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Institut
- Fachbereich 7 (73)
- Institut für Informatik (29)
- Institut für Integrierte Naturwissenschaften, Abt. Biologie (23)
- Fachbereich 8 (20)
- Institut für Umweltwissenschaften (19)
- Institute for Web Science and Technologies (11)
- Institut für Computervisualistik (9)
- Institut für Integrierte Naturwissenschaften, Abt. Chemie (9)
- Mathematisches Institut (8)
- Institut für Anglistik und Amerikanistik (7)
Chemical plant protection is an essential element in integrated pest management and hence, in current crop production. The use of Plant Protection Products (PPPs) potentially involves ecological risk. This risk has to be characterised, assessed and managed.
For the coming years, an increasing need for agricultural products is expected. At the same time, preserving our natural resources and biodiversity per se is of equally fundamental importance. The relationship of our economic success and cultural progress to protecting the environment has been made plain in the Ecosystem Service concept. These distinct 'services' provide the foundation for defining ecological protection goals (Specific Protection Goals, SPGs) which can serve in the development of methods for ecological risk characterisation, assessment and management.
Ecological risk management (RM) of PPPs is a comprehensive process that includes different aspects and levels. RM is an implicit part of tiered risk assessment (RA) schemes and scenarios, yet RM also explicitly occurs as risk mitigation measures. At higher decision levels, RM takes further risks, besides ecological risk, into account (e.g., economic). Therefore, ecological risk characterisation can include RM (mitigation measures) and can be part of higher level RM decision-making in a broader Ecosystem Service context.
The aim of this thesis is to contribute to improved quantification of ecological risk as a basis for RA and RM. The initial general objective had been entitled as "… to estimate the spatial and temporal extent of exposure and effects…" and was found to be closely related to forthcoming SPGs with their defined 'Risk Dimension'.
An initial exploration of the regulatory framework of ecological RA and RM of PPPs and their use, carried out in the present thesis, emphasised the value of risk characterisation at landscape-scale. The landscape-scale provides the necessary and sufficient context, including abiotic and biotic processes, their interaction at different scales, as well as human activities. In particular, spatially (and temporally) explicit landscape-scale risk characterisation and RA can provide a direct basis for PPP-specific or generic RM. From the general need for tiered landscape-scale context in risk characterisation, specific requirements relevant to a landscape-scale model were developed in the present thesis, guided by the key objective of improved ecological risk quantification. In principle, for an adverse effect (Impact) to happen requires a sensitive species and life stage to co-occur with a significant exposure extent in space and time. Therefore, the quantification of the Probability of an Impact occurring is the basic requirement of the model. In a landscape-scale context, this means assessing the spatiotemporal distribution of species sensitivity and their potential exposure to the chemical.
The core functionality of the model should reflect the main problem structures in ecological risk characterisation, RA and RM, with particular relationship to SPGs, while being adaptable to specific RA problems. This resulted in the development of a modelling framework (Xplicit-Framework), realised in the present thesis. The Xplicit-Framework provides the core functionality for spatiotemporally explicit and probabilistic risk characterisation, together with interfaces to external models and services which are linked to the framework using specific adaptors (Associated-Models, e.g., exposure, eFate and effect models, or geodata services). From the Xplicit-Framework, and using Associated-Models, specific models are derived, adapted to RA problems (Xplicit-Models).
Xplicit-Models are capable of propagating variability (and uncertainty) of real-world agricultural and environmental conditions to exposure and effects using Monte Carlo methods and, hence, to introduce landscape-scale context to risk characterisation. Scale-dependencies play a key role in landscape-scale processes and were taken into account, e.g., in defining and sampling Probability Density Functions (PDFs). Likewise, evaluation of model outcome for risk characterisation is done at ecologically meaningful scales.
