Local scale air quality model with several pollutant sources

[EN]This paper shows a finite element method for pollutant transport with several pollutant sources. An Eulerian convection–diffusion–reaction model to simulate the pollutant dispersion is used. The discretization of the different sources allows to impose the emissions as boundary conditions. The Eulerian description can deal with the coupling of several plumes. An adaptive stabilized finite element formulation, specifically Least-Squares, with a Crank-Nicolson temporal integration is proposed to solve the problem. An splitting scheme has been used to treat separately the transport and the reaction. A mass-consistent model has been used to compute the wind field of the problem…

Knowledge Flows and Networks: the Interplay between Local and Global Linkages within Bangalore IT Cluster

This doctoral work gains deeper insight into the dynamics of knowledge flows within and across clusters, unfolding their features, directions and strategic implications. Alliances, networks and personnel mobility are acknowledged as the three main channels of inter-firm knowledge flows, thus offering three heterogeneous measures to analyze the phenomenon. The interplay between the three channels and the richness of available research methods, has allowed for the elaboration of three different papers and perspectives. The common empirical setting is the IT cluster in Bangalore, for its distinguished features as a high-tech cluster and for its steady yearly two-digit growth around the service-based business model. The first paper deploys both a firm-level and a tie-level analysis, exploring the cases of 4 domestic companies and of 2 MNCs active the cluster, according to a cluster-based perspective. The distinction between business-domain knowledge and technical knowledge emerges from the qualitative evidence, further confirmed by quantitative analyses at tie-level. At firm-level, the specialization degree seems to be influencing the kind of knowledge shared, while at tie-level both the frequency of interaction and the governance mode prove to determine differences in the distribution of knowledge flows. The second paper zooms out and considers the inter-firm networks; particularly focusing on the role of cluster boundary, internal and external networks are analyzed, in their size, long-term orientation and exploration degree. The research method is purely qualitative and allows for the observation of the evolving strategic role of internal network: from exploitation-based to exploration-based. Moreover, a causal pattern is emphasized, linking the evolution and features of the external network to the evolution and features of internal network. The final paper addresses the softer and more micro-level side of knowledge flows: personnel mobility. A social capital perspective is here developed, which considers both employees’ acquisition and employees’ loss as building inter-firm ties, thus enhancing company’s overall social capital. Negative binomial regression analyses at dyad-level test the significant impact of cluster affiliation (cluster firms vs non-cluster firms), industry affiliation (IT firms vs non-IT fims) and foreign affiliation (MNCs vs domestic firms) in shaping the uneven distribution of personnel mobility, and thus of knowledge flows, among companies.

Spatial and temporal variation in settlement, growth and condition of the rockfish species Sebastes caurinus and Sebastes carnatus in the Channel Islands region, Santa Barbara, CA

