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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.
Water is used in a way as if it were available infinitely. Droughts, increased rainfall or flooding already lead to water shortages and, thus, deprive entire population groups of the basis of their livelihoods. There is a growing fear that conflicts over water will increase, especially in arid climate zones, because life without water - whether for humans, animals or plants - is not possible.
More than 60 % of the African population depend on land and water resources for their livelihoods through pastoralism, fishing and farming. The water levels of rivers and lakes are decreasing. Hence, the rural population which is dependent on land and water move towards water-rich and humid areas. This internal migration increases the pressure on available water resources. Driven by the desire to strengthen the economic development, African governments align their political agendas with the promotion of macro international and national economic projects.
This doctoral thesis examines the complex interrelationships between water shortages, governance, vulnerability, adaptive capacity and violent and non-violent conflicts at Lake Naivasha in Kenya and Lake Wamala in Uganda. In order to satisfy the overall complexity, this doctoral thesis combines various theoretical and empirical aspects in which a variety of methods are applied to different geographical regions, across disciplines, and cultural and political boundaries.
The investigation reveals that Lake Naivasha is more affected by violent conflicts than Lake Wamala. Reasons for this include population growth, historically grown ethnic conflicts, corruption and the preferential treatment of national and international economic actors. The most common conflict response tools are raiding and the blockage of water access. However, deathly encounters, destruction of property and cattle slaughtering are increasingly used to gain access to water and land.
The insufficient implementation of the political system and the governments’ prioritization to foster economic development results, on the one hand, in the commercialization of water resources and increases, on the other hand, non-violent conflict between national and sub-national political actors. While corruption, economic favours and patronage defuse this conflict, resource access becomes more difficult for the local population. Resulting thereof, a final hypothesis is developed which states that the localization of the political conflict aggravates the water situation for the local population and, thereby, favours violent conflicts over water access and water use in water-rich areas.
Soziale Netzwerke spielen im Alltagsleben der Schülerinnen und Schüler eine entscheidende Rolle. Im Rahmen der vorliegenden Masterarbeit wurde ein Konzept für die Anzeige von Profilvorschlägen innerhalb des sozialen Netzwerks „InstaHub“, welches ein speziell für den Informatikunterricht programmiertes Werkzeug zum Thema „Datenbanken“ darstellt, entwickelt. Als Hürde stellte sich dabei dar, dass von den etablierten sozialen Netzwerken nur wenig bis gar keine Informationen über die Berechnung von Profil- oder Freundschaftsvorschlägen preisgegeben werden. Daher wurde zunächst das Wesen von Beziehungen zwischen Menschen in nicht-internetbasierten und in internetbasierten sozialen Netzwerken sowie die Gründe für Beziehungen zwischen Menschen in diesen Netzwerken dargelegt. Anhand der Beobachtung von Vorschlägen in anderen sozialen Netzwerken sowie der in InstaHub gespeicherten Nutzerdaten wurde ein Algorithmus für Profilvorschläge in InstaHub entworfen und mitsamt einer passenden Visualisierung entsprechend implementiert. Den zweiten Teil der Arbeit bildete eine Unterrichtseinheit für die Sekundarstufe II mit dem Thema Gefahren der Erzeugung und Verarbeitung von personenbezogenen Daten. In der Unterrichtseinheit dienen die Profilvorschläge in InstaHub, die auf von InstaHub über dessen Nutzer gesammelten Daten aufbauen, als Einstieg in die Thematik. Anschließend wird der Fokus von sozialen Netzwerken auf andere Online-Dienste erweitert und auf die Verarbeitung und Weitergabe dieser Daten eingegangen.
