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Thousands of chemicals from daily use are being discharged from civilization into the water cycle via different pathways. Ingredients of personal care products, detergents, pharmaceuticals, pesticides, and industrial chemicals thus find their way into the aquatic ecosystems and may cause adverse impacts on the ecology. Pharmaceuticals for instance, represent a central group of anthropogenic chemicals, because of their designed potency to interfere with physiological functions in organisms. Ecotoxicological effects from pharmaceutical burden have been verified in the past. Therapeutic groups with pronounced endocrine disrupting potentials such as steroid hormones gain increasing focus in environmental research as it was reported that they cause endocrine disruption in aquatic organisms even when exposed to environmentally relevant concentrations. This thesis considers the comprehensive investigation of the occurrence of corticosteroids and progestogens in wastewater treatment plant (WWTP) effluents and surface waters as well as the elucidation of the fate and biodegradability of these steroid families during activated sludge treatment. For the first goal of the thesis, a robust and highly sensitive analytical method based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed in order to simultaneously determine the occurrence of around 60 mineralocorticoids, glucocorticoids and progestogens in the aquatic environment. A special focus was set to the compound selection due to the diversity of marketed synthetic steroids. Some analytical challenges have been approved by individual approaches regarding sensitivity enhancement and compound stabilities. These results may be important for further research in environmental analysis of steroid hormones. Reliable and low quantification limits are the perquisite for the determination of corticosteroids and progestogens at relevant concentrations due to low consumption volumes and simultaneously low effect-based trigger values. Achieved quantification limits for all target analytes ranged between 0.02 ng/L and 0.5 ng/L in surface water and 0.05 ng/L to 5 ng/L in WWTP effluents. This sensitivity enabled the detection of three mineralocorticoids, 23 glucocorticoids and 10 progestogens within the sampling campaign around Germany. Many of them were detected for the first time in the environment, particularly in Germany and the EU. To the best of our knowledge, this in-depth steroid screening provided a good overview of single steroid burden and allowed for the identification of predominantly steroids of each steroid
type analyzed for the first time. The frequent detection of highly potent synthetic steroids (e.g. triamcinolone acetonide, clobetasol propionate, betamethasone valerate, dienogest, cyproterone acetate) highlighted insufficient removal during conventional Summary wastewater treatment and indicated the need for regulation to control their emission since the steroid concentrations were found to be above the reported effect-based trigger values for biota. Overall, the study revealed reliable environmental data of poorly or even not analyzed steroids. The results complement the existing knowledge in this field but also providednew information which can beused particularly for compound prioritization in ecotoxicological research and environmental analysis. Based on the data obtained from the monitoring campaign, incubation experiments were conducted to enable the comparison of the biodegradability and transformation processes in activated sludge treatment for structure-related steroids under aerobic and standardized experimental conditions. The compounds were accurately selected to cover manifold structural moieties of commonly used glucocorticoids, including non-halogenated and halogenated steroids, their mono- and diesters, and several acetonide-type steroids. This approach allowed for a structure-based interpretation of the results. The obtained biodegradation rate constants suggested large variations in the biodegradability (half-lifes ranged from < 0.5 h to > 14 d). An increasing stability was identified in the order from non-halogenated steroids (e.g. hydrocortisone), over 9α-halogenated steroids (e.g. betamethasone), to C17-monoesters (e.g. betamethasone 17-valerate, clobetasol propionate), and finally to acetonides (e.g. triamcinolone acetonide), thus suggesting a strong relationship of the biodegradability with the glucocorticoid structure. Some explanations for this behavior have been received by identifying the transformation products (TPs) and elucidating individual transformation pathways. The results revealed the identification of the likelihood of transformation reactions depending on the chemical steroid structure for the first time. Among the identified TPs, the carboxylates (e.g. TPs of fluticasone propionate, triamcinolone acetonide) have been shown persistency in the subsequent incubation experiments. The newly identified TPs furthermore were frequently detected in the effluents of full-scale wastewater treatment plants. These findings emphasized i) the transferability of the lab-scale degradation experiments to real world and that ii) insufficient removals may cause adverse effects in the aquatic environment due to the ability of the precursor steroids and TPs to interact with the endocrine system in biota. For the last goal, the conceptual study for glucocorticoids was applied to progestogens.
