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This study addressed the geochemical drivers of Mn removal, including pH, alkalinity and the presence of mineral particles. We conducted laboratory experiments and field monitoring at two drinking water reservoirs in southwestern Virginia – Falling Creek Reservoir (FCR) and Carvins Cove Reservoir (CCR). In laboratory experiments in pH and alkalinity-adjusted nanopure water solutions, we observed substantial Mn removal within 14 days only under high pH conditions (pH≥10). In experiments with high pH and moderate to high alkalinity (> 80 mg/L CaCO3), near-total Mn removal occurred within 2 hours, at a rate of 0.25 mg/L-1 hr-1. Mn removal occurred alongside precipitation of microscopic (<5 μm diameter) and macroscopic (>100 μm diameter) particles. Elemental analysis of particles with energy-dispersive X-ray spectroscopy (EDS) supports their identification as Mn(IV) oxides (MnOx), which suggests Mn removal driven by oxidation. Elevated alkalinity in high pH solutions promotes Mn oxidation by maintaining high pH through buffering, which sustains conditions favorable for Mn oxidation. Our results also suggest sorption of Mn and mineral-catalyzed Mn oxidation by Mn oxides formed through oxidation by dissolved oxygen. In experiments using filtered and unfiltered water from the two reservoirs, we observed significant Mn removal in experiments with unfiltered water, suggesting that particles may remove Mn by catalyzing oxidation or nucleating Mn oxide precipitation. Mn removal occurred at 0.05 d-1 in unfiltered FCR water and 0.002 d-1 in unfiltered CCR water. We observed no Mn removal in filtered water from either reservoir. Scanning electron microscope (SEM) and EDS of visible particles from reservoir water experiments suggests that quartz and clay minerals present in the water column may nucleate or catalyze Mn oxide formation. Overall, this research shows that Mn removal under HOx operation is influenced by a variety of factors, including pH, alkalinity and suspended particles. / Master of Science / Elevated concentrations of manganese (Mn), a naturally occurring contaminant, can impair drinking water quality in several ways – by introducing poor taste and smell, staining pipes and appliances, and potentially harming the health of young children. Hypolimnetic oxygenation (HOx) is a novel water treatment method deployed in lakes and reservoirs to control water column contamination of metals and nutrients, including Mn. By pumping oxygen into lakes and reservoirs, HOx systems create conditions favorable for Mn removal from the water column. Previous work in two southwestern Virginia drinking water reservoirs documented differences between sites in how effectively HOx systems are able to remove Mn. These reservoirs have significant differences in their chemical profiles – most notably in pH and alkalinity, which suggests a role for background water chemistry in influencing removal rates in lakes and reservoirs with HOx systems. We used laboratory experiments to simulate the effects of pH and alkalinity on Mn removal rates in oxygenated lakes and reservoirs. We observed substantial Mn removal within 14 days under high pH conditions (pH 10-11) and negligible removal in solutions at or under pH 8. In experiments with pH 10-11 and alkalinity over 80 mg/L, near-total Mn removal occurred within 24 hours. During the 24 hour removal window, we observed yellow-brown discoloration of our experimental solutions within 12 hours, followed by formation of loosely aggregated brown to black particles. Microscopy and elemental analyses indicate that initial discoloration occurs due to formation of 1-2 μm wide manganese oxides with needle-like crystals. The visible aggregates are also manganese oxides. Based on mineral characterization and the time series of Mn removal observed in our experiments, we believe that initial formation of Mn oxides creates a positive feedback loop in solutions of pH 10-11 and alkalinity over 80 mg/L. Mn oxides promote further Mn oxide formation by facilitating conversion of Mn in solution into forms that easily settle from water. Observations of particulate formation and solution chemistry in filtered vs. filtered reservoir water from FCR and CCR supports a pivotal role for particles in facilitating Mn removal. Our research addresses the impacts of water chemistry Mn removal in drinking water, and improves understanding of Mn cycling in natural freshwaters.

