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The Salt Range in Pakistan exposes Precambrian to Pleistocene strata outcropping along the Salt Range Thrust (SRT). To better understand the in-situ Cambrian and Pliocene tectonic evolution of the Pakistan Subhimalaya, we have conducted low-temperature thermochronological analysis using apatite (U-Th-Sm)/He and fission track dating. We combine cooling ages from different samples located along the thrust front of the SRT into a thermal model that shows two major cooling events associated with rifting and regional erosion in the Late Palaeozoic and SRT activity since the Pliocene. Our results suggest that the SRT maintained a long-term average shortening rate of similar to 5-6 mm/yr and a high exhumation rate above the SRT ramp since similar to 4 Ma.
The Kohat fold and thrust belt in Pakistan shows a significantly different structural style due to the structural evolution on the double décollement compared to the rest of the Subhimalaya. In order to better understand the spatio-temporal structural evolution of the Kohat fold and thrust belt, we combine balanced cross sections with apatite (U?Th-Sm)/He (AHe) and apatite fission track (AFT) dating. The AHe and AFT ages appear to be totally reset, allowing us to date exhumation above structural ramps. The results suggest that deformation began on the frontal Surghar thrust at-15 Ma, predating or coeval with the development of the Main Boundary thrust at-12 Ma. Deformation propagated southward from the Main Boundary thrust on double de?collements between 10 Ma and 2 Ma, resulting in a disharmonic structural style inside the Kohat fold and thrust belt. Thermal modeling of the thermochronologic data suggest that samples inside Kohat fold and thrust belt experienced cooling due to formation of the duplexes; this deformation facilitated tectonic thickening of the wedge and erosion of the Miocene to Pliocene foreland strata. The spatial distribution of AHe and AFT ages in combination with the structural forward model suggest that, in the Kohat fold and thrust belt, the wedge deformed in-sequence as a supercritical wedge (-15-12 Ma), then readjusted by out-sequence deformation (-12-0 Ma) within the Kohat fold and thrust belt into a sub-critical wedge.
Fold and thrust belts are characteristic features of collisional orogen that grow laterally through time by deforming the upper crust in response to stresses caused by convergence. The deformation propagation in the upper crust is accommodated by shortening along major folds and thrusts. The formation of these structures is influenced by the mechanical strength of décollements, basement architecture, presence of preexisting structures and taper of the wedge. These factors control not only the sequence of deformation but also cause differences in the structural style.
The Himalayan fold and thrust belt exhibits significant differences in the structural style from east to west. The external zone of the Himalayan fold and thrust belt, also called the Subhimalaya, has been extensively studied to understand the temporal development and differences in the structural style in Bhutan, Nepal and India; however, the Subhimalaya in Pakistan remains poorly studied. The Kohat and Potwar fold and thrust belts (herein called Kohat and Potwar) represent the Subhimalaya in Pakistan. The Main Boundary Thrust (MBT) marks the northern boundary of both Kohat and Potwar, showing that these belts are genetically linked to foreland-vergent deformation within the Himalayan orogen, despite the pronounced contrast in structural style. This contrast becomes more pronounced toward south, where the active strike-slip Kalabagh Fault Zone links with the Kohat and Potwar range fronts, known as the Surghar Range and the Salt Range, respectively. The Surghar and Salt Ranges developed above the Surghar Thrust (SGT) and Main Frontal Thrust (MFT). In order to understand the structural style and spatiotemporal development of the major structures in Kohat and Potwar, I have used structural modeling and low temperature thermochronolgy methods in this study. The structural modeling is based on construction of balanced cross-sections by integrating surface geology, seismic reflection profiles and well data. In order to constrain the timing and magnitude of exhumation, I used apatite (U-Th-Sm)/He (AHe) and apatite fission track (AFT) dating. The results obtained from both methods are combined to document the Paleozoic to Recent history of Kohat and Potwar.
The results of this research suggest two major events in the deformation history. The first major deformation event is related to Late Paleozoic rifting associated with the development of the Neo-Tethys Ocean. The second major deformation event is related to the Late Miocene to Pliocene development of the Himalayan fold and thrust belt in the Kohat and Potwar. The Late Paleozoic rifting is deciphered by inverse thermal modelling of detrital AFT and AHe ages from the Salt Range. The process of rifting in this area created normal faulting that resulted in the exhumation/erosion of Early to Middle Paleozoic strata, forming a major unconformity between Cambrian and Permian strata that is exposed today in the Salt Range. The normal faults formed in Late Paleozoic time played an important role in localizing the Miocene-Pliocene deformation in this area. The combination of structural reconstructions and thermochronologic data suggest that deformation initiated at 15±2 Ma on the SGT ramp in the southern part of Kohat. The early movement on the SGT accreted the foreland into the Kohat deforming wedge, forming the range front. The development of the MBT at 12±2 Ma formed the northern boundary of Kohat and Potwar. Deformation propagated south of the MBT in the Kohat on double décollements and in the Potwar on a single basal décollement. The double décollement in the Kohat adopted an active roof-thrust deformation style that resulted in the disharmonic structural style in the upper and lower parts of the stratigraphic section. Incremental shortening resulted in the development of duplexes in the subsurface between two décollements and imbrication above the roof thrust. Tectonic thickening caused by duplexes resulted in cooling and exhumation above the roof thrust by removal of a thick sequence of molasse strata. The structural modelling shows that the ramps on which duplexes formed in Kohat continue as tip lines of fault propagation folds in the Potwar. The absence of a double décollement in the Potwar resulted in the preservation of a thick sequence of molasse strata there. The temporal data suggest that deformation propagated in-sequence from ~ 8 to 3 Ma in the northern part of Kohat and Potwar; however, internal deformation in the Kohat was more intense, probably required for maintaining a critical taper after a significant load was removed above the upper décollement. In the southern part of Potwar, a steeper basement slope (β≥3°) and the presence of salt at the base of the stratigraphic section allowed for the complete preservation of the stratigraphic wedge, showcased by very little internal deformation. Activation of the MFT at ~4 Ma allowed the Salt Range to become the range front of the Potwar. The removal of a large amount of molasse strata above the MFT ramp enhanced the role of salt in shaping the structural style of the Salt Range and Kalabagh Fault Zone. Salt accumulation and migration resulted in the formation of normal faults in both areas. Salt migration in the Kalabagh fault zone has triggered out-of-sequence movement on ramps in the Kohat.
