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Optical frequency combs (OFC) constitute an array of phase-correlated equidistant spectral lines with nearly equal intensities over a broad spectral range. The adaptations of combs generated in mode-locked lasers proved to be highly efficient for the calibration of high-resolution (resolving power > 50000) astronomical spectrographs. The observation of different galaxy structures or the studies of the Milky Way are done using instruments in the low- and medium resolution range. To such instruments belong, for instance, the Multi Unit Spectroscopic Explorer (MUSE) being developed for the Very Large Telescope (VLT) of the European Southern Observatory (ESO) and the 4-metre Multi-Object Spectroscopic Telescope (4MOST) being in development for the ESO VISTA 4.1 m Telescope. The existing adaptations of OFC from mode-locked lasers are not resolvable by these instruments.
Within this work, a fibre-based approach for generation of OFC specifically in the low- and medium resolution range is studied numerically. This approach consists of three optical fibres that are fed by two equally intense continuous-wave (CW) lasers. The first fibre is a conventional single-mode fibre, the second one is a suitably pumped amplifying Erbium-doped fibre with anomalous dispersion, and the third one is a low-dispersion highly nonlinear optical fibre. The evolution of a frequency comb in this system is governed by the following processes: as the two initial CW-laser waves with different frequencies propagate through the first fibre, they generate an initial comb via a cascade of four-wave mixing processes. The frequency components of the comb are phase-correlated with the original laser lines and have a frequency spacing that is equal to the initial laser frequency separation (LFS), i.e. the difference in the laser frequencies. In the time domain, a train of pre-compressed pulses with widths of a few pico-seconds arises out of the initial bichromatic deeply-modulated cosine-wave. These pulses undergo strong compression in the subsequent amplifying Erbium-doped fibre: sub-100 fs pulses with broad OFC spectra are formed. In the following low-dispersion highly nonlinear fibre, the OFC experience a further broadening and the intensity of the comb lines are fairly equalised. This approach was mathematically modelled by means of a Generalised Nonlinear Schrödinger Equation (GNLS) that contains terms describing the nonlinear optical Kerr effect, the delayed Raman response, the pulse self-steepening, and the linear optical losses as well as the wavelength-dependent Erbium gain profile for the second fibre. The initial condition equation being a deeply-modulated cosine-wave mimics the radiation of the two initial CW lasers. The numerical studies are performed with the help of Matlab scripts that were specifically developed for the integration of the GNLS and the initial condition according to the proposed approach for the OFC generation. The scripts are based on the Fourth-Order Runge-Kutta in the Interaction Picture Method (RK4IP) in combination with the local error method.
This work includes the studies and results on the length optimisation of the first and the second fibre depending on different values of the group-velocity dispersion of the first fibre. Such length optimisation studies are necessary because the OFC have the biggest possible broadband and exhibit a low level of noise exactly at the optimum lengths. Further, the optical pulse build-up in the first and the second fibre was studied by means of the numerical technique called Soliton Radiation Beat Analysis (SRBA). It was shown that a common soliton crystal state is formed in the first fibre for low laser input powers. The soliton crystal continuously dissolves into separated optical solitons as the input power increases. The pulse formation in the second fibre is critically dependent on the features of the pulses formed in the first fibre. I showed that, for low input powers, an adiabatic soliton compression delivering low-noise OFC occurs in the second fibre. At high input powers, the pulses in the first fibre have more complicated structures which leads to the pulse break-up in the second fibre with a subsequent degradation of the OFC noise performance. The pulse intensity noise studies that were performed within the framework of this thesis allow making statements about the noise performance of an OFC. They showed that the intensity noise of the whole system decreases with the increasing value of LFS.
The high-latitudinal thermospheric processes driven by the solar wind and Interplanetary Magnetic Field (IMF) interaction with the Earth magnetosphere are highly variable parts of the complex dynamic plasma environment, which represent the coupled Magnetosphere – Ionosphere – Thermosphere (MIT) system. The solar wind and IMF interactions transfer energy to the MIT system via reconnection processes at the magnetopause. The Field Aligned Currents (FACs) constitute the energetic links between the magnetosphere and the Earth ionosphere. The MIT system depends on the highly variable solar wind conditions, in particular on changes of the strength and orientation of the IMF.
In my thesis, I perform an investigation on the physical background of the complex MIT system using the global physical - numerical, three-dimensional, time-dependent and self-consistent Upper Atmosphere Model (UAM). This model describes the thermosphere, ionosphere, plasmasphere and inner magnetosphere as well as the electrodynamics of the coupled MIT system for the altitudinal range from 80 (60) km up to the 15 Earth radii.
In the present study, I developed and investigated several variants of the high-latitudinal electrodynamic coupling by including the IMF dependence of FACs into the UAM model. For testing, the various variants were applied to simulations of the coupled MIT system for different seasons, geomagnetic activities, various solar wind and IMF conditions. Additionally, these variants of the theoretical model with the IMF dependence were compared with global empirical models. The modelling results for the most important thermospheric parameters like neutral wind and mass density were compared with satellite measurements. The variants of the UAM model with IMF dependence show a good agreement with the satellite observations. In comparison with the empirical models, the improved variants of the UAM model reproduce a more realistic meso-scale structures and dynamics of the coupled MIT system than the empirical models, in particular at high latitudes. The new configurations of the UAM model with IMF dependence contribute to the improvement of space weather prediction.
Peak oil is forcing our society to shift from fossil to renewable resources. However, such renewable resources are also scarce, and they too must be used in the most efficient and sustainable way possible. Biorefining is a concept that represents both resource efficiency and sustainability. This approach initiates a cascade use, which means food and feed production before material use, and an energy-related use at the end of the value-added chain. However, sustainability should already start in the fields, on the agricultural side, where the industrially-used biomass is produced. Therefore, the aim of my doctoral thesis is to analyse the sustainable feedstock supply for biorefineries. In contrast to most studies on biorefineries, I focus on the sustainable provision of feedstock and not on the bioengineering processing of whatever feedstock is available.
Grasslands provide a high biomass potential. They are often inefficiently used, so a new utilisation concept based on the biorefining approach can increase the added value from grasslands. Fodder legumes from temporary and permanent grasslands were chosen for this study. Previous research shows that they are a promising feedstock for industrial uses, and their positive environmental impact is an important byproduct to promote sustainable agricultural production systems.
Green Biorefineries are a class of biorefineries that use fresh green biomass, such as grasses or fodder legumes, as feedstock. After fractionation, an organic solution (press juice) forms; this is used for the production of organic acids, chemicals and extracts, as well as fertilisers. A fibre component (press cake) is also created to produce feed, biomaterials and biogas. This thesis examines a specific value chain, using alfalfa and clover/grass as feedstock and generating lactic acid and one type of cattle feed from it. The research question is if biomass production needs to be adapted for the utilisation of fodder legumes in the Green Biorefinery approach. I have attempted to give a holistic analysis of cultivation, processing and utilisation of two specific grassland crops. Field trials with alfalfa and clover/grass at different study sites were carried out to obtain information on biomass quality and quantity depending on the crop, study site and harvest time. The fresh biomass was fractionated with a screw press and the composition of press juices and cakes was analysed. Fermentation experiments took place to determine the usability of press juices for lactic acid production. The harvest time is not of high importance for the quality of press juices as a fermentation medium. For permanent grasslands, late cuts, often needed for reasons of nature conservation, are possible without a major influence on feedstock quality. The press cakes were silaged for feed-value determination.
Following evidence that both intermediate products are suitable feedstocks in the Green Biorefinery approach, I developed a cost-benefit analysis, comparing different production scenarios on a farm. Two standard crop rotations for Brandenburg, producing either only market crops or market crops and fodder legumes for ruminant feed production, were compared to a system that uses the cultivated fodder legumes for the Green Biorefinery value chain instead of only feed production. Timely processing of the raw material is important to maintain quality for industrial uses, so on-site processing at the farm is assumed in Green Biorefinery scenario. As a result, more added value stays in the rural area. Two farm sizes, common for many European regions, were chosen to examine the influence of scale. The cost site of farmers has also been analysed in detail to assess which farm characteristics make production of press juices for biochemical industries viable. Results show that for large farm sizes in particular, the potential profits are high. Additionally, the wider spectrum of marketable products generates new sources of income for farmers.
The holistic analysis of the supply chain provides evidence that the cultivation processes for fodder legumes do not need to be adapted for use in Green Biorefineries. In fact, the new utilisation approach even widens the cultivation and processing spectrum and can increase economic viability of fodder legume production in conventional farming.
Earthquake clustering has proven the most useful tool to forecast changes in seismicity rates in the short and medium term (hours to months), and efforts are currently being made to extend the scope of such models to operational earthquake forecasting. The overarching goal of the research presented in this thesis is to improve physics-based earthquake forecasts, with a focus on aftershock sequences. Physical models of triggered seismicity are based on the redistribution of stresses in the crust, coupled with the rate-and-state constitutive law proposed by Dieterich to calculate changes in seismicity rate. This type of models are known as Coulomb- rate and-state (CRS) models. In spite of the success of the Coulomb hypothesis, CRS models typically performed poorly in comparison to statistical ones, and they have been underepresented in the operational forecasting context. In this thesis, I address some of these issues, and in particular these questions: (1) How can we realistically model the uncertainties and heterogeneity of the mainshock stress field? (2) What is the effect of time dependent stresses in the postseismic phase on seismicity? I focus on two case studies from different tectonic settings: the Mw 9.0 Tohoku megathrust and the Mw 6.0 Parkfield strike slip earthquake. I study aleatoric uncertainties using a Monte Carlo method. I find that the existence of multiple receiver faults is the most important source of intrinsic stress heterogeneity, and CRS models perform better when this variability is taken into account. Epistemic uncertainties inherited from the slip models also have a significant impact on the forecast, and I find that an ensemble model based on several slip distributions outperforms most individual models. I address the role of postseismic stresses due to aseismic slip on the mainshock fault (afterslip) and to the redistribution of stresses by previous aftershocks (secondary triggering). I find that modeling secondary triggering improves model performance. The effect of afterslip is less clear, and difficult to assess for near-fault aftershocks due to the large uncertainties of the afterslip models. Off-fault events, on the other hand, are less sensitive to the details of the slip distribution: I find that following the Tohoku earthquake, afterslip promotes seismicity in the Fukushima region. To evaluate the performance of the improved CRS models in a pseudo-operational context, I submitted them for independent testing to a collaborative experiment carried out by CSEP for the 2010-2012 Canterbury sequence. Preliminary results indicate that physical models generally perform well compared to statistical ones, suggesting that CRS models may have a role to play in the future of operational forecasting. To facilitate efforts in this direction, and to enable future studies of earthquake triggering by time dependent processes, I have made the code open source. In the final part of this thesis I summarize the capabilities of the program and outline technical aspects regarding performance and parallelization strategies.
Most of the baryonic matter in the Universe resides in a diffuse gaseous phase in-between galaxies consisting mostly of hydrogen and helium. This intergalactic medium (IGM) is distributed in large-scale filaments as part of the overall cosmic web. The luminous extragalactic objects that we can observe today, such as galaxies and quasars, are surrounded by the IGM in the most dense regions within the cosmic web. The radiation of these objects contributes to the so-called ultraviolet background (UVB) which keeps the IGM highly ionized ever since the epoch of reionization.
Measuring the amount of absorption due to intergalactic neutral hydrogen (HI) against extragalactic background sources is a very useful tool to constrain the energy input of ionizing sources into the IGM. Observations suggest that the HI Lyman-alpha effective optical depth, τ_eff, decreases with decreasing redshift, which is primarily due to the expansion of the Universe. However, some studies find a smaller value of the effective optical depth than expected at the specific redshift z~3.2, possibly related to the complete reionization of helium in the IGM and a hardening of the UVB. The detection and possible cause of a decrease in τ_eff at z~3.2 is controversially debated in the literature and the observed features need further explanation.
To better understand the properties of the mean absorption at high redshift and to provide an answer for whether the detection of a τ_eff feature is real we study 13 high-resolution, high signal-to-noise ratio quasar spectra observed with the Ultraviolet and Visual Echelle Spectrograph (UVES) at the Very Large Telescope (VLT). The redshift evolution of the effective optical depth, τ_eff(z), is measured in the redshift range 2.7≤z≤3.6. The influence of metal absorption features is removed by performing a comprehensive absorption-line-fitting procedure.
In the first part of the thesis, a line-parameter analysis of the column density, N, and Doppler parameter, b, of ≈7500 individually fitted absorption lines is performed. The results are in good agreement with findings from previous surveys.
The second (main) part of this thesis deals with the analysis of the redshift evolution of the effective optical depth. The τ_eff measurements vary around the empirical power law τ_eff(z)~(1+z)^(γ+1) with γ=2.09±0.52. The same analysis as for the observed spectra is performed on synthetic absorption spectra. From a comparison between observed and synthetic spectral data it can be inferred that the uncertainties of the τ_eff values are likely underestimated and that the scatter is probably caused by high-column-density absorbers with column densities in the range 15≤logN≤17. In the real Universe, such absorbers are rarely observed, however. Hence, the difference in τ_eff from different observational data sets and absorption studies is most likely caused by cosmic variance. If, alternatively, the disagreement between such data is a result of an too optimistic estimate of the (systematic) errors, it is also possible that all τ_eff measurements agree with a smooth evolution within the investigated redshift range. To explore in detail the different analysis techniques of previous studies an extensive literature comparison to the results of this work is presented in this thesis.
Although a final explanation for the occurrence of the τ_eff deviation in different studies at z~3.2 cannot be given here, our study, which represents the most detailed line-fitting analysis of its kind performed at the investigated redshifts so far, represents another important benchmark for the characterization of the HI Ly-alpha effective optical depth at high redshift and its indicated unusual behavior at z~3.2.
Electron transfer (ET) reactions play a crucial role in the metabolic pathways of all organisms. In biotechnological approaches, the redox properties of the protein cytochrome c (cyt c), which acts as an electron shuttle in the respiratory chain, was utilized to engineer ET chains on electrode surfaces. With the help of the biopolymer DNA, the redox protein assembles into electro active multilayer (ML) systems, providing a biocompatible matrix for the entrapment of proteins.
In this study the characteristics of the cyt c and DNA interaction were defined on the molecular level for the first time and the binding sites of DNA on cyt c were identified. Persistent cyt c/DNA complexes were formed in solution under the assembly conditions of ML architectures, i.e. pH 5.0 and low ionic strength. At pH 7.0, no agglomerates were formed, permitting the characterization of the NMR spectroscopy. Using transverse relaxation-optimized spectroscopy (TROSY)-heteronuclear single quantum coherence (HSQC) experiments, DNAs’ binding sites on the protein were identified. In particular, negatively charged AA residues, which are known interaction sites in cyt c/protein binding were identified as the main contact points of cyt c and DNA.
Moreover, the sophisticated task of arranging proteins on electrode surfaces to create functional ET chains was addressed. Therefore, two different enzyme types, the flavin dependent fructose dehydrogenase (FDH) and the pyrroloquinoline quinone dependent glucose dehydrogenase (PQQ-GDH), were tested as reaction partners of freely diffusing cyt c and cyt c immobilized on electrodes in mono- and MLs. The characterisation of the ET processes was performed by means of electrochemistry and the protein deposition was monitored by microgravimetric measurements. FDH and PQQ-GDH were found to be generally suitable for combination with the cyt c/DNA ML system, since both enzymes interact with cyt c in solution and in the immobilized state. The immobilization of FDH and cyt c was achieved with the enzyme on top of a cyt c monolayer electrode without the help of a polyelectrolyte. Combining FDH with the cyt c/DNA ML system did not succeed, yet. However, the basic conditions for this protein-protein interaction were defined. PQQ-GDH was successfully coupled with the ML system, demonstrating that that the cyt c/DNA ML system provides a suitable interface for enzymes and that the creation of signal chains, based on the idea of co-immobilized proteins is feasible.
Future work may be directed to the investigation of cyt c/DNA interaction under the precise conditions of ML assembly. Therefore, solid state NMR or X-ray crystallography may be required. Based on the results of this study, the combination of FDH with the ML system should be addressed. Moreover, alternative types of enzymes may be tested as catalytic component of the ML assembly, aiming on the development of innovative biosensor applications.
Plant cell walls are complex structures that underpin plant growth and are widely exploited in diverse human activities thus placing them with a central importance in biology. Cell walls have been a prominent area of research for a long time, but the chemical complexity and diversity of cell walls not just between species, but also within plants, between cell-types, and between cell wall micro-domains pose several challenges. Progress accelerated several-fold in cell wall biology owing to advances in sequencing technology, aided soon thereafter by advances in omics and imaging technologies. This development provides additional perspectives of cell walls across a rapidly growing number of species, highlighting a myriad of architectures, compositions, and functions.
Furthermore, rather than the component centric view, integrative analysis of the different cell wall components across system-levels help to gain a more in-depth understanding of the structure and biosynthesis of the cell envelope and its interactions with the environment.
