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The terrestrial biosphere impacts considerably on the global carbon cycle. In particular, ecosystems contribute to set off anthropogenic induced fossil fuel emissions and hence decelerate the rise of the atmospheric CO₂ concentration. However, the future net sink strength of an ecosystem will heavily depend on the response of the individual processes to a changing climate. Understanding the makeup of these processes and their interaction with the environment is, therefore, of major importance to develop long-term climate mitigation strategies. Mathematical models are used to predict the fate of carbon in the soil-plant-atmosphere system under changing environmental conditions. However, the underlying processes giving rise to the net carbon balance of an ecosystem are complex and not entirely understood at the canopy level. Therefore, carbon exchange models are characterised by considerable uncertainty rendering the model-based prediction into the future prone to error. Observations of the carbon exchange at the canopy scale can help learning about the dominant processes and hence contribute to reduce the uncertainty associated with model-based predictions. For this reason, a global network of measurement sites has been established that provides long-term observations of the CO₂ exchange between a canopy and the atmosphere along with micrometeorological conditions. These time series, however, suffer from observation uncertainty that, if not characterised, limits their use in ecosystem studies. The general objective of this work is to develop a modelling methodology that synthesises physical process understanding with the information content in canopy scale data as an attempt to overcome the limitations in both carbon exchange models and observations. Similar hybrid modelling approaches have been successfully applied for signal extraction out of noisy time series in environmental engineering. Here, simple process descriptions are used to identify relationships between the carbon exchange and environmental drivers from noisy data. The functional form of these relationships are not prescribed a priori but rather determined directly from the data, ensuring the model complexity to be commensurate with the observations. Therefore, this data-led analysis results in the identification of the processes dominating carbon exchange at the ecosystem scale as reflected in the data. The description of these processes may then lead to robust carbon exchange models that contribute to a faithful prediction of the ecosystem carbon balance. This work presents a number of studies that make use of the developed data-led modelling approach for the analysis and interpretation of net canopy CO₂ flux observations. Given the limited knowledge about the underlying real system, the evaluation of the derived models with synthetic canopy exchange data is introduced as a standard procedure prior to any real data employment. The derived data-led models prove successful in several different applications. First, the data-based nature of the presented methods makes them particularly useful for replacing missing data in the observed time series. The resulting interpolated CO₂ flux observation series can then be analysed with dynamic modelling techniques, or integrated to coarser temporal resolution series for further use e.g., in model evaluation exercises. However, the noise component in these observations interferes with deterministic flux integration in particular when long time periods are considered. Therefore, a method to characterise the uncertainties in the flux observations that uses a semi-parametric stochastic model is introduced in a second study. As a result, an (uncertain) estimate of the annual net carbon exchange of the observed ecosystem can be inferred directly from a statistically consistent integration of the noisy data. For the forest measurement sites analysed, the relative uncertainty for the annual sum did not exceed 11 percent highlighting the value of the data. Based on the same models, a disaggregation of the net CO₂ flux into carbon assimilation and respiration is presented in a third study that allows for the estimation of annual ecosystem carbon uptake and release. These two components can then be further analysed for their separate response to environmental conditions. Finally, a fourth study demonstrates how the results from data-led analyses can be turned into a simple parametric model that is able to predict the carbon exchange of forest ecosystems. Given the global network of measurements available the derived model can now be tested for generality and transferability to other biomes. In summary, this work particularly highlights the potential of the presented data-led methodologies to identify and describe dominant carbon exchange processes at the canopy level contributing to a better understanding of ecosystem functioning.
