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The presence of anthropogenic chemicals in the natural environment may impact both habitats and human use of natural resources. In particular the contamination of aquatic resources by organic compounds used as pharmaceuticals or household chemicals has become evident. The newly identified environmental pollutants, also known as micropollutants, often have i) unknown ecotoxicological impacts, ii) unknown partitioning mechanisms, e.g. sorption to sediments, and iii) limited regulation to control their emission. Furthermore, like any compound, micropollutants can be transformed while in the environmental matrix to unknown transformation products (TPs), which add to the number of unknown chemicals to consider and thus increase the complexity of risk management. Transformation is at the same time a natural mechanism for the removal of anthropogenic compounds, either by complete degradation (mineralisation) or to innocuous TPs. However, how transformation occurs in real-world conditions is still largely unknown. During the transport of micropollutants from household wastewater to surface water, a large amount of transformation can occur during wastewater treatment—specifically during biological nitrifying–denitrifying treatment processes. The thesis considers the systematic optimisation of laboratory investigative techniques, application of sensitive mass-spectrometry-based analysis techniques and the monitoring of full-scale wastewater treatment plants (WWTPs) to elucidate transformation processes of five known micropollutants.
The first of the five compounds investigated was the antibiotic trimethoprim. Incubation experiments were conducted at different analyte spike concentrations and different sludge to wastewater ratios. Using high-resolution mass spectrometry, a total of six TPs were identified from trimethoprim. The types of TPs formed was clearly influenced by the spike concentration. To the best of our knowledge, such impacts have not been previously described in the literature. Beginning from the lower spike concentration, a relatively stable final TP was formed (2,4-diaminopyrimidine-5-carboxylic acid, DAPC), which could account for almost all of the transformed trimethoprim quantity. The results were compared to the process in a reference reactor. Both by the detection of TPs (e.g., DAPC) and by modelling the removal kinetics, it could be concluded that only experimental results at the low spike concentrations mirrored the real reactor. The limits of using elevated spike concentrations in incubation experiments could thus be shown.
Three phenolic micropollutants, the antiseptic ortho-phenylphenol (OPP), the plastics additive bisphenol A (BPA) and the psychoactive drug dextrorphan were investigated with regard to the formation of potentially toxic, nitrophenolic TPs. Nitrite is an intermediate in the nitrification– denitrification process occurring in activated sludge and was found to cause nitration of these phenols. To elucidate the processes, incubation experiments were conducted in purified water in the presence of nitrite with OPP as the test substance. The reactive species HNO2, N2O3 and the radicals ·NO and ·NO2 were likely involved as indicated by scavenger experiments. In conditions found at WWTPs the wastewater is usually at neutral pH, and nitrite, being an intermediate, usually has a low concentration. By conducting incubation experiments inoculated with sludge from a conventional WWTP, it was found that the three phenolic micropollutants, OPP, BPA and dextrorphan were quickly transformed to biological TPs. Nitrophenolic TPs were only formed after artificial increase of the nitrite concentration or lowering of the pH. However, nitrophenolic-TPs can be formed as sample preparation artefacts through acidification or freezing for preservation, creating optimal conditions for the reaction to take place.
The final micropollutant to be studied was the pain-reliever diclofenac, a micropollutant on the EU-watch list due to ecotoxicological effects on rainbow trout. The transformation was compared in two different treatment systems, one employing a reactor with suspended carriers as a biofilm growth surface, while the other system employed conventional activated sludge. In the biofilm-based system, the pathway was found to produce many TPs each at relatively low concentration, many of which were intermediate TPs that were further degraded to unknown tertiary TPs. In the conventional activated sludge system some of the same reactions took place but all at much slower rates. The main difference between the two systems was due to different reaction rates rather than different transformation pathways. The municipal WWTPs were monitored to verify these results. In the biofilm system, a 10-day monitoring campaign confirmed an 88% removal of diclofenac and the formation of the same TPs as those observed in the laboratory experiments. The proposed environmental quality standard of 0.05 μg/L might thus be met without the need for additional treatment processes such as activated carbon filtration or ozonation.
Grassland management has been increasingly intensified throughout centuries since mankind started to control and modify the landscape. Species communities were always shaped alongside management changes leading to huge alterations in species richness and diversity up to the point where land use intensity exceeded the threshold. Since then biodiversity became increasingly lost. Today, global biodiversity and especially grassland biodiversity is pushed beyond its boundaries. Policymakers and conservationists seek for management options which fulfill the requirements of agronomic interests as well as biodiversity conservation alongside with the maintenance of ecosystem processes. However, there is and will always be a trade-off.
Earlier in history, natural circumstances in a landscape mainly determined regionally adapted land use. These regional adaptions shaped islands for many specialist species, and thus diverse species communities, favoring the establishment of a high β-diversity. With the raising food demand, these regional and traditional management regimes became widely unprofitable, and the invention of mineral fertilizers ultimately led to a wide homogenization of grassland management and, as follows, the loss of biotic heterogeneity. In the course of the green revolution, this immediate coherence and the dependency between grassland biodiversity and traditional land use practices becomes increasingly noticed. Indeed, some traditional forms of management such as meadow irrigation have been preserved in a few regions and thus give us the opportunity to directly investigate their long-term relevance for the species communities and ecosystem processes. Traditional meadow irrigation was a common management practice to improve productivity in lowland, but also alpine hay meadows throughout Europe until the 20th century. Nowadays, meadow irrigation is only practiced as a relic in a few remnant areas. In parts of the Queichwiesen meadows flood irrigation goes back to the Middle Ages, which makes them a predestined as a model region to study the long- and short-term effects of lowland meadow irrigation on the biodiversity and ecosystem processes.