To this end, in this work three case studies are detailed, all pertaining to the integrative analysis of heterogeneous cell wall related data arising from different system-levels and analytical techniques. A detailed account of multiblock methods is provided and in particular canonical correlation and regression methods of data integration are discussed. In the first integrative analysis, by employing canonical correlation analysis - a multivariate statistical technique to study the association between two datasets - novel insight to the relationship between glycans and phenotypic traits is gained. In addition, sparse partial least squares regression approach that adapts Lasso penalization and allows for the selection of a subset of variables was employed. The second case study focuses on an integrative analysis of images obtained from different spectroscopic techniques. By employing yet another multiblock approach - multiple co-inertia analysis, insitu biochemical composition of cell walls from different cell-types is studied thereby highlighting the common and complementary parts of the two hyperspectral imaging techniques. Finally, the third integrative analysis facilitates gene expression analysis of the Arabidopsis root transcriptome and translatome for the identification of cell wall related genes and compare expression patterns of cell wall synthesis genes. The computational analysis considered correlation and variation of expression across cell-types at both system-levels, and also provides insight into the degree of co-regulatory relationships that are preserved between the two processes.
The integrative analysis of glycan data and phenotypic traits in cotton fibers using canonical methods led to the identification of specific polysaccharides which may play a major role during fiber development for the final fiber characteristics. Furthermore, this analysis provides a base for future studies on glycan arrays in case of developing cotton fibers. The integrative analysis of images from infrared and Raman spectroscopic approaches allowed the coupling of different analytical techniques to characterize complex biological material, thereby, representing various facets of their chemical properties. Moreover, the results from the co-inertia analysis demonstrated that the study was well adapted as it is relevant for coupling data tables in a symmetric way. Several indicators are proposed to investigate how the global and block scores are related. In addition, studying the root cells of \textit{Arabidopsis thaliana} allowed positing a novel pipeline to systematically investigate and integrate the different levels of information available at the global and single-cell level. The conducted analysis also confirms that previously identified key transcriptional activators of secondary cell wall development display highly conserved patterns of transcription and translation across the investigated cell-types. Moreover, the biological processes that display conserved and divergent patterns based on the cell-type-specific expression and translation levels are identified.
Semi-empirical sea-level models (SEMs) exploit physically motivated empirical relationships between global sea level and certain drivers, in the following global mean temperature. This model class evolved as a supplement to process-based models (Rahmstorf (2007)) which were unable to fully represent all relevant processes. They thus failed to capture past sea-level change (Rahmstorf et al. (2012)) and were thought likely to underestimate future sea-level rise. Semi-empirical models were found to be a fast and useful tool for exploring the uncertainties in future sea-level rise, consistently giving significantly higher projections than process-based models.
In the following different aspects of semi-empirical sea-level modelling have been studied. Models were first validated using various data sets of global sea level and temperature. SEMs were then used on the glacier contribution to sea level, and to infer past global temperature from sea-level data via inverse modelling. Periods studied encompass the instrumental period, covered by tide gauges (starting 1700 CE (Common Era) in Amsterdam) and satellites (first launched in 1992 CE), the era from 1000 BCE (before CE) to present, and the full length of the Holocene (using proxy data). Accordingly different data, model formulations and implementations have been used. It could be shown in Bittermann et al. (2013) that SEMs correctly predict 20th century sea-level when calibrated with data until 1900 CE. SEMs also turned out to give better predictions than the Intergovernmental Panel on Climate Change (IPCC) 4th assessment report (AR4, IPCC (2007)) models, for the period from 1961–2003 CE.
With the first multi-proxy reconstruction of global sea-level as input, estimate of the human-induced component of modern sea-level change and projections of future sea-level rise were calculated (Kopp et al. (2016)). It turned out with 90% confidence that more than 40 % of the observed 20th century sea-level rise is indeed anthropogenic. With the new semi-empirical and IPCC (2013) 5th assessment report (AR5) projections the gap between SEM and process-based model projections closes, giving higher credibility to both. Combining all scenarios, from strong mitigation to business as usual, a global sea-level rise of 28–131 cm relative to 2000 CE, is projected with 90% confidence. The decision for a low carbon pathway could halve the expected global sea-level rise by 2100 CE.
Present day temperature and thus sea level are driven by the globally acting greenhouse-gas forcing. Unlike that, the Milankovich forcing, acting on Holocene timescales, results mainly in a northern-hemisphere temperature change. Therefore a semi-empirical model can be driven with northernhemisphere temperatures, which makes it possible to model the main subcomponent of sea-level change over this period. It showed that an additional positive constant rate of the order of the estimated Antarctic sea-level contribution is then required to explain the sea-level evolution over the Holocene. Thus the global sea level, following the climatic optimum, can be interpreted as the sum of a temperature induced sea-level drop and a positive long-term contribution, likely an ongoing response to deglaciation coming from Antarctica.
Obesity is a major health problem for many developing and industrial countries. Increasing rates reach almost 50 % of the population in some countries and related metabolic diseases including cardiovascular events and T2DM are challenging the health systems. Adiposity, an increase in body fat mass, is a major hallmark of obesity. Adipose tissue is long known not only to store lipids but also to influence whole-body metabolism including food intake, energy expenditure and insulin sensitivity. Adipocytes can store lipids and thereby protect other tissue from lipotoxic damage. However, if the energy intake is higher than the energy expenditure over a sustained time period, adipose tissue will expand. This can lead to an impaired adipose tissue function resulting in higher levels of plasma lipids, which can affect other tissue like skeletal muscle, finally leading to metabolic complications. Several studies showed beneficial metabolic effects of weight reduction in obese subjects immediately after weight loss. However, weight regain is frequently observed along with potential negative effects on cardiovascular risk factors and a high intra-individual response.
We performed a body weight maintenance study investigating the mechanisms of weight maintenance after intended WR. Therefore we used a low caloric diet followed by a 12-month life-style intervention. Comprehensive phenotyping including fat and muscle biopsies was conducted to investigate hormonal as well as metabolic influences on body weight regulation. In this study, we showed that weight reduction has numerous potentially beneficial effects on metabolic parameters. After 3-month WR subjects showed significant weight and fat mass reduction, lower TG levels as well as higher insulin sensitivity. Using RNA-Seq to analyse whole fat and muscle transcriptome a strong impact of weight reduction on adipose tissue gene expression was observed. Gene expression alterations over weight reduction included several cellular metabolic genes involved in lipid and glucose metabolism as well as insulin signalling and regulatory pathways. These changes were also associated with anthropometric parameters assigning body composition. Our data indicated that weight reduction leads to a decreased expression of several lipid catabolic as well as anabolic genes. Long-term body weight maintenance might be influenced by several parameters including hormones, metabolic intermediates as well as the transcriptional landscape of metabolic active tissues. Our data showed that genes involved in biosynthesis of unsaturated fatty acids might influence the BMI 18-month after a weight reduction phase. This was further supported by analysing metabolic parameters including RQ and FFA levels. We could show that subjects maintaining their lost body weight had a higher RQ and lower FFA levels, indicating increased metabolic flexibility in subjects.
Using this transcriptomic approach we hypothesize that low expression levels of lipid synthetic genes in adipose tissue together with a higher mitochondrial activity in skeletal muscle tissue might be beneficial in terms of body weight maintenance.
Microsaccades
(2015)
The first thing we do upon waking is open our eyes. Rotating them in our eye sockets, we scan our surroundings and collect the information into a picture in our head. Eye movements can be split into saccades and fixational eye movements, which occur when we attempt to fixate our gaze. The latter consists of microsaccades, drift and tremor. Before we even lift our eye lids, eye movements – such as saccades and microsaccades that let the eyes jump from one to another position – have partially been prepared in the brain stem. Saccades and microsaccades are often assumed to be generated by the same mechanisms. But how saccades and microsaccades can be classified according to shape has not yet been reported in a statistical manner. Research has put more effort into the investigations of microsaccades’ properties and generation only since the last decade. Consequently, we are only beginning to understand the dynamic processes governing microsaccadic eye movements. Within this thesis, the dynamics governing the generation of microsaccades is assessed and the development of a model for the underlying processes. Eye movement trajectories from different experiments are used, recorded with a video-based eye tracking technique, and a novel method is proposed for the scale-invariant detection of saccades (events of large amplitude) and microsaccades (events of small amplitude). Using a time-frequency approach, the method is examined with different experiments and validated against simulated data. A shape model is suggested that allows for a simple estimation of saccade- and microsaccade related properties. For sequences of microsaccades, in this thesis a time-dynamic Markov model is proposed, with a memory horizon that changes over time and which can best describe sequences of microsaccades.
The rise of evolutionary novelties is one of the major drivers of evolutionary diversification. African weakly-electric fishes (Teleostei, Mormyridae) have undergone an outstanding adaptive radiation, putatively owing to their ability to communicate through species-specific Electric Organ Discharges (EODs) produced by a novel, muscle-derived electric organ. Indeed, such EODs might have acted as effective pre-zygotic isolation mechanisms, hence favoring ecological speciation in this group of fishes. Despite the evolutionary importance of this organ, genetic investigations regarding its origin and function have remained limited.
The ultimate aim of this study is to better understand the genetic basis of EOD production by exploring the transcriptomic profiles of the electric organ and of its ancestral counterpart, the skeletal muscle, in the genus Campylomormyrus. After having established a set of reference transcriptomes using “Next-Generation Sequencing” (NGS) technologies, I performed in silico analyses of differential expression, in order to identify sets of genes that might be responsible for the functional differences observed between these two kinds of tissues. The results of such analyses indicate that: i) the loss of contractile activity and the decoupling of the excitation-contraction processes are reflected by the down-regulation of the corresponding genes in the electric organ; ii) the metabolic activity of the electric organ might be specialized towards the production and turnover of membrane structures; iii) several ion channels are highly expressed in the electric organ in order to increase excitability, and iv) several myogenic factors might be down-regulated by transcription repressors in the EO.
A secondary task of this study is to improve the genus level phylogeny of Campylomormyrus by applying new methods of inference based on the multispecies coalescent model, in order to reduce the conflict among gene trees and to reconstruct a phylogenetic tree as closest as possible to the actual species-tree. By using 1 mitochondrial and 4 nuclear markers, I was able to resolve the phylogenetic relationships among most of the currently described Campylomormyrus species. Additionally, I applied several coalescent-based species delimitation methods, in order to test the hypothesis that putatively cryptic species, which are distinguishable only from their EOD, belong to independently evolving lineages. The results of this analysis were additionally validated by investigating patterns of diversification at 16 microsatellite loci. The results suggest the presence of a new, yet undescribed species of Campylomormyrus.
Adjustment of empirically derived ground motion prediction equations (GMPEs), from a data- rich region/site where they have been derived to a data-poor region/site, is one of the major challenges associated with the current practice of seismic hazard analysis. Due to the fre- quent use in engineering design practices the GMPEs are often derived for response spectral ordinates (e.g., spectral acceleration) of a single degree of freedom (SDOF) oscillator. The functional forms of such GMPEs are based upon the concepts borrowed from the Fourier spectral representation of ground motion. This assumption regarding the validity of Fourier spectral concepts in the response spectral domain can lead to consequences which cannot be explained physically.
In this thesis, firstly results from an investigation that explores the relationship between Fourier and response spectra, and implications of this relationship on the adjustment issues of GMPEs, are presented. The relationship between the Fourier and response spectra is explored by using random vibration theory (RVT), a framework that has been extensively used in earthquake engineering, for instance within the stochastic simulation framework and in the site response analysis. For a 5% damped SDOF oscillator the RVT perspective of response spectra reveals that no one-to-one correspondence exists between Fourier and response spectral ordinates except in a limited range (i.e., below the peak of the response spectra) of oscillator frequencies. The high oscillator frequency response spectral ordinates are dominated by the contributions from the Fourier spectral ordinates that correspond to the frequencies well below a selected oscillator frequency. The peak ground acceleration (PGA) is found to be related with the integral over the entire Fourier spectrum of ground motion which is in contrast to the popularly held perception that PGA is a high-frequency phenomenon of ground motion.
This thesis presents a new perspective for developing a response spectral GMPE that takes the relationship between Fourier and response spectra into account. Essentially, this frame- work involves a two-step method for deriving a response spectral GMPE: in the first step two empirical models for the FAS and for a predetermined estimate of duration of ground motion are derived, in the next step, predictions from the two models are combined within the same RVT framework to obtain the response spectral ordinates. In addition to that, a stochastic model based scheme for extrapolating the individual acceleration spectra beyond the useable frequency limits is also presented. To that end, recorded acceleration traces were inverted to obtain the stochastic model parameters that allow making consistent extrapola- tion in individual (acceleration) Fourier spectra. Moreover an empirical model, for a dura- tion measure that is consistent within the RVT framework, is derived. As a next step, an oscillator-frequency-dependent empirical duration model is derived that allows obtaining the most reliable estimates of response spectral ordinates. The framework of deriving the response spectral GMPE presented herein becomes a self-adjusting model with the inclusion of stress parameter (∆σ) and kappa (κ0) as the predictor variables in the two empirical models. The entire analysis of developing the response spectral GMPE is performed on recently compiled RESORCE-2012 database that contains recordings made from Europe, the Mediterranean and the Middle East. The presented GMPE for response spectral ordinates should be considered valid in the magnitude range of 4 ≤ MW ≤ 7.6 at distances ≤ 200 km.
The lives of more than 1/6 th of the world population is directly affected by the caprices of the South Asian summer monsoon rainfall. India receives around 78 % of the annual precipitation during the June-September months, the summer monsoon season of South Asia. But, the monsoon circulation is not consistent throughout the entire summer season. Episodes of heavy rainfall (active periods) and low rainfall (break periods) are inherent to the intraseasonal variability of the South Asian summer monsoon. Extended breaks or long-lasting dryness can result in droughts and hence trigger crop failures and in turn famines. Furthermore, India's electricity generation from renewable sources (wind and hydro-power), which is increasingly important in order to satisfy the rapidly rising demand for energy, is highly reliant on the prevailing meteorology. The major drought years 2002 and 2009 for the Indian summer monsoon during the last decades, which are results of the occurrence of multiple extended breaks, emphasise exemplary that the understanding of the monsoon system and its intraseasonal variation is of greatest importance. Although, numerous studies based on observations, reanalysis data and global model simulations have been carried out with the focus on monsoon active and break phases over India, the understanding of the monsoon intraseasonal variability is only in the infancy stage. Regional climate models could benefit the comprehension of monsoon breaks by its resolution advantage.
This study investigates moist dynamical processes that initiate and maintain breaks during the South Asian summer monsoon using the atmospheric regional climate model HIRHAM5 at a horizontal resolution of 25 km forced by the ECMWF ERA Interim reanalysis for the period 1979-2012. By calculating moisture and moist static energy budgets the various competing mechanisms leading to extended breaks are quantitatively estimated. Advection of dry air from the deserts of western Asia towards central India is the dominant moist dynamical process in initiating extended break conditions over South Asia. Once initiated, the extended breaks are maintained due to many competing mechanisms: (i) the anomalous easterlies at the southern flank of this anticyclonic anomaly weaken the low-level cross-equatorial jet and thus the moisture transport into the monsoon region, (ii) differential radiative heating over the continental and the oceanic tropical convergence zone induces a local Hadley circulation with anomalous rising over the equatorial Indian Ocean and descent over central India, and (iii) a cyclonic response to positive rainfall anomalies over the near-equatorial Indian Ocean amplifies the anomalous easterlies over India and hence contributes to the low-level divergence over central India.
A sensitivity experiment that mimics a scenario of higher atmospheric aerosol concentrations over South Asia addresses a current issue of large uncertainty: the role aerosols play in suppressing monsoon rainfall and hence in triggering breaks. To study the indirect aerosol effects the cloud droplet number concentration was increased to imitate the aerosol's function as cloud condensation nuclei. The sensitivity experiment with altered microphysical cloud properties shows a reduction in the summer monsoon precipitation together with a weakening of the South Asian summer monsoon. Several physical mechanisms are proposed to be responsible for the suppressed monsoon rainfall: (i) according to the first indirect radiative forcing the increase in the number of cloud droplets causes an increase in the cloud reflectivity of solar radiation, leading to a climate cooling over India which in turn reduces the hydrological cycle, (ii) a stabilisation of the troposphere induced by a differential cooling between the surface and the upper troposphere over central India inhibits the growth of deep convective rain clouds, (iii) an increase of the amount of low and mid-level clouds together with a decrease in high-level cloud amount amplify the surface cooling and hence the atmospheric stability, and (iv) dynamical changes of the monsoon manifested as a anomalous anticyclonic circulation over India reduce the moisture transport into the monsoon region. The study suggests that the changes in the total precipitation, which are dominated by changes in the convective precipitation, mainly result from the indirect radiative forcing. Suppression of rainfall due to the direct microphysical effect is found to be negligible over India. Break statistics of the polluted cloud scenario indicate an increase in the occurrence of short breaks (3 days), while the frequency of extended breaks (> 7 days) is clearly not affected. This disproves the hypothesis that more and smaller cloud droplets, caused by a high load of atmospheric aerosols trigger long drought conditions over central India.
This work investigates the influence of the Coriolis force on mass motion related to the Rheasilvia impact basin on asteroid (4) Vesta's southern hemisphere. The giant basin is 500km in diameter, with a centre which nearly coincides with the rotation axis of Vesta. The Rheasilvia basin partially overlaps an earlier, similarly large impact basin, Veneneia.
Mass motion within and in the vicinity of the Rheasilvia basin includes slumping and landslides, which, primarily due to their small linear extents, have not been noticeably affected by the Coriolis force. However, a series of ridges related to the basin exhibit significant curvature, which may record the effect of the Coriolis force on the mass motion which generated them.
In this thesis 32 of these curved ridges, in three geologically distinct regions, were examined. The mass motion velocities from which the ridge curvatures may have resulted during the crater modification stage were investigated. Velocity profiles were derived by fitting inertial circles along the curved ridges and considering both the current and past rotation states of Vesta. An iterative, statistical approach was used, whereby the radii of inertial circles were obtained through repeated fitting to triplets of points across the ridges. The most frequently found radius for each central point was then used for velocity derivation at that point.