Polyelectrolyte microcapsules containing stimuli-responsive polymers have potential applications in the fields of sensors or actuators, stimulable microcontainers and controlled drug delivery. Such capsules were prepared, with the focus on pH-sensitivity and carbohydrate-sensing. First, pH-responsive polyelectrolyte capsules were produced by means of electrostatic layer-by-layer assembly of oppositely charged weak polyelectrolytes onto colloidal templates that were subsequently removed. The capsules were composed of poly(allylamine hydrochloride) (PAH) and poly(methacrylic acid) (PMA) or poly(4-vinylpyridine) (P4VP) and PMA and varied considerably in their hydrophobicity and the influence of secondary interactions. These polymers were assembled onto CaCO3 and SiO2 particles with diameters of ~ 5 µm, and a new method for the removal of the silica template under mild conditions was proposed. The pH-dependent stability of PAH/PMA and P4VP/PMA capsules was studied by confocal laser scanning microscopy (CLSM). They were stable over a wide pH-range and exhibited a pronounced swelling at the edges of stability, which was attributed to uncompensated positive or negative charges within the multilayers. The swollen state could be stabilized when the electrostatic repulsion was counteracted by hydrogen-bonding, hydrophobic interactions or polymeric entanglement. This stabilization made it possible to reversibly swell and shrink the capsules by tuning the pH of the solution. The pH-dependent ionization degree of PMA was used to modulate the binding of calcium ions. In addition to the pH-sensitivity, the stability and the swelling degree of these capsules at a given pH could be modified, when the ionic strength of the medium was altered. The reversible swelling was accompanied by reversible permeability changes for low and high molecular weight substances. The permeability for glucose was evaluated by studying the time-dependence of the buckling of the capsule walls in glucose solutions and the reversible permeability modulation was used for the encapsulation of polymeric material. A theoretical model was proposed to explain the pH-dependent size variations that took into account an osmotic expanding force and an elastic restoring force to evaluate the pH-dependent size changes of weak polyelectrolyte capsules. Second, sugar-sensitive multilayers were assembled using the reversible covalent ester formation between the polysaccharide mannan and phenylboronic acid moieties that were grafted onto poly(acrylic acid) (PAA). The resulting multilayer films were sensitive to several carbohydrates, showing the highest sensitivity to fructose. The response to carbohydrates resulted from the competitive binding of small molecular weight sugars and mannan to the boronic acid groups within the film, and was observed as a fast dissolution of the multilayers, when they were brought into contact with the sugar-containing solution above a critical concentration. It was also possible to prepare carbohydrate-sensitive multilayer capsules, and their sugar-dependent stability was investigated by following the release of encapsulated rhodamine-labeled bovine serum albumin (TRITC-BSA).
When top sports performers fail or “choke” under pressure, everyone asks: why? Research has identified a number of conditions (e.g. an audience) that elicit choking and that moderate (e.g. trait-anxiety) pressure – performance relation. Furthermore, mediating processes have been investigated. For example, explicit monitoring theories link performance failure under psychological stress to an increase in attention paid to a skill and its step-by-step execution (Beilock & Carr, 2001). Many studies have provided support for these ideas. However, so far only overt performance measures have been investigated which do not allow more thorough analyses of processes or performance strategies. But also a theoretical framework has been missing, that could (a) explain the effects of explicit monitoring on skill execution and that (b) makes predictions as to what is being monitored during execution. Consequently in this study, the nodalpoint hypothesis of motor control (Hossner & Ehrlenspiel, 2006) was taken to predict movement changes on three levels of analysis at certain “nodalpoints” within the movement sequence. Performance in two different laboratory tasks was assessed with respect to overt performance (the observable result, for example accuracy in the target), covert performance (description of movement execution, for example the acceleration of body segements) and task exploitation (the utilization of task properties such as covariation). A fake competition (see Beilock & Carr, 2002) was used to invoke pressure. In study 1 a ball bouncing task in a virtual-reality set-up was chosen. Previous studies (de Rugy, Wei, Müller, & Sternad, 2003) have shown that learners are usually able to “passively” exploit the dynamical stability of the system. According to explicit monitoring theories, choking should be expected either if the task itself evokes an “active control” (Experiment 1) or if learners are provided with explicit instructions (Experiment 2). In both experiments, participants first went through a practice phase on day 1. On day 2, following the Baseline Test participants were divided into a High-Stress or No-Stress Group for the final Performance Test. The High-Stress Group entered a fake competition. Overt performance was measured by the Absolute Error (AE) of ball amplitudes from target height; covert performance was measured by Period Modulation between successive hits and task exploitation was measured by Acceleration (AC) at ball-racket impact and Covariation (COV) of impact parameters. To evoke active control in Exp. 1 (N=20), perturbations to the ball flight were introduced. In Exp. 2 (N=39) half of the participants received explicit skill-focused instructions during learning. For overt performance, results generally show an interaction between Stress Group and Test, with better performance (i. e. lower AE) for the High-Stress group in the final Performance Test. This effect is also independent of the Instructions that participants had received during learning (Exp. 2). Similar effects were found for COV but not for AC. In study 2 a visuomotor tracking task in which participants had to pursuit a target cross that was moving on an invisible curve. This curve consisted of 3 segments of 6 turning points sequentially ordered around the x-axis. Participants learned two short movement sequences which were then concatenated to form a single sequence. It was expected that under pressure, this sequence should “fall apart” at the point of concatenation. Overt Performance was assessed by the Root Mean Square Error between target and pursuit cross as well as the Absolute Error at the turning points, covert performance was measured by the Latency from target to pursuit turning and task exploitation was measured by the temporal covariation between successive intervals between turning points. Experiment 3 (intraindividual variation) as well as Experiment 4 (interindividual variation) show performance enhancement in the pressure situation on the overt level with matching results on covert and task exploitation level. Thus, contrary to previous studies, no choking under pressure was found in any of the experiments. This may be interpreted as a failure in the experimental manipulation. But certainly also important characteristics of the task are highlighted. Choking should occur in tasks where performers do not have the time to use action or thought control strategies, that are more relevant to their “self” and that are discrete in nature.