Our study pointed out the conservation value of traditional meadow irrigation for the preservation of local species communities as well as the plant diversity at the landscape scale. The structurally more complex irrigated meadows lead to the assumption of a higher arthropod diversity (Orthodoptera, Carabidae, Araneae), which could not be detected. However, irrigated meadows are a significant habitat for moisture dependent arthropod species. In the light of the agronomic potential, flood irrigation could be a way to at least reduce fertilizer costs to a certain degree and possibly prevent overfertilization pulses which are necessarily hazardous to non-target ecosystems. Still, the reestablishment of flood irrigation in formerly irrigated meadows, or even the establishment of new irrigation systems needs ecological and economic evaluation dependent on regional circumstances and specific species communities, at which this study could serve as a reference point.
Hintergrund: Veränderte gesetzliche Rahmenbedingungen in der stationären Altenhilfe, die demografische Entwicklung mit dem steigenden Bedarf an Pflegekräften einerseits und die Tatsache, dass immer weniger Menschen aufgrund des Images des Berufes und der Arbeitsbedingungen in der Pflege tätig sein wollen andererseits, machen es notwendig neue Wege zu suchen. Die Träger im Sozial- und Gesundheitswesen sind gefordert, Konzepte zu entwickeln, die ihre Wirtschaftlichkeit sichern, gleichzeitig aber auch den Belastungen und der Unzufriedenheit von Mitarbeitenden entgegenwirken. Es braucht Gestaltungsräume, um Lösungen im Konflikt zwischen Anspruch und Machbarkeit zu finden und so dem alltäglichen Stress, der Mitarbeiterfluktuation und dem drohenden Leistungsabfall entgegenzuwirken. Durch das Praxisprojekt eines sozial-karitativen Trägers zur Implementierung einer ´Konstruktiven Konfliktkultur´ in einer stationären Altenhilfeeinrichtung sollte eine Organisationskultur geschaffen werden, in der Konflikte offen angesprochen werden, eine Offenheit für Veränderungsprozesse entsteht, Belastungen reduziert und die Mitarbeitenden an die Organisation gebunden werden. Dazu wurden drei pädagogische Interventionen entwickelt, durch die die Mitarbeitenden und die Führungskräfte in ihrer Konfliktfähigkeit geschult werden sollten. Methode: Die wissenschaftliche Begleitung dieses Praxisprojektes fand als Evaluationsstudie statt. Zu drei Erhebungszeitpunkten wurde eine repräsentative Mitarbeitergruppe dieser Einrichtung zu den Themen Konflikterleben, Führungsverhalten, Macht/ Regeln und Veränderungen durch qualitative Leitfadeninterviews befragt. Die Auswertung und Analyse der Daten erfolgte im Sinne der qualitativen Inhaltsanalyse nach Mayring und floss ein in eine formative Prozessevaluation der einzelnen Interventionen und einer summativen Effektevaluation zu Bewertung der Zielerreichung des Projektes. Ergebnis: Die einzelnen Interventionen des Projektes konnten nicht dazu beitragen, dass eine ´Konstruktiven Konfliktkultur´ nachhaltig entwickelt werden konnte. Zwar gab es in der Bewusstseinsspanne des Projektes einen expliziten Wissensgewinn, jedoch mehr bei den Führungskräften als bei den Mitarbeitenden. Die Führungskräfte sahen im Projekt einen Gewinn, für einen Teil der Mitarbeitenden war es sogar Zeitverschwendung. Anhand der Ergebnisse lassen sich drei Merkmale herauskristallisieren, die kennzeichnend sind für die zugrundeliegenden Denk-, Urteils-, und Handlungsstrukturen in sozialen Organisationen im Umgang mit Konflikten: Konflikte sind nicht wahrnehmbare Konstrukte der Alltagswelt. Sie manifestieren sich aufgrund fehlender Legitimation in Überforderung und eine ´Konstruktiven Konfliktkultur´ kann nicht auf das Wissen Einzelner aufbauen, sondern benötigt verbindliche Handlungsstrukturen für alle Organisationsmitglieder gleichermaßen. Ergebnisinterpretation: Durch die Einbeziehung wissenssoziologischer und konfliktsoziologischer Theorien und deren Einordnung in Institutionen – und Organisationstheorien konnten die Ergebnisse diskutiert und neue Erkenntnisse über Konflikte in Organisationen, die sich in drei Spannungsfeldern zeigen, gewonnen werden. Die Spannungsfelder bewegen sich zwischen dem Konflikt als nicht-wahrnehmbarem Alltagsphänomen auf der einen Seite und einer manifestierten Belastung auf der anderen Seite, dem Gewohnheitswissen im alltäglichen Umgang einerseits und einem fehlenden Handlungswissen andererseits, einer funktional-positiven Sicht hier und einer dysfunktional-negativen Sicht dort. Anhand dieser Spannungsfelder kann die Konfliktmentalität und ihre Entstehung und auch die Möglichkeit ihrer Veränderbarkeit reflektiert und können Erfolgsfaktoren für die Implementierung einer ´Konstruktiven Konfliktkultur´ entwickelt werden.
