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Kollaborative, partizipative Instrumente zur Krisenbekämpfung haben in den letzten Jahren zunehmend an Aufmerksamkeit gewonnen. Ein Beispiel hierfür ist der #WirVsVirus-Hackathon, der als Reaktion auf die COVID-19-Pandemie durchgeführt wurde und über 28.000 Teilnehmer:innen erreichte. Bislang wurden die Auswirkungen solch groß angelegter, kollaborativer Ansätze zur Krisenbewältigung auf staatliches Krisenmanagement nur selten untersucht. Diese Studie analysiert den Hackathon und die daraus entstandenen Projekte aus der Perspektive des Open Governance-Paradigmas. Auf Grundlage von neun Experteninterviews untersuchen wir, wie sich digitale Open Governance auf die Regierungsfähigkeit und Legitimität in Krisenzeiten auswirkt. Unsere Analyse zeigt, dass digitale Open Governance zur Leistungsfähigkeit und Legitimität staatlichen Handelns in Krisenzeiten beitragen kann, da solche Projekte eine breite und diverse Teilnehmerschaft mobilisieren und in kurzer Zeit bürgerzentrierte, nutzbare Lösungen für krisenbezogene Probleme entwickeln können. Dem stehen allerdings Zweifel an der langfristigen Beständigkeit der Projekte, ihrer Skalierbarkeit, sowie Risiken hinsichtlich der Legitimität und Rechenschaftspflicht entgegen.
Quenching mechanism of uranyl(VI) by chloride and bromide in aqueous and non-aqueous solutions
(2021)
A major hindrance in utilizing uranyl(VI) luminescence as a standard analytical tool, for example, in environmental monitoring or nuclear industries, is quenching by other ions such as halide ions, which are present in many relevant matrices of uranyl(VI) speciation. Here, we demonstrate through a combination of time-resolved laser-induced fluorescence spectroscopy, transient absorption spectroscopy, and quantum chemistry that coordinating solvent molecules play a crucial role in U(VI) halide luminescence quenching. We show that our previously suggested quenching mechanism based on an internal redox reaction of the 1:2-uranyl-halide-complex holds also true for bromide-induced quenching of uranyl(VI). By adopting specific organic solvents, we were able to suppress the separation of the oxidized halide ligand X-2(center dot-) and the formed uranyl(V) into fully solvated ions, thereby "reigniting" U(VI) luminescence. Time-dependent density functional theory calculations show that quenching occurs through the outer-sphere complex of U(VI) and halide in water, while the ligand-to-metal charge transfer is strongly reduced in acetonitrile.
We study the classical, two-sided stable marriage problem under pairwise preferences. In the most general setting, agents are allowed to express their preferences as comparisons of any two of their edges, and they also have the right to declare a draw or even withdraw from such a comparison. This freedom is then gradually restricted as we specify six stages of orderedness in the preferences, ending with the classical case of strictly ordered lists. We study all cases occurring when combining the three known notions of stability-weak, strong, and super-stability-under the assumption that each side of the bipartite market obtains one of the six degrees of orderedness. By designing three polynomial algorithms and two NP-completeness proofs, we determine the complexity of all cases not yet known and thus give an exact boundary in terms of preference structure between tractable and intractable cases.
We establish a new approach of treating elliptic boundary value problems (BVPs) on manifolds with boundary and regular corners, up to singularity order 2. Ellipticity and parametrices are obtained in terms of symbols taking values in algebras of BVPs on manifolds of corresponding lower singularity orders. Those refer to Boutet de Monvel's calculus of operators with the transmission property, see Boutet de Monvel (Acta Math 126:11-51, 1971) for the case of smooth boundary. On corner configuration operators act in spaces with multiple weights. We mainly study the case of upper left entries in the respective 2 x 2 operator block-matrices of such a calculus. Green operators in the sense of Boutet de Monvel (Acta Math 126:11-51, 1971) analogously appear in singular cases, and they are complemented by contributions of Mellin type. We formulate a result on ellipticity and the Fredholm property in weighted corner spaces, with parametrices of analogous kind.