Our work goes in two directions. At first we want to transfer definitions, concepts and results of the theory of hyperidentities and solid varieties from the total to the partial case. (1) We prove that the operators chi^A_RNF and chi^E_RNF are only monotone and additive and we show that the sets of all fixed points of these operators are characterized only by three instead of four equivalent conditions for the case of closure operators. (2) We prove that V is n − SF-solid iff clone^SF V is free with respect to itself, freely generated by the independent set {[fi(x_1, . . . , x_n)]Id^SF_n V | i \in I}. (3) We prove that if V is n-fluid and ~V |P(V ) =~V −iso |P(V ) then V is kunsolid for k >= n (where P(V ) is the set of all V -proper hypersubstitutions of type \tau ). (4) We prove that a strong M-hyperquasi-equational theory is characterized by four equivalent conditions. The second direction of our work is to follow ideas which are typical for the partial case. (1) We characterize all minimal partial clones which are strongly solidifyable. (2)We define the operator Chi^A_Ph where Ph is a monoid of regular partial hypersubstitutions.Using this concept, we define the concept of a Phyp_R(\tau )-solid strong regular variety of partial algebras and we prove that a PHyp_R(\tau )-solid strong regular variety satisfies four equivalent conditions.
The formation of colloids by the controlled reduction, nucleation, and growth of inorganic precursor salts in different media has been investigated for more than a century. Recently, the preparation of ultrafine particles has received much attention since they can offer highly promising and novel options for a wide range of technical applications (nanotechnology, electrooptical devices, pharmaceutics, etc). The interest derives from the well-known fact that properties of advanced materials are critically dependent on the microstructure of the sample. Control of size, size distribution and morphology of the individual grains or crystallites is of the utmost importance in order to obtain the material characteristics desired. Several methods can be employed for the synthesis of nanoparticles. On the one hand, the reduction can occur in diluted aqueous or alcoholic solutions. On the other hand, the reduction process can be realized in a template phase, e.g. in well-defined microemulsion droplets. However, the stability of the nanoparticles formed mainly depends on their surface charge and it can be influenced with some added protective components. Quite different types of polymers, including polyelectrolytes and amphiphilic block copolymers, can for instance be used as protecting agents. The reduction and stabilization of metal colloids in aqueous solution by adding self-synthesized hydrophobically modified polyelectrolytes were studied in much more details. The polymers used are hydrophobically modified derivatives of poly(sodium acrylate) and of maleamic acid copolymers as well as the commercially available branched poly(ethyleneimine). The first notable result is that the polyelectrolytes used can act alone as both reducing and stabilizing agent for the preparation of gold nanoparticles. The investigation was then focused on the influence of the hydrophobic substitution of the polymer backbone on the reduction and stabilization processes. First of all, the polymers were added at room temperature and the reduction process was investigated over a longer time period (up to 8 days). In comparison, the reduction process was realized faster at higher temperature, i.e. 100°C. In both cases metal nanoparticles of colloidal dimensions can be produced. However, the size and shape of the individual nanoparticles mainly depends on the polymer added and the temperature procedure used. In a second part, the influence of the prior mentioned polyelectrolytes was investigated on the phase behaviour as well as on the properties of the inverse micellar region (L2 phase) of quaternary systems consisting of a surfactant, toluene-pentanol (1:1) and water. The majority of the present work has been made with the anionic surfactant sodium dodecylsulfate (SDS) and the cationic surfactant cetyltrimethylammonium bromide (CTAB) since they can interact with the oppositely charged polyelectrolytes and the microemulsions formed using these surfactants present a large water-in-oil region. Subsequently, the polymer-modified microemulsions were used as new templates for the synthesis of inorganic particles, ranging from metals to complex crystallites, of very small size. The water droplets can indeed act as nanoreactors for the nucleation and growth of the particles, and the added polymer can influence the droplet size, the droplet-droplet interactions, as well as the stability of the surfactant film by the formation of polymer-surfactant complexes. One further advantage of the polymer-modified microemulsions is the possibility to stabilize the primary formed nanoparticles via a polymer adsorption (steric and/or electrostatic stabilization). Thus, the polyelectrolyte-modified nanoparticles formed can be redispersed without flocculation after solvent evaporation.
