Disponibilidade dos recursos energéticos junto com o despertar da consciência ambiental criaram um interesse por uma condição climática sensível compatível com os recursos disponíveis. Dentro desse cenário o trabalho se volta à necessidade de se criarem e manterem ambientes industriais termicamente adequados aos processos de produção para minimizar as interferências que as condições ambientais exercem sobre os custos dos processos de produtivos e sobre o consumo energético. Os sistemas de resfriamento evaporativo, por sua vez, têm sido a ferramenta de maior potencial de aplicação na criação de ambientes termicamente adequados aos processos. Este modelo revisto de conforto térmico nos coloca um passo à frente para o aumento eficiência energética na construção de projeto de climatização vinculados a temperaturas interiores que atendam conjuntamente tanto aos ocupantes como às atividades que desenvolvem no interior da área climatizada. Apesar de esse sistema apresentar vantagens operacionais, quando comparado a outros sistemas convencionais, existem certas limitações no seu desempenho. Uma das maiores dificuldades das instalações destes sistemas reside na existência de incertezas em qualquer resultado. Possibilitar um controle dos parâmetros, minimizando os erros de aplicação, evitando criar no ambiente um desconforto de tal grau que inviabilize sua aplicação, é o fundamento deste trabalho. A busca passa a ser pela garantia da aceitabilidade dos resultados do sistema projetado e seus limites de aplicabilidade. O estudo das variáveis que interferem no processo do resfriamento por micro aspersão permitiu desenvolver um processo que alterara esses parâmetros durante o funcionamento do sistema, interferindo, conforme a necessidade no seu desempenho, garantindo a completa evaporação da água micro aspergida. / Energy resources along with an environmental conscience awakening has created an interest in sensitive climate together with a more understanding regarding the use of available resources. Inside this scenario our work focus on the needs of creating and maintaining industrial environments thermally suited to these production processes that seeking to minimize interference that environmental conditions have on the costs of production processes and energy consumption. Evaporative cooling systems, in turn, has been a interesting tool to be used in the creation of thermally suitable environments to these processes. This new revised thermal comfort model puts us a step forward to increase energy efficiency in elaborating air treatment projects linked to indoor temperatures that meet both the occupants and the activities that develop inside the controlled area. Although this system has operational advantages when compared to other conventional systems, there are some limitations in their performance. A major difficulty of the installation envolving these systems is about the existence of uncertainty in any results. To allow the control of these parameters in order to minimize the errors in this kind of application and to avoid creating environmental discomfort to such a degree that prevent the implementation, it is the foundation of this work. The search is to ensure the acceptability of the results of the system designed and their limits of applicability. The study of the variables that affect the cooling process by misting allowed us to develop a process that altered these parameters during operation of the system, interfering, as required in its performance, ensuring complete evaporation of water applied by misting in the area.

Le transfert de masse et de chaleur dans les vêtements est un phénomène faisant appel àdifférents mécanismes physiques : les échanges de chaleurs sèches et les transferts de vapeur etde liquide. Ces mécanismes sont fortement influencés par les facteurs liés à la construction, laforme du vêtement par rapport à celle du corps et l’utilisation du vêtement. Ces facteurs peuventêtre optimisés en changeant la taille et la forme des différentes couches d’air emprisonnées entrela peau et les vêtements. La plupart des modèles mathématiques de vêtements font l’hypothèse que l’épaisseur d’air entrela peau et l’étoffe est uniforme, ou alors ils l’ignorent. La non-uniformité et de la non-linéaritédes transferts de chaleur et d’eau ne sont alors pas prises en compte. En effet, le processus detranspiration dépend non seulement de l’aire de contact et de l’épaisseur d’air emprisonnée entrela peau et le vêtement mais également de la région du corps. Nous proposons une méthode permettant de déterminer, avec une plus grande précision que lestechniques existantes, l’épaisseur d’air et l’aire de contact entre le corps et un vêtement à l’aided’une analyse avancée de scans 3D d’un mannequin homme nu et habillé. L’effet du tauxd’humidité sur l’aire de contact et l’épaisseur du film d’air a été étudié en fonction de la zone ducorps et ceci pour différentes tailles, structures de l’étoffe et fibres. Cette méthode contribue àévaluer de façon plus réaliste les échanges de masse et de chaleur au travers de plusieurs couchesde vêtements et ainsi de fournir des données d’entrée précises aux modèles pour la conception devêtements avec prise en compte du confort et de l’ergonomie. / The heat and mass transfer within the clothing system is