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The Lombok Island is part of the Lesser Sunda Islands (LSI) region – Indonesia, situated along the Sunda-Banda Arcs transition. It lies between zones characterized by the highest intensity geomagnetic anomalies of this region, remarkable as one of the eight most important features provided on the 1st edition of World Digital Magnetic Anomaly Map. The seismicity of this region during the last years is high, while the geological and tectonic structures of this region are still not known in detail. Some local magnetic surveys have been conducted previously during 2004–2005. However, due to the lower accuracy of the used equipment and a limited number of stations, the qualities of the previous measurements are questionable for more interpretations. Thus a more detailed study to better characterize the geomagnetic anomaly -spatially and temporally- over this region and to deeply explore the related regional geology, tectonic and seismicity is needed. The intriguing geomagnetic anomalies over this island region vis-à-vis the socio-cultural situations lead to a study with a special aim to contribute to the assessment of the potential of natural hazards (earthquakes) as well as a new natural resource of energy (geothermal potential).
This study is intended to discuss several crucial questions, including:
i. The real values and the general pattern of magnetic anomalies over the island, as well as their relation to the regional one.
ii. Any temporal changes of regional anomalies over the recent time.
iii. The relationships between the anomalies and the geology and tectonic of this region, especially new insights that can be gained from the geomagnetic observations.
iv. The relationships between the anomalies and the high seismicity of this region, especially some possible links between their variations to the earthquake occurrence.
First, all available geomagnetic data of this region and results of the previous measurements are evaluated. The new geomagnetic surveys carried out in 2006 and 2007/2008 are then presented in detail, followed by the general description of data processing and data quality evaluation. The new results show the general pattern of contiguous negative-positive anomalies, revealing an active arc related subduction region. They agree with earlier results obtained by satellite, aeromagnetic, and marine platforms; and provide a much more detailed picture of the strong anomalies on this island. The temporal characteristics of regional anomalies show a decreasing strength of the dipolar structure, where decreasing of the field intensities is faster than the regional secular variations as defined by the global model (the 10th generation of IGRF). However, some exceptions (increasing of anomalies) have to be noted and further analyzed for several locations.
Thereafter, simultaneous magnetic anomalies and gravity models are generated and interpreted in detail. Three profiles are investigated, providing new insights into the tectonics and geological evolution of the Lombok Island. Geological structure of this island can be divided as two main parts with different consecutive ages: an old part (from late Oligocene to late Miocene) in the South and a younger one (from Pliocene to Holocene) in the North. A new subduction in the back arc region (the Flores Thrust zone) is considered mature and active, showing a tendency of progressive subduction during 2005–2008. Geothermal potential in the northern part of this island can be mapped in more detail using these geomagnetic regional survey data. The earlier estimates of reservoir depth can be confirmed further to a depth of about 800 m. Evaluation of temporal changes of the anomalies gives some possible explanations related to the evolution of the back arc region, large stress accumulations over the LSI region, a specific electrical characteristic of the crust of the Lombok Island region, and a structural discontinuity over this island.
Based on the results, several possible advanced studies involving geomagnetic data and anomaly investigations over the Lombok Island region can be suggested for the future:
i. Monitoring the subduction activity of the back arc region (the Flores Thrust zone) and the accumulated stress over the LSI, that could contribute to middle term hazard assessment with a special attention to the earthquake occurrence in this region. Continuous geomagnetic field measurements from a geomagnetic observatory which can be established in the northern part of the Lombok Island and systematic measurements at several repeat stations can be useful in this regards.
ii. Investigating the specific electrical characteristic (high conductivity) of the crust, that is probably related to some aquifer layers or metal mineralization. It needs other complementary geophysical methods, such as magnetotelluric (MT) or preferably DC resistivity measurements.
iii. Determining the existence of an active structural fault over the Lombok Island, that could be related to long term hazard assessment over the LSI region. This needs an extension of geomagnetic investigations over the neighbouring islands (the Bali Island in the West and the Sumbawa Island in the East; probably also the Sumba and the Flores islands). This seems possible because the regional magnetic lineations might be used to delineate some structural discontinuities, based on the modelling of contrasts in crustal magnetizations.
This work describes the realization of physically crosslinked networks based on gelatin by the introduction of functional groups enabling specific supramolecular interactions. Molecular models were developed in order to predict the material properties and permit to establish a knowledge-based approach to material design. The effect of additional supramolecular interactions with hydroxyapaptite was then studied in composite materials. The calculated properties are compared to experimental results to validate the models. The models are then further used for the study of physically crosslinked networks. Gelatin was functionalized with desaminotyrosine (DAT) and desaminotyrosyl-tyrosine (DATT) side groups, derived from the natural amino acid tyrosine. These group can potentially undergo to π-π and hydrogen bonding interactions also under physiological conditions. Molecular dynamics (MD) simulations were performed on models with 0.8 wt.-% or 25 wt.-% water content, using the second generation forcefield CFF91. The validation of the models was obtained by the comparison with specific experimental data such as, density, peptide conformational angles and X-ray scattering spectra. The models were then used to predict the supramolecular organization of the polymer chain, analyze the formation of physical netpoints and calculate the mechanical properties. An important finding of simulation was that with the increase of aromatic groups also the number of observed physical netpoints increased. The number of relatively stable physical netpoints, on average zero 0 for natural gelatin, increased to 1 and 6 for DAT and DATT functionalized gelatins respectively. A comparison with the Flory-Rehner model suggested reduced equilibrium swelling by factor 6 of the DATT-functionalized materials in water. The functionalized gelatins could be synthesized by chemoselective coupling of the free carboxylic acid groups of DAT and DATT to the free amino groups of gelatin. At 25 wt.-% water content, the simulated and experimentally determined elastic mechanical properties (e.g. Young Modulus) were both in the order of GPa and were not influenced by the degree of aromatic modification. The experimental equilibrium degree of swelling in water decreased with increasing the number of inserted aromatic functions (from 2800 vol.-% for pure gelatin to 300 vol.-% for the DATT modified gelatin), at the same time, Young’s modulus, elongation at break, and maximum tensile strength increased. It could be show that the functionalization with DAT and DATT influences the chain organization of gelatin based materials together with a controlled drying condition. Functionalization with DAT and DATT lead to a drastic reduction of helical renaturation, that could be more finely controlled by the applied drying conditions. The properties of the materials could then be influenced by application of two independent methods. Composite materials of DAT and DATT functionalized gelatins with hydroxyapatite (HAp) show a drastic reduction of swelling degree. In tensile tests and rheological measurements, the composites equilibrated in water had increased Young’s moduli (from 200 kPa up to 2 MPa) and tensile strength (from 57 kPa up to 1.1 MPa) compared to the natural polymer matrix without affecting the elongation at break. Furthermore, an increased thermal stability from 40 °C to 85 °C of the networks could be demonstrated. The differences of the behaviour of the functionalized gelatins to pure gelatin as matrix suggested an additional stabilizing bond between the incorporated aromatic groups to the hydroxyapatite.