Schlussfolgerung: Wissen, Legitimation und Institutionalisierung und die Stärkung der Wahrnehmungen sind der Schlüssel für die Veränderung der Konfliktmentalität in sozialen Organisationen. Nachhaltigkeit erhält die Thematik aber erst, wenn alle Organisationsmitglieder eine gewisse Handlungsnotwendigkeit für sich erkennen. Aktuell steht die Organisationsentwicklung für den expliziten Veränderungswillen von Management, der jedoch auf ein gewisses Beharrungsvermögen von Mitarbeitenden trifft.
Natural pest control and pollination are important ecosystem services for agriculture. They can be supported by organic farming and by seminatural habitats at the local and landscape scale.
The potential of seminatural habitats to support predatory flies (chapters 2 and 3) and bees(chapter 7) at the local and landscape scale was investigated in seminatural habitats. Predatory flies were more abundant in woody habitats and positively related to landscape complexity. The diversity and the abundance of honey and wild bees were positively related to the supply of flowers offered in the seminatural habitats.
The influence of organic farming, adjacent seminatural habitats and landscape complexity on pest control (chapter 4) and pollination (chapter 6) was investigated in 18 pumpkin fields. Organic farming lacked strong effects both on the pest control and on the pollination of pumpkin.
Pest control is best supported at the local scale by the flower abundance in the adjacent habitat. The flower supply positively affected the density of natural enemies and tended to reduce aphid densities in pumpkin fields.
Pumpkin provides a striking example for a dominant role of wild pollinators for pollination success, because bumble bees are the key pollinators of pumpkin in Germany, despite a higher visitation frequency of honey bees. Pollination is best supported by landscape complexity. Bumble bee visits and as a result pollen delivery in pumpkin were negatively related to the dominance of agricultural land in the surrounding landscape.
The influence of aphid density (chapter 8) and pollination (chapter 5) on pumpkin yield was evaluated. Pumpkin yields were not affected by aphid densities observed in the pumpkin fields and not limited by pollination at the current levels of bee visitation.
In conclusion, especially seminatural habitats, that provide diverse, continuous floral resources, are important for natural enemies and pollinators. A sufficient proportion of different seminatural habitat types in agricultural landscapes should be maintained and restored. Thereby natural enemies such as predatory flies, wild pollinators such as bumble bees, and the pest control and pollination provided by them can be supported.
For a comprehensive understanding of evolutionary processes and for providing reliable prognoses about the future consequences of environmental change, it is essential to reveal the genetic basis underlying adaptive responses. The importance of this goal increases in light of ongoing climate change, which confronts organisms worldwide with new selection pressures and requires rapid evolutionary change to avoid local extinction. Thereby, freshwater ectotherms like daphnids are particularly threatened. Unraveling the genetic basis of local adaptation is complicated by the interplay of forces affecting patterns of genetic divergence among populations. Due to their key position in freshwater communities, cyclic parthenogenetic mode of reproduction and resting propagules (which form biological archives), daphnids are particularly suited for this purpose.
The aim of this thesis was to assess the impact of local thermal selection on the Daphnia longispina complex and to reveal the underlying genetic loci. Therefore, I compared genetic differentiation among populations containing Daphnia galeata, Daphnia longispina and their interspecific hybrids across time, space, and species boundaries. I revealed strongly contrasting patterns of genetic differentiation between selectively neutral and functional candidate gene markers, between the two species, and among samples from different lakes, suggesting (together with a correlation with habitat temperatures) local thermal selection acting on candidate gene TRY5F and indicating adaptive introgression. To reveal the candidate genes’ impact on fitness, I performed association analyses among data on genotypes and phenotypic traits of D. galeata clones from seven populations. The tests revealed a general temperature effect as well as inter-population differences in phenotypic traits and imply a possible contribution of the candidate genes to life-history traits. Finally, utilizing a combined population transcriptomic and reverse ecology approach, I introduced a methodology with a wide range of applications in evolutionary biology and revealed that local thermal selection was probably a minor force in shaping sequence and gene expression divergence among four D. galeata populations, but contributed to sequence divergence among two populations. I identified many transcripts possibly under selection or contributing strongly to population divergence, a large amount thereof putatively under local thermal selection, and showed that genetic and gene expression variation is not depleted specifically in temperature-related candidate genes.
In conclusion, I detected signs of local adaptation in the D. longispina complex across space, time, and species barriers. Populations and species remained genetically divergent, although increased gene flow possibly contributed, together with genotypes recruited from the resting egg bank, to the maintenance of standing genetic variation. Further work is required to accurately determine the influence of introgression and the effects of candidate genes on individual fitness. While I found no evidence suggesting a response to intense local thermal selection, the high resilience and adaptive potential regarding environmental change I observed suggest positive future prospects for the populations of the D. longispina complex. However, overall, due to the continuing environmental degradation, daphnids and other aquatic invertebrates remain vulnerable and threatened.
Die Dissertation bietet einen internationalen Vergleich von Gestaltungsmustern der Flexibilitätssteuerung von Unternehmen mit Schwerpunkt auf die Automobilindustrie. Vor dem Hintergrund unterschiedlicher nationaler institutioneller Systeme werden betriebliche Flexibilitätsstrategien analysiert und deren Hintergründe und Funktionsweisen detailliert erläutert. Die Analyse institutioneller Rahmenbedingungen erfolgt mittels der "Varieties of Capitalism". Die Eruierung von Flexibilitätsstrategien basiert auf einer internationalen Fallstudie.
