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Intuitively, strongly constraining contexts should lead to stronger probabilistic representations of sentences in memory. Encountering unexpected words could therefore be expected to trigger costlier shifts in these representations than expected words. However, psycholinguistic measures commonly used to study probabilistic processing, such as the N400 event-related potential (ERP) component, are sensitive to word predictability but not to contextual constraint. Some research suggests that constraint-related processing cost may be measurable via an ERP positivity following the N400, known as the anterior post-N400 positivity (PNP). The PNP is argued to reflect update of a sentence representation and to be distinct from the posterior P600, which reflects conflict detection and reanalysis. However, constraint-related PNP findings are inconsistent. We sought to conceptually replicate Federmeier et al. (2007) and Kuperberg et al. (2020), who observed that the PNP, but not the N400 or the P600, was affected by constraint at unexpected but plausible words. Using a pre-registered design and statistical approach maximising power, we demonstrated a dissociated effect of predictability and constraint: strong evidence for predictability but not constraint in the N400 window, and strong evidence for constraint but not predictability in the later window. However, the constraint effect was consistent with a P600 and not a PNP, suggesting increased conflict between a strong representation and unexpected input rather than greater update of the representation. We conclude that either a simple strong/weak constraint design is not always sufficient to elicit the PNP, or that previous PNP constraint findings could be an artifact of smaller sample size.
Weathering the storm?
(2023)
Democratization scholars are currently debating if we are indeed witnessing a third wave of autocratization. While this has led to an extensive debate about the future of the liberal international order, we still know relatively little about the consequences of autocratization for international organizations (IOs). In this article, we explore to what extent autocratization has led to changes in the composition of IO membership. We propose three different ways of conceptualizing autocratization of IO membership. We argue that we should move away from a dichotomous understanding of regime type and regime change, but rather focus on composition of subregime types to understand current developments. We build on updated membership data for 73 IOs through 2020 to map membership configurations based on the V-Dem Electoral Democracy Index. Contrary to current debates on the crisis of the liberal order, we find that many IOs are not (yet) affected by broad autocratization of their membership that would endanger democratic majorities or overall democratic densities. However, we also observe the disappearance of formerly homogenous democratic clubs due to democratic backsliding in a number of European and Latin American IO member states, as well as a return of autocratic clubs in Southeast Asia and Southern Africa. These findings have important implications for the broader research agenda on international democracy promotion and human right protection as well as the study of legitimacy and the effectiveness of international organizations.
Introduction:
Decision making results not only from logical analyses, but seems to be further guided by the ability to perceive somatic information (interoceptive accuracy). Relations between interoceptive accuracy and decision making have been exclusively studied in adults and with regard to complex, uncertain situations (as measured by the Iowa Gambling Task, IGT).
Methods:
In the present study, 1454 children (6-11 years) were examined at two time points (approximately 1 year apart) using an IGT as well as a delay-of-gratification task for sweets-items and toy-items. Interoceptive accuracy was measured using a child-adapted version of the Heartbeat Perception Task.
Results:
The present results revealed that children with higher, as compared to lower, interoceptive accuracy showed more advantageous choices in the IGT and delayed more sweets-items, but not toy-items, in a delay-of-gratification task at time point 2 but not at time point 1. However, no longitudinal relation between interoceptive accuracy and decision making 1 year later could be shown.
Discussion:
Results indicate that interoceptive accuracy relates to decision-making abilities in situations of varying complexity already in middle childhood, and that this link might consolidate across the examined 1-year period. Furthermore, the association of interoceptive accuracy and the delay of sweets-items might have implications for the regulation of body weight at a later age.
FicucariconeD (1) and its 4 '-demethyl congener 2 are isoflavones isolated from fruits of Ficus carica that share a 5,7-dimethoxy-6-prenyl-substituted A-ring. Both naturalproducts were, for the first time, obtained by chemical synthesisin six steps, starting from 2,4,6-trihydroxyacetophenone. Key stepsare a microwave-promoted tandem sequence of Claisen- and Cope-rearrangementsto install the 6-prenyl substituent and a Suzuki-Miyaura crosscoupling for installing the B-ring. By using various boronic acids,non-natural analogues become conveniently available. All compoundswere tested for cytotoxicity against drug-sensitive and drug-resistanthuman leukemia cell lines, but were found to be inactive. The compoundswere also tested for antimicrobial activities against a panel of eightGram-negative and two Gram-positive bacterial strains. Addition ofthe efflux pump inhibitor phenylalanine-arginine-beta-naphthylamide(PA beta N) significantly improved the antibiotic activity in mostcases, with MIC values as low as 2.5 mu M and activity improvementfactors as high as 128-fold.
The near-Earth space environment is a highly complex system comprised of several regions and particle populations hazardous to satellite operations. The trapped particles in the radiation belts and ring current can cause significant damage to satellites during space weather events, due to deep dielectric and surface charging. Closer to Earth is another important region, the ionosphere, which delays the propagation of radio signals and can adversely affect navigation and positioning. In response to fluctuations in solar and geomagnetic activity, both the inner-magnetospheric and ionospheric populations can undergo drastic and sudden changes within minutes to hours, which creates a challenge for predicting their behavior. Given the increasing reliance of our society on satellite technology, improving our understanding and modeling of these populations is a matter of paramount importance.
In recent years, numerous spacecraft have been launched to study the dynamics of particle populations in the near-Earth space, transforming it into a data-rich environment. To extract valuable insights from the abundance of available observations, it is crucial to employ advanced modeling techniques, and machine learning methods are among the most powerful approaches available. This dissertation employs long-term satellite observations to analyze the processes that drive particle dynamics, and builds interdisciplinary links between space physics and machine learning by developing new state-of-the-art models of the inner-magnetospheric and ionospheric particle dynamics.
