Dissertations / Theses on the topic 'EDAX analysis'

Els utillatges lítics tallats que van produir i emprar les comunitats de l’Edat del Bronze (II mil·lenni cal ANE) han sigut escassament o res estudiats al llarg de les investigacions realitzades fins el moment per tota la Península Ibérica. Pel cas del Nord-est, l’aparició de les primeres metal·lúrgies del Bronze ha sigut recurrentment assenyalat com la conseqüència de l'obsolescència de l'ús de instruments lítics tallats. No obstant això, els jaciments que s’analitzen en aquesta Tesis Doctoral aporten uns utillatges de sílex nombrosos sobre els quals es possible profunditzar en la seva caracterització. D’aquesta manera, es discuteix sobre el valor que van tenir ambdues tecnologies pel desenvolupament econòmic i social de tres dels jaciments més importants del Nord-est pel període tractat: Minferri (Juneda, Lleida), Mas d’En Boixos (Pacs del Penedés, Barcelona) i Moncín (Borja, Zaragoza). Per mitjà d’una metodologia interdisciplinar a la que s’integren anàlisis de procedència de matèries primes, anàlisis tecno-morfològiques i traceològiques, es possible fer-se una idea amplia del rol econòmic i social que va tenir l’utillatge lític tallat. Així es fa incidència a les estratègies de gestió del territori, el mode en que es van produir els instruments i en quines produccions domèstiques s’inclouen com a instruments de treball. Aquesta informació, i especialment a partir de l’anàlisi funcional, es possible obtenir hipòtesis sobre l’organització dels assentaments estudiats, i finalment, sobre l’impacte de la implantació de les primeres metal·lúrgies del Bronze a la vida quotidiana.<br>Los utillajes líticos tallados que produjeron y emplearon las comunidades de la Edad del Bronce (II milenio ANE) han sido escasamente o nada estudiados a lo largo de las investigaciones realizadas hasta el momento para toda la Península Ibérica. Para el caso del Nordeste, la aparición de las primeras metalurgias del Bronce, ha sido recurrentemente señalado como la consecuencia de la obsolescencia del uso de instrumentos líticos tallados. Sin embargo, los yacimientos que se analizan en esta Tesis Doctoral, aportan unos utillajes de sílex numerosos sobre los que es posible profundizar en su caracterización. De esta manera, se discute sobre el valor que tuvieron ambas tecnologías para el desarrollo económico y social de tres de los yacimientos más importantes del Nordeste para el periodo tratado: Minferri (Juneda, Lleida), Mas d’En Boixos (Pacs del Penedés, Barcelona) y Moncín (Borja, Zaragoza). Mediante una metodología interdisplinar, en la que se integran análisis de procedencia de materias primas, análisis tecno-morfológicos y traceológicos, es posible hacerse una idea amplia del rol económico y social que tubo el utillaje lítico tallado. Así, se hace hincapié en las estrategias de gestión del territorio, el modo en que se produjeron tales instrumentos y en que producciones domésticas se incluyeron como instrumentos de trabajo. Esta información, y especialmente a partir del análisis funcional, permite obtener hipótesis sobre la organización de los asentamientos estudiados, y finalmente, sobre el impacto de la implantación de las primeras metalurgias del Bronce en la vida cotidiana.<br>The chipped stone tools that were produced and used by the Bronze Age communities (II millennium BC) have been a little bit studied until today in the Iberian Peninsula archaeological research. In the case of the Northeast regions, the appearance of the first bronze metallurgy has been indicated as the consequence of the use obsolescence for the chipped stone tools. Nevertheless, the archaeological sites analysed in that PhD provide numerous lithic assemblies about which is possible to develop a broad characterization. In this manner, it is possible to discuss about the valour that both technologies had for the economic and social development in three of the most important archaeological sites of the Northeast in the treated period: Minferri (Juneda, Lleida), Mas d’En Boixos (Pacs del Penedés, Barcelona) and Moncín (Borja, Zaragoza). With a broad methodology which are integrated raw materials analysis, tecno-morphological analysis and microscopic use wear analysis is possible to obtain a broad knowledge about the social and economic role that the chipped stone tools had. This work focuses in the raw materials management in the territory, the lithic tools production procedures and in which domestic productions were included as working tools. This information, and specially through the functional analysis, allows to obtain some hypothesis about the settlement organization, and finally, about the impact of the first bronze metallurgy over the everyday people life.

This thesis considers the tasks involved in exploratory analysis of temporal graph data, and the visual techniques which are able to support these tasks. There has been an enormous increase in the amount and availability of graph (network) data, and in particular, graph data that is changing over time. Understanding the mechanisms involved in temporal change in a graph is of interest to a wide range of disciplines. While the application domain may differ, many of the underlying questions regarding the properties of the graph and mechanism of change are the same. The research area of temporal graph visualisation seeks to address the challenges involved in visually representing change in a graph over time. While most graph visualisation tools focus on static networks, recent research has been directed toward the development of temporal visualisation systems. By representing data using computer-generated graphical forms, Information Visualisation techniques harness human perceptual capabilities to recognise patterns, spot anomalies and outliers, and find relationships within the data. Interacting with these graphical representations allow individuals to explore large datasets and gain further insightinto the relationships between different aspects of the data. Visual approaches are particularly relevant for Exploratory Data Analysis (EDA), where the person performing the analysis may be unfamiliar with the data set, and their goal is to make new discoveries and gain insight through its exploration. However, designing visual systems for EDA can be difficult, as the tasks which a person may wish to carry out during their analysis are not always known at outset. Identifying and understanding the tasks involved in such a process has given rise to a number of task taxonomies which seek to elucidate the tasks and structure them in a useful way. While task taxonomies for static graph analysis exist, no suitable temporal graph taxonomy has yet been developed. The first part of this thesis focusses on the development of such a taxonomy. Through the extension and instantiation of an existing formal task framework for general EDA, a task taxonomy and a task design space are developed specifically for exploration of temporal graph data. The resultant task framework is evaluated with respect to extant classifications and is shown to address a number of deficiencies in task coverage in existing works. Its usefulness in both the design and evaluation processes is also demonstrated. Much research currently surrounds the development of systems and techniques for visual exploration of temporal graphs, but little is known about how the different types of techniques relate to one another and which tasks they are able to support. The second part of this thesis focusses on the possibilities in this area: a design spaceof the possible visual encodings for temporal graph data is developed, and extant techniques are classified into this space, revealing potential combinations of encodings which have not yet been employed. These may prove interesting opportunities for further research and the development of novel techniques. The third part of this work addresses the need to understand the types of analysis the different visual techniques support, and indeed whether new techniques are required. The techniques which are able to support the different task dimensions are considered. This task-technique mapping reveals that visual exploration of temporalgraph data requires techniques not only from temporal graph visualisation, but also from static graph visualisation and comparison, and temporal visualisation. A number of tasks which are unsupported or less-well supported, which could prove interesting opportunities for future research, are identified. The taxonomies, design spaces, and mappings in this work bring order to the range of potential tasks of interest when exploring temporal graph data and the assortmentof techniques developed to visualise this type of data, and are designed to be of use in both the design and evaluation of temporal graph visualisation systems.

EDS is a tool for quantitative and qualitative analysis of the materials. In electron microscopy, the energy of the electrons determines the depth of the region where the X-rays come from. By varying the energy of the electrons, the depth of the region where the X-rays come from can be changed. If a thin film is used as a specimen, different quantitative ratios of the elements for different electron energies can be obtained. Unique thickness of a specific film on a specific substrate gives unique energy-ratio diagram so the thickness of a thin film can be calculated by analyzing the fingerprints of the energy-ratio diagram of the EDS data obtained from the film.

L’objectif général de cette thèse concerne la mise en place et l’évaluation d’une approche de type effect directed analysis (EDA), couplant bioessais in vitro et analyses physico-chimiques, pour la caractérisation de la contamination des milieux aquatiques par les perturbateurs endocriniens (PE) et leur identification. De nouveaux outils in vitro ont été développés et intégrés à une approche multi-bioessais pour la détection de polluants émergents afin de permettre un large diagnostic de la contamination par les PE. Parmi eux, le bioessai basé sur le pregnane X receptor humain s’est avéré complémentaire des cibles classiquement étudiées (e.g. récepteurs des œstrogènes (ER), des androgènes (AR) ou des hydrocarbures aromatiques (AhR)). Combinés, ces bioessais ont permis de déterminer des profils intégrés de la contamination inédits dans le sédiment et les eaux de surface, mettant en lumière la nécessité de considérer d’autres cibles biologiques que ER et AhR et de s’intéresser à l’ensemble des compartiments du milieu aquatique pour une meilleure évaluation de la contamination. En particulier, l’utilisation combinée de ces nouveaux outils à des capteurs passifs de type POCIS (polar organic compound integrative sampler) s’est révélée pertinente pour évaluer la contamination de la colonne d’eau par des composés hydrosolubles. Enfin, une démarche EDA, intégrant ces bioessais et des méthodes physico-chimiques d’extraction et de fractionnement adaptées, a été validée pour l’identification des composés détectés. Son application sur deux sites soumis à des contaminations chimiques différentes (mixte urbaine/agricole et pharmaceutique) a permis d’évaluer la contribution des polluants cibles, dont les prioritaires, dans les réponses des bioessais et d’identifier de nouveaux PE<br>The aim of this thesis was to develop and to evaluate an effect directed analysis (EDA) approach, combining in vitro bioassays and chemical analysis for the characterization of aquatic systems contamination by endocrine disrupting chemicals (EDCs) and their identification. For integrative contamination assessment, new in vitro tools have been developed and evaluated for the detection of emerging pollutants, and then integrated in a multi-bioassays approach. In particular, the human pregnane X receptor (PXR) based bioassay provided further information on bioactive contaminants and thereby enhanced the environmental diagnostic as regard to classical biological target (e.g. estrogen (ER), androgen (AR) or aryl hydrocarbon receptors (AhR)). Such multi-receptors approach allowed determining novel integrative toxicity profiles in sediment and surface water. Overall, our results demonstrated the need to integrate other biological target than ER and AhR, and to assess contamination partitioning for a better hazard/risk assessment. For such purpose, combined use of polar organic compound integrative sampler and in vitro bioassays provided suitable tools to assess active hydrosoluble chemicals in surface water. Finally, in order to identify the compounds responsible for the detected activities, the multi-receptors approach has been integrated in EDA strategy applied to two river sites under different chemical pressures (urban/agricultural and pharmaceutical). To tackle this challenge, extraction and fractionation methods were developed and evaluated in order to encompass a diversity of active chemicals that are detected by in vitro bioassays. The EDA approach allowed determining partial contribution of priority pollutants in biological responses as well as the identification of new EDCs

