulnerability of an encryption algorithm previously assumed to be secure requires a change of the system design. Some security requirements cannot be checked by the system’s design but only at run time. Furthermore, the sudden discovery of a security violation requires an immediate reaction to prevent a system shutdown. Knowledge regarding security best practices, attacks, and mitigations is generally available, yet rarely integrated part of software development or covering evolution.
This thesis examines how the security of long-living software systems can be preserved taking into account the influence of context evolutions. The goal of the proposed approach, S²EC²O, is to recover the security of model-based software systems using co-evolution.
An ontology-based knowledge base is introduced, capable of managing common, as well as system-specific knowledge relevant to security. A transformation achieves the connection of the knowledge base to the UML system model. By using semantic differences, knowledge inference, and the detection of inconsistencies in the knowledge base, context knowledge evolutions are detected.
A catalog containing rules to manage and recover security requirements uses detected context evolutions to propose potential co-evolutions to the system model which reestablish the compliance with security requirements.
S²EC²O uses security annotations to link models and executable code and provides support for run-time monitoring. The adaptation of running systems is being considered as is round-trip engineering, which integrates insights from the run time into the system model.
S²EC²O is amended by prototypical tool support. This tool is used to show S²EC²O’s applicability based on a case study targeting the medical information system iTrust.
This thesis at hand contributes to the development and maintenance of long-living software systems, regarding their security. The proposed approach will aid security experts: It detects security-relevant changes to the system context, determines the impact on the system’s security and facilitates co-evolutions to recover the compliance with the security requirements.
This work is mainly concerned with multiple goals as indicators of stable as well as situation-specific motivation. During school lessons, pupils strive for competence-oriented goals as well as goals which target psychological well-being. The goal to enlarge one- competence and to acquire deeper knowledge (mastery goal), to attain normative competence (performance approach goal) as well as the goal to avoid the demonstration of lack ofrncompetence (performance avoidance goal) belong to the category of academic goals. The category of well-being goals includes the goal to avoid hard work (work avoidance goal) as well as the aim to interact socially with relevant peers (affiliation goal).
It is still unclear, however, if goals are best defined as fluctuating state or stable trait variables. Here, both aspects of goals are conceptualized differentially and their connection is explored in two studies based on a longitudinal design. Another question that is raised here is concerned with the explanation of state-goal-genesis. Different motivational theories serve as the basis for the development of a new framework model, which explores the genesis of state goal-components due to trait goal-components, situational appraisals and their interaction. In the literature, three effect models between appraisals and trait goals regarding the state goals are identified: a) appraisals and trait goals might predict state goals additively (additive effect), b) trait goals might influence the state goals mediated by the appraisals (reactive effect), or c) the trait goals may have differential effects on the state goals for low or high values of the appraisals (interaction effect). Moreover, assumptions on proximal consequences of state-goals are made within the framework model.
Study 1 comprised of two samples (N = 197 and N = 297). Both multiple goal factors as well as their state- and trait-components were validated empirically in a longitudinal design. State goal measures proved to be sensitive to situational influences and to be differentially valid compared to trait goal measures. Study 2 primarily dealt with the explanationrnof the genesis of state goals in actual learning situations. The basic assumptions of the framework model as well as the three effect models were explored systematically in a longitudinal design (N = 542). As expected, competence oriented goals correlated with adaptive indicators of learning processes (e.g., flow), while the well-being goals did not. The additive effect hypothesis was confirmed while the reactive effect hypothesis was rejected. With the help of latent moderator models, some interaction effects were identified which showed that trait goals were differentially predictive for state goals depending on the level of situational appraisals.