The first aim of this thesis is to investigate the behavior of electrons in Earth's radiation belts and ring current. Using ~18 years of electron flux observations from the Global Positioning System (GPS), we developed the first machine learning model of hundreds-of-keV electron flux at Medium Earth Orbit (MEO) that is driven solely by solar wind and geomagnetic indices and does not require auxiliary flux measurements as inputs. We then proceeded to analyze the directional distributions of electrons, and for the first time, used Fourier sine series to fit electron pitch angle distributions (PADs) in Earth's inner magnetosphere. We performed a superposed epoch analysis of 129 geomagnetic storms during the Van Allen Probes era and demonstrated that electron PADs have a strong energy-dependent response to geomagnetic activity. Additionally, we showed that the solar wind dynamic pressure could be used as a good predictor of the PAD dynamics. Using the observed dependencies, we created the first PAD model with a continuous dependence on L, magnetic local time (MLT) and activity, and developed two techniques to reconstruct near-equatorial electron flux observations from low-PA data using this model.
The second objective of this thesis is to develop a novel model of the topside ionosphere. To achieve this goal, we collected observations from five of the most widely used ionospheric missions and intercalibrated these data sets. This allowed us to use these data jointly for model development, validation, and comparison with other existing empirical models. We demonstrated, for the first time, that ion density observations by Swarm Langmuir Probes exhibit overestimation (up to ~40-50%) at low and mid-latitudes on the night side, and suggested that the influence of light ions could be a potential cause of this overestimation. To develop the topside model, we used 19 years of radio occultation (RO) electron density profiles, which were fitted with a Chapman function with a linear dependence of scale height on altitude. This approximation yields 4 parameters, namely the peak density and height of the F2-layer and the slope and intercept of the linear scale height trend, which were modeled using feedforward neural networks (NNs). The model was extensively validated against both RO and in-situ observations and was found to outperform the International Reference Ionosphere (IRI) model by up to an order of magnitude. Our analysis showed that the most substantial deviations of the IRI model from the data occur at altitudes of 100-200 km above the F2-layer peak. The developed NN-based ionospheric model reproduces the effects of various physical mechanisms observed in the topside ionosphere and provides highly accurate electron density predictions.
This dissertation provides an extensive study of geospace dynamics, and the main results of this work contribute to the improvement of models of plasma populations in the near-Earth space environment.
Aquatic ecosystems are frequently overlooked as fungal habitats, although there is increasing evidence that their diversity and ecological importance are greater than previously considered. Aquatic fungi are critical and abundant components of nutrient cycling and food web dynamics, e.g., exerting top-down control on phytoplankton communities and forming symbioses with many marine microorganisms. However, their relevance for microphytobenthic communities is almost unexplored. In the light of global warming, polar regions face extreme changes in abiotic factors with a severe impact on biodiversity and ecosystem functioning. Therefore, this study aimed to describe, for the first time, fungal diversity in Antarctic benthic habitats along the salinity gradient and to determine the co-occurrence of fungal parasites with their algal hosts, which were dominated by benthic diatoms. Our results reveal that Ascomycota and Chytridiomycota are the most abundant fungal taxa in these habitats. We show that also in Antarctic waters, salinity has a major impact on shaping not just fungal but rather the whole eukaryotic community composition, with a diversity of aquatic fungi increasing as salinity decreases. Moreover, we determined correlations between putative fungal parasites and potential benthic diatom hosts, highlighting the need for further systematic analysis of fungal diversity along with studies on taxonomy and ecological roles of Chytridiomycota.
Search for light primordial black holes with VERITAS using gamma γ-ray and optical observations
(2023)
The Very Energetic Radiation Imaging Telescope Array System (VERITAS) is an array of four imaging atmospheric Cherenkov telescopes (IACTs). VERITAS is sensitive to very-high-energy gamma-rays in the range of 100 GeV to >30 TeV. Hypothesized primordial black holes (PBHs) are attractive targets for IACTs. If they exist, their potential cosmological impact reaches beyond the candidacy for constituents of dark matter. The sublunar mass window is the largest unconstrained range of PBH masses. This thesis aims to develop novel concepts searching for light PBHs with VERITAS. PBHs below the sublunar window lose mass due to Hawking radiation. They would evaporate at the end of their lifetime, leading to a short burst of gamma-rays. If PBHs formed at about 10^15 g, the evaporation would occur nowadays. Detecting these signals might not only confirm the existence of PBHs but also prove the theory of Hawking radiation. This thesis probes archival VERITAS data recorded between 2012 and 2021 for possible PBH signals. This work presents a new automatic approach to assess the quality of the VERITAS data. The array-trigger rate and far infrared temperature are well suited to identify periods with poor data quality. These are masked by time cuts to obtain a consistent and clean dataset which contains about 4222 hours. The PBH evaporations could occur at any location in the field of view or time within this data. Only a blind search can be performed to identify these short signals. This thesis implements a data-driven deep learning based method to search for short transient signals with VERITAS. It does not depend on the modelling of the effective area and radial acceptance. This work presents the first application of this method to actual observational IACT data. This thesis develops new concepts dealing with the specifics of the data and the transient detection method. These are reflected in the developed data preparation pipeline and search strategies. After correction for trial factors, no candidate PBH evaporation is found in the data. Thus, new constraints of the local rate of PBH evaporations are derived. At the 99% confidence limit it is below <1.07 * 10^5 pc^-3 yr^-1. This constraint with the new, independent analysis approach is in the range of existing limits for the evaporation rate.
