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(1) Background: People with HIV (PWH) may perform more than one type of exercise cumulatively. The objective of this study is to investigate recreational exercise and its association with health-related quality of life (HRQOL) and comorbidities in relation to potential covariates. (2) Methods: The HIBES study (HIV-Begleiterkrankungen-Sport) is a cross-sectional study for people with HIV. The differences between non-exercisers versus exercisers (cumulated vs. single type of exercises) were investigated using regression models based on 454 participants. (3) Results: Exercisers showed a higher HRQOL score compared to non-exercisers (Wilcox r = 0.2 to 0.239). Psychological disorders were identified as the main covariate. Participants performing exercise cumulatively showed higher scores in duration, frequency, and intensity when compared to participants performing only one type of exercise. The mental health summary score was higher for the cumulated and single type of exercise if a psychological disorder existed. Duration and intensity were associated with an increase of HRQOL, whilst a stronger association between psychological disorders and exercise variables were evident. Exercise duration (minutes) showed a significant effect on QOL (standardized beta = 0.1) and for participants with psychological disorders (standardized beta = 0.3), respectively. (4) Conclusions: Psychological disorders and other covariates have a prominent effect on HRQOL and its association with exercise. For PWH with a psychological disorder, a stronger relationship between HRQOL with exercise duration and intensity emerged. However, differentiation of high-HRQOL individuals warrants further investigation by considering additional factors.
This work describes the realization of physically crosslinked networks based on gelatin by the introduction of functional groups enabling specific supramolecular interactions. Molecular models were developed in order to predict the material properties and permit to establish a knowledge-based approach to material design. The effect of additional supramolecular interactions with hydroxyapaptite was then studied in composite materials. The calculated properties are compared to experimental results to validate the models. The models are then further used for the study of physically crosslinked networks. Gelatin was functionalized with desaminotyrosine (DAT) and desaminotyrosyl-tyrosine (DATT) side groups, derived from the natural amino acid tyrosine. These group can potentially undergo to π-π and hydrogen bonding interactions also under physiological conditions. Molecular dynamics (MD) simulations were performed on models with 0.8 wt.-% or 25 wt.-% water content, using the second generation forcefield CFF91. The validation of the models was obtained by the comparison with specific experimental data such as, density, peptide conformational angles and X-ray scattering spectra. The models were then used to predict the supramolecular organization of the polymer chain, analyze the formation of physical netpoints and calculate the mechanical properties. An important finding of simulation was that with the increase of aromatic groups also the number of observed physical netpoints increased. The number of relatively stable physical netpoints, on average zero 0 for natural gelatin, increased to 1 and 6 for DAT and DATT functionalized gelatins respectively. A comparison with the Flory-Rehner model suggested reduced equilibrium swelling by factor 6 of the DATT-functionalized materials in water. The functionalized gelatins could be synthesized by chemoselective coupling of the free carboxylic acid groups of DAT and DATT to the free amino groups of gelatin. At 25 wt.-% water content, the simulated and experimentally determined elastic mechanical properties (e.g. Young Modulus) were both in the order of GPa and were not influenced by the degree of aromatic modification. The experimental equilibrium degree of swelling in water decreased with increasing the number of inserted aromatic functions (from 2800 vol.-% for pure gelatin to 300 vol.-% for the DATT modified gelatin), at the same time, Young’s modulus, elongation at break, and maximum tensile strength increased. It could be show that the functionalization with DAT and DATT influences the chain organization of gelatin based materials together with a controlled drying condition. Functionalization with DAT and DATT lead to a drastic reduction of helical renaturation, that could be more finely controlled by the applied drying conditions. The properties of the materials could then be influenced by application of two independent methods. Composite materials of DAT and DATT functionalized gelatins with hydroxyapatite (HAp) show a drastic reduction of swelling degree. In tensile tests and rheological measurements, the composites equilibrated in water had increased Young’s moduli (from 200 kPa up to 2 MPa) and tensile strength (from 57 kPa up to 1.1 MPa) compared to the natural polymer matrix without affecting the elongation at break. Furthermore, an increased thermal stability from 40 °C to 85 °C of the networks could be demonstrated. The differences of the behaviour of the functionalized gelatins to pure gelatin as matrix suggested an additional stabilizing bond between the incorporated aromatic groups to the hydroxyapatite.
The XI international conference Stochastic and Analytic Methods in Mathematical Physics was held in Yerevan 2 – 7 September 2019 and was dedicated to the memory of the great mathematician Robert Adol’fovich Minlos, who passed away in January 2018.
The present volume collects a large majority of the contributions presented at the conference on the following domains of contemporary interest: classical and quantum statistical physics, mathematical methods in quantum mechanics, stochastic analysis, applications of point processes in statistical mechanics. The authors are specialists from Armenia, Czech Republic, Denmark, France, Germany, Italy, Japan, Lithuania, Russia, UK and Uzbekistan.
A particular aim of this volume is to offer young scientists basic material in order to inspire their future research in the wide fields presented here.
This thesis focuses on the study of marked Gibbs point processes, in particular presenting some results on their existence and uniqueness, with ideas and techniques drawn from different areas of statistical mechanics: the entropy method from large deviations theory, cluster expansion and the Kirkwood--Salsburg equations, the Dobrushin contraction principle and disagreement percolation.
We first present an existence result for infinite-volume marked Gibbs point processes. More precisely, we use the so-called entropy method (and large-deviation tools) to construct marked Gibbs point processes in R^d under quite general assumptions. In particular, the random marks belong to a general normed space S and are not bounded. Moreover, we allow for interaction functionals that may be unbounded and whose range is finite but random. The entropy method relies on showing that a family of finite-volume Gibbs point processes belongs to sequentially compact entropy level sets, and is therefore tight.
We then present infinite-dimensional Langevin diffusions, that we put in interaction via a Gibbsian description. In this setting, we are able to adapt the general result above to show the existence of the associated infinite-volume measure. We also study its correlation functions via cluster expansion techniques, and obtain the uniqueness of the Gibbs process for all inverse temperatures β and activities z below a certain threshold. This method relies in first showing that the correlation functions of the process satisfy a so-called Ruelle bound, and then using it to solve a fixed point problem in an appropriate Banach space. The uniqueness domain we obtain consists then of the model parameters z and β for which such a problem has exactly one solution.
Finally, we explore further the question of uniqueness of infinite-volume Gibbs point processes on R^d, in the unmarked setting. We present, in the context of repulsive interactions with a hard-core component, a novel approach to uniqueness by applying the discrete Dobrushin criterion to the continuum framework. We first fix a discretisation parameter a>0 and then study the behaviour of the uniqueness domain as a goes to 0. With this technique we are able to obtain explicit thresholds for the parameters z and β, which we then compare to existing results coming from the different methods of cluster expansion and disagreement percolation.
Throughout this thesis, we illustrate our theoretical results with various examples both from classical statistical mechanics and stochastic geometry.
When it comes to teacher attitudes towards teaching and learning, research relies heavily on explicit measures (e.g., questionnaires). These attitudes are generally conceptualized as constructivist and transmissive views on teaching and learning with constructivism often considered to be more desirable. In explicit measures, this can have drawbacks like socially desirable responding. It is for this reason that, in this study, we investigated implicit attitudes as well as explicit attitudes towards constructivism and transmission. N = 100 preservice teachers worked on a questionnaire and two Single-Target Implicit Association Tests (ST-IAT constructivism and ST-IAT transmission) before (T1) and after (T2) a single master’s semester. One group (n = 50) did student teaching while a second group (n = 50) took master’s courses. We evaluated preservice teachers’ views on teaching at the end of their masters’ studies. Participants agreed with transmission and constructivism (T1) on both an explicit and implicit level. Implicit measures seem to exceed explicit measures in differentially assessing constructivist and transmissive views on teaching and learning. After student teaching (T2), there was no overall effect of attitude development but changes in rank indicate that participants’ implicit attitudes towards constructivism and transmission developed differently for each individual.
In this paper, we present a finite-state approach to constituency and therewith an analysis of coordination phenomena involving so-called non-constituents. We show that non-constituents can be seen as parts of fully-fledged constituents and therefore be coordinated in the same way. We have implemented an algorithm based on finite state automata that generates an LFG grammar assigning valid analyses to non-constituent coordination structures in the German language.
Taking advantage of ATRP and using functionalized initiators, different functionalities were introduced in both α and ω chain-ends of synthetic polymers. These functionalized polymers could then go through modular synthetic pathways such as click cycloaddition (copper-catalyzed or copper-free) or amidation to couple synthetic polymers to other synthetic polymers, biomolecules or silica monoliths. Using this general strategy and designing these co/polymers so that they are thermoresponsive, yet bioinert and biocompatible with adjustable cloud point values (as it is the case in the present thesis), the whole generated system becomes "smart" and potentially applicable in different branches. The applications which were considered in the present thesis were in polymer post-functionalization (in situ functionalization of micellar aggregates with low and high molecular weight molecules), hydrophilic/hydrophobic tuning, chromatography and bioconjugation (enzyme thermoprecipitation and recovery, improvement of enzyme activity). Different α-functionalized co/polymers containing cholesterol moiety, aldehyde, t-Boc protected amine, TMS-protected alkyne and NHS-activated ester were designed and synthesized in this work.
Ecosystems with highly pulsed water supply must be better understood as climate change may increase frequency and severity of intense storms, droughts and floods. Here we collected data over 3 years (2016-2018) in the episodic wetland outflow channel (Aluize), Banhine National Park, in which the system state changed from dry to wet to dry. Field sampling included vegetation records, small-scale vegetation zoning, the seed bank and water and soil quality. The same main plant species were found in both dry and wet conditions across the riverbed of the outflow channel. We found only very few diaspores of plants in the soil after prolonged drought. In the subsequent flooded state, we examined very dense vegetation on the water surface, which was dominated by the gramineous species Paspalidium obtusifolium. This species formed a compact floating mat that was rooted to the riverbed. The Cyperaceae Bolboschoenus glaucus showed high clonal growth in the form of root tubers, which likely serve as important food reservoir during drought. Soil and water analyses do not indicate a limitation by nutrients. We outline how resident people may change the plant community structure with an increasing practice of setting fire to the meadows in the dried-up riverbed to facilitate plant regrowth as food for their livestock.
