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Perfluorcarbonsäuren (PFCA) sind Substanzen anthropogenen Ursprungs und werden seit mehreren Jahrzehnten verwendet. In der Literatur werden diese Verbindungen als eine neue Klasse von Umweltschadstoffen beschrieben. Ihre hohe thermische Stabilität, Oberflächenaktivität, Amphipathizität und schwache intermolekulare Wechselwirkungen führen zur Persistenz dieser organisch-chemischen Verbindungen und zur Bioakkumulation. Um diese Stoffgruppe sicher nachzuweisen, müssen zuverlässige analytische Methoden eingesetzt werden. GC-MS stellt eine kostengünstige Alternative und Ergänzung zu etablierten LC-MS/MS Methoden dar. Um jedoch die GC-MS erfolgreich einsetzen zu können, müssen die PFCA derivatisiert werden. Viele der bisher veröffentlichten Derivatisierungsreaktionen für PFCA, sind zeitaufwändig und erfordern hohe Reaktionstemperaturen und/oder toxische Reagenzien.
In der vorliegenden Dissertation wurden zwei neue Derivatisierungsreaktionen methodologisch entwickelt und optimiert. Der erste Teil der Arbeit beschreibt die Entwicklung und Optimierung der Derivatisierung mit Triethylsilanol in Wasser. Zusätzlich zur Reaktionsoptimierung, wurde die klassische Festphasenextraktion modifiziert, um die Probenvorbereitung zu vereinfachen.
Im zweiten Teil der Arbeit, wurden die Reaktionsprodukte von Perfluoroktansäure (PFOA) mit Dimethylformamid-dimethylacetal (DMF-DMA) und –diethylacetal (DMF-DEA) identifiziert. Zu diesem Zweck, wurden verschiedene massenspektrometrische Techniken angewandt. Anhand der Messergebnisse konnte gezeigt werden, dass sowohl DMF-DMA als auch DMF-DEA in Gegenwart von PFOA ein Iminium-Kation bildet, was zur Salzbildung führt. Dieses PFOA-Salz reagiert im GC-Injektor weiter zu einem entsprechenden Amin.
Abschließend, im letzten Teil der Arbeit, wurden reale Proben mit der neu entwickelten Methode auf Basis der DMF-DMA Reaktion analysiert. Die Matrixeffekte wurden ausführlich beschrieben. Die Methode wurde erfolgreich für drei Arten von Proben verwendet: Zahnseide, Textilien und Klärschlamm. Die Ergebnisse wurden mittels LC-MS/MS in einem externen Labor verifiziert. Die Unterschiede zwischen den PFCA-Werten, für eine aufgestockte Probe, wurden mittels GC-MS und LC-MS/MS gemessen und waren kleiner als 10 %.
Fresh water resources like rivers and reservoirs are exposed to a drastically changing world. In order to safeguard these lentic ecosystems, they need stronger protection in times of global change and population growth. In the last years, the exploitation pressure on drinking water reservoirs has increased steadily worldwide. Besides securing the demands of safe drinking water supply, international laws especially in Europe (EU Water Framework Directive) stipulate to minimize the impact of dams on downstream rivers. In this study we investigate the potential of a smart withdrawal strategy at Grosse Dhuenn Reservoir to improve the temperature and discharge regime downstream without jeopardizing drinking water production. Our aim is to improve the existing withdrawal strategy for operating the reservoir in a sustainable way in terms of water quality and quantity. First, we set-up and calibrated a 1D numerical model for Grosse Dhuenn Reservoir with the open-source community model “General Lake Model” (GLM) together with its water quality module “Aquatic Ecodynamics” library (AED2). The reservoir model reproduced water temperatures and hypolimnetic dissolved oxygen concentrations accurately over a 5 year period. Second, we extended the model source code with a selective withdrawal functionality (adaptive offtake) and added operational rules for a realistic reservoir management. Now the model is able to autonomously determine the best withdrawal height according to the temperature and flow requirements of the downstream river and the raw water quality objectives. Criteria for the determination of the withdrawal regime are selective withdrawal, development of stratification and oxygen content in the deep hypolimnion. This functionality is not available in current reservoir models, where withdrawal heights are generally provided a priori to the model and kept fixed during the simulation. Third, we ran scenario simulations identifying an improved reservoir withdrawal strategy to balance the demands for downstream river and raw water supply. Therefore we aimed at finding an optimal parallel withdrawal ratio between cold hypolimnetic water and warm epilimnetic or metalimnetic water in order to provide a pre-defined temperature in the downstream river. The reservoir model and the proposed withdrawal strategy provide a simple and efficient tool to optimize reservoir management in a multi-objective view for mastering future reservoir management challenges.