En esta tesis se ha abordado el problema histórico de la estandardización cultural que caracteriza las fases finales de la Edad del Bronce. En particular, se han analizado diferentes fenómenos de expansión y adopción de innovación que tuvieron lugar en Europa en el segundo milenio a.C. Al abordar estos temas hemos decidido seguir un enfoque cuantitativo. Desde un punto de vista metodológico, el punto de partida ha sido el desarrollo de la base de datos EUBAR que recoge más de 1700 dataciones radiocarbónicas de contextos arqueológicos georreferenciados, definidos por un conjunto de variables de presencia/ausencia de algunos tipos funcionales. La región analizada abarca un área desde el Ebro hasta el río Danubio (NE de la Península Ibérica, sur de Francia, norte de Italia, Suiza, Austria y sur de Alemania); la horquilla cronológica va de 1750 a 750 a.C. El análisis crítico de cada datación, en relación a la información tafonómica y estratigráfica de cada muestra, representa la columna vertebral de la base de datos. El primer logro ha sido proporcionar un nuevo modelo cronológico basado en el análisis estadístico bayesiano de las dataciones 14C procedentes de contextos arqueológicos fiables ubicados en el norte de Italia y en el sur de Francia. Aunque el número de fechas fiables sigue siendo bajo, ha sido posible desarrollar cuatro modelos diferentes con el programa OxCal, dos contiguos y dos secuenciales. Centrándose en la estadística descriptiva, la cronología radiocarbónica del norte de Italia parece ser ligeramente más alta que la convencional, mientras que para el sur de Francia la cronología tradicional se ve confirmada por los modelos bayesianos. El segundo logro ha sido utilizar las dataciones recolectadas para averiguar la presencia de episodios de cambio demográfico en el área investigado entre 1800 y 800 a.C. A través del análisis de frecuencias de las fechas radiocarbónicas incluidas en la base de datos EUBAR hemos podido inferir la estacionariedad poblacional a escala macro del Danubio al Ebro. Por el contrario, las funciones de densidad de probabilidad acumulada y los histogramas de las medianas muestran la existencia de discontinuidades a nivel local. El tercer logro ha sido detectar tres fenómenos de adopción de innovación, que tuvieron lugar en el segundo milenio a.C., es decir, las necrópolis de incineración, las vasijas con asas de apéndice de botón y los cuchillos de metal. En particular, se ha podido observar que la adopción del ritual funerario de la cremación dentro del fenómeno de los Campos de Urnas siguió una tendencia exponencial positiva a escala macro con fechas de aparición diferentes en regiones diferentes. Asimismo, se ha podido modelizar la difusión en el espacio y en el tiempo de la adopción del nuevo ritual funerario. El resultado ha sido la existencia de un claro gradiente espacio-temporal de Este hacia Oeste, del Noroeste de la región alpina hacia el noreste de la Península Ibérica. La misma direccionalidad ha sido reconocida también para la adopción de las asas de apéndice de botón. Finalmente la tesis propone la arquitectura de un modelo basado en agentes para explicar los fenómenos de difusión y adopción de innovación en las primeras sociedades complejas.<br>In this thesis we have approached the historical problem of cultural standardization at the end of Bronze Age. In particular, we have analyzed phenomena of expansion and adoption of innovation which took place in the 2nd millennium BC in Europe. To tackle this issue, we have decided to follow a quantitative approach. From a methodological point of view, the starting point has been the development of the EUBAR database which collects more than 1700 14C dates of georeferenced archaeological contexts, defined by a set of variables of presence/absence of some functional types. The analyzed region embraces an area from the Ebro to the Danube River (namely, NE Iberian Peninsula, Southern France, Northern Italy, Switzerland, Austria and Southern Germany); the time-span is 1750-750 BC. The critical analysis of each dating, concerning the taphonomic and stratigraphic information of each sample, represents the backbone of the database. The first goal has been to propose a new chronological model based on Bayesian statistical analysis of 14C dates from reliable archaeological contexts in northern Italy and southern France. Although the number of reliable dates for macroscale research remains low, it has been possible to develop four different models with the software OxCal, two contiguous ones and two sequential ones. Focusing on descriptive statistics, the 14C chronology of northern Italy seemed to be slightly higher than the conventional one, while that of southern France is confirmed by the Bayesian models. In both cases, the results claim the absolute necessity of an increase in the amount of 14C dates from selected archaeological contexts. The second goal has been to model demographic continuities and discontinuities between 1800 and 800 BC; the last term is due to the “Hallstatt disaster”. Through the analysis of frecuency of radiocarbon dates collected in the EUBAR database we have infered population stationarity on a macro-scale from the Danube to the Ebro. On the contrary, summed probability calibrated distributions (SCPDs) and histograms of medians show that episodes of change express locally. The third goal has been to detect three phenomena of adoption of innovation which took place in the 2nd millennium BC, i.e. cremation burials, vases with handles with vertical expansion and metal knives. In particular we have been able to observe that the adoption of cremation rite within the Urnfield culture followed a positive exponential trend on a macro-scale with different beginnings in different regions. Such an assumption allowed modeling the spatio-temporal diffusion of cremation burials which has shown to be characterized by a clear east to west gradient from the North-Western Alpine region to the NE of Iberian Peninsula. The same east to west directivity has been recognized for vases with handles with vertical expansion. Eventually the thesis proposes the architecture of an Agent Based Model for explaining phenomena of diffusion and adoption of innovation in early complex societies.

It has long been known that chronic exposures to high concentrations of respirable coal mine dust can lead to the development of lung diseases such as Coal Worker's Pneumoconiosis, commonly referred to as "black lung", and silicosis. Since the mid-1990s, an alarming resurgence of diseases has been documented in central Appalachia, where underground mining often necessitates significant extraction of rock strata along with the thin seams of coal. These circumstances have prompted concern over if or how changing dust composition might be a factor in contemporary disease prevalence. Until now, the total mass concentration and quartz mass fraction of respirable dust have been regulated and monitored in US coal mines. Unfortunately, however, these two metrics alone do not paint a full picture of dust composition. Earlier work in the author's research group established a preliminary thermogravimetric analysis (TGA) method for coal mine dust. The method is intended to allow estimation of three key mass fractions of the dust from separate sources: coal from the coal strata being mined; non-carbonate minerals from the rock strata being mined or drilled; and carbonates that are primarly sourced from application of rock dust products to the mine floor or ribs. However, accuracy of the preliminary method was substantially limited by poor dust recovery from the fibrous filter media used for sample collection. This thesis includes two studies: The first study aims to establish an improved TGA method. It uses smooth polycarbonate (PC) filters for dust sampling and a modified thermal ramping routine. The method is verified using laboratory-generated respirable dust samples. In the second study, the improved TGA method is used to analyze 75 respirable mine dust samples, collected in 15 US mines. Replicate samples are also analyzed by scanning electron microscopy using energy dispersive X-ray (SEM-EDX). TGA and SEM-EDX results are compared to gain insights regarding the analytical methods and general trends in dust composition within and between mines.<br>Master of Science<br>It has long been known that chronic exposures to excessive respirable coal mine dust can lead to the development of lung diseases such as Coal Worker’s Pneumoconiosis (“Black Lung”) and silicosis. Disease rates in central Appalachia have shown an alarming and unexpected increase since the mid-1990s, despite declining dust concentrations evident from regulatory compliance monitoring data. Clearly, there is a need to better understand coal mine dust composition, which will require additional analytical methods. Thermogravimetric analysis (TGA) has been proposed as one possible method, because it should allow estimation of three key dust components from separate sources: coal from the coal strata being mined; non-carbonate minerals from the rock strata being mined or drilled; and carbonates from application of rock dust products to the mine floor and ribs. However, preliminary work with TGA showed limited accuracy, mostly due to sampling materials. In this thesis, two studies were performed. The first study aims to establish an improved TGA method using smooth, polycarbonate (PC) filters. The second study demonstrates the method on a large number of mine dust samples, and compares the results to those gained by an alternative method that uses electron microscopy.

This study investigates the tool wear of advanced PVD TiALN/TiN multilayer coated end mill inserts when dry and semi-dry machining 4340 low alloy medium carbon steel. A factorial design of experiment setup consisting of two levels of speed, three levels of feed, two levels of depth of cut, and two levels of cutting conditions (semi-dry and dry) was used for the study. The combination of cutting conditions that gave the best response for different components of cutting force, cutting power, surface roughness and tool life were determined using MANOVA & ANOVA analysis and Tukey comparison of means test using MINITAB statistical software package. From a study of the Energy Dispersive X ray (EDX) analysis and primary back scatter images obtained from the worn out crater surface of the insert, it was observed that diffusion wear prevailed under both dry and semi-dry machining conditions. A tool life model was developed using multiple regression analysis within the range of cutting conditions selected. A model for flank wear progression was also developed using mixed effects modeling technique using S Plus statistical software package. This technique takes into account between and within work piece variations during end milling and produces a very accurate model for tool wear progression. This is the first time application of the mixed effects modeling technique in metal cutting literature.

This thesis refers to Fe-based biodegradable materials and their potencial aplications in medicine, especially as temporary bone implants. This work generaly summaries aplications of biomaterial in medicine with more interest kept on biodegradable materials and their in-vivo corrosion. The experimental part refers to conduction of porous Fe-based materials with silica addition. The structure of prepared specimens is identified by EDX and XRD analysis. The imersion test and electrochemical studies were conducted to observe corrosion behaviour with respect to different concentration of silica. Potenciodynamic curves were obtained to determine corrosion potencial and corrosion current density of prepared samples.

La present tesi doctoral arqueològica neix de l'interès de l'estudi del territori i societat de les comunitats que van viure en el període de transició entre l'època clàssica i l'Alta Edat mitjana. La caiguda de l'Imperi Romà i la progressiva arribada de noves elits a la península Ibèrica suposarà tota una sèrie de canvis socials, econòmics i d'organització territorial que establiran en certa manera les bases sociopolítiques de l'època medieval. Aquest projecte pretén estudiar els canvis en les dinàmiques de poblament rural entre època romana i l'Alta Edat mitjana en zones del nord-oest de la conca del Duero a través de tècniques pròpies de l'Arqueologia del Paisatge com l'anàlisi arqueomorfològic. De la mateixa manera, es pretén aprofundir en els processos de transformació social, econòmica i política que es van desenvolupar en aquest període de transició entre època clàssica i medieval, per a la qual es documenten aparentment nous patrons d'ocupació de l'espai. El desenvolupament de la tesi incideix en diverses problemàtiques associades a aquest estudi, com el creixent interès pels processos de canvi i noves formes de gestió territorial en els últims segles del món romà, l'arqueologia dels espais agraris i dels despoblats, i finalment l'escassetat d'informació arqueològica en zones rurals especialment entre els segles *tardorromanos i altmedievals. Els resultats mostren la pervivència d'un paisatge tradicional, un sistema de comunicacions i distribució del poblament actual que s'ha configurat i modificat en diferents períodes històrics, especialment entre els segles V i VIII n. e..<br>La presente tesis doctoral arqueológica nace del interés del estudio del territorio y sociedad de las comunidades que vivieron en el período de transición entre la época clásica y la Alta Edad Media. La caída del Imperio Romano y la progresiva llegada de nuevas élites a la península Ibérica supondrá toda una serie de cambios sociales, económicos y de organización territorial que establecerán en cierta medida las bases sociopolíticas de la época medieval. Este proyecto pretende estudiar los cambios en las dinámicas de poblamiento rural entre época romana y la Alta Edad Media en zonas del noroeste de la cuenca del Duero a través de técnicas propias de la Arqueología del Paisaje como el análisis arqueomorfológico. Del mismo modo, se pretende profundizar en los procesos de transformación social, económica y política que se desarrollaron en este período de transición entre época clásica y medieval, para la que se documentan aparentemente nuevos patrones de ocupación del espacio. El desarrollo de la tesis incide en diversas problemáticas asociadas a este estudio, como el creciente interés por los procesos de cambio y nuevas formas de gestión territorial en los últimos siglos del mundo romano, la arqueología de los espacios agrarios y de los despoblados, y finalmente la escasez de información arqueológica en zonas rurales especialmente entre los siglos tardorromanos y altomedievales. Los resultados muestran la pervivencia de un paisaje tradicional, un sistema de comunicaciones y distribución del poblamiento actual que se ha configurado y modificado en distintos períodos históricos, en especial entre los siglos V y VIII n. e..<br>This archaeological doctoral thesis arises from the interest of the study of the territory and society of the communities that lived in the transition period between the classical period and the Early Middle Ages. The fall of the Roman Empire and the progressive arrival of new elites to the Iberian Peninsula will suppose a whole series of social, economic and territorial organization changes that will establish to a certain extent the socio-political foundations of medieval times. This project aims to study the changes in the dynamics of rural settlement patterns between Roman times and the High Middle Ages in areas of the northwest of the Duero basin through techniques of Landscape Archeology such as archeomorphological analysis. In the same way, it is intended to deepen the processes of social, economic and political transformation that took place in this period of transition between classical and medieval times, for which apparently new patterns of space occupation are documented. The development of the thesis affects various problems associated with this study, such as the growing interest in the processes of change and new forms of territorial management in the last centuries of the Roman world, the archeology of agrarian and unpopulated spaces, and finally the scarcity of archaeological information in rural areas especially between the late Roman and high medieval centuries. The results show the survival of a traditional landscape, a communication system and distribution of the current settlement that has been configured and modified in different historical periods, especially between the 5th and 8th centuries CE.

NATO has provided security for the Western Hemisphere for more than half a century now and there is little doubt that it is one of the most successful security alliances the world has ever known. However, after the end of the Cold War, its future become increasingly uncertain, thus leaving space for other another security actor: the EU. During the last two decades, the EU became more active in security matters and even launched its own, first ever anti-piracy and peacekeeping operations, despite a strong NATO presence in the same areas, at the same time. We will take a step back from these specific cases and approach the question of: To what extent, if any, has the EU developed into a security actor which is similar NATO? This question has been approached by constructing a deductive mixed methods study of a longitudinal design, in which we have compared the security regimes of the EU and NATO, and the military expenditures of the two organisations. The results of this study were that: the EU has, in fact, developed into a security actor, but it aligns more closely with the neoliberal institutionalist notion of a security institution.

