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We report on new mass-loss rate estimates for O stars in six massive binaries using the amplitude of orbital-phase dependent, linear-polarimetric variability caused by electron scattering off free electrons in the winds. Our estimated mass-loss rates for luminous O stars are independent of clumping. They suggest similar clumping corrections as for WR stars and do not support the recently proposed reduction in mass-loss rates of O stars by one or two orders of magnitude.
We examine how the gender of business-owners is related to the wages paid to female relative to male employees working in their firms. Using Finnish register data and employing firm fixed effects, we find that the gender pay gap is – starting from a gender pay gap of 11 to 12 percent - two to three percentage-points lower for hourly wages in female-owned firms than in male-owned firms. Results are robust to how the wage is measured, as well as to various further robustness checks. More importantly, we find substantial differences between industries. While, for instance, in the manufacturing sector, the gender of the owner plays no role for the gender pay gap, in several service sector industries, like ICT or business services, no or a negligible gender pay gap can be found, but only when firms are led by female business owners. Businesses in male ownership maintain a gender pay gap of around 10 percent also in the latter industries. With increasing firm size, the influence of the gender of the owner, however, fades. In large firms, it seems that others – firm managers – determine wages and no differences in the pay gap are observed between male- and female-owned firms.
We investigate whether political ideology has an observable effect on decarbonization ambition, renewable power aims, and preferences for power system balancing technologies in four European countries. Based on the Energy Logics framework, we identify ideologically different transition strategies (state-centered, market-centered, grassroots-centered) contained in government policies and opposition party programs valid in 2019. We compare these policies and programs with citizen poll data. We find that ideology has a small effect: governments and political parties across the spectrum have similar, and relatively ambitious, decarbonization and renewables targets. This mirrors citizens' strong support for ambitious action regardless of their ideological self-description. However, whereas political positions on phasing out fossil fuel power are clear across the policy space, positions on phasing in new flexibility options to balance intermittent renewables are vague or non-existent. As parties and citizens agree on strong climate and renewable power aims, the policy ambition is likely to remain high, even if governments change.
Expanding public or publicly subsidized childcare has been a top social policy priority in many industrialized countries. It is supposed to increase fertility, promote children’s development and enhance mothers’ labor market attachment. In this paper, we analyze the causal effect of one of the largest expansions of subsidized childcare for children up to three years among industrialized countries on the employment of mothers in Germany. Identification is based on spatial and temporal variation in the expansion of publicly subsidized childcare triggered by two comprehensive childcare policy reforms. The empirical analysis is based on the German Microcensus that is matched to county level data on childcare availability. Based on our preferred specification which includes time and county fixed effects we find that an increase in childcare slots by one percentage point increases mothers’ labor market participation rate by 0.2 percentage points. The overall increase in employment is explained by the rise in part-time employment with relatively long hours (20-35 hours per week). We do not find a change in full-time employment or lower part-time employment that is causally related to the childcare expansion. The effect is almost entirely driven by mothers with medium-level qualifications. Mothers with low education levels do not profit from this reform calling for a stronger policy focus on particularly disadvantaged groups in coming years.
Dryland vulnerability : typical patterns and dynamics in support of vulnerability reduction efforts
(2011)
The pronounced constraints on ecosystem functioning and human livelihoods in drylands are frequently exacerbated by natural and socio-economic stresses, including weather extremes and inequitable trade conditions. Therefore, a better understanding of the relation between these stresses and the socio-ecological systems is important for advancing dryland development. The concept of vulnerability as applied in this dissertation describes this relation as encompassing the exposure to climate, market and other stresses as well as the sensitivity of the systems to these stresses and their capacity to adapt. With regard to the interest in improving environmental and living conditions in drylands, this dissertation aims at a meaningful generalisation of heterogeneous vulnerability situations. A pattern recognition approach based on clustering revealed typical vulnerability-creating mechanisms at global and local scales. One study presents the first analysis of dryland vulnerability with global coverage at a sub-national resolution. The cluster analysis resulted in seven typical patterns of vulnerability according to quantitative indication of poverty, water stress, soil degradation, natural agro-constraints and isolation. Independent case studies served to validate the identified patterns and to prove the transferability of vulnerability-reducing approaches. Due to their worldwide coverage, the global results allow the evaluation of a specific system’s vulnerability in its wider context, even in poorly-documented areas. Moreover, climate vulnerability of smallholders was investigated with regard to their food security in the Peruvian Altiplano. Four typical groups of households were identified in this local dryland context using indicators for harvest failure risk, agricultural resources, education and non-agricultural income. An elaborate validation relying on independently acquired information demonstrated the clear correlation between weather-related damages and the identified clusters. It also showed that household-specific causes of vulnerability were consistent with the mechanisms implied by the corresponding patterns. The synthesis of the local study provides valuable insights into the tailoring of interventions that reflect the heterogeneity within the social group of smallholders. The conditions necessary to identify typical vulnerability patterns were summarised in five methodological steps. They aim to motivate and to facilitate the application of the selected pattern recognition approach in future vulnerability analyses. The five steps outline the elicitation of relevant cause-effect hypotheses and the quantitative indication of mechanisms as well as an evaluation of robustness, a validation and a ranking of the identified patterns. The precise definition of the hypotheses is essential to appropriately quantify the basic processes as well as to consistently interpret, validate and rank the clusters. In particular, the five steps reflect scale-dependent opportunities, such as the outcome-oriented aspect of validation in the local study. Furthermore, the clusters identified in Northeast Brazil were assessed in the light of important endogenous processes in the smallholder systems which dominate this region. In order to capture these processes, a qualitative dynamic model was developed using generalised rules of labour allocation, yield extraction, budget constitution and the dynamics of natural and technological resources. The model resulted in a cyclic trajectory encompassing four states with differing degree of criticality. The joint assessment revealed aggravating conditions in major parts of the study region due to the overuse of natural resources and the potential for impoverishment. The changes in vulnerability-creating mechanisms identified in Northeast Brazil are well-suited to informing local adjustments to large-scale intervention programmes, such as “Avança Brasil”. Overall, the categorisation of a limited number of typical patterns and dynamics presents an efficient approach to improving our understanding of dryland vulnerability. Appropriate decision-making for sustainable dryland development through vulnerability reduction can be significantly enhanced by pattern-specific entry points combined with insights into changing hotspots of vulnerability and the transferability of successful adaptation strategies.
In this paper, we consider families of time Markov fields (or reciprocal classes) which have the same bridges as a Brownian diffusion. We characterize each class as the set of solutions of an integration by parts formula on the space of continuous paths C[0; 1]; R-d) Our techniques provide a characterization of gradient diffusions by a duality formula and, in case of reversibility, a generalization of a result of Kolmogorov.
Dynamical simulation of the “velocity-porosity” reduction in observed strength of stellar wind lines
(2007)
I use dynamical simulations of the line-driven instability to examine the potential role of the resulting flow structure in reducing the observed strength of wind absorption lines. Instead of the porosity length formalism used to model effects on continuum absorption, I suggest reductions in line strength can be better characterized in terms of a velocity clumping factor that is insensitive to spatial scales. Examples of dynamic spectra computed directly from instability simulations do exhibit a net reduction in absorption, but only at a modest 10-20% level that is well short of the ca. factor 10 required by recent analyses of PV lines.
