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The work presented here develops a gamma-ray spectral construction and analysis software tool that was used to analyze multi-detector data collected using a digital spectrometer with list mode capabilities. The tool was used to parse the output from three detectors and generate new spectra that the user chooses from post-processing suppression routines, such as simulated anticoincidence and coincidence spectra. Part of this research was also to characterize the improvements in the detection limits and the various detector efficiencies from this method as opposed to creating these spectra using traditional electronic gating systems. A focus is placed on the detection capability improvements for nuclear forensics purposes, particularly the identification and quantification of fission product samples, and structuring the code framework for handling these types of time-dependent samples while increasing the versatility of the detector system. Improvements to the minimum detectable activity for a series of fission products was accomplished through post-processing suppression methods and multi-dimensional spectral data structures are now achievable. / text

The goal of the research conducted for this master's thesis is to understand if active thermography is a suitable technique to detect (identify) and measure (approximate depth and or size) defects in additive manufacturing (AM) processes. Although other non-destructive measurement techniques exist, active thermography is an attractive option for AM applications because of the short measurement times that could be implemented between each layer of a print, and because of the relatively inexpensive equipment required. However, pulse thermography is typically applied to detect larger defects (>1 mm) in materials with high thermal conductivity. It was uncertain if active thermography was sensitive enough to detect the small defects (μm) commonly introduced during AM. Defects of this size are common in AM, and their presence significantly impacts the mechanical properties of the final part. For this reason, the detection limits of active thermography in common AM materials were investigated. Numerical models were created to simulate the heat transfer during active thermography in AM structures (polymer and stainless steel) with defects of varying size. The models included non-ideal conditions such as spectral in-depth absorption of the irradiative pulse and free convection from the object's surface. The spectral properties of acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), and polyamide 12 (PA 12) were measured (see chapter 2) and used in the numerical models. The numerical data indicates that active thermography is sensitive enough to detect the existence of defects smaller than 100 μm in AM materials (see chapter 3). Furthermore, it demonstrates that the defect aspect ratio (defect diameter divided by defect depth) for which traditional 1D thermography models may be used to approximate the depth of defects in 3D systems is approximately 6 (see chapter 4). In addition, the depth of defects with lower aspect ratios (~4) may also be approximated with relatively low error (~10% error). Non-ideal systems (those with convection and spectral in-depth absorption) were simulated, and figures are provided which facilitate the approximation of defect depth using simple, ideal thermography models. Active thermography has shown potential as being an efficient technique for detecting and measuring small defects common in AM.

Development of the advanced, real-time methods for monitoring of bioaerosols is becoming increasingly important. At present, the Ultraviolet Aerodynamic Particle Sizer (UVAPS, Model 3312, TSI, St. Paul., MN) is the only commercially available method for in-situ, continuous measurements of viable airborne microorganisms. Research included in this thesis aimed towards comprehensive evaluation of the method over a wide range of operating conditions, linking the experimental results to the theoretical basis of its design and operation, and to developing a scientific basis for its application to real-time monitoring of bioaerosols. Specifically, due to a growing concern in the general community about the environmental and health aspects of biological aerosols originated from various types of agricultural operations including animal farming, this research was focussed on developing a research methodology/strategy for applying the method to the investigation of bioaerosols in the swine confinement buildings (SCB). Investigations under controlled laboratory conditions were primarily concerned with selectivity, sensitivity, counting efficiency, and detection limits