The results of the velocity analysis are strongly supportive of a Coriolis force origin for the curved ridges. Derived velocities (29.6 ± 24.6 m/s) generally agree well with previously published predictions from numerical simulations of mass motion during the impact process. Topographical features such as local slope gradient and mass deposition regions on the curved ridges also independently agree with regions in which the calculated mass motion accelerates or decelerates.
Sections of constant acceleration, deceleration and constant velocity are found, showing that mass motion is being governed by varying conditions of topography, regolith structure and friction. Estimates of material properties such as the effective viscosities (1.9-9.0·10⁶ Pa·s) and coefficients of friction (0.02-0.81) are derived from the velocity profile information in these sections. From measured accelerations of mass motions on the crater wall, it is also shown that the crater walls must have been locally steeper at the time of the mass motion.
Together with these novel insights into the state and behaviour of material moving during the modification stage of Rheasilvia's formation, this work represents the first time that the Coriolis Effect on mass motions during crater formation has been shown to result in diagnostic features preserved until today.
The size and morphology control of precipitated solid particles is a major economic issue for numerous industries. For instance, it is interesting for the nuclear industry, concerning the recovery of radioactive species from used nuclear fuel.
The precipitates features, which are a key parameter from the post-precipitate processing, depend on the process local mixing conditions. So far, the relationship between precipitation features and hydrodynamic conditions have not been investigated.
In this study, a new experimental configuration consisting of coalescing drops is set to investigate the link between reactive crystallization and hydrodynamics. Two configurations of aqueous drops are examined. The first one corresponds to high contact angle drops (>90°) in oil, as a model system for flowing drops, the second one correspond to sessile drops in air with low contact angle (<25°). In both cases, one reactive is dissolved in each drop, namely oxalic acid and cerium nitrate. When both drops get into contact, they may coalesce; the dissolved species mix and react to produce insoluble cerium oxalate. The precipitates features and effect on hydrodynamics are investigated depending on the solvent. In the case of sessile drops in air, the surface tension difference between the drops generates a gradient which induces a Marangoni flow from the low surface tension drop over the high surface tension drop. By setting the surface tension difference between the two drops and thus the Marangoni flow, the hydrodynamics conditions during the drop coalescence could be modified. Diols/water mixtures are used as solvent, in order to fix the surface tension difference between the liquids of both drops regardless from the reactant concentration. More precisely, the used diols, 1,2-propanediol and 1,3-propanediol, are isomer with identical density and close viscosity. By keeping the water volume fraction constant and playing with the 1,2-propanediol and 1,3-propanediol volume fractions of the solvents, the mixtures surface tensions differ up to 10 mN/m for identical/constant reactant concentration, density and viscosity. 3 precipitation behaviors were identified for the coalescence of water/diols/recatants drops depending on the oxalic excess. The corresponding precipitates patterns are visualized by optical microscopy and the precipitates are characterized by confocal microscopy SEM, XRD and SAXS measurements. In the intermediate oxalic excess regime, formation of periodic patterns can be observed. These patterns consist in alternating cerium oxalate precipitates with distinct morphologies, namely needles and “microflowers”. Such periodic fringes can be explained by a feedback mechanism between convection, reaction and the diffusion.
The relationship between nutrition and the development of chronic diseases including metabolic syndrome, diabetes mellitus, cancer and cardiovascular disease has been well studied. On the other hand, changes in the GH-IGF-1 axis in association with nutrition-related diseases have been reported. The interplay between GH, total IGF-1 and different inhibitory and stimulatory kinds of IGF-1 binding proteins (IGFBPs) results in IGF-1 bioactivity, the ability of IGF-1 to induce phosphorylation of its receptor and consequently its signaling. Moreover, IGF-1 bioactivity is sufficient to reflect any change in the GH-IGF-1 system. Accumulating evidence suggests that both of high protein diet, characterized by increased glucagon secretion, and insulin-induced hypoglycemia increase mortality rate and the mechanisms are unclear. However both of glucagon and insulin-induced hypoglycemia are potent stimuli of GH secretion. The aim of the current study was to identify the impact of glucagon and insulin-induced hypoglycemia on IGF-1 bioactivity as possible mechanisms. In a double-blind placebo-controlled study, glucagon was intramuscularly administrated in 13 type 1 diabetic patients (6 males /7 females; [BMI]: 24.8 ± 0.95 kg/m2), 11 obese subjects (OP; 5/ 6; 34.4 ± 1.7 kg/m2), and 13 healthy lean participants (LP; 6/ 7; 21.7 ± 0.6 kg/m2), whereas 12 obese subjects (OP; 6/ 6; 34.4 ± 1.7 kg/m2), and 13 healthy lean participants (LP; 6/ 7; 21.7 ± 0.6 kg/m2) performed insulin tolerance test in another double-blind placebo-controlled study and changes in GH, total IGF-1, IGF binding proteins (IGFBPs) and IGF-1 bioactivity, measured by the cell-based KIRA method, were investigated. In addition, the interaction between the metabolic hormones (glucagon and insulin) and the GH-IGF-1 system on the transcriptional level was studied using mouse primary hepatocytes. In this thesis, glucagon decreased IGF-1 bioactivity in humans independently of endogenous insulin levels, most likely through modulation of IGFBP-1 and-2 levels. The glucagon-induced reduction in IGF-1 bioactivity may represent a novel mechanism underlying the impact of glucagon on GH secretion and may explain the negative effect of high protein diet related to increased cardiovascular risk and mortality rate. In addition, insulin-induced hypoglycemia was correlated with a decrease in IGF-1 bioactivity through up-regulation of IGFBP-2. These results may refer to a possible and poorly explored mechanism explaining the strong association between hypoglycemia and increased cardiovascular mortality among diabetic patients.
We study segregation of the subducted oceanic crust (OC) at the core mantle boundary and its ability to accumulate and form large thermochemical piles (such as the seismically observed Large Low Shear Velocity Provinces - LLSVPs). Our high-resolution numerical simulations suggest that the longevity of LLSVPs for up to three billion years, and possibly longer, can be ensured by a balance in the rate of segregation of high-density OC-material to the CMB, and the rate of its entrainment away from the CMB by mantle upwellings.
For a range of parameters tested in this study, a large-scale compositional anomaly forms at the CMB, similar in shape and size to the LLSVPs. Neutrally buoyant thermochemical piles formed by mechanical stirring - where thermally induced negative density anomaly is balanced by the presence of a fraction of dense anomalous material - best resemble the geometry of LLSVPs. Such neutrally buoyant piles tend to emerge and survive for at least 3Gyr in simulations with quite different parameters. We conclude that for a plausible range of values of density anomaly of OC material in the lower mantle - it is likely that it segregates to the CMB, gets mechanically mixed with the ambient material, and forms neutrally buoyant large scale compositional anomalies similar in shape to the LLSVPs.
We have developed an efficient FEM code with dynamically adaptive time and space resolution, and marker-in-cell methodology. This enabled us to model thermochemical mantle convection at realistically high convective vigor, strong thermally induced viscosity variations, and long term evolution of compositional fields.
In this thesis we study reciprocal classes of Markov chains. Given a continuous time Markov chain on a countable state space, acting as reference dynamics, the associated reciprocal class is the set of all probability measures on path space that can be written as a mixture of its bridges. These processes possess a conditional independence property that generalizes the Markov property, and evolved from an idea of Schrödinger, who wanted to obtain a probabilistic interpretation of quantum mechanics.
Associated to a reciprocal class is a set of reciprocal characteristics, which are space-time functions that determine the reciprocal class. We compute explicitly these characteristics, and divide them into two main families: arc characteristics and cycle characteristics. As a byproduct, we obtain an explicit criterion to check when two different Markov chains share their bridges.
Starting from the characteristics we offer two different descriptions of the reciprocal class, including its non-Markov probabilities.
The first one is based on a pathwise approach and the second one on short time asymptotic. With the first approach one produces a family of functional equations whose only solutions are precisely the elements of the reciprocal class. These equations are integration by parts on path space associated with derivative operators which perturb the paths by mean of the addition of random loops. Several geometrical tools are employed to construct such formulas. The problem of obtaining sharp characterizations is also considered, showing some interesting connections with discrete geometry. Examples of such formulas are given in the framework of counting processes and random walks on Abelian groups, where the set of loops has a group structure.
In addition to this global description, we propose a second approach by looking at the short time behavior of a reciprocal process. In the same way as the Markov property and short time expansions of transition probabilities characterize Markov chains, we show that a reciprocal class is characterized by imposing the reciprocal property and two families of short time expansions for the bridges. Such local approach is suitable to study reciprocal processes on general countable graphs. As application of our characterization, we considered several interesting graphs, such as lattices, planar
graphs, the complete graph, and the hypercube.
Finally, we obtain some first results about concentration of measure implied by lower bounds on the reciprocal characteristics.
Spots on stellar surfaces are thought to be stellar analogues of sunspots. Thus, starspots are direct manifestations of strong magnetic fields. Their decay rate is directly related to the magnetic diffusivity, which itself is a key quantity for the deduction of an activity cycle length. So far, no single starspot decay has been observed, and thus no stellar activity cycle was inferred from its corresponding turbulent diffusivity.
We investigate the evolution of starspots on the rapidly-rotating K0 giant XX Triangulum. Continuous high-resolution and phase-resolved spectroscopy was obtained with the robotic 1.2-m STELLA telescope on Tenerife over a timespan of six years. With our line-profile inversion code iMap we reconstruct a total of 36 consecutive Doppler maps. To quantify starspot area decay and growth, we match the observed images with simplified spot models based on a Monte-Carlo approach.
It is shown that the surface of XX Tri is covered with large high-latitude and even polar spots and with occasional small equatorial spots. Just over the course of six years, we see a systematically changing spot distribution with various time scales and morphology such as spot fragmentation and spot merging as well as spot decay and formation.
For the first time, a starspot decay rate on another star than the Sun is determined. From our spot-decay analysis we determine an average linear decay rate of D = -0.067±0.006 Gm^2/day. From this decay rate, we infer a turbulent diffusivity of η_τ = (6.3±0.5) x 10^14 cm^2/s and consequently predict an activity cycle of 26±6 years. The obtained cycle length matches very well with photometric observations.
Our time-series of Doppler maps further enables to investigate the differential rotation of XX Tri. We therefore applied a cross-correlation analysis. We detect a weak solar-like differential rotation with a surface shear of α = 0.016±0.003. This value agrees with similar studies of other RS CVn stars.
Furthermore, we found evidence for active longitudes and flip-flops. Whereas the more active longitude is located in phase towards the (unseen) companion star, the weaker active longitude is located at the opposite stellar hemisphere. From their periodic appearance, we infer a flip-flop cycle of ~2 years. Both activity phenomena are common on late-type binary stars.
Last but not least we redetermine several astrophysical properties of XX Tri and its binary system, as large datasets of photometric and spectroscopic observations are available since its last determination in 1999. Additionally, we compare the rotational spot-modulation from photometric and spectroscopic studies.
In this thesis we investigate the evaporation behaviour of sessile droplets of aqueous saline solutions on planar inert and metallic surfaces and characterise the corrosion phenomenon for iron surfaces. First we study the evaporation behaviour of sessile salty droplets on inert surfaces for a wide range of salt concentrations, relative humidities, droplet sizes and contact angles. Our study reveals the range of validity of the well-accepted diffusion-controlled evaporation model and highlights the impact of salt concentration (surface tension) gradients driven Marangoni flows on the evaporation behaviour and the subsequent salty deposit patterns. Furthermore we study the spatial-temporal evolution of sessile droplets from saline solutions on metallic surfaces. In contrast to the simple, generally accepted Evans droplet model, we show that the corrosion spreads ahead of the macroscopic contact line with a peripheral film. The three-phase contact line is destabilized by surface tension gradients induced by ionic composition changes during the course of the corrosion process and migration of cations towards the droplet perimeter. Finally we investigate the corrosion behaviour under drying salty sessile droplets on metallic surfaces. The corrosion process, in particular the location of anodic and cathodic activities over the footprint droplet area is correlated to the spatial distribution of the salt inside the drying droplet.
This study presents the development of 1D and 2D Surface Evolution Codes (SECs) and their coupling to any lithospheric-scale (thermo-)mechanical code with a quadrilateral structured surface mesh.
Both SECs involve diffusion as approach for hillslope processes and the stream power law to reflect riverbed incision. The 1D SEC settles sediment that was produced by fluvial incision in the appropriate minimum, while the supply-limited 2D SEC DANSER uses a fast filling algorithm to model sedimantation. It is based on a cellular automaton. A slope-dependent factor in the sediment flux extends the diffusion equation to nonlinear diffusion. The discharge accumulation is achieved with the D8-algorithm and an improved drainage accumulation routine. Lateral incision enhances the incision's modelling. Following empirical laws, it incises channels of several cells width.
The coupling method enables different temporal and spatial resolutions of the SEC and the thermo-mechanical code. It transfers vertical as well as horizontal displacements to the surface model. A weighted smoothing of the 3D surface displacements is implemented. The smoothed displacement vectors transmit the deformation by bilinear interpolation to the surface model. These interpolation methods ensure mass conservation in both directions and prevent the two surfaces from drifting apart.
The presented applications refer to the evolution of the Pamir orogen. A calibration of DANSER's parameters with geomorphological data and a DEM as initial topography highlights the advantage of lateral incision. Preserving the channel width and reflecting incision peaks in narrow channels, this closes the huge gap between current orogen-scale incision models and observed topographies.
River capturing models in a system of fault-bounded block rotations reaffirm the importance of the lateral incision routine for capturing events with channel initiation. The models show a low probability of river capturings with large deflection angles. While the probability of river capturing is directly depending on the uplift rate, the erodibility inside of a dip-slip fault speeds up headward erosion along the fault: The model's capturing speed increases within a fault.
Coupling DANSER with the thermo-mechanical code SLIM 3D emphasizes the versatility of the SEC. While DANSER has minor influence on the lithospheric evolution of an indenter model, the brittle surface deformation is strongly affected by its sedimentation, widening a basin in between two forming orogens and also the southern part of the southern orogen to south, east and west.
Organic bulk heterojunction (BHJ) solar cells based on polymer:fullerene blends are a promising alternative for a low-cost solar energy conversion. Despite significant improvements of the power conversion efficiency in recent years, the fundamental working principles of these devices are yet not fully understood. In general, the current output of organic solar cells is determined by the generation of free charge carriers upon light absorption and their transport to the electrodes in competition to the loss of charge carriers due to recombination.
The object of this thesis is to provide a comprehensive understanding of the dynamic processes and physical parameters determining the performance. A new approach for analyzing the characteristic current-voltage output was developed comprising the experimental determination of the efficiencies of charge carrier generation, recombination and transport, combined with numerical device simulations.
Central issues at the beginning of this work were the influence of an electric field on the free carrier generation process and the contribution of generation, recombination and transport to the current-voltage characteristics. An elegant way to directly measure the field dependence of the free carrier generation is the Time Delayed Collection Field (TDCF) method. In TDCF charge carriers are generated by a short laser pulse and subsequently extracted by a defined rectangular voltage pulse. A new setup was established with an improved time resolution compared to former reports in literature. It was found that charge generation is in general independent of the electric field, in contrast to the current view in literature and opposed to the expectations of the Braun-Onsager model that was commonly used to describe the charge generation process. Even in cases where the charge generation was found to be field-dependend, numerical modelling showed that this field-dependence is in general not capable to account for the voltage dependence of the photocurrent. This highlights the importance of efficient charge extraction in competition to non-geminate recombination, which is the second objective of the thesis.
Therefore, two different techniques were combined to characterize the dynamics and efficiency of non-geminate recombination under device-relevant conditions. One new approach is to perform TDCF measurements with increasing delay between generation and extraction of charges. Thus, TDCF was used for the first time to measure charge carrier generation, recombination and transport with the same experimental setup. This excludes experimental errors due to different measurement and preparation conditions and demonstrates the strength of this technique. An analytic model for the description of TDCF transients was developed and revealed the experimental conditions for which reliable results can be obtained. In particular, it turned out that the $RC$ time of the setup which is mainly given by the sample geometry has a significant influence on the shape of the transients which has to be considered for correct data analysis.
Secondly, a complementary method was applied to characterize charge carrier recombination under steady state bias and illumination, i.e. under realistic operating conditions. This approach relies on the precise determination of the steady state carrier densities established in the active layer. It turned out that current techniques were not sufficient to measure carrier densities with the necessary accuracy. Therefore, a new technique {Bias Assisted Charge Extraction} (BACE) was developed. Here, the charge carriers photogenerated under steady state illumination are extracted by applying a high reverse bias. The accelerated extraction compared to conventional charge extraction minimizes losses through non-geminate recombination and trapping during extraction. By performing numerical device simulations under steady state, conditions were established under which quantitative information on the dynamics can be retrieved from BACE measurements.
The applied experimental techniques allowed to sensitively analyse and quantify geminate and non-geminate recombination losses along with charge transport in organic solar cells. A full analysis was exemplarily demonstrated for two prominent polymer-fullerene blends.
The model system P3HT:PCBM spincast from chloroform (as prepared) exhibits poor power conversion efficiencies (PCE) on the order of 0.5%, mainly caused by low fill factors (FF) and currents. It could be shown that the performance of these devices is limited by the hole transport and large bimolecular recombination (BMR) losses, while geminate recombination losses are insignificant. The low polymer crystallinity and poor interconnection between the polymer and fullerene domains leads to a hole mobility of the order of 10^-7 cm^2/Vs which is several orders of magnitude lower than the electron mobility in these devices. The concomitant build up of space charge hinders extraction of both electrons and holes and promotes bimolecular recombination losses.
