Ready-to-eat meat products have been implicated in several foodborne listeriosis outbreaks. Microbial contamination of these products can occur after the product has been thermally processed and is being rapidly chilled using salt brines. The objective of this study was to determine the effect of ultraviolet irradiation on the inactivation of Listeria monocytogenes and lactic acid bacteria in a model brine chiller system. Two concentrations of brines (7.9%w/w or 13.2%w/w) were inoculated with a ~6.0 log10 CFU/ml cocktail of L. monocytogenes or lactic acid bacteria and passed through the ultraviolet (UV) treatment system for 60 minutes. Three replications of each bacteria and brine combination were performed and resulted in at least a 4.5 log reduction in microbial numbers in all treated brines after exposure to ultraviolet light. Bacterial populations were significantly reduced after five minutes exposure to UV light in the model brine chiller as compared to the control, which received no UV light exposure (P<0.05). The maximum rate of inactivation for both microorganisms in treated brines occurred between minute 1 and 15 of ultraviolet exposure. Overall, results indicate that inline treatment of chill brines with ultraviolet light (UVC) shows promise in inactivating L. monocytogenes and lactic acid bacteria. Due to the low capital involved in initiating a continuous inline UV system, the use of ultraviolet energy may prove to be beneficial for effectively controlling pathogens in recycled chill brines without interrupting the chilling operation. An inline ultraviolet system could be used in a hazard analysis and critical control points plan. / Master of Science

Die Frage nach der Möglichkeit von Leben auf anderen Planeten, vor allem auf dem Mars, steht in einem engen Zusammenhang mit der Verfügbarkeit von flüssigem Wasser. Dies ist bei den vorherrschenden klimatischen Bedingungen, vor allem der tiefen Temperatur, nur mittels einer Gefrierpunktserniedrigung durch Salze erklärbar. Die vorliegende Arbeit beschäftigt sich daher mit Phasengleichgewichten verschiedener Salz-Wasser-Systeme bei tiefen Temperaturen. Dabei wurden nach einer Sammlung von Literaturdaten und einer Ermittlung der Lücken innerhalb dieser verschiedene Systeme nach Mars-Relevanz, sowie chemischer Systematik ausgewählt und experimentell untersucht. Insgesamt wurden dabei 22 binäre Phasendiagramme von Salz-Wasser-Systemen betrachtet und 29 festen Phasen mittels Röntgen-Einkristallstrukturanalyse aufgeklärt. Aus diesen Strukturen wurde ein Modell zur Beschreibung einer zweiten Hydratationssphäre über eine Wechselwirkungsbilanz abgeleitet und an den verfügbaren Strukturen geprüft.

Die Frage nach der Möglichkeit von Leben auf anderen Planeten, vor allem auf dem Mars, steht in einem engen Zusammenhang mit der Verfügbarkeit von flüssigem Wasser. Dies ist bei den vorherrschenden klimatischen Bedingungen, vor allem der tiefen Temperatur, nur mittels einer Gefrierpunktserniedrigung durch Salze erklärbar. Die vorliegende Arbeit beschäftigt sich daher mit Phasengleichgewichten verschiedener Salz-Wasser-Systeme bei tiefen Temperaturen. Dabei wurden nach einer Sammlung von Literaturdaten und einer Ermittlung der Lücken innerhalb dieser verschiedene Systeme nach Mars-Relevanz, sowie chemischer Systematik ausgewählt und experimentell untersucht. Insgesamt wurden dabei 22 binäre Phasendiagramme von Salz-Wasser-Systemen betrachtet und 29 festen Phasen mittels Röntgen-Einkristallstrukturanalyse aufgeklärt. Aus diesen Strukturen wurde ein Modell zur Beschreibung einer zweiten Hydratationssphäre über eine Wechselwirkungsbilanz abgeleitet und an den verfügbaren Strukturen geprüft.