a composition of a number of physicalprocesses, such as: dry heat and vapour and liquid water transfer. Factors associated with theconstruction and use of the garment, such as body posture and movement, and clothing fitinfluence these processes significantly. This is achieved mainly by changing the size and theshape of the different layers of air trapped between the skin and clothing. Most existing mathematical clothing models assume uniform air gap between the body and fabric layers or ignore it. However, this approach disregards the non-uniform and non-linear heat,vapour and liquid water transfer, which depend on presence of contact between surfaces and onthe shape of the air layers trapped within clothing and the body regions which are not equivalentin terms of sweating process. In this study, we propose a method to accurately determine the air gap thickness and the contactarea between clothing and the human body through an advanced analysis of 3D body scans of thenude and dressed body of a male manikin. This method allowed more accurate measurement ofthe air gap thickness and the contact area than other existing methods. Additionally, in two casestudies the effect of garment design and moisture gain in fabric combined with effects of bodypart, garment type and its overall and regional fit, fabric structure and fibre type were determined.Consequently, this method will contribute to a more realistic evaluation of heat and massexchange rates through clothing systems and provide more accurate input for ergonomic andcomfort design of clothing.

De nos jours, l'humidité dans les bâtiments est une problématique majeure car elle impacte simultanément la consommation énergétique, le confort des occupants, ainsi que les risques de moisissures dans l'envelope du bâtiment. Les matériaux de construction ont la capacité d'absorber et de libérer de grandes quantités de vapeur d'eau et peuvent par conséquent amortir les variations d'humidité relative intérieure. Cette proporiété est appelée tampon hygrique. Elle est liée aux échanges de vapeur d'eau entre l'air intérieur et les parois, à la ventilation, et aux sources de vapeur. Cet effet a été précédemment mis en évidence à l'échelle du matériau et de la paroi par des expériences de laboratoire et des modèles numériques. Cependant, peu de modèles décrivent de manière réaliste les sources intérieures dues à la présence et aux activités des occupants. Dans ce travail, un modèle hygrothermique à l'échelle de la pièce a été développé en Python afin d'investiguer l'influence du scénario d'occupation, et l'impact du tampon hygrique des parois sur l'air intérieur. Ce modèle regroupe les transferts couplés d'énergie et de masse dans les parois, ainsi que les sources intérieures décrites par un système de conditionnement d'air et par la présence et les activités des occupants. Ce dernier étant modélisé de manière stochastique par un modèle implémenté dans une plateforme nommée No-MASS. Des indicateurs de performance sur les besoins énergétiques, le confort hygrique intérieur, et les risques liés aux moisissures dans les parois ont été définis pour quantifier la performance hygrothermique d'une pièce. La sensibilité des indicateurs de performance vis-à-vis du scénario d'occupation a été évaluée en simulant des scénarios stochastique, déterministe et constant. Les résultats ont montré une influence marginale du scénario à l'échelle de l'année. [...} / Humidity in buildings has nowadays become a major concern as it impacts simultaneously the energy consumption, the occupants' comfort and the moisture related risks in the buildings envelope. Buildings materials have the ability to absorb and release large amounts of moisture and therefore they may dampen the indoor relative humidity variations. This is called the moisture buffering capacity. It depends on the vapour exchanges between the air and the walls, the ventilation and the indoor moisture sources. This property was previously highlighted at material and wall scales through laboratory experiments and numerical models. However, few models describe the indoor sources due to the occupants' presence and activities in a realistic way. In this work, a hygrothermal room model was developed in Python to investigate the influence of the occupancy scenario and of the impact of the walls moisture buffering on indoor air balance. This model regroups the coupled heat and mass transfer in the walls, as well as the indoor sources depicted by the air-conditioning system and the occupants' presence and activities. The numerical modelling of the latter relies on a stochastic occupancy model implemented in a platform called No-MASS. Performance indicators on the energy demand, the indoor hygric comfort and the moisture related risks in the walls were defined to quantify the hygothermal performance of a room. The sensitivity of the performance indicators towards the occupancy scenario was assessed by simulating a stochastic occupancy scenario, a deterministic one and a constant one. Results showed a marginal influence of the scenario at year scale. However, at smaller time scales (seasonal or monthly), their impact on the indoor relative humidity dampening was not negligible, mainly due to the consideration of a seasonal effect for the stochastic scenario. [...]