of the spectrometer. This study also examined the effect of physiological state (metabolic activity) of bacteria on the performance characteristics of the method. The practical implications of the research findings are discussed in this thesis. Further field investigations undertaken on a pig farm advanced understanding of the UVAPS performance in the real-life environmental settings. The research also provided a new insight on the particle size distribution and the effect of on-farm-activities on aerosol load inside the SCBs, for both biological and non-biological aerosols. This study has proved that the UVAPS is a powerful tool for investigation of viable bioaerosols in the environment. However, this method is limited to detection of active metabolising bacteria that excludes dormant bacterial spores. In addition, the method is very sensitive to physiological state of bacteria and to the effect of adverse environmental conditions on metabolic activity of airborne bacteria, which may decrease the amount of the intrinsic fluorophores in the cells below sensitivity level iv of the monitor. Possible limitations of this technology include also the lack of selectivity and thus interferences from the non-microbial organic components of airborne particles. In addition, the sensitivity of the method is insufficient for monitoring viable bacteria in the environments with relatively low concentrations of bioaerosols. In order to increase sensitivity of the method, it would be desirable to concentrate the bioaerosols into a smaller volume with the aim of high-volume virtual impactors (aerosol concentrators) prior to the monitoring. Therefore, in the indoor environments where an application of the concentrator is not feasible, the utilisation of the UVAPS may be problematic. Due to the intrinsic limitations, the method is not recommended for the direct measurements of viable bioaerosols and should be used in conjunction with the conventional biosamplers for obtaining more realistic insights into the microbial air quality. Nevertheless, the UVAPS has been found to be an adequate method for the investigation of the dynamics of biological aerosols in real-time. Overall, this thesis contributes to the advancing of the understanding of the method and may assist in developing new, more advanced technologies for the real-time monitoring of viable bioaerosols, as well as in developing sampling strategies for the application of the method to various bioaerosol studies.

Volatile and semi-volatile organic compounds are ubiquitous, and some of them are hazardous. The ability to rapidly detect and identify trace levels of them in air has become increasingly important. The conventional device used today for sampling and concentrating them in air is thermal desorption tubes filled with specific sorbents, which can only collect air samples at flow rates of 100-200 mL/min. In order to detect low concentration (ppt level) VOC compounds, long sampling time (>2 h) and sensitive detection are required. At the same time, portable instrumentation for on-site analysis has been developing rapidly. The somewhat lower performance of portable instruments compared to benchtop systems requires the sampling of even greater sample volume in order to reach the same detection limits. In this study, two high flow rate air sampling devices, i.e., a multi-capillary trap and a concentric packed trap, were developed to sample a large volume of air in a short time period. The multi-capillary trap was constructed by bundling analytical capillary gas chromatography columns together in parallel. As low as single digit ppt detection limits were reached in less than 25 min with this trap, and as high as 8.0 L/min flow rate was sampled. The simple and compact multi-capillary trap could be easily used with a conventional thermal desorption system to perform high flow rate sampling. A concentric packed high flow rate trap was also developed by packing sorbent layers concentrically around an empty tube. The concentric packed trap achieved a high flow rate (>10 L/min) because it had a high surface area and short sorbent bed. Also, its large sorbent amount (>1 g) provided large breakthrough volume (>100 L) required to achieve low detection limits. An equilibrium distribution sampling system was developed by absorbing selected analytes in granular PDMS to provide calibration for on-site instrumentation. Furthermore, a needle trap device was coupled in tandem to both high flow rate air samplers to perform second-stage concentration of VOCs down to the ppt level. Concentration factors of 104 to 105 were achieved within 30 min using both systems, i.e., over 10 to 100 times more sample was collected compared to conventional TD systems.