In the past two decades we witnessed a decrease in both the number of oil spill incidents, and of the quantity of oil released in these incidents, which led to a diminished interest for basic oil spill science. With the introduction of more stringent oil spill legislation, much of the spill response, assessment and restoration activities were passed to governmental agencies and other stakeholders. Their capabilities were perhaps sufficient to deal with the most frequently occurring small-scale spills, however, recent large, catastrophic incidents such as the sinking of Prestige in 2002, or the Deepwater Horizon blowout in 2010, renewed the need for fundamental science in order to be able to fully understand and estimate the scope of the impacts such spills can have on the environment, economy and society. This is particularly important in the context of new explorations and discoveries of hydrocarbon resources in pristine regions such as Arctic, where extreme weather and the lack of infrastructure emphasize even more the need for a comprehensive assessment of all of the possible effects the future oil production could cause. The objectives of this thesis were set to provide new approaches and methodologies, and to improve and reevaluate the previously existing ones, in a way which can contribute to this comprehensive and proactive strategy. Their scope is comprehensive because it covers all the important aspects of marine oil spills – the sources, environmental fate and possible toxic effects. In addition, particular relevance of this thesis is drawn from the fact that the studies presented here include the investigation of real major oil spills (Prestige, DWH), and of a broad range of oils and oil products that are currently produced and transported worldwide. In order to fulfill the abovementioned general objectives, the following specific objectives had to be accomplished: Firstly, a physicochemical database of frequently transported crude and refined oils was created using elemental analysis, thin-layer liquid chromatography (TLC) with flame ionization detector (FID) analysis of principal oil compound groups, gas chromatography-mass spectrometry (GC-MS) fingerprinting of polycyclic aromatic hydrocarbons (PAHs) and biomarkers, and available oil assays. This database was then applied to assess their possible fate in the case of a spill, and to model three spill scenarios in different European regional seas using ADIOS2 software from NOAA (National Oceanic and Atmospheric Administration). Fingerprints of selected oils were assessed and statistically compared to discover the most relevant compositional differences that could facilitate the identification of oil spill sources. Secondly, the GC-MS methodology used to create the fingerprint database of selected oils was evaluated in an international interlaboratory ring test. The objective was to test the capability of this fingerprinting methodology to identify the type and source of weathered (biodegraded) oil samples. Thirdly, the weathering of oil samples from Prestige and Deepwater Horizon spills, in particular the photooxidation, was studied. Samples weathered in field and in laboratory experiments were analyzed using TLC-FID, GC-MS, comprehensive two dimensional gas chromatography (GCxGC) with FID, and Fourier transform infrared spectrometry (FT-IR) to discover compositional changes on the bulk level as well as on the molecular level. PAHs and triaromatic steranes (TAS) were of particular interest, as well as the effects of the photooxidation on the robustness of the oil fingerprinting methodology. Finally, the effects of selected fresh and weathered (evaporated, photooxidized) crude and refined oils were studied, using the effect-directed analysis (EDA). The samples were sequentially fractionated using open-column liquid chromatography and normal-phase semipreparative HPLC, and the obtained fractions were subjected to bioassays to test their AhR agonist and AR antagonist activity. The most active fractions were then analyzed using GCxGC coupled to time-of-flight mass spectrometry (TOFMS), and this data was related to bioassay results using N-way partial least square (N-PLS) chemometric model, in order to identify the compounds responsible for the observed effects.<br>A pesar de las tendencias positivas en las últimas décadas, los vertidos ocasionados por la exploración, extracción y transporte de petróleo siguen siendo una importante amenaza para los ecosistemas marinos y especialmente costeros. Esta Tesis se ocupa de todos los aspectos importantes sobre los vertidos marinos de petróleo: el origen, el destino ambiental y sus posibles efectos. Para permitir su comprensión global, se utilizaron diferentes metodologías complementarias. En primer lugar, se ha creado una base de datos físico-químicos de diferentes petróleos (crudos y refinados) que se transportan frecuentemente usando el análisis elemental, la cromatografía en capa fina (TLC) acoplada a un detector de ionización de llama (FID) de los principales grupos de compuestos de petróleo, la toma de huellas químicas de los hidrocarburos aromáticos policíclicos (HAP) y los biomarcadores mediante cromatografía de gases acoplada a espectrometría de masas (GC-MS), y ensayos de petróleo disponibles. A continuación, se aplicó esta base de datos para evaluar su posible destino en el caso de un vertido, y para modelar tres escenarios de vertidos en diferentes mares regionales europeos usando el software ADIOS2 de la Administración Nacional Oceánica y Atmosférica (NOAA). Las huellas químicas de los petróleos seleccionados fueron evaluadas y comparadas estadísticamente para investigar las diferencias de composición más relevantes que podrían facilitar la identificación del origen de vertido. En segundo lugar, la metodología de GC-MS utilizada para crear la base de datos de las huellas químicas de los petróleos seleccionados se ha evaluado en una prueba interlaboratorio internacional. El objetivo fue investigar la capacidad que tiene esta metodología de toma de huellas químicas para identificar el tipo y el origen de las muestras envejecidas (biodegradadas) de petróleo. En tercer lugar, se ha estudiado el envejecimiento de las muestras de petróleo de los vertidos de Prestige (2002) y de la plataforma Deepwater Horizon (2010), en particular, debido a la fotooxidación. Se analizaron muestras envejecidas en el campo y en experimentos de laboratorio mediante TLC-FID, GCMS, cromatografía de gases bidimensional integrada (GCxGC) acoplada a un FID, y espectroscopia infrarroja por transformada de Fourier (FT-IR) para investigar los cambios de composición tanto a nivel global como a nivel molecular. Los HAP y esteranos triaromáticos fueron de especial interés, así como los efectos de la fotooxidación en la robustez de la metodología de toma de huellas químicas de petróleo. Finalmente, se estudiaron los efectos de las muestras no tratadas y envejecidas (evaporadas, fotooxidadas) de los petróleos crudos y refinados seleccionados, utilizando el análisis dirigido por los efectos tóxicos (EDA). Las muestras se fraccionaron secuencialmente usando la cromatografía líquida en columna abierta y la cromatografía líquida de alta eficacia (HPLC) semipreparativa en fase normal. Las fracciones obtenidas se sometieron a bioensayos para investigar su actividad agonista de los receptores AhR y la actividad antagonista de los receptores AR. En el siguiente paso, las fracciones más activas fueron analizadas mediante GCxGC acoplada a espectrometría de masas en tiempo de vuelo (TOFMS), y estos datos se relacionaron con los resultados de los bioensayos utilizando un modelo quimiométrico de regresión por mínimos cuadrados parciales en N direcciones (N-PLS), con el fin de identificar los compuestos responsables de los efectos observados.

The focus of this study was analytical investigations of Egyptian paintings, mainly Coptic icons and Islamic wooden ceilings, dating from 1300-1900 using multi-instrumental techniques. Twenty three Coptic icons and three wooden ceilings dated from different periods and painted by different painters in case of icons were examined. The materials used including pigments, media, varnishes, ground layers and gold layers. The surface stratigraphy of paint samples, their layered structured and the composition of materials used in each layer were analysed. Variations in painting techniques, pigments palettes, paint media and varnishes applied in Egyptian paintings according to painters, time and type of paintings were revealed. A total of twenty-eight organic and inorganic pigments were identified in this study, of which nine have never been previously included as a part of the Egyptian pigment palettes, namely; smalt, lapis lazuli, indigo, pararealgar, Prussian blue, chrome yellow, barium yellow, barium white and hydromagnesite. The identification of hydromagnesite, which has never been to date considered as a pigment either in Egypt or elsewhere and the identification of smalt from the mid-14th century, whose reported earliest large scale use was in the 16th century. Two types of resins were identified as a constituent of the oil/resin varnish applied on Coptic icons of which Venice turpentine has been identified for the first time as an ingredient of Egyptian varnishes. The identification of mosaic gold in an 18th C. icon, a novel usage of dammar resin and the multilayered structure of the white ground layers were revealed.

The focus of this study was analytical investigations of Egyptian paintings, mainly Coptic icons and Islamic wooden ceilings, dating from 1300-1900 using multiinstrumental techniques. Twenty three Coptic icons and three wooden ceilings dated from different periods and painted by different painters in case of icons were examined. The materials used including pigments, media, varnishes, ground layers and gold layers. The surface stratigraphy of paint samples, their layered structured and the composition of materials used in each layer were analysed. Variations in painting techniques, pigments palettes, paint media and varnishes applied in Egyptian paintings according to painters, time and type of paintings were revealed. A total of twenty-eight organic and inorganic pigments were identified in this study, of which nine have never been previously included as a part of the Egyptian pigment palettes, namely; smalt, lapis lazuli, indigo, pararealgar, Prussian blue, chrome yellow, barium yellow, barium white and hydromagnesite. The identification of hydromagnesite, which has never been to date considered as a pigment either in Egypt or elsewhere and the identification of smalt from the mid-14th century, whose reported earliest large scale use was in the 16th century. Two types of resins were identified as a constituent of the oil/resin varnish applied on Coptic icons of which Venice turpentine has been identified for the first time as an ingredient of Egyptian varnishes. The identification of mosaic gold in an 18th C. icon, a novel usage of dammar resin and the multilayered structure of the white ground layers were revealed.<br>Egyptian Ministry of Higher Educations

The Random Forest model is commonly used as a predictor function and the model have been proven useful in a variety of applications. Their popularity stems from the combination of providing high prediction accuracy, their ability to model high dimensional complex data, and their applicability under predictor correlations. This report investigates the random forest variable importance measure (VIM) as a means to find a ranking of important variables. The robustness of the VIM under imputation of categorical noise, and the capability to differentiate informative predictors from non-informative variables is investigated. The selection of variables may improve robustness of the predictor, improve the prediction accuracy, reduce computational time, and may serve as a exploratory data analysis tool. In addition the partial dependency plot obtained from the random forest model is examined as a means to find underlying relations in a non-linear simulation study.<br>Random Forest (RF) är en populär prediktormodell som visat goda resultat vid en stor uppsättning applikationsstudier. Modellen ger hög prediktionsprecision, har förmåga att modellera komplex högdimensionell data och modellen har vidare visat goda resultat vid interkorrelerade prediktorvariabler. Detta projekt undersöker ett mått, variabel importance measure (VIM) erhållna från RF modellen, för att beräkna graden av association mellan prediktorvariabler och målvariabeln. Projektet undersöker känsligheten hos VIM vid kvalitativt prediktorbrus och undersöker VIMs förmåga att differentiera prediktiva variabler från variabler som endast, med aveende på målvariableln, beskriver brus. Att differentiera prediktiva variabler vid övervakad inlärning kan användas till att öka robustheten hos klassificerare, öka prediktionsprecisionen, reducera data dimensionalitet och VIM kan användas som ett verktyg för att utforska relationer mellan prediktorvariabler och målvariablel.

In this thesis complexes of acylchalcogoureas with cadmium (II), lead (II) and nickel (II) have been synthesised and investigated as single source precursors for the formation of metal chalcogenide thin films viaaerosol assisted chemical vapour deposition (AACVD). Routes to binary thin films have been explored using homoleptic complexes of the general structure bis(N,N-diethyl-N'-naphthoylchalcogoureato)metal(II). Analysis of the thin films produced showed the successful deposition of the binary materials from the synthesised complexes when characterised by powder XRD, ICP-OES, SEM and EDX. Routes to ternary thin films with the general structure MExE'1-x, where M represents a metal (Cd, Ni and Pb); and E chalcogen (S or Se) have been investigated using heteroleptic metal complexes of cadmium, nickel or lead including different chalcogen containing N,N-diethyl-N'-naphthoylchalcogoureato ligands and diethyldithiocarbamate. The precursors were fully characterised and novel compounds had their crystal structures determined. The heteroleptic complexes were thermolysed by AACVD forming the MExE'1-x thin films. In the cases of lead, nickel and cadmium the thin films produced showed that the composition of the film tended heavily towards the metal selenide. Ternary films of type MS1-xSex was prepared by mixing their binary precursors of type bis(N,N-diethyl-N'-naphthoylselenoureato)metal(II) and bis(N,N-diethyl-N'-naphthoylthioureato)metal(II) [metal = Cd, Ni and Pb]. In the case of lead and cadmium chalcogenide films variation of the ratio of sulphur and selenium containing precursors allowed for the full transition in composition between metal sulphide and metal selenide. In the case of CdS1-xSexthe band gap of the films was determined from UV-visible spectroscopy to vary from 2.4 eV (CdS) to 1.7 eV(CdSe). In the case of NiS1-xSex the movement from sulphide to selenide was less simple with multiple phases of nickel chalcogenides produced.

