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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.
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.
Learners' Little Helper
(2015)
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.
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.
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.
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.
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.
Spectral fingerprinting
(2015)
Current research on runoff and erosion processes, as well as an increasing demand for sustainable watershed management emphasize the need for an improved understanding of sediment dynamics. This involves the accurate assessment of erosion rates and sediment transfer, yield and origin. A variety of methods exist to capture these processes at the catchment scale. Among these, sediment fingerprinting, a technique to trace back the origin of sediment, has attracted increasing attention by the scientific community in recent years. It is a two-step procedure, based on the fundamental assumptions that potential sources of sediment can be reliably discriminated based on a set of characteristic ‘fingerprint’ properties, and that a comparison of source and sediment fingerprints allows to quantify the relative contribution of each source.
This thesis aims at further assessing the potential of spectroscopy to assist and improve the sediment fingerprinting technique. Specifically, this work focuses on (1) whether potential sediment sources can be reliably identified based on spectral features (‘fingerprints’), whether (2) these spectral fingerprints permit the quantification of relative source contribution, and whether (3) in situ derived source information is sufficient for this purpose. Furthermore, sediment fingerprinting using spectral information is applied in a study catchment to (4) identify major sources and observe how relative source contributions change between and within individual flood events. And finally, (5) spectral fingerprinting results are compared and combined with simultaneous sediment flux measurements to study sediment origin, transport and storage behaviour.
For the sediment fingerprinting approach, soil samples were collected from potential sediment sources within the Isábena catchment, a meso-scale basin in the central Spanish Pyrenees. Undisturbed samples of the upper soil layer were measured in situ using an ASD spectroradiometer and subsequently sampled for measurements in the laboratory. Suspended sediment was sampled automatically by means of ISCO samplers at the catchment as well as at the five major subcatchment outlets during flood events, and stored fine sediment from the channel bed was collected from 14 cross-sections along the main river. Artificial mixtures of known contributions were produced from source soil samples. Then, all source, sediment and mixture samples were dried and spectrally measured in the laboratory. Subsequently, colour coefficients and physically based features with relation to organic carbon, iron oxide, clay content and carbonate, were calculated from all in situ and laboratory spectra. Spectral parameters passing a number of prerequisite tests were submitted to principal component analyses to study natural clustering of samples, discriminant function analyses to observe source differentiation accuracy, and a mixing model for source contribution assessment. In addition, annual as well as flood event based suspended sediment fluxes from the catchment and its subcatchments were calculated from rainfall, water discharge and suspended sediment concentration measurements using rating curves and Quantile Regression Forests. Results of sediment flux monitoring were interpreted individually with respect to storage behaviour, compared to fingerprinting source ascriptions and combined with fingerprinting to assess their joint explanatory potential.
In response to the key questions of this work, (1) three source types (land use) and five spatial sources (subcatchments) could be reliably discriminated based on spectral fingerprints. The artificial mixture experiment revealed that while (2) laboratory parameters permitted source contribution assessment, (3) the use of in situ derived information was insufficient. Apparently, high discrimination accuracy does not necessarily imply good quantification results. When applied to suspended sediment samples of the catchment outlet, the spectral fingerprinting approach was able to (4) quantify the major sediment sources: badlands and the Villacarli subcatchment, respectively, were identified as main contributors, which is consistent with field observations and previous studies. Thereby, source contribution was found to vary both, within and between individual flood events. Also sediment flux was found to vary considerably, annually as well as seasonally and on flood event base. Storage was confirmed to play an important role in the sediment dynamics of the studied catchment, whereas floods with lower total sediment yield tend to deposit and floods with higher yield rather remove material from the channel bed. Finally, a comparison of flux measurements with fingerprinting results highlighted the fact that (5) immediate transport from sources to the catchment outlet cannot be assumed. A combination of the two methods revealed different aspects of sediment dynamics that none of the techniques could have uncovered individually.