The Web contains some extremely valuable information; however, often poor quality, inaccurate, irrelevant or fraudulent information can also be found. With the increasing amount of data available, it is becoming more and more difficult to distinguish truth from speculation on the Web. One of the most, if not the most, important criterion used to evaluate data credibility is the information source, i.e., the data origin. Trust in the information source is a valuable currency users have to evaluate such data. Data popularity, recency (or the time of validity), reliability, or vagueness ascribed to the data may also help users to judge the validity and appropriateness of information sources. We call this knowledge derived from the data the provenance of the data. Provenance is an important aspect of the Web. It is essential in identifying the suitability, veracity, and reliability of information, and in deciding whether information is to be trusted, reused, or even integrated with other information sources. Therefore, models and frameworks for representing, managing, and using provenance in the realm of Semantic Web technologies and applications are critically required. This thesis highlights the benefits of the use of provenance in different Web applications and scenarios. In particular, it presents management frameworks for querying and reasoning in the Semantic Web with provenance, and presents a collection of Semantic Web tools that explore provenance information when ranking and updating caches of Web data. To begin, this thesis discusses a highly exible and generic approach to the treatment of provenance when querying RDF datasets. The approach re-uses existing RDF modeling possibilities in order to represent provenance. It extends SPARQL query processing in such a way that given a SPARQL query for data, one may request provenance without modifying it. The use of provenance within SPARQL queries helps users to understand how RDF facts arederived, i.e., it describes the data and the operations used to produce the derived facts. Turning to more expressive Semantic Web data models, an optimized algorithm for reasoning and debugging OWL ontologies with provenance is presented. Typical reasoning tasks over an expressive Description Logic (e.g., using tableau methods to perform consistency checking, instance checking, satisfiability checking, and so on) are in the worst case doubly exponential, and in practice are often likewise very expensive. With the algorithm described in this thesis, however, one can efficiently reason in OWL ontologies with provenance, i.e., provenance is efficiently combined and propagated within the reasoning process. Users can use the derived provenance information to judge the reliability of inferences and to find errors in the ontology. Next, this thesis tackles the problem of providing to Web users the right content at the right time. The challenge is to efficiently rank a stream of messages based on user preferences. Provenance is used to represent preferences, i.e., the user defines his preferences over the messages' popularity, recency, etc. This information is then aggregated to obtain a joint ranking. The aggregation problem is related to the problem of preference aggregation in Social Choice Theory. The traditional problem formulation of preference aggregation assumes a I fixed set of preference orders and a fixed set of domain elements (e.g. messages). This work, however, investigates how an aggregated preference order has to be updated when the domain is dynamic, i.e., the aggregation approach ranks messages 'on the y' as the message passes through the system. Consequently, this thesis presents computational approaches for online preference aggregation that handle the dynamic setting more efficiently than standard ones. Lastly, this thesis addresses the scenario of caching data from the Linked Open Data (LOD) cloud. Data on the LOD cloud changes frequently and applications relying on that data - by pre-fetching data from the Web and storing local copies of it in a cache - need to continually update their caches. In order to make best use of the resources (e.g., network bandwidth for fetching data, and computation time) available, it is vital to choose a good strategy to know when to fetch data from which data source. A strategy to cope with data changes is to check for provenance. Provenance information delivered by LOD sources can denote when the resource on the Web has been changed last. Linked Data applications can benefit from this piece of information since simply checking on it may help users decide which sources need to be updated. For this purpose, this work describes an investigation of the availability and reliability of provenance information in the Linked Data sources. Another strategy for capturing data changes is to exploit provenance in a time-dependent function. Such a function should measure the frequency of the changes of LOD sources. This work describes, therefore, an approach to the analysis of data dynamics, i.e., the analysis of the change behavior of Linked Data sources over time, followed by the investigation of different scheduling update strategies to keep local LOD caches up-to-date. This thesis aims to prove the importance and benefits of the use of provenance in different Web applications and scenarios. The exibility of the approaches presented, combined with their high scalability, make this thesis a possible building block for the Semantic Web proof layer cake - the layer of provenance knowledge.
An assistance system has been developed for the purpuse of supporting the surgeon during the repositioning phase of intramedullary nailing of femural shaft fractures. As a basic principle the high forces generated by femural muscles and ligaments are taken by a linear sledge and a threaded rod. In order to move bone fragments directly Schanz screws are used as bone-machine interface. Two more Schanz screws are used for fine tuning orientation and position of the fragments according to the well known Joystick technique. The screws are fixed to two articulated arms, one passive and one fully robotic with manipulator. Thanks to the serial kinematic configuration of the system only minmal space of the surgeons working area gets occupied. Running a realtime operating system, the central control unit consits could be implemented as an embedded system comprising of a ARM Cortex-M0 microcontroller at it’s heart. This enables realtime computation and motor control of each joints value of the robotic arm using inverse kinematics. As inverse kinematics solver the iterative FABRIK algorithm was chosen. Serving as innovative and single user interface for the surgeon an optical force-torque sensor is used. The robotic arm always follows the surgeons motion when interacting with the sensor. Using the proposed demonstrator system a positioning resulution of <0,1mm could be accomplished. Thus by using the proposed solution during intramedullary nailing of femural shaft fractures a tremendous gain in positioning precision of bone fragments can be achieved. Furthermore a massive reduction of x-ray exposition of the surgeon is possible when applying the proposed approach. Also this approach enables the chance of cost reduction of femural fracture therapy due to reduction of needed time and staff.
