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The use of agricultural plastic covers has become common practice for its agronomic benefits such as improving yields and crop quality, managing harvest times better, and increasing pesticide and water use efficiency. However, plastic covers are suspected of partially breaking down into smaller debris and thereby contributing to soil pollution with microplastics. A better understanding of the sources and fate of plastic debris in terrestrial systems has so far been hindered by the lack of adequate analytical techniques for the mass-based and polymer-selective quantification of plastic debris in soil. The aim of this dissertation was thus to assess, develop, and validate thermoanalytical methods for the mass-based quantification of relevant polymers in and around agricultural fields previously covered with fleeces, perforated foils, and plastic mulches. Thermogravimetry/mass spectrometry (TGA/MS) enabled direct plastic analyses of 50 mg of soil without any sample preparation. With polyethylene terephthalate (PET) as a preliminary model, the method limit of detection (LOD) was 0.7 g kg−1. But the missing chromatographic separation complicated the quantification of polymer mixtures. Therefore, a pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) method was developed that additionally exploited the selective solubility of polymers in specific solvents prior to analysis. By dissolving polyethylene (PE), polypropylene (PP), and polystyrene (PS) in a mixture of 1,2,4-trichlorobenzene and p-xylene after density separation, up to 50 g soil became amenable to routine plastic analysis. Method LODs were 0.7–3.3 mg kg−1, and the recovery of 20 mg kg−1 PE, PP, and PS from a reference loamy sand was 86–105%. In the reference silty clay, however, poor PS recoveries, potentially induced by the additional separation step, suggested a qualitative evaluation of PS. Yet, the new solvent-based Py-GC/MS method enabled a first exploratory screening of plastic-covered soil. It revealed PE, PP, and PS contents above LOD in six of eight fields (6% of all samples). In three fields, PE levels of 3–35 mg kg−1 were associated with the use of 40 μm thin perforated foils. By contrast, 50 μm PE films were not shown to induce plastic levels above LOD. PP and PS contents of 5–19 mg kg−1 were restricted to single observations in four fields and potentially originated from littering. The results suggest that the short-term use of thicker and more durable plastic covers should be preferred to limit plastic emissions and accumulation in soil. By providing mass-based information on the distribution of the three most common plastics in agricultural soil, this work may facilitate comparisons with modeling and effect data and thus contribute to a better risk assessment and regulation of plastics. However, the fate of plastic debris in the terrestrial environment remains incompletely understood and needs to be scrutinized in future, more systematic research. This should include the study of aging processes, the interaction of plastics with other organic and inorganic compounds, and the environmental impact of biodegradable plastics and nanoplastics.
In the last decades, it became evident that the world is facing an unprecedented, human-induced global biodiversity crisis with amphibians being one of the most threatened species groups. About 41% of the amphibian species are classified as endangered by the IUCN, but even in amphibian species that are listed as "least concern", population declines can be observed on a local level. With land-use change and agrochemicals (i.e. pesticides), two of the main drivers for this amphibian decline are directly linked to intensive agriculture, which is the dominant landscape type in large parts of Europe. Thus, understanding the situation of amphibians in the agricultural landscape is crucial for conservation measures. In the present thesis, I investigated the effects of viticulture on amphibian populations around Landau in der Pfalz (Germany) in terms of habitat use, pesticide exposure, biometric traits as well as genetic and age structure. From the perspective of amphibians, land-use change means usually the destruction of habitats in agricultural landscapes, which often leads to landscape fragmentation. Thus, I followed the question if also vineyards lead to the fragmentation of the landscape and if pesticides that are frequently used in viticulture have to be considered as a factor too, so if there is a chemical landscape fragmentation. Using telemetry, I could show that common toads (Bufo bufo) can be found directly in vineyards, but that they tend to avoid them as habitat. Analysing the genetic structure of common frogs (Rana temporaria) revealed that vineyards have to be considered as a barrier for amphibians. To identify if pesticides contribute to the resulting landscape fragmentation, I conducted an arena choice experiment in the laboratory in which I found evidence for an avoidance of pesticide-contaminated