Here, two sub-types of the steroid family frequently used for hormonal contraception were selected (17α-hydroxyprogesterone and 19-norstestosterone type). The progestogens showed a fast and complete degradation within six hours, and thus empathizes pronounced biodegradability. However, cyproterone acetate and dienogest Summary have been found to be more recalcitrant in activated sludge treatment. This was consistent with their ubiquitously occurrence during the previous monitoring campaign. The elucidation of TPs again revealed some crucial information regarding the observed behavior and highlighted furthermore the formation of hazardous TPs. It was shown that 19-nortestosterone type steroids are able to undergo aromatization at ring A in contact with activated sludge, leading to the formation of estrogen-like TPs with a phenolic moiety at ring A. In the case of norethisterone the formation of 17α-ethinylestradiol was confirmed, which is a well-known potent synthetic estrogen with elevated ecotoxicological potency. Thus, the results indicated for the very first time an unknown source of estrogenic compounds, particularly for 17α-ethinylestradiol. In conclusion, some steroids were found to be very stable in activated sludge treatment, others degrade well, and others which do degrade but predominantly to active TPs depending on their chemical structure. Fluorinated acetal steroids such as triamcinolone acetonide and fluocinolone acetonide are poorly biodegradable, which is reflected in high concentrations detected ubiquitously in WWTP effluents. Endogenous steroids and their most related synthetic once such as hydrocortisone, prednisolone or 17α-hydroxyprogesterone are readily biodegradable. Regardless their high influent concentrations, they are almost completely removed in conventional WWTPs. Steroids between this range have been found to form elevated quantities of TPs which are partially still active, which particularly the case for betamethasone, fluticasone propionate, cyproterone acetate or dienogest. The thesis illustrates the need for an extensive evaluation of the environmental risks and carried out that corticosteroids and progestogens merit more attention in environmental regulatory and research than it is currently the case
The protected areas of Rwanda are facing various challenges resulting from the anthropogenic activities of the surrounding communities especially in the adjacent area to Cyamudongo isolated rain forest, which results in climate change, soil degradation, and loss of biodiversity. Therefore, this study aims to broaden current knowledge on the impact of sustainable Agroforestry (AF) on the Carbon (C) stock and Biodiversity conservation on the surroundings of Cyamudongo isolated rain forest and Ruhande Arboretum.
To understand this, the permanent sample plots (PSPs) were established mainly in the designed four transects of four km long originating on the boundary of the Cyamudongo isolated rain forest following the slope gradient ranging from 1286 to 2015 m asl. A total number of 73 PSPs were established in the Cyamudongo study area while 3 PSPs were established in the Ruhande AF plot. The Arc Map GIS 10.4 was used to design and map the sampling areas while GPS was used for localization of collected items. Statistical significance was analyzed through the R-software especially for wood and soil variables while for biodiversity indicator species, MVSP Software 3.0 was used to determine the Shannon Diversity indices and similarities among species.
In this study, I have obtained comprehensive results demonstrating that in all study areas, the various AF tree species contribute differently to C stock and C sequestration and the amount of C stored and removed from the atmosphere depends on different factors such as tree species, plantation density, growth stage, or the age of establishment, applied management practices, wood specific density (WSD), wood C concentration, and climatic conditions. The estimated quantity of sequestrated C for 2 years and 34 years AF species were 13.11 t C ha -1 yr-1 (equivalent to 48 t CO2 ha -1 yr-1) and 6.85 t ha-1 yr-1 (equivalent to 25.1 t CO2 ha -1 yr-1) in Cyamudongo and Ruhande respectively. The estimated quantity of C stored by the Ruhande AF plot is 232.94 t ha-1. In Cyamudongo, the overall C stored by the AF systems was 823 t ha-1 by both young tree species established by the Cyamudongo Project (35.84 t ha-1) and C stored by existed AF species before the existence of the Project (787.12 t ha-1). In all study areas, the Grevillea robusta was found to contribute more to overall stored C compared to other species under this study.
The tests revealed differences in terms of nutrient contents (C, N, C: N ratio, K, Na, Ca, and Mg) for various AF tree species of Cyamudongo and Ruhande study areas. The differences in terms of correlation for various variables of AF tree species in different study areas varied with tree species, age, stage of growth, and tree shape. By comparing the correlation coefficients for various tree variables for young and mature AF tree species, the results showed a high correlation variability for young species than mature or old species recorded in different environmental conditions of Cyamudongo and Ruhande study areas.