Im schulischen Kontext wird dem Prozess der Erkenntnisgewinnung in eigenverantwortlichen Lernprozessen immer mehr Bedeutung beigemessen. Experimentelles Arbeiten wird in den nationalen Bildungsstandards als Prozess beschrieben, welcher vier Teil-schritte durchläuft: (1) Fragestellung entwickeln, (2) Experimente durchführen, (3) Daten notieren und (4) Schlussfolgerung ziehen [1]. In der fachdidaktischen Forschung gibt es bisher keine Untersuchungen, die explizit den Teilschritt der Datenaufnahme und dessen Bedeutung behandeln.
In dieser Arbeit werden die unterschiedlichen Definitionen der naturwissenschaftlichen Protokollformen voneinander abgegrenzt sowie im Rahmen von drei Teilstudien die Bedeutung des Protokollierens für die Lernwirksamkeit untersucht. Zusätzlich wird eine Auswertungsmethode für die Qualität von Erarbeitungsprotokollen vorgestellt.
This dissertation will discuss the theories of exponents of the philosophy of dialogue. Through that it shall establish the basis to reflect entrepreneurial leadership action. The goal is to find an approach for the development of a dialogical leadership culture.
The empirical part shall examine on what basis, in correlation with a dialogical leadership style, subjective assumptions are made by managers in their leadership action who work in inpatient nursing services. Furthermore, it shall address the question of how those subjective assumptions can be considered and utilized towards establishing future dialogically oriented leadership cultures and the development of coinciding management personnel.
It shall also debate the question to what extent the philosophy of dialogue includes theoretical concepts which can be used to describe a leadership culture. The intellectual approach of Martin Bubers is especially taken into consideration.
Based on these theoretical grounds, the attempt shall be made to develop the basic intention of a dialogical leadership culture which will appropriately justify a didactical concept for the development of management personnel in nursing services.
Pelagic oxyclines, the transition zone between oxygen rich surface waters and oxygen depleted deep waters, are a common characteristic of eutrophic lakes during summer stratification. They can have tremendous effects on the biodiversity and the ecosystem functioning of lakes and, to add insult to injury, are expected to become more frequent and more pronounced as climate warming progresses. On these grounds, this thesis endeavors to advance the understanding of formation, persistence, and consequences of pelagic oxyclines: We test, whether the formation of metalimnetic oxygen minima is intrinsically tied to a locally enhanced oxygen consuming process, investigate the relative importance of vertical physical oxygen transport and biochemical oxygen consumption for the persistence of pelagic oxyclines, and finally assess their potential consequences for whole lake cycling. To pursue these objectives, the present thesis nearly exclusively resorts to in situ measurements. Field campaigns were conducted at three lakes in Germany featuring different types of oxyclines and resolved either a short (hours to days) or a long (weeks to months) time scale. Measurements comprised temperature, current velocity, and concentrations of oxygen and reduced substances in high temporal and vertical resolution. Additionally, vertical transport was estimated by applying the eddy correlation technique within the pelagic region for the first time. The thesis revealed, that the formation of metalimnetic oxygen minima does not necessarily depend on locally enhanced oxygen depletion, but can solely result from gradients and curvatures of oxygen concentration and depletion and their relative position to each other. Physical oxygen transport was found to be relevant for oxycline persistence when it considerably postponed anoxia on a long time scale. However, its influence on oxygen dynamics was minor on short time scales, although mixing and transport were highly variable. Biochemical consumption always dominated the fate of oxygen in pelagic oxyclines. It was primarily determined by the oxidative breakdown of organic matter originating from the epilimnion, whereas in meromictic lakes, the oxidation of reduced substances dominated. Beyond that, the results of the thesis emphasize that pelagic oxyclines can be a hotspot of mineralization and, hence, short-circuit carbon and nutrient cycling in the upper part of the water column. Overall, the present thesis highlights the importance of considering physical transport as well as biochemical cycling in future studies.
Die Analyse ortsbezogener Strukturdaten und Merkmale ist eine der wesentlichen Voraussetzungen für die Bewertung von Standorten und Räumen. Durch die Erfassung der lokalen Ausprägung ausgewählter Standortfaktoren und unter Zuhilfenahme eines Geographischen Informationssystems werden in der vorliegenden Dissertation die Städte und Gemeinden des hessischen Rheingau-Taunus-Kreises kategorisiert und miteinander verglichen. Hierbei erfolgt eine besondere Fokussierung auf die lokal bestehende technische und soziale Infrastruktur, um vorrangig das vorhandene Gewerbe- und Wohnumfeld sowie die darüber hinaus existierenden räumlichen Disparitäten eingehend veranschaulichen und beurteilen zu können.
World’s ecosystems are under great pressure satisfying anthropogenic demands, with freshwaters being of central importance. The Millennium Ecosystem Assessment has identified anthropogenic land use and associated stressors as main drivers in jeopardizing stream ecosystem functions and the
biodiversity supported by freshwaters. Adverse effects on the biodiversity of freshwater organisms, such as macroinvertebrates, may propagate to fundamental ecosystem functions, such as organic matter breakdown (OMB) with potentially severe consequences for ecosystem services. In order to adequately protect and preserve freshwater ecosystems, investigations regarding potential and observed as well as direct and indirect effects of anthropogenic land use and associated stressors (e.g. nutrients, pesticides or heavy metals) on ecosystem functioning and stream biodiversity are needed. While greater species diversity most likely benefits ecosystem functions, the direction and magnitude of changes in ecosystem functioning depends primarily on species functional traits. In this context, the functional diversity of stream organisms has been suggested to be a more suitable predictor of changes in ecosystem functions than taxonomic diversity.