Xplicit-Models can be designed to explicitly address risk dimensions of SPGs. Their definition depends on the RA problem and tier. Thus, the Xplicit approach allows for stepwise introduction of landscape-scale context (factors and processes), e.g., starting at the definitions of current standard RA (lower-tier) levels by centring on a specific PPP use, while introducing real-world landscape factors driving risk. With its generic and modular design, the Xplicit-Framework can also be employed by taking an ecological entity-centric perspective. As the predictive power of landscape-scale risk characterisation increases, it is possible that Xplicit-Models become part of an explicit Ecosystem Services-oriented RM (e.g., cost/benefit level).
This thesis is concerned with an issue of considerable importance to the development of revision skills: the role of teacher feedback. Prompted by the concern to develop a model of instruction which will help students write to the best of their capacities, the present study forms a proposal: an interactive model of revision. The study researches whether the kind of feedback proposed in this model is indeed a helpful tool for revision and whether the kind of negotiated revision that occurs is a vehicle for learning. The first section of the thesis reviews different areas of literature which are relevant to the study. More specifically, Chapter 2 presents the historical and theoretical foundations of different writing instructional practices and sheds light on issues concerning the use of the process approach. It also reviews research based on sociocognitive theoretical perspectives in an attempt to delineate the impact of interpersonal or social activity on individual performance and progress. Chapter 3 examines issues associated with the process approach in particular and illustrates how theory and method come together in a process writing classroom. Chapter 4 presents the differences in revising behaviours between experienced and inexperienced writers in both L1 and L2 contexts and the various ways these differences have been justified. It also highlights a number of issues which have been identified as contributing to effective revision. Particular attention is paid to the role that teacher feedback has to play as a means of promoting substantive student revision with an instructional emphasis on fluency, organisation and language. Chapter 5 presents an interactive model of revision, which envisions a communicative exchange between two partners, the student-writer and the teacher-reader, collaborating in order to develop awareness of revision strategies and establish criteria for effective writing. Chapter 6 investigates the epistemological basis of the research and presents a set of research questions and hypotheses, which guided the investigation. Chapter 7 frames the context of the research and details the methods used to collect the data from the study. The study involved 100 Year 7 students in two gymnasia in Koblenz, Germany. During the time of the investigation, the students wrote and revised five tasks. Three of these tasks were revised after receiving teacher feedback, which focused on aspects such as appropriacy and sufficiency of information, organization, coherence and grammatical accuracy. The study investigates the effects of this kind of focused feedback on the students" revisions and explores the relationship between revision and text improvement. Large quantitative and qualitative data sets were generated during the research. The quantitative data was based on the student documents (1000 original and revised drafts) whereas the qualitative data emerged from student questionnaires and seven case studies. Chapter 8 presents descriptions of the data analyses. More specifically, it describes the initial and final coding of the revisions traced in the student documents. Then it focuses on the type of qualitative analysis employed in the case studies in order to investigate the relationship between revision and text improvement. The final section of the chapter describes the questionnaire analysis, which was carried out to investigate attitudes, benefits and constraints from the implementation of the model. Chapter 9 examines the statistical results from the analysis of the students" revisions. More specifically, it explores the revisions made by the students across tasks and the relationships between the features of the teacher feedback and these revisions. The analysis highlights patterns in the development of revision skills and positive correlations of student revisions with features of the teacher feedback. Chapter 10 looks at the descriptive data from the case studies of seven individual student writers. The analysis of this data illustrates how the specific students negotiated the revisions and sheds more light on the relationship between feedback, revision and text improvement. Chapter 11 contains the analysis of the students" answers to the questionnaire, which provide illuminative information about the feedback-related attitudes. In Chapter 12, the thesis reaches its final destination. The journey over the paths of literature exploration, data gathering and data analysis ends with reflections on the messages that emerge from the data analysis. The conclusion reached is that young students can learn how to revise their writing and focused feedback is a viable pedagogic option for teaching revision. In addition to discussing the findings, this final section considers the pedagogical implications for the teaching of writing and suggests possible avenues for further work.
