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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.
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.
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.
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.
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.
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 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.
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.
Bacterial communication via chemical messengers, also called quorum sensing (QS), plays a major role in bioluminescence, pathogenicity and biofilm formation of bacteria. For humans, biofilm formation is undesired in areas as shipping, healthcare and water treatment because it hinders technical processes and there may be health risks for humans. To prevent the formation of unwanted biofilms (so-called biofouling), for example in shipping industry, different antifouling agents such as copper oxide are used. In water treatment, disinfectants such as sodium hypochlorite are used to reduce the occurrence of pathogens as well as build-up biofilms to ensure microbiologically safe water. Common antifouling agents in the marine industry are usually based on their toxicity and their release into the environment. These agents could be dangerous for the ecosystem and sustainable alternatives are needed. For this purpose, nanomaterials were developed which, according to the researcher’s hypothesis, influence the QS-system of Gram-negative bacteria and thus prevent biofouling. The hypothesis claims that the nanomaterials mimic the defence strategy of marine organisms with vanadium-bromoperoxidases (V-BrPO) and produce via a catalytic process reactive halogen species such as hypobromous acid. Reactive halogen species also play a major role in disinfection with e.g. sodium hypochlorite. The disinfecting effect is based on oxidation processes with biological material of the microorganism. But, also an influence on the QS system of Gram-negative bacteria was described, which has not yet been investigated in detail. In this thesis, the hypothesized influence of the developed nanomaterials and that of the disinfectant free active chlorine (FAC) on the QS-system of Gram-negative bacteria are investigated. The aim of this thesis was to expand the knowledge about QS molecules (QSM) with regard to degradation processes induced by reactive halogen species and how to analyse QSMs and their transformation products (TP). This allows better assessment at the level of bacterial communication of processes such as antifouling and disinfection. In order to study the communication of Gram-negative bacteria, liquid chromatography – tandem mass spectrometry (LC-ESI-MS/MS) was used to develop a sensitive and selective method for the quantification of QSMs N-acyl-homoserine lactones (AHL), which provide information about QS. Due to the high diversity of AHLs and their low concentrations in the environment a solid-phase extraction was developed and optimized for 34 AHLs. The validated method can measure AHLs in the low ng/L concentration range in several matrices such as surface water, treated wastewater or bacterial supernatants. AHLs were detected in river water (in total 5 AHLs) and treated wastewater (in total 3 AHLs), which shows that the developed method is satisfactory for the detection of environmental concentrations. Furthermore, an unanticipated variety of AHLs was detected in the bacterial supernatants of Pseudomonas aeruginosa (in total 8 AHLs), Phaeobacter gallaeciensis (in total 6 AHLs), and Methylobacterium mesophilicum (in total 15 AHLs). To our knowledge these AHLs have not been described in the literature for these bacterial cultures so far. Quantification of AHLs was performed using a standard addition method and concentrations up to 7.3±1.0 μg/L (3-Oxo-C12-AHL in the bacterial supernatant of P. aeruginosa) were determined. Batch experiments were performed with cerium dioxide nanocrystals (NC) and V-BrPO to investigate the antifouling effects and the proposed biomimetic action of the NCs. Additionally, free active bromine (FAB) was used to elucidate the influence of reactive halogen species on QSMs and the mechanism of both catalysts. The batch experiments were performed for three QSMs and the formation of brominated, hydrolysed and oxidized TPs was identified with high resolution mass spectrometry (HRMS). For N-β-ketocaproyl-homoserine lactone (3-Oxo-C6-AHL), N-cis-tetradec-9Z-enoyl-homoserine lactone (C14:1-AHL) and 2-heptyl-4-quinolone (HHQ) a fast degradation and moiety-specific transformations were observed. In total, 17 TPs were identified at different levels of