Our input is a complete graph G on n vertices where each vertex has a strict ranking of all other vertices in G. The goal is to construct a matching in G that is popular. A matching M is popular if M does not lose a head-to-head election against any matching M ': here each vertex casts a vote for the matching in {M,M '} in which it gets a better assignment. Popular matchings need not exist in the given instance G and the popular matching problem is to decide whether one exists or not. The popular matching problem in G is easy to solve for odd n. Surprisingly, the problem becomes NP-complete for even n, as we show here. This is one of the few graph theoretic problems efficiently solvable when n has one parity and NP-complete when n has the other parity.
How different are the results of constant-rate resetting of anomalous-diffusion processes in terms of their ensemble-averaged versus time-averaged mean-squared displacements (MSDs versus TAMSDs) and how does stochastic resetting impact nonergodicity? We examine, both analytically and by simulations, the implications of resetting on the MSD- and TAMSD-based spreading dynamics of particles executing fractional Brownian motion (FBM) with a long-time memory, heterogeneous diffusion processes (HDPs) with a power-law space-dependent diffusivity D(x) = D0|x|gamma and their "combined" process of HDP-FBM. We find, inter alia, that the resetting dynamics of originally ergodic FBM for superdiffusive Hurst exponents develops disparities in scaling and magnitudes of the MSDs and mean TAMSDs indicating weak ergodicity breaking. For subdiffusive HDPs we also quantify the nonequivalence of the MSD and TAMSD and observe a new trimodal form of the probability density function. For reset FBM, HDPs and HDP-FBM we compute analytically and verify by simulations the short-time MSD and TAMSD asymptotes and long-time plateaus reminiscent of those for processes under confinement. We show that certain characteristics of these reset processes are functionally similar despite a different stochastic nature of their nonreset variants. Importantly, we discover nonmonotonicity of the ergodicitybreaking parameter EB as a function of the resetting rate r. For all reset processes studied we unveil a pronounced resetting-induced nonergodicity with a maximum of EB at intermediate r and EB similar to(1/r )-decay at large r. Alongside the emerging MSD-versus-TAMSD disparity, this r-dependence of EB can be an experimentally testable prediction. We conclude by discussing some implications to experimental systems featuring resetting dynamics.
In recent decades, slope instability in high-mountain regions has often been linked to increase in temperature and the associated permafrost degradation and/or the increase in frequency/intensity of rainstorm events. In this context we analyzed the spatiotemporal evolution and potential controlling mechanisms of small- to medium-sized mass movements in a high-elevation catchment of the Italian Alps (Sulden/Solda basin). We found that slope-failure events (mostly in the form of rockfalls) have increased since the 2000s, whereas the occurrence of debris flows has increased only since 2010. The current climate-warming trend registered in the study area apparently increases the elevation of rockfall-detachment areas by approximately 300 m, mostly controlled by the combined effects of frost-cracking and permafrost thawing. In contrast, the occurrence of debris flows does not exhibit such an altitudinal shift, as it is primarily driven by extreme precipitation events exceeding the 75th percentile of the intensity-duration rainfall distribution. Potential debris-flow events in this environment may additionally be influenced by the accumulation of unconsolidated debris over time, which is then released during extreme rainfall events. Overall, there is evidence that the upper Sulden/Solda basin (above ca. 2500 m above sea level [a.s.l.]), and especially the areas in the proximity of glaciers, have experienced a significant decrease in slope stability since the 2000s, and that an increase in rockfalls and debris flows during spring and summer can be inferred. Our study thus confirms that "forward-looking" hazard mapping should be undertaken in these increasingly frequented, high-elevation areas of the Alps, as environmental change has elevated the overall hazard level in these regions.