In the arable soil landscape of hummocky ground moraines, an erosion-affected spatial differentiation of soils can be observed. Man-made erosion leads to soil profile modifications along slopes with changed solum thickness and modified properties of soil horizons due to water erosion in combination with tillage operations. Soil erosion creates, thereby, spatial patterns of soil properties (e.g., texture and organic matter content) and differences in crop development. However, little is known about the manner in which water fluxes are affected by soil-crop interactions depending on contrasting properties of differently-developed soil horizons and how water fluxes influence the carbon transport in an eroded landscape. To identify such feedbacks between erosion-induced soil profile modifications and the 1D-water and solute balance, high-precision weighing lysimeters equipped with a wide range of sensor technique were filled with undisturbed soil monoliths that differed in the degree of past soil erosion. Furthermore, lysimeter effluent concentrations were analyzed for dissolved carbon fractions in bi-weekly intervals.
The water balance components measured by high precision lysimeters varied from the most eroded to the less eroded monolith up to 83 % (deep drainage) primarily caused due to varying amounts of precipitation and evapotranspiration for a 3-years period. Here, interactions between crop development and contrasting rainfall interception by above ground biomass could explain differences in water balance components. Concentrations of dissolved carbon in soil water samples were relatively constant in time, suggesting carbon leaching was mainly affected by water fluxes in this observation period. For the lysimeter-based water balance analysis, a filtering scheme was developed considering temporal autocorrelation. The minute-based autocorrelation analysis of mass changes from lysimeter time series revealed characteristic autocorrelation lengths ranging from 23 to 76 minutes. Thereby, temporal autocorrelation provided an optimal approximation of precipitation quantities. However, the high temporal resolution in lysimeter time series is restricted by the lengths of autocorrelation.
Erosion-induced but also gradual changes in soil properties were reflected by dynamics of soil water retention properties in the lysimeter soils. Short-term and long-term hysteretic water retention data suggested seasonal wettability problems of soils increasingly limited rewetting of previously dried pore regions. Differences in water retention were assigned to soil tillage operations and the erosion history at different slope positions. The threedimensional spatial pattern of soil types that result from erosional soil profile modifications were also reflected in differences of crop root development at different landscape positions. Contrasting root densities revealed positive relations of root and aboveground plant characteristics. Differences in the spatially-distributed root growth between different eroded soil types provided indications that root development was affected by the erosion-induced soil evolution processes.
Overall, the current thesis corroborated the hypothesis that erosion-induced soil profile modifications affect the soil water balance, carbon leaching and soil hydraulic properties, but also the crop root system is influenced by erosion-induced spatial patterns of soil properties in the arable hummocky post glacial soil landscape. The results will help to improve model predictions of water and solute movement in arable soils and to understand interactions between soil erosion and carbon pathways regarding sink-or-source terms in landscapes.
Data obtained from foreign data sources often come with only superficial structural information, such as relation names and attribute names. Other types of metadata that are important for effective integration and meaningful querying of such data sets are missing. In particular, relationships among attributes, such as foreign keys, are crucial metadata for understanding the structure of an unknown database. The discovery of such relationships is difficult, because in principle for each pair of attributes in the database each pair of data values must be compared. A precondition for a foreign key is an inclusion dependency (IND) between the key and the foreign key attributes. We present with Spider an algorithm that efficiently finds all INDs in a given relational database. It leverages the sorting facilities of DBMS but performs the actual comparisons outside of the database to save computation. Spider analyzes very large databases up to an order of magnitude faster than previous approaches. We also evaluate in detail the effectiveness of several heuristics to reduce the number of necessary comparisons. Furthermore, we generalize Spider to find composite INDs covering multiple attributes, and partial INDs, which are true INDs for all but a certain number of values. This last type is particularly relevant when integrating dirty data as is often the case in the life sciences domain - our driving motivation.
To achieve a sustainable energy economy, it is necessary to turn back on the combustion of fossil fuels as a means of energy production and switch to renewable sources. However, their temporal availability does not match societal consumption needs, meaning that renewably generated energy must be stored in its main generation times and allocated during peak consumption periods. Electrochemical energy storage (EES) in general is well suited due to its infrastructural independence and scalability. The lithium ion battery (LIB) takes a special place, among EES systems due to its energy density and efficiency, but the scarcity and uneven geological occurrence of minerals and ores vital for many cell components, and hence the high and fluctuating costs will decelerate its further distribution.
The sodium ion battery (SIB) is a promising successor to LIB technology, as the fundamental setup and cell chemistry is similar in the two systems. Yet, the most widespread negative electrode material in LIBs, graphite, cannot be used in SIBs, as it cannot store sufficient amounts of sodium at reasonable potentials. Hence, another carbon allotrope, non-graphitizing or hard carbon (HC) is used in SIBs. This material consists of turbostratically disordered, curved graphene layers, forming regions of graphitic stacking and zones of deviating layers, so-called internal or closed pores.
The structural features of HC have a substantial impact of the charge-potential curve exhibited by the carbon when it is used as the negative electrode in an SIB. At defects and edges an adsorption-like mechanism of sodium storage is prevalent, causing a sloping voltage curve, ill-suited for the practical application in SIBs, whereas a constant voltage plateau of relatively high capacities is found immediately after the sloping region, which recent research attributed to the deposition of quasimetallic sodium into the closed pores of HC.
Literature on the general mechanism of sodium storage in HCs and especially the role of the closed pore is abundant, but the influence of the pore geometry and chemical nature of the HC on the low-potential sodium deposition is yet in an early stage. Therefore, the scope of this thesis is to investigate these relationships using suitable synthetic and characterization methods. Materials of precisely known morphology, porosity, and chemical structure are prepared in clear distinction to commonly obtained ones and their impact on the sodium storage characteristics is observed. Electrochemical impedance spectroscopy in combination with distribution of relaxation times analysis is further established as a technique to study the sodium storage process, in addition to classical direct current techniques, and an equivalent circuit model is proposed to qualitatively describe the HC sodiation mechanism, based on the recorded data. The obtained knowledge is used to develop a method for the preparation of closed porous and non-porous materials from open porous ones, proving not only the necessity of closed pores for efficient sodium storage, but also providing a method for effective pore closure and hence the increase of the sodium storage capacity and efficiency of carbon materials.
The insights obtained and methods developed within this work hence not only contribute to the better understanding of the sodium storage mechanism in carbon materials of SIBs, but can also serve as guidance for the design of efficient electrode materials.