Instructor feedback on written assignments is one of the most important elements in the writing process, especially for students writing in English as a foreign language. However, students are often critical of both the amount and quality of the feedback they receive. In order to better understand what makes feedback effective, this study explored the nature of students’ assessments of the educational alliance, and how their receptivity to, perceptions of, and decisions about using their instructors’ feedback differed depending on how strong they believed the educational alliance to be. This exploratory case study found that students not only assessed the quality of the educational alliance based on goal compatibility, task relevance, and teacher effectiveness, but that there was also a reciprocal relationship between these elements. Furthermore, students’ perceptions of the educational alliance directly influenced how they perceived the feedback, which made the instructor’s choice of feedback method largely irrelevant. Stronger educational alliances resulted in higher instances of critical engagement, intrinsic motivation, and feelings of self-efficacy. The multidirectional influence of goal, task, and bond mean that instructors who want to maximize their feedback efforts need to attend to all three.
The trends of industry 4.0 and the further enhancements toward an ever changing factory lead to more mobility and flexibility on the factory floor. With that higher need of mobility and flexibility the requirements on wireless communication rise. A key requirement in that setting is the demand for wireless Ultra-Reliability and Low Latency Communication (URLLC). Example use cases therefore are cooperative Automated Guided Vehicles (AGVs) and mobile robotics in general. Working along that setting this thesis provides insights regarding the whole network stack. Thereby, the focus is always on industrial applications. Starting on the physical layer, extensive measurements from 2 GHz to 6 GHz on the factory floor are performed. The raw data is published and analyzed. Based on that data an improved Saleh-Valenzuela (SV) model is provided. As ad-hoc networks are highly depended onnode mobility, the mobility of AGVs is modeled. Additionally, Nodal Encounter Patterns (NEPs) are recorded and analyzed. A method to record NEP is illustrated. The performance by means of latency and reliability are key parameters from an application perspective. Thus, measurements of those two parameters in factory environments are performed using Wireless Local Area Network (WLAN) (IEEE 802.11n), private Long Term Evolution (pLTE) and 5G. This showed auto-correlated latency values. Hence, a method to construct confidence intervals based on auto-correlated data containing rare events is developed. Subsequently, four performance improvements for wireless networks on the factory floor are proposed. Of those optimization three cover ad-hoc networks, two deal with safety relevant communication, one orchestrates the usage of two orthogonal networks and lastly one optimizes the usage of information within cellular networks.
Finally, this thesis is concluded by an outlook toward open research questions. This includes open questions remaining in the context of industry 4.0 and further the ones around 6G. Along the research topics of 6G the two most relevant topics concern the ideas of a network of networks and overcoming best-effort IP.
Aktuelle Schätzungen bestätigten, dass Binnengewässer eine erhebliche Menge Methan (CH4) und Kohlendioxid (CO2) sowohl auf regionaler Ebene, als auch global freisetzen. Jedoch basieren diese Schätzungen auf extrapolierten gemessenen Daten, ungenügender Auflösung der räumlich-zeitlichen Variabilität und es mangelt an Daten aus ariden und semi-ariden Gebieten, sowie den Kohlestoffquellen aus Kläranlagen.
Für die hier vorliegende Studie analysierten wir monatliche hydrologische und meteorologische Daten sowie Daten zur Wasserqualität von drei Stauseen aus dem Gebiet des unteren Jordans, die zur Trinkwassergewinnung und zur Bewässerung genutzt werden, und schätzten damit deren Emissionsrate an CO2 ab. Wir untersuchten den Effekt von Kläranlagen auf die umliegenden Gewässer im Hinblick auf CH4 und CO2-Emissionen indem wir saisonal aufgelöste Daten der Konzentration der beiden gelösten Gase in Kläranlagenauslässen und in Vorflutern von neun Kläranlagen in Deutschland analysierten. Mithilfe von Low-Cost-Methoden die die CO2-Transportrate und die Ausgasungsrate über Gasblasen messen, untersuchten wir die räumliche und zeitliche Variabilität der CH4 und CO2-Emissionen von aquatischen Süßwasser-Ökosystemen.
Unsere Schätzungen zeigen, dass Stauseen in semi-ariden Regionen CO2 übersättigt sind und somit CO2 an die Atmosphäre abgeben, also eine Netto-Quelle sind.
