Caves, the cornerstone feature of karst aquifers, are little understood in Florida. This dissertation, which analyzes the morphology, elevation, lithologic setting, and hydrology of caves in west-central Florida, demonstrates that the karst of the unconfined Floridan aquifer differs from the paradigm view of karst presented in modern geology textbooks. The differences reflect setting: eogenetic (west-central Florida) vs. telogenetic (conventional). Interpretations about the architecture of cavernous porosity in this dissertation come from detailed surveys (497 stations) of seven air-filled caves.The surveys reveal that solution cavities within the unconfined Floridan aquifer align along NE-SW and NW-SE fractures. The surveys further identify tabular zones of cavernous porosity that extend for tens of meters. Characteristic "plus-sign" passages occur at the intersection of solution-enlarged fractures and the tabular horizons. The caves, as surveyed, do not connect points of discrete aquifer input to springs. Rather, they are separated by intact bocks of aquifer matrix, ever- narrowing fissures, sediment fills, and breakdown. With an additional 574 spot elevations from 63 previously surveyed air-filled and submerged caves and 526 foot-length cavities encountered in 26 drilled wells, the assembled data reveal that cave passages above and below the watertable of the unconfined Floridan aquifer cluster at similar elevations throughout west-central Florida. At the largest scale, the levels of cavities cut across geologic structure, thus suggesting a water-table origin. The close linkage of the water table and sea level this coastal setting suggests the levels reflect positions of paleosea level. Given that the air-filled caves in west-central Florida reflect higher sea levels,the coastline would have been close when the air-filled caves formed. The levels organize according to a sea-level datum at elevations of 30 m, 20-22 m, 12-15 m,and 3-5 m. The levels are similar in elevation to nearby terraces evident in GIS and LIDAR topographic data. The terraces correspond to the classic, Quaternary marine terraces of the coastal plain of the southeastern U.S.A. Given that the now-submerged caves reflect lower sea levels, the coastline was far from the caves when they formed. They organize according to a watertable datum at depths of 15 m, 30-40 m, 60-70 m, and > 100 m with some correspondence to marine terrace and paleoshoreline features identified on the sea floor of the west florida shelf using GIS and multibeam bathymetry. The multigenerational origin of these deeper caves masks the correspondence. Although past water tables are seen to be the first-order control of cave passages regionally, lithology appears to play a significant role at the scale of an individual cave. Approximately 2,000 measurements of matrix permeability from more than 228 m of continuous core from the unconfined Floridan aquifer of west-central Florida reveal a wide-ranging facies-dependent matrix permeability[log k(m2)= -12.9 +/- 1.6, total range]. Solution passages tend to be wider where the matrix permeability is greater. Time-series analysis on measurements of spring discharge from 31 springs and published time series from 28 additional sites reveal key differences between eogenetic and telogenetic karst aquifers, reflecting the difference in matrix permeability of the eogenetic [log k(m2) from -14 to -11] and telogenetic[log k(m2) from -15 to -20] limestones. For instance, log Q/Qmin flow-duration curves have greater slopes at eogenetic karst springs, a manifestation of lowerratios between the maximum and mean discharge (Qmax/Qmean). Additionally,aquifer inertia as defined on auto correlograms is greater in eogenetic karst than telogenetic karst.Hydrographs of spring flow and water level vary on a seasonal or longertime scale. The localized, convective-style storm events typical of the Florida summer rainy season are not realized as individual peaks in these hydrographs.Apparently, large, widespread, storm events, such as hurricanes in the late summer and fall and frontal systems in the winter and spring, are necessary to produce significant changes in storage. Data from nine pressure transducers in caves and in the aquifer matrix across the unconfined Floridan aquifer all record immediate increases in the water level due to Hurricanes Frances and Jeanne in September of 2004. The increases are simultaneous over large regions. These changes do not propagate through the aquifer as a pulse like the classic scenario of conduit flow in telogenetic karst aquifers.

