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- Institut für Integrierte Naturwissenschaften (6)
- Institut für Musikwissenschaft und Musikpädagogik (6)
- Institut für Philosophie (6)
- Institut für Kulturwissenschaft (5)
- Institut für Sozialwissenschaften (5)
- Arbeitsbereich Diagnostik, Differentielle und Persönlichkeitspsychologie, Methodik und Evaluation (4)
- Institut für Kunstwissenschaft (4)
- Institut für Soziologie und Politikwissenschaft (4)
- Institut für Pädagogik, Abteilung Schulpädagogik/Allgemeine Didaktik (3)
- Arbeitsbereich Entwicklungspsychologie und Pädagogische Psychologie (2)
- Fachbereich 4 (2)
- Institut für Kunstwissenschaft und Bildende Kunst (2)
- Institut für Mathematik (2)
- Arbeitsbereich Allgemeine und Pädagogische Psychologie (1)
- Arbeitsbereich Kognitive Psychologie (1)
- Arbeitsbereich Sozial- und Wirtschaftspsychologie (1)
- Institut für Bildung im Kindes- und Jugendalter (1)
- Institut für Geschichte (1)
- Institut für Grundschulpädagogik (1)
- Institut für Kommunikationspsychologie und Medienpädagogik (1)
- Institut für Pflegewissenschaften (1)
- Institut für Sonderpädagogik (1)
- Institut für fremdsprachliche Philologien (1)
This study investigated the acquisition of skills by future maths teachers in Rhineland-Palatinate during
their final internship phase before entering the so-called `Vorbereitungsdienst´, a kind of in-depth in-
ternship/ practical training.
In order to record the students' learning progress, a pre/post-test approach was chosen in which the
participants each analysed five short teaching sequences in an online questionnaire and then answered
questions on mathematical argumentation. So the test reflected a central content of the internship,
the observation and reflection of maths lessons.
All video sequences were focussed on aspects of mathematical argumentation in the classroom. Ma-
thematical reasoning not only describes one of the general competences laid down in the educational
standards and curricula for the subject of mathematics, but also goes beyond the other general com-
petences in terms of its fundamental importance for mathematics lessons.
In the test group, a total of 54 trainees was surveyed at the beginning and at the end of their in-depth
internship in four internship periods in 2022 and 2023. The control group consisted of 28 student tea-
chers of mathematics, who were also surveyed twice at 3-week intervals without completing a school
placement in the meantime.
The collected data sets, which essentially consist of free text responses, were analysed using the qua-
litative content analysis method. In addition, the interpretative uncertainty that arises here was mini-
mised through backward testing. In this way, the quantity and quality of the video analysis as well as
the knowledge and understanding of mathematical argumentation could be determined and com-
pared for each respondent in both tests.
As a result, the study confirms previous findings regarding the perception of teaching by experts and
novices and also the fundamental increase in knowledge through practical phases. In addition the
study shows that both quantitative and qualitative response behaviour improved after the practical
training and the test participants were able to identify aspects of argumentation in the lesson excerpts
and justify their importance for good mathematics teaching. This was more successful in teaching si-
tuations that are not very dynamic than in teaching situations that are very dynamic, such as those
arising from conversational situations. In addition, a deeper understanding of the competence `ma-
thematical argumentation´ could be demonstrated after the internship and it could be seen that the
didactic knowledge and the ability to analyse videos correlate more strongly with each other in the
post-test than in the pre-test.
The effects described were only evident in the test group, but not in the control group without the
work placement.
Positron Emission Tomography (PET) is becoming more and more important in clinical routine
applications. One of the major limitations is the sensitivity to patient motion especially in the thorax
to periodic respiratory movement. Another open point of discussion is the method how to define the
tumor volume, especially when the precise knowledge of the tumor borders is important as in
radiation treatment planning. Therefore, in this work these two topics to improve quantification in
PET imaging have been addressed. First a new motion correction algorithm was implemented using
image deblurring including movement information of a 4D Computed Tomography (CT). This method,
which has the advantage of not increasing the PET acquisition time as other motion correction
techniques, was applied to phantom and patient data and showed promising result in improvement of lesion quantification. In phantom studies an improvement of up to 49% in lesion volume and in
patient studies of up to 33.3% could be demonstrated.
In the second part of this work, a new segmentation method based on textural parameters was
implemented and validated as well in phantom and patient data. In the latter a validation with
histopathological data was performed showing a very good performance of the new algorithms,
especially in larger lesions. Best result could be shown in phantom data and patient data for the
segmentation algorithm based in the local entropy.
In summary, two algorithms were implemented and validated which can improve quantification of
PET imaging furthermore
In recent decades, there has been a growing awareness in our society of the impor-
tance of medicines that are personalized to the needs of patients. This dissertation
contributes to the research on personalized dosage forms with controlled drug release.
The basis of our investigations is the simulation of the expected diffusion properties
of these personalized dosage forms using computer-aided statistical methods and the
subsequent adaptation of suitable models to experimentally obtained data. This
novel approach makes it possible to verify the parameters determined from exper-
imental data, such as the diffusion coefficient. A key finding is that, for instance,
the homogeneity of the sample, the precision of the measurement data collection
and the consideration of the measurement environment have a greater influence on
the validity of the diffusion coefficient than the choice of the diffusion model. The
experimental part of this thesis comprises the development and characterization of
drug-loaded polymer resins, the implant fabrication, and the pharmaceutical and
physical investigation of the polymer-drug implants. The formulation of polymer
resins and their suitability for 3D printing (3DP), as well as their use in pharmaceu-
tical applications, are extensively addressed. The release properties and, in partic-
ular, the polymer network’s mesh size influence on the active ingredient’s diffusion
rate in aqueous solution are studied. In addition, the production of polymer sam-
ples by means of UV photopolymerization in a molding process developed for this
purpose, as well as by using stereolithographic 3DP, are examined comparatively.
The polymerization process and the polymer properties resulting from the different
production methods are presented. The major findings from these studies include
the successful development of a polymer resin formulation whose release and swelling
properties are comprehensively demonstrated using a model drug. Furthermore, the
optimization of this resin for the use of the active pharmaceutical ingredient (API)
testosterone was achieved. A comparison of the two developed resin formulations
clearly shows the limitations and the possibilities of transferability of both systems.
In addition, the results concerning the release of API from the polymer, as well as
the diffusion of the solvent into the polymer and the resulting increase in the volume,
provide insight into the changed interfacial diffusion resistance in 3D printed poly-
mers compared to molded polymers. This work thus contributes to the development
of personalized drug forms and paves the way for the production of release-controlled
polymer resin implants for future follow-up work.
The rapid evolution of wireless communication technologies, particularly the introduction
of Fifth-Generation (5G) networks and the anticipated transition to Sixth-Generation (6G)
systems, ushers in a new era of connectivity, enabling transformative applications across
industrial automation, the Internet of Everything (IoE), and the Industrial Internet of Things
(IIoT). However, the exponential growth in the number of connected devices, stringent reliability
requirements, and increasing security challenges pose significant hurdles for current network
architectures. This dissertation addresses these challenges by proposing innovative frameworks
and mechanisms that enhance reliability, optimize resource utilization, and strengthen security
and trust management in next-generation mobile networks.
The first contribution of this dissertation focuses on reliability enhancements in 5G networks.
While existing mechanisms, such as Dual Connectivity (DC) and Network Function (NF)
redundancy, provide partial solutions, they do not fully resolve application-layer reliability
and dynamic server failover. To bridge this gap, this work introduces the Make-Before-Break-
Reliability (MBBR) and enhanced Make-Before-Break-Reliability (eMBBR) mechanisms. These
frameworks proactively establish redundant communication paths, ensuring seamless failovers
with minimal latency and service disruption. By extending reliability to the application layer
and integrating adaptive path selection and dynamic failover capabilities, these mechanisms
offer robust solutions for latency-sensitive and mission-critical applications.