The article starts with an overview of modernization theories, its history of ups and downs as well as its present status. This first part is followed by an analysis of basic social structure distributions and trends in human development in selected countries. One major focal point of the paper is the Non-Western world and the Arab countries, in particular. The author looks at modernization and modernity in that region and comes to the conclusion that the Western world can no longer expect to be able to simply export its own values and its way of life to the rest of the world.
Marked along-strike changes in stratigraphy, mountain belt morphology, basement exhumation, and deformation styles characterize the Andean retroarc; these changes have previously been related to spatiotemporal variations in the subduction angle. We modeled new apatite fission track and apatite (U-Th-Sm)/He data from nine ranges located between 26 degrees S and 28 degrees S. Using new and previously published data, we constructed a Cretaceous to Pliocene paleogeographic model that delineates a four-stage tectonic evolution: extensional tectonics during the Cretaceous (120-75 Ma), the formation of a broken foreland basin between 55 and 30 Ma, reheating due to burial beneath sedimentary rocks (18-13 Ma), and deformation, exhumation, and surface uplift during the Late Miocene and the Pliocene (13-3 Ma). Our model highlights how preexisting upper plate structures control the deformation patterns of broken foreland basins. Because retroarc deformation predates flat-slab subduction, we propose that slab anchoring may have been the precursor of Eocene-Oligocene compression in the Andean retroarc. Our model challenges models which consider broken foreland basins and retroarc deformation in the NW Argentinian Andes to be directly related to Miocene flat subduction.
Interactions and feedbacks between tectonics, climate, and upper plate architecture control basin geometry, relief, and depositional systems. The Andes is part of a longlived continental margin characterized by multiple tectonic cycles which have strongly modified the Andean upper plate architecture. In the Andean retroarc, spatiotemporal variations in the structure of the upper plate and tectonic regimes have resulted in marked along-strike variations in basin geometry, stratigraphy, deformational style, and mountain belt morphology. These along-strike variations include high-elevation plateaus (Altiplano and Puna) associated with a thin-skin fold-and-thrust-belt and thick-skin deformation in broken foreland basins such as the Santa Barbara system and the Sierras Pampeanas. At the confluence of the Puna Plateau, the Santa Barbara system and the Sierras Pampeanas, major along-strike changes in upper plate architecture, mountain belt morphology, basement exhumation, and deformation style can be recognized. I have used a source to sink approach to unravel the spatiotemporal tectonic evolution of the Andean retroarc between 26 and 28°S. I obtained a large low-temperature thermochronology data set from basement units which includes apatite fission track, apatite U-Th-Sm/He, and zircon U-Th/He (ZHe) cooling ages. Stratigraphic descriptions of Miocene units were temporally constrained by U-Pb LA-ICP-MS zircon ages from interbedded pyroclastic material.
Modeled ZHe ages suggest that the basement of the study area was exhumed during the Famatinian orogeny (550-450 Ma), followed by a period of relative tectonic quiescence during the Paleozoic and the Triassic. The basement experienced horst exhumation during the Cretaceous development of the Salta rift. After initial exhumation, deposition of thick Cretaceous syn-rift strata caused reheating of several basement blocks within the Santa Barbara system. During the Eocene-Oligocene, the Andean compressional setting was responsible for the exhumation of several disconnected basement blocks. These exhumed blocks were separated by areas of low relief, in which humid climate and low erosion rates facilitated the development of etchplains on the crystalline basement. The exhumed basement blocks formed an Eocene to Oligocene broken foreland basin in the back-bulge depozone of the Andean foreland. During the Early Miocene, foreland basin strata filled up the preexisting Paleogene topography. The basement blocks in lower relief positions were reheated; associated geothermal gradients were higher than 25°C/km. Miocene volcanism was responsible for lateral variations on the amount of reheating along the Campo-Arenal basin. Around 12 Ma, a new deformational phase modified the drainage network and fragmented the lacustrine system. As deformation and rock uplift continued, the easily eroded sedimentary cover was efficiently removed and reworked by an ephemeral fluvial system, preventing the development of significant relief. After ~6 Ma, the low erodibility of the basement blocks which began to be exposed caused relief increase, leading to the development of stable fluvial systems. Progressive relief development modified atmospheric circulation, creating a rainfall gradient. After 3 Ma, orographic rainfall and high relief lead to the development of proximal fluvial-gravitational depositional systems in the surrounding basins.
The dynamics of external contributions to the geomagnetic field is investigated by applying time-frequency methods to magnetic observatory data. Fractal models and multiscale analysis enable obtaining maximum quantitative information related to the short-term dynamics of the geomagnetic field activity. The stochastic properties of the horizontal component of the transient external field are determined by searching for scaling laws in the power spectra. The spectrum fits a power law with a scaling exponent β, a typical characteristic of self-affine time-series. Local variations in the power-law exponent are investigated by applying wavelet analysis to the same time-series. These analyses highlight the self-affine properties of geomagnetic perturbations and their persistence. Moreover, they show that the main phases of sudden storm disturbances are uniquely characterized by a scaling exponent varying between 1 and 3, possibly related to the energy contained in the external field. These new findings suggest the existence of a long-range dependence, the scaling exponent being an efficient indicator of geomagnetic activity and singularity detection. These results show that by using magnetogram regularity to reflect the magnetosphere activity, a theoretical analysis of the external geomagnetic field based on local power-law exponents is possible.
Venomous snakes often display extensive variation in venom composition both between and within species. However, the mechanisms underlying the distribution of different toxins and venom types among populations and taxa remain insufficiently known. Rattlesnakes (Crotalus, Sistrurus) display extreme inter-and intraspecific variation in venom composition, centered particularly on the presence or absence of presynaptically neurotoxic phospholipases A2 such as Mojave toxin (MTX). Interspecific hybridization has been invoked as a mechanism to explain the distribution of these toxins across rattlesnakes, with the implicit assumption that they are adaptively advantageous. Here, we test the potential of adaptive hybridization as a mechanism for venom evolution by assessing the distribution of genes encoding the acidic and basic subunits of Mojave toxin across a hybrid zone between MTX-positive Crotalus scutulatus and MTX-negative C. viridis in southwestern New Mexico, USA. Analyses of morphology, mitochondrial and single copy-nuclear genes document extensive admixture within a narrow hybrid zone. The genes encoding the two MTX subunits are strictly linked, and found in most hybrids and backcrossed individuals, but not in C. viridis away from the hybrid zone. Presence of the genes is invariably associated with presence of the corresponding toxin in the venom. We conclude that introgression of highly lethal neurotoxins through hybridization is not necessarily favored by natural selection in rattlesnakes, and that even extensive hybridization may not lead to introgression of these genes into another species.
Picosecond X-ray absorption spectroscopy (XAS) is used to investigate the electronic and structural dynamics initiated by plasmon excitation of 1.8 nm diameter Au nanoparticles (NPs) functionalised with 1-hexanethiol. We show that 100 ps after photoexcitation the transient XAS spectrum is consistent with an 8% expansion of the Au–Au bond length and a large increase in disorder associated with melting of the NPs. Recovery of the ground state occurs with a time constant of ∼1.8 ns, arising from thermalisation with the environment. Simulations reveal that the transient spectrum exhibits no signature of charge separation at 100 ps and allows us to estimate an upper limit for the quantum yield (QY) of this process to be <0.1.
The recent discovery of an intricate and nontrivial interaction topology among the elements of a wide range of natural systems has altered the manner we understand complexity. For example, the axonal fibres transmitting electrical information between cortical regions form a network which is neither regular nor completely random. Their structure seems to follow functional principles to balance between segregation (functional specialisation) and integration. Cortical regions are clustered into modules specialised in processing different kinds of information, e.g. visual or auditory. However, in order to generate a global perception of the real world, the brain needs to integrate the distinct types of information. Where this integration happens, nobody knows. We have performed an extensive and detailed graph theoretical analysis of the cortico-cortical organisation in the brain of cats, trying to relate the individual and collective topological properties of the cortical areas to their function. We conclude that the cortex possesses a very rich communication structure, composed of a mixture of parallel and serial processing paths capable of accommodating dynamical processes with a wide variety of time scales. The communication paths between the sensory systems are not random, but largely mediated by a small set of areas. Far from acting as mere transmitters of information, these central areas are densely connected to each other, strongly indicating their functional role as integrators of the multisensory information. In the quest of uncovering the structure-function relationship of cortical networks, the peculiarities of this network have led us to continuously reconsider the stablished graph measures. For example, a normalised formalism to identify the “functional roles” of vertices in networks with community structure is proposed. The tools developed for this purpose open the door to novel community detection techniques which may also characterise the overlap between modules. The concept of integration has been revisited and adapted to the necessities of the network under study. Additionally, analytical and numerical methods have been introduced to facilitate understanding of the complicated statistical interrelations between the distinct network measures. These methods are helpful to construct new significance tests which may help to discriminate the relevant properties of real networks from side-effects of the evolutionary-growth processes.