Within the field of Business Process Management, business rules are commonly used to model company decision logic and govern allowed company behavior. An exemplary business rule in the financial sector could be for example:
”A customer with a mental condition is not creditworthy”. Business rules are
usually created and maintained collaboratively and over time. In this setting,
modelling errors can occur frequently. A challenging problem in this context is
that of inconsistency, i.e., contradictory rules which cannot hold at the same
time. For instance, regarding the exemplary rule above, an inconsistency would
arise if a (second) modeller entered an additional rule: ”A customer with a mental condition is always creditworthy”, as the two rules cannot hold at the same
time. In this thesis, we investigate how to handle such inconsistencies in business
rule bases. In particular, we develop methods and techniques for the detection,
analysis and resolution of inconsistencies in business rule bases
Virtueller Konsum - Warenkörbe, Wägungsschemata und Verbraucherpreisindizes in virtuellen Welten
(2015)
Virtual worlds have been investigated by several academic disciplines for several years, e.g. sociology, psychology, law and education. Since the developers of virtual worlds have implemented aspects like scarcity and needs, even economic research has become interested in these virtual environments. Exploring virtual economies mainly deals with the research of trade regarding the virtual goods used to supply the emerged needs. On the one hand, economics analyzes the meaning of virtual trade according to the overall interpretation of the economical characteristics of virtual worlds. As some virtual worlds allow the change of virtual world money with real money and vice versa, virtual goods are traded by the users for real money, researchers on the other hand, study the impact of the interdependencies between virtual economies and the real world. The presented thesis mainly focuses on the trade within virtual worlds in the context of virtual consumption and the observation of consumer prices. Therefore, the four virtual worlds World of Warcraft, RuneScape, Entropia Universe and Second Life have been selected. There are several components required to calculate consumer price indices. First, a market basket, which contains the relevant consumed goods existing in virtual worlds, must be developed. Second, a weighting scheme has to be established, which shows the dispersion of consumer tendencies. Third, prices of relevant consumer goods have to be taken. Following real world methods, it is the challenge to apply those methods within virtual worlds. Therefore, this dissertation contains three corresponding investigation parts. Within a first analysis, it will be evaluated, in how far virtual worlds can be explored to identify consumable goods. As a next step, the consumption expenditures of the avatars will be examined based on an online survey. At last, prices of consumable goods will be recorded. Finally, it will be possible to calculate consumer price indices. While investigating those components, the thesis focuses not only on the general findings themselves, but also on methodological issues arising, like limited access to relevant data, missing legal legitimation or security concerns of the users. Beside these aspects, the used methods also allow the examination of several other economic aspects like the consumption habits of the avatars. At the end of the thesis, it will be considered to what extent virtual world economic characteristics can be compared with the real world.
Aspects like the important role of weapons or the different usage of food show significant differences to the real world, caused by the business models of virtual worlds.
Computer modelling of human partial body structures is becoming increasingly important for medical application. This is an interdisciplinary field of research in which new methods can be developed through the cooperation of physics, mathematics, computer visualistics and medicine. These methods can be used to make more precise statements about the mechanical loads of internal force-transmitting structures, such as intervertebral discs, ligaments, joints and muscles, during motion sequences.
At the beginning of this work, the importance of the need for research in computer modeling, specialized in the area of the spine, is presented.
In the following, the basic anatomical structures will be discussed, including intervertebral discs, ligaments, facet joints and musculature.
Algorithms are then developed to create individual lumbar spine models from CT data in a short time and semi-automatically. Methods will be developed to model the presented force transmitting structures of the spine, such as the intervertebral discs, ligaments, facet joints and muscles.
In addition different imaging methods (MRT data, x-ray film, x-ray functional images) will be presented and validate the lumbar spine models.
Finally, the algorithms developed will be used to create a larger number of individual lumbar spine models, which will then be examined for similarities and differences with regard to internal loads as well as for physiologically correct movement sequences. In particular, the relative momentary center of rotation between two adjacent vertebrae is calculated.