The second major contribution addresses bandwidth optimization for industrial networks.
The black channel paradigm, widely adopted for industrial safety applications, relies heavily on
cyclic keep-alive messages to detect connection loss, leading to significant signaling overhead.
This dissertation proposes a novel solution leveraging 5G Channel State Information (CSI)
to replace cyclic messaging with real-time connection quality monitoring. By exposing CSI
metrics, such as Signal-to-Noise Ratio (SNR) and Channel Quality Indicator (CQI), to the
application layer, the proposed mechanism reduces bandwidth consumption while maintaining
the safety and reliability requirements of industrial networks.
Addressing the growing complexity of security requirements in IIoT, the third contribution
introduces the AF-based Security Framework (AERO) framework. This framework empowers
application providers to dynamically apply cryptographic mechanisms to the user plane,
overcoming the limitations of legacy protocols and eliminating the need for redundant security
layers. By ensuring backward compatibility and enabling both static and dynamic configuration
of user plane encryption, AERO enhances security while minimizing computational overhead
and reducing transmission delays.
The fourth and final contribution redefines trust management in mobile networks through
the SecUre deleGAtion of tRust (SUGAR) framework. Traditional trust models, which rely
on identity chips for each connected device, are becoming increasingly impractical in the
IoE era, where billions of devices require connectivity. The SUGAR framework introduces a
delegation-based trust model, allowing Parent Devices (PaDs) to delegate trust to multiple
Child Devices (ChDs) securely. This approach eliminates the need for individual identity chips,
significantly reducing costs and enhancing scalability. Integration with System-on-a-Chip
(SoC)-based identity enclaves further strengthens the security of trust credentials.
The findings of this dissertation offer substantial contributions to both academia and
industry. The proposed frameworks effectively address critical gaps in current 5G standards
and provide valuable contributions for developing the 6G framework. By enhancing reliability,
optimizing bandwidth, and redefining security and trust management, this dissertation provides
a comprehensive foundation for the design and deployment of next-generation mobile networks.
Furthermore, the solutions presented are adaptable to a wide range of applications, including
industrial automation, autonomous systems, and smart city infrastructures.
In conclusion, this dissertation represents a significant step toward realizing the full
potential of next-generation mobile networks. By addressing key challenges in reliability,
resource optimization, security, and trust management, the proposed frameworks pave the way
for scalable, secure, and efficient mobile ecosystems that are essential for the dynamic and
interconnected world of the future.
Improving patient care is an ongoing process, evolving from early evidence-based practices to modern AI-driven approaches. This thesis explores three key research directions aimed at improving clinical decisionmaking through AI. Adverse events, defined as negative and harmful outcomes that occur during medical care, present major challenges for hospitals. Most data-driven research using electronic health records relies on data from tertiary referral hospitals, but their patient population differs from those in hospitals of medium level of care. The first major contribution of this thesis is a data-driven Trigger Tool for predicting adverse events trained on data from a hospital of medium level of care. This tool uses a concise set of laboratory values measured within the first 24 hours of hospitalization. In addition to models using numerical features, we devised models using dichotomized features that indicate whether a laboratory value falls below or above a reference threshold. Our findings show that models using numerical features achieve high accuracy in predicting acute kidney injury and the COVID-19 associated adverse events in-hospital mortality and transfer to the ICU. Models using dichotomous features performonly slightly worse but offer better interpretability.
The second major contribution is the online-updateable AI model OptAB for selecting optimal antibiotics in sepsis patients. OptAB aims to minimize the sepsis-related organ failure score (SOFA-Score) while accounting for nephrotoxic and hepatotoxic side effects. OptAB relies on a hybrid neural network differential equation algorithm tailored to the special properties of patient data, including irregular measurements, missing values, and time-dependent confounding. Time-dependent confounding describes a dependence between time-varying covariates and treatment decisionsmade by physicians, often leading to biased treatment effect estimates. OptAB generates disease course forecasts for (combinations of ) the antibiotics vancomycin, ceftriaxone, and piperacillin/tazobactam and learns realistic treatment effects on the SOFA-Score and side effect indicative laboratory values. Results indicate that OptAB’s recommendations achieve faster efficacy than the administered antibiotics while reducing side effects.
The third major contribution is DoseAI, an online-updateable AI model that extends OptAB to optimize dosing regimens. DoseAI mitigates time-dependent confounding in dosage selection by minimizing the absolute spearman correlation between predicted and future treatment dosages. It forecasts disease progression under alternative dosing regimens and proposes optimal chemotherapy and radiotherapy dosing regimens for synthetic cancer patients. These regimens effectively reduce the tumor volume while adhering to varying maximum allowed weight loss constraints, used as a measure of toxicity.
Mathematiklehrkräfte sind bisher unzureichend auf die Digitalisierung des Mathematikunterrichts vorbereitet. Daher ist es notwendig bereits im Studium passende Lernangebote zur Entwicklung professioneller Kompetenzen für den Einsatz digitaler Mathematikwerkzeuge zu schaffen. Im Rahmen der vorliegenden Arbeit wird eine fachdidaktische Lehrveranstaltung für angehende Mathematiklehrkräfte der Sekundarstufen
konzipiert, um deren professionellen Kompetenzen mit Blick auf den Einsatz digitaler Mathematikwerkzeuge im Kontext der Leitidee Strukturen und funktionaler Zusammenhang zu fördern. Neben Werkzeugkompetenzen zur Nutzung der digitalen Mathematikwerkzeuge sollen die Kompetenzen zur Planung und Gestaltung von Mathematikunterricht entwickelt werden. Für das Themenfeld funktionale Zusammenhänge sind die beiden digitalen Mathematikwerkzeuge GeoGebra und Tabellenkalkulationsprogramm besonders relevant. Deren Potentiale für das funktionale Denken werden insbesondere in Bezug auf Darstellungsformen und Repräsentationswechsel sowie Lernschwierigkeiten thematisiert. Ergänzend zu den genannten Kompetenzen werden zudem Überzeugungen zum Einsatz digitaler Mathematikwerkzeuge in den Blick genommen. Diese haben einen erheblichen Einfluss darauf, ob die erworbenen Kompetenzen im eigenen Unterricht eingesetzt werden oder nicht.
Zur Ermittlung des Ist-Zustands bei Kompetenzen und Überzeugungen der angehenden
Mathematiklehrkräfte vor dem Besuch der Lehrveranstaltung wurden zwei Erhebungsinstrumente entwickelt und eingesetzt. Neben einem Fragebogen zur Selbsteinschätzung erfolgte die Datenerhebung mittels eines neu entwickelten Kompetenztests
im Sinne eines Leistungstests. Es zeigte sich, dass die professionellen Kompetenzen und Vorerfahrungen bei den Studierenden äußerst heterogen sind.
Um Rückschlüsse auf die Wirksamkeit der Lehrveranstaltung ziehen zu können, wurden die beiden Erhebungsinstrumente im Pre-Post-Design eingesetzt. Die Ergebnisse nach Besuch der Lehrveranstaltung lassen auf positive Effekte schließen. Gleichzeitig wird deutlich, dass eine einzelne Lehrveranstaltungen im Studium nicht ausreicht. Zudem besteht Bedarf an weiterer Forschung in diesem Bereich, insbesondere was die Untersuchung langfristiger Effekte und die Zusammenhänge zwischen den verschiedenen Kompetenzfacetten und Überzeugungen betrifft.