La banane plantain est un fruit couramment consommé au Congo-Brazzaville sous la forme cuite en tant qu’accompagnement. Le procédé de friture profonde de la banane plantain est une pratique très répandue, souvent mal maitrisé, compte tenu de l’utilisation prolongée des huiles de friture entrainant la formation de composés néfastes à la santé. En effet, depuis un certain nombre d’années, la consommation d’huiles locales (soja, palme) et leurs dégradations après chauffage constituent une des préoccupations principales pour la sécurité sanitaire du consommateur. Les objectifs de cette thèse consistaient à étudier l’influence du procédé de la friture profonde appliqué à la banane plantain Musa AAB, variété « Harton » au stade de maturité 7, consommée sous la forme de disque. Nous avons dans un premier temps appliqué la méthodologie des surfaces de réponse au procédé de friture profonde, afin de déterminer l’influence de trois paramètres (temps / température / quantité) sur différentes réponses (couleur, dureté, teneurs en huile et en eau des produits frits) en fonction de la nature de l’huile utilisée (soja, palme, huile Frial). Une fois les conditions optimales obtenues sur la banane plantain en condition domestique, l’étude s’est focalisée sur l’évolution de la stabilité des huiles de friture par le suivi des paramètres physico-chimiques de dégradation de ces dernières (composés polaires totaux, acides gras libres, composés primaires et secondaires d’oxydation). Des analyses de la couleur, du point de cristallisation et de la viscosité sont venues compléter l’étude et ont permis d’établir la durée d’utilisation optimale de ces huiles en fonction de la quantité de banane plantain à frire. Enfin, les mécanismes de transfert d’eau et d’absorption d’huile dans la matrice ont été étudiés et modélisés en fonction de la température, de l’épaisseur et du temps d’immersion. / Plantain is a fruit commonly consumed in Congo - Brazzaville in its cooked form, as an accompaniment. The process of deep frying plantain is a widespread practice, often poorly mastered, given the prolonged use of frying oils, leading to the formation of compounds harmful to health. Indeed, for a number of years, the consumption of local oils (soybean, palm) and their degradation after heating are cause of major concern for consumer safety. The objectives of this study were to investigate the influences of the deep frying process applied on the Musa AAB plantain of "harton" variety, maturity level 7, as consumed in sliced form. We initially applied response surface methodology (RSM) to the deep frying process to determine the influence of three parameters (time / temperature / quantity) on different responses (color, hardness, oil uptake and water content) according to the type of oil used (soybean, palm, Frial oils). Once optimal conditions were obtained from the plantain in domestic conditions, the study focused on the evolution of frying oil stability, by monitoring physicochemical parameters of the degradation of the aforementioned (total polar compounds, free fatty acids, primary and secondary oxidation products). Analyses of color, crystallization point and viscosity, were added to the study and helped establish the optimal duration of use for these oils depending on the quantity of plantains fried. Lastly, the mechanisms of water transfer and oil uptake in the matrix has been studied and modeled according to temperature, thickness and immersion time.

Mars est entourée d'une atmosphère ténue, composée à 95% de dioxyde de carbone (CO2). Au cours d'une année martienne, des transferts de masse (jusqu'à 30% du CO2 atmosphérique) entre l'atmosphère et les calottes polaires produisent des variations temporelles à très grande longueur d'onde du champ de gravité, notamment des harmoniques zonaux de son développement en harmoniques sphériques (de fait les coefficients ”composites” de degré 2 et 3). D'un autre côté, le potentiel gravitationnel du Soleil induit des déformations, dites de marée, du volume martien. Ces déformations produisent un potentiel perturbateur en tout point extérieur à la planète, proportionnel à son nombre de Love de degré 2 k2. k2 traduit la réponse élastique de la planète au potentiel solaire et permet de caractériser physiquement le noyau de Mars (sa nature, solide ou liquide, et son rayon). Une manière de quantifier les transferts de la masse atmosphérique et l'état du noyau est de déterminer les perturbations inhérentes sur le mouvement d'un satellite artificiel. Le cycle saisonnier du CO2 et l'état du noyau impliquent aussi des variations de la rotation de Mars. Une autre manière de quantifier les transferts de la masse atmosphérique et l'état du noyau est donc d'observer leurs effets sur la rotation. Des simulations d'observations de trajectographie de satellites (comme celles de Mars Global Surveyor, MGS, Odyssey, MODY) et/ou de la position d'un réseau de stations à la surface de Mars (comme dans l'expérience NEIGE) nous ont permis de voir s'il est possible de restituer précisément les variations des harmoniques zonaux de gravité de bas degré et/ou la rotation. Avec les observations réelles de trajectographie des missions américaines MGS et MODY, on a restitué les variations des harmoniques zonaux de gravité de bas degré et k2.

