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Institute
- Extern (147) (remove)
The potential increase in frequency and magnitude of extreme floods is currently discussed in terms of global warming and the intensification of the hydrological cycle. The profound knowledge of past natural variability of floods is of utmost importance in order to assess flood risk for the future. Since instrumental flood series cover only the last ~150 years, other approaches to reconstruct historical and pre-historical flood events are needed. Annually laminated (varved) lake sediments are meaningful natural geoarchives because they provide continuous records of environmental changes > 10000 years down to a seasonal resolution. Since lake basins additionally act as natural sediment traps, the riverine sediment supply, which is preserved as detrital event layers in the lake sediments, can be used as a proxy for extreme discharge events. Within my thesis I examined a ~ 8.50 m long sedimentary record from the pre-Alpine Lake Mondsee (Northeast European Alps), which covered the last 7000 years. This sediment record consists of calcite varves and intercalated detrital layers, which range in thickness from 0.05 to 32 mm. Detrital layer deposition was analysed by a combined method of microfacies analysis via thin sections, Scanning Electron Microscopy (SEM), μX-ray fluorescence (μXRF) scanning and magnetic susceptibility. This approach allows characterizing individual detrital event layers and assigning a corresponding input mechanism and catchment. Based on varve counting and controlled by 14C age dates, the main goals of this thesis are (i) to identify seasonal runoff processes, which lead to significant sediment supply from the catchment into the lake basin and (ii) to investigate flood frequency under changing climate boundary conditions. This thesis follows a line of different time slices, presenting an integrative approach linking instrumental and historical flood data from Lake Mondsee in order to evaluate the flood record inferred from Lake Mondsee sediments. The investigation of eleven short cores covering the last 100 years reveals the abundance of 12 detrital layers. Therein, two types of detrital layers are distinguished by grain size, geochemical composition and distribution pattern within the lake basin. Detrital layers, which are enriched in siliciclastic and dolomitic material, reveal sediment supply from the Flysch sediments and Northern Calcareous Alps into the lake basin. These layers are thicker in the northern lake basin (0.1-3.9 mm) and thinner in the southern lake basin (0.05-1.6 mm). Detrital layers, which are enriched in dolomitic components forming graded detrital layers (turbidites), indicate the provenance from the Northern Calcareous Alps. These layers are generally thicker (0.65-32 mm) and are solely recorded within the southern lake basin. In comparison with instrumental data, thicker graded layers result from local debris flow events in summer, whereas thin layers are deposited during regional flood events in spring/summer. Extreme summer floods as reported from flood layer deposition are principally caused by cyclonic activity from the Mediterranean Sea, e.g. July 1954, July 1997 and August 2002. During the last two millennia, Lake Mondsee sediments reveal two significant flood intervals with decadal-scale flood episodes, during the Dark Ages Cold Period (DACP) and the transition from the Medieval Climate Anomaly (MCA) into the Little Ice Age (LIA) suggesting a linkage of transition to climate cooling and summer flood recurrences in the Northeastern Alps. In contrast, intermediate or decreased flood episodes appeared during the MWP and the LIA. This indicates a non-straightforward relationship between temperature and flood recurrence, suggesting higher cyclonic activity during climate transition in the Northeast Alps. The 7000-year flood chronology reveals 47 debris flows and 269 floods, with increased flood activity shifting around 3500 and 1500 varve yr BP (varve yr BP = varve years before present, before present = AD 1950). This significant increase in flood activity shows a coincidence with millennial-scale climate cooling that is reported from main Alpine glacier advances and lower tree lines in the European Alps since about 3300 cal. yr BP (calibrated years before present). Despite relatively low flood occurrence prior to 1500 varve yr BP, floods at Lake Mondsee could have also influenced human life in early Neolithic lake dwellings (5750-4750 cal. yr BP). While the first lake dwellings were constructed on wetlands, the later lake dwellings were built on piles in the water suggesting an early flood risk adaptation of humans and/or a general change of the Late Neolithic Culture of lake-dwellers because of socio-economic reasons. However, a direct relationship between the final abandonment of the lake dwellings and higher flood frequencies is not evidenced.
What are the consequences of unemployment and precarious employment for individuals' health in Europe? What are the moderating factors that may offset (or increase) the health consequences of labor-market risks? How do the effects of these risks vary across different contexts, which differ in their institutional and cultural settings? Does gender, regarded as a social structure, play a role, and how? To answer these questions is the aim of my cumulative thesis. This study aims to advance our knowledge about the health consequences that unemployment and precariousness cause over the life course. In particular, I investigate how several moderating factors, such as gender, the family, and the broader cultural and institutional context, may offset or increase the impact of employment instability and insecurity on individual health.
In my first paper, 'The buffering role of the family in the relationship between job loss and self-perceived health: Longitudinal results from Europe, 2004-2011', I and my co-authors measure the causal effect of job loss on health and the role of the family and welfare states (regimes) as moderating factors. Using EU-SILC longitudinal data (2004-2011), we estimate the probability of experiencing 'bad health' following a transition to unemployment by applying linear probability models and undertake separate analyses for men and women. Firstly, we measure whether changes in the independent variable 'job loss' lead to changes in the dependent variable 'self-rated health' for men and women separately. Then, by adding into the model different interaction terms, we measure the moderating effect of the family, both in terms of emotional and economic support, and how much it varies across different welfare regimes. As an identification strategy, we first implement static fixed-effect panel models, which control for time-varying observables and indirect health selection—i.e., constant unobserved heterogeneity. Secondly, to control for reverse causality and path dependency, we implement dynamic fixed-effect panel models, adding a lagged dependent variable to the model.
We explore the role of the family by focusing on close ties within households: we consider the presence of a stable partner and his/her working status as a source of social and economic support. According to previous literature, having a partner should reduce the stress from adverse events, thanks to the symbolic and emotional dimensions that such a relationship entails, regardless of any economic benefits. Our results, however, suggest that benefits linked to the presence of a (female) partner also come from the financial stability that (s)he can provide in terms of a second income. Furthermore, we find partners' employment to be at least as important as the mere presence of the partner in reducing the negative effect of job loss on the individual's health by maintaining the household's standard of living and decreasing economic strain on the family. Our results are in line with previous research, which has highlighted that some people cope better than others with adverse life circumstances, and the support provided by the family is a crucial resource in that regard.
We also reported an important interaction between the family and the welfare state in moderating the health consequences of unemployment, showing how the compensation effect of the family varies across welfare regimes. The family plays a decisive role in cushioning the adverse consequences of labor market risks in Southern and Eastern welfare states, characterized by less developed social protection systems and –especially the Southern – high level of familialism.
The first paper also found important gender differences concerning job loss, family and welfare effects. Of particular interest is the evidence suggesting that health selection works differently for men and women, playing a more prominent role for women than for men in explaining the relationship between job loss and self-perceived health. The second paper, 'Gender roles and selection mechanisms across contexts: A comparative analysis of the relationship between unemployment, self-perceived health, and gender.' investigates more in-depth the gender differential in health driven by unemployment.
Being a highly contested issue in literature, we aim to study whether men are more penalized than women or the other way around and the mechanisms that may explain the gender difference. To do that, we rely on two theoretical arguments: the availability of alternative roles and social selection. The first argument builds on the idea that men and women may compensate for the detrimental health consequences of unemployment through the commitment to 'alternative roles,' which can provide for the resources needed to fulfill people's socially constructed needs. Notably, the availability of alternative options depends on the different positions that men and women have in society.
Further, we merge the availability of the 'alternative roles' argument with the health selection argument. We assume that health selection could be contingent on people's social position as defined by gender and, thus, explain the gender differential in the relationship between unemployment and health. Ill people might be less reluctant to fall or remain (i.e., self-select) in unemployment if they have alternative roles. In Western societies, women generally have more alternative roles than men and thus more discretion in their labor market attachment. Therefore, health selection should be stronger for them, explaining why unemployment is less menace for women than for their male counterparts.
Finally, relying on the idea of different gender regimes, we extended these arguments to comparison across contexts. For example, in contexts where being a caregiver is assumed to be women's traditional and primary roles and the primary breadwinner role is reserved to men, unemployment is less stigmatized, and taking up alternative roles is more socially accepted for women than for men (Hp.1). Accordingly, social (self)selection should be stronger for women than for men in traditional contexts, where, in the case of ill-health, the separation from work is eased by the availability of alternative roles (Hp.2).
By focusing on contexts that are representative of different gender regimes, we implement a multiple-step comparative approach. Firstly, by using EU-SILC longitudinal data (2004-2015), our analysis tests gender roles and selection mechanisms for Sweden and Italy, representing radically different gender regimes, thus providing institutional and cultural variation. Then, we limit institutional heterogeneity by focusing on Germany and comparing East- and West-Germany and older and younger cohorts—for West-Germany (SOEP data 1995-2017). Next, to assess the differential impact of unemployment for men and women, we compared (unemployed and employed) men with (unemployed and employed) women. To do so, we calculate predicted probabilities and average marginal effect from two distinct random-effects probit models. Our first step is estimating random-effects models that assess the association between unemployment and self-perceived health, controlling for observable characteristics. In the second step, our fully adjusted model controls for both direct and indirect selection. We do this using dynamic correlated random-effects (CRE) models. Further, based on the fully adjusted model, we test our hypotheses on alternative roles (Hp.1) by comparing several contexts – models are estimated separately for each context. For this hypothesis, we pool men and women and include an interaction term between unemployment and gender, which has the advantage to allow for directly testing whether gender differences in the effect of unemployment exist and are statistically significant. Finally, we test the role of selection mechanisms (Hp.2), using the KHB method to compare coefficients across nested nonlinear models. Specifically, we test the role of selection for the relationship between unemployment and health by comparing the partially-adjusted and fully-adjusted models. To allow selection mechanisms to operate differently between genders, we estimate separate models for men and women.
We found support to our first hypotheses—the context where people are embedded structures the relationship between unemployment, health, and gender. We found no gendered effect of unemployment on health in the egalitarian context of Sweden. Conversely, in the traditional context of Italy, we observed substantive and statistically significant gender differences in the effect of unemployment on bad health, with women suffering less than men. We found the same pattern for comparing East and West Germany and younger and older cohorts in West Germany.
On the contrary, our results did not support our theoretical argument on social selection. We found that in Sweden, women are more selected out of employment than men. In contrast, in Italy, health selection does not seem to be the primary mechanism behind the gender differential—Italian men and women seem to be selected out of employment to the same extent. Namely, we do not find any evidence that health selection is stronger for women in more traditional countries (Hp2), despite the fact that the institutional and the cultural context would offer them a more comprehensive range of 'alternative roles' relative to men. Moreover, our second hypothesis is also rejected in the second and third comparisons, where the cross-country heterogeneity is reduced to maximize cultural differences within the same institutional context. Further research that addresses selection into inactivity is needed to evaluate the interplay between selection and social roles across gender regimes.
While the health consequences of unemployment have been on the research agenda for a pretty long time, the interest in precarious employment—defined as the linking of the vulnerable worker to work that is characterized by uncertainty and insecurity concerning pay, the stability of the work arrangement, limited access to social benefits, and statutory protections—has emerged only later. Since the 80s, scholars from different disciplines have raised concerns about the social consequences of de-standardization of employment relationships. However, while work has become undoubtedly more precarious, very little is known about its causal effect on individual health and the role of gender as a moderator. These questions are at the core of my third paper : 'Bad job, bad health? A longitudinal analysis of the interaction between precariousness, gender and self-perceived health in Germany'. Herein, I investigate the multidimensional nature of precarious employment and its causal effect on health, particularly focusing on gender differences.
With this paper, I aim at overcoming three major shortcomings of earlier studies: The first one regards the cross-sectional nature of data that prevents the authors from ruling out unobserved heterogeneity as a mechanism for the association between precarious employment and health. Indeed, several unmeasured individual characteristics—such as cognitive abilities—may confound the relationship between precarious work and health, leading to biased results. Secondly, only a few studies have directly addressed the role of gender in shaping the relationship. Moreover, available results on the gender differential are mixed and inconsistent: some found precarious employment being more detrimental for women's health, while others found no gender differences or stronger negative association for men. Finally, previous attempts to an empirical translation of the employment precariousness (EP) concept have not always been coherent with their theoretical framework. EP is usually assumed to be a multidimensional and continuous phenomenon; it is characterized by different dimensions of insecurity that may overlap in the same job and lead to different "degrees of precariousness." However, researchers have predominantly focused on one-dimensional indicators—e.g., temporary employment, subjective job insecurity—to measure EP and study the association with health. Besides the fact that this approach partially grasps the phenomenon's complexity, the major problem is the inconsistency of evidence that it has produced. Indeed, this line of inquiry generally reveals an ambiguous picture, with some studies finding substantial adverse effects of temporary over permanent employment, while others report only minor differences.
To measure the (causal) effect of precarious work on self-rated health and its variation by gender, I focus on Germany and use four waves from SOEP data (2003, 2007, 2011, and 2015). Germany is a suitable context for my study. Indeed, since the 1980s, the labor market and welfare system have been restructured in many ways to increase the German economy's competitiveness in the global market. As a result, the (standard) employment relationship has been de-standardized: non-standard and atypical employment arrangements—i.e., part-time work, fixed-term contracts, mini-jobs, and work agencies—have increased over time while wages have lowered, even among workers with standard work. In addition, the power of unions has also fallen over the last three decades, leaving a large share of workers without collective protection. Because of this process of de-standardization, the link between wage employment and strong social rights has eroded, making workers more powerless and more vulnerable to labor market risks than in the past. EP refers to this uneven distribution of power in the employment relationship, which can be detrimental to workers' health. Indeed, by affecting individuals' access to power and other resources, EP puts precarious workers at risk of experiencing health shocks and influences their ability to gain and accumulate health advantages (Hp.1).
Further, the focus on Germany allows me to investigate my second research question on the gender differential. Germany is usually regarded as a traditionalist gender regime: a context characterized by a configuration of roles. Here, being a caregiver is assumed to be women's primary role, whereas the primary breadwinner role is reserved for men. Although many signs of progress have been made over the last decades towards a greater equalization of opportunities and more egalitarianism, the breadwinner model has barely changed towards a modified version. Thus, women usually take on the double role of workers (the so-called secondary earner) and caregivers, and men still devote most of their time to paid work activities. Moreover, the overall upward trend towards more egalitarian gender ideologies has leveled off over the last decades, moving notably towards more traditional gender ideologies.
In this setting, two alternative hypotheses are possible. Firstly, I assume that the negative relationship between EP and health is stronger for women than for men. This is because women are systematically more disadvantaged than men in the public and private spheres of life, having less access to formal and informal sources of power. These gender-related power asymmetries may interact with EP-related power asymmetries resulting in a stronger effect of EP on women's health than on men's health (Hp.2).
An alternative way of looking at the gender differential is to consider the interaction that precariousness might have with men's and women's gender identities. According to this view, the negative relationship between EP and health is weaker for women than for men (Hp.2a). In a society with a gendered division of labor and a strong link between masculine identities and stable and well-rewarded job—i.e., a job that confers the role of primary family provider—a male worker with precarious employment might violate the traditional male gender role. Men in precarious jobs may perceive themselves (and by others) as possessing a socially undesirable characteristic, which conflicts with the stereotypical idea of themselves as the male breadwinner. Engaging in behaviors that contradict stereotypical gender identity may decrease self-esteem and foster feelings of inferiority, helplessness, and jealousy, leading to poor health.
I develop a new indicator of EP that empirically translates a definition of EP as a multidimensional and continuous phenomenon. I assume that EP is a latent construct composed of seven dimensions of insecurity chosen according to the theory and previous empirical research: Income insecurity, social insecurity, legal insecurity, employment insecurity, working-time insecurity, representation insecurity, worker's vulnerability. The seven dimensions are proxied by eight indicators available in the four waves of the SOEP dataset. The EP composite indicator is obtained by performing a multiple correspondence analysis (MCA) on the eight indicators. This approach aims to construct a summary scale in which all dimensions contribute jointly to the measured experience of precariousness and its health impact.
Further, the relationship between EP and 'general self-perceived health' is estimated by applying ordered probit random-effects estimators and calculating average marginal effect (further AME). Then, to control for unobserved heterogeneity, I implement correlated random-effects models that add to the model the within-individual means of the time-varying independent variables. To test the significance of the gender differential, I add an interaction term between EP and gender in the fully adjusted model in the pooled sample.
My correlated random-effects models showed EP's negative and substantial 'effect' on self-perceived health for both men and women. Although nonsignificant, the evidence seems in line with previous cross-sectional literature. It supports the hypothesis that employment precariousness could be detrimental to workers' health. Further, my results showed the crucial role of unobserved heterogeneity in shaping the health consequences of precarious employment. This is particularly important as evidence accumulates, yet it is still mostly descriptive.
Moreover, my results revealed a substantial difference among men and women in the relationship between EP and health: when EP increases, the risk of experiencing poor health increases much more for men than for women. This evidence falsifies previous theory according to whom the gender differential is contingent on the structurally disadvantaged position of women in western societies. In contrast, they seem to confirm the idea that men in precarious work could experience role conflict to a larger extent than women, as their self-standard is supposed to be the stereotypical breadwinner worker with a good and well-rewarded job. Finally, results from the multiple correspondence analysis contribute to the methodological debate on precariousness, showing that a multidimensional and continuous indicator can express a latent variable of EP.
All in all, complementarities are revealed in the results of unemployment and employment precariousness, which have two implications: Policy-makers need to be aware that the total costs of unemployment and precariousness go far beyond the economic and material realm penetrating other fundamental life domains such as individual health. Moreover, they need to balance the trade-off between protecting adequately unemployed people and fostering high-quality employment in reaction to the highlighted market pressures. In this sense, the further development of a (universalistic) welfare state certainly helps mitigate the adverse health effects of unemployment and, therefore, the future costs of both individuals' health and welfare spending. In addition, the presence of a working partner is crucial for reducing the health consequences of employment instability. Therefore, policies aiming to increase female labor market participation should be promoted, especially in those contexts where the welfare state is less developed.
Moreover, my results support the significance of taking account of a gender perspective in health research. The findings of the three articles show that job loss, unemployment, and precarious employment, in general, have adverse effects on men's health but less or absent consequences for women's health. Indeed, this suggests the importance of labor and health policies that consider and further distinguish the specific needs of the male and female labor force in Europe. Nevertheless, a further implication emerges: the health consequences of employment instability and de-standardization need to be investigated in light of the gender arrangements and the transforming gender relationships in specific cultural and institutional contexts. My results indeed seem to suggest that women's health advantage may be a transitory phenomenon, contingent on the predominant gendered institutional and cultural context. As the structural difference between men's and women's position in society is eroded, egalitarianism becomes the dominant normative status, so will probably be the gender difference in the health consequences of job loss and precariousness. Therefore, while gender equality in opportunities and roles is a desirable aspect for contemporary societies and a political goal that cannot be postponed further, this thesis raises a further and maybe more crucial question: What kind of equality should be pursued to provide men and women with both good life quality and equal chances in the public and private spheres? In this sense, I believe that social and labor policies aiming to reduce gender inequality in society should focus on improving women's integration into the labor market, implementing policies targeting men, and facilitating their involvement in the private sphere of life. Equal redistribution of social roles could activate a crucial transformation of gender roles and the cultural models that sustain and still legitimate gender inequality in Western societies.
Abzug unter Beobachtung
(2022)
Mehr als vier Jahrzehnte lang beobachteten die Streitkräfte und Militärnachrichtendienste der NATO-Staaten die sowjetischen Truppen in der DDR. Hierfür übernahm in der Bundesrepublik Deutschland der Bundesnachrichtendienst (BND) die militärische Auslandsaufklärung unter Anwendung nachrichtendienstlicher Mittel und Methoden. Die Bundeswehr betrieb dagegen taktische Fernmelde- und elektronische Aufklärung und hörte vor allem den Funkverkehr der „Gruppe der sowjetischen Streitkräfte in Deutschland“ (GSSD) ab. Mit der Aufstellung einer zentralen Dienststelle für das militärische Nachrichtenwesen, dem Amt für Nachrichtenwesen der Bundeswehr, bündelte und erweiterte zugleich das Bundesministerium für Verteidigung in den 1980er Jahren seine analytischen Kapazitäten. Das Monopol des BND in der militärischen Auslandsaufklärung wurde von der Bundeswehr dadurch zunehmend infrage gestellt.
Nach der deutschen Wiedervereinigung am 3. Oktober 1990 befanden sich immer noch mehr als 300.000 sowjetische Soldaten auf deutschem Territorium. Die 1989 in Westgruppe der Truppen (WGT) umbenannte GSSD sollte – so der Zwei-plus-Vier-Vertrag – bis 1994 vollständig abziehen. Der Vertrag verbot auch den drei Westmächten, in den neuen Bundesländern militärisch tätig zu sein. Die für die Militäraufklärung bis dahin unverzichtbaren Militärverbindungsmissionen der Westmächte mussten ihre Dienste einstellen. Doch was geschah mit diesem „alliierten Erbe“? Wer übernahm auf deutscher Seite die Aufklärung der sowjetischen Truppen und wer kontrollierte den Truppenabzug?