In view of the requirement that students (e.g. in Rhineland-Palatinate) from grade 7 onwards
have to work independently with dynamic geometry software (e.g. GeoGebra) and a
spreadsheet program, teachers have a special role in the integration of digital mathematics
toolsin mathematics lessons. For example this can be implemented, with regard to the guiding
idea L4 (Functional connection), since the use of digital mathematics tools is recommended to
promote functional thinking. Within the qualitive offensive for pre-service-teacher training,
which has been established by the Ministry of Education, the project MoSAiK provided a
Digital Research Workshop Multiple Representations in Mathematics Education using the
topic of elementary functions on secondary school level. On the one hand this workshop
examined tool skills of students in relation to the two softwares GeoGebra and spreadsheets
that apply for secondary schools, high schools and vocational schools. On the other hand
(technology-related) beliefs of the students were researched according to the function
concept.
For that reason a specific didactic workshop, which included on the one hand the fostering of
operating skills for the tools GeoGebra and spreadsheet and on the other hand the
subsequent planning and teaching of lessons had been conceived. Before and after attending
the workshop the operating and selection skills in both tools have been measured in a sample
of 55 students using a self-developed competency test. In addition, the sub-areas TK, TPK and
TCK of the TPACK-framework, self-efficacy beliefs and technology-related beliefs regarding
the advantages and disadvantages of using digital mathematics tools were collected using a
student questionnaire. The workshop intervention achieved a significant effect on the
development of the students' operating skills for both tools – GeoGebra and spreadsheet. The
results of a qualitative content analysis with quantitative elements show that in particular the
visualizing of functions and the checking of results were viewed as advantages of the digital
tools when teaching functional thinking. The most frequently cited disadvantage was a danger
to manual calculation methods. With regard to the time required, on the one hand, savings
were expected when using digital tools, but on the other hand, there were fears of high
expenditure if pupils do not have the necessary tool skills.
Mit der Demographischen Dividende (DD) wird ein wirtschaftlicher Vorteil beschrieben, der aus einer Verschiebung der Altersstruktur einer Gesellschaft hin zu einem höheren Anteil erwerbsfähiger Bevölkerung resultiert. Ursprünglich am Beispiel der so genannten ‚Tigerstaaten‘ Südostasiens entwickelt, gilt die DD als ein Modell für wirtschaftliches Wachstum durch Fertilitätsrückgänge. Die vorliegende Dissertation befasst sich diskursanalytisch mit der Verwendung des Konzepts in Entwicklungszusammenarbeit, Politikberatung und Bevölkerungsforschung sowie dessen Übertragung auf den Globalen Süden als ein leitendes Paradigma in der internationalen Entwicklungszusammenarbeit. Hierzu wurden teilstrukturierte Interviews mit Expertinnen und Experten geführt.
Die Debatte um die DD ist von uneinheitlichen Definitionen darüber geprägt, was die DD genau ist. Eine technisch-mathematische Perspektive sieht die DD als reine Folge der Altersstrukturverschiebung, während eine behavioristische Sicht zusätzlich die Auswirkungen individueller Faktoren wie Bildung, Emanzipation und wirtschaftlichen Handelns mit einbezieht. Ein Wachstumseffekt durch Altersstrukturverschiebungen wird im Globalen Südens voraussichtlich weniger stark ausfallen als in Südostasien. Gründe hierfür sind langsamere Fertilitätsrückgänge, geringere Arbeitsmarktanteile und unterschiedliche sozioökonomische Rahmenbedingungen. Hinzu kommt, dass heute die Prinzipien von sexueller und reproduktiver Gesundheit und Rechte (SRGR) zu respektieren sind, die während des südostasiatischen Wirtschaftswunders nicht etabliert waren. Dieses Leitbild wurde im Jahr 1994 auf der Konferenz für Bevölkerung und Entwicklung in Kairo hegemonial. Faktoren wie Bildung, soziale Sicherungssysteme, politische Stabilität und globale Abhängigkeiten sind jedoch ebenso entscheidend für den sozialen und wirtschaftlichen Fortschritt.
Entwicklungspolitische Programme propagieren vielfach Familienplanung als Schlüssel zur DD, doch stoßen diese Programme auch auf Kritik. Denn die Institutionen, welche den Diskurs um die DD dominieren, haben zum Teil eine problematische historische Verbindung zu eugenischen oder rassistischen Programmen, was der Glaubwürdigkeit ihrer Positionen schaden kann. Zudem werden die Programme in großen Teilen von eben diesen privaten Stiftungen und Initiativen mit fragwürdiger Historie finanziert, so dass die Macht über die Ausgestaltung derartiger Programme von staatlichen Akteurinnen und Akteuren hin zu privaten Akteuren verschoben wird. Die Interviews und die weiterhin verwendete Literatur zeigen auf, dass langfristige Investitionen in Bildung, Gesundheitsversorgung und soziale Sicherungssysteme größere und nachhaltigere wirtschaftliche Fortschritte bewirken als rein demographische Ansätze. Und trotz ihrer Einschränkungen bleibt die DD ein nützliches Konzept, sofern sie in einen breiteren Kontext eingebettet wird. Die Herausforderung besteht darin das Konzept so anzuwenden, dass es nicht nur in einem technokratischen Verständnis hegemonial wird, sondern dass die Verbindungen zwischen der Verschiebung von Bevölkerungsanteilen, Bildung, Stärkung des Gesundheitswesens und Wirtschafts- wie Arbeitsmarktpolitik verstanden werden.
The integration of the different stakeholder needs and environmental constraints is the key goal of requirements engineering. This demands collaborations between involved parties, to reach “understandability of the system”, what is particularly challenging for collaborations over different organisations. High quality requirements engineering is the key factor to address these challenges. Requirements are input to all development steps and carry the knowledge to exchange—requirements engineering is an overall life-cycle spanning and in its essence a knowledge management task.
The main goal of the T-Reqs framework presented in this thesis is to enable semantic interoperability and to sustain the knowledge by conceptualization of the requirements engineering process applied to European space projects. T-Reqs’ objective is to formally capture the information carried by the requirements to provide top-shelf inputs for the consecutive system and discipline-specific development tasks, in particular within model-based systems engineering. Emphasis is placed on the nature of relationships that exist among requirements and requirement documents. The T-Reqs formalism addresses the structuring of requirements as well as their potential reuse, e.g., in product line development or even between different projects. This implies an overall System Requirements Specification that is distributed in many specifications documents and involves requirements of different levels of abstractions from abstract goals to implementation details. This thesis especially focuses the specification and validation of such requirements documents.
The T-Reqs traceability model provides a means to trace not only individual requirements,
but also consider relations among views such as documents, taking into account the role
they play for stakeholders, especially in reuse. It is shown, how formalization of dependencies, such as for tailoring of standards, enables automated quality checks to facilitate reviews and enhance completeness and consistency of the overall specification.
Towards the structuring of requirements itself, different syntactic template systems aim to
increase the quality of requirement documentation. Within this thesis a comparative evaluation of these notations is conducted, supporting that claim and differentiating the strength and weaknesses of different approaches. Special emphasis is not only laid on documentation quality, but also the usefulness of these semi-formal notations for integration with model-based development methods. This is achieved through the representation of concepts, which can be managed in special contextualised glossaries.
Overall it can be shown that conceptualization of requirements engineering knowledge can support requirements engineering in different aspects and a holistic approach to integrate different tasks lays the foundation for semantic interoperability spanning organizations and life cycle phases.