soil. Such an avoidance could be one of the underlying reasons for a potential chemical landscape fragmentation. By combining telemetry data with information about pesticide applications from local wine growers, I could show that a large part of the common toads is likely to come in contact with pesticides. Further, I demonstrated that the agricultural landscape, probably due to the application of pesticides, can have negative effects on the reproduction capacity of common toads. By studying palmate newts (Lissotriton helveticus) I found that adult newts from agricultural ponds are smaller than those from forest ponds. As I did not find differences in the age structure and growth, these differences might be carry-over effects from earlier life stages. While agricultural ponds might be suitable habitats for adult palmate newts, the potential carry-over effect indicates suboptimal conditions for larvae and/or juveniles. I conclude that the best management measure for sustaining amphibians in the agricultural landscape would be a heterogeneous cultural landscape with a mosaic of different habitat patches that work without or at least a reduced amount of pesticides. Green corridors between populations and different habitats would allow migrating individuals to avoid agricultural and thus pesticide-contaminated areas. This would reduce the pesticide exposure risk of amphibians, while preventing the fragmentation of the landscape and thus the isolation of populations.
Der Zweck dieser Arbeit ist es, sich auf die kritischen Forschungsherausforderungen und -themen zu konzentrieren, die UI/UX-Designprinzipien umgeben, mit einem Schwerpunkt auf kulturübergreifenden Konzepten aus der Perspektive von E-Learning-Plattformen. Zu diesem Zweck betrachten wir zunächst die kulturellen Dimensionen auf der Grundlage des Hofstede-Rahmens mit dem Ziel, wichtige kulturelle Werte zu identifizieren. Als zweites Ziel der Forschung erleichtert eine Reihe von Kriterien, die so genannte Usability-Heuristik von Nielsen, die Erkennung von Usability Problemen bei der Gestaltung von Benutzeroberflächen (UI). Die Usability-Heuristiken umfassen zehn Variablen, die die Interaktion zwischen dem Benutzer und einem Produkt oder System beeinflussen. Wenn wir uns näher mit
diesen Themen befassen, werden wir in der Lage sein, eine Matrix mit Beziehungen zwischen der heuristischen Bewertung von Nielsen und dem kulturellen Rahmen von Geert Hofstede aufzudecken. Abschließend erörtern wir das mögliche Potenzial kultureller Werte zur Beeinflussung von Benutzeroberflächen für E-Learning-Plattformen. In der Tat gibt es einige Funktionen in E-Learning-Plattformen, die aufgrund der Kultur weniger diskutiert werden, obwohl sie sehr praktisch in die Plattformen integriert werden können.
Agricultural plastic covers made from polyethylene (PE) and polypropylene (PP) provide increased yields and an improved crop quality. However, such covers are suspected of partially breaking down into smaller debris and thereby contributing to soil pollution with microplastics. To scrutinize this, we randomly sampled 240 topsoil cores (0–5 cm) from eight fields which were covered with fleeces, perforated foils, and plastic mulches for less than 2 years. Samples from the field periphery (50 m perimeter) served as a reference. Visual plastic debris > 2 mm was analyzed by Fourier transform infrared spectroscopy. Smaller, soil-associated plastic debris was dispersed from 50 g of fine soil (≤ 2 mm) using sodium hexametaphosphate solution and density-separated with saturated NaCl solution. The collected PE, PP, and polystyrene (PS) debris was selectively dissolved in a mixture of 1,2,4-trichlorobenzene and p-xylene at 150 °C and quantified by pyrolysis–gas chromatography–mass spectrometry (Py-GC/MS). We counted six PE and PS fragments > 2 mm in two out of eight fields. By contrast, Py-GC/MS detected PE, PP, and PS contents in the fine soil of six fields (6 % of all samples). In three fields, PE levels of 3–35 mg kg−1 were potentially associated with the use of thinner and less durable perforated foils (40 µm thickness). This was slightly more pronounced at field edges where the plastic covers are turned and weighed down. By contrast, 50 µm thick PE films were not shown to emit any plastic debris. PP contents of 5–10 mg kg−1 were restricted to single observations in the field centers of three sites. At one site, we found expanded PS particles > 2 mm that concurred with elevated PS levels (8–19 mg kg−1) in the fine soil. Both PP and PS were distributed indistinctly across sites so that their source remained unresolved. In addition, the extent to which plastic contents of up to 7 mg kg−1 in the field periphery of some sites were attributed to wind drift from the covered fields or from external sources needs to be investigated in future studies. Our results suggest that the short-term use of thicker and more durable plastic covers should be preferred over thinner or perforated films to limit plastic emissions and accumulation in soil.
