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This study presents the development of 1D and 2D Surface Evolution Codes (SECs) and their coupling to any lithospheric-scale (thermo-)mechanical code with a quadrilateral structured surface mesh.
Both SECs involve diffusion as approach for hillslope processes and the stream power law to reflect riverbed incision. The 1D SEC settles sediment that was produced by fluvial incision in the appropriate minimum, while the supply-limited 2D SEC DANSER uses a fast filling algorithm to model sedimantation. It is based on a cellular automaton. A slope-dependent factor in the sediment flux extends the diffusion equation to nonlinear diffusion. The discharge accumulation is achieved with the D8-algorithm and an improved drainage accumulation routine. Lateral incision enhances the incision's modelling. Following empirical laws, it incises channels of several cells width.
The coupling method enables different temporal and spatial resolutions of the SEC and the thermo-mechanical code. It transfers vertical as well as horizontal displacements to the surface model. A weighted smoothing of the 3D surface displacements is implemented. The smoothed displacement vectors transmit the deformation by bilinear interpolation to the surface model. These interpolation methods ensure mass conservation in both directions and prevent the two surfaces from drifting apart.
The presented applications refer to the evolution of the Pamir orogen. A calibration of DANSER's parameters with geomorphological data and a DEM as initial topography highlights the advantage of lateral incision. Preserving the channel width and reflecting incision peaks in narrow channels, this closes the huge gap between current orogen-scale incision models and observed topographies.
River capturing models in a system of fault-bounded block rotations reaffirm the importance of the lateral incision routine for capturing events with channel initiation. The models show a low probability of river capturings with large deflection angles. While the probability of river capturing is directly depending on the uplift rate, the erodibility inside of a dip-slip fault speeds up headward erosion along the fault: The model's capturing speed increases within a fault.
Coupling DANSER with the thermo-mechanical code SLIM 3D emphasizes the versatility of the SEC. While DANSER has minor influence on the lithospheric evolution of an indenter model, the brittle surface deformation is strongly affected by its sedimentation, widening a basin in between two forming orogens and also the southern part of the southern orogen to south, east and west.
Organic bulk heterojunction (BHJ) solar cells based on polymer:fullerene blends are a promising alternative for a low-cost solar energy conversion. Despite significant improvements of the power conversion efficiency in recent years, the fundamental working principles of these devices are yet not fully understood. In general, the current output of organic solar cells is determined by the generation of free charge carriers upon light absorption and their transport to the electrodes in competition to the loss of charge carriers due to recombination.
The object of this thesis is to provide a comprehensive understanding of the dynamic processes and physical parameters determining the performance. A new approach for analyzing the characteristic current-voltage output was developed comprising the experimental determination of the efficiencies of charge carrier generation, recombination and transport, combined with numerical device simulations.
Central issues at the beginning of this work were the influence of an electric field on the free carrier generation process and the contribution of generation, recombination and transport to the current-voltage characteristics. An elegant way to directly measure the field dependence of the free carrier generation is the Time Delayed Collection Field (TDCF) method. In TDCF charge carriers are generated by a short laser pulse and subsequently extracted by a defined rectangular voltage pulse. A new setup was established with an improved time resolution compared to former reports in literature. It was found that charge generation is in general independent of the electric field, in contrast to the current view in literature and opposed to the expectations of the Braun-Onsager model that was commonly used to describe the charge generation process. Even in cases where the charge generation was found to be field-dependend, numerical modelling showed that this field-dependence is in general not capable to account for the voltage dependence of the photocurrent. This highlights the importance of efficient charge extraction in competition to non-geminate recombination, which is the second objective of the thesis.
Therefore, two different techniques were combined to characterize the dynamics and efficiency of non-geminate recombination under device-relevant conditions. One new approach is to perform TDCF measurements with increasing delay between generation and extraction of charges. Thus, TDCF was used for the first time to measure charge carrier generation, recombination and transport with the same experimental setup. This excludes experimental errors due to different measurement and preparation conditions and demonstrates the strength of this technique. An analytic model for the description of TDCF transients was developed and revealed the experimental conditions for which reliable results can be obtained. In particular, it turned out that the $RC$ time of the setup which is mainly given by the sample geometry has a significant influence on the shape of the transients which has to be considered for correct data analysis.