Modern anthropogenic forcing of atmospheric chemistry poses the question of how the Earth System will respond as thousands of gigatons of greenhouse gas are rapidly added to the atmosphere. A similar, albeit nonanthropogenic, situation occurred during the early Paleogene, when catastrophic release of carbon to the atmosphere triggered abrupt increase in global temperatures. The best documented of these events is the Paleocene-Eocene Thermal Maximum (PETM, ~55 Ma) when the magnitude of carbon addition to the oceans and atmosphere was similar to those expected for the future. This event initiated global warming, changes in hydrological cycles, biotic extinction and migrations. A recently proposed hypothesis concerning changes in marine ecosystems suggests that this global warming strongly influenced the shallow-water biosphere, triggering extinctions and turnover in the Larger Foraminifera (LF) community and the demise of corals. The successions from the Adriatic Carbonate Platform (SW Slovenia) represent an ideal location to test the hypothesis of a possible causal link between the PETM and evolution of shallow-water organisms because they record continuous sedimentation from the Late Paleocene to the Early Eocene and are characterized by a rich biota, especially LF, fundamental for detailed biostratigraphic studies. In order to reconstruct paleoenvironmental conditions during deposition, I focused on sedimentological analysis and paleoecological study of benthic assemblages. During the Late Paleocene-earliest Eocene, sedimentation occurred on a shallow-water carbonate ramp system characterized by enhanced nutrient levels. LF represent the common constituent of the benthic assemblages that thrived in this setting throughout the Late Paleocene to the Early Eocene. With detailed biostratigraphic and chemostratigraphic analyses documenting the most complete record to date available for the PETM event in a shallow-water marine environment, I correlated chemostratigraphically for the first time the evolution of LF with the δ¹³C curves. This correlation demonstrated that no major turnover in the LF communities occurred synchronous with the PETM; thus the evolution of LF was mainly controlled by endogenous biotic forces. The study of Late Thanetian metric-sized microbialite-coral mounds which developed in the middle part of the ramp, documented the first Cenozoic occurrence of microbially-cemented mounds. The development of these mounds, with temporary dominance of microbial communities over corals, suggest environmentally-triggered “phase shifts” related to frequent fluctuations of nutrient/turbidity levels during recurrent wet phases which preceding the extreme greenhouse conditions of the PETM. The paleoecological study of the coral community in the microbialites-coral mounds, the study of corals from Early Eocene platform from SW France, and a critical, extensive literature research of Late Paleocene – Early Eocene coral occurrences from the Tethys, the Atlantic, the Caribbean realms suggested that these corals types, even if not forming extensive reefs, are common in the biofacies as small isolated colonies, piles of rubble or small patch-reefs. These corals might have developed ‘alternative’ life strategies to cope with harsh conditions (high/fluctuating nutrients/turbidity, extreme temperatures, perturbation of aragonite saturation state) during the greenhouse times of the early Paleogene, representing a good fossil analogue to modern corals thriving close to their thresholds for survival. These results demonstrate the complexity of the biological responses to extreme conditions, not only in terms of temperature but also nutrient supply, physical disturbance and their temporal variability and oscillating character.
Records from ocean bottom seismometers (OBSs) are highly contaminated by noise, which is much stronger
compared to data from most land stations, especially on the horizontal components. As a consequence, the high energy of the oceanic noise at frequencies below 1 Hz considerably complicates the analysis of the teleseismic earthquake signals recorded by OBSs.
Previous studies suggested different approaches to remove low-frequency noises from OBS recordings but mainly focused on the vertical component. The records of horizontal components, which are crucial for the application of many methods in passive seismological analysis of body and surface waves, could not be much improved in the teleseismic frequency band. Here we introduce a noise reduction method, which is derived from the harmonic–percussive separation algorithms used in Zali et al. (2021), in order to separate long-lasting narrowband signals from broadband transients in the OBS signal. This leads to significant noise reduction of OBS records on both the vertical and horizontal components and increases the earthquake signal-to-noise ratio (SNR) without distortion of the broadband earthquake waveforms. This is demonstrated through tests with synthetic data. Both SNR and cross-correlation coefficients showed significant improvements for different realistic noise realizations. The application of denoised signals in surface wave analysis and receiver functions is discussed through tests with synthetic and real data.
Volcanoes are one of the Earth’s most dynamic zones and responsible for many changes in our planet. Volcano seismology aims to provide an understanding of the physical processes in volcanic systems and anticipate the style and timing of eruptions by analyzing the seismic records. Volcanic tremor signals are usually observed in the seismic records before or during volcanic eruptions. Their analysis contributes to evaluate the evolving volcanic activity and potentially predict eruptions. Years of continuous seismic monitoring now provide useful information for operational eruption forecasting. The continuously growing amount of seismic recordings, however, poses a challenge for analysis, information extraction, and interpretation, to support timely decision making during volcanic crises. Furthermore, the complexity of eruption processes and precursory activities makes the analysis challenging.
A challenge in studying seismic signals of volcanic origin is the coexistence of transient signal swarms and long-lasting volcanic tremor signals. Separating transient events from volcanic tremors can, therefore, contribute to improving our understanding of the underlying physical processes. Some similar issues (data reduction, source separation, extraction, and classification) are addressed in the context of music information retrieval (MIR). The signal characteristics of acoustic and seismic recordings comprise a number of similarities. This thesis is going beyond classical signal analysis techniques usually employed in seismology by exploiting similarities of seismic and acoustic signals and building the information retrieval strategy on the expertise developed in the field of MIR.
First, inspired by the idea of harmonic–percussive separation (HPS) in musical signal processing, I have developed a method to extract harmonic volcanic tremor signals and to detect transient events from seismic recordings. This provides a clean tremor signal suitable for tremor investigation along with a characteristic function suitable for earthquake detection. Second, using HPS algorithms, I have developed a noise reduction technique for seismic signals. This method is especially useful for denoising ocean bottom seismometers, which are highly contaminated by noise. The advantage of this method compared to other denoising techniques is that it doesn’t introduce distortion to the broadband earthquake waveforms, which makes it reliable for different applications in passive seismological analysis. Third, to address the challenge of extracting information from high-dimensional data and investigating the complex eruptive phases, I have developed an advanced machine learning model that results in a comprehensive signal processing scheme for volcanic tremors. Using this method seismic signatures of major eruptive phases can be automatically detected. This helps to provide a chronology of the volcanic system. Also, this model is capable to detect weak precursory volcanic tremors prior to the eruption, which could be used as an indicator of imminent eruptive activity. The extracted patterns of seismicity and their temporal variations finally provide an explanation for the transition mechanism between eruptive phases.
We consider synchronization properties of arrays of spin-torque nano-oscillators coupled via an RC load. We show that while the fully synchronized state of identical oscillators may be locally stable in some parameter range, this synchrony is not globally attracting. Instead, regimes of different levels of compositional complexity are observed. These include chimera states (a part of the array forms a cluster while other units are desynchronized), clustered chimeras (several clusters plus desynchronized oscillators), cluster state (all oscillators form several clusters), and partial synchronization (no clusters but a nonvanishing mean field). Dynamically, these states are also complex, demonstrating irregular and close to quasiperiodic modulation. Remarkably, when heterogeneity of spin-torque oscillators is taken into account, dynamical complexity even increases: close to the onset of a macroscopic mean field, the dynamics of this field is rather irregular.
One of the classical ways to describe the dynamics of nonlinear systems is to analyze theur Fourier spectra. For periodic and quasiperiodic processes the Fourier spectrum consists purely of discrete delta-functions. On the contrary, the spectrum of a chaotic motion is marked by the presence of the continuous component. In this work, we describe the peculiar, neither regular nor completely chaotic state with so called singular-continuous power spectrum. Our investigations concern various cases from most different fields, where one meets the singular continuous (fractal) spectra. The examples include both the physical processes which can be reduced to iterated discrete mappings or even symbolic sequences, and the processes whose description is based on the ordinary or partial differential equations.
In this work the first observation of new type of liquid crystals is presented. This is ionic self-assembly (ISA) liquid crystals formed by introduction of oppositely charged ions between different low molecular tectonic units. As practically all conventional liquid crystals consist of rigid core and alkyl chains the attention is focused to the simplest case where oppositely charged ions are placed between a rigid core and alkyl tails. The aim of this work is to investigate and understand liquid crystalline and alignment properties of these materials. It was found that ionic interactions within complexes play the main role. Presence of these interactions restricts transition to isotropic phase. In addition, these interactions hold the system (like network) allowing crystallization into a single domain from aligned LC state. Alignment of these simple ISA complexes was spontaneous on a glass substrate. In order to show potentials for application perylenediimide and azobenzene containing ISA complexes have been investigated for correlations between phase behavior and their alignment properties. The best results of macroscopic alignment of perylenediimide-based ISA complexes have been obtained by zone-casting method. In the aligned films the columns of the complex align perpendicular to the phase-transition front. The obtained anisotropy (DR = 18) is thermally stable. The investigated photosensitive (azobenzene-based) ISA complexes show formation of columnar LC phases. It was demonstrated that photo alignment of such complexes was very effective (DR = 50 has been obtained). It was shown that photo-reorientation in the photosensitive ISA complexes is cooperative process. The size of domains has direct influence on efficiency of the photo-reorientation process. In the case of small domains the photo-alignment is the most effective. Under irradiation with linearly polarized light domains reorient in the plane of the film leading to macroscopic alignment of columns parallel to the light polarization and joining of small domains into big ones. Finally, the additional distinguishable properties of the ISA liquid crystalline complexes should be noted: (I) the complexes do not solve in water but readily solve in organic solvents; (II) the complexes have good film-forming properties when cast or spin-coated from organic solvent; (III) alignment of the complexes depends on their structure and secondary interactions between tectonic units.
Analysis and modeling of transient earthquake patterns and their dependence on local stress regimes
(2015)
Investigations in the field of earthquake triggering and associated interactions, which includes aftershock triggering as well as induced seismicity, is important for seismic hazard assessment due to earthquakes destructive power. One of the approaches to study earthquake triggering and their interactions is the use of statistical earthquake models, which are based on knowledge of the basic seismicity properties, in particular, the magnitude distribution and spatiotemporal properties of the triggered events.