The Web is an essential component of moving our society to the digital age. We use it for communication, shopping, and doing our work. Most user interaction in the Web happens with Web page interfaces. Thus, the usability and accessibility of Web page interfaces are relevant areas of research to make the Web more useful. Eye tracking is a tool that can be helpful in both areas, performing usability testing and improving accessibility. It can be used to understand users' attention on Web pages and to support usability experts in their decision-making process. Moreover, eye tracking can be used as an input method to control an interface. This is especially useful for people with motor impairment, who cannot use traditional input devices like mouse and keyboard. However, interfaces on Web pages become more and more complex due to dynamics, i.e., changing contents like animated menus and photo carousels. We need general approaches to comprehend dynamics on Web pages, allowing for efficient usability analysis and enjoyable interaction with eye tracking. In the first part of this thesis, we report our work on improving gaze-based analysis of dynamic Web pages. Eye tracking can be used to collect the gaze signals of users, who browse a Web site and its pages. The gaze signals show a usability expert what parts in the Web page interface have been read, glanced at, or skipped. The aggregation of gaze signals allows a usability expert insight into the users' attention on a high-level, before looking into individual behavior. For this, all gaze signals must be aligned to the interface as experienced by the users. However, the user experience is heavily influenced by changing contents, as these may cover a substantial portion of the screen. We delineate unique states in Web page interfaces including changing contents, such that gaze signals from multiple users can be aggregated correctly. In the second part of this thesis, we report our work on improving the gaze-based interaction with dynamic Web pages. Eye tracking can be used to retrieve gaze signals while a user operates a computer. The gaze signals may be interpreted as input controlling an interface. Nowadays, eye tracking as an input method is mostly used to emulate mouse and keyboard functionality, hindering an enjoyable user experience. There exist a few Web browser prototypes that directly interpret gaze signals for control, but they do not work on dynamic Web pages. We have developed a method to extract interaction elements like hyperlinks and text inputs efficiently on Web pages, including changing contents. We adapt the interaction with those elements for eye tracking as the input method, such that a user can conveniently browse the Web hands-free. Both parts of this thesis conclude with user-centered evaluations of our methods, assessing the improvements in the user experience for usability experts and people with motor impairment, respectively.
In der Masterthesis von Benjamin Waldmann mit dem Titel „Flusskrebse in Deutschland – Aktueller Stand der Verbreitung heimischer und invasiver gebietsfremder Flusskrebse in Deutschland; Überblick über die erfolgten Schutzmaßnahmen und den damit verbundenen Erfahrungen; Vernetzung der Akteure im Flusskrebsschutz“ wurden erstmals für alle heimischen wie gebietsfremden Flusskrebsarten (Zehnfußkrebse) Verbreitungskarten für Deutschland vorgelegt. Grundlage der Arbeit waren umfangreiche Recherchen und Abfragen zur Verbreitung der Arten in den Bundesländern bei den zuständigen Behörden, Institutionen, Artexperten und Privatpersonen. Die Rohdaten wurden qualitätsgesichert und in einem Geoinformationssystem aufbereitet und dargestellt, so dass daraus bundesweite Verbreitungskarten für jede Art in einem zehn Kilometerraster (UTM-Gitter im Bezugssystem ETRS89) erstellt werden konnten. Darüber hinaus wurden, ebenfalls auf Basis umfangreicher Recherchen und Abfragen, die unterschiedlichen Möglichkeiten für Schutzmaßnahmen für heimische Flusskrebspopulationen aufgezeigt, bewertet und daraus Empfehlungen abgeleitet. Besonderes Augenmerk wurde dabei auf das Management invasiver gebietsfremder Flusskrebsarten sowie der Umgang mit der Tierseuche Krebspest (Aphanomyces astaci) gelegt. Abschließend wurden Empfehlungen zur Vernetzung der Akteure im Flusskrebsschutz gegeben sowie die Ansprechpartner:innen in den einzelnen Bundesländern aufgeführt.
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.
In dieser wiederkehrenden Zeitschriftenreihe wollen wir die Arbeit junger Wissenschaftlerinnen und Wissenschaftler an der Universität Koblenz-Landau kommunizieren und Studierenden Austausch- und Publikationsmöglichkeiten für den wissenschaftlichen Werdegang eröffnen.
In dieser Ausgabe:
Pfefferkorn, Luca. Auswirkungen von Lückenskripten auf das Arbeiten und Lernen in mathematischen Vorlesungen der Studieneingangsphase.
Steffen, Theresa. Der Einfluss von Musik auf die kognitive Leistungsfähigkeit von Schülerinnen.
Kuhlmann, Fiene. Die Geschlechterpolitik der Alternative für Deutschland (AfD): Eine diskursanalytische Betrachtung zu den Verschränkungen von Anti-Gender und der Ethnisierung von Sexismus.
Dany, Matthias. „Findet Nemo!“: Eine multimodale Kommunikationsanalyse digitaler Protestkultur von Fridays-For-Future.
Reifenhäuser, Mona. Sprachwissenschaftliche Analyse von Auswandererbriefen des 19. Jahrhunderts im Spannungsfeld zwischen Nähe und Distanz.
Schmitt, Katharina. Die Emigration aus dem Hunsrück nach Brasilien – eine postkoloniale Analyse der von Nachfahr*innen Ausgewanderter verfassten Familienbiografien.
Bednarz, Julia. Artenkenntnis – vom Aussterben bedroht? Eine empirische Untersuchung der Artenkenntnis volljähriger Personen in Deutschland, Österreich und der Schweiz am Beispiel einheimischer Vogelarten.