Die Größenordnung der beobachteten Transportraten der drei jordanischen Stauseen ist vergleichbar mit denen von tropischen Stauseen (3,3 g CO2 m-2 Tag-1). Die CO2-Emissionsrate ist abhängig von Änderungen der Wasseroberfläche, welche durch den Betrieb der Stauseen verursacht sind. Kläranlagen entlassen eine beachtlichen Menge an CH4 (30.9±40.7 kg Jahr-1) und CO2 (0.06±0.05 Gg Jahr-1) in ihre umgebenden Flüsse und Bäche. Deren Emissionsraten sind durch diese Einleitung der Kläranlagen um 1,2-fach für CH4 oder 8,6-fach für CO2 erhöht. Unsere Ergebnisse zeigen, dass sowohl die diffusive als auch die Gasblasenemissionsrate räumlich und zeitlich variabel ist, weshalb beide Emissionsraten bei zukünftigen Studien auch in der nötigen Auflösung gemessen werden sollten.
Wir schlussfolgern, dass bei zukünftigen Emissionsmessungen und –schätzungen von Binnengewässern auch die Gewässerbewirtschaftung, die Kohlenstoffquelle von Kläranlagen und die räumliche und zeitliche Variabilität der Emissionen beachtet werden sollten.
Ziel der vorliegenden Arbeit ist die Erforschung von Einstellungen und prosozialem Verhalten zwischen Arbeitsgruppen aus Sicht der Theorie der sozialen Identität und der Kontakthypothese. Dem Rekategorisierungsmodell von Gaertner und Dovidio (2000) folgend wird angenommen, dass "optimale" Kontaktbedingungen (Allport, 1954) eine gemeinsame organisationale Identität anregen. Diese gemeinsame Identität sollte verschiedene Arbeitsgruppen dazu motivieren, zusammenzuarbeiten und freiwilliges Arbeitsverhalten zu zeigen anstelle von Voreingenommenheiten. Vorhersagen des Rekategorisierungsmodells werden zusätzlich durch Annahmen aus dem Eigengruppen-Projektionsmodell (Mummendey & Wenzel, 1999) und dem Selbstkategorisierungsmodell der Gruppennormen (Terry & Hogg, 1996) ergänzt. Die abgeleiteten Hypothesen werden an einer Stichprobe von N1 = 281 MitarbeiterInnen aus N2 = 49 Abteilungen und den entsprechenden AbteilungsleiterInnen eines deutschen Versandhandelsunternehmens überprüft (Studie 1). Die Ergebnisse zeigen, dass Kontaktbedingungen auf Gruppen- und Personenebene weniger Voreingenommenheit zwischen Arbeitsgruppen, sowie mehr prosoziales Verhalten (d. h. Kooperation und Hilfeverhalten) vorhersagen. Die Repräsentation als gemeinsame Gruppe vermittelt diesen Zusammenhang für die Variablen Bewertung der Fremdgruppe und Kooperation. Dagegen wird der Zusammenhang zwischen gemeinsamer organisationaler Identität und Voreingenommenheit durch die relative Prototypikalität der Abteilung moderiert, wie es das Eigengruppen-Projektionsmodell vorhersagt. Der Effekt einer prosozialen Gruppennorm auf Hilfeverhalten wird durch die Identifikation mit der Arbeitsgruppe moderiert. In einer Längsschnittstudie mit insgesamt N = 57 Mitgliedern studentischer Projektgruppen wird der Befund repliziert, dass Kontakt unter "optimalen" Bedingungen zu mehr prosozialem Verhalten und weniger Voreingenommenheit zwischen organisationalen Gruppen führt. Der Mediationseffekt durch eine gemeinsame Gruppenidentität zeigt sich jedoch in Studie 2 nicht. Die Ergebnisse der ersten Studie lassen vermuten, dass interpersonales Hilfeverhalten besser durch Prädiktoren auf der gleichen Kategorisierungsebene (d. h. Personenebene) vorhergesagt werden kann (vgl. Haslam, 2004). Daher wird die zusätzliche Annahme getroffen, dass Kontakt in einem Kontext, welcher persönliche Identitäten salient macht (d. h. zu Dekategorisierung führt), interpersonales Verhalten besser vorhersagen kann. Dagegen sollte Kontakt in einem Kontext, welcher Gruppenidentitäten salient macht (d. h. zu Kategorisierung führt), intergruppales Verhalten besser vorhersagen können (vgl. Tajfel, 1978). Zusätzliche Daten aus Studie 1 belegen diesen