CHAMP (CHAllenging Minisatellite Payload) is a German small satellite mission to study the earth's gravity field, magnetic field and upper atmosphere. Thanks to the good condition of the satellite so far, the planned 5 years mission is extended to year 2009. The satellite provides continuously a large quantity of measurement data for the purpose of Earth study. The measurements of the magnetic field are undertaken by two Fluxgate Magnetometers (vector magnetometer) and one Overhauser Magnetometer (scalar magnetometer) flown on CHAMP. In order to ensure the quality of the data during the whole mission, the calibration of the magnetometers has to be performed routinely in orbit. The scalar magnetometer serves as the magnetic reference and its readings are compared with the readings of the vector magnetometer. The readings of the vector magnetometer are corrected by the parameters that are derived from this comparison, which is called the scalar calibration. In the routine processing, these calibration parameters are updated every 15 days by means of scalar calibration. There are also magnetic effects coming from the satellite which disturb the measurements. Most of them have been characterized during tests before launch. Among them are the remanent magnetization of the spacecraft and fields generated by currents. They are all considered to be constant over the mission life. The 8 years of operation experience allow us to investigate the long-term behaviors of the magnetometers and the satellite systems. According to the investigation, it was found that for example the scale factors of the FGM show obvious long-term changes which can be described by logarithmic functions. The other parameters (offsets and angles between the three components) can be considered constant. If these continuous parameters are applied for the FGM data processing, the disagreement between the OVM and the FGM readings is limited to \pm1nT over the whole mission. This demonstrates, the magnetometers on CHAMP exhibit a very good stability. However, the daily correction of the parameter Z component offset of the FGM improves the agreement between the magnetometers markedly. The Z component offset plays a very important role for the data quality. It exhibits a linear relationship with the standard deviation of the disagreement between the OVM and the FGM readings. After Z offset correction, the errors are limited to \pm0.5nT (equivalent to a standard deviation of 0.2nT). We improved the corrections of the spacecraft field which are not taken into account in the routine processing. Such disturbance field, e.g. from the power supply system of the satellite, show some systematic errors in the FGM data and are misinterpreted in 9-parameter calibration, which brings false local time related variation of the calibration parameters. These corrections are made by applying a mathematical model to the measured currents. This non-linear model is derived from an inversion technique. If the disturbance field of the satellite body are fully corrected, the standard deviation of scalar error \triangle B remains about 0.1nT. Additionally, in order to keep the OVM readings a reliable standard, the imperfect coefficients of the torquer current correction for the OVM are redetermined by solving a minimization problem. The temporal variation of the spacecraft remanent field is investigated. It was found that the average magnetic moment of the magneto-torquers reflects well the moment of the satellite. This allows for a continuous correction of the spacecraft field. The reasons for the possible unknown systemic error are discussed in this thesis. Particularly, both temperature uncertainties and time errors have influence on the FGM data. Based on the results of this thesis the data processing of future magnetic missions can be designed in an improved way. In particular, the upcoming ESA mission Swarm can take advantage of our findings and provide all the auxiliary measurements needed for a proper recovery of the ambient magnetic field.
The availability of large data sets has allowed researchers to uncover complex properties in complex systems, such as complex networks and human dynamics. A vast number of systems, from the Internet to the brain, power grids, ecosystems, can be represented as large complex networks. Dynamics on and of complex networks has attracted more and more researchers’ interest. In this thesis, first, I introduced a simple but effective dynamical optimization coupling scheme which can realize complete synchronization in networks with undelayed and delayed couplings and enhance the small-world and scale-free networks’ synchronizability. Second, I showed that the robustness of scale-free networks with community structure was enhanced due to the existence of communities in the networks and some of the response patterns were found to coincide with topological communities. My results provide insights into the relationship between network topology and the functional organization in complex networks from another viewpoint. Third, as an important kind of nodes of complex networks, human detailed correspondence dynamics was studied by both data and the model. A new and general type of human correspondence pattern was found and an interacting priority-queues model was introduced to explain it. The model can also embrace a range of realistic social interacting systems such as email and letter communication. My findings provide insight into various human activities both at the individual and network level. Fourth, I present clearly new evidence that human comment behavior in on-line social systems, a different type of interacting human dynamics, is non-Poissonian and a model based on the personal attraction was introduced to explain it. These results are helpful for discovering regular patterns of human behavior in on-line society and the evolution of the public opinion on the virtual as well as real society. Finally, there are conclusion and outlook of human dynamics and complex networks.
This thesis presents methods, techniques and tools for developing three-dimensional representations of tactical intelligence assessments. Techniques from GIScience are combined with crime mapping methods. The range of methods applied in this study provides spatio-temporal GIS analysis as well as 3D geovisualisation and GIS programming. The work presents methods to enhance digital three-dimensional city models with application specific thematic information. This information facilitates further geovisual analysis, for instance, estimations of urban risks exposure. Specific methods and workflows are developed to facilitate the integration of spatio-temporal crime scene analysis results into 3D tactical intelligence assessments. Analysis comprises hotspot identification with kernel-density-estimation techniques (KDE), LISA-based verification of KDE hotspots as well as geospatial hotspot area characterisation and repeat victimisation analysis. To visualise the findings of such extensive geospatial analysis, three-dimensional geovirtual environments are created. Workflows are developed to integrate analysis results into these environments and to combine them with additional geospatial data. The resulting 3D visualisations allow for an efficient communication of complex findings of geospatial crime scene analysis.