In my PhD thesis I focus on some specific aspects of aftershock properties, namely, the relative seismic moment release of the aftershocks with respect to the mainshocks; the spatial correlation between aftershock occurrence and fault deformation; and on the influence of aseismic transients on the aftershock parameter estimation. For the analysis of aftershock sequences I choose a statistical approach, in particular, the well known Epidemic Type Aftershock Sequence (ETAS) model, which accounts for the input of background and triggered seismicity. For my specific purposes, I develop two ETAS model modifications in collaboration with Sebastian Hainzl. By means of this approach, I estimate the statistical aftershock parameters and performed simulations of aftershock sequences as well.
In the case of seismic moment release of aftershocks, I focus on the ratio of cumulative seismic moment release with respect to the mainshocks. Specifically, I investigate the ratio with respect to the focal mechanism of the mainshock and estimate an effective magnitude, which represents the cumulative aftershock energy (similar to Bath's law, which defines the average difference between mainshock and the largest aftershock magnitudes). Furthermore, I compare the observed seismic moment ratios with the results of the ETAS simulations. In particular, I test a restricted ETAS (RETAS) model which is based on results of a clock advanced model and static stress triggering.
To analyze spatial variations of triggering parameters I focus in my second approach on the aftershock occurrence triggered by large mainshocks and the study of the aftershock parameter distribution and their spatial correlation with the coseismic/postseismic slip and interseismic locking. To invert the aftershock parameters I improve the modified ETAS (m-ETAS) model, which is able to take the extension of the mainshock rupture into account. I compare the results obtained by the classical approach with the output of the m-ETAS model.
My third approach is concerned with the temporal clustering of seismicity, which might not only be related to earthquake-earthquake interactions, but also to a time-dependent background rate, potentially biasing the parameter estimations. Thus, my coauthors and I also applied a modification of the ETAS model, which is able to take into account time-dependent background activity. It can be applicable for two different cases: when an aftershock catalog has a temporal incompleteness or when the background seismicity rate changes with time, due to presence of aseismic forces.
An essential part of any research is the testing of the developed models using observational data sets, which are appropriate for the particular study case. Therefore, in the case of seismic moment release I use the global seismicity catalog. For the spatial distribution of triggering parameters I exploit two aftershock sequences of the Mw8.8 2010 Maule (Chile) and Mw 9.0 2011 Tohoku (Japan) mainshocks. In addition, I use published geodetic slip models of different authors. To test our ability to detect aseismic transients my coauthors and I use the data sets from Western Bohemia (Central Europe) and California.
Our results indicate that:
(1) the seismic moment of aftershocks with respect to mainshocks depends on the static stress changes and is maximal for the normal, intermediate for thrust and minimal for strike-slip stress regimes, where the RETAS model shows a good correspondence with the results;
(2) The spatial distribution of aftershock parameters, obtained by the m-ETAS model, shows anomalous values in areas of reactivated crustal fault systems. In addition, the aftershock density is found to be correlated with coseismic slip gradient, afterslip, interseismic coupling and b-values. Aftershock seismic moment is positively correlated with the areas of maximum coseismic slip and interseismically locked areas. These correlations might be related to the stress level or to material properties variations in space;
(3) Ignoring aseismic transient forcing or temporal catalog incompleteness can lead to the significant under- or overestimation of the underlying trigger parameters. In the case when a catalog is complete, this method helps to identify aseismic sources.
A numerical MHD model is developed to investigate acceleration and heating of both thermal and auroral plasma. This is done for magnetospheric flux tubes in which intensive field aligned currents flow. To give each of these tubes, the empirical Tsyganenko model of the magnetospheric field is used. The parameters of the background plasma outside the flux tube as well as the strength of the electric field of magnetospheric convection are given. Performing the numerical calculations, the distributions of the plasma densities, velocities, temperatures, parallel electric field and current, and of the coefficients of thermal conductivity are obtained in a self-consistent way. It is found that EIC turbulence develops effectively in the thermal plasma. The parallel electric field develops under the action of the anomalous resistivity. This electric field accelerates both the thermal and the auroral plasma. The thermal turbulent plasma is also subjected to an intensive heating. The increase of the plasma of the Earth's ionosphere. Besides, studying the growth and dispersion properties of oblique ion cyclotron waves excited in a drifting magnetized plasma, it is shown that under non-stationary conditions such waves may reveal the properties of bursts of polarized transverse electromagnetic waves at frequencies near the patron gyrofrequency.
Background: Individuals with aphasia after stroke (IWA) often present with working memory (WM) deficits. Research investigating the relationship between WM and language abilities has led to the promising hypothesis that treatments of WM could lead to improvements in language, a phenomenon known as transfer. Although recent treatment protocols have been successful in improving WM, the evidence to date is scarce and the extent to which improvements in trained tasks of WM transfer to untrained memory tasks, spoken sentence comprehension, and functional communication is yet poorly understood.
Aims: We aimed at (a) investigating whether WM can be improved through an adaptive n-back training in IWA (Study 1–3); (b) testing whether WM training leads to near transfer to unpracticed WM tasks (Study 1–3), and far transfer to spoken sentence comprehension (Study 1–3), functional communication (Study 2–3), and memory in daily life in IWA (Study 2–3); and (c) evaluating the methodological quality of existing WM treatments in IWA (Study 3). To address these goals, we conducted two empirical studies – a case-controls study with Hungarian speaking IWA (Study 1) and a multiple baseline study with German speaking IWA (Study 2) – and a systematic review (Study 3).
Methods: In Study 1 and 2 participants with chronic, post-stroke aphasia performed an adaptive, computerized n-back training. ‘Adaptivity’ was implemented by adjusting the tasks’ difficulty level according to the participants’ performance, ensuring that they always practiced at an optimal level of difficulty. To assess the specificity of transfer effects and to better understand the underlying mechanisms of transfer on spoken sentence comprehension, we included an outcome measure testing specific syntactic structures that have been proposed to involve WM processes (e.g., non-canonical structures with varying complexity).
Results: We detected a mixed pattern of training and transfer effects across individuals: five participants out of six significantly improved in the n-back training. Our most important finding is that all six participants improved significantly in spoken sentence comprehension (i.e., far transfer effects). In addition, we also found far transfer to functional communication (in two participants out of three in Study 2) and everyday memory functioning (in all three participants in Study 2), and near transfer to unpracticed n-back tasks (in four participants out of six). Pooled data analysis of Study 1 and 2 showed a significant negative relationship between initial spoken sentence comprehension and the amount of improvement in this ability, suggesting that the more severe the participants’ spoken sentence comprehension deficit was at the beginning of training, the more they improved after training. Taken together, we detected both near far and transfer effects in our studies, but the effects varied across participants. The systematic review evaluating the methodological quality of existing WM treatments in stroke IWA (Study 3) showed poor internal and external validity across the included 17 studies. Poor internal validity was mainly due to use of inappropriate design, lack of randomization of study phases, lack of blinding of participants and/or assessors, and insufficient sampling. Low external validity was mainly related to incomplete information on the setting, lack of use of appropriate analysis or justification for the suitability of the analysis procedure used, and lack of replication across participants and/or behaviors. Results in terms of WM, spoken sentence comprehension, and reading are promising, but further studies with more rigorous methodology and stronger experimental control are needed to determine the beneficial effects of WM intervention.
Conclusions: Results of the empirical studies suggest that WM can be improved with a computerized and adaptive WM training, and improvements can lead to transfer effects to spoken sentence comprehension and functional communication in some individuals with chronic post-stroke aphasia. The fact that improvements were not specific to certain syntactic structures (i.e., non-canonical complex sentences) in spoken sentence comprehension suggest that WM is not involved in the online, automatic processing of syntactic information (i.e., parsing and interpretation), but plays a more general role in the later stage of spoken sentence comprehension (i.e., post-interpretive comprehension). The individual differences in treatment outcomes call for future research to clarify how far these results are generalizable to the population level of IWA. Future studies are needed to identify a few mechanisms that may generalize to at least a subpopulation of IWA as well as to investigate baseline non-linguistic cognitive and language abilities that may play a role in transfer effects and the maintenance of such effects. These may require larger yet homogenous samples.
Optical frequency combs (OFC) constitute an array of phase-correlated equidistant spectral lines with nearly equal intensities over a broad spectral range. The adaptations of combs generated in mode-locked lasers proved to be highly efficient for the calibration of high-resolution (resolving power > 50000) astronomical spectrographs. The observation of different galaxy structures or the studies of the Milky Way are done using instruments in the low- and medium resolution range. To such instruments belong, for instance, the Multi Unit Spectroscopic Explorer (MUSE) being developed for the Very Large Telescope (VLT) of the European Southern Observatory (ESO) and the 4-metre Multi-Object Spectroscopic Telescope (4MOST) being in development for the ESO VISTA 4.1 m Telescope. The existing adaptations of OFC from mode-locked lasers are not resolvable by these instruments.
Within this work, a fibre-based approach for generation of OFC specifically in the low- and medium resolution range is studied numerically. This approach consists of three optical fibres that are fed by two equally intense continuous-wave (CW) lasers. The first fibre is a conventional single-mode fibre, the second one is a suitably pumped amplifying Erbium-doped fibre with anomalous dispersion, and the third one is a low-dispersion highly nonlinear optical fibre. The evolution of a frequency comb in this system is governed by the following processes: as the two initial CW-laser waves with different frequencies propagate through the first fibre, they generate an initial comb via a cascade of four-wave mixing processes. The frequency components of the comb are phase-correlated with the original laser lines and have a frequency spacing that is equal to the initial laser frequency separation (LFS), i.e. the difference in the laser frequencies. In the time domain, a train of pre-compressed pulses with widths of a few pico-seconds arises out of the initial bichromatic deeply-modulated cosine-wave. These pulses undergo strong compression in the subsequent amplifying Erbium-doped fibre: sub-100 fs pulses with broad OFC spectra are formed. In the following low-dispersion highly nonlinear fibre, the OFC experience a further broadening and the intensity of the comb lines are fairly equalised. This approach was mathematically modelled by means of a Generalised Nonlinear Schrödinger Equation (GNLS) that contains terms describing the nonlinear optical Kerr effect, the delayed Raman response, the pulse self-steepening, and the linear optical losses as well as the wavelength-dependent Erbium gain profile for the second fibre. The initial condition equation being a deeply-modulated cosine-wave mimics the radiation of the two initial CW lasers. The numerical studies are performed with the help of Matlab scripts that were specifically developed for the integration of the GNLS and the initial condition according to the proposed approach for the OFC generation. The scripts are based on the Fourth-Order Runge-Kutta in the Interaction Picture Method (RK4IP) in combination with the local error method.