Our dynamic Sun manifests its activity by different phenomena: from the 11-year cyclic sunspot pattern to the unpredictable and violent explosions in the case of solar flares. During flares, a huge amount of the stored magnetic energy is suddenly released and a substantial part of this energy is carried by the energetic electrons, considered to be the source of the nonthermal radio and X-ray radiation. One of the most important and still open question in solar physics is how the electrons are accelerated up to high energies within (the observed in the radio emission) short time scales. Because the acceleration site is extremely small in spatial extent as well (compared to the solar radius), the electron acceleration is regarded as a local process. The search for localized wave structures in the solar corona that are able to accelerate electrons together with the theoretical and numerical description of the conditions and requirements for this process, is the aim of the dissertation. Two models of electron acceleration in the solar corona are proposed in the dissertation: I. Electron acceleration due to the solar jet interaction with the background coronal plasma (the jet--plasma interaction) A jet is formed when the newly reconnected and highly curved magnetic field lines are relaxed by shooting plasma away from the reconnection site. Such jets, as observed in soft X-rays with the Yohkoh satellite, are spatially and temporally associated with beams of nonthermal electrons (in terms of the so-called type III metric radio bursts) propagating through the corona. A model that attempts to give an explanation for such observational facts is developed here. Initially, the interaction of such jets with the background plasma leads to an (ion-acoustic) instability associated with growing of electrostatic fluctuations in time for certain range of the jet initial velocity. During this process, any test electron that happen to feel this electrostatic wave field is drawn to co-move with the wave, gaining energy from it. When the jet speed has a value greater or lower than the one, required by the instability range, such wave excitation cannot be sustained and the process of electron energization (acceleration and/or heating) ceases. Hence, the electrons can propagate further in the corona and be detected as type III radio burst, for example. II. Electron acceleration due to attached whistler waves in the upstream region of coronal shocks (the electron--whistler--shock interaction) Coronal shocks are also able to accelerate electrons, as observed by the so-called type II metric radio bursts (the radio signature of a shock wave in the corona). From in-situ observations in space, e.g., at shocks related to co-rotating interaction regions, it is known that nonthermal electrons are produced preferably at shocks with attached whistler wave packets in their upstream regions. Motivated by these observations and assuming that the physical processes at shocks are the same in the corona as in the interplanetary medium, a new model of electron acceleration at coronal shocks is presented in the dissertation, where the electrons are accelerated by their interaction with such whistlers. The protons inflowing toward the shock are reflected there by nearly conserving their magnetic moment, so that they get a substantial velocity gain in the case of a quasi-perpendicular shock geometry, i.e, the angle between the shock normal and the upstream magnetic field is in the range 50--80 degrees. The so-accelerated protons are able to excite whistler waves in a certain frequency range in the upstream region. When these whistlers (comprising the localized wave structure in this case) are formed, only the incoming electrons are now able to interact resonantly with them. But only a part of these electrons fulfill the the electron--whistler wave resonance condition. Due to such resonant interaction (i.e., of these electrons with the whistlers), the electrons are accelerated in the electric and magnetic wave field within just several whistler periods. While gaining energy from the whistler wave field, the electrons reach the shock front and, subsequently, a major part of them are reflected back into the upstream region, since the shock accompanied with a jump of the magnetic field acts as a magnetic mirror. Co-moving with the whistlers now, the reflected electrons are out of resonance and hence can propagate undisturbed into the far upstream region, where they are detected in terms of type II metric radio bursts. In summary, the kinetic energy of protons is transfered into electrons by the action of localized wave structures in both cases, i.e., at jets outflowing from the magnetic reconnection site and at shock waves in the corona.
The self-employed faced strong income losses during the Covid-19 pandemic. Many governments introduced programs to financially support the self-employed during the pandemic, including Germany. The German Ministry for Economic Affairs announced a €50bn emergency-aid program in March 2020, offering one-off lump-sum payments of up to €15,000 to those facing substantial revenue declines. By reassuring the self- employed that the government ‘would not let them down’ during the crisis, the program had also the important aim of motivating the self-employed to get through the crisis. We investigate whether the program affected the confidence of the self-employed to survive the crisis using real-time online-survey data comprising more than 20,000 observations. We employ propensity score matching, making use of a rich set of variables that influence the subjective survival probability as main outcome measure. We observe that this program had significant effects, with the subjective survival probability of the self- employed being moderately increased. We reveal important effect heterogeneities with respect to education, industries, and speed of payment. Notably, positive effects only occur among those self-employed whose application was processed quickly. This suggests stress-induced waiting costs due to the uncertainty associated with the administrative processing and the overall pandemic situation. Our findings have policy implications for the design of support programs, while also contributing to the literature on the instruments and effects of entrepreneurship policy interventions in crisis situations.
We study the effect of energy and transport policies on pollution in two developing country cities. We use a quantitative equilibrium model with choice of housing, energy use, residential location, transport mode, and energy technology. Pollution comes from commuting and residential energy use. The model parameters are calibrated to replicate key variables for two developing country cities, Maputo, Mozambique, and Yogyakarta, Indonesia. In the counterfactual simulations, we study how various transport and energy policies affect equilibrium pollution. Policies may be induce rebound effects from increasing residential energy use or switching to high emission modes or locations. In general, these rebound effects tend to be largest for subsidies to public transport or modern residential energy technology.
During the National Multiplication Training in Kenya in 2018, participants raised concerns about attrition, completion rates and quality of PhD programmes in Kenya’s public universities. This led the authors of this article to further examine the question of PhD completion rates. Available data underlined that PhD students across various disciplines in Kenya’s public universities take unnecessarily long to complete their studies due to a myriad of factors that are related to their supervisors, university guidelines for post-graduate studies, or the students themselves. This article examines inertia areas along the PhD training pathway at three public universities in Kenya and provides suggestions on structural and operational changes universities must make to shorten completion periods.
This article collected the results of a qualitative study focused on Colombian Higher Education Institutions’ representatives partaking in the training ‘Internationalisation for Peacebuilding 2018’. The selected Higher Education Institutions and representatives were all located in regions acutely affected by the Colombian armed conflict, now experiencing multifaceted challenges and opportunities in a post-conflict scenario. Interviews with participants of the training were conducted to analyse the skills acquired and to identify possible improvements brought about by the training at the institutions. The article further identifies specific needs of the institutions, to be taken into account for future courses on internationalisation for higher education institutions.
The aim of our article is to collect and present information about contemporary programming environments that are suitable for primary education. We studied the ways they implement (or do not implement) some programming concepts, the ways programs are represented and built in order to support young and novice programmers, as well as their suitability to allow different forms of sharing the results of pupils’ work. We present not only a short description of each considered environment and the taxonomy in the form of a table, but also our understanding and opinions on how and why the environments implement the same concepts and ideas in different ways and which concepts and ideas seem to be important to the creators of such environments.
The spatially-resolved winds of the massive binary, Eta Carinae, extend an arcsecond on the sky, well beyond the 10 to 20 milliarcsecond binary orbital dimension. Stellar wind line profiles, observed at very different angular resolutions of VLTI/AMBER, HST/STIS and VLT/UVES, provide spatial information on the extended wind interaction structure as it changes with orbital phase. These same wind lines, observable in the starlight scattered off the foreground lobe of the dusty Homunculus, provide time-variant line profiles viewed from significantly different angles. Comparisons of direct and scattered wind profiles observed in the same epoch and at different orbital phases provide insight on the extended wind structure and promise the potential for three-dimensional imaging of the outer wind structures. Massive, long-lasting clumps, including the nebularWeigelt blobs, originated during the two historical ejection events. Wind interactions with these clumps are quite noticeable in spatially-resolved spectroscopy. As the 2009.0 minimum approaches, analysis of existing spectra and 3-D modeling are providing bases for key observations to gain further understanding of this complex massive binary.
