Finite-element discretization of 3D energy-transport equations for semiconductors

In this thesis a mathematical model was derived that describes the charge and energy transport in semiconductor devices like transistors. Moreover, numerical simulations of these physical processes are performed. In order to accomplish this, methods of theoretical physics, functional analysis, numerical mathematics and computer programming are applied. After an introduction to the status quo of semiconductor device simulation methods and a brief review of historical facts up to now, the attention is shifted to the construction of a model, which serves as the basis of the subsequent derivations in the thesis. Thereby the starting point is an important equation of the theory of dilute gases. From this equation the model equations are derived and specified by means of a series expansion method. This is done in a multi-stage derivation process, which is mainly taken from a scientific paper and which does not constitute the focus of this thesis. In the following phase we specify the mathematical setting and make precise the model assumptions. Thereby we make use of methods of functional analysis. Since the equations we deal with are coupled, we are concerned with a nonstandard problem. In contrary, the theory of scalar elliptic equations is established meanwhile. Subsequently, we are preoccupied with the numerical discretization of the equations. A special finite-element method is used for the discretization. This special approach has to be done in order to make the numerical results appropriate for practical application. By a series of transformations from the discrete model we derive a system of algebraic equations that are eligible for numerical evaluation. Using self-made computer programs we solve the equations to get approximate solutions. These programs are based on new and specialized iteration procedures that are developed and thoroughly tested within the frame of this research work. Due to their importance and their novel status, they are explained and demonstrated in detail. We compare these new iterations with a standard method that is complemented by a feature to fit in the current context. A further innovation is the computation of solutions in three-dimensional domains, which are still rare. Special attention is paid to applicability of the 3D simulation tools. The programs are designed to have justifiable working complexity. The simulation results of some models of contemporary semiconductor devices are shown and detailed comments on the results are given. Eventually, we make a prospect on future development and enhancements of the models and of the algorithms that we used.

Foliation boudinage

In this thesis foliation boudinage and related structures have been studied based on field observations and numerical modeling. Foliation boudinage occurs in foliated rocks independent of lithology contrast. The developing structures are called ‘Foliation boudinage structures (FBSs)’ and show evidence for both ductile and brittle deformation. They are recognized in rocks by perturbations in monotonous foliation adjacent to a central discontinuity, mostly filled with vein material. Foliation boudinage structures have been studied in the Çine Massif in SW-Turkey and the Furka Pass-Urseren Zone in central Switzerland. Four common types have been distinguished in the field, named after vein geometries in their boudin necks in sections normal to the boudin axis: lozenge-, crescent-, X- and double crescent- type FBSs. Lozengetype FBSs are symmetric and characterized by lozenge-shaped veins in their boudin neck with two cusps facing opposite sides. A symmetrical pair of flanking folds occurs on the two sides of the vein. Crescent-type FBSs are asymmetric with a single smoothly curved vein in the boudin neck, with vein contacts facing to one side. X- and double crescent- type FBSs are asymmetric. The geometry of the neck veins resembles that of cuspate-lobate structures. The geometry of flanking structures is related to the shape of the veins. The veins are mostly filled with massive quartz in large single crystals, commonly associated with tourmaline, feldspar and biotite and in some cases with chlorite. The dominance of large facetted single quartz crystals and spherulitic chlorite in the veins suggest that the minerals grew into open fluidfilled space. FLAC experiments show that fracture propagation during ductile deformation strongly influences the geometry of developing veins. The cusps of the veins are better developed in the case of propagating fractures. The shape of the boudin neck veins in foliation boudinage depends on the initial orientation and shape of the fracture, the propagation behaviour of the fracture, the geometry of bulk flow, and the stage at which mineral filling takes place. A two dimensional discrete element model was used to study the progressive development of foliation boudinage structures and the behavior of visco-elastic material deformed under pure shear conditions. Discrete elements are defined by particles that are connected by visco-elastic springs. Springs can break. A number of simulations was Abstract vii performed to investigate the effect of material properties (Young’s modulus, viscosity and breaking strength) and anisotropy on the developing structures. The models show the development of boudinage in single layers, multilayers and in anisotropic materials with random mica distribution. During progressive deformation different types of fractures develop from mode I, mode II to the combination of both. Voids develop along extension fractures, at intersections of conjugate shear fractures and in small pull-apart structures along shear fractures. These patterns look similar to the natural examples. Fractures are more localized in the models where the elastic constants are low and the competence contrast is high between the layers. They propagate through layers where the constants are high and the competence contrast is relatively low. Flow localize around these fractures and voids. The patterns similar to symmetric boudinage structures and extensional neck veins (e.g. lozenge type) more commonly develop in the models with lower elastic constants and anisotropy. The patterns similar to asymmetric foliation boudinage structures (e.g. X-type) develop associated with shear fractures in the models where elastic constants and anisotropy of the materials are relatively high. In these models boudin neck veins form commonly at pull-aparts along the shear fractures and at the intersection of fractures.