This thesis also investigates an alternative novel approach to searching for PBHs with IACTs. Above the sublunar window, the PBH abundance is constrained by optical microlensing studies. The sampling speed, which is of order of minutes to hours for traditional optical telescopes, is a limiting factor in expanding the limits to lower masses. IACTs are also powerful instruments for fast transient optical astronomy with up to O(ns) sampling. This thesis investigates whether IACTs might constrain the sublunar window with optical microlensing observations. This study confirms that, in principle, the fast sampling speed might allow extending microlensing searches into the sublunar mass window. However, the limiting factor for IACTs is the modest sensitivity to detect changes in optical fluxes. This thesis presents the expected rate of detectable events for VERITAS as well as prospects of possible future next-generation IACTs. For VERITAS, the rate of detectable microlensing events in the sublunar range is ~10^-6 per year of observation time. The future prospects for a 100 times more sensitive instrument are at ~0.05 events per year.
Supernova remnants are considered to be the primary sources of galactic cosmic rays. These cosmic rays are assumed to be accelerated by the diffusive shock acceleration mechanism, specifically at shocks in the remnants. Particularly in the core-collapse scenario, these supernova remnant shocks expand inside the wind-blown bubbles structured by massive progenitors during their lifetime. Therefore, the complex environment of wind bubbles can influence the particle acceleration and radiation from the remnants. Further, the evolution of massive stars depends on their Zero Age Main Sequence mass, rotation, and metallicity. Consequently, the structures of the wind bubbles generated during the lifetime of massive stars should be considerably different. Hence, the particle acceleration in the core-collapse supernova remnants should vary, not only from the remnants evolving in the uniform environment but also from one another, depending on their progenitor stars.
A core-collapse supernova remnant with a very massive 60 𝑀 ⊙ progenitor star has been considered to study the particle acceleration at the shock considering Bohm-like diffusion. This dissertation demonstrates the modification in particle acceleration and radiation while the remnant propagates through different regions of the wind bubble by impacts from the profiles of gas density, the temperature of the bubble and the magnetic field structure. Subsequently, in this thesis, I discuss the impacts of the non-identical ambient environment of core-collapse supernova remnants on particle spectra and the non-thermal emissions, considering 20 𝑀 ⊙ and 60 𝑀⊙ massive progenitors having different evolutionary tracks. Additionally, I also analyse the effect of cosmic ray streaming instabilities on particle spectra.
To model the particle acceleration in the remnants, I have performed simulations in one-dimensional spherical symmetry using RATPaC code. The transport equation for cosmic rays and magnetic turbulence in test-particle approximation, along with the induction equation for the evolution of the large-scale magnetic field, have been solved simultaneously with the hydrodynamic equations for the expansion of remnants inside the pre-supernova circumstellar medium.
The results from simulations describe that the spectra of accelerated particles in supernova remnants are regulated by density fluctuations, temperature variations, the large-scale magnetic field configuration and scattering turbulence. Although the diffusive shock acceleration mechanism at supernova remnant shock predicts the spectral index of 2 for the accelerated non-thermal particles, I have obtained the particle spectra that deviate from this prediction, in the core-collapse scenario. I have found that the particle spectral index reaches 2.5 for the supernova remnant with 60 𝑀 ⊙ progenitor when the remnant resides inside the shocked wind region of the wind bubble, and this softness persists at later evolutionary stages even with Bohm-like diffusion for accelerated particles. However, the supernova remnant with 20 𝑀 ⊙ progenitor does not demonstrate persistent softness in particle spectra from the influence of the hydrodynamics of the corresponding wind bubble. At later stages of evolution, the particle spectra illustrate softness at higher energies for both remnants as the consequence of the escape of high-energy particles from the remnants while considering the cosmic ray streaming instabilities. Finally, I have probed the emission morphology of remnants that varies depending on the progenitors, particularly in earlier evolutionary stages. This dissertation provides insight into different core-collapse remnants expanding inside wind bubbles, for instance, the calculated gamma-ray spectral index from the supernova remnant with 60 𝑀 ⊙ progenitor at later evolutionary stages is consistent with that of the observed supernova remnants expanding in dense molecular clouds.
The relevance of physical fitness for children’s and adolescents’ health is indisputable and it is crucial to regularly assess and evaluate children’s and adolescents’ individual physical fitness development to detect potential negative health consequences in time. Physical fitness tests are easy-to-administer, reliable, and valid which is why they should be widely used to provide information on performance development and health status of children and adolescents. When talking about development of physical fitness, two perspectives can be distinguished. One perspective is how the physical fitness status of children and adolescents changed / developed over the past decades (i.e., secular trends). The other perspective covers the analyses how physical fitness develops with increasing age due to growth and maturation processes. Although, the development of children’s and adolescents’ physical fitness has been extensively described and analyzed in the literature, still some questions remain to be uncovered that will be addressed in the present doctoral thesis.
Previous systematic reviews and meta-analyses have examined secular trends in children’s and adolescents’ physical fitness. However, considering that those analyses are by now 15 years old and that updates are available only to limited components of physical fitness, it is time to re-analyze the literature and examine secular trends for selected components of physical fitness (i.e., cardiorespiratory endurance, muscle strength, proxies of muscle power, and speed). Fur-thermore, the available studies on children’s development of physical fitness as well as the ef-fects of moderating variables such as age and sex have been investigated within a long-term ontogenetic perspective. However, the effects of age and sex in the transition from pre-puberty to puberty in the ninth year of life using a short-term ontogenetic perspective and the effect of timing of school enrollment on children’s development of physical fitness have not been clearly identified. Therefore, the present doctoral thesis seeks to complement the knowledge of children’s and adolescents’ physical fitness development by updating secular trend analysis in selected components of physical fitness, by examining short-term ontogenetic cross-sectional developmental differences in children`s physical fitness, and by comparing physical fitness of older- and younger-than-keyage children versus keyage-children. These findings provide valuable information about children’s and adolescents’ physical fitness development to help prevent potential deficits in physical fitness as early as possible and consequently ensure a holistic development and a lifelong healthy life.