Thermal annealing of P3HT:PCBM blends directly after spin coating improves crystallinity and interconnection of the polymer and the fullerene phase and results in comparatively high electron and hole mobilities in the order of 10^-3 cm^2/Vs and 10^-4 cm^2/Vs, respectively. In addition, a coarsening of the domain sizes leads to a reduction of the BMR by one order of magnitude. High charge carrier mobilities and low recombination losses result in comparatively high FF (>65%) and short circuit current (J_SC ≈ 10 mA/cm^2). The overall device performance (PCE ≈ 4%) is only limited by a rather low spectral overlap of absorption and solar emission and a small V_OC, given by the energetics of the P3HT.
From this point of view the combination of the low bandgap polymer PTB7 with PCBM is a promising approach. In BHJ solar cells, this polymer leads to a higher V_OC due to optimized energetics with PCBM. However, the J_SC in these (unoptimized) devices is similar to the J_SC in the optimized blend with P3HT and the FF is rather low (≈ 50%). It turned out that the unoptimized PTB7:PCBM blends suffer from high BMR, a low electron mobility of the order of 10^-5 cm^2/Vs and geminate recombination losses due to field dependent charge carrier generation.
The use of the solvent additive DIO optimizes the blend morphology, mainly by suppressing the formation of very large fullerene domains and by forming a more uniform structure of well interconnected donor and acceptor domains of the order of a few nanometers. Our analysis shows that this results in an increase of the electron mobility by about one order of magnitude (3 x 10^-4 cm^2/Vs), while BMR and geminate recombination losses are significantly reduced. In total these effects improve the J_SC (≈ 17 mA/cm^2) and the FF (> 70%). In 2012 this polymer/fullerene combination resulted in a record PCE for a single junction OSC of 9.2%.
Remarkably, the numerical device simulations revealed that the specific shape of the J-V characteristics depends very sensitively to the variation of not only one, but all dynamic parameters. On the one hand this proves that the experimentally determined parameters, if leading to a good match between simulated and measured J-V curves, are realistic and reliable. On the other hand it also emphasizes the importance to consider all involved dynamic quantities, namely charge carrier generation, geminate and non-geminate recombination as well as electron and hole mobilities. The measurement or investigation of only a subset of these parameters as frequently found in literature will lead to an incomplete picture and possibly to misleading conclusions.
Importantly, the comparison of the numerical device simulation employing the measured parameters and the experimental $J-V$ characteristics allows to identify loss channels and limitations of OSC. For example, it turned out that inefficient extraction of charge carriers is a criticical limitation factor that is often disobeyed. However, efficient and fast transport of charges becomes more and more important with the development of new low bandgap materials with very high internal quantum efficiencies. Likewise, due to moderate charge carrier mobilities, the active layer thicknesses of current high-performance devices are usually limited to around 100 nm. However, larger layer thicknesses would be more favourable with respect to higher current output and robustness of production. Newly designed donor materials should therefore at best show a high tendency to form crystalline structures, as observed in P3HT, combined with the optimized energetics and quantum efficiency of, for example, PTB7.
Reconstructing climate from the Dead Sea sediment record using high-resolution micro-facies analyses
(2015)
The sedimentary record of the Dead Sea is a key archive for reconstructing climate in the eastern Mediterranean region, as it stores the environmental and tectonic history of the Levant for the entire Quaternary. Moreover, the lake is located at the boundary between Mediterranean sub-humid to semi-arid and Saharo-Arabian hyper-arid climates, so that even small shifts in atmospheric circulation are sensitively recorded in the sediments. This DFG-funded doctoral project was carried out within the ICDP Dead Sea Deep Drilling Project (DSDDP) that intended to gain the first long, continuous and high-resolution sediment core from the deep Dead Sea basin. The drilling campaign was performed in winter 2010-11 and more than 700 m of sediments were recovered. The main aim of this thesis was (1) to establish the lithostratigraphic framework for the ~455 m long sediment core from the deep Dead Sea basin and (2) to apply high-resolution micro-facies analyses for reconstructing and better understanding climate variability from the Dead Sea sediments.
Addressing the first aim, the sedimentary facies of the ~455 m long deep-basin core 5017-1 were described in great detail and characterised through continuous overview-XRF element scanning and magnetic susceptibility measurements. Three facies groups were classified: (1) the marl facies group, (2) the halite facies group and (3) a group involving different expressions of massive, graded and slumped deposits including coarse clastic detritus. Core 5017-1 encompasses a succession of four main lithological units. Based on first radiocarbon and U-Th ages and correlation of these units to on-shore stratigraphic sections, the record comprises the last ca 220 ka, i.e. the upper part of the Amora Formation (parts of or entire penultimate interglacial and glacial), the last interglacial Samra Fm. (~135-75 ka), the last glacial Lisan Fm. (~75-14 ka) and the Holocene Ze’elim Formation. A major advancement of this record is that, for the first time, also transitional intervals were recovered that are missing in the exposed formations and that can now be studied in great detail.
Micro-facies analyses involve a combination of high-resolution microscopic thin section analysis and µXRF element scanning supported by magnetic susceptibility measurements. This approach allows identifying and characterising micro-facies types, detecting event layers and reconstructing past climate variability with up to seasonal resolution, given that the analysed sediments are annually laminated. Within this thesis, micro-facies analyses, supported by further sedimentological and geochemical analyses (grain size, X-ray diffraction, total organic carbon and calcium carbonate contents) and palynology, were applied for two time intervals:
(1) The early last glacial period ~117-75 ka was investigated focusing on millennial-scale hydroclimatic variations and lake level changes recorded in the sediments. Thereby, distinguishing six different micro-facies types with distinct geochemical and sedimentological characteristics allowed estimating relative lake level and water balance changes of the lake. Comparison of the results to other records in the Mediterranean region suggests a close link of the hydroclimate in the Levant to North Atlantic and Mediterranean climates during the time of the build-up of Northern hemisphere ice sheets during the early last glacial period.
(2) A mostly annually laminated late Holocene section (~3700-1700 cal yr BP) was analysed in unprecedented detail through a multi-proxy, inter-site correlation approach of a shallow-water core (DSEn) and its deep-basin counterpart (5017-1). Within this study, a ca 1500 years comprising time series of erosion and dust deposition events was established and anchored to the absolute time-scale through 14C dating and age modelling. A particular focus of this study was the characterisation of two dry periods, from ~3500 to 3300 and from ~3000 to 2400 cal yr BP, respectively. Thereby, a major outcome was the coincidence of the latter dry period with a period of moist and cold climate in Europe related to a Grand Solar Minimum around 2800 cal yr BP and an increase in flood events despite overall dry conditions in the Dead Sea region during that time. These contrasting climate signatures in Europe and at the Dead Sea were likely linked through complex teleconnections of atmospheric circulation, causing a change in synoptic weather patterns in the eastern Mediterranean.
In summary, within this doctorate the lithostratigraphic framework of a unique long sediment core from the deep Dead Sea basin is established, which serves as a base for any further high-resolution investigations on this core. It is demonstrated in two case studies that micro-facies analyses are an invaluable tool to understand the depositional processes in the Dead Sea and to decipher past climate variability in the Levant on millennial to seasonal time-scales. Hence, this work adds important knowledge helping to establish the deep Dead Sea record as a key climate archive of supra-regional significance.
This thesis investigates temporal and aspectual reference in the typologically unrelated African languages Hausa (Chadic, Afro–Asiatic) and Medumba (Grassfields Bantu).
It argues that Hausa is a genuinely tenseless language and compares the interpretation of temporally unmarked sentences in Hausa to that of morphologically tenseless sentences in Medumba, where tense marking is optional and graded.
The empirical behavior of the optional temporal morphemes in Medumba motivates an analysis as existential quantifiers over times and thus provides new evidence suggesting that languages vary in whether their (past) tense is pronominal or quantificational (see also Sharvit 2014).
The thesis proposes for both Hausa and Medumba that the alleged future tense marker is a modal element that obligatorily combines with a prospective future shifter (which is covert in Medumba). Cross-linguistic variation in whether or not a future marker is compatible with non-future interpretation is proposed to be predictable from the aspectual architecture of the given language.
Business process management (BPM) is a systematic and structured approach to model, analyze, control, and execute business operations also referred to as business processes that get carried out to achieve business goals. Central to BPM are conceptual models. Most prominently, process models describe which tasks are to be executed by whom utilizing which information to reach a business goal. Process models generally cover the perspectives of control flow, resource, data flow, and information systems.
Execution of business processes leads to the work actually being carried out. Automating them increases the efficiency and is usually supported by process engines. This, though, requires the coverage of control flow, resource assignments, and process data. While the first two perspectives are well supported in current process engines, data handling needs to be implemented and maintained manually. However, model-driven data handling promises to ease implementation, reduces the error-proneness through graphical visualization, and reduces development efforts through code generation.
This thesis addresses the modeling, analysis, and execution of data in business processes and presents a novel approach to execute data-annotated process models entirely model-driven. As a first step and formal grounding for the process execution, a conceptual framework for the integration of processes and data is introduced. This framework is complemented by operational semantics through a Petri net mapping extended with data considerations. Model-driven data execution comprises the handling of complex data dependencies, process data, and data exchange in case of communication between multiple process participants. This thesis introduces concepts from the database domain into BPM to enable the distinction of data operations, to specify relations between data objects of the same as well as of different types, to correlate modeled data nodes as well as received messages to the correct run-time process instances, and to generate messages for inter-process communication. The underlying approach, which is not limited to a particular process description language, has been implemented as proof-of-concept.
Automation of data handling in business processes requires data-annotated and correct process models. Targeting the former, algorithms are introduced to extract information about data nodes, their states, and data dependencies from control information and to annotate the process model accordingly. Usually, not all required information can be extracted from control flow information, since some data manipulations are not specified. This requires further refinement of the process model. Given a set of object life cycles specifying allowed data manipulations, automated refinement of the process model towards containment of all data manipulations is enabled. Process models are an abstraction focusing on specific aspects in detail, e.g., the control flow and the data flow views are often represented through activity-centric and object-centric process models. This thesis introduces algorithms for roundtrip transformations enabling the stakeholder to add information to the process model in the view being most appropriate.
Targeting process model correctness, this thesis introduces the notion of weak conformance that checks for consistency between given object life cycles and the process model such that the process model may only utilize data manipulations specified directly or indirectly in an object life cycle. The notion is computed via soundness checking of a hybrid representation integrating control flow and data flow correctness checking. Making a process model executable, identified violations must be corrected. Therefore, an approach is proposed that identifies for each violation multiple, alternative changes to the process model or the object life cycles.
Utilizing the results of this thesis, business processes can be executed entirely model-driven from the data perspective in addition to the control flow and resource perspectives already supported before. Thereby, the model creation is supported by algorithms partly automating the creation process while model consistency is ensured by data correctness checks.
The Brazilian Cerrado is recognised as one of the most threatened biomes in the world, as the region has experienced a striking change from natural vegetation to intense cash crop production. The impacts of rapid agricultural expansion on soil and water resources are still poorly understood in the region. Therefore, the overall aim of the thesis is to improve our understanding of the ecohydrological processes causing water and soil degradation in the Brazilian Cerrado.
I first present a metaanalysis to provide quantitative evidence and identifying the main impacts of soil and water alterations resulting from land use change. Second, field studies were conducted to (i) examine the effects of land use change on soils of natural cerrado transformed to common croplands and pasture and (ii) indicate how agricultural production affects water quality across a meso-scale catchment. Third, the ecohydrological process-based model SWAT was tested with simple scenario analyses to gain insight into the impacts of land use and climate change on the water cycling in the upper São Lourenço catchment which experienced decreasing discharges in the last 40 years.
Soil and water quality parameters from different land uses were extracted from 89 soil and 18 water studies in different regions across the Cerrado. Significant effects on pH, bulk density and available P and K for croplands and less-pronounced effects on pastures were evident. Soil total N did not differ between land uses because most of the cropland sites were N-fixing soybean cultivations, which are not artificially fertilized with N. By contrast, water quality studies showed N enrichment in agricultural catchments, indicating fertilizer impacts and potential susceptibility to eutrophication. Regardless of the land use, P is widely absent because of the high-fixing capacities of deeply weathered soils and the filtering capacity of riparian vegetation. Pesticides, however, were consistently detected throughout the entire aquatic system. In several case studies, extremely high-peak concentrations exceeded Brazilian and EU water quality limits, which pose serious health risks.
My field study revealed that land conversion caused a significant reduction in infiltration rates near the soil surface of pasture (–96 %) and croplands (–90 % to –93 %). Soil aggregate stability was significantly reduced in croplands than in cerrado and pasture. Soybean crops had extremely high extractable P (80 mg kg–1), whereas pasture N levels declined. A snapshot water sampling showed strong seasonality in water quality parameters. Higher temperature, oxi-reduction potential (ORP), NO2–, and very low oxygen concentrations (<5 mg•l–1) and saturation (<60 %) were recorded during the rainy season. By contrast, remarkably high PO43– concentrations (up to 0.8 mg•l–1) were measured during the dry season. Water quality parameters were affected by agricultural activities at all sampled sub-catchments across the catchment, regardless of stream characteristic. Direct NO3– leaching appeared to play a minor role; however, water quality is affected by topsoil fertiliser inputs with impact on small low order streams and larger rivers. Land conversion leaving cropland soils more susceptible to surface erosion by increased overland flow events.
In a third study, the field data were used to parameterise SWAT. The model was tested with different input data and calibrated in SWAT-CUP using the SUFI-2 algorithm. The model was judged reliable to simulate the water balance in the Cerrado. A complete cerrado, pasture and cropland cover was used to analyse the impact of land use on water cycling as well as climate change projections (2039–2058) according to the projections of the RCP 8.5 scenario. The actual evapotranspiration (ET) for the cropland scenario was higher compared to the cerrado cover (+100 mm a–1). Land use change scenarios confirmed that deforestation caused higher annual ET rates explaining partly the trend of decreased streamflow. Taking all climate change scenarios into account, the most likely effect is a prolongation of the dry season (by about one month), with higher peak flows in the rainy season. Consequently, potential threats for crop production with lower soil moisture and increased erosion and sediment transport during the rainy season are likely and should be considered in adaption plans.
From the three studies of the thesis I conclude that land use intensification is likely to seriously limit the Cerrado’s future regarding both agricultural productivity and ecosystem stability. Because only limited data are available for the vast biome, we recommend further field studies to understand the interaction between terrestrial and aquatic systems. This thesis may serve as a valuable database for integrated modelling to investigate the impact of land use and climate change on soil and water resources and to test and develop mitigation measures for the Cerrado in the future.
In many procedures of seismic risk mitigation, ground motion simulations are needed to test systems or improve their effectiveness. For example they may be used to estimate the level of ground shaking caused by future earthquakes. Good physical models for ground motion simulation are also thought to be important for hazard assessment, as they could close gaps in the existing datasets. Since the observed ground motion in nature shows a certain variability, part of which cannot be explained by macroscopic parameters such as magnitude or position of an earthquake, it would be desirable that a good physical model is not only able to produce one single seismogram, but also to reveal this natural variability.
In this thesis, I develop a method to model realistic ground motions in a way that is computationally simple to handle, permitting multiple scenario simulations. I focus on two aspects of ground motion modelling. First, I use deterministic wave propagation for the whole frequency range – from static deformation to approximately 10 Hz – but account for source variability by implementing self-similar slip distributions and rough fault interfaces. Second, I scale the source spectrum so that the modelled waveforms represent the correct radiated seismic energy. With this scaling I verify whether the energy magnitude is suitable as an explanatory variable, which characterises the amount of energy radiated at high frequencies – the advantage of the energy magnitude being that it can be deduced from observations, even in real-time.
Applications of the developed method for the 2008 Wenchuan (China) earthquake, the 2003 Tokachi-Oki (Japan) earthquake and the 1994 Northridge (California, USA) earthquake show that the fine source discretisations combined with the small scale source variability ensure that high frequencies are satisfactorily introduced, justifying the deterministic wave propagation approach even at high frequencies. I demonstrate that the energy magnitude can be used to calibrate the high-frequency content in ground motion simulations.
Because deterministic wave propagation is applied to the whole frequency range, the simulation method permits the quantification of the variability in ground motion due to parametric uncertainties in the source description. A large number of scenario simulations for an M=6 earthquake show that the roughness of the source as well as the distribution of fault dislocations have a minor effect on the simulated variability by diminishing directivity effects, while hypocenter location and rupture velocity more strongly influence the variability. The uncertainty in energy magnitude, however, leads to the largest differences of ground motion amplitude between different events, resulting in a variability which is larger than the one observed.
For the presented approach, this dissertation shows (i) the verification of the computational correctness of the code, (ii) the ability to reproduce observed ground motions and (iii) the validation of the simulated ground motion variability. Those three steps are essential to evaluate the suitability of the method for means of seismic risk mitigation.
This PhD thesis is essentially a collection of six sequential articles on dynamics of accountability in the reformed employment and welfare administration in different countries. The first article examines how recent changes in the governance of employment services in three European countries (Denmark, Germany and Norway) have influenced accountability relationships from a very wide-ranging perspective. It starts from the overall assumption in the literature that accountability relationships are becoming more numerous and complex, and that these changes may lead to multiple accountability disorder. The article explores these assumptions by analyzing the different actors involved and the information requested in the new governance arrangements in all three countries. It concludes that the considerable changes in organizational arrangements and more managerial information demanded and provided have led to more shared forms of accountability. Nevertheless, a clear development towards less political or administrative accountability could not be observed.