The thesis aims at investigating effects of anthropogenic land use on (i) three ecosystem functions by anthropogenic toxicants to identify effect thresholds (chapter 2), (ii) the organic matter breakdown by three land use categories to identify effects on the functional level (chapter 3) and (iii)on the stream community along an established land-use gradient to identify effects on the community level.
In chapter 2, I reviewed the literature regarding pesticide and heavy metal effects on OMB, primary production and community respiration. From each reviewed study that met inclusion criteria, the toxicant concentration resulting in a reduction of at least 20% in an ecosystem function was standardized based on laboratory toxicity data. Effect thresholds were based on the relationship between ecosystem functions and standardized concentration-effect relationships. The analysis revealed that more than one third of pesticide observations indicated reductions in ecosystem functions at concentrations that are assumed being protective in regulation. However, high variation within and between studies hampered the derivation of a concentration-effect relationship and thus effect thresholds.
In chapter 3, I conducted a field study to determine the microbial and invertebrate-mediated OMB by deploying fine and coarse mesh leaf bags in streams with forested, agricultural, vinicultural
and urban riparian land use. Additionally, physicochemical, geographical and habitat parameters were monitored to explain potential differences in OMB among land use types and sites. Regarding results, only microbial OMB differed between land use types. The microbial OMB showed a negative relationship with pH while the invertebrate-mediated OMB was positively related to tree cover. OMB responded to stressor gradients rather than directly to land use.
In chapter 4, macroinvertebrates were sampled in concert with leaf bag deployment and after species identification (i) the taxonomic diversity in terms of Simpson diversity and total taxonomic
richness (TTR) and (ii) the functional diversity in terms of bio-ecological traits and Rao’s quadratic entropy was determined for each community. Additionally, a land-use gradient was established and the response of the taxonomic and functional diversity of invertebrate communities along this gradient was investigated to examine whether these two metrics of biodiversity are predictive for the rate of OMB. Neither bio-ecological traits nor the functional diversity showed a significant relationship with
OMB. Although, TTR decreased with increasing anthropogenic stress and also the community structure and 26 % of bio-ecological traits were significantly related to the stress gradient, any of these shifts propagated to OMB.
Our results show that the complexity of real-world situations in freshwater ecosystems impedes the effect assessment of chemicals and land use for functional endpoints, and consequently our potential to predict changes. We conclude that current safety factors used in chemical risk assessment may not be sufficient for pesticides to protect functional endpoints. Furthermore, simplifying real-world stressor gradients into few land use categories was unsuitable to predict and quantify losses in OMB. Thus, the monitoring of specific stressors may be more relevant than crude land use categories to detect effects on ecosystem functions. This may, however, limit the large scale assessment of the status of OMB. Finally, despite several functional changes in the communities the functional diversity over several trait modalities remained similar. Neither taxonomic nor functional diversity were suitable predictors of OMB. Thus, when understanding anthropogenic impacts on the linkage between biodiversity and ecosystem functioning is of main interest, focusing on diversity metrics that are clearly linked to the stressor in question (Jackson et al. 2016) or integrating taxonomic and functional metrics (Mondy et al., 2012) might enhance our predictive capacity.
Key mechanisms for the release of metal(loid)s from a construction material in hydraulic engineering
(2017)
Hydraulic engineering and thus construction materials are necessary to enable the navigability of water ways. Since, a variety of natural as well as artificial materials are used, this materials are world wide tested on a potential release of dangerous substances to prevent adverse effects on the environment. To determine the potential release, it is important to identify and to understand key mechanisms which are decisive for the release of hazardous substances. A limited correlation between the conditions used in regulatory tests and those found in environmental systems is given and hence, often the significance of results from standardised tests on construction materials is questioned, since they are not designed to mimic environmental conditions.
In Germany industrial by-products are used as armour stones in hydraulic engineering. Especially the by-product copper slag is used during the last 40 years for the construction of embankments, groynes and coastal protection. On the one hand, this material has a high density and natural resources (landscape) are protected. One the other hand, the material contains high quantities of metal(loid)s. Therefore the copper slag (product name: iron silicate stones) is very suitable as test material. Metal(loid)s examined were As, Sb and Mo as representatives for (hydr)oxide forming elements and Cd, Co, Cu, Fe, Ni, Pb and Zn were studied as representatives for elements forming cations during the release.
Questions addressed in this Thesis were: (i) can we transfer the results from batch experiments to construction scenarios under the prevalent environmental conditions, (ii) which long-term trends exist for the release of metal(loid)s from copper slags and (iii) how environmental conditions influence the leaching of metal(loid)s from water construction materials?
To answer the first question the surface depending release of the metal(loid)s from the construction materials was examined. Therefore, batch leaching experiments with different particle sizes and a constant liquid/solid ratio were performed. In a second step a comparison between different methods for the determination of the specific surface area of armour stones with a 3D laser scanning method as a reference were performed. In a last step it was possible to show that via a roughness factor the results of the specific surface area from small stones, measured with gas adsorption, can be connected with the results from armour stones, determined with an aluminium foil method. Based on calculations of the specific surface area, it was possible to significantly improve catchment scale calculation about the release of metal(loid)s and to evaluate a potential impact of construction materials in hydraulic engineering on the water chemistry of rivers and streams.