In 1915, Alfred Wegener published his hypotheses of plate tectonics that revolutionised the world for geologists. Since then, many scientists have studied the evolution of continents and especially the geologic structure of orogens: the most visible consequence of tectonic processes. Although the morphology and landscape evolution of mountain belts can be observed due to surface processes, the driving force and dynamics at lithosphere scale are less well understood despite the fact that rocks from deeper levels of orogenic belts are in places exposed at the surface. In this thesis, such formerly deeply-buried (ultra-) high-pressure rocks, in particular eclogite facies series, have been studied in order to reveal details about the formation and exhumation conditions and rates and thus provide insights into the geodynamics of the most spectacular orogenic belt in the world: the Himalaya. The specific area investigated was the Kaghan Valley in Pakistan (NW Himalaya). Following closure of the Tethyan Ocean by ca. 55-50 Ma, the northward subduction of the leading edge of India beneath the Eurasian Plate and subsequent collision initiated a long-lived process of intracrustal thrusting that continues today. The continental crust of India – granitic basement, Paleozoic and Mesozoic cover series and Permo-Triassic dykes, sills and lavas – has been buried partly to mantle depths. Today, these rocks crop out as eclogites, amphibolites and gneisses within the Higher Himalayan Crystalline between low-grade metamorphosed rocks (600-640°C/ ca. 5 kbar) of the Lesser Himalaya and Tethyan sediments. Beside tectonically driven exhumation mechanisms the channel flow model, that describes a denudation focused ductile extrusion of low viscosity material developed in the middle to lower crust beneath the Tibetan Plateau, has been postulated. To get insights into the lithospheric and crustal processes that have initiated and driven the exhumation of this (ultra-) high-pressure rocks, mineralogical, petrological and isotope-geochemical investigations have been performed. They provide insights into 1) the depths and temperatures to which these rocks were buried, 2) the pressures and temperatures the rocks have experienced during their exhumation, 3) the timing of these processes 4) and the velocity with which these rocks have been brought back to the surface. In detail, through microscopical studies, the identification of key minerals, microprobe analyses, standard geothermobarometry and modelling using an effective bulk rock composition it has been shown that published exhumation paths are incomplete. In particular, the eclogites of the northern Kaghan Valley were buried to depths of 140-100 km (36-30 kbar) at 790-640°C. Subsequently, cooling during decompression (exhumation) towards 40-35 km (17-10 kbar) and 630-580°C has been superseded by a phase of reheating to about 720-650°C at roughly the same depth before final exhumation has taken place. In the southern-most part of the study area, amphibolite facies assemblages with formation conditions similar to the deduced reheating phase indicate a juxtaposition of both areas after the eclogite facies stage and thus a stacking of Indian Plate units. Radiometric dating of zircon, titanite and rutile by U-Pb and amphibole and micas by Ar-Ar reveal peak pressure conditions at 47-48 Ma. With a maximum exhumation rate of 14 cm/a these rocks reached the crust-mantle boundary at 40-35 km within 1 Ma. Subsequent exhumation (46-41 Ma, 40-35 km) decelerated to ca. 1 mm/a at the base of the continental crust but rose again to about 2 mm/a in the period of 41-31 Ma, equivalent to 35-20 km. Apatite fission track (AFT) and (U-Th)/He ages from eclogites, amphibolites, micaschists and gneisses yielded moderate Oligocene to Miocene cooling rates of about 10°C/Ma in the high altitude northern parts of the Kaghan Valley using the mineral-pair method. AFT ages are of 24.5±3.8 to 15.6±2.1 Ma whereas apatite (U-Th)/He analyses yielded ages between 21.0±0.6 and 5.3±0.2 Ma. The southern-most part of the Valley is dominated by younger late Miocene to Pliocene apatite fission track ages of 7.6±2.1 and 4.0±0.5 Ma that support earlier tectonically and petrologically findings of a juxtaposition and stack of Indian Plate units. As this nappe is tectonically lowermost, a later distinct exhumation and uplift driven by thrusting along the Main Boundary Thrust is inferred. A multi-stage exhumation path is evident from petrological, isotope-geochemical and low temperature thermochronology investigations. Buoyancy driven exhumation caused an initial rapid exhumation: exhumation as fast as recent normal plate movements (ca. 10 cm/a). As the exhuming units reached the crust-mantle boundary the process slowed down due to changes in buoyancy. Most likely, this exhumation pause has initiated the reheating event that is petrologically evident (e.g. glaucophane rimmed by hornblende, ilmenite overgrowth of rutile). Late stage processes involved widespread thrusting and folding with accompanied regional greenschist facies metamorphism, whereby contemporaneous thrusting on the Batal Thrust (seen by some authors equivalent to the MCT) and back sliding of the Kohistan Arc along the inverse reactivated Main Mantle Thrust caused final exposure of these rocks. Similar circumstances have been seen at Tso Morari, Ladakh, India, 200 km further east where comparable rock assemblages occur. In conclusion, as exhumation was already done well before the initiation of the monsoonal system, climate dependent effects (erosion) appear negligible in comparison to far-field tectonic effects.
Calibration of the global hydrological model WGHM with water mass variations from GRACE gravity data
(2010)
Since the start-up of the GRACE (Gravity Recovery And Climate Experiment) mission in 2002 time dependent global maps of the Earth's gravity field are available to study geophysical and climatologically-driven mass redistributions on the Earth's surface. In particular, GRACE observations of total water storage changes (TWSV) provide a comprehensive data set for analysing the water cycle on large scales. Therefore they are invaluable for validation and calibration of large-scale hydrological models as the WaterGAP Global Hydrology Model (WGHM) which simulates the continental water cycle including its most important components, such as soil, snow, canopy, surface- and groundwater. Hitherto, WGHM exhibits significant differences to GRACE, especially for the seasonal amplitude of TWSV. The need for a validation of hydrological models is further highlighted by large differences between several global models, e.g. WGHM, the Global Land Data Assimilation System (GLDAS) and the Land Dynamics model (LaD). For this purpose, GRACE links geodetic and hydrological research aspects. This link demands the development of adequate data integration methods on both sides, forming the main objectives of this work. They include the derivation of accurate GRACE-based water storage changes, the development of strategies to integrate GRACE data into a global hydrological model as well as a calibration method, followed by the re-calibration of WGHM in order to analyse process and model responses. To achieve these aims, GRACE filter tools for the derivation of regionally averaged TWSV were evaluated for specific river basins. Here, a decorrelation filter using GRACE orbits for its design is most efficient among the tested methods. Consistency in data and equal spatial resolution between observed and simulated TWSV were realised by the inclusion of all most important hydrological processes and an equal filtering of both data sets. Appropriate calibration parameters were derived by a WGHM sensitivity analysis against TWSV. Finally, a multi-objective calibration framework was developed to constrain model predictions by both river discharge and GRACE TWSV, realised with a respective evolutionary method, the ε-Non-dominated-Sorting-Genetic-Algorithm-II (ε-NSGAII). Model calibration was done for the 28 largest river basins worldwide and for most of them improved simulation results were achieved with regard to both objectives. From the multi-objective approach more reliable and consistent simulations of TWSV within the continental water cycle were gained and possible model structure errors or mis-modelled processes for specific river basins detected. For tropical regions as such, the seasonal amplitude of water mass variations has increased. The findings lead to an improved understanding of hydrological processes and their representation in the global model. Finally, the robustness of the results is analysed with respect to GRACE and runoff measurement errors. As a main conclusion obtained from the results, not only soil water and snow storage but also groundwater and surface water storage have to be included in the comparison of the modelled and GRACE-derived total water budged data. Regarding model calibration, the regional varying distribution of parameter sensitivity suggests to tune only parameter of important processes within each region. Furthermore, observations of single storage components beside runoff are necessary to improve signal amplitudes and timing of simulated TWSV as well as to evaluate them with higher accuracy. The results of this work highlight the valuable nature of GRACE data when merged into large-scale hydrological modelling and depict methods to improve large-scale hydrological models.