The recorded soil pH mean value across in Cyamudongo study area is 4.2, which is very strongly acidic. The tests revealed that the soil pH, C, C: N ratio, OM, NH4+, NO3-+NO2-, PO43-, and CEC were significantly (P < 0.05) different in various soil depths whereas the N was not statistically significant. The pH, N, C: N ratio, CEC, NH4+, PO43-, and Al3+ showed a significant difference across land uses whereas the C and NO3-+NO2- did not show any statistical difference. All tested chemical elements showed a statistical difference as far as altitude ranges are concerned. The only NH4+, PO43-, and CEC showed significant differences with time whereas all other remaining chemical elements did not show any statistical significance. The bulk density of soil was statistically different across land uses and altitude ranges. The soil pH was very strongly correlated with CEC, Mg, and Ca in cropland (CL) whereas it was strongly correlated in both AF and natural forest (NF) except for Mg, which was moderately correlated in AF. Furthermore, its correlation with K was strong in CL, moderate in AF while it was weak in NF. Finally, the pH correlation with Na was weak in both AF and CL whereas it was negligible in NF. The overall estimated soil C stock of the study area was 16848 t ha -1.
The sustainable AF practices changed significantly the frequency of reptiles, amphibians, and flowering plants while there was no statistical change observed on ferns with time. In terms of species richness, 16 flowering plants, 14 ferns, 5 amphibians, and 3 reptiles were recorded and monitored. These findings add to a growing body of literature on the impact of AF on the C stock, soil improvement, and Biodiversity. It is recommended that further researches should be undertaken for the contribution of other AF tree species to the C stock found in the agricultural landscape around all protected areas of Rwanda and the impact on them on the soil and biodiversity.
We consider variational discretization of three different optimal control problems.
The first being a parabolic optimal control problem governed by space-time measure controls. This problem has a nice sparsity structure, which motivates our aim to achieve maximal sparsity on the discrete level. Due to the measures on the right hand side of the partial differential equation, we consider a very weak solution theory for the state equation and need an embedding into the continuous functions for the pairings to make sense. Furthermore, we employ Fenchel duality to formulate the predual problem and give results on solution theory of both the predual and the primal problem. Later on, the duality is also helpful for the derivation of algorithms, since the predual problem can be differentiated twice so that we can apply a semismooth Newton method. We then retrieve the optimal control by duality relations.
For the state discretization we use a Petrov-Galerkin method employing piecewise constant states and piecewise linear and continuous test functions in time. For the space discretization we choose piecewise linear and continuous functions. As a result the controls are composed of Dirac measures in space-time, centered at points on the discrete space-time grid. We prove that the optimal discrete states and controls converge strongly in L^q and weakly-* in Μ, respectively, to their smooth counterparts, where q ϵ (1,min{2,1+2/d}] is the spatial dimension. The variational discrete version of the state equation with the above choice of spaces yields a Crank-Nicolson time stepping scheme with half a Rannacher smoothing step.
Furthermore, we compare our approach to a full discretization of the corresponding control problem, precisely a discontinuous Galerkin method for the state discretization, where the discrete controls are piecewise constant in time and Dirac measures in space. Numerical experiments highlight the sparsity features of our discrete approach and verify the convergence results.
The second problem we analyze is a parabolic optimal control problem governed by bounded initial measure controls. Here, the cost functional consists of a tracking term corresponding to the observation of the state at final time. Instead of a regularization term for the control in the cost functional, we consider a bound on the measure norm of the initial control. As in the first problem we observe a sparsity structure, but here the control resides only in space at initial time, so we focus on the space discretization to achieve maximal sparsity of the control. Again, due to the initial measure in the partial differential equation, we rely on a very weak solution theory of the state equation.
We employ a dG(0) approximation of the state equation, i.e. we choose piecewise linear and continuous functions in space, which are piecewise constant in time for our ansatz and test space. Then, the variational discretization of the problem together with the optimality conditions induce maximal discrete sparsity of the initial control, i.e. Dirac measures in space. We present numerical experiments to illustrate our approach and investigate the sparsity structure
As third problem we choose an elliptic optimal control governed by functions of bounded variation (BV) in one space dimension. The cost functional consists of a tracking term for the state and a BV-seminorm in terms of the derivative of the control. We derive a sparsity structure for the derivative of the BV control. Additionally, we utilize the mixed formulation for the state equation.