Die Studie untersucht die Rolle von Bundeswehr und BND beim Abzug der WGT zwischen 1990 und 1994 und fragt dabei nach Kooperation und Konkurrenz zwischen Streitkräften und Nachrichtendiensten. Welche militärischen und nachrichtendienstlichen Mittel und Fähigkeiten stellte die Bundesregierung zur Bewältigung des Truppenabzugs zur Verfügung, nachdem die westlichen Militärverbindungsmissionen aufgelöst wurden? Wie veränderten sich die Anforderungen an die militärische Auslandsaufklärung des BND? Inwieweit setzten sich Konkurrenz und Kooperation von Bundeswehr und BNDbeim Truppenabzug fort? Welche Rolle spielten dabei die einstigen Westmächte? Die Arbeit versteht sich nicht nur als Beitrag zur Militärgeschichte, sondern auch zur deutschen Nachrichtendienstgeschichte.
In the present thesis, AC electrokinetic forces, like dielectrophoresis and AC electroosmosis, were demonstrated as a simple and fast method to functionalize the surface of nanoelectrodes with submicrometer sized biological objects. These nanoelectrodes have a cylindrical shape with a diameter of 500 nm arranged in an array of 6256 electrodes. Due to its medical relevance influenza virus as well as anti-influenza antibodies were chosen as a model organism. Common methods to bring antibodies or proteins to biosensor surfaces are complex and time-consuming. In the present work, it was demonstrated that by applying AC electric fields influenza viruses and antibodies can be immobilized onto the nanoelectrodes within seconds without any prior chemical modification of neither the surface nor the immobilized biological object. The distribution of these immobilized objects is not uniform over the entire array, it exhibits a decreasing gradient from the outer row to the inner ones. Different causes for this gradient have been discussed, such as the vortex-shaped fluid motion above the nanoelectrodes generated by, among others, electrothermal fluid flow. It was demonstrated that parts of the accumulated material are permanently immobilized to the electrodes. This is a unique characteristic of the presented system since in the literature the AC electrokinetic immobilization is almost entirely presented as a method just for temporary immobilization. The spatial distribution of the immobilized viral material or the anti-influenza antibodies at the electrodes was observed by either the combination of fluorescence microscopy and deconvolution or by super-resolution microscopy (STED). On-chip immunoassays were performed to examine the suitability of the functionalized electrodes as a potential affinity-based biosensor. Two approaches were pursued: A) the influenza virus as the bio-receptor or B) the influenza virus as the analyte. Different sources of error were eliminated by ELISA and passivation experiments. Hence, the activity of the immobilized object was inspected by incubation with the analyte. This resulted in the successful detection of anti-influenza antibodies by the immobilized viral material. On the other hand, a detection of influenza virus particles by the immobilized anti-influenza antibodies was not possible. The latter might be due to lost activity or wrong orientation of the antibodies. Thus, further examinations on the activity of by AC electric fields immobilized antibodies should follow. When combined with microfluidics and an electrical read-out system, the functionalized chips possess the potential to serve as a rapid, portable, and cost-effective point-of-care (POC) device. This device can be utilized as a basis for diverse applications in diagnosing and treating influenza, as well as various other pathogens.
This Thesis puts its focus on the physics of neutron stars and its description with methods of numerical relativity. In the first step, a new numerical framework the Whisky2D code will be developed, which solves the relativistic equations of hydrodynamics in axisymmetry. Therefore we consider an improved formulation of the conserved form of these equations. The second part will use the new code to investigate the critical behaviour of two colliding neutron stars. Considering the analogy to phase transitions in statistical physics, we will investigate the evolution of the entropy of the neutron stars during the whole process. A better understanding of the evolution of thermodynamical quantities, like the entropy in critical process, should provide deeper understanding of thermodynamics in relativity. More specifically, we have written the Whisky2D code, which solves the general-relativistic hydrodynamics equations in a flux-conservative form and in cylindrical coordinates. This of course brings in 1/r singular terms, where r is the radial cylindrical coordinate, which must be dealt with appropriately. In the above-referenced works, the flux operator is expanded and the 1/r terms, not containing derivatives, are moved to the right-hand-side of the equation (the source term), so that the left hand side assumes a form identical to the one of the three-dimensional (3D) Cartesian formulation. We call this the standard formulation. Another possibility is not to split the flux operator and to redefine the conserved variables, via a multiplication by r. We call this the new formulation. The new equations are solved with the same methods as in the Cartesian case. From a mathematical point of view, one would not expect differences between the two ways of writing the differential operator, but, of course, a difference is present at the numerical level. Our tests show that the new formulation yields results with a global truncation error which is one or more orders of magnitude smaller than those of alternative and commonly used formulations. The second part of the Thesis uses the new code for investigations of critical phenomena in general relativity. In particular, we consider the head-on-collision of two neutron stars in a region of the parameter space where two final states a new stable neutron star or a black hole, lay close to each other. In 1993, Choptuik considered one-parameter families of solutions, S[P], of the Einstein-Klein-Gordon equations for a massless scalar field in spherical symmetry, such that for every P > P⋆, S[P] contains a black hole and for every P < P⋆, S[P] is a solution not containing singularities. He studied numerically the behavior of S[P] as P → P⋆ and found that the critical solution, S[P⋆], is universal, in the sense that it is approached by all nearly-critical solutions regardless of the particular family of initial data considered. All these phenomena have the common property that, as P approaches P⋆, S[P] approaches a universal solution S[P⋆] and that all the physical quantities of S[P] depend only on |P − P⋆|. The first study of critical phenomena concerning the head-on collision of NSs was carried out by Jin and Suen in 2007. In particular, they considered a series of families of equal-mass NSs, modeled with an ideal-gas EOS, boosted towards each other and varied the mass of the stars, their separation, velocity and the polytropic index in the EOS. In this way they could observe a critical phenomenon of type I near the threshold of black-hole formation, with the putative solution being a nonlinearly oscillating star. In a successive work, they performed similar simulations but considering the head-on collision of Gaussian distributions of matter. Also in this case they found the appearance of type-I critical behaviour, but also performed a perturbative analysis of the initial distributions of matter and of the merged object. Because of the considerable difference found in the eigenfrequencies in the two cases, they concluded that the critical solution does not represent a system near equilibrium and in particular not a perturbed Tolmann-Oppenheimer-Volkoff (TOV) solution. In this Thesis we study the dynamics of the head-on collision of two equal-mass NSs using a setup which is as similar as possible to the one considered above. While we confirm that the merged object exhibits a type-I critical behaviour, we also argue against the conclusion that the critical solution cannot be described in terms of equilibrium solution. Indeed, we show that, in analogy with what is found in, the critical solution is effectively a perturbed unstable solution of the TOV equations. Our analysis also considers fine-structure of the scaling relation of type-I critical phenomena and we show that it exhibits oscillations in a similar way to the one studied in the context of scalar-field critical collapse.
Advancing charge selective contacts for efficient monolithic perovskite-silicon tandem solar cells
(2019)
Hybrid organic-inorganic perovskites are one of the most promising material classes for photovoltaic energy conversion. In solar cells, the perovskite absorber is sandwiched between n- and p-type contact layers which selectively transport electrons and holes to the cell’s cathode and anode, respectively. This thesis aims to advance contact layers in perovskite solar cells and unravel the impact of interface and contact properties on the device performance. Further, the contact materials are applied in monolithic perovskite-silicon heterojunction (SHJ) tandem solar cells, which can overcome the single junction efficiency limits and attract increasing attention. Therefore, all contact layers must be highly transparent to foster light harvesting in the tandem solar cell design. Besides, the SHJ device restricts processing temperatures for the selective contacts to below 200°C.
A comparative study of various electron selective contact materials, all processed below 180°C, in n-i-p type perovskite solar cells highlights that selective contacts and their interfaces to the absorber govern the overall device performance. Combining fullerenes and metal-oxides in a TiO2/PC60BM (phenyl-C60-butyric acid methyl ester) double-layer contact allows to merge good charge extraction with minimized interface recombination. The layer sequence thereby achieved high stabilized solar cell performances up to 18.0% and negligible current-voltage hysteresis, an otherwise pronounced phenomenon in this device design. Double-layer structures are therefore emphasized as a general concept to establish efficient and highly selective contacts.
Based on this success, the concept to combine desired properties of different materials is transferred to the p-type contact. Here, a mixture of the small molecule Spiro-OMeTAD [2,2’,7,7’-tetrakis(N,N-di-p-methoxyphenylamine)-9,9’-spirobifluoren] and the doped polymer PEDOT [poly(3,4-ethylenedioxythiophene)] is presented as a novel hole selective contact. PEDOT thereby remarkably suppresses charge recombination at the perovskite surface, allowing an increase of quasi-Fermi level splitting in the absorber. Further, the addition of Spiro-OMeTAD into the PEDOT layer is shown to enhance charge extraction at the interface and allow high efficiencies up to 16.8%.
Finally, the knowledge on contact properties is applied to monolithic perovskite-SHJ tandem solar cells. The main goal is to optimize the top contact stack of doped Spiro-OMeTAD/molybdenum oxide(MoOx)/ITO towards higher transparency by two different routes. First, fine-tuning of the ITO deposition to mitigate chemical reduction of MoOx and increase the transmittance of MoOx/ITO stacks by 25%. Second, replacing Spiro-OMeTAD with the alternative hole transport materials PEDOT/Spiro-OMeTAD mixtures, CuSCN or PTAA [poly(triaryl amine)]. Experimental results determine layer thickness constrains and validate optical simulations, which subsequently allow to realistically estimate the respective tandem device performances. As a result, PTAA represents the most promising replacement for Spiro-OMeTAD, with a projected increase of the optimum tandem device efficiency for the herein used architecture by 2.9% relative to 26.5% absolute. The results also reveal general guidelines for further performance gains of the technology.
Die Arbeit beschreibt die Analyse von Beobachtungen zweier Sonnenflecken in zweidimensionaler Spektro-Polarimetrie. Die Daten wurden mit dem Fabry-Pérot-Interferometer der Universität Göttingen am Vakuum-Turm-Teleskop auf Teneriffa erfasst. Von der aktiven Region NOAA 9516 wurde der volle Stokes-Vektor des polarisierten Lichts in der Absorptionslinie bei 630,249 nm in Einzelaufnahmen beobachtet, und von der aktiven Region NOAA 9036 wurde bei 617,3 nm Wellenlänge eine 90-minütige Zeitserie des zirkular polarisierten Lichts aufgezeichnet. Aus den reduzierten Daten werden Ergebniswerte für Intensität, Geschwindigkeit in Beobachtungsrichtung, magnetische Feldstärke sowie verschiedene weitere Plasmaparameter abgeleitet. Mehrere Ansätze zur Inversion solarer Modellatmosphären werden angewendet und verglichen. Die teilweise erheblichen Fehlereinflüsse werden ausführlich diskutiert. Das Frequenzverhalten der Ergebnisse und Abhängigkeiten nach Ort und Zeit werden mit Hilfe der Fourier- und Wavelet-Transformation weiter analysiert. Als Resultat lässt sich die Existenz eines hochfrequenten Bandes für Geschwindigkeitsoszillationen mit einer zentralen Frequenz von 75 Sekunden (13 mHz) bestätigen. In größeren photosphärischen Höhen von etwa 500 km entstammt die Mehrheit der damit zusammenhängenden Schockwellen den dunklen Anteilen der Granulen, im Unterschied zu anderen Frequenzbereichen. Die 75-Sekunden-Oszillationen werden ebenfalls in der aktiven Region beobachtet, vor allem in der Lichtbrücke. In den identifizierten Bändern oszillatorischer Power der Geschwindigkeit sind in einer dunklen, penumbralen Struktur sowie in der Lichtbrücke ausgeprägte Strukturen erkennbar, die sich mit einer Horizontalgeschwindigkeit von 5-8 km/s in die ruhige Sonne bewegen. Diese zeigen einen deutlichen Anstieg der Power, vor allem im 5-Minuten-Band, und stehen möglicherweise in Zusammenhang mit dem Phänomen der „Evershed-clouds“. Eingeschränkt durch ein sehr geringes Signal-Rausch-Verhältnis und hohe Fehlereinflüsse werden auch Magnetfeldvariationen mit einer Periode von sechs Minuten am Übergang von Umbra zu Penumbra in der Nähe einer Lichtbrücke beobachtet. Um die beschriebenen Resultate zu erzielen, wurden bestehende Visualisierungsverfahren der Frequenzanalyse verbessert oder neu entwickelt, insbesondere für Ergebnisse der Wavelet-Transformation.
The present thesis introduces an iterative expert-based Bayesian approach for assessing greenhouse gas (GHG) emissions from the 2030 German new vehicle fleet and quantifying the impacts of their main drivers. A first set of expert interviews has been carried out in order to identify technologies which may help to lower car GHG emissions and to quantify their emission reduction potentials. Moreover, experts were asked for their probability assessments that the different technologies will be widely adopted, as well as for important prerequisites that could foster or hamper their adoption. Drawing on the results of these expert interviews, a Bayesian Belief Network has been built which explicitly models three vehicle types: Internal Combustion Engine Vehicles (which include mild and full Hybrid Electric Vehicles), Plug-In Hybrid Electric Vehicles, and Battery Electric Vehicles. The conditional dependencies of twelve central variables within the BBN - battery energy, fuel and electricity consumption, relative costs, and sales shares of the vehicle types - have been quantified by experts from German car manufacturers in a second series of interviews. For each of the seven second-round interviews, an expert's individually specified BBN results. The BBN have been run for different hypothetical 2030 scenarios which differ, e.g., in regard to battery development, regulation, and fuel and electricity GHG intensities. The present thesis delivers results both in regard to the subject of the investigation and in regard to its method. On the subject level, it has been found that the different experts expect 2030 German new car fleet emission to be at 50 to 65% of 2008 new fleet emissions under the baseline scenario. They can be further reduced to 40 to 50% of the emissions of the 2008 fleet though a combination of a higher share of renewables in the electricity mix, a larger share of biofuels in the fuel mix, and a stricter regulation of car CO$_2$ emissions in the European Union. Technically, 2030 German new car fleet GHG emissions can be reduced to a minimum of 18 to 44% of 2008 emissions, a development which can not be triggered by any combination of measures modeled in the BBN alone but needs further commitment. Out of a wealth of existing BBN, few have been specified by individual experts through elicitation, and to my knowledge, none of them has been employed for analyzing perspectives for the future. On the level of methods, this work shows that expert-based BBN are a valuable tool for making experts' expectations for the future explicit and amenable to the analysis of different hypothetical scenarios. BBN can also be employed for quantifying the impacts of main drivers. They have been demonstrated to be a valuable tool for iterative stakeholder-based science approaches.
Technological progress allows for producing ever more complex predictive models on the basis of increasingly big datasets. For risk management of natural hazards, a multitude of models is needed as basis for decision-making, e.g. in the evaluation of observational data, for the prediction of hazard scenarios, or for statistical estimates of expected damage. The question arises, how modern modelling approaches like machine learning or data-mining can be meaningfully deployed in this thematic field. In addition, with respect to data availability and accessibility, the trend is towards open data. Topic of this thesis is therefore to investigate the possibilities and limitations of machine learning and open geospatial data in the field of flood risk modelling in the broad sense. As this overarching topic is broad in scope, individual relevant aspects are identified and inspected in detail.
A prominent data source in the flood context is satellite-based mapping of inundated areas, for example made openly available by the Copernicus service of the European Union. Great expectations are directed towards these products in scientific literature, both for acute support of relief forces during emergency response action, and for modelling via hydrodynamic models or for damage estimation. Therefore, a focus of this work was set on evaluating these flood masks. From the observation that the quality of these products is insufficient in forested and built-up areas, a procedure for subsequent improvement via machine learning was developed. This procedure is based on a classification algorithm that only requires training data from a particular class to be predicted, in this specific case data of flooded areas, but not of the negative class (dry areas). The application for hurricane Harvey in Houston shows the high potential of this method, which depends on the quality of the initial flood mask.
Next, it is investigated how much the predicted statistical risk from a process-based model chain is dependent on implemented physical process details. Thereby it is demonstrated what a risk study based on established models can deliver. Even for fluvial flooding, such model chains are already quite complex, though, and are hardly available for compound or cascading events comprising torrential rainfall, flash floods, and other processes. In the fourth chapter of this thesis it is therefore tested whether machine learning based on comprehensive damage data can offer a more direct path towards damage modelling, that avoids explicit conception of such a model chain. For that purpose, a state-collected dataset of damaged buildings from the severe El Niño event 2017 in Peru is used. In this context, the possibilities of data-mining for extracting process knowledge are explored as well. It can be shown that various openly available geodata sources contain useful information for flood hazard and damage modelling for complex events, e.g. satellite-based rainfall measurements, topographic and hydrographic information, mapped settlement areas, as well as indicators from spectral data. Further, insights on damaging processes are discovered, which mainly are in line with prior expectations. The maximum intensity of rainfall, for example, acts stronger in cities and steep canyons, while the sum of rain was found more informative in low-lying river catchments and forested areas. Rural areas of Peru exhibited higher vulnerability in the presented study compared to urban areas. However, the general limitations of the methods and the dependence on specific datasets and algorithms also become obvious.
In the overarching discussion, the different methods – process-based modelling, predictive machine learning, and data-mining – are evaluated with respect to the overall research questions. In the case of hazard observation it seems that a focus on novel algorithms makes sense for future research. In the subtopic of hazard modelling, especially for river floods, the improvement of physical models and the integration of process-based and statistical procedures is suggested. For damage modelling the large and representative datasets necessary for the broad application of machine learning are still lacking. Therefore, the improvement of the data basis in the field of damage is currently regarded as more important than the selection of algorithms.
Antarctic glacier forfields are extreme environments and pioneer sites for ecological succession. The Antarctic continent shows microbial community development as a natural laboratory because of its special environment, geographic isolation and little anthropogenic influence. Increasing temperatures due to global warming lead to enhanced deglaciation processes in cold-affected habitats and new terrain is becoming exposed to soil formation and accessible for microbial colonisation. This study aims to understand the structure and development of glacier forefield bacterial communities, especially how soil parameters impact the microorganisms and how those are adapted to the extreme conditions of the habitat. To this effect, a combination of cultivation experiments, molecular, geophysical and geochemical analysis was applied to examine two glacier forfields of the Larsemann Hills, East Antarctica. Culture-independent molecular tools such as terminal restriction length polymorphism (T-RFLP), clone libraries and quantitative real-time PCR (qPCR) were used to determine bacterial diversity and distribution. Cultivation of yet unknown species was carried out to get insights in the physiology and adaptation of the microorganisms. Adaptation strategies of the microorganisms were studied by determining changes of the cell membrane phospholipid fatty acid (PLFA) inventory of an isolated bacterium in response to temperature and pH fluctuations and by measuring enzyme activity at low temperature in environmental soil samples. The two studied glacier forefields are extreme habitats characterised by low temperatures, low water availability and small oligotrophic nutrient pools and represent sites of different bacterial succession in relation to soil parameters. The investigated sites showed microbial succession at an early step of soil formation near the ice tongue in comparison to closely located but rather older and more developed soil from the forefield. At the early step the succession is influenced by a deglaciation-dependent areal shift of soil parameters followed by a variable and prevalently depth-related distribution of the soil parameters that is driven by the extreme Antarctic conditions. The dominant taxa in the glacier forefields are Actinobacteria, Acidobacteria, Proteobacteria, Bacteroidetes, Cyanobacteria and Chloroflexi. The connection of soil characteristics with bacterial community structure showed that soil parameter and soil formation along the glacier forefield influence the distribution of certain phyla. In the early step of succession the relative undifferentiated bacterial diversity reflects the undifferentiated soil development and has a high potential to shift according to past and present environmental conditions. With progressing development environmental constraints such as water or carbon limitation have a greater influence. Adapting the culturing conditions to the cold and oligotrophic environment, the number of culturable heterotrophic bacteria reached up to 108 colony forming units per gram soil and 148 isolates were obtained. Two new psychrotolerant bacteria, Herbaspirillum psychrotolerans PB1T and Chryseobacterium frigidisoli PB4T, were characterised in detail and described as novel species in the family of Oxalobacteraceae and Flavobacteriaceae, respectively. The isolates are able to grow at low temperatures tolerating temperature fluctuations and they are not specialised to a certain substrate, therefore they are well-adapted to the cold and oligotrophic environment. The adaptation strategies of the microorganisms were analysed in environmental samples and cultures focussing on extracellular enzyme activity at low temperature and PLFA analyses. Extracellular phosphatases (pH 11 and pH 6.5), β-glucosidase, invertase and urease activity were detected in the glacier forefield soils at low temperature (14°C) catalysing the conversion of various compounds providing necessary substrates and may further play a role in the soil formation and total carbon turnover of the habitat. The PLFA analysis of the newly isolated species C. frigidisoli showed that the cold-adapted strain develops different strategies to maintain the cell membrane function under changing environmental conditions by altering the PLFA inventory at different temperatures and pH values. A newly discovered fatty acid, which was not found in any other microorganism so far, significantly increased at decreasing temperature and low pH and thus plays an important role in the adaption of C. frigidisoli. This work gives insights into the diversity, distribution and adaptation mechanisms of microbial communities in oligotrophic cold-affected soils and shows that Antarctic glacier forefields are suitable model systems to study bacterial colonisation in connection to soil formation.