The amount of shortening calculated between the MBT and the SGT in Kohat is 75±5 km and between the MBT and the MFT in Potwar is 65±5 km. A comparable amount of shortening is accommodated in the Kohat and Potwar despite their different widths: 70 km Kohat and 150 km Potwar. In summary, this research suggests that deformation switched between different structures during the last ~15 Ma through different modes of fault propagation, resulting in different structural styles and the out-of-sequence development of Kohat and Potwar.
The electrical conductivity of organic semiconductors can be enhanced by orders of magnitude via doping with strong molecular electron acceptors or donors. Ground-state integer charge transfer and charge-transfer complex formation between organic semiconductors and molecular dopants have been suggested as the microscopic mechanisms causing these profound changes in electrical materials properties. Here, we study charge-transfer interactions between the common molecular p-dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane and a systematic series of thiophene-based copolymers by a combination of spectroscopic techniques and electrical measurements. Subtle variations in chemical structure are seen to significantly impact the nature of the charge-transfer species and the efficiency of the doping process, underlining the need for a more detailed understanding of the microscopic doping mechanism in organic semiconductors to reliably guide targeted chemical design.
Nucleation and growth of unsubstituted metal phthalocyanine films from solution on planar substrates
(2012)
In den vergangenen Jahren wurden kosteneffiziente nasschemische Beschichtungsverfahren für die Herstellung organischer Dünnfilme für verschiedene opto-elektronische Anwendungen entdeckt und weiterentwickelt. Unter anderem wurden Phthalocyanin-Moleküle in photoaktiven Schichten für die Herstellung von Solarzellen intensiv erforscht. Aufgrund der kleinen bzw. unbekannten Löslichkeit wurden Phthalocyanin-Schichten durch Aufdampfverfahren im Vakuum hergestellt. Des Weiteren wurde die Löslichkeit durch chemische Synthese erhöht, was aber die Eigenschaften von Pc beeinträchtigte. In dieser Arbeit wurde die Löslichkeit, optische Absorption und Stabilität von 8 verschiedenen unsubstituierten Metall-Phthalocyaninen in 28 verschiedenen Lösungsmitteln quantitativ gemessen. Wegen ausreichender Löslichkeit, Stabilität und Anwendbarkeit in organischen Solarzellen wurde Kupferphthalocyanin (CuPc) in Trifluoressigsäure (TFA) für weitere Untersuchungen ausgewählt. Durch die Rotationsbeschichtung von CuPc aus TFA Lösung wurde ein dünner Film aus der verdampfenden Lösung auf dem Substrat platziert. Nach dem Verdampfen des Lösungsmittels, die Nanobändern aus CuPc bedecken das Substrat. Die Nanobänder haben eine Dicke von etwa ~ 1 nm (typische Dimension eines CuPc-Molekül) und variierender Breite und Länge, je nach Menge des Materials. Solche Nanobändern können durch Rotationsbeschichtung oder auch durch andere Nassbeschichtungsverfahren, wie Tauchbeschichtung, erzeugt werden. Ähnliche Fibrillen-Strukturen entstehen durch Nassbeschichtung von anderen Metall-Phthalocyaninen, wie Eisen- und Magnesium-Phthalocyanin, aus TFA-Lösung sowie auf anderen Substraten, wie Glas oder Indium Zinnoxid. Materialeigenschaften von aufgebrachten CuPc aus TFA Lösung und CuPc in der Lösung wurden ausführlich mit Röntgenbeugung, Spektroskopie- und Mikroskopie Methoden untersucht. Es wird gezeigt, dass die Nanobänder nicht in der Lösung, sondern durch Verdampfen des Lösungsmittels und der Übersättigung der Lösung entstehen. Die Rasterkraftmikroskopie wurde dazu verwendet, um die Morphologie des getrockneten Films bei unterschiedlicher Konzentration zu studieren. Der Mechanismus der Entstehung der Nanobändern wurde im Detail studiert. Gemäß der Keimbildung und Wachstumstheorie wurde die Entstehung der CuPc Nanobänder aus einer übersättigt Lösung diskutiert. Die Form der Nanobändern wurde unter Berücksichtigung der Wechselwirkung zwischen den Molekülen und dem Substrat diskutiert. Die nassverarbeitete CuPc-Dünnschicht wurde als Donorschicht in organischen Doppelschicht Solarzellen mit C60-Molekül, als Akzeptor eingesetzt. Die Effizienz der Energieumwandlung einer solchen Zelle wurde entsprechend den Schichtdicken der CuPc Schicht untersucht.
After endosymbiosis, chloroplasts lost most of their genome. Many former endosymbiotic genes are now nucleus-encoded and the products are re-imported post-translationally. Consequently, photosynthetic complexes are built of nucleus- and plastid-encoded subunits in a well-defined stoichiometry. In Chlamydomonas, the translation of chloroplast-encoded photosynthetic core subunits is feedback-regulated by the assembly state of the complexes they reside in. This process is called Control by Epistasy of Synthesis (CES) and enables the efficient production of photosynthetic core subunits in stoichiometric amounts. In chloroplasts of embryophytes, only Rubisco subunits have been shown to be feedback-regulated. That opens the question if there is additional CES regulation in embryophytes. I analyzed chloroplast gene expression in tobacco and Arabidopsis mutants with assembly defects for each photosynthetic complex to broadly answer this question. My results (i) confirmed CES within Rubisco and hint to potential translational feedback regulation in the synthesis of (ii) cytochrome b6f (Cyt b6f) and (iii) photosystem II (PSII) subunits. This work suggests a CES network in PSII that links psbD, psbA, psbB, psbE, and potentially psbH expression by a feedback mechanism that at least partially differs from that described in Chlamydomonas. Intriguingly, in the Cyt b6f complex, a positive feedback regulation that coordinates the synthesis of PetA and PetB was observed, which was not previously reported in Chlamydomonas. No evidence for CES interactions was found in the expression of NDH and ATP synthase subunits of embryophytes. Altogether, this work provides solid evidence for novel assembly-dependent feedback regulation mechanisms controlling the expression of photosynthetic genes in chloroplasts of embryophytes.