Secondly, a complementary method was applied to characterize charge carrier recombination under steady state bias and illumination, i.e. under realistic operating conditions. This approach relies on the precise determination of the steady state carrier densities established in the active layer. It turned out that current techniques were not sufficient to measure carrier densities with the necessary accuracy. Therefore, a new technique {Bias Assisted Charge Extraction} (BACE) was developed. Here, the charge carriers photogenerated under steady state illumination are extracted by applying a high reverse bias. The accelerated extraction compared to conventional charge extraction minimizes losses through non-geminate recombination and trapping during extraction. By performing numerical device simulations under steady state, conditions were established under which quantitative information on the dynamics can be retrieved from BACE measurements.
The applied experimental techniques allowed to sensitively analyse and quantify geminate and non-geminate recombination losses along with charge transport in organic solar cells. A full analysis was exemplarily demonstrated for two prominent polymer-fullerene blends.
The model system P3HT:PCBM spincast from chloroform (as prepared) exhibits poor power conversion efficiencies (PCE) on the order of 0.5%, mainly caused by low fill factors (FF) and currents. It could be shown that the performance of these devices is limited by the hole transport and large bimolecular recombination (BMR) losses, while geminate recombination losses are insignificant. The low polymer crystallinity and poor interconnection between the polymer and fullerene domains leads to a hole mobility of the order of 10^-7 cm^2/Vs which is several orders of magnitude lower than the electron mobility in these devices. The concomitant build up of space charge hinders extraction of both electrons and holes and promotes bimolecular recombination losses.
Thermal annealing of P3HT:PCBM blends directly after spin coating improves crystallinity and interconnection of the polymer and the fullerene phase and results in comparatively high electron and hole mobilities in the order of 10^-3 cm^2/Vs and 10^-4 cm^2/Vs, respectively. In addition, a coarsening of the domain sizes leads to a reduction of the BMR by one order of magnitude. High charge carrier mobilities and low recombination losses result in comparatively high FF (>65%) and short circuit current (J_SC ≈ 10 mA/cm^2). The overall device performance (PCE ≈ 4%) is only limited by a rather low spectral overlap of absorption and solar emission and a small V_OC, given by the energetics of the P3HT.
From this point of view the combination of the low bandgap polymer PTB7 with PCBM is a promising approach. In BHJ solar cells, this polymer leads to a higher V_OC due to optimized energetics with PCBM. However, the J_SC in these (unoptimized) devices is similar to the J_SC in the optimized blend with P3HT and the FF is rather low (≈ 50%). It turned out that the unoptimized PTB7:PCBM blends suffer from high BMR, a low electron mobility of the order of 10^-5 cm^2/Vs and geminate recombination losses due to field dependent charge carrier generation.
The use of the solvent additive DIO optimizes the blend morphology, mainly by suppressing the formation of very large fullerene domains and by forming a more uniform structure of well interconnected donor and acceptor domains of the order of a few nanometers. Our analysis shows that this results in an increase of the electron mobility by about one order of magnitude (3 x 10^-4 cm^2/Vs), while BMR and geminate recombination losses are significantly reduced. In total these effects improve the J_SC (≈ 17 mA/cm^2) and the FF (> 70%). In 2012 this polymer/fullerene combination resulted in a record PCE for a single junction OSC of 9.2%.
Remarkably, the numerical device simulations revealed that the specific shape of the J-V characteristics depends very sensitively to the variation of not only one, but all dynamic parameters. On the one hand this proves that the experimentally determined parameters, if leading to a good match between simulated and measured J-V curves, are realistic and reliable. On the other hand it also emphasizes the importance to consider all involved dynamic quantities, namely charge carrier generation, geminate and non-geminate recombination as well as electron and hole mobilities. The measurement or investigation of only a subset of these parameters as frequently found in literature will lead to an incomplete picture and possibly to misleading conclusions.