The production and use of polymeric materials have been increasing continuously for
years. At the same time, the entry of microplastics (MP) – tiny particles resulting from the
wear and tear of these materials – into our environment is growing as well. By now,
awareness of MP has reached broad sections of the population and also research and
development on this field are similarly becoming increasingly important. However,
insufficient standardization and the lack of suitable analytical methods still make
recording and tracking of MP difficult, so that it remains largely unregulated. Mass-based
analytical methods are particularly advantageous for the establishment of legal
regulations. Apart from thermogravimetric methods, however, there are currently few
alternatives in this field. In this context, the use of nuclear magnetic resonance
spectroscopy (NMR), previously only qualitatively applied to MP, has now also been
examined for its quantitative benefits. This work deals with the current state of
quantitative NMR spectroscopy (qNMR) and tests possibilities for optimization and further
development for this purpose. Initially, the reduction of sample volumes and thus
minimized effort and measurement time of the method will be examined by combining
different polymer types into simultaneously measurable groups, as well as the suitability
of homopolymer calibrations for the detection of copolymers. Existing restrictions during
measurement will be adopted, and thus extractive procedures for sample preparation are
implemented. Finally, the influence of real environmental samples will be assessed, and
measures to reduce interfering factors will be taken in to account. As a result, the method
encompasses at least six polymer types, from PMMA, PS, BR, and PVC to PA and PET, as
well as separate approaches for polymers such as PAN and LDPE. A modular sample
preparation protocol, including extractive fractionation into measurement groups and a
chemical digestion method for matrix reduction, will be established and expanded to
include options for diffusion measurement and application to low-field instruments.
Practical application will be presented using real-world examples, such as freshwater
biofilms, as well as the use for quality control of certified reference materials.
Furthermore, initial insights into future development possibilities, like for the detection of
tire abrasion, will be provided.
The presence of synthetic chemicals in the environment can affect both ecosystems and
human health. In particular, the increasing contamination of the aquatic environment by
complex mixtures of anthropogenic trace substances has become a major global concern.
Once released into the environment, these compounds can undergo diverse
transformation processes to form a wide range of transformation products (TPs), which
are commonly unknown. Transformation inevitably alters the pattern of contamination and
exposure, as new substances are formed with frequently different physicochemical
properties, environmental behavior and toxicity in comparison to their precursor
compounds. For instance, TPs can exhibit significantly greater persistence and mobility in
the aquatic environment, posing a threat to both aquatic ecosystems and drinking water
resources. Therefore, TPs need to be considered in the risk assessment and authorization
process of chemicals. However, due to a combination of predictive, analytical, and
regulatory challenges, TPs currently remain largely unrecognized and unregulated. By
addressing these challenges, this thesis comprehensively characterizes the entry paths,
occurrence, fate, and (eco)toxicological relevance of selected TPs in the aquatic system in
Germany. These TPs have been largely overlooked in environmental studies and aquatic
monitoring programs for decades, despite their precursors being produced and used in
large quantities on a global scale.
The highly persistent and mobile substance trifluoroacetate (TFA) has garnered
significant attention in recent years due to its diverse sources, widespread occurrence in
the aquatic environment, and the lack of economically viable options to remove TFA from
contaminated waters. One of the most frequently discussed diffuse sources is the
formation of TFA in the atmosphere through the oxidation of volatile precursors and its
subsequent scavenging from the atmosphere by wet deposition. Despite the previously
reported occurrence of TFA in precipitation, the lack of recent and comprehensive data
has severely limited the understanding of the significance of wet deposition as a source of
TFA to the (aquatic) environment. Thus, in the present work, a nationwide field monitoring
campaign covering all precipitation events over a one-year sampling period was
conducted at eight sites across Germany. Samples were analyzed for TFA using ion
exchange chromatography (IC) coupled to negative-ion electrospray tandem mass
spectrometry (ESI-MS/MS). Of the analyzed samples, 16% exhibited TFA concentrations
≥ 1 μg/L. The precipitation-weighted average TFA concentration of 0.34 μg/L highlighted
that wet deposition alone is responsible for approximately 0.3 to 0.4 μg/L of TFA in
surface waters in Germany. The annual wet deposition fluxes ranged from 91 to
400 μg/m², with the highest fluxes observed in densely populated regions. The annual wet
deposition of TFA for Germany during the observation period was estimated to be 68 t.
The sampling revealed a pronounced seasonality, with the highest concentrations and wet
deposition fluxes of TFA observed in summer. Pearson correlation analyses indicated that
the transformation of TFA precursors in the troposphere is enhanced in summer due to
elevated concentrations of photochemically generated oxidants, primarily •OH, which
ultimately results in increased atmospheric TFA deposition. Overall, the study provided the
first published data on TFA in precipitation in Germany since 1995/96. The derived data
serves as a benchmark for future studies. In addition, it allows for the establishment of
mass balances and can be used to develop models to predict the loads of TFA entering
the aquatic environment from multiple sources.
The lack of robust historical data on the wet deposition fluxes of TFA also impeded long-
term trend analyses. Specifically, a postulated increase in atmospheric formation and
deposition of TFA due to substantial emission increases of numerous volatile TFA
precursors in recent decades remained unquantified. To address this knowledge gap,
archived plant samples were analyzed to evaluate the long-term temporal trends in the
atmospheric deposition of TFA in Germany. A robust and highly sensitive analytical
method for TFA in plant matrices was developed and validated. The method
encompassed a three-step sequential extraction procedure followed by the analysis of the
diluted sample extracts using IC-ESI-MS/MS. Subsequently, archived leaf samples of
various tree species and sampling sites from the German Environmental Specimen Bank
(observation period: 1989−2020) were analyzed for TFA. Statistical analysis revealed
significant (p < 0.05) positive trends in TFA concentrations in plant leaves, which is likely
the result of both phytoaccumulation and increasing emissions of gaseous TFA precursors
over the observation period. The concentrations increased by factors of up to 12 from
1989 to 2020. The highest concentrations (up to ∼1,000 μg/kg dry weight) were found in
Lombardy poplar leaves. Overall, the study presents the first trend analysis of TFA in biota
and raises awareness of the escalating atmospheric deposition of TFA over the past three
decades.
Sulfamate has previously been identified as a TP of the artificial sweeteners cyclamate
and acesulfame in wastewater and drinking water treatment. The preliminary results
indicated that sulfamate concentrations in wastewater treatment plant (WWTP) effluent
are substantially higher than those of other wastewater-borne contaminants. However,
despite its high global production and usage, no information was available on the sources,
occurrence, and environmental significance of sulfamate in the aquatic system in
Germany. To close this knowledge gap, a quantitative monitoring approach of different
urban water cycle compartments was conducted. Target analysis based on IC-ESI-MS/MS
revealed exceptionally high concentrations of sulfamate in wastewater (up to 1,900 μg/L),
surface water (up to 580 μg/L), and finished drinking water (up to 140 μg/L) in Germany.
Considering the limited data on short-term ecotoxicity, approximately 30% of the
sulfamate concentrations detected in groundwater and surface water samples exceeded
the derived predicted no-effect concentration (PNEC) of sulfamate. Therefore, the
potential impact of sulfamate on the aquatic ecosystem in Germany cannot be excluded.
Municipal WWTP effluent was identified as the primary source of sulfamate for the aquatic
system, as its concentrations correlated positively (r > 0.77) with the municipal wastewater
tracer carbamazepine in samples from different waterbodies. Ozonation and activated
sludge experiments demonstrated that sulfamate can be formed through chemical and
biological degradation of various precursors containing a sulfonamide group.