Umgang mit Verschiedenheit als Aspekt von Schulkultur: Haltung zu und Interaktion mit verhaltensauffälligen Schülern an Freinet-Schulen

Zusammenfassung Die Integration verhaltensauffälliger Schülerinnen und Schüler stellt besondere Herausforderungen an die Kompetenz von Lehrerinnen und Lehrern. Zum einen wirkt sich die spezielle Problematik dieser Schülergruppe auf die Beziehungsgestaltung mit Peers und Lehrpersonen aus, zum anderen werden auch spezifische methodische Änderungen im Unterrichts- und Lerngeschehen notwendig, um den Anforderungen, die auffällige Schüler an die Unterrichtsgestaltung stellen, gerecht zu werden. Dabei ist die Gruppe der auffälligen Schülerinnen und Schüler selbst sehr heterogen. Vor dem Hintergrund einer systemisch-konstruktivistischen Sichtweise von Auffälligkeit nähert sich diese Arbeit der Themenstellung der Integration verhaltensauffälliger Schülerinnen und Schüler und legt dar, dass hier vor allem das Passungsverhältnis zwischen (auffälligem) Individuum und sämtlichen Systemen seiner Umwelt in eine Schieflage geraten ist. Auf dieser Basis wurde nach erfolgreichen Modellen der Integration verhaltensauffälliger Schülerinnen und Schüler gesucht, wobei dem immer wiederkehrenden Verweis auf den hilfreichen Beitrag der Freinet-Pädagogik hierbei mit einer eigenen empirischen Studie nachgegangen wurde. An zwei Freinet-Schulen in Deutschland wurde mit Hilfe von teilnehmender Beobachtung, Interviews und Gruppendiskussion die Lehrersichtweise fördernder und hemmender Bedingungen des Integrationsgeschehens erhoben und analysiert. Dabei trat vor allem eine spezifische Haltung der Freinet-Lehrerinnen und Lehrer gegenüber den in der Literatur immer wieder als besonders schwierig dargestellten auffälligen Schülerinnen und Schülern zutage. Diese Einstellung besteht vor allem in der kompetenzorientierten Sicht der auffälligen Schülerinnen und Schüler, die ihre Stärken unterstützt. Auf dieser Basis wird durch viele pädagogische, beraterische und therapeutische Angebote bei den Prozessen, die noch nicht gelingen, angesetzt. Diese Haltung, die sich auch in entsprechenden Rahmenbedingungen ausdrückt (z.B. in Gremien, die die Partizipation der Kinder gewährleisten, oder in auf das Individuum abgestimmten Arbeitstechniken), wurde zusammen mit den Rahmenbedingungen als „Kernkategorie“ Schulkultur im Sinne der Grounded Theory gefasst. Indem die Lehrerinnen und Lehrer an beiden Schulen zuerst die besonderen Begabungen aller ihrer Schülerinnen und Schüler sahen und die auffälligen nicht als spezielle Gruppe heraushoben (die zudem nicht als immer störend oder „schwierig“ klassifiziert wurden), trugen sie nicht nur entscheidend zur gelingenden Integration dieser konkreten Schülerinnen und Schüler bei, sondern stellen auch ein Beispiel für die Erweiterung der pädagogischen Professionalität von Lehrern dar. Die anfängliche enge Fragestellung auf das Integrationsgeschehen von auffälligen Schülerinnen und Schülern konnte durch den Bezug zur Schulkultur und zum schulkulturellen Passungsverhältnis der Schüler erweitert werden. Die vorliegende Arbeit gibt so nicht nur Aufschluss über die Integrationspraxis an Freinet-Schulen, sondern auch über die verschiedenen Dimensionen ihrer jeweiligen Schulkultur.

Large-scale coupled-cluster calculations

Coupled-cluster theory provides one of the most successful concepts in electronic-structure theory. This work covers the parallelization of coupled-cluster energies, gradients, and second derivatives and its application to selected large-scale chemical problems, beside the more practical aspects such as the publication and support of the quantum-chemistry package ACES II MAB and the design and development of a computational environment optimized for coupled-cluster calculations. The main objective of this thesis was to extend the range of applicability of coupled-cluster models to larger molecular systems and their properties and therefore to bring large-scale coupled-cluster calculations into day-to-day routine of computational chemistry. A straightforward strategy for the parallelization of CCSD and CCSD(T) energies, gradients, and second derivatives has been outlined and implemented for closed-shell and open-shell references. Starting from the highly efficient serial implementation of the ACES II MAB computer code an adaptation for affordable workstation clusters has been obtained by parallelizing the most time-consuming steps of the algorithms. Benchmark calculations for systems with up to 1300 basis functions and the presented applications show that the resulting algorithm for energies, gradients and second derivatives at the CCSD and CCSD(T) level of theory exhibits good scaling with the number of processors and substantially extends the range of applicability. Within the framework of the ’High accuracy Extrapolated Ab initio Thermochemistry’ (HEAT) protocols effects of increased basis-set size and higher excitations in the coupled- cluster expansion were investigated. The HEAT scheme was generalized for molecules containing second-row atoms in the case of vinyl chloride. This allowed the different experimental reported values to be discriminated. In the case of the benzene molecule it was shown that even for molecules of this size chemical accuracy can be achieved. Near-quantitative agreement with experiment (about 2 ppm deviation) for the prediction of fluorine-19 nuclear magnetic shielding constants can be achieved by employing the CCSD(T) model together with large basis sets at accurate equilibrium geometries if vibrational averaging and temperature corrections via second-order vibrational perturbation theory are considered. Applying a very similar level of theory for the calculation of the carbon-13 NMR chemical shifts of benzene resulted in quantitative agreement with experimental gas-phase data. The NMR chemical shift study for the bridgehead 1-adamantyl cation at the CCSD(T) level resolved earlier discrepancies of lower-level theoretical treatment. The equilibrium structure of diacetylene has been determined based on the combination of experimental rotational constants of thirteen isotopic species and zero-point vibrational corrections calculated at various quantum-chemical levels. These empirical equilibrium structures agree to within 0.1 pm irrespective of the theoretical level employed. High-level quantum-chemical calculations on the hyperfine structure parameters of the cyanopolyynes were found to be in excellent agreement with experiment. Finally, the theoretically most accurate determination of the molecular equilibrium structure of ferrocene to date is presented.