Schöller, Kathrin. Mord mit Opferbeseitigung: Eine quantitative Analyse der Insektenbesiedlung bei unterschiedlichen Leichenverbergungsstrategien.
Heimann, Florian.Parameter Estimation of Physico-Biological Muscle Models: Comparing Günthers Biomechanical Four-Element Model to Macroscopic Hill-Equations.
Mikliss, Annika C.. Registrierung von 3D-Modellen auf Basis von Röntgenaufnahmen zur Darstellung von Hüftgelenksdysplasie bei Hunden.
Nagel, Sabine. Analysis of Task Management Functionalities and their Implementation and Use in Enterprise Collaboration Systems.
Hansen, Christian. Declarative Process Mining: a Method for the Discovery of Collaboration Scenarios in Enterprise Collaboration Systems.
Blatt, Jonas. Entwicklung eines Prototypen für die Verifikation von Decision Model and Notation.
Lienen, Dominik. Orchestrierung von Daten und Services einer KI im Unternehmenskontext.
Method development for the quantification of pharmaceuticals in aqueous environmental matrices
(2021)
As a consequence of the world population increase and the resulting water scarcity, water quality is the object of growing attention. In that context, organic anthropogenic molecules — often defined as micropollutants— represent a threat for water resources. Among them, pharmaceuticals are the object of particular concerns due to their permanent discharge, their increasing consumption and their effect-based structures. Pharmaceuticals are mainly introduced in the environment via wastewater treatment plants (WWTPs), along with their metabolites and the on-site formed transformation products (TPs). Once in the aquatic environment, they partition between the different environmental compartments in particular the aqueous phase, suspended particulate matter(SPM) and biota. In the last decades, pharmaceuticals have been widely investigated in the water phase. However, extreme polar pharmaceuticals have rarely been monitored due to the lack of robust analytical methods. Moreover, metabolites and TPs have seldom been included in routine analysis methods although their environmental relevance is proven. Furthermore, pharmaceuticals have been only sporadically investigated in SPM and biota and adequate multi-residue methods are lacking to obtain comprehensive results about their occurrence in these matrices. This thesis endeavors to cover these gaps of knowledge by the development of generic multi-residue methods for pharmaceuticals determination in the water phase, SPM and biota and to evaluate the occurrence and partition of pharmaceuticals into these compartments. For a complete overview, a particular focus was laid on extreme polar pharmaceuticals, pharmaceutical metabolites and TPs. In total, three innovative multi-residue methods were developed, they include analytes covering a broad range of physico-chemical properties. First, a reliable multi-residue method was developed for the analysis of extreme polar pharmaceuticals, metabolites and TPs dissolved in water. The selected analytes covered a significant range of elevated polarity and the method would be easily expendable to further analytes. This versatility could be achieved by the utilization of freeze-drying as sample preparation and zwitterionic hydrophilic interaction liquid chromatography (HILIC) in gradient elution mode. The suitability of HILIC chromatography to simultaneously quantify a large range of micropollutants in aqueous environmental samples was thoroughly studied. Several limitations were pointed out: a very complex and time-consuming method development, a very high sensitivity with regards to modification of the acetonitrile to water ratio in the eluent or the diluent and high positive matrix effects for certain analytes. However, these limitations can be overcome by the utilization of a precise protocol and appropriate labeled internal standards. They are overmatched by the benefits of HILIC which permits the chromatographic separation of extreme polar micropollutants. Investigation of environmental samples showed elevated concentrations of the analytes in the water phase. In particular, gabapentin, metformin, guanylurea and oxypurinol were measured at concentrations in the µg/L range in surface water. Subsequently, a reliable multi-residue method was established for the determination of 57 pharmaceuticals, 47 metabolites and TPs sorbed to SPM down to the low ng/g range. This method was conceived to cover a large range of polarity in particular with the inclusion of extreme polar pharmaceuticals. The extraction procedure was based on pressurized liquid extraction (PLE) followed by a clean-up via solvent exchange and detection via direct injection-reversed-phase LC-MS/MS and freeze-drying HILIC-MS/MS. Pharmaceutical sorption was examined using laboratory experiments. Derived distribution coefficients Kd varied by five orders of magnitude among the analytes and confirmed a high sorption potential for positively charged and nonpolar pharmaceuticals. The occurrence of pharmaceuticals in German rivers SPM was evaluated by the investigation of annual composite SPM samples taken at four sites at the river Rhine and one site at the river Saar between the years 2005 and 2015. It revealed the ubiquitous presence of pharmaceuticals sorbed to SPM in these rivers. In particular, positively charged analytes, even very polar and nonpolar pharmaceuticals