Survival during the early life stages of marine species, including nearshore temperate reef fishes, is typically very low, and small changes in mortality rates, due to physiological and environmental conditions, can have marked effects on survival of a cohort and, on a larger scale, on the success of a recruitment season. Moreover, trade offs between larval growth and accumulation of energetic resources prior to settlement are likely to influence growth and survival until this critical period and afterwards. Rockfish recruitment rates are notoriously variable between years and across geographic locations. Monitoring of rates of onshore delivery of pelagic juveniles (defined here as settlement) of two species of nearshore rockfishes, Sebastes caurinus and Sebastes carnatus, was done between 2003-2009 years using artificial collectors placed at San Miguel and Santa Cruz Island, off Southern California coast. I investigated spatiotemporal variation in settlement rate, lipid content, pelagic larval duration and larval growth of the newly settled fishes; I assessed relationships between birth date, larval growth, early life-history characteristics and lipid content at settlement, considering also interspecific differences; finally, I attempt to relate interannual patterns of settlement and of early life history traits to easily accessible, local and regional indices of ocean conditions including in situ ocean temperature and regional upwelling, sea surface temperature (SST) and Chlorophyll-a (Chl-a) concentration. Spatial variations appeared to be of low relevance, while significant interannual differences were detected in settlement rate, pelagic larval duration and larval growth. The amount of lipid content of the newly settled fishes was highly variable in space and time, but did not differ between the two species and did not show any relationships with early life history traits, indicating that no trade off involved these physiological processes or they were masked by high individual variability in different periods of larval life. Significant interspecific differences were found in the timing of parturition and settlement and in larval growth rates, with S. carnatus growing faster and breeding and settling later than S. caurinus. The two species exhibited also different patterns of correlations between larval growth rates and larval duration. S. carnatus larval duration was longer when the growth in the first two weeks post-hatch was faster, while S. caurinus had a shorter larval duration when grew fast in the middle and in the end of larval life, suggesting different larval strategies. Fishes with longer larval durations were longer in size at settlement and exhibited longer planktonic phase in periods of favourable environmental conditions. Ocean conditions had a low explanatory power for interannual variation in early life history traits, but a very high explanatory power for settlement fluctuations, with regional upwelling strength being the principal indicator. Nonetheless, interannual variability in larval duration and growth were related to great phenological changes in upwelling happened during the period of this study and that caused negative consequences at all trophic levels along the California coast. Despite the low explanatory power of the environmental variables used in this study on the variation of larval biological traits, environmental processes were differently related with early life history characteristics analyzed to species, indicating possible species-specific susceptibility to ocean conditions and local environmental adaptation, which should be further investigated. These results have implications for understanding the processes influencing larval and juvenile survival, and consequently recruitment variability, which may be dependent on biological characteristics and environmental conditions.

Spatio-temporal variation of macrofaunal assemblages in the deep Blanes submarine canyon

The spatio-temporal variations in diversity and abundance of deep-sea macrofaunal assemblages (excluding meiofaunal taxa, as Nematoda, Copepoda and Ostracoda) from the Blanes Canyon (BC) and adjacent open slope are described. The Catalan Sea basin is characterized by the presence of numerous submarine canyons, which are globally acknowledged as biodiversity hot-spots, due to their disturbance regime and incremented conveying of organic matter. This area is subjected to local deep-sea fisheries activities, and to recurrent cold water cascading events from the shelf. The upper canyon (~900 m), middle slope (~1200 m) and lower slope (~1500 m) habitats were investigated during three different months (October 2008, May 2009 and September 2009). A total of 624 specimens belonging to 16 different taxa were found into 67 analyzed samples, which had been collected from the two study areas. Of these, Polychaeta, Mollusca and Crustacea were always the most abundant groups. As expected, the patterns of species diversity and evenness were different in time and space. Both in BC and open slope, taxa diversity and abundance are higher in the shallowest depth and lowest at -1500 m depth. This is probably due to different trophic regimes at these depths. The abundance of filter-feeders is higher inside BC than in the adjacent open slope, which is also related with an increment of predator polychaetes. Surface deposit-feeders are more abundant in the open slope than in BC, along with a decrement of filter-feeders and their predators. Probably these differences are due to higher quantities of suspended organic matter reaching the canyon. The multivariate analyses conducted on major taxa point out major differences effective taxa richness between depths and stations. In September 2009 the analyzed communities double their abundances, with a corresponding increase in richness of taxa. This could be related to a mobilizing event, like the release of accumulated food-supply in a nepheloid layer associated to the arrival of autumn. The highest abundance in BC is detected in the shallowest depth and in late summer (September), probably due to higher food availability caused by stronger flood events coming from Tordera River. The effects of such events seemed to involve adjacent open slope too. The nMDS conducted on major taxa abundance shows a slight temporal difference between the three campaigns samples, with a clear clustering between samples of Sept 09. All depth and all months were dominated by Polychaeta, which have been identified to family level and submitted to further analysis. Family richness have clearly minimum at the -1200 m depth of BC, highlighting the presence of a general impact affecting the populations in the middle slope. Three different matrices have been created, each with a different taxonomic level (All Taxa “AT”, Phylum Level “PL” and Polychaeta Families “PF”). Multivariate analysis (MDS, SIMPER) conducted on PL matrix showed a clear spatial differences between stations (BC and open slope) and depths. MDSs conducted on other two matrices (AT and PF) showed similar patterns, but different from PL analysis. A 2 nd stage analysis have been conducted to understand differences between different taxonomic levels, and PL level has been chosen as the most representative of variation. The faunal differences observed were explained by depth, station and season. All work has been accomplished in the Centre d’estudis avançats de Blanes (CEAB-CSIC), within the framework of Spanish PROMETEO project "Estudio Integrado de Cañones y Taludes PROfundos del MEdiTErráneo Occidental: un hábitat esencial", Ref. CTM2007-66316-C02- 01/MAR.