kontextspezifischen Effekt von Kontakt auf interpersonales bzw. intergruppales prosoziales Verhalten. Im letzten Schritt wird das längsschnittliche Kontaktmodell von Pettigrew (1998) untersucht, welches Kontakt in Kontexten, die zu Dekategorisierung, Kategorisierung bzw. Rekategorisierung führen, in einer zeitlichen Abfolge miteinander verbindet. Erste Befunde aus Studie 2 zeigen, dass eine Abfolge der Kategorisierungsprozesse beginnend bei Dekategorisierung über Kategorisierung hin zu Rekategorisierung eine besonders effektive Möglichkeit zur Verbesserung der Kooperation zwischen Gruppen bieten könnte. Zum Abschluss wird ein Kontextspezifisches Kontaktmodell vorgeschlagen, das Befunde aus den beiden vorgestellten Studien integriert und zu weiterer Forschung an prosozialem Verhalten zwischen Arbeitsgruppen anregen soll. Mögliche Mediatoren und Moderatoren werden neben einer Reihe von Implikationen für die Forschung und Praxis diskutiert.
By the work presented in this thesis, the CH4 emissions of the River Saar were quantified in space and time continuously and all relevant processes leading to the observed pattern were identified. The direct comparison between reservoir zones and free-flowing intermediate reaches revealed, that the reservoir zones are CH4 emission hot spots and emitted over 90% of the total CH4. On average, the reservoir zones emitted over 80 times more CH4 per square meter than the intermediate reaches between dams (0.23 vs. 19.7 mol CH4 m-2 d-1). The high emission rates measured in the reservoir zones fall into the range of emissions observed in tropical reservoirs. The main reason for this is the accumulation of thick organic rich sediments and we showed that the net sedimentation rate is an excellent proxy for estimating ebullitive emissions. Within the hot spot zones, the ebullitive flux enhanced also the diffusive surface emissions as well as the degassing emissions at dams.
To resolve the high temporal variability, we developed an autonomous instrument for continuous measurements of the ebullition rate over long periods (> 4 weeks). With this instrument we could quantify the variability and identify the relevant trigger mechanisms. At the Saar, ship-lock induces surges and ship waves were responsible for over 85% of all large ebullition events. This dataset was also used to determine the error associated with short sampling periods and we found that with sampling periods of 24 hours as used in other studies, the ebullition rates were systematically underestimated by ~50%. Measuring the temporal variability enabled us to build up a conceptual framework for estimating the temporal pattern of ebullition in other aquatic systems. With respect to the contribution of freshwater systems to the global CH4 emissions, hot spot emission sites in impounded rivers have the potential to increase the current global estimate by up to 7%.
Graph-based data formats are flexible in representing data. In particular semantic data models, where the schema is part of the data, gained traction and commercial success in recent years. Semantic data models are also the basis for the Semantic Web - a Web of data governed by open standards in which computer programs can freely access the provided data. This thesis is concerned with the correctness of programs that access semantic data. While the flexibility of semantic data models is one of their biggest strengths, it can easily lead to programmers accidentally not accounting for unintuitive edge cases. Often, such exceptions surface during program execution as run-time errors or unintended side-effects. Depending on the exact condition, a program may run for a long time before the error occurs and the program crashes.
