No description available.

Fluid flow mechanisms in a large naturally fractured heterogeneous carbonate reservoir were investigated in this manuscript. A very thin layer with high permeability that produces the majority of production from specific wells and is deemed the Super-K Zone was investigated. It is known that these zones are connected to naturally occurring fractures. Fluid flow in naturally fractured reservoirs is a very difficult mechanism to understand. To accomplish this mission, the Super-K Zone and fractures were treated as two systems. Reservoir management practices and decisions should be very carefully reviewed and executed in this dual continuum reservoir based on the results of this work. Studying this dual media flow behavior is vital for better future completion strategies and for enhanced reservoir management decisions. The reservoir geology, Super-K identification and natural fractures literature were reviewed. To understand how fluid flows in such a dual continuum reservoir, a dual permeability simulation model has been studied. Some geological and production iv data were used; however, due to unavailability of some critical values of the natural fractures, the model was assumed hypothetical. A reasonable history match was achieved and was set as a basis of the reservoir model. Several sensitivity studies were run to understand fluid flow behavior and prediction runs were executed to help make completion recommendations for future wells based on the results obtained. Conclusions and recommended completions were highlighted at the end of this research. It was realized that the natural fractures are the main source of premature water breakthrough, and the Super-K acts as a secondary cause of water channeling to the wellbore.

Numerous isolated carbonate platforms developed in the Central Luconia Province of offshore Sarawak (during Middle to Late Miocene time). Fault-bounded highs produced largely by extensional deformation and later overprinted by strike-slip deformation provided substrates for the platforms and affected their growth histories. Flooding of these structural highs at ~16.5 Ma initiated carbonate sedimentation nearly simultaneously across the area. Later, third-order sea-level fluctuations and extrinsic factors such as differential subsidence, paleowind patterns and siliciclastic influx then controlled the internal architecture of the platforms. 2-D regional seismic lines, publicdomain data and published literature were used to analyze growth patterns and demise of carbonate platforms across the study area. Five Growth Stages were recognized in the carbonate platforms based on seismic facies analysis and stratigraphic relationships between reflectors. Platforms from the southeastern part of Central Luconia are thicker and larger than platforms located toward the central and northwestern areas, which reflect greater long-term tectonic subsidence to the southeast. Additionally, northwestward prograding siliciclastic sediments from mainland Borneo caused additional flexural subsidence in the eastern part of the area and environmental deterioration for platforms located beyond the range of active siliciclastic sedimentation. Both of these factors reduced the growth potential of platforms and thus subdued carbonate development. Platform termination was regionally diachronous and was produced in two steps. The first platforms drowned (~12.5-9.7 Ma) were in the eastern parts of the study area which were affected by incoming siliciclastic sediments and high local subsidence. Platforms drowned later (~6.3-5.5 Ma) were caused by a rapid sea-level rise combined with an intense local subsidence. Carbonate accumulation rates were measured between intraplatform markers, resulting in a trend that indicates a decrease in sedimentation rate with the square root of time. Comparisons between Central Luconia carbonates and age-equivalent carbonate platforms elsewhere in East Natuna Basin showed that Central Luconia carbonate platforms were drowned earlier (latest late Miocene time) than East Natuna carbonate platforms (Early Pliocene time).

Isolated carbonate platforms and buildups of the Likas Formation provide a long record of carbonate sedimentation in the southern end of the Southwest Palawan Basin. While most carbonate platforms terminated in early Miocene and middle Miocene time in northern parts of western offshore Palawan (i.e. Northwest Palawan Basin and central South Palawan), carbonate deposition began later in the south during late middle Miocene time. Carbonate platforms of the Likas Formation developed in the Paragua sub-basin, which is interpreted to be a depozone eastward of the Palawan accretionary wedge in the structurally complex Southwest Palawan Basin. A regional 2D seismic grid and borehole data from four wells were used to analyze the growth patterns of the carbonate platforms, identify seismic facies, and reconstruct the evolution of the platforms. The carbonate platforms developed on the folded and faulted middle to premiddle Miocene siliciclastic strata. These older siliciclastic units were thrusted onto the southern end of the North Palawan microcontinental fragment, which represents a block of continental crust that drifted southward from South China during early Tertiary time. The platforms aggraded over time and backstepped to keep pace with increasing rates of relative sea level rise. Karst features are recognizable on seismic sections and indicate that the platforms were subaerially exposed at various times during their development. The platforms exhibit variable morphology from faulting and tilting. The platforms terminated in early Pliocene time, as relative sea level continued to rise, and were buried by deep-marine siliciclastic units.