Microswimmers, i.e. swimmers of micron size experiencing low Reynolds numbers, have received a great deal of attention in the last years, since many applications are envisioned in medicine and bioremediation. A promising field is the one of magnetic swimmers, since magnetism is biocom-patible and could be used to direct or actuate the swimmers. This thesis studies two examples of magnetic microswimmers from a physics point of view.
The first system to be studied are magnetic cells, which can be magnetic biohybrids (a swimming cell coupled with a magnetic synthetic component) or magnetotactic bacteria (naturally occurring bacteria that produce an intracellular chain of magnetic crystals). A magnetic cell can passively interact with external magnetic fields, which can be used for direction. The aim of the thesis is to understand how magnetic cells couple this magnetic interaction to their swimming strategies, mainly how they combine it with chemotaxis (the ability to sense external gradient of chemical species and to bias their walk on these gradients). In particular, one open question addresses the advantage given by these magnetic interactions for the magnetotactic bacteria in a natural environment, such as porous sediments. In the thesis, a modified Active Brownian Particle model is used to perform simulations and to reproduce experimental data for different systems such as bacteria swimming in the bulk, in a capillary or in confined geometries. I will show that magnetic fields speed up chemotaxis under special conditions, depending on parameters such as their swimming strategy (run-and-tumble or run-and-reverse), aerotactic strategy (axial or polar), and magnetic fields (intensities and orientations), but it can also hinder bacterial chemotaxis depending on the system.
The second example of magnetic microswimmer are rigid magnetic propellers such as helices or random-shaped propellers. These propellers are actuated and directed by an external rotating magnetic field. One open question is how shape and magnetic properties influence the propeller behavior; the goal of this research field is to design the best propeller for a given situation. The aim of the thesis is to propose a simulation method to reproduce the behavior of experimentally-realized propellers and to determine their magnetic properties. The hydrodynamic simulations are based on the use of the mobility matrix. As main result, I propose a method to match the experimental data, while showing that not only shape but also the magnetic properties influence the propellers swimming characteristics.
In biological cells, the long-range intracellular traffic is powered by molecular motors which transport various cargos along microtubule filaments. The microtubules possess an intrinsic direction, having a 'plus' and a 'minus' end. Some molecular motors such as cytoplasmic dynein walk to the minus end, while others such as conventional kinesin walk to the plus end. Cells typically have an isopolar microtubule network. This is most pronounced in neuronal axons or fungal hyphae. In these long and thin tubular protrusions, the microtubules are arranged parallel to the tube axis with the minus ends pointing to the cell body and the plus ends pointing to the tip. In such a tubular compartment, transport by only one motor type leads to 'motor traffic jams'. Kinesin-driven cargos accumulate at the tip, while dynein-driven cargos accumulate near the cell body. We identify the relevant length scales and characterize the jamming behaviour in these tube geometries by using both Monte Carlo simulations and analytical calculations. A possible solution to this jamming problem is to transport cargos with a team of plus and a team of minus motors simultaneously, so that they can travel bidirectionally, as observed in cells. The presumably simplest mechanism for such bidirectional transport is provided by a 'tug-of-war' between the two motor teams which is governed by mechanical motor interactions only. We develop a stochastic tug-of-war model and study it with numerical and analytical calculations. We find a surprisingly complex cooperative motility behaviour. We compare our results to the available experimental data, which we reproduce qualitatively and quantitatively.
Basaltic fissure eruptions, such as on Hawai'i or on Iceland, are thought to be driven by the lateral propagation of feeder dikes and graben subsidence. Associated solid earth processes, such as deformation and structural development, are well studied by means of geophysical and geodetic technologies. The eruptions themselves, lava fountaining and venting dynamics, in turn, have been much less investigated due to hazardous access, local dimension, fast processes, and resulting poor data availability.
This thesis provides a detailed quantitative understanding of the shape and dynamics of lava fountains and the morphological changes at their respective eruption sites. For this purpose, I apply image processing techniques, including drones and fixed installed cameras, to the sequence of frames of video records from two well-known fissure eruptions in Hawai'i and Iceland. This way I extract the dimensions of multiple lava fountains, visible in all frames. By putting these results together and considering the acquisition times of the frames I quantify the variations in height, width and eruption velocity of the lava fountains. Then I analyse these time-series in both time and frequency domains and investigate the similarities and correlations between adjacent lava fountains. Following this procedure, I am able to link the dynamics of the individual lava fountains to physical parameters of the magma transport in the feeder dyke of the fountains.
The first case study in this thesis focuses on the March 2011 Pu'u'O'o eruption, Hawai'i, where a continuous pulsating behaviour at all eight lava fountains has been observed. The lava fountains, even those from different parts of the fissure that are closely connected, show a similar frequency content and eruption behaviour. The regular pattern in the heights of lava fountain suggests a controlling process within the magma feeder system like a hydraulic connection in the underlying dyke, affecting or even controlling the pulsating behaviour.
The second case study addresses the 2014-2015 Holuhraun fissure eruption, Iceland. In this case, the feeder dyke is highlighted by the surface expressions of graben-like structures and fault systems. At the eruption site, the activity decreases from a continuous line of fire of ~60 vents to a limited number of lava fountains. This can be explained by preferred upwards magma movements through vertical structures of the pre-eruptive morphology. Seismic tremors during the eruption reveal vent opening at the surface and/or pressure changes in the feeder dyke. The evolving topography of the cinder cones during the eruption interacts with the lava fountain behaviour. Local variations in the lava fountain height and width are controlled by the conduit diameter, the depth of the lava pond and the shape of the crater. Modelling of the fountain heights shows that long-term eruption behaviour is controlled mainly by pressure changes in the feeder dyke.
This research consists of six chapters with four papers, including two first author and two co-author papers. It establishes a new method to analyse lava fountain dynamics by video monitoring. The comparison with the seismicity, geomorphologic and structural expressions of fissure eruptions shows a complex relationship between focussed flow through dykes, the morphology of the cinder cones, and the lava fountain dynamics at the vents of a fissure eruption.
Solar photocatalysis is the one of leading concepts of research in the current paradigm of sustainable chemical industry. For actual practical implementation of sunlight-driven catalytic processes in organic synthesis, a cheap, efficient, versatile and robust heterogeneous catalyst is necessary. Carbon nitrides are a class of organic semiconductors who are known to fulfill these requirements.
First, current state of solar photocatalysis in economy, industry and lab research is overviewed, outlining EU project funding, prospective synthetic and reforming bulk processes, small scale solar organic chemistry, and existing reactor designs and prototypes, concluding feasibility of the approach.
Then, the photocatalytic aerobic cleavage of oximes to corresponding aldehydes and ketones by anionic poly(heptazine imide) carbon nitride is discussed. The reaction provides a feasible method of deprotection and formation of carbonyl compounds from nitrosation products and serves as a convenient model to study chromoselectivity and photophysics of energy transfer in heterogeneous photocatalysis.
Afterwards, the ability of mesoporous graphitic carbon nitride to conduct proton-coupled electron transfer was utilized for the direct oxygenation of 1,3-oxazolidin-2-ones to corresponding 1,3-oxazlidine-2,4-diones. This reaction provides an easier access to a key scaffold of diverse types of drugs and agrochemicals.
Finally, a series of novel carbon nitrides based on poly(triazine imide) and poly(heptazine imide) structure was synthesized from cyanamide and potassium rhodizonate. These catalysts demonstrated a good performance in a set of photocatalytic benchmark reactions, including aerobic oxidation, dual nickel photoredox catalysis, hydrogen peroxide evolution and chromoselective transformation of organosulfur precursors.
Concluding, the scope of carbon nitride utilization for net-oxidative and net-neutral photocatalytic processes was expanded, and a new tunable platform for catalyst synthesis was discovered.
Causes for slow weathering and erosion in the steep, warm, monsoon-subjected Highlands of Sri Lanka
(2018)
In the Highlands of Sri Lanka, erosion and chemical weathering rates are among the lowest for global mountain denudation. In this tropical humid setting, highly weathered deep saprolite profiles have developed from high-grade metamorphic charnockite during spheroidal weathering of the bedrock. The spheroidal weathering produces rounded corestones and spalled rindlets at the rock-saprolite interface. I used detailed textural, mineralogical, chemical, and electron-microscopic (SEM, FIB, TEM) analyses to identify the factors limiting the rate of weathering front advance in the profile, the sequence of weathering reactions, and the underlying mechanisms. The first mineral attacked by weathering was found to be pyroxene initiated by in situ Fe oxidation, followed by in situ biotite oxidation. Bulk dissolution of the primary minerals is best described with a dissolution – re-precipitation process, as no chemical gradients towards the mineral surface and sharp structural boundaries are observed at the nm scale. Only the local oxidation in pyroxene and biotite is better described with an ion by ion process. The first secondary phases are oxides and amorphous precipitates from which secondary minerals (mainly smectite and kaolinite) form. Only for biotite direct solid state transformation to kaolinite is likely. The initial oxidation of pyroxene and biotite takes place in locally restricted areas and is relatively fast: log J = -11 molmin/(m2 s). However, calculated corestone-scale mineral oxidation rates are comparable to corestone-scale mineral dissolution rates: log R = -13 molpx/(m2 s) and log R = -15 molbt/(m2 s). The oxidation reaction results in a volume increase. Volumetric calculations suggest that this observed oxidation leads to the generation of porosity due to the formation of micro-fractures in the minerals and the bedrock allowing for fluid transport and subsequent dissolution of plagioclase. At the scale of the corestone, this fracture reaction is responsible for the larger fractures that lead to spheroidal weathering and to the formation of rindlets. Since these fractures have their origin from the initial oxidational induced volume increase, oxidation is the rate limiting parameter for weathering to take place. The ensuing plagioclase weathering leads to formation of high secondary porosity in the corestone over a distance of only a few cm and eventually to the final disaggregation of bedrock to saprolite. As oxidation is the first weathering reaction, the supply of O2 is a rate-limiting factor for chemical weathering. Hence, the supply of O2 and its consumption at depth connects processes at the weathering front with erosion at the surface in a feedback mechanism. The strength of the feedback depends on the relative weight of advective versus diffusive transport of O2 through the weathering profile. The feedback will be stronger with dominating diffusive transport. The low weathering rate ultimately depends on the transport of O2 through the whole regolith, and on lithological factors such as low bedrock porosity and the amount of Fe-bearing primary minerals. In this regard the low-porosity charnockite with its low content of Fe(II) bearing minerals impedes fast weathering reactions. Fresh weatherable surfaces are a pre-requisite for chemical weathering. However, in the case of the charnockite found in the Sri Lankan Highlands, the only process that generates these surfaces is the fracturing induced by oxidation. Tectonic quiescence in this region and low pre-anthropogenic erosion rate (attributed to a dense vegetation cover) minimize the rejuvenation of the thick and cohesive regolith column, and lowers weathering through the feedback with erosion.
Recent years witnessed a vast advent of stalagmites as palaeoclimate archives. The multitude of geochemical and physical proxies and a promise of a precise and accurate age model greatly appeal to palaeoclimatologists. Although substantial progress was made in speleothem-based palaeoclimate research and despite high-resolution records from low-latitudinal regions, proving that palaeo-environmental changes can be archived on sub-annual to millennial time scales our comprehension of climate dynamics is still fragmentary. This is in particular true for the summer monsoon system on the Indian subcontinent. The Indian summer monsoon (ISM) is an integral part of the intertropical convergence zone (ITCZ). As this rainfall belt migrates northward during boreal summer, it brings monsoonal rainfall. ISM strength depends however on a variety of factors, including snow cover in Central Asia and oceanic conditions in the Indic and Pacific. Presently, many of the factors influencing the ISM are known, though their exact forcing mechanism and mutual relations remain ambiguous. Attempts to make an accurate prediction of rainfall intensity and frequency and drought recurrence, which is extremely important for South Asian countries, resemble a puzzle game; all interaction need to fall into the right place to obtain a complete picture. My thesis aims to create a faithful picture of climate change in India, covering the last 11,000 ka. NE India represents a key region for the Bay of Bengal (BoB) branch of the ISM, as it is here where the monsoon splits into a northwestward and a northeastward directed arm. The Meghalaya Plateau is the first barrier for northward moving air masses and receives excessive summer rainfall, while the winter season is very dry. The proximity of Meghalaya to the Tibetan Plateau on the one hand and the BoB on the other hand make the study area a key location for investigating the interaction between different forcings that governs the ISM. A basis for the interpretation of palaeoclimate records, and a first important outcome of my thesis is a conceptual model which explains the observed pattern of seasonal changes in stable isotopes (d18O and d2H) in rainfall. I show that although in tropical and subtropical regions the amount effect is commonly called to explain strongly depleted isotope values during enhanced rainfall, alone it cannot account for observed rainwater isotope variability in Meghalaya. Monitoring of rainwater isotopes shows no expected negative correlation between precipitation amount and d18O of rainfall. In turn I find evidence that the runoff from high elevations carries an inherited isotopic signature into the BoB, where during the ISM season the freshwater builds a strongly depleted plume on top of the marine water. The vapor originating from this plume is likely to memorize' and transmit further very negative d18O values. The lack of data does not allow for quantication of this plume effect' on isotopes in rainfall over Meghalaya but I suggest that it varies on seasonal to millennial timescales, depending on the runoff amount and source characteristics. The focal point of my thesis is the extraction of climatic signals archived in stalagmites from NE India. High uranium concentration in the stalagmites ensured excellent age control required for successful high-resolution climate reconstructions. Stable isotope (d18O and d13C) and grey-scale data allow unprecedented insights into millennial to seasonal dynamics of the summer and winter monsoon in NE India. ISM strength (i. e. rainfall amount) is recorded in changes in d18Ostalagmites. The d13C signal, reflecting drip rate changes, renders a powerful proxy for dry season conditions, and shows similarities to temperature-related changes on the Tibetan Plateau. A sub-annual grey-scale profile supports a concept of lower drip rate and slower stalagmite growth during dry conditions. During the Holocene, ISM followed a millennial-scale decrease of insolation, with decadal to centennial failures resulting from atmospheric changes. The period of maximum rainfall and enhanced seasonality corresponds to the Holocene Thermal Optimum observed in Europe. After a phase of rather stable conditions, 4.5 kyr ago, the strengthening ENSO system dominated the ISM. Strong El Nino events weakened the ISM, especially when in concert with positive Indian Ocean dipole events. The strongest droughts of the last 11 kyr are recorded during the past 2 kyr. Using the advantage of a well-dated stalagmite record at hand I tested the application of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to detect sub-annual to sub-decadal changes in element concentrations in stalagmites. The development of a large ablation cell allows for ablating sample slabs of up to 22 cm total length. Each analyzed element is a potential proxy for different climatic parameters. Combining my previous results with the LAICP- MS-generated data shows that element concentration depends not only on rainfall amount and associated leaching from the soil. Additional factors, like biological activity and hydrogeochemical conditions in the soil and vadose zone can eventually affect the element content in drip water and in stalagmites. I present a theoretical conceptual model for my study site to explain how climatic signals can be transmitted and archived in stalagmite carbonate. Further, I establish a first 1500 year long element record, reconstructing rainfall variability. Additionally, I hypothesize that volcanic eruptions, producing large amounts of sulfuric acid, can influence soil acidity and hence element mobilization.
In this work, binding interactions between biomolecules were analyzed by a technique that is based on electrically controllable DNA nanolevers. The technique was applied to virus-receptor interactions for the first time. As receptors, primarily peptides on DNA nanostructures and antibodies were utilized. The DNA nanostructures were integrated into the measurement technique and enabled the presentation of the peptides in a controllable geometrical order. The number of peptides could be varied to be compatible to the binding sites of the viral surface proteins.
Influenza A virus served as a model system, on which the general measurability was demonstrated. Variations of the receptor peptide, the surface ligand density, the measurement temperature and the virus subtypes showed the sensitivity and applicability of the technology. Additionally, the immobilization of virus particles enabled the measurement of differences in oligovalent binding of DNA-peptide nanostructures to the viral proteins in their native environment.
When the coronavirus pandemic broke out in 2020, work on binding interactions of a peptide from the hACE2 receptor and the spike protein of the SARS-CoV-2 virus revealed that oligovalent binding can be quantified in the switchSENSE technology. It could also be shown that small changes in the amino acid sequence of the spike protein resulted in complete loss of binding. Interactions of the peptide and inactivated virus material as well as pseudo virus particles could be measured. Additionally, the switchSENSE technology was utilized to rank six antibodies for their binding affinity towards the nucleocapsid protein of SARS-CoV-2 for the development of a rapid antigen test device.
The technique was furthermore employed to show binding of a non-enveloped virus (adenovirus) and a virus-like particle (norovirus-like particle) to antibodies. Apart from binding interactions, the use of DNA origami levers with a length of around 50 nm enabled the switching of virus material. This proved that the technology is also able to size objects with a hydrodynamic diameter larger than 14 nm.
A theoretical work on diffusion and reaction-limited binding interactions revealed that the technique and the chosen parameters enable the determination of binding rate constants in the reaction-limited regime.
Overall, the applicability of the switchSENSE technique to virus-receptor binding interactions could be demonstrated on multiple examples. While there are challenges that remain, the setup enables the determination of affinities between viruses and receptors in their native environment. Especially the possibilities regarding the quantification of oligo- and multivalent binding interactions could be presented.
Das Borna Disease Virus (BDV, Bornavirus) besitzt ein einzelsträngiges RNA-Genom negativer Polarität und ist innerhalb der Ordnung Mononegavirales der Prototyp einer eigenen Virusfamilie, die der Bornaviridae. Eine außergewöhnliche Eigenschaft des Virus ist seine nukleäre Transkription und Replikation, eine weitere besteht in seiner Fähigkeit, als neurotropes Virus sowohl in vivo als auch in vitro persistente Infektionen zu etablieren. Die zugrunde liegenden Mechanismen sowohl der Replikation als auch der Persistenz sind derzeit noch unzureichend verstanden, auch deshalb, weil das Virus noch relativ „jung“ ist: Erste komplette Sequenzen des RNA-Genoms wurden 1994 publiziert und erst vor einigen Monaten gelang die Generierung rekombinanter Viren auf der Basis klonierter cDNA. Im Mittelpunkt dieser Arbeit standen das p10 Protein und das Phosphoprotein (P), die von der gemeinsamen Transkriptionseinheit II in überlappenden Leserahmen kodiert werden. Als im Kern der Wirtszelle replizierendes Virus ist das Bornavirus auf zelluläre Importmechanismen angewiesen, um den Kernimport aller an der Replikation beteiligten viralen Proteine zu gewährleisten. Das p10 Protein ist ein negativer Regulator der viralen RNA-abhängigen RNA-Polymerase (L). In vitro Importexperimente zeigten, dass p10 über den klassischen Importin alpha/beta abhängigen Kernimportweg in den Nukleus transportiert wird. Dies war unerwartet, da p10 kein vorhersagbares klassisches Kernlokalisierungssignal (NLS) besitzt und weist darauf hin, dass der zelluläre Importapparat offensichtlich flexibler ist als allgemein angenommen. Die ersten 20 N-terminalen AS vermitteln sowohl Kernimport als auch die Bindung an den Importrezeptor Importin alpha. Durch Di-Alanin-Austauschmutagenese wurden die für diesen Transportprozess essentiellen AS identifiziert und die Bedeutung hydrophober und polarer AS-Reste demonstriert. Die Fähigkeit des Bornavirus, persistente Infektionen zu etablieren, wirft die Frage auf, wie das Virus die zellulären antiviralen Abwehrmechanismen, insbesondere das Typ I Interferon (IFN)-System, unterwandert. Das virale P Protein wurde in dieser Arbeit als potenter Antagonist der IFN-Induktion charakterisiert. Es verhindert die Phosphorylierung des zentralen Transkriptionsfaktors IRF3 durch die zelluläre Kinase TBK1 und somit dessen Aktivierung. Der Befund, dass P mit TBK1 Komplexe bildet und zudem auch als Substrat für die zelluläre Kinase fungiert, erlaubt es, erstmalig einen Mechanismus zu postulieren, in dem ein virales Protein (BDV-P) als putatives TBK1-Pseudosubstrat die IRF3-Aktivierung kompetitiv hemmt.
The Milky Way is only one out of billions of galaxies in the universe. However, it is a special galaxy because it allows to explore the main mechanisms involved in its evolution and formation history by unpicking the system star-by-star. Especially, the chemical fingerprints of its stars provide clues and evidence of past events in the Galaxy’s lifetime. These information help not only to decipher the current structure and building blocks of the Milky Way, but to learn more about the general formation process of galaxies.
In the past decade a multitude of stellar spectroscopic Galactic surveys have scanned millions of stars far beyond the rim of the solar neighbourhood. The obtained spectroscopic information provide unprecedented insights to the chemo-dynamics of the Milky Way. In addition analytic models and numerical simulations of the Milky Way provide necessary descriptions and predictions suited for comparison with observations in order to decode the physical properties that underlie the complex system of the Galaxy.