Importantly, the comparison of the numerical device simulation employing the measured parameters and the experimental $J-V$ characteristics allows to identify loss channels and limitations of OSC. For example, it turned out that inefficient extraction of charge carriers is a criticical limitation factor that is often disobeyed. However, efficient and fast transport of charges becomes more and more important with the development of new low bandgap materials with very high internal quantum efficiencies. Likewise, due to moderate charge carrier mobilities, the active layer thicknesses of current high-performance devices are usually limited to around 100 nm. However, larger layer thicknesses would be more favourable with respect to higher current output and robustness of production. Newly designed donor materials should therefore at best show a high tendency to form crystalline structures, as observed in P3HT, combined with the optimized energetics and quantum efficiency of, for example, PTB7.
This thesis contains three experimental studies addressing the interplay between deformation and the mineral reaction between natural calcite and magnesite. The solid-solid mineral reaction between the two carbonates causes the formation of a magnesio-calcite precursor layer and a dolomite reaction rim in every experiment at isostatic annealing and deformation conditions.
CHAPTER 1 briefly introduces general aspects concerning mineral reactions in nature and diffusion pathways for mass transport. Moreover, results of previous laboratory studies on the influence of deformation on mineral reactions are summarized. In addition, the main goals of this study are pointed out.
In CHAPTER 2, the reaction between calcite and magnesite single crystals is examined at isostatic annealing conditions. Time series performed at a fixed temperature revealed a diffusion-controlled dolomite rim growth. Two microstructural domains could be identified characterized by palisade-shaped dolomite grains growing into the magnesite and granular dolomite growing towards calcite. A model was provided for the dolomite rim growth based on the counter-diffusion of CaO and MgO. All reaction products exhibited a characteristic crystallographic relationship with respect to the calcite reactant. Moreover, kinetic parameters of the mineral reaction were determined out of a temperature series at a fixed time. The main goal of the isostatic test series was to gain information about the microstructure evolution, kinetic parameters, chemical composition and texture development of the reaction products. The results were used as a reference to quantify the influence of deformation on the mineral reaction.
CHAPTER 3 deals with the influence of non-isostatic deformation on dolomite and magnesio-calcite layer production between calcite and magnesite single crystals. Deformation was achieved by triaxial compression and by torsion. Triaxial compression up to 38 MPa axial stress at a fixed time showed no significant influence of stress and strain on dolomite formation. Time series conducted at a fixed stress yield no change in growth rates for dolomite and magnesio-calcite at low strains. Slightly larger magnesio-calcite growth rates were observed at strains above >0.1. High strains at similar stresses were caused by the activation of additional glide systems in the calcite single crystal and more mobile dislocations in the magnesio-calcite grains, providing fast diffusion pathways. In torsion experiments a gradual decrease in dolomite and magnesio-calcite layer thickness was observed at a critical shear strain. During deformation, crystallographic orientations of reaction products rearranged with respect to the external framework. A direct effect of the mineral reaction on deformation could not be recognized due to the relatively small reaction product widths.
In CHAPTER 4, the influence of starting material microfabrics and the presence of water on the reaction kinetics was evaluated. In these experimental series polycrystalline material was in contact with single crystals or two polycrystalline materials were used as reactants. Isostatic annealing resulted in different dolomite and magnesio-calcite layer thicknesses, depending on starting material microfabrics. The reaction progress at the magnesite interface was faster with smaller magnesite grain size, because grain boundaries provided fast pathways for diffusion and multiple nucleation sites for dolomite formation. Deformation by triaxial compression and torsion yield lower dolomite rim thicknesses compared to annealed samples for the same time. This was caused by grain coarsening of polycrystalline magnesite during deformation. In contrast, magnesio-calcite layers tended to be larger during deformation, which triggered enhanced diffusion along grain boundaries. The presence of excess water had no significant influence on the reaction kinetics, at least if the reactants were single crystals.
In CHAPTER 5 general conclusions about the interplay between deformation and the mineral reaction in the carbonate system are presented.
Finally, CHAPTER 6 highlights possible future work in the carbonate system based on the results of this study.