Made available in DSpace on 2016-03-15T19:37:30Z (GMT). No. of bitstreams: 1 Rafael Silveira Xavier.pdf: 2553779 bytes, checksum: a8f662532337688fc1c41c478b790a6a (MD5) Previous issue date: 2010-12-22 / Fundo Mackenzie de Pesquisa / Molecular replication was introduced as a possible theory to explain the origin of life. Since their proposal they have been extensively studied from a biochemical perspective. This work proposes a taxonomy for the main properties of replicators that are important for building computational tools to solve complex problems as well as introduces two computational models for these entities in order to observe and analyze the behavior of these models in light of the natural properties of replicators introduced. / A replicação molecular foi introduzida como uma possível teoria para explicar a origem da vida. Desde sua proposição, ela vem sendo estudada extensivamente a partir de uma perspectiva bioquímica. Baseado na literatura de replicadores moleculares, esta dissertação organiza e propõe uma taxonomia para as principais propriedades dos replicadores que sejam interessantes para a construção de ferramentas computacionais voltadas para a solução de problemas complexos na engenharia e na computação, bem como introduz dois modelos computacionais baseado nessas entidades a fim de observar e analisar o comportamento destes modelos sob a luz das propriedades dos replicadores naturais discutidas nesta dissertação.

Molecular recognition plays an essential role in the self-assembly and self-organisation of biological and chemical systems alike—allowing individual components to form complex interconnected networks. Within these systems, the nature of the recognition and reactive processes determines their functional and structural properties, and even small changes in their identity or orientation can exert a dramatic effect on the observed properties. The rapidly developing field of systems chemistry aims to move away from the established paradigm in which molecules are studied in isolation, towards the study of networks of molecules that interact and react with each other. Taking inspiration from complex natural systems, where recognition processes never operate in isolation, systems chemistry aims to study chemical networks with the view to examining the system-level properties that arise from the interactions and reactions between the components within these systems. The work presented in this thesis aims to advance the nascent field of systems chemistry by bringing together small organic molecules that can react and interact together to form interconnected networks, exhibiting complex behaviour, such as self-replication, as a result. Three simple building blocks are used to construct a network of two structurally similar replicators and their kinetic behaviour is probed through a comprehensive kinetic analysis. The selectivity for one of the recognition-mediated reactive processes over another is examined within the network in isolation as well as in a scenario where the network is embedded within a pool of exchanging components. The interconnected, two-replicator network is examined under far-from-equilibrium reaction-diffusion conditions, showing that chemical replicating networks can exhibit signs of selective replication—a complex phenomenon normally associated with biological systems. Finally, a design of a well-characterised replicator is exploited for the construction of a network integrating self-replication with a another recognition-directed process, leading to the formation of a mechanically-interlocked architecture—a [2]rotaxane.

Opération de tête des procédés hydrométallurgiques de recyclage des combustibles nucléaires usés, la dissolution est une étape importante : la mise en solution des éléments chimiques est indispensable avant la réalisation des étapes d’extraction liquide-liquide permettant de faire le tri entre matière valorisable et déchets ultimes. Cette étude a pour objectif de mieux appréhender les phénomènes chimiques, physico-chimiques et hydrodynamiques de la réaction de dissolution du dioxyde d’uranium en milieu nitrique. Elle s’inscrit dans une démarche de modélisation du procédé par l’expression des vitesses intrinsèques de réaction et la description des phénomènes physico-chimiques aux interfaces. Une approche par microscopie optique a permis de confirmer le caractère fortement autocatalytique de la réaction et de mesurer, pour la première fois, les vitesses « vraies » de la réaction chimique. L’attaque des massifs, obtenus par frittage, se fait par des sites préférentiels d’attaque et entraîne le développement de failles dans les massifs qui peuvent aller jusqu’à déliter le massif. Cette attaque non uniforme est rendue possible par l’établissement d’un bullage dans ces failles qui permet un renouvellement périodiquement des réactifs et entretient la réaction en leur sein. Ce point constitue un élément clef du mécanisme : un lien fort entre développement des failles, bullage dans les failles, et vitesses de dissolution globales est mis en évidence dans ce travail. Enfin, un modèle intégrant les bilans couplés de matière liés à l’évolution