The second article analyzes how the structure and development of reform processes affect accountability relationships and via what mechanisms. It is distinguished between an instrumental perspective and an institutional perspective and each of these perspectives takes a different view on the link between reforms and concrete action and results. By taking the welfare reforms in Norway and Germany as an example, it is shown that the reform outcomes in both countries are the result of a complex process of powering, puzzling and institutional constraints where different situational interpretations of problems, interests and administrative legacies had to be balanced. Accountability thus results not from a single process of environmental necessity or strategic choice, but from a dynamic interplay between different actors and institutional spheres.
The third article then covers a specific instrument of public sector reforms, i.e. the increasing use of performance management. The article discusses the challenges and ambiguities between performance management and different forms of accountability based on the cases of the reformed welfare administration in Norway and Germany. The findings are that the introduction of performance management creates new accountability structures which influence service delivery, but not necessarily in the direction expected by reform agents. Observed unintended consequences include target fixation, the displacement of political accountability and the predominance of control aspects of accountability.
The fourth article analyzes the accountability implications of the increasingly marketized models of welfare governance. It has often been argued that relocating powers and discretion to private contractors involve a trade-off between democratic accountability and efficiency. However, there is limited empirical evidence of how contracting out shapes accountability or is shaped by alternative democratic or administrative forms of accountability. Along these lines the article examines employment service accountability in the era of contracting out in Germany, Denmark and Great Britain. It is found that market accountability instruments are complementary instruments, not substitutes. The findings highlight the importance of administrative and political instruments in legitimizing marketized service provision and shed light on the processes that lead to the development of a hybrid accountability model.
The fifth and sixth articles focus on the diagonal accountability relationships between public agencies, supreme audit institutions (SAI) and parental ministry or parliament.
The fifth article examines the evolving role of SAIs in Denmark, Germany and Norway focusing particularly on their contribution to public accountability and their ambivalent relationship with some aspects of public sector reform in the welfare sector. The article analyzes how SAIs assess New Public Management inspired reforms in the welfare sector in the three countries. The analysis shows that all three SAIs have taken on an evaluative role when judging New Public Management instruments. At the same time their emphasis on legality and compliance can be at odds with some of the operating principles introduced by New Public Management reforms.
The sixth article focuses on the auditing activities of the German SAI in the field of labor market administration as a single in-depth case study. The purpose is to analyze how SAIs gain impact in diagonal accountability settings. The results show that the direct relationship between auditor and auditee based on cooperation and trust is of outstanding importance for SAIs to give effect to their recommendations. However, if an SAI has to rely on actors of diagonal accountability, it is in a vulnerable position as it might lose control over the interpretation of its results.
The main research question of this thesis concerns the relation between focus interpretation, focus realization, and association with focus in the West Chadic language Ngamo.
Concerning the relation between focus realization and interpretation, this thesis contributes to the question, cross-linguistically, what factors influence a marked realization of the focus/background distinction. There is background-marking rather than focus-marking in Ngamo, and the background marker is related to the definite determiner in the language. Using original fieldwork data as a basis, a formal semantic analysis of the background marker as a definite determiner of situations is proposed.
Concerning the relation between focus and association with focus, the thesis adds to the growing body of crosslinguistic evidence that not all so-called focus-sensitive operators always associate with focus. The thesis shows that while the exclusive particle yak('i) (= "only") in Ngamo conventionally associates
with focus, the particles har('i) (= "even, as far as, until, already"), and ke('e) (= "also, and") do not.
The thesis provides an analysis of these phenomena in a situation semantic framework.
Business Process Management has become an integral part of modern organizations in the private and public sector for improving their operations. In the course of Business Process Management efforts, companies and organizations assemble large process model repositories with many hundreds and thousands of business process models bearing a large amount of information. With the advent of large business process model collections, new challenges arise as structuring and managing a large amount of process models, their maintenance, and their quality assurance.
This is covered by business process architectures that have been introduced for organizing and structuring business process model collections. A variety of business process architecture approaches have been proposed that align business processes along aspects of interest, e. g., goals, functions, or objects. They provide a high level categorization of single processes ignoring their interdependencies, thus hiding valuable information. The production of goods or the delivery of services are often realized by a complex system of interdependent business processes. Hence, taking a holistic view at business processes interdependencies becomes a major necessity to organize, analyze, and assess the impact of their re-/design. Visualizing business processes interdependencies reveals hidden and implicit information from a process model collection.
In this thesis, we present a novel Business Process Architecture approach for representing and analyzing business process interdependencies on an abstract level. We propose a formal definition of our Business Process Architecture approach, design correctness criteria, and develop analysis techniques for assessing their quality. We describe a methodology for applying our Business Process Architecture approach top-down and bottom-up. This includes techniques for Business Process Architecture extraction from, and decomposition to process models while considering consistency issues between business process architecture and process model level. Using our extraction algorithm, we present a novel technique to identify and visualize data interdependencies in Business Process Data Architectures. Our Business Process Architecture approach provides business process experts,managers, and other users of a process model collection with an overview that allows reasoning about a large set of process models,
understanding, and analyzing their interdependencies in a facilitated way. In this regard we evaluated our Business Process Architecture approach in an experiment and provide implementations of selected techniques.
Magnetite nanoparticles and their assembly comprise a new area of development for new technologies. The magnetic particles can interact and assemble in chains or networks. Magnetotactic bacteria are one of the most interesting microorganisms, in which the assembly of nanoparticles occurs. These microorganisms are a heterogeneous group of gram negative prokaryotes, which all show the production of special magnetic organelles called magnetosomes, consisting of a magnetic nanoparticle, either magnetite (Fe3O4) or greigite (Fe3S4), embedded in a membrane. The chain is assembled along an actin-like scaffold made of MamK protein, which makes the magnetosomes to arrange in mechanically stable chains. The chains work as a compass needle in order to allow cells to orient and swim along the magnetic field of the Earth.
The formation of magnetosomes is known to be controlled at the molecular level. The physico–chemical conditions of the surrounding environment also influence biomineralization. The work presented in this manuscript aims to understand how such external conditions, in particular the extracellular oxidation reduction potential (ORP) influence magnetite formation in the strain Magnetospirillum magneticum AMB-1. A controlled cultivation of the microorganism was developed in a bioreactor and the formation of magnetosomes was characterized.
Different techniques have been applied in order to characterize the amount of iron taken up by the bacteria and in consequence the size of magnetosomes produced at different ORP conditions. By comparison of iron uptake, morphology of bacteria, size and amount of magnetosomes per cell at different ORP, the formation of magnetosomes was inhibited at ORP 0 mV, whereas reduced conditions, ORP – 500 mV facilitate biomineralization process.
Self-assembly of magnetosomes occurring in magnetotactic bacteria became an inspiration to learn from nature and to construct nanoparticles assemblies by using the bacteriophage M13 as a template. The M13 bacteriophage is an 800 nm long filament with encapsulated single-stranded DNA that has been recently used as a scaffold for nanoparticle assembly. I constructed two types of assemblies based on bacteriophages and magnetic nanoparticles. A chain – like assembly was first formed where magnetite nanoparticles are attached along the phage filament. A sperm – like construct was also built with a magnetic head and a tail formed by phage filament.
The controlled assembly of magnetite nanoparticles on the phage template was possible due to two different mechanism of nanoparticle assembly. The first one was based on the electrostatic interactions between positively charged polyethylenimine coated magnetite nanoparticles and negatively charged phages. The second phage –nanoparticle assembly was achieved by bioengineered recognition sites. A mCherry protein is displayed on the phage and is was used as a linker to a red binding nanobody (RBP) that is fused to the one of the proteins surrounding the magnetite crystal of a magnetosome.
Both assemblies were actuated in water by an external magnetic field showing their swimming behavior and potentially enabling further usage of such structures for medical applications. The speed of the phage - nanoparticles assemblies are relatively slow when compared to those of microswimmers previously published. However, only the largest phage-magnetite assemblies could be imaged and it is therefore still unclear how fast these structures can be in their smaller version.
The Central Pontides is an accretionary-type orogenic area within the Alpine-Himalayan orogenic belt characterized by pre-collisional tectonic continental growth. The region comprises Mesozoic subduction-accretionary complexes and an accreted intra-oceanic arc that are sandwiched between the Laurasian active continental margin and Gondwana-derived the Kırşehir Block. The subduction-accretion complexes mainly consist of an Albian-Turonian accretionary wedge representing the Laurasian active continental margin. To the north, the wedge consists of slate/phyllite and metasandstone intercalation with recrystallized limestone, Na-amphibole-bearing metabasite (PT= 7–12 kbar and 400 ± 70 ºC) and tectonic slices of serpentinite representing accreted distal part of a large Lower Cretaceous submarine turbidite fan deposited on the Laurasian active continental margin that was subsequently accreted and metamorphosed. Raman spectra of carbonaceous material (RSCM) of the metapelitic rocks revealed that the metaflysch sequence consists of metamorphic packets with distinct peak metamorphic temperatures. The majority of the metapelites are low-temperature (ca. 330 °C) slates characterized by lack of differentiation of the graphite (G) and D2 defect bands. They possibly represent offscraped distal turbidites along the toe of the Albian accretionary wedge. The rest are phyllites that are characterized by slightly pronounced G band with D2 defect band occurring on its shoulder. Peak metamorphic temperatures of these phyllites are constrained to 370-385 °C. The phyllites are associated with a strip of incipient blueschist facies metabasites which are found as slivers within the offscraped distal turbidites. They possibly represent underplated continental metasediments together with oceanic crustal basalt along the basal décollement. Tectonic emplacement of the underplated rocks into the offscraped distal turbidites was possibly achieved by out-of-sequence thrusting causing tectonic thickening and uplift of the wedge. 40Ar/39Ar phengite ages from the phyllites are ca. 100 Ma, indicating Albian subduction and regional HP metamorphism.
The accreted continental metasediments are underlain by HP/LT metamorphic rocks of oceanic origin along an extensional shear zone. The oceanic metamorphic sequence mainly comprises tectonically thickened deep-seated eclogite to blueschist facies metabasites and micaschists. In the studied area, metabasites are epidote-blueschists locally with garnet (PT= 17 ± 1 kbar and 500 ± 40 °C). Lawsonite-blueschists are exposed as blocks along the extensional shear zone (PT= 14 ± 2 kbar and 370–440 °C). They are possibly associated with low shear stress regime of the initial stage of convergence. Close to the shear zone, the footwall micaschists consist of quartz, phengite, paragonite, chlorite, rutile with syn-kinematic albite porphyroblast formed by pervasive shearing during exhumation. These types of micaschists are tourmaline-bearing and their retrograde nature suggests high-fluid flux along shear zones. Peak metamorphic mineral assemblages are partly preserved in the chloritoid-micaschist farther away from the shear zone representing the zero strain domains during exhumation. Three peak metamorphic assemblages are identified and their PT conditions are constrained by pseudosections produced by Theriak-Domino and by Raman spectra of carbonaceous material: 1) garnet-chloritoid-glaucophane with lawsonite pseudomorphs (P= 17.5 ± 1 kbar, T: 390-450 °C) 2) chloritoid with glaucophane pseudomorphs (P= 16-18 kbar, T: 475 ± 40 °C) and 3) relatively high-Mg chloritoid (17%) with jadeite pseudomorphs (P= 22-25 kbar; T: 440 ± 30 °C) in addition to phengite, paragonite, quartz, chlorite, rutile and apatite. The last mineral assemblage is interpreted as transformation of the chloritoid + glaucophane assemblage to chloritoid + jadeite paragenesis with increasing pressure. Absence of tourmaline suggests that the chloritoid-micaschist did not interact with B-rich fluids during zero strain exhumation. 40Ar/39Ar phengite age of a pervasively sheared footwall micaschist is constrained to 100.6 ± 1.3 Ma and that of a chloritoid-micaschist is constrained to 91.8 ± 1.8 Ma suggesting exhumation during on-going subduction with a southward younging of the basal accretion and the regional metamorphism. To the south, accretionary wedge consists of blueschist and greenschist facies metabasite, marble and volcanogenic metasediment intercalation. 40Ar/39Ar phengite dating reveals that this part of the wedge is of Middle Jurassic age partly overprinted during the Albian. Emplacement of the Middle Jurassic subduction-accretion complexes is possibly associated with obliquity of the Albian convergence.
Peak metamorphic assemblages and PT estimates of the deep-seated oceanic metamorphic sequence suggest tectonic stacking within wedge with different depths of burial. Coupling and exhumation of the distinct metamorphic slices are controlled by decompression of the wedge possibly along a retreating slab. Structurally, decompression of the wedge is evident by an extensional shear zone and the footwall micaschists with syn-kinematic albite porphyroblasts. Post-kinematic garnets with increasing grossular content and pseudomorphing minerals within the chloritoid-micaschists also support decompression model without an extra heating.
Thickening of subduction-accretionary complexes is attributed to i) significant amount of clastic sediment supply from the overriding continental domain and ii) deep level basal underplating by propagation of the décollement along a retreating slab. Underplating by basal décollement propagation and subsequent exhumation of the deep-seated subduction-accretion complexes are connected and controlled by slab rollback creating a necessary space for progressive basal accretion along the plate interface and extension of the wedge above for exhumation of the tectonically thickened metamorphic sequences. This might be the most common mechanism of the tectonic thickening and subsequent exhumation of deep-seated HP/LT subduction-accretion complexes.
To the south, the Albian-Turonian accretionary wedge structurally overlies a low-grade volcanic arc sequence consisting of low-grade metavolcanic rocks and overlying metasedimentary succession is exposed north of the İzmir-Ankara-Erzincan suture (İAES), separating Laurasia from Gondwana-derived terranes. The metavolcanic rocks mainly consist of basaltic andesite/andesite and mafic cognate xenolith-bearing rhyolite with their pyroclastic equivalents, which are interbedded with recrystallized pelagic limestone and chert. The metavolcanic rocks are stratigraphically overlain by recrystallized micritic limestone with rare volcanogenic metaclastic rocks. Two groups can be identified based on trace and rare earth element characteristics. The first group consists of basaltic andesite/andesite (BA1) and rhyolite with abundant cognate gabbroic xenoliths. It is characterized by relative enrichment of LREE with respect to HREE. The rocks are enriched in fluid mobile LILE, and strongly depleted in Ti and P reflecting fractionation of Fe-Ti oxides and apatite, which are found in the mafic cognate xenoliths. Abundant cognate gabbroic xenoliths and identical trace and rare earth elements compositions suggest that rhyolites and basaltic andesites/andesites (BA1) are cogenetic and felsic rocks were derived from a common mafic parental magma by fractional crystallization and accumulation processes. The second group consists only of basaltic andesites (BA2) with flat REE pattern resembling island arc tholeiites. Although enriched in LILE, this group is not depleted in Ti or P.
Geochemistry of the metavolcanic rocks indicates supra-subduction volcanism evidenced by depletion of HFSE and enrichment of LILE. The arc sequence is sandwiched between an Albian-Turonian subduction-accretionary complex representing the Laurasian active margin and an ophiolitic mélange. Absence of continent derived detritus in the arc sequence and its tectonic setting in a wide Cretaceous accretionary complex suggest that the Kösdağ Arc was intra-oceanic. This is in accordance with basaltic andesites (BA2) with island arc tholeiite REE pattern.
Zircons from two metarhyolite samples give Late Cretaceous (93.8 ± 1.9 and 94.4 ± 1.9 Ma) U/Pb ages. Low-grade regional metamorphism of the intra-oceanic arc sequence is constrained 69.9 ± 0.4 Ma by 40Ar/39Ar dating on metamorphic muscovite from a metarhyolite indicating that the arc sequence became part of a wide Tethyan Cretaceous accretionary complex by the latest Cretaceous. The youngest 40Ar/39Ar phengite age from the overlying subduction-accretion complexes is 92 Ma confirming southward younging of an accretionary-type orogenic belt. Hence, the arc sequence represents an intra-oceanic paleo-arc that formed above the sinking Tethyan slab and finally accreted to Laurasian active continental margin. Abrupt non-collisional termination of arc volcanism was possibly associated with southward migration of the arc volcanism similar to the Izu-Bonin-Mariana arc system.
The intra-oceanic Kösdağ Arc is coeval with the obducted supra-subduction ophiolites in NW Turkey suggesting that it represents part of the presumed but missing incipient intra-oceanic arc associated with the generation of the regional supra-subduction ophiolites. Remnants of a Late Cretaceous intra-oceanic paleo-arc and supra-subduction ophiolites can be traced eastward within the Alp-Himalayan orogenic belt. This reveals that Late Cretaceous intra-oceanic subduction occurred as connected event above the sinking Tethyan slab. It resulted as arc accretion to Laurasian active margin and supra-subduction ophiolite obduction on Gondwana-derived terranes.
Development of geophysical methods to characterize methane hydrate reservoirs on a laboratory scale
(2015)
Gas hydrates are crystalline solids composed of water and gas molecules. They are stable at elevated pressure and low temperatures. Therefore, natural gas hydrate deposits occur at continental margins, permafrost areas, deep lakes, and deep inland seas. During hydrate formation, the water molecules rearrange to form cavities which host gas molecules. Due to the high pressure during hydrate formation, significant amounts of gas can be stored in hydrate structures. The water-gas ratio hereby can reach up to 1:172 at 0°C and atmospheric pressure. Natural gas hydrates predominantly contain methane. Because methane constitutes both a fuel and a greenhouse gas, gas hydrates are a potential energy resource as well as a potential source for greenhouse gas.