Plate tectonics describes the movement of rigid plates at the surface of the Earth as well as their complex deformation at three types of plate boundaries: 1) divergent boundaries such as rift zones and mid-ocean ridges, 2) strike-slip boundaries where plates grind past each other, such as the San Andreas Fault, and 3) convergent boundaries that form large mountain ranges like the Andes. The generally narrow deformation zones that bound the plates exhibit complex strain patterns that evolve through time. During this evolution, plate boundary deformation is driven by tectonic forces arising from Earth’s deep interior and from within the lithosphere, but also by surface processes, which erode topographic highs and deposit the resulting sediment into regions of low elevation. Through the combination of these factors, the surface of the Earth evolves in a highly dynamic way with several feedback mechanisms. At divergent boundaries, for example, tensional stresses thin the lithosphere, forcing uplift and subsequent erosion of rift flanks, which creates a sediment source. Meanwhile, the rift center subsides and becomes a topographic low where sediments accumulate. This mass transfer from foot- to hanging wall plays an important role during rifting, as it prolongs the activity of individual normal faults. When rifting continues, continents are eventually split apart, exhuming Earth’s mantle and creating new oceanic crust. Because of the complex interplay between deep tectonic forces that shape plate boundaries and mass redistribution at the Earth’s surface, it is vital to understand feedbacks between the two domains and how they shape our planet.
In this study I aim to provide insight on two primary questions: 1) How do divergent and strike-slip plate boundaries evolve? 2) How is this evolution, on a large temporal scale and a smaller structural scale, affected by the alteration of the surface through erosion and deposition? This is done in three chapters that examine the evolution of divergent and strike-slip plate boundaries using numerical models. Chapter 2 takes a detailed look at the evolution of rift systems using two-dimensional models. Specifically, I extract faults from a range of rift models and correlate them through time to examine how fault networks evolve in space and time. By implementing a two-way coupling between the geodynamic code ASPECT and landscape evolution code FastScape, I investigate how the fault network and rift evolution are influenced by the system’s erosional efficiency, which represents many factors like lithology or climate. In Chapter 3, I examine rift evolution from a three-dimensional perspective. In this chapter I study linkage modes for offset rifts to determine when fast-rotating plate-boundary structures known as continental microplates form. Chapter 4 uses the two-way numerical coupling between tectonics and landscape evolution to investigate how a strike-slip boundary responds to large sediment loads, and whether this is sufficient to form an entirely new type of flexural strike-slip basin.
Mathematical modeling of biological phenomena has experienced increasing interest since new high-throughput technologies give access to growing amounts of molecular data. These modeling approaches are especially able to test hypotheses which are not yet experimentally accessible or guide an experimental setup. One particular attempt investigates the evolutionary dynamics responsible for today's composition of organisms. Computer simulations either propose an evolutionary mechanism and thus reproduce a recent finding or rebuild an evolutionary process in order to learn about its mechanism. The quest for evolutionary fingerprints in metabolic and gene-coexpression networks is the central topic of this cumulative thesis based on four published articles. An understanding of the actual origin of life will probably remain an insoluble problem. However, one can argue that after a first simple metabolism has evolved, the further evolution of metabolism occurred in parallel with the evolution of the sequences of the catalyzing enzymes. Indications of such a coevolution can be found when correlating the change in sequence between two enzymes with their distance on the metabolic network which is obtained from the KEGG database. We observe that there exists a small but significant correlation primarily on nearest neighbors. This indicates that enzymes catalyzing subsequent reactions tend to be descended from the same precursor. Since this correlation is relatively small one can at least assume that, if new enzymes are no "genetic children" of the previous enzymes, they certainly be descended from any of the already existing ones. Following this hypothesis, we introduce a model of enzyme-pathway coevolution. By iteratively adding enzymes, this model explores the metabolic network in a manner similar to diffusion. With implementation of an Gillespie-like algorithm we are able to introduce a tunable parameter that controls the weight of sequence similarity when choosing a new enzyme. Furthermore, this method also defines a time difference between successive evolutionary innovations in terms of a new enzyme. Overall, these simulations generate putative time-courses of the evolutionary walk on the metabolic network. By a time-series analysis, we find that the acquisition of new enzymes appears in bursts which are pronounced when the influence of the sequence similarity is higher. This behavior strongly resembles punctuated equilibrium which denotes the observation that new species tend to appear in bursts as well rather than in a gradual manner. Thus, our model helps to establish a better understanding of punctuated equilibrium giving a potential description at molecular level. From the time-courses we also extract a tentative order of new enzymes, metabolites, and even organisms. The consistence of this order with previous findings provides evidence for the validity of our approach. While the sequence of a gene is actually subject to mutations, its expression profile might also indirectly change through the evolutionary events in the cellular interplay. Gene coexpression data is simply accessible by microarray experiments and commonly illustrated using coexpression networks where genes are nodes and get linked once they show a significant coexpression. Since the large number of genes makes an illustration of the entire coexpression network difficult, clustering helps to show the network on a metalevel. Various clustering techniques already exist. However, we introduce a novel one which maintains control of the cluster sizes and thus assures proper visual inspection. An application of the method on Arabidopsis thaliana reveals that genes causing a severe phenotype often show a functional uniqueness in their network vicinity. This leads to 20 genes of so far unknown phenotype which are however suggested to be essential for plant growth. Of these, six indeed provoke such a severe phenotype, shown by mutant analysis. By an inspection of the degree distribution of the A.thaliana coexpression network, we identified two characteristics. The distribution deviates from the frequently observed power-law by a sharp truncation which follows after an over-representation of highly connected nodes. For a better understanding, we developed an evolutionary model which mimics the growth of a coexpression network by gene duplication which underlies a strong selection criterion, and slight mutational changes in the expression profile. Despite the simplicity of our assumption, we can reproduce the observed properties in A.thaliana as well as in E.coli and S.cerevisiae. The over-representation of high-degree nodes could be identified with mutually well connected genes of similar functional families: zinc fingers (PF00096), flagella, and ribosomes respectively. In conclusion, these four manuscripts demonstrate the usefulness of mathematical models and statistical tools as a source of new biological insight. While the clustering approach of gene coexpression data leads to the phenotypic characterization of so far unknown genes and thus supports genome annotation, our model approaches offer explanations for observed properties of the coexpression network and furthermore substantiate punctuated equilibrium as an evolutionary process by a deeper understanding of an underlying molecular mechanism.
In this paper we consider a simple syntactic extension of Answer Set Programming (ASP) for dealing with (nested) existential quantifiers and double negation in the rule bodies, in a close way to the recent proposal RASPL-1. The semantics for this extension just resorts to Equilibrium Logic (or, equivalently, to the General Theory of Stable Models), which provides a logic-programming interpretation for any arbitrary theory in the syntax of Predicate Calculus. We present a translation of this syntactic class into standard logic programs with variables (either disjunctive or normal, depending on the input rule heads), as those allowed by current ASP solvers. The translation relies on the introduction of auxiliary predicates and the main result shows that it preserves strong equivalence modulo the original signature.
Controlling interactions in synthetic polymers as precisely as in proteins would have a strong impact on polymer science. Advanced structural and functional control can lead to rational design of, integrated nano- and microstructures. To achieve this, properties of monomer sequence defined oligopeptides were exploited. Through their incorporation as monodisperse segments into synthetic polymers we learned in recent four years how to program the structure formation of polymers, to adjust and exploit interactions in such polymers, to control inorganic-organic interfaces in fiber composites and induce structure in Biomacromolecules like DNA for biomedical applications.
