Continuous milli-scale and micro-scale structures such as FlowPlate® microreactors have emerged as a promising element of process intensification due to their inherently effective rates of mass and heat transfer. These microfluidic devices have proven to be a preferred solution in place of energy-intensive batch processes for certain pathways of fine chemical and pharmaceutical synthesis, most notably fast reactions taking place on the scale of milliseconds to seconds. Computational fluid dynamics (CFD) has become an increasingly valuable tool in the field of microreactor design and optimization for its ability to locally map complex fluid flow patterns and resolve microscopic scales of reactive mixing that are challenging to characterize experimentally. The primary objective of this research was thus to develop and validate a mathematical model for the simulation of chaotic flow and homogeneous mixing in continuous microreactors. The model needed to be versatile enough to handle transition between flow regimes within a given reactor as well as the coexistence of both chaotic and laminar flow patterns in the micromixing elements that comprise said reactors. This was successfully achieved through the implementation of a k-ω SST (shear-stress transport) turbulence model that accounts for the impact of small-scale temporal and spatial fluctuations generated in the micromixer geometries studied herein; be it a liquid-liquid mixer (LLM), a serpentine (SZ) or a tangential (TG) mixer. In a first CFD study, the computational predictions were validated based on excellent agreement with experimental pressure loss (R^2 > 0.997) and residence time distribution (RTD) data (R^2 > 0.97) in several LL microreactors at Reynolds numbers ranging from 210 to 2140. Furthermore, the local velocity distribution and streamlines were mapped across the 3D domain of these reactors and it was discovered, based on the emergence of advective recirculation zones and turbulent dispersion, that a drastic change in flow behaviour occurred in these mixing elements at a Reynolds number of about 640. The interspacing of LLM elements with straight microchannels proved to be a suitable approach to modulating pressure loss while concurrently maintaining the chaotic secondary flow patterns generated from the mixers. In a second CFD study, the impact of micromixer geometry on the local velocity fields and advective transport performance was investigated both from a macromixing and micromixing perspective. Like the LLM, the SZ and TG mixers conferred chaotic secondary flow patterns at characteristic Reynolds numbers between 500 and 1000. As such, it was concluded that it would be ideal to operate these mixers at water flow rates of at least 30 ml/min. Contour plots of the velocity magnitude coupled with the computation of RTD showed that the SZ virtually mimics a plug-flow profile over a volume of 77 mm3 or greater at 50 g/min. The RTD of the LLM and TG resembles that of a mixed flow pattern given that approximately 65-80% of their fluid volume is occupied by recirculation zones. As such, it required 65 LLMs in series (3105 mm3) and 80 TGs (1142 mm3) to approach the same pattern as 10 SZs (77 mm3) from a macromixing perspective. Micromixing time distributions (MTD) were also characterized by locally computing the decay time of small-scale segregation (t_SSS) as a function of flow rate, wherein higher flow rates generated lower characteristic mixing times. The TG and LLM conferred the broadest range of mixing times, spanning nearly four orders of magnitude in the range of [0.02 ms, 10 ms], whereas the SZ generated a much narrower MTD ranging between [0.024 ms, 0.69 ms]. Finally, the impact of geometry and flow conditions on reaction yield was assessed by characterizing the extent of a finite-rate reaction relative to an infinitely fast reaction taking place in parallel. The calculated yield for the competitive-parallel reaction scheme showed that the second Damköhler number (Dall) computed based on the mean tSSS provides useful information about whether the process will be limited by the intrinsic rate of reaction or by the rate of mass transfer, even though the reaction process is controlled by a combination of the RTD as well as loss of LSS and SSS. It was concluded that the change in MTD as a function of power dissipation should coincide with the reaction yield response, and that any deviation in that relationship is because of macroscopic blending of reactants in the entrance region.