The aim of this thesis is the design, expression and purification of human cytochrome c mutants and their characterization with regard to electrochemical and structural properties as well as with respect to the reaction with the superoxide radical and the selected proteins sulfite oxidase from human and fungi bilirubin oxidase. All three interaction partners are studied here for the first time with human cyt c and with mutant forms of cyt c. A further aim is the incorporation of the different cyt c forms in two bioelectronic systems: an electrochemical superoxide biosensor with an enhanced sensitivity and a protein multilayer assembly with and without bilirubin oxidase on electrodes. The first part of the thesis is dedicated to the design, expression and characterization of the mutants. A focus is here the electrochemical characterization of the protein in solution and immobilized on electrodes. Further the reaction of these mutants with superoxide was investigated and the possible reaction mechanisms are discussed. In the second part of the work an amperometric superoxide biosensor with selected human cytochrome c mutants was constructed and the performance of the sensor electrodes was studied. The human wild-type and four of the five mutant electrodes could be applied successfully for the detection of the superoxide radical. In the third part of the thesis the reaction of horse heart cyt c, the human wild-type and seven human cyt c mutants with the two proteins sulfite oxidase and bilirubin oxidase was studied electrochemically and the influence of the mutations on the electron transfer reactions was discussed. Finally protein multilayer electrodes with different cyt form including the mutant forms G77K and N70K which exhibit different reaction rates towards BOD were investigated and BOD together with the wild-type and engineered cyt c was embedded in the multilayer assembly. The relevant electron transfer steps and the kinetic behavior of the multilayer electrodes are investigated since the functionality of electroactive multilayer assemblies with incorporated redox proteins is often limited by the electron transfer abilities of the proteins within the multilayer. The formation via the layer-by-layer technique and the kinetic behavior of the mono and bi-protein multilayer system are studied by SPR and cyclic voltammetry. In conclusion this thesis shows that protein engineering is a helpful instrument to study protein reactions as well as electron transfer mechanisms of complex bioelectronic systems (such as bi-protein multilayers). Furthermore, the possibility to design tailored recognition elements for the construction of biosensors with an improved performance is demonstrated.
Monitoring virtual team collaboration : methods, applications and experiences in engineering design
(2010)
This work presents the development of entropy-elastic gelatin based networks in the form of films or scaffolds. The materials have good prospects for biomedical applications, especially in the context of bone regeneration. Entropy-elastic gelatin based hydrogel films with varying crosslinking densities were prepared with tailored mechanical properties. Gelatin was covalently crosslinked above its sol gel transition, which suppressed the gelatin chain helicity. Hexamethylene diisocyanate (HDI) or ethyl ester lysine diisocyanate (LDI) were applied as chemical crosslinkers, and the reaction was conducted either in dimethyl sulfoxide (DMSO) or water. Amorphous films were prepared as measured by Wide Angle X-ray Scattering (WAXS), with tailorable degrees of swelling (Q: 300-800 vol. %) and wet state Young’s modulus (E: 70 740 kPa). Model reactions showed that the crosslinking reaction resulted in a combination of direct crosslinks (3-13 mol.-%), grafting (5-40 mol.-%), and blending of oligoureas (16-67 mol.-%). The knowledge gained with this bulk material was transferred to the integrated process of foaming and crosslinking to obtain porous 3-D gelatin-based scaffolds. For this purpose, a gelatin solution was foamed in the presence of a surfactant, Saponin, and the resulting foam was fixed by chemical crosslinking with a diisocyanate. The amorphous crosslinked scaffolds were synthesized with varied gelatin and HDI concentrations, and analyzed in the dry state by micro computed tomography (µCT, porosity: 65±11–73±14 vol.-%), and scanning electron microscopy (SEM, pore size: 117±28–166±32 µm). Subsequently, the work focused on the characterization of the gelatin scaffolds in conditions relevant to biomedical applications. Scaffolds showed high water uptake (H: 630-1680 wt.-%) with minimal changes in outer dimension. Since a decreased scaffold pore size (115±47–130±49 µm) was revealed using confocal laser scanning microscopy (CLSM) upon wetting, the form stability could be explained. Shape recoverability was observed after removal of stress when compressing wet scaffolds, while dry scaffolds maintained the compressed shape. This was explained by a reduction of the glass transition temperature upon equilibration with water (dynamic mechanical analysis at varied temperature (DMTA)). The composition dependent compression moduli (Ec: 10 50 kPa) were comparable to the bulk micromechanical Young’s moduli, which were measured by atomic force microscopy (AFM). The hydrolytic degradation profile could be adjusted, and a controlled decrease of mechanical properties was observed. Partially-degraded scaffolds displayed an increase of pore size. This was likely due to the pore wall disintegration during degradation, which caused the pores to merge. The scaffold cytotoxicity and immunologic responses were analyzed. The porous scaffolds enabled proliferation of human dermal fibroblasts within the implants (up to 90 µm depth). Furthermore, indirect eluate tests were carried out with L929 cells to quantify the material cytotoxic response. Here, the effect of the sterilization method (Ethylene oxide sterilization), crosslinker, and surfactant were analyzed. Fully cytocompatible scaffolds were obtained by using LDI as crosslinker and PEO40 PPO20-PEO40 as surfactant. These investigations were accompanied by a study of the endotoxin material contamination. The formation of medical-grade materials was successfully obtained (<0.5 EU/mL) by using low-endotoxin gelatin and performing all synthetic steps in a laminar flow hood.
Production of regular and non-regular verbs : evidence for a lexical entry complexity account
(2010)
The incredible productivity and creativity of language depends on two fundamental resources: a mental lexicon and a mental grammar. Rules of grammar enable us to produce and understand complex phrases we have not encountered before and at the same time constrain the computation of complex expressions. The concepts of the mental lexicon and mental grammar have been thoroughly tested by comparing the use of regular versus non-regular word forms. Regular verbs (e.g. walk-walked) are computed using a suffixation rule in a neural system for grammatical processing; non-regular verbs (run-ran) are retrieved from associative memory. The role of regularity has only been explored for the past tense, where regularity is overtly visible. To explore the representation and encoding of regularity as well as the inflectional processes involved in the production of regular and non-regular verbs, this dissertation investigated three groups of German verbs: regular, irregular and hybrid verbs. Hybrid verbs in German have completely regular conjugation in the present tense and irregular conjugation in the past tense. Articulation latencies were measured while participants named pictures of actions, producing the 3rd person singular of regular, hybrid, and irregular verbs in present and past tense. Studying the production of German verbs in past and present tense, this dissertation explored the complexity of lexical entries as a decisive factor in the production of verbs.