The limited capacity of working memory forces people to update its contents continuously. Two aspects of the updating process were investigated in the present experimental series. The first series concerned the question if it is possible to update several representations in parallel. Similar results were obtained for the updating of object features as well as for the updating of whole objects, participants were able to update representations in parallel. The second experimental series addressed the question if working memory representations which were replaced in an updating disappear directly or interfere with the new representations. Evidence for the existence of old representations was found under working memory conditions and under conditions exceeding working memory capacity. These results contradict the hypothesis that working memory contents are protected from proactive interference of long-term memory contents.
Semiclassical asymptotics for the scattering amplitude in the presence of focal points at infinity
(2006)
We consider scattering in $\R^n$, $n\ge 2$, described by the Schr\"odinger operator $P(h)=-h^2\Delta+V$, where $V$ is a short-range potential. With the aid of Maslov theory, we give a geometrical formula for the semiclassical asymptotics as $h\to 0$ of the scattering amplitude $f(\omega_-,\omega_+;\lambda,h)$ $\omega_+\neq\omega_-$) which remains valid in the presence of focal points at infinity (caustics). Crucial for this analysis are precise estimates on the asymptotics of the classical phase trajectories and the relationship between caustics in euclidean phase space and caustics at infinity.
Soils contain a large amount of carbon (C) that is a critical regulator of the global C budget. Already small changes in the processes governing soil C cycling have the potential to release considerable amounts of CO2, a greenhouse gas (GHG), adding additional radiative forcing to the atmosphere and hence to changing climate. Increased temperatures will probably create a feedback, causing soils to release more GHGs. Furthermore changes in soil C balance impact soil fertility and soil quality, potentially degrading soils and reducing soils function as important resource. Consequently the assessment of soil C dynamics under present, recent past and future environmental conditions is not only of scientific interest and requires an integrated consideration of main factors and processes governing soil C dynamics. To perform this assessment an eco-hydrological modelling tool was used and extended by a process-based description of coupled soil carbon and nitrogen turnover. The extended model aims at delivering sound information on soil C storage changes beside changes in water quality, quantity and vegetation growth under global change impacts in meso- to macro-scale river basins, exemplary demonstrated for a Central European river basin (the Elbe). As a result this study: ▪ Provides information on joint effects of land-use (land cover and land management) and climate changes on croplands soil C balance in the Elbe river basin (Central Europe) presently and in the future. ▪ Evaluates which processes, and at what level of process detail, have to be considered to perform an integrated simulation of soil C dynamics at the meso- to macro-scale and demonstrates the model’s capability to simulate these processes compared to observations. ▪ Proposes a process description relating soil C pools and turnover properties to readily measurable quantities. This reduces the number of model parameters, enhances the comparability of model results to observations, and delivers same performance simulating long-term soil C dynamics as other models. ▪ Presents an extensive assessment of the parameter and input data uncertainty and their importance both temporally and spatially on modelling soil C dynamics. For the basin scale assessments it is estimated that croplands in the Elbe basin currently act as a net source of carbon (net annual C flux of 11 g C m-2 yr-1, 1.57 106 tons CO2 yr-1 entire croplands on average). Although this highly depends on the amount of harvest by-products remaining on the field. Future anticipated climate change and observed climate change in the basin already accelerates soil C loss and increases source strengths (additional 3.2 g C m-2 yr-1, 0.48 106 tons CO2 yr-1 entire croplands). But anticipated changes of agro-economic conditions, translating to altered crop share distributions, display stronger effects on soil C storage than climate change. Depending on future use of land expected to fall out of agricultural use in the future (~ 30 % of croplands area as “surplus” land), the basin either considerably looses soil C and the net annual C flux to the atmosphere increases (surplus used as black fallow) or the basin converts to a net sink of C (sequestering 0.44 106 tons CO2 yr-1 under