Typescript (photocopy). / Digitized by Kansas Correctional Industries

Le lithium est une matière première en demande croissante suite au fort développement des appareils nomades et des véhicules électriques. Ce manuscrit s’intéresse à la production de lithium à partir d’une ressource naturelle : les saumures lithinifères. Une étude bibliographique sur l’extraction du lithium présent dans les saumures a mis en avant que cette dernière requiert des quantités importantes d’énergie, d’eau et de réactifs. Cela met ainsi en évidence l’enjeu environnemental et la nécessité d’améliorer les procédés existants. A cette fin, la présente étude allie la modélisation à un travail expérimental. Le modèle sélectionné pour calculer les coefficients d’activité des éléments dissous dans les saumures est le modèle de Pitzer (1991). Un travail de paramétrisation a été effectué pour mettre au point une base de données thermodynamiques disposant des éléments nécessaires (propriétés des sels, paramètres d’interaction) à la description des systèmes électrolytiques d’intérêt. Après un travail de validation appuyé sur des données expérimentales issues de la bibliographie, cette base de données, associée au logiciel PhreeqC pour les calculs géochimiques, permet de simuler différentes transformations des saumures (dilution, évaporation, ajout de réactifs). L’outil mis en place a permis d’analyser des scenarios exploratoires de production de zabuyelite (Li2CO3) et d’effectuer une étude de sensibilité des paramètres opératoires. Des travaux expérimentaux sur des saumures modèles ont été effectués sur deux pilotes distincts : une enceinte climatique et une unité d’évaporation. Les techniques d’analyses utilisées pour suivre l’évolution de la composition de la saumure et la qualité des cristaux sont la chromatographie ionique, la DRX et l’EDX. Le modèle mis au point permet de décrire les systèmes salés complexes à l’équilibre à 25°C. Il parvient à décrire les essais dans le pilote d’évaporation du LaTEP à condition que l’on émette l’hypothèse que la zabuyelite ne précipite pas au cours du temps (sursaturation nécessaire). Il pourrait certainement être optimisé au niveau thermodynamique (spéciations, constantes de solubilité), mais également en y ajoutant une dimension cinétique et transferts liquide-vapeur. / Lithium is a critical element regarding to the development of portable devices and electric vehicles. This manuscript is dedicated to lithium production from natural lithium bearing brines. A bibliographic review shows that lithium production consumes lots of water, energy and reactive. It underlines environmental issues and the necessity to improve existing processes. In order to achieve this, modeling and experimental work are associated for this study. The Pitzer model (Pitzer, 1991) is used to calculate the activity coefficients of dissolved aqueous species in brines. After parametrization (salt properties, interaction parameters) and validation with experimental data from literature, a database was optimized to allow the description of key electrolytic systems. Associated with phreeQC software, it is possible to simulate transformations of the brine (such as dilution, evaporation, reactions). It can be used as a predictive tool to explore zabuyelite (Li2CO3) production and study the sensibility of the operative parameters (temperature, pH, pCO2). Experimental work on model-brines was done on two separate pilots: a climatic chamber and a crystallization unit. The evolution of the brine composition and quality of crystals produced was monitored by ionic chromatography, XRD and EDX. The model designed in this study can describe the equilibrium of complex brines at 25°C. It can also describe the experiment in the crystallization unit if a hypothesis of supersaturation (Li2CO3) is used. It could be improved thermodynamically with more speciation and solubility constants, and also with kinetics and liquid-vapor transfers.

L’Anti-Atlas marocain est une vaste province géologique composée d’un socle précambrien et d’une couverture sédimentaire tardi-néoprotérozoïque à paléozoïque. Plus de 200 occurrences cuprifères sont répertoriées dans cette couverture. Avec l’augmentation de la demande mondiale en cuivre depuis les années 2000, ces minéralisations, considérées non rentables dans les années 1980, sont désormais d’intérêt économique majeur pour les compagnies minières. Outre cet intérêt économique, ces occurrences restent un mystère scientifique du point de vue de leur genèse. En effet, les quelques études existantes sur ces objets ne permettent pas d’établir un modèle métallogénique clair expliquant la formation de ces concentrations à cuivre. Notre étude est centrée sur la boutonnière de Bou Azzer-El Graara (Anti-Atlas central). Elle propose de réaliser une synthèse des minéralisations de ce secteur basée sur quatre axe : (1) une étude de terrain à l’échelle des objets minéralisés, (2) une caractérisation minéralogique et texturale des minéralisations, (3) une approche statistique appliquée aux bases de données roche totale de ces occurrences, (4) une étude des inclusions fluides des minéraux de gangue associés au cuivre. Les résultats ont montré que l’ensemble des minéralisations de la couverture avait une texture en stockwork et une minéralogie identique auto-similaire à toute les échelles d’observation, et ce indépendamment de la morphologie des corps. Ce stockwork est contemporain de zones plissées et faillées. Il est contemporain du mouvement de failles du socle Précambrien rejouant au Varisque et induisant la circulation de saumures profondes minéralisant le socle précambrien comme la couverture néoprotérozoïque à cambrienne de cette boutonnière. / The Anti-Atlas belt is a large geological province. It is composed by a Precambrian basement and a Neoproterozoic to Paleozoic sedimentary cover. More than 200 copper occurrences are localized in this cover. Since the 2000s, with the increase of global copper demand, these mineralizations have a great economic interest for mining company. Besides economic interests, the scientific understanding of these mineralizations in this area are not clear. It does not exist a global model to explain the formation of these deposits. Our study is focus on the Bou Azzer-El Graara inlier (central Anti-Atlas). We proposed to realize a synthesis of copper deposits in this area based on four axes: (1) a field study at the ore bodies’ scale, (2) a mineralogical and textural characterization of these mineralizations, (3) a statistical approach applied to rock total data bases of these deposits, (4) a study of fluid inclusions associated to the ore gangue minerals. Results showed that the whole of mineralizations in the Neoproterozoic to Cambrian cover have a same stockwork texture and a same mineralogy at all scales of observations and that, independently of the ore bodies morphology. This stockwork is synchronous of folded and faulted zones. It is too synchronous of Precambrian basement faults movements during the Variscan compression. These movements are link to deep brines circulations responsible of copper mineralizations localized in the Precambrian basement and in the Neoproterozoic to Cambrian cover of this inlier.