Eine Ursache des Insektenrückgangs ist die Abnahme der für Arthropoden wichtigen Lebensräume. Der kleinstrukturierte Obstanbau als Dauerkultur mit vielfältigen Strukturen (Bäume, Grünland, offener Boden) kann als Refugium wirken. Gerade Dauerkulturen, welche über viele Jahre bestehen bleiben, können einen großen ökologischen Wert für Insekten und Spinnentiere darstellen, wenn die negativen Einflüsse der Bewirtschaftung durch gezielte Maßnahmen minimiert werden. Im Gegensatz zu den gut untersuchten Streuobstwiesen liegen bisher nur wenige oder ungenaue Daten über die Arthropodenfauna in Erwerbsobstanlagen vor. Ziele dieser Arbeit sind eine genauere Erfassung der Arthropodenfauna in Erwerbsobstanlagen, Benennung der Einflussfaktoren und Erarbeitung einer indikatorgestützten Bewertungsmethode mit Entwicklung von Maßnahmen zur Förderung der Biodiversität. Es wurde eine intensive Erfassung der Insekten und Spinnentiere auf Basis von Individuenzahlen, Verteilung der Tiere auf Großgruppen, Artenzahlen der Käfer (inkl. Rote Liste) und Wanzen, deren Diversität und der sie beeinflussenden Faktoren auf vier Erwerbsobstflächen und einer Streuobstwiese als Referenzfläche in der Gemeinde Zornheim (Rheinland-Pfalz) untersucht. Mittels des erarbeiteten Bewertungsbogens wurden die Auswirkungen der fünf Faktorenkomplexe: Sonderstrukturen, Anlagenstruktur, Beschattung, Mahdregime und Einsatz von Pflanzenschutzmitteln auf die Arthropodenfauna erhoben und die auf der Fläche zu erwartende Biodiversität ermittelt. Die visuelle Darstellung der Einflussfaktoren mit Netzdiagrammen zeigt biodiversitätsbeeinträchtigende Faktoren und ermöglicht so Empfehlungen zur Aufwertung der Biodiversität. Die Bewertungsmethode kann nach Verifizierung im Rahmen von erfolgsorientierten Agrarumwelt- und Klimamaßnahmen (AUKM), zur Anerkennung von Kompensationsmaßnahmen (z.B. PIK) und zur Ermittlung des ökologischen Wertes (Ökosystemdienstleistung) von Obstanlagen genutzt werden. In modifizierter Form könnte es ebenfalls im Bereich der Flächenbewertung in Landschafts- und Bauleitplanung eingesetzt werden.
The diversity within amphibian communities in cultivated areas in Rwanda and within two selected, taxonomically challenging groups, the genera Ptychadena and Hyperolius, were investigated in this thesis. The amphibian community of an agricultural wetland near Butare in southern Rwanda comprised 15 anuran species. Rarefaction and jackknife analyses corroborated that the complete current species richness of the assemblage had been recorded, and the results of acoustic niche analysis suggested species saturation of the community. Surveys at many other Rwandan localities showed that the species recorded in Butare are widespread in cultivated and pristine wetlands. The species were readily distinguishable using morphological, bioacoustic, and molecular (DNA barcoding) features, but only eight of the 15 species could be assigned unambiguously to nominal species. The remaining represented undescribed or currently unrecognized taxa, including three species of Hyperolius, two Phrynobatrachus species, one Ptychadena species, and one species of Amietia. The diversity of the Ridged Frogs in Rwanda was investigated in two studies (Chapters III and IV). Three species of Ptychadena were recorded in wetlands in the catchment of the Nile. They can be distinguished by morphological characters (morphometrics and qualitative features) as well as by their advertisement calls and genetics. The Rwandan species of the P. mascareniensis group was shown to differ from the topotypic population as well as from other genetic lineages in sub-Saharan Africa and an old available name, P. nilotica, was resurrected from synonymy for this lineage. Two further Ptychadena species were identified among voucher specimens from Rwanda deposited in the collection of the RMCA, P. chrysogaster and P. uzungwensis. Morphologically they can be unambiguously distinguished from each other and the three other Rwandan species. A key based on qualitative morphological characters was developed, which allows unequivocal identification of specimens of all species that have been recorded from Rwanda. DNA was isolated from a Rwandan voucher specimen of P. chrysogaster, and the genetic analysis corroborated the species" distinct status.