Nevertheless, the transformation of precursors to sulfamate in WWTPs and receiving
waters was found to be quantitatively insignificant, due to the substantial direct use of
sulfamic acid as a descaling agent in domestic and industrial applications. Laboratory
batch experiments, in conjunction with the findings from the sampling conducted at full-
scale waterworks, demonstrated that the commonly applied drinking water treatment
techniques, including ozonation and activated carbon filtration, are largely ineffective in
removing sulfamate. Bank filtration was identified as the only option to efficiently eliminate
sulfamate from contaminated raw water resources (removal: 62% to 99%). Overall, the
study presents the first comprehensive analysis of sulfamate in the urban water cycle and
suggests that there may be other high production volume inorganic chemicals that are
currently overlooked in environmental studies and monitoring programs.
Despite pantoprazole (PPZ) being one of the most widely prescribed human
pharmaceuticals globally, consistently low concentrations of this proton-pump inhibitor in
environmental water samples have been documented. This can be attributed to the
extensive metabolism of PPZ within the human body, with only minor amounts of the
parent compound being excreted. Since environmental monitoring and risk assessment
for regulatory purposes focus on the parent substances of pharmaceuticals, it was
assumed that the current environmental exposure associated with the use of PPZ is
considerably underestimated. In the presented thesis, 4′-O-demethyl-PPZ sulfide (M1)
was identified as the most relevant PPZ metabolite for environmental analysis. This was
achieved by applying reversed-phase high-performance liquid chromatography (RP-
HPLC) coupled to high-resolution mass spectrometry (HRMS) to urine samples of a PPZ
user, as well as to municipal wastewater. M1, which had not been investigated in previous
monitoring studies, was found to be ubiquitous in WWTP influent and effluent (max.:
3 μg/L, detention frequency: 100%) as well as in surface water (max.: 1.2 μg/L; detection
frequency: 97%) in Germany. Its average surface water concentration was approximately
30 times higher than that of the parent compound PPZ. Moreover, quantitative structure-
toxicity relationship (QSTR) modeling indicated a lower preliminary freshwater PNEC for
M1 (4.8 μg/L) compared to PPZ (28 μg/L). The analysis of archived suspended particulate
matter (SPM) samples from the Rhine at Koblenz revealed that the concentrations of M1
increased significantly from 2005 to 2015 and were positively correlated with the
prescription volume of PPZ. Conventional biological wastewater treatment was found to
be insufficient to remove M1 (average removal: 22%). Laboratory-scale experiments and
the analysis of samples taken after different treatment steps of an advanced full-scale
WWTP demonstrated that post-treatment with activated carbon as well as ozonation can
significantly improve the removal of M1 and PPZ during wastewater treatment, thereby
reducing their release to the aquatic environment. During ozonation, a rapid oxidation of
M1 was observed, accompanied by the formation of several ozonation products, which
were proposed for the first time. The identity of the main ozonation TPs of M1 was
confirmed through the synthesis of reference compounds. Their detection in samples
collected after the ozonation step of a full-scale WWTP demonstrated the transferability of
the laboratory-scale ozonation experiments. M1 was found to be sufficiently removed from
contaminated source waters (max. raw water concentration: 0.25 μg/L) by bank filtration
under different redox conditions (removal ≥ 80 %) and by other commonly applied
purification processes in drinking water production. In summary, this study revealed that
the environmental exposure and risk associated with the use of PPZ have been previously
underestimated, which likely extends to other human pharmaceuticals. Therefore, these
findings call for more sophisticated approaches to environmental monitoring and risk
assessment of pharmaceuticals that take TPs into account.
This thesis provides an in-depth understanding of the entry paths, occurrence, fate, and
environmental significance of selected TPs in the aquatic system in Germany. It
significantly advances our understanding of the introduction of TFA into the water cycle,
by characterizing the source of wet deposition and elucidating long-term temporal trends
of atmospherically deposited TFA. Additionally, the thesis gives comprehensive insights
into the formation, behavior, removability, and potential (eco)toxicological risks of
sulfamate, PPZ and its TPs. The thesis addresses key challenges in assessing and
integrating TPs into chemical management and presents solutions to overcome these
challenges. Finally, it highlights the urgent need for increased focus on TPs in research,
aquatic monitoring, and regulation to safeguard the environment and human health.
Age-structure changes are an intrinsic feature of the demographic transition from high mortality and
fertility to low mortality and fertility. Initially, the demographic transition increases the share of the
working-age population, creating opportunities for economic boosts through demographic dividends.
Particularly some Asian countries have benefited greatly from such demographic dividends in the past.
Overtime, however, the demographic transition leads to population ageing, which brings various
implications for economies and societies worldwide. In Asia, many countries are ageing rapidly, while
others continue to maintain a relatively young age structure. These differences may also be related to
migration. Migration is also often discussed as a possible policy response to counteract population
ageing. This thesis identifies global patterns in changes in the share of working-age population and
examines associated demographic factors. With a specific focus on Asian countries, it assesses the
impact of migration on population ageing in the past and its potential impact in the future.
All analyses in this thesis are based on data from the United Nations’ World Population Prospects 2022.
First, past, present and projected age-structure changes are analyzed in the context of demographic
dividends, covering 148 countries worldwide. Cluster analyses are conducted to identify patterns of
age-structure changes between 1950 and 2100, while linear regression models are used to detect
associations between these changes and relevant demographic factors. Second, the impact of
migration on past age-structure changes is assessed for the period 1990-2020 in 51 Asian countries
using decomposition analysis. An existing decomposition approach is extended to incorporate the
concept of prospective age, which accounts for differences in life expectancy when assessing
population ageing. Third, the potential impact of migration on population ageing between 2022 and
2050 is analyzed in eleven Asian countries by adopting the United Nations’ replacement migration
concept. In this analysis, both chronological and prospective indicators of population ageing are
applied.
The results underline the heterogeneity of global age-structure changes in the course of the
demographic transition. This underscores the need to take into account a country’s specific
demographic development when assessing its potential for a demographic dividend. The experience
of some Asian countries, where rapid fertility declines in the past have been followed by sharp
increases in the share of the working-age population, is only one of several global patterns. Differences
in age-structure changes are associated with differences in fertility, but also with migration and
population momentum – two factors that have so far received relatively little attention in the
discussion of demographic dividends. Focusing on Asian countries, this thesis reveals that differences
in population ageing across countries are at least partly driven by migration. However, the volume of
migration potentially required to offset population ageing over the next decades seems unrealistically
high in most countries. The results emphasize that migration can play a role in age-structure changes,
but population ageing can barely be halted by immigration alone. Thus, comprehensive policies seem
to be a key factor in ensuring further development in ageing countries in Asia and beyond.
In der Dissertation Freiheit und Werte bei Jean-Paul Sartre wird das Verhältnis zwischen
Freiheit und Werten in der Philosophie von Jean-Paul Sartre analysiert. Es wird untersucht, auf
welche Weise die existenzielle Freiheit des Menschen mit seinen moralischen und
außermoralischen Werten nach Sartre zusammenhängt. Ziel der Untersuchung ist es, einen
Beitrag zum Verständnis von Sartres Wertlehre sowie seiner Ethik der Authentizität zu leisten.
Grundlage für die Untersuchung bilden neben Sartres philosophischen Werken, seine
literaturtheoretischen sowie politisch-gesellschaftlichen Schriften. Ausgehend von einer
Analyse der existenziellen Freiheit bei Sartre wird der vielschichtige Zusammenhang zwischen
Freiheit und Werten bei Sartre analysiert und in den Gesamtkontext seiner Philosophie gestellt.
Die Dissertation zeigt, dass sich in Sartres Werk sowohl eine subjektivistische als auch eine
objektivistische Wertlehre ausmachen lässt. Während Sartre in vielen Passagen seines Werkes
die subjektivistische Position vertritt, dass alle moralischen und außermoralischen Werte auf
das bewertende Subjekt zurückgehen, präsentiert er an anderen Stellen seines Werkes den
moralischen Wert der Freiheit sowie den außermoralischen Wert des An-sich-für-sich.