Interactions of the antimicrobial peptide Arenicin with amphiphiles at planar and curved interfaces
(2010)
This thesis is focused on the electronic, spin-dependent and dynamical properties of thin magnetic systems. Photoemission-related techniques are combined with synchrotron radiation to study the spin-dependent properties of these systems in the energy and time domains. In the first part of this thesis, the strength of electron correlation effects in the spin-dependent electronic structure of ferromagnetic bcc Fe(110) and hcp Co(0001) is investigated by means of spin- and angle-resolved photoemission spectroscopy. The experimental results are compared to theoretical calculations within the three-body scattering approximation and within the dynamical mean-field theory, together with one-step model calculations of the photoemission process. From this comparison it is demonstrated that the present state of the art many-body calculations, although improving the description of correlation effects in Fe and Co, give too small mass renormalizations and scattering rates thus demanding more refined many-body theories including nonlocal fluctuations. In the second part, it is shown in detail monitoring by photoelectron spectroscopy how graphene can be grown by chemical vapour deposition on the transition-metal surfaces Ni(111) and Co(0001) and intercalated by a monoatomic layer of Au. For both systems, a linear E(k) dispersion of massless Dirac fermions is observed in the graphene pi-band in the vicinity of the Fermi energy. Spin-resolved photoemission from the graphene pi-band shows that the ferromagnetic polarization of graphene/Ni(111) and graphene/Co(0001) is negligible and that graphene on Ni(111) is after intercalation of Au spin-orbit split by the Rashba effect. In the last part, a time-resolved x-ray magnetic circular dichroic-photoelectron emission microscopy study of a permalloy platelet comprising three cross-tie domain walls is presented. It is shown how a fast picosecond magnetic response in the precessional motion of the magnetization can be induced by means of a laser-excited photoswitch. From a comparision to micromagnetic calculations it is demonstrated that the relatively high precessional frequency observed in the experiments is directly linked to the nature of the vortex/antivortex dynamics and its response to the magnetic perturbation. This includes the time-dependent reversal of the vortex core polarization, a process which is beyond the limit of detection in the present experiments.
With the rise of nanotechnology in the last decade, nanofluidics has been established as a research field and gained increased interest in science and industry. Natural aqueous nanofluidic systems are very complex, there is often a predominance of liquid interfaces or the fluid contains charged or differently shaped colloids. The effects, promoted by these additives, are far from being completely understood and interesting questions arise with regards to the confinement of such complex fluidic systems. A systematic study of nanofluidic processes requires designing suitable experimental model nano – channels with required characteristics. The present work employed thin liquid films (TLFs) as experimental models. They have proven to be useful experimental tools because of their simple geometry, reproducible preparation, and controllable liquid interfaces. The thickness of the channels can be adjusted easily by the concentration of electrolyte in the film forming solution. This way, channel dimensions from 5 – 100 nm are possible, a high flexibility for an experimental system. TLFs have liquid IFs of different charge and properties and they offer the possibility to confine differently shaped ions and molecules to very small spaces, or to subject them to controlled forces. This makes the foam films a unique “device” available to obtain information about fluidic systems in nanometer dimensions. The main goal of this thesis was to study nanofluidic processes using TLFs as models, or tools, and to subtract information about natural systems plus deepen the understanding on physical chemical conditions. The presented work showed that foam films can be used as experimental models to understand the behavior of liquids in nano – sized confinement. In the first part of the thesis, we studied the process of thinning of thin liquid films stabilized with the non – ionic surfactant n – dodecyl – β – maltoside (β – C₁₂G₂) with primary interest in interfacial diffusion processes during the thinning process dependent on surfactant concentration 64. The surfactant concentration in the film forming solutions was varied at constant electrolyte (NaCl) concentration. The velocity of thinning was analyzed combining previously developed theoretical approaches. Qualitative information about the mobility of the surfactant molecules at the film surfaces was obtained. We found that above a certain limiting surfactant concentration the film surfaces were completely immobile and they behaved as non – deformable, which decelerated the thinning process. This follows the predictions for Reynolds flow of liquid between two non – deformable disks. In the second part of the thesis, we designed a TLF nanofluidic system containing rod – like multivalent ions and compared this system to films containing monovalent ions. We presented first results which recognized for the first time the existence of an additional attractive force in the foam films based on the electrostatic interaction between rod – like ions and oppositely charged surfaces. We may speculate that this is an ion bridging component of the disjoining pressure. The results show that for films prepared in presence of spermidine the transformation of the thicker CF to the thinnest NBF is more probable as films prepared with NaCl at similar conditions of electrostatic interaction. This effect is not a result of specific adsorption of any of the ions at the fluid surfaces and it does not lead to any changes in the equilibrium properties of the CF and NBF. Our hypothesis was proven using the trivalent ion Y3+ which does not show ion bridging. The experimental results are compared to theoretical predictions and a quantitative agreement on the system’s energy gain for the change from CF to NBF could be obtained. In the third part of the work, the behavior of nanoparticles in confinement was investigated with respect to their impact on the fluid flow velocity. The particles altered the flow velocity by an unexpected high amount, so that the resulting changes in the dynamic viscosity could not be explained by a realistic change of the fluid viscosity. Only aggregation, flocculation and plug formation can explain the experimental results. The particle systems in the presented thesis had a great impact on the film interfaces due to the stabilizer molecules present in the bulk solution. Finally, the location of the particles with respect to their lateral and vertical arrangement in the film was studied with advanced reflectivity and scattering methods. Neutron Reflectometry studies were performed to investigate the location of nanoparticles in the TLF perpendicular to the IF. For the first time, we study TLFs using grazing incidence small angle X – ray scattering (GISAXS), which is a technique sensitive to the lateral arrangement of particles in confined volumes. This work provides preliminary data on a lateral ordering of particles in the film.
Development of techniques for earthquake microzonation studies in different urban environment
(2010)
The proliferation of megacities in many developing countries, and their location in areas where they are exposed to a high risk from large earthquakes, coupled with a lack of preparation, demonstrates the requirement for improved capabilities in hazard assessment, as well as the rapid adjustment and development of land-use planning. In particular, within the context of seismic hazard assessment, the evaluation of local site effects and their influence on the spatial distribution of ground shaking generated by an earthquake plays an important role. It follows that the carrying out of earthquake microzonation studies, which aim at identify areas within the urban environment that are expected to respond in a similar way to a seismic event, are essential to the reliable risk assessment of large urban areas. Considering the rate at which many large towns in developing countries that are prone to large earthquakes are growing, their seismic microzonation has become mandatory. Such activities are challenging and techniques suitable for identifying site effects within such contexts are needed. In this dissertation, I develop techniques for investigating large-scale urban environments that aim at being non-invasive, cost-effective and quickly deployable. These peculiarities allow one to investigate large areas over a relative short time frame, with a spatial sampling resolution sufficient to provide reliable microzonation. Although there is a negative trade-off between the completeness of available information and extent of the investigated area, I attempt to mitigate this limitation by combining two, what I term layers, of information: in the first layer, the site effects at a few calibration points are well constrained by analyzing earthquake data or using other geophysical information (e.g., shear-wave velocity profiles); in the second layer, the site effects over a larger areal coverage are estimated by means of single-station noise measurements. The microzonation is performed in terms of problem-dependent quantities, by considering a proxy suitable to link information from the first layer to the second one. In order to define the microzonation approach proposed in this work, different methods for estimating site effects have been combined and tested in Potenza (Italy), where a considerable amount of data was available. In particular, the horizontal-to-vertical spectral ratio computed for seismic noise recorded at different sites has been used as a proxy to combine the two levels of information together and to create a microzonation map in terms of spectral intensity ratio (SIR). In the next step, I applied this two-layer approach to Istanbul (Turkey) and Bishkek (Kyrgyzstan). A similar hybrid approach, i.e., combining earthquake and noise data, has been used for the microzonation of these two different urban environments. For both cities, after having calibrated the fundamental frequencies of resonance estimated from seismic noise with those obtained by analysing earthquakes (first layer), a fundamental frequency map has been computed using the noise measurements carried out within the town (second layer). By applying this new approach, maps of the fundamental frequency of resonance for Istanbul and Bishkek have been published for the first time. In parallel, a microzonation map in terms of SIR has been incorporated into a risk scenario for the Potenza test site by means of a dedicated regression between spectral intensity (SI) and macroseismic intensity (EMS). The scenario study confirms the importance of site effects within the risk chain. In fact, their introduction into the scenario led to an increase of about 50% in estimates of the number of buildings that would be partially or totally collapsed. Last, but not least, considering that the approach developed and applied in this work is based on measurements of seismic noise, their reliability has been assessed. A theoretical model describing the self-noise curves of different instruments usually adopted in microzonation studies (e.g., those used in Potenza, Istanbul and Bishkek) have been considered and compared with empirical data recorded in Cologne (Germany) and Gubbio (Italy). The results show that, depending on the geological and environmental conditions, the instrumental noise could severely bias the results obtained by recording and analysing ambient noise. Therefore, in this work I also provide some guidelines for measuring seismic noise.