Magnetite nanoparticles and their assembly comprise a new area of development for new technologies. The magnetic particles can interact and assemble in chains or networks. Magnetotactic bacteria are one of the most interesting microorganisms, in which the assembly of nanoparticles occurs. These microorganisms are a heterogeneous group of gram negative prokaryotes, which all show the production of special magnetic organelles called magnetosomes, consisting of a magnetic nanoparticle, either magnetite (Fe3O4) or greigite (Fe3S4), embedded in a membrane. The chain is assembled along an actin-like scaffold made of MamK protein, which makes the magnetosomes to arrange in mechanically stable chains. The chains work as a compass needle in order to allow cells to orient and swim along the magnetic field of the Earth.
The formation of magnetosomes is known to be controlled at the molecular level. The physico–chemical conditions of the surrounding environment also influence biomineralization. The work presented in this manuscript aims to understand how such external conditions, in particular the extracellular oxidation reduction potential (ORP) influence magnetite formation in the strain Magnetospirillum magneticum AMB-1. A controlled cultivation of the microorganism was developed in a bioreactor and the formation of magnetosomes was characterized.
Different techniques have been applied in order to characterize the amount of iron taken up by the bacteria and in consequence the size of magnetosomes produced at different ORP conditions. By comparison of iron uptake, morphology of bacteria, size and amount of magnetosomes per cell at different ORP, the formation of magnetosomes was inhibited at ORP 0 mV, whereas reduced conditions, ORP – 500 mV facilitate biomineralization process.
Self-assembly of magnetosomes occurring in magnetotactic bacteria became an inspiration to learn from nature and to construct nanoparticles assemblies by using the bacteriophage M13 as a template. The M13 bacteriophage is an 800 nm long filament with encapsulated single-stranded DNA that has been recently used as a scaffold for nanoparticle assembly. I constructed two types of assemblies based on bacteriophages and magnetic nanoparticles. A chain – like assembly was first formed where magnetite nanoparticles are attached along the phage filament. A sperm – like construct was also built with a magnetic head and a tail formed by phage filament.
The controlled assembly of magnetite nanoparticles on the phage template was possible due to two different mechanism of nanoparticle assembly. The first one was based on the electrostatic interactions between positively charged polyethylenimine coated magnetite nanoparticles and negatively charged phages. The second phage –nanoparticle assembly was achieved by bioengineered recognition sites. A mCherry protein is displayed on the phage and is was used as a linker to a red binding nanobody (RBP) that is fused to the one of the proteins surrounding the magnetite crystal of a magnetosome.
Both assemblies were actuated in water by an external magnetic field showing their swimming behavior and potentially enabling further usage of such structures for medical applications. The speed of the phage - nanoparticles assemblies are relatively slow when compared to those of microswimmers previously published. However, only the largest phage-magnetite assemblies could be imaged and it is therefore still unclear how fast these structures can be in their smaller version.
The continuously increasing demand for rare earth elements in technical components of modern technologies, brings the detection of new deposits closer into the focus of global exploration. One promising method to globally map important deposits might be remote sensing, since it has been used for a wide range of mineral mapping in the past. This doctoral thesis investigates the capacity of hyperspectral remote sensing for the detection of rare earth element deposits. The definition and the realization of a fundamental database on the spectral characteristics of rare earth oxides, rare earth metals and rare earth element bearing materials formed the basis of this thesis. To investigate these characteristics in the field, hyperspectral images of four outcrops in Fen Complex, Norway, were collected in the near-field. A new methodology (named REEMAP) was developed to delineate rare earth element enriched zones. The main steps of REEMAP are: 1) multitemporal weighted averaging of multiple images covering the sample area; 2) sharpening the rare earth related signals using a Gaussian high pass deconvolution technique that is calibrated on the standard deviation of a Gaussian-bell shaped curve that represents by the full width of half maxima of the target absorption band; 3) mathematical modeling of the target absorption band and highlighting of rare earth elements. REEMAP was further adapted to different hyperspectral sensors (EO-1 Hyperion and EnMAP) and a new test site (Lofdal, Namibia). Additionally, the hyperspectral signatures of associated minerals were investigated to serve as proxy for the host rocks. Finally, the capacity and limitations of spectroscopic rare earth element detection approaches in general and of the REEMAP approach specifically were investigated and discussed. One result of this doctoral thesis is that eight rare earth oxides show robust absorption bands and, therefore, can be used for hyperspectral detection methods. Additionally, the spectral signatures of iron oxides, iron-bearing sulfates, calcite and kaolinite can be used to detect metasomatic alteration zones and highlight the ore zone. One of the key results of this doctoral work is the developed REEMAP approach, which can be applied from near-field to space. The REEMAP approach enables rare earth element mapping especially for noisy images. Limiting factors are a low signal to noise ratio, a reduced spectral resolution, overlaying materials, atmospheric absorption residuals and non-optimal illumination conditions. Another key result of this doctoral thesis is the finding that the future hyperspectral EnMAP satellite (with its currently published specifications, June 2015) will be theoretically capable to detect absorption bands of erbium, dysprosium, holmium, neodymium and europium, thulium and samarium. This thesis presents a new methodology REEMAP that enables a spatially wide and rapid hyperspectral detection of rare earth elements in order to meet the demand for fast, extensive and efficient rare earth exploration (from near-field to space).