A species of Hyperolius collected in the Nyungwe National Park was compared to all other Rwandan species of the genus and to morphologically or genetically similar species from neighbouring countries. Its distinct taxonomic status was justified by morphological, bioacoustic, and molecular evidence and it was described as a new species, H. jackie. A species of the H. nasutus group collected at agricultural sites in Rwanda was described as a new species in the course of a revision of the species of the Hyperolius nasutus group. The group was shown to consist of 15 distinct species which can be distinguished from each other genetically, bioacoustically, and morphologically.
The aerial performance, i.e. parachuting, of the Disc-fingered Reed Frog, Hyperolius discodactylus, was described. It represents a novel observation of a behaviour that has been known from a number of Southeast Asian and Neotropical frog species. Parachuting frogs, including H. discodactylus, exhibit certain morphological characteristics and, while airborne, assume a distinct posture which is best-suited for maneuvering in the air. Another study on the species addressed the validity of the taxon H. alticola which had been considered either a synonym of H. discodactylus or a distinct species. Type material of both taxa was re-examined and the status of H. alticola reassessed using morphological data from historic and new collections, call recordings, and molecular data from animals collected on recent expeditions. A northern and a southern genetic clade were identified, a divide that is weakly supported by diverging morphology of the vouchers from the respective localities. No distinction in advertisement call features could be recovered to support this split and both genetic and morphological differences between the two geographic clades are marginal and not always congruent and more likely reflect population-level variation. Therefore it was concluded that H. alticola is not a valid taxon and should be treated as a synonym of H. discodactylus.
Tagging systems are intriguing dynamic systems, in which users collaboratively index resources with the so-called tags. In order to leverage the full potential of tagging systems, it is important to understand the relationship between the micro-level behavior of the individual users and the macro-level properties of the whole tagging system. In this thesis, we present the Epistemic Dynamic Model, which tries to bridge this gap between the micro-level behavior and the macro-level properties by developing a theory of tagging systems. The model is based on the assumption that the combined influence of the shared background knowledge of the users and the imitation of tag recommendations are sufficient for explaining the emergence of the tag frequency distribution and the vocabulary growth in tagging systems. Both macro-level properties of tagging systems are closely related to the emergence of the shared community vocabulary. rnrnWith the help of the Epistemic Dynamic Model, we show that the general shape of the tag frequency distribution and of the vocabulary growth have their origin in the shared background knowledge of the users. Tag recommendations can then be used for selectively influencing this general shape. In this thesis, we especially concentrate on studying the influence of recommending a set of popular tags. Recommending popular tags adds a feedback mechanism between the vocabularies of individual users that increases the inter-indexer consistency of the tag assignments. How does this influence the indexing quality in a tagging system? For this purpose, we investigate a methodology for measuring the inter-resource consistency of tag assignments. The inter-resource consistency is an indicator of the indexing quality, which positively correlates with the precision and recall of query results. It measures the degree to which the tag vectors of indexed resources reflect how the users perceive the similarity between resources. We argue with our model, and show it with a user experiment, that recommending popular tags decreases the inter-resource consistency in a tagging system. Furthermore, we show that recommending the user his/her previously used tags helps to increase the inter-resource consistency. Our measure of the inter-resource consistency complements existing measures for the evaluation and comparison of tag recommendation algorithms, moving the focus to evaluating their influence on the indexing quality.