In order to obtain a comprehensive inventory of the rbcL and psbA RNA-binding proteomes (including factors that regulate their expression, especially factors involved in CES), an aptamer based affinity purification method was adapted and refined for the specific purification these transcripts from tobacco chloroplasts. To this end, three different aptamers (MS2, Sephadex ,and streptavidin binding) were stably introduced into the 3’ UTRs of psbA and rbcL by chloroplast transformation. RNA aptamer based purification and subsequent chip analysis (RAP Chip) demonstrated a strong enrichment of psbA and rbcL transcripts and currently, ongoing mass spectrometry analyses shall reveal potential regulatory factors. Furthermore, the suborganellar localization of MS2 tagged psbA and rbcL transcripts was analyzed by a combined affinity, immunology, and electron microscopy approach and demonstrated the potential of aptamer tags for the examination of the spatial distribution of chloroplast transcripts.
Magnetosome Organization in Magnetotactic Bacteria Unraveled by Ferromagnetic Resonance Spectroscopy
(2017)
Magnetotactic bacteria form assemblies of magnetic nanoparticles called magnetosomes. These magnetosomes are typically arranged in chains, but other forms of assemblies such as clusters can be observed in some species and genetic mutants. As such, the bacteria have developed as a model for the understanding of how organization of particles can influence the magnetic properties. Here, we use ferromagnetic resonance spectroscopy to measure the magnetic anisotropies in different strains of Magnetosprillum gtyphiswaldense MSR-1, a bacterial species that is amendable to genetic mutations. We combine our experimental results with a model describing the spectra. The model includes chain imperfections and misalignments following a Fisher distribution function, in addition to the intrinsic magnetic properties of the magnetosomes. Therefore, by applying the model to analyze the ferromagnetic resonance data, the distribution of orientations in the bulk sample can be retrieved in addition to the average magnetosome arrangement. In this way, we quantitatively characterize the magnetosome arrangement in both wild-type cells and Delta mamJ mutants, which exhibit differing magnetosome organization.
Improving scalability and reward of utility-driven self-healing for large dynamic architectures
(2020)
Self-adaptation can be realized in various ways. Rule-based approaches prescribe the adaptation to be executed if the system or environment satisfies certain conditions. They result in scalable solutions but often with merely satisfying adaptation decisions. In contrast, utility-driven approaches determine optimal decisions by using an often costly optimization, which typically does not scale for large problems. We propose a rule-based and utility-driven adaptation scheme that achieves the benefits of both directions such that the adaptation decisions are optimal, whereas the computation scales by avoiding an expensive optimization. We use this adaptation scheme for architecture-based self-healing of large software systems. For this purpose, we define the utility for large dynamic architectures of such systems based on patterns that define issues the self-healing must address. Moreover, we use pattern-based adaptation rules to resolve these issues. Using a pattern-based scheme to define the utility and adaptation rules allows us to compute the impact of each rule application on the overall utility and to realize an incremental and efficient utility-driven self-healing. In addition to formally analyzing the computational effort and optimality of the proposed scheme, we thoroughly demonstrate its scalability and optimality in terms of reward in comparative experiments with a static rule-based approach as a baseline and a utility-driven approach using a constraint solver. These experiments are based on different failure profiles derived from real-world failure logs. We also investigate the impact of different failure profile characteristics on the scalability and reward to evaluate the robustness of the different approaches.
Evaluating the performance of self-adaptive systems is challenging due to their interactions with often highly dynamic environments. In the specific case of self-healing systems, the performance evaluations of self-healing approaches and their parameter tuning rely on the considered characteristics of failure occurrences and the resulting interactions with the self-healing actions. In this paper, we first study the state-of-the-art for evaluating the performances of self-healing systems by means of a systematic literature review. We provide a classification of different input types for such systems and analyse the limitations of each input type. A main finding is that the employed inputs are often not sophisticated regarding the considered characteristics for failure occurrences. To further study the impact of the identified limitations, we present experiments demonstrating that wrong assumptions regarding the characteristics of the failure occurrences can result in large performance prediction errors, disadvantageous design-time decisions concerning the selection of alternative self-healing approaches, and disadvantageous deployment-time decisions concerning parameter tuning. Furthermore, the experiments indicate that employing multiple alternative input characteristics can help with reducing the risk of premature disadvantageous design-time decisions.
Evaluating the performance of self-adaptive systems (SAS) is challenging due to their complexity and interaction with the often highly dynamic environment. In the context of self-healing systems (SHS), employing simulators has been shown to be the most dominant means for performance evaluation. Simulating a SHS also requires realistic fault injection scenarios. We study the state of the practice for evaluating the performance of SHS by means of a systematic literature review. We present the current practice and point out that a more thorough and careful treatment in evaluating the performance of SHS is required.
The landscape of software self-adaptation is shaped in accordance with the need to cost-effectively achieve and maintain (software) quality at runtime and in the face of dynamic operation conditions. Optimization-based solutions perform an exhaustive search in the adaptation space, thus they may provide quality guarantees. However, these solutions render the attainment of optimal adaptation plans time-intensive, thereby hindering scalability. Conversely, deterministic rule-based solutions yield only sub-optimal adaptation decisions, as they are typically bound by design-time assumptions, yet they offer efficient processing and implementation, readability, expressivity of individual rules supporting early verification. Addressing the quality-cost trade-of requires solutions that simultaneously exhibit the scalability and cost-efficiency of rulebased policy formalism and the optimality of optimization-based policy formalism as explicit artifacts for adaptation. Utility functions, i.e., high-level specifications that capture system objectives, support the explicit treatment of quality-cost trade-off. Nevertheless, non-linearities, complex dynamic architectures, black-box models, and runtime uncertainty that makes the prior knowledge obsolete are a few of the sources of uncertainty and subjectivity that render the elicitation of utility non-trivial.