In the thesis various approaches are taken to connect modern theoretical modelling of galaxy formation and evolution with observations from Galactic stellar surveys. With its focus on the chemo-kinematics of the Galactic disk this work aims to determine new observational constraints on the formation of the Milky Way providing also proper comparisons with two different models. These are the population synthesis model TRILEGAL based on analytical distribution functions, which aims to simulate the number and distribution of stars in the Milky Way and its different components, and a hybrid model (MCM) that combines an N-body simulation of a Milky Way like galaxy in the cosmological framework with a semi-analytic chemical evolution model for the Milky Way. The major observational data sets in use come from two surveys, namely the “Radial Velocity Experiment” (RAVE) and the “Sloan Extension for Galactic Understanding and Exploration” (SEGUE).
In the first approach the chemo-kinematic properties of the thin and thick disk of the Galaxy as traced by a selection of about 20000 SEGUE G-dwarf stars are directly compared to the predictions by the MCM model. As a necessary condition for this, SEGUE's selection function and its survey volume are evaluated in detail to correct the spectroscopic observations for their survey specific selection biases. Also, based on a Bayesian method spectro-photometric distances with uncertainties below 15% are computed for the selection of SEGUE G-dwarfs that are studied up to a distance of 3 kpc from the Sun.
For the second approach two synthetic versions of the SEGUE survey are generated based on the above models. The obtained synthetic stellar catalogues are then used to create mock samples best resembling the compiled sample of observed SEGUE G-dwarfs. Generally, mock samples are not only ideal to compare predictions from various models. They also allow validation of the models' quality and improvement as with this work could be especially achieved for TRILEGAL. While TRILEGAL reproduces the statistical properties of the thin and thick disk as seen in the observations, the MCM model has shown to be more suitable in reproducing many chemo-kinematic correlations as revealed by the SEGUE stars. However, evidence has been found that the MCM model may be missing a stellar component with the properties of the thick disk that the observations clearly show. While the SEGUE stars do indicate a thin-thick dichotomy of the stellar Galactic disk in agreement with other spectroscopic stellar studies, no sign for a distinct metal-poor disk is seen in the MCM model.
Usually stellar spectroscopic surveys are limited to a certain volume around the Sun covering different regions of the Galaxy’s disk. This often prevents to obtain a global view on the chemo-dynamics of the Galactic disk. Hence, a suitable combination of stellar samples from independent surveys is not only useful for the verification of results but it also helps to complete the picture of the Milky Way. Therefore, the thesis closes with a comparison of the SEGUE G-dwarfs and a sample of RAVE giants. The comparison reveals that the chemo-kinematic relations agree in disk regions where the samples of both surveys show a similar number of stars. For those parts of the survey volumes where one of the surveys lacks statistics they beautifully complement each other. This demonstrates that the comparison of theoretical models on the one side, and the combined observational data gathered by multiple surveys on the other side, are key ingredients to understand and disentangle the structure and formation history of the Milky Way.
In the living cell, the organization of the complex internal structure relies to a large extent on molecular motors. Molecular motors are proteins that are able to convert chemical energy from the hydrolysis of adenosine triphosphate (ATP) into mechanical work. Being about 10 to 100 nanometers in size, the molecules act on a length scale, for which thermal collisions have a considerable impact onto their motion. In this way, they constitute paradigmatic examples of thermodynamic machines out of equilibrium. This study develops a theoretical description for the energy conversion by the molecular motor myosin V, using many different aspects of theoretical physics. Myosin V has been studied extensively in both bulk and single molecule experiments. Its stepping velocity has been characterized as a function of external control parameters such as nucleotide concentration and applied forces. In addition, numerous kinetic rates involved in the enzymatic reaction of the molecule have been determined. For forces that exceed the stall force of the motor, myosin V exhibits a 'ratcheting' behaviour: For loads in the direction of forward stepping, the velocity depends on the concentration of ATP, while for backward loads there is no such influence. Based on the chemical states of the motor, we construct a general network theory that incorporates experimental observations about the stepping behaviour of myosin V. The motor's motion is captured through the network description supplemented by a Markov process to describe the motor dynamics. This approach has the advantage of directly addressing the chemical kinetics of the molecule, and treating the mechanical and chemical processes on equal grounds. We utilize constraints arising from nonequilibrium thermodynamics to determine motor parameters and demonstrate that the motor behaviour is governed by several chemomechanical motor cycles. In addition, we investigate the functional dependence of stepping rates on force by deducing the motor's response to external loads via an appropriate Fokker-Planck equation. For substall forces, the dominant pathway of the motor network is profoundly different from the one for superstall forces, which leads to a stepping behaviour that is in agreement with the experimental observations. The extension of our analysis to Markov processes with absorbing boundaries allows for the calculation of the motor's dwell time distributions. These reveal aspects of the coordination of the motor's heads and contain direct information about the backsteps of the motor. Our theory provides a unified description for the myosin V motor as studied in single motor experiments.
Chloroplasts as bioreactors : high-yield production of active bacteriolytic protein antibiotics
(2008)
Plants, more precisely their chloroplasts with their bacterial-like expression machinery inherited from their cyanobacterial ancestors, can potentially offer a cheap expression system for proteinaceous pharmaceuticals. This system would be easily scalable and provides appropriate safety due to chloroplasts maternal inheritance. In this work, it was shown that three phage lytic enzymes (Pal, Cpl-1 and PlyGBS) could be successfully expressed at very high levels and with high stability in tobacco chloroplasts. PlyGBS expression reached an amount of foreign protein accumulation (> 70% TSP) that has never been obtained before. Although the high expression levels of PlyGBS caused a pale green phenotype with retarded growth, presumably due to exhaustion of plastid protein synthesis capacity, development and seed production were not impaired under greenhouse conditions. Since Pal and Cpl-1 showed toxic effects when expressed in E. coli, a special plastid transformation vector (pTox) was constructed to allow DNA amplification in bacteria. The construction of the pTox transformation vector allowing a recombinase-mediated deletion of an E. coli transcription block in the chloroplast, leading to an increase of foreign protein accumulation to up to 40% of TSP for Pal and 20% of TSP for Cpl-1. High dose-dependent bactericidal efficiency was shown for all three plant-derived lytic enzymes using their pathogenic target bacteria S. pyogenes and S. pneumoniae. Confirmation of specificity was obtained for the endotoxic proteins Pal and Cpl-1 by application to E. coli cultures. These results establish tobacco chloroplasts as a new cost-efficient and convenient production platform for phage lytic enzymes and address the greatest obstacle for clinical application. The present study is the first report of lysin production in a non-bacterial system. The properties of chloroplast-produced lysins described in this work, their stability, high accumulation rate and biological activity make them highly attractive candidates for future antibiotics.
Die Anpassung von Sektoren an veränderte klimatische Bedingungen erfordert ein Verständnis von regionalen Vulnerabilitäten. Vulnerabilität ist als Funktion von Sensitivität und Exposition, welche potentielle Auswirkungen des Klimawandels darstellen, und der Anpassungsfähigkeit von Systemen definiert. Vulnerabilitätsstudien, die diese Komponenten quantifizieren, sind zu einem wichtigen Werkzeug in der Klimawissenschaft geworden. Allerdings besteht von der wissenschaftlichen Perspektive aus gesehen Uneinigkeit darüber, wie diese Definition in Studien umgesetzt werden soll. Ausdiesem Konflikt ergeben sich viele Herausforderungen, vor allem bezüglich der Quantifizierung und Aggregierung der einzelnen Komponenten und deren angemessenen Komplexitätsniveaus. Die vorliegende Dissertation hat daher zum Ziel die Anwendbarkeit des Vulnerabilitätskonzepts voranzubringen, indem es in eine systematische Struktur übersetzt wird. Dies beinhaltet alle Komponenten und schlägt für jede Klimaauswirkung (z.B. Sturzfluten) eine Beschreibung des vulnerablen Systems vor (z.B. Siedlungen), welches direkt mit einer bestimmten Richtung eines relevanten klimatischen Stimulus in Verbindung gebracht wird (z.B. stärkere Auswirkungen bei Zunahme der Starkregentage). Bezüglich der herausfordernden Prozedur der Aggregierung werden zwei alternative Methoden, die einen sektorübergreifenden Überblick ermöglichen, vorgestellt und deren Vor- und Nachteile diskutiert. Anschließend wird die entwickelte Struktur einer Vulnerabilitätsstudie mittels eines indikatorbasierten und deduktiven Ansatzes beispielhaft für Gemeinden in Nordrhein-Westfalen in Deutschland angewandt. Eine Übertragbarkeit auf andere Regionen ist dennoch möglich. Die Quantifizierung für die Gemeinden stützt sich dabei auf Informationen aus der Literatur. Da für viele Sektoren keine geeigneten Indikatoren vorhanden waren, werden in dieser Arbeit neue Indikatoren entwickelt und angewandt, beispielsweise für den Forst- oder Gesundheitssektor. Allerdings stellen fehlende empirische Daten bezüglich relevanter Schwellenwerte eine Lücke dar, beispielsweise welche Stärke von Klimaänderungen eine signifikante Auswirkung hervorruft. Dies führt dazu, dass die Studie nur relative Aussagen zum Grad der Vulnerabilität jeder Gemeinde im Vergleich zum Rest des Bundeslandes machen kann. Um diese Lücke zu füllen, wird für den Forstsektor beispielhaft die heutige und zukünftige Sturmwurfgefahr von Wäldern berechnet. Zu diesem Zweck werden die Eigenschaften der Wälder mit empirischen Schadensdaten eines vergangenen Sturmereignisses in Verbindung gebracht. Der sich daraus ergebende Sensitivitätswert wird anschließend mit den Windverhältnissen verknüpft. Sektorübergreifende Vulnerabilitätsstudien erfordern beträchtliche Ressourcen, was oft deren Anwendbarkeit erschwert. In einem nächsten Schritt wird daher das Potential einer Vereinfachung der Komplexität anhand zweier sektoraler Beispiele untersucht. Um das Auftreten von Waldbränden vorherzusagen, stehen zahlreiche meteorologische Indices zur Verfügung, welche eine Spannbreite unterschiedlicher Komplexitäten aufweisen. Bezüglich der Anzahl monatlicher Waldbrände weist die relative Luftfeuchtigkeit für die meisten deutschen Bundesländer eine bessere Vorhersagekraft als komplexere Indices auf. Dies ist er Fall, obgleich sie selbst als Eingangsvariable für die komplexeren Indices verwendet wird. Mit Hilfe dieses einzelnen meteorologischen Faktors kann also die Waldbrandgefahr in deutschen Region ausreichend genau ausgedrückt werden, was die Ressourceneffizienz von Studien erhöht. Die Methodenkomplexität wird auf ähnliche Weise hinsichtlich der Anwendung des ökohydrologischen Modells SWIM für die Region Brandenburg untersucht. Die interannuellen Bodenwasserwerte, welche durch dieses Modell simuliert werden, können nur unzureichend durch ein einfacheres statistisches Modell, welches auf denselben Eingangsdaten aufbaut, abgebildet werden. Innerhalb eines Zeithorizonts von Jahrzehnten, kann der statistische Ansatz jedoch das Bodenwasser zufriedenstellend abbilden und zeigt eine Dominanz der Bodeneigenschaft Feldkapazität. Dies deutet darauf hin, dass die Komplexität im Hinblick auf die Anzahl der Eingangsvariablen für langfristige Berechnungen reduziert werden kann. Allerdings sind die Aussagen durch fehlende beobachtete Bodenwasserwerte zur Validierung beschränkt. Die vorliegenden Studien zur Vulnerabilität und ihren Komponenten haben gezeigt, dass eine Anwendung noch immer wissenschaftlich herausfordernd ist. Folgt man der hier verwendeten Vulnerabilitätsdefinition, treten zahlreiche Probleme bei der Implementierung in regionalen Studien auf. Mit dieser Dissertation wurden Fortschritte bezüglich der aufgezeigten Lücken bisheriger Studien erzielt, indem eine systematische Struktur für die Beschreibung und Aggregierung von Vulnerabilitätskomponenten erarbeitet wurde. Hierfür wurden mehrere Ansätze diskutiert, die jedoch Vor- und Nachteile besitzen. Diese sollten vor der Anwendung von zukünftigen Studien daher ebenfalls sorgfältig abgewogen werden. Darüber hinaus hat sich gezeigt, dass ein Potential besteht einige Ansätze zu vereinfachen, jedoch sind hierfür weitere Untersuchungen nötig. Insgesamt konnte die Dissertation die Anwendung von Vulnerabilitätsstudien als Werkzeug zur Unterstützung von Anpassungsmaßnahmen stärken.
Being living systems unable to adjust their location to changing environmental conditions, plants display homeostatic networks that have evolved to maintain transition metal levels in a very narrow concentration range in order to avoid either deficiency or toxicity. Hence, plants possess a broad repertoire of mechanisms for the cellular uptake, compartmentation and efflux, as well as for the chelation of transition metal ions. A small number of plants are hypertolerant to one or a few specific transition metals. Some metal tolerant plants are also able to hyperaccumulate metal ions. The Brassicaceae family member Arabidopis halleri ssp. halleri (L.) O´KANE and AL´SHEHBAZ is a hyperaccumulator of zinc (Zn), and it is closely related to the non-hypertolerant and non-hyperaccumulating model plant Arabidopsis thaliana (L.) HEYNHOLD. The close relationship renders A. halleri a promising emerging model plant for the comparative investigation of the molecular mechanisms behind hypertolerance and hyperaccumulation. Among several potential candidate genes that are probably involved in mediating the zinc-hypertolerant and zinc-hyperaccumulating trait is AhHMA3. The AhHMA3 gene is highly similar to AtHMA3 (AGI number: At4g30120) in A. thaliana, and its encoded protein belongs to the P-type IB ATPase family of integral membrane transporter proteins that transport transition metals. In contrast to the low AtHMA3 transcript levels in A. thaliana, the gene was found to be constitutively highly expressed across different Zn treatments in A. halleri, especially in shoots. In this study, the cloning and characterisation of the HMA3 gene and its promoter from Arabidopsis halleri (L.) O´KANE and AL´SHEHBAZ and Arabidopsis thaliana (L.) HEYNHOLD is described. Heterologously expressed AhHMA3 mediated enhanced tolerance to Zn and to a much lesser degree to cadmium (Cd) but not to cobalt (Co) in metal-sensitive mutant strains of budding yeast. It is demonstrated that the genome of A. halleri contains at least four copies of AhHMA3, AhHMA3-1 to AhHMA3-4. A copy-specific real-time RT-PCR indicated that an AhHMA3-1 related gene copy is the source of the constitutively high transcript level in A. halleri and not a gene copy similar to AhHMA3-2 or AhHMA3-4. In accordance with the enhanced AtHMA3mRNA transcript level in A. thaliana roots, an AtHMA3 promoter-GUS gene construct mediated GUS activity predominantly in the vascular tissues of roots and not in shoots. However, the observed AhHMA3-1 and AhHMA3-2 promoter-mediated GUS activity in A. thaliana or A. halleri plants did not reflect the constitutively high expression of AhHMA3 in shoots of A. halleri. It is suggested that other factors e. g. characteristic sequence inserts within the first intron of AhHMA3-1 might enable a constitutively high expression. Moreover, the unknown promoter of the AhHMA3-3 gene copy could be the source of the constitutively high AhHMA3 transcript levels in A. halleri. In that case, the AhHMA3-3 sequence is predicted to be highly homologous to AhHMA3-1. The lack of solid localisation data for the AhHMA3 protein prevents a clear functional assignment. The provided data suggest several possible functions of the AhHMA3 protein: Like AtHMA2 and AtHMA4 it might be localised to the plasma membrane and could contribute to the efficient translocation of Zn from root to shoot and/or to the cell-to-cell distribution of Zn in the shoot. If localised to the vacuolar membrane, then a role in maintaining a low cytoplasmic zinc concentration by vacuolar zinc sequestration is possible. In addition, AhHMA3 might be involved in the delivery of zinc ions to trichomes and mesophyll leaf cells that are major zinc storage sites in A. halleri.
The natural abundance of Coiled Coil (CC) motifs in cytoskeleton and extracellular matrix proteins suggests that CCs play an important role as passive (structural) and active (regulatory) mechanical building blocks. CCs are self-assembled superhelical structures consisting of 2-7 α-helices. Self-assembly is driven by hydrophobic and ionic interactions, while the helix propensity of the individual helices contributes additional stability to the structure. As a direct result of this simple sequence-structure relationship, CCs serve as templates for protein design and sequences with a pre-defined thermodynamic stability have been synthesized de novo. Despite this quickly increasing knowledge and the vast number of possible CC applications, the mechanical function of CCs has been largely overlooked and little is known about how different CC design parameters determine the mechanical stability of CCs. Once available, this knowledge will open up new applications for CCs as nanomechanical building blocks, e.g. in biomaterials and nanobiotechnology.
With the goal of shedding light on the sequence-structure-mechanics relationship of CCs, a well-characterized heterodimeric CC was utilized as a model system. The sequence of this model system was systematically modified to investigate how different design parameters affect the CC response when the force is applied to opposing termini in a shear geometry or separated in a zipper-like fashion from the same termini (unzip geometry). The force was applied using an atomic force microscope set-up and dynamic single-molecule force spectroscopy was performed to determine the rupture forces and energy landscape properties of the CC heterodimers under study. Using force as a denaturant, CC chain separation is initiated by helix uncoiling from the force application points. In the shear geometry, this allows uncoiling-assisted sliding parallel to the force vector or dissociation perpendicular to the force vector. Both competing processes involve the opening of stabilizing hydrophobic (and ionic) interactions. Also in the unzip geometry, helix uncoiling precedes the rupture of hydrophobic contacts.
In a first series of experiments, the focus was placed on canonical modifications in the hydrophobic core and the helix propensity. Using the shear geometry, it was shown that both a reduced core packing and helix propensity lower the thermodynamic and mechanical stability of the CC; however, with different effects on the energy landscape of the system. A less tightly packed hydrophobic core increases the distance to the transition state, with only a small effect on the barrier height. This originates from a more dynamic and less tightly packed core, which provides more degrees of freedom to respond to the applied force in the direction of the force vector. In contrast, a reduced helix propensity decreases both the distance to the transition state and the barrier height. The helices are ‘easier’ to unfold and the remaining structure is less thermodynamically stable so that dissociation perpendicular to the force axis can occur at smaller deformations.
Having elucidated how canonical sequence modifications influence CC mechanics, the pulling geometry was investigated in the next step. Using one and the same sequence, the force application points were exchanged and two different shear and one unzipping geometry were compared. It was shown that the pulling geometry determines the mechanical stability of the CC. Different rupture forces were observed in the different shear as well as in the unzipping geometries, suggesting that chain separation follows different pathways on the energy landscape. Whereas the difference between CC shearing and unzipping was anticipated and has also been observed for other biological structures, the observed difference for the two shear geometries was less expected. It can be explained with the structural asymmetry of the CC heterodimer. It is proposed that the direction of the α-helices, the different local helix propensities and the position of a polar asparagine in the hydrophobic core are responsible for the observed difference in the chain separation pathways. In combination, these factors are considered to influence the interplay between processes parallel and perpendicular to the force axis.
To obtain more detailed insights into the role of helix stability, helical turns were reinforced locally using artificial constraints in the form of covalent and dynamic ‘staples’. A covalent staple bridges to adjacent helical turns, thus protecting them against uncoiling. The staple was inserted directly at the point of force application in one helix or in the same terminus of the other helix, which did not experience the force directly. It was shown that preventing helix uncoiling at the point of force application reduces the distance to the transition state while slightly increasing the barrier height. This confirms that helix uncoiling is critically important for CC chain separation. When inserted into the second helix, this stabilizing effect is transferred across the hydrophobic core and protects the force-loaded turns against uncoiling. If both helices were stapled, no additional increase in mechanical stability was observed. When replacing the covalent staple with a dynamic metal-coordination bond, a smaller decrease in the distance to the transition was observed, suggesting that the staple opens up while the CC is under load.
Using fluorinated amino acids as another type of non-natural modification, it was investigated how the enhanced hydrophobicity and the altered packing at the interface influences CC mechanics. The fluorinated amino acid was inserted into one central heptad of one or both α-helices. It was shown that this substitution destabilized the CC thermodynamically and mechanically. Specifically, the barrier height was decreased and the distance to the transition state increased. This suggests that a possible stabilizing effect of the increased hydrophobicity is overruled by a disturbed packing, which originates from a bad fit of the fluorinated amino acid into the local environment. This in turn increases the flexibility at the interface, as also observed for the hydrophobic core substitution described above. In combination, this confirms that the arrangement of the hydrophobic side chains is an additional crucial factor determining the mechanical stability of CCs.
In conclusion, this work shows that knowledge of the thermodynamic stability alone is not sufficient to predict the mechanical stability of CCs. It is the interplay between helix propensity and hydrophobic core packing that defines the sequence-structure-mechanics relationship. In combination, both parameters determine the relative contribution of processes parallel and perpendicular to the force axis, i.e. helix uncoiling and uncoiling-assisted sliding as well as dissociation. This new mechanistic knowledge provides insight into the mechanical function of CCs in tissues and opens up the road for designing CCs with pre-defined mechanical properties. The library of mechanically characterized CCs developed in this work is a powerful starting point for a wide spectrum of applications, ranging from molecular force sensors to mechanosensitive crosslinks in protein nanostructures and synthetic extracellular matrix mimics.