This study investigates the physical properties of methane hydrate bearing sediments on a laboratory scale. To do so, an electrical resistivity tomography (ERT) array was developed and mounted in a large reservoir simulator (LARS). For the first time, the ERT array was applied to hydrate saturated sediment samples under controlled temperature, pressure, and hydrate saturation conditions on a laboratory scale. Typically, the pore space of (marine) sediments is filled with electrically well conductive brine. Because hydrates constitute an electrical isolator, significant contrasts regarding the electrical properties of the pore space emerge during hydrate formation and dissociation. Frequent measurements during hydrate formation experiments permit the recordings of the spatial resistivity distribution inside LARS. Those data sets are used as input for a new data processing routine which transfers the spatial resistivity distribution into the spatial distribution of hydrate saturation. Thus, the changes of local hydrate saturation can be monitored with respect to space and time.
This study shows that the developed tomography yielded good data quality and resolved even small amounts of hydrate saturation inside the sediment sample. The conversion algorithm transforming the spatial resistivity distribution into local hydrate saturation values yielded the best results using the Archie-var-phi relation. This approach considers the increasing hydrate phase as part of the sediment frame, metaphorically reducing the sample’s porosity. In addition, the tomographical measurements showed that fast lab based hydrate formation processes cause small crystallites to form which tend to recrystallize.
Furthermore, hydrate dissociation experiments via depressurization were conducted in order to mimic the 2007/2008 Mallik field trial. It was observed that some patterns in gas and water flow could be reproduced, even though some setup related limitations arose.
In two additional long-term experiments the feasibility and performance of CO2-CH4 hydrate exchange reactions were studied in LARS. The tomographical system was used to monitor the spatial hydrate distribution during the hydrate formation stage. During the subsequent CO2 injection, the tomographical array allowed to follow the CO2 migration front inside the sediment sample and helped to identify the CO2 breakthrough.
This thesis contains three experimental studies addressing the interplay between deformation and the mineral reaction between natural calcite and magnesite. The solid-solid mineral reaction between the two carbonates causes the formation of a magnesio-calcite precursor layer and a dolomite reaction rim in every experiment at isostatic annealing and deformation conditions.
CHAPTER 1 briefly introduces general aspects concerning mineral reactions in nature and diffusion pathways for mass transport. Moreover, results of previous laboratory studies on the influence of deformation on mineral reactions are summarized. In addition, the main goals of this study are pointed out.
In CHAPTER 2, the reaction between calcite and magnesite single crystals is examined at isostatic annealing conditions. Time series performed at a fixed temperature revealed a diffusion-controlled dolomite rim growth. Two microstructural domains could be identified characterized by palisade-shaped dolomite grains growing into the magnesite and granular dolomite growing towards calcite. A model was provided for the dolomite rim growth based on the counter-diffusion of CaO and MgO. All reaction products exhibited a characteristic crystallographic relationship with respect to the calcite reactant. Moreover, kinetic parameters of the mineral reaction were determined out of a temperature series at a fixed time. The main goal of the isostatic test series was to gain information about the microstructure evolution, kinetic parameters, chemical composition and texture development of the reaction products. The results were used as a reference to quantify the influence of deformation on the mineral reaction.
CHAPTER 3 deals with the influence of non-isostatic deformation on dolomite and magnesio-calcite layer production between calcite and magnesite single crystals. Deformation was achieved by triaxial compression and by torsion. Triaxial compression up to 38 MPa axial stress at a fixed time showed no significant influence of stress and strain on dolomite formation. Time series conducted at a fixed stress yield no change in growth rates for dolomite and magnesio-calcite at low strains. Slightly larger magnesio-calcite growth rates were observed at strains above >0.1. High strains at similar stresses were caused by the activation of additional glide systems in the calcite single crystal and more mobile dislocations in the magnesio-calcite grains, providing fast diffusion pathways. In torsion experiments a gradual decrease in dolomite and magnesio-calcite layer thickness was observed at a critical shear strain. During deformation, crystallographic orientations of reaction products rearranged with respect to the external framework. A direct effect of the mineral reaction on deformation could not be recognized due to the relatively small reaction product widths.
In CHAPTER 4, the influence of starting material microfabrics and the presence of water on the reaction kinetics was evaluated. In these experimental series polycrystalline material was in contact with single crystals or two polycrystalline materials were used as reactants. Isostatic annealing resulted in different dolomite and magnesio-calcite layer thicknesses, depending on starting material microfabrics. The reaction progress at the magnesite interface was faster with smaller magnesite grain size, because grain boundaries provided fast pathways for diffusion and multiple nucleation sites for dolomite formation. Deformation by triaxial compression and torsion yield lower dolomite rim thicknesses compared to annealed samples for the same time. This was caused by grain coarsening of polycrystalline magnesite during deformation. In contrast, magnesio-calcite layers tended to be larger during deformation, which triggered enhanced diffusion along grain boundaries. The presence of excess water had no significant influence on the reaction kinetics, at least if the reactants were single crystals.
In CHAPTER 5 general conclusions about the interplay between deformation and the mineral reaction in the carbonate system are presented.
Finally, CHAPTER 6 highlights possible future work in the carbonate system based on the results of this study.
In this thesis we utilize resolved stellar populations to improve our understanding of galaxy formation and evolution. In the first part we improve a method for metallicity determination of faint old stellar systems, in the second and third part we analyze the individual history of six nearby disk galaxies outside the Local Group.
A New Calibration of the Color Metallicity Relation of Red Giants for HST data:
It is well known, that the color distribution of stars on the the Red Giant Branch (RGB) can be used to determine metallicities of old stellar populations that have only shallow photometry. Based on the largest sample of globular clusters ever used for such studies, we quantify the relation between metallicity and color in the widely used HST ACS filters F606W and F814W.
We use a sample of globular clusters from the ACS Globular Cluster Survey and measure their RGB color at given absolute magnitudes to derive the color-metallicity relation. We find a clear relation between metallicity and RGB color; we investigate the scatter and the uncertainties in this relation and show its limitations. A comparison with isochrones shows reasonably good agreement with BaSTI models, a small offset to Dartmouth models, and a larger offset to Padua models.
Even for the best globular cluster data available, the metallicity of a simple stellar population can be determined from the RGB alone only with an accuracy of 0.3 dex for [M/H]<-1, and 0.15 dex for [M/H]>-1. For mixed populations, as they are observed in external galaxies, the uncertainties will be even larger due to uncertainties in extinction, age, etc. Therefore caution is necessary when interpreting photometric metallicities.
The Structural History of Nearby Low Mass Disk Galaxies:
We study the individual evolution histories of three nearby, low-mass, edge-on galaxies (IC5052, NGC4244, NGC5023).
Using the color magnitude diagrams of resolved stellar populations, we construct star count density maps for populations of different ages and analyze the change of structural parameters with stellar age within each galaxy.
The three galaxies show low vertical heating rates, which are much lower than the heating rate of the Milky Way. This indicates that heating agents, as giant molecular clouds and spiral structure are weak in low mass galaxies.
We do not detect a separate thick disk in any of the three galaxies, even though our observations cover a larger range in equivalent surface brightness than any integrated light study. While scaleheights increase with age, each population can be well described by a single disk. Only two of the galaxies contain a very weak additional component, which we identify as the faint halo. The mass of these faint halos is less than 1% of the mass of the disk.
All populations in the three galaxies exhibit no or only little flaring. While this finding is consistent with previous integrated light studies, it poses strong constraints on galaxy formation models, because most theoretical simulations often find strong flaring due to interactions or radial migration.
Furthermore, we find breaks in the radial profiles of all three galaxies. The radii of these breaks are independent of age, and the break strength is decreasing with age in two of the galaxies (NGC4244 and NGC5023). This is consistent with break formation models, that combine a star formation cutoff with radial migration. The differing behavior of IC5052 can be explained by a recent interaction or minor merger.
The Structural History of Massive Disk Galaxies:
We extend the structural analysis of stellar populations with distinct ages to three massive galaxies, NGC891, NGC4565 and NGC7814. While confusion effects due to the high stellar number densities in their central region, and the prominent dust lanes inhibit an detailed analysis of the radial profiles, we can study their vertical structure.
These massive galaxies also have a slower heating than the Milky Way, comparable to the low mass galaxies. This can be traced back to their already thick young populations and thick layers of their interstellar medium.
We do not find a clear separate thick disk in any of these three galaxies; all populations can be described by a single disk plus a S\'ersic bulge/halo component. In contrast to the low mass galaxies, we cannot rule out the presence of thick disks in the massive galaxies, because of the strong influence of the halo, that might hide the possible contribution of the thick disk to the vertical star count profiles. However, the faintness of the possible thick disks still points to problems in the earlier ubiquitous findings of thick disks in external galaxies.
Welfare states and policies have changed greatly over the past decades, mostly characterized by retrenchments in terms of government spending or in terms of restricted access to certain benefits. In the area of family policies, however, a lot of countries have simultaneously expanded provisions and transfers for families. Bringing together the macro analysis of policy variation and household income changes on the micro-level, the main research question of the dissertation is to what extent economic consequences following separation and divorce in families with children have changed between the 1980s and the 2000s in Germany and the United States. The second research question of the dissertation regards the differences in dissolution outcomes between married and cohabiting parents in Germany.
The dissertation thus aims to link institutional regulations of welfare states with the actual income situation of families. To achieve this, a research design was developed that has never been used for the analysis of the economic consequences of family dissolution. For this, the two longest running panel datasets, German Socio-economic Panel (GSOEP) and the US American Panel Study of Income Dynamics (PSID), have been used. The analytic strategy applied to estimate the effects of family dissolution on household income is a difference-in-difference design combined with coarsened exact matching (CEM).
To begin with, the dissertation confirmed many findings of previous research, for example regarding the gender differences in family dissolution outcomes. Mothers experience clearly higher relative income losses and consequently higher risks of poverty than fathers. This finding is universal, that is it holds for both countries, for all time periods observed, and for all measures of economic outcome that were employed. Another confirmed finding is the higher level of welfare state intervention in Germany compared to the United States.
The dissertation also revealed a number of novel findings. The results show that the expansion of family policies in Germany over time has not been accompanied by substantially decreasing income losses for mothers. Though income losses have slightly decreased over time, they have become more persistent during the years following family dissolution. The impact of the German welfare state has meanwhile been quite stable.
American mothers’ income losses took place on a slightly lower level than those of German mothers. Only during the 1980s their relative losses were clearly lower than those of German mothers. And also American mothers did not recover as much from their income losses during the 2000s than they used to during the 1980s. For them, the 1996 welfare reform brought a considerable decrease in welfare state support. Accordingly, the results for American mothers can certainly be described as a shift from public to private provision.
The general finding of previous studies that fathers do not have to suffer income losses, or if at all rather moderate ones compared to mothers, can be confirmed. Nevertheless, both German and US American fathers face a deterioration of the economic consequences of family dissolution over time. German fathers’ relative income changes are still positive though they have decreased over time. One reason for this decrease is the increasing loss of partner earnings following union dissolution. Also among American fathers, income gains still prevail in the year of family dissolution. Two years later, however, they have been facing income losses already since the 1980s which have furthermore increased considerably over time.
Zooming in on Germany, family dissolution outcomes by marital status show negligible differences between cohabiting and married mothers in disposable income, but considerable differences in losses of income before taxes and transfers. It is the impact of the welfare state that equalizes the differences in income losses between these two groups of mothers. For married mothers, losses are not as high in the year of event but they have difficulties to recover from these losses. Without the income buffering of the welfare state, married mothers would, three years after family dissolution, remain with relative income losses double as high as for cohabiting mothers.
Compared to mothers, differences between married and cohabiting fathers are visible in changes of income before as well as after taxes and transfers. The welfare state does not alter the difference between the two groups of fathers. With regard to both income concepts, cohabiting fathers fare worse than married fathers. Cohabiting fathers suffer moderate income losses of disposable income while married fathers experience moderate income gains. Accounting for support payments is decisive for fathers’ income changes. If these payments are not deducted from disposable income, both married and cohabiting fathers experience gains in disposable income following family dissolution.
The main focus of the present thesis was to investigate the stabilization ability of poly(ionic liquid)s (PILs) in several examples as well as develop novel chemical structures and synthetic routes of PILs. The performed research can be specifically divided into three parts that include synthesis and application of hybrid material composed of PIL and cellulose nanofibers (CNFs), thiazolium-containing PILs, and main-chain imidazolium-type PILs.
In the first chapter, a vinylimidazolium-type IL was polymerized in water in the presence of CNFs resulting in the in situ electrostatic grafting of polymeric chains onto the surface of CNFs. The synthesized hybrid material merged advantages of its two components, that is, superior mechanical strength of CNFs and anion dependent solution properties of PILs. In contrast to unmodified CNFs, the hybrid could be stabilized and processed in organic solvents enabling its application as reinforcing agent for porous polyelectrolyte membranes.
In the second part, PILs and ionic polymers containing two types of thiazolium repeating units were synthesized. Such polymers displayed counterion dependent thermal stability and solubility in organic solvents of various dielectric constants. This new class of PILs was tested as stabilizers and phase transfer agents for carbon nanotubes in aqueous and organic media, and as binder materials to disperse electroactive powders and carbon additives in solid electrode in lithium-ion batteries. The incorporation of S and N atoms into the polymeric structures make such PILs also potential precursors for S, N - co-doped carbons.
In the last chapter, reactants originating from biomass were successfully harnessed to synthesize main-chain imidazolium-type PILs. An imidazolium-type diester IL obtained via a modified Debus-Radziszewski reaction underwent transesterification with diol in a polycondensation reaction. This yielded a polyester-type PIL which CO2 sorption properties were investigated. In the next step, the modified Debus-Radziszewski reaction was further applied to synthesize main-chain PILs according to a convenient, one-step protocol, using water as a green solvent and simple organic molecules as reagents. Depending on the structure of the employed diamine, the synthesized PILs after anion exchange showed superior thermal stability with unusually high carbonization yields.
Overall, the outcome of these studies will actively contribute to the current research on PILs by introducing novel PIL chemical structures, improved synthetic routes, and new examples of stabilized materials. The synthesis of main-chain imidazolium-type PILs by a modified Debus-Radziszewski reaction is of a special interest for the future work on porous ionic liquid networks as well as colloidal PIL nanoparticles.
Injection of nanoscale zero-valent iron (nZVI) is an innovative technology for in situ installation of a permeable reactive barrier in the subsurface. Zerovalent iron (ZVI) is highly reactive with chlorinated hydrocarbons (CHCs) and renders them into less harmful substances. Application of nZVI instead of granular ZVI can increase rates of dechlorination of CHCs by orders of magnitude, due to its higher surface area. This approach is still difficult to apply due to fast agglomeration and sedimentation of colloidal suspensions of nZVI, which leads to very short transport distances. To overcome this issue of limited mobility, polyanionic stabilisers are added to increase surface charge and stability of suspensions. In field experiments maximum transport distances of a few metres were achieved. A new approach, which is investigated in this thesis, is enhanced mobility of nZVI by a more mobile carrier colloid. The investigated composite material consists of activated carbon, which is loaded with nZVI.
In this cumulative thesis, transport characteristics of carbon-colloid supported nZVI (c-nZVI) are investigated. Investigations started with column experiments in 40 cm columns filled with various porous media to investigate on physicochemical influences on transport characteristics. The experimental setup was enlarged to a transport experiment in a 1.2-m-sized two-dimensional aquifer tank experiment, which was filled with granular porous media. Further, a field experiment was performed in a natural aquifer system with a targeted transport distance of 5.3 m. Parallel to these investigations, alternative methods for transport observations were investigated by using noninvasive tomographic methods. Experiments using synchrotron radiation and magnetic resonance (MRI) were performed to investigate in situ transport characteristics in a non-destructive way.
Results from column experiments show potentially high mobility under environmental relevant conditions. Addition of mono-and bivalent salts, e.g. more than 0.5 mM/L CaCl2, might decrease mobility. Changes in pH to values below 6 can inhibit mobility at all. Measurements of colloid size show changes in the mean particle size by a factor of ten. Measurements of zeta potential revealed an increase of –62 mV to –82 mV. Results from the 2D-aquifer test system suggest strong particle deposition in the first centimetres and only weak straining in the further travel path and no gravitational influence on particle transport. Straining at the beginning of the travel path in the porous medium was observed with tomographic investigations of transport. MRI experiments revealed similar results to the previous experiments, and observations using synchrotron radiation suggest straining of colloids at pore throats. The potential for high transport distances, which was suggested from laboratory experiments, was confirmed in the field experiment, where the transport distance of 5.3 m was reached by at least 10% of injected nZVI. Altogether, transport distances of the investigated carbon-colloid supported nZVI are higher than published results of traditional nZVI.
Stream water and groundwater are important fresh water resources but their water quality is deteriorated by harmful solutes introduced by human activities. The interface between stream water and the subsurface water is an important zone for retention, transformation and attenuation of these solutes. Streambed structures enhance these processes by increased water and solute exchange across this interface, denoted as hyporheic exchange.