This thesis proposes a twofold solution for incremental self-adaptation of dynamic architectures. First, we introduce Venus, a solution that combines in its design a ruleand an optimization-based formalism enabling optimal and scalable adaptation of dynamic architectures. Venus incorporates rule-like constructs and relies on utility theory for decision-making. Using a graph-based representation of the architecture, Venus captures rules as graph patterns that represent architectural fragments, thus enabling runtime extensibility and, in turn, support for dynamic architectures; the architecture is evaluated by assigning utility values to fragments; pattern-based definition of rules and utility enables incremental computation of changes on the utility that result from rule executions, rather than evaluating the complete architecture, which supports scalability. Second, we introduce HypeZon, a hybrid solution for runtime coordination of multiple off-the-shelf adaptation policies, which typically offer only partial satisfaction of the quality and cost requirements. Realized based on meta-self-aware architectures, HypeZon complements Venus by re-using existing policies at runtime for balancing the quality-cost trade-off.
The twofold solution of this thesis is integrated in an adaptation engine that leverages state- and event-based principles for incremental execution, therefore, is scalable for large and dynamic software architectures with growing size and complexity. The utility elicitation challenge is resolved by defining a methodology to train utility-change prediction models. The thesis addresses the quality-cost trade-off in adaptation of dynamic software architectures via design-time combination (Venus) and runtime coordination (HypeZon) of rule- and optimization-based policy formalisms, while offering supporting mechanisms for optimal, cost-effective, scalable, and robust adaptation. The solutions are evaluated according to a methodology that is obtained based on our systematic literature review of evaluation in self-healing systems; the applicability and effectiveness of the contributions are demonstrated to go beyond the state-of-the-art in coverage of a wide spectrum of the problem space for software self-adaptation.
We examined how the frequency of the fixated word influences the spatiotemporal distribution of covert attention during reading. Participants discriminated gaze-contingent probes that occurred with different spatial and temporal offsets from randomly chosen fixation points during reading. We found that attention was initially focused at fixation and that subsequent defocusing was slower when the fixated word was lower in frequency. Later in a fixation, attention oriented more towards the next saccadic target for high- than for low-frequency words. These results constitute the first report of the time course of the effect of load on attentional engagement and orienting in reading. They are discussed in the context of serial and parallel models of reading.
Perceptuomotor compatibility between phonemically identical spoken and perceived syllables has been found to speed up response times (RTs) in speech production tasks. However, research on compatibility effects between perceived and produced stimuli at the subphonemic level is limited. Using a cue-distractor task, we investigated the effects of phonemic and subphonemic congruency in pairs of vowels. On each trial, a visual cue prompted individuals to produce a response vowel, and after the visual cue appeared a distractor vowel was auditorily presented while speakers were planning to produce the response vowel. The results revealed effects on RTs due to phonemic congruency (same vs. different vowels) between the response and distractor vowels, which resemble effects previously seen for consonants. Beyond phonemic congruency, we assessed how RTs are modulated as a function of the degree of subphonemic similarity between the response and distractor vowels. Higher similarity between the response and distractor in terms of phonological distance-defined by number of mismatching phonological features-resulted in faster RTs. However, the exact patterns of RTs varied across response-distractor vowel pairs. We discuss how different assumptions about phonological feature representations may account for the different patterns observed in RTs across response-distractor pairs. Our findings on the effects of perceived stimuli on produced speech at a more detailed level of representation than phonemic identity necessitate a more direct and specific formulation of the perception-production link. Additionally, these results extend previously reported perceptuomotor interactions mainly involving consonants to vowels.
This study compares the classification of Azerbaijani fricatives based on two sets of features: (a) spectral moments, spectral peak, amplitude, duration, and (b) cepstral coefficients employing Hidden Markov Models to divide each fricative into three regions such that the variances of the measures within each region are minimized. The cepstral coefficients were found to be more reliable predictors in the classification of all nine Azerbaijani fricatives and the cepstral measures yielded highly successful classification rates (91.21% across both genders) in the identification of the full set of fricatives of Azerbaijani.
Fast and easy tests for quantifying fat-soluble vitamins such as vitamin E and vitamin A, as well as beta-carotene, in whole blood without a need to preprocess blood samples could facilitate assessment of the vitamin status of dairy cattle. The objective of this study was to validate a field-portable fluorometer/spectrophotometer assay for the rapid quantification of these vitamins in whole blood and plasma of dairy cows and calves. We measured the concentrations of vitamin E and beta-carotene in whole blood and plasma from 28 dairy cows and 11 calves using the iCheck test (Bio-Analyt GmbH, Teltow, Germany) and compared the results with the current analytical standard (HPLC) in 2 independent laboratories, one at the University of Potsdam (Germany) and at one at DSM Nutritional Products Ltd. (Kaiseraugst, Switzerland). For vitamin A, the HPLC measurements were done only in the laboratory in Germany. The whole-blood concentrations of vitamin E as determined by iCheck (blood-hematocritcorrected) ranged from 1.82 to 4.99 mg/L in dairy cows and 0.34 to 3.40 mg/L in calves. These findings were moderately correlated (R-2 = 0.66) with the values assessed by HPLC in dairy cattle (cows + calves). When calves were excluded, the correlation was higher (R-2 = 0.961). The beta-carotene and vitamin A values obtained by the reference method HPLC were highly correlated with the iCheck methods in whole blood (R-2 = 0.99 and 0.88, respectively). In plasma, we observed strong correlations between the concentrations assessed by iCheck and those of HPLC for vitamin E (R-2 = 0.97), beta-carotene (R-2 = 0.98), and vitamin A (R-2 = 0.92) in dairy cattle (cows + calves). For vitamin E, beta-carotene, and vitamin A, we compared the relationship between the differences obtained by the iCheck assay and the HPLC measurements, as well as the magnitude of measurements, using Bland-Altman plots to test for systematic bias. For all 3 vitamins, the differences values were not outside the 95% acceptability limits; we found no systematic error between the 2 methods for all 3 analytes.