In summary, spectral properties provide a fast, non-destructive, and cost-efficient means to discriminate and quantify sediment sources, whereas, unfortunately, straight-forward in situ collected source information is insufficient for the approach. Mixture modelling using artificial mixtures permits valuable insights into the capabilities and limitations of the method and similar experiments are strongly recommended to be performed in the future. Furthermore, a combination of techniques such as e.g. (spectral) sediment fingerprinting and sediment flux monitoring can provide comprehensive understanding of sediment dynamics.
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.
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).
The sea level rise induced intensification of coastal floods is a serious threat to many regions in proximity to the ocean. Although severe flood events are rare they can entail enormous damage costs, especially when built-up areas are inundated. Fortunately, the mean sea level advances slowly and there is enough time for society to adapt to the changing environment. Most commonly, this is achieved by the construction or reinforcement of flood defence measures such as dykes or sea walls but also land use and disaster management are widely discussed options. Overall, albeit the projection of sea level rise impacts and the elaboration of adequate response strategies is amongst the most prominent topics in climate impact research, global damage estimates are vague and mostly rely on the same assessment models. The thesis at hand contributes to this issue by presenting a distinctive approach which facilitates large scale assessments as well as the comparability of results across regions. Moreover, we aim to improve the general understanding of the interplay between mean sea level rise, adaptation, and coastal flood damage.
Our undertaking is based on two basic building blocks. Firstly, we make use of macroscopic flood-damage functions, i.e. damage functions that provide the total monetary damage within a delineated region (e.g. a city) caused by a flood of certain magnitude. After introducing a systematic methodology for the automatised derivation of such functions, we apply it to a total of 140 European cities and obtain a large set of damage curves utilisable for individual as well as comparative damage assessments. By scrutinising the resulting curves, we are further able to characterise the slope of the damage functions by means of a functional model. The proposed function has in general a sigmoidal shape but exhibits a power law increase for the relevant range of flood levels and we detect an average exponent of 3.4 for the considered cities. This finding represents an essential input for subsequent elaborations on the general interrelations of involved quantities.
The second basic element of this work is extreme value theory which is employed to characterise the occurrence of flood events and in conjunction with a damage function provides the probability distribution of the annual damage in the area under study. The resulting approach is highly flexible as it assumes non-stationarity in all relevant parameters and can be easily applied to arbitrary regions, sea level, and adaptation scenarios. For instance, we find a doubling of expected flood damage in the city of Copenhagen for a rise in mean sea levels of only 11 cm. By following more general considerations, we succeed in deducing surprisingly simple functional expressions to describe the damage behaviour in a given region for varying mean sea levels, changing storm intensities, and supposed protection levels. We are thus able to project future flood damage by means of a reduced set of parameters, namely the aforementioned damage function exponent and the extreme value parameters. Similar examinations are carried out to quantify the aleatory uncertainty involved in these projections. In this regard, a decrease of (relative) uncertainty with rising mean sea levels is detected. Beyond that, we demonstrate how potential adaptation measures can be assessed in terms of a Cost-Benefit Analysis. This is exemplified by the Danish case study of Kalundborg, where amortisation times for a planned investment are estimated for several sea level scenarios and discount rates.
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.
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.
Water resources from Central Asia’s mountain regions have a high relevance for the water supply of the water scarce lowlands. A good understanding of the water cycle in these mountain regions is therefore needed to develop water management strategies. Hydrological modeling helps to improve our knowledge of the regional water cycle, and it can be used to gain a better understanding of past changes or estimate future hydrologic changes in view of projected changes in climate. However, due to the scarcity of hydrometeorological data, hydrological modeling for mountain regions in Central Asia involves large uncertainties.