We present a system for the linguistic exploration and analysis of lexical cohesion in English texts. Using an electronic thesaurus-like resource, Princeton WordNet, and the Brown Corpus of English, we have implemented a process of annotating text with lexical chains and a graphical user interface for inspection of the annotated text. We describe the system and report on some sample linguistic analyses carried out using the combined thesaurus-corpus resource.
Arctic warming has implications for the functioning of terrestrial Arctic ecosystems, global climate and socioeconomic systems of northern communities. A research gap exists in high spatial resolution monitoring and understanding of the seasonality of permafrost degradation, spring snowmelt and vegetation phenology. This thesis explores the diversity and utility of dense TerraSAR-X (TSX) X-Band time series for monitoring ice-rich riverbank erosion, snowmelt, and phenology of Arctic vegetation at long-term study sites in the central Lena Delta, Russia and on Qikiqtaruk (Herschel Island), Canada. In the thesis the following three research questions are addressed:
• Is TSX time series capable of monitoring the dynamics of rapid permafrost degradation in ice-rich permafrost on an intra-seasonal scale and can these datasets in combination with climate data identify the climatic drivers of permafrost degradation?
• Can multi-pass and multi-polarized TSX time series adequately monitor seasonal snow cover and snowmelt in small Arctic catchments and how does it perform compared to optical satellite data and field-based measurements?
• Do TSX time series reflect the phenology of Arctic vegetation and how does the recorded signal compare to in-situ greenness data from RGB time-lapse camera data and vegetation height from field surveys?
To answer the research questions three years of TSX backscatter data from 2013 to 2015 for the Lena Delta study site and from 2015 to 2017 for the Qikiqtaruk study site were used in quantitative and qualitative analysis complimentary with optical satellite data and in-situ time-lapse imagery.
The dynamics of intra-seasonal ice-rich riverbank erosion in the central Lena Delta, Russia were quantified using TSX backscatter data at 2.4 m spatial resolution in HH polarization and validated with 0.5 m spatial resolution optical satellite data and field-based time-lapse camera data. Cliff top lines were automatically extracted from TSX intensity images using threshold-based segmentation and vectorization and combined in a geoinformation system with manually digitized cliff top lines from the optical satellite data and rates of erosion extracted from time-lapse cameras. The results suggest that the cliff top eroded at a constant rate throughout the entire erosional season. Linear mixed models confirmed that erosion was coupled with air temperature and precipitation at an annual scale, seasonal fluctuations did not influence 22-day erosion rates. The results highlight the potential of HH polarized X-Band backscatter data for high temporal resolution monitoring of rapid permafrost degradation.
The distinct signature of wet snow in backscatter intensity images of TSX data was exploited to generate wet snow cover extent (SCE) maps on Qikiqtaruk at high temporal resolution. TSX SCE showed high similarity to Landsat 8-derived SCE when using cross-polarized VH data. Fractional snow cover (FSC) time series were extracted from TSX and optical SCE and compared to FSC estimations from in-situ time-lapse imagery. The TSX products showed strong agreement with the in-situ data and significantly improved the temporal resolution compared to the Landsat 8 time series. The final combined FSC time series revealed two topography-dependent snowmelt patterns that corresponded to in-situ measurements. Additionally TSX was able to detect snow patches longer in the season than Landsat 8, underlining the advantage of TSX for detection of old snow. The TSX-derived snow information provided valuable insights into snowmelt dynamics on Qikiqtaruk previously not available.
The sensitivity of TSX to vegetation structure associated with phenological changes was explored on Qikiqtaruk. Backscatter and coherence time series were compared to greenness data extracted from in-situ digital time-lapse cameras and detailed vegetation parameters on 30 areas of interest. Supporting previous results, vegetation height corresponded to backscatter intensity in co-polarized HH/VV at an incidence angle of 31°. The dry, tall shrub dominated ecological class showed increasing backscatter with increasing greenness when using the cross polarized VH/HH channel at 32° incidence angle. This is likely driven by volume scattering of emerging and expanding leaves. Ecological classes with more prostrate vegetation and higher bare ground contributions showed decreasing backscatter trends over the growing season in the co-polarized VV/HH channels likely a result of surface drying instead of a vegetation structure signal. The results from shrub dominated areas are promising and provide a complementary data source for high temporal monitoring of vegetation phenology.
Overall this thesis demonstrates that dense time series of TSX with optical remote sensing and in-situ time-lapse data are complementary and can be used to monitor rapid and seasonal processes in Arctic landscapes at high spatial and temporal resolution.
The emergence of information extraction (IE) oriented pattern engines has been observed during the last decade. Most of them exploit heavily finite-state devices. This paper introduces ExPRESS – a new extraction pattern engine, whose rules are regular expressions over flat feature structures. The underlying pattern language is a blend of two previously introduced IE oriented pattern formalisms, namely, JAPE, used in the widely known GATE system, and the unificationbased XTDL formalism used in SProUT. A brief and technical overview of ExPRESS, its pattern language and the pool of its native linguistic components is given. Furthermore, the implementation of the grammar interpreter is addressed too.
There are two common approaches to implement a virtual machine (VM) for a dynamic object-oriented language. On the one hand, it can be implemented in a C-like language for best performance and maximum control over the resulting executable. On the other hand, it can be implemented in a language such as Java that allows for higher-level abstractions. These abstractions, such as proper object-oriented modularization, automatic memory management, or interfaces, are missing in C-like languages but they can simplify the implementation of prevalent but complex concepts in VMs, such as garbage collectors (GCs) or just-in-time compilers (JITs). Yet, the implementation of a dynamic object-oriented language in Java eventually results in two VMs on top of each other (double stack), which impedes performance. For statically typed languages, the Maxine VM solves this problem; it is written in Java but can be executed without a Java virtual machine (JVM). However, it is currently not possible to execute dynamic object-oriented languages in Maxine. This work presents an approach to bringing object models and execution models of dynamic object-oriented languages to the Maxine VM and the application of this approach to Squeak/Smalltalk. The representation of objects in and the execution of dynamic object-oriented languages pose certain challenges to the Maxine VM that lacks certain variation points necessary to enable an effortless and straightforward implementation of dynamic object-oriented languages' execution models. The implementation of Squeak/Smalltalk in Maxine as a feasibility study is to unveil such missing variation points.
In the past decades, scholars and courts have paid considerable attention to the extraterritorial applicability of human rights treaties. By contrast, the extraterritorial application of constitutional rights has received comparable scholarly attention only in the United States. Specifically, there is a paucity of comparative research in this area, which contributes to the prevailing view that human rights law provides the proper framework under which domestic courts should examine extraterritoriality questions under constitutional law.
This article argues that domestic constitutional regimes and their judicial enforcers can and should provide an important counterweight to the deadlocked extraterritoriality debate at the international level. Using two case studies from Germany and the United States, it shows that domestic constitutional courts are sometimes better suited than treaty bodies to guard the normative values of human dignity and universality in an extraterritoriality context. This is most apparent in the case of Germany, which has a long tradition of integration into international multi-level governance systems and "bottom-up" resistance based on fundamental rights within such systems. Recent cases from the Federal Constitutional Court (Bundesverfassungsgericht) about the extraterritorial application of the Basic Law (Grundgesetz) to foreign intelligence gathering and climate change support this theory. However, an independent constitutional approach can also achieve some normative effects in domestic systems that are more isolated from the international human rights system. Thus, the US Supreme Court likewise used domestic constitutional doctrine to sidestep the American government's strictly territorial interpretation of the ICCPR and employ a functional approach to the extraterritorial applicability of fundamental rights in the case of detention of suspected terrorists in the Guantánamo Bay naval base.