A variational discretization approach with piecewise constant discretization of the state and piecewise linear and continuous discretization of the adjoint state yields that the derivative of the control is a sum of Dirac measures. Consequently the control is a piecewise constant function. Under a structural assumption we even get that the number of jumps of the control is finite. We prove error estimates for the variational discretization approach in combination with the mixed formulation of the state equation and confirm our findings in numerical experiments that display the convergence rate.
In summary we confirm the use of variational discretization for optimal control problems with measures that inherit a sparsity. We are able to preserve the sparsity on the discrete level without discretizing the control variable.
This thesis focuses on approximate inference in assumption-based argumentation frameworks. Argumentation provides a significant idea in the computerization of theoretical and practical reasoning in AI. And it has a close connection with AI, engaging in arguments to perform scientific reasoning. The fundamental approach in this field is abstract argumentation frameworks developed by Dung. Assumption-based argumentation can be regarded as an instance of abstract argumentation with structured arguments. When facing a large scale of data, a challenge of reasoning in assumption-based argumentation is how to construct arguments and resolve attacks over a given claim with minimal cost of computation and acceptable accuracy at the same time. This thesis proposes and investigates approximate methods that randomly select and construct samples of frameworks based on graphical dispute derivations to solve this problem. The presented approach aims to improve reasoning performance and get an acceptable trade-off between computational time and accuracy. The evaluation shows that for reasoning in assumption-based argumentation, in general, the running time is reduced with the cost of slightly low accuracy by randomly sampling and constructing inference rules for potential arguments over a query.
Echzeitbetriebssysteme für Systeme mit gemischten Kritikalitäten müssen unterschiedliche Arten von Software, wie z.B. Echtzeitanwendungen und Allzweckanwendungen, gleichzeitig unterstützen. Dabei müssen sie eine solide räumliche und zeitliche Isolation zwischen unabhängigen Softwarekomponenten bieten. Daher fokussieren sich aktuelle Echtzeitbetriebssysteme hauptsächlich auf Vorhersagbarkeit und ein berechenbares Worst-Case-Verhalten.
Allerdings bieten Allzweck-Betriebssysteme wie Linux häufig effizientere, aber weniger deterministische Mechanismen, welche die durchschnittliche Ausführungszeit signifikant erhöhen. Diese Thesis befasst sich mit der Kombination der beiden gegensätzlichen Anforderungen und zeigt Mechanismen zur Thread-Synchronisation mit einem effizienten Durchschnittsverhalten, ohne jedoch die Vorhersagbarkeit und das Worst-Case-Verhalten zu beeinträchtigen. Diese Thesis untersucht und bewertet den Entwurfsraum von Abkürzungen (engl. fast paths) bei der Umsetzung von typischen blockierenden Synchronisationsmechanismen wie Mutexen, Bedingungsvariablen, Zähl-Semaphoren, Barrieren oder Nachrichtenwarteschlangen. Der Ansatz ist dabei, unnötige Systemaufrufe zu vermeiden. Systemaufrufe haben im Vergleich zu anderen Prozessoroperationen, die im Benutzermodus verfügbar sind, wie z.B. atomaren Operationen, höhere Kosten. Insbesondere erforscht die Thesis Futexe, ein aktuelles Design für blockierende Synchronisationsmechanismen in Linux, welches den konkurrenzfreien Fall der Synchronisierung mithilfe atomarer Operationen im Benutzermodus löst und den Kern nur aufruft, um Threads zu suspendieren und aufzuwecken. Die Thesis untersucht auch nicht-unterbrechbare Monitore mit aktivem Warten. Dort wird ein effizienter Mechanismus mit Prioritätsschranken verwendet, um das sogenannte Lock-Holder-Preemption-Problem ohne Systemaufrufe zu vermeiden. Ebenfalls werden passende niedere Kernprimitive beschrieben, die effiziente Warte- und Benachrichtigungsoperationen ermöglichen. Die Evaluation zeigt, dass die vorgestellten Ansätze die durchschnittliche Leistung vergleichbar zu aktuellen Ansätzen in Linux verbessern. Gleichzeitig zeigt eine Analyse des Worst-Case Zeitverhaltens, dass die Ansätze nur konstante oder begrenzte zeitliche Mehraufwände auf der Ebene des Betriebssystemkerns benötigen. Die Nutzung dieser Abkürzungen ist ein lohnender Ansatz für den Entwurf von Systemen, die nicht nur Echtzeitanforderungen erfüllen, sondern auch Allzweckanwendungen gut unterstützen sollen.