Development of a multi-species method by GC-coupling with inductively coupled plasma isotope dilution mass spectrometry for the simultaneous determination of alkylated lead, mercury and tin compounds

An accurate and sensitive species-specific GC-ICP-IDMS (gas chromatography inductively coupled plasma isotope dilution mass spectrometry) method for the determination of trimethyllead and a multi-species-specific GC-ICP-IDMS method for the simultaneous determination of trimethyllead, methylmercury, and butyltins in biological and environmental samples were developed. They allow the determination of corresponding elemental species down to the low ng g-1 range. The developed synthesis scheme for the formation of isotopically labeled Me3206Pb+ can be used for future production of this spike. The novel extraction technique, stir bar sorptive extraction (SBSE), was applied for the first time in connection with species-specific isotope dilution GC-ICP-MS for the determination of trimethyllead, methylmercury and butyltins. The results were compared with liquid-liquid extraction. The developed methods were validated by the analysis of certified reference materials. The liquid-liquid extraction GC-ICP-IDMS method was applied to seafood samples purchased from a supermarket. The methylated lead fraction in these samples, correlated to total lead, varied in a broad range of 0.01-7.6 %. On the contrary, the fraction of methylmercury is much higher, normally in the range of 80-98 %. The highest methylmercury content of up to 12 µg g-1 has been determined in shark samples, an animal which is at the end of the marine food chain, whereas in other seafood samples a MeHg+ content of less than 0.2 µg g-1 was found. Butyltin species could only be determined in samples, where anthropogenic contaminations must be assumed. This explains the observed broad variation of the butylated tin fraction in the range of <0.3-49 % in different seafood samples. Because all isotope-labelled spike compounds, except trimethyllead, are commercially available, the developed multi-species-specific GC-ICP-IDMS method has a high potential in future for routine analysis.