Praktika als gängige Lehr-Lernformate in hochschulischen Kontexten setzen stets die Zusammenarbeit verschiedener Institutionen und Personen voraus, da Studierende mit einem Praktikum den Lernort der Universität verlassen und in einen beruflichen Handlungszusammenhang mit den zugehörigen organisationalen Strukturen versetzt werden. Praktika werden unter anderem als Elemente der Berufsorientierung gesellschaftliche Implikationen zugeschrieben. Als Format innerhalb eines hochschulischen Bildungsgangs sind sie darüber hinaus mit didaktischen Begründungen verbunden und durch die Beteiligung verschiedener Personen auch mit individuellen Interessen. Studierende sind während eines Praktikums in der Rolle als Praktikant*in in besonderer Weise individuell gefordert. Ergänzt werden diese Perspektiven durch die Betrachtung disziplinärer und professioneller Implikationen, die sich für Praktika erziehungswissenschaftlicher Studiengänge ergeben. Zusammenarbeit findet in Praktika zwischen Organisationen, in Organisationen und zwischen Personen statt. Der geringe Forschungsstand zu Perspektiven auf Fragen der Zusammenarbeit für in erziehungswissenschaftliche Studiengänge integrierte Praktika bietet den Anlass der Studie. Um die verschiedenen Perspektiven auf Praktika als Zusammenarbeit zu erheben, werden qualitative episodische Interviews sowohl mit den Studierenden und Lehrenden einer Universität, als auch mit für Praktika verantwortlichen Tätigen aus dem beruflichen Bereich durchgeführt, die nach der qualitativen inhaltlich strukturierenden Inhaltsanalyse ausgewertet werden. Aus der Auswertung der geführten Interviews mit den drei Akteur*innen-Gruppen ergibt sich ein Einblick darin, wie sich Zusammenarbeit zwischen pädagogisch tätigen Institutionen, Universitäten und Studierenden in und durch Praktika konkretisiert. Es werden beispielsweise Aspekte der Interaktionsbezogenen Dimensionen beschrieben, wie auftauchende Dilemmata, Resonanzen, Kulturen des Umgangs, Interessenslagen und Konstellationen von Akteur*innen. Diese werden ergänzt um Aspekte der Dimensionen mit Bezug zu Institutionen, Umwelt, Aufgaben und Personen. Die Interviewaussagen von drei interviewten Akteur*innen-Gruppen Studierende, Praxisanleiter*innen, universitäre Lehrende werden vergleichend anhand dieser Dimensionen betrachtet und als Ergebnisse dieser Studie dargestellt. Die Ergebnisse liefern Aussagen dazu, wie Zusammenarbeit in Praktika erziehungswissenschaftlicher Studiengänge von den beteiligten Akteur*innen-Gruppen wahrgenommen wird. Dies kann dazu beitragen die differierenden Perspektiven anschlussfähig zu machen für die didaktische und organisatorische Gestaltung von Praktika durch Institutionen wie Universitäten und Praktikumseinrichtungen, aber auch durch Initiative von Studierenden in der Rolle als Praktikant*innen während eines erziehungswissenschaftlichen Studiums. Auch für weitere Forschungsprojekte zum Zusammenwirken der Beteiligten in Praktika kann die Studie Anstöße bieten.
Absicherung der analytischen Interpretation von Geolokalisierungsdaten in der Mobilfunkforensik
(2019)
Abstract
Location based services maybe are within one of the most outstanding features of modern mobile devices. Despite the fact, that cached geolocation data could be used to reconstruct motion profiles, the amount of devices capable to provide these information in the field of criminal investigations is growing.
Motivation
The aim of this work is to generate in-depth knowledge to questions concerning geolocation in the field of mobile forensics, making especially somehow cached geolocation data forensically valuable. On top, tools meeting the specific requirements of law enforcement personnel shall be developed.
Problems
Geolocation processes within smartphones are quite complex. For the device to locate its position, different reference systems like GPS, cell towers or WiFi hot\-spots are used in a variety of ways. The whole mobile geolocation mechanism is proprietary to the device manufacturer and not build with forensic needs in mind. One major problem regarding forensic investigations is, that mainly reference points are being extracted and processed instead of real life device location data. In addition, these geolocation information only consist of bits and bytes or numeric values that have to be securely assigned to their intended meaning. The location data recovered are full of gaps providing only a part of the process or device usage. This possible loss of data has to be determined deriving a reliable measurement for the completeness, integrity and accuracy of data. Last but not least, as for every evidence within a criminal investigation, it has to be assured, that manipulations of the data or errors in position estimation have no disadvantageous effect on the analysis.
Research Questions
In the context of localisation services in modern smartphones, it always comes back to similar questions during forensic everyday life:
* Can locations be determined at any time?
* How accurate is the location of a smartphone?
* Can location data from smartphones endure in court?