Development of geophysical methods to characterize methane hydrate reservoirs on a laboratory scale
(2015)
Gas hydrates are crystalline solids composed of water and gas molecules. They are stable at elevated pressure and low temperatures. Therefore, natural gas hydrate deposits occur at continental margins, permafrost areas, deep lakes, and deep inland seas. During hydrate formation, the water molecules rearrange to form cavities which host gas molecules. Due to the high pressure during hydrate formation, significant amounts of gas can be stored in hydrate structures. The water-gas ratio hereby can reach up to 1:172 at 0°C and atmospheric pressure. Natural gas hydrates predominantly contain methane. Because methane constitutes both a fuel and a greenhouse gas, gas hydrates are a potential energy resource as well as a potential source for greenhouse gas.
This study investigates the physical properties of methane hydrate bearing sediments on a laboratory scale. To do so, an electrical resistivity tomography (ERT) array was developed and mounted in a large reservoir simulator (LARS). For the first time, the ERT array was applied to hydrate saturated sediment samples under controlled temperature, pressure, and hydrate saturation conditions on a laboratory scale. Typically, the pore space of (marine) sediments is filled with electrically well conductive brine. Because hydrates constitute an electrical isolator, significant contrasts regarding the electrical properties of the pore space emerge during hydrate formation and dissociation. Frequent measurements during hydrate formation experiments permit the recordings of the spatial resistivity distribution inside LARS. Those data sets are used as input for a new data processing routine which transfers the spatial resistivity distribution into the spatial distribution of hydrate saturation. Thus, the changes of local hydrate saturation can be monitored with respect to space and time.
This study shows that the developed tomography yielded good data quality and resolved even small amounts of hydrate saturation inside the sediment sample. The conversion algorithm transforming the spatial resistivity distribution into local hydrate saturation values yielded the best results using the Archie-var-phi relation. This approach considers the increasing hydrate phase as part of the sediment frame, metaphorically reducing the sample’s porosity. In addition, the tomographical measurements showed that fast lab based hydrate formation processes cause small crystallites to form which tend to recrystallize.
Furthermore, hydrate dissociation experiments via depressurization were conducted in order to mimic the 2007/2008 Mallik field trial. It was observed that some patterns in gas and water flow could be reproduced, even though some setup related limitations arose.
In two additional long-term experiments the feasibility and performance of CO2-CH4 hydrate exchange reactions were studied in LARS. The tomographical system was used to monitor the spatial hydrate distribution during the hydrate formation stage. During the subsequent CO2 injection, the tomographical array allowed to follow the CO2 migration front inside the sediment sample and helped to identify the CO2 breakthrough.