The study of these two examples does not purport to be comprehensive or even representative of the world’s diverse array of constitutions and their relationships with international human rights law. However, the independent power of constitutional frameworks in these two disparate cases should all the more provide an impetus for increased comparative research into constitutional extraterritoriality regimes and their value for the project of human rights.
We report FUSE observations in 2005–2006 of three O-type, double-lined spectroscopic binaries in the Magellanic Clouds. The systems have very short periods (1.4–2.25 d), represent rare, young evolutionary stages of massive stars and binaries, and provide a unique glimpse at some of the most massive systems that form in dense clusters of massive stars. Improved orbit parameters, including revised masses, for LH54-425 are derived from new ctio spectroscopy. The systems are: LH54-425 in the LMC (O3V + O5V, P=2.25d, 62+37M⊙), J053441-693139 in the LMC (O2-3If+O6V, P=1.4 d, 41+27M⊙), and Hodge 53-47 in the SMC (O6V + O4-5IIIf, P=2.2 d, 24+14M⊙, where the O4 star appears to be less massive than the O6 star). Their short periods indicates that wind interaction and mass transfer are likely important factors in their evolution. The spectra provide quantitative and systematic studies of phase-dependent stellar wind properties, wind collision effects in O+O binaries at lower metallicities, improved radial velocity curves, and FUV spectro-photometric changes as a function of orbital phase.
Metals are often used in environments that are conducive to corrosion, which leads to a reduction in their mechanical properties and durability. Coatings are applied to corrosion-prone metals such as aluminum alloys to inhibit the destructive surface process of corrosion in a passive or active way. Standard anticorrosive coatings function as a physical barrier between the material and the corrosive environment and provide passive protection only when intact. In contrast, active protection prevents or slows down corrosion even when the main barrier is damaged. The most effective industrially used active corrosion inhibition for aluminum alloys is provided by chromate conversion coatings. However, their toxicity and worldwide restriction provoke an urgent need for finding environmentally friendly corrosion preventing systems. A promising approach to replace the toxic chromate coatings is to embed particles containing nontoxic inhibitor in a passive coating matrix. This work presents the development and optimization of effective anticorrosive coatings for the industrially important aluminum alloy, AA2024-T3 using this approach. The protective coatings were prepared by dispersing mesoporous silica containers, loaded with the nontoxic corrosion inhibitor 2-mercaptobenzothiazole, in a passive sol-gel (SiOx/ZrOx) or organic water-based layer. Two types of porous silica containers with different sizes (d ≈ 80 and 700 nm, respectively) were investigated. The studied robust containers exhibit high surface area (≈ 1000 m² g-1), narrow pore size distribution (dpore ≈ 3 nm) and large pore volume (≈ 1 mL g-1) as determined by N2 sorption measurements. These properties favored the subsequent adsorption and storage of a relatively large amount of inhibitor as well as its release in response to pH changes induced by the corrosion process. The concentration, position and size of the embedded containers were varied to ascertain the optimum conditions for overall anticorrosion performance. Attaining high anticorrosion efficiency was found to require a compromise between delivering an optimal amount of corrosion inhibitor and preserving the coating barrier properties. This study broadens the knowledge about the main factors influencing the coating anticorrosion efficiency and assists the development of optimum active anticorrosive coatings doped with inhibitor loaded containers.
Earthquake modeling is the key to a profound understanding of a rupture. Its kinematics or dynamics are derived from advanced rupture models that allow, for example, to reconstruct the direction and velocity of the rupture front or the evolving slip distribution behind the rupture front. Such models are often parameterized by a lattice of interacting sub-faults with many degrees of freedom, where, for example, the time history of the slip and rake on each sub-fault are inverted. To avoid overfitting or other numerical instabilities during a finite-fault estimation, most models are stabilized by geometric rather than physical constraints such as smoothing.
As a basis for the inversion approach of this study, we build on a new pseudo-dynamic rupture model (PDR) with only a few free parameters and a simple geometry as a physics-based solution of an earthquake rupture. The PDR derives the instantaneous slip from a given stress drop on the fault plane, with boundary conditions on the developing crack surface guaranteed at all times via a boundary element approach. As a side product, the source time function on each point on the rupture plane is not constraint and develops by itself without additional parametrization. The code was made publicly available as part of the Pyrocko and Grond Python packages. The approach was compared with conventional modeling for different earthquakes. For example, for the Mw 7.1 2016 Kumamoto, Japan, earthquake, the effects of geometric changes in the rupture surface on the slip and slip rate distributions could be reproduced by simply projecting stress vectors. For the Mw 7.5 2018 Palu, Indonesia, strike-slip earthquake, we also modelled rupture propagation using the 2D Eikonal equation and assuming a linear relationship between rupture and shear wave velocity. This allowed us to give a deeper and faster propagating rupture front and the resulting upward refraction as a new possible explanation for the apparent supershear observed at the Earth's surface.
The thesis investigates three aspects of earthquake inversion using PDR: (1) to test whether implementing a simplified rupture model with few parameters into a probabilistic Bayesian scheme without constraining geometric parameters is feasible, and whether this leads to fast and robust results that can be used for subsequent fast information systems (e.g., ground motion predictions). (2) To investigate whether combining broadband and strong-motion seismic records together with near-field ground deformation data improves the reliability of estimated rupture models in a Bayesian inversion. (3) To investigate whether a complex rupture can be represented by the inversion of multiple PDR sources and for what type of earthquakes this is recommended.
I developed the PDR inversion approach and applied the joint data inversions to two seismic sequences in different tectonic settings. Using multiple frequency bands and a multiple source inversion approach, I captured the multi-modal behaviour of the Mw 8.2 2021 South Sandwich subduction earthquake with a large, curved and slow rupturing shallow earthquake bounded by two faster and deeper smaller events. I could cross-validate the results with other methods, i.e., P-wave energy back-projection, a clustering analysis of aftershocks and a simple tsunami forward model.
The joint analysis of ground deformation and seismic data within a multiple source inversion also shed light on an earthquake triplet, which occurred in July 2022 in SE Iran. From the inversion and aftershock relocalization, I found indications for a vertical separation between the shallower mainshocks within the sedimentary cover and deeper aftershocks at the sediment-basement interface. The vertical offset could be caused by the ductile response of the evident salt layer to stress perturbations from the mainshocks.
The applications highlight the versatility of the simple PDR in probabilistic seismic source inversion capturing features of rather different, complex earthquakes. Limitations, as the evident focus on the major slip patches of the rupture are discussed as well as differences to other finite fault modeling methods.
This paper describes a two-level formalism where feature structures are used in contextual rules. Whereas usual two-level grammars describe rational sets over symbol pairs, this new formalism uses tree structured regular expressions. They allow an explicit and precise definition of the scope of feature structures. A given surface form may be described using several feature structures. Feature unification is expressed in contextual rules using variables, like in a unification grammar. Grammars are compiled in finite state multi-tape transducers.
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.