Structural isomers are molecules that have the same number and type of atoms but arranged in different manner. The isomerization energy is the energy difference between two isomers, i.e. the energy cost corresponding to the transformation of one isomer into another. In this thesis, the PhD student has focused on isomers that can be built from the same fragments, but simply connecting them differently, with a new methodology called "turn-upside-down." Basically one starts with the same two fragments and they are connected in different way to build the two isomers. Later, the energies involved in the bonding between the fragments are studied by an energy decomposition analysis in order to find the reason for the difference in stability between the two isomers. The computational results obtained have allowed us to justify the energy of isomerization of organic or inorganic or organometallic compounds<br>Isòmers estructurals són molècules que presenten el mateix nombre i tipus d’àtoms, però ordenats de diferent manera. L’energia d’isomerització és la diferència d’energia entre dos isòmers, o sigui, el cost energètic corresponent a la transformació d’un isòmer a l’altre. En aquesta tesi, el doctorand s’ha centrat en isòmers que es poden construir a partir dels mateixos fragments, però simplement unint-los de diferent manera, amb una nova metodologia anomenada “turn-upside-down”. Bàsicament es parteix dels mateixos dos fragments que unim de diferent manera per construir els dos isòmers. Posteriorment, les energies involucrades en la unió entre els fragments s’estudien amb una anàlisi de descomposició de l’energia per tal de saber la raó de la diferència d’estabilitat entre els dos isòmers. Els resultats computacionals obtinguts han permès justificar l’energia d’isomerització de compostos tant orgànics com inorgànics o organometàl·lics

Les méthodes actuellement disponibles pour la surveillance de la qualité du milieu se réfèrent au suivi de composés définis par les réglementations et ne permettent pas d’appréhender l’(éco)toxicité réelle de tous les composés présents dans l’environnement (e.g. composés inconnus, produits de transformation, effets de mélange…). Dans ce contexte, une méthode d’analyse pluridisciplinaire intégrative, l’analyse dirigée par l’effet (EDA), a été développée. Cette approche bio-analytique vise à établir un lien de causalité entre une exposition aux contaminants et l’effet biologique observé. La démarche est basée sur la simplification séquentielle d’un échantillon guidée par les bio-essais afin d’individualiser puis identifier, par des techniques analytiques chimiques performantes, les composés biologiquement actifs. Les objectifs de cette thèse ont porté sur (1) le développement et la validation d’une méthodologie, allant du pré-traitement jusqu’au fractionnement, adaptée à différentes matrices environnementales ; (2) la mise en place d’une stratégie d’identification moléculaire par spectrométrie de masse haute résolution ; (3) l’application de la démarche EDA à plusieurs échantillons afin d’illustrer l’adaptabilité et l’apport d’une telle méthode à des problématiques environnementales. Ces travaux de thèse permettent de disposer aujourd’hui d’une démarche bio-analytique complète de la préparation d’échantillon à l’identification de molécules, et adaptée à tous types d’échantillons. Les différentes études environnementales réalisées au cours de ces travaux ont permis, entre autre, d’établir une liste de composés diverses non recherchés pouvant représenter un risque pour l’environnement<br>To date, environmental risk assessment is based on targeted chemical analyses. These analyses allow the detection of known active compounds and this preselected set does not often explain the observed toxic effects in complex environmental samples (e.g. unknown compounds, transformation product, cocktail effect...). For an integrative contamination assessment, a multidisciplinary approach, Effect-Directed Analysis (EDA) was developed. This approach combining biological tools and chemical analyses allows determining active compounds and identitying them in such environmental complex mixtures. EDA aims at the establishment of cause-effect relationships by sequential reduction of the complexity of environmental mixtures, eventually to individual toxicants. The aims of this thesis were (1) to develop and to validate the EDA-based strategy on various environmental complex samples; (2) to set up an identification strategy for identifying non targeted or unknown molecules using high resolution mass spectrometry; (3) to prove the usefulness of EDA approach for the identification of active compounds in environnemental complex samples. This thesis work provides to a complet bio-analytical approach from the preparation step of samples to the identification of molecules. The potential of this tool was fully confirmed on various environmental studies. These investigations allowed establishing a list of non-target compounds which can represent a risk for the environment

Tesis por compendio de publicaciones<br>Objetivo. Determinar el número total y la topografía de la población de conos en roedores adultos utilizando rutinas automatizadas que nos permita investigar objetivamente los efectos de diferentes modelos experimentales de patologías humanas tales como la degeneración macular asociada a la edad (DMAE), retinosis pigmentaria (RP) y la neuropatía óptica glaucomatosa (NOG) sobre la población de fotorreceptores. Material y métodos. Se han utilizado cinco cepas distinta de roedores: Sprague-Dawley (SD), Piebald Virol Glaxo (PVG) y la rata transgénica P23H-1, y ratones Swiss y C57/BL6. Todos los experimentos y procedimientos se han realizado bajo el estricto cumplimiento de las recomendaciones de la “Guide for the Care and Use of Laboratory Animals of the Association for Research in Vision and Ophthalmology (ARVO)” y la “European Union guidelines for the use of animals in research”, y todos los procedimientos utilizados han sido previamente aprobados por el Comité Ético de Experimentación Animal (CEEA) de la Universidad de Murcia. Se han utilizado diferentes técnicas para el estudio histológico y morfológico y se han analizado en retinas montadas a plano y en secciones transversales; se han utilizado tecnologías de imagen avanzadas como la Spectral Domain Optical Coherence Tomography (SD-OCT)y se ha realizado análisis de proteínas mediante Western Blot. Como modelo de RP se ha utilizado la rata transgénica P23H-1, esta rata es portadora de una mutación autosómica dominante en el gen de la rodopsina que causa distrofia y muerte de los fotorreceptores. Se ha desarrollado un nuevo modelo experimental útil para la comprensión de la patología de la DMAE, la fototoxicidad localizada de los fotorreceptores tipo cono inducida por LED (FTIL). Por último se ha utilizado un modelo experimental de hipertensión ocular (HTO) inducida mediante láser que permite la evaluación de los efectos de la NOG sobre la población de fotorreceptores. Resultados. El número medio de conos que expresan la opsina-L es de 231.736 ± 14.517 en la rata SD; 239.939 ± 6.494 en la rata PVG; 117.424 ± 17.721 en el ratón Swiss y 135.155 ± 8.742 en el ratón C57/BL6. El número medio de conos que expresan la opsina-S es de 41.028 ± 5.074 en la rata SD; 27.316 ± 2.235 en la rata PVG; 146.682 ± 24.958 en ratones Swiss y 119.616 ± 8.756 en ratones C57/BL6. El porcentaje de conos duales en la rata SD es del 3,2%, del 2,9% en la PVG, de un 73% en el ratón Swiss y de un 40% en el C57/BL6. En todas las cepas de ambas especies existe un paralelismo en la distribución de las células ganglionares de retina (CGR) y los conos-L. La topografía de los conos-L en todas las cepas de rata y ratón analizadas es similar, se observan zonas de alta densidad en el eje nasotemporal superior, las densidades medias alrededor del nervio óptico y un descenso de densidad gradual desde las zonas centrales hacia las periféricas. Sin embargo, existen claras diferencias en la distribución de los conos-S entre las especies y cepas analizadas. El la rata P23H-1, la degeneración de los bastones ocurre antes que la de los conos y de forma rápida: primero con el acortamiento de los segmentos externos, a P30 existe una gran pérdida de bastones y a P180 la pérdida es prácticamente en la totalidad de la retina exceptuando la extrema periferia. La degeneración de bastones y conos está espaciotemporalmente relacionada, ocurre en forma de anillos que aparecen alrededor de P90 y se extiende por toda la retina. A P180, los anillos de degeneración son más abundantes en la retina ecuatorial y de mayor tamaño en la retina dorsal. En un nuevo modelo in vivo de fototoxicidad focal de los fotorreceptores inducido por LED, la SD-OCT muestra un daño en una región circular situado en la retina superotemporal. En esta región se observa una disminución progresiva del espesor de la retina desde 183,4 ± 5 mm (12 h) hasta 114,6 ± 6 mm (7 d). Las secciones transversales muestras una pérdida masiva de bastones y conos en la región dañada por la luz. En las retinas montadas a plano se observa una región circular con disminución del número de conos-L y conos-S. En este área circular en las retinas izquierdas y en la región correspondiente de la retina control derecha, el número total de conos-L o conos-S es de 7.118 ± 842 ó 661 ± 125 en las retinas fotoexpuestas (n=7) y de 14.040 ± 1.860 ó 2.255 ± 193 en las retinas control (n=7), respectivamente. Aunque el CNTF no, la brimonidina, el BDNF, PEDF y el bFGF muestran efectos neuroprotectores significativos sobre los conos-L y conos-S. La HTO provoca sectores con su vértice en el disco óptico carentes de CGR Brn3a pero que aún contienen gran número de núcleos DAPI positivos. Los niveles de todas las opsinas disminuyen a las 2 semanas y esta disminución progresa hasta el 20% de los niveles basales a los 3 meses. Las secciones transversales revelan áreas focales de degeneración en las capas externas de la retina (CER). Las CGR supervivientes a los 15 días representan aproximadamente el 28% y no cambian con el tiempo, mientras que de las poblaciones de conos-L y conos-S sobreviven un 80% y un 65% a un mes o un 35% y un 20% a 6 meses, respectivamente. Conclusiones. Se ha establecido, por primera vez, el número total y la distribución topográfica de los conos-L y conos-S en dos cepas de rata y dos de ratón y se ha demostrado el paralelismo topológico de la distribución de los conos-L y las CGR. Se han proporcionado las bases para estudiar la degeneración de conos y su prevención en condiciones patológicas. Se ha descrito por primera vez que, en la rata P23H-1, la degeneración de bastones y conos está espaciotemporalmente relacionada y se produce en anillos. La pérdida de conos sigue a la pérdida de bastones, que comienza de forma temprana, incluso antes de P30, la primera edad analizada. Las características de los anillos sugieren que la degeneración secundaria de conos está influenciada por la localización en la retina y / u otros factores intrínsecos o extrínsecos. Se ha evidenciado que la FTIL provoca una pérdida de conos y bastones y es un modelo fiable, cuantificable y reproducible para estudiar la degeneración de los fotorreceptores. La administración intravítrea de BDNF, PEDF o bFGF, o la administración tópica de brimonidina proporcionan neuroprotección significativa sobre los conos, en este modelo. Se ha demostrado que la HTO induce una pérdida selectiva de CGR en la capa de la CGR que no progresa después de 1 mes, mientras que los conos-L y conos-S presentan una pérdida progresiva hasta los 6 meses. Por lo tanto, HTO provoca graves daños tanto en las capas más internas como en las CER.<br>Purpose. To determine the total number and topography of the cone population in two rat and two mouse strains using automated routines which allowed us to investigate objectively the effects of different experimental models of human pathologies such as Aging Macular Degeneration (AMD), Retinitis Pigmentosa (RP) and Glaucomatous Optic Neuropathy (GON) on the photoreceptor population. Material y methods. A total of 303 rats and 23 mice were used in this thesis, five different strains of rodents were used: albino Sprague-Dawley (SD), pigmented Piebald Virol Glaxo (PVG) and P23H-1 transgenic rats, albino Swiss and pigmented C57/BL6 mice. All experimets and procedures were carried out in strict accordance with the recommendations in the Guide for the Care and Use of Laboratory Animals of the Association for Research in Vision and Ophthalmology (ARVO) and the European Union guidelines for the use of animals in research, and all the protocols were approved by the Ethical and Animal Studies Committee of the University of Murcia. Several techniques such as, the identification of the three different types of photoreceptors and other retinal populations by immunohistofluorescence analyzed in whole flat-mounted retinas and in oriented radial sections, classical staining as H-E, imaging advanced technologies as Spectral Domain Optical Coherence Tomography (SD-OCT), and protein analysis by western blot, have been used. In this thesis the P23H-1transgenic rat has been used as a model of RP, this animal bears an autoasomal dominat mutation in the rhodopsin gene (proline to histidine substitution at codon 23 of the rodopsin protein) that causes photorecptor dystrophy and death. A new experimental model useful to understand the AMD pathology, has been developed for this thesis, Light Emmitting Dioede (LED)-induced cone-photoreceptor phototoxicity (LIP), the blue-light LED exposition on the rat retina causes a damage-area located in the retinal zone with maximun L-cones densities and a cone to rod ratio similar to the human macular fovea. And finally, an experimental model of Laser-induced ocular hypertension developed recently in our Laboratory of Experimental Ophthalmology at the University of Murcia has been used to understand the effects of GON on the cone population. Results. The mean number of L-opsin+cones is 231,736 ± 14,517 in SD rat; 239,939 ± 6,494 in PVG rat; 117,424 ± 17,721 in Swiss mouse and 135,155 ± 8,742 in C57/BL6 mouse. The mean number of S-opsin+cones 41,028 ± 5,074 in SD rat; 27,316 ± 2,235 in PVG rat; 146,682 ± 24,958 in Swiss mouse and 119,616 ± 8,756 in C57/BL6 mouse. The percentage of dual cones is 3.2% in SD rat; 2.9% in PVG rat; 73% in Swiss mouse and 40% in C57/BL6 mouse. In all strains, and both species, there is a parallel distribution of retinal ganglion cells (RGC) and L-cones. The topography of L-cones is similar in all strains of rats and mice analyzed, the highest densities are observed in the superior nasotemporal axis, medium densities around the optic nerve, and this density gradually decreases from the center to the periphery. However, obvious differences are found in S-cones distribution. While in the two rat strains there is a increasing gradient of S-cones density along the inferonasal quadrant and the highest densities are found in the retinal rim, in the Swiss mouse strains S-cones are abundant in the dorsal retina although their highest densities are ventral but the C57/BL6 mouse shows a low number of S-cones in the dorsal retina and very dense population in the ventral retina, being densest in its nasal aspect. In P23H-1 rats, rod degeneration occurs rapidly: first the rod outer segment shortens, at P30 there is extensive rod loss, and by P180 rod loss is almost complete except for the most peripheral retina. The numbers of L cones are, at all postnatal ages, lower in P23H-1 rats than in control SD rats, and decrease significantly with age (by P180). Rod and cone degeneration is spatiotemporally related and occurs in rings that appear already at P90 and spread throughout the entire retina. At P180, the rings of rod-cone degeneration are more abundant in the equatorial retina and are larger in the dorsal retina. In a novel in vivo model of focal LED-induced photoreceptor phototoxicity SD-OCT showed damage in a circular region of the superotemporal retina, whose diameter varied from 1,842.4 ± 84.5 mm (at 24 hours) to 1,407.7 ± 52.8 mm (at 7 days). This region had a progressive thickness disminution from 183.4 ± 5 mm (at 12 h) to 114.6 ± 6 mm (at 7 d). Oriented cross-sections showed within the light-damaged region of the retina massive loss of rods and cone-photoreceptors. Wholemounts documented a circular region containing lower numbers of L- and S-cones. Within a circular area (1 mm or 1.3 mm radius, respectively) in the left and in its corresponding region of the contralateral-fellow-retina, total L- or S-cones were 7,118 ± 842 or 661 ± 125 for the LED exposed retinas (n=7) and 14,040 ± 1,860 or 2,255 ± 193 for the fellow retinas (n=7), respectively. Brimonidine, BDNF, PEDF and bFGF but not CNTF showed significant neuroprotective effects on L- and S-cones. Ocular hypertension (OHT) resulted in wedge-like sectors with their apex on the optic disc devoid of Brn3aRGC but with large numbers of DAPI+nuclei. The levels of all opsins diminished by 2 weeks and further decreased to 20% of basal-levels by 3 months. Cross-sections revealed focal areas of outer retinal layers (ORL) degeneration. RGC survival at 15 days represented approximately 28% and did not change with time, whereas the L-cone and S- populations diminished to 80% and 65%, or to 35% and 20% at 1 or 6 months, respectively. Conclusions. It has been established, for the first time, the total number and the topographical distribution of S- and L-cones in two rat and two mouse strains and demonstrated the correlation of L-cones and RGC spatial distribution. It has been provided the basis to study cone degeneration and its prevention in pathologic conditions. It has been described for the first time that in the P23H-1 rat, rod and cone degeneration is spatiotemporally related and occurs in rings. Cone loss follows rod loss and starts very soon, even before P30, the first age analyzed here. The characteristics of the rings suggest that secondary cone degeneration is influenced by retinal position and/or other intrinsic or extrinsic factors. It has been evidenced that LIP results in rod and cone-photoreceptor loss, and is a reliable, quantifiable model to study cone-photoreceptor degeneration. Intravitreal BDNF, PEDF or bFGF, or topical BMD afford significant cone neuroprotection in this model. It has been demostrated that OHT induces in the ganglion cell layer selective RGC loss that does not progress after 1 month, whereas the S- and L-cones exhibit progressive loss up to 6 months. Thus, OHT results in severe damage to both the innermost and the ORL.