This work includes the studies and results on the length optimisation of the first and the second fibre depending on different values of the group-velocity dispersion of the first fibre. Such length optimisation studies are necessary because the OFC have the biggest possible broadband and exhibit a low level of noise exactly at the optimum lengths. Further, the optical pulse build-up in the first and the second fibre was studied by means of the numerical technique called Soliton Radiation Beat Analysis (SRBA). It was shown that a common soliton crystal state is formed in the first fibre for low laser input powers. The soliton crystal continuously dissolves into separated optical solitons as the input power increases. The pulse formation in the second fibre is critically dependent on the features of the pulses formed in the first fibre. I showed that, for low input powers, an adiabatic soliton compression delivering low-noise OFC occurs in the second fibre. At high input powers, the pulses in the first fibre have more complicated structures which leads to the pulse break-up in the second fibre with a subsequent degradation of the OFC noise performance. The pulse intensity noise studies that were performed within the framework of this thesis allow making statements about the noise performance of an OFC. They showed that the intensity noise of the whole system decreases with the increasing value of LFS.
Our every-day experience is connected with different acoustical noise or music. Usually noise plays the role of nuisance in any communication and destroys any order in a system. Similar optical effects are known: strong snowing or raining decreases quality of a vision. In contrast to these situations noisy stimuli can also play a positive constructive role, e.g. a driver can be more concentrated in a presence of quiet music. Transmission processes in neural systems are of especial interest from this point of view: excitation or information will be transmitted only in the case if a signal overcomes a threshold. Dr. Alexei Zaikin from the Potsdam University studies noise-induced phenomena in nonlinear systems from a theoretical point of view. Especially he is interested in the processes, in which noise influences the behaviour of a system twice: if the intensity of noise is over a threshold, it induces some regular structure that will be synchronized with the behaviour of neighbour elements. To obtain such a system with a threshold one needs one more noise source. Dr. Zaikin has analyzed further examples of such doubly stochastic effects and developed a concept of these new phenomena. These theoretical findings are important, because such processes can play a crucial role in neurophysics, technical communication devices and living sciences.
At present, carbon sequestration in terrestrial ecosystems slows the growth rate of atmospheric CO2 concentrations, and thereby reduces the impact of anthropogenic fossil fuel emissions on the climate system. Changes in climate and land use affect terrestrial biosphere structure and functioning at present, and will likely impact on the terrestrial carbon balance during the coming decades - potentially providing a positive feedback to the climate system due to soil carbon releases under a warmer climate. Quantifying changes, and the associated uncertainties, in regional terrestrial carbon budgets resulting from these effects is relevant for the scientific understanding of the Earth system and for long-term climate mitigation strategies. A model describing the relevant processes that govern the terrestrial carbon cycle is a necessary tool to project regional carbon budgets into the future. This study (1) provides an extensive evaluation of the parameter-based uncertainty in model results of a leading terrestrial biosphere model, the Lund-Potsdam-Jena Dynamic Global Vegetation Model (LPJ-DGVM), against a range of observations and under climate change, thereby complementing existing studies on other aspects of model uncertainty; (2) evaluates different hypotheses to explain the age-related decline in forest growth, both from theoretical and experimental evidence, and introduces the most promising hypothesis into the model; (3) demonstrates how forest statistics can be successfully integrated with process-based modelling to provide long-term constraints on regional-scale forest carbon budget estimates for a European forest case-study; and (4) elucidates the combined effects of land-use and climate changes on the present-day and future terrestrial carbon balance over Europe for four illustrative scenarios - implemented by four general circulation models - using a comprehensive description of different land-use types within the framework of LPJ-DGVM. This study presents a way to assess and reduce uncertainty in process-based terrestrial carbon estimates on a regional scale. The results of this study demonstrate that simulated present-day land-atmosphere carbon fluxes are relatively well constrained, despite considerable uncertainty in modelled net primary production. Process-based terrestrial modelling and forest statistics are successfully combined to improve model-based estimates of vegetation carbon stocks and their change over time. Application of the advanced model for 77 European provinces shows that model-based estimates of biomass development with stand age compare favourably with forest inventory-based estimates for different tree species. Driven by historic changes in climate, atmospheric CO2 concentration, forest area and wood demand between 1948 and 2000, the model predicts European-scale, present-day age structure of forests, ratio of biomass removals to increment, and vegetation carbon sequestration rates that are consistent with inventory-based estimates. Alternative scenarios of climate and land-use change in the 21<sup>st century suggest carbon sequestration in the European terrestrial biosphere during the coming decades will likely be on magnitudes relevant to climate mitigation strategies. However, the uptake rates are small in comparison to the European emissions from fossil fuel combustion, and will likely decline towards the end of the century. Uncertainty in climate change projections is a key driver for uncertainty in simulated land-atmosphere carbon fluxes and needs to be accounted for in mitigation studies of the terrestrial biosphere.
Metal-containing ionic liquids (ILs) are of interest for a variety of technical applications, e.g., particle synthesis and materials with magnetic or thermochromic properties. In this paper we report the synthesis of, and two structures for, some new tetrabromidocuprates(II) with several “onium” cations in comparison to the results of electron paramagnetic resonance (EPR) spectroscopic analyses. The sterically demanding cations were used to separate the paramagnetic Cu(II) ions for EPR measurements. The EPR hyperfine structure in the spectra of these new compounds is not resolved, due to the line broadening resulting from magnetic exchange between the still-incomplete separated paramagnetic Cu(II) centres. For the majority of compounds, the principal g values (g|| and gK) of the tensors could be determined and information on the structural changes in the [CuBr4]2- anions can be obtained. The complexes have high potential, e.g., as ionic liquids, as precursors for the synthesis of copper bromide particles, as catalytically active or paramagnetic ionic liquids.
X-ray free-electron lasers (XFELs) and table-top sources of x-rays based upon high harmonic generation (HHG) have revolutionized the field of ultrafast x-ray atomic and molecular physics, largely due to an explosive growth in capabilities in the past decade. XFELs now provide unprecedented intensity (1020 W cm−2) of x-rays at wavelengths down to ~1 Ångstrom, and HHG provides unprecedented time resolution (~50 attoseconds) and a correspondingly large coherent bandwidth at longer wavelengths. For context, timescales can be referenced to the Bohr orbital period in hydrogen atom of 150 attoseconds and the hydrogen-molecule vibrational period of 8 femtoseconds; wavelength scales can be referenced to the chemically significant carbon K-edge at a photon energy of ~280 eV (44 Ångstroms) and the bond length in methane of ~1 Ångstrom. With these modern x-ray sources one now has the ability to focus on individual atoms, even when embedded in a complex molecule, and view electronic and nuclear motion on their intrinsic scales (attoseconds and Ångstroms). These sources have enabled coherent diffractive imaging, where one can image non-crystalline objects in three dimensions on ultrafast timescales, potentially with atomic resolution. The unprecedented intensity available with XFELs has opened new fields of multiphoton and nonlinear x-ray physics where behavior of matter under extreme conditions can be explored. The unprecedented time resolution and pulse synchronization provided by HHG sources has kindled fundamental investigations of time delays in photoionization, charge migration in molecules, and dynamics near conical intersections that are foundational to AMO physics and chemistry. This roadmap coincides with the year when three new XFEL facilities, operating at Ångstrom wavelengths, opened for users (European XFEL, Swiss-FEL and PAL-FEL in Korea) almost doubling the present worldwide number of XFELs, and documents the remarkable progress in HHG capabilities since its discovery roughly 30 years ago, showcasing experiments in AMO physics and other applications. Here we capture the perspectives of 17 leading groups and organize the contributions into four categories: ultrafast molecular dynamics, multidimensional x-ray spectroscopies; high-intensity x-ray phenomena; attosecond x-ray science.
The world energy consumption has constantly increased every year due to economic development and population growth. This inevitably caused vast amount of CO2 emission, and the CO2 concentration in the atmosphere keeps increasing with economic growth. To reduce CO2 emission, various methods have been developed but there are still many bottlenecks to be solved. Solvents easily absorbing CO2 such as monoethanol-amine (MEA) and diethanolamine, for example, have limitations of solvent loss, amine degradation, vulnerability to heat and toxicity, and the high cost of regeneration which is especially caused due to chemisorption process. Though some of these drawbacks can be compensated through physisorption with zeolites and metal-organic frameworks (MOFs) by displaying significant adsorption selectivity and capacity even in ambient conditions, limitations for these materials still exist. Zeolites demand relatively high regeneration energy and have limited adsorption kinetics due to the exceptionally narrow pore structure. MOFs have low stability against heat and moisture and high manufacturing cost.
Nanoporous carbons have recently received attention as an attractive functional porous material due to their unique properties. These materials are crucial in many applications of modern science and industry such as water and air purification, catalysis, gas separation, and energy storage/conversion due to their high chemical and thermal stability, and in particular electronic conductivity in combination with high specific surface areas. Nanoporous carbons can be used to adsorb environmental pollutants or small gas molecules such as CO2 and to power electrochemical energy storage devices such as batteries and fuel cells. In all fields, their pore structure or electrical properties can be modified depending on their purposes.