Abgesehen von jenem Spannungsverhältnis macht die Untersuchung deutlich, dass der
moralische Wert der Freiheit für Sartre innerhalb seiner gesamten Philosophie von großer
Bedeutung ist. Eine Verwirklichung jenes Wertes ist nach Sartre nicht nur zentraler Bestandteil
einer engagierten Literatur, sondern auch für eine gerechte Gesellschaft wesentlich.
Eisenbahnunternehmen setzen Condition Monitoring Systeme (CMS) zur Überwachung ihrer Anlagen und Komponenten ein. CMS sind im Risikomanagement der Branche relevant, aber ihr Einsatz leidet unter einem Präventionsparadoxon: Sie werden oft erst nach Schäden oder Richtlinien eingeführt. CMS können auch den Instandhaltungsaufwand reduzieren. Bei den streckenseitigen WTMS tragen Infrastrukturbetreiber die Kosten, während Verkehrs-unternehmen den Nutzen durch effizientere Instandhaltung sehen. Um fundierte Geschäftsmodelle zu entwickeln, muss deshalb der Nutzen von CMS quantifiziert werden. Die Informationsqualität, einschließlich der Sensoren und der Symptomaussagekraft, beeinflusst diesen Nutzen. Diese Verbindung von Anwendungswert und Nutzen ist bisher unzureichend erforscht. Aufgrund dessen ist das Forschungsziel folgendermaßen gesetzt worden: Entwicklung eines systemdynamischen Modells und eines Verfahrens zur Erfassung des Informationswertes von Condition Monitoring Systems, anhand des Fallbeispiels der Radsatzlagerüberwachung im Eisenbahnverkehr.“
Das Forschungsziel dieser Arbeit umfasst als Erkenntnisziel das Verständnis der Zusammenhänge und Wechselwirkungen im CMS und dabei den Nutzen des Einsatzes der Systeme zu bewerten. Das Gestaltungsziel beinhaltet die Untersuchung der Eignung des systemdynamischen Verfahrens. Zur Erreichung dieser Ziele sollen folgende Forschungsfragen beantwortet werden:
1. Welche Ziele verfolgen die Eisenbahnorganisationen in Bezug auf den Betrieb ihrer Radsatzlager und inwiefern können die Informationen aus den Messdaten der heutzutage eingesetzten Radsatzlagerüberwachungssysteme zur Zielerreichung beitragen?
2. Lassen sich mit der systemdynamischen Vorgehensweise, die für die Bewertung von CMS relevanten Wechselwirkungen im Eisenbahnsystem abbilden?
3. Lässt sich anhand der systemdynamischen Vorgehensweise untersuchen, welche Informationen für die Erhöhung des Nutzens der Radsatzlagerüberwachungssysteme relevant sind?
Die Ergebnisse der Arbeit erwirken die Erkenntnis, dass die Methodik dazu geeignet ist, die relevanten Zusammenhänge und Wechselwirkungen darzustellen und mithilfe der Simulationsergebnisse relevante Instandhaltungsstrategien und der Nutzen von RDMT zu bewerten. Damit sind die Ergebnisse sowohl für die Forschung als auch für Entscheidungsträger in der Eisenbahnbranche relevant.
Water is the basis of all life, a biotope for a variety of organisms and an important component of the
natural balance. For this reason, it is essential to protect water from contamination by anthropogenic
organic micropollutants (MPs) and to develop various innovative strategies for the treatment and reuse
of wastewater. Conventionally biologically treated municipal wastewater contains many organic MPs
that pose a potential threat to aquatic ecosystems and drinking water resources. To date, the focus has
been on physicochemical processes such as activated carbon treatment or ozonation to improve the
removal of MPs in wastewater treatment plants (WWTPs), while knowledge of biological removal
processes and ways to optimize the biological removal of organic MPs is comparatively limited.
Especially in arid and semi-arid regions, treated wastewater is also an important resource for wastewater
reuse for irrigation or drinking water treatment. In consequence of increasing droughts due to climate
change, the reuse of treated wastewater is also increasingly being discussed in Germany. Often the water
is reused after targeted groundwater recharge, while concepts for optimizing the removal of MPs during
soil passages are still scare. In order to assess the potential and limitations of biological wastewater
treatment as well as targeted groundwater recharge for the removal of organic MPs, a better knowledge
of the biological biotransformation processes and the environmental conditions influencing them is
required. Microbial communities and their enzyme pools play a key role in these processes. However,
the influence of environmental conditions on the composition and functional characteristics of microbial
communities, and how this in turn affects the biotransformation potential of MPs with different
structural characteristics, has been little studied. In addition, knowledge about MP-biotransforming
bacteria is often derived from enrichment or even pure culture studies, which are not directly transferable
to the environment.
Against this background, this dissertation focuses on the systematic investigation of the
biotransformation of MPs in contact with activated sludge (simulation of biotransformation processes
in biological treatment stages of WWTPs) and filter materials (simulation of processes in groundwater
recharge systems) under defined laboratory conditions. The aim is to elucidate relationships between
the composition and functional characteristics of microbial communities, microbiologically determined
biotransformation processes and their optimal process conditions, as well as the chemical structure and
primary enzymatically catalyzed biotransformation reactions of MPs.
The first part of the work focuses on the composition of microbial communities and the
biotransformation of MPs depending on defined process parameters in five differently operated
wastewater reactors, divided into two reactor cascades at pilot scale and one full-scale WWTP. The first
cascade consisted of three reactors, the first of which served as a reference reactor with conventional
activated sludge (CAS) treatment. The following reactors operate under anoxic to anaerobic and strictly
anaerobic conditions, respectively. The other cascade consists of two reactors, the first anaerobic and the second aerobic, followed by a simplified vessel to prevent nitrate output, as half of the effluent was
recirculated to the first anaerobic reactor. All five reactors and the WWTP were analyzed for the
biotransformation of 33 MPs and the composition of the microbial community by LC-MS/MS and 16S
rRNA gene sequencing, respectively. The results showed a slight but significant improvement in the
overall biotransformation of MPs in the reactor cascades (about 20%) compared to the WWTP. In
particular, the biotransformation of compounds that are not or only slightly degradable (< 30%) in
conventional wastewater treatment, such as diatrizoate, venlafaxine and diclofenac, was significantly
improved (about 70%). Twelve of the 33 MPs showed an increase in biotransformation of at least 30%
compared to the reference reactor and the WWTP. In detail, the reactor cascade consisting of the
anaerobic pre-treatment showed three times more MPs than the reactor cascade with the anaerobic post-
treatment. Although the environmental conditions (nutrient availability and redox conditions) differed
considerably between the reactors, molecular analysis of the microbial community revealed a core
community of 143 genera, with 54% of the taxa belonging to the phylum Proteobacteria, with the beta
subdivision as the most dominant class. On the other hand, a specialized community consisting of 90
genera was identified that contributed most to the differences between the reactor communities. These
genera were shown to reflect the prevailing nutrient, redox and operating conditions of each treatment.
It was also found that the relative abundances of several genera of the specialized community correlated
with the biotransformation of certain MPs as well as with process parameters (especially redox
conditions). These genera may not necessarily be directly involved in the biotransformation of MPs, but
could be promising biological indicators for the establishment and control of operating conditions
favorable to the biotransformation of certain MPs. For the two reactor cascades analyzed, it was
concluded that the redox conditions as well as the carbon supply were essential factors for the
composition of the specialized community and the biotransformation of the MPs. In addition, the 16S
rRNA gene amplicon sequencing proved to be a complementary tool to confirm process conditions by
correlation. In conclusion, the efficiency of MP biotransformation in conventional WWTPs depends on
key parameters such as redox conditions, biodiversity or the presence of several genera of specialized
microbial communities identified as indicator organisms.