Agricultural intensification is leading to a severe decline in farmland biodiversity worldwide. The resulting landscape simplification through the expansion of monocultures and removal of non-crop habitats has a major impact on arthropod communities in agricultural landscapes. While arable fields are often highly disturbed and ephemeral habitats that are unsuitable for many species, non-crop habitats in agroecosystems can provide important refugia. The creation of non-crop habitats through agri-environmental schemes (AES) in intensive agricultural landscapes, such as the ‘Maifeld’ region in western Germany, is intended to mitigate the negative effects of agricultural intensification, although the effectiveness of these measures for nature conservation is still controversial. Therefore, this work focuses on the taxonomic and functional diversity of beetles (Coleoptera) and spiders (Araneida), being important providers of ecosystem services, between wheat fields and different non-crop habitats, namely grassy field margins adjacent to wheat and oilseed rape fields, small- and large-scale set-aside areas sown with wildflowers, and permanent grassland fallows. Arthropods were collected between 2019 and 2020 using pitfall traps and suction sampling. Land-use type influenced beetle and spider diversity in the study area, with significantly higher values in grassland fallows than wheat fields. Surprisingly, species diversity differed little among all non-crop habitats, but all harboured distinct species assemblages. In particular, large long-term grassland fallows showed the largest within-group variation of beetle and spider assemblages and represented important habitats, especially for habitat specialists and threatened species, likely due to their variable soil moisture and complex habitat structure. In contrast, the homogeneous arthropod assemblages of wheat fields exhibited lower trait richness and were dominated by a few predatory species adapted to such disturbed, man-made habitats. Interestingly, all conservation measures complemented each other in that they contributed in different ways to supporting beetles and spiders in agricultural landscapes. Even small-scale non-crop habitats and existing habitat boundaries in an agricultural matrix appear to be valuable habitats for farmland arthropods by enhancing taxonomic diversity. Field margins and small wildflower-sown patches can link isolated non-crop habitats and contribute to a heterogeneous agricultural landscape. Consequently, a combination of various small- and large-scale greening measures leads to increased compositional and configurational landscape heterogeneity, resulting in improved beetle and spider diversity. Considering the ongoing loss of farmland biodiversity worldwide, agri-environmental schemes should be promoted in the future, as they are particularly important for arthropod conservation in intensive agricultural landscapes such as the Maifeld region.
The growing numbers of breeding rooks (Corvus frugilegus) in the city of Landau (Rhineland- Palatinate, Germany) increase the potential for conflict between rooks and humans, which is mainly associated with noise and faeces. Therefore, the aim of this work is a better understanding of the breeding tree selection of the rook in order to develop options for action and management in the future.
Part I of this thesis provides general background information on the rook and includes mapping of the rookeries in the Anterior Palatinate and South Palatinate including Landau in the year 2020. That mapping revealed that the number of rural colonies has decreased, while the number of urban colonies has increased in the study area in the last few years. In line with current literature, tree species and tree size were important criteria for breeding tree selection. However, the mapping showed that additional factors must be important as well.