Approach
For a better understanding of geolocation processes in modern smartphones and to evaluate the quality and reliability of the geolocation artefacts, information from different platforms shall be theoretically analysed as well as observed in-place during the geolocation process. The connection between data points and localisation context will be examined in predefined live experiments as well as desktop- and native applications on smartphones.
Results
Within the scope of this thesis self developed tools have been used for forensic investigations as well as analytical interpretation of geodata from modern smartphones. Hereby a generic model for assessing the quality of location data has emerged, which can be generally applied to geodata from mobile devices.
Die vorliegende Dissertation leistet einen Beitrag zur historischen Frauenbildung in Deutschland. Gegenstand der Studie ist die Mädchenbildung im Zeitalter der Aufklärung. Da diese von der Pädagogik der Jungen stets getrennt betrachtet wurde und Bildung sich nach dem allgemeinen Verständnis bürgerlichen theoretischen Verstandes nur auf die Erziehung des jungen männlichen Geschlechts bezog, blieb die Frau von öffentlicher Bildung im 18. Jahrhundert weitgehend ausgeschlossen. An den Bildungsformen der Lesegesellschaften, der Salonkultur und der "Moralischen Wochenschriften" wird zunächst aufgezeigt, in welcher Weise es Frauen möglich war, sich dennoch Zugang zur Bildung zu verschaffen. Die beiden folgenden Kapitel behandeln La Roches und Campes Biografie. Im Fokus steht dabei ihrer beider Handeln im Feld der Mädchenerziehung und des Reisejournalismus. Vergleichend werden bildende Elemente hinsichtlich ihrer Hinwendung zur Französischen Revolution und des Reisejournalismus dargelegt. Die Betrachtung der Reiseberichte beider Autoren klärt, in welcher Form La Roche und Campe den politischen Reformbestrebungen des späten 18. Jahrhunderts folgen bzw. in welchem Maß sie den Idealen der voraufklärerischen Zeit unterliegen. Im Mittelpunkt der Arbeit stehen La Roches Briefe an Lina (1783/84) und Campes Väterlicher Rath für meine Tochter (1789). Die Mädchenratgeber spiegeln das pädagogische Konzept der Mädchenbildung beider Autoren wider. Eine Gegenüberstellung der Mädchenratgeber wird zeigen, inwieweit La Roche und Campe konservativen bzw. progressiven Leitbildern der Mädchenbildung folgen. Die Studie geht von der Ambivalenzthese aus, nach der La Roche und Campe innerhalb ihrer Denkweisen als Pädagogen und Reiseschriftsteller Gegensätze und Widersprüche aufweisen. Es soll geklärt werden, inwiefern La Roches Mädchenbildungskonzept von emanzipativen Vorstellungen geprägt ist, ihr politisches Denken hingegen konservativ erscheint, während Campes Mädchenbildungstheorie eher traditionell angelegt ist, seine politischen Ideale aber innovativ sind. In einer abschließenden Betrachtung werden die Ambivalenzen zwischen La Roches und Campes pädagogischen und politischen Anschauungen geklärt.
Technical products have become more than practical tools to us. Mobile phones, for example, are a constant companion in daily life. Besides purely pragmatic tasks, they fulfill psychological needs such as relatedness, stimulation, competence, popularity, or security. Their potential for the mediation of positive experience makes interactive products a rich source of pleasure. Research acknowledged this: in parallel to the hedonic/utilitarian model in consumer research, Human-Computer Interaction (HCI) researchers broadened their focus from mere task-fulfillment (i.e., the pragmatic) to a holistic view, encompassing a product's ability for need-fulfillment and positive experience (i.e., the hedonic). Accordingly, many theoretical models of User Experience (UX) acknowledge both dimensions as equally important determinants of a product's appeal: pragmatic attributes (e.g., usability) as well as hedonic attributes (e.g., beauty). In choice situations, however, people often overemphasize the pragmatic, and fail to acknowledge the hedonic. This phenomenon may be explained by justification. Due to their need for justification, people attend to the justifiability of hedonic and pragmatic attributes rather than to their impact on experience. Given that pragmatic attributes directly contribute to task-fulfillment, they are far easier to justify than hedonic attributes. People may then choose the pragmatic over the hedonic, despite a true preference for the hedonic. This can be considered a dilemma, since people choose what is easy to justify and not what they enjoy the most. The present thesis presents a systematic exploration of the notion of a hedonic dilemma in the context of interactive products.