Social media has changed how customers, businesses, employees, and job seekers form their reputation perceptions of a company, that is, how they form their evaluative judgements about a company’s products, services and behaviors towards constituencies. In pre-social media times, companies had control over what they communicated to their stakeholders, for example, by using corporate websites to convey a predefined image. With social media, multiple opinions, experiences, and company perceptions reach the wider public via multiple channels such as Twitter, Facebook, and other social networking sites that enable user-generated content. Although companies usually try to nurture an online reputation by running their own Facebook and Twitter profiles, a large amount of online content related to a company is produced by social media users and thus is beyond companies’ control. This habilitation thesis is devoted to studying consumer and employee responses to employee behavior in social media. Across eight different articles, with multiple studies each, this thesis aims to draw a full picture of how employee behavior in social media affects customers, other employees, job seekers, and the employing company as a whole.
Environmental processes transforming inorganic nanoparticles: implications on aquatic invertebrates
(2020)
Engineered inorganic nanoparticles (EINPs) are produced and utilized on a large scale and will end up in surface waters. Once in surface waters, EINPs are subjected to transformations induced by environmental processes altering the particles’ fate and inherent toxicity. UV irradiation of photoactive EINPs is defined as one effect-inducing pathway, leading to the formation of reactive oxygen species (ROS), increasing EINP toxicity by exerting oxidative stress in aquatic life. Simultaneously, UV irradiation of photoactive EINP alters the toxicity of co-occurring micropollutants (e.g. pesticides) by affecting their degradation. The presence of natural organic matter (NOM) reduces the agglomeration and sedimentation of EINPs, extending the exposure of pelagic species, while delaying the exposure of benthic species living in and on the sediment, which is suggested as final sink for EINPs. However, the joint impact of NOM and UV irradiation on EINP-induced toxicity, but also EINP-induced degradation of micropollutants, and the resulting risk for aquatic biota, is poorly understood. Although potential effects of EINPs on benthic species are increasingly investigated, the importance of exposure pathways (waterborne or dietary) is unclear, along with the reciprocal pathway of EINPs, i.e. the transport back from aquatic to terrestrial ecosystems. Therefore, this thesis investigates: (i) how the presence of NOM affects the UV-induced toxicity of the model EINP titanium dioxide (nTiO2) on the pelagic organism Daphnia magna, (ii) to which extent UV irradiation of nTiO2 in the presence and absence of NOM modifies the toxicity of six selected pesticides in D. magna, (iii) potential exposure pathway dependent effects of nTiO2 and silver (nAg) EINPs on the benthic organism Gammarus fossarum, and (iv) the transport of nTiO2 and gold EINPs (nAu) via the merolimnic aquatic insect Chaetopteryx villosa back to terrestrial ecosystems. nTiO2 toxicity in D. magna increased up to 280-fold in the presence of UV light, and was mitigated by NOM up to 12-fold. Depending on the pesticide, UV irradiation of nTiO2 reduced but also enhanced pesticide toxicity, by (i) more efficient pesticide degradation, and presumably (ii) formation of toxic by-products, respectively. Likewise, NOM reduced and increased pesticide toxicity, induced by (i) protection of D. magna against locally acting ROS, and (ii) mitigation of pesticide degradation, respectively. Gammarus’ energy assimilation was significantly affected by both EINPs, however, with distinct variation in direction and pathway dependence between nTiO2 and nAg. EINP presence delayed C. villosa emergence by up to 30 days, and revealed up to 40% reduced lipid reserves, while the organisms carried substantial amounts of nAu (~1.5 ng/mg), and nTiO2 (up to 2.7 ng/mg). This thesis shows, that moving test conditions of EINPs towards a more field-relevant approach, meaningfully modifies the risk of EINPs for aquatic organisms. Thereby, more efforts need to be made to understand the relative importance of EINP exposure pathways, especially since a transferability between different types of EINPs may not be given. When considering typically applied risk assessment factors, adverse effects on aquatic systems might already be expected at currently predicted environmental EINP concentrations in the low ng-µg/L range.