Therefore, as rooks seem to often breed along traffic axes, Part II of this thesis examines how temperature, artificial light and noise, which are all linked to traffic axes, affect the breeding tree selection of the rook in the city of Landau. The following three hypotheses are developed: (1) manually selected breeding trees (Bm) have a warmer microclimate than manually selected non-breeding trees (Nm) or randomly selected non-breeding trees (Nr), (2) Bm are exposed to a higher light level than Nm or Nr and (3) Bm are exposed to a higher noise level than Nm or Nr. To test these hypotheses, 15 Bm, 13 Nm and 16 Nr are investigated.
The results show that Bm were exposed to more noise than both types of non-breeding trees (μBm, noise = 36.52481 dB, μNm, noise = 31.27229 dB, μNr, noise = 29.17417 dB) where the difference between Bm and Nr was significant. In addition, there was a tendency for Bm to be exposed to less light (μBm, light = 0.356 lx) than Nm (μNm, light = 0.4107692 lx) and significantly less light than Nr (μNr, light = 1.995 lx), while temperature did not differ between the groups (μBm, temp = 16.90549 °C, μNm, temp = 16.93118 °C, μNr, temp = 17.28639 °C).
This study shows for the first time that rooks prefer trees which are exposed to low light levels and high noise levels, i.e. more intense traffic noise, for breeding. It can only be speculated that the cause of this is lower enemy pressure at such sites. The fact that temperature does not seem to have any influence on breeding tree selection may be due to only small temperature differences at nest height, which might be compensated by breeding behaviour. Consequently, in the long term one management approach could be to divert traffic from inner-city areas, especially schools and hospitals, to bypasses. If tree genera suitable for rooks, such as plane trees, are planted along the bypasses, those sites could provide suitable alternative habitats to inner-city breeding locations, which become less attractive for breeding due to noise reduction. In the short term in addition to locally implemented repellent measures the most effective approach is to strengthen rook acceptance among the population. However, further research is needed to verify the results of this thesis and to gain further insights into rook breeding site selection in order to develop effective management measures.
Objectives: Crayfish plague disease, caused by the oomycete pathogen Aphanomyces astaci represents one of the greatest risks for the biodiversity of the freshwater crayfish. This data article covers the de novo transcriptome assembly and annotation data of the noble crayfish and the marbled crayfish challenged with Ap. astaci. Following the controlled infection experiment (Francesconi et al. in Front Ecol Evol, 2021, https://doi.org/10.3389/fevo.2021.647037), we conducted a differential gene expression analysis described in (Boštjančić et al. in BMC Genom, 2022, https://doi.org/10.1186/s12864-022-08571-z) Data description: In total, 25 noble crayfish and 30 marbled crayfish were selected. Hepatopancreas tissue was isolated, followed by RNA sequencing using the Illumina NovaSeq 6000 platform. Raw data was checked for quality with FastQC, adapter and quality trimming were conducted using Trimmomatic followed by de novo assembly with Trinity. Assembly quality was assessed with BUSCO, at 93.30% and 93.98% completeness for the noble crayfish and the marbled crayfish, respectively. Transcripts were annotated using the Dammit! pipeline and assigned to KEGG pathways. Respective transcriptome and raw datasets may be reused as the reference transcriptome assemblies for future expression studies.
To render the surface of a material capable of withstanding mechanical and electrochemical loads, and to perform well in service, the deposition of a thin film or coating is a solution. In this project, such a thin film deposition is carried out. The coating material chosen is titanium nitride (TiN) which is a ceramic material known to possess a high hardness (>10 GPa) as well as good corrosion resistance. The method of deposition selected is high power impulse magnetron sputtering (HiPIMS) that results in coatings with high quality and enhanced properties. Sputtering is a physical process that represents the removal or dislodgment of surface atoms by energetic particle bombardment. The term magnetron indicates that a magnetic field is utilized to increase the efficiency of the sputtering process. In HiPIMS, a high power is applied in pulses of low duty cycles to a cathode that is sputtered and that consists of the coating material. As result of the high power, the ionization of the sputtered material takes place giving the possibility to control these species with electric and magnetic field allowing thereby the improvement and tuning of coating properties. However, the drawback of HiPIMS is a low deposition rate.