Soil biogenic emissions of nitric oxide from arid and semi-arid ecosystems

The biogenic production of NO in the soil accounts for between 10% and 40% of the global total. A large degree of the uncertainty in the estimation of the biogenic emissions stems from a shortage of measurements in arid regions, which comprise 40% of the earth’s land surface area. This study examined the emission of NO from three ecosystems in southern Africa which cover an aridity gradient from semi-arid savannas in South Africa to the hyper-arid Namib Desert in Namibia. A laboratory method was used to determine the release of NO as a function of the soil moisture and the soil temperature. Various methods were used to up-scale the net potential NO emissions determined in the laboratory to the vegetation patch, landscape or regional level. The importance of landscape, vegetation and climatic characteristics is emphasized. The first study occurred in a semi-arid savanna region in South Africa, where soils were sampled from 4 landscape positions in the Kruger National Park. The maximum NO emission occurred at soil moisture contents of 10%-20% water filled pore space (WFPS). The highest net potential NO emissions came from the low lying landscape positions, which have the largest nitrogen (N) stocks and the largest input of N. Net potential NO fluxes obtained in the laboratory were converted in field fluxes for the period 2003-2005, for the four landscape positions, using soil moisture and temperature data obtained in situ at the Kruger National Park Flux Tower Site. The NO emissions ranged from 1.5-8.5 kg ha-1 a-1. The field fluxes were up-scaled to a regional basis using geographic information system (GIS) based techniques, this indicated that the highest NO emissions occurred from the Midslope positions due to their large geographical extent in the research area. Total emissions ranged from 20x103 kg in 2004 to 34x103 kg in 2003 for the 56000 ha Skukuza land type. The second study occurred in an arid savanna ecosystem in the Kalahari, Botswana. In this study I collected soils from four differing vegetation patch types including: Pan, Annual Grassland, Perennial Grassland and Bush Encroached patches. The maximum net potential NO fluxes ranged from 0.27 ng m-2 s-1 in the Pan patches to 2.95 ng m-2 s-1 in the Perennial Grassland patches. The net potential NO emissions were up-scaled for the year December 2005-November 2006. This was done using 1) the net potential NO emissions determined in the laboratory, 2) the vegetation patch distribution obtained from LANDSAT NDVI measurements 3) estimated soil moisture contents obtained from ENVISAT ASAR measurements and 4) soil surface temperature measurements using MODIS 8 day land surface temperature measurements. This up-scaling procedure gave NO fluxes which ranged from 1.8 g ha-1 month-1 in the winter months (June and July) to 323 g ha-1 month-1 in the summer months (January-March). Differences occurred between the vegetation patches where the highest NO fluxes occurred in the Perennial Grassland patches and the lowest in the Pan patches. Over the course of the year the mean up-scaled NO emission for the studied region was 0.54 kg ha-1 a-1 and accounts for a loss of approximately 7.4% of the estimated N input to the region. The third study occurred in the hyper-arid Namib Desert in Namibia. Soils were sampled from three ecosystems; Dunes, Gravel Plains and the Riparian zone of the Kuiseb River. The net potential NO flux measured in the laboratory was used to estimate the NO flux for the Namib Desert for 2006 using modelled soil moisture and temperature data from the European Centre for Medium Range Weather Forecasts (ECMWF) operational model on a 36km x 35km spatial resolution. The maximum net potential NO production occurred at low soil moisture contents (<10%WFPS) and the optimal temperature was 25°C in the Dune and Riparian ecosystems and 35°C in the Gravel Plain Ecosystems. The maximum net potential NO fluxes ranged from 3.0 ng m-2 s-1 in the Riparian ecosystem to 6.2 ng m-2 s-1 in the Gravel Plains ecosystem. Up-scaling the net potential NO flux gave NO fluxes of up to 0.062 kg ha-1 a-1 in the Dune ecosystem and 0.544 kg h-1 a-1 in the Gravel Plain ecosystem. From these studies it is shown that NO is emitted ubiquitously from terrestrial ecosystems, as such the NO emission potential from deserts and scrublands should be taken into account in the global NO models. The emission of NO is influenced by various factors such as landscape, vegetation and climate. This study looks at the potential emissions from certain arid and semi-arid environments in southern Africa and other parts of the world and discusses some of the important factors controlling the emission of NO from the soil.