Photoemissions-Elektronenmikroskopie an Adsorbatsystemen

Die Photoemissions-Elektronenmikroskopie ist eine hervorragend geeignete Methode zur Untersuchung dynamischer Vorgänge auf realen polykristallinen Oberflächen im sub-μm Bereich. Bei der Anwendung auf Adsorbatsysteme lassen sich geringe Bedeckungsunterschiede, sowie Adsorbatstrukturen und -phasen unterscheiden. Die Methode erlaubt dabei ein breites Anwendungsspektrum über weite Temperaturbereiche und Systeme unterschiedlichster Bindungsenergie. Bei der Chemisorption von Sauerstoff auf polykristallinen Metallen wird unterschiedliches Aufwachsverhalten in den Helligkeitswerten im Mikroskopbild widergespiegelt. Bei Kupferproben zeigen Oberflächen mit unterschiedlicher kristalliner Richtung aufgrund der Symmetrie des fcc-Gitters ein ähnliches Verhalten. Das hexagonale Gitter des Titans zeigt dagegen große Unterschiede im Adsorptionsverhalten in Abhängigkeit der kristallinen Richtung. Diese Unterschiede konnten auf verschiedene Haftkoeffizienten und Oxidationsstufen der Metalle zurückgeführt werden. In einem Modell zur Photostromanalyse konnte beim Kupfer der Übergang von verschiedenen Überstrukturen bei wachsender Bedeckung gezeigt und die Übergänge ermittelt werden.. Auf den Titanoberflächen wurde so das Wachstum der Oxide TiO, TiO₂ und Ti₂O₃ unterschieden und die Übergänge des unterschiedlichen Wachstums ermittelt. Bei der thermischen Desorption der Schichten konnten unterschiedliche Haftkoeffizient auf einzelnen Kristalliten qualitativ gezeigt werden. Diese erstmalig eingesetzte Analysemethode weist Ähnlichkeiten zur Thermo-Desorptions-Spektroskopie (TDS) auf, zeigt jedoch ortsaufgelöst lokale Unterschiede auf polykristallinen Oberflächen. Bei thermisch gestützten Oberflächenreaktionen ließen sich die Reaktionskeime deutlich identifizieren und mit einer Grauwertanalyse konnte die Oxidation der karbidischen Lagen zu Kohlenmonoxid und die Metalloxidation unterschieden werden. Dabei konnte gezeigt werden, daß die Reaktionskeime nur an Plattengrenzen auftreten, nicht jedoch auf der Oberfläche. Durch die Aufrauhung der Plattengrenzen mit zunehmender Reaktionsdauer nimmt die Zahl der Reaktionskeime kontinuierlich zu, die laterale Ausdehnung der Einzelreaktionen bleibt aber konstant. Bei der Physisorption von Xenon auf Graphit wurde erstmals für die Photoemissionsmikroskopie die resonanten Anregung ausgenutzt. Die verschiedenen Phasen des Adsorbats können dabei deutlich unterschieden werden; bei niedrigen Temperaturen (40K) findet ein gleichmäßiges Wachstum auf der gesamten Oberfläche statt, bei höheren Temperaturen von 60-65K ist dagegen ein Inselwachstum in verschiedenen Phasen zu beobachten. Die zeitliche Entwicklung des Wachstums, die örtliche Lage der Phasen und die Phasenübergänge (gas, fest inkommensurabel, fest kommensurabel) konnten bestimmt werden. Bei der Desorption der Schichten konnten die einzelnen Phasen ebenfalls getrennt werden und das unterschiedliche Desorptionsverhalten sowie die Phasenübergänge selber verifiziert werden.

Query rewriting in information retrieval: automatic context extraction from local user documents to improve query results

The central objective of research in Information Retrieval (IR) is to discover new techniques to retrieve relevant information in order to satisfy an Information Need. The Information Need is satisfied when relevant information can be provided to the user. In IR, relevance is a fundamental concept which has changed over time, from popular to personal, i.e., what was considered relevant before was information for the whole population, but what is considered relevant now is specific information for each user. Hence, there is a need to connect the behavior of the system to the condition of a particular person and his social context; thereby an interdisciplinary sector called Human-Centered Computing was born. For the modern search engine, the information extracted for the individual user is crucial. According to the Personalized Search (PS), two different techniques are necessary to personalize a search: contextualization (interconnected conditions that occur in an activity), and individualization (characteristics that distinguish an individual). This movement of focus to the individual's need undermines the rigid linearity of the classical model overtaken the ``berry picking'' model which explains that the terms change thanks to the informational feedback received from the search activity introducing the concept of evolution of search terms. The development of Information Foraging theory, which observed the correlations between animal foraging and human information foraging, also contributed to this transformation through attempts to optimize the cost-benefit ratio. This thesis arose from the need to satisfy human individuality when searching for information, and it develops a synergistic collaboration between the frontiers of technological innovation and the recent advances in IR. The search method developed exploits what is relevant for the user by changing radically the way in which an Information Need is expressed, because now it is expressed through the generation of the query and its own context. As a matter of fact the method was born under the pretense to improve the quality of search by rewriting the query based on the contexts automatically generated from a local knowledge base. Furthermore, the idea of optimizing each IR system has led to develop it as a middleware of interaction between the user and the IR system. Thereby the system has just two possible actions: rewriting the query, and reordering the result. Equivalent actions to the approach was described from the PS that generally exploits information derived from analysis of user behavior, while the proposed approach exploits knowledge provided by the user. The thesis went further to generate a novel method for an assessment procedure, according to the "Cranfield paradigm", in order to evaluate this type of IR systems. The results achieved are interesting considering both the effectiveness achieved and the innovative approach undertaken together with the several applications inspired using a local knowledge base.