This thesis defines type systems that can detect and avoid such run-time errors based on schema languages available for the Semantic Web. In particular, this thesis uses the Web Ontology Language (OWL) and its theoretic underpinnings, i.e., description logics, as well as the Shapes Constraint Language (SHACL) to define type systems that provide type-safe data access to semantic data graphs. Providing a safe type system is an established methodology for proving the absence of run-time errors in programs without requiring execution. Both schema languages are based on possible world semantics but differ in the treatment of incomplete knowledge. While OWL allows for modelling incomplete knowledge through an open-world semantics, SHACL relies on a fixed domain and closed-world semantics. We provide the formal underpinnings for type systems based on each of the two schema languages. In particular, we base our notion of types on sets of values which allows us to specify a subtype relation based on subset semantics. In case of description logics, subsumption is a routine problem. For
the type system based on SHACL, we are able to translate it into a description
logic subsumption problem.
In vielen Teilen der Welt, vor allem in Subsahara-Afrika, ist Wasserknappheit bereits ein allgegenwärtiges Problem. Doch die Trockenjahre 2018 und 2019 zeigten, dass auch in Deutschland die Wasserressourcen endlich sind. Projektionen und Vorhersagen für die nächsten Jahrzehnte weisen zudem darauf hin, dass durch den steigenden Einfluss des Klimawandels die Erneuerungsraten der bestehenden Wasserressourcen zurückgehen, die Entnahmemengen aber aufgrund von Populationswachstum steigen werden. Es ist demnach an der Zeit, alternative und nachhaltige Methoden zu finden, die derzeit vorhandenen Wasserressourcen optimal zu nutzen. Daher rückte in den vergangenen Jahren die Wiederverwendung von geklärtem Abwasser zur Bewässerung landwirtschaftlicher Flächen und/oder der Grundwasseranreicherung in den Fokus der Wissenschaft. Dabei ist aber zu berücksichtigen, dass in geklärtem Abwasser sogenannte Spurenstoffe zu finden sind, d.h. Substanzen, die durch anthropogenen Einfluss in den Wasserkreislauf gelangen. Dabei handelt es sich z.B. um Pharmazeutika, Pestizide und Industriechemikalien, aber auch um Metabolite, die im menschlichen Körper gebildet werden und in das Abwasser gelangen. Durch die Wasseraufbereitungsschritte in den Kläranlagen als auch durch biologische, chemische und physikalische Prozesse in der Bodenpassage bei der Wiederverwendung des geklärten Abwassers werden diese Spurenstoffe zu anderen Substanzen, den Transformationsprodukten (TPs), umgewandelt, die das Spektrum der Spurenstffe zusätzlich erweitern.
Trotz der Tatsache, dass das Vorhandensein von Human-Metaboliten und TPs in ungeklärtem und geklärten Abwasser seit langem bekannt ist, werden sie in gängigen Routine-Messmethoden nur selten berücksichtigt. Daher war es ein erstes Ziel dieser Dissertation eine Analyse-Methode zu erstellen, basierend auf Flüssigchromatographie-Tandem Massenspektrometrie (LC-MS/MS), die ein möglichst breites Spektrum an Spurenstoffen inklusive bekannter Metabolite und TPs enthält. Die entwickelte Multi-Analyt-Methode umfasst insgesamt 80 Ausgangssubstanzen und 74 Metabolite und TPs verschiedener Substanzklassen und ist für die Anwendung in verschiedenen Wassermatrices (Zu- und Ablauf von Kläranlagen, Oberflächenwasser und Grundwasser aus einer Uferfiltrationsanlage) validiert. Dabei wurde auch der Einfluss der MS-Parameter auf die Qualität der Analysedaten untersucht. Trotz der hohen Anzahl an Substanzen konnte eine ausreichende Anzahl an Datenpunkten je Peak generiert werden, wodurch eine hohe Empfindlichkeit und Präzision sowie eine gute Wiederfindung für alle Matrices erreicht wurden. Die Auswahl der Analyten erwies sich als relevant für die Untersuchung von Umweltmatrices, da 95% der Substanzliste in mindestens einer Probe nachgewiesen wurden. Mehrere Spurenstoffe, die bisher nicht im Fokus der gegenwärtigen Multi-Analyt-Methoden standen, wurden bei erhöhten Konzentrationen im Wasserkreislauf quantifiziert (z.B. Oxypurinol). Die Relevanz der Untersuchung von Metaboliten und TPs zeigte sich durch den Nachweis von z.B. Clopidogrel-Säure und Valsartansäure mit deutlich höheren Konzentrationen als ihre Ausgangssubstanzen. Valsartansäure konnte zudem sogar im Uferfiltrat detektiert werden.