confidence. In addition, the same TPs were observed in the batch experiments with FAB as in the batch experiments with NC and V-BrPO. This shows on the one hand that the used cerium dioxide NCs led to a biomimetic transformation behaviour for QSMs of Gram-negative bacteria as known for the enzymes V-BrPO. And on the other hand, the results of the FAB experiments indicate that the catalytic processes take place via the formation of reactive halogen species. Furthermore, the transformation pathways for the QS groups unsaturated AHLs and alkyl quinolones have not yet been described in the literature and the knowledge about their degradation could be expanded with this study. Reactive halogen species also play a major role in disinfection processes with FAC. Additionally, FAC is one of the most potent inhibitors of QS compared to other disinfectants. However, a profound knowledge of degradation mechanisms of QSMs is lacking as well as knowledge on a possible impact on QS-controlled processes such as pathogenicity or biofilm formation. Therefore, the degradation behaviour of six representative QSMs of Gram-negative bacteria with FAC was investigated. A complete primary degradation was observed for para-coumaroyl AHL (pC-AHL), C14:1-AHL, HHQ and 3-Oxo-C14-AHL. In our study the primary kinetics and transformation pathways were studied in detail for pC-AHL, C14:1-AHL and HHQ. The reaction order varied between 1.19 (±0.07) (pC-AHL) to 1.62 (±0.13) (HHQ) at pH 7.0, indicating that different reactive species (e.g. hypochlorous acid and dichlorine monoxide) are involved in the transformation. In batch experiments with varying pH, the first-order rate constants show different trends for the investigated QSMs. For C14:1-AHL and HHQ, the first-order rate constants decreased from pH 6.0 to pH 8.5, which was mainly caused by the decreasing concentration of the reactive species hypochlorous acid and dichlorine monoxide in this pH range. In contrast, a maximum of the first order rate constant was observed for pC-AHL at pH 8.5 ranging from pH 6.0 to 10. In addition to the concentrations of reactive species, the phenol/phenolate ratio strongly influenced the first-order rate constants for pC-AHL. In total, 29 TPs (pH = 7.0) were identified by LC-ESI-HRMS and the related transformation pathways were proposed. The impact of FAC on QS can be expanded to the QSM groups unsaturated AHLs, quinolones and coumaroyl AHLs. Furthermore, the observed reaction mechanisms can be transferred to structurally similar QSMs such as 2-heptyl-1-hydroxyquinolin-4(1H)-one (HQNO) to further understand QS-controlled processes during chlorination. Finally, an interdisciplinary approach with the cooperation partners (microbiology and synthetic chemistry) of the University of Mainz was carried out for a profound understanding of the antifouling effect of cerium dioxide NCs in bacterial cultures. The developed methods and the results of the degradation experiments obtained in the previous studies were used to elucidate the processes also in a more complex biological system. Gram-negative specific inhibition of the biofilm formation was observed for synthesised and characterised cerium dioxide NCs for five different bacterial cultures. Due to the different QSMs used by the bacterial species, an influence on the AHL-system of the Gram-negative bacteria was suspected. In bioassays (Agrobacterium tumefaciens), a reduced QS activity was determined for the experiments with cerium dioxide NCs and measurements of the bromide concentration indicated the consumption of bromide. However, the detected brominated TPs from the previous studies could not be observed with LC-ESI-HRMS and LC-ESI-MS/MS in liquid-liquid extracts of the bacterial supernatant. Further biological degradation processes are here suspected. However, using non-target approaches, the catalytical bromination of HQNO was observed, which can be associated with QS. The bromination was verified by an additional batch experiment with HQNO and cerium dioxide NCs. The repression of the Pseudomonas quinolone signal (PQS) production and biofilm formation in P. aeruginosa through the formed brominated HQNO on surfaces with coating (cerium dioxide NCs) indicates the non-toxic nature of this strategy. The results of this thesis provide a new insight into the occurrence of QSMs and their transformation in relation to halogenation. In addition, the mechanistic investigations on cerium dioxide NCs show the possible relevance of these transformation processes. This new knowledge can be an important basis for the development of new sustainable antifouling agents and possibly for a better understanding and optimisation of disinfection processes.