The global climate crisis is significantly contributing to changing ecosystems, loss of biodiversity and is putting numerous species on the verge of extinction. In principle, many species are able to adapt to changing conditions or shift their habitats to more suitable regions. However, change is progressing faster than some species can adjust, or potential adaptation is blocked and disrupted by direct and indirect human action. Unsustainable anthropogenic land use in particular is one of the driving factors, besides global heating, for these ecologically critical developments. Precisely because land use is anthropogenic, it is also a factor that could be quickly and immediately corrected by human action.
In this thesis, I therefore assess the impact of three climate change scenarios of increasing intensity in combination with differently scheduled mowing regimes on the long-term development and dispersal success of insects in Northwest German grasslands. The large marsh grasshopper (LMG, Stethophyma grossum, Linné 1758) is used as a species of reference for the analyses. It inhabits wet meadows and marshes and has a limited, yet fairly good ability to disperse. Mowing and climate conditions affect the development and mortality of the LMG differently depending on its life stage.
The specifically developed simulation model HiLEG (High-resolution Large Environmental
Gradient) serves as a tool for investigating and projecting viability and dispersal success under different climate conditions and land use scenarios. It is a spatially explicit, stage- and cohort-based model that can be individually configured to represent the life cycle and characteristics of terrestrial insect species, as well as high-resolution environmental data and the occurrence of external disturbances. HiLEG is a freely available and adjustable software that can be used to support conservation planning in cultivated grasslands.
In the three case studies of this thesis, I explore various aspects related to the structure of simulation models per se, their importance in conservation planning in general, and insights regarding the LMG in particular. It became apparent that the detailed resolution of model processes and components is crucial to project the long-term effect of spatially and temporally confined events. Taking into account conservation measures at the regional level has further proven relevant, especially in light of the climate crisis. I found that the LMG is benefiting from global warming in principle, but continues to be constrained by harmful mowing regimes. Land use measures could, however, be adapted in such a way that they allow the expansion and establishment of the LMG without overly affecting agricultural yields.
Overall, simulation models like HiLEG can make an important contribution and add value
to conservation planning and policy-making. Properly used, simulation results shed light
on aspects that might be overlooked by subjective judgment and the experience of individual stakeholders. Even though it is in the nature of models that they are subject to limitations and only represent fragments of reality, this should not keep stakeholders from using them, as long as these limitations are clearly communicated. Similar to HiLEG, models could further be designed in such a way that not only the parameterization can be adjusted as required, but also the implementation itself can be improved and changed as desired. This openness and flexibility should become more widespread in the development of simulation models.
The Arctic is a particularly sensitive area with respect to climate change due to the high surface albedo of snow and ice and the extreme radiative conditions. Clouds and aerosols as parts of the Arctic atmosphere play an important role in the radiation budget, which is, as yet, poorly quantified and understood. The LIDAR (Light Detection And Ranging) measurements presented in this PhD thesis contribute with continuous altitude resolved aerosol profiles to the understanding of occurrence and characteristics of aerosol layers above Ny-Ålesund, Spitsbergen. The attention was turned to the analysis of periods with high aerosol load. As the Arctic spring troposphere exhibits maximum aerosol optical depths (AODs) each year, March and April of both the years 2007 and 2009 were analyzed. Furthermore, stratospheric aerosol layers of volcanic origin were analyzed for several months, subsequently to the eruptions of the Kasatochi and Sarychev volcanoes in summer 2008 and 2009, respectively. The Koldewey Aerosol Raman LIDAR (KARL) is an instrument for the active remote sensing of atmospheric parameters using pulsed laser radiation. It is operated at the AWIPEV research base and was fundamentally upgraded within the framework of this PhD project. It is now equipped with a new telescope mirror and new detection optics, which facilitate atmospheric profiling from 450m above sea level up to the mid-stratosphere. KARL provides highly resolved profiles of the scattering characteristics of aerosol and cloud particles (backscattering, extinction and depolarization) as well as water vapor profiles within the lower troposphere. Combination of KARL data with data from other instruments on site, namely radiosondes, sun photometer, Micro Pulse LIDAR, and tethersonde system, resulted in a comprehensive data set of scattering phenomena in the Arctic atmosphere. The two spring periods March and April 2007 and 2009 were at first analyzed based on meteorological parameters, like local temperature and relative humidity profiles as well as large scale pressure patterns and air mass origin regions. Here, it was not possible to find a clear correlation between enhanced AOD and air mass origin. However, in a comparison of two cloud free periods in March 2007 and April 2009, large AOD values in 2009 coincided with air mass transport through the central Arctic. This suggests the occurrence of aerosol transformation processes during the aerosol transport to Ny-Ålesund. Measurements on 4 April 2009 revealed maximum AOD values of up to 0.12 and aerosol size distributions changing with altitude. This and other performed case studies suggest the differentiation between three aerosol event types and their origin: Vertically limited aerosol layers in dry air, highly variable hygroscopic boundary layer aerosols and enhanced aerosol load across wide portions of the troposphere. For the spring period 2007, the available KARL data were statistically analyzed using a characterization scheme, which is based on optical characteristics of the scattering particles. The scheme was validated using several case studies. Volcanic eruptions in the northern hemisphere in August 2008 and June 2009 arose the opportunity to analyze volcanic aerosol layers within the stratosphere. The rate of stratospheric AOD change was similar within both years with maximum values above 0.1 about three to five weeks after the respective eruption. In both years, the stratospheric AOD persisted at higher rates than usual until the measurements were stopped in late September due to technical reasons. In 2008, up to three aerosol layers were detected, the layer structure in 2009 was characterized by up to six distinct and thin layers which smeared out to one broad layer after about two months. The lowermost aerosol layer was continuously detected at the tropopause altitude. Three case studies were performed, all revealed rather large indices of refraction of m = (1.53–1.55) - 0.02i, suggesting the presence of an absorbing carbonaceous component. The particle radius, derived with inversion calculations, was also similar in both years with values ranging from 0.16 to 0.19 μm. However, in 2009, a second mode in the size distribution was detected at about 0.5 μm. The long term measurements with the Koldewey Aerosol Raman LIDAR in Ny-Ålesund provide the opportunity to study Arctic aerosols in the troposphere and the stratosphere not only in case studies but on longer time scales. In this PhD thesis, both, tropospheric aerosols in the Arctic spring and stratospheric aerosols following volcanic eruptions have been described qualitatively and quantitatively. Case studies and comparative studies with data of other instruments on site allowed for the analysis of microphysical aerosol characteristics and their temporal evolution.
Localisation of deformation is a ubiquitous feature in continental rift dynamics and observed across drastically different time and length scales. This thesis comprises one experimental and two numerical modelling studies investigating strain localisation in (1) a ductile shear zone induced by a material heterogeneity and (2) in an active continental rift setting. The studies are related by the fact that the weakening mechanisms on the crystallographic and grain size scale enable bulk rock weakening, which fundamentally enables the formation of shear zones, continental rifts and hence plate tectonics. Aiming to investigate the controlling mechanisms on initiation and evolution of a shear zone, the torsion experiments of the experimental study were conducted in a Patterson type apparatus with strong Carrara marble cylinders with a weak, planar Solnhofen limestone inclusion. Using state-of-the-art numerical modelling software, the torsion experiments were simulated to answer questions regarding localisation procedure like stress distribution or the impact of rheological weakening. 2D numerical models were also employed to integrate geophysical and geological data to explain characteristic tectonic evolution of the Southern and Central Kenya Rift. Key elements of the numerical tools are a randomized initial strain distribution and the usage of strain softening. During the torsion experiments, deformation begins to localise at the limestone inclusion tips in a process zone, which propagates into the marble matrix with increasing deformation until a ductile shear zone is established. Minor indicators for coexisting brittle deformation are found close to the inclusion tip and presumed to slightly facilitate strain localisation besides the dominant ductile deformation processes. The 2D numerical model of the torsion experiment successfully predicts local stress concentration and strain rate amplification ahead of the inclusion in first order agreement with the experimental results. A simple linear parametrization of strain weaking enables high accuracy reproduction of phenomenological aspects of the observed weakening. The torsion experiments suggest that loading conditions do not affect strain localisation during high temperature deformation of multiphase material with high viscosity contrasts. A numerical simulation can provide a way of analysing the process zone evolution virtually and extend the examinable frame. Furthermore, the nested structure and anastomosing shape of an ultramylonite band was mimicked with an additional second softening step. Rheological weakening is necessary to establish a shear zone in a strong matrix around a weak inclusion and for ultramylonite formation.
Such strain weakening laws are also incorporated into the numerical models of the
Southern and Central Kenya Rift that capture the characteristic tectonic evolution. A three-stage early rift evolution is suggested that starts with (1) the accommodation of strain by a single border fault and flexure of the hanging-wall crust, after which (2) faulting in the hanging-wall and the basin centre increases before (3) the early-stage asymmetry is lost and basinward localisation of deformation occurs. Along-strike variability of rifts can be produced by modifying the initial random noise distribution. In summary, the three studies address selected aspects of the broad range of mechanisms and processes that fundamentally enable the deformation of rock and govern the localisation patterns across the scales. In addition to the aforementioned results, the first and second manuscripts combined, demonstrate a procedure to find new or improve on existing numerical formulations for specific rheologies and their dynamic weakening. These formulations are essential in addressing rock deformation from the grain to the global scale. As within the third study of this thesis, where geodynamic controls on the evolution of a rift were examined and acquired by the integration of geological and geophysical data into a numerical model.
In my doctoral thesis, I examine continuous gravity measurements for monitoring of the geothermal site at Þeistareykir in North Iceland. With the help of high-precision superconducting gravity meters (iGravs), I investigate underground mass changes that are caused by operation of the geothermal power plant (i.e. by extraction of hot water and reinjection of cold water). The overall goal of this research project is to make a statement about the sustainable use of the geothermal reservoir, from which also the Icelandic energy supplier and power plant operator Landsvirkjun should benefit.
As a first step, for investigating the performance and measurement stability of the gravity meters, in summer 2017, I performed comparative measurements at the gravimetric observatory J9 in Strasbourg. From the three-month gravity time series, I examined calibration, noise and drift behaviour of the iGravs in comparison to stable long-term time series of the observatory superconducting gravity meters. After preparatory work in Iceland (setup of gravity stations, additional measuring equipment and infrastructure, discussions with Landsvirkjun and meetings with the Icelandic partner institute ISOR), gravity monitoring at Þeistareykir was started in December 2017. With the help of the iGrav records of the initial 18 months after start of measurements, I carried out the same investigations (on calibration, noise and drift behaviour) as in J9 to understand how the transport of the superconducting gravity meters to Iceland may influence instrumental parameters.
In the further course of this work, I focus on modelling and reduction of local gravity contributions at Þeistareykir. These comprise additional mass changes due to rain, snowfall and vertical surface displacements that superimpose onto the geothermal signal of the gravity measurements. For this purpose, I used data sets from additional monitoring sensors that are installed at each gravity station and adapted scripts for hydro-gravitational modelling. The third part of my thesis targets geothermal signals in the gravity measurements.
Together with my PhD colleague Nolwenn Portier from France, I carried out additional gravity measurements with a Scintrex CG5 gravity meter at 26 measuring points within the geothermal field in the summers of 2017, 2018 and 2019. These annual time-lapse gravity measurements are intended to increase the spatial coverage of gravity data from the three continuous monitoring stations to the entire geothermal field. The combination of CG5 and iGrav observations, as well as annual reference measurements with an FG5 absolute gravity meter represent the hybrid gravimetric monitoring method for Þeistareykir. Comparison of the gravimetric data to local borehole measurements (of groundwater levels, geothermal extraction and injection rates) is used to relate the observed gravity changes to the actually extracted (and reinjected) geothermal fluids. An approach to explain the observed gravity signals by means of forward modelling of the geothermal production rate is presented at the end of the third (hybrid gravimetric) study. Further modelling with the help of the processed gravity data is planned by Landsvirkjun. In addition, the experience from time-lapse and continuous gravity monitoring will be used for future gravity measurements at the Krafla geothermal field 22 km south-east of Þeistareykir.
The complex hierarchical structure of bone undergoes a lifelong remodeling process, where it adapts to mechanical needs. Hereby, bone resorption by osteoclasts and bone formation by osteoblasts have to be balanced to sustain a healthy and stable organ. Osteocytes orchestrate this interplay by sensing mechanical strains and translating them into biochemical signals. The osteocytes are located in lacunae and are connected to one another and other bone cells via cell processes through small channels, the canaliculi. Lacunae and canaliculi form a network (LCN) of extracellular spaces that is able to transport ions and enables cell-to-cell communication. Osteocytes might also contribute to mineral homeostasis by direct interactions with the surrounding matrix. If the LCN is acting as a transport system, this should be reflected in the mineralization pattern. The central hypothesis of this thesis is that osteocytes are actively changing their material environment. Characterization methods of material science are used to achieve the aim of detecting traces of this interaction between osteocytes and the extracellular matrix. First, healthy murine bones were characterized. The properties analyzed were then compared with three murine model systems: 1) a loading model, where a bone of the mouse was loaded during its life time; 2) a healing model, where a bone of the mouse was cut to induce a healing response; and 3) a disease model, where the Fbn1 gene is dysfunctional causing defects in the formation of the extracellular tissue.
The measurement strategy included routines that make it possible to analyze the organization of the LCN and the material components (i.e., the organic collagen matrix and the mineral particles) in the same bone volumes and compare the spatial distribution of different data sets. The three-dimensional network architecture of the LCN is visualized by confocal laser scanning microscopy (CLSM) after rhodamine staining and is then subsequently quantified. The calcium content is determined via quantitative backscattered electron imaging (qBEI), while small- and wide-angle X-ray scattering (SAXS and WAXS) are employed to determine the thickness and length of local mineral particles.
First, tibiae cortices of healthy mice were characterized to investigate how changes in LCN architecture can be attributed to interactions of osteocytes with the surrounding bone matrix. The tibial mid-shaft cross-sections showed two main regions, consisting of a band with unordered LCN surrounded by a region with ordered LCN. The unordered region is a remnant of early bone formation and exhibited short and thin mineral particles. The surrounding, more aligned bone showed ordered and dense LCN as well as thicker and longer mineral particles. The calcium content was unchanged between the two regions.
In the mouse loading model, the left tibia underwent two weeks of mechanical stimulation, which results in increased bone formation and decreased resorption in skeletally mature mice. Here the specific research question addressed was how do bone material characteristics change at (re)modeling sites? The new bone formed in response to mechanical stimulation showed similar properties in terms of the mineral particles, like the ordered calcium region but lower calcium content compared to the right, non-loaded control bone of the same mice. There was a clear, recognizable border between mature and newly formed bone. Nevertheless, some canaliculi went through this border connecting the LCN of mature and newly formed bone.
Additionally, the question should be answered whether the LCN topology and the bone matrix material properties adapt to loading. Although, mechanically stimulated bones did not show differences in calcium content compared to controls, different correlations were found between the local LCN density and the local Ca content depending on whether the bone was loaded or not. These results suggest that the LCN may serve as a mineral reservoir.
For the healing model, the femurs of mice underwent an osteotomy, stabilized with an external fixator and were allowed to heal for 21 days. Thus, the spatial variations in the LCN topology with mineral properties within different tissue types and their interfaces, namely calcified cartilage, bony callus and cortex, could be simultaneously visualized and compared in this model. All tissue types showed structural differences across multiple length scales. Calcium content increased and became more homogeneous from calcified cartilage to bony callus to lamellar cortical bone. The degree of LCN organization increased as well, while the lacunae became smaller, as did the lacunar density between these different tissue types that make up the callus. In the calcified cartilage, the mineral particles were short and thin. The newly formed callus exhibited thicker mineral particles, which still had a low degree of orientation. While most of the callus had a woven-like structure, it also served as a scaffold for more lamellar tissue at the edges. The lamelar bone callus showed thinner mineral particles, but a higher degree of alignment in both, mineral particles and the LCN. The cortex showed the highest values for mineral length, thickness and degree of orientation. At the same time, the lacunae number density was 34% lower and the lacunar volume 40% smaller compared to bony callus. The transition zone between cortical and callus regions showed a continuous convergence of bone mineral properties and lacunae shape. Although only a few canaliculi connected callus and the cortical region, this indicates that communication between osteocytes of both tissues should be possible. The presented correlations between LCN architecture and mineral properties across tissue types may suggest that osteocytes have an active role in mineralization processes of healing.
A mouse model for the disease marfan syndrome, which includes a genetic defect in the fibrillin-1 gene, was investigated. In humans, Marfan syndrome is characterized by a range of clinical symptoms such as long bone overgrowth, loose joints, reduced bone mineral density, compromised bone microarchitecture, and increased fracture rates. Thus, fibrillin-1 seems to play a role in the skeletal homeostasis. Therefore, the present work studied how marfan syndrome alters LCN architecture and the surrounding bone matrix. The mice with marfan syndrome showed longer tibiae than their healthy littermates from an age of seven weeks onwards. In contrast, the cortical development appeared retarded, which was observed across all measured characteristics, i. e. lower endocortical bone formation, looser and less organized lacuno-canalicular network, less collagen orientation, thinner and shorter mineral particles.
In each of the three model systems, this study found that changes in the LCN architecture spatially correlated with bone matrix material parameters. While not knowing the exact mechanism, these results provide indications that osteocytes can actively manipulate a mineral reservoir located around the canaliculi to make a quickly accessible contribution to mineral homeostasis. However, this interaction is most likely not one-sided, but could be understood as an interplay between osteocytes and extra-cellular matrix, since the bone matrix contains biochemical signaling molecules (e.g. non-collagenous proteins) that can change osteocyte behavior. Bone (re)modeling can therefore not only be understood as a method for removing defects or adapting to external mechanical stimuli, but also for increasing the efficiency of possible osteocyte-mineral interactions during bone homeostasis. With these findings, it seems reasonable to consider osteocytes as a target for drug development related to bone diseases that cause changes in bone composition and mechanical properties. It will most likely require the combined effort of materials scientists, cell biologists, and molecular biologists to gain a deeper understanding of how bone cells respond to their material environment.
The origin and structure of magnetic fields in the Galaxy are largely unknown. What is known is that they are essential for several astrophysical processes, in particular the propagation of cosmic rays. Our ability to describe the propagation of cosmic rays through the Galaxy is severely limited by the lack of observational data needed to probe the structure of the Galactic magnetic field on many different length scales. This is particularly true for modelling the propagation of cosmic rays into the Galactic halo, where our knowledge of the magnetic field is particularly poor.
In the last decade, observations of the Galactic halo in different frequency regimes have revealed the existence of out-of-plane bubble emission in the Galactic halo. In gamma rays these bubbles have been termed Fermi bubbles with a radial extent of ≈ 3 kpc and an azimuthal height of ≈ 6 kpc. The radio counterparts of the Fermi bubbles were seen by both the S-PASS telescopes and the Planck satellite, and showed a clear spatial overlap. The X-ray counterparts of the Fermi bubbles were named eROSITA bubbles after the eROSITA satellite, with a radial width of ≈ 7 kpc and an azimuthal height of ≈ 14 kpc. Taken together, these observations suggest the presence of large extended Galactic Halo Bubbles (GHB) and have stimulated interest in exploring the less explored Galactic halo.
In this thesis, a new toy model (GHB model) for the magnetic field and non-thermal electron distribution in the Galactic halo has been proposed. The new toy model has been used to produce polarised synchrotron emission sky maps. Chi-square analysis was used to compare the synthetic skymaps with the Planck 30 GHz polarised skymaps. The obtained constraints on the strength and azimuthal height were found to be in agreement with the S-PASS radio observations.
The upper, lower and best-fit values obtained from the above chi-squared analysis were used to generate three separate toy models. These three models were used to propagate ultra-high energy cosmic rays. This study was carried out for two potential sources, Centaurus A and NGC 253, to produce magnification maps and arrival direction skymaps. The simulated arrival direction skymaps were found to be consistent with the hotspots of Centaurus A and NGC 253 as seen in the observed arrival direction skymaps provided by the Pierre Auger Observatory (PAO).
The turbulent magnetic field component of the GHB model was also used to investigate the extragalactic dipole suppression seen by PAO. UHECRs with an extragalactic dipole were forward-tracked through the turbulent GHB model at different field strengths. The suppression in the dipole due to the varying diffusion coefficient from the simulations was noted. The results could also be compared with an analytical analogy of electrostatics. The simulations of the extragalactic dipole suppression were in agreement with similar studies carried out for galactic cosmic rays.