Durch die Einbindung der Metabolite, die durch biologische Prozesse im Körper entstehen, und den biologischen und chemischen TPs, eignet sich die Multi-Analyt-Methode auch zur Aufklärung von Abbaumechanismen in natürlichen Behandlungssystemen zur Wasserwiederverwendung, wozu es in der Literatur bisher nur wenige Angaben gibt. Im Rahmen der Dissertation wurden Proben aus zwei Systemen analysiert, einem im Pilotmaßstab entwickelten oberirdischen sequenziellen Biofiltrationssystem (SBF) und einem großmaßstäblichen Bodenpassagen-System (SAT). Im SBF-System konnten hauptsächlich biologische Abbaumechanismen beobachtet werden, was durch die Entstehung biologischer TPs deutlich gezeigt wurde. Die Effizienz des Abbaus wurde dabei durch eine Zwischenbelüftung erhöht, die oxische Bedingungen hervorrief. Im SAT-System kam es zu einer Kombination von Bioabbau- und Sorptionsprozessen. Es wurde beobachtet, dass bei einigen biologisch abbaubaren Spurenstoffen ein geringerer Abbau erreicht wurde als im SBF-System, was auf unterschiedliche Redox-Bedingungen und eine andere mikrobielle Gemeinschaft zurückzuführen war. Als Vorteil des SAT-Systems gegenüber des SBF erwies sich die Sorptionsfähigkeit des natürlichen Bodens. Vor allem positiv geladene Spurenstoffe zeigten eine Entfernung aufgrund von ionischen Wechselwirkungen mit negativ geladenen Bodenpartikeln. Auf der Grundlage ihrer physikalisch-chemischen Eigenschaften bei Umgebungs-pH, ihres Entfernungsgrades in den untersuchten Systemen und ihres Vorkommens im einfließenden Wasser konnte eine Auswahl von prozessbasierten Indikatorsubstanzen vorgeschlagen werden.
In den vorherigen Arbeiten wurde in Kläranlagenabläufen häufig ein Spurenstoff in erhöhten Konzentrationen nachgewiesen, der bisher wenig im Fokus der Umweltforschung stand: das Antidiabetikum Sitagliptin (STG). STG zeigt nur eine geringe Abbaubarkeit in biologischen Systemen. Daher wurde untersucht, inwieweit eine chemische Aufbereitung mittels Ozonung einen Abbau gewährleisten kann. STG weist in seiner Struktur ein aliphatisches primäres Amin als entscheidende Angriffsstelle für das Ozonmolekül auf. In der Literatur finden sich kaum Informationen zum Verhalten dieser funktionellen Gruppe während der Ozonung. Die in dieser Dissertation erzielten Ergebnisse können daher exemplarisch für andere Spurenstoffe mit Amingruppen herangezogen werden. Es zeigte sich eine pH-abhängige Abbaukinetik aufgrund der Protonierung des primären Amins bei niedrigen pH-Werten. Bei für die Umwelt und Kläranlagen typischen pH-Werten im Bereich 6 – 8 wies STG Abbaukinetiken mittels Ozon im Bereich 103 M-1s-1 auf, mit einem vollständigen Abbau kann allerdings erst bei deutlich höheren pH-Werten > 9 gerechnet werden. Die Transformation des primären Amins zu einer Nitro-Gruppe wurde als Hauptabbaumechanismus in der Ozonung identifiziert. Ebenfalls wurde die Entstehung weiterer TPs wie z.B. eines Diketons und Trifluoressigsäure (TFA) beobachtet. Untersuchungen an einer Pilotanlage, bei der die Ozonung unter realen Bedingungen mit dem Ablauf einer konventionellen Kläranlage durchgeführt wurde, bestätigte die Ergebnisse der Laboruntersuchungen: STG wurde auch bei einer hohen Ozondosis nicht vollständig entfernt und die Nitro-Verbindung erwies sich als Haupt-TP, das weder bei weiterer Ozonung noch in einer nachgeschalteten biologischen Behandlung abgebaut wurde. Es ist daher davon auszugehen, dass unter realen Bedingungen sowohl eine Restkonzentration an STG als auch das Haupt-TP sowie weitere TPs wie TFA im Ablauf einer Kläranlage bestehend aus konventioneller biologischer Aufreinigung, Ozonung und nachgeschalteter biologischer Aufreinigung auffindbar sind.