Semi-distributed hydrological and water quality models are increasingly used as innovative and scientific-based management tools.
However, their application is usually restricted to the gauging stations where they are originally calibrated, limiting their spatial capability.
In this study, the semi-distributed hydrological water quality model HYPE (HYdrological Predictions for the Environment) was tested spatially to represent nitrate-N (NO3- N) and total phosphorus (TP) concentrations and loads of the nested and heterogeneous Selke catchment (463 km(2)) in central Germany.
First, an automatic calibration procedure and uncertainty analysis were conducted using the DiffeRential Evolution Adaptive Metropolis (DREAM) tool to simulate discharge, NO3--N and TP concentrations. A multi-site and multi-objective calibration approach was applied using three main gauging stations, covering the most important hydro-meteorological and physiographical characteristics of the whole catchment. Second, the model's capability was tested to represent further internal stations, which were not initially considered for calibration. Results showed that discharge was well represented by the model at all three main stations during both calibration (1994-1998) and validation (1999-2014) periods with lowest Nash-Sutcliffe Efficiency (NSE) of 0.71 and maximum Percentage BIAS (PBIAS) of 18.0%.
The model was able to reproduce the seasonal dynamics of NO3--N and TP concentrations with low predictive uncertainty at the three main stations, reflected by PBIAS values in the ranges from 16.1% to 6.4% and from 20.0% to 11.5% for NO3--N and TP load simulations, respectively.
At internal stations, the model could represent reasonably well the seasonal variation of nutrient concentrations with PBIAS values in the ranges from 9.0% to 14.2% for NO3--N and from 25.3% to 34.3% for TP concentration simulations.
Overall, results suggested that the spatial validation of a nutrient transport model can be better ensured when a multi-site and multi-objective calibration approach using archetypical gauging stations is implemented.
Further, results revealed that the delineation of sub-catchments should put more focus on hydro-meteorological conditions than on land-use features.
Vegetation with an adequate supply of water might contribute to cooling the land surface around it through the latent heat flux of transpiration. This study investigates the potential estimation of evaporative cooling at plot scale, using soybean as example. Some of the plants' physiological parameters were monitored and sampled at weekly intervals. A physics-based model was then applied to estimate the irrigation-induced cooling effect within and above the canopy during the middle and late season of the soybean growth period. We then examined the results of the temperature changes at a temporal resolution of ten minutes between every two irrigation rounds. During the middle and late season of growth, the cooling effects caused by evapotranspiration within and above the canopy were, on average, 4.4 K and 2.9 K, respectively. We used quality indicators such as R-squared (R-2) and mean absolute error (MAE) to evaluate the performance of the model simulation. The performance of the model in this study was better above the canopy (R-2 = 0.98, MAE = 0.3 K) than below (R-2 = 0.87, MAE = 0.9 K) due to the predefined thermodynamic condition used to estimate evaporative cooling. Moreover, the study revealed that canopy cooling contributes to mitigating heat stress conditions during the middle and late seasons of crop growth.
Forest microclimate can buffer biotic responses to summer heat waves, which are expected to become more extreme under climate warming. Prediction of forest microclimate is limited because meteorological observation standards seldom include situations inside forests.
We use eXtreme Gradient Boosting - a Machine Learning technique - to predict the microclimate of forest sites in Brandenburg, Germany, using seasonal data comprising weather features.
The analysis was amended by applying a SHapley Additive explanation to show the interaction effect of variables and individualised feature attributions.
We evaluate model performance in comparison to artificial neural networks, random forest, support vector machine, and multi-linear regression.
After implementing a feature selection, an ensemble approach was applied to combine individual models for each forest and improve robustness over a given single prediction model.
The resulting model can be applied to translate climate change scenarios into temperatures inside forests to assess temperature-related ecosystem services provided by forests.
Poröse Sol-Gel-Materialien finden in vielen Bereichen Anwendung bzw. sind Gegenstand der aktuellen Forschung. Zu diesen Bereichen zählen sowohl klassische Anwendungen, wie z. B. die Verwendung als Katalysator, Molekularsieb oder Trockenmittel, als auch nichtklassische Anwendungen, wie z. B. der Einsatz als Kontrastmittel in der Magnet-Resonanz-Tomographie oder in Form von dünnen Zeolithfilmen als Isolatoren in Mikrochips. Auch für den Einsatz in der Photonik werden poröse Materialien in Betracht gezogen, wie die Entwicklung des Zeolith-Farbstoff-Lasers zeigt. Mikroporöse Zeolithe können generell über einfache Ionenaustauschreaktionen mit Lanthanoidionen in lumineszente Materialien umgewandelt werden. Neben der Erzeugung eines lumineszenten Materials, dessen Lumineszenzeigenschaften charakterisiert werden müssen, bietet die Nutzung von Lanthanoidionen die Möglichkeit diese Ionen als Sonde zur Charakterisierung der Ion-Wirt-Wechselwirkungen zu funktionalisieren, was z. B. in Bezug auf die Anwendung als Katalysator von großer Bedeutung ist. Dabei werden die einzigartigen Lumineszenzeigenschaften der Lanthanoidionen, in diesem Fall von Europium(III) und Terbium(III), genutzt. In dieser Arbeit wurden Lanthanoid-dotierte mikroporöse Zeolithe, mikroporös-mesoporöse Hybridmaterialien und mesoporöse Silikate hinsichtlich ihrer Lumineszenzeigenschaften und ihrer Wechselwirkung des Wirtsmaterials mit den Lanthanoidionen mittels zeitaufgelöster Lumineszenzspektroskopie untersucht. Zeitaufgelöste Emissionsspektren (TRES) liefern dabei sowohl Informationen in der Wellenlängen- als auch in der Zeitdomäne. Erstmalig wurden die TRES mittels einer umfangreichen Auswertemethodik behandelt. Neben der Anpassung des Abklingverhaltens mit einer diskreten Zahl von Exponentialfunktionen, wurden unterstützend auch Abklingzeitverteilungsanalysen