In this project, it is demonstrated first that it is possible to deposit TiN coating using HiPIMS with an optimized deposition rate, by varying the magnetic field strength. It was found that low magnetic field strength (here 22mT) results in a deposition rate similar to that of conventional magnetron sputtering in which the average power is applied continuously, called also direct current magnetron sputtering (dcMS). The high deposition rate at low magnetic field strength was attributed to a reduction in the back attraction probability of the sputtered species. The magnetic field strength did not show noticeable influence on the mechanical properties. The proposed explanation was that the considered peak current density interval 1.22-1.72 A∙cm-2 does not exhibit dramatic changes in the plasma dynamics.
In a second part, using the optimized deposition rate, the optimized chemical composition of TiN was determined. It was shown that the chemical composition of TiN does not significantly influence the corrosion performance but impacts considerably the mechanical properties. It was also shown that the corrosion resistance of the coatings deposited using HiPIMS was higher than that of the coatings deposited using dcMS.
The third study was the effect of annealing post deposition on the properties of TiN coating deposited using HiPIMS. The hardness of the coatings showed a maximum at 400°C reaching 24.8 GPa. Above 400°C however, a lowering of the hardness was measured and was due to the oxidation of TiN which led to the formation of TiN-TiO2 composites with lower mechanical properties.
The coating microscopic properties such as crystal orientation, residual stresses, average grain size were determined from X-ray diffraction data and the roughness was measured using atomic force microscopy. These properties were found to vary with the magnetic field strength, the chemical composition as well as the annealing temperature.
Diet-related effects of antimicrobials in aquatic decomposer-shredder and periphyton-grazer systems
(2022)
Leaf-associated microbial decomposers as well as periphyton serve as important food sources for detritivorous and herbivorous macroinvertebrates (shredders and grazers) in streams. Shredders and grazers, in turn, provide not only collectors with food but also serve as prey for predators. Therefore, decomposer-shredder and periphyton-grazer systems (here summarized as freshwater biofilm-consumer systems) are highly important for the energy and nutrient supply in heterotrophic and autotrophic stream food webs. However, both systems can be affected by chemical stressors, amongst which antimicrobials (e.g., antibiotics, fungicides and algaecides) are of particular concern. Antimicrobials can impair shredders and grazers not only via waterborne exposure (waterborne effect pathway) but also through dietary exposure and microorganism-mediated alterations in the food quality of their diet (dietary effect pathway). Even though the relevance of the latter pathway received more attention in recent years, little is known about the mechanisms that are responsible for the observed effects in shredders and grazers. Therefore, the first objective of this thesis was to broaden the knowledge of indirect antimicrobial effects in a model shredder and grazer via the dietary pathway. Moreover, although freshwater biofilm-consumer systems are most likely exposed to antimicrobial mixtures comprised of different stressor groups, virtually nothing is known of these mixture effects in both systems. Therefore, the second objective was to assess and predict diet-related antimicrobial mixture effects in a model freshwater biofilm-consumer system. During this thesis, positive diet-related effects of a model antibiotic on the energy processing and physiology of the shredder Gammarus fossarum were observed. They were probably triggered by shifts in the leaf-associated microbial community in favor of aquatic fungi that increased the food quality of leaves for the shredder. Contrary to that, a model fungicide induced negative effects on the energy processing of G. fossarum via the dietary pathway, which can be explained by negative impacts on the microbial decomposition efficiency leading to a reduced food quality of leaf litter for gammarids. For diet-related antimicrobial effects in periphyton-grazer systems, a model algaecide altered the periphyton community composition by increasing nutritious and palatable algae. This resulted in an enhanced consumption and physiological fitness of the grazer Physella acuta. Finally, it was shown that complex horizontal interactions among leaf-associated microorganisms are involved, making diet-related antimicrobial mixture effects in the shredder G. fossarum difficult to predict. Thus, this thesis provides new insights into indirect diet-related effects of antimicrobials on shredders and grazers as well as demonstrates uncertainties of antimicrobial mixture effect predictions for freshwater biofilm-consumer systems. Moreover, the findings in this thesis are not only informative for regulatory authorities, as indirect effects and effects of mixtures across chemical classes are not considered in the environmental risk assessment of chemical substances, but also stimulate future research to close knowledge gaps identified during this work.