Messung der CP-verletzenden Asymmetrie von K + - pi + - pi 0 pi 0 mit dem NA48-Detektor

Bis heute ist die Frage nicht geklärt, warum bei der Entstehung des Universums Materie gegenüber der Antimaterie bevorzugt war und das heutige Materieuniversum entstanden ist. Eine Voraussetzung für die Entstehung dieser Materie-Antimaterie-Asymmetrie ist die Verletzung der Kombination von Ladungs- (C) und Punktsymmetrie (P), die CP-Verletzung. CP-Verletzung kann sich unter anderem in den Zerfällen K+- -> pi+- pi0 pi0 zeigen. Die NA48/2"=Kollaboration zeichnete während den Jahren 2003 und 2004 über 200~TB Daten von Zerfällen geladener Kaonen auf. In dieser Arbeit wurde die CP"=verletzende Asymmetrie der Zerfälle K+- -> pi+- pi0 pi0 mit über 90~Millionen ausgewählten Ereignissen aus diesem Datensatz gemessen. Vorhersagen im Standardmodell der Teilchenphysik sagen hier eine CP"=verletzende Asymmetrie in der Größenordnung zwischen $10^{-6}$ und $10^{-5}$ voraus. In Modellen außerhalb des Standardmodells kann es aber auch größere Asymmetrien geben. Das NA48/2"=Experiment war darauf ausgelegt, mögliche systematische Unsicherheiten zu begrenzen. Um dies zu erreichen, wurden positive und negative Kaonen simultan an einem Target erzeugt und ihr Impuls durch ein Strahlsystem mit zwei Strahlengängen auf ca. $60~GeV/c$ begrenzt. Die Strahlen wurden auf wenige Millimeter genau überlagert in die Zerfallsregion geleitet. Die Strahlengänge von positiven und negativen Kaonen sowie die Polarität des Magneten des Impulsspektrometers wurden regelmäßig gewechselt. Dies erlaubte eine Symmetrisierung von Strahlführung und Detektor für positive und negative Kaonen während der Analyse. Durch ein Vierfachverhältnis der vier Datensätze mit den unterschiedlichen Konfigurationen konnte sichergestellt werden, dass alle durch Strahlführung oder Detektor erzeugten Asymmetrien sich in erster Ordnung aufheben. Um die unterschiedlichen Produktionsspektren von positiven und negativen Kaonen auszugleichen wurde in dieser Arbeit eine Ereignisgewichtung durchgeführt. Die Analyse wurde auf mögliche systematische Unsicherheiten untersucht. Dabei zeigte sich, dass die systematischen Unsicherheiten in der Analyse deutlich kleiner als der statistischer Fehler sind. Das Ergebnis der Messung des die CP-verletzende Asymmetrie beschreibenden Parameters $A_g$ ist: begin{equation} A_g= (1,2 pm 1,7_{mathrm{(stat)}} pm 0,7_{mathrm{(sys)}}) cdot 10^{-4}. end{equation} Diese Messung ist fast zehnmal genauer als bisherige Messungen und stimmt innerhalb ihrer Unsicherheit mit dem Standardmodell überein. Modelle, die eine größere CP-Verletzung in diesem Zerfall vorhersagen, können ausgeschlossen werden.

Identification of preferentially targeted tumor-associated antigens in melanoma patients via mRNA stimulation of CD8+ blood lymphocytes

Until now, therapeutic vaccination of cancer patients has mainly relied on rather few T cell epitopes processed from structurally normal shared tumor antigens and presented by frequent HLA alleles. So far the design of these studies has not addressed the individuality of tumor-host interactions, which are not only determined by the antigenic tumor phenotype or the natural HLA polymorphism, but also by the individual T cell repertoire. The procedure described herein was developed to identify the preferential targets of the individual repertoire from a panel of known shared tumor-associated antigens. Lymphocytes were isolated from the peripheral blood of cancer patients or healthy donors and stimulated twice with autologous mRNA-transfected FastDC (Dauer et al., J Immunol. 170:4069, 2003). FastDC were generated from blood monocytes and separately transfected via lipofection with in vitro transcribed mRNAs encoding the panel antigens. Responder lymphocytes were tested on day 12 in a 20-hour IFN-g ELISPOT assay for recognition of 293T cells co-transfected pairwise with plasmids encoding the stimulation antigens and the respective individual’s HLA class I alleles. In a first step, stimulation parameters were optimized for the detection of anti-HCMV pp65 responses. A maximum amplification of pp65-specific CD8+ T cell responses was obtained at a rather low IL-2 concentration (25 IU/ml) and at a minimum APC-to-effector ratio of 1:10. Addition of IL-4, IL-7 or IL-15 did not substantially improve the stimulatory potential. The test was applied to the human melanoma models D05 and MZ2, in both of which multiple T cell-defined antigens had previously been identified by expression screening. Blood lymphocytes were stimulated in parallel with autologous tumor cells and with mRNA-transfected FastDC. In D05, T cell reactivities against three out of eleven epitopes induced by stimulation with tumor cells were also found after stimulation with mRNA-transfected FastDC. Two further T cell target epitopes were identified with mRNA but not with tumor cell stimulation. In MZ2, T cell responses against five distinct epitopes were detected on day 12 after stimulation with mRNA transfectants. The same responses were detectable after stimulation with tumor cells only on day 32. mRNA stimulations against 21 tumor-associated antigens in addition to HCMV pp65 were performed in four healthy individuals. In all cases, CD8+ T cells against HCMV pp65 could be expanded. Among tumor-associated antigens, only reactivity against Melan-A/MART-1 in association with HLA-A*0201 was detectable in one of the donors. The vaccination of patients with targets a priori known to be recognized by their T cell repertoire may help to improve the outcome of therapeutic vaccination.