Initially, a systematic review to provide an ‘update’ on secular trends in selected components of physical fitness (i.e., cardiorespiratory endurance, relative muscle strength, proxies of muscle power, speed) in children and adolescents aged 6 to 18 years was conducted using the Preferred Reporting Items for Systematic Reviews and Meta-Analysis statement guidelines. To examine short-term ontogenetic cross-sectional developmental differences and to compare physical fitness of older- and younger-than-keyage children versus keyage-children physical fitness data of 108,295 keyage-children (i.e., aged 8.00 to 8.99 years), 2,586 younger-than-keyage children (i.e., aged 7.00 to 7.99 years), and 26,540 older-than-keyage children (i.e., aged 9.00 to 9.99 years) from the third grade were analyzed. Physical fitness was assessed through the EMOTIKON test battery measuring cardiorespiratory endurance (i.e., 6-min-run test), coordina-tion (i.e., star-run test), speed (i.e., 20-m linear sprint test), and proxies of lower (i.e., standing long jump test) and upper limbs (i.e., ball-push test) muscle power. Statistical inference was based on Linear Mixed Models.
Findings from the systematic review revealed a large initial improvement and an equally large subsequent decline between 1986 and 2010 as well as a stabilization between 2010 and 2015 in cardiorespiratory endurance, a general trend towards a small improvement in relative muscle strength from 1972 to 2015, an overall small negative quadratic trend for proxies of muscle power from 1972 to 2015, and a small-to-medium improvement in speed from 2002 to 2015. Findings from the cross-sectional studies showed that even in a single prepubertal year of life (i.e., ninth year) physical fitness performance develops linearly with increasing chronological age, boys showed better performances than girls in all physical fitness components, and the components varied in the size of sex and age effects. Furthermore, findings revealed that older-than-keyage children showed poorer performance in physical fitness compared to keyage-children, older-than-keyage girls showed better performances than older-than-keyage boys, and younger-than-keyage children outperformed keyage-children.
Due to the varying secular trends in physical fitness, it is recommended to promote initiatives for physical activity and physical fitness for children and adolescents to prevent adverse effects on health and well-being. More precisely, public health initiatives should specifically consider exercising cardiorespiratory endurance and muscle strength because both components showed strong positive associations with markers of health. Furthermore, the findings implied that physical education teachers, coaches, or researchers can utilize a proportional adjustment to individually interpret physical fitness of prepubertal school-aged children. Special attention should be given to the promotion of physical fitness of older-than-keyage children because they showed poorer performance in physical fitness than keyage-children. Therefore, it is necessary to specifically consider this group and provide additional health and fitness programs to reduce their deficits in physical fitness experienced during prior years to guarantee a holistic development.
In the last century, several astronomical measurements have supported that a significant percentage (about 22%) of the total mass of the Universe, on galactic and extragalactic scales, is composed of a mysterious ”dark” matter (DM). DM does not interact with the electromagnetic force; in other words it does not reflect, absorb or emit light. It is possible that DM particles are weakly interacting massive particles (WIMPs) that can annihilate (or decay) into Standard Model (SM) particles, and modern very- high-energy (VHE; > 100 GeV) instruments such as imaging atmospheric Cherenkov telescopes (IACTs) can play an important role in constraining the main properties of such DM particles, by detecting these products. One of the most privileged targets where to look for DM signal are dwarf spheroidal galaxies (dSphs), as they are expected to be high DM-dominated objects with a clean, gas-free environment. Some dSphs could be considered as extended sources, considering the angular resolution of IACTs; their angu- lar resolution is adequate to detect extended emission from dSphs. For this reason, we performed an extended-source analysis, by taking into account in the unbinned maximum likelihood estimation both the energy and the angular extension dependency of observed events. The goal was to set more constrained upper limits on the velocity-averaged cross-section annihilation of WIMPs with VERITAS data. VERITAS is an array of four IACTs, able to detect γ-ray photons ranging between 100 GeV and 30 TeV. The results of this extended analysis were compared against the traditional spectral analysis. We found that a 2D analysis may lead to more constrained results, depending on the DM mass, channel, and source. Moreover, in this thesis, the results of a multi-instrument project are presented too. Its goal was to combine already published 20 dSphs data from five different experiments, such as Fermi-LAT, MAGIC, H.E.S.S., VERITAS and HAWC, in order to set upper limits on the WIMP annihilation cross-section in the widest mass range ever reported.
The first part of the thesis studies the properties of fast mode in magneto hydro-dynamic (MHD) turbulence. 1D and 3D numerical simulations are carried out to generate decaying fast mode MHD turbulence. The injection of waves are carried out in a collinear and isotropic fashion to generate fast mode turbulence. The properties of fast mode turbulence are analyzed by studying their energy spectral density, 2D structure functions and energy decay/cascade time. The injection wave vector is varied to study the dependence of the above properties on the injection wave vectors. The 1D energy spectrum obtained for the velocity and magnetic fields has 𝐸 (𝑘) ∝ 𝑘−2. The 2D energy spectrum and 2D structure functions in parallel and perpendicular directions shows that fast mode turbulence generated is isotropic in nature. The cascade/decay rate of fast mode MHD turbulence is proportional to 𝑘−0.5 for different kinds of wave vector injection. Simulations are also carried out in 1D and 3D to compare balanced and imbalanced turbulence. The results obtained shows that while 1D imbalanced turbulence decays faster than 1D balanced turbulence, there is no difference in the decay of 3D balanced and imbalanced turbulence for the current resolution of 512 grid points.