Treatment wetlands play an important role in reducing nitrogen content in wastewater and agricultural run-off water. The main removal process is denitrification and the removal efficiency depends on the hydrological and microbiological features of the wetland, especially in terms of water residence times and denitrification rates. The aim of this thesis was to increase the understanding of the coupled hydrological and microbiological processes regulating the denitrification capacity. This was done by applying a broad spectrum of analyses methods, including tracer experiment, water flow modeling, denitrification rate measurements, and analyses of the microbial community structures. The tracer experiment and flow modeling revealed that the wetland design, especially the vegetation, largely can affect the water residence time distributions in wetlands. In the investigated wetland, vegetation dominated the water flow, explaining 60-80% of the variance in water residence times, whereas basin shape only explained about 10% of the variance, but also mixing phenomena significantly affected the residence times and could considerably delay solutes. Measured potential denitrification rates in the wetland exhibited significant spatial variations, and the variations were best described by concentration of nitrogen in sediments and water residence time. Analyses of the denitrifying bacteria populations indicated that a few key populations dominated and that the community diversity increased with decreasing nutrient levels and increasing water residence times. Moreover, it was found that denitrification rates in terms of Menten and first order kinetics can be evaluated by fitting a mathematical expression, considering denitrification and other nitrogen transforming processes to measured product formation in nitrate limited experiments. / QC 20101110

Atrial fibrillation (AF) is the most common arrhythmia that leads to thrombus formation, mostly in the left atrial appendage (LAA). The current standard of stratifying stroke risk, based on the CHA2DS2-VASc score, does not consider LAA morphology, and the clinically accepted LAA morphology-based classification is highly subjective. The aim of this study was to determine whether LAA blood-borne particle residence time distribution and the proposed quantitative index of LAA 3D geometry can add independent information to the CHA2DS2-VASc score. Data were collected from 16 AF subjects. Subject-specific measurements included left atrial (LA) and LAA 3D geometry obtained by cardiac computed tomography, cardiac output, and heart rate.We quantified 3D LAA appearance in terms of a novel LAA appearance complexity index (LAA-ACI). We employed computational fluid dynamics analysis and a systems-based approach to quantify residence time distribution and associated calculated variable (LAA mean residence time, tm) in each subject. The LAA-ACI captured the subject-specific LAA 3D geometry in terms of a single number. LAA tm varied significantly within a given LAA morphology as defined by the current subjectivemethod and it was not simply a reflection of LAA geometry/appearance. In addition, LAA-ACI and LAA tm varied significantly for a given CHA2DS2-VASc score, indicating that these two indices of stasis are not simply a reflection of the subjects’ clinical status. We conclude that LAA-ACI and LAA tm add independent information to the CHA2DS2-VASc score about stasis risk and thereby can potentially enhance its ability to stratify stroke risk in AF patients.

No description available.

No description available.

Sediment deposit ages inferred from radiocarbon dating of stream bank material were used to estimate residence times of valley-floor deposits in headwater valleys of the Oregon Coast Range, USA. Inherited ages of radiocarbon-dated material, i.e., time between carbon fixation in wood and its incorporation in a sediment deposit, can result in over-estimation of the ages of those deposits and, hence, the residence times of sediment within those units. Calibrated radiocarbon dates of 126 charcoal pieces sampled from Knowles Creek were used to estimate the distribution of inherited ages in fourteen depositional units representing three deposit types: fluvial fines, fluvial gravels, and debris flows. Within a depositional unit, the inherited age distribution of a piece of charcoal was estimated by convolving its calibrated age distribution with that of the piece of charcoal with the smallest weighted-mean calibrated age (i.e., an approximation of a unit's date of deposition) within that unit. All inherited age distributions for a particular deposit type were then added and normalized to provide a probability distribution of inherited ages for that deposit type. Probability distributions of inherited ages average 688, 1506, and 666 yr for fluvial fines, fluvial gravels, and debris flow units, respectively. Curves were fit to inherited age distributions for each deposit type. These curve fits were then convolved with deposit age distributions (i.e., equal to calibrated age distributions of woody material sampled from stream banks) of samples from Bear Creek (Lancaster and Casebeer, 2007) to correct these deposit ages for inherited age. This convolution gives a corrected deposit age. In cases in which