Dans l’analyse des émetteurs alpha et beta dans l’eau par scintillation liquide, la problématique de la discrimination des rayonnements se pose afin d’atteindre les limites de détection souhaitées. Dans le cas rare ou les énergies permettent une discrimination, nous avons mis en place un protocole d’analyse simultanée tritium/alpha sur des frottis. A l’aide d’une méthode a trois fenêtres il permet d’atteindre les limites de détection de 0,4 Bq/cm2 en tritium et de 0,04 Bq/cm2 en alpha.De façon générale, aucune distinction entre les spectres n’est possible et un ajustement du fond sous le pic alpha ne permet pas d’atteindre les limites de détection définies par les normes. Cependant le processus physique de scintillation permet une distinction des rayonnements, phénomène utilise par certains appareils, ceux-ci proposent donc le réglage par l’utilisateur d’un paramètre discriminant seuil. Nous avons développé un protocole de réglage permettant de reconstituer les spectres alpha et beta discrimines au mieux, rendant accessible une limite de détection de 0,03 Bq/L en alpha.Nous avons par ailleurs développé une approche innovante utilisant un détecteur en coïncidence dont les photomultiplicateurs sont connectes directement a une carte numérique d’acquisition. Chaque impulsion numérisée est ensuite traitée selon plusieurs critères simultanément, à la place des deux habituels. Aucun ne permet a lui seul d’obtenir une discrimination selon un seuil unique, mais la distribution des évènements dans chaque spectre est différente : un fenêtrage des évènements alpha permet d’atteindre une limite de détection de 0,2 Bq/L, quatre fois moindre que par une discrimination en énergie seule. / Analysis of water for alpha and beta emitters by liquid scintillation suffers from poor discrimination between the emissions and prevents reaching the lowest detection limits. In the rare cases where well separated energies permit discrimination, we can use a three-window protocol for simultaneous analysis of tritium and alphas of swipes that yields detection limits of 0.4 Bq/cm2 for tritium and 0.04 Bq/cm2 for alphas. In the general case, no distinction between the two radiations is possible. An adjustment of the background under the alpha peak does not allow reaching detection limits defined by the norms. However the physical process of scintillation offers users of certain models of apparatus to adjust a discrimination threshold that will separate the emissions. We have developed a protocol that reconstitutes spectra using independent settings that gives a detection limit for alphas of 0.03 Bq/L. We have also developed an innovative approach using a scintillation counter with its photomultipliers plugged directly into a fast analog-to-digital acquisition converter. Then each digitized pulse is simultaneously processed according to several criteria, instead of the usual two. No impulsion can be discriminated on the basis of a single threshold but the distribution of events in each spectrum is different: a window setting on the alphas permits attaining a detection limit of 0.2 Bq/L for alphas, four times lower than with a selection on energy alone.

L’objectif de ce projet doctoral a été de coupler la chromatographie en phase supercritique (SFC) avec un spectromètre de masse haute résolution pour l’analyse de substances naturelles apolaires. La SFC est une technique dite « verte » contrairement à la chromatographie liquide en phase normale (NPLC), très consommatrice de solvants organiques toxiques pour l’environnement, puisque la phase mobile est principalement constituée de CO2. Le CO2 ayant une faible viscosité, cela implique une diffusivité, des débits élevés et des temps d’analyse courts. Notre attention a été focalisée sur des molécules apolaires : les lipides. Le but était de mettre au point des dosages dans des matrices alimentaires et biologiques et de débuter une approche lipidomique d’étude de la maladie de Parkinson. La première partie a été dédiée au développement du système SFC avec une détection UV, prêté par le constructeur Agilent Technologies. La première étude s’est portée sur 6 composés de la famille des vitamines A. Une phase d’optimisation a été réalisée afin d’obtenir une séparation satisfaisante des composés, en testant différents paramètres chromatographiques comme le type de phase stationnaire ou encore la composition de la phase mobile, afin d’obtenir une résolution optimale. Ensuite, des études de linéarité et de répétabilité ont été réalisées et des limites de détection et de quantification ont été déterminées afin d’obtenir une méthode fiable et robuste. Une deuxième partie a concerné la mise en place du couplage entre la SFC et un spectromètre de masse de type quadripôle-temps de vol (Q-TOF), afin d’améliorer la spécificité et la sensibilité des analyses. Différentes sources d’ionisation ont été utilisées : ESI, APCI et APPI. Chacune des sources présente des modes d’ionisation différents, qui permettent de pouvoir balayer une large gamme de polarité des analytes. Nous avons choisi 8 dérivés de la vitamine E, composés apolaires pour lesquels la SFC paraît être la technique d’analyse