"The second part of the thesis studies cosmic ray (CR) transport in driven MHD turbulence and is strongly dependent on it’s properties. Test particle simulations are carried out to study CR interaction with both total MHD turbulence and decomposed MHD modes. The spatial diffusion coefficients and the pitch angle scattering diffusion coefficients are calculated from the test particle trajectories in turbulence. The results confirms that the fast modes dominate the CR propagation, whereas Alfvén, slow modes are much less efficient with similar pitch angle scattering rates. The cross field transport on large and small scales are investigated next. On large/global scales, normal diffusion is observed and the diffusion coefficient is suppressed by 𝑀𝜁𝐴 compared to the parallel diffusion coefficients, with 𝜁 closer to 4 in Alfvén modes than that in total turbulence as theoretically expected. For the CR transport on scales smaller than the turbulence injection scale 𝐿, both the local and global magnetic reference frames are adopted. Super diffusion is observed on such small scales in all the cases. Particularly, CR transport in Alfvén modes show clear Richardson diffusion in the local reference frame. The diffusion transition smoothly from the Richardson’s one with index 1.5 to normal diffusion as particle’s mean free path decreases from 𝜆∥ ≫ 𝐿 to 𝜆∥ ≪ 𝐿. These results have broad applications to CRs in various astrophysical environments".
We tested whether a brief self-affirmation writing intervention protected against identity-threats (i.e., stereotyping and discrimination) for adolescents' school-related adjustment. The longitudinal study followed 639 adolescents in Germany (65% of immigrant descent, 50% female, M-age = 12.35 years, SDage = .69) from 7(th) grade (pre-intervention at T1, five to six months post-intervention at T2) to the end of 8(th) grade (one-year follow-up at T3). We tested for direct and moderated (by heritage group, discrimination, classroom cultural diversity climate) effects using regression and latent change models. The self-affirmation intervention did not promote grades or math competence. However, in the short-term and for adolescents of immigrant descent, the intervention prevented a downward trajectory in mastery reactions to academic challenges for those experiencing greater discrimination. Further, it protected against a decline in behavioral school engagement for those in positive classroom cultural diversity climates. In the long-term and for all adolescents, the intervention lessened an upward trajectory in disruptive behavior. Overall, the self-affirmation intervention benefited some aspects of school-related adjustment for adolescents of immigrant and non-immigrant descent. The intervention context is important, with classroom cultural diversity climate acting as a psychological affordance enhancing affirmation effects. Our study supports the ongoing call for theorizing and empirically testing student and context heterogeneity to better understand for whom and under which conditions this intervention may work.
Predicting entrepreneurial development based on individual and business-related characteristics is a key objective of entrepreneurship research. In this context, we investigate whether the motives of becoming an entrepreneur influence the subsequent entrepreneurial development. In our analysis, we examine a broad range of business outcomes including survival and income, as well as job creation, and expansion and innovation activities for up to 40 months after business formation. Using the self-determination theory as conceptual background, we aggregate the start-up motives into a continuous motivational index. We show – based on a unique dataset of German start-ups from unemployment and non-unemployment – that the later business performance is better, the higher they score on this index. Effects are particularly strong for growth-oriented outcomes like innovation and expansion activities. In a next step, we examine three underlying motivational categories that we term opportunity, career ambition, and necessity. We show that individuals driven by opportunity motives perform better in terms of innovation and business expansion activities, while career ambition is positively associated with survival, income, and the probability of hiring employees. All effects are robust to the inclusion of a large battery of covariates that are proven to be important determinants of entrepreneurial performance.
Additive manufacturing (AM) processes enable the production of metal structures with exceptional design freedom, of which laser powder bed fusion (PBF-LB) is one of the most common. In this process, a laser melts a bed of loose feedstock powder particles layer-by-layer to build a structure with the desired geometry. During fabrication, the repeated melting and rapid, directional solidification create large temperature gradients that generate large thermal stress. This thermal stress can itself lead to cracking or delamination during fabrication. More often, large residual stresses remain in the final part as a footprint of the thermal stress. This residual stress can cause premature distortion or even failure of the part in service. Hence, knowledge of the residual stress field is critical for both process optimization and structural integrity.
Diffraction-based techniques allow the non-destructive characterization of the residual stress fields. However, such methods require a good knowledge of the material of interest, as certain assumptions must be made to accurately determine residual stress. First, the measured lattice plane spacings must be converted to lattice strains with the knowledge of a strain-free material state. Second, the measured lattice strains must be related to the macroscopic stress using Hooke's law, which requires knowledge of the stiffness of the material. Since most crystal structures exhibit anisotropic material behavior, the elastic behavior is specific to each lattice plane of the single crystal. Thus, the use of individual lattice planes in monochromatic diffraction residual stress analysis requires knowledge of the lattice plane-specific elastic properties. In addition, knowledge of the microstructure of the material is required for a reliable assessment of residual stress.
This work presents a toolbox for reliable diffraction-based residual stress analysis. This is presented for a nickel-based superalloy produced by PBF-LB. First, this work reviews the existing literature in the field of residual stress analysis of laser-based AM using diffraction-based techniques. Second, the elastic and plastic anisotropy of the nickel-based superalloy Inconel 718 produced by PBF-LB is studied using in situ energy dispersive synchrotron X-ray and neutron diffraction techniques. These experiments are complemented by ex situ material characterization techniques. These methods establish the relationship between the microstructure and texture of the material and its elastic and plastic anisotropy. Finally, surface, sub-surface, and bulk residual stress are determined using a texture-based approach. Uncertainties of different methods for obtaining stress-free reference values are discussed.