This paper discusses how focus changes prosodic structure in Tokyo Japanese. It is generally believed that focus blocks the intonational process of downstep and causes a pitch reset. This paper presents experimental evidence against this traditional view by looking at the prosodic behavior of Wh words, which receive focus lexically in Japanese as in other languages. It is demonstrated, specifically, that the focused Wh element does not block downstep although it receives a much higher pitch than its preceding element. This suggests that presence of lexical focus does not trigger pitch reset in Japanese.
Focus strategies in chadic
(2004)
We argue that the standard focus theories reach their limits when confronted with the focus systems of the Chadic languages. The backbone of the standard focus theories consists of two assumptions, both called into question by the languages under consideration. Firstly, it is standardly assumed that focus is generally marked by stress. The Chadic languages, however, exhibit a variety of different devices for focus marking. Secondly, it is assumed that focus is always marked. In Tangale, at least, focus is not marked consistently on all types of constituents. The paper offers two possible solutions to this dilemma.
The concepts of food deficit, hunger, undernourishment and food security are discussed. Axioms and indices for the assessment of nutrition of individuals and groups are suggested. Furthermore a measure for food aid donor performance is developed and applied to a sample of bilateral and multilateral donors providing food aid for African countries.
We demonstrate how the incentives of firms that partially own their suppliers or customers to foreclose rivals depend on how the partial owner can extract profits from the target (tunneling). Compared to a fully vertically integrated firm, a partial owner may obtain only a share of the target’s profit but influence the target’s strategy significantly. We show that the incentives for customer and input foreclosure can be higher, equal, or even lower with partial ownership than with a vertical merger, depending on how the protection of minority shareholders and transfer price regulations affect the scope for profit extraction.
We present a formal analysis of iconic coverbal gesture. Our model describes the incomplete meaning of gesture that’s derivable from its form, and the pragmatic reasoning that yields a more specific interpretation. Our formalism builds on established models of discourse interpretation to capture key insights from the descriptive literature on gesture: synchronous speech and gesture express a single thought, but while the form of iconic gesture is an important clue to its interpretation, the content of gesture can be resolved only by linking it to its context.
Steep mountain channels are an important component of the fluvial system. On geological timescales, they shape mountain belts and counteract tectonic uplift by erosion. Their channels are strongly coupled to hillslopes and they are often the main source of sediment transported downstream to low-gradient rivers and to alluvial fans, where commonly settlements in mountainous areas are located. Hence, mountain streams are the cause for one of the main natural hazards in these regions. Due to climate change and a pronounced populating of mountainous regions the attention given to this threat is even growing. Although quantitative studies on sediment transport have significantly advanced our knowledge on measuring and calibration techniques we still lack studies of the processes within mountain catchments. Studies examining the mechanisms of energy and mass exchange on small temporal and spatial scales in steep streams remain sparse in comparison to low-gradient alluvial channels.
In the beginning of this doctoral project, a vast amount of experience and knowledge of a steep stream in the Swiss Prealps had to be consolidated in order to shape the principal aim of this research effort. It became obvious, that observations from within the catchment are underrepresented in comparison to experiments performed at the catchment’s outlet measuring fluxes and the effects of the transported material. To counteract this imbalance, an examination of mass fluxes within the catchment on the process scale was intended. Hence, this thesis is heavily based on direct field observations, which are generally rare in these environments in quantity and quality. The first objective was to investigate the coupling of the channel with surrounding hillslopes, the major sources of sediment. This research, which involved the monitoring of the channel and adjacent hillslopes, revealed that alluvial channel steps play a key role in coupling of channel and hillslopes. The observations showed that hillslope stability is strongly associated with the step presence and an understanding of step morphology and stability is therefore crucial in understanding sediment mobilization. This finding refined the way we think about the sediment dynamics in steep channels and motivated continued research of the step dynamics. However, soon it became obvious that the technological basis for developing field tests and analyzing the high resolution geometry measured in the field was not available. Moreover, for many geometrical quantities in mountain channels definitions and a clear scientific standard was not available. For example, these streams are characterized by a high spatial variability of the channel banks, preventing straightforward calculations of the channel width without a defined reference. Thus, the second and inevitable part of this thesis became the development and evaluation of scientific tools in order to investigate the geometrical content of the study reach thoroughly. The developed framework allowed the derivation of various metrics of step and channel geometry which facilitated research on the a large data set of observations of channel steps. In the third part, innovative, physically-based metrics have been developed and compared to current knowledge on step formation, suggested in the literature. With this analyses it could be demonstrated that the formation of channel steps follow a wide range of hydraulic controls. Due to the wide range of tested parameters channel steps observed in a natural stream were attributed to different mechanisms of step formation, including those based on jamming and those based on key-stones. This study extended our knowledge on step formation in a steep stream and harmonized different, often time seen as competing, processes of step formation. This study was based on observations collected at one point in time. In the fourth part of this project, the findings of the snap-shot observations were extended in the temporal dimension and the derived concepts have been utilized to investigate reach-scale step patterns in response to large, exceptional flood events. The preliminary results of this work based on the long-term analyses of 7 years of long profile surveys showed that the previously observed channel-hillslope mechanism is the responsible for the short-term response of step formation.
The findings of the long-term analyses of step patterns drew a bow to the initial observations of a channel-hillslope system which allowed to join the dots in the dynamics of steep stream. Thus, in this thesis a broad approach has been chosen to gain insights into the complex system of steep mountain rivers. The effort includes in situ field observations (article I), the development of quantitative scientific tools (article II), the reach-scale analyses of step-pool morphology (article III) and its temporal evolution (article IV). With this work our view on the processes within the catchment has been advanced towards a better mechanistic understanding of these fluvial system relevant to improve applied scientific work.
We present a new analysis of illocutionary forces in dialogue. We analyze them as complex conversational moves involving two dimensions: what Speaker commits herself to and what she calls on Addressee to perform. We start from the analysis of speech acts such as confirmation requests or whimperatives, and extend the analysis to seemingly simple speech acts, such as statements and queries. Then, we show how to integrate our proposal in the framework of the Grammar for Conversation (Ginzburg, to app.), which is adequate for modelling agents' information states and how they get updated.
Decisions for the conservation of biodiversity and sustainable management of natural resources are typically related to large scales, i.e. the landscape level. However, understanding and predicting the effects of land use and climate change on scales relevant for decision-making requires to include both, large scale vegetation dynamics and small scale processes, such as soil-plant interactions. Integrating the results of multiple BIOTA subprojects enabled us to include necessary data of soil science, botany, socio-economics and remote sensing into a high resolution, process-based and spatially-explicit model. Using an example from a sustainably-used research farm and a communally used and degraded farming area in semiarid southern Namibia we show the power of simulation models as a tool to integrate processes across disciplines and scales.
How do children determine the syntactic category of novel words? In this article we present the results of 2 experiments that investigated whether German children between 12 and 16 months of age can use distributional knowledge that determiners precede nouns and subject pronouns precede verbs to syntactically categorize adjacent novel words. Evidence from the head-turn preference paradigm shows that, although 12- to 13-month-olds cannot do this, 14- to 16-month-olds are able to use a determiner to categorize a following novel word as a noun. In contrast, no categorization effect was found for a novel word following a subject pronoun. To understand this difference we analyzed adult child-directed speech. This analysis showed that there are in fact stronger co-occurrence relations between determiners and nouns than between subject pronouns and verbs. Thus, in German determiners may be more reliable cues to the syntactic category of an adjacent novel word than are subject pronouns. We propose that the capacity to syntactically categorize novel words, demonstrated here for the first time in children this young, mediates between the recognition of the specific morphosyntactic frame in which a novel word appears and the word-to-world mapping that is needed to build up a semantic representation for the novel word.