Method development using ICP-MS and LA-ICP-MS and their application in environmental and material science

Within this PhD thesis several methods were developed and validated which can find applicationare suitable for environmental sample and material science and should be applicable for monitoring of particular radionuclides and the analysis of the chemical composition of construction materials in the frame of ESS project. The study demonstrated that ICP-MS is a powerful analytical technique for ultrasensitive determination of 129I, 90Sr and lanthanides in both artificial and environmental samples such as water and soil. In particular ICP-MS with collision cell allows measuring extremely low isotope ratios of iodine. It was demonstrated that isotope ratios of 129I/127I as low as 10-7 can be measured with an accuracy and precision suitable for distinguishing sample origins. ICP-MS with collision cell, in particular in combination with cool plasma conditions, reduces the influence of isobaric interferences on m/z = 90 and is therefore well-suited for 90Sr analysis in water samples. However, the applied ICP-CC-QMS in this work is limited for the measurement of 90Sr due to the tailing of 88Sr+ and in particular Daly detector noise. Hyphenation of capillary electrophoresis with ICP-MS was shown to resolve atomic ions of all lanthanides and polyatomic interferences. The elimination of polyatomic and isobaric ICP-MS interferences was accomplished without compromising the sensitivity by the use of a high resolution mode as available on ICP-SFMS. Combination of laser ablation with ICP-MS allowed direct micro and local uranium isotope ratio measurements at the ultratrace concentrations on the surface of biological samples. In particular, the application of a cooled laser ablation chamber improves the precision and accuracy of uranium isotopic ratios measurements in comparison to the non-cooled laser ablation chamber by up to one order of magnitude. In order to reduce the quantification problem, a mono gas on-line solution-based calibration was built based on the insertion of a microflow nebulizer DS-5 directly into the laser ablation chamber. A micro local method to determine the lateral element distribution on NiCrAlY-based alloy and coating after oxidation in air was tested and validated. Calibration procedures involving external calibration, quantification by relative sensitivity coefficients (RSCs) and solution-based calibration were investigated. The analytical method was validated by comparison of the LA-ICP-MS results with data acquired by EDX.

A Phase Space Box-counting based Method for Arrhythmia Prediction from Electrocardiogram Time Series

Arrhythmia is one kind of cardiovascular diseases that give rise to the number of deaths and potentially yields immedicable danger. Arrhythmia is a life threatening condition originating from disorganized propagation of electrical signals in heart resulting in desynchronization among different chambers of the heart. Fundamentally, the synchronization process means that the phase relationship of electrical activities between the chambers remains coherent, maintaining a constant phase difference over time. If desynchronization occurs due to arrhythmia, the coherent phase relationship breaks down resulting in chaotic rhythm affecting the regular pumping mechanism of heart. This phenomenon was explored by using the phase space reconstruction technique which is a standard analysis technique of time series data generated from nonlinear dynamical system. In this project a novel index is presented for predicting the onset of ventricular arrhythmias. Analysis of continuously captured long-term ECG data recordings was conducted up to the onset of arrhythmia by the phase space reconstruction method, obtaining 2-dimensional images, analysed by the box counting method. The method was tested using the ECG data set of three different kinds including normal (NR), Ventricular Tachycardia (VT), Ventricular Fibrillation (VF), extracted from the Physionet ECG database. Statistical measures like mean (μ), standard deviation (σ) and coefficient of variation (σ/μ) for the box-counting in phase space diagrams are derived for a sliding window of 10 beats of ECG signal. From the results of these statistical analyses, a threshold was derived as an upper bound of Coefficient of Variation (CV) for box-counting of ECG phase portraits which is capable of reliably predicting the impeding arrhythmia long before its actual occurrence. As future work of research, it was planned to validate this prediction tool over a wider population of patients affected by different kind of arrhythmia, like atrial fibrillation, bundle and brunch block, and set different thresholds for them, in order to confirm its clinical applicability.