Addressing this problem, the first aim of this thesis was to develop hydrological modeling approaches that can increase the credibility of hydrological models in data sparse mountain regions. This was achieved by using additional data from remote sensing and atmospheric modeling. It was investigated whether spatial patterns from downscaled reanalysis data can be used for the interpolation of station-based precipitation data. This approach was compared to other precipitation estimates using a hydrologic evaluation based on hydrological modeling and a comparison of simulated and observed discharge, which demonstrated a generally good performance of this method. The study further investigated the value of satellite-derived snow cover data for model calibration. Trade-offs of good model performance in terms of discharge and snow cover were explicitly evaluated using a multiobjective optimization algorithm, and the results were contrasted with single-objective calibration and Monte Carlo simulations. The study clearly shows that the additional use of snow cover data improved the internal consistency of the hydrological model. In this context, it was further investigated for the first time how many snow cover scenes were required for hydrological model calibration.
The second aim of this thesis was the application of the hydrological model in order to investigate the causes of observed streamflow increases in two headwater catchments of the Tarim River over the recent decades. This simulation-based approach for trend attribution was complemented by a data-based approach. The hydrological model was calibrated to discharge and glacier mass balance data and considered changes in glacier geometry over time. The results show that in the catchment with a lower glacierization, increasing precipitation and temperature both contributed to the streamflow increases, while in the catchment with a stronger glacierization, increasing temperatures were identified as the dominant driver.
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.
How does perceptual experience make us knowledgeable? This book argues that the answer lies in the nature of perceptual experience: this experience involves conceptual capacities and is a relation between perceiver and world. The author develops her position via a critical examination of conceptualist and relationist theories of perception. A discussion of recent work in vision science rounds up this contribution to the philosophy of perception.
This dissertation addresses the question of how linguistic structures can be represented in working memory. We propose a memory-based computational model that derives offline and online complexity profiles in terms of a top-down parser for minimalist grammars (Stabler, 2011). The complexity metric reflects the amount of time an item is stored in memory. The presented architecture links grammatical representations stored in memory directly to the cognitive behavior by deriving predictions about sentence processing difficulty.
Results from five different sentence comprehension experiments were used to evaluate the model's assumptions about memory limitations. The predictions of the complexity metric were compared to the locality (integration and storage) cost metric of Dependency Locality Theory (Gibson, 2000). Both metrics make comparable offline and online predictions for four of the five phenomena. The key difference between the two metrics is that the proposed complexity metric accounts for the structural complexity of intervening material. In contrast, DLT's integration cost metric considers the number of discourse referents, not the syntactic structural complexity.
We conclude that the syntactic analysis plays a significant role in memory requirements of parsing. An incremental top-down parser based on a grammar formalism easily computes offline and online complexity profiles, which can be used to derive predictions about sentence processing difficulty.
Physical fitness is an important marker of health that enables people to carry out activities of daily living with vigour and alertness but without undue fatigue and with sufficient reserve to enjoy active leisure pursuits and to meet unforeseen emergencies. Especially, due to scientific findings that the onset of civilization diseases (e.g., obesity, cardiovascular disease) begins in childhood and that physical fitness tracks (at least) into young adulthood, the regular monitoring and promotion of physical fitness in children is risen up to a public health issue. In relation to the evaluation of a child’s physical fitness over time (i.e., development) the use of longitudinally-based percentile values is of particular interest due to their underlined dedication of true physical fitness development within subjects (i.e., individual changes in timing and tempo of growth and maturation). Besides its genetic determination (e.g., sex, body height), physical fitness is influenced by factors that refer to children’s environment and behaviour. For instance, disparities in physical fitness according to children’s living area are frequently reported concerning the fact that living in rural areas as compared to urban areas seems to be more favourable for children’s physical fitness. In addition, cross-sectional studies found higher fitness values in children participating in sports clubs as compared to non-participants. However, up to date, the observed associations between both (i.e., living area and sports club participating) and children’s physical fitness are unresolved concerning a long-term effect. In addition, social inequality as determined by the socioeconomic status (SES) extends through many areas of children’s life. While evidence indicates that the SES is inversely related to various indices of child’s daily life and behaviour like educational success, nutritional habits, and sedentary- and physical activity behaviour, a potential relationship between child’s physical fitness and the SES is hardly investigated and indicated inconsistent results.