Biodegradable aliphatic polycarbonates are important components of non-toxic thermoplastic elastomers, which have a variety of medical applications. Industrially, aliphatic polycarbonates derived from six-membered cyclic carbonates such as trimethylene carbonate (TMC or 1,3-dioxan-2-one) are produced via ring-opening polymerization (ROP) processes in the presence of a tin catalyst. It is worth mentioning that TMC is readily obtained by transesterification of 1,3-propanediol with various reagents including phosgene and its derivatives. Therefore, it has been of great interest to investigate greener routes for the production of this important class of polymers. Toward this goal, the synthesis of aliphatic polycarbonates via the metal catalyzed alternative coupling of oxetanes and carbon dioxide represents an attractive alternative. The use of an abundant, inexpensive, non-toxic, and biorenewable resource, carbon dioxide, makes this method very valuable. Furthermore, in this reaction, the sixmembered cyclic carbonate byproduct, TMC, can also be ring-opened and transformed into the same polycarbonate. For over a decade, the Darensbourg research group has successfully utilized metal salen complexes as catalysts for the epoxide/CO2 copolymerization process. Hence, this dissertation focuses on the examination of these complexes as catalysts for the oxetane/CO2 copolymerization reaction and the further elucidation of its mechanism. Chromium(III) salen derivatives in the presence of an azide ion initiator were determined to be very effective catalysts for the coupling of oxetanes and carbon dioxide providing polycarbonates with minimal amounts of ether linkages. Kinetic and mechanistic investigations performed on this process suggested that copolymer formation proceeded by two routes. These are the direct enchainment of oxetane and CO2, and the intermediacy of trimethylene carbonate, which was observed as a minor product of the coupling reaction. Anion initiators which are good leaving groups, e.g. bromide and iodide, are effective at affording TMC, and hence, more polycarbonate can be formed by the ROP of preformed trimethylene carbonate. Research efforts at tuning the selectivity of the oxetane/CO2 coupling process for TMC and/or polycarbonate produced from the homopolymerization of preformed TMC have been performed using cobalt(II) salen derivatives along with anion initiators. Lastly, investigations of this process involving 3-methoxy-methyl-3-methyloxetane will be presented.

The equatorial Pacific is a major region of biological production in the world oceans and an important part of the global carbon cycle. Changes in climate during the Cenozoic (65 Ma to present) have impacted the carbon cycle, and it is important to assess these impacts. This study focuses on the primary productivity of the equatorial Pacific during the early to middle Miocene (24 - 12 Ma) as recorded by Deep Sea Drilling Project (DSDP) Site 574, and investigates the sedimentary components potentially linked to productivity: bio-Ba, bio-SiO₂, Corg, CaCO₃, and uranium, as well as detrital thorium to estimate clay-bound barium. Within this time frame the plate beneath Site 574 traveled northwesterly across the equator and allows a unique opportunity to monitor changes in productivity and the carbon cycle in this region. It is difficult to determine directly primary productivity from the sedimentary record because the preservation of different proxies for this parameter - Corg, bio-CaCO₃, and bio-SiO₂, can be highly variable. The variability has many causes, including nutrient recycling in the water column and the depth of the carbonate compensation depth (CCD), which prevents the preservation and ultimate burial of plankton debris at the seafloor. To interpret the production versus deposition rates during the early and middle Miocene, proxies were used in conjunction with direct measurements of biogenic remains. By determining the concentrations of biogenically produced barium (bio-Ba), which is less affected by degradation, it is evident that the mass of Corg produced was much greater than that preserved in the sediments. We observed higher deposition of bio-Ba and bio- SiO₂ as the site was transported over the equatorial divergence by plate tectonics, as expected. In contrast, CaCO₃, accumulation was low in the divergence region, and coincides with a dissolution event known from other site studies in the equatorial Pacific. The pattern of uranium deposition resembles CaCO₃ and Corg, and average U concentrations suggest that it was primarily deposited as a trace element in the shell material of biogenic carbonate. Corg also resembles CaCO₃ and appears to represent primarily a dissolution signal. Total uranium analysis proved to be a useful proxy for Corg and CaCO₃ preservation, and analysis of detrital thorium (²³²Th) concentration suggests very limited terrigenous clay input. Comparison of the different proxies reveals carbonate preservation events, changes in Corg preservation, and changes in deposition as DSDP Site 574 migrated northwesterly across the equator.