Grâce à ses propriétés d'antioxydant, d'anti-usure et éventuellement d'extrême pression le dithiophosphate de zinc (ZDDP) fait partie des additifs les plus utilisés dans les lubrifiants pour moteurs thermiques. De nos jours, dans un souci de respect de l'environnement, de nouveaux lubrifiants possédant de bonnes performances en lubrification (frottement faible et usure limitée) sont développés en prenant compte des limitations d'utilisations actuelles du ZDDP. L'idée étant de réduire dans ceux-ci les teneurs en phosphore et soufre (Normes euros VI), éléments essentiels du ZDDP qui endommagent les pots catalytiques. L'objectif de cette thèse est l'étude du comportement tribologique du phosphate de zinc di alkyl (ZP) en comparaison avec le ZDDP. La méthodologie expérimentale étudiée pour comprendre le mécanisme d'action de ces additifs, associe des essais de frottement à descaractérisations physico-chimiques des surfaces frottantes après essais.Cette comparaison a été effectuée en fonction de la température (25°C et 100°C), la vitesse de glissement (25, 50 et 100 mm/s) et la concentration en additif (200 et 600 ppm dephosphore). Les meilleures actions anti-usure sont obtenues avec le ZDDP pour une température de 100°C et une vitesse de glissement de 100 mm/s et le ZP pour une température de 25°C et une vitesse de glissement de 25 mm/s. Les analyses de surface XPS, AES, XANES et MET-EDX ont permis de mettre en évidence la présence d'un film protecteur constitué principalement de phosphate de zinc, ceci pour les deux additifs.Une synergie de comportement tribologique a été mise en évidence avec un lubrifiantconstitué de ZP (usure faible) et d'oléate d'urée (frottement faible). Des essais complémentaires sur un tribomètre dynamique ont permis d'étudier le niveau de frottement du tribofilm formé à partir du ZDDP. Le caractère visqueux du tribofilm de ZDDP a été mis en évidence.

The design of molecular catalysts is an ambitious task implying the fundamental issue of relating the molecular structure to the reactivity, i.e., to the catalytic activity. The rationalization of the experimental data is often not straightforward and mechanistic schemes are not transferrable when the conditions of the process are changed or the catalyst is modified even slightly. Computer-aided investigations proved to be a more and more valid support in the last decade, but in most of the cases the aim is limited to investigate in detail the catalytic mechanism of a specific reaction and no general conclusions are drawn that can be used as a guide for designing novel catalysts for the same or analogous processes. In this Project, a computational approach has been set up to investigate the family of organometallic complexes displaying catalytic activity toward [2+2+2] cycloadditions of unsaturated molecules. In a recent book (Transition-metal-mediated aromatic ring construction, John Wiley & Sons, 2013, Chapter 4), Ken Tanaka describes Rhodium mediated [2+2+2] cycloadditions and writes ‘…Although mechanistic aspects of these reactions attract interest, only a few studies have been reported in specific catalysts and substrates…’. Thus this project, abbreviated with the acronym of STREGA (Filling the Structure-Reactivity Gap: in silico approaches to rationalize the design of molecular catalysts), aims at filling the gap between the goldmine of experimental data on this class of very important reactions and their mechanistic rationalization with the purpose of outlining the essential electronic and structural features of the catalyst leading to optimal performance, selectivity, and product yield. In particular, the roles of different metal, different ancillary ligands, different aromatic ligands, and substrates have been accurately investigated; existing data from the literature were also employed for this analysis. Larger polycyclic ligands can in principle host more than a metal center; for example, Cr can be coordinated to the benzene moiety of a rhodium indenyl complex. This might lead to interesting inter metal cooperative effects which might enhance or inhibit the catalytic activity; thus bimetallic catalysts have been considered. The effect of different cooperative metal nuclei was explored changing from Cr to Mo and W, which all belong to Group 6. Finally, the role of the polycyclic aromatic ligand was investigated and found that indeed it is an important factor since it influences rhodium hapticity and consequently its reactivity. All these results allowed to establish a solid structure-activity relationship which is of general validity for rhodium half-sandwich catalysts towards alkyne [2+2+2] cycloadditions and likely is transferrable to analogous Co, Ru, and Ir based fragments.

De nos jours, l’évaluation de la qualité d’un milieu naturel repose traditionnellement sur des analyses ciblant des molécules déjà connues pour être biologiquement actives. Cependant ces molécules ne reflètent que partiellement les effets biologiques observés et la complexité des matrices environnementales. Par ailleurs, les contaminants dans l’environnement subissent des phénomènes de dégradation (hydrolyse, biodégradation, photodégradation). Ces processus peuvent conduire à la génération de produits de transformation qui sont encore trop peu pris en compte dans l’évaluation du risque, alors qu’ils sont susceptibles d’occasionner des effets toxiques plus importants que les molécules mères. L’impact écotoxicologique de ces mélanges nécessite préalablement l’obtention d’une vision globale quant à la présence et au devenir de ces molécules.Dans ce contexte, ces travaux appliquent une méthodologie pluridisciplinaire afin d’identifier des molécules préoccupantes et pertinentes à surveiller. Pour cela, ce travail s’appuie sur des analyses ciblées ultra-traces, des outils bioanalytiques, et des analyses non ciblées, qui ont été appliqués sur des échantillons environnementaux ou issus d’études en laboratoire mimant l’évolution des matrices environnementales. Au final, cette étude a permis : (1) d’identifier des molécules préoccupantes en estuaire de Seine sur la base de leur occurrence et de leur persistance, (2) d’identifier de nouveaux produits de transformation et (3) d’identifier les molécules responsables d’activités biologiques dans des matrices très complexes<br>To date, environmental risk assessment is based on a restricted number of molecules assessed by targeted chemical analyses. However, this approach give a partial picture of co-occurrence of known and unknown compounds. Moreover, in the aquatic environment, chemicals are not completely mineralized and are subject to abiotic and biotic processes. Transformation products (TPs) can be more toxic and more persistent than the parent compound. However, TPs are not typically included in classical monitoring and risk assessment. Because of complexity and variability of these matrices and the restricted number of molecules focused in targeted chemical analyses, selection of relevant molecules for environmental monitoring is often laborious.In this context, an integrative approach was used in order to identify chemicals of concern for a classical monitoring. This work has been realized on environmental complex samples and on laboratory-generated samples. A combination of targeted, non-targeted analyses and in vitro bioassays was performed and allowed to: (1) identify polar chemical of concern in the Seine estuary on the basis of occurrence and persistence, (2) identify new transformation products and (3) identify compounds responsible of biological activity observed in complexes matrices

Aquesta tesi avalua l'existència de diferencies per gènere en la relació entre discapacitat i mortalitat, i aspectes metodològics en l'anàlisi de supervivènciad'estudis de gent gran. Es van utilitzar les dades provinents d'una cohort de 1.315 subjectes amb edats superiors o iguals a 65 anys que van ser seguits durant un periode de 8 anys. La discapacitat es va mesurar mitjançant la capacitat que declarava l'individu per dur a terme activitats de la vida diària bàsiques. <br/>La discapacitat va evolucionar al llarg del temps empitjorant amb l'edat, però una proporció no menyspreable va ser capaç de recuperar-se. Es van observar diferències per gènere en l'evolució de la discapacitat: les dones tenien més dificultats en recuperar la seva capacitat funcional un cop esdevenien discapacitades. La força de l'associació entre la discapacitat i la mortalitat disminuia a edats avançades. Es van trobar diferencies per sexe: les dones depenents mostraven un risc de morir més alt que el homes depenents. <br/>Polítiques de salut dirigides a dones discapacitades haurien de ser implementades degut a la proporció més elevada de dones discapacitades, la probabilitat menor que tenen de recuperar la capacitat funcional, i el risc de morir més elevat que presenten comparat amb homes dicapacitats.<br>This thesis evaluates the existence of gender differences in the relationship between disability and mortality, as well as methodological aspects of the survival analysis for elderly studies. Data from a cohort of 1,315 subjects aged 65 years and older followed-up 8 years was used. Disability was assessed by self-reported difficulty to perform basic activities of daily living. <br/>Disability evolved over time worsening with age, but a non-negligible proportion was able to recover. There were gender differences in the evolution of disability: women were less able to regain functional capacity once they become disabled. The strength of the association between disability and mortality decreased in the older ages. But differences by gender were found: dependent elderly women showed a higher risk of dying compared to dependent men. <br/>Health policies focusing on disabled women should be implemented, due to the higher proportion of disabled women, the lower probability of regaining functional capacity, and their higher risk of dying compared to disabled men.