Determination of the gluon polarisation from open charm production at COMPASS

One of the main goals of the COMPASS experiment at CERN is the determination of the gluon polarisation in the nucleon. It is determined from spin asymmetries in the scattering of 160 GeV/c polarised muons on a polarised LiD target. The gluon polarisation is accessed by the selection of photon-gluon fusion (PGF) events. The PGF-process can be tagged through hadrons with high transverse momenta or through charmed hadrons in the final state. The advantage of the open charm channel is that, in leading order, the PGF-process is the only process for charm production, thus no physical background contributes to the selected data sample. This thesis presents a measurement of the gluon polarisation from the COMPASS data taken in the years 2002-2004. In the analysis, charm production is tagged through a reconstructed D0-meson decaying in $D^{0}-> K^{-}pi^{+}$ (and charge conjugates). The reconstruction is done on a combinatorial basis. The background of wrong track pairs is reduced using kinematic cuts to the reconstructed D0-candidate and the information on particle identification from the Ring Imaging Cerenkov counter. In addition, the event sample is separated into D0-candidates, where a soft pion from the decay of the D*-meson to a D0-meson, is found, and the D0-candidates without this tag. Due to the small mass difference between D*-meson and D0-meson the signal purity of the D*-tagged sample is about 7 times higher than in the untagged sample. The gluon polarisation is measured from the event asymmetries for the for the different spin configurations of the COMPASS target. To improve the statistical precision of the final results, the events in the final sample are weighted. This method results in an average value of the gluon polarisation in the x-range covered by the data. For the COMPASS data from 2002-2004, the resulting value of the gluon polarisation is $=-0.47+-0.44 (stat)+-0.15(syst.)$. The result is statistically compatible with the existing measurements of $$ in the high-pT channel. Compared to these, the open charm measurement has the advantage of a considerably smaller model dependence.

The impact of ice crystals on radiative forcing and remote sensing of arctic boundary-layer mixed-phase clouds

This PhD thesis is embedded into the Arctic Study of Tropospheric Aerosol, Clouds and Radiation (ASTAR) and investigates the radiative transfer through Arctic boundary-layer mixed-phase (ABM) clouds. For this purpose airborne spectral solar radiation measurements and simulations of the solar and thermal infrared radiative transfer have been performed. This work reports on measurements with the Spectral Modular Airborne Radiation measurement sysTem (SMART-Albedometer) conducted in the framework of ASTAR in April 2007 close to Svalbard. For ASTAR the SMART-Albedometer was extended to measure spectral radiance. The development and calibration of the radiance measurements are described in this work. In combination with in situ measurements of cloud particle properties provided by the Laboratoire de M¶et¶eorologie Physique (LaMP) and simultaneous airborne lidar measurements by the Alfred Wegener Institute for Polar and Marine Research (AWI) ABM clouds were sampled. The SMART-Albedometer measurements were used to retrieve the cloud thermodynamic phase by three different approaches. A comparison of these results with the in situ and lidar measurements is presented in two case studies. Beside the dominating mixed-phase clouds pure ice clouds were found in cloud gaps and at the edge of a large cloud field. Furthermore the vertical distribution of ice crystals within ABM clouds was investigated. It was found that ice crystals at cloud top are necessary to describe the observed SMART-Albedometer measurements. The impact of ice crystals on the radiative forcing of ABM clouds is in vestigated by extensive radiative transfer simulations. The solar and net radiative forcing was found to depend on the ice crystal size, shape and the mixing ratio of ice crystals and liquid water droplets.

Rekonstruktion der eiszeitlichen Verbreitung und Artbildung vier alpiner Primeln durch Artenverbreitungsmodelle und Phylogeographie

Aim: Previous studies revealed that diversification events in the western clade of the alpine Primula sect. Auricula were concentrated in the Quaternary cold periods. This implies that allopatric speciation in isolated glacial refugia was the most common mode of speciation. In the first part of the present dissertation, this hypothesis is further investigated by locating refugial areas of two sister species, Primula marginata & P. latifolia during the last glacial maximum, 21,000 years ago. In the second part, the glacial and postglacial history of P. hirsuta and P. daonensis is investigated. Location: European Alps. Methods: Glacial refugia were located using species distribution models, which are projected to last glacial maximum climate. These refugia are validated with geographic distribution patterns of intra-specific genetic diversity, rarity and variation. Results 1) Speciation: Glacial refugia of the sister taxa Primula marginata and P. latifolia were largely separated, only a small overlapping zone at the southern margin of the former glacier in the Maritime Alps exists. This overlapping zone is too small to indicate sympatric speciation. The largely separated glacial distribution of both species rather confirms our hypothesis of allopatric speciation in isolated glacial refugia. Results 2) Glacial and postglacial history: Surprizingly, the modelled potential refugia of three out of four Primula species are situated within the former ice-shield, except for P. marginata. This indicates that peripheral and central nunataks played an important role for the glacial survival in P. latifolia, P. hirsuta and P. daonensis, while peripheral refugia outside the maximum extend of the glacier were crucial in P. marginata. In P. hirsuta and P. latifolia SDMs allowed to exclude several hypothetical refugial areas that overlap with today’s distribution as potential refugia for the species. In P. marginata, hypothetical refugial areas at the periphery of the former ice-shield that overlap with today’s distribution were confirmed by the models. The results from the SDMs are confirmed by population genetic patterns in three out of four species. P. daonensis represents an exception, where population genetic data contradict the SDMs. Main conclusions: Species distribution models provide species specific scenarios of glacial distribution and postglacial re-colonization, which can be validated using population genetic analyses. This combined approach is useful and helps to understand the complex processes that have lead to the genetic and floristic patterns of biodiversity that is found today in the Alps.