A first set of four studies explored the assumed phenomenon. Study 1 (N = 422) revealed a reluctance to pay for a hedonic attribute compared to a pragmatic attribute. Study 2 (N = 134) demonstrated that people (secretly) prefer a more hedonic product, but justify their choice by spurious pragmatic advantages. Study 3 (N = 118) confronted participants with a trade-off between hedonic and pragmatic quality. Even though the prospect of receiving a hedonic product was related to more positive affect, participants predominantly chose the pragmatic, especially those with a high need for justification. This correlation between product choice and perceived need for justification lent further support to the notion that justification lies at the heart of the dilemma. Study 4 (N = 125) explored affective consequences and justifications provided for hedonic and pragmatic choice. Data on positive affect suggested a true preference for the hedonic - even among those who chose the pragmatic product.
A second set of three studies tested different ways to reduce the dilemma by manipulating justification. Manipulations referred to the justifiability of attributes as well as the general need for justification. Study 5 (N = 129) enhanced the respective justifiability of hedonic and pragmatic choice by ambiguous product information, which could be interpreted according to latent preferences. As expected, enhanced justifiability led to an increase in hedonic but not in pragmatic choice. Study 6 (N = 178) manipulated the justifiability of hedonic choice through product information provided by a "test report", which suggested hedonic attributes as legitimate. Again, hedonic choice increased with increased justifiability. Study 7 (N = 133) reduced the general need for justification by framing a purchase as gratification. A significant positive effect of the gratification frame on purchase rates occurred for a hedonic but not for a pragmatic product.
Altogether, the present studies revealed a desire for hedonic attributes, even in interactive products, which often are still understood as purely pragmatic "tools". But precisely because of this predominance of pragmatic quality, people may hesitate to give in to their desire for hedonic quality in interactive products - at least, as long as they feel a need for justification. The present findings provide an enhanced understanding of the complex consequences of hedonic and pragmatic attributes, and indicate a general necessity to expand the scope of User Experience research to the moment of product choice. Limitations of the present studies, implications for future research as well as practical implications for design and marketing are discussed.
Abstract The present work investigates the wetting characteristics of soils with regard to their dependence on environmental parameters such as water content (WC), pH, drying temperature and wetting temperature of wettable and repellent soils from two contrasting anthropogenic sites, the former sewage disposal field Berlin-Buch and the inner-city park Berlin-Tiergarten. The aim of this thesis is to deepen the understanding of processes and mechanisms leading to changes in soil water repellency. This helps to gain further insight into the behaviour of soil organic matter (SOM) and identifying ways to prevent or reduce the negative effects of soil water repellency (SWR). The first focus of this work is to determine whether chemical reactions are required for wetting repellent samples. This hypothesis was tested by time and temperature dependence of sessile drop spreading on wettable and repellent samples. Additionally, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy was used to determine whether various drying regimes cause changes in the relative abundance of hydrophobic and hydrophilic functional groups in the outer layer of soil particles and whether these changes can be correlated with water content and the degree of SWR. Finally, by artificially altering the pH in dried samples applying acidic and alkaline reagents in a gaseous state, the influence of only pH on the degree of SWR was investigated separately from the influence of changes in moisture status. The investigation of the two locations Buch and Tiergarten, each exceptionally different in the nature of their respective wetting properties, leads to new insights in the variety of appearance of SWR. The results of temperature, water content and pH dependency of SWR on the two contrasting sites resulted in one respective hypothetical model of nature of repellency for each site which provides an explanation for most of the observations made in this and earlier studies: At the Tiergarten site, wetting characteristics are most likely determined by micelle-like arrangement of amphiphiles which depends on the concentration of water soluble amphiphilic substances, pH and ionic strength in soil solution. At low pH and at high ionic strength, repulsion forces between hydrophilic charged groups are minimized allowing their aggregation