idéale. La séparation de ces composés a été optimisée de façon à obtenir une bonne résolution chromatographique et un temps d’analyse minimal. L’ionisation des composés est réalisée avec les 3 sources disponibles en faisant varier les paramètres de sources ou encore le solvant « make-up », de façon à obtenir une sensibilité optimale. La source APPI a été finalement choisie après une étude sur les performances de la méthode. Cette source présente une bonne répétabilité, linéarité et des limites de détection de l’ordre de celles retrouvées dans la littérature par HPLC-MS. Nous avons ensuite réalisé la quantification des ces composés dans 2 types de matrices alimentaire et biologique : l’huile de soja et le plasma de rat. Une troisième partie a été débutée sur le profilage de lipides à polarités variées par SFC-MS. Cette technique se révèle idéale de par la faible polarité de ces composés et leur absence d’absorbance dans le domaine UV. En effet, l’intégrité des lipides peut être altérée suite aux dommages causés par les radicaux libres, qui sont potentiellement impliqués dans de nombreuses maladies neurodégénératives. Il parait primordial de développer des outils analytiques présentant une haute sensibilité et résolution et la possibilité d’accéder aux informations structurales. La source d’ionisation ESI nous a permis de détecter 12 lipides sur les 20 sous-classes analysées en mode positif et 8 lipides en mode négatif. Une application a été réalisée sur un échantillon de plasma humain. Il serait intéressant à l’avenir d’effectuer cette étude en utilisant la source APPI, source propice à l’analyse structurale de lipides et présentant une bonne sensibilité et répétabilité. Ce couplage SFC-MS, présentant une bonne sensibilité et répétabilité, sera par la suite étendu à l’analyse de lipides dans diverses matrices biologiques et pourra à l’avenir être appliqué à l’étude de nouveaux biomarqueurs et au screening rapide d’un grand nombre d’échantillons / The aim of this PhD project was to couple supercritical fluid chromatography (SFC) with a high resolution mass spectrometer for apolar natural compounds analysis. Because mobile phase is principally constituted of CO2, SFC is called “green technic” contrary to normal phase liquid chromatography (NPLC), which uses lot of organic solvents toxic for environment. The CO2 presents a low viscosity, in this way high diffusivity and flow rate, and lower analysis times are obtained. Our work was focused on apolar molecules: the lipids. The aim was to quantify molecules in alimentary and biological matrices and to a lipidomic approach to study Parkinson disease. The first part was to develop the system SFC with a UV detection on a system on loan by Agilent Technologies. This first study was carried out on 6 vitamin A compounds. An optimization of chromatographic parameters has been realized in order to obtain a good separation of the compounds. Then, linearity, repeatability, detection and quantification limits have been determined in order to have a reliable and robust method. A second part concerned the coupling of SFC and a quadrupole time-of-flight mass spectrometer (Q-TOF), in order to improve specificity and sensitivity of analysis. Different ionization sources have been tested: ESI, APCI and APPI. Each ion source presents different ionization mode, which permits to analyze a wide range of polarities of compounds. We have chosen 8 vitamin E derivatives, which are apolar compounds for which SFC seems to be well suited. Separation compounds have been optimized in order to have a good chromatographic resolution and a short analysis time. This compounds ionization is realized with the 3 sources, varying ionization parameters and make-up solvent, to have an optimal sensitivity. The APPI source has been chosen after a performance evaluation method. This source presents a good repeatability, linearity and detection limit in the same order of magnitude than those found in the literature by HPLC-MS. Then we have quantified these compounds in alimentary and biological matrices: a soya oil and plasma rat. A third study has been started on lipid profiling with various polarities by SFC-MS. This technic is well suited because of the low polarity of this molecules and their lack of absorbance in the UV range. The integrity of lipids can be altered with damages caused by free radicals, and are potentially involved in neurodegenerative diseases. It is essential to develop analytical systems with a high sensitivity and resolution and the possibility to access to structural information. The ESI source permits to detect 12 lipids on the 20 sub-classes analyzed in positive ion mode and 8 lipids in negative mode. An application has been realized on human plasma. In the future, it will be interesting to analyze these lipids with the APPI source, which is good choice for structural analysis of lipids, with good sensitivity and repeatability. Studies with this SFC-MS system, presenting good sensitivity and repeatability, will be extended to lipid analysis in biological matrices and could be applied to new biomarkers study and for fast screening of a large number of samples