structurelle du solide et des compositions en phase liquide, et tenant compte du transport aux interfaces, est proposé. Les simulations fondées sur ce modèle sont proches des observations expérimentales, et permettent de reproduire pour la première fois l’effet de différents paramètres réactionnels, comme celui de la diminution des cinétiques lors d’une augmentation de la turbulence / Dissolution is a milestone of the head-end of hydrometallurgical processes used for recycling spent nuclear fuel. The solubilization of the chemical elements is essential before performing the liquid-liquid extraction steps to separate reusable material and final waste. This study aims at better understanding the chemical, physico-chemical and hydrodynamic phenomena of uranium dioxide dissolution reactions in nitric medium. This study is also part of a modeling approach aiming at expressing the intrinsic reaction rates and describing of the physico-chemical phenomena at interfaces. Optical microscopy confirmed the highly autocatalytic nature of the reaction and led to measurements, for the very first time, of "true" chemical kinetics of the reaction. The acid attack of sintering-manufactured solids occurs through preferential attack sites. It develops cracks in the solids that can lead to the cleavage of the solid. This inhomogeneous attack is made possible by the establishment of bubbling in the cracks which allows periodic renewal of the reagents and thus maintains the reaction within the cracks. This point is a key component of the mechanism: a strong link between the development of cracks, bubbling through the cracks, and overall dissolution kinetics is demonstrated in this work. Finally, a model coupling material balance to the structural evolution of the solid and liquid phase compositions, and taking into account the interfacial transport is proposed. The simulations based on this model are close to the experimental observations, and allow to reproduce for the very the first time the effect of various reaction parameters, such as the reduction of overall kinetics when turbulence increases

La dissolution du dioxyde d’uranium en milieu nitrique est une étape clef du traitement des combustibles nucléaires usés. Elle précède en effet le procédé PUREX, qui permet l’extraction liquide - liquide des radionucléides valorisables. Cette dissolution est triphasique et autocatalytique, ce qui fait que de nombreux phénomènes impactent la réaction. Une bonne compréhension de ces phénomènes, autant à l’échelle microscopique que macroscopique, est nécessaire pour pouvoir proposer un modèle de la vitesse de disparition du solide au sein des dissolveurs. Les paramètres cinétiques de la réaction de dissolution ont été déterminés, en intégrant son aspect autocatalytique. L’étude cinétique a été réalisée en suivant la dissolution par microscopie optique. Cette technique d’analyse permet une approche uni-particulaire, qui est nécessaire car elle permet de limiter l’accumulation de l’espèce autocatalytique à l’interface solide – liquide. De plus, la dissolution du dioxyde d’uranium produit des oxydes d’azote. Une réaction volumique entre ces gaz et le catalyseur a été mise en évidence. Les cinétiques de cette réaction ont été estimées à partir des résultats expérimentaux. L’importance de la prise en compte des échanges à l’interface gaz – liquide pour définir la concentration de catalyseur en solution a été démontrée. Un modèle a été réalisé sur Matlab pour permettre de discriminer l’influence de ces différents éléments. Ce modèle donne des résultats cohérents avec l’expérimental, aussi bien à l’échelle microscopique que macroscopique. Plusieurs nombres adimensionnels ont également été mis en évidence pour cerner les phénomènes dont l’impact est prépondérant, en fonction de la géométrie et de l’hydrodynamique du dissolveur. Ce modèle a permis de cerner quelques pistes d’optimisation de procédés mettant en jeux des réactions autocatalytiques. Notamment, le fait que pour ces réactions particulières, les échanges aux interfaces solide - liquide et liquide - gaz peuvent être utilisés comme leviers pour maitriser la vitesse de disparition du solide / Recycling of nuclear fuel is based on liquid – liquid extraction. The dissolution of uranium dioxide in nitric medium is hence a key step at the head - end of the entire process. This particular dissolution is triphasic and autocatalytic, which means that numerous phenomena must be taken into account. A complete understanding of these phenomena, at macroscopic and microscopic scale, is necessary in order to model the solid disappearance rate in dissolvers. The kinetical parameters of the reaction were determined for both the catalyzed and non-catalyzed reactions. The kinetic study was realized thanks to a single particle approach. The reaction rates were measured by optical microscopy. This analytical technic enables to limit the catalyst accumulation at the solid - liquid interface. Moreover, nitrous oxides are products of the uranium dioxide dissolution. Evidence of a volumic reaction between these gases and the catalyst were found, and the kinetics of this reaction was estimated from the experimental results. Gas – liquid exchanges were shown to have an important impact on the catalyst concentration in the reactor. A model was realized thanks to the software Matlab to simulate these different phenomena. It was shown to be in good agreement with experimental results, at the microscopic and macroscopic scale. Dimensionless numbers were highlighted to describe the impact of each phenomenon on the solid disappearance, including the influence of the geometry and hydrodynamics of the reactor. Finally, ways of process optimization for autocatalytic reactions were determined thanks to the model. For instance, gas – liquid and solid – liquid exchanges were shown to be an interesting lever to fix the catalyst concentration in the reactor and at the solid surface