This thesis investigates the influence of hydrological and morphological factors on hyporheic water and solute exchange as well as redox-reactions in fluvial streambed structures on the intermediate scale (10–30m). For this purpose, a three-dimensional numerical modeling approach for coupling stream water flow with porous media flow is used. Multiple steady state stream water flow scenarios over different generic pool-riffle morphologies and a natural in-stream gravel bar are simulated by a computational fluid dynamics code that provides the hydraulic head distribution at the streambed. These heads are subsequently used as the top boundary condition of a reactive transport groundwater model of the subsurface beneath the streambed. Ambient groundwater that naturally interacts with the stream water is considered in scenarios of different magnitudes of downwelling stream water (losing case) and upwelling groundwater (gaining case). Also, the neutral case, where stream stage and groundwater levels are balanced is considered. Transport of oxygen, nitrate and dissolved organic carbon and their reaction by aerobic respiration and denitrification are modeled.
The results show that stream stage and discharge primarily induce hyporheic exchange flux and solute transport with implications for specific residence times and reactions at both the fully and partially submerged structures. Gaining and losing conditions significantly diminish the extent of the hyporheic zone, the water exchange flux, and shorten residence times for both the fully and partially submerged structures. With increasing magnitude of gaining or losing conditions, these metrics exponentially decrease.
Stream water solutes are transported mainly advectively into the hyporheic zone and hence their influx corresponds directly to the infiltrating water flux. Aerobic respiration takes place in the shallow streambed sediments, coinciding to large parts with the extent of the hyporheic exchange flow. Denitrification occurs mainly as a “reactive fringe” surrounding the aerobic zone, where oxygen concentration is low and still a sufficient amount of stream water carbon source is available. The solute consumption rates and the efficiency of the aerobic and anaerobic reactions depend primarily on the available reactive areas and the residence times, which are both controlled by the interplay between hydraulic head distribution at the streambed and the gradients between stream stage and ambient groundwater. Highest solute consumption rates can be expected under neutral conditions, where highest solute flux, longest residence times and largest extent of the hyporheic exchange occur. The results of this thesis show that streambed structures on the intermediate scale have a significant potential to contribute to a net solute turnover that can support a healthy status of the aquatic ecosystem.
In the last decade, the number and dimensions of catastrophic flooding events in the Niger River Basin (NRB) have markedly increased. Despite the devastating impact of the floods on the population and the mainly agriculturally based economy of the riverine nations, awareness of the hazards in policy and science is still low. The urgency of this topic and the existing research deficits are the motivation for the present dissertation.
The thesis is an initial detailed assessment of the increasing flood risk in the NRB. The research strategy is based on four questions regarding (1) features of the change in flood risk, (2) reasons for the change in the flood regime, (3) expected changes of the flood regime given climate and land use changes, and (4) recommendations from previous analysis for reducing the flood risk in the NRB.
The question examining the features of change in the flood regime is answered by means of statistical analysis. Trend, correlation, changepoint, and variance analyses show that, in addition to the factors exposure and vulnerability, the hazard itself has also increased significantly in the NRB, in accordance with the decadal climate pattern of West Africa. The northern arid and semi-arid parts of the NRB are those most affected by the changes.
As potential reasons for the increase in flood magnitudes, climate and land use changes are attributed by means of a hypothesis-testing framework. Two different approaches, based on either data analysis or simulation, lead to similar results, showing that the influence of climatic changes is generally larger compared to that of land use changes. Only in the dry areas of the NRB is the influence of land use changes comparable to that of climatic alterations.
Future changes of the flood regime are evaluated using modelling results. First ensembles of statistically and dynamically downscaled climate models based on different emission scenarios are analyzed. The models agree with a distinct increase in temperature. The precipitation signal, however, is not coherent. The climate scenarios are used to drive an eco-hydrological model. The influence of climatic changes on the flood regime is uncertain due to the unclear precipitation signal. Still, in general, higher flood peaks are expected. In a next step, effects of land use changes are integrated into the model. Different scenarios show that regreening might help to reduce flood peaks. In contrast, an expansion of agriculture might enhance the flood peaks in the NRB. Similarly to the analysis of observed changes in the flood regime, the impacts of climate- and land use changes for the future scenarios are also most severe in the dry areas of the NRB.
In order to answer the final research question, the results of the above analysis are integrated into a range of recommendations for science and policy on how to reduce flood risk in the NRB. The main recommendations include a stronger consideration of the enormous natural climate variability in the NRB and a focus on so called “no-regret” adaptation strategies which account for high uncertainty, as well as a stronger consideration of regional differences. Regarding the prevention and mitigation of catastrophic flooding, the most vulnerable and sensitive areas in the basin, the arid and semi-arid Sahelian and Sudano-Sahelian regions, should be prioritized. Eventually, an active, science-based and science-guided flood policy is recommended. The enormous population growth in the NRB in connection with the expected deterioration of environmental and climatic conditions is likely to enhance the region´s vulnerability to flooding. A smart and sustainable flood policy can help mitigate these negative impacts of flooding on the development of riverine societies in West Africa.
Effect of mass wasting on soil organic carbon storage and coastal erosion in permafrost environments
(2015)
Accelerated permafrost thaw under the warming Arctic climate can have a significant impact on Arctic landscapes. Areas underlain by permafrost store high amounts of soil organic carbon (SOC). Permafrost disturbances may contribute to increased release of carbon dioxide and methane to the atmosphere. Coastal erosion, amplified through a decrease in Arctic sea-ice extent, may also mobilise SOC from permafrost. Large expanses of permafrost affected land are characterised by intense mass-wasting processes such as solifluction, active-layer detachments and retrogressive thaw slumping. Our aim is to assess the influence of mass wasting on SOC storage and coastal erosion.
We studied SOC storage on Herschel Island by analysing active-layer and permafrost samples, and compared non-disturbed sites to those characterised by mass wasting. Mass-wasting sites showed decreased SOC storage and material compaction, whereas sites characterised by material accumulation showed increased storage. The SOC storage on Herschel Island is also significantly correlated to catenary position and other slope characteristics. We estimated SOC storage on Herschel Island to be 34.8 kg C m-2. This is comparable to similar environments in northwest Canada and Alaska.
Coastal erosion was analysed using high resolution digital elevation models (DEMs). Two LIDAR scanning of the Yukon Coast were done in 2012 and 2013. Two DEMs with 1 m horizontal resolution were generated and used to analyse elevation changes along the coast. The results indicate considerable spatial variability in short-term coastline erosion and progradation. The high variability was related to the presence of mass-wasting processes. Erosion and deposition extremes were recorded where the retrogressive thaw slump (RTS) activity was most pronounced. Released sediment can be transported by longshore drift and affects not only the coastal processes in situ but also along adjacent coasts.
We also calculated volumetric coastal erosion for Herschel Island by comparing a stereo-photogrammetrically derived DEM from 2004 with LIDAR DEMs. We compared this volumetric erosion to planimetric erosion, which was based on coastlines digitised from satellite imagery. We found a complex relationship between planimetric and volumetric coastal erosion, which we attribute to frequent occurrence of mass-wasting processes along the coasts. Our results suggest that volumetric erosion corresponds better with environmental forcing and is more suitable for the estimation of organic carbon fluxes than planimetric erosion.
Mass wasting can decrease SOC storage by several mechanisms. Increased aeration following disturbance may increase microbial activity, which accelerates organic matter decomposition. New hydrological conditions that follow the mass wasting event can cause leaching of freshly exposed material. Organic rich material can also be directly removed into the sea or into a lake. On the other hand the accumulation of mobilised material can result in increased SOC storage. Mass-wasting related accumulations of mobilised material can significantly impact coastal erosion in situ or along the adjacent coast by longshore drift. Therefore, the coastline movement observations cannot completely resolve the actual sediment loss due to these temporary accumulations. The predicted increase of mass-wasting activity in the course of Arctic warming may increase SOC mobilisation and coastal erosion induced carbon fluxes.
The standing stock and production of organismal biomass depends strongly on the organisms’ biotic environment, which arises from trophic and non-trophic interactions among them. The trophic interactions between the different groups of organisms form the food web of an ecosystem, with the autotrophic and bacterial production at the basis and potentially several levels of consumers on top of the producers. Feeding interactions can regulate communities either by severe grazing pressure or by shortage of resources or prey production, termed top-down and bottom-up control, respectively. The limitations of all communities conglomerate in the food web regulation, which is subject to abiotic and biotic forcing regimes arising from external and internal constraints. This dissertation presents the effects of alterations in two abiotic, external forcing regimes, terrestrial matter input and long-lasting low temperatures in winter. Diverse methodological approaches, a complex ecosystem model study and the analysis of two whole-lake measurements, were performed to investigate effects for the food web regulation and the resulting consequences at the species, community and ecosystem scale. Thus, all types of organisms, autotrophs and heterotrophs, at all trophic levels were investigated to gain a comprehensive overview of the effects of the two mentioned altered forcing regimes. In addition, an extensive evaluation of the trophic interactions and resulting carbon fluxes along the pelagic and benthic food web was performed to display the efficiencies of the trophic energy transfer within the food webs. All studies were conducted in shallow lakes, which is worldwide the most abundant type of lakes. The specific morphology of shallow lakes allows that the benthic production contributes substantially to the whole-lake production. Further, as shallow lakes are often small they are especially sensitive to both, changes in the input of terrestrial organic matter and the atmospheric temperature. Another characteristic of shallow lakes is their appearance in alternative stable states. They are either in a clear-water or turbid state, where macrophytes and phytoplankton dominate, respectively. Both states can stabilize themselves through various mechanisms.
These two alternative states and stabilizing mechanisms are integrated in the complex ecosystem model PCLake, which was used to investigate the effects of the enhanced terrestrial particulate organic matter (t-POM) input to lakes. The food web regulation was altered by three distinct pathways: (1) Zoobenthos received more food, increased in biomass which favored benthivorous fish and those reduced the available light due to bioturbation. (2) Zooplankton substituted autochthonous organic matter in their diet by suspended t-POM, thus the autochthonous organic matter remaining in the water reduced its transparency. (3) T-POM suspended into the water and reduced directly the available light. As macrophytes are more light-sensitive than phytoplankton they suffered the most from the lower transparency. Consequently, the resilience of the clear-water state was reduced by enhanced t-POM inputs, which makes the turbid state more likely at a given nutrient concentration. In two subsequent winters long-lasting low temperatures and a concurrent long duration of ice coverage was observed which resulted in low overall adult fish biomasses in the two study lakes – Schulzensee and Gollinsee, characterized by having and not having submerged macrophytes, respectively. Before the partial winterkill of fish Schulzensee allowed for a higher proportion of piscivorous fish than Gollinsee. However, the partial winterkill of fish aligned both communities as piscivorous fish are more sensitive to low oxygen concentrations. Young of the year fish benefitted extremely from the absence of adult fish due to lower predation pressure. Therefore, they could exert a strong top-down control on crustaceans, which restructured the entire zooplankton community leading to low crustacean biomasses and a community composition characterized by copepodites and nauplii. As a result, ciliates were released from top-down control, increased to high biomasses compared to lakes of various trophic states and depths and dominated the zooplankton community. While being very abundant in the study lakes and having the highest weight specific grazing rates among the zooplankton, ciliates exerted potentially a strong top-down control on small phytoplankton and particle-attached bacteria. This resulted in a higher proportion of large phytoplankton compared to other lakes. Additionally, the phytoplankton community was evenly distributed presumably due to the numerous fast growing and highly specific ciliate grazers. Although, the pelagic food web was completely restructured after the subsequent partial winterkills of fish, both lakes were resistant to effects of this forcing regime at the ecosystem scale. The consistently high predation pressure on phytoplankton prevented that Schulzensee switched from the clear-water to the turbid state. Further mechanisms, which potentially stabilized the clear-water state, were allelopathic effects by macrophytes and nutrient limitation in summer. The pelagic autotrophic and bacterial production was an order of magnitude more efficient transferred to animal consumers than the respective benthic production, despite the alterations of the food web structure after the partial winterkill of fish. Thus, the compiled mass-balanced whole-lake food webs suggested that the benthic bacterial and autotrophic production, which exceeded those of the pelagic habitat, was not used by animal consumers. This holds even true if the food quality, additional consumers such as ciliates, benthic protozoa and meiobenthos, the pelagic-benthic link and the potential oxygen limitation of macrobenthos were considered. Therefore, low benthic efficiencies suggest that lakes are primarily pelagic systems at least at the animal consumer level.
Overall, this dissertation gives insights into the regulation of organism groups in the pelagic and benthic habitat at each trophic level under two different forcing regimes and displays the efficiency of the carbon transfer in both habitats. The results underline that the alterations of external forcing regimes affect all hierarchical level including the ecosystem.
The main goal of this cumulative thesis is the derivation of surface emissivity data in the infrared from radiance measurements of Venus. Since these data are diagnostic of the chemical composition and grain size of the surface material, they can help to improve knowledge of the planet’s geology. Spectrally resolved images of nightside emissions in the range 1.0-5.1 μm were recently acquired by the InfraRed Mapping channel of the Visible and InfraRed Thermal Imaging Spectrometer (VIRTIS-M-IR) aboard ESA’s Venus EXpress (VEX). Surface and deep atmospheric thermal emissions in this spectral range are strongly obscured by the extremely opaque atmosphere, but three narrow spectral windows at 1.02, 1.10, and 1.18 μm allow the sounding of the surface. Additional windows between 1.3 and 2.6 μm provide information on atmospheric parameters that is required to interpret the surface signals. Quantitative data on surface and atmosphere can be retrieved from the measured spectra by comparing them to simulated spectra. A numerical radiative transfer model is used in this work to simulate the observable radiation as a function of atmospheric, surface, and instrumental parameters. It is a line-by-line model taking into account thermal emissions by surface and atmosphere as well as absorption and multiple scattering by gases and clouds. The VIRTIS-M-IR measurements are first preprocessed to obtain an optimal data basis for the subsequent steps. In this process, a detailed detector responsivity analysis enables the optimization of the data consistency. The measurement data have a relatively low spectral information content, and different parameter vectors can describe the same measured spectrum equally well. A usual method to regularize the retrieval of the wanted parameters from a measured spectrum is to take into account a priori mean values and standard deviations of the parameters to be retrieved. This decreases the probability to obtain unreasonable parameter values. The multi-spectrum retrieval algorithm MSR is developed to additionally consider physically realistic spatial and temporal a priori correlations between retrieval parameters describing different measurements. Neglecting geologic activity, MSR also allows the retrieval of an emissivity map as a parameter vector that is common to several spectrally resolved images that cover the same surface target. Even applying MSR, it is difficult to obtain reliable emissivity maps in absolute values. A detailed retrieval error analysis based on synthetic spectra reveals that this is mainly due to interferences from parameters that cannot be derived from the spectra themselves, but that have to be set to assumed values to enable the radiative transfer simulations. The MSR retrieval of emissivity maps relative to a fixed emissivity is shown to effectively avoid most emissivity retrieval errors. Relative emissivity maps at 1.02, 1.10, and 1.18 μm are finally derived from many VIRTIS-M-IR measurements that cover a surface target at Themis Regio. They are interpreted as spatial variations relative to an assumed emissivity mean of the target. It is verified that the maps are largely independent of the choice of many interfering parameters as well as the utilized measurement data set. These are the first Venus IR emissivity data maps based on a consistent application of a full radiative transfer simulation and a retrieval algorithm that respects a priori information. The maps are sufficiently reliable for future geologic interpretations.
Nowadays, business processes are increasingly supported by IT services that produce massive amounts of event data during process execution. Aiming at a better process understanding and improvement, this event data can be used to analyze processes using process mining techniques. Process models can be automatically discovered and the execution can be checked for conformance to specified behavior. Moreover, existing process models can be enhanced and annotated with valuable information, for example for performance analysis. While the maturity of process mining algorithms is increasing and more tools are entering the market, process mining projects still face the problem of different levels of abstraction when comparing events with modeled business activities. Mapping the recorded events to activities of a given process model is essential for conformance checking, annotation and understanding of process discovery results. Current approaches try to abstract from events in an automated way that does not capture the required domain knowledge to fit business activities. Such techniques can be a good way to quickly reduce complexity in process discovery. Yet, they fail to enable techniques like conformance checking or model annotation, and potentially create misleading process discovery results by not using the known business terminology.
In this thesis, we develop approaches that abstract an event log to the same level that is needed by the business. Typically, this abstraction level is defined by a given process model. Thus, the goal of this thesis is to match events from an event log to activities in a given process model. To accomplish this goal, behavioral and linguistic aspects of process models and event logs as well as domain knowledge captured in existing process documentation are taken into account to build semiautomatic matching approaches. The approaches establish a pre--processing for every available process mining technique that produces or annotates a process model, thereby reducing the manual effort for process analysts. While each of the presented approaches can be used in isolation, we also introduce a general framework for the integration of different matching approaches.
The approaches have been evaluated in case studies with industry and using a large industry process model collection and simulated event logs. The evaluation demonstrates the effectiveness and efficiency of the approaches and their robustness towards nonconforming execution logs.
Methicillin resistant Staphylococcus aureus (MRSA) is one of the most important antibiotic-resistant pathogens in hospitals and the community. Recently, a new generation of MRSA, the so called livestock associated (LA) MRSA, has emerged occupying food producing animals as a new niche. LA-MRSA can be regularly isolated from economically important live-stock species including corresponding meats. The present thesis takes a methodological approach to confirm the hypothesis that LA-MRSA are transmitted along the pork, poultry and beef production chain from animals at farm to meat on consumers` table. Therefore two new concepts were developed, adapted to differing data sets.