A compact air separator demonstrator based on centrifugally enhanced distillation has been studied. The full size device is meant to be used on board of a Two Stage To Orbit vehicle launcher. The air separation system must be able to extract oxygen in highly concentrated liquid form (LEA, Liquid Enriched Air) from atmospheric air. The LEA is stored before being used in a subsequent rocket propulsion phase by the second stage of the launcher. Two reference vehicles are defined, one with a subsonic first stage and one with a supersonic first stage. In both cases, oxygen collection is performed during a cruise phase (M 0.7 and M 2.5 respectively). The aim of the project is to demonstrate the feasibility of the air separation system, investigate the separation cycle design, and assess that the separator design selected is suitable for the reference vehicles. The project is described from original base ideas to design, construction, extended testing and analysis of experimental results. Preliminary computations for a realistic layout have been performed and the motivations for the choices made during the process are explained. Test rig design, separator design and technical discussion are provided for a subscale pilot unit. Mass transport parameters and flooding limits have been estimated and experimentally measured. Performance has been assessed and shown to be sufficient for the reference Two Stage To Orbit vehicles. The technology developed is found suitable without further optimization, although some volume and mass reduction would be desirable for the supersonic first stage concept. There are many ways of optimisation that can be further investigated. The aim of this program, however, is not to fully optimize the device, but to demonstrate that a device based on a simple, robust, low-risk design is already suitable for the launch vehicles. On top of that analysis, directions for improvements are suggested and their potentials estimated. A complete assessment of those improvements requires further maturation of the technological concept through further testing and practical implementations. Directions for future work, general conclusions and a vehicle development roadmap have also been provided.

Nitrogen is the major component of biosphere. Paradoxically, nitrogen pollution is the concern globally. Ammonia pollution is due to its unceasing rejection into nature such as groundwater, current water and the atmosphere. This phenomenon constitutes a threat for the humanity, land and aquatic flora, and consequently disturbs the balance of natural ecosystem. Recently, that situation has lead to develop various techniques and/or technologies for ammonia removal from municipal and industrial wastewaters. Particularly in the environmental biotechnology area, two main objectives were recently aimed in many research activities: the development of new configurations of competitive bioreactors and the monitoring of partial nitrification process, which are the fundamental basis of this thesis project. In this study, the partial ammonium oxidation process, also called nitrite route, was studied in a 60 litre jet-loop submerged membrane bioreactor pilot plant. The research was organized around six chapters. An exhaustive literature review of the state-of- art of the biological nitrification process and the membrane technologies was performed. The materials and measurement methods were presented. The colorimetric method, the chromatography analysis, the biomass estimation by the suspended solids (SS), the aggregates size measurement, the gas holdup, the gas-liquid mass transfer, the bubbles gas diameter determination, the medium rheology aspects, etc., and the complete equipment of the bioreactor were studied in detail. The plant automation functioning was also studied. Membrane module (Mitsubishi Sterapore-L) characterization was carried out and three characteristic parameters were estimated: the membrane intrinsic resistance Rm, the membrane permeability Lp and the membrane porosity εm. Estimations revealed good agreement between experimental results and theoretical methods based on the Darcys