Crustal deformation can be the result of volcanic and tectonic activity such as fault dislocation and magma intrusion. The crustal deformation may precede and/or succeed the earthquake occurrence and eruption. Mitigating the associated hazard, continuous monitoring of the crustal deformation accordingly has become an important task for geo-observatories and fast response systems. Due to highly non-linear behavior of the crustal deformation fields in time and space, which are not always measurable using conventional geodetic methods (e.g., Leveling), innovative techniques of monitoring and analysis are required. In this thesis I describe novel methods to improve the ability for precise and accurate mapping the spatiotemporal surface deformation field using multi acquisitions of satellite radar data. Furthermore, to better understand the source of such spatiotemporal deformation fields, I present novel static and time dependent model inversion approaches. Almost any interferograms include areas where the signal decorrelates and is distorted by atmospheric delay. In this thesis I detail new analysis methods to reduce the limitations of conventional InSAR, by combining the benefits of advanced InSAR methods such as the permanent scatterer InSAR (PSI) and the small baseline subsets (SBAS) with a wavelet based data filtering scheme. This novel InSAR time series methodology is applied, for instance, to monitor the non-linear deformation processes at Hawaii Island. The radar phase change at Hawaii is found to be due to intrusions, eruptions, earthquakes and flank movement processes and superimposed by significant environmental artifacts (e.g., atmospheric). The deformation field, I obtained using the new InSAR analysis method, is in good agreement with continuous GPS data. This provides an accurate spatiotemporal deformation field at Hawaii, which allows time dependent source modeling. Conventional source modeling methods usually deal with static deformation field, while retrieving the dynamics of the source requires more sophisticated time dependent optimization approaches. This problem I address by combining Monte Carlo based optimization approaches with a Kalman Filter, which provides the model parameters of the deformation source consistent in time. I found there are numerous deformation sources at Hawaii Island which are spatiotemporally interacting, such as volcano inflation is associated to changes in the rifting behavior, and temporally linked to silent earthquakes. I applied these new methods to other tectonic and volcanic terrains, most of which revealing the importance of associated or coupled deformation sources. The findings are 1) the relation between deep and shallow hydrothermal and magmatic sources underneath the Campi Flegrei volcano, 2) gravity-driven deformation at Damavand volcano, 3) fault interaction associated with the 2010 Haiti earthquake, 4) independent block wise flank motion at the Hilina Fault system, Kilauea, and 5) interaction between salt diapir and the 2005 Qeshm earthquake in southern Iran. This thesis, written in cumulative form including 9 manuscripts published or under review in peer reviewed journals, improves the techniques for InSAR time series analysis and source modeling and shows the mutual dependence between adjacent deformation sources. These findings allow more realistic estimation of the hazard associated with complex volcanic and tectonic systems.
The Dynamics of M&A Strategy
(2010)
In the high mountains of Asia, glaciers cover an area of approximately 115,000 km² and constitute one of the largest continental ice accumulations outside Greenland and Antarctica. Their sensitivity to climate change makes them valuable palaeoclimate archives, but also vulnerable to current and predicted Global Warming. This is a pressing problem as snow and glacial melt waters are important sources for agriculture and power supply of densely populated regions in south, east, and central Asia. Successful prediction of the glacial response to climate change in Asia and mitigation of the socioeconomic impacts requires profound knowledge of the climatic controls and the dynamics of Asian glaciers. However, due to their remoteness and difficult accessibility, ground-based studies are rare, as well as temporally and spatially limited. We therefore lack basic information on the vast majority of these glaciers. In this thesis, I employ different methods to assess the dynamics of Asian glaciers on multiple time scales. First, I tested a method for precise satellite-based measurement of glacier-surface velocities and conducted a comprehensive and regional survey of glacial flow and terminus dynamics of Asian glaciers between 2000 and 2008. This novel and unprecedented dataset provides unique insights into the contrasting topographic and climatic controls of glacial flow velocities across the Asian highlands. The data document disparate recent glacial behavior between the Karakoram and the Himalaya, which I attribute to the competing influence of the mid-latitude westerlies during winter and the Indian monsoon during summer. Second, I tested whether such climate-related longitudinal differences in glacial behavior also prevail on longer time scales, and potentially account for observed regionally asynchronous glacial advances. I used cosmogenic nuclide surface exposure dating of erratic boulders on moraines to obtain a glacial chronology for the upper Tons Valley, situated in the headwaters of the Ganges River. This area is located in the transition zone from monsoonal to westerly moisture supply and therefore ideal to examine the influence of these two atmospheric circulation regimes on glacial advances. The new glacial chronology documents multiple glacial oscillations during the last glacial termination and during the Holocene, suggesting largely synchronous glacial changes in the western Himalayan region that are related to gradual glacial-interglacial temperature oscillations with superimposed monsoonal precipitation changes of higher frequency. In a third step, I combine results from short-term satellite-based climate records and surface velocity-derived ice-flux estimates, with topographic analyses to deduce the erosional impact of glaciations on long-term landscape evolution in the Himalayan-Tibetan realm. The results provide evidence for the long-term effects of pronounced east-west differences in glaciation and glacial erosion, depending on climatic and topographic factors. Contrary to common belief the data suggest that monsoonal climate in the central Himalaya weakens glacial erosion at high elevations, helping to maintain a steep southern orographic barrier that protects the Tibetan Plateau from lateral destruction. The results of this thesis highlight how climatic and topographic gradients across the high mountains of Asia affect glacier dynamics on time scales ranging from 10^0 to 10^6 years. Glacial response times to climate changes are tightly linked to properties such as debris cover and surface slope, which are controlled by the topographic setting, and which need to be taken into account when reconstructing mountainous palaeoclimate from glacial histories or assessing the future evolution of Asian glaciers. Conversely, the regional topographic differences of glacial landscapes in Asia are partly controlled by climatic gradients and the long-term influence of glaciers on the topographic evolution of the orogenic system.