The development of stylolites, from small-scale heterogeneities to multi-scale roughness

Stylolites are rough paired surfaces, indicative of localized stress-induced dissolution under a non-hydrostatic state of stress, separated by a clay parting which is believed to be the residuum of the dissolved rock. These structures are the most frequent deformation pattern in monomineralic rocks and thus provide important information about low temperature deformation and mass transfer. The intriguing roughness of stylolites can be used to assess amount of volume loss and paleo-stress directions, and to infer the destabilizing processes during pressure solution. But there is little agreement on how stylolites form and why these localized pressure solution patterns develop their characteristic roughness.rnNatural bedding parallel and vertical stylolites were studied in this work to obtain a quantitative description of the stylolite roughness and understand the governing processes during their formation. Adapting scaling approaches based on fractal principles it is demonstrated that stylolites show two self affine scaling regimes with roughness exponents of 1.1 and 0.5 for small and large length scales separated by a crossover length at the millimeter scale. Analysis of stylolites from various depths proved that this crossover length is a function of the stress field during formation, as analytically predicted. For bedding parallel stylolites the crossover length is a function of the normal stress on the interface, but vertical stylolites show a clear in-plane anisotropy of the crossover length owing to the fact that the in-plane stresses (σ2 and σ3) are dissimilar. Therefore stylolite roughness contains a signature of the stress field during formation.rnTo address the origin of stylolite roughness a combined microstructural (SEM/EBSD) and numerical approach is employed. Microstructural investigations of natural stylolites in limestones reveal that heterogeneities initially present in the host rock (clay particles, quartz grains) are responsible for the formation of the distinctive stylolite roughness. A two-dimensional numerical model, i.e. a discrete linear elastic lattice spring model, is used to investigate the roughness evolving from an initially flat fluid filled interface induced by heterogeneities in the matrix. This model generates rough interfaces with the same scaling properties as natural stylolites. Furthermore two coinciding crossover phenomena in space and in time exist that separate length and timescales for which the roughening is either balanced by surface or elastic energies. The roughness and growth exponents are independent of the size, amount and the dissolution rate of the heterogeneities. This allows to conclude that the location of asperities is determined by a polimict multi-scale quenched noise, while the roughening process is governed by inherent processes i.e. the transition from a surface to an elastic energy dominated regime.rn

Supernova-Detektion mit dem IceCube-Neutrinoteleskop

IceCube, ein Neutrinoteleskop, welches zur Zeit am Südpol aufgebaut und voraussichtlich 2011 fertiggestellt sein wird, kann galaktische Kernkollaps-Supernovae mit hoher Signifikanz und unübertroffener statistischer Genauigkeit der Neutrinolichtkurve detektieren. Derartige Supernovae werden begleitet von einem massiven Ausbruch niederenergetischer Neutrinos aller Flavour. Beim Durchfliegen des Detektormediums Eis entstehen Positronen und Elektronen, welche wiederum lokale Tscherenkowlichtschauer produzieren, die in ihrer Summe das gesamte Eis erleuchten. Ein Nachweis ist somit, trotz der Optimierung IceCubes auf hochenergetische Teilchenspuren, über eine kollektive Rauschratenerhöhung aller optischen Module möglich. Die vorwiegende Reaktion ist der inverse Betazerfall der Antielektronneutrinos, welcher über 90,% des gesamten Signals ausmacht.rnrnDiese Arbeit beschreibt die Implementierung und Funktionsweise der Supernova-Datennahme-Software sowie der Echtzeitanalyse, mit welcher die oben genannte Nachweismethode seit August 2007 realisiert ist. Die Messdaten der ersten zwei Jahre wurden ausgewertet und belegen ein extrem stabiles Verhalten des Detektors insgesamt sowie fast aller Lichtsensoren, die eine gemittelte Ausfallquote von lediglich 0,3,% aufweisen. Eine Simulation der Detektorantwort nach zwei unterschiedlichen Supernova-Modellen ergibt eine Sichtweite IceCubes, die im besten Falle bis zur 51,kpc entfernten Großen Magellanschen Wolke reicht. Leider ist der Detektor nicht in der Lage, die Deleptonisierungsspitze aufzulösen, denn Oszillationen der Neutrinoflavour innerhalb des Sterns modifizieren die Neutrinospektren ungünstig. Jedoch können modellunabhängig anhand des frühesten Signalanstiegs die inverse Massenhierarchie sowie $sin^2 2theta_{13} > 10^{-3}$ etabliert werden, falls die Entfernung zur Supernova $leq$,6,kpc beträgt. Gleiches kann durch Auswertung eines möglichen Einflusses der Erdmaterie auf die Neutrinooszillation mit Hilfe der Messung eines zweiten Neutrinodetektors erreicht werden.