law and the Carman-Kozeny law applicable in microfiltration system. Hydrodynamics and aeration aspects were studied. The mixing in the jet-loop system was characterized by the mixing time (tmix) and the circulation time (tc), respectively. The results showed that the characteristic times (tmix and tc) decrease with an increase in input gas flowrate and the circulated liquid flowrate. A model correlation involving the air and the combined liquid effects was proposed to describe the circulation time evolution. The classical non-steady state clean water test was used to determine the gas-liquid mass transfer coefficient (kLa). It was found to be influenced by the combined action of air and recirculated-liquid flowrates and a correlation has been proposed to describe their influence. The interpretation of kLa results and the system mixing data showed that the developed reactor corresponds to a near perfect mixing tank. This criterion was satisfactorily verified by literature data. The gas holdup (εg) was directly measured by the volume expansion method. In the absence of liquid circulation, εg ranged between 1 and 4% for the investigated range of gas liquid superficial velocities. It was found to increase linearly with the air superficial velocity, which corresponds to the bubbly flow regime. However, in the presence of liquid flowrate, εg slightly increased (from 1 to 6%) with increase in the superficial liquid velocity. A model has been proposed to correlate εg and the air and the recirculated-liquid velocities. The average diameter of the bubbles gas (dB) in the system was also estimated by the Leibson theoretical model based on the Reynolds number at the orifice of the gas distributor. Finally, biological aspects were studied. Respirometry measurements were conducted to characterize the process medium. The mass transfer, the gas holdup and the medium viscosity were determined. The obtained data allowed estimating the α factor and the β factor, respectively. The interaction of the growth of microorganisms into the process and the membrane performance was also investigated and a correlation model was proposed to describe membrane fouling with time. The optimal conditions for ammonium partial oxidation were determined using process monitoring and simulation. Dissolved oxygen (DO), temperature (T) and hydraulic retention time (HRT) were selected to achieve a high nitrite accumulation in the system. The results obtained showed that the selected parameters should be fixed at DO ≈ 2 mgO2.l-1, HRT ≈ 6 7 h and T = 30°C, respectively. The partial nitrification was simulated by the use of the TwoPopNitrification model included into the BioWin 2.2 software. For these simulations, a sequencing ammonia oxidation assumption was adopted: the nitrozation followed by the nitration step, respectively. The corresponding kinetics and stoichiometric constants were estimated by combining literature data and experimental nitrification results. For these estimates, the ammonium oxidation was monitored on several process samples taken at different times. The estimates were also delivered by monitoring the ammonium oxidation on the process operated in the batch mode. The plotting of simulations and experimental results revealed good agreement. In order to investigate the process performance in terms of biological stability, a long time period (≈ 600 days) was simulated. The results showed that a high stable nitrite accumulation (> 95%) could be achieved when the above optimal conditions are imposed to the system. However, after a long time, the accumulated nitrite is converted into nitrate and then the system is disrupted. For the simulated experimental conditions, the process disruption period was located between 180 and 350 days. At this period, a corresponding theoretical purge flowrate was found to range between 0.15 10-3 m3.d-1 and 3.0 10-3 m3.d-1. Simulations also showed that increasing the purge flowrate decreases the sludge retention time and then favours nitrite accumulation into the process. That is an interesting strategy to increase the performance of the biological partial nitrification process.

