No description available.

No description available.

Résumé : Au cours de ce projet, la faisabilité de l’insertion du CO[indice inférieur 2] dans une fonction éther aliphatique à été démontrée pour la première fois. Cette découverte à été effectuée suite à la résolution cinétique et thermodynamique de la décarboxylation du diméthyle carbonate (DMC) en diméthyle éther (DME) et CO[indice inférieur 2] à la surface d’un catalyseur faujasite échangé avec du zinc(II) (Zn-FAU). Un profile réversible typique aux carbonates a été observé, soit que le CO[indice inférieur 2] est relâché à plus haute température et inséré aux plus basses températures. La structure de l’état de transition entre le DMC et DME a ensuite été résolue en corrélant des calculs en modélisation moléculaire aux mesures thermodynamiques effectuées entre le DMC et Zn-FAU. La méthode de calcul développée lors de l’analyse mécanistique a ensuite été appliquée à l’évaluation théorique de plusieurs structures catalytiques, ce qui a permis d’identifier les paramètres structurels des catalyseurs qui sont favorables à la réaction de carboxylation du DME. // Abstract : In this study, the feasibility of the insertion of CO[subscript 2] in an aliphatic ether function was demonstrated for the first time. This finding results from a thermodynamic and kinetic study on dimethyl carbonate (DMC) decarboxylation into dimethyl ether (DME) and CO[subscript 2] at the surface of a zinc(II) exchanged faujasite catalyst. The typical reversible profile of carbonates synthesis chemistry was observed, higher temperature being favorable to CO[subscript 2] release and lower temperature being favorable to CO[subscript 2] insertion. A structural resolution of the rate determining transition structure between DMC and DME was then achieved by correlating molecular modelling calculations to the thermodynamic measurements on DMC decarboxylation. The calculation method developed during the mechanistical analysis was further applied to theoretical catalyst activity screening, which allowed determining structural catalytic sites parameters that favor DME carboxylation over DMC decarboxylation.

Although karst processes in south central Kentucky have been studied extensively, the Haney Limestone Member of the Golconda Formation has not been studied in detail in contrast to limestones stratigraphically below it that are thicker. In addition, the relationship between petrographic features of the Haney Limestone and the formation of caves and karst features has not been studied extensively compared to lithographic, petrographic, or structural variables Petrographic data were collected using core and surface exposures across the study area of south central Kentucky from northern Logan and Warren counties up toward the Rough Creek Graben region, and stratigraphic columns were constructed. Twenty-three petrographic thin-sections were made from samples collected at these sites, described, and photo documented. These studies have revealed that grain size and silica content play a role in how the Haney weathers both in surface exposure and in a cave setting. Petrographic thin-section analysis suggests that the Haney possesses a complex diagenetic history that involves several generations of calcite cementation, dolomitization, silicification, and pressure-dissolution features in the form of microstylolites and stylolites. A basal shale in the Big Clifty occurs commonly at the Big Clifty/Haney contact and acts as a confining hydrogeologic unit, which is favorable for the development of springs and caves. Studying the Haney Limestone petrographically provides an opportunity not only to study a lesser known unit, but also in the context of relating petrographic influences or controls on the morphology of Haney cave-passage development under both vadose and phreatic hydrologic regimens. Heretofore, the vast majority of cave morphological studies have only linked the hydrologic regimen to formation of cave passages, but such studies have not considered petrographic variance. This study not only relates karst features to petrographic variance, but also provides a petrographical description of the Haney across south central Kentucky, whereas many previous studies focused on Illinois and Indiana. Understanding Haney petrographic characteristics also provides context for potential carbonate hydrocarbon reservoirs and groundwater resources in the Illinois Basin region.

No description available.