means of corrected deposit age distributions for an upper unit were older than those of a lower unit within a stratigraphic column, the upper sample’s corrected deposit age distribution was set to that of the youngest lower in the stratigraphic section. Convolution shifted individual deposit age distributions towards zero and increased their standard deviation by an average of 365%. However, convolution decreased the standard deviations of normalized probability distribution functions of deposit ages inferred from many samples from 1340 to 1197 yr, and from 471 to 416 yr for lower and upper reaches, respectively, of the Bear Creek valley in the Oregon Coast Range. Convolution decreased estimates of mean deposit ages from 1296 to 1051 yr, and from 308 to 245 yr for lower and upper reaches, respectively, of the Bear Creek. Estimates of percentages of basin denudation passing through each reach's deposit ("trapping efficiency") increased from 11.6% to 14.4%, and from 25.4% to 31.9% for lower and upper Bear Creek, respectively. However, basic shapes of residence time distributions and, thus, inferences regarding removal of sediment from the reaches did not change after deposit dates were corrected. Sediment residence times in the lower Bear Creek valley are exponentially distributed, which implies that all sediment has a uniform probability of evacuation from deposits, whereas the power-law-distributed residence times in upper Bear imply preferential evacuation of younger deposits and preservation of older deposits. Much of the sediment transported onto valley floors via debris flows is deposited, and then is evacuated over longer times. Volumes and residence times of stored sediment in these deposits at the transition from debris flow to fluvial evacuation, and their associated width of valley floors, vary throughout a network. Export volumes and frequencies from tributaries are controls on deposit volumes and may control valley widening of mainstem valley floors. In addition, closely spaced tributaries may exert composite effects on valley floor landforms. It is hypothesized that the volumes of sediment stored at confluences increases with contributing watershed area of tributaries to the point where tributary slopes are low enough to cause most debris flows to be deposited within tributary valleys instead of in the mainstem valley. In four ~1 km reaches with contributing watershed areas of 0.3 to 5.0 km², field surveys provided measures of width of valley floors and volume of deposits, and radiocarbon dating of charcoal provided residence times of sediment in these deposits. Mean residence times of reaches vary between 1.1 and 2.5 kyr. Exponential distributions fit to residence times within two of the reaches imply evacuation of sediment independent of deposit ages. Power-law fits to residence times of the other two reaches imply age-dependent evacuation of deposits. Distribution shapes of residence times, and their means, do not vary systematically with contributing watershed area of mainstems. Mean width of mainstem valley floors increases with contributing watershed areas of both mainstems and their respective tributaries. Volumes of sediment stored on the valley floor increase with contributing areas of mainstems, and these volumes at tributary junctions peaked at tributary contributing areas of ~0.1 km². Percentage of basin denudation entering storage decreases with contributing area of mainstem. This decrease may be due to increasing percentages of sediment supply via fluvial transport for larger watersheds, and much, if not most, of this supply routes through the system quickly. / Graduation date: 2012

L’objectif de ce travail était de tester l’utilisation des radioisotopes naturels à courte période (234Th, 7Be et 210Pb) comme traceurs des transferts des particules dans le bassin versant de la Garonne-Dordogne-Gironde. Dans un premier temps, la faisabilité de la méthode basée sur le 234Th a été testée dans les rivières. Les résultats ont montré qu’une valeur de 5 mBq l-1 correspondant au seuil en 238UD est nécessaire pour l’application du 234Th en rivière. Dans un deuxième temps, le suivi sur deux années (2006-2007) des radioéléments naturels, 234Th, 7Be et 210Pb, et artificiels, 137Cs et 131I, dans le Lot, la Garonne et l’estuaire de la Gironde, a permis de distinguer les différentes étapes du transport des particules en relation avec l’hydrologie. L’atout de l’utilisation de ces traceurs est d’accéder à de premières estimations du temps de résidence des sédiments et du pourcentage des fractions anciennes et récentes. Dans le Lot et la Garonne, il existe une rétention des particules (2-89 jours) pendant l’étiage et les débits moyens, et de fortes remises en suspension des sédiments anciens à débits élevés. La moyenne du pourcentage des sédiments récents dans les rivières est d’environ 25 %, ce qui montre que les matériaux en suspension (MES) dans les rivières sont dominés par des sédiments anciens. Dans l’estuaire de la Gironde, le temps de résidence varie en fonction de l’hydrologie des rivières : pendant les périodes de forts débits, le temps de transit des particules de la Réole jusqu’à l’océan est seulement de quelque mois (~150 jours) ; alors que pendant les périodes d’étiage, l’âge des sédiments augmente