The lives of more than 1/6 th of the world population is directly affected by the caprices of the South Asian summer monsoon rainfall. India receives around 78 % of the annual precipitation during the June-September months, the summer monsoon season of South Asia. But, the monsoon circulation is not consistent throughout the entire summer season. Episodes of heavy rainfall (active periods) and low rainfall (break periods) are inherent to the intraseasonal variability of the South Asian summer monsoon. Extended breaks or long-lasting dryness can result in droughts and hence trigger crop failures and in turn famines. Furthermore, India's electricity generation from renewable sources (wind and hydro-power), which is increasingly important in order to satisfy the rapidly rising demand for energy, is highly reliant on the prevailing meteorology. The major drought years 2002 and 2009 for the Indian summer monsoon during the last decades, which are results of the occurrence of multiple extended breaks, emphasise exemplary that the understanding of the monsoon system and its intraseasonal variation is of greatest importance. Although, numerous studies based on observations, reanalysis data and global model simulations have been carried out with the focus on monsoon active and break phases over India, the understanding of the monsoon intraseasonal variability is only in the infancy stage. Regional climate models could benefit the comprehension of monsoon breaks by its resolution advantage.
This study investigates moist dynamical processes that initiate and maintain breaks during the South Asian summer monsoon using the atmospheric regional climate model HIRHAM5 at a horizontal resolution of 25 km forced by the ECMWF ERA Interim reanalysis for the period 1979-2012. By calculating moisture and moist static energy budgets the various competing mechanisms leading to extended breaks are quantitatively estimated. Advection of dry air from the deserts of western Asia towards central India is the dominant moist dynamical process in initiating extended break conditions over South Asia. Once initiated, the extended breaks are maintained due to many competing mechanisms: (i) the anomalous easterlies at the southern flank of this anticyclonic anomaly weaken the low-level cross-equatorial jet and thus the moisture transport into the monsoon region, (ii) differential radiative heating over the continental and the oceanic tropical convergence zone induces a local Hadley circulation with anomalous rising over the equatorial Indian Ocean and descent over central India, and (iii) a cyclonic response to positive rainfall anomalies over the near-equatorial Indian Ocean amplifies the anomalous easterlies over India and hence contributes to the low-level divergence over central India.
A sensitivity experiment that mimics a scenario of higher atmospheric aerosol concentrations over South Asia addresses a current issue of large uncertainty: the role aerosols play in suppressing monsoon rainfall and hence in triggering breaks. To study the indirect aerosol effects the cloud droplet number concentration was increased to imitate the aerosol's function as cloud condensation nuclei. The sensitivity experiment with altered microphysical cloud properties shows a reduction in the summer monsoon precipitation together with a weakening of the South Asian summer monsoon. Several physical mechanisms are proposed to be responsible for the suppressed monsoon rainfall: (i) according to the first indirect radiative forcing the increase in the number of cloud droplets causes an increase in the cloud reflectivity of solar radiation, leading to a climate cooling over India which in turn reduces the hydrological cycle, (ii) a stabilisation of the troposphere induced by a differential cooling between the surface and the upper troposphere over central India inhibits the growth of deep convective rain clouds, (iii) an increase of the amount of low and mid-level clouds together with a decrease in high-level cloud amount amplify the surface cooling and hence the atmospheric stability, and (iv) dynamical changes of the monsoon manifested as a anomalous anticyclonic circulation over India reduce the moisture transport into the monsoon region. The study suggests that the changes in the total precipitation, which are dominated by changes in the convective precipitation, mainly result from the indirect radiative forcing. Suppression of rainfall due to the direct microphysical effect is found to be negligible over India. Break statistics of the polluted cloud scenario indicate an increase in the occurrence of short breaks (3 days), while the frequency of extended breaks (> 7 days) is clearly not affected. This disproves the hypothesis that more and smaller cloud droplets, caused by a high load of atmospheric aerosols trigger long drought conditions over central India.
The present study addresses the question of how German vowels are perceived and produced by Polish learners of German as a Foreign Language. It comprises three main experiments: a discrimination experiment, a production experiment, and an identification experiment. With the exception of the discrimination task, the experiments further investigated the influence of orthographic marking on the perception and production of German vowel length. It was assumed that explicit markings such as the Dehnungs-h ("lengthening h") could help Polish GFL learners in perceiving and producing German words more correctly.