En base als reptes sorgits a conseqüència de l'escalat de la tecnologia, la present tesis desenvolupa i analitza un conjunt d'eines orientades a avaluar la sensibilitat a la propagació d'esdeveniments SET en circuits microelectrònics. S'han proposant varies mètriques de propagació de SETs considerant l'impacto dels emmascaraments lògic, elèctric i combinat lògic-elèctric. Aquestes mètriques proporcionen una via d'anàlisi per quantificar tant les regions més susceptibles a propagar SETs com les sortides més susceptibles de rebre'ls. S'ha desenvolupat un conjunt d'algorismes de cerca de camins sensibilitzables altament adaptables a múltiples aplicacions, un sistema lògic especific i diverses tècniques de simplificació de circuits. S'ha demostrat que el retard d'un camí donat depèn dels vectors de sensibilització aplicats a les portes que formen part del mateix, essent aquesta variació de retard comparable a la atribuïble a les variacions paramètriques del proces.<br>En base a los desafíos surgidos a consecuencia del escalado de la tecnología, la presente tesis desarrolla y analiza un conjunto de herramientas orientadas a evaluar la sensibilidad a la propagación de eventos SET en circuitos microelectrónicos. Se han propuesto varias métricas de propagación de SETs considerando el impacto de los enmascaramientos lógico, eléctrico y combinado lógico-eléctrico. Estas métricas proporcionan una vía de análisis para cuantificar tanto las regiones más susceptibles a propagar eventos SET como las salidas más susceptibles a recibirlos. Ha sido desarrollado un conjunto de algoritmos de búsqueda de caminos sensibilizables altamente adaptables a múltiples aplicaciones, un sistema lógico especifico y diversas técnicas de simplificación de circuitos. Se ha demostrado que el retardo de un camino dado depende de los vectores de sensibilización aplicados a las puertas que forman parte del mismo, siendo esta variación de retardo comparable a la atribuible a las variaciones paramétricas del proceso.<br>Based on the challenges arising as a result of technology scaling, this thesis develops and evaluates a complete framework for SET propagation sensitivity. The framework comprises a number of processing tools capable of handling circuits with high complexity in an efficient way. Various SET propagation metrics have been proposed considering the impact of logic, electric and combined logic-electric masking. Such metrics provide a valuable vehicle to grade either in-circuit regions being more susceptible of propagating SETs toward the circuit outputs or circuit outputs more susceptible to produce SET. A quite efficient and customizable true path finding algorithm with a specific logic system has been constructed and its efficacy demonstrated on large benchmark circuits. It has been shown that the delay of a path depends on the sensitization vectors applied to the gates within the path. In some cases, this variation is comparable to the one caused by process parameters variations.

Cardiovascular disease (CVD) is the leading cause of morbidity, mortality, premature death and reduced quality of life for the citizens of the EU. It has been reported that CVD represents a major economic load on health care sys- tems in terms of hospitalizations, rehabilitation services, physician visits and medication. Data Mining techniques with clinical data has become an interesting tool to prevent, diagnose or treat CVD. In this thesis, Knowledge Dis- covery and Data Mining (KDD) was employed to analyse clinical and demographic data, which could be used to diagnose coronary artery disease (CAD). The exploratory data analysis (EDA) showed that female patients at an el- derly age with a higher level of cholesterol, maximum achieved heart rate and ST-depression are more prone to be diagnosed with heart disease. Furthermore, patients with atypical angina are more likely to be at an elderly age with a slightly higher level of cholesterol and maximum achieved heart rate than asymptotic chest pain patients. More- over, patients with exercise induced angina contained lower values of maximum achieved heart rate than those who do not experience it. We could verify that patients who experience exercise induced angina and asymptomatic chest pain are more likely to be diagnosed with heart disease. On the other hand, Logistic Regression, K-Nearest Neighbors, Support Vector Machines, Decision Tree, Bagging and Boosting methods were evaluated by adopting a stratified 10 fold cross-validation approach. The learning models provided an average of 78-83% F-score and a mean AUC of 85-88%. Among all the models, the highest score is given by Radial Basis Function Kernel Support Vector Machines (RBF-SVM), achieving 82.5% ± 4.7% of F-score and an AUC of 87.6% ± 5.8%. Our research con- firmed that data mining techniques can support physicians in their interpretations of heart disease diagnosis in addition to clinical and demographic characteristics of patients.

Ces travaux de thèse réalisés entre l'IRT Saint Exupéry et le CEMES, Université de Toulouse, CNRS ont pour objet l'étude d’alliages de la série 2000 pour des utilisations à des températures intermédiaires, de l'ordre de 200°C. La possibilité d'utiliser ces matériaux à cette température permettrait aux industriels du secteur aéronautique de réduire les coûts de production d'une part, et de diminuer les coûts d'exploitation des aéronefs ainsi plus légers d'autre part. Afin de répondre à cette problématique industrielle, deux nuances commerciales ont été considérées : le 2219-T851 et le 2050-T84. Ces nuances, déjà utilisées dans l'industrie aéronautique, ont été caractérisées à différentes échelles d'observation tout au long d'un vieillissement isotherme à 200°C allant jusqu’à 10000 h. Des observations effectuées à l'aide de divers microscopes optiques et électroniques et couplées à des essais mécaniques macroscopiques ont permis de déterminer l'évolution de ces nuances vieillies dans de telles conditions. Les résultats de cette étude montrent une importante stabilité thermodynamique des précipités nanométriques θ'-Al2Cu. Ces précipités constituent la microstructure fine de la nuance 2219-T851 à réception et apparaissent au cours du vieillissement au sein de la nuance 2050-T84 au détriment des précipités T1-Al2CuLi pourtant à l'origine des meilleures performances mécaniques avant vieillissement. Les évolutions microstructurales sont mises en lien avec les propriétés mécaniques en traction. Ces résultats montrent un intérêt industriel pour la nuance 2219-T851 dont la stabilité des propriétés a été montrée dès 1000h de vieillissement<br>The main objective of this work which has been conducted between the IRT Saint Exupéry and the CEMES, Université de Toulouse, CNRS laboratory is to reduce production and exploitation costs of aircraft primary structures by evaluating the potential increase of operating temperatures of aluminum alloys. To do so, two already fit-to-fly Al-Cu alloys have been selected and studied: the 2219-T851 and the 2050-T84. These alloys have been characterized throughout ageing treatments up to 10,000h at 200°C with electronic and optical microscopies in order to evaluate the microstructural changes. Standardized mechanical tests have also been conducted to follow the effects of such ageing on the alloys’ properties. The results have shown the stability of the mechanical properties and the microstructure of the 2219-T851 from 1,000h to 10,000h of ageing. This is attributed to the nano-precipitation of θ'-Al2 Cu, stable during the ageing treatment. Moreover, those precipitates tend to form during the ageing of the 2050-T84 by replacing the well known T1-Al2CuLi phase, unstable during medium range temperature ageing. During this thesis, special attention has been paid on the link between the mechanical properties and the fine scale microstructures of both alloys

La present tesi proposa una metodologia de disseny conceptual d'estacions depuradores d'aigües residuals (EDAR) mitjançant la combinació del procés de decisió jeràrquic i l'anàlisi de decisions multicriteri. El document s'inicia amb una breu introducció als principals camps abordats pel treball: el disseny dels processos químics en general, el disseny de les estacions depuradores d'aigües residuals en particular, i l'anàlisi de decisions multicriteri aplicada a la gestió ambiental. Seguidament, es fixen els objectius del treball i es descriuen tant la metodologia com el material de suport informàtic utilitzats. Per validar i contrastar la metodologia de disseny presentada, es desenvolupa un cas d'estudi on es porta a terme el disseny conceptual d'una EDAR que presenta els mateixos requeriments que l'EDAR que opera actualment al municipi de Granollers. Inicialment es presenta la informació de partida i tot seguit es defineixen els objectius de disseny, així com el conjunt de criteris que s'utilitzaran per avaluar en quina mesura es compleixen aquests objectius. Els objectius de disseny són de diferents tipus: ambientals, tècnics, socials i econòmics, i el conjunt de criteris utilitzats, concretament 33, també es classifica segons aquestes quatre categories. Cadascun dels criteris presenta un determinat pes d'importància relativa en la presa de decisions. Finalment, es desenvolupa tot el procés de decisió fins a obtenir el disseny complet de l'EDAR. El procés de decisió s'ha dividit en dues parts diferenciades però que alhora s'entrellacen: la línia d'aigua i la línia de fang. El procés de decisió presenta un total de divuit qüestions amb un màxim de quatre alternatives per pregunta (dotze qüestions corresponen a la línia d'aigua, i sis a la línia de fangs). Per solucionar cadascuna d'aquestes qüestions, s'avaluen les alternatives proposades respecte a un conjunt de criteris triats de la llista inicial. Aplicant el procés de decisió multicriteri anomenat SMART (simple multiattribute rating technique), es combinen els resultats de les alternatives respecte a cada criteri, tenint en compte la importància de cada criteri per obtenir un sol valor per alternativa. Per quantificar els criteris referents a l'operació del procés i les de tipus econòmic s'han utilitzat els programes GPS-X i CapdetWorks respectivament. Pel que fa als criteris no quantificats mitjançant aquests programes, s'han resolt de manera qualitativa i <br/>mitjançant manuals de disseny i també tenint en compte l'opinió d'experts en aquest camp. L'alternativa que obté un pes més elevat és la recomanada per al procés de decisió. El cas d'estudi finalitza un cop s'obté el disseny complet de l'EDAR. Per integrar tots aquests elements que hem esmentat i donar suport al desenvolupament del procés de decisió s'ha utilitzat el programa DRAMA (Design Rationale Management). A continuació, es fa una anàlisi comparativa entre l'EDAR que hi ha actualment al municipi de Granollers i l'EDAR resultat del cas d'estudi. Es descriu el diagrama de flux que conforma l'EDAR de Granollers i el diagrama de flux de l'EDAR resultat de l'estudi, se'n fa una anàlisi comparativa justificant cadascuna de les decisions preses en el cas d'estudi i, finalment, es fa una discussió de resultats on es reflecteixen els avantatges associats d'aplicar la metodologia de disseny conceptual proposada. Finalment, es presenten les conclusions de la tesi. Els principals resultats de la tesi es van publicar el 2002 a la revista internacional Industrial and Engineering Chemistry Research (N. Vidal, R. Bañares-Alcántara, I. Rodríguez-Roda i M. Poch: "Design of wastewater treatment plants using a conceptual design methodology", Industrial and Engineering Chemistry Research, 41 (20), pàg. 4993-5005) i la continuació de la línia de recerca al Laboratori d'Enginyeria Química i Ambiental de la UdG ha comportat la presentació del treball de recerca de Xavi Flores "Procés de decisió jeràrquic combinat amb anàlisi multicriteri per al suport al disseny conceptual de sistemes de fangs actius d'una estació depuradora d'aigües residuals" i la presentació dels resultats parcials al congrés internacional de la 9th IWA Conference on Design, Operation and Economics of Large Wastewater Treatment, que va tenir lloc el setembre passat a Praga ("Combining hierarchical decision process with multi-criteria analysis for conceptual design of WWTP", X. Flores, N. Vidal, A. Bonmatí, J. B. Copp i I. Rodríguez-Roda).<br>This thesis proposes a methodology for the conceptual design of wastewater treatment plants (WWTP) via a combination of a hierarchical decision process and multicriteria decision analysis. We begin with a brief introduction into the main fields of study involved in this work: the design of chemical processes in general; the design of wastewater treatment plants in particular and multicriteria decision analysis as applied to environmental management. We go on to outline the objectives of the study and then describe our methodology as well as the computer-based support tools used. In order to evaluate and contrast our design methodology, we present a study case in which a conceptual design is developed for a WWTP which has the same requirements as the actual WWTP currently in operation in the town of Granollers. First, we present the initial information and then define the design objectives, as well as the set of criteria that will be used in order to evaluate the degree to which the objectives have been met.<br/>The design objectives are of different types: environmental, technical, social and economical; the set of criteria, of which there are 33 in all, are also classified into these four categories. Each of the criteria has a specific weighting in terms of their importance in taking decisions. Next, we go through the whole decision process leading to the completion of the design of the WWTP. The decision process has been divided into two parts which are differentiated but at the same time, interconnected: the water line and the sludge line. The decision process involves a total of eighteen questions (twelve for the water line and six for the sludge line) with a maximum of four alternatives per question. In order to answer each question, the proposed alternatives are evaluated in relation to a set of criteria chosen from the initial list. Applying the multicriteria decision process known as SMART (simple multiattribute rating technique), the results for the alternatives with respect to each criteria are combined, bearing in mind the importance of each criteria, in order to get a single value for each alternative. To get the results for those alternatives relating to the operation of the process and those to do with economical factors, we used the GPS-X and CapdetWorks programmes, respectively. The criteria not quantified by means of these programmes were resolved by qualitative means and through the use of design manuals, in addition to taking expert opinion into account. The alternative that obtains the highest weighting is the one which is recommended by the decision process. The study case is completed once a complete design of the WWTP is obtained. In order to integrate all the elements we have mentioned, and to assist the development of the decision process, we employed the programme known as DRAMA (Design Rationale Management). We then go on to give a comparative analysis between the real WWTP in Granollers and the WWTP resulting from our study case. We describe and compare the flow diagrams in both cases, providing justification for each of the decisions taken in the study case and then discuss the results, reflecting on the advantages to be gained from using the methodology of conceptual design we propose. Finally, we present the conclusions of our thesis.<br/>The main results of this thesis were published, in 2002, in the international magazine, Industrial and Engineering Chemistry Research (N. Vidal, R. Bañares-Alcántara, I. Rodríguez-Roda and M. Poch: "Design of wastewater treatment plants using a conceptual design methodology", Industrial and Engineering Chemistry Research, 41 (20), pages 4993-5005). Continuing work in this line of research at the Laboratori d'Enginyeria Química i Ambiental at the University of Girona has led to the research work by Xavi Flores, Procés de decisió jeràrquic combinat amb anàlisi multicriteri per al suport al disseny conceptual de sistemes de fangs actius d'una estació depuradora d'aigües residuals (A hierarchical decision process combined with multicriteria analysis to assist conceptual design of active sludge systems in a wastewater treatment plant) and the presentation of the preliminary results at the 9th IWA Conference on Design, Operation and Economics of Large Wastewater Treatment, which took place in September, 2003, in Prague ("Combining hierarchical decision process with multi-criteria analysis for conceptual design of WWTP", X. Flores, Núria Vidal, August Bonmatí, J. B. Copp and Ignasi Rodríguez-Roda).