dans la zone de turbidité maximum atteignant jusqu’à 400 jours. / The main objective of this study was to develop short-lived radioisotopes (234Th, 7Be and 210Pb) as tracers of particle transport in the Garonne-Dordogne-Gironde watershed. Firstly, the possibility to use 234Th/238U pair to study particle residence time in the Gironde fluvial-estuarine system was tested. The results show that dissolved 238U should be greater than 5 mBq l-1 to permit this application in fluvial systems. Secondly, the two years monitoring of natural radioisotopes, 234Th, 7Be and 210Pb, and artificial radioisotopes, 137Cs and 131I, in the Garonne and Lot rivers and in the Gironde Estuary, had allowed to observe the dynamic of particle transport, linked to the river flow. Based on this database, preliminary particle residence times and percentages of the new and old sediments were estimated. In the Lot and Garonne rivers, the particle retention ranges between 2-89 days during low and mean river discharges. The percentage of the new sediments is average 25 %, which indicates that the old resuspended sediments are dominated the suspended particulate matters (SPM). In the Gironde estuary, the particle residence time is mainly controlled by river discharge. The particle residence time during low river discharge is about 400 days. When the river discharge is increasing, the freshwaters are predominant in the estuary, the maximum turbidity zone (TMZ) is dispersed and the old sediments transported toward the ocean. During this period the particle residence time is only few months.

Les aquifères fracturés sont un enjeu majeur de l’hydrogéologie actuelle. Ils constituent une ressource essentielle pour de nombreuses populations. Le massif de l’Ursuya (France, 64), en est une illustration. Constitué de formations métamorphiques fracturées, il est intensément exploité pour l’alimentation en eau potable. Une approche multidisciplinaire a permis la compréhension du fonctionnement de ce système. Les résultats obtenus constituent une avancée dans la connaissance des aquifères discontinus et offrent des pistes pour une gestion raisonnée de cette ressource.Le signal d’entrée est caractérisé dans sa composante quantitative et qualitative. Le suivi des paramètres climatiques permet d’estimer la lame d’eau participant à la recharge de l’aquifère. La caractérisation isotopique de l’eau précipitée met ensuite en évidence une origine majoritairement atlantique des masses d’air, responsables des précipitations sur le nord-ouest du Pays Basque. Des circulations atmosphériques sur la péninsule Ibérique, l’Europe du Nord et la région méditerranéenne sont cependant responsables de certains événements pluvieux. La composition chimique de l’eau de pluie, résultant de ces origines, est caractérisée par une faible acidité et par des concentrations en éléments anthropiques parfois élevées.L’hydrochimie des eaux souterraines est étudiée conjointement avec des données de temps de séjour acquises par l’interprétation des concentrations en 3H, CFC et SF6. Les caractéristiques physico-chimiques, les temps de séjours mesurés (moins de 10 ans à plus de 50 ans) et les phénomènes de mélanges associés permettent de proposer un modèle conceptuel des écoulements souterrains. Celui-ci met en exergue le rôle prépondérant du profil d’altération développé dans les milieux cristallins (de la surface vers la profondeur : altérites, roche fissurée et roche saine), du point de vue de la minéralisation de l’eau comme de celui des modalités d’écoulement.Une approche quantitative est finalement proposée. Du point de vue hydrodynamique, l’hétérogénéité spatiale est importante (10–4 m s–1 < K < 10–8 m s–1). Les altérites offrent une capacité de stockage et de régulation de la recharge. Un modèle numérique synthétise et valide ces résultats. Les simulations montrent de fortes interactions entre les réseaux d’écoulements superficiel et souterrain et de faibles impacts de l’exploitation actuelle sur les flux d’eau souterraine. Les évolutions climatiques ne modifieront pas significativement les écoulements durant les prochaines décennies. Une diminution des débits des sources et des cours d’eau est toutefois probable. Ce modèle numérique et l’ensemble des résultats obtenus serviront de base pour une gestion raisonnée de la ressource en eau de l’aquifère de l’Ursuya. / Hard-rock aquifers are one of the major challenges for the current hydrogeology. These fractured formations are intensively exploited for drinking water supply becoming an essential resource for many people. The metamorphic massif of Ursuya (France, 64) is one of this strategic aquifer. A multidisciplinary approach has led to understand the functioning of this system. The results help to progress in the knowledge of discontinuous media and they provide supports for a rational management of this resource.The input signal is characterized by both quantitative and qualitative methods. Monitoring of climate parameters is used to estimate the amount of aquifer recharge. Isotopic characterization of rainwater highlights the principal Atlantic origin of air masses which are responsible of precipitation on the north-western Basque Country. Some rainfall events are also due to atmospheric circulation over the Iberian Peninsula, the Northern Europe