The tensile behavior in the as-built condition is shown to be controlled by texture and cellular sub-grain structure, while in the heat-treated condition the precipitation of strengthening phases and grain morphology dictate the behavior. In fact, the results of this thesis show that the diffraction elastic constants depend on the underlying microstructure, including texture and grain morphology. For columnar microstructures in both as-built and heat-treated conditions, the diffraction elastic constants are best described by the Reuss iso-stress model. Furthermore, the low accumulation of intergranular strains during deformation demonstrates the robustness of using the 311 reflection for the diffraction-based residual stress analysis with columnar textured microstructures. The differences between texture-based and quasi-isotropic approaches for the residual stress analysis are shown to be insignificant in the observed case. However, the analysis of the sub-surface residual stress distributions show, that different scanning strategies result in a change in the orientation of the residual stress tensor. Furthermore, the location of the critical sub-surface tensile residual stress is related to the surface roughness and the microstructure. Finally, recommendations are given for the diffraction-based determination and evaluation of residual stress in textured additively manufactured alloys.
The European Water Framework Directive (WFD) has identified river morphological alteration and diffuse pollution as the two main pressures affecting water bodies in Europe at the catchment scale. Consequently, river restoration has become a priority to achieve the WFD's objective of good ecological status. However, little is known about the effects of stream morphological changes, such as re-meandering, on in-stream nitrate retention at the river network scale. Therefore, catchment nitrate modeling is necessary to guide the implementation of spatially targeted and cost-effective mitigation measures. Meanwhile, Germany, like many other regions in central Europe, has experienced consecutive summer droughts from 2015-2018, resulting in significant changes in river nitrate concentrations in various catchments. However, the mechanistic exploration of catchment nitrate responses to changing weather conditions is still lacking.
Firstly, a fully distributed, process-based catchment Nitrate model (mHM-Nitrate) was used, which was properly calibrated and comprehensively evaluated at numerous spatially distributed nitrate sampling locations. Three calibration schemes were designed, taking into account land use, stream order, and mean nitrate concentrations, and they varied in spatial coverage but used data from the same period (2011–2019). The model performance for discharge was similar among the three schemes, with Nash-Sutcliffe Efficiency (NSE) scores ranging from 0.88 to 0.92. However, for nitrate concentrations, scheme 2 outperformed schemes 1 and 3 when compared to observed data from eight gauging stations. This was likely because scheme 2 incorporated a diverse range of data, including low discharge values and nitrate concentrations, and thus provided a better representation of within-catchment heterogenous. Therefore, the study suggests that strategically selecting gauging stations that reflect the full range of within-catchment heterogeneity is more important for calibration than simply increasing the number of stations.
Secondly, the mHM-Nitrate model was used to reveal the causal relations between sequential droughts and nitrate concentration in the Bode catchment (3200 km2) in central Germany, where stream nitrate concentrations exhibited contrasting trends from upstream to downstream reaches. The model was evaluated using data from six gauging stations, reflecting different levels of runoff components and their associated nitrate-mixing from upstream to downstream. Results indicated that the mHM-Nitrate model reproduced dynamics of daily discharge and nitrate concentration well, with Nash-Sutcliffe Efficiency ≥ 0.73 for discharge and Kling-Gupta Efficiency ≥ 0.50 for nitrate concentration at most stations. Particularly, the spatially contrasting trends of nitrate concentration were successfully captured by the model. The decrease of nitrate concentration in the lowland area in drought years (2015-2018) was presumably due to (1) limited terrestrial export loading (ca. 40% lower than that of normal years 2004-2014), and (2) increased in-stream retention efficiency (20% higher in summer within the whole river network). From a mechanistic modelling perspective, this study provided insights into spatially heterogeneous flow and nitrate dynamics and effects of sequential droughts, which shed light on water-quality responses to future climate change, as droughts are projected to be more frequent.
Thirdly, this study investigated the effects of stream restoration via re-meandering on in-stream nitrate retention at network-scale in the well-monitored Bode catchment. The mHM-Nitrate model showed good performance in reproducing daily discharge and nitrate concentrations, with median Kling-Gupta values of 0.78 and 0.74, respectively. The mean and standard deviation of gross nitrate retention efficiency, which accounted for both denitrification and assimilatory uptake, were 5.1 ± 0.61% and 74.7 ± 23.2% in winter and summer, respectively, within the stream network. The study found that in the summer, denitrification rates were about two times higher in lowland sub-catchments dominated by agricultural lands than in mountainous sub-catchments dominated by forested areas, with median ± SD of 204 ± 22.6 and 102 ± 22.1 mg N m-2 d-1, respectively. Similarly, assimilatory uptake rates were approximately five times higher in streams surrounded by lowland agricultural areas than in those in higher-elevation, forested areas, with median ± SD of 200 ± 27.1 and 39.1 ± 8.7 mg N m-2 d-1, respectively. Therefore, restoration strategies targeting lowland agricultural areas may have greater potential for increasing nitrate retention. The study also found that restoring stream sinuosity could increase net nitrate retention efficiency by up to 25.4 ± 5.3%, with greater effects seen in small streams. These results suggest that restoration efforts should consider augmenting stream sinuosity to increase nitrate retention and decrease nitrate concentrations at the catchment scale.