Local Earthquake Tomography by trans-dimensional Monte Carlo Sampling

In this study a new, fully non-linear, approach to Local Earthquake Tomography is presented. Local Earthquakes Tomography (LET) is a non-linear inversion problem that allows the joint determination of earthquakes parameters and velocity structure from arrival times of waves generated by local sources. Since the early developments of seismic tomography several inversion methods have been developed to solve this problem in a linearized way. In the framework of Monte Carlo sampling, we developed a new code based on the Reversible Jump Markov Chain Monte Carlo sampling method (Rj-McMc). It is a trans-dimensional approach in which the number of unknowns, and thus the model parameterization, is treated as one of the unknowns. I show that our new code allows overcoming major limitations of linearized tomography, opening a new perspective in seismic imaging. Synthetic tests demonstrate that our algorithm is able to produce a robust and reliable tomography without the need to make subjective a-priori assumptions about starting models and parameterization. Moreover it provides a more accurate estimate of uncertainties about the model parameters. Therefore, it is very suitable for investigating the velocity structure in regions that lack of accurate a-priori information. Synthetic tests also reveal that the lack of any regularization constraints allows extracting more information from the observed data and that the velocity structure can be detected also in regions where the density of rays is low and standard linearized codes fails. I also present high-resolution Vp and Vp/Vs models in two widespread investigated regions: the Parkfield segment of the San Andreas Fault (California, USA) and the area around the Alto Tiberina fault (Umbria-Marche, Italy). In both the cases, the models obtained with our code show a substantial improvement in the data fit, if compared with the models obtained from the same data set with the linearized inversion codes.

Thermal fluctuations and boundary conditions in the lattice Boltzmann method

The lattice Boltzmann method is a popular approach for simulating hydrodynamic interactions in soft matter and complex fluids. The solvent is represented on a discrete lattice whose nodes are populated by particle distributions that propagate on the discrete links between the nodes and undergo local collisions. On large length and time scales, the microdynamics leads to a hydrodynamic flow field that satisfies the Navier-Stokes equation. In this thesis, several extensions to the lattice Boltzmann method are developed. In complex fluids, for example suspensions, Brownian motion of the solutes is of paramount importance. However, it can not be simulated with the original lattice Boltzmann method because the dynamics is completely deterministic. It is possible, though, to introduce thermal fluctuations in order to reproduce the equations of fluctuating hydrodynamics. In this work, a generalized lattice gas model is used to systematically derive the fluctuating lattice Boltzmann equation from statistical mechanics principles. The stochastic part of the dynamics is interpreted as a Monte Carlo process, which is then required to satisfy the condition of detailed balance. This leads to an expression for the thermal fluctuations which implies that it is essential to thermalize all degrees of freedom of the system, including the kinetic modes. The new formalism guarantees that the fluctuating lattice Boltzmann equation is simultaneously consistent with both fluctuating hydrodynamics and statistical mechanics. This establishes a foundation for future extensions, such as the treatment of multi-phase and thermal flows. An important range of applications for the lattice Boltzmann method is formed by microfluidics. Fostered by the "lab-on-a-chip" paradigm, there is an increasing need for computer simulations which are able to complement the achievements of theory and experiment. Microfluidic systems are characterized by a large surface-to-volume ratio and, therefore, boundary conditions are of special relevance. On the microscale, the standard no-slip boundary condition used in hydrodynamics has to be replaced by a slip boundary condition. In this work, a boundary condition for lattice Boltzmann is constructed that allows the slip length to be tuned by a single model parameter. Furthermore, a conceptually new approach for constructing boundary conditions is explored, where the reduced symmetry at the boundary is explicitly incorporated into the lattice model. The lattice Boltzmann method is systematically extended to the reduced symmetry model. In the case of a Poiseuille flow in a plane channel, it is shown that a special choice of the collision operator is required to reproduce the correct flow profile. This systematic approach sheds light on the consequences of the reduced symmetry at the boundary and leads to a deeper understanding of boundary conditions in the lattice Boltzmann method. This can help to develop improved boundary conditions that lead to more accurate simulation results.