A mathematical model of the pig slaughter process was developed which simulates the change in MRSA carcass prevalence during slaughter with special emphasis on identifying critical process steps for MRSA transmission. Based on prevalences as sole input variables the model framework is able to estimate the average value range of both the MRSA elimination and contamination rate of each of the slaughter steps. These rates are then used to set up a Monte Carlo simulation of the slaughter process chain. The model concludes that regardless of the initial extent of MRSA contamination low outcome prevalences ranging between 0.15 and 1.15 % can be achieved among carcasses at the end of slaughter. Thus, the model demonstrates that the standard procedure of pig slaughtering in principle includes process steps with the capacity to limit MRSA cross contamination. Scalding and singeing were identified as critical process steps for a significant reduction of superficial MRSA contamination.
In the course of the German national monitoring program for zoonotic agents MRSA prevalence and typing data are regularly collected covering the key steps of different food production chains. A new statistical approach has been proposed for analyzing this cross sectional set of MRSA data with regard to show potential farm to fork transmission. For this purpose, chi squared statistics was combined with the calculation of the Czekanowski similarity index to compare the distributions of strain specific characteristics between the samples from farm, carcasses after slaughter and meat at retail. The method was implemented on the turkey and veal production chains and the consistently high degrees of similarity which have been revealed between all sample pairs indicate MRSA transmission along the chain.
As the proposed methods are not specific to process chains or pathogens they offer a broad field of application and extend the spectrum of methods for bacterial transmission assessment.
The continuously increasing demand for rare earth elements in technical components of modern technologies, brings the detection of new deposits closer into the focus of global exploration. One promising method to globally map important deposits might be remote sensing, since it has been used for a wide range of mineral mapping in the past. This doctoral thesis investigates the capacity of hyperspectral remote sensing for the detection of rare earth element deposits. The definition and the realization of a fundamental database on the spectral characteristics of rare earth oxides, rare earth metals and rare earth element bearing materials formed the basis of this thesis. To investigate these characteristics in the field, hyperspectral images of four outcrops in Fen Complex, Norway, were collected in the near-field. A new methodology (named REEMAP) was developed to delineate rare earth element enriched zones. The main steps of REEMAP are: 1) multitemporal weighted averaging of multiple images covering the sample area; 2) sharpening the rare earth related signals using a Gaussian high pass deconvolution technique that is calibrated on the standard deviation of a Gaussian-bell shaped curve that represents by the full width of half maxima of the target absorption band; 3) mathematical modeling of the target absorption band and highlighting of rare earth elements. REEMAP was further adapted to different hyperspectral sensors (EO-1 Hyperion and EnMAP) and a new test site (Lofdal, Namibia). Additionally, the hyperspectral signatures of associated minerals were investigated to serve as proxy for the host rocks. Finally, the capacity and limitations of spectroscopic rare earth element detection approaches in general and of the REEMAP approach specifically were investigated and discussed. One result of this doctoral thesis is that eight rare earth oxides show robust absorption bands and, therefore, can be used for hyperspectral detection methods. Additionally, the spectral signatures of iron oxides, iron-bearing sulfates, calcite and kaolinite can be used to detect metasomatic alteration zones and highlight the ore zone. One of the key results of this doctoral work is the developed REEMAP approach, which can be applied from near-field to space. The REEMAP approach enables rare earth element mapping especially for noisy images. Limiting factors are a low signal to noise ratio, a reduced spectral resolution, overlaying materials, atmospheric absorption residuals and non-optimal illumination conditions. Another key result of this doctoral thesis is the finding that the future hyperspectral EnMAP satellite (with its currently published specifications, June 2015) will be theoretically capable to detect absorption bands of erbium, dysprosium, holmium, neodymium and europium, thulium and samarium. This thesis presents a new methodology REEMAP that enables a spatially wide and rapid hyperspectral detection of rare earth elements in order to meet the demand for fast, extensive and efficient rare earth exploration (from near-field to space).
Analysis and modeling of transient earthquake patterns and their dependence on local stress regimes
(2015)
Investigations in the field of earthquake triggering and associated interactions, which includes aftershock triggering as well as induced seismicity, is important for seismic hazard assessment due to earthquakes destructive power. One of the approaches to study earthquake triggering and their interactions is the use of statistical earthquake models, which are based on knowledge of the basic seismicity properties, in particular, the magnitude distribution and spatiotemporal properties of the triggered events.
In my PhD thesis I focus on some specific aspects of aftershock properties, namely, the relative seismic moment release of the aftershocks with respect to the mainshocks; the spatial correlation between aftershock occurrence and fault deformation; and on the influence of aseismic transients on the aftershock parameter estimation. For the analysis of aftershock sequences I choose a statistical approach, in particular, the well known Epidemic Type Aftershock Sequence (ETAS) model, which accounts for the input of background and triggered seismicity. For my specific purposes, I develop two ETAS model modifications in collaboration with Sebastian Hainzl. By means of this approach, I estimate the statistical aftershock parameters and performed simulations of aftershock sequences as well.
In the case of seismic moment release of aftershocks, I focus on the ratio of cumulative seismic moment release with respect to the mainshocks. Specifically, I investigate the ratio with respect to the focal mechanism of the mainshock and estimate an effective magnitude, which represents the cumulative aftershock energy (similar to Bath's law, which defines the average difference between mainshock and the largest aftershock magnitudes). Furthermore, I compare the observed seismic moment ratios with the results of the ETAS simulations. In particular, I test a restricted ETAS (RETAS) model which is based on results of a clock advanced model and static stress triggering.
To analyze spatial variations of triggering parameters I focus in my second approach on the aftershock occurrence triggered by large mainshocks and the study of the aftershock parameter distribution and their spatial correlation with the coseismic/postseismic slip and interseismic locking. To invert the aftershock parameters I improve the modified ETAS (m-ETAS) model, which is able to take the extension of the mainshock rupture into account. I compare the results obtained by the classical approach with the output of the m-ETAS model.
My third approach is concerned with the temporal clustering of seismicity, which might not only be related to earthquake-earthquake interactions, but also to a time-dependent background rate, potentially biasing the parameter estimations. Thus, my coauthors and I also applied a modification of the ETAS model, which is able to take into account time-dependent background activity. It can be applicable for two different cases: when an aftershock catalog has a temporal incompleteness or when the background seismicity rate changes with time, due to presence of aseismic forces.
An essential part of any research is the testing of the developed models using observational data sets, which are appropriate for the particular study case. Therefore, in the case of seismic moment release I use the global seismicity catalog. For the spatial distribution of triggering parameters I exploit two aftershock sequences of the Mw8.8 2010 Maule (Chile) and Mw 9.0 2011 Tohoku (Japan) mainshocks. In addition, I use published geodetic slip models of different authors. To test our ability to detect aseismic transients my coauthors and I use the data sets from Western Bohemia (Central Europe) and California.
Our results indicate that:
(1) the seismic moment of aftershocks with respect to mainshocks depends on the static stress changes and is maximal for the normal, intermediate for thrust and minimal for strike-slip stress regimes, where the RETAS model shows a good correspondence with the results;
(2) The spatial distribution of aftershock parameters, obtained by the m-ETAS model, shows anomalous values in areas of reactivated crustal fault systems. In addition, the aftershock density is found to be correlated with coseismic slip gradient, afterslip, interseismic coupling and b-values. Aftershock seismic moment is positively correlated with the areas of maximum coseismic slip and interseismically locked areas. These correlations might be related to the stress level or to material properties variations in space;
(3) Ignoring aseismic transient forcing or temporal catalog incompleteness can lead to the significant under- or overestimation of the underlying trigger parameters. In the case when a catalog is complete, this method helps to identify aseismic sources.
By perturbing the differential of a (cochain-)complex by "small" operators, one obtains what is referred to as quasicomplexes, i.e. a sequence whose curvature is not equal to zero in general. In this situation the cohomology is no longer defined. Note that it depends on the structure of the underlying spaces whether or not an operator is "small." This leads to a magical mix of perturbation and regularisation theory. In the general setting of Hilbert spaces compact operators are "small." In order to develop this theory, many elements of diverse mathematical disciplines, such as functional analysis, differential geometry, partial differential equation, homological algebra and topology have to be combined. All essential basics are summarised in the first chapter of this thesis. This contains classical elements of index theory, such as Fredholm operators, elliptic pseudodifferential operators and characteristic classes. Moreover we study the de Rham complex and introduce Sobolev spaces of arbitrary order as well as the concept of operator ideals. In the second chapter, the abstract theory of (Fredholm) quasicomplexes of Hilbert spaces will be developed. From the very beginning we will consider quasicomplexes with curvature in an ideal class. We introduce the Euler characteristic, the cone of a quasiendomorphism and the Lefschetz number. In particular, we generalise Euler's identity, which will allow us to develop the Lefschetz theory on nonseparable Hilbert spaces. Finally, in the third chapter the abstract theory will be applied to elliptic quasicomplexes with pseudodifferential operators of arbitrary order. We will show that the Atiyah-Singer index formula holds true for those objects and, as an example, we will compute the Euler characteristic of the connection quasicomplex. In addition to this we introduce geometric quasiendomorphisms and prove a generalisation of the Lefschetz fixed point theorem of Atiyah and Bott.
A main limitation in the field of flood hydrology is the short time period covered by instrumental flood time series, rarely exceeding more than 50 to 100 years. However, climate variability acts on short to millennial time scales and identifying causal linkages to extreme hydrological events requires longer datasets. To extend instrumental flood time series back in time, natural geoarchives are increasingly explored as flood recorders. Therefore, annually laminated (varved) lake sediments seem to be the most suitable archives since (i) lake basins act as natural sediment traps in the landscape continuously recording land surface processes including floods and (ii) individual flood events are preserved as detrital layers intercalated in the varved sediment sequence and can be dated with seasonal precision by varve counting.
The main goal of this thesis is to improve the understanding about hydrological and sedimentological processes leading to the formation of detrital flood layers and therewith to contribute to an improved interpretation of lake sediments as natural flood archives. This goal was achieved in two ways: first, by comparing detrital layers in sediments of two dissimilar peri-Alpine lakes, Lago Maggiore in Northern Italy and Mondsee in Upper Austria, with local instrumental flood data and, second, by tracking detrital layer formation during floods by a combined hydro-sedimentary monitoring network at Lake Mondsee spanning from the rain fall to the deposition of detrital sediment at the lake floor.
Successions of sub-millimetre to 17 mm thick detrital layers were detected in sub-recent lake sediments of the Pallanza Basin in the western part of Lago Maggiore (23 detrital layers) and Lake Mondsee (23 detrital layers) by combining microfacies and high-resolution micro X-ray fluorescence scanning techniques (µ-XRF). The detrital layer records were dated by detailed intra-basin correlation to a previously dated core sequence in Lago Maggiore and varve counting in Mondsee. The intra-basin correlation of detrital layers between five sediment cores in Lago Maggiore and 13 sediment cores in Mondsee allowed distinguishing river runoff events from local erosion. Moreover, characteristic spatial distribution patterns of detrital flood layers revealed different depositional processes in the two dissimilar lakes, underflows in Lago Maggiore as well as under- and interflows in Mondsee. Comparisons with runoff data of the main tributary streams, the Toce River at Lago Maggiore and the Griesler Ache at Mondsee, revealed empirical runoff thresholds above which the deposition of a detrital layer becomes likely. Whereas this threshold is the same for the whole Pallanza Basin in Lago Maggiore (600 m3s-1 daily runoff), it varies within Lake Mondsee. At proximal locations close to the river inflow detrital layer deposition requires floods exceeding a daily runoff of 40 m3s-1, whereas at a location 2 km more distal an hourly runoff of 80 m3s-1 and at least 2 days with runoff above 40 m3s-1 are necessary. A relation between the thickness of individual deposits and runoff amplitude of the triggering events is apparent for both lakes but is obviously further influenced by variable influx and lake internal distribution of detrital sediment.
To investigate processes of flood layer formation in lake sediments, hydro-sedimentary dynamics in Lake Mondsee and its main tributary stream, Griesler Ache, were monitored from January 2011 to December 2013. Precipitation, discharge and turbidity were recorded continuously at the rivers outlet to the lake and compared to sediment fluxes trapped close to the lake bottom on a basis of three to twelve days and on a monthly basis in three different water depths at two locations in the lake basin, in a distance of 0.9 (proximal) and 2.8 km (distal) to the Griesler Ache inflow. Within the three-year observation period, 26 river floods of different amplitude (10-110 m3s-1) were recorded resulting in variable sediment fluxes to the lake (4-760 g m-2d-1). Vertical and lateral variations in flood-related sedimentation during the largest floods indicate that interflows are the main processes of lake internal sediment transport in Lake Mondsee. The comparison of hydrological and sedimentological data revealed (i) a rapid sedimentation within three days after the peak runoff in the proximal and within six to ten days in the distal lake basin, (ii) empirical runoff thresholds for triggering sediment flux at the lake floor increasing from the proximal (20 m3s-1) to the distal lake basin (30 m3s-1) and (iii) factors controlling the amount of detrital sediment deposition at a certain location in the lake basin. The total influx of detrital sediment is mainly driven by runoff amplitude, catchment sediment availability and episodic sediment input by local sediment sources. A further role plays the lake internal sediment distribution which is not the same for each event but is favoured by flood duration and the existence of a thermocline and, therewith, the season in which a flood occurred.
In summary, the studies reveal a high sensitivity of lake sediments to flood events of different intensity. Certain runoff amplitudes are required to supply enough detrital material to form a visible detrital layer at the lake floor. Reasonable are positive feedback mechanisms between rainfall, runoff, erosion, fluvial sediment transport capacity and lake internal sediment distribution. Therefore, runoff thresholds for detrital layer formation are site-specific due to different lake-catchment characteristics. However, the studies also reveal that flood amplitude is not the only control for the amount of deposited sediment at a certain location in the lake basin even for the strongest flood events. The sediment deposition is rather influenced by a complex interaction of catchment and in-lake processes. This means that the coring location within a lake basin strongly determines the significance of a flood layer record. Moreover, the results show that while lake sediments provide ideal archives for reconstructing flood frequencies, the reconstruction of flood amplitudes is a more complex issue and requires detailed knowledge about relevant catchment and in-lake sediment transport and depositional processes.
The non-linear behaviour of the atmospheric dynamics is not well understood and makes the evaluation and usage of regional climate models (RCMs) difficult. Due to these non-linearities, chaos and internal variability (IV) within the RCMs are induced, leading to a sensitivity of RCMs to their initial conditions (IC). The IV is the ability of RCMs to realise different solutions of simulations that differ in their IC, but have the same lower and lateral boundary conditions (LBC), hence can be defined as the across-member spread between the ensemble members.
For the investigation of the IV and the dynamical and diabatic contributions generating the IV four ensembles of RCM simulations are performed with the atmospheric regional model HIRHAM5. The integration area is the Arctic and each ensemble consists of 20 members. The ensembles cover the time period from July to September for the years 2006, 2007, 2009 and 2012. The ensemble members have the same LBC and differ in their IC only. The different IC are arranged by an initialisation time that shifts successively by six hours. Within each ensemble the first simulation starts on 1st July at 00 UTC and the last simulation starts on 5th July at 18 UTC and each simulation runs until 30th September. The analysed time period ranges from 6th July to 30th September, the time period that is covered by all ensemble members. The model runs without any nudging to allow a free development of each simulation to get the full internal variability within the HIRHAM5.
As a measure of the model generated IV, the across-member standard deviation and the across-member variance is used and the dynamical and diabatic processes influencing the IV are estimated by applying a diagnostic budget study for the IV tendency of the potential temperature developed by Nikiema and Laprise [2010] and Nikiema and Laprise [2011]. The diagnostic budget study is based on the first law of thermodynamics for potential temperature and the mass-continuity equation. The resulting budget equation reveals seven contributions to the potential temperature IV tendency.
As a first study, this work analyses the IV within the HIRHAM5. Therefore, atmospheric circulation parameters and the potential temperature for all four ensemble years are investigated. Similar to previous studies, the IV fluctuates strongly in time. Further, due to the fact that all ensemble members are forced with the same LBC, the IV depends on the vertical level within the troposphere, with high values in the lower troposphere and at 500 hPa and low values in the upper troposphere and at the surface. By the same reason, the spatial distribution shows low values of IV at the boundaries of the model domain.
The diagnostic budget study for the IV tendency of potential temperature reveals that the seven contributions fluctuate in time like the IV. However, the individual terms reach different absolute magnitudes. The budget study identifies the horizontal and vertical ‘baroclinic’ terms as the main contributors to the IV tendency, with the horizontal ‘baroclinic’ term producing and the vertical ‘baroclinic’ term reducing the IV. The other terms fluctuate around zero, because they are small in general or are balanced due to the domain average.
The comparison of the results obtained for the four different ensembles (summers 2006, 2007, 2009 and 2012) reveals that on average the findings for each ensemble are quite similar concerning the magnitude and the general pattern of IV and its contributions. However, near the surface a weaker IV is produced with decreasing sea ice extent. This is caused by a smaller impact of the horizontal 'baroclinic' term over some regions and by the changing diabatic processes, particularly a more intense reducing tendency of the IV due to condensative heating. However, it has to be emphasised that the behaviour of the IV and its dynamical and diabatic contributions are influenced mainly by complex atmospheric feedbacks and large-scale processes and not by the sea ice distribution.
Additionally, a comparison with a second RCM covering the Arctic and using the same LBCs and IC is performed. For both models very similar results concerning the IV and its dynamical and diabatic contributions are found. Hence, this investigation leads to the conclusion that the IV is a natural phenomenon and is independent from the applied RCM.