Sorption and direct speciation of neptunium(V) on aluminium oxide and montmorillonite

This study comprised batch experiments, direct speciation studies via EXAFS, and modelling with the 2SPNE SC/CE model to elucidate the mechanisms of Np(V) sorption on montmorillonite and, for reference, on γ-Al2O3. The sorption of pM 239Np(V) and µM 237Np(V) on montmorillonite (STx-1, 4 g/L) and γ-Al2O3 (0.5 g/L) was studied at room temperature in the presence and absence of ambient CO2 covering a pH-range from 2.5 (STx-1) or 5 (γ-Al2O3) to 10.5 with 0.01 or 0.1M NaClO4 as background electrolyte. The Np(V) uptake was determined by γ spectroscopy of the supernatants and calculated as percentage as well as distribution coefficient Kd. Sorption starts from pH ~6 and, under exclusion of CO2, increases continuously, while, in the presence of ambient air, it reaches a maximum at pH ~8.5 (γ-Al2O3: log Kd max ≈ 4 mL/g; STx-1: log Kd max ≈ 2.7 mL/g). Beyond that it decreases again due to the formation of queous neptunium carbonate complexes. Furthermore, neptunium sorption on montmorillonite is influenced by ionic strength at pH <6 through ion exchange processes pointing towards the formation of outer-sphere surface complexes there. Isotherms measured at the sorption maximum showed the precipitation of resumably neptunium carbonate complexes above 3∙10^-5 M under ambient air conditions. Additionally, they indicated progressive saturation of the sorption sites of γ-Al2O3. At selected pH (STx-1: 5.0, 7.0, 8.0, 8.5, 9.0, 9.5; γ-Al2O3: 8.5, 9.5) EXAFS samples were prepared as wet pastes with µM 237Np and measured at room temperature in fluorescence mode at ANKA and ESRF. Several spectra were averaged and analysed with EXAFSPAK and FEFF 8.20 employing models of NaNpO2(CO3) or soddyite, (UO2)2SiO4∙2(H2O). The shorter atomic distances of the neptunyl ion at pH 5 compared to the others hinted at the retention of the hydration shell and, thus, at outer-sphere sorption. On average the bond lengths for Np(V) sorbed on STx-1 at high pH were Oax ≈ 1.84 Å and Oeq ≈ 2.53 Å. At high pH, ternary neptunyl carbonate surface complexes could be identified for montmorillonite (C ≈ 3.00 Å), but not for γ-Al2O3, where an interaction of neptunium with the aluminium surface atoms according to the soddyite model gave better agreement with the experimental data. However, neither structure as suggested by the two models could be excluded for both systems rendering a combination most likely. Modelling of the sorption data provided further evidence for the existence of ternary neptunium carbonate surface complexes in both cases. The results of this study can aid environmental risk assessment for clay-based nuclear waste repositories by providing valuable input data for simulations of radionuclide migration from a final disposal site.

Das wasserlösliche Chlorophyll-Protein (WSCP): biochemische Charakterisierung und Untersuchungen zur biologischen Funktion

Das WSCP (water-soluble chlorophyll protein) der Brassicaceen ist das einzig bekannte Chlorophyll-bindende Protein, welches keine Carotinoide bindet. Es ist ein wasserlösliches, ca. 80 kDa großes Homotetramer mit 1-4 gebundenen Chlorophyllen. Das Protein ist äußerst stabil und vermag die gebundenen Chlorophylle vor Photooxidation zu schützen. Seine Funktion in der Pflanze ist bis heute ein Rätsel und sollte in dieser Arbeit zusammen mit seinen biochemischen Eigenschaften weiter aufgeklärt werden. Es wurden Versuche durchgeführt mit nativem und rekombinantem WSCP aus Blumenkohl (BoWSCP bzw. BoWSCPhis) und aus Arabidopsis thaliana (AtWSCP bzw. AtWSCPhis). Die Expressionsausbeute von BoWSCPhis konnte verbessert werden und zusätzlich wurde die Rekonstitutionsmethode für das rekombinante WSCP optimiert, sodass das pigmentierte Protein mit hoher Ausbeute und großer Reinheit gewonnen werden konnte. Zudem wurde ein neuer WSCP-Klon hergestellt, mBoWSCPhis, der in seiner Sequenz dem maturen nativen BoWSCP entspricht und weitaus weniger Aggregationsprobleme zeigte als BoWSCPhis. Weiterführende Versuche zur Stabilität und dem Oligomerisierungsgrad von WSCP haben die neue Erkenntnis erbracht, dass die Phytolschwänze der von WSCP gebundenen Chlorophylle zwar essentiell sind für die Stabilität von WSCP-Oligomeren, nicht aber für die Oligomerisierung selbst, wie es in der Literatur bislang postuliert wurde. Zusätzlich zu ihrer außerordentlichen Hitzestabilität erwiesen sich die Chl-WSCP-Komplexe als stabil in einem breiten pH-Spektrum. AtWSCPhis besaß eine vergleichbare Stabilität, und auch das Oligomerisierungsverhalten zeigte Ähnlichkeiten zu BoWSCPhis. Im Rahmen einer Forschungskooperation mit dem Institut für Optik und Atomare Physik der TU Berlin wurden zeitaufgelöste Absorptionsspektren sowie Tieftemperatur-Fluoreszenzspektren an Chl-WSCP-Komplexen gemessen. Die Ergebnisse zeigten deutlich, dass die WSCP-gebundenen Chlorophylle excitonisch gekoppelt sind und wiesen zudem auf unterschiedliche Chl-Bindungsmodi hin. Aufgrund seines einfachen Aufbaus und seines geringen Chlorophyllgehalts hat sich WSCP bei diesen Versuchen als sehr geeignetes Modellsystem erwiesen, um Messungen zur Chlorophyllbindung mit Vorhersagen aus theoretischen Modellen zu vergleichen. Bei den Experimenten zur biologischen Funktion wurden einerseits Arabidopsis thaliana WSCP-„knock-out“-Pflanzen unter verschiedenen Bedingungen charakterisiert, andererseits wurden Experimente mit rekombinantem WSCP durchgeführt, um eine mögliche Interaktion mit anderen Proteinen zu detektieren. Die vegetativen Stadien der Mutante zeigten keinen Phänotyp; das native Arabidopsis-WSCP konnte später bei der Wildtyp-Pflanze ausschließlich in jungen Schoten lokalisiert werden, was eine Erklärung hierfür lieferte. Rekombinantes WSCP konnte Chlorophylle aus nativem LHCII entfernen, eine Interaktion mit Chlorophyllase konnte jedoch nicht nachgewiesen werden; daher konnte auch die Hypothese, WSCP sei ein Chl-Carrier beim Chl-Abbau, nicht untermauert werden. Bei den durchgeführten Enzym-Assays wurde eine geringfügige Inhibition der Cysteinprotease Papain beobachtet, aber keine Inhibition der Serinprotease Trypsin, obwohl Blumenkohl-WSCP N-proximal das Motiv der Künitz-Proteaseinhibitoren besitzt. Die Frage nach der biologischen Funktion von WSCP bleibt also weiterhin offen.