New regularization method for EXAFS analysis: Application to uranium and plutonium sorption onto kaolinite

Die Röntgenabsorptionsspektroskopie (Extended X-ray absorption fine structure (EXAFS) spectroscopy) ist eine wichtige Methode zur Speziation von Schwermetallen in einem weiten Bereich von umweltrelevanten Systemen. Um Strukturparameter wie Koordinationszahl, Atomabstand und Debye-Waller Faktoren für die nächsten Nachbarn eines absorbierenden Atoms zu bestimmen, ist es für experimentelle EXAFS-Spektren üblich, unter Verwendung von Modellstrukturen einen „Least-Squares-Fit“ durchzuführen. Oft können verschiedene Modellstrukturen mit völlig unterschiedlicher chemischer Bedeutung die experimentellen EXAFS-Daten gleich gut beschreiben. Als gute Alternative zum konventionellen Kurven-Fit bietet sich das modifizierte Tikhonov-Regularisationsverfahren an. Ergänzend zur Tikhonov-Standardvariationsmethode enthält der in dieser Arbeit vorgestellte Algorithmus zwei weitere Schritte, nämlich die Anwendung des „Method of Separating Functionals“ und ein Iterationsverfahren mit Filtration im realen Raum. Um das modifizierte Tikhonov-Regularisationsverfahren zu testen und zu bestätigen wurden sowohl simulierte als auch experimentell gemessene EXAFS-Spektren einer kristallinen U(VI)-Verbindung mit bekannter Struktur, nämlich Soddyit (UO2)2SiO4 x 2H2O, untersucht. Die Leistungsfähigkeit dieser neuen Methode zur Auswertung von EXAFS-Spektren wird durch ihre Anwendung auf die Analyse von Proben mit unbekannter Struktur gezeigt, wie sie bei der Sorption von U(VI) bzw. von Pu(III)/Pu(IV) an Kaolinit auftreten. Ziel der Dissertation war es, die immer noch nicht voll ausgeschöpften Möglichkeiten des modifizierten Tikhonov-Regularisationsverfahrens für die Auswertung von EXAFS-Spektren aufzuzeigen. Die Ergebnisse lassen sich in zwei Kategorien einteilen. Die erste beinhaltet die Entwicklung des Tikhonov-Regularisationsverfahrens für die Analyse von EXAFS-Spektren von Mehrkomponentensystemen, insbesondere die Wahl bestimmter Regularisationsparameter und den Einfluss von Mehrfachstreuung, experimentell bedingtem Rauschen, etc. auf die Strukturparameter. Der zweite Teil beinhaltet die Speziation von sorbiertem U(VI) und Pu(III)/Pu(IV) an Kaolinit, basierend auf experimentellen EXAFS-Spektren, die mit Hilfe des modifizierten Tikhonov-Regularisationsverfahren ausgewertet und mit Hilfe konventioneller EXAFS-Analyse durch „Least-Squares-Fit“ bestätigt wurden.

Local Trigonometric Methods for Time Series Smoothing.