Against the background of previous knowledge that biofilms from moving bed biofilm reactors
(MBBRs), which have been used so far in a few WWTPs, are more efficient in biotransforming certain
MPs, the second study used laboratory batch experiments to investigate the extent to which the
biotransformation potential of carrier-attached biofilms and suspended sludge from hybrid MBBRs
differ between three WWTPs, and whether these differences were also reflected in the composition of
the bacterial communities. The 31 MPs investigated were grouped according to their biotransformation
rates and examined for relationships between the biotransformation behavior and the known primary
biotransformation reactions are discernible. In general, the study confirmed the potential of hybrid
MBBRs for improved biotransformation of a variety of MPs. This could be attributed to an increased
biotransformation potential of the carrier-attached biofilms, especially for oxidatively degradable substances such as trimethoprim, diclofenac and mecoprop. Correlation analyses showed statistically
significant relationships between the occurrence of certain bacterial genera (e.g. Acidibacter, Nitrospira
or Rhizomicrobium) and the biotransformation rates of certain MPs. Thus, some of the identified genera
were also discussed as suitable indicators for the biotransformation potential of suspended sludge or
carrier-attached biofilm.
In the third part of the work, the biotransformation of up to 78 MPs was investigated under different
redox and substrate conditions in a defined column system at laboratory scale as well as ex situ under
uniform incubation conditions by incubating the column filter material in batch experiments. MPs were
categorized based on their biotransformation behavior and how well these categories matched primary
transformation reactions known from the literature or predicted using the Eawag pathway prediction
system for modelling microbial biotransformation pathways. The column system investigated consisted
of two large columns filled with technical sand, an intermediate aeration and four smaller columns, all
connected in series. In the first column, characterized by a carbon-rich environment with high biomass
and strong oxygen depletion, 23 MPs were efficiently removed (>80% removal), while 19 substances
were better or exclusively removed under carbon-limited oligotrophic conditions in the columns after
re-aeration. While the MPs removed predominantly in the first column were mostly attributed to
biotransformation by comparatively ubiquitous and fast transformation reactions such as the oxidation
of alcohols or amide hydrolysis, the biotransformation of MPs removed more efficiently under the oxic
and oligotrophic conditions in the rear columns was characterized by slower transformation reactions
such as N-dealkylation of primary and secondary amines or the hydroxylation of aromatic rings. In
addition, several specific reactions described in the literature, such as the cleavage of C-Cl and C-O
bonds, could only be identified under oligotrophic conditions. The results suggest that conditions of
limited carbon availability may favor the development of alternative metabolic biotransformation
pathways. Furthermore, the observed association between system-specific MP removal and the expected
primary biotransformation reactions from the literature and prediction systems could serve as a basis for
accurately identifying the relevant enzymes in future studies, using metagenomic or metatranscriptomic
data.
Based on these considerations, molecular biological investigations were carried out in the fourth part of
this work by generating sequence-based data complementary to the biotransformation rate constants
during the batch experiments carried out in the third study. A first aim was to identify a statistical relation
between the microbial composition, the process conditions and the nutrient availability as well as the
biotransformation potential of 42 MPs depending on the biomass in the columns of the system.
Furthermore, the metabolic activities of the microbial communities of the first two columns of the
system were analyzed and the identified active enzymes were assigned to known metabolic pathways
and the activities were compared. In addition, the extent to which the biotransformation potential of the
columns was also reflected in the activity of enzymes that have been proven to belong to biotransformation pathways of MPs was investigated. To this end, modern sequencing methods were
used to generate data on the composition of the microbial community (16S rRNA gene sequencing) and
its actual activity in the form of expressed genes (metatranscriptome sequencing). The biotransformation
rates from the batch experiments of the third study were used by normalizing them with the gene copy
numbers (kbio), which were representative of the biomass. For half of the MPs, the highest normalized
kbio values were identified in the rear columns with increased carbon-limiting conditions. Furthermore,
most of the MPs investigated, such as sulfathiazole, sulfamethoxazole or rufinamide, showed an
improved biotransformation potential in these columns. The higher biotransformation potential under
carbon-limiting conditions was also confirmed by metatranscriptomic analysis, where an increased
metabolic capability and a higher functional activity to degrade MPs were observed in the carbon-
limiting column compared to the first nutrient-rich column. Taxonomic analysis revealed a decreasing
trend in biodiversity with a simultaneous increase in carbon-limiting conditions. Furthermore, the
microbial community differed depending on the nutrient and process conditions of the column materials
analyzed. However, within the carbon-limiting columns, the microbial community was similar and were
dominated by the genus Pseudomonas. By relating the biotransformation of MPs to the relative
abundance of taxa in the carbon-limiting columns, the genera of the phylum Acidobacteria and the
classes Alpha- and Gammaproteobacteria showed particularly high associations. In addition, four genera
showed a statistically positive correlation with the two structurally similar MPs sulfamethoxazole and
sulfathiazole.
Overall, no general improvement in biotransformation could be found for all MPs under the conditions
considered, with system- and condition-specific changes observed for individual compounds. However,
the studies indicated favorable environmental conditions for groups of MPs that showed increased
biotransformation linked with high abundant taxa, especially under carbon-limiting conditions and in
carrier-attached biofilms.
Within the scope of this work, new test methods were developed to determine the characteristic product properties of ladle well filler sands. Background is that up to now, there are no approved test methods for these product properties such as pourability, sintering behavior and infiltration behavior.
To substantiate this deficiency in testing methods, the general state-of-the-art testing methods of cohesionless bulk materials is presented and a variety of publications on ladle well filler sands are reviewed for their applied testing methodology.
The development of new test methods for the characterization of ladle well filler sands was based on test methods that were in part already standardized, such as the permeability measurement (infiltration) according to DIN 18130-1 from the field of geotechnics, the determination of the flow time with flow cups for coating materials (flowability) according to DIN EN ISO 2431:2011 and the monotonic heating method (MMH) according to ASTM E2584-20 for determining the thermal conductivity.
Since these test methods were not designed for examining free-flowing, non-cohesive bulk materials and therefore not for examining ladle well filler sand, it was necessary to adapt the parameters of the standardized test methods for use with well filler.
The parameters of the test methods mentioned (DIN 18130-1; DIN EN ISO 2431 and ASTM E2584-20) were checked for applicability and transferability to ladle well filler sand and new suitable parameters were added. The reproducibility of the results of the test methods was checked by a series of tests and the decisive influencing factors of ladle well filler sand on the results were determined.
The relevance of the results of the newly developed test methods was verified based on results from the European research project ILORA ("Improvement of Ladle Opening Rates", funded by the "Research Fund for Coal and Steel" RFCS, 2013-2016) and numerous publications with results from other research projects.
From the results of the newly developed test methods, key figures for the pourability, sintering behavior and infiltration behavior of ladle well filler sands were derived. The combination of these key figures was converted into a holistic analysis of ladle well filler sands, finally leading to an evaluation grid for well fillers. It is exactly that grid respectively network, that now allows for the first time to make qualified and reliable statements about the suitability for use of ladle well filler sands prior to industry application, which significantly facilitates the new development of such well fillers.
Microplastics (MP), i.e., plastic particles < 5 mm, are perceived as a threatening envi-
ronmental and human health issue. Growing public interest in this class of contaminants
requires standardized and harmonized methods for their quantification. While an abun-
dance of analytical methods (both particle-based and mass-based) for the detection of
microplastics is available, existing studies on the quantity of MP in the environment lack
comparability. Therefore, the aim of this work was to establish a fast, reliable screen-
ing method for the quantification of the most common synthetic polymers in complex
environmental samples.