Es ist bekannt, dass Änderungen im Kohlenstoff- bzw. Stickstoffstaus der Pflanzen zu einer parallelen statt reziproken Änderung der kohlenstoff- und stickstoffhaltigen Primärmetabolite führen. Unter diesem Gesichtspunkt wurden in der vorliegenden Arbeit der Aminosäurestoffwechsel und der Sekundärstoffwechsel unter reduzierten Stickstoffbedingungen untersucht. Zur Beeinflussung des Stickstoffstoffwechsels wurden nitratmangelernährte Tabakwildtyppflanzen und Genotypen mit unterschiedlich stark reduzierter Nitratreduktase-Aktivität verwendet. Dieses experimentelle System erlaubt zusätzlich durch den Vergleich Nitrat defizienter Wildtyppflanzen mit Nitrat akkumulierenden NIA-Transformanten Prozesse zu identifizieren, die durch Nitrat gesteuert werden. Die Analysen der Primär- und Sekundärmetabolite wurde in allen Genotypen diurnal durchgeführt, um auch tageszeitlich abhängige Prozesse zu identifizieren. Die Analyse der absoluten Gehalte aller individuellen Aminosäuren enthüllte bei den meisten erstaunlich stabile diurnale Muster mit einem Anstieg während des Tages und einem Abfall in der Nacht in Wildtyppflanzen gewachsen mit ausreichend Nitrat. Dieses Ergebnis legt die Schlussfolgerung nahe, dass die Biosynthese der Aminosäuren koordiniert abläuft. In Pflanzen mit reduziertem Stickstoffstatus haben diese diurnalen Muster jedoch keinen Bestand. Die Kombination des erzeugten stickstoffbasierten Aminosäuredatensatz in Kombination mit einem bereits erzeugten Aminosäuredatensatz unter kohlenstofflimitierten Bedingungen von Matt et al. (2002) führte durch Hauptkomponentenanalyse (PCA) und Korrelationsanalyse zu dem Ergebnis, dass die Hypothese nach einer koordinierten Aminosäurebiosynthese nicht allgemeine Gültigkeit hat. Die PCA identifizierte Glutamin, Glutamat, Aspartat, Glycin, Pheny-lalanin und Threonin als Faktoren, die den Datensätzen ihre charakteristische Eigenschaft und deren Varianz verleihen. Die Korrelationsanalyse zeigte, dass die sehr guten Korrelationen der individuellen Aminosäuren untereinander in reduzierten Stickstoff- und Kohlenstoffbedingungen sich verschlechtern. Das Verhältnis einer einzelnen Aminosäure relativ zu den anderen führte zur Identifizierung einiger Aminosäuren, die individuelle Antworten auf Stickstoff- und/oder Kohlenstoffstatus zeigen, und/oder speziell auf Nitrat, Licht und/oder den E-nergiestatus der Thylakoidmembran. Glutamat beispielsweise verhält sich in den meisten Situationen stabil, Phenylalanin dagegen zeigt in jeder physiologischen Situation eine individuelle Antwort. Die Ergebnisse dieser Arbeit führen zu einer Erweiterung der Hypothese einer koordinierten Synthese der Aminosäuren dahingehend, dass diese nicht generell für alle Aminosäuren angenommen werden kann. Es gibt einige Aminosäuren deren, Anteile sich situationsbedingt anpassen. Die Reduktion des Stickstoffstatus in nitratmangelernährten Tabakwildtyppflanzen führte zu der, nach der „Carbon-Nutrient-Balance“ Hypothese erwarteten Verlagerung der kohlenstoffreichen Phenylpropanoide und des stickstoffreichen Nikotins. Die Erhöhung der Phenylpropanoidgehalte war nicht in der Nitrat akkumulierenden NIA-Transformante zu beobachten und somit konnte Nitrat als regulatorisches Element identifiziert werden. Ein Einfluss der Vorläufermetabolite konnte ausgeschlossen werden, da sowohl nitratmangelernährter Wildtyp als auch die Nitrat akkumulierende NIA-Transformante ähnliche Gehalte dieser aufwiesen. Genexpressionsanalysen über Mikroarray-Hybridisierung und quantitative RT-PCR zeigten, dass Nitrat durch noch nicht geklärte Mechanismen Einfluss auf die Expression einiger Gene nimmt, die dem Phenylpropanoidstoffwechsels zugeordnet sind. Aus der Arbeit hervorgegangene Veröffentlichungen: Christina Fritz, Natalia Palacios-Rojas, Regina Feil und Mark Stitt (2006) Regulation of Secondary Metabolism by the Carbon-Nitrogen Status in Tobacco: Nitrate Inhibits Large Sectors of Phenylpropanoid Metabolism. Plant Journal 46, 533 - 548 Christina Fritz, Petra Matt, Cathrin Müller, Regina Feil und Mark Stitt (2006) Impact of the Carbon-Nitrogen Status on the Amino Acid Profile in Tobacco Source Leaves. Plant, Cell and Environment 29 (11), 2009 - 2111
It is desirable to reduce the potential threats that result from the variability of nature, such as droughts or heat waves that lead to food shortage, or the other extreme, floods that lead to severe damage. To prevent such catastrophic events, it is necessary to understand, and to be capable of characterising, nature's variability. Typically one aims to describe the underlying dynamics of geophysical records with differential equations. There are, however, situations where this does not support the objectives, or is not feasible, e.g., when little is known about the system, or it is too complex for the model parameters to be identified. In such situations it is beneficial to regard certain influences as random, and describe them with stochastic processes. In this thesis I focus on such a description with linear stochastic processes of the FARIMA type and concentrate on the detection of long-range dependence. Long-range dependent processes show an algebraic (i.e. slow) decay of the autocorrelation function. Detection of the latter is important with respect to, e.g. trend tests and uncertainty analysis. Aiming to provide a reliable and powerful strategy for the detection of long-range dependence, I suggest a way of addressing the problem which is somewhat different from standard approaches. Commonly used methods are based either on investigating the asymptotic behaviour (e.g., log-periodogram regression), or on finding a suitable potentially long-range dependent model (e.g., FARIMA[p,d,q]) and test the fractional difference parameter d for compatibility with zero. Here, I suggest to rephrase the problem as a model selection task, i.e.comparing the most suitable long-range dependent and the most suitable short-range dependent model. Approaching the task this way requires a) a suitable class of long-range and short-range dependent models along with suitable means for parameter estimation and b) a reliable model selection strategy, capable of discriminating also non-nested models. With the flexible FARIMA model class together with the Whittle estimator the first requirement is fulfilled. Standard model selection strategies, e.g., the likelihood-ratio test, is for a comparison of non-nested models frequently not powerful enough. Thus, I suggest to extend this strategy with a simulation based model selection approach suitable for such a direct comparison. The approach follows the procedure of a statistical test, with the likelihood-ratio as the test statistic. Its distribution is obtained via simulations using the two models under consideration. For two simple models and different parameter values, I investigate the reliability of p-value and power estimates obtained from the simulated distributions. The result turned out to be dependent on the model parameters. However, in many cases the estimates allow an adequate model selection to be established. An important feature of this approach is that it immediately reveals the ability or inability to discriminate between the two models under consideration. Two applications, a trend detection problem in temperature records and an uncertainty analysis for flood return level estimation, accentuate the importance of having reliable methods at hand for the detection of long-range dependence. In the case of trend detection, falsely concluding long-range dependence implies an underestimation of a trend and possibly leads to a delay of measures needed to take in order to counteract the trend. Ignoring long-range dependence, although present, leads to an underestimation of confidence intervals and thus to an unjustified belief in safety, as it is the case for the return level uncertainty analysis. A reliable detection of long-range dependence is thus highly relevant in practical applications. Examples related to extreme value analysis are not limited to hydrological applications. The increased uncertainty of return level estimates is a potentially problem for all records from autocorrelated processes, an interesting examples in this respect is the assessment of the maximum strength of wind gusts, which is important for designing wind turbines. The detection of long-range dependence is also a relevant problem in the exploration of financial market volatility. With rephrasing the detection problem as a model selection task and suggesting refined methods for model comparison, this thesis contributes to the discussion on and development of methods for the detection of long-range dependence.
Die durch Phosphatidylserin Decarboxylase (PSD) katalysierte Decarboxylierung von Phosphatidylserin (PS) zu Phosphatidylethanolamin (PE) ist für Mitochondrien in Hefe und Mäusen von essentieller Bedeutung. Im Rahmen der vorliegenden Dissertation wurde erstmals die Rolle dieses PE-Syntheseweges in Pflanzen untersucht. Die drei in Arabidopsis identifizierten PSD Gene atPSD1, atPSD2, atPSD3 codieren für Enzyme, die in Membranen der Mitochondrien (atPSD1), der Tonoplasten (atPSD2) und des Endoplasmatischen Retikulums (atPSD3) lokalisiert sind. Der Beitrag der einzelnen PSDs zur PE-Synthese wurde anhand von psd Null-Mutanten untersucht. Dabei stellte sich atPSD3 als das Enzym mit der höchsten Aktivität heraus. Alternativ zum PSD-Weg wird in Arabidopsis PE auch mittels Aminoalkohol-phosphotransferase synthetisiert. Der Verlust der gesamten PSD-Aktivität, wie es in der erzeugten psd Dreifachmutante der Fall ist, wirkt sich ausschließlich auf die Lipidzusammensetzung in der Mitochondrienmembran aus. Demzufolge wird extramitochondriales PE hauptsächlich über die Aminoalkoholphosphotransferase synthetisiert. Die veränderte Lipidzusammensetzung der Mitochondrienmembran hatte jedoch keinen Einfluss auf die Anzahl, Größe und Ultrastruktur der Mitochondrien sowie auf das ADP/ATP-Verhältnis und die Respiration. Neben der Bereitstellung von Reduktionsäquivalenten beeinflusst die Funktionalität der Mitochondrien auch die Bildung von Blüten- und Staubblättern. Diese Blütenorgane waren in der psd Dreifachmutante stark verändert, und der Blütenphänotyp ähnelte der APETALA3-Mutante. Dieses homöotische Gen ist für die Ausbildung von Blüten- und Staubblättern verantwortlich. Für die Erzeugung der Mutanten psd2-1 und psd3-1 wurde ein T-DNA Vektor verwendet, der den Promotor des APETALA3 Gens enthielt, welcher in den Mutanten psd2-1, psd3-1 sowie psd2-1psd3-1 und der psd1psd2-1psd3-1 Dreifachmutante eine vergleichbare Co-Suppression des APETALA3 Gens hervorruft. Der Blütenphänotyp trat jedoch nur in der psd Dreifachmutante auf, da nur in ihr die Kombination von geringen Funktionstörungen der Mitochondrien, hervorgerufen durch veränderte Lipidzusammensetzung, mit der Co-Suppression von APETALA3 auftritt.
Aminosäuren sind lebensnotwendige Moleküle für alle Organismen. Ihre Erkennung im Körper ermöglicht eine bedarfsgerechte Regulation ihrer Aufnahme und ihrer Verwertung. Welcher Chemosensor für diese Erkennung jedoch hauptverantwortlich ist, ist bisher unklar. In der vorliegenden Arbeit wurde die Rolle der Umamigeschmacksrezeptoruntereinheit Tas1r1 jenseits ihrer gustatorischen Bedeutung für die Aminosäuredetektion in der Mundhöhle untersucht.
In der histologischen Tas1r1-Expressionsanalyse nichtgustatorischer Gewebe der Mauslinie Tas1r1-Cre/ROSA26-tdRFP wurde über die Detektion des Reporterproteins tdRFP die Expression des Tas1r1 in allen untersuchten Geweben (Speiseröhre, Magen, Darm, Bauchspeicheldrüse, Leber, Niere, Muskel- und Fettgewebe, Milz, Thymus, Lymphknoten, Lunge sowie Hoden) nachgewiesen. Mit Ausnahme von Dünndarm und Hoden gelang hierbei der Nachweis erstmals spezifisch auf zellulärer Ebene. Caecum und Lymphknoten wurden zudem neu als Expressionsorte des Tas1r1 identifiziert.
Trotz der beobachteten weiten Verbreitung des Tas1r1 im Organismus – unter anderem auch in Geweben, die für den Proteinstoffwechsel besonders relevant sind – waren im Zuge der durchgeführten Untersuchung potentieller extraoraler Funktionen des Rezeptors durch phänotypische Charakterisierung der Mauslinie Tas1r1-BLiR nur schwache Auswirkungen auf Aminosäurestoffwechsel bzw. Stickstoffhaushalt im Falle eines Tas1r1-Knockouts detektierbar. Während sich Ernährungsverhalten, Gesamtphysiologie, Gewebemorphologie sowie Futterverdaulichkeit unverändert zeigten, war die renale Stickstoffausscheidung bei Tas1r1-Knockout-Mäusen auf eiweißarmer sowie auf eiweißreicher Diät signifikant verringert. Eine Überdeckung der Auswirkungen des Tas1r1-Knockouts aufgrund kompensatorischer Effekte durch den Aminosäuresensor CaSR oder den Peptidsensor Gpr93 war nicht nachweisbar. Es bleibt offen, ob andere Mechanismen oder andere Chemosensoren an einer Kompensation beteiligt sind oder aber Tas1r1 in extraoralem Gewebe andere Funktionen als die der Aminosäuredetektion übernimmt. Unterschiede im extraoralen Expressionsmuster der beiden Umamirezeptor-untereinheiten Tas1r1 und Tasr3 lassen Spekulationen über andere Partner, Liganden und Funktionen zu.
Cargo transport by molecular motors is ubiquitous in all eukaryotic cells and is typically driven cooperatively by several molecular motors, which may belong to one or several motor species like kinesin, dynein or myosin. These motor proteins transport cargos such as RNAs, protein complexes or organelles along filaments, from which they unbind after a finite run length. Understanding how these motors interact and how their movements are coordinated and regulated is a central and challenging problem in studies of intracellular transport. In this thesis, we describe a general theoretical framework for the analysis of such transport processes, which enables us to explain the behavior of intracellular cargos based on the transport properties of individual motors and their interactions. Motivated by recent in vitro experiments, we address two different modes of transport: unidirectional transport by two identical motors and cooperative transport by actively walking and passively diffusing motors. The case of cargo transport by two identical motors involves an elastic coupling between the motors that can reduce the motors’ velocity and/or the binding time to the filament. We show that this elastic coupling leads, in general, to four distinct transport regimes. In addition to a weak coupling regime, kinesin and dynein motors are found to exhibit a strong coupling and an enhanced unbinding regime, whereas myosin motors are predicted to attain a reduced velocity regime. All of these regimes, which we derive both by analytical calculations and by general time scale arguments, can be explored experimentally by varying the elastic coupling strength. In addition, using the time scale arguments, we explain why previous studies came to different conclusions about the effect and relevance of motor-motor interference. In this way, our theory provides a general and unifying framework for understanding the dynamical behavior of two elastically coupled molecular motors. The second mode of transport studied in this thesis is cargo transport by actively pulling and passively diffusing motors. Although these passive motors do not participate in active transport, they strongly enhance the overall cargo run length. When an active motor unbinds, the cargo is still tethered to the filament by the passive motors, giving the unbound motor the chance to rebind and continue its active walk. We develop a stochastic description for such cooperative behavior and explicitly derive the enhanced run length for a cargo transported by one actively pulling and one passively diffusing motor. We generalize our description to the case of several pulling and diffusing motors and find an exponential increase of the run length with the number of involved motors.
The widespread usage of products containing volatile organic compounds (VOC) has lead to a general human exposure to these chemicals in work places or homes being suspected to contribute to the growing incidence of environmental diseases. Since the causal molecular mechanisms for the development of these disorders are not completely understood, the overall objective of this thesis was to investigate VOC-mediated molecular effects on human lung cells in vitro at VOC concentrations comparable to exposure scenarios below current occupational limits. Although differential expression of single proteins in response to VOCs has been reported, effects on complex protein networks (proteome) have not been investigated. However, this information is indispensable when trying to ascertain a mechanism for VOC action on the cellular level and establishing preventive strategies. For this study, the alveolar epithelial cell line A549 has been used. This cell line, cultured in a two-phase (air/liquid) model allows the most direct exposure and had been successfully applied for the analysis of inflammatory effects in response to VOCs. Mass spectrometric identification of 266 protein spots provided the first proteomic map of A549 cell line to this extent that may foster future work with this frequently used cellular model. The distribution of three typical air contaminants, monochlorobenzene (CB), styrene and 1,2 dichlorobenzene (1,2-DCB), between gas and liquid phase of the exposure model has been analyzed by gas chromatography. The obtained VOC partitioning was in agreement with available literature data. Subsequently the adapted in vitro system has been successfully employed to characterize the effects of the aromatic compound styrene on the proteome of A549 cells (Chapter 4). Initially, the cell toxicity has been assessed in order to ensure that most of the concentrations used in the following proteomic approach were not cytotoxic. Significant changes in abundance and phosphorylation in the total soluble protein fraction of A549 cells have been detected following styrene exposure. All proteins have been identified using mass spectrometry and the main cellular functions have been assigned. Validation experiments on protein and transcript level confirmed the results of the 2-DE experiments. From the results, two main cellular pathways have been identified that were induced by styrene: the cellular oxidative stress response combined with moderate pro-apoptotic signaling. Measurement of cellular reactive oxygen species (ROS) as well as the styrene-mediated induction of oxidative stress marker proteins confirmed the hypothesis of oxidative stress as the main molecular response mechanism. Finally, adducts of cellular proteins with the reactive styrene metabolite styrene 7,8 oxide (SO) have been identified. Especially the SO-adducts observed at both the reactive centers of thioredoxin reductase 1, which is a key element in the control of the cellular redox state, may be involved in styrene-induced ROS formation and apoptosis. A similar proteomic approach has been carried out with the halobenzenes CB and 1,2-DCB (Chapter 5). In accordance with previous findings, cell toxicity assessment showed enhanced toxicity compared to the one caused by styrene. Significant changes in abundance and phosphorylation of total soluble proteins of A549 cells have been detected following exposure to subtoxic concentrations of CB and 1,2-DCB. All proteins have been identified using mass spectrometry and the main cellular functions have been assigned. As for the styrene experiment, the results indicated two main pathways to be affected in the presence of chlorinated benzenes, cell death signaling and oxidative stress response. The strong induction of pro-apoptotic signaling has been confirmed for both treatments by detection of the cleavage of caspase 3. Likewise, the induction of redox-sensitive protein species could be correlated to an increased cellular level of ROS observed following CB treatment. Finally, common mechanisms in the cellular response to aromatic VOCs have been investigated (Chapter 6). A similar number (4.6-6.9%) of all quantified protein spots showed differential expression (p<0.05) following cell exposure to styrene, CB or 1,2-DCB. However, not more than three protein spots showed significant regulation in the same direction for all three volatile compounds: voltage-dependent anion-selective channel protein 2, peroxiredoxin 1 and elongation factor 2. However, all of these proteins are important molecular targets in stress- and cell death-related signaling pathways.
Dryland vulnerability : typical patterns and dynamics in support of vulnerability reduction efforts
(2011)
The pronounced constraints on ecosystem functioning and human livelihoods in drylands are frequently exacerbated by natural and socio-economic stresses, including weather extremes and inequitable trade conditions. Therefore, a better understanding of the relation between these stresses and the socio-ecological systems is important for advancing dryland development. The concept of vulnerability as applied in this dissertation describes this relation as encompassing the exposure to climate, market and other stresses as well as the sensitivity of the systems to these stresses and their capacity to adapt. With regard to the interest in improving environmental and living conditions in drylands, this dissertation aims at a meaningful generalisation of heterogeneous vulnerability situations. A pattern recognition approach based on clustering revealed typical vulnerability-creating mechanisms at global and local scales. One study presents the first analysis of dryland vulnerability with global coverage at a sub-national resolution. The cluster analysis resulted in seven typical patterns of vulnerability according to quantitative indication of poverty, water stress, soil degradation, natural agro-constraints and isolation. Independent case studies served to validate the identified patterns and to prove the transferability of vulnerability-reducing approaches. Due to their worldwide coverage, the global results allow the evaluation of a specific system’s vulnerability in its wider context, even in poorly-documented areas. Moreover, climate vulnerability of smallholders was investigated with regard to their food security in the Peruvian Altiplano. Four typical groups of households were identified in this local dryland context using indicators for harvest failure risk, agricultural resources, education and non-agricultural income. An elaborate validation relying on independently acquired information demonstrated the clear correlation between weather-related damages and the identified clusters. It also showed that household-specific causes of vulnerability were consistent with the mechanisms implied by the corresponding patterns. The synthesis of the local study provides valuable insights into the tailoring of interventions that reflect the heterogeneity within the social group of smallholders. The conditions necessary to identify typical vulnerability patterns were summarised in five methodological steps. They aim to motivate and to facilitate the application of the selected pattern recognition approach in future vulnerability analyses. The five steps outline the elicitation of relevant cause-effect hypotheses and the quantitative indication of mechanisms as well as an evaluation of robustness, a validation and a ranking of the identified patterns. The precise definition of the hypotheses is essential to appropriately quantify the basic processes as well as to consistently interpret, validate and rank the clusters. In particular, the five steps reflect scale-dependent opportunities, such as the outcome-oriented aspect of validation in the local study. Furthermore, the clusters identified in Northeast Brazil were assessed in the light of important endogenous processes in the smallholder systems which dominate this region. In order to capture these processes, a qualitative dynamic model was developed using generalised rules of labour allocation, yield extraction, budget constitution and the dynamics of natural and technological resources. The model resulted in a cyclic trajectory encompassing four states with differing degree of criticality. The joint assessment revealed aggravating conditions in major parts of the study region due to the overuse of natural resources and the potential for impoverishment. The changes in vulnerability-creating mechanisms identified in Northeast Brazil are well-suited to informing local adjustments to large-scale intervention programmes, such as “Avança Brasil”. Overall, the categorisation of a limited number of typical patterns and dynamics presents an efficient approach to improving our understanding of dryland vulnerability. Appropriate decision-making for sustainable dryland development through vulnerability reduction can be significantly enhanced by pattern-specific entry points combined with insights into changing hotspots of vulnerability and the transferability of successful adaptation strategies.