The physiological benefits of flaxseed against pathological disturbances, such as cancers and heart diseases, are mainly attributed to its high lignan content. This study (Experiment 1) examined the application of pressurized low polarity water (PLPW) for extraction of lignans, proteins and carbohydrates from defatted flaxseed meal. Key processing conditions included temperature (130, 160, 190°C), solvent pH (4, 6.5 and 9), solvent to solid ratio (S/S) (90, 150 and 210 mL/g) and introduction of co-packing material (0 and 3 g glass beads). The addition of 3 g glass beads as co-packing material facilitated extraction by enhancing surface contact between the liquid and solid thus shortening extraction time. Elevated temperature accelerated the extraction rate by increasing the solid diffusion coefficient thereby reducing the extraction time. The maximum yield of lignans (99 %) was obtained at temperatures ranging from 160°C to 190°C, with solvent volume of 180 mL (90 mL/g meal) at pH 9. Optimal conditions for protein extraction (70 %) were pH 9, extraction volume of 420 mL (210 mL/g meal) and 160°C. Total carbohydrates yield was maximized at 50% recovery at pH 4 and 160°C with 420 mL solvent (210 mL/g meal). Increased temperature accelerated extraction, thus reducing solvent volume and time to reach equilibrium. For the extraction of proteins, however, a temperature of 130-160°C is recommended, as proteins are vulnerable to thermal degradation due to heat decomposition. The effects of flow rate and geometric dimensions for extraction of lignans and other flaxseed meal bioactives were further investigated in Experiment 2, based on the variables optimized in the previous experiment. Defatted flaxseed meal was extracted with pH 9 buffered water with meal to co-packing glass beads ratio of 1:1.5 at 5.2 MPa (750 psi) and 180°C. The aqueous extracts were analyzed for lignan, protein and carbohydrate using HPLC and colorimetric methods. The optimal extraction yields for lignan, protein and carbohydrate were found at flow rates of 1 to 2 mL/min with bed depth between 20 and 26 cm and a S/S ratio of 40 to 100 mL/g. The combination of low flow rate and high bed depth allowed the use of lower S/S ratio with reduced total solvent volume consumption. This study also evaluated the mass transfer kinetics governing the process of lignan extraction from flaxseed meal in a fixed bed extraction cell. Diffusion of solute into the continuously flowing solvent was mainly responsible for the mass transfer mechanism as flow rate did not increase proportionally with the yield and rate of extraction. The extraction kinetics were studied on the basis of two approaches: Fick’s diffusion equation and a two-site exponential kinetic model. The proposed two-site exponential kinetic model corresponding to the two-stage extraction (rapid and slow phases) successfully described the experimental data. Diffusivities attained from Fick’s diffusion model ranged from 2 x 10-13 to 9 x 10-13 m2s-1 while mass transfer coefficients were between 4.5 x 10-8 and 2.3 x 10-7 ms-1 for extraction of lignans at 180°C, pH 9 with 1:1.5 meal to co-packing material ratio. / February 2007

Calibration methods for quantitative on-site sampling using solid phase microextraction (SPME) were developed based on diffusion mass transfer theory. This was investigated using adsorptive polydimethylsiloxane/divinylbenzene (PDMS/DVB) and Carboxen/polydimethylsiloxane (CAR/PDMS) SPME fiber coatings with volatile aromatic hydrocarbons (BTEX: benzene, toluene, ethylbenzene, and o-xylene) as test analytes. Parameters that affected the extraction process (sampling time, analyte concentration, water velocity, and temperature) were investigated. Very short sampling times (10-300 s) and sorbents with a strong affinity and large capacity were used to ensure a 'zero sink' effect calibrate process. It was found that mass uptake of analyte changed linearly with concentration. Increase of water velocity increased mass uptake, though the increase is not linear. Temperature did not affect mass uptake significantly under typical field sampling conditions. To further describe rapid SPME analysis of aqueous samples, a new model translated from heat transfer to a circular cylinder in cross flow was used. An empirical correlation to this model was used to predict the mass transfer coefficient. Findings indicated that the predicted mass uptake compared well with experimental mass uptake. The new model also predicted rapid air sampling accurately. To further integrate the sampling and analysis processes, especially for on-site or <i>in-vivo</i> investigations where the composition of the sample matrix is very complicated and/or agitation of the sample matrix is variable or unknown, a new approach for calibration was developed. This involved the loading internal standards onto the extraction fiber prior to the extraction step. During sampling, the standard partially desorbs into the sample matrix and the rate at which this process occurs, was for calibration. The kinetics of the absorption/desorption was investigated, and the isotropy of the two processes was demonstrated, thus validating this approach for calibration. A modified SPME device was used as a passive sampler to determine the time-weighted average (TWA) concentration of volatile organic compounds (VOCs) in air. The sampler collects the VOCs by the mechanism of molecular diffusion and sorption on to a coated fiber as collection medium. This process was shown to be described by Fick's first law of diffusion, whereby the amount of analyte accumulated over time enable measurement of the TWA concentration to which the sampler was exposed. TWA passive sampling with a SPME device was shown to be almost independent of face velocity, and to be more tolerant of high and low analyte concentrations and long and short sampling times, because of the ease with which the diffusional path length could be changed. Environmental conditions (temperature, pressure, relative humidity, and ozone) had little or no effect on sampling rate. When the SPME device was tested in the field and the results compared with those from National Institute of Occupational Health and Safety (NIOSH) method 1501 good agreement was obtained. To facilitate the use of SPME for field sampling, a new field sampler was designed and tested. The sampler was versatile and user-friendly. The SPME fiber can be positioned precisely inside the needle for TWA sampling, or exposed completely outside the needle for rapid sampling. The needle is protected within a shield at all times hereby eliminating the risk of operator injury and fiber damage. A replaceable Teflon cap is used to seal the needle to preserve sample integrity. Factors that affect the preservation of sample integrity (sorbent efficiency, temperature, and sealing materials) were studied. The use of a highly efficient sorbent is recommended as the first choice for the preservation of sample integrity. Teflon was a good material for sealing the fiber needle, had little memory effect, and could be used repeatedly. To address adsorption of high boiling point compounds on fiber needles, several kinds of deactivated needles were evaluated. RSC-2 blue fiber needles were the more effective. A preliminary field sampling investigation demonstrated the validity of the new SPME device for field applications.