To answer the second question long-term leaching diffuse gradient in thin films supported experiments were performed for half a year. Diffuse gradients in thin films (DGT) is an in situ method to passive sample metal(loid)s in water, sediments and soils. They were used as a sink for metal(loid)s in the eluate to provide solution equilibriums. Thus the exchange of the eluent, which is performed normally in long-term experiments, was superfluous and long-term effects under undisturbed conditions were studied. The long-term leaching experiments with DGT have proven to be capable (i) to differentiate between the depletion of the material surface and the solution equilibriums and (ii) to study sorption processes with or without a further release of the analytes. This means for the practically relevant test material copper slag that: (i) the cations Cd, Co, Cu, Ni and Pb are confirmed to be released from the slag over the whole time period of six months, (ii) a surface depletion of Zn was detected, and (iii) that the (hydr)oxide forming elements As, Mo and Sb were released from the slag over the hole periods of six months but the release was masked by adsorption to Fe-oxide colloids, which were formed during the leaching experiments. It was confirmed, that sulphide minerals are the main source for long-term release of Cd, Cu, Ni, Pb and Mo.
To answer the third question short-term leaching experiments simulating environmental conditions in hydraulic engineering were performed. One factor is the salinity. The influence of this parameter was tested in batch experiments with sea salt solution (30 g/l), river Rhine water, ultra pure water and in addition with different NaCl concentration (5, 10, 20 and 30 g/l). In general, the ionic strength is an important factor for the metal(loid) release but the composition of the water (e.g. the HCO3- content) may superimpose this effect. Therefore, the concentrations of the metal(loid)s in the experiments with ultra-pure water spiked with sea salt or native river water and the ultra-pure water spiked with NaCl were significantly different. In a second experiment the influence of the environmental parameters and the interactions between the environmental parameters pH (4–10), sediment content (0 g–3.75 g), temperature (4 °C–36 °C) and ionic strength (0 g/l–30 g/l NaCl) on the release of metal(loid)s from the test material was examined. The statistical Design of Experiments (DoE) was used to study the influence of these factors as well as their interactions. All studied factors may impact the release of metal(loid)s from the test material to the eluent, whereas the release and the partitioning between sediment and eluate of metal(loid)s was impacted by interactions between the studied factors. The main processes were sorption, complexation, solubility, buffering and ion exchange. In addition, by separating the sediment from the slag after the experiments by magnetic separation, the enrichment of metal(loid)s in the sediment was visible. Thus, the sediment was the most important factor for the release of the metal(loid)s, via pH, temperature and ionic strength, because the sediment acted as a sink.
In der vorliegenden Arbeit wird das thermochemische Wechselwirkungsverhalten verschiedener Magnesiakohlenstoffmaterialen in Abhängigkeit verschiedener Einflussgrößen wissenschaftlich untersucht. Schwerpunkte der experimentellen Arbeiten bilden thermoanalytische Experimente, Gefügeuntersuchungen der Magnesiakohlenstoff-Proben sowie thermodyna-mische Berechnungen und Auswertungen durch CAT (Computer Aided Thermochemistry) mittels des Softwarepakets FactSage.
Erster Themenbereich dieser Arbeit ist die Untersuchung des Einflusses der in dem Rohstoff Magnesia enthaltenen mineralogischen Nebenphasen Merwinit (C3MS2), Monticellit (CMS) und Belit (C2S) auf den carbothermisch induzierten Verschleiß im MgO-C-Material. Für die Messreihen wurden die Nebenphasen eigens synthetisiert und hiermit MgO-C-Nebenphase-Modellwerkstoffe hergestellt. Die Nebenphase Monticellit ist unbeständig gegenüber der carbothermischen Reduktion. Monticellit wird im MgO-C-Gefüge durch Kohlenstoff reduziert und hieraus ergibt sich ein erhöhter Gewichtsverlust des Probenmaterials. Auch Merwinit wird bei T = 1600°C reduziert, der Gewichtsverlust wird dadurch allerdings nicht erhöht. Belit ist im MgO-C-Gefüge stabil gegenüber carbothermischer Reduktion.
Ein weiterer Schwerpunkt der Arbeit lag auf der Untersuchung des Einflusses des klassischen Antioxidans Aluminium auf die thermochemische Stabilität von MgO-C. Bei geringen Sauerstoffpartialdrücken ist die Reaktion des Aluminium-Metalls bzw. des bereits zu Al4C3 carbidisierten Aluminiums mit dem steineigenen Periklas unter Mg(g)-Bildung möglich, was einen erhöhten Gewichtsverlust zur Folge hat. Aber auch nach der Oxidation zu Al2O3 bzw. Spinell liegt Aluminium in signifikanten Mengen als Al(g) und Al2O(g) in der Gasphase vor und greift des Weiteren die Nebenphasen an, was ebenfalls zu einem messbaren Gewichtsverlust führt.
Dritter Arbeitsschwerpunkt war die Untersuchung des Einflusses des Umgebungsdruckes auf die carbothermische Reduktion von MgO. Die Ergebnisse zeigen, dass der Druck sich in zweierlei Hinsicht auf die carbothermische Reduktion von MgO auswirkt. Zum einen bewirkt ein sinkender Umgebungsdruck eine Beschleunigung der carbothermischen Reduktion durch die Verschiebung des thermodynamischen Gleichgewichts auf die Produktseite. Des Weiteren sorgt er für einen schnelleren Abtransport der Produktgase vom Reaktionsort und ver-hindert somit die Einstellung eines lokalen Gleichgewichts im Gefüge. Dritter Effekt ist die mit steigendem Druck verstärkt ablaufende Kohlenstoffoxidation durch Umgebungssauerstoff, da die Sauerstoffmenge in der Umgebung des MgO-C-Materials vom Umgebungsdruck bestimmt wird. Für die Geschwindigkeit des thermochemischen Verschleißes von Magnesiakohlenstoffmaterialien, der immer eine Kombination aus Kohlenstoffoxidation und carbothermischer Reduktion darstellt, bedeutet dies, dass sie in Abhängigkeit vom Umgebungsdruck in unterschiedlichem Ausmaß von diesen beiden Reaktionen beeinflusst wird.
