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.

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.

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.

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.

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.