Vertical stacking—based on modern manufacturing and integration technologies—of multiple 2D chips enables three-dimensional integrated circuits (3D ICs). This exploitation of the third dimension is generally accepted for aiming at higher packing densities, heterogeneous integration, shorter interconnects, reduced power consumption, increased data bandwidth, and realizing highly-parallel systems in one device. However, the commercial acceptance of 3D ICs is currently behind its expectations, mainly due to challenges regarding manufacturing and integration technologies as well as design automation. This work addresses three selected, practically relevant design challenges: (i) increasing the constrained reusability of proven, reliable 2D intellectual property blocks, (ii) planning different types of (comparatively large) through-silicon vias with focus on their impact on design quality, as well as (iii) structural planning of massively-parallel, 3D-IC-specific interconnect structures during 3D floorplanning. A key concept of this work is to account for interconnect structures and their properties during early design phases in order to support effective and high-quality 3D-IC-design flows. To tackle the above listed challenges, modular design-flow extensions and methodologies have been developed. Experimental investigations reveal the effectiveness and efficiency of the proposed techniques, and provide findings on 3D integration with particular focus on interconnect structures. We suggest consideration of these findings when formulating guidelines for successful 3D-IC design automation<br>Dreidimensional integrierte Schaltkreise (3D-ICs) beruhen auf neuartigen Herstellungs- und Integrationstechnologien, wobei vor allem “klassische” 2D-ICs vertikal zu einem neuartigen 3D-System gestapelt werden. Dieser Ansatz zur Erschließung der dritten Dimension im Schaltkreisentwurf ist nach Expertenmeinung dazu geeignet, höhere Integrationsdichten zu erreichen, heterogene Integration zu realisieren, kürzere Verdrahtungswege zu ermöglichen, Leistungsaufnahmen zu reduzieren, Datenübertragungsraten zu erhöhen, sowie hoch-parallele Systeme in einer Baugruppe umzusetzen. Aufgrund von technologischen und entwurfsmethodischen Schwierigkeiten bleibt jedoch bisher die kommerzielle Anwendung von 3D-ICs deutlich hinter den Erwartungen zurück. In dieser Arbeit werden drei ausgewählte, praktisch relevante Problemstellungen der Entwurfsautomatisierung von 3D-ICs bearbeitet: (i) die Verbesserung der (eingeschränkten) Wiederverwendbarkeit von zuverlässigen 2D-Intellectual-Property-Blöcken, (ii) die komplexe Planung von verschiedenartigen, verhältnismäßig großen Through-Silicion Vias unter Beachtung ihres Einflusses auf die Entwurfsqualität, und (iii) die strukturelle Einbindung von massiv-parallelen, 3D-IC-spezifischen Verbindungsstrukturen während der Floorplanning-Phase. Das Ziel dieser Arbeit besteht darin, Verbindungsstrukturen mit deren wesentlichen Eigenschaften bereits in den frühen Phasen des Entwurfsprozesses zu berücksichtigen. Dies begünstigt einen qualitativ hochwertigen Entwurf von 3D-ICs. Die in dieser Arbeit vorgestellten modularen Entwurfsprozess-Erweiterungen bzw. -Methodiken dienen zur effizienten Lösung der oben genannten Problemstellungen. Experimentelle Untersuchungen bestätigen die Wirksamkeit sowie die Effektivität der erarbeiten Methoden. Darüber hinaus liefern sie praktische Erkenntnisse bezüglich der Anwendung von 3D-ICs und der Planung deren Verbindungsstrukturen. Diese Erkenntnisse sind zur Ableitung von Richtlinien für den erfolgreichen Entwurf von 3D-ICs dienlich

The Sámi’s past activities have been documented historically from a European perspective, and more recently from an anthropological viewpoint, giving a generalised observation of the Sámi, during the study period of AD200-AD1800, as semi-nomadic hunter gatherers, with several theories suggesting that interaction with Europeans, through trade, led to the adoption of European activities by certain groups of the Sámi (Eiermann, 1923; Paine, 1957; Manker and Vorren, 1962; Bratrein, 1981; Mathiesen et al, 1981; Meriot, 1984). However, there is almost no information on the impact the Sámi had on the landscape, either before or after any adoption of European activities, and none investigating what cultural footprint or indicators would remain from Sámi or European occupation and/or activity within the typically podzolic soils of Northern Sweden. Consequently the thesis aims to contribute to the gap in knowledge through the formation of a podzol model identifying the links between anthropogenic activity and the alteration of podzol soils, and through the creation of soils based models which identify the cultural indicators associated with both Sámi and European activity; formed from the identification of cultural indicators retained within known Sámi and European sites. The methods used to obtain the information needed to achieve this were the pH and magnetic susceptibility from bulk soil samples and micromorphological and chemical analysis of thin section slides through the use of standard microscopy and X-ray fluorescence from a scanning electron microscope. The analysis revealed that the Sámi had an extremely low impact on the landscape, leaving hard to detect cultural indicators related to reindeer herding in the form of reindeer faecal material with corresponding phosphorous peaks in the thin section slides. The European footprint however, was markedly different and very visible even within the acidic soil environment. The European indicators were cultivation based and included phosphorous and aluminium peaks as well as a deepened, highly homogenised plaggen style anthropogenic topsoil rich in ‘added’ materials. An abandoned European site which visibly and chemically shows the formation of a secondary albic horizon within the anthropogenic topsoil also provides an insight into the delicate balance of cultivated soil in northern Sweden, whilst reinforcing the outputs identified in the podzol model. Due to the almost invisible Sámi footprint on the landscape, areas of overlap were impossible to identify however, there was no evidence of the adoption of European cultivation activities at any of the Sámi sites investigated. The only known area of interaction between the two cultures was an official market place which had been a Sámi winter settlement prior to its use as a market site. This site showed none of the reindeer based Sámi indicators or the cultivation based European indicators, but did contain pottery fragments which could be linked to trade or occupation. Overall, the thesis reinforces the low impact expected of the semi-nomadic Sámi and sheds light on the underlying podzolic processes influencing the anthropogenically modified soils of Northern Sweden. The podzol model is reinforced by several findings throughout the thesis and the soils based cultural indicator models for both Sámi and European activity have been successfully tested against independent entomological and palynological data and therefore provide reliable reference material for future studies.

2007/2008<br>This thesis is devoted to the study of the growth of III-V nanowires (NWs) by catalyst assisted and catalyst free molecular beam epitaxy (MBE). The nanostructures have been routinely characterized by scanning electron microscopy (SEM) and, to a minor extent by transmission electron microscopy (TEM). X-ray photoemission spectroscopy (XPS), scanning photoemission microscopy (SPEM), extended X-ray absrorption fi ne structure analysis (EXAFS), photoluminescence (PL) and trans- port measurements have given an important contribution on specifi c topics. The first section of this thesis reports on GaAs, InAs, and InGaAs NWs growth by Au assisted MBE. A substrate treatment is proposed that improves uniformity in the NWS morphology. Thanks to a careful statistical analysis of the NWs shape and dimensions as a function of growth temperature and duration, evidence is found of radial growth of the NWs taking place together with the axial growth at the tip. This eff ect is interpreted in term of temperature dependent diff usion length of the cations on the NWs lateral surface. The control of the NWs radial growth allowed to grow core shell InGaAs/GaAs NWs, displaying superior optical quality. A new procedure is proposed to protect NWs surface from air exposure. This procedure allowed to perform ex-situ SPEM studies of electronic properties of the NWs. The second part of this thesis is devoted to Au-free NWs growth. GaAs and InAs NWs were successfully grown for the first time using Mn as catalyst. Incorporation of Mn in the NW is studied using EXAFS technique. It is shown that Mn atoms are incorporated in the body of GaAs NWs. Use of low growth temperature is suggested in order to improve the Mn incorporation inside GaAs NWs and obtain NWs with magnetic properties. Finally, growth of GaAs and InAs NWs on cleaved Si subtrate is demonstrated without the use of any outside metal catalyst. Two kinds of nanowires have been obtained. The experimental findings suggest that the two types of nanowires grow after di fferent growth processes.<br>Questa tesi e' dedicata allo studio della crescita di nanofili di semiconduttori III- V tramite epitassia da fasci molecolari (MBE) assistita da catalizzatore e senza l'uso di catalizzatori. Le nanostrutture sono state caratterizzate sistematicamente tramite microscopia elettronica a scansione (SEM), e in maniera minore microscopia elettronica in trasmissione (TEM). Altre tecniche come la spettroscopia di fotoemissione da raggi x (XPS), la microscopia da fotoemissione in scansione (SPEM), la spettroscopia di assorbimento x (in particolare la extended X-ray absorpition fine structure analysis (EXAFS)) la fotoluminescenza (PL), e il trasporto elettrico hanno dato importanti contributi su problematiche specifiche. La prima parte di questa tesi riguarda la crescita di nanofili di GaAs, InAs e InGaAs tramite MBE assistita da oro. Viene proposto un trattamento del substrato che migliora nettamente l'omogeneita' morfologica dei nanofili. Grazie ad un'attenta analisi statistica della forma e delle dimensioni dei nanofili in funzione della temperatura e del tempo di crescita e' stata dimostrata la crescita radiale dei nanofili, che avviene insieme alla crescita assiale che ha luogo alla punta del nanofilo. Le osservazioni sperimentali sono state interpretate in termini di dipendenza dalla temperatura della lunghezza di diffusione dei cationi sulle super ci laterali dei nanofili. Il controllo della crescita radiale ha permesso di crescere nanofili di InGaAs/GaAs core shell, costituiti cioe' da una anima centrale di InGaAs (core) e uno strato esterno di GaAs (shell) , che hanno dimostrato eccellente qualita' ottica. Viene quindi proposta una nuova procedura per proteggere la super ficie dei nanofili durante l'esposizione all'aria. Grazie a questa e' stato possibile realizzare ex-situ uno studio SPEM delle proprieta' elettroniche dei nanofili. La seconda parte della tesi riguarda la crescita di nanofili senza l'uso di oro. Viene per la prima volta dimostrata la possibilita' di crescere nanofili di GaAs e InAs usando il manganese come catalizzatore. L'incorporazione del Mn come impurezza nei nanofili e' stata studiata tramite EXAFS. Le misure hanno dimostrato che atomi di Mn sono effettivamente incorporate nel corpo dei nano fili. La crescita delle nanostrutture a temperatura piu' bassa potrebbe migliorare qualitativamente l'incorporazione del Mn e permettere la crescita di nanofili con proprieta' magnetiche. Viene in fine dimostrata la crescita di nanofili di GaAs e di InAs senza l'utilizzo di materiali diversi da quelli costituenti il semiconduttore. Tale risultato e' ottenuto su superfici sfaldate di silicio. Sono state osservate nanostrutture di due tipi, che sulla base dei dati sperimentali sembrano essere dovuti a due diversi meccanismi di crescita.<br>XXI Ciclo<br>1977