and the Mediterranean region. The chemical composition of rainwater, resulting from these origins, is characterized by a low acidity and sometimes by high concentrations of anthropogenic elements.The hydrochemistry of groundwater is studied in conjunction with residence time data. These are acquired by the interpretation of 3H, CFCs and SF6 concentrations. The chemical characteristics, the measured residence times (less than 10 years to over than 50 years) and the associated mixing processes allow the achievement of a conceptual model of groundwater flow. It points out the role of the weathering profile (from the surface to the depth : weathered layer, fractured rock and fresh bedrock) from the point of view of the mineralization as well as the flowpaths.A quantitative approach is finally proposed. Boreholes studies show highly heterogeneous hydrodynamic properties (10-4 m s-1 < K <10-8 m s-1). Weathered materials provide a storage capacity and a smoothing of the recharge variations, these results are synthesized and validated by a numerical model. The simulations show strong interactions between the surface flow network and the water table. It also highlights the low impact of the current groundwater exploitation on the aquifer and that climate change will not significantly modify the groundwater flows in the coming decades. Nevertheless, a decrease of the springs and streams flow is probable. This numerical model and all these results constitute the basis for a rational management of water resources from the Ursuya aquifer.

L’aquifère molassique du Bas-Dauphiné est situé le long de la vallée du Rhône, dans le Sud-Est de la France. Cet aquifère d’une superficie proche de3000 km², et d’une épaisseur moyenne de 400m renferme une eau d’excellente qualité, utilisée par de nombreuses collectivités pour l’alimentation en eau potable. Cependant certains secteurs montrent une forte vulnérabilité de la nappe aux activités agricoles. L’utilisation d’outils géochimiques etisotopiques a permis de préciser le fonctionnement hydrodynamique de l’aquifère. Dans un premier temps, nous avons montré que la stratification des écoulements décrite par De La Vaissière (2006) sur la partie drômoise de l’aquifère s’étend au secteur isérois. Les eaux les plus profondes ont des vitesses de circulation de l’ordre du mètre par an alors que les flux superficiels ont des vitesses de circulations d’une centaine de mètres par an. D’autre part, le marquage des nappes superficielles et des rivières par des teneurs faibles en tritium (de 3 à 4 UT) et forte en magnésium (jusqu’à 18 mg/L)indique un apport d’eaux anciennes, issues de l’aquifère molassique vers ces eaux superficielles. La définition de deux pôles d’eaux et l’application d’une équation de mélange couplés à la réalisation de bilans hydrogéologique a permis d’appréhender les volumes échangés. Il apparaît finalement que les réservoirs d’eaux superficiels constituent l’exutoire principal de l’aquifère molassique. L’utilisation des éléments traces a mis en avant le rôleessentiel du temps de séjour des eaux dans l’aquifère ainsi que des conditions d’oxydo-réduction dans l’acquisition de la minéralisation. L’évaluation de la qualité naturelle des eaux de la nappe a montré l’impact des activités agricoles sur l’aquifère, avec prés de 80% des échantillons ayant une teneur en nitrates supérieure à la concentration naturelle supposée. L’étude des teneurs en pesticides conforte ce constat. De plus l’étude de l’évolution des concentrations en polluants montre une dégradation de la ressource. / The molassic basin of Bas-Dauphiné is located in south-eastern France, in the Rhône valley. With an averagethickness of about 400 m, and a surface area of about 2900 km², this aquifer is an important groundwaterresource for freshwater supply and agriculture. However, this resource is also vulnerable and is impacted byhuman activities. The use of geochemical and isotopic analyses made it possible to understand the hydrodynamicsurvey of the aquifer. Firstly, we showed the stratification of the groundwater previously described in thesouthern part of the molassic aquifer could be extended to the north. The groundwater flow velocity is about onemeter / year for the deepest flow and around 100-200 meter /year for the shallowest flow. Secondly, superficialaquifers and rivers are marked by low tritium activities (3 to 4 UT) and high magnesium concentrations (until 18mg/L), which indicate ancient molassic water contribution. The definition of two water types and the applicationof a mixing equation combined with hydrogeological balances lead to an estimation of the contribution of thedeep aquifer to the shallow aquifer. It is finally established that surface water (aquifers and rivers) constitute themain outlet of the molassic aquifer. The use of trace elements shows the importance of the groundwaterresidence time and of redox conditions in the water mineralization. The assessment of baseline quality shows theimpact of agricultural activities upon the aquifer, with nearly 80 % of samples showing higher nitrateconcentration than the maximal natural concentration. This is confirmed by the study of pesticidesconcentrations. Furthermore, the evolution of pollutants concentrations points out a deterioration of the resource.