Despite the significant presence of neuroactive substances in the environment, bioassays that allow to detect diverse groups of neuroactive mechanisms of action are not well developed and not properly integrated into environmental monitoring and chemical regulation. Therefore, there is a need to develop testing methods which are amenable for fast and high-throughput neurotoxicity testing. The overall goal of this thesis work is to develop a test method for the toxicological characterization and screening of neuroactive substances and their mixtures which could be used for prospective and diagnostic hazard assessment.
In this thesis, the behavior of zebrafish embryos was explored as a promising tool to distinguish between different neuroactive mechanisms of action. Recently, new behavioral tests have been developed including photomotor response (PMR), locomotor response (LMR) and spontaneous tail coiling (STC) tests. However, the experimental parameters of these tests lack consistency in protocols such as exposure time, imaging time, age of exposure, endpoint parameter etc. To understand how experimental parameters may influence the toxicological interpretation of behavior tests, a systematic review of existing behavioral assays was conducted in Chapter 2. Results show that exposure concentration and exposure duration highly influenced the comparability between different test methods and the spontaneous tail coiling (STC) test was selected for further testing based on its relative higher sensitivity and capacity to detect neuroactive substances (Chapter 2).
STC is the first observable motor activity generated by the developing neural network of the embryo which is assumed to occur as a result of the innervation of the muscle by the primary motor neurons. Therefore, STC could be a useful endpoint to detect effect on the muscle innervation and also the on the whole nervous system. Consequently, important parameters of the STC test were optimized and an automated workflow to evaluate the STC with the open access software KNIME® was developed (Chapter 3).
To appropriately interpret the observed effect of a single chemical and especially mixture effects, requires the understanding of toxicokinetics and biotransformation. Most importantly, the biotransformation capacity of zebrafish embryos might be limited and this could be a challenge for assessment of chemicals such as organophosphates which require a bioactivation step to effectively inhibit the acetylcholinesterase (AChE) enzyme. Therefore, the influence of the potential limited biotransformation on the toxicity pathway of a typical organophosphate, chlorpyrifos, was investigated in Chapter 5. Chlorpyrifos could not inhibit AChE and this was attributed to possible lack of biotransformation in 24 hpf embryos (Chapter 5).
Since neuroactive substances occur in the environment as mixtures, it is therefore more realistic to assess their combined effect rather than individually. Therefore, mixture toxicity was predicted using the concentration addition and independent action models. Result shows that mixtures of neuroactive substances with different mechanisms of action but similar effects can be predicted with concentration addition and independent action (Chapter 4). Apart
from being able to predict the combined effect of neuroactive substances for prospective risk assessment, it is also important to assess in retrospect the combined neurotoxic effect of environmental samples since neuroactive substances are the largest group of chemicals occurring in the environment. In Chapter 6, the STC test was found to be capable of detecting neurotoxic effects of a wastewater effluent sample. Hence, the STC test is proposed as an effect based tool for monitoring environmental acute and neurotoxic effects.
Overall, this thesis shows the utility and versatility of zebrafish embryo behavior testing for screening neuroactive substances and this allows to propose its use for prospective and diagnostic hazard assessment. This will enhance the move away from expensive and demanding animal testing. The information contained in this thesis is of great potential to provide precautionary solutions, not only for the exposure of humans to neuroactive chemicals but for the environment at large.