The presented study was motivated by the dynamic phenomena observed in basic catalytic surface reactions, especially by bi- and tristability, and the interactions between these stable states. In this regard, three reaction-diffusion models were developed and examined using bifurcation theory and numerical simulations.
A first model was designed to extend the bistable CO oxidation on Ir(111) to include hydrogen and its oxidation. The differential equation system was analyzed within the framework of bifurcation theory, revealing three branches of stable solutions.
One state is characterized by high formation rates (upper rate state, UR), while the other two branches display low formation rates (lower rate (LR) \& very low rate (VLR) states).
The overlapping branches form the shape of a `swallowtail', the curve of saddle-node bifurcations forming two cusps. Increasing the temperature leads to a subsequent unfolding and hence decreases the system complexity.
A series of numerical simulations representing possible experiments was conducted to illustrate the experimental accessibility (or the lack) of said states. Relaxation experiments show partially long decay times. Quasistatic scanning illustrates the existence of all three states within the tristable regime and their respective conversion once crossing a fold.
A first attempt regarding the state dominance in reaction-diffusion fronts was done. While UR seems to dominate in 1D, a 2D time-evolution shows that LR invades the interphase between UR and VLR.
Subsequently, a generic monospecies mock model was used for the comprehensive study of reaction-diffusion fronts. A quintic polynomial as reaction term was chosen, derived by the sixth-order potential associated with the `butterfly bifurcation'. This ensures up to three stable solutions($u_{0}$,$u_{1}$,$u_{2}$), depending on the four-dimensional parameter space.
The model was explored extensively, identifying regions with similar behaviors.
A term for the front velocity connecting two stable states was derived, depending only on the relative difference of the states' potential wells.
Equipotential curves were found, where the front velocity vanishes of a given front. Numerical simulations on a two-dimensional, finite disk using a triangulated mesh supported these findings.
Additionally, the front-splitting instability was observed for certain parameters. The front solution $u_{02}$ becomes unstable and divides into $u_{01}$ and $u_{12}$, exhibiting different front velocities. A good estimate for the limit of the front splitting region was given and tested using time evolutions.
Finally, the established mock model was modified from continuous to discrete space, utilizing a simple domain in 1D and three different lattices in 2D (square, hexagonal, triangular).
For low diffusivities or large distances between coupling nodes, fronts can become pinned, if the parameters are within range of the equipotential lines. This phenomenon is known as propagation failure and its extent in parameter space was explored in 1D. In 2D, an estimate was given for remarkable front orientations respective to the lattice using a pseudo-2D approximation. Near the pinning region, front velocities differ significantly from the continuous expectation as the shape of the curve potential becomes significant. Factors that decide the size and shape of the pinning regions are the coupling strength, the lattice, the front orientation relative to the lattice, and the front itself. The bifurcation diagram shows a snaking curve in the pinning region, each alternating branch representing a stable or unstable frozen front solution. Numerical simulations supported the observations concerning propagation failure and lattice dependence.
Furthermore, the influence of front orientation on the front velocity was explored in greater detail, showing that fronts with certain lattice-dependent orientations are more or less prone to propagation failure. This leads to the possibility of pattern formation, reflecting the lattice geometry. An attempt to quantify the front movement depending on angular front orientation has shown reasonable results and good agreement with the pseudo-2D approach.