Epithermal vein and carbonate replacement deposits in Cunningham Gulch are located within the western San Juan Tertiary volcanic field in southwestern Colorado. The Pride of the West epithermal vein system is hosted within the intracaldera facies of the Sapinero Mesa Tuff, a voluminous ash-flow tuff that erupted from and resulted in the formation of the San Juan Caldera at 28 mybp. The Pride of the West vein system is developed along a radial fracture formed during resurgence of the San Juan Caldera prior to eruption of the Crystal Lake Tuff (27.5 mybp). This eruption led to the concomitant collapse of the Silverton Caldera, nested within the larger San Juan Caldera. The Pride of the West, Osceola, and Little Fanny mines are positioned near the intersection of the Pride radial fracture system and the buried structural margin of the San Juan Caldera, suggesting that ore concentration was controlled by this structural setting. Large limestone blocks of the Mississippian Leadville Formation are incorporated into the intracaldera fill volcanics in the mine area. These blocks appear to have been engulfed within mudflow breccias of the Tertiary San Juan Formation (32.1 mybp). They were then emplaced in their present structural position within a caldera-collapse breccia which caved from the oversteepened margin of the San Juan Caldera. Regional propylitic alteration of the hosting volcanics to a chlorite-calcite-pyrite assemblage preceded vein-associated alteration and mineralization. The veins are enveloped by a narrow phyllic alteration assemblage of quartz, sericite, illite, kaolinite, and pyrite. The veins are comprised of sphalerite, galena, chalcopyrite, pyrite, hematite, magnetite, quartz, pyroxmangite, calcite, and minor barite. Substantial bodies of replacement ore are present where the vein structures intersect the limestone blocks; the mineral assemblages of the replacement deposits are identical to those of the feeding vein structures. Commonly, replacement textures are spectacular concentrations, especially the "zebra ore" which primarily consists of regularly spaced, alternating bands of sulfides and quartz. These "zebra" laminations are stratigraphically controlled and appear to represent replacement of a depositional or diagenetic fabric. Main ore-stage mineralization began with widespread deposition of quartz with or without pyrite, followed by sphalerite, chalcopyrite, and galena. Post ore-stage brecciation and silicification events are evident and were followed by deposition of calcite and minor barite during the waning stages of the hydrothermal system. The distributions of Fe, Mn, Pb, and Ca suggest a lateral component of fluid flow from northwest the southeast, away from the structural margin of the Silverton Caldera. Fluid inclusion data from both vein and replacement-type sphalerite and quartz indicate that mineral deposition occurred over a range of 200 to 312°C (mean 243°C) from solutions containing 1 to 5% total salts. The high base metal to precious metal content of the ore, the phyllic alteration assemblage, and the temperature and composition of the ore-forming fluid indicate that the mine workings are within the lower portion of a fossil geothermal system. / text

3 pp. / Originally published: 2002 / It is important to know how much calcium you need to consume each day as more than 2500 mg of calcium each day can be harmful. Calcium should be obtained from foods and beverages first, then from supplements if necessary. Taking more than 500 mg of calcium at one time should be avoided. If you choose to take a calcium supplement, calcium citrate or calcium carbonate should be chosen.

Chemical sediments in a variety of geomorphic environments (pedogenic, fluvial, palustrine, lacustrine and pan) were investigated from seven regions (SW Kalahari, Kgalagadi, Kalkweissrand, Etosha, Linyanti, Okavango and Ngami) in the Kalahari of southern Africa. These primary and multi-phase sediments were characterised by a range of pure and intergrade silcrete, calcrete and dolocrete fabrics which contained an array of structures indicative of the crystalline and biogenic processes responsible for their precipitation, epigenesis and paragenesis. Petrography, mineralogy and isotope geochemistry provided significant insight regarding the environmental and geochemical conditions at the time of precipitation. Petrography indicated that the majority of chemical sediments were undergoing epigenetic modification as a consequence of the desiccation induced transition from phreatic to vadose diagenetic and geochemical conditions. The role of rapidly infiltrating meteoric water, associated with unstable wetting fronts, is believed to be instrumental in vadose diagenesis and the precipitation of crystalline/alpha fabric carbonate. Salinisation within the capillary fringe and deeper vadose zone is believed to be responsible for the sequence dolomitisation of crystalline calcite within mature sequences. Highly saline pan conditions instigate the precipitation of authigenic dolomite, calcite and K-feldspar within the surface sediments and authigenic silica at depth. Phreatic water beneath the islands, floodplains and fluvial systems of the Okavango, which undergoes evapotranspirational and transmission salinisation and ultimately terminal desiccation, are similarly precipitating silcrete. Pedogenic processes principally associated with C₄ vegetation are responsible for the gratification of carbonate mud within desiccating lacustrine, palustrine and pan sediments. Within the thin sandy Kalahari soils, pedogenesis is limited, but biogenic/beta fabric precipitation linked to mycorrihizae and tree/shrub savanna vegetation is instrumental in the formation of hardpans and the modification of upper calcrete horizons. The dominance of a distinct assemblage (smectite/kaolinite or sepiolite/palygorskite) of authigenic clay minerals present within all the environments provides evidence of semi-arid precipitation within Mg and Ca enriched saline/rapidly evaporating water or brackish/reduced permeability environments.

