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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.
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.
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.
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.
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.
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.
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.
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.
This thesis investigates the application of polyelectrolyte multilayers in plasmonics and picosecond acoustics. The observed samples were fabricated by the spin-assisted layer-by-layer deposition technique that allowed a precise tuning of layer thickness in the range of few nanometers.
The first field of interest deals with the interaction of light-induced localized surface plasmons (LSP) of rod-shaped gold nanoparticles with the particles' environment. The environment consists of an air phase and a phase of polyelectrolytes, whose ratio affects the spectral position of the LSP resonance.
Measured UV-VIS spectra showed the shift of the LSP absorption peak as a function of the cover layer thickness of the particles. The data are modeled using an average dielectric function instead of the dielectric functions of air and polyelectrolytes. In addition using a measured dielectric function of the gold nanoparticles, the position of the LSP absorption peak could be simulated with good agreement to the data.
The analytic model helps to understand the optical properties of metal nanoparticles in an inhomogeneous environment.
The second part of this work discusses the applicability of PAzo/PAH and dye-doped PSS/PAH polyelectrolyte multilayers as transducers to generate hypersound pulses. The generated strain pulses were detected by time-domain Brillouin scattering (TDBS) using a pump-probe laser setup. Transducer layers made of polyelectrolytes were compared qualitatively to common aluminum transducers in terms of measured TDBS signal amplitude, degradation due to laser excitation, and sample preparation.
The measurements proved that fast and easy prepared polyelectrolyte transducers provided stronger TDBS signals than the aluminum transducer. AFM topography measurements showed a degradation of the polyelectrolyte structures, especially for the PAzo/PAH sample.
To quantify the induced strain, optical barriers were introduced to separate the transducer material from the medium of the hypersound propagation. Difficulties in the sample preparation prohibited a reliable quantification. But the experiments showed that a coating with transparent polyelectrolytes increases the efficiency of aluminum transducers and modifies the excited phonon distribution.
The adoption of polyelectrolytes to the scientific field of picosecond acoustics enables a cheap and fast fabrication of transducer layers on most surfaces. In contrast to aluminum layers the polyelectrolytes are transparent over a wide spectral range. Thus, the strain modulation can be probed from surface and back.
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.