Climate change fundamentally transforms glaciated high-alpine regions, with well-known cryospheric and hydrological implications, such as accelerating glacier retreat, transiently increased runoff, longer snow-free periods and more frequent and intense summer rainstorms. These changes affect the availability and transport of sediments in high alpine areas by altering the interaction and intensity of different erosion processes and catchment properties.
Gaining insight into the future alterations in suspended sediment transport by high alpine streams is crucial, given its wide-ranging implications, e.g. for flood damage potential, flood hazard in downstream river reaches, hydropower production, riverine ecology and water quality. However, the current understanding of how climate change will impact suspended sediment dynamics in these high alpine regions is limited. For one, this is due to the scarcity of measurement time series that are long enough to e.g. infer trends. On the other hand, it is difficult – if not impossible – to develop process-based models, due to the complexity and multitude of processes involved in high alpine sediment dynamics. Therefore, knowledge has so far been confined to conceptual models (which do not facilitate deriving concrete timings or magnitudes for individual catchments) or qualitative estimates (‘higher export in warmer years’) that may not be able to capture decreases in sediment export. Recently, machine-learning approaches have gained in popularity for modeling sediment dynamics, since their black box nature tailors them to the problem at hand, i.e. relatively well-understood input and output data, linked by very complex processes.
Therefore, the overarching aim of this thesis is to estimate sediment export from the high alpine Ötztal valley in Tyrol, Austria, over decadal timescales in the past and future – i.e. timescales relevant to anthropogenic climate change. This is achieved by informing, extending, evaluating and applying a quantile regression forest (QRF) approach, i.e. a nonparametric, multivariate machine-learning technique based on random forest.
The first study included in this thesis aimed to understand present sediment dynamics, i.e. in the period with available measurements (up to 15 years). To inform the modeling setup for the two subsequent studies, this study identified the most important predictors, areas within the catchments and time periods. To that end, water and sediment yields from three nested gauges in the upper Ötztal, Vent, Sölden and Tumpen (98 to almost 800 km² catchment area, 930 to 3772 m a.s.l.) were analyzed for their distribution in space, their seasonality and spatial differences therein, and the relative importance of short-term events. The findings suggest that the areas situated above 2500 m a.s.l., containing glacier tongues and recently deglaciated areas, play a pivotal role in sediment generation across all sub-catchments. In contrast, precipitation events were relatively unimportant (on average, 21 % of annual sediment yield was associated to precipitation events). Thus, the second and third study focused on the Vent catchment and its sub-catchment above gauge Vernagt (11.4 and 98 km², 1891 to 3772 m a.s.l.), due to their higher share of areas above 2500 m. Additionally, they included discharge, precipitation and air temperature (as well as their antecedent conditions) as predictors.
The second study aimed to estimate sediment export since the 1960s/70s at gauges Vent and Vernagt. This was facilitated by the availability of long records of the predictors, discharge, precipitation and air temperature, and shorter records (four and 15 years) of turbidity-derived sediment concentrations at the two gauges. The third study aimed to estimate future sediment export until 2100, by applying the QRF models developed in the second study to pre-existing precipitation and temperature projections (EURO-CORDEX) and discharge projections (physically-based hydroclimatological and snow model AMUNDSEN) for the three representative concentration pathways RCP2.6, RCP4.5 and RCP8.5.
The combined results of the second and third study show overall increasing sediment export in the past and decreasing export in the future. This suggests that peak sediment is underway or has already passed – unless precipitation changes unfold differently than represented in the projections or changes in the catchment erodibility prevail and override these trends. Despite the overall future decrease, very high sediment export is possible in response to precipitation events. This two-fold development has important implications for managing sediment, flood hazard and riverine ecology.
This thesis shows that QRF can be a very useful tool to model sediment export in high-alpine areas. Several validations in the second study showed good performance of QRF and its superiority to traditional sediment rating curves – especially in periods that contained high sediment export events, which points to its ability to deal with threshold effects. A technical limitation of QRF is the inability to extrapolate beyond the range of values represented in the training data. We assessed the number and severity of such out-of-observation-range (OOOR) days in both studies, which showed that there were few OOOR days in the second study and that uncertainties associated with OOOR days were small before 2070 in the third study. As the pre-processed data and model code have been made publically available, future studies can easily test further approaches or apply QRF to further catchments.
Large parts of the Earth’s interior are inaccessible to direct observation, yet global geodynamic processes are governed by the physical material properties under extreme pressure and temperature conditions. It is therefore essential to investigate the deep Earth’s physical properties through in-situ laboratory experiments. With this goal in mind, the optical properties of mantle minerals at high pressure offer a unique way to determine a variety of physical properties, in a straight-forward, reproducible, and time-effective manner, thus providing valuable insights into the physical processes of the deep Earth. This thesis focusses on the system Mg-Fe-O, specifically on the optical properties of periclase (MgO) and its iron-bearing variant ferropericlase ((Mg,Fe)O), forming a major planetary building block. The primary objective is to establish links between physical material properties and optical properties. In particular the spin transition in ferropericlase, the second-most abundant phase of the lower mantle, is known to change the physical material properties. Although the spin transition region likely extends down to the core-mantle boundary, the ef-fects of the mixed-spin state, where both high- and low-spin state are present, remains poorly constrained.