This thesis provides an in-depth look at novel nanoporous carbons from the synthetic and the application point of view. The interplay between pore structure, atomic construction, and the adsorption properties of nanoporous carbon materials are investigated. Novel nanoporous carbon materials are synthesized by using simple precursor molecules containing heteroatoms through a facile
templating method. The affinity, and in turn the adsorption capacity, of carbon materials toward polar gas molecules (CO2 and H2O) is enhanced by the modification of their chemical construction. It is also shown that these properties are important in electrochemical energy storage, here especially for supercapacitors with aqueous electrolytes which are basically based on the physisorption of ions on carbon surfaces. This shows that nanoporous carbons can be a “functional” material with specific physical or chemical interactions with guest species just like zeolites and MOFs.
The synthesis of sp2-conjugated materials with high heteroatom content from a mixture of citrazinic acid and melamine in which heteroatoms are already bonded in specific motives is illustrated. By controlling the removal procedure of the salt-template and the condensation temperature, the role of salts in the formation of porosity and as coordination sites for the stabilization of heteroatoms is proven. A high amount of nitrogen of up to 20 wt. %, oxygen contents of up to 19 wt.%, and a high CO2/N2 selectivity with maximum CO2 uptake at 273 K of 5.31 mmol g–1 are achieved. Besides, the further controlled thermal condensation of precursor molecules and advanced functional properties on applications of the synthesized porous carbons are described. The materials have different porosity and atomic construction exhibiting a high nitrogen content up to 25 wt. % as well as a high porosity with a specific surface area of more than 1800 m2 g−1, and a high performance in selective CO2 gas adsorption of 62.7. These pore structure as well as properties of surface affect to water adsorption with a remarkably high Qst of over 100 kJ mol−1 even higher than that of zeolites or CaCl2 well known as adsorbents. In addition to that, the pore structure of HAT-CN-derived carbon materials during condensation in vacuum is fundamentally understood which is essential to maximize the utilization of porous system in materials showing significant difference in their pore volume of 0.5 cm3 g−1 and 0.25 cm3 g−1 without and with vacuum, respectively.
The molecular designs of heteroatom containing porous carbon derived from abundant and simple molecules are introduced in the presented thesis. Abundant precursors that already containing high amount of nitrogen or oxygen are beneficial to achieve enhanced interaction with adsorptives. The physical and chemical properties of these heteroatom-doped porous carbons are affected by mainly two parameters, that is, the porosity from the pore structure and the polarity from the atomic composition on the surface. In other words, controlling the porosity as well as the polarity of the carbon materials is studied to understand interactions with different guest species which is a fundamental knowledge for the utilization on various applications.
The Milky Way is a spiral galaxy consisting of a disc of gas, dust and stars embedded in a halo of dark matter. Within this dark matter halo there is also a diffuse population of stars called the stellar halo, that has been accreting stars for billions of years from smaller galaxies that get pulled in and disrupted by the large gravitational potential of the Milky Way. As they are disrupted, these galaxies leave behind long streams of stars that can take billions of years to mix with the rest of the stars in the halo. Furthermore, the amount of heavy elements (metallicity) of the stars in these galaxies reflects the rate of chemical enrichment that occurred in them, since the Universe has been slowly enriched in heavy elements (e.g. iron) through successive generations of stars which produce them in their cores and supernovae explosions. Therefore, stars that contain small amounts of heavy elements (metal-poor stars) either formed at early times before the Universe was significantly enriched, or in isolated environments. The aim of this thesis is to develop a better understanding of the substructure content and chemistry of the Galactic stellar halo, in order to gain further insight into the formation and evolution of the Milky Way.
The Pristine survey uses a narrow-band filter which specifically targets the Ca II H & K spectral absorption lines to provide photometric metallicities for a large number of stars down to the extremely metal-poor (EMP) regime, making it a very powerful data set for Galactic archaeology studies. In Chapter 2, we quantify the efficiency of the survey using a preliminary spectroscopic follow-up sample of ~ 200 stars. We also use this sample to establish a set of selection criteria to improve the success rate of selecting EMP candidates for follow-up spectroscopy. In Chapter 3, we extend this work and present the full catalogue of ~ 1000 stars from a three year long medium resolution spectroscopic follow-up effort conducted as part of the Pristine survey. From this sample, we compute success rates of 56% and 23% for recovering stars with [Fe/H] < -2.5 and [Fe/H] < -3.0, respectively. This demonstrates a high efficiency for finding EMP stars as compared to previous searches with success rates of 3-4%.
In Chapter 4, we select a sample of ~ 80000 halo stars using colour and magnitude cuts to select a main sequence turnoff population in the distance range 6 < dʘ < 20 kpc. We then use the spectroscopic follow-up sample presented in Chapter 3 to statistically rescale the Pristine photometric metallicities of this sample, and present the resulting corrected metallicity distribution function (MDF) of the halo. The slope at the metal-poor end is significantly shallower than previous spectroscopic efforts have shown, suggesting that there may be more metal-poor stars with [Fe/H] < -2.5 in the halo than previously thought. This sample also shows evidence that the MDF of the halo may not be bimodal as was proposed by previous works, and that the lack of globular clusters in the Milky Way may be the result of a physical truncation of the MDF rather than just statistical under-sampling.
Chapter 5 showcases the unexpected capability of the Pristine filter for separating blue horizontal branch (BHB) stars from Blue Straggler (BS) stars. We demonstrate a purity of 93% and completeness of 91% for identifying BHB stars, a substantial improvement over previous works. We then use this highly pure and complete sample of BHB stars to trace the halo density profile out to d > 100 kpc, and the Sagittarius stream substructure out to ~ 130 kpc.
In Chapter 6 we use the photometric metallicities from the Pristine survey to perform a clustering analysis of the halo as a function of metallicity. Separating the Pristine sample into four metallicity bins of [Fe/H] < -2, -2 < [Fe/H] < -1.5, -1.5 < [Fe/H] < -1 and -0.9 < [Fe/H] < -0.8, we compute the two-point correlation function to measure the amount of clustering on scales of < 5 deg. For a smooth comparison sample we make a mock Pristine data set generated using the Galaxia code based on the Besançon model of the Galaxy. We find enhanced clustering on small scales (< 0.5 deg) for some regions of the Galaxy for the most metal-poor bin ([Fe/H] < -2), while in others we see large scale signals that correspond to known substructures in those directions. This confirms that the substructure content of the halo is highly anisotropic and diverse in different Galactic environments. We discuss the difficulties of removing systematic clustering signals from the data and the limitations of disentangling weak clustering signals from real substructures and residual systematic structure in the data.
Taken together, the work presented in this thesis approaches the problem of better understanding the halo of our Galaxy from multiple angles. Firstly, presenting a sizeable sample of EMP stars and improving the selection efficiency of EMP stars for the Pristine survey, paving the way for the further discovery of metal-poor stars to be used as probes to early chemical evolution. Secondly, improving the selection of BHB distance tracers to map out the halo to large distances, and finally, using the large samples of metal-poor stars to derive the MDF of the inner halo and analyse the substructure content at different metallicities. The results of this thesis therefore expand our understanding of the physical and chemical properties of the Milky Way stellar halo, and provide insight into the processes involved in its formation and evolution.
Nested complementation plays an important role in expressing counter- i.e. star-free and first-order definable languages and their hierarchies. In addition, methods that compile phonological rules into finite-state networks use double-nested complementation or “double negation”. This paper reviews how the double-nested complementation extends to a relatively new operation, generalized restriction (GR), coined by the author (Yli-Jyrä and Koskenniemi 2004). This operation encapsulates a double-nested complementation and elimination of a concatenation marker, diamond, whose finite occurrences align concatenations in the arguments of the operation. The paper demonstrates that the GR operation has an interesting potential in expressing regular languages, various kinds of grammars, bimorphisms and relations. This motivates a further study of optimized implementation of the operator.
Generalized Two-Level Grammar (GTWOL) provides a new method for compilation of parallel replacement rules into transducers. The current paper identifies the role of generalized lenient composition (GLC) in this method. Thanks to the GLC operation, the compilation method becomes bipartite and easily extendible to capture various application modes. In the light of three notions of obligatoriness, a modification to the compilation method is proposed. We argue that the bipartite design makes implementation of parallel obligatoriness, directionality, length and rank based application modes extremely easy, which is the main result of the paper.
In this paper, we discuss the global existence of solutions for Chemotaxis models with saturation growth. If the coe±cients of the equations are all positive smooth T-periodic functions, then the problem has a positive T-periodic solution, and meanwhile we discuss here the stability problems for the T-periodic solutions.
In this paper, the problem on formation and construction of a shock wave for three dimensional compressible Euler equations with the small perturbed spherical initial data is studied. If the given smooth initial data satisfies certain nondegenerate condition, then from the results in [20], we know that there exists a unique blowup point at the blowup time such that the first order derivates of smooth solution blow up meanwhile the solution itself is still continuous at the blowup point. From the blowup point, we construct a weak entropy solution which is not uniformly Lipschitz continuous on two sides of shock curve, moreover the strength of the constructed shock is zero at the blowup point and then gradually increases. Additionally, some detailed and precise estimates on the solution are obtained in the neighbourhood of the blowup point.
This note is devoted to the study on the global existence of a shock wave for the supersonic flow past a curved wedge. When the curved wedge is a small perturbation of a straight wedge and the angle of the wedge is less than some critical value, wwe show that a shock attached at the wedge will exist globally.
