La miniaturisation et la complexification croissante des composants microélectroniques induit une sensibilisation et une fragilisation accrue des composants vis-à-vis des contaminations présentes dans les zones de productions appelées “salles blanches”. Dans ces espaces, le contrôle actuel de la contamination organique n’est pas suffisant puisqu’il ne permet pas d’éviter la contamination de surface des plaquettes de silicium et des optiques des robots de production utilisés pour la photolithographie. Un contrôle accru des concentrations des contaminants organiques dans les atmosphères des salles blanches devient donc nécessaire et de nouvelles méthodes analytiques doivent être développées et validées. Dans le cadre de ce travail, des méthodes d’analyse ont été développées et validées afin de disposer d’une gamme d’outils permettant un suivi rigoureux des contaminations. Ces outils permettent d’identifier et de quantifier les contaminations surfaciques des plaquettes de silicium par des composés organiques semi-volatils (phtalates et organophosphorés) mais aussi de déterminer les concentrations de composés organiques volatils présents dans l’atmosphère des salles blanches. Ces méthodes font appel aux technologies du WOS/ATD-GC-MS « Wafer Outgassing System/Automated Thermal Desorber–Gas Chromatography–Mass Spectrometry » et de la DART-ToF-MS « Direct Analysis in Real Time-Time of Flight–Mass Spectrometry » pour les analyses de surfaces et au PTR-ToF-MS « Proton Transfer Reaction – Time of Flight - Mass Spectrometry » pour l’analyse de l’atmosphère. / The recent advances in the miniaturization and complexification of microelectronic components induce an increase in the sensitivity of these components regarding the organic contamination present in the production zone called “clean room”. Although, the control of organic contamination in the clean room is very rigorous it does not avoid the contamination of silicon wafer surfaces and robot lenses used in the photolithography process. The later implies that new analytical methodologies should be developed and validated. In this work, analytical methods were developed and validated in order to have a panel of tools which allows careful monitoring of organic contaminants. These tools allow the identification and quantitation of the contamination of silicon wafer surface by semi-volatiles organic compounds (phthalates and organophosphates) and the determination of volatile organic compounds concentrations in the clean room atmosphere. These methods uses the WOS/ATD-GC-MS « Wafer Outgassing System/Automated Thermal Desorber–Gas Chromatography–Mass Spectrometry » technology and the DART-ToF-MS « Direct Analysis in Real Time-Time of Flight–Mass Spectrometry » technology for wafer surface analysis and the PTR-ToF-MS « Proton Transfer Reaction – Time of Flight - Mass Spectrometry » technology for gas-phase analysis.

<p>U doktorskoj disertaciji evaluirani su interkorelacioni rezultati odnosa ključnih fizičko-hemijskih parametara i katjona metala u površinskoj vodi Dunava, Tise (na po tri selektovana reprezentativna lokaliteta) i kanala Dunav-Tisa-Dunav (na dva lokaliteta). U<br />Kanalu Dunav-Tisa-Dunav praćene su i rezidualne katjonske koncentracije metala u sedimentu. Na osnovu podataka prisutnosti katjona metala u heterogenom sistemu tečno/čvrsto izračunate su po prvi put konstante podeonih procesa za ispitivane katjone metala. Primenom multivarijantnih statističkih metoda analizirani su korelacioni odnosi između ključnih fizičko-hemijskih parametara i koncentracionih nivoa rezidula katjona teških, lakih i semimetala. Faktorskom analizom (PCA) i klaster analizom sa dendogramima tumačeni, analizirani i diskutovani su dobijeni rezultati. Za optimalnog uočavanja korelacionih odnosa primenjeno je unapređeno rangiranje određenih skupova podataka (interkorelacije ključnih fizičko-hemijskih parametara i rezidua katjona metala) i grafički prikazanih Haseovih dijagrama primenom DART softvera (Decision Analysis by Ranking Techniques) za definisani model procene uticaja raspodele katjona toksičnih metala u heterogenom sistemu tečno/čvrsto na kvalitet površinskih voda.</p> / <p>In the doctoral thesis are evaluated inter correlational results of key physicochemical parameters and metal cations in surface water of Danube, Tisa (on three selected representative sampling points) and canal Danube-Tisa-Danube (on two sampling sites). In the canal Danube-Tisa-Danube are also followed residual metal cations concentrations in sediment. Based on metal cations presence data in heterogeneous system liquid/solid for the first time partitioning processes constants are calculated for<br />selected metal cations. Appling multivariate statistical methods correlations between key physicochemical parameters and concentration levels of residual heavy, light and semimetals cations are analysed. Using factorial analyse (PCA) and cluster analyse with dendograms obtained results were interpreted, analysed and discussed. For optimal comprehension of correlations, advanced method ranking of finite order sets is applied (inter correlations key physicochemical parameters and residual metal cations) and graphically shown Hasse diagrams obtained by DART software (Decision Analysis by Ranking Techniques) for defined impact assessment model of toxic metal cations partitioning in heterogeneous system liquid/solid for surface water quality.</p>