This was accomplished by a two-step pressurized liquid extraction (PLE) followed by
analysis via pyrolysis coupled to gas chromatography and mass spectrometry (Py–GC–
MS). In the first extraction step, a large part of the organic matrix was removed with
methanol at 100 ∘C and 100 bar, followed by a second step with tetrahydrofuran at
185 ∘C and 100 bar to extract the polymers that were subsequently adsorbed to silica
gel and measured with Py–GC–MS. With the developed method, limits of quantification
in an environmentally relevant concentration range of 7–8 μg g−1 for the most common
thermoplastic polymers polyethylene (PE), polypropylene (PP), and polystyrene (PS)
were achieved.
In order to improve the robustness of the method, poly(styrene-d5) (PSd5) was initially
applied as internal standard. However, further analyses revealed a deuterium–hydrogen
exchange during Py–GC–MS measurement, which was catalyzed by the inorganic ma-
trix. This effect was thereupon systematically investigated and poly(4-fluorostyrene) was
established as a new, stable internal standard.
While the developed method enabled the quantification of PE, PP, and PS, several other
polymers had to be excluded. In particular, the quantification of poly(ethylene tereph-
thalate) (PET) proved challenging via Py–GC–MS. A variety of catalytic effects by the
inorganic matrix was revealed and systematically investigated, e.g., changes in pyrolysis
product distribution. Several different sample preparation approaches failed to resolve
these issues. PLE led to a depolymerization of PET which was also catalyzed by the
inorganic sample matrix.
After further optimization and reduction of false positives, the developed method has
the potential to be included in future standardized procedures for MP quantification. It
provides a fast, robust analysis of MP in complex samples, while also considering widely overlooked matrix effects. Potential quantification approaches for other polymers that are
not included in the developed method (e.g., tire wear particles, paint particles) are also
discussed in this thesis.
Invasive crayfish are a serious threat and ecosystem engineers that compete with native species for shelter and food resources, show combative interactions against native species, and negatively affect species diversity. In this work, I used two North American invasive crayfish species that have successfully spread across Europe spinycheek crayfish (Faxonius limosus) and signal crayfish (Pacifastacus leniusculus) as models to assess their potential Impacts on native benthic fish, stone loach (Barbatula barbatula) and bullhead (Cottus gobio), which are among the most common benthic fish in Europe. I have investigated the competition for shelter and agonistic interactions between these invasive crayfish species and the native benthic fish species under laboratory conditions have employed a multi-object tracking algorithm to monitor and visualize the fish's and crayfish's activity inside the experimental tank. Spinycheek and signal crayfish successfully displaced both benthic fish species from their shelter. Both crayfish species attected the behaviour of stone loach, reducing its activity and increasing its hiding outside the shelter. Although bullheads did not reduce shelter use, they displayed similar behavioural changes, if less intense, In addition, I demonstrated remarkable aggressive interactions by both crayfish species against stone loaches and bullheads. Further investigations were performed to assess how variations in crayfish density influence the structure of invertebrate communities. I conducted comparative analyses of community composition across nine stream sites with varying densities of signal crayfish in Wied Stream, Germany. These findings revealed a correlation between crayfish density and diversity and evenness of invertebrates, suggesting that signal crayfish pose a substantial threat to Invertebrate biodiversity
In conclusion, this thesis reveals that these invasive crayfish species not only compete with native biota for essential resources but also fundamentally alter the ecological dynamics of freshwater habitats. This thesis emphasises the urgent need to manage and mitigate the potential consequences of crayfish invasion and to preserve native aquatic ecosystems.
In sowohl den Kulturwissenschaften als auch den Kognitionswissenschaften haben sich neuere
Theorien etabliert, welche verstärkt die Verkörperung und Materialität unseres Denkens, Fühlens und
Handelns betonen. Diese Dissertation untersucht aus der Perspektive der philosophischen
Anthropologie, wie die ‚material culture studies‘ sowie die ‚embodied cognition‘-Forschungen
zusammengedacht werden können. Im Fokus liegt hier der Phänomenbereich der Musik: Denn nicht
nur spielen bei dieser eine Vielzahl von Gegenständen der materiellen Kultur eine zentrale Rolle
(Instrumente, Tonträger, etc.), sondern auch der Körper des hörenden oder musizierenden Subjekts.
Die philosophische Reflexion erfolgte vor allem aus der Perspektive des Enaktivismus, einer
spezifischen Strömung der ‚embodied cognition‘, ergänzt durch Konzepte und Ansätze aus den
Traditionen der Phänomenologie und des Pragmatismus. Diese wurden nicht nur herangezogen, um
zusammen mit dem enaktivistischen Denken auf der Sachebene die verkörperte Natur der Musik
darzustellen, sondern auch um die methodische Problemstellung zu behandeln: Der
phänomenologische Gedanke des Doppelaspekts von Leib und Körper (Fuchs) und die pragmatistische
Anthropologie der Artikulation (Jung) dienten eben dazu, das Zusammendenken von Kognitions- und
Kulturwissenschaften in Bezug auf Musik zu ermöglichen.
So ließen sich verschiedene Detailfragen zu den beiden größeren Themenkomplexen der
Wahrnehmung von und des Umgangs mit Musik(-kultur) beantworten, inklusive solche bezüglich der
Rolle des Affektiven und des Sozialen sowie nach der möglichen Ausdehnung von Kognition und Leib.
Zusätzlich ergab sich so auch eine exemplarische Demonstration der methodologischen Gedanken, da
diese Fragestellungen anhand der genannten Konzepte untersucht wurden und so deren Fruchtbarkeit
für das Verbinden von natur- und kulturwissenschaftlichen Forschungen dargelegt werden konnte.
Schülerinnen und Schülern eine wirkungsvolle Begegnung mit Literatur zu ermöglichen, stellt hohe Anforderungen an die Unterrichtsvorbereitung: Material muss ausgewählt und gestaltet, Lernaufgaben müssen vorbereitet und eingesetzt und Unterrichtsgespräche müssen antizipiert und moderiert werden. Gerade von Referendarinnen und Referendaren können die damit verbundenen Anforderungen als sehr herausfordernd – auch als überfordernd – empfunden werden.
Mit dem Ziel, den auszubildenden Lehrerinnen und Lehrern ein erstes handhabbares Instrumentarium zur Planung und Gestaltung des Literaturunterrichts an die Hand zu geben und ihnen dadurch zu frühen ‚Gelingenserfahrungen‘ zu verhelfen, wurde am Studienseminar für das Lehramt an Gymnasien in Koblenz ein Ausbildungsmodell entwickelt. Der Erörterung, wie die Implikationen dieses Modells auch auf den Literaturunterricht übertragen werden können, widmet sich die Dissertation.
Auf die verschiedenen Faktoren zur Steuerung des Unterrichts – die Phasierung der Stunde, die Formulierung von Lernaufgaben, die Darbietung des Materials und die Moderation der Unterrichtsgespräche – blickend, werden unterschiedliche Handlungsoptionen vorgestellt und didaktisch ausdifferenziert. Stichprobenuntersuchungen aus zwei Unterrichtsstunden – zu Rilkes Gedicht ‚Natur ist glücklich‘ (Klasse 9) und zu Bettina Wegners Lied ‚Gebote‘ (Klasse 12) – veranschaulichen und konkretisieren die Positionen.
Aus der Verbindung der didaktischen Überlegungen mit den empirischen Stichprobenuntersuchungen entsteht der Entwurf eines neu nuancierten Ausbildungsmodells für den hermeneutisch-diskursiven Literaturunterricht.