CHAMP (CHAllenging Minisatellite Payload) is a German small satellite mission to study the earth's gravity field, magnetic field and upper atmosphere. Thanks to the good condition of the satellite so far, the planned 5 years mission is extended to year 2009. The satellite provides continuously a large quantity of measurement data for the purpose of Earth study. The measurements of the magnetic field are undertaken by two Fluxgate Magnetometers (vector magnetometer) and one Overhauser Magnetometer (scalar magnetometer) flown on CHAMP. In order to ensure the quality of the data during the whole mission, the calibration of the magnetometers has to be performed routinely in orbit. The scalar magnetometer serves as the magnetic reference and its readings are compared with the readings of the vector magnetometer. The readings of the vector magnetometer are corrected by the parameters that are derived from this comparison, which is called the scalar calibration. In the routine processing, these calibration parameters are updated every 15 days by means of scalar calibration. There are also magnetic effects coming from the satellite which disturb the measurements. Most of them have been characterized during tests before launch. Among them are the remanent magnetization of the spacecraft and fields generated by currents. They are all considered to be constant over the mission life. The 8 years of operation experience allow us to investigate the long-term behaviors of the magnetometers and the satellite systems. According to the investigation, it was found that for example the scale factors of the FGM show obvious long-term changes which can be described by logarithmic functions. The other parameters (offsets and angles between the three components) can be considered constant. If these continuous parameters are applied for the FGM data processing, the disagreement between the OVM and the FGM readings is limited to \pm1nT over the whole mission. This demonstrates, the magnetometers on CHAMP exhibit a very good stability. However, the daily correction of the parameter Z component offset of the FGM improves the agreement between the magnetometers markedly. The Z component offset plays a very important role for the data quality. It exhibits a linear relationship with the standard deviation of the disagreement between the OVM and the FGM readings. After Z offset correction, the errors are limited to \pm0.5nT (equivalent to a standard deviation of 0.2nT). We improved the corrections of the spacecraft field which are not taken into account in the routine processing. Such disturbance field, e.g. from the power supply system of the satellite, show some systematic errors in the FGM data and are misinterpreted in 9-parameter calibration, which brings false local time related variation of the calibration parameters. These corrections are made by applying a mathematical model to the measured currents. This non-linear model is derived from an inversion technique. If the disturbance field of the satellite body are fully corrected, the standard deviation of scalar error \triangle B remains about 0.1nT. Additionally, in order to keep the OVM readings a reliable standard, the imperfect coefficients of the torquer current correction for the OVM are redetermined by solving a minimization problem. The temporal variation of the spacecraft remanent field is investigated. It was found that the average magnetic moment of the magneto-torquers reflects well the moment of the satellite. This allows for a continuous correction of the spacecraft field. The reasons for the possible unknown systemic error are discussed in this thesis. Particularly, both temperature uncertainties and time errors have influence on the FGM data. Based on the results of this thesis the data processing of future magnetic missions can be designed in an improved way. In particular, the upcoming ESA mission Swarm can take advantage of our findings and provide all the auxiliary measurements needed for a proper recovery of the ambient magnetic field.
The aim of this thesis is to achieve a deep understanding of the working mechanism of polymer based solar cells and to improve the device performance. Two types of the polymer based solar cells are studied here: all-polymer solar cells comprising macromolecular donors and acceptors based on poly(p-phenylene vinylene) and hybrid cells comprising a PPV copolymer in combination with a novel small molecule electron acceptor. To understand the interplay between morphology and photovoltaic properties in all-polymer devices, I compared the photocurrent characteristics and excited state properties of bilayer and blend devices with different nano-morphology, which was fine tuned by using solvents with different boiling points. The main conclusion from these complementary measurements was that the performance-limiting step is the field-dependent generation of free charge carriers, while bimolecular recombination and charge extraction do not compromise device performance. These findings imply that the proper design of the donor-acceptor heterojunction is of major importance towards the goal of high photovoltaic efficiencies. Regarding polymer-small molecular hybrid solar cells I combined the hole-transporting polymer M3EH-PPV with a novel Vinazene-based electron acceptor. This molecule can be either deposited from solution or by thermal evaporation, allowing for a large variety of layer architectures to be realized. I then demonstrated that the layer architecture has a large influence on the photovoltaic properties. Solar cells with very high fill factors of up to 57 % and an open circuit voltage of 1V could be achieved by realizing a sharp and well-defined donor-acceptor heterojunction. In the past, fill factors exceeding 50 % have only been observed for polymers in combination with soluble fullerene-derivatives or nanocrystalline inorganic semiconductors as the electron-accepting component. The finding that proper processing of polymer-vinazene devices leads to similar high values is a major step towards the design of efficient polymer-based solar cells.
Almost half of the political life has been experienced under the
state of emergency and state of siege policies in the Turkish
Republic. In spite of such a striking number and continuity in the
deployment of legal emergency powers, there are just a few legal
and political studies examining the reasons for such permanency
in governing practices. To fill this gap, this paper aims to discuss
one of the most important sources of the ‘permanent’ political
crisis in the country: the historical evolution of legal emergency
power. In order to highlight how these policies have intensified
the highly fragile citizenship regime by weakening the separation
of power, repressing the use of political rights and increasing the
discretionary power of both the executive and judiciary authori-
ties, the paper sheds light on the emergence and production of
a specific form of legality based on the idea of emergency and the
principle of executive prerogative. In that context, it aims to
provide a genealogical explanation of the evolution of the excep-
tional form of the nation-state, which is based on the way political
society, representation, and legitimacy have been instituted and
accompanying failure of the ruling classes in building hegemony
in the country.
In this work, the role of the TusA protein was investigated for the cell functionality and FtsZ ring assembly in Escherichia coli. TusA is the tRNA-2-thiouridine synthase that acts as a sulfur transferase in tRNA thiolation for the formation of 2-thiouridine at the position 34 (wobble base) of tRNALys, tRNAGlu and tRNAGln. It binds the persulfide form of sulfur and transfers it to further proteins during mnm5s2U tRNA modification at wobble position and for Moco biosynthesis. With this thiomodification of tRNA, the ribosome binding is more efficient and frameshifting is averted during the protein translation. Previous studies have revealed an essential role of TusA in bacterial cell physiology since deletion of the tusA gene resulted in retarded growth and filamentous cells during the exponential growth phase in a rich medium which suddenly disappeared during the stationary phase. This indicates a problem in the cell division process. Therefore the focus of this work was to investigate the role of TusA for cell functionality and FtsZ ring formation and thus the cell separation.
The reason behind the filamentous growth of the tusA mutant strain was investigated by growth and morphological analyses. ΔtusA cells showed a retarded growth during the exponential phase compared to the WT strain. Also, morphological analysis of ΔtusA cells confirmed the filamentous cell shape. The growth and cell division defects in ΔtusA indicated a defect in FtsZ protein as a key player of cell division. The microscopic investigation revealed that filamentous ΔtusA cells possessed multiple DNA parts arranged next to each other. This suggested that although the DNA replication occurred correctly, there was a defect in the step where FtsZ should act; probably FtsZ is unable to assemble to the ring structure or the assembled ring is not able to constrict. All tested mutant strains (ΔtusD, ΔtusE and ΔmnmA) involved in the mnm5s2U34 tRNA modification pathway shared the similar retarded growth and filamentous cell shape like ΔtusA strain. Thus, the cell division defect arises from a defect in mnm5s2U34 tRNA thiolation.
Since the FtsZ ring formation was supposed to be defective in filaments, a possible intracellular interaction of TusA and FtsZ was examined by fluorescent (EGFP and mCherry) fusion proteins expression and FRET. FtsZ expressing tusA mutant (DE3) cells showed a red mCherry signal at the cell poles, indicating that FtsZ is still in the assembling phase. Interestingly, the cellular region of EGFP-TusA fusion protein expressed in ΔtusA (DE3) was conspicuous; the EGFP signal was spread throughout the whole cell and, in addition, a slight accumulation of the EGFP-TusA fluorescence was detectable at the cell poles, the same part of the cell as for mCherry-FtsZ. Thus, this strongly suggested an interaction of TusA and FtsZ.
Furthermore, the cellular FtsZ and Fis concentrations, and their change during different growth phases were determined via immunoblotting. All tested deletion strains of mnm5s2U34 tRNA modification show high cellular FtsZ and Fis levels in the exponential phase, shifting to the later growth phases. This shift reflects the retarded growth, whereby the deletion strains reach later the exponential phase. Conclusively, the growth and cell division defect, and thus the formation of filaments, is most likely caused by changes in the cellular FtsZ and Fis concentrations.
Finally, the translation efficiencies of certain proteins (RpoS, Fur, Fis and mFis) in tusA mutant and in additional gene deletion strains were studied whether they were affected by using unmodified U34 tRNAs of Lys, Glu and Gln. The translation efficiency is decreased in mnm5s2U34 tRNA modification-impaired strains in addition to their existing growth and cell division defect due to the elimination of these three amino acids. Finally, these results confirm and reinforce the importance of Lys, Glu and Gln and the mnm5s2U34 tRNA thiolation for efficient protein translation. Thus, these findings verify that the translation of fur, fis and rpoS is regulated by mnm5s2U34 tRNA modifications, which is growth phase-dependent.
In total, this work showed the importance of the role of TusA for bacterial cell functionality and physiology. The deletion of the tusA gene disrupted a complex regulatory network within the cell, that most influenced by the decreased translation of Fis and RpoS, caused by the absence of mnm5s2U34 tRNA modifications. The disruption of RpoS and Fis cellular network influences in turn the cellular FtsZ level in the early exponential phase. Finally, the reduced FtsZ concentration leads to elongated, filamentous E. coli cells, which are unable to divide.
Synchronization is a fundamental phenomenon in nature. It can be considered as a general property of self-sustained oscillators to adjust their rhythm in the presence of an interaction.
In this work we investigate complex regimes of synchronization phenomena by means of theoretical analysis, numerical modeling, as well as practical analysis of experimental data.