L’industrie des biocarburants de deuxième génération utilise, entre autre, la biomasse lignocellulosique issue de résidus forestiers et agricoles et celle issue de cultures énergétiques. Le sorgho sucré [Sorghum bicolor (L.) Moench] fait partie de ces cultures énergétiques. L’intérêt croissant de l’industrie agroalimentaire et des biocarburants pour cette plante est dû à sa haute teneur en sucres (jusqu’à 60% en masse sèche). En plus de se développer rapidement (en 5-6 mois), le sorgho sucré a l’avantage de pouvoir croître sur des sols pauvres en nutriments et dans des conditions de faibles apports en eau, ce qui en fait une matière première intéressante pour l’industrie, notamment pour la production de bioéthanol. Le concept de bioraffinerie alliant la production de biocarburants à celle de bioénergies ou de bioproduits est de plus en plus étudié afin de valoriser la production des biocarburants. Dans le contexte d’une bioraffinerie exploitant la biomasse lignocellulosique, il est nécessaire de s’intéresser aux différents métabolites extractibles en plus des macromolécules permettant la fabrication de biocarburants et de biocommodités. Ceux-ci pouvant avoir une haute valeur ajoutée et intéresser l’industrie pharmaceutique ou cosmétique par exemple. Les techniques classiques pour extraire ces métabolites sont notamment l’extraction au Soxhlet et par macération ou percolation, qui sont longues et coûteuses en énergie. Ce projet s’intéresse donc à une méthode d’extraction des métabolites primaires et secondaires du sorgho sucré, moins coûteuse et plus courte, permettant de valoriser économiquement l’exploitation industrielle du de cette culture énergétique. Ce travail au sein de la CRIEC-B a porté spécifiquement sur l’utilisation d’une émulsion ultrasonique eau/carbonate de diméthyle permettant de diminuer les temps d’opération (passant à moins d’une heure au lieu de plusieurs heures) et les quantités de solvants mis en jeu dans le procédé d’extraction. Cette émulsion extractive permet ainsi de solubiliser à la fois les métabolites hydrophiles et ceux hydrophobes. De plus, l’impact environnemental est limité par l’utilisation de solvants respectueux de l’environnement (80 % d’eau et 20 % de carbonate de diméthyle). L’utilisation de deux systèmes d’extraction a été étudiée. L’un consiste en la recirculation de l’émulsion, en continu, au travers du lit de biomasse; le deuxième permet la mise en contact de la biomasse et des solvants avec la sonde à ultrasons, créant l’émulsion et favorisant la sonolyse de la biomasse. Ainsi, en réacteur « batch » avec recirculation de l’émulsion eau/DMC, à 370 mL.min[indice supérieur -1], au sein du lit de biomasse, l’extraction est de 37,91 % en 5 minutes, ce qui est supérieur à la méthode ASTM D1105-96 (34,01 % en 11h). De plus, en réacteur « batch – piston », où la biomasse est en contact direct avec les ultrasons et l’émulsion eau/DMC, les meilleurs rendements sont de 35,39 % en 17,5 minutes, avec 15 psig de pression et 70 % d’amplitude des ultrasons. Des tests effectués sur des particules de sorgho grossières ont donné des résultats similaires avec 30,23 % d’extraits en réacteur « batch » avec recirculation de l’émulsion (5 min, 370 mL.min[indice supérieur -1]) et 34,66 % avec le réacteur « batch-piston » (30 psig, 30 minutes, 95 % d’amplitude).

Master of Science / Department of Geology / Matthew Totten / The Viola Limestone is a prominent petroleum reservoir in the Mid-Continent Region, particularly in Oklahoma and Kansas. Coral Coast Petroleum established production from the Viola Ls. in 2011 in their Stephens Ranch lease in Clark County, south-central Kansas. Development of this lease has been hindered by the unpredictable production rates encountered in each of the subsequent eleven development wells. Infield drilling locations to date were chosen by favorable structural position as determined by 3D seismic. The best reservoir conditions, however, do not necessarily coincide with structural position. It was the purpose of this study to determine whether the ideal porosity and permeability are controlled by depositional environment, diagenetic alterations, or a combination of these factors. Several approaches to solve this question were implemented and utilized, including well log analysis, petrographic inspection of well cuttings and thin sections, and the application of the Scanning Electron Microscope (SEM). An exploration model of the Viola Ls. in this field was developed, where the Viola A and B zones were dolomitized during during marine transgressions by mixing of sea water with other Mg-rich fluids. Reservoir conditions are found where these facies were preserved as paleotopographic highs during a subsequent sea level low-stand. These preserved dolomitized facies correspond to the seismic facies identified by seismic attributes in a 3D seismic study by Vohs (2016).