extensified use as ley-arable) or reacts with decrease in source strength when using bioenergy crops. Bioenergy crops additionally offer a considerable potential for fossil fuel substitution (~37 PJ, 1015 J per year), whereas the basin wide use of harvest by-products for energy generation has to be seen critically although offering an annual energy potential of approximately 125 PJ. Harvest by-products play a central role in soil C reproduction and a percentage between 50 and 80 % should remain on the fields in order to maintain soil quality and fertility. The established modelling tool allows quantifying climate, land use and major land management impacts on soil C balance. New is that the SOM turnover description is embedded in an eco-hydrological river basin model, allowing an integrated consideration of water quantity, water quality, vegetation growth, agricultural productivity and soil carbon changes under different environmental conditions. The methodology and assessment presented here demonstrates the potential for integrated assessment of soil C dynamics alongside with other ecosystem services under global change impacts and provides information on the potentials of soils for climate change mitigation (soil C sequestration) and on their soil fertility status.
The primary objective of this work was to develop a laser source for fundamental investigations in the field of laser – materials interactions. In particular it is supposed to facilitate the study of the influence of the temporal energy distribution such as the interaction between adjacent pulses on ablation processes. Therefore, the aim was to design a laser with a highly flexible and easily controllable temporal energy distribution. The laser to meet these demands is an SBS-laser with optional active mode-locking. The nonlinear reflectivity of the SBS-mirror leads to a passive Q-switching and issues ns-pulse bursts with µs spacing. The pulse train parameters such as pulse duration, pulse spacing, pulse energy and number of pulses within a burst can be individually adjusted by tuning the pump parameters and the starting conditions for the laser. Another feature of the SBS-reflection is phase conjugation, which leads to an excellent beam quality thanks to the compensation of phase distortions. Transverse fundamental mode operation and a beam quality better than 1.4 times diffraction limited can be maintained for average output powers of up to 10 W. In addition to the dynamics on a ns-timescale described above, a defined splitting up of each ns-pulse into a train of ps-pulses can be achieved by additional active mode-locking. This twofold temporal focussing of the intensity leads to single pulse energies of up to 2 mJ at pulse durations of approximately 400 ps which corresponds to a pulse peak power of 5 MW. While the pulse duration is of the same order of magnitude as those of other passively Q-switched lasers with simultaneous mode-locking, the pulse energy and pulse peak power exceeds the values of these systems found in the literature by an order of magnitude. To the best of my knowledge the laser presented here is the first implementation of a self-starting mode-locked SBS-laser oscillator. In order to gain a better understanding and control of the transient output of the laser two complementary numerical models were developed. The first is based on laser rate equations which are solved for each laser mode individually while the mode-locking dynamics are calculated from the resultant transient spectrum. The rate equations consider the mean photon densities in the resonator, therefore the propagation of the light inside the resonator is not properly displayed. The second model, in contrast, introduces a spatial resolution of the resonator and hence the propagation inside the resonator can more accurately be considered. Consequently, a mismatch between the loss modulation frequency and the resonator round trip time can be conceived. The model calculates all dynamics in the time domain and therefore the spectral influences such as the Stokes-shift have to be neglected. Both models achieve an excellent reproduction of the ns-dynamics that are generated by the SBS-Q-switch. Separately, each model fails to reproduce all aspects of the ps-dynamics of the SBS-laser in detail. This can be attributed to the complexity of the numerous physical processes involved in this system. But thanks to their complementary nature they provide a very useful tool for investigating the various influences on the dynamics of the mode-locked SBS-laser individually. These aspects can eventually be recomposed to give a complete picture of the mechanisms which govern the output dynamics. Among the aspects under scrutiny were in particular the start resonator quality which determines the starting condition for the SBS-Q-switch, the modulation depth of the AOM and the