The Arctic environments constitute rich and dynamic ecosystems, dominated by microorganisms extremely well adapted to survive and function under severe conditions. A range of physiological adaptations allow the microbiota in these habitats to withstand low temperatures, low water and nutrient availability, high levels of UV radiation, etc. In addition, other adaptations of clear competitive nature are directed at not only surviving but thriving in these environments, by disrupting the metabolism of neighboring cells and affecting intermicrobial communication. Since Arctic microbes are bioindicators which amplify climate alterations in the environment, the Arctic region presents the opportunity to study local microbiota and carry out research about interesting, potentially virulent phenotypes that could be dispersed into other habitats around the globe as a consequence of accelerating climate change. In this context, exploration of Arctic habitats as well as descriptions of the microbes inhabiting them are abundant but microbial competitive strategies commonly associated with virulence and pathogens are rarely reported. In this project, environmental samples from the Arctic region were collected and microorganisms (bacteria and fungi) were isolated. The clinical relevance of these microorganisms was assessed by observing the following virulence markers: ability to grow at a range of temperatures, expression of antimicrobial resistance and production of hemolysins. The aim of this project is to determine the frequency and relevance of these characteristics in an effort to understand microbial adaptations in habitats threatened by climate change. The isolates obtained and described here were able to grow at a range of temperatures, in some cases more than 30 °C higher than their original isolation temperature. A considerable number of them consistently expressed compounds capable of lysing sheep and bovine erythrocytes on blood agar at different incubation temperatures. Ethanolic extracts of these bacteria were able to cause rapid and complete lysis of erythrocyte suspensions and might even be hemolytic when assayed on human blood. In silico analyses showed a variety of resistance elements, some of them novel, against natural and synthetic antimicrobial compounds. In vitro experiments against a number of antimicrobial compounds showed resistance phenotypes belonging to wild-type populations and some non-wild type which clearly denote human influence in the acquisition of antimicrobial resistance. The results of this project demonstrate the presence of virulence-associated factors expressed by microorganisms of natural, non-clinical environments. This study contains some of the first reports, to the best of our knowledge, of hemolytic microbes isolated from the Arctic region. In addition, it provides additional information about the presence and expression of intrinsic and acquired antimicrobial resistance in environmental isolates, contributing to the understanding of the evolution of relevant pathogenic species and opportunistic pathogens. Finally, this study highlights some of the potential risks associated with changes in the polar regions (habitat melting and destruction, ecosystem transition and re-colonization) as important indirect consequences of global warming and altered climatic conditions around the planet.
Development of functional and stable solid polymer electrolytes (SPEs) for battery applications is an important step towards both safer batteries and for the realization of lithium-based or anode-less batteries. The interface between the lithium and the solid polymer electrolyte is one of the bottlenecks, where severe degradation is expected. Here, the stability of three different SPEs - poly(ethylene oxide) (PEO), poly(epsilon-caprolactone) (PCL) and poly(trimethylene carbonate) (PTMC) - together with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, is investigated after they have been exposed to lithium metal under UHV conditions. Degradation compounds, e.g. Li-O-R, LiF and LixSyOz, are identified for all SPEs using soft X-ray photoelectron spectroscopy. A competing degradation between polymer and salt is identified in the outermost surface region (<7 nm), and is dependent on the polymer host. PTMC:LiTFSI shows the most severe decomposition of both polymer and salt followed by PCL:LiTFSI and PEO:LiTFSI. In addition, the movement of lithium species through the decomposed interface shows large variation depending on the polymer electrolyte system.
Diffusion maps is a manifold learning algorithm widely used for dimensionality reduction. Using a sample from a distribution, it approximates the eigenvalues and eigenfunctions of associated Laplace-Beltrami operators. Theoretical bounds on the approximation error are, however, generally much weaker than the rates that are seen in practice. This paper uses new approaches to improve the error bounds in the model case where the distribution is supported on a hypertorus. For the data sampling (variance) component of the error we make spatially localized compact embedding estimates on certain Hardy spaces; we study the deterministic (bias) component as a perturbation of the Laplace-Beltrami operator's associated PDE and apply relevant spectral stability results. Using these approaches, we match long-standing pointwise error bounds for both the spectral data and the norm convergence of the operator discretization. We also introduce an alternative normalization for diffusion maps based on Sinkhorn weights. This normalization approximates a Langevin diffusion on the sample and yields a symmetric operator approximation. We prove that it has better convergence compared with the standard normalization on flat domains, and we present a highly efficient rigorous algorithm to compute the Sinkhorn weights.