Calibration methods for quantitative on-site sampling using solid phase microextraction (SPME) were developed based on diffusion mass transfer theory. This was investigated using adsorptive polydimethylsiloxane/divinylbenzene (PDMS/DVB) and Carboxen/polydimethylsiloxane (CAR/PDMS) SPME fiber coatings with volatile aromatic hydrocarbons (BTEX: benzene, toluene, ethylbenzene, and o-xylene) as test analytes. Parameters that affected the extraction process (sampling time, analyte concentration, water velocity, and temperature) were investigated. Very short sampling times (10-300 s) and sorbents with a strong affinity and large capacity were used to ensure a 'zero sink' effect calibrate process. It was found that mass uptake of analyte changed linearly with concentration. Increase of water velocity increased mass uptake, though the increase is not linear. Temperature did not affect mass uptake significantly under typical field sampling conditions. To further describe rapid SPME analysis of aqueous samples, a new model translated from heat transfer to a circular cylinder in cross flow was used. An empirical correlation to this model was used to predict the mass transfer coefficient. Findings indicated that the predicted mass uptake compared well with experimental mass uptake. The new model also predicted rapid air sampling accurately. To further integrate the sampling and analysis processes, especially for on-site or <i>in-vivo</i> investigations where the composition of the sample matrix is very complicated and/or agitation of the sample matrix is variable or unknown, a new approach for calibration was developed. This involved the loading internal standards onto the extraction fiber prior to the extraction step. During sampling, the standard partially desorbs into the sample matrix and the rate at which this process occurs, was for calibration. The kinetics of the absorption/desorption was investigated, and the isotropy of the two processes was demonstrated, thus validating this approach for calibration. A modified SPME device was used as a passive sampler to determine the time-weighted average (TWA) concentration of volatile organic compounds (VOCs) in air. The sampler collects the VOCs by the mechanism of molecular diffusion and sorption on to a coated fiber as collection medium. This process was shown to be described by Fick's first law of diffusion, whereby the amount of analyte accumulated over time enable measurement of the TWA concentration to which the sampler was exposed. TWA passive sampling with a SPME device was shown to be almost independent of face velocity, and to be more tolerant of high and low analyte concentrations and long and short sampling times, because of the ease with which the diffusional path length could be changed. Environmental conditions (temperature, pressure, relative humidity, and ozone) had little or no effect on sampling rate. When the SPME device was tested in the field and the results compared with those from National Institute of Occupational Health and Safety (NIOSH) method 1501 good agreement was obtained. To facilitate the use of SPME for field sampling, a new field sampler was designed and tested. The sampler was versatile and user-friendly. The SPME fiber can be positioned precisely inside the needle for TWA sampling, or exposed completely outside the needle for rapid sampling. The needle is protected within a shield at all times hereby eliminating the risk of operator injury and fiber damage. A replaceable Teflon cap is used to seal the needle to preserve sample integrity. Factors that affect the preservation of sample integrity (sorbent efficiency, temperature, and sealing materials) were studied. The use of a highly efficient sorbent is recommended as the first choice for the preservation of sample integrity. Teflon was a good material for sealing the fiber needle, had little memory effect, and could be used repeatedly. To address adsorption of high boiling point compounds on fiber needles, several kinds of deactivated needles were evaluated. RSC-2 blue fiber needles were the more effective. A preliminary field sampling investigation demonstrated the validity of the new SPME device for field applications.