The present thesis addressed three objectives: (1) to generate physical fitness percentiles for 9- to 12- year-old boys and girls using a longitudinal approach and to analyse the age- and sex-specific development of physical fitness, (2) to investigate the long-term effect of living area and sports club participation on physical fitness in third- to sixth-grade primary school students, and (3) to examine associations between the SES and physical fitness in a large and representative (i.e., for a German federal state) sample of third grade primary school students.
Methods
(i/ii) Healthy third graders were followed over four consecutive years (up to grade 6), including annually assessment of physical fitness and parental questionnaire (i.e., status of sports club participation and living area). Six tests were conducted to estimate various components of physical fitness: speed (50-m sprint test), upper body muscular power (1-kg ball push test), lower body muscular power (triple hop test), flexibility (stand-and-reach test), agility (star agility run test), and cardiorespiratory fitness (CRF) (9-min run test). (iii) Within a cross-sectional study (i.e., third objective), physical fitness of third graders was assessed by six physical fitness tests including: speed (20-m sprint test), upper body muscular power (1-kg ball push test), lower body muscular power (standing long jump [SLJ] test), flexibility (stand-and-reach test), agility (star agility run test), and CRF (6-min run test). By means of questionnaire, students reported their status of organized sports participation (OSP).
Results
(i) With respect to percentiles of physical fitness development, test performances increased in boys and girls from age 9 to 12, except for males’ flexibility (i.e., stable performance over time). Girls revealed significantly better performance in flexibility, whereas boys scored significantly higher in the remaining physical fitness tests. In girls as compared to boys, physical fitness development was slightly faster for upper body muscular power but substantially faster for flexibility. Generated physical fitness percentile curves indicated a timed and capacity-specific physical fitness development (curvilinear) for upper body muscular power, agility, and CRF. (ii) Concerning the effect of living area and sports club participation on physical fitness development, children living in urban areas showed a significantly faster performance development in physical fitness components of upper and lower body muscular power as compared to peers from rural areas. The same direction was noted as a trend in CRF. Additionally, children that regularly participated in a sports club, when compared to those that not continuously participated in a sports club demonstrated a significantly faster performance development in lower body muscular power. A trend of faster performance development in sports club participants occurred in CRF too. (iii) Regarding the association of SES with physical fitness, the percentage of third graders that achieved a high physical fitness level in lower body muscular power and CRF was significantly higher in students attending schools in communities with high SES as compared to middle and low SES, irrespective of sex. Similar, students from the high SES-group performed significantly better in lower body muscular power and CRF than students from the middle and/or the low SES-group.
Conclusion
(i) The generated percentile values provide an objective tool to estimate childrenʼs physical fitness within the frame of physical education (e.g., age- and sex-specific grading of motor performance) and further to detect children with specific fitness characteristics (low fit or high fit) that may be indicative for the necessity of preventive health promotion or long term athlete development. (ii) It is essential to consider variables of different domains (e.g., environment and behavior) in order to improve knowledge of potential factors which influence physical fitness during childhood. In this regard, the present thesis provide a first input to clarify the causality of living area and sports club participation on physical fitness development in school-aged children. Living in urban areas as well as a regular participation in sports clubs positively affected children´s physical fitness development (i.e., muscular power and CRF). Herein, sports club participation seems to be a key factor within the relationship between living area and physical fitness. (iii) The findings of the present thesis imply that attending schools in communities with high SES refers to better performance in specific physical fitness test items (i.e., muscular power, CRF) in third graders. Extra-curricular physical education classes may represent an important equalizing factor for physical activity opportunities in children of different SES backgrounds. In regard to strong evidence of a positive relationship between physical fitness - in particular muscular fitness/ CRF - and health, more emphasis should be laid on establishing sports clubs and extra-curricular physical education classes as an easy and attractive means to promote fitness-, and hence health- enhancing daily physical activity for all children (i.e. public health approach).
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.
Effects of a novel non-steroidal mineralocorticoid receptor antagonist on cardiac hypertrophy
(2015)
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.
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.
Lost in a liminal space?
(2015)
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.
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.