The wastewater treatment plays an important role in the maintenance of natural water resources. However, regardless of the technology used or the level of treatment required, the treatment plants of the XXI century are highly complex systems that not only need to meet technical requirements, but also environmental and economic criteria. In this context, decision support systems for environmental domains (English, Environmental Decision Support Systems or EDSS) are configured as an effective tool to support the selection and evaluation of integrated water treatment alternatives. The EDSS designed can be defined as interactive software, flexible and adaptable, which links the numerical models / algorithms, techniques and environmental ontologies, knowledge-based environment, and is capable of supporting decision making, either in choosing between different alternatives, improving potential solutions, or in the integrated assessment using methodologies ranging from environmental (Life Cycle Analysis) to economic<br>La depuració d’aigües residuals juga un paper fonamental en el manteniment dels recursos hídrics naturals. Tanmateix, sigui quina sigui la tecnologia emprada o el nivell de depuració requerit, les plantes de tractament del segle XXI són sistemes d’alta complexitat, que no només han de satisfer requeriments de tipus tècnic, sinó també de tipus ambiental i econòmic. En aquest context, els sistemes de suport a la decisió en dominis ambientals (en anglès, Environmental Decision Support Systems o EDSS) es configuren com una eina eficaç per donar suport a la selecció i a l’avaluació integrada de diferents alternatives de depuració d’aigües. El EDSS dissenyat pot definir-se com un programari interactiu, flexible i adaptable, que vincula els models numèrics/algoritmes amb tècniques basades en el coneixement i ontologies ambientals, i que és capaç de donar suport a la presa de decisió, ja sigui en l’elecció entre diferents alternatives, millorant una solució, o bé en l’avaluació integrada a través de metodologies ambientals (Anàlisi de Cicle de Vida) i econòmiques

碩士<br>國立交通大學<br>管理學院高階主管管理碩士學程<br>102<br>The semiconductor industry has been under flourishing development for twenty to thirty years in Taiwan. The Electronic Design Automation (EDA) also becomes indispensible to the industry, for it becomes more complicated to produce smaller chips. Integrated Circuit (IC) is manufactured from six inches wafer to twelve inches now. Moreover, IC and process line width convert from micrometre (um) to nanometre (nm) today. EDA is an industry to assist IC design about developing more complicated and high-class design and solving problems. EDA plays an important role of supporting IC design and manufacturing. EDA inustry has some unique attributes; such as the scale of EDA market to grow is pretty small. Because of the lean startup concept, the new EDA firms are popping up quickly. Under the circumstance of minor market share, the large frims need to combine some specific small firms in order to acquire their unique skills to maintain their expertise. By doing so, the big firms then can create enough economic scale to hold their development of new skills and their business. Nowadays, the top three of the EDA firms are Synopsys、Mentor Graphics and Cadence. Due to numerous merge，these firms are able to develop EDA tools in different design phases. Their market shares are up to 70% to 80%. Under the highly concentrated industry environment, these EDA firms should consider how to sustain their business critically. The goal of this research is to discuss one of the EDA firm's business model analysis.

Cerium oxide nanoparticles have been proposed as an anticancer agent, thanks to their ability of tuning the redox activity in accordance to different conditions, which lead to selective roles on healthy and cancer cells. Recent evidence suggested the ability of these nanoparticles to be toxic against cancer cells, while confer protection from oxidative stress, toward healthy cells. The main focus of this study was to determine the ultrastructural effects of cerium oxide nanoparticles over multiple incubation time of 1, 3, and 7 days on breast healthy and cancer cells. Cellular characterizations were carried out using electron microscopes, both transmission and scanning electron microscopes, while the viability assessments were performed by propidium iodide and trypan blue viability assays. The obtained results of the viability assays and electron microscopy suggested higher toxic effects on the cancer cell line viability by using a nanoceria dose of 300 μg/mL after 1 day of treatment. Such effects were shown to be preserved at 3 days, and in a longer time point of 7 days. On the contrary, the healthy cells underwent less effects on their viability at time point of 1 and 7 days. The 3 days treatment demonstrated a reduction on the number of cells that did not correlate with an increase of the dead cells, which suggested a possible initial decrease of the cell growth rate, which could be due to the high intracellular loading of nanoparticles. To conclude, the overall result of this experiment suggested that 300 μg/mL of CeO2 nanoparticles is the most suitable dose, within the range and the time point tested, which induces long-lasting cytotoxic effects in breast cancer cells, without harming the normal cells, as highlighted by the viability assays and ultrastructural characterization of electron microscopy analysis.

Dissertação apresentada como requisito parcial para obtenção do grau de Mestre em Ciência e Sistemas de Informação Geográfica<br>The rapidly increasing volume of digital geographic data is overwhelming for conventional analysis techniques and methods. Therefore new approaches are needed to transform data into information, and ultimately, into knowledge. Exploratory data analysis is a foundation stone in this process. It is concerned with the formation of a simplified overview of data sets. Clustering and projection are among the examples of useful methods to achieve this task. The Self-Organizing Map (SOM) algorithm performs both, in a non-linear mapping from a high-dimensional data space to a low-dimensional space aiming to preserve the topological relations in the data. The aim of this thesis is to demonstrate the effectiveness of SOM application in visual exploration of physical geography data to support the delineation of Portuguese mainland regions. The main justifications for the application of SOM in this issue are its features of stressing local factors and topological ordering. For experimental assessment, the public domain thematic maps from Instituto do Ambiente are used. Several authors’ maps of Portuguese regions are used for evaluation of empirical results.(...)

Résumé L’hypothèse de la période critique, émise par Lenneberg dans les années 60, affirmait qu’un enfant pouvait acquérir une langue seconde, sans difficulté, environ jusqu’à l’âge de la puberté. Après cette période, l’apprentissage d’un autre idiome serait difficile, dû à la latéralisation du cerveau. En même temps, les travaux de Chomsky enrichirent cette théorie avec l’idée de la Grammaire universelle, laquelle établit que nous possédons tous, dès la naissance, les éléments linguistiques universels qui nous permettent d’acquérir une langue maternelle. Tant que la Grammaire universelle est active, notre langue maternelle se développe et c’est pourquoi, si nous apprenons une autre langue pendant cette période, l’acquisition de celle-ci se produit de manière presque naturelle. Pour cette raison, plus une langue est apprise tôt, plus elle sera maîtrisée avec succès. En nous appuyant sur ce cadre théorique ainsi que sur l’Analyse d’erreurs, outil qui permet au professeur de prédire quelques erreurs avec la finalité de créer des stratégies d’apprentissage d’une langue seconde, nous tenterons de vérifier dans le présent travail si l’âge est un facteur qui influence positivement ou négativement l’apprentissage d’une langue seconde, l’espagnol dans ce cas-ci, par le biais de l’analyse comparative des prépositions a/ en dans deux groupes d’étudiants différents.<br>Abstract According to Leeneberg's critical period hypothesis from the sixties, a child can acquire a second language approximately until puberty, for afterwards the lateralization of the brain takes place and the acquisition of second language becomes more difficult. Further on, Chomsky’s research would contribute to this theory with the Universal Grammar idea or the inborn universal linguistic elements that we use in order to acquire mother tongue. While the Universal Grammar is still on, the already acquired Mother Tongue continues to develop. As a result, the acquisition of another language during this period becomes a natural process, leading to the conclusion that the earlier a child starts learning a second language, the better its acquisition will be. Therefore and for the purpose of this research, a theoretical framework and the error analysis, the tool allowing the teacher to predict some error in order to create the adequate language strategies for effective second language acquisition, are used. I will try to verify the age-factor influence positively or negatively in the acquisition of a second language, in this special case the Spanish language, by means of the comparative analysis of the a/ en prepositional pair with two different groups of apprentices.

Soy flour (SF), a by-product of the soybean oil extraction processing, was investigated for its application in soy-polypropylene composites for interior automotive applications. The emphasis of this work was the understanding of this new type of filler material and the contribution of its major constituents to its thermal stability and impact properties. For this reason, reference materials were selected to represent the protein (soy protein isolate (SPI)) and carbohydrate (soy hulls (SH)) constituents of the soy flour. Additional materials were also investigated: the residue obtained after the protein removal from the soy flour which was called insoluble soy (IS), and the remaining liquid solution after acid precipitation of the proteins, containing mostly sugars and minerals, which was called soluble sugar extract (SSE). Two treatments, potassium permanganate and autoclave, were analyzed for their potential to modify the properties of the soy composite materials. An acid treatment with sulfuric acid conducted on soy flour was also considered. The soy materials were studied by thermogravimetric analysis (TGA) under isothermal (in air) and dynamic (in nitrogen) conditions. SPI had the highest thermal stability and SSE the lowest thermal stability for the early stage of the heating process. Those two materials had the highest amount of residual mass at the end of the dynamic TGA in nitrogen. The two treatments showed minimal effect on the isothermal thermal stability of the soy materials at 200 ??C. A minor improvement was observed for the autoclave treated soy materials. Fourier transformed infrared (FTIR) spectroscopy indicated that the chemical surface composition differed according to type of the soy materials but no difference could be observed for the treatments within one type of soy material. Contact angle analysis and surface energy estimation indicated differences of the surface hydrophobicity of the soy materials according to type of material and treatment. The initial water contact angle ranged from 57 ?? for SF to 85 ?? for SH. The rate of water absorption increased dramatically after the autoclave treatment for IS and SPI. Both materials showed the highest increase in the polar surface energy fraction. In general, the major change of the surface energy was associated with change of the polar fraction. After KMnO4 treatment, the polar surface energy of SF, IS and SPI decreased while SH showed a slight increase after KMnO4 treatment. A relationship between protein content and polar surface energy was observed and seen to be more pronounced when high protein containing soy materials were treated with KMnO4 and autoclave. Based on the polar surface energy results, the most suitable soy materials for polypropylene compounding are SPI (KMnO4), SH, and IS (KMnO4) because their polar surface energy are the lowest which should make them more compatible with non-polar polymers such as polypropylene. The soy materials were compounded as 30 wt-% material loading with an injection moulding grade polypropylene blend for different combinations of soy material treatment and coupling agents. Notched Izod impact and flexural strength as well as flexural modulus estimates indicated that the mechanical properties of the autoclaved SF decreased when compared to untreated soy flour while the potassium permanganate treated SF improved in impact and flexural properties. Combinations of the two treatments and two selected (maleic anhydride grafted polypropylene) coupling agents showed improved impact and flexural properties for the autoclaved soy flour but decreased properties for the potassium permanganate treated soy flour. Scanning electron microscopy of the fractured section, obtained after impact testing of the composite material, revealed different crack propagation mechanisms for the treated SF. Autoclaved SF had a poor interface with large gaps between the material and the polypropylene matrix. After the addition of a maleic anhydride coupling agent to the autoclaved SF and polypropylene formulation, the SF was fully embedded in the polymer matrix. Potassium permanganate treated SF showed partial bonding between the material and the polymer matrix but some of the material showed poor bonding to the matrix. The acid treated SF showed cracks through the dispersed phase and completely broken components that did not bind to the polypropylene matrix. In conclusion, the two most promising soy materials in terms of impact and flexural properties improvement of soy polypropylene composites were potassium permanganate treated SF and the autoclaved SF combined with maleic anhydride coupling agent formulation.