As a subject of our investigation we consider chimera state, where due to spontaneous symmetry-breaking of an initially homogeneous oscillators lattice split the system into two parts with different dynamics. Chimera state as a new synchronization phenomenon was first found in non-locally coupled oscillators system, and has attracted a lot of attention in the last decade. However, the recent studies indicate that this state is also possible in globally coupled systems. In the first part of this work, we show under which conditions the chimera-like state appears in a system of globally coupled identical oscillators with intrinsic delayed feedback. The results of the research explain how initially monostable oscillators became effectivly bistable in the presence of the coupling and create a mean field that sustain the coexistence of synchronized and desynchronized states. Also we discuss other examples, where chimera-like state appears due to frequency dependence of the phase shift in the bistable system.
In the second part, we make further investigation of this topic by modeling influence of an external periodic force to an oscillator with intrinsic delayed feedback. We made stability analysis of the synchronized state and constructed Arnold tongues. The results explain formation of the chimera-like state and hysteric behavior of the synchronization area. Also, we consider two sets of parameters of the oscillator with symmetric and asymmetric Arnold tongues, that correspond to mono- and bi-stable regimes of the oscillator.
In the third part, we demonstrate the results of the work, which was done in collaboration with our colleagues from Psychology Department of University of Potsdam. The project aimed to study the effect of the cardiac rhythm on human perception of time using synchronization analysis. From our part, we made a statistical analysis of the data obtained from the conducted experiment on free time interval reproduction task. We examined how ones heartbeat influences the time perception and searched for possible phase synchronization between heartbeat cycles and time reproduction responses. The findings support the prediction that cardiac cycles can serve as input signals, and is used for reproduction of time intervals in the range of several seconds.
Enlisted History
(2018)
Zeev Jawitz (1847–1924) was active in all spheres of culture: history, language, literature and pedagogy, all the while striving for harmonization with the Orthodox outlook. He understood that a people returning to its homeland needed a national culture, one that was both broad and deep, and that the narrow world of the Halakhah would no longer suffice. His main work was the multi-volume Toldot Israel (History of Israel, published 1895–1924) which encompasses Jewish history from its beginning – Patriarchs – until the end of the 19th century. His historical writing, with its emphasis on internal religious Jewish sources, the unity and continuity of Jewish history, and respect of Orthodox principles, comes as an alternative to the historiography of the celebrated historian Heinrich Graetz. The alternative that Jawitz tried to substitute for Wissenschaft des Judentums, was influenced not only by Orthodox ideology, which he supported, but also by his nationalist ideology. He saw himself and his disciples as the “priests of memory,” presenting the true and immanent history and character of the Jewish nation as a platform to the Jewish future in the land of Israel.
Inverted perovskite solar cells still suffer from significant non-radiative recombination losses at the perovskite surface and across the perovskite/C₆₀ interface, limiting the future development of perovskite-based single- and multi-junction photovoltaics. Therefore, more effective inter- or transport layers are urgently required. To tackle these recombination losses, we introduce ortho-carborane as an interlayer material that has a spherical molecular structure and a three-dimensional aromaticity. Based on a variety of experimental techniques, we show that ortho-carborane decorated with phenylamino groups effectively passivates the perovskite surface and essentially eliminates the non-radiative recombination loss across the perovskite/C₆₀ interface with high thermal stability. We further demonstrate the potential of carborane as an electron transport material, facilitating electron extraction while blocking holes from the interface. The resulting inverted perovskite solar cells deliver a power conversion efficiency of over 23% with a low non-radiative voltage loss of 110 mV, and retain >97% of the initial efficiency after 400 h of maximum power point tracking. Overall, the designed carborane based interlayer simultaneously enables passivation, electron-transport and hole-blocking and paves the way toward more efficient and stable perovskite solar cells.
Electrochemical methods offer the simple characterization of the synthesis of molecularly imprinted polymers (MIPs) and the readouts of target binding. The binding of electroinactive analytes can be detected indirectly by their modulating effect on the diffusional permeability of a redox marker through thin MIP films. However, this process generates an overall signal, which may include nonspecific interactions with the nonimprinted surface and adsorption at the electrode surface in addition to (specific) binding to the cavities. Redox-active low-molecular-weight targets and metalloproteins enable a more specific direct quantification of their binding to MIPs by measuring the faradaic current. The in situ characterization of enzymes, MIP-based mimics of redox enzymes or enzyme-labeled targets, is based on the indication of an electroactive product. This approach allows the determination of both the activity of the bio(mimetic) catalyst and of the substrate concentration.
We present an electrochemical MIP sensor for tamoxifen (TAM)-a nonsteroidal anti-estrogen-which is based on the electropolymerisation of an O-phenylenediamine. resorcinol mixture directly on the electrode surface in the presence of the template molecule. Up to now only. bulk. MIPs for TAM have been described in literature, which are applied for separation in chromatography columns. Electro-polymerisation of the monomers in the presence of TAM generated a film which completely suppressed the reduction of ferricyanide. Removal of the template gave a markedly increased ferricyanide signal, which was again suppressed after rebinding as expected for filling of the cavities by target binding. The decrease of the ferricyanide peak of the MIP electrode depended linearly on the TAM concentration between 1 and 100 nM. The TAM-imprinted electrode showed a 2.3 times higher recognition of the template molecule itself as compared to its metabolite 4-hydroxytamoxifen and no cross-reactivity with the anticancer drug doxorubucin was found. Measurements at + 1.1 V caused a fouling of the electrode surface, whilst pretreatment of TAM with peroxide in presence of HRP generated an oxidation product which was reducible at 0 mV, thus circumventing the polymer formation and electrochemical interferences.
Molecularly imprinted polymers (MIPs) have the potential to complement antibodies in bioanalysis, are more stable under harsh conditions, and are potentially cheaper to produce. However, the affinity and especially the selectivity of MIPs are in general lower than those of their biological pendants. Enzymes are useful tools for the preparation of MIPs for both low and high-molecular weight targets: As a green alternative to the well-established methods of chemical polymerization, enzyme-initiated polymerization has been introduced and the removal of protein templates by proteases has been successfully applied. Furthermore, MIPs have been coupled with enzymes in order to enhance the analytical performance of biomimetic sensors: Enzymes have been used in MIP-sensors as tracers for the generation and amplification of the measuring signal. In addition, enzymatic pretreatment of an analyte can extend the analyte spectrum and eliminate interferences.
Water quality in river systems is of growing concern due to rising anthropogenic pressures and climate change. Mitigation efforts have been placed under the guidelines of different governance conventions during last decades (e.g., the Water Framework Directive in Europe). Despite significant improvement through relatively straightforward measures, the environmental status has likely reached a plateau. A higher spatiotemporal accuracy of catchment nitrate modeling is, therefore, needed to identify critical source areas of diffuse nutrient pollution (especially for nitrate) and to further guide implementation of spatially differentiated, cost-effective mitigation measures. On the other hand, the emerging high-frequency sensor monitoring upgrades the monitoring resolution to the time scales of biogeochemical processes and enables more flexible monitoring deployments under varying conditions. The newly available information offers new prospects in understanding nitrate spatiotemporal dynamics. Formulating such advanced process understanding into catchment models is critical for model further development and environmental status evaluation. This dissertation is targeting on a comprehensive analysis of catchment and in-stream nitrate dynamics and is aiming to derive new insights into their spatial and temporal variabilities through the new fully distributed model development and the new high-frequency data.
Firstly, a new fully distributed, process-based catchment nitrate model (the mHM-Nitrate model) is developed based on the mesoscale Hydrological Model (mHM) platform. Nitrate process descriptions are adopted from the Hydrological Predictions for the Environment (HYPE), with considerable improved implementations. With the multiscale grid-based discretization, mHM-Nitrate balances the spatial representation and the modeling complexity. The model has been thoughtfully evaluated in the Selke catchment (456 km2), central Germany, which is characterized by heterogeneous physiographic conditions. Results show that the model captures well the long-term discharge and nitrate dynamics at three nested gauging stations. Using daily nitrate-N observations, the model is also validated in capturing short-term fluctuations due to changes in runoff partitioning and spatial contribution during flooding events. By comparing the model simulations with the values reported in the literature, the model is capable of providing detailed and reliable spatial information of nitrate concentrations and fluxes. Therefore, the model can be taken as a promising tool for environmental scientists in advancing environmental modeling research, as well as for stakeholders in supporting their decision-making, especially for spatially differentiated mitigation measures.
Secondly, a parsimonious approach of regionalizing the in-stream autotrophic nitrate uptake is proposed using high-frequency data and further integrated into the new mHM-Nitrate model. The new regionalization approach considers the potential uptake rate (as a general parameter) and effects of above-canopy light and riparian shading (represented by global radiation and leaf area index data, respectively). Multi-parameter sensors have been continuously deployed in a forest upstream reach and an agricultural downstream reach of the Selke River. Using the continuous high-frequency data in both streams, daily autotrophic uptake rates (2011-2015) are calculated and used to validate the regionalization approach. The performance and spatial transferability of the approach is validated in terms of well-capturing the distinct seasonal patterns and value ranges in both forest and agricultural streams. Integrating the approach into the mHM-Nitrate model allows spatiotemporal variability of in-stream nitrate transport and uptake to be investigated throughout the river network.
Thirdly, to further assess the spatial variability of catchment nitrate dynamics, for the first time the fully distributed parameterization is investigated through sensitivity analysis. Sensitivity results show that parameters of soil denitrification, in-stream denitrification and in-stream uptake processes are the most sensitive parameters throughout the Selke catchment, while they all show high spatial variability, where hot-spots of parameter sensitivity can be explicitly identified. The Spearman rank correlation is further analyzed between sensitivity indices and multiple catchment factors. The correlation identifies that the controlling factors vary spatially, reflecting heterogeneous catchment responses in the Selke catchment. These insights are, therefore, informative in informing future parameter regionalization schemes for catchment water quality models. In addition, the spatial distributions of parameter sensitivity are also influenced by the gauging information that is being used for sensitivity evaluation. Therefore, an appropriate monitoring scheme is highly recommended to truly reflect the catchment responses.