Carbonate reservoirs are heterogeneous; therefore, proper acid placement/diversion is required to make matrix acid treatments effective. Viscoelastic surfactants (VES) are used as diverting agents in carbonate matrix acidizing. However, these surfactants can adversely affect wettability around the wellbore area. Lab and field studies show that significant amounts of VES are retained in the reservoir, even after an EGMBE postflush. Optimizing acid treatments requires a study of the effect of VES on wettability. In a previous study using contact angle experiments, it was reported that spent acid solutions with VES only, and with VES and EGMBE are water-wetting. In this thesis, we studied the effect of two amphoteric amine-oxide VES', designated as "A" and "B" on the wettability of Austin cream chalk using contact angle experiments. We extended the previous study by using outcrop rocks prepared to simulate reservoir conditions, by demonstrating that VES adsorbs on the rock using two-phase titration experiments, by studying the effect of temperature on wettability and adsorption, and by developing a detailed procedure for contact angle experiments. We found that for initially oil-wet rocks, simulated acid treatments with VES "A" and "B" diversion stages and an EGMBE preflush and postflush made rocks water-wet at 25, 80, and 110 degrees C. Simulated acid treatments with a VES "A" diversion stage only made rocks water-wet at 25 degrees C. Our results suggest that both VES formulations cause a favorable wettability change for producing oil. The two-phase titration experiments show that both VES "A" and "B" adsorb on the rock surface. From our literature review, many surfactant wettability studies use contact angle measurements that represent advancing contact angles. However, wettability during stimulation is represented by receding contact angles. Results of static receding contact angles may be misinterpreted if low oil-acid IFT's cause oil droplets to spread. Spreading could be a reflection of the effect of the surfactants on the fluid-fluid interface rather than the rock-fluid interface. The new procedure shows the effect of VES and EGMBE on the rock-fluid interface only, and so represents the actual wettability.

Pointe du Hoc overlooking the English Channel in Normandy, France was host to one of the most important military engagements of World War II. While the site is a valuable historic cultural resource, it is vulnerable to cliff collapses that already have endangered the observation post and Rudder?s command post. The observation post has been closed to visitors for some time due to safety concerns. Geophysical techniques have been used increasingly in recent years for slope stability investigation purposes. The objective of this study is to apply advanced 3?D resistivity tomography toward a detailed site stability assessment with special attention to the two at-risk buildings. 3?D resistivity tomography datasets at Pointe du Hoc in the presence of extreme topography and dense cultural clutter have been successfully acquired, inverted, and interpreted. The cliff stability in the areas around the two at?risk buildings has been analyzed. A hazard assessment scheme has been designed in which regions of high resistivity are interpreted as zones of open, dry fractures with a moderate mass movement potential. Regions of low resistivity are zones of wet, clay?filled fractures with a high mass movement potential. The observation post tomography results indicate that the highest mass movement hazard appears to be associated with the marine caverns at the base of the cliff that are positioned at the point of strongest wave attack. These caverns likely occupy the future site of development of a sea arch which will definitely threaten the observation post building. A high probability of a soil wedge failure is on the east?facing cliff edge close to the observation post that could damage or destroy the building. The mass movement potential at the Rudder?s command post area is low to moderate. The greatest risk is associated with soil wedge failures at the top of the cliffs. The resistivity geophysical data add great value to the natural geohazard assessment at Pointe du Hoc and constitute an integral component of an interdisciplinary approach to the problem of cultural resource preservation at the site. Geophysics is a non?invasive and relatively inexpensive technology that provides unique constraints which are unobtainable using traditional engineering geology methods for site characterization. However, the technology is difficult to master and the inherent limitations must be carefully understood to ensure a reliable geotechnical interpretation.

Growth and dissolution of the mineral calcite is important for prediction and control of surface and subsurface water quality, calculation of past sea-surface temperatures using paleoenvironmental proxies, and sequestration of contaminants through engineered calcite precipitation. At high concentrations of strontium, calcite growth is known to be inhibited, but the mechanism by which strontium inhibits growth is not well understood. Seeking to better understand this mechanism, atomic force microscopy is used with a flow-through fluid cell to measure real time growth rates of the obtuse and acute monomolecular step orientations on the calcite surface. Growth was measured at two saturation indices as a function of the ratio of the concentrations of aqueous calcium-to-carbonate and varying aqueous strontium concentration. It was found that the amount of strontium required to inhibit growth correlated with the aqueous calcium concentration, but did not correlate with carbonate concentration. This suggests that strontium inhibits attachment of calcium, but not carbonate, during growth. Analytical models of nucleation and propagation of steps are expanded from previous studies to capture multiple saturation indices.

Thesis (M.A.)--University of Texas at Austin, 1984. / Vita. Includes bibliographical references (leaves 119-124).