Advocates of urban light rail transit argue that positive developments around station area(s) should offset the costs of implementing a transit system by creating more livable communities and enhance surrounding residential property values. In some cases, decreased urban landscape aesthetics have been reported. The purpose of this study is to contribute to this debate via an analysis of the impact of the Dallas Area Rapid Transit system on residential property values in Dallas County. By examining the impact of distance on property values of two features of the DART system: the transit station and the rail line, and by holding a series of structural variables constant, a net change in value can be calculated using a multi-regression model.

The aim of this thesis is to examine how the central museums in Stockholm, Sweden, design and market their offerings by utilizing consumer knowledge. Current museum marketing research suggests that museums should be marketed as any organization; however, public museums are challenged by their mission to provide an offering that is framed by the state, and at the same time to attract visitors. Through semi-structured interviews with representatives from seven of the central museums in Stockholm, and a case study of a marketing campaign for an exhibition, information concerning the museums’ designing and marketing of offerings has been gathered. This information was analysed according to the theoretical framework which, building on co-creation of value theory, is an extended version of the DART-model to include word of mouth. The authors conclude that the museums are limited in their ability to adapt their offerings to consumer preferences due to their state given mission and a desire to be credible. Instead, online communication platforms are used to make the offerings available to more people and to market the offerings through the consumers’ online social networks.

Molecular ionization is owed much of its development from the early implementation of electron ionization (EI). Although dramatically increasing the library of compounds discovered, an inherent problem with EI was the low abundance of molecular ions detected due to high fragmentation leading to the difficult task of the correct chemical identification after mass spectrometry (MS). These problems stimulated the research into new ionization methods which sought to "soften" the ionization process. In the late 1980s the advancements of ionization techniques was thought to have reached its pinnacle with both electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). Both ionization techniques allowed for "soft" ionization of large molecular weight and/or labile compounds for intact characterization by MS. Albeit pervasive, neither ESI nor MALDI can be viewed as "magic bullet" ionization techniques. Both techniques require sample preparation which often included native sample destruction, and operation of these techniques took place in sealed enclosures and often, reduced pressure conditions. New open-air ionization techniques termed "ambient MS" enable direct analysis of samples of various physical states, sizes and shapes. One particular technique named Direct Analysis In Real Time (DART) has been steadily growing as one of the ambient tools of choice to ionize small molecular weight (< 1000 Da) molecules with a wide range of polarities. Although there is a large list of reported applications using DART as an ionization source, there have not been many studies investigating the fundamental properties of DART desorption and ionization mechanisms. The work presented in this thesis is aimed to provide in depth findings on the physicochemical phenomena during open-air DART desorption and ionization MS and current application developments. A review of recent ambient plasma-based desorption/ionization techniques for analytical MS is presented in Chapter 1. Chapter 2 presents the first investigations into the atmospheric pressure ion transport phenomena during DART analysis. Chapter 3 provides a comparison on the internal energy deposition processes during DART and pneumatically assisted-ESI. Chapter 4 investigates the complex spatially-dependent sampling sensitivity, dynamic range and ion suppression effects present in most DART experiments. New implementations and applications with DART are shown in Chapters 5 and 6. In Chapter 5, DART is coupled to multiplexed drift tube ion mobility spectrometry as a potential fieldable platform for the detection of toxic industrial chemicals and chemical warfare agents simulants. In Chapter 6, transmission-mode DART is shown to be an effective method for reproducible sampling from materials which allow for gas to flow through it. Also, Chapter 6 provides a description of a MS imaging platform coupling infrared laser ablation and DART-like phenomena. Finally, in Chapter 7 I will provide perspective on the work completed with DART and the tasks and goals that future studies should focus on.