durchgeführt. Zeitaufgelöste flächennormierte Emissionsspektren (TRANES), eine Erweiterung der normalen TRES, konnten erstmals zur Bestimmung der Zahl der emittierenden Lanthanoidspezies in porösen Materialien genutzt werden. Durch die Berechnung der Decayassoziierten Spektren (DAS) konnten den Lanthanoidspezies die entsprechenden Lumineszenzspektren zugeordnet werden. Zusätzlich konnte, speziell im Fall der Europium-Lumineszenz, durch Kombination von zeitlicher und spektraler Information das zeitabhängige Asymmetrieverhältnis R und die spektrale Evolution des 5D0-7F0-Übergangs mit der Zeit t untersucht und somit wesentliche Informationen über die Verteilung der Europiumionen im Wirtsmaterial erhalten werden. Über die Abklingzeit und das Asymmetrieverhältnis R konnten Rückschlüsse auf die Zahl der OH-Oszillatoren in der ersten Koordinationssphäre und die Symmetrie der Koordinationsumgebung gezogen werden. Für die mikroporösen und mikroporös-mesoporösen Materialien wurden verschiedene Lanthanoidspezies, im Regelfall zwei, gefunden, welche entsprechend der beschriebenen Methoden charakterisiert wurden. Diese Lanthanoidspezies konnten Positionen in den Materialien zugeordnet werden, die sich im tief Inneren des Porensystems oder auf bzw. nahe der äußeren Oberfläche oder in den Mesoporen befinden. Erstere Spezies ist aufgrund ihrer Position im Material gut vor Feuchtigkeitseinflüssen geschützt, was sich deutlich in entsprechend langen Lumineszenzabklingzeiten äußert. Zusätzlich ist diese Europiumspezies durch unsymmetrische Koordinationsumgebung charakterisiert, was auf einen signifikanten Anteil an Koordination der Lanthanoidionen durch die Sauerstoffatome im Wirtsgitter zurückzuführen ist. Ionen, die sich nahe oder auf der äußeren Oberfläche befinden, sind dagegen für Feuchtigkeit zugänglicher, was in kürzeren Lumineszenzabklingzeiten und einer symmetrischeren Koordinationsumgebung resultiert. Der Anteil von Wassermolekülen in der ersten Koordinationssphäre ist hier deutlich größer, als bei den Ionen, die sich tiefer im Porensystem befinden und entspricht in vielen Fällen der Koordinationszahl eines vollständig hydratisierten Lanthanoidions. Auch der Einfluss von Oberflächenmodifikationen auf die Speziesverteilung und das Verhalten der Materialien gegenüber Feuchtigkeit wurde untersucht. Dabei gelang es den Einfluss der Feuchtigkeit auf die Lumineszenzeigenschaften und die Speziesverteilung durch die Oberflächenmodifikation zu verringern und die Lumineszenzeigenschaften teilweise zu konservieren. Im Fall der mesoporösen Silikamonolithe wurde auch eine heterogene Verteilung der Lanthanoidionen im Porensystem gefunden. Hier wechselwirkt ein Teil der Ionen mit der Porenwand, während sich die restlichen Ionen in der wäßrigen Phase innerhalb des Porensystems aufhalten. Das Aufbringen von Oberflächenmodifikationen führte zu einer Wechselwirkung der Ionen mit diesen Oberflächenmodifikationen, was sich in Abhängigkeit von der Oberflächenbeladung in den enstprechenden Lumineszenzeigenschaften niederschlug.
Conservation actions need to account for global climate change and adapt to it. The body of the literature on adaptation options is growing rapidly, but their feasibility and current state of implementation are rarely assessed. We discussed the practicability of adaptation options with conservation managers analysing three fields of action: reducing the vulnerability of conservation management, reducing the vulnerability of conservation targets (i.e. biodiversity) and climate change mitigation. For all options, feasibility, current state of implementation and existing obstacles to implementation were analysed, using the Federal State of Brandenburg, Germany, as a case study. Practitioners considered a large number of options useful, most of which have already been implemented at least in part. Those options considered broadly implemented resemble mainly conventional measures of conservation without direct relation to climate change. Managers are facing several obstacles for adapting to climate change, including political reluctance to change, financial and staff shortages in conservation administrations and conflictive EU funding schemes in agriculture. A certain reluctance to act, due to the high degree of uncertainty with regard to climate change scenarios and impacts, is widespread. A lack of knowledge of appropriate methods such as adaptive management often inhibits the implementation of adaptation options in the field of planning and management. Based on the findings for Brandenburg, we generally conclude that it is necessary to focus in particular on options that help to reduce vulnerability of conservation management itself, i.e. those that enhance management effectiveness. For instance, adaptive and proactive risk management can be applied as a no-regrets option, independently from specific climate change scenarios or impacts, strengthening action under uncertainty.
Protected areas are arguably the most important instrument of biodiversity conservation. To keep them fit under climate change, their management needs to be adapted to address related direct and indirect changes. In our study we focus on the adaptation of conservation management planning, evaluating management plans of 60 protected areas throughout Germany with regard to their climate change-robustness. First, climate change-robust conservation management was defined using 11 principles and 44 criteria, which followed an approach similar to sustainability standards. We then evaluated the performance of individual management plans concerning the climate change-robustness framework. We found that climate change-robustness of protected areas hardly exceeded 50 percent of the potential performance, with most plans ranking in the lower quarter. Most Natura 2000 protected areas, established under conservation legislation of the European Union, belong to the sites with especially poor performance, with lower values in smaller areas. In general, the individual principles showed very different rates of accordance with our principles, but similarly low intensity. Principles with generally higher performance values included holistic knowledge management, public accountability and acceptance as well as systemic and strategic coherence. Deficiencies were connected to dealing with the future and uncertainty. Lastly, we recommended the presented principles and criteria as essential guideposts that can be used as a checklist for working towards more climate change-robust planning.
