Rapid and reliable techniques are necessary for the analysis of accelerants, including gasoline, from fire debris evidence in forensic arson investigations. Gasoline additives can be used as chemical attribute signatures (CAS) to distinguish between source locations due to the variation in additives used. Source attribution using CAS is needed in forensic chemistry, as the determination of a single gasoline source could be a potential investigation tool for law enforcement and other agencies conducting arson investigation. Direct analysis in real time-mass spectrometry (DART-MS) has had increasing popularity in the field of forensic chemistry for chemical analysis, and it has been applied to fire debris analysis. DART-MS has great capacity for gasoline source attribution due to its ionization technique and inclusion of higher molecular weight ions, which correspond to the CAS in gasoline. To test the hypothesis of gasoline source attribution, 21 gasoline samples were collected across Massachusetts, New Hampshire, and Connecticut. DART-MS data were generated for each sample of gasoline in replicates of 10. The data were grouped based on geographical location and evaluated by Principal Component Analysis (PCA). PCA was used to evaluate the similarities and differences in gasoline DART-MS data by generating and classifying the gasoline sample groups formed. Leave-one-out cross-validation (LOOCV) was performed on each geographical group after PCA. LOOCV was used as the validation technique to determine the validity of the model and asses its capability at classifying unknown gasoline samples. DART-MS data across geographical groups was found to have varying levels of similarity and difference through visual inspection of the mass spectra. PCA showed distinct groupings of individual gasoline samples across all tested geographical groups, with 3 out of 6 geographical groups showing no overlap between gasoline sample classifications. Two groups showed minimal overlapping, while 1 group had overlapping between multiple gasoline sample classifications. Three groups had a LOOCV of 100% with no misclassifications. The other LOOCV were 98%, 96.67%, and 85%. The PCA and comparison of DART-MS data provides evidence of successful differentiation between gasoline samples of the same brand across Massachusetts, New Hampshire, and Connecticut. This research aims to provide an overview and understanding of chemometrics and DART-MS and how these techniques may be applied for forensic source attribution purposes.

I Sverige har vi flera stora idrottsevenemang som var för sig lockar tiotusentals deltagare varje år. Arrangörerna av dessa idrottsevenemang har i uppgift att leva upp till varje deltagares (kunds) förväntningar och tillfredsställa deras behov. Kundvärde är ett centralt begrepp inom både kvalitetsutveckling och marknadsföring och kundvärdeskapande anses vara en viktig framgångsfaktor för alla organisationer. Inte minst i framtiden då konsumenterna allt mer vill vara med och utforma produkterna de köper. Syftet med studien var att uppnå ökad förståelse för kundvärdeskapande inom idrottsevenemang genom att undersöka hur arrangörer arbetar idag och vill arbeta i framtiden för att främja ett högt upplevt kundvärde hos sina deltagare. Empiri samlades in genom fem intervjuer med arrangörer av idrottsevenemang. Analys av datamaterialet visade att arrangörerna som ingick i studien idag använder strategier och aktiviteter inom 12 olika teman med syfte att främja ett högt upplevt kundvärde. Efter analys drogs slutsatsen att arrangörerna idag erbjuder sina deltagare möjlighet till samskapande av kundvärde framförallt genom att tillföra de tre förutsättningarna dialog, riskbedömning och transparens. Inför framtiden identifierades tre områden för fortsatt utveckling och förbättring kring kundvärdeskapande: utökad/differentierad dialog med deltagarna, fler samarbeten och ett tydligt socialt ansvar samt att ge deltagarna mer mandat att vara med och driva utveckling och vara delaktiga i utformningen av evenemangen. / In Sweden we have several major sports events and each of them attracts tens of thousands of participants each year. The organizers of these sporting events have the task of meeting the expectations of each participant (customer) and satisfy their needs. Customer value is a key concept in both Total Quality Management (TQM) and marketing and customer value creation is considered an important success factor for all organizations. Not least in the future when consumers increasingly want to be involved in designing the products they buy. The aim of the study was to achieve increased understanding of customer value creation in sports events by examining how organizers work todayand want to work in the future to promote a high level of customer value for their participants. Data was collected through five interviews with organizers of sports events. Analysis of the data showed that the organizers today use strategies and activities within 12 different themes with the aim of promoting a high level of customer value. A conclusion from the analysis was that organizers today offer their participants the opportunity to co-create customer value by adding the three building blocks dialogue, risk assessment and transparency. For future improvements and continued development in customer value creation three areas were identified: expanded/differentiated dialogue with participants, more collaborations and clear social responsibility and giving participants more mandate to participate in development and participate in the design of the events. / <p>2018-06-27</p>

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.