In the arable soil landscape of hummocky ground moraines, an erosion-affected spatial differentiation of soils can be observed. Man-made erosion leads to soil profile modifications along slopes with changed solum thickness and modified properties of soil horizons due to water erosion in combination with tillage operations. Soil erosion creates, thereby, spatial patterns of soil properties (e.g., texture and organic matter content) and differences in crop development. However, little is known about the manner in which water fluxes are affected by soil-crop interactions depending on contrasting properties of differently-developed soil horizons and how water fluxes influence the carbon transport in an eroded landscape. To identify such feedbacks between erosion-induced soil profile modifications and the 1D-water and solute balance, high-precision weighing lysimeters equipped with a wide range of sensor technique were filled with undisturbed soil monoliths that differed in the degree of past soil erosion. Furthermore, lysimeter effluent concentrations were analyzed for dissolved carbon fractions in bi-weekly intervals.
The water balance components measured by high precision lysimeters varied from the most eroded to the less eroded monolith up to 83 % (deep drainage) primarily caused due to varying amounts of precipitation and evapotranspiration for a 3-years period. Here, interactions between crop development and contrasting rainfall interception by above ground biomass could explain differences in water balance components. Concentrations of dissolved carbon in soil water samples were relatively constant in time, suggesting carbon leaching was mainly affected by water fluxes in this observation period. For the lysimeter-based water balance analysis, a filtering scheme was developed considering temporal autocorrelation. The minute-based autocorrelation analysis of mass changes from lysimeter time series revealed characteristic autocorrelation lengths ranging from 23 to 76 minutes. Thereby, temporal autocorrelation provided an optimal approximation of precipitation quantities. However, the high temporal resolution in lysimeter time series is restricted by the lengths of autocorrelation.
Erosion-induced but also gradual changes in soil properties were reflected by dynamics of soil water retention properties in the lysimeter soils. Short-term and long-term hysteretic water retention data suggested seasonal wettability problems of soils increasingly limited rewetting of previously dried pore regions. Differences in water retention were assigned to soil tillage operations and the erosion history at different slope positions. The threedimensional spatial pattern of soil types that result from erosional soil profile modifications were also reflected in differences of crop root development at different landscape positions. Contrasting root densities revealed positive relations of root and aboveground plant characteristics. Differences in the spatially-distributed root growth between different eroded soil types provided indications that root development was affected by the erosion-induced soil evolution processes.
Overall, the current thesis corroborated the hypothesis that erosion-induced soil profile modifications affect the soil water balance, carbon leaching and soil hydraulic properties, but also the crop root system is influenced by erosion-induced spatial patterns of soil properties in the arable hummocky post glacial soil landscape. The results will help to improve model predictions of water and solute movement in arable soils and to understand interactions between soil erosion and carbon pathways regarding sink-or-source terms in landscapes.
Moderne Softwaresysteme sind komplexe Gebilde, welche häufig im Verbund mit anderen technischen und betriebswirtschaftlichen Systemen eingesetzt werden. Für die Hersteller solcher Systeme stellt es oft eine große Herausforderung dar, den oft weit reichenden Anforderungen bezüglich der Anpassbarkeit solcher Systeme gerecht zu werden. Zur Erfüllung dieser Anforderungen hat es sich vielfach bewährt, eine virtuelle Maschine in das betreffende System zu integrieren. Die Dissertation richtet sich insbesondere an Personen, die vor der Aufgabe der Integration virtueller Maschinen in bestehende Systeme stehen und zielt darauf ab, solche für die Entscheidung über Integrationsfragen wichtigen Zusammenhänge klar darzustellen. Typischerweise treten bei der Integration einer virtuellen Maschine in ein System eine Reihe unterschiedlicher Problemstellungen auf. Da diese Problemstellungen oft eng miteinander verzahnt sind, ist eine isolierte Betrachtung meist nicht sinnvoll. Daher werden die Problemstellungen anhand eines zentral gewählten, sehr umfangreichen Beispiels aus der industriellen Praxis eingeführt. Dieses Beispiel hat die Integration der "Java Virtual Machine" in den SAP R/3 Application Server zum Gegenstand. Im Anschluss an dieses Praxisbeispiel wird die Diskussion der Integrationsproblematik unter Bezug auf eine Auswahl weiterer, in der Literatur beschriebener Integrationsbeispiele vertieft. Das Hauptproblem bei der Behandlung der Integrationsproblematik bestand darin, dass die vorgefundenen Beschreibungen, der als Beispiel herangezogenen Systeme, nur bedingt als Basis für die Auseinandersetzung mit der Integrationsproblematik geeignet waren. Zur Schaffung einer verwertbaren Diskussionsgrundlage war es daher erforderlich, eine homogene, durchgängige Modellierung dieser Systeme vorzunehmen. Die Modellierung der Systeme erfolgte dabei unter Verwendung der "Fundamental Modeling Concepts (FMC)". Die erstellten Modelle sowie die auf Basis dieser Modelle durchgeführte Gegenüberstellung der unterschiedlichen Ansätze zur LÖsung typischer Integrationsprobleme bilden den Hauptbeitrag der Dissertation. Im Zusammenhang mit der Integration virtueller Maschinen in bestehende Systeme besteht häufig der Bedarf, zeitgleich mehrere "Programme" durch die integrierte virtuelle Maschine ausführen zu lassen. Angesichts der Konstruktionsmerkmale vieler heute verbreiteter virtueller Maschinen stellt die Realisierung eines "betriebsmittelschonenden Mehrprogrammbetriebs" eine große Herausforderung dar. Die Darstellung des Spektrums an Maßnahmen zur Realisierung eines "betriebsmittelschonenden Mehrprogrammbetriebs" bildet einen zweiten wesentlichen Beitrag der Dissertation.
Ziel der vorliegenden Arbeit war es, die Auswirkungen von Glucose- und Lipidtoxizität auf die Funktion der β-Zellen von Langerhans-Inseln in einem diabetesresistenten (B6.V-Lepob/ob, ob/ob) sowie diabetessuszeptiblen (New Zealand Obese, NZO) Mausmodell zu untersuchen. Es sollten molekulare Mechanismen identifiziert werden, die zum Untergang der β-Zellen in der NZO-Maus führen bzw. zum Schutz der β-Zellen der ob/ob-Maus beitragen. Zunächst wurde durch ein geeignetes diätetisches Regime in beiden Modellen durch kohlenhydratrestriktive Ernährung eine Adipositas(Lipidtoxizität) induziert und anschließend durch Fütterung einer kohlenhydrathaltigen Diät ein Zustand von Glucolipotoxizität erzeugt. Dieses Vorgehen erlaubte es, in der NZO-Maus in einem kurzen Zeitfenster eine Hyperglykämie sowie einen β-Zelluntergang durch Apoptose auszulösen. Im Vergleich dazu blieben ob/ob-Mäuse längerfristig normoglykämisch und wiesen keinen β-Zelluntergang auf. Die Ursache für den β-Zellverlust war die Inaktivierung des Insulin/IGF-1-Rezeptor-Signalwegs, wie durch Abnahme von phospho-AKT, phospho-FoxO1 sowie des β-zellspezifischen Transkriptionsfaktors PDX1 gezeigt wurde. Mit Ausnahme des Effekts einer Dephosphorylierung von FoxO1, konnten ob/ob-Mäuse diesen Signalweg aufrechterhalten und dadurch einen Verlust von β-Zellen abwenden. Die glucolipotoxischen Effekte wurden in vitro an isolierten Inseln beider Stämme und der β-Zelllinie MIN6 bestätigt und zeigten, dass ausschließlich die Kombination hoher Glucose und Palmitatkonzentrationen (Glucolipotoxizität) negative Auswirkungen auf die NZO-Inseln und MIN6-Zellen hatte, während ob/ob-Inseln davor geschützt blieben. Die Untersuchung isolierter Inseln ergab, dass beide Stämme unter glucolipotoxischen Bedingungen keine Steigerung der Insulinexpression aufweisen und sich bezüglich ihrer Glucose-stimulierten Insulinsekretion nicht unterscheiden. Mit Hilfe von Microarray- sowie immunhistologischen Untersuchungen wurde gezeigt, dass ausschließlich ob/ob-Mäuse nach Kohlenhydratfütterung eine kompensatorische transiente Induktion der β-Zellproliferation aufwiesen, die in einer nahezu Verdreifachung der Inselmasse nach 32 Tagen mündete. Die hier erzielten Ergebnisse lassen die Schlussfolgerung zu, dass der β-Zelluntergang der NZO-Maus auf eine Beeinträchtigung des Insulin/IGF-1-Rezeptor-Signalwegs sowie auf die Unfähigkeit zur β- Zellproliferation zurückgeführt werden kann. Umgekehrt ermöglichen der Erhalt des Insulin/IGF-1-Rezeptor-Signalwegs und die Induktion der β-Zellproliferation in der ob/ob-Maus den Schutz vor einer Hyperglykämie und einem Diabetes.
To achieve a sustainable energy economy, it is necessary to turn back on the combustion of fossil fuels as a means of energy production and switch to renewable sources. However, their temporal availability does not match societal consumption needs, meaning that renewably generated energy must be stored in its main generation times and allocated during peak consumption periods. Electrochemical energy storage (EES) in general is well suited due to its infrastructural independence and scalability. The lithium ion battery (LIB) takes a special place, among EES systems due to its energy density and efficiency, but the scarcity and uneven geological occurrence of minerals and ores vital for many cell components, and hence the high and fluctuating costs will decelerate its further distribution.
The sodium ion battery (SIB) is a promising successor to LIB technology, as the fundamental setup and cell chemistry is similar in the two systems. Yet, the most widespread negative electrode material in LIBs, graphite, cannot be used in SIBs, as it cannot store sufficient amounts of sodium at reasonable potentials. Hence, another carbon allotrope, non-graphitizing or hard carbon (HC) is used in SIBs. This material consists of turbostratically disordered, curved graphene layers, forming regions of graphitic stacking and zones of deviating layers, so-called internal or closed pores.
The structural features of HC have a substantial impact of the charge-potential curve exhibited by the carbon when it is used as the negative electrode in an SIB. At defects and edges an adsorption-like mechanism of sodium storage is prevalent, causing a sloping voltage curve, ill-suited for the practical application in SIBs, whereas a constant voltage plateau of relatively high capacities is found immediately after the sloping region, which recent research attributed to the deposition of quasimetallic sodium into the closed pores of HC.
Literature on the general mechanism of sodium storage in HCs and especially the role of the closed pore is abundant, but the influence of the pore geometry and chemical nature of the HC on the low-potential sodium deposition is yet in an early stage. Therefore, the scope of this thesis is to investigate these relationships using suitable synthetic and characterization methods. Materials of precisely known morphology, porosity, and chemical structure are prepared in clear distinction to commonly obtained ones and their impact on the sodium storage characteristics is observed. Electrochemical impedance spectroscopy in combination with distribution of relaxation times analysis is further established as a technique to study the sodium storage process, in addition to classical direct current techniques, and an equivalent circuit model is proposed to qualitatively describe the HC sodiation mechanism, based on the recorded data. The obtained knowledge is used to develop a method for the preparation of closed porous and non-porous materials from open porous ones, proving not only the necessity of closed pores for efficient sodium storage, but also providing a method for effective pore closure and hence the increase of the sodium storage capacity and efficiency of carbon materials.
The insights obtained and methods developed within this work hence not only contribute to the better understanding of the sodium storage mechanism in carbon materials of SIBs, but can also serve as guidance for the design of efficient electrode materials.
Our dynamic Sun manifests its activity by different phenomena: from the 11-year cyclic sunspot pattern to the unpredictable and violent explosions in the case of solar flares. During flares, a huge amount of the stored magnetic energy is suddenly released and a substantial part of this energy is carried by the energetic electrons, considered to be the source of the nonthermal radio and X-ray radiation. One of the most important and still open question in solar physics is how the electrons are accelerated up to high energies within (the observed in the radio emission) short time scales. Because the acceleration site is extremely small in spatial extent as well (compared to the solar radius), the electron acceleration is regarded as a local process. The search for localized wave structures in the solar corona that are able to accelerate electrons together with the theoretical and numerical description of the conditions and requirements for this process, is the aim of the dissertation. Two models of electron acceleration in the solar corona are proposed in the dissertation: I. Electron acceleration due to the solar jet interaction with the background coronal plasma (the jet--plasma interaction) A jet is formed when the newly reconnected and highly curved magnetic field lines are relaxed by shooting plasma away from the reconnection site. Such jets, as observed in soft X-rays with the Yohkoh satellite, are spatially and temporally associated with beams of nonthermal electrons (in terms of the so-called type III metric radio bursts) propagating through the corona. A model that attempts to give an explanation for such observational facts is developed here. Initially, the interaction of such jets with the background plasma leads to an (ion-acoustic) instability associated with growing of electrostatic fluctuations in time for certain range of the jet initial velocity. During this process, any test electron that happen to feel this electrostatic wave field is drawn to co-move with the wave, gaining energy from it. When the jet speed has a value greater or lower than the one, required by the instability range, such wave excitation cannot be sustained and the process of electron energization (acceleration and/or heating) ceases. Hence, the electrons can propagate further in the corona and be detected as type III radio burst, for example. II. Electron acceleration due to attached whistler waves in the upstream region of coronal shocks (the electron--whistler--shock interaction) Coronal shocks are also able to accelerate electrons, as observed by the so-called type II metric radio bursts (the radio signature of a shock wave in the corona). From in-situ observations in space, e.g., at shocks related to co-rotating interaction regions, it is known that nonthermal electrons are produced preferably at shocks with attached whistler wave packets in their upstream regions. Motivated by these observations and assuming that the physical processes at shocks are the same in the corona as in the interplanetary medium, a new model of electron acceleration at coronal shocks is presented in the dissertation, where the electrons are accelerated by their interaction with such whistlers. The protons inflowing toward the shock are reflected there by nearly conserving their magnetic moment, so that they get a substantial velocity gain in the case of a quasi-perpendicular shock geometry, i.e, the angle between the shock normal and the upstream magnetic field is in the range 50--80 degrees. The so-accelerated protons are able to excite whistler waves in a certain frequency range in the upstream region. When these whistlers (comprising the localized wave structure in this case) are formed, only the incoming electrons are now able to interact resonantly with them. But only a part of these electrons fulfill the the electron--whistler wave resonance condition. Due to such resonant interaction (i.e., of these electrons with the whistlers), the electrons are accelerated in the electric and magnetic wave field within just several whistler periods. While gaining energy from the whistler wave field, the electrons reach the shock front and, subsequently, a major part of them are reflected back into the upstream region, since the shock accompanied with a jump of the magnetic field acts as a magnetic mirror. Co-moving with the whistlers now, the reflected electrons are out of resonance and hence can propagate undisturbed into the far upstream region, where they are detected in terms of type II metric radio bursts. In summary, the kinetic energy of protons is transfered into electrons by the action of localized wave structures in both cases, i.e., at jets outflowing from the magnetic reconnection site and at shock waves in the corona.
El plateau Andino es el segundo plateau orogénico más grande del mundo y se ubica en los Andes Centrales, desarrollado en un sistema orogénico no colisional. Se extiende desde el sur del Perú (15°S), hasta el norte de Argentina y Chile (27°30´S). A partir de los 24°S y prologándose hacia el sur, el plateau Andino se denomina Puna y está caracterizado por un sistema de cuencas endorreicas y salares delimitados por cordones montañosos. Entre los 26° y 27°30´S, la Puna encuentra su límite austral en una zona de transición entre una zona de subducción normal y una zona de subducción plana o “flat slab” que se prolonga hasta los 33°S. Diversos estudios documentan la ocurrencia de un aumento del espesor cortical, y levantamiento episódico y diacrónico del relieve, alcanzando su configuración actual durante el Mioceno tardío. Posteriormente, el plateau habría experimentado un cambio en el estilo de deformación dominado por procesos extensionales evidenciado por fallas y terremotos de cinemática normal. Sin embargo, en el borde sur del plateau de la Puna y en las áreas delimitadas con el resto del orógeno, la variación del campo de esfuerzo no está del todo comprendida, reflejando una excelente oportunidad para evaluar cómo el campo de esfuerzo puede evolucionar durante el desarrollo del orógeno y cómo puede verse afectado por la presencia/ausencia de un plateau orogénico, así como también por la existencia de anisotropías estructurales propias de cada unidad morfotectónica.
Esta Tesis investiga la relación entre la deformación cortical somera y la evolución en tiempo y espacio del campo de esfuerzos en el sector sur del plateau Andino, durante el cenozoico tardío. Para realizar esta investigación, se utilizaron técnicas de obtención de edades radiométricas con el método Uranio-Plomo (U-Pb), análisis de fallas mesoscópicas para la obtención de tensores de esfuerzos y delimitación de la orientación de los ejes principales de esfuerzos, análisis de anisotropía de susceptibilidad magnética en rocas sedimentarias y volcanoclásticas para estimar direcciones de acortamiento o direcciones de transporte sedimentario, técnicas de modelado cinemático para llegar a una aproximación de las estructuras corticales profundas asociadas a la deformación allí registrada, y un análisis morfométrico para la identificación de indicadores geomorfológicos asociados a deformación producto de la actividad tectónica cuaternaria.
Combinando estos resultados con los antecedentes previamente documentados, el estudio revela una compleja variación del campo de esfuerzo caracterizado por cambios en la orientación y permutaciones verticales de los ejes principales de esfuerzos, durante cada régimen de deformación, durante los últimos ~24 Ma. La evolución del campo de esfuerzos puede ser asociada temporalmente a tres fases orogénicas involucradas con la evolución de los Andes Centrales en esta latitud: (1) una primera fase con un régimen de esfuerzos compresivos de acortamiento E-O documentado desde el Eoceno, Oligoceno tardío hasta el Mioceno medio en el área, coincide con la fase de construcción andina, engrosamiento y crecimiento de la corteza y levantamiento topográfico; (2) una segunda fase caracterizada por un régimen de esfuerzos de transcurrencia, a partir de los ~11 Ma en el borde occidental y compresión y transcurrencia a los~5 Ma en el borde oriental del plateau de la Puna, y un régimen de esfuerzo compresivos en Famatina y las Sierras Pampeanas interpretado como una transición entre la construcción orogénica del Neógeno y la máxima acumulación de deformación y el alzamiento topográfico del plateau de la Puna, y (3) una tercera fase donde el régimen se caracteriza por la transcurrencia en la Puna y en su borde occidental y en su borde oriental con las Sierras Pampeanas, después de ~5-4 Ma, interpretado como un régimen de esfuerzos controlados por el engrosamiento cortical desarrollado a lo largo del borde sur del plateau Altiplano/Puna, previo a un colapso orogénico. Los resultados dejan en evidencia que el borde del plateau experimentó el paso desde un régimen compresivo hacia uno transcurrente, que se diferencia de la extensión documentada hacia el norte en el plateau Andino para el mismo período. Cambios en los esfuerzos similares han sido documentado durante la construcción del plateau Tibetano, en donde un régimen de esfuerzo predominantemente compresivo cambió a un régimen de transcurrente cuando el plateau habría alcanzado la mitad de su elevación actual, y que posteriormente derivó en un régimen extensional, entre 14 y 4 Ma, cuando la altitud del plateau fue superior al 80% respecto a su actitud actual, lo que podría estar indicando que los regímenes transcurrentes representan etapas transicionales entre las zonas externas del plateau bajo compresión y las zonas internas, en las que los regímenes extensionales son más viables de ocurrir.
Plate tectonics describes the movement of rigid plates at the surface of the Earth as well as their complex deformation at three types of plate boundaries: 1) divergent boundaries such as rift zones and mid-ocean ridges, 2) strike-slip boundaries where plates grind past each other, such as the San Andreas Fault, and 3) convergent boundaries that form large mountain ranges like the Andes. The generally narrow deformation zones that bound the plates exhibit complex strain patterns that evolve through time. During this evolution, plate boundary deformation is driven by tectonic forces arising from Earth’s deep interior and from within the lithosphere, but also by surface processes, which erode topographic highs and deposit the resulting sediment into regions of low elevation. Through the combination of these factors, the surface of the Earth evolves in a highly dynamic way with several feedback mechanisms. At divergent boundaries, for example, tensional stresses thin the lithosphere, forcing uplift and subsequent erosion of rift flanks, which creates a sediment source. Meanwhile, the rift center subsides and becomes a topographic low where sediments accumulate. This mass transfer from foot- to hanging wall plays an important role during rifting, as it prolongs the activity of individual normal faults. When rifting continues, continents are eventually split apart, exhuming Earth’s mantle and creating new oceanic crust. Because of the complex interplay between deep tectonic forces that shape plate boundaries and mass redistribution at the Earth’s surface, it is vital to understand feedbacks between the two domains and how they shape our planet.