Light Rail Transit (LRT) has been getting more attention in U.S. cities due to its socio-economic benefits, such as reducing pollution and congestion, as well as promoting regional economic development. However, huge capital costs remain an obstacle to the construction of a new light rail system. For this reason, cities in the planning phases of LRT want to use value capture tools to finance transit construction and operation. In theory, any improvement in a transportation structure that increases accessibility and reduces transportation cost can be capitalized into property values in an area. In turn, governments levy taxes on a portion of the additional value of adjacent properties. This study, however, aims to empirically examine whether value capture is possible in the recession when property and land values continue to decrease. The study uses the case of the DART Green Line, which started to run in 2009 just after a financial crisis in the U.S. The 5745 residential parcels are analyzed with using a hedonic price model in order to detect the Green Line’s influence on residential values before and after the recession. To enhance the proficiency of the regression, this study includes several structure and neighborhood characteristics. The statistical results found the Green Line’s benefits on residential values both in the pre-Green Line period (before the recession) and the post-Green Line period (during the recession). It is noteworthy there are still positive influences of transit accessibility on residential values even in the unstable housing market, although the magnitude of the variable has diminished compared to the pre-Green Line period. / text

One of the most fundamental challenges in analytical mass spectrometry (MS) is the efficient conversion of neutral molecules into intact gas-phase ions. In this thesis, I investigate the capabilities of various new and established ionization techniques including (a) the Array of Micromachined UltraSonic Electrosprays (AMUSE), (b) Direct Analysis in Real Time (DART) and (c) Electrospray Ionization (ESI) for bioanalytical and biomedical analysis purposes. The AMUSE is a MicroElectroMechanical System (MEMS)-based device that was created as an alternative, and more sensitive approach for ion generation in an array format. In the AMUSE, the processes of droplet formation and DC droplet charging are separated allowing ionization of liquid samples using low charging voltages and a wide variety of solvents. Our analytical characterization work with the AMUSE showed that ion generation with this device was indeed possible, and that incorporation of a Venturi device increased signal stability and sensitivity due to enhanced droplet desolvation and increased ion transfer efficiency. A detailed investigation to determine the optimal source parameters for ionization of aqueous solutions of model compounds including reserpine, leucine enkephalin and cytochrome C was carried out and it was found that ionization was possible even without the application of a DC charging potential. Subsequent experiments using the thermometer ion method to characterize the AMUSE from a more fundamental point of view, showed that AMUSE ions are lower in internal energy than ESI ions, opening interesting possibilities for the mass spectrometric study of labile species. Furthermore, it was found that it was possible to manipulate the internal energy of the ion population by varying the parameters that most strongly affect desolvation and focusing. Our studies with DART were directed at investigating its analytical potential for application to the identification of active ingredients (AIs) in low quality combination medicines and counterfeit antimalarials that are commonly sold in regions of the world (particularly Southeast Asia) where drug resistant malaria is endemic as their use may engender increased resistance against the few remaining effective antimalarials.

Que ce soit lors de la prévention d'actes malveillants ou l'expertise post-attentat, les techniques de prélèvement par frottis et d'analyse d'explosifs se doivent d'être à la fois fiables et sensibles. La méthode par chromatographie en phase liquide (HPLC) couplée à la spectrométrie de masse (MS) présente les caractéristiques requises mais nécessite une étape importante de préparation de l'échantillon et un temps d'analyse conséquent. L'évaluation des performances du couplage HPLC-MS pour l'analyse de frottis réalisés sur des matrices textiles et le développement d'une méthode d'analyse directe et quasi-instantanée de la surface de l'échantillon constituent l'objet de ce mémoire. Pour ce second objectif, les sources d'ionisation ambiante DESI et DART, couplées à la spectrométrie de masse haute résolution (HRMS) ont été utilisées. Une part importante de ce travail a été consacrée à l'étude des mécanismes CID des explosifs, lors de laquelle la HRMS a montré tout son intérêt. Si l'utilisation de la source DESI est plus délicate pour l'étude des surfaces textiles hydrophiles et absorbantes, le potentiel qualitatif de la source DART a été démontré avec succès sur des échantillons simulés et réels. Des résultats prometteurs illustrent la validité de cette approche analytique à la fois sensible, rapide et facile à mettre en ¿uvre, et encouragent à poursuivre les travaux vers une analyse quantitative. / Swabbing and analysis protocols for trace explosives detection have to be both reliable and sensitive, either for prevention measures against bomb attacks or for post-blast scene investigations. The coupling of mass spectrometry (MS) with liquid chromatography (HPLC) offers the required features but important sample preparation steps are often needed and chromatographic separations can require long run times. The evaluation of an LC-MS coupling for the analysis of fabric swabs and the development of a direct and nearly instantaneous method for sample surface analysis are the subjects of this dissertation. DESI and DART ion sources coupled with high resolution mass spectrometry (HRMS) were used for this second method. Part of this work was devoted to the study of CID mechanisms of explosives, in which HRMS appears to present a great interest. Even though the use of DESI source for hydrophilic and absorbent fabric samples analysis is tricky, DART source was successfully applied to qualitative analysis of simulated as well as real samples. Very promising results strengthen the relevance of this direct approach both sensitive, rapid and easily implementable, and encourage pursuing the studies toward quantitative analysis. Keywords: Forensic, explosives, fabrics, extraction, high resolution mass spectrometry, ESI, ambient ionization/desorption (DESI, DART), CID mechanisms, negative ions.