The discrimination experiment with manipulated nonce words showed that Polish GFL learners detect pure length differences in German vowels less accurately than German native speakers, while this was not the case for pure quality differences. The results of the identification experiment contrast with the results of the discrimination task in that Polish GFL learners were better at judging incorrect vowel length than incorrect vowel quality in manipulated real words. However, orthographic marking did not turn out to be the driving factor and it is suggested that metalinguistic awareness can explain the asymmetry between the two perception experiments. The production experiment supported the results of the identification task in that lengthening h did not help Polish learners in producing German vowel length more correctly. Yet, as far as vowel quality productions are concerned, it is argued that orthography does influence L2 sound productions because Polish learners seem to be negatively influenced by their native grapheme-to-phoneme correspondences.
It is concluded that it is important to differentiate between the influence of the L1 and L2 orthographic system. On the one hand, the investigation of the influence of orthographic vowel length markers in German suggests that Polish GFL learners do not make use of length information provided by the L2 orthographic system. On the other hand, the vowel quality data suggest that the L1 orthographic system plays a crucial role in the acquisition of a foreign language. It is therefore proposed that orthography influences the acquisition of foreign sounds, but not in the way it was originally assumed.
The standing stock and production of organismal biomass depends strongly on the organisms’ biotic environment, which arises from trophic and non-trophic interactions among them. The trophic interactions between the different groups of organisms form the food web of an ecosystem, with the autotrophic and bacterial production at the basis and potentially several levels of consumers on top of the producers. Feeding interactions can regulate communities either by severe grazing pressure or by shortage of resources or prey production, termed top-down and bottom-up control, respectively. The limitations of all communities conglomerate in the food web regulation, which is subject to abiotic and biotic forcing regimes arising from external and internal constraints. This dissertation presents the effects of alterations in two abiotic, external forcing regimes, terrestrial matter input and long-lasting low temperatures in winter. Diverse methodological approaches, a complex ecosystem model study and the analysis of two whole-lake measurements, were performed to investigate effects for the food web regulation and the resulting consequences at the species, community and ecosystem scale. Thus, all types of organisms, autotrophs and heterotrophs, at all trophic levels were investigated to gain a comprehensive overview of the effects of the two mentioned altered forcing regimes. In addition, an extensive evaluation of the trophic interactions and resulting carbon fluxes along the pelagic and benthic food web was performed to display the efficiencies of the trophic energy transfer within the food webs. All studies were conducted in shallow lakes, which is worldwide the most abundant type of lakes. The specific morphology of shallow lakes allows that the benthic production contributes substantially to the whole-lake production. Further, as shallow lakes are often small they are especially sensitive to both, changes in the input of terrestrial organic matter and the atmospheric temperature. Another characteristic of shallow lakes is their appearance in alternative stable states. They are either in a clear-water or turbid state, where macrophytes and phytoplankton dominate, respectively. Both states can stabilize themselves through various mechanisms.
These two alternative states and stabilizing mechanisms are integrated in the complex ecosystem model PCLake, which was used to investigate the effects of the enhanced terrestrial particulate organic matter (t-POM) input to lakes. The food web regulation was altered by three distinct pathways: (1) Zoobenthos received more food, increased in biomass which favored benthivorous fish and those reduced the available light due to bioturbation. (2) Zooplankton substituted autochthonous organic matter in their diet by suspended t-POM, thus the autochthonous organic matter remaining in the water reduced its transparency. (3) T-POM suspended into the water and reduced directly the available light. As macrophytes are more light-sensitive than phytoplankton they suffered the most from the lower transparency. Consequently, the resilience of the clear-water state was reduced by enhanced t-POM inputs, which makes the turbid state more likely at a given nutrient concentration. In two subsequent winters long-lasting low temperatures and a concurrent long duration of ice coverage was observed which resulted in low overall adult fish biomasses in the two study lakes – Schulzensee and Gollinsee, characterized by having and not having submerged macrophytes, respectively. Before the partial winterkill of fish Schulzensee allowed for a higher proportion of piscivorous fish than Gollinsee. However, the partial winterkill of fish aligned both communities as piscivorous fish are more sensitive to low oxygen concentrations. Young of the year fish benefitted extremely from the absence of adult fish due to lower predation pressure. Therefore, they