with outward orientated hydrophobic molecule moieties. At high pH and low ionic strength, higher repulsion forces between hydrophilic functional groups lead to an aggregation of hydrophobic groups during drying, which results in a layer with outward oriented hydrophilic moieties on soil organic matter surface leading to enhanced wettability. For samples from the Buch site, chemical reactions are necessary for the wetting process. The strong dependence of SWR on water content indicates that hydrolysis-condensation reactions are the controlling mechanisms. Since acid catalyzed hydrolysis is an equilibrium reaction dependent on water content, an excess of water favours hydrolysis leading to an increasing number of hydrophilic functional groups. In contrast, water deficiency favours condensation reactions leading to a reduction of hydrophilic functional groups and thus a reduction of wettability. The results of the present investigation and its comparison with earlier investigations clearly show that SWR is subject to numerous antagonistically and synergistically interacting environmental factors. The degree of influence, which a single factor exerts on SWR, is site-specific, e.g., it is dependent on special characteristics of mineral constituents and SOM which underlies the influence of climate, soil texture, topography, vegetation and the former and current use of the respective site.
This dissertation presents the application of the molecular LIBS method, a novelapproach of Laser-Induced Breakdown Spectroscopy (LIBS), to optimize the detection of pitting chlorides in concrete structures, which are e.g. contaminated bydeicing salt in winter. Potentiometric titration as the standard method for chloride determination in building material analysis is costly and time-consuming. Ithas the decisive disadvantage that the determination of chloride concentrationis based on the total mass of the concrete and not on the cement content asrequired by the European standard EN 206. The imaging capabilities of LIBS forphase separation of the concrete meet this requirement. LIBS was already usedby BAM in 1998 in building material analysis, but the detection of chlorides withLIBS requires expensive helium purging and spectrometers outside the visiblespectral range to detect emissions of atomic chlorine. The approach of molecular LIBS is to quantify the emission of chloride-containing molecular radicalsformed during the cooling phase of the laser-induced plasma. The advantagescompared to conventional LIBS method are the emission in the visible spectralrange and the applicability without noble gas purging. In this thesis the influenceof the experimental components on the time behaviour of the relevant molecularemission bands is investigated, signal deviations due to plasma fluctuations aresignificantly reduced and for plasma analysis the molecular formation is simulated on atomistic scales and compared with standard methods. In simultaneousmeasurements, atomic and molecular Cl emission are directly compared and the quantification is optimized by data combination. Molecular LIBS will be extended to a quantifying and imaging method that can detect chlorides withoutnoble gas purging.
Navigation is a natural way to explore and discover content in a digital environment. Hence, providers of online information systems such as Wikipedia---a free online encyclopedia---are interested in providing navigational support to their users. To this end, an essential task approached in this thesis is the analysis and modeling of navigational user behavior in information networks with the goal of paving the way for the improvement and maintenance of web-based systems. Using large-scale log data from Wikipedia, this thesis first studies information access by contrasting search and navigation as the two main information access paradigms on the Web. Second, this thesis validates and builds upon existing navigational hypotheses to introduce an adaptation of the well-known PageRank algorithm. This adaptation is an improvement of the standard PageRank random surfer navigation model that results in a more "reasonable surfer" by accounting for the visual position of links, the information network regions they lead to, and the textual similarity between the link source and target articles. Finally, using agent-based simulations, this thesis compares user models that have a different knowledge of the network topology in order to investigate the amount and type of network topological information needed for efficient navigation. An evaluation of agents' success on four different networks reveals that in order to navigate efficiently, users require only a small amount of high-quality knowledge of the network topology. Aside from the direct benefits to content ranking provided by the "reasonable surfer" version of PageRank, the empirical insights presented in this thesis may also have an impact on system design decisions and Wikipedia editor guidelines, i.e., for link placement and webpage layout.