During the development phase of plastic components, simulations are being used to an increasing extent. Against the background of product requirements and the inevitable necessity of conserving resources, the expanded use of simulation tools is an essential part of the solution. Among available methods, but so far underutilized with respect to real-life processes, is the molecular dynamics simulation. By the use of this method it is possible to visualize the physical processes occurring on the microscopic level, as e.g. those that arise during plastics processing. This thesis examines how boundary conditions, which mimic the extrusion blow molding process, affect the behavior of polyethylene on the microscopic level. A mesoscopic model (coarse-graining) is applied to describe the polymer. Initially, this model is verified by determining material properties. The uniaxial tensile test is modeled on the micro-scale to identify parameters such as the elastic modulus, yield stress, and Poisson’s ratio. Additionally, thermal properties, particularly those characterizing the crystallization behavior, are identified. The objective of these investigations is the microscopic observation and quantification of effects that occur during dynamic stretching and crystallization processes. The calculated properties show good agreement with the experimental data, especially regarding the thermal parameters. Qualitatively, the stress-strain behavior is reproduced in alignment with experimentally observed results. However, the short time scale of the simulation models leads to micromechanical behavior that is more extreme than what is monitored on a macroscopic level. By extending the simulation models, biaxial stretching processes are simulated. These stretching processes resemble the situation during the inflation of the parison in the extrusion blow molding process. The examination of various cooling conditions, particularly by the use of mold constraints, is another focus of the investigations. The analysis of the biaxially stretched simulations reveals that disentanglement processes during stretching dominate the further development of polymer systems. It is possible to quantify the dynamics of crystallization processes depending on the degree of stretching and cooling conditions through various parameters (distribution of entanglement points, local orientations). The results indicate that coarse-grained molecular dynamics simulations are able to significantly enhance the micromechanical understanding of local events occurring during plastic processing.
Gender disparities in STEM (Science, Technology, Engineering, and Mathematics) fields remain a significant challenge, with women often underrepresented. Spatial abilities, particularly mental rotation (MR), are crucial for success in STEM, yet significant gender differences in these skills persist. This research aims to explore the factors contributing to these differences, focusing on emotional reactivity, self-concept, anxiety, and their impact on performance in mathematical and spatial tasks among primary school children. This research synthesizes findings from three related studies involving N=303 primary school students, consisting of 146 girls and 155 boys with a mean age=8.70 (SD=1.11) years. Data were collected through standardized questionnaires assessing self-concept, spatial and maths anxiety, and preferences for STEM subjects. Cognitive performance was evaluated using a computerized, novel Mental Rotation Task (nMRT) incorporating gender-congruent and neutral stimuli and various maths tasks correlating with mental rotation. Physiological responses were measured using galvanic skin response (GSR) to assess the impact of emotional reactivity on task performance. All data were collected in the classroom environment to increase ecological validity and generalizability of findings. Across studies, girls demonstrated higher maths and spatial anxiety, lower maths self-concept, and a lower preference for maths as a STEM subject compared to boys. These factors were significantly associated with performance differences in both maths and MR tasks. Higher emotional reactivity, as evidenced by GSR, and increased response time were associated with better scores on difficult items, that is, abstract stimuli rotated in-depth. Emotional reactivity also affected maths task completion times, with girls demonstrating lower physiological arousal linked to shorter processing time. Gender, subject preference, math self-concept and anxiety levels emerged as significant predictors of task performance on both maths and spatial tasks. The results underscore the influence of self concept, anxiety and physiological responses on cognitive performance, highlighting significant gender differences. Girls demonstrated higher subjective anxiety and physiological arousal during maths tasks. However, in the same group, lower emotional reactivity and maths anxiety served as protective influences, leading to improved scores and shorter completion times. Moreover, girls and tweens demonstrated lower maths self-concept and preference for maths, indicating that stereotype effects are already impacting their interest during primary school. These findings suggest that psychological factors play a crucial role in learning outcomes, particularly in STEM subjects. This integrated research contributes to a deeper understanding of how psychological factors such as self-concept, subjective anxiety but also physiological arousal and subject preferences affect mathematical and spatial performance in primary school children. The findings have practical implications for educators and policymakers, advocating for the development of strategies to enhance self-concept, manage anxiety and support emotional regulation, particularly in girls, fostering a supportive learning environment that mitigates the impact of stereotype threat. Enhanced self-efficacy and reduced anxiety thereby increase the likelihood of their engagement with maths, subsequently improving their performance and expanding their future career options
in STEM fields.