In the studies presented herein, we show how optical properties are linked to physical properties such as electrical conductivity, radiative thermal conductivity and viscosity. We also show how the optical properties reveal changes in the chemical bonding. Furthermore, we unveil how the chemical bonding, the optical and other physical properties are affected by the iron spin transition. We find opposing trends in the pres-sure dependence of the refractive index of MgO and (Mg,Fe)O. From 1 atm to ~140 GPa, the refractive index of MgO decreases by ~2.4% from 1.737 to 1.696 (±0.017). In contrast, the refractive index of (Mg0.87Fe0.13)O (Fp13) and (Mg0.76Fe0.24)O (Fp24) ferropericlase increases with pressure, likely because Fe Fe interactions between adjacent iron sites hinder a strong decrease of polarizability, as it is observed with increasing density in the case of pure MgO. An analysis of the index dispersion in MgO (decreasing by ~23% from 1 atm to ~103 GPa) reflects a widening of the band gap from ~7.4 eV at 1 atm to ~8.5 (±0.6) eV at ~103 GPa. The index dispersion (between 550 and 870 nm) of Fp13 reveals a decrease by a factor of ~3 over the spin transition range (~44–100 GPa). We show that the electrical band gap of ferropericlase significantly widens up to ~4.7 eV in the mixed spin region, equivalent to an increase by a factor of ~1.7. We propose that this is due to a lower electron mobility between adjacent Fe2+ sites of opposite spin, explaining the previously observed low electrical conductivity in the mixed spin region. From the study of absorbance spectra in Fp13, we show an increasing covalency of the Fe-O bond with pressure for high-spin ferropericlase, whereas in the low-spin state a trend to a more ionic nature of the Fe-O bond is observed, indicating a bond weakening effect of the spin transition. We found that the spin transition is ultimately caused by both an increase of the ligand field-splitting energy and a decreasing spin-pairing energy of high-spin Fe2+.
The reliance on fossil fuels has resulted in an abnormal increase in the concentration of greenhouse gases, contributing to the global climate crisis. In response, a rapid transition to renewable energy sources has begun, particularly lithium-ion batteries, playing a crucial role in the green energy transformation. However, concerns regarding the availability and geopolitical implications of lithium have prompted the exploration of alternative rechargeable battery systems, such as sodium-ion batteries. Sodium is significantly abundant and more homogeneously distributed in the crust and seawater, making it easier and less expensive to extract than lithium. However, because of the mysterious nature of its components, sodium-ion batteries are not yet sufficiently advanced to take the place of lithium-ion batteries. Specifically, sodium exhibits a more metallic character and a larger ionic radius, resulting in a different ion storage mechanism utilized in lithium-ion batteries. Innovations in synthetic methods, post-treatments, and interface engineering clearly demonstrate the significance of developing high-performance carbonaceous anode materials for sodium-ion batteries. The objective of this dissertation is to present a systematic approach for fabricating efficient, high-performance, and sustainable carbonaceous anode materials for sodium-ion batteries. This will involve a comprehensive investigation of different chemical environments and post-modification techniques as well.
This dissertation focuses on three main objectives. Firstly, it explores the significance of post-synthetic methods in designing interfaces. A conformal carbon nitride coating is deposited through chemical vapor deposition on a carbon electrode as an artificial solid-electrolyte interface layer, resulting in improved electrochemical performance. The interaction between the carbon nitride artificial interface and the carbon electrode enhances initial Coulombic efficiency, rate performance, and total capacity. Secondly, a novel process for preparing sulfur-rich carbon as a high-performing anode material for sodium-ion batteries is presented. The method involves using an oligo-3,4-ethylenedioxythiophene precursor for high sulfur content hard carbon anode to investigate the sulfur heteroatom effect on the electrochemical sodium storage mechanism. By optimizing the condensation temperature, a significant transformation in the materials’ nanostructure is achieved, leading to improved electrochemical performance. The use of in-operando small-angle X-ray scattering provides valuable insights into the interaction between micropores and sodium ions during the electrochemical processes. Lastly, the development of high-capacity hard carbon, derived from 5-hydroxymethyl furfural, is examined. This carbon material exhibits exceptional performance at both low and high current densities. Extensive electrochemical and physicochemical characterizations shed light on the sodium storage mechanism concerning the chemical environment, establishing the material’s stability and potential applications in sodium-ion batteries.
The evaluation of process-oriented cognitive theories through time-ordered observations is crucial for the advancement of cognitive science. The findings presented herein integrate insights from research on eye-movement control and sentence comprehension during reading, addressing challenges in modeling time-ordered data, statistical inference, and interindividual variability. Using kernel density estimation and a pseudo-marginal likelihood for fixation durations and locations, a likelihood implementation of the SWIFT model of eye-movement control during reading (Engbert et al., Psychological Review, 112, 2005, pp. 777–813) is proposed. Within the broader framework of data assimilation, Bayesian parameter inference with adaptive Markov Chain Monte Carlo techniques is facilitated for reliable model fitting. Across the different studies, this framework has shown to enable reliable parameter recovery from simulated data and prediction of experimental summary statistics. Despite its complexity, SWIFT can be fitted within a principled Bayesian workflow, capturing interindividual differences and modeling experimental effects on reading across different geometrical alterations of text. Based on these advancements, the integrated dynamical model SEAM is proposed, which combines eye-movement control, a traditionally psychological research area, and post-lexical language processing in the form of cue-based memory retrieval (Lewis & Vasishth, Cognitive Science, 29, 2005, pp. 375–419), typically the purview of psycholinguistics. This proof-of-concept integration marks a significant step forward in natural language comprehension during reading and suggests that the presented methodology can be useful to develop complex cognitive dynamical models that integrate processes at levels of perception, higher cognition, and (oculo-)motor control. These findings collectively advance process-oriented cognitive modeling and highlight the importance of Bayesian inference, individual differences, and interdisciplinary integration for a holistic understanding of reading processes. Implications for theory and methodology, including proposals for model comparison and hierarchical parameter inference, are briefly discussed.