Statistical eco(-toxico)logy
(2017)
Freshwaters are of immense importance for human well-being.
Nevertheless, they are currently facing unprecedented levels of threat from habitat loss and degradation, overexploitation, invasive species and
pollution.
To prevent risks to aquatic ecosystems, chemical substances, like agricultural pesticides, have to pass environmental risk assessment (ERA) before entering the market.
Concurrently, large-scale environmental monitoring is used for surveillance of biological and chemical conditions in freshwaters.
This thesis examines statistical methods currently used in ERA.
Moreover, it presents a national-scale compilation of chemical monitoring data, an analysis of drivers and dynamics of chemical pollution in streams and, provides a large-scale risk assessment by combination with results from ERA.
Additionally, software tools have been developed to integrate different datasets used in ERA.
The thesis starts with a brief introduction to ERA and environmental monitoring and gives an overview of the objectives of the thesis.
Chapter 2 addresses experimental setups and their statistical analyses using simulations.
The results show that current designs exhibit unacceptably low statistical power, that statistical methods chosen to fit the type of data provide higher power and that statistical practices in ERA need to be revised.
In chapter 3 we compiled all available pesticide monitoring data from Germany.
Hereby, we focused on small streams, similar to those considered in ERA and used threshold concentrations derived during ERA for a large-scale assessment of threats to freshwaters from pesticides.
This compilation resulted in the most comprehensive dataset on pesticide exposure currently available for Germany.
Using state-of-the-art statistical techniques, that explicitly take the limits of quantification into account, we demonstrate that 25% of small streams are at threat from pesticides.
In particular neonicotinoid pesticides are responsible for these threats.
These are associated with agricultural intensity and can be detected even at low levels of agricultural use.
Moreover, our results indicated that current monitoring underestimates pesticide risks, because of a sampling decoupled from precipitation events.
Additionally, we provide a first large-scale study of annual pesticide exposure dynamics.
Chapters 4 and 5 describe software solutions to simplify and accelerate the integration of data from ERA, environmental monitoring and ecotoxicology that is indispensable for the development of landscape-level risk assessment.
Overall, this thesis contributes to the emerging discipline of statistical ecotoxicology and shows that pesticides pose a large-scale threat to small streams.
Environmental monitoring can provide a post-authorisation feedback to ERA.
However, to protect freshwater ecosystems ERA and environmental monitoring need to be further refined and we provide software solutions to utilise existing data for this purpose.
Agricultural land-use may lead to brief pulse exposures of pesticides in edge-of-field streams, potentially resulting in adverse effects on aquatic macrophytes, invertebrates and ecosystem functions. The higher tier risk assessment is mainly based on pond mesocosms which are not designed to mimic stream-typical conditions. Relatively little is known on exposure and effect assessment using stream mesocosms.
Thus the present thesis evaluates the appliacability of the stream mesocosms to mimic stream-typical pulse exposures, to assess resulting effects on flora and fauna and to evaluate aquatic-terrestrial food web coupling. The first objective was to mimic stream-typical pulse exposure scenarios with different durations (≤ 1 to ≥ 24 hours). These exposure scenarios established using a fluorescence tracer were the methodological basis for the effect assessment of an herbicide and an insecticide. In order to evaluate the applicability of stream mesocosms for regulatory purposes, the second objective was to assess effects on two aquatic macrophytes following a 24-h pulse exposure with the herbicide iofensulfuron-sodium (1, 3, 10 and 30 µg/L; n = 3). Growth inhibition of up to 66 and 45% was observed for the total shoot length of Myriophyllum spicatum and Elodea canadensis, respectively. Recovery of this endpoint could be demonstrated within 42 days for both macrophytes. The third objective was to assess effects on structural and functional endpoints following a 6-h pulse exposure of the pyrethroid ether etofenprox (0.05, 0.5 and 5 µg/L; n = 4). The most sensitive structural (abundance of Cloeon simile) and functional (feeding rates of Asellus aquaticus) endpoint revealed significant effects at 0.05 µg/L etofenprox. This concentration was below field-measured etofenprox concentrations and thus suggests that pulse exposures adversely affect invertebrate populations and ecosystem functions in streams. Such pollutions of streams may also result in decreased emergence of aquatic insects and potentially lead to an insect-mediated transfer of pollutants to adjacent food webs. Test systems capable to assess aquatic-terrestrial effects are not yet integrated in mesocosm approaches but might be of interest for substances with bioaccumulation potential. Here, the fourth part provides an aquatic-terrestrial model ecosystem capable to assess cross-ecosystem effects. Information on the riparian food web such as the contribution of aquatic (up to 71%) and terrestrial (up to 29%) insect prey to the diet of the riparian spider Tetragnatha extensa was assessed via stable isotope ratios (δ13C and δ15N). Thus, the present thesis provides the methodological basis to assess aquatic-terrestrial pollutant transfer and effects on the riparian food web.
Overall the results of this thesis indicate, that stream mesocosms can be used to mimic stream-typical pulse exposures of pesticides, to assess resulting effects on macrophytes and invertebrates within prospective environmental risk assessment (ERA) and to evaluate changes in riparian food webs.