phonon lifetime as well as the Brillouin-frequency of the SBS-medium. The numerical simulations and the experiments have opened several doors inviting further investigations and promising a potential for further improvement of the experimental results: The results of the simulations in combination with the experimental results which determined the starting conditions for the simulations leave no doubt that the bandwidth generation can primarily be attributed to the SBS-Stokes-shift during the buildup of the Q-switch pulse. For each resonator round trip, bandwidth is generated by shifting a part of the revolving light in frequency. The magnitude of the frequency shift corresponds to the Brillouin-frequency which is a constant of the SBS material and amounts in the case of SF6 to 240 MHz. The modulation of the AOM merely provides an exchange of population between spectrally adjacent modes and therefore diminishes a modulation in the spectrum. By use of a material with a Brillouin-frequency in the GHz range the bandwidth generation can be considerably accelerated thereby shortening the pulse duration. Also, it was demonstrated that yet another nonlinear effect of the SBS can be exploited: If the phonon lifetime is short compared to the resonator round trip time we obtain a modulation in the SBS-reflectivity that supports the modulation of the AOM. The application of an external optical feedback by a conventional mirror turns out to be an alternative to the AOM in synchronizing the longitudinal resonator modes. The interesting feature about this system is that it is ― although highly complex in the physical processes and the temporal output dynamics ― very simple and inexpensive from a technical point of view. No expensive modulators and no control electronics are necessary. Finally, the numerical models constitute a powerful tool for the investigation of emission dynamics of complex laser systems on arbitrary timescales and can also display the spectral evolution of the laser output. In particular it could be demonstrated that differences in the results of the complementary models vanish for systems of lesser complexity.
The aim of this study was to provide deeper insights in passerine phylogenetic relationships using new molecular markers. The monophyly of the largest avian order Passeriformes (~59% of all living birds) and the division into its suborders suboscines and oscines are well established. Phylogenetic relationships within the group have been extremely puzzling, as most of the evolutionary lineages originated through rapid radiation. Numerous studies have hypothesised conflicting passerine phylogenies and have repeatedly stimulated further research with new markers. In the present study, I used three different approaches to contribute to the ongoing phylogenetic debate in Passeriformes. I investigated the recently introduced gene ZENK for its phylogenetic utility for passerine systematics in combination and comparison to three already established nuclear markers. My phylogenetic analyses of a comprehensive data set yielded highly resolved, consistent and strongly supported trees. I was able to show the high utility of ZENK for elucidating phylogenetic relationships within Passeriformes. For the second and third approach, I used chicken repeat 1 (CR1) retrotransposons as phylogenetic markers. I presented two specific CR1 insertions as apomorphic characters, whose presence/absence pattern significantly contributed to the resolution of a particular phylogenetic uncertainty, namely the position of the rockfowl species Picathartes spp. in the passerine tree. Based on my results, I suggest a closer relationship of these birds to crows, ravens, jays, and allies. For the third approach, I showed that CR1 sequences contain phylogenetic signal and investigated their applicability in more detail. In this context, I screened for CR1 elements in different passerine birds, used sequences of several loci to construct phylogenetic trees, and evaluated their reliability. I was able to corroborate existing hypotheses and provide strong evidence for some new hypotheses, e.g. I suggest a revision of the taxa Corvidae and Corvinae as vireos are closer related to crows, ravens, and allies. The subdivision of the Passerida into three superfamilies, Sylvioidea, Passeroidea, and Muscicapoidea was strongly supported. I found evidence for a split within Sylvioidea into two clades, one consisting of tits and the other comprising warblers, bulbuls, laughingthrushes, whitethroats, and allies. Whereas Passeridae appear to be paraphyletic, monophyly of weavers and estrild finches as a separate clade was strongly supported. The sister taxon relationships of dippers and the thrushes/flycatcher/chat assemblage was corroborated and I suggest a closer relationship of waxwings and kinglets to wrens, tree-creepers, and nuthatches.