could exert a strong top-down control on crustaceans, which restructured the entire zooplankton community leading to low crustacean biomasses and a community composition characterized by copepodites and nauplii. As a result, ciliates were released from top-down control, increased to high biomasses compared to lakes of various trophic states and depths and dominated the zooplankton community. While being very abundant in the study lakes and having the highest weight specific grazing rates among the zooplankton, ciliates exerted potentially a strong top-down control on small phytoplankton and particle-attached bacteria. This resulted in a higher proportion of large phytoplankton compared to other lakes. Additionally, the phytoplankton community was evenly distributed presumably due to the numerous fast growing and highly specific ciliate grazers. Although, the pelagic food web was completely restructured after the subsequent partial winterkills of fish, both lakes were resistant to effects of this forcing regime at the ecosystem scale. The consistently high predation pressure on phytoplankton prevented that Schulzensee switched from the clear-water to the turbid state. Further mechanisms, which potentially stabilized the clear-water state, were allelopathic effects by macrophytes and nutrient limitation in summer. The pelagic autotrophic and bacterial production was an order of magnitude more efficient transferred to animal consumers than the respective benthic production, despite the alterations of the food web structure after the partial winterkill of fish. Thus, the compiled mass-balanced whole-lake food webs suggested that the benthic bacterial and autotrophic production, which exceeded those of the pelagic habitat, was not used by animal consumers. This holds even true if the food quality, additional consumers such as ciliates, benthic protozoa and meiobenthos, the pelagic-benthic link and the potential oxygen limitation of macrobenthos were considered. Therefore, low benthic efficiencies suggest that lakes are primarily pelagic systems at least at the animal consumer level.
Overall, this dissertation gives insights into the regulation of organism groups in the pelagic and benthic habitat at each trophic level under two different forcing regimes and displays the efficiency of the carbon transfer in both habitats. The results underline that the alterations of external forcing regimes affect all hierarchical level including the ecosystem.
Earthquake clustering has proven the most useful tool to forecast changes in seismicity rates in the short and medium term (hours to months), and efforts are currently being made to extend the scope of such models to operational earthquake forecasting. The overarching goal of the research presented in this thesis is to improve physics-based earthquake forecasts, with a focus on aftershock sequences. Physical models of triggered seismicity are based on the redistribution of stresses in the crust, coupled with the rate-and-state constitutive law proposed by Dieterich to calculate changes in seismicity rate. This type of models are known as Coulomb- rate and-state (CRS) models. In spite of the success of the Coulomb hypothesis, CRS models typically performed poorly in comparison to statistical ones, and they have been underepresented in the operational forecasting context. In this thesis, I address some of these issues, and in particular these questions: (1) How can we realistically model the uncertainties and heterogeneity of the mainshock stress field? (2) What is the effect of time dependent stresses in the postseismic phase on seismicity? I focus on two case studies from different tectonic settings: the Mw 9.0 Tohoku megathrust and the Mw 6.0 Parkfield strike slip earthquake. I study aleatoric uncertainties using a Monte Carlo method. I find that the existence of multiple receiver faults is the most important source of intrinsic stress heterogeneity, and CRS models perform better when this variability is taken into account. Epistemic uncertainties inherited from the slip models also have a significant impact on the forecast, and I find that an ensemble model based on several slip distributions outperforms most individual models. I address the role of postseismic stresses due to aseismic slip on the mainshock fault (afterslip) and to the redistribution of stresses by previous aftershocks (secondary triggering). I find that modeling secondary triggering improves model performance. The effect of afterslip is less clear, and difficult to assess for near-fault aftershocks due to the large uncertainties of the afterslip models. Off-fault events, on the other hand, are less sensitive to the details of the slip distribution: I find that following the Tohoku earthquake, afterslip promotes seismicity in the Fukushima region. To evaluate the performance of the improved CRS models in a pseudo-operational context, I submitted them for independent testing to a collaborative experiment carried out by CSEP for the 2010-2012 Canterbury sequence. Preliminary results indicate that physical models generally perform well compared to statistical ones, suggesting that CRS models may have a role to play in the future of operational forecasting. To facilitate efforts in this direction, and to enable future studies of earthquake triggering by time dependent processes, I have made the code open source. In the final part of this thesis I summarize the capabilities of the program and outline technical aspects regarding performance and parallelization strategies.