Thesis (Ph. D.)--University of Wyoming, 2006. / Title from PDF title page (viewed on Dec. 17, 2007). Includes bibliographical references (p. 187-197).

Two new analytical methodologies were developed for chlorine and bromine stable isotope analyses of inorganic samples by Continuous-Flow Isotope Ratio Mass Spectrometry (CF-IRMS) coupled with gas chromatography (GC). Inorganic chloride and bromide were precipitated as silver halides (AgCl and AgBr) and then converted to methyl halide (CH3Cl and CH3Br) gases and analyzed. These new techniques require small samples sizes (1.4 µmol of Cl- and 1 µmol of Br-). The internal precision using pure CH3Cl gas is better than ∓0.04 ‰ (∓STDV) while the external precision using seawater standard is better than ∓0.07 ‰ (∓STDV). The internal precision using pure CH3Br gas is better than ∓0.03 ‰ (∓STDV) and the external precision using seawater standard is better than ∓0.06 ‰ (∓STDV). Moreover, the sample analysis time is much shorter than previous techniques. The analyses times for chlorine and bromine stable isotopes are 16 minutes which are 3-5 times shorter than all previous techniques. Formation waters from three sedimentary settings (the Paleozoic sequences in southern Ontario and Michigan, the Williston Basin and the Siberian Platform) were analyzed for 37Cl and 81Br isotopes. The δ37Cl and δ81Br values of the formation waters from these basins are characterized by large variations (between -1.31 ‰ and +1.82 ‰ relative to SMOC and between -1.50 ‰ and +3.35 ‰ relative to SMOB, respectively). A positive trend between δ81Br and δ37Cl values was found in all basins, where an enrichment of δ81Br is coupled by an enrichment of δ37Cl. In the Paleozoic sequences in southern Ontario and Michigan, the δ37Cl and δ81Br signatures of formation water collected from northwest of the Algonquin Arch are distinct from those collected from southeast of the Arch. All of the brines from the northwest of the Algonquin Arch are characterized by depleted isotopic values in comparison with the isotopic values from the brines from southeast of the Arch. The δ81Br signatures of the two brines show total separation with no overlaps. The δ37Cl values show some overlap between the two groups. One of the scenarios that can be put forward is that the Arch forms a water divide, where sediments southeast of the Arch are dominated by Appalachian Basin formation waters, and the sediments located northwest of the Arch are dominated by the Michigan Basin formation waters. The δ81Br and δ37Cl signatures of the Williston Basin brines suggest the existence of several different brines that are isotopically distinct and located in different stratigraphic units, even though they are chemically similar. The relatively wide range of δ37Cl and δ81Br of the formation waters suggests that the ocean isotopic signatures were variable over geologic time. A seawater temporal curve for δ81Br and δ37Cl was proposed with a larger variation of δ81Br in comparison with δ37Cl. The isotopic variations of these two elements agree very well with 87Sr/86Sr seawater variation during the same period. In general, the use of chlorine and bromine stable isotopes can be very useful in assessing the origin and the evolutionary processes involved in evolving formation waters and also in distinguishing different brines (end members). Furthermore, they can be employed to investigate the hydrogeological dynamics of sedimentary basins.