Large-scale volcanic deformation recently detected by radar interferometry (InSAR) provides new information and thus new scientific challenges for understanding volcano-tectonic activity and magmatic systems. The destabilization of such a system at depth noticeably affects the surrounding environment through magma injection, ground displacement and volcanic eruptions. To determine the spatiotemporal evolution of the Lazufre volcanic area located in the central Andes, we combined short-term ground displacement acquired by InSAR with long-term geological observations. Ground displacement was first detected using InSAR in 1997. By 2008, this displacement affected 1800 km2 of the surface, an area comparable in size to the deformation observed at caldera systems. The original displacement was followed in 2000 by a second, small-scale, neighbouring deformation located on the Lastarria volcano. We performed a detailed analysis of the volcanic structures at Lazufre and found relationships with the volcano deformations observed with InSAR. We infer that these observations are both likely to be the surface expression of a long-lived magmatic system evolving at depth. It is not yet clear whether Lazufre may trigger larger unrest or volcanic eruptions; however, the second deformation detected at Lastarria and the clear increase of the large-scale deformation rate make this an area of particular interest for closer continuous monitoring.
This thesis is concerned with the issue of extinction of populations composed of different types of individuals, and their behavior before extinction and in case of a very late extinction. We approach this question firstly from a strictly probabilistic viewpoint, and secondly from the standpoint of risk analysis related to the extinction of a particular model of population dynamics. In this context we propose several statistical tools. The population size is modeled by a branching process, which is either a continuous-time multitype Bienaymé-Galton-Watson process (BGWc), or its continuous-state counterpart, the multitype Feller diffusion process. We are interested in different kinds of conditioning on non-extinction, and in the associated equilibrium states. These ways of conditioning have been widely studied in the monotype case. However the literature on multitype processes is much less extensive, and there is no systematic work establishing connections between the results for BGWc processes and those for Feller diffusion processes. In the first part of this thesis, we investigate the behavior of the population before its extinction by conditioning the associated branching process X_t on non-extinction (X_t≠0), or more generally on non-extinction in a near future 0≤θ<∞ (X_{t+θ}≠0), and by letting t tend to infinity. We prove the result, new in the multitype framework and for θ>0, that this limit exists and is non-degenerate. This reflects a stationary behavior for the dynamics of the population conditioned on non-extinction, and provides a generalization of the so-called Yaglom limit, corresponding to the case θ=0. In a second step we study the behavior of the population in case of a very late extinction, obtained as the limit when θ tends to infinity of the process conditioned by X_{t+θ}≠0. The resulting conditioned process is a known object in the monotype case (sometimes referred to as Q-process), and has also been studied when X_t is a multitype Feller diffusion process. We investigate the not yet considered case where X_t is a multitype BGWc process and prove the existence of the associated Q-process. In addition, we examine its properties, including the asymptotic ones, and propose several interpretations of the process. Finally, we are interested in interchanging the limits in t and θ, as well as in the not yet studied commutativity of these limits with respect to the high-density-type relationship between BGWc processes and Feller processes. We prove an original and exhaustive list of all possible exchanges of limit (long-time limit in t, increasing delay of extinction θ, diffusion limit). The second part of this work is devoted to the risk analysis related both to the extinction of a population and to its very late extinction. We consider a branching population model (arising notably in the epidemiological context) for which a parameter related to the first moments of the offspring distribution is unknown. We build several estimators adapted to different stages of evolution of the population (phase growth, decay phase, and decay phase when extinction is expected very late), and prove moreover their asymptotic properties (consistency, normality). In particular, we build a least squares estimator adapted to the Q-process, allowing a prediction of the population development in the case of a very late extinction. This would correspond to the best or to the worst-case scenario, depending on whether the population is threatened or invasive. These tools enable us to study the extinction phase of the Bovine Spongiform Encephalopathy epidemic in Great Britain, for which we estimate the infection parameter corresponding to a possible source of horizontal infection persisting after the removal in 1988 of the major route of infection (meat and bone meal). This allows us to predict the evolution of the spread of the disease, including the year of extinction, the number of future cases and the number of infected animals. In particular, we produce a very fine analysis of the evolution of the epidemic in the unlikely event of a very late extinction.
About the relation between implicit Theory of Mind & the comprehension of complement sentences
(2010)
Previous studies on the relation between language and social cognition have shown that children’s mastery of embedded sentential complements plays a causal role for the development of a Theory of Mind (ToM). Children start to succeed on complementation tasks in which they are required to report the content of an embedded clause in the second half of the fourth year. Traditional ToM tasks test the child’s ability to predict that a person who is holding a false belief (FB) about a situation will act "falsely". In these task, children do not represent FBs until the age of 4 years. According the linguistic determinism hypothesis, only the unique syntax of complement sentences provides the format for representing FBs. However, experiments measuring children’s looking behavior instead of their explicit predictions provided evidence that already 2-year olds possess an implicit ToM. This dissertation examined the question of whether there is an interrelation also between implicit ToM and the comprehension of complement sentences in typically developing German preschoolers. Two studies were conducted. In a correlational study (Study 1 ), 3-year-old children’s performance on a traditional (explicit) FB task, on an implicit FB task and on language tasks measuring children’s comprehension of tensed sentential complements were collected and tested for their interdependence. Eye-tracking methodology was used to assess implicit ToM by measuring participants’ spontaneous anticipatory eye movements while they were watching FB movies. Two central findings emerged. First, predictive looking (implicit ToM) was not correlated with complement mastery, although both measures were associated with explicit FB task performance. This pattern of results suggests that explicit, but not implicit ToM is language dependent. Second, as a group, 3-year-olds did not display implicit FB understanding. That is, previous findings on a precocious reasoning ability could not be replicated. This indicates that the characteristics of predictive looking tasks play a role for the elicitation of implicit FB understanding as the current task was completely nonverbal and as complex as traditional FB tasks. Study 2 took a methodological approach by investigating whether children display an earlier comprehension of sentential complements when using the same means of measurement as used in experimental tasks tapping implicit ToM, namely anticipatory looking. Two experiments were conducted. 3-year-olds were confronted either with a complement sentence expressing the protagonist’s FB (Exp. 1) or with a complex sentence expressing the protagonist’s belief without giving any information about the truth/ falsity of the belief (Exp. 2). Afterwards, their expectations about the protagonist’s future behavior were measured. Overall, implicit measures reveal no considerably earlier understanding of sentential complementation. Whereas 3-year-olds did not display a comprehension of complex sentences if these embedded a false proposition, children from 3;9 years on were proficient in processing complement sentences if the truth value of the embedded proposition could not be evaluated. This pattern of results suggests that (1) the linguistic expression of a person’s FB does not elicit implicit FB understanding and that (2) the assessment of the purely syntactic understanding of complement sentences is affected by competing reality information. In conclusion, this dissertation found no evidence that the implicit ToM is related to the comprehension of sentential complementation. The findings suggest that implicit ToM might be based on nonlinguistic processes. Results are discussed in the light of recently proposed dual-process models that assume two cognitive mechanisms that account for different levels of ToM task performance.