La congélation partielle du mix dans un échangeur de chaleur à surface raclée (ECSR)est l'étape la plus critique dans la fabrication d'un sorbet, car c'est la seule étape où de nouveaux cristaux de glace se forment; par la suite ces cristaux ne font que grossir. L'objectif principal est de produire un grand nombre de cristaux les plus petits possibles afin d'obtenir une texture onctueuse. Pendant le procédé de congélation, le produit est soumis à des interactions couplées d'écoulement du fluide, de transfert de chaleur, de changement de phase et de cisaillement. Ces interactions sont déterminées par les conditions opératoires du procédé de congélation et affectent l'évolution de la distribution de taille des cristaux de glace, ainsi que la texture finale du produit. Ce travail présente la caractérisation expérimentale et la modélisation du procédé de congélation d'un sorbet. La congélation du sorbet à été effectuée dans un ECSR à l'échelle pilote. L'objectif principal de ce travail est l'étude de l'influence des conditions opératoires du procédé de congélation sur les caractéristiques finales du produit: distribution de taille de cristaux de glace, température du produit, fraction volumique de glace et viscosité apparente. Le comportement de l'écoulement du produit dans l'ECSR a été caractérisé par une étude expérimentale et une modélisation de la distribution du temps de séjour (DTS). Une approche de modélisation de la cristallisation de la glace couplant le modèle de DTS avec des équations de transfert de chaleur et de bilan de population des différentes classes de taille de cristaux a été développée. À partir d'une première estimation des paramètres, le modèle de cristallisation prédit de façon satisfaisante les tendances expérimentales et donne un bon aperçu de l'évolution de la distribution de taille des cristaux de glace au cours du procédé de congélation dans l'ECSR. / The partial freezing of the mix inside the scraped surface heat exchanger (SSHE) is the most critical step in sorbet manufacturing, since it is the only stage where new ice crystals are produced; further in the process these ice crystals will only grow. The main objective of the freezing process is to form the smallest possible ice crystals, so as to assure a smooth texture in the final product. During the freezing process the product is subjected to coupled interactions of fluid flow, heat transfer, ice phase change and shear. These interactions are determined by the freezing operating conditions and affect the evolution of the ice crystals size distribution (CSD) and the final texture of the product. This work presents the experimental characterization and the modelling of the initial freezing process of a sorbet. The freezing of sorbet was carried out in a SSHE at the pilot scale. The main objective of this work was the study of the influence of the freezing operating conditions on the final product characteristics: ice CSD, product temperature, ice volume fraction, apparent viscosity. The product flow behaviour in the SSHE was characterized by an experimental and modelling study of the residence time distribution (RTD) of the product. An ice crystallization modelling approach, taking into account the coupling of an empirical RTD model with heat transfer equations and a population balance of the different ice crystal size classes was developed. With a first set of estimated parameters, the ice crystallization model predicts satisfactorily the experimental trends, and made it possible to have an insight on the evolution of ice CSD during the freezing process in the SSHE.