Conservation actions need to account for and be adapted to address changes that will occur under global climate change. The identification of stresses on biological diversity (as defined in the Convention on Biological Diversity) is key in the process of adaptive conservation management. We considered any impact of climate change on biological diversity a stress because such an effect represents a change (negative or positive) in key ecological attributes of an ecosystem or parts of it. We applied a systemic approach and a hierarchical framework in a comprehensive classification of stresses to biological diversity that are caused directly by global climate change. Through analyses of 20 conservation sites in 7 countries and a review of the literature, we identified climate-change-induced stresses. We grouped the identified stresses according to 3 levels of biological diversity: stresses that affect individuals and populations, stresses that affect biological communities, and stresses that affect ecosystem structure and function. For each stress category, we differentiated 3 hierarchical levels of stress: stress class (thematic grouping with the coarsest resolution, 8); general stresses (thematic groups of specific stresses, 21); and specific stresses (most detailed definition of stresses, 90). We also compiled an overview of effects of climate change on ecosystem services using the categories of the Millennium Ecosystem Assessment and 2 additional categories. Our classification may be used to identify key climate-change-related stresses to biological diversity and may assist in the development of appropriate conservation strategies. The classification is in list format, but it accounts for relations among climate-change-induced stresses.
The public promotion of renewable energies is expected to increase the number of biogas plants and stimulate energy crops cultivation (e. g. maize) in Germany. In order to assess the indirect effects of the resulting land-use changes on biodiversity, we developed six land-use scenarios and simulated the responses of six farmland wildlife species with the spatially explicit agent-based model system ALMaSS. The scenarios differed in composition and spatial configuration of arable crops. We implemented scenarios where maize for energy production replaced 15% and 30% of the area covered by other cash crops. Biogas maize farms were either randomly distributed or located within small or large aggregation clusters. The animal species investigated were skylark (Alauda arvensis), grey partridge (Perdix perdix), European brown hare (Lepus europaeus), field vole (Microtus agrestis), a linyphiid spider (Erigone atra) and a carabid beetle (Bembidion lampros). The changes in crop composition had a negative effect on the population sizes of skylark, partridge and hare and a positive effect on the population sizes of spider and beetle and no effect on the population size of vole. An aggregated cultivation of maize amplified these effects for skylark. Species responses to changes in the crop composition were consistent across three differently structured landscapes. Our work suggests that with the compliance to some recommendations, negative effects of biogas-related land-use change on the populations of the six representative farmland species can largely be avoided.
Modern data analysis tasks often involve control flow statements, such as the iterations in PageRank and K-means. To achieve scalability, developers usually implement these tasks in distributed dataflow systems, such as Spark and Flink. Designers of such systems have to choose between providing imperative or functional control flow constructs to users. Imperative constructs are easier to use, but functional constructs are easier to compile to an efficient dataflow job. We propose Mitos, a system where control flow is both easy to use and efficient. Mitos relies on an intermediate representation based on the static single assignment form. This allows us to abstract away from specific control flow constructs and treat any imperative control flow uniformly both when building the dataflow job and when coordinating the distributed execution.
Grazing incidence x-ray diffraction (GIXD) measurements of uranyl arachidate (UO2A2) LB films
(1998)
Formation of a buried density grating on thermal erasure of azobenzene polymer surface gratings
(2002)
Gleichstellungspolitik als „Querschnittspolitik“ ist eine der oft genannten politische Metapher unserer Zeit. Ob in der Arbeitsmarkt-, Steuer-, Familien- oder Bildungspolitik, Gleichstellung ist in allen diesen Bereichen von hoher Relevanz. Der „Querschnittscharakter“ der Gleichstellungspolitik trägt dazu bei, dass in diesem Politikbereich viele unterschiedliche Akteure mit ebenso unterschiedlichen Handlungslogiken sowie Zielen aufeinandertreffen. Um Gleichstellungprogramme planen und darüber Gleichstellungspolitiken gestalten zu können, müssen die Handlungen dieser Akteure koordiniert werden.
In dieser Arbeit wird unter Verwendung des Governance-Ansatzes der Frage nachgegangen, wie die Handlungskoordination zwischen unterschiedlichen Akteuren im System der deutschen Gleichstellungspolitik erfolgt. Analysiert und rekonstruiert werden die gleichstellungspolitischen Entwicklungen in der BRD seit den 1990er Jahren, anhand der Auswertung relevanter Regierungsdokumente und wissenschaftlicher Sekundärliteratur. Hierarchien, Netzwerke und Verhandlungen – Ausprägungen der Governance-Formen – stehen bei der Rekonstruktion und Analyse der Akteurskonstellationen im Mittelpunkt.
Im Ergebnis konnten im Falle Deutschlands zwei verschiedene „Gleichstellungsgovernance-Regime“ identifiziert werden. Diese sind gekennzeichnet durch die in den Regimen je dominierenden Handlugskoordinationsmechanismen der „wirtschaftlichen-Selbstkoordination“ (2001) und der „wechselseitigen-Beobachtung“ (2003-2012). Der Vergleich dieser beiden Regime zeigt, dass sie sich vor allem in Hinblick auf ihre Akteurskonstellationen unterscheiden. In ihnen herrschen je eigene Handlungslogiken und als Folge daraus unterschiedliche gleichstellungspolitische Ergebnisse.
Die Frühe Neuzeit war durch Herrschaftswechsel unterschiedlichster Art und Reichweite geprägt. Diese waren oftmals durch das Aufeinandertreffen einander fremder neuer Herrscher und Untertanen gekennzeichnet. In der Folge war es erforderlich, das Verhältnis zwischen Herrschern und Beherrschten (neu) auszuhandeln. Ein Instrument hierzu konnte der Militärdienst sein. Er erlaubte über die Öffnung respektive Schließung der Offizierslaufbahn den Weg zur In- oder Exklusion der Eliten neuer Herrschaftsgebiete und barg durch die Verpflichtung breiterer Kreise der Bevölkerung Disziplinierungspotentiale. Wie diese Optionen eingesetzt wurden bzw. welche Reaktionen ihre Realisierung nach sich zog, wird in den Aufsätzen des vorliegenden Bandes thematisiert.