Gel effect induced by mucilage in the pore space and consequences on soil physical properties
(2020)
Wasseraufnahme, Atmung und Exsudation sind biologische Schlüsselfunktionen der Wurzeln höherer Pflanzen. Sie steuern das Pflanzenwachstum, indem sie die biogeochemischen Parameter des Bodens in unmittelbarer Nähe der Wurzeln, der Rhizosphäre, verändern. Folglich sind Bodenprozesse wie beispielsweise Wasserflüsse, Kohlen- und Stickstoffaustausch oder mikrobielle Aktivitäten in der Rhizosphäre im Vergleich zu freiem Boden begünstigt. Insbesondere die Exsudation von Mucilage durch die Pflanzenwurzeln scheint ein wichtiger Mechanismus zu sein, um Trockenstress vorzubeugen. Durch diese gelartige Substanz wird bei negativen Wasserpotentialen sowohl der Bodenwassergehalt als auch die ungesättigte hydraulische Leitfähigkeit erhöht. Die Veränderung der Bodeneigenschaften durch Mucilage ist Gegenstand aktueller Forschung. Ein umfassendes Verständnis der Mechanismen im Porenraum der Rhizosphäre ist bisher allerdings noch unzureichend.
Ziel dieser Arbeit war die Aufklärung der Gel-Eigenschaften von Mucilage im Porenraum der Rhizosphäre, um Veränderungen der physiko-chemischen Eigenschaften der Rhizosphäre auf dieses interpartikuläre Mucilage zurückzuführen. Dabei stellten sich drei Herausforderungen: Zunächst einmal mangelte es an Methoden zur in situ Detektion von Mucilage im Boden. Außerdem fehlten detaillierte Kenntnisse bezüglich der Eigenschaften von interpartikulärem Mucilage. Desweiteren war die Beziehung zwischen der Zusammensetzung und den Eigenschaften von Modelsubstanzen und wurzelstämmigem Mucilage verschiedener Spezies unbekannt. Diese Fragen werden in den verschiedenen Kapiteln der Arbeit thematisiert.
Zunächst erfolgte eine Literaturrecherche, um Informationen aus verschiedenen Wissenschaftsbereichen über Methoden zur Charakterisierung von Gelen und Gel-Phasen im Boden zusammenzustellen. Die Änderung von Bodeneigenschaften aufgrund vorhandener Biohydrogelphasen im Boden kann als „Gel-Effekt“ bezeichnet werden. Die kombinierte Studie von Wassereinschlüssen in Gelen und Boden-Gel-Phasen mit der Untersuchung struktureller Eigenschaften von Boden hinsichtlich der mechanischen Stabilität und visueller Strukturen, zeigte sich als vielversprechend, um den Gel-Effekt im Boden zu charakterisieren.
Das erworbene methodische Wissen wurde in den nächsten Untersuchungen angewendet, um die Eigenschaften von interpartikulären Gelen zu detektieren und zu charakterisieren. 1H NMR Relaxometrie erlaubt die nicht-invasive Bestimmung der Wassermobilität in porösen Medien. Ein konzeptuelles Modell wurde aus Gleichungen entwickelt, welche die Proton-Relaxation in gelhaltigen porösen Medien beschreiben. Dieses Modell berücksichtigt den beschriebenen Gel-Effekt bei der Wahl der NMR Parameter und quantifiziert den Einfluss von Mucilage auf die Proton-Relaxation. Darüber hinaus wurde mithilfe von Rheometrie die Viskosität von Mucilage sowie die mikrostrukturelle Bodenstabilität bestimmt. Mittels Rasterelektronenmikroskopie wurde die Netzwerkstruktur von interpartikulärem Gel visualisiert. Die kombinierte Auswertung dieser Ergebnisse identifizierte drei wichtige Eigenschaften von interpartikulärem Gel: Der „Spinnennetz-Effekt“ schränkt die Dehnung der Polymerketten aufgrund der Verbindung zwischen dem Polymer Netzwerk und der Oberfläche von Bodenpartikeln ein. Der „Polymer-Netzwerk-Effekt“ veranschaulicht die Anordnung des Polymernetzwerks im Porenraum gemäß der räumliche Umgebung. Der „Mikroviskositäts-Effekt“ beschreibt die erhöhte Viskosität von interpartikulärem Gel im Vergleich zu freiem Gel. Die Auswirkungen dieser Eigenschaften auf die Wassermobilität und auf die mikrostrukturelle Stabilität des Bodens wurden untersucht und daraus resultierende Konsequenzen für hydraulische und mechanische Eigenschaften des Bodens diskutiert.