The thesis is concerned with local trigonometric regression methods. The aim was to develop a method for extraction of cyclical components in time series. The main results of the thesis are the following. First, a generalization of the filter proposed by Christiano and Fitzgerald is furnished for the smoothing of ARIMA(p,d,q) process. Second, a local trigonometric filter is built, with its statistical properties. Third, they are discussed the convergence properties of trigonometric estimators, and the problem of choosing the order of the model. A large scale simulation experiment has been designed in order to assess the performance of the proposed models and methods. The results show that local trigonometric regression may be a useful tool for periodic time series analysis.

Seismic tomographic full-waveform inversion for the Vrancea sinking lithosphere structure using the adjoint method.

The Vrancea region, at the south-eastern bend of the Carpathian Mountains in Romania, represents one of the most puzzling seismically active zones of Europe. Beside some shallow seismicity spread across the whole Romanian territory, Vrancea is the place of an intense seismicity with the presence of a cluster of intermediate-depth foci placed in a narrow nearly vertical volume. Although large-scale mantle seismic tomographic studies have revealed the presence of a narrow, almost vertical, high-velocity body in the upper mantle, the nature and the geodynamic of this deep intra-continental seismicity is still questioned. High-resolution seismic tomography could help to reveal more details in the subcrustal structure of Vrancea. Recent developments in computational seismology as well as the availability of parallel computing now allow to potentially retrieve more information out of seismic waveforms and to reach such high-resolution models. This study was aimed to evaluate the application of a full waveform inversion tomography at regional scale for the Vrancea lithosphere using data from the 1999 six months temporary local network CALIXTO. Starting from a detailed 3D Vp, Vs and density model, built on classical travel-time tomography together with gravity data, I evaluated the improvements obtained with the full waveform inversion approach. The latter proved to be highly problem dependent and highly computational expensive. The model retrieved after the first two iterations does not show large variations with respect to the initial model but remains in agreement with previous tomographic models. It presents a well-defined downgoing slab shape high velocity anomaly, composed of a N-S horizontal anomaly in the depths between 40 and 70km linked to a nearly vertical NE-SW anomaly from 70 to 180km.

Genetic and morphological variation and differentiation of Raja clavata populations in the European seas: marker development and preliminary data

In this study the population structure and connectivity of the Mediterranean and Atlantic Raja clavata (L., 1758) were investigated by analyzing the genetic variation of six population samples (N = 144) at seven nuclear microsatellite loci. The genetic dataset was generated by selecting population samples available in the tissue databases of the GenoDREAM laboratory (University of Bologna) and of the Department of Life Sciences and Environment (University of Cagliari), all collected during past scientific surveys (MEDITS, GRUND) from different geographical locations in the Mediterranean basin and North-east Atlantic sea, as North Sea, Sardinian coasts, Tuscany coasts and Cyprus Island. This thesis deals with to estimate the genetic diversity and differentiation among 6 geographical samples, in particular, to assess the presence of any barrier (geographic, hydrogeological or biological) to gene flow evaluating both the genetic diversity (nucleotide diversity, observed and expected heterozygosity, Hardy- Weinberg equilibrium analysis) and population differentiation (Fst estimates, population structure analysis). In addition to molecular analysis, quantitative representation and statistical analysis of morphological individuals shape are performed using geometric morphometrics methods and statistical tests. Geometric coordinates call landmarks are fixed in 158 individuals belonging to two population samples of Raja clavata and in population samples of closely related species, Raja straeleni (cryptic sibling) and Raja asterias, to assess significant morphological differences at multiple taxonomic levels. The results obtained from the analysis of the microsatellite dataset suggested a geographic and genetic separation between populations from Central-Western and Eastern Mediterranean basins. Furthermore, the analysis also showed that there was no separation between geographic samples from North Atlantic Ocean and central-Western Mediterranean, grouping them to a panmictic population. The Landmark-based geometric morphometry method results showed significant differences of body shape able to discriminate taxa at tested levels (from species to populations).