Monitoring Ultrafast Chemical Dynamics by Time-Domain X-ray Photo- and Auger-Electron Spectroscopy
(2016)
The directed flow of charge and energy is at the heart of all chemical processes. Extraordinary efforts are underway to monitor and understand the concerted motion of electrons and nuclei with ever increasing spatial and temporal sensitivity. The element specificity, chemical sensitivity, and temporal resolution of ultrafast X-ray spectroscopy techniques hold great promise to provide new insight into the fundamental interactions underlying chemical dynamics in systems ranging from isolated molecules to application-like devices. Here, we focus on the potential of ultrafast X-ray spectroscopy techniques based on the detection of photo- and Auger electrons to provide new fundamental insight into photochemical processes of systems with various degrees of complexity. Isolated nucleobases provide an excellent testing ground for our most fundamental understanding of intramolecular coupling between electrons and nuclei beyond the traditionally applied Born-Oppenheimer approximation. Ultrafast electronic relaxation dynamics enabled by the breakdown of this approximation is the major component of the nucleobase photoprotection mechanisms. Transient X-ray induced Auger electron spectroscopy on photoexcited thymine molecules provides atomic-site specific details of the extremely efficient coupling that converts potentially bond changing ultraviolet photon energy into benign heat. In particular, the time-dependent spectral shift of a specific Auger band is sensitive to the length of a single bond within the molecule. The X-ray induced Auger transients show evidence for an electronic transition out of the initially excited state within only similar to 200 fs in contrast to theoretically predicted picosecond population trapping behind a reaction barrier. Photoinduced charge transfer dynamics between transition metal complexes and semiconductor nanostructures are of central importance for many emerging energy and climate relevant technologies. Numerous demonstrations of photovoltaic and photocatalytic activity have been performed based on the combination of strong light absorption in dye molecules with charge separation and transport in adjacent semiconductor nanostructures. However, a fundamental understanding of the enabling and limiting dynamics on critical atomic length- and time scales is often still lacking. Femtosecond time-resolved X-ray photoelectron spectroscopy is employed to gain a better understanding of a short-lived intermediate that may be linked to the unexpectedly limited performance of ZnO based dye-sensitized solar cells by delaying the generation of free charge carriers. The transient spectra strongly suggest that photoexcited dye molecules attached to ZnO nanocrystals inject their charges into the substrate within less than 1 ps but the electrons are then temporarily trapped at the surface of the semiconductor in direct vicinity of the injecting molecules. The experiments are extended to monitor the electronic response of the semiconductor substrate to the collective injection from a monolayer of dye molecules and the subsequent electron-ion recombination dynamics. The results indicate some qualitative similarities but quantitative differences between the recombination dynamics at molecule-semiconductor interfaces and previously studied bulk-surface electron-hole recombination dynamics in photoexcited semiconductors.
More than one century ago, sturgeons were prevalent species in the fish communities of all major German rivers both in the North and the Baltic seas drainages. Since then, the populations declined rapidly due to river damming, overfishing and pollution. The last sturgeon catches in the Baltic drainage system occurred during the late 1960ies. Only a few individual captures have been reported during the last 30 years with the most recent records in the Lake Ladoga ( Russia), where the last confirmed catch was recorded in 1984, and a single individual caught off Estonia in 1996. Today, sturgeons are considered missing or extinct in German waters. First attempts for remediation of the species were undertaken in the mid 1990ies. Subsequently, phylogenetic and population genetic analyses of the species were carried out using mtDNA, microsatellites, and nuclear markers ( SNPs). These genetic analyses using recent and historic material have proven the existence of two different species in the Baltic Sea in what was previously considered to represent the European Atlantic sturgeon only. In the Baltic Sea, the American Atlantic sturgeon ( A. oxyrinchus) succeeded to colonize this brackish water system during the Middle Ages. In the North Sea, the European Atlantic sturgeon ( A. sturio) is considered to be the endemic species. These results led to the separation of the remediation activities in the North Sea and the Baltic Sea tributaries. Further studies on the mechanism that lead to the extinction of A. sturio in Germany and the subsequent succession of the A. oxyrinchus mtDNA haplotype are currently been carried out. Broodstock development using the northernmost populations of A. oxyrinchus is currently under way. As a further prerequisite to re-introduce this species into the Baltic, the evaluation of the status of critical habitats for the early life stages of the American Atlantic sturgeon in the River Odra has been performed in collaboration with the Institute for Inland Fisheries of Poland. Alternative fisheries techniques, based on the data of by-catch of exotic sturgeons in the fishery, are presently developed in close cooperation with the fishery to reduce fisheries related mortality in juvenile sturgeons upon release. Monitoring of habitat utilization and migration characteristics of juvenile fish upon experimental release will have to be carried out shortly, using acoustic telemetry, with the aim to follow the fate of the released fish and to determine the best time-size-release-window for future release programmes.
Untersuchungsgebiet ist das heutige Bundesland Brandenburg. In diesem Raum werden von alters her germanische und slawische, seit dem Mittelalter a uch niederdeutsche (= plattdeutsche) und hochdeutsche Mundarten gesprochen. Mit der Industrialisierung im 19. Jahrhundert breitete sich die Stadtsprache Berlins als Umgangssprache auch in Brandenburg aus und trat vielerorts an die Stelle der alten Mundarten (= Dialekte). Dieser Vorgang dauert bis heute an. Das Forschungsprojekt soll seinen Stand Mitte der 90er Jahre erfassen und so Material für Vergleiche mit älteren und mit zukünftigen Erhebungen liefern. Untersuchungsmethode: Erhebung sprachlicher Daten und Ermittlung von Einstellungen zur Sprache mittels eines Fragebogens, der in einer Auflage von 8.000 Stück über Schulen, Pfarrämter, Heimatpfleger, freiwillige Helfer und Studierende der Universität Potsdam im ganzen Land Brandenburg verteilt wurde. Im Februar 1996 wurden zudem in ausgewählten Regionen insgesamt 20 Tonbandaufnahmen von Sprechern unterschiedlicher Mundarten und auch des Berlinischen als aktueller Umgangssprache aufgezeichnet. Erhebungszeitraum: Pilotstudie 1994, Erhebung 1995, Nacherhebung und Sprachaufnahmen 1996