The decline of biodiversity can be observed worldwide and its consequences are alarming. It is therefore crucial that nature must be protected and, where possible, restored. A wide variety of different project options are possible. Yet in the context of limited availability of resources, the selection of the most efficient measures is increasingly important. For this purpose, there is still a lack of information. This pertains, as outlined in the next paragraph, in particular, to information at different scales of projects.
Firstly, there is a lack of information on the concrete added value of biodiversity protection projects. Secondly, there is a lack of information on the actual impacts of such projects and on the costs and benefits associated with a project. Finally, there is a lack of information on the links between the design of a project, the associated framework conditions and the perception of specific impacts. This paper addresses this knowledge gap by providing more information on the three scales by means of three empirical studies on three different biodiversity protection projects in order to help optimize future projects.
The first study “Assessing the trade-offs in more nature-friendly mosquito control in the Upper Rhine region” examines the added value of a more nature-friendly mosquito control in the Upper Rhine Valley of Germany using a contingent valuation method. Recent studies show that the widely used biocide Bti, which is used as the main mosquito control agent in many parts of the world, has more negative effects on nature than previously expected. However, it is not yet clear whether the population supports a more nature-friendly mosquito control, as such an adaptation could potentially lead to higher nuisance. This study attempts to answer this question by assessing the willingness to pay for an adapted mosquito control strategy that reduces the use of Bti, while maintaining nuisance protection within settlements. The results show that the majority of the surveyed population attaches a high value to a more nature-friendly mosquito control and is willing to accept a higher nuisance outside of the villages.
The second study “Inner city river restoration projects: the role of project components for acceptance” examines the acceptance of a river restoration project in Rhineland-Palatinate, Germany. Despite much effort, many rivers worldwide are still in poor condition. Therefore, a rapid implementation of river restoration projects is of great importance. In this context, acceptance by society plays a fundamental role, however, the factors determining such acceptance are still poorly understood. In particular, the complex interplay between the acceptance or rejection of specific project components and the acceptance of the overall project require further exploration. This study addresses this knowledge gap by assessing the acceptance of the project, its various ecological and social components, and the perception of real and fictitious costs as well as the benefits of the components. Our findings demonstrate that while acceptance of the overall project is generally rather high, many respondents reject one or more of the project's components. Complementary social project components, like a playground, find less support than purely ecological components. Overall, our research shows that complementary components may increase or decrease acceptance of the overall project. We, furthermore, found that differences in the acceptance of the individual components depend on individual concerns, such as perceived flood risk, construction costs, expected noise and littering as well as the quality of communication, attachment to the site, and the age of the respondents.
The third study “What determines preferences for semi-natural habitats in agrarian landscapes? A choice-modelling approach across two countries using attributes characterizing vegetation” investigates people's aesthetic preferences for semi-natural habitats in agricultural landscapes. The EU-Common Agricultural Policy promotes the introduction of woody and grassy semi-natural habitats (SNH) in agricultural landscapes. While the benefits of these structures in terms of regulating ecosystem services are already well understood, the effects of SNH on visual landscape quality is still not clear. This study investigates the factors determining people’s visual preferences in the context of grassy and woody SNH elements in Swiss and Hungarian landscapes using picture-based choice experiments. The results suggest that respondents’ choices strongly depend on specific vegetation characteristics that appear and disappear over the year. In particular, flowers as a source of colours and green vegetation as well as ordered structure and the proportion of uncovered soil in the picture play an important role regarding respondents’ aesthetic perceptions of the pictures.
The three empirical studies can help to make future projects in the study areas of biodiversity protection more efficient. While this thesis highlights the importance of exploring biodiversity protection projects at different scales, further analyses of the different scales of biodiversity protection projects are needed to provide a sound basis to develop guidance on identifying the most efficient biodiversity protection projects.