Analysis of structure and variability of major histocompatibility complex in different vertebrates
(2010)
Situated in an active tectonic region, Santiago de Chile, the country´s capital with more than six million inhabitants, faces tremendous earthquake hazard. Macroseismic data for the 1985 Valparaiso and the 2010 Maule events show large variations in the distribution of damage to buildings within short distances indicating strong influence of local sediments and the shape of the sediment-bedrock interface on ground motion. Therefore, a temporary seismic network was installed in the urban area for recording earthquake activity, and a study was carried out aiming to estimate site amplification derived from earthquake data and ambient noise. The analysis of earthquake data shows significant dependence on the local geological structure with regards to amplitude and duration. Moreover, the analysis of noise spectral ratios shows that they can provide a lower bound in amplitude for site amplification and, since no variability in terms of time and amplitude is observed, that it is possible to map the fundamental resonance frequency of the soil for a 26 km x 12 km area in the northern part of the Santiago de Chile basin. By inverting the noise spectral rations, local shear wave velocity profiles could be derived under the constraint of the thickness of the sedimentary cover which had previously been determined by gravimetric measurements. The resulting 3D model was derived by interpolation between the single shear wave velocity profiles and shows locally good agreement with the few existing velocity profile data, but allows the entire area, as well as deeper parts of the basin, to be represented in greater detail. The wealth of available data allowed further to check if any correlation between the shear wave velocity in the uppermost 30 m (vs30) and the slope of topography, a new technique recently proposed by Wald and Allen (2007), exists on a local scale. While one lithology might provide a greater scatter in the velocity values for the investigated area, almost no correlation between topographic gradient and calculated vs30 exists, whereas a better link is found between vs30 and the local geology. When comparing the vs30 distribution with the MSK intensities for the 1985 Valparaiso event it becomes clear that high intensities are found where the expected vs30 values are low and over a thick sedimentary cover. Although this evidence cannot be generalized for all possible earthquakes, it indicates the influence of site effects modifying the ground motion when earthquakes occur well outside of the Santiago basin. Using the attained knowledge on the basin characteristics, simulations of strong ground motion within the Santiago Metropolitan area were carried out by means of the spectral element technique. The simulation of a regional event, which has also been recorded by a dense network installed in the city of Santiago for recording aftershock activity following the 27 February 2010 Maule earthquake, shows that the model is capable to realistically calculate ground motion in terms of amplitude, duration, and frequency and, moreover, that the surface topography and the shape of the sediment bedrock interface strongly modify ground motion in the Santiago basin. An examination on the dependency of ground motion on the hypocenter location for a hypothetical event occurring along the active San Ramón fault, which is crossing the eastern outskirts of the city, shows that the unfavorable interaction between fault rupture, radiation mechanism, and complex geological conditions in the near-field may give rise to large values of peak ground velocity and therefore considerably increase the level of seismic risk for Santiago de Chile.
The widespread usage of products containing volatile organic compounds (VOC) has lead to a general human exposure to these chemicals in work places or homes being suspected to contribute to the growing incidence of environmental diseases. Since the causal molecular mechanisms for the development of these disorders are not completely understood, the overall objective of this thesis was to investigate VOC-mediated molecular effects on human lung cells in vitro at VOC concentrations comparable to exposure scenarios below current occupational limits. Although differential expression of single proteins in response to VOCs has been reported, effects on complex protein networks (proteome) have not been investigated. However, this information is indispensable when trying to ascertain a mechanism for VOC action on the cellular level and establishing preventive strategies. For this study, the alveolar epithelial cell line A549 has been used. This cell line, cultured in a two-phase (air/liquid) model allows the most direct exposure and had been successfully applied for the analysis of inflammatory effects in response to VOCs. Mass spectrometric identification of 266 protein spots provided the first proteomic map of A549 cell line to this extent that may foster future work with this frequently used cellular model. The distribution of three typical air contaminants, monochlorobenzene (CB), styrene and 1,2 dichlorobenzene (1,2-DCB), between gas and liquid phase of the exposure model has been analyzed by gas chromatography. The obtained VOC partitioning was in agreement with available literature data. Subsequently the adapted in vitro system has been successfully employed to characterize the effects of the aromatic compound styrene on the proteome of A549 cells (Chapter 4). Initially, the cell toxicity has been assessed in order to ensure that most of the concentrations used in the following proteomic approach were not cytotoxic. Significant changes in abundance and phosphorylation in the total soluble protein fraction of A549 cells have been detected following styrene exposure. All proteins have been identified using mass spectrometry and the main cellular functions have been assigned. Validation experiments on protein and transcript level confirmed the results of the 2-DE experiments. From the results, two main cellular pathways have been identified that were induced by styrene: the cellular oxidative stress response combined with moderate pro-apoptotic signaling. Measurement of cellular reactive oxygen species (ROS) as well as the styrene-mediated induction of oxidative stress marker proteins confirmed the hypothesis of oxidative stress as the main molecular response mechanism. Finally, adducts of cellular proteins with the reactive styrene metabolite styrene 7,8 oxide (SO) have been identified. Especially the SO-adducts observed at both the reactive centers of thioredoxin reductase 1, which is a key element in the control of the cellular redox state, may be involved in styrene-induced ROS formation and apoptosis. A similar proteomic approach has been carried out with the halobenzenes CB and 1,2-DCB (Chapter 5). In accordance with previous findings, cell toxicity assessment showed enhanced toxicity compared to the one caused by styrene. Significant changes in abundance and phosphorylation of total soluble proteins of A549 cells have been detected following exposure to subtoxic concentrations of CB and 1,2-DCB. All proteins have been identified using mass spectrometry and the main cellular functions have been assigned. As for the styrene experiment, the results indicated two main pathways to be affected in the presence of chlorinated benzenes, cell death signaling and oxidative stress response. The strong induction of pro-apoptotic signaling has been confirmed for both treatments by detection of the cleavage of caspase 3. Likewise, the induction of redox-sensitive protein species could be correlated to an increased cellular level of ROS observed following CB treatment. Finally, common mechanisms in the cellular response to aromatic VOCs have been investigated (Chapter 6). A similar number (4.6-6.9%) of all quantified protein spots showed differential expression (p<0.05) following cell exposure to styrene, CB or 1,2-DCB. However, not more than three protein spots showed significant regulation in the same direction for all three volatile compounds: voltage-dependent anion-selective channel protein 2, peroxiredoxin 1 and elongation factor 2. However, all of these proteins are important molecular targets in stress- and cell death-related signaling pathways.