Hlavním cílem práce bylo zlepšení kvantitativních odhadů vegetačních parametrů smrkových porostů pomocí spektrálních simulací trojrozměrného modelu přenosu záření. Prvně bylo potřeba vytvořit přesný 3D model smrku. Implementace přesného 3D modelu smrku pro parametrizaci celých lesních porostů je v současné době výpočetně nemožné, bylo tedy nutné tento 3D model smrku zjednodušit. Přesný 3D model smrku společně s dostupnými leteckými daty sloužil pro nalezení optimálního zjednodušení. Optimální model vedl ke kompromisu mezi výpočetní náročností a přesností výsledné odrazivosti z modelu přenosu záření. Následně byl optimální model smrku využit pro odhady vegetačních parametrů ze satelitních snímků. Přesnost odhadů byla ověřena oproti pozemním měřením odhadovaných parametrů. Na závěr byly porovnány výsledky z odhadů vegetačních parametrů pomocí optimálního 3D modelu smrku s výsledky z tradičního přístupu pomocí modelů stromu s geometricky jednodušími tvary korun.

La curiethérapie est une méthode pour traiter les tumeurs cancéreuses qui consiste à placer à leur proximité des sources radioactives dont les rayonnements endommagent les cellules et mènent éventuellement à leur destruction. En curiethérapie conventionnelle, les sources utilisées sont scellées et seuls des rayonnements bêta et gamma s’en échappent. Dans une méthode de curiethérapie récemment commercialisée, la source n’est pas scellée et permet à des radionucléides, situés à quelques nanomètres sous sa surface, de s’échapper par mouvement de recul lors de leur désintégration. Ces radionucléides se diffusent par la suite dans la tumeur tout en poursuivant une chaîne de désintégration au cours de laquelle ils émettent principalement des particules alpha. L’énergie déposée par les particules alpha par unité de masse de tissu tumoral constitue la dose alpha. Les outils numériques de la curiethérapie conventionnelle ne tiennent pas compte de la diffusion des émetteurs et sont de ce fait inaptes à calculer correctement la distribution spatiale de la dose alpha. Le travail présenté ici avait pour but de développer des outils numériques incluant la modélisation de la diffusion, permettant ainsi un calcul adéquat de la distribution de dose. La méthode des volumes fnis a été utilisée pour développer des modèles en une, deux et trois dimensions, en coordonnées cylindriques et cartésiennes. Ces modèles déterminent où et quand se produisent les désintégrations, une information clé dans ce travail qui pourra aussi être utilisée dans des travaux futurs comme donnée d’entrée des outils numériques de la curiethérapie conventionnelle pour calculer les doses bêta et gamma. / Brachytherapy is a method for treating cancerous tumors which consists of placing near them radioactive sources whose radiation damages cells which eventually leads to their destruction. In conventional brachytherapy, the sources are sealed and only beta and gamma radiations escape. In a recently commercialized method of brachytherapy, the source is not sealed and allows radionuclides, located a few nanometers below its surface, to be released by recoil during their decay. These radionuclides then diffuse into the tumor while continuing to follow a decay chain during which they mainly emit alpha particles. The energy deposited by alpha particles per unit mass of tumor tissue constitutes the alpha dose. The numerical tools of conventional brachytherapy do not take into account the diffusion of emitters and are therefore unable to correctly calculate the spatial distribution of the alpha dose. The work presented here aimed at developing numerical tools including diffusion modeling, thus allowing an adequate calculation of the dose distribution. The finite volume method was used to develop models in one, two and three dimensions, in cylindrical and Cartesian coordinates. These models determine where and when radioactive decays occur, a key information in this work having also the potential of being used in future work as an input data for conventional brachytherapy numerical tools to calculate beta and gamma doses.