In this study I aim to provide insight on two primary questions: 1) How do divergent and strike-slip plate boundaries evolve? 2) How is this evolution, on a large temporal scale and a smaller structural scale, affected by the alteration of the surface through erosion and deposition? This is done in three chapters that examine the evolution of divergent and strike-slip plate boundaries using numerical models. Chapter 2 takes a detailed look at the evolution of rift systems using two-dimensional models. Specifically, I extract faults from a range of rift models and correlate them through time to examine how fault networks evolve in space and time. By implementing a two-way coupling between the geodynamic code ASPECT and landscape evolution code FastScape, I investigate how the fault network and rift evolution are influenced by the system’s erosional efficiency, which represents many factors like lithology or climate. In Chapter 3, I examine rift evolution from a three-dimensional perspective. In this chapter I study linkage modes for offset rifts to determine when fast-rotating plate-boundary structures known as continental microplates form. Chapter 4 uses the two-way numerical coupling between tectonics and landscape evolution to investigate how a strike-slip boundary responds to large sediment loads, and whether this is sufficient to form an entirely new type of flexural strike-slip basin.
Mathematical modeling of biological phenomena has experienced increasing interest since new high-throughput technologies give access to growing amounts of molecular data. These modeling approaches are especially able to test hypotheses which are not yet experimentally accessible or guide an experimental setup. One particular attempt investigates the evolutionary dynamics responsible for today's composition of organisms. Computer simulations either propose an evolutionary mechanism and thus reproduce a recent finding or rebuild an evolutionary process in order to learn about its mechanism. The quest for evolutionary fingerprints in metabolic and gene-coexpression networks is the central topic of this cumulative thesis based on four published articles. An understanding of the actual origin of life will probably remain an insoluble problem. However, one can argue that after a first simple metabolism has evolved, the further evolution of metabolism occurred in parallel with the evolution of the sequences of the catalyzing enzymes. Indications of such a coevolution can be found when correlating the change in sequence between two enzymes with their distance on the metabolic network which is obtained from the KEGG database. We observe that there exists a small but significant correlation primarily on nearest neighbors. This indicates that enzymes catalyzing subsequent reactions tend to be descended from the same precursor. Since this correlation is relatively small one can at least assume that, if new enzymes are no "genetic children" of the previous enzymes, they certainly be descended from any of the already existing ones. Following this hypothesis, we introduce a model of enzyme-pathway coevolution. By iteratively adding enzymes, this model explores the metabolic network in a manner similar to diffusion. With implementation of an Gillespie-like algorithm we are able to introduce a tunable parameter that controls the weight of sequence similarity when choosing a new enzyme. Furthermore, this method also defines a time difference between successive evolutionary innovations in terms of a new enzyme. Overall, these simulations generate putative time-courses of the evolutionary walk on the metabolic network. By a time-series analysis, we find that the acquisition of new enzymes appears in bursts which are pronounced when the influence of the sequence similarity is higher. This behavior strongly resembles punctuated equilibrium which denotes the observation that new species tend to appear in bursts as well rather than in a gradual manner. Thus, our model helps to establish a better understanding of punctuated equilibrium giving a potential description at molecular level. From the time-courses we also extract a tentative order of new enzymes, metabolites, and even organisms. The consistence of this order with previous findings provides evidence for the validity of our approach. While the sequence of a gene is actually subject to mutations, its expression profile might also indirectly change through the evolutionary events in the cellular interplay. Gene coexpression data is simply accessible by microarray experiments and commonly illustrated using coexpression networks where genes are nodes and get linked once they show a significant coexpression. Since the large number of genes makes an illustration of the entire coexpression network difficult, clustering helps to show the network on a metalevel. Various clustering techniques already exist. However, we introduce a novel one which maintains control of the cluster sizes and thus assures proper visual inspection. An application of the method on Arabidopsis thaliana reveals that genes causing a severe phenotype often show a functional uniqueness in their network vicinity. This leads to 20 genes of so far unknown phenotype which are however suggested to be essential for plant growth. Of these, six indeed provoke such a severe phenotype, shown by mutant analysis. By an inspection of the degree distribution of the A.thaliana coexpression network, we identified two characteristics. The distribution deviates from the frequently observed power-law by a sharp truncation which follows after an over-representation of highly connected nodes. For a better understanding, we developed an evolutionary model which mimics the growth of a coexpression network by gene duplication which underlies a strong selection criterion, and slight mutational changes in the expression profile. Despite the simplicity of our assumption, we can reproduce the observed properties in A.thaliana as well as in E.coli and S.cerevisiae. The over-representation of high-degree nodes could be identified with mutually well connected genes of similar functional families: zinc fingers (PF00096), flagella, and ribosomes respectively. In conclusion, these four manuscripts demonstrate the usefulness of mathematical models and statistical tools as a source of new biological insight. While the clustering approach of gene coexpression data leads to the phenotypic characterization of so far unknown genes and thus supports genome annotation, our model approaches offer explanations for observed properties of the coexpression network and furthermore substantiate punctuated equilibrium as an evolutionary process by a deeper understanding of an underlying molecular mechanism.
Arctic warming has implications for the functioning of terrestrial Arctic ecosystems, global climate and socioeconomic systems of northern communities. A research gap exists in high spatial resolution monitoring and understanding of the seasonality of permafrost degradation, spring snowmelt and vegetation phenology. This thesis explores the diversity and utility of dense TerraSAR-X (TSX) X-Band time series for monitoring ice-rich riverbank erosion, snowmelt, and phenology of Arctic vegetation at long-term study sites in the central Lena Delta, Russia and on Qikiqtaruk (Herschel Island), Canada. In the thesis the following three research questions are addressed:
• Is TSX time series capable of monitoring the dynamics of rapid permafrost degradation in ice-rich permafrost on an intra-seasonal scale and can these datasets in combination with climate data identify the climatic drivers of permafrost degradation?
• Can multi-pass and multi-polarized TSX time series adequately monitor seasonal snow cover and snowmelt in small Arctic catchments and how does it perform compared to optical satellite data and field-based measurements?
• Do TSX time series reflect the phenology of Arctic vegetation and how does the recorded signal compare to in-situ greenness data from RGB time-lapse camera data and vegetation height from field surveys?
To answer the research questions three years of TSX backscatter data from 2013 to 2015 for the Lena Delta study site and from 2015 to 2017 for the Qikiqtaruk study site were used in quantitative and qualitative analysis complimentary with optical satellite data and in-situ time-lapse imagery.
The dynamics of intra-seasonal ice-rich riverbank erosion in the central Lena Delta, Russia were quantified using TSX backscatter data at 2.4 m spatial resolution in HH polarization and validated with 0.5 m spatial resolution optical satellite data and field-based time-lapse camera data. Cliff top lines were automatically extracted from TSX intensity images using threshold-based segmentation and vectorization and combined in a geoinformation system with manually digitized cliff top lines from the optical satellite data and rates of erosion extracted from time-lapse cameras. The results suggest that the cliff top eroded at a constant rate throughout the entire erosional season. Linear mixed models confirmed that erosion was coupled with air temperature and precipitation at an annual scale, seasonal fluctuations did not influence 22-day erosion rates. The results highlight the potential of HH polarized X-Band backscatter data for high temporal resolution monitoring of rapid permafrost degradation.
The distinct signature of wet snow in backscatter intensity images of TSX data was exploited to generate wet snow cover extent (SCE) maps on Qikiqtaruk at high temporal resolution. TSX SCE showed high similarity to Landsat 8-derived SCE when using cross-polarized VH data. Fractional snow cover (FSC) time series were extracted from TSX and optical SCE and compared to FSC estimations from in-situ time-lapse imagery. The TSX products showed strong agreement with the in-situ data and significantly improved the temporal resolution compared to the Landsat 8 time series. The final combined FSC time series revealed two topography-dependent snowmelt patterns that corresponded to in-situ measurements. Additionally TSX was able to detect snow patches longer in the season than Landsat 8, underlining the advantage of TSX for detection of old snow. The TSX-derived snow information provided valuable insights into snowmelt dynamics on Qikiqtaruk previously not available.
The sensitivity of TSX to vegetation structure associated with phenological changes was explored on Qikiqtaruk. Backscatter and coherence time series were compared to greenness data extracted from in-situ digital time-lapse cameras and detailed vegetation parameters on 30 areas of interest. Supporting previous results, vegetation height corresponded to backscatter intensity in co-polarized HH/VV at an incidence angle of 31°. The dry, tall shrub dominated ecological class showed increasing backscatter with increasing greenness when using the cross polarized VH/HH channel at 32° incidence angle. This is likely driven by volume scattering of emerging and expanding leaves. Ecological classes with more prostrate vegetation and higher bare ground contributions showed decreasing backscatter trends over the growing season in the co-polarized VV/HH channels likely a result of surface drying instead of a vegetation structure signal. The results from shrub dominated areas are promising and provide a complementary data source for high temporal monitoring of vegetation phenology.
Overall this thesis demonstrates that dense time series of TSX with optical remote sensing and in-situ time-lapse data are complementary and can be used to monitor rapid and seasonal processes in Arctic landscapes at high spatial and temporal resolution.
Metals are often used in environments that are conducive to corrosion, which leads to a reduction in their mechanical properties and durability. Coatings are applied to corrosion-prone metals such as aluminum alloys to inhibit the destructive surface process of corrosion in a passive or active way. Standard anticorrosive coatings function as a physical barrier between the material and the corrosive environment and provide passive protection only when intact. In contrast, active protection prevents or slows down corrosion even when the main barrier is damaged. The most effective industrially used active corrosion inhibition for aluminum alloys is provided by chromate conversion coatings. However, their toxicity and worldwide restriction provoke an urgent need for finding environmentally friendly corrosion preventing systems. A promising approach to replace the toxic chromate coatings is to embed particles containing nontoxic inhibitor in a passive coating matrix. This work presents the development and optimization of effective anticorrosive coatings for the industrially important aluminum alloy, AA2024-T3 using this approach. The protective coatings were prepared by dispersing mesoporous silica containers, loaded with the nontoxic corrosion inhibitor 2-mercaptobenzothiazole, in a passive sol-gel (SiOx/ZrOx) or organic water-based layer. Two types of porous silica containers with different sizes (d ≈ 80 and 700 nm, respectively) were investigated. The studied robust containers exhibit high surface area (≈ 1000 m² g-1), narrow pore size distribution (dpore ≈ 3 nm) and large pore volume (≈ 1 mL g-1) as determined by N2 sorption measurements. These properties favored the subsequent adsorption and storage of a relatively large amount of inhibitor as well as its release in response to pH changes induced by the corrosion process. The concentration, position and size of the embedded containers were varied to ascertain the optimum conditions for overall anticorrosion performance. Attaining high anticorrosion efficiency was found to require a compromise between delivering an optimal amount of corrosion inhibitor and preserving the coating barrier properties. This study broadens the knowledge about the main factors influencing the coating anticorrosion efficiency and assists the development of optimum active anticorrosive coatings doped with inhibitor loaded containers.
Earthquake modeling is the key to a profound understanding of a rupture. Its kinematics or dynamics are derived from advanced rupture models that allow, for example, to reconstruct the direction and velocity of the rupture front or the evolving slip distribution behind the rupture front. Such models are often parameterized by a lattice of interacting sub-faults with many degrees of freedom, where, for example, the time history of the slip and rake on each sub-fault are inverted. To avoid overfitting or other numerical instabilities during a finite-fault estimation, most models are stabilized by geometric rather than physical constraints such as smoothing.
As a basis for the inversion approach of this study, we build on a new pseudo-dynamic rupture model (PDR) with only a few free parameters and a simple geometry as a physics-based solution of an earthquake rupture. The PDR derives the instantaneous slip from a given stress drop on the fault plane, with boundary conditions on the developing crack surface guaranteed at all times via a boundary element approach. As a side product, the source time function on each point on the rupture plane is not constraint and develops by itself without additional parametrization. The code was made publicly available as part of the Pyrocko and Grond Python packages. The approach was compared with conventional modeling for different earthquakes. For example, for the Mw 7.1 2016 Kumamoto, Japan, earthquake, the effects of geometric changes in the rupture surface on the slip and slip rate distributions could be reproduced by simply projecting stress vectors. For the Mw 7.5 2018 Palu, Indonesia, strike-slip earthquake, we also modelled rupture propagation using the 2D Eikonal equation and assuming a linear relationship between rupture and shear wave velocity. This allowed us to give a deeper and faster propagating rupture front and the resulting upward refraction as a new possible explanation for the apparent supershear observed at the Earth's surface.
The thesis investigates three aspects of earthquake inversion using PDR: (1) to test whether implementing a simplified rupture model with few parameters into a probabilistic Bayesian scheme without constraining geometric parameters is feasible, and whether this leads to fast and robust results that can be used for subsequent fast information systems (e.g., ground motion predictions). (2) To investigate whether combining broadband and strong-motion seismic records together with near-field ground deformation data improves the reliability of estimated rupture models in a Bayesian inversion. (3) To investigate whether a complex rupture can be represented by the inversion of multiple PDR sources and for what type of earthquakes this is recommended.
I developed the PDR inversion approach and applied the joint data inversions to two seismic sequences in different tectonic settings. Using multiple frequency bands and a multiple source inversion approach, I captured the multi-modal behaviour of the Mw 8.2 2021 South Sandwich subduction earthquake with a large, curved and slow rupturing shallow earthquake bounded by two faster and deeper smaller events. I could cross-validate the results with other methods, i.e., P-wave energy back-projection, a clustering analysis of aftershocks and a simple tsunami forward model.
The joint analysis of ground deformation and seismic data within a multiple source inversion also shed light on an earthquake triplet, which occurred in July 2022 in SE Iran. From the inversion and aftershock relocalization, I found indications for a vertical separation between the shallower mainshocks within the sedimentary cover and deeper aftershocks at the sediment-basement interface. The vertical offset could be caused by the ductile response of the evident salt layer to stress perturbations from the mainshocks.
The applications highlight the versatility of the simple PDR in probabilistic seismic source inversion capturing features of rather different, complex earthquakes. Limitations, as the evident focus on the major slip patches of the rupture are discussed as well as differences to other finite fault modeling methods.
Steep mountain channels are an important component of the fluvial system. On geological timescales, they shape mountain belts and counteract tectonic uplift by erosion. Their channels are strongly coupled to hillslopes and they are often the main source of sediment transported downstream to low-gradient rivers and to alluvial fans, where commonly settlements in mountainous areas are located. Hence, mountain streams are the cause for one of the main natural hazards in these regions. Due to climate change and a pronounced populating of mountainous regions the attention given to this threat is even growing. Although quantitative studies on sediment transport have significantly advanced our knowledge on measuring and calibration techniques we still lack studies of the processes within mountain catchments. Studies examining the mechanisms of energy and mass exchange on small temporal and spatial scales in steep streams remain sparse in comparison to low-gradient alluvial channels.
In the beginning of this doctoral project, a vast amount of experience and knowledge of a steep stream in the Swiss Prealps had to be consolidated in order to shape the principal aim of this research effort. It became obvious, that observations from within the catchment are underrepresented in comparison to experiments performed at the catchment’s outlet measuring fluxes and the effects of the transported material. To counteract this imbalance, an examination of mass fluxes within the catchment on the process scale was intended. Hence, this thesis is heavily based on direct field observations, which are generally rare in these environments in quantity and quality. The first objective was to investigate the coupling of the channel with surrounding hillslopes, the major sources of sediment. This research, which involved the monitoring of the channel and adjacent hillslopes, revealed that alluvial channel steps play a key role in coupling of channel and hillslopes. The observations showed that hillslope stability is strongly associated with the step presence and an understanding of step morphology and stability is therefore crucial in understanding sediment mobilization. This finding refined the way we think about the sediment dynamics in steep channels and motivated continued research of the step dynamics. However, soon it became obvious that the technological basis for developing field tests and analyzing the high resolution geometry measured in the field was not available. Moreover, for many geometrical quantities in mountain channels definitions and a clear scientific standard was not available. For example, these streams are characterized by a high spatial variability of the channel banks, preventing straightforward calculations of the channel width without a defined reference. Thus, the second and inevitable part of this thesis became the development and evaluation of scientific tools in order to investigate the geometrical content of the study reach thoroughly. The developed framework allowed the derivation of various metrics of step and channel geometry which facilitated research on the a large data set of observations of channel steps. In the third part, innovative, physically-based metrics have been developed and compared to current knowledge on step formation, suggested in the literature. With this analyses it could be demonstrated that the formation of channel steps follow a wide range of hydraulic controls. Due to the wide range of tested parameters channel steps observed in a natural stream were attributed to different mechanisms of step formation, including those based on jamming and those based on key-stones. This study extended our knowledge on step formation in a steep stream and harmonized different, often time seen as competing, processes of step formation. This study was based on observations collected at one point in time. In the fourth part of this project, the findings of the snap-shot observations were extended in the temporal dimension and the derived concepts have been utilized to investigate reach-scale step patterns in response to large, exceptional flood events. The preliminary results of this work based on the long-term analyses of 7 years of long profile surveys showed that the previously observed channel-hillslope mechanism is the responsible for the short-term response of step formation.
The findings of the long-term analyses of step patterns drew a bow to the initial observations of a channel-hillslope system which allowed to join the dots in the dynamics of steep stream. Thus, in this thesis a broad approach has been chosen to gain insights into the complex system of steep mountain rivers. The effort includes in situ field observations (article I), the development of quantitative scientific tools (article II), the reach-scale analyses of step-pool morphology (article III) and its temporal evolution (article IV). With this work our view on the processes within the catchment has been advanced towards a better mechanistic understanding of these fluvial system relevant to improve applied scientific work.
Functional nanoporous carbon-based materials derived from oxocarbon-metal coordination complexes
(2017)
Nanoporous carbon based materials are of particular interest for both science and industry due to their exceptional properties such as a large surface area, high pore volume, high electroconductivity as well as high chemical and thermal stability. Benefiting from these advantageous properties, nanoporous carbons proved to be useful in various energy and environment related applications including energy storage and conversion, catalysis, gas sorption and separation technologies. The synthesis of nanoporous carbons classically involves thermal carbonization of the carbon precursors (e.g. phenolic resins, polyacrylonitrile, poly(vinyl alcohol) etc.) followed by an activation step and/or it makes use of classical hard or soft templates to obtain well-defined porous structures. However, these synthesis strategies are complicated and costly; and make use of hazardous chemicals, hindering their application for large-scale production. Furthermore, control over the carbon materials properties is challenging owing to the relatively unpredictable processes at the high carbonization temperatures.
In the present thesis, nanoporous carbon based materials are prepared by the direct heat treatment of crystalline precursor materials with pre-defined properties. This synthesis strategy does not require any additional carbon sources or classical hard- or soft templates. The highly stable and porous crystalline precursors are based on coordination compounds of the squarate and croconate ions with various divalent metal ions including Zn2+, Cu2+, Ni2+, and Co2+, respectively. Here, the structural properties of the crystals can be controlled by the choice of appropriate synthesis conditions such as the crystal aging temperature, the ligand/metal molar ratio, the metal ion, and the organic ligand system. In this context, the coordination of the squarate ions to Zn2+ yields porous 3D cube crystalline particles. The morphology of the cubes can be tuned from densely packed cubes with a smooth surface to cubes with intriguing micrometer-sized openings and voids which evolve on the centers of the low index faces as the crystal aging temperature is raised. By varying the molar ratio, the particle shape can be changed from truncated cubes to perfect cubes with right-angled edges.
These crystalline precursors can be easily transformed into the respective carbon based materials by heat treatment at elevated temperatures in a nitrogen atmosphere followed by a facile washing step. The resulting carbons are obtained in good yields and possess a hierarchical pore structure with well-organized and interconnected micro-, meso- and macropores. Moreover, high surface areas and large pore volumes of up to 1957 m2 g-1 and 2.31 cm3 g-1 are achieved, respectively, whereby the macroscopic structure of the precursors is preserved throughout the whole synthesis procedure.
Owing to these advantageous properties, the resulting carbon based materials represent promising supercapacitor electrode materials for energy storage applications. This is exemplarily demonstrated by employing the 3D hierarchical porous carbon cubes derived from squarate-zinc coordination compounds as electrode material showing a specific capacitance of 133 F g-1 in H2SO4 at a scan rate of 5 mV s-1 and retaining 67% of this specific capacitance when the scan rate is increased to 200 mV s-1.
In a further application, the porous carbon cubes derived from squarate-zinc coordination compounds are used as high surface area support material and decorated with nickel nanoparticles via an incipient wetness impregnation. The resulting composite material combines a high surface area, a hierarchical pore structure with high functionality and well-accessible pores. Moreover, owing to their regular micro-cube shape, they allow for a good packing of a fixed-bed flow reactor along with high column efficiency and a minimized pressure drop throughout the packed reactor. Therefore, the composite is employed as heterogeneous catalyst in the selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran showing good catalytic performance and overcoming the conventional problem of column blocking.
Thinking about the rational design of 3D carbon geometries, the functions and properties of the resulting carbon-based materials can be further expanded by the rational introduction of heteroatoms (e.g. N, B, S, P, etc.) into the carbon structures in order to alter properties such as wettability, surface polarity as well as the electrochemical landscape. In this context, the use of crystalline materials based on oxocarbon-metal ion complexes can open a platform of highly functional materials for all processes that involve surface processes.