Der Einfluss von den chemischen Eigenschaften von Polymeren auf Gel-Bildungsmechanismen und Gel-Eigenschaften wurde untersucht. Dafür wurden Modelsubstanzen mit verschiedenen Uronsäure-Gehalt, Veresterungsgrade und Calcium-Gehalt getestet und die Menge an Materialanteil mit hohem Molekulargewicht quantifiziert. Die untersuchten Modelsubstanzen waren verschiedenen Pektin Polymeren und Chia Samen Mucilage. Darüber hinaus wurde Mucilage aus Winterweizen und Mais Wurzeln isoliert und untersucht. Polygalakturonsäure und Niedermethyliertes Pektin erwiesen sich als nicht geeignete Modelpolymere für Samen und Wurzelmucilage, da ionische Wechselwirkungen mit Calcium ihre Eigenschaften dominieren. Die dem Mucilage zuzurechnenden Eigenschaften scheinen eher durch schwache elektrostatische Wechselwirkungen zwischen verstrickten Polymerketten beherrscht zu sein. Die Menge an Material mit hohem Molekulargewicht variiert deutlich, abhängig von dem Ursprung des Mucilages. Dies scheint ein bedeutender Faktor für den Gel-Effekt von Mucilage im Boden zu sein. Zusätzlich zu der chemischen Charakterisierung der hochmolekulargewichtigen Polymere ist die exakte Bestimmung der Molekularmassen und der Konformation in verschiedenen Mucilagesorten notwendig, um Zusammensetzungs-Eigenschafts-Profile aufzeichnen zu können. Die Abweichungen zwischen den verschiedenen Mucilagestypen, welche sich durch die Messungen ergeben, haben die Notwendigkeit weiterer Untersuchungen unterstrichen. Nur so lässt sich die Frage klären, wie die spezifischen Eigenschaften von verschiedenen Mucilagestypen auf die Bedürfnisse der Pflanze abgestimmt sind, der sie entstammen.
Schließlich wurde diskutiert, wie die Betrachtung von molekularen Wechselwirkungen im Gel und interpartikulären Gel-Eigenschaften das Verständnis über die physikalischen Eigenschaften der Rhizosphäre erweitert. Dieser Ansatz ist vielversprechend, um zum Beispiel der Wassergehalt oder die hydraulische Leitfähigkeit entsprechend die Eigenschaften vom exudierten Mucilage zu klären. Darüber hinaus liegt die Vermutung nahe, dass der Gel-Effekt allgemein für alle Bodenexsudate mit Gel-Charakter Gültigkeit besitzt. Eine Klassifizierung natürlicher Boden-Gel-Phasen einschließlich der von Wurzeln, Samen, Bakterien, Hyphen oder Regenwürmern exsudierten, gelartigen Materialien nach ihren gemeinsamen physiko-chemischen Gel-Eigenschaften wird für die zukünftige Forschung empfohlen. Als Ergebnis könnten die physiko-chemische Eigenschaften von solchen Gelen zum Gel-Effekt den Auswirkungen auf die Bodeneigenschaften und den Funktionen von den Gelen im Boden zugeschrieben worden.