showed appreciable concentrations. For many pharmaceuticals, a distinct correlation was observed between the annual quantities consumed in Germany and the concentrations measured in SPM. Studies of composite SPM spatial distribution permitted to get hints about specific industrial discharge by comparing the pollution pattern along the river. For the first time, these results showed the potential of SPM for the monitoring of positively charged and nonpolar pharmaceuticals in surface water. Finally, a reliable and generic multi residue method was developed to investigate 35 pharmaceuticals and 28 metabolites and TPs in fish plasma, fish liver and fish fillet. For this matrix, it was very challenging to develop an adequate clean-up allowing for the sufficient separation of the matrix disturbances from the analytes. In the final method, fish tissue extraction was performed by cell disruption followed by a non-discriminating clean-up based on silica gel solid-phase extraction(SPE) and restrictive access media (RAM) chromatography. Application of the developed method to the measurement of bream and carp tissues from German rivers revealed that even polar micropollutants such as pharmaceuticals are ubiquitously present in fish tissues. In total, 17 analytes were detected for the first time in fish tissues, including 10 metabolites/TPs. The importance of monitoring metabolites and TPs in fish tissues was confirmed with their detection at similar concentrations as their parents. Liver and fillet were shown to be appropriate for the monitoring of pharmaceuticals in fish, whereas plasma is more inconvenient due to very low concentrations and collection difficulties. Elevated concentrations of certain metabolites suggest possible formation of human metabolites in fish. Measured concentrations indicate a low bioaccumulation potential for pharmaceuticals in fish tissues.
The sediments of surface waters are temporary or final depository of many chemical compounds, including trace metals and metalloids (metal(loid)s) from natural and anthropogenic sources. Whether they act as a source or sink of metal(loid)s depends strongly on the dynamics of the biogeochemical processes that take place at the sediment-water interface (SWI). Important information on biogeochemical processes as well as on the exposure, the fate and the transport of pollutants at the SWI can be obtained by determining chemical concentration profiles in the sediment pore water. A major challenge is to conduct experiments with a spatial resolution, which allows to adequately record existing gradients and to log all the parameters needed, to describe and better understand the complex processes at the SWIs. At the same time, it is from major importance to prevent the formation of any artifacts during sampling, which may occur due to the labile nature of the SWIs and the very steep biogeochemical gradients.
In this context, in the first part of this work, a system was developed and tested that enables the automated, minimal invasive sampling of sediment pore water of undisturbed or manipulated sediments while simultaneously recording parameters such as redox potential, oxygen content and pH value. In an incubation experiment the impact of acidification and mechanical disturbance (re-suspension) on the mobility of 13 metal(loid)s was investigated using a triple quadrupole inductively coupled plasma-mass spectrometry (ICP-QQQ-MS) multi-element approach. Most metals were released as consequence of sulfide weathering whereas mechanical disturbance had a major impact on the mobility of the oxide forming elements As, Mo, Sb, U and V. Additionally, options were demonstrated to address with the system the size fractionation of metal(loid)s in pore water samples and the speciation of As(III/V) and Sb(III/V).
In the second part, the focus, with a similar experimental design, was placed on the processes leading to the release of metal(loid)s. For this purpose, two incubation experiments with different oxygen supply were conducted in parallel. For the first time the nonmetals carbon, phosphorus and sulfur were analyzed simultaneous to 13 metal(loid)s in sediment pore water by ICP-QQQ-MS. Throughout the experiment metal(loid) size fractionation was monitored. It was confirmed that resuspension promotes the mobility of metalloids such as As, Sb and V, while the release of most metals was largely attributed to pyrite weathering. The colloidal (0.45-16 μm) contribution in terms of mobilization was only relevant for a few elements.
Finally, the sampling system was used as part of a new approach to sediment risk assessment. Undisturbed sediment cores from differently contaminated positions in the Trave estuary were examined, considering 16 metal(loid)s, the non-metals C, P and S and the ions NH4+, PO43- and SO42-. By the first in-depth comparison with in-situ dialysis-based pore water sampling the ability of the suction-based approach to represent field conditions was proven. The pore water studies together with supplementing resuspension experiments in bio-geochemical microcosms and sequential extraction identified the most “pristine” sediment of the study area as posing the greatest risk of metal(loid) release. However, the potentially released amounts per kg of sediment are only a few parts per thousand of the average daily loads of the Trave river.