Two new analytical methodologies were developed for chlorine and bromine stable isotope analyses of inorganic samples by Continuous-Flow Isotope Ratio Mass Spectrometry (CF-IRMS) coupled with gas chromatography (GC). Inorganic chloride and bromide were precipitated as silver halides (AgCl and AgBr) and then converted to methyl halide (CH3Cl and CH3Br) gases and analyzed. These new techniques require small samples sizes (1.4 µmol of Cl- and 1 µmol of Br-). The internal precision using pure CH3Cl gas is better than ∓0.04 ‰ (∓STDV) while the external precision using seawater standard is better than ∓0.07 ‰ (∓STDV). The internal precision using pure CH3Br gas is better than ∓0.03 ‰ (∓STDV) and the external precision using seawater standard is better than ∓0.06 ‰ (∓STDV). Moreover, the sample analysis time is much shorter than previous techniques. The analyses times for chlorine and bromine stable isotopes are 16 minutes which are 3-5 times shorter than all previous techniques. Formation waters from three sedimentary settings (the Paleozoic sequences in southern Ontario and Michigan, the Williston Basin and the Siberian Platform) were analyzed for 37Cl and 81Br isotopes. The δ37Cl and δ81Br values of the formation waters from these basins are characterized by large variations (between -1.31 ‰ and +1.82 ‰ relative to SMOC and between -1.50 ‰ and +3.35 ‰ relative to SMOB, respectively). A positive trend between δ81Br and δ37Cl values was found in all basins, where an enrichment of δ81Br is coupled by an enrichment of δ37Cl. In the Paleozoic sequences in southern Ontario and Michigan, the δ37Cl and δ81Br signatures of formation water collected from northwest of the Algonquin Arch are distinct from those collected from southeast of the Arch. All of the brines from the northwest of the Algonquin Arch are characterized by depleted isotopic values in comparison with the isotopic values from the brines from southeast of the Arch. The δ81Br signatures of the two brines show total separation with no overlaps. The δ37Cl values show some overlap between the two groups. One of the scenarios that can be put forward is that the Arch forms a water divide, where sediments southeast of the Arch are dominated by Appalachian Basin formation waters, and the sediments located northwest of the Arch are dominated by the Michigan Basin formation waters. The δ81Br and δ37Cl signatures of the Williston Basin brines suggest the existence of several different brines that are isotopically distinct and located in different stratigraphic units, even though they are chemically similar. The relatively wide range of δ37Cl and δ81Br of the formation waters suggests that the ocean isotopic signatures were variable over geologic time. A seawater temporal curve for δ81Br and δ37Cl was proposed with a larger variation of δ81Br in comparison with δ37Cl. The isotopic variations of these two elements agree very well with 87Sr/86Sr seawater variation during the same period. In general, the use of chlorine and bromine stable isotopes can be very useful in assessing the origin and the evolutionary processes involved in evolving formation waters and also in distinguishing different brines (end members). Furthermore, they can be employed to investigate the hydrogeological dynamics of sedimentary basins.

Unconformity-type uranium deposits from the Athabasca Basin are considered to be the result of mixing between oxidized basinal brines and basement-derived reduced fluids/gases, and/or reduced basement rocks. Graphite and/or its breakdown products are suggested to be responsible for uranium mineralization by acting as a reductant that could trigger deposition of uranium. Also, graphite is considered to be indicative of basement structures; being often concentrated along structures which can be identified as electromagnetic (EM) conductors. Thus, exploration for uranium deposits is often focused on the search for EM conductors. Underlying the sedimentary rocks of the basin in the Dufferin Lake zone are variably graphitic pelitic schists (VGPS); altered to chlorite and hematite (Red/Green Zone: RGZ), and locally bleached equivalents near the unconformity during paleoweathering or later fluid interactions. These altered zones are texturally similar rocks within “graphite-depleted zones” as the unconformity is approached. Both zones are characterized by a lower concentration of carbon and sulfur, with the bleached zone showing higher concentrations of uranium and boron, the latter corresponding to high dravite content. The major element composition of the graphite-bearing pelitic schists and altered equivalents (RGZ) are similar. Raman analyses indicate that well-ordered carbon species (graphite to semi-graphite) are present in the pelitic schists, with both types more common within shear zones. In contrast, only rare low-ordered carbon species (carbonaceous matter) were detected in the graphite-depleted samples within the RGZ. This variation is interpreted to be the result of graphite consumption by oxidizing fluids migrating downward from the Athabasca Group. This graphite consumption may have resulted in the production of a mobile reductant (gas or fluid), which may have played a subsequent role in the deposition of uranium mineralization. Secondary fluid inclusions (FI) examined in different quartz vein generations using microthermometry and Raman analysis, provide an indication of the fluids that have interacted with these rocks. Monophase vapor are the dominant type of fluid inclusions in the VGPS, whereas aqueous two-phase (L+V) and three-phase (L+V+Halite) FI occur in the RGZ. CH4-dominant and N2-dominant FI identified using Raman could be the result of fluid(s) interaction with the graphitic lithologies. This would have generated the breakdown of graphite to CH4 and associated feldspars/micas to NH4/N2. CH4, N2 and H2 (resulting from the decomposition of NH4+) represent possible reductants of uranium-bearing brines. Two brines in the RGZ: a regional basinal fluid and an evolved fluid possibly related to U mineralization; similar to other nearby deposits, are observed. These suggest that the basinal brines have circulated in the basement rocks and have been able to evolve by interaction with the basement rocks to possibly be related to uranium mineralization.