Dans les réacteurs industriels ou dans la nature, l'écoulement de fluides peut être couplé à des réactions chimiques. Dans de nombreux cas, il en résulte l'apparition de structures complexes dont les propriétés dépendent entre autres de la géométrie du système.<p><p>Dans ce contexte, le but de notre thèse a été d'étudier de manière théorique et sur des modèles réaction-diffusion-convection simples les propriétés de dynamiques spatio-temporelles résultant du couplage chimie-hydrodynamique. <p>Nous nous sommes focalisés sur les instabilités hydrodynamiques de digitation visqueuse et de densité qui apparaissent respectivement lorsqu'un fluide dense est placé au-dessus d'un fluide moins dense dans le champ de gravité et lorsqu'un fluide visqueux est déplacé par un fluide moins visqueux dans un milieu poreux.<p><p>En particulier, nous avons étudié les problèmes suivants:<p>- L'influence d'une réaction chimique de type A + B → C sur la digitation visqueuse. Nous avons montré que les structures formées lors de cette instabilité varient selon que le réactif A est injecté dans le réactif B ou vice-versa si ces réactifs n'ont pas un coefficient de diffusion ou une concentration initiale identiques.<p>- Le rôle de pertes de chaleur par les parois du réacteur dans le cadre de la digitation de densité de fronts autocatalytiques exothermiques. Nous avons caractérisé les conditions de stabilité de fronts en fonction des pertes de chaleur et expliqué l'apparition de zones anormalement chaudes lors de cette instabilité.<p>- L'influence de l'inhomogénéité du milieu sur la digitation de densité de solutions réactives ou non. Nous avons montré que les variations spatiales de perméabilité d'un milieu poreux peuvent figer ou faire osciller la structure de digitation dans certaines conditions.<p>- L'influence d'un champ électrique transverse sur l'instabilité diffusive et la digitation de densité de fronts autocatalytiques. Il a été montré que cette interaction peut donner lieu à des nouvelles structures et changer les propriétés du front.<p><p>En conclusion, nous avons montré que le couplage entre réactions chimiques et mouvements hydrodynamiques est capable de générer de nouvelles structures spatio-temporelles dont les propriétés dépendent entre autres des conditions imposées au système.<p>/<p>In industrial reactors or in nature, fluid flows can be coupled to chemical reactions. In many cases, the result is the emergence of complex structures whose properties depend among others on the geometry of the system.<p>In this context, the purpose of our thesis was to study theoretically using simple models of reaction-diffusion-convection, the properties of dynamics resulting from the coupling between chemistry and hydrodynamics.<p><p>We focused on the hydrodynamic instabilities of viscous and density fingering that occur respectively when a dense fluid is placed above a less dense one in the gravity field and when a viscous fluid is displaced by a less viscous fluid in a porous medium.<p><p>In particular, we studied the following issues:<p>- The influence of a chemical reaction type A + B → C on viscous fingering. We have shown that the fingering patterns observed during this instability depends on whether the reactant A is injected into the reactant B or vice versa if they do not have identical diffusion coefficients or initial concentrations.<p>- The role of heat losses through the reactor walls on the density fingering of exothermic autocatalytic fronts. We have characterized the conditions of stability of fronts depending on heat losses and explained the appearance of unusually hot areas during this instability.<p>- The influence of the inhomogeneity of the medium on the density fingering of reactive solutions or not. We have shown that spatial variations of permeability of a porous medium may freeze or generate oscillating fingering pattern under certain conditions.<p>- The influence of a transverse electric field on the Rayleigh-Taylor and diffusive instabilities of autocatalytic fronts. It was shown that this interaction may lead to new structures and may change the properties of the front.<p><p>In conclusion, we showed that the coupling between chemical reactions and hydrodynamic motions can generate new space-time structures whose properties depend among others, on the conditions imposed on the system. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished