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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.