Functional nanoporous carbon-based materials derived from oxocarbon-metal coordination complexes
(2017)
Nanoporous carbon based materials are of particular interest for both science and industry due to their exceptional properties such as a large surface area, high pore volume, high electroconductivity as well as high chemical and thermal stability. Benefiting from these advantageous properties, nanoporous carbons proved to be useful in various energy and environment related applications including energy storage and conversion, catalysis, gas sorption and separation technologies. The synthesis of nanoporous carbons classically involves thermal carbonization of the carbon precursors (e.g. phenolic resins, polyacrylonitrile, poly(vinyl alcohol) etc.) followed by an activation step and/or it makes use of classical hard or soft templates to obtain well-defined porous structures. However, these synthesis strategies are complicated and costly; and make use of hazardous chemicals, hindering their application for large-scale production. Furthermore, control over the carbon materials properties is challenging owing to the relatively unpredictable processes at the high carbonization temperatures.
In the present thesis, nanoporous carbon based materials are prepared by the direct heat treatment of crystalline precursor materials with pre-defined properties. This synthesis strategy does not require any additional carbon sources or classical hard- or soft templates. The highly stable and porous crystalline precursors are based on coordination compounds of the squarate and croconate ions with various divalent metal ions including Zn2+, Cu2+, Ni2+, and Co2+, respectively. Here, the structural properties of the crystals can be controlled by the choice of appropriate synthesis conditions such as the crystal aging temperature, the ligand/metal molar ratio, the metal ion, and the organic ligand system. In this context, the coordination of the squarate ions to Zn2+ yields porous 3D cube crystalline particles. The morphology of the cubes can be tuned from densely packed cubes with a smooth surface to cubes with intriguing micrometer-sized openings and voids which evolve on the centers of the low index faces as the crystal aging temperature is raised. By varying the molar ratio, the particle shape can be changed from truncated cubes to perfect cubes with right-angled edges.
These crystalline precursors can be easily transformed into the respective carbon based materials by heat treatment at elevated temperatures in a nitrogen atmosphere followed by a facile washing step. The resulting carbons are obtained in good yields and possess a hierarchical pore structure with well-organized and interconnected micro-, meso- and macropores. Moreover, high surface areas and large pore volumes of up to 1957 m2 g-1 and 2.31 cm3 g-1 are achieved, respectively, whereby the macroscopic structure of the precursors is preserved throughout the whole synthesis procedure.
Owing to these advantageous properties, the resulting carbon based materials represent promising supercapacitor electrode materials for energy storage applications. This is exemplarily demonstrated by employing the 3D hierarchical porous carbon cubes derived from squarate-zinc coordination compounds as electrode material showing a specific capacitance of 133 F g-1 in H2SO4 at a scan rate of 5 mV s-1 and retaining 67% of this specific capacitance when the scan rate is increased to 200 mV s-1.
In a further application, the porous carbon cubes derived from squarate-zinc coordination compounds are used as high surface area support material and decorated with nickel nanoparticles via an incipient wetness impregnation. The resulting composite material combines a high surface area, a hierarchical pore structure with high functionality and well-accessible pores. Moreover, owing to their regular micro-cube shape, they allow for a good packing of a fixed-bed flow reactor along with high column efficiency and a minimized pressure drop throughout the packed reactor. Therefore, the composite is employed as heterogeneous catalyst in the selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran showing good catalytic performance and overcoming the conventional problem of column blocking.
Thinking about the rational design of 3D carbon geometries, the functions and properties of the resulting carbon-based materials can be further expanded by the rational introduction of heteroatoms (e.g. N, B, S, P, etc.) into the carbon structures in order to alter properties such as wettability, surface polarity as well as the electrochemical landscape. In this context, the use of crystalline materials based on oxocarbon-metal ion complexes can open a platform of highly functional materials for all processes that involve surface processes.
An exhaustive and disjoint decomposition of social choice situations is derived in a general set theoretical framework using the new tools of the Lifted Pareto relation on the power set of social states representing a pre-choice comparison of choice option sets. The main result is the classification of social choice situations which include three types of social choice problems. First, we usually observe the common incompleteness of the Pareto relation. Second, a kind of non-compactness problem of a choice set of social states can be generated. Finally, both can be combined. The first problem root can be regarded as natural everyday dilemma of social choice theory whereas the second may probably be much more due to modeling technique implications. The distinction is enabled at a very general set theoretical level. Hence, the derived classification of social choice situations is applicable on almost every relevant economic model.
General Discussion
(2007)
Salt deposits offer a variety of usage types. These include the mining of rock salt and potash salt as important raw materials, the storage of energy in man-made underground caverns, and the disposal of hazardous substances in former mines. The most serious risk with any of these usage types comes from the contact with groundwater or surface water. It causes an uncontrolled dissolution of salt rock, which in the worst case can result in the flooding or collapse of underground facilities. Especially along potash seams, cavernous structures can spread quickly, because potash salts show a much higher solubility than rock salt. However, as their chemical behavior is quite complex, previous models do not account for these highly soluble interlayers. Therefore, the objective of the present thesis is to describe the evolution of cavernous structures along potash seams in space and time in order to improve hazard mitigation during the utilization of salt deposits.
The formation of cavernous structures represents an interplay of chemical and hydraulic processes. Hence, the first step is to systematically investigate the dissolution and precipitation reactions that occur when water and potash salt come into contact. For this purpose, a geochemical reaction model is used. The results show that the minerals are only partially dissolved, resulting in a porous sponge like structure. With the saturation of the solution increasing, various secondary minerals are formed, whose number and type depend on the original rock composition. Field data confirm a correlation between the degree of saturation and the distance from the center of the cavern, where solution is entering. Subsequently, the reaction model is coupled with a flow and transport code and supplemented by a novel approach called ‘interchange’. The latter enables the exchange of solution and rock between areas of different porosity and mineralogy, and thus ultimately the growth of the cavernous structure. By means of several scenario analyses, cavern shape, growth rate and mineralogy are systematically investigated, taking also heterogeneous potash seams into account. The results show that basically four different cases can be distinguished, with mixed forms being a frequent occurrence in nature. The classification scheme is based on the dimensionless numbers Péclet and Damköhler, and allows for a first assessment of the hazard potential. In future, the model can be applied to any field case, using measurement data for calibration.
The presented research work provides a reactive transport model that is able to spatially and temporally characterize the propagation of cavernous structures along potash seams for the first time. Furthermore, it allows to determine thickness and composition of transition zones between cavern center and unaffected salt rock. The latter is particularly important in potash mining, so that natural cavernous structures can be located at an early stage and the risk of mine flooding can thus be reduced. The models may also contribute to an improved hazard prevention in the construction of storage caverns and the disposal of hazardous waste in salt deposits. Predictions regarding the characteristics and evolution of cavernous structures enable a better assessment of potential hazards, such as integrity or stability loss, as well as of suitable mitigation measures.