Die vorliegende Dissertation hat sich unter dem Titel >>„Woher soll ich denn vorher wissen, ob ich den Job liebe?“ – Eine qualitative Längsschnitt-Studie zur Differenzierung der Phasenstruktur vorliegender Modelle beruflicher Orientierung anhand von Jugendlichen aus drei kontrastierenden institutionellen Ausgangslagen<< dem Erkenntnisinteresse gewidmet, Modelle zur beruflichen Orientierung anhand eines ethnografischen Zugangs aus der Perspektive unterschiedlicher institutioneller Settngs weiterzuentwickeln, um der Komplexität gegenwärtiger Lebenswelten besser gerecht zu werden. Dabei wurde unter Betrachtung von Berufsorientierungsaspekten als Forschungsgegenstand sowie unter Betrachtung der Gestalt der Berufsorientierung als Forschungsfeld der Fragestellung nachgegangen, inwiefern sich das in der Debatte zentrale Sechs-Phasenmodell der Berufswahl nach Herzog et. al. (2006) im Licht ethnografischer Forschung, welche die Perspektiven Jugendlicher eines allgemeinbildenden Gymnasiums, eines beruflichen Gymnasiums sowie eines Freiwilligen Sozialen Jahres umfasst, ausdifferenzieren lässt. Dabei wurde die Grounded Theory-Methodologie als Forschungsstil zugrunde gelegt, der wiederum im Rahmen der Datenerhebung die Ethnografie, im Rahmen der Datenanalyse die Grounded Theory untergeordnet wurde.
Als zentrales Untersuchungsergebnis lässt sich zum einen aufführen, dass das bestehende Berufswahlmodell deutlich modifiziert, ausdifferenziert und folglich erweitert werden konnte. Mit dieser Erweiterung ist eine Spezifikation dahingehend verbunden, dass viele Komponenten und Ebenen hinzugekommen sind, die bei dem ursprünglichen Modell nicht bedacht waren, im Gegenzug jedoch auch solche Komponenten gestrichen und als irrelevant deklariert wurden, die sich anhand der Untersuchungsdaten nicht zu bestätigen wussten. So konnte ein Neun-Phasenmodell der Berufsorientierung in Gestalt eines Ablaufdiagramms
entstehen, das den Prozessverlauf beruflicher Orientierung anschaulich in Phasen eingebettet darzustellen vermag. Dabei ist es gelungen, das Modell derart auszugestalten, dass es institutionsübergreifend anwendbar und nicht lediglich auf eine bestimmte institutionelle Ausgangslage beschränkt ist. Zum anderen kann statuiert werden, dass das vorliegende neunphasige Modell vor allem Phasen der Orientierungslosigkeit und der Desorientierung, des Entscheidungsaufschubs, der Überprüfung und der Überbrückung sowie der Um- und Neuorientierung explizit zu nutzen weiß, um diejenigen Situationen zu berücksichtigen, die den beruflichen Orientierungsprozess der Untersuchungsteilnehmenden aus allen drei
institutionellen Ausgangslagen maßgeblich geprägt haben.
The political targets for CO2 reduction in industrial processes are leading to a technological change in the area of pig iron production. In future, pig iron will be produced by using the direct reduction process instead of the blast furnace process. Direct reduction plants are currently operated with natural gas, this is to be replaced by hydrogen in the future in order to meet the climate targets. Within this work, the influence of hydrogen-containing atmospheres on currently used refractory materials from the Al2O3-SiO2 system was investigated. An experiment was developed to simulate the corrosion of refractory materials in the laboratory under realistic test conditions. Taking into account the atmosphere, the temperature and the sample material, a variety of practical corrosion tests were carried out. By applying a comprehensive analysis strategy, relevant corrosion effects on the materials were subsequently described as a result of the gas composition. The test temperature was in the range of 716 °C < T < 1150 °C. Physical and chemical-mineralogical tests were used to investigate the corrosion effects. In addition, the intensity of the corrosion effects was evaluated based on the gas compositions used. Pure hydrogen atmospheres in particular led to strong gas corrosion, while the presence of water vapor inhibited the chemical reactions. The mixture of methane and hydrogen can create an aggressive H2 / CO atmosphere, which also can lead to the formation of solid carbon. This phenomenon changes the possible causes of damage to refractory material; the crystallization pressure of carbon inside the structure of the refractory can also contribute to material failure. Furthermore, the corrosion reactions could be described by coupling imaging analysis methods and element determination. It was shown that, in contrast to the general opinion in the state of the art, there was not exclusively a decrease in SiO2-amount. Several reactions took place in the investigated, industrially used materials, which led to the local chemical attack of SiO2 (silicate glass phase) and caused a parallel crystallization of cristobalite. The chemical attack of hydrogen on the silicate glass phase can be defined as the primary corrosion reaction in the range of 716 °C < T < 1150 °C in a pure hydrogen atmosphere. In addition, the reaction kinetics as a function of temperature were experimentally investigated and described. Based on these analyses, material properties can be defined that are particularly suitable for the future use of defined refractory qualities within reduction processes.
Cross Cultural Adaptation of Design Thinking in Entrepreneurship Higher Education in Indonesia
(2024)
Entrepreneurship and entrepreneurship education have expanded together, and their conceptual and methodological challenges do not prevent the implementation of entrepreneurial education in educational contexts. The desire for a global workforce that can handle uncertainties and solve problems that cannot be solved by pure analytical inquiry drives the rapidly expanding number of educational programs and activities that are design-based. A growing number of educational programs for entrepreneurs increasingly incorporate design-based methods. However, design thinking-based theoretical assumptions may also be lacking. Despite growing academic interest in design thinking and entrepreneurship education, little is known about design thinking in higher entrepreneurship education, especially in Eastern nations. A Western teaching method, entrepreneurial design thinking may be adapted to many cultures. In this instance, the West has established entrepreneurship education as a respectable study subject and teaching practice in higher education over the past 40 years. The Eastern nations' occurrence varies, including Indonesia. Indonesia is an intriguing research subject since it has over 50% youth due to its abundant natural resources. However, it needs more opportunity-based entrepreneurs and requires assistance in implementing entrepreneurship education with a more innovative, design-based, and successful method. Entrepreneurial design thinking fulfills this demand. Indonesian students and teachers' norm-based attitudes and cultural mindsets towards a new western creative method may hinder entrepreneurial design thinking's acceptance. The literature review found that Indonesian university students are collaborative, compassionate, and practical, like design thinkers. However, they may also be risk-averse, self-restrained, and dependent on teachers as stereotypical Asians. Classroom space, educators' design thinking competence, and university or institution support are further barriers. Additional study into these challenges is needed to adapt design thinking to Indonesian entrepreneurial higher education culturally.
Based on the above research needs, the purpose of this research endeavor is to look into the cultural nuances of the design thinking technique for entrepreneurial higher education and postulate how it could be adapted to other cultures, especially in Indonesia. This thesis uses deductive and qualitative case-study research methods. In particular, the latter used thematic analysis (Braun & Clarke, 2006; Terry & Hayfield, 2021) as the data analysis technique to provide a means and tools for understanding from interviews, class observation, and literature studies. Since this thesis follows the constructivist-relativist research paradigm, it explores contextual and cultural differences in Indonesian entrepreneurship education and its potential and obstacles to adapt the Western teaching methodology of entrepreneurial design thinking in higher education. In summary, this study searches for elements that might aid or hinder the cross-cultural adaption of entrepreneurial design thinking. This research wants to understand how cross-cultural adaptability fits into entrepreneurial design thinking research, especially for Indonesia. This thesis aims to provide new theoretical insights and practical advice on adapting entrepreneurial design thinking from Western to Eastern cultures.
From the findings, this thesis concluded at least seven educational value differentials before adaptation from the exhaustive literature and case study evaluations. For Indonesian entrepreneurship higher education institutions to use entrepreneurial design thinking, they must consider educational culture, technological infrastructure, language, primary audience, learning and teaching style, reasoning patterns, and social-cultural environment. This study provides four practical adaptation recommendations: socialization, externalization, combination, and internalization. Finally, this research demonstrated that cross-cultural adaption of entrepreneurial design thinking in Indonesia might be difficult but worthwhile. This thesis' case study, "School of Business Management – Bandung Institute of Technology (SBM ITB)", showed that Indonesian entrepreneurial higher education might use design thinking as a teaching approach. All stakeholders must improve internally and publicly. Thus, this study recommended integrating most Indonesian higher education institutions' entrepreneurship teaching approaches with a "student-centered" approach that stresses business mentorship, uses design thinking tools and processes, and links them to students' entrepreneurial initiatives.
To summarize, this research contributes to the field since it draws on and combines the findings of several other fields of study, including entrepreneurial education, design thinking, and cross-cultural adaptation. This study stepped out of the "usual and proper" pedagogical ruts to investigate "non-human" cross-cultural adaptability. It has attempted to apply these ideas to a real-world, unique case study in a developing nation (in this case, Indonesia).
The digital transformation of the public sector and the development of suitable implementation mechanisms are currently major challenges in the area of E-Government. While Germany is one of the leading countries in the private sector in terms of digital offerings, the digital transformation processes in the public sector are progressing only slowly. In particular, compared to other European countries, German administrations offer few digital and interoperable services, which prevents them from catching up with a government-wide dig-ital transformation.
The aim of this dissertation is to investigate the reasons for the slow progress of digital transformation in the public sector and to understand why Germany is not making significant progress in the digitization of administrative services compared to other European member states. Furthermore, it aims to gradually build a comprehensive understanding of why digital transformation is not being driven, supported or applied in the public sector and what positive or negative factors ultimately prevent cross-organizational exchange.
The focus of this dissertation is on organizational and interdisciplinary collaboration in socio-technical systems and its influence on the digital transformation of public administrations. The investigation of science and practice is based on the principles of qualitative social research and qualitative content analysis according to Mayring. Deductive categories are systematically derived and supplemented by further inductive categories along the empirical investigation in the five case studies.
The identified phenomena are analyzed in a scientific explanatory model and described with the help of the holistic approach and the actor-network theory. On this basis, solutions are developed that can either prevent or at least reduce the influencing factors. An interdiscipli-nary approach that combines theoretical foundations from business informatics, administrative informatics/e-government and organizational science not only creates a comprehensive understanding of the problem, but also develops approaches for the scientific description of informatics phenomena with the help of social constructivist approaches.
The goal of this PhD thesis is to investigate possibilities of using symbol elimination for solving problems over complex theories and analyze the applicability of such uniform approaches in different areas of application, such as verification, knowledge representation and graph theory. In the thesis we propose an approach to symbol elimination in complex theories that follows the general idea of combining hierarchical reasoning with symbol elimination in standard theories. We analyze how this general approach can be specialized and used in different areas of application.
In the verification of parametric systems it is important to prove that certain safety properties hold. This can be done by showing that a property is an inductive invariant of the system, i.e. it holds in the initial state of the system and is invariant under updates of the system. Sometimes this is not the case for the condition itself, but for a stronger condition it is. In this thesis we propose a method for goal-directed invariant strengthening.
In knowledge representation we often have to deal with huge ontologies. Combining two ontologies usually leads to new consequences, some of which may be false or undesired. We are interested in finding explanations for such unwanted consequences. For this we propose a method for computing interpolants in the description logics EL and EL⁺, based on a translation to the theory of semilattices with monotone operators and a certain form of interpolation in this theory.
In wireless network theory one often deals with classes of geometric graphs in which the existence or non-existence of an edge between two vertices in a graph relies on properties on their distances to other nodes. One possibility to prove properties of those graphs or to analyze relations between the graph classes is to prove or disprove that one graph class is contained in the other. In this thesis we propose a method for checking inclusions between geometric graph classes.
How to begin? This short question addresses a problem that is anything but simple, especially when regarding something as sophisticated and multilayered as musical theatre. However, scholars of this vast research area have mostly neglected this question so far. This study analyses and compares the initial sections of late Victorian popular musical theatre and is therefore a contribution to several fields of research: the analysis of initial sections of musical theatre in general, the analysis of the music of popular musical theatre in particular, and therefore operetta studies. The 1890s are especially interesting times for popular musical theatre in London: The premiered works include the last collaborations of Gilbert and Sullivan as well as offshoots of Savoy opera; but the so-called ‘naughty nineties’ also saw the emergence of a new genre, musical comedy, which captured the late Victorian zeitgeist like no other. This new form of theatrical entertainment was carefully and consciously constructed and promoted as modern and fashionable, walking a fine line between respectability and mildly risqué excitement.
Because a deep understanding of the developments and new tendencies concerning popular musical theatre in the 1890s is crucial in order to interpret differences as well as similarities, the analyses of the opening numbers are preceded by a detailed discussion of the relevant genres: comic opera, musical comedy, musical play and operetta. Since the producers of the analysed works wanted to distance themselves from former and supposedly old-fashioned traditions, this book also considers influences from their British predecessors, but also from Viennese operetta and French opéra bouffe.