Geomorphologische Untersuchungen im Land der tausend Hügel - oder: Wie europäisch ist die rwandische Landschaftsentwicklung?

Das ursprüngliche Ziel der vorliegenden Dissertation war die Untersuchung der Talgenese im Zentralen Hügelland Rwandas. Entstehung und Form der Täler, die Stratigraphie und das Alter der Hang- und Talsedimente sowie die wirkenden reliefgestaltenden Prozesse sind bei weitem nicht abschließend erforscht. Da Strukturen und Prozesse im Rahmen von Prozessresponssystemen in Wechselwirkung stehen, bietet die Untersuchung der Strukturen gleich zwei Möglichkeiten, sich den Prozessen zu nähern: Strukturen sind sowohl Verursacher als auch Indikatoren von Prozessen. Entsprechend der ursprünglichen Fragestellung sollten nach einer Beschreibung der gegenwärtigen Strukturen (morphographische Geomorphologie) die formbildenden Prozesse ergründet werden (funktionale Geomorphologie), um dann die Entwicklung der Strukturen und Prozesse unter Einbeziehung der relevanten Phasen der Erdgeschichte und des Paläoklimas zu rekonstruieren (genetische Geomorphologie). Im Verlauf der zu diesem Zweck durchgeführten geomorphologisch-stratigraphischen Untersuchungen in den Tälern der Region von Butare (Südrwanda) stellten sich aber die holozänen Hangdeckschichten und Talfüllungen als derart mächtig heraus, dass tiefer liegende Sedimente nicht erschlossen werden konnten. Die älteren Strukturen ließen sich daher nur unzureichend rekonstruieren und die eingangs formulierte Fragestellung konnte nicht wie erwartet bearbeitet werden. Angesichts der Mächtigkeit der Sedimente wurde offensichtlich, dass sowohl die spätpleistozäne als auch die holozäne Dimension der Sedimentbildung völlig unterschätzt wurde. Diese Beobachtungen warfen zwei grundlegende Fragen auf: einerseits die Frage warum die holozänen Sedimente so mächtig ausgebildet sind, und andererseits, weshalb ihre Mächtigkeit derartig unterschätzt wurde. Rasch stellte sich heraus, dass die Bearbeitung der ersten Frage eine interdisziplinäre Öffnung und die der zweiten Frage eine interkulturelle Öffnung der Fragestellung erforderte. Dabei stellen sich vor allem zwei Fragen: Zum einen, inwiefern der europäische Ursprung der Begriffe, Theorien und Modelle, die zur Beschreibung und Interpretation der rwandischen landschaftlichen und landschaftsgestaltenden Prozesse verwendet werden, eben jene Beschreibung und Interpretation beeinflusst, und zum anderen, ob und inwiefern auch naturwissenschaftliche Disziplinen in ihrem Umgang mit ‚natürlich gedachten’ Strukturen und Prozessen von diesen Konstruktionen betroffen sind. Ziel der Dekonstruktion der Begriffe, Theorien und Modelle ist kein ‚richtigerer’ oder ‚wahrhaftigerer’, sondern ein ‚bewussterer’ Umgang mit den Begriffen, Theorien und Modellen und dadurch eine bewusstere Rekonstruktion der Strukturen und Prozesse der Landschaften und Paläolandschaften des rwandischen Zentralen Hügellandes.rn