Amphibian populations are declining worldwide for multiple reasons such as habitat destruction and climate change. An example for an endangered European amphibian is the yellow-bellied toad Bombina variegata. Populations have been declining for decades, particularly at the northern and western range margin. One of the extant northern range centres is the Westerwald region in Rhineland-Palatinate, Germany. To implement informed conservation activities on this threatened species, knowledge of its life-history strategy is crucial. This study therefore focused on different developmental stages to test predictions of life-history theory. It addressed (1) developmental, (2) demographic and (3) genetic issues of Bombina variegata as a model organism: (1) Carry-over effects from larval environment to terrestrial stages and associated vulnerability to predators were investigated using mesocosm approaches, fitness tests and predation trials. (2) The dynamics and demography of B. variegata populations were studied applying a capture-mark-recapture analysis and skeletochronology. The study was complemented through (3) an analysis of genetic diversity and structuring of B. variegata populations using 10 microsatellite loci. In order to reveal general patterns and characteristics among B. variegata populations, the study focused on three geographical scales: local (i.e. a former military training area), regional (i.e. the Westerwald region) and continental scale (i.e. the geographical range of B. variegata). The study revealed carry-over effects of larval environment on metamorph phenotype and behaviour causing variation in fitness in the early terrestrial stage of B. variegata. Metamorph size and condition are crucial factors for survival, as small-sized individuals were particularly prone to predator attacks. Yellow-bellied toads show a remarkable fast-slow continuum of the life-history trait longevity. A populations’ position within this continuum may be determined by local environmental stochasticity, i.e. an extrinsic source of variation, and the efficiency of chemical antipredator protection, i.e. an intrinsic source of variation. Extreme longevity seems to be an exception in B. variegata. Senescence was absent in this study. Weather variability affected reproductive success and thus population dynamics. The dispersal potential was low and short-term fragmentation of populations caused significant genetic differentiation at the local scale. Long-term isolation resulted in increased genetic distance at the regional scale. At the continental scale, populations inhabiting the marginal regions were deeply structured with reduced allelic richness. As consequence of environmental changes, short-lived and isolated B. variegata populations at the range margin may face an increased risk of extinction. Conservation measures should thus improve the connectivity among local populations and reinforce annual reproductive success. Further research on the intraspecific variation in B. variegata skin toxins is required to reveal potential effects on palatability and thus longevity.
Initial goal of the current dissertation was the determination of image-based biomarkers sensitive for neurodegenerative processes in the human brain. One such process is the demyelination of neural cells characteristic for Multiple sclerosis (MS) - the most common neurological disease in young adults for which there is no cure yet. Conventional MRI techniques are very effective in localizing areas of brain tissue damage and are thus a reliable tool for the initial MS diagnosis. However, a mismatch between the clinical fndings and the visualized areas of damage is observed, which renders the use of the standard MRI diffcult for the objective disease monitoring and therapy evaluation. To address this problem, a novel algorithm for the fast mapping of myelin water content using standard multiecho gradient echo acquisitions of the human brain is developed in the current work. The method extents a previously published approach for the simultaneous measurement of brain T1, T∗ 2 and total water content. Employing the multiexponential T∗ 2 decay signal of myelinated tissue, myelin water content is measured based on the quantifcation of two water pools (myelin water and rest) with different relaxation times. Whole brain in vivo myelin water content maps are acquired in 10 healthy controls and one subject with MS. The in vivo results obtained are consistent with previous reports. The acquired quantitative data have a high potential in the context of MS. However, the parameters estimated in a multiparametric acquisition are correlated and constitute therefore an ill-posed, nontrivial data analysis problem. Motivated by this specific problem, a new data clustering approach is developed called Nuclear Potential Clustering, NPC. It is suitable for the explorative analysis of arbitrary dimensional and possibly correlated data without a priori assumptions about its structure. The developed algorithm is based on a concept adapted from nuclear physics. To partition the data, the dynamic behavior of electrically even charged nucleons interacting in a d-dimensional feature space is modeled. An adaptive nuclear potential, comprised of a short-range attractive (Strong interaction) and a long-range repulsive term (Coulomb potential), is assigned to each data point. Thus, nucleons that are densely distributed in space fuse to build nuclei (clusters), whereas single point clusters are repelled (noise). The algorithm is optimized and tested in an extensive study with a series of synthetic datasets as well as the Iris data. The results show that it can robustly identify clusters even when complex configurations and noise are present. Finally, to address the initial goal, quantitative MRI data of 42 patients are analyzed employing NPC. A series of experiments with different sets of image-based features show a consistent grouping tendency: younger patients with low disease grade are recognized as cohesive clusters, while those of higher age and impairment are recognized as outliers. This allows for the definition of a reference region in a feature space associated with phenotypic data. Tracking of the individual's positions therein can disclose patients at risk and be employed for therapy evaluation.