Studies of planktic foraminifers have been, and continue to be, very important to paleoceanographic reconstructions and are dependent on the integrity of the carbonate tests. This study investigates the methods and procedures that can be used to obtain an accurate planktic foraminifer assemblage. Samples from Orca Basin boxcore OB-BC4D were processed and examined to obtain census data on planktic foraminifers. Experimentation of the splitting technique demonstrates the method is acceptable for estimating a planktic foraminifer assemblage. The effects of a sonication step in the processing of the faunal assemblage were also examined and revealed that sonication is not recommended for processing planktic foraminifers for faunal-assemblage analyses. Census data revealed downcore variation in the foraminifer species and intervals of increased dissolution over the last 1000 years.

The sorption behavior of yttrium and the rare earth elements (YREEs) was investigated using a variety of hydroxide precipitates over a range of solution conditions. Experiments with amorphous hydroxides of Al, Ga, and In were conducted at constant pH (~6.0) and constant ionic strength (I = 0.01 M), while YREE sorption by amorphous ferric hydroxide was examined over a range of ionic strength (0.01 M <̲ I <̲ 0.09 M), pH (3.9 <̲ pH <̲ 7.1), carbonate concentration (0 M <̲ [CO32-]T <̲ 150 micro-M), and temperature (10°C <̲ T <̲ 40°C). Sorption results were quantified via distribution coefficients, expressed as ratios of YREE concentrations between the solid and the solution, and normalized to concentrations of the sorptive solid substrate. Distribution coefficient patterns for Al, Ga, and In hydroxides were well correlated with the pattern for YREE hydrolysis. In contrast, amorphous ferric hydroxide developed a distinct pattern that was different than those for Al, Ga, and In precipitates but similar to the pattern predicted for natural marine particles. YREE sorption was shown to be strongly dependent on pH and carbonate concentration, significantly dependent on temperature, and weakly dependent on ionic strength. Distribution coefficients for amorphous ferric hydroxide (iKFe) were used to develop a surface complexation model that contained (i) two equilibrium constants for sorption of free YREE ions (M3+) by surface hydroxyl groups, (ii) one equilibrium constant for sorption of YREE carbonate complexes (MCO3+), (iii) solution complexation constants for YREE carbonates and bicarbonates, (iv) a surface protonation constant for amorphous ferric hydroxide, and (v) enthalpies for M3+ sorption. This quantitative model accurately described (i) an increase in iKFe with increasing pH, (ii) an initial increase in iKFe with increasing carbonate concentration due to sorption of MCO3+, in addition to M3+, (iii) a subsequent decrease in iKFe due to increasing YREE complexation by carbonate ions (especially extensive for the heavy REEs), and (iv) an increase in iKFe with increasing temperature.

No description available.

The mixed carbonate–siliciclastic Abrigo Formation of middle and late Cambrian age, which crops out in southeastern Arizona, was deposited during the Sauk transgression in the craton interior, landward of the passive margin of Laurentia. The Abrigo Formation consists of ten basic rock types: claystone, siltstone, sandstone, lime mudstone, wackestone, bioclastic grainstone, packstone, oolitic packstone, oncolitic packstone, and intraclastic conglomerate. These comprise fifteen lithofacies, which are grouped into eight facies associations. They represent an array of shallow-marine environments that were dominated by wave and storm activity. The interpreted paleoenvironments include lower offshore, upper offshore, offshore transition, and lower, middle and upper shoreface. One hundred eighty-two collections, yielding 940 trilobite remains have been found in the Abrigo Formation. They represent 69 species and 42 genera. Eight of the species are new. The fossil age ranges from early Marjuman to late Steptoean. Eight trilobite biofacies are defined from the generic relative abundance data: Ehmaniella, Olenoides–Bolaspidella, Blairella, Eldoradia, Modocia–Paracedaria, Cedaria, Coosella–Coosina, and Camaraspis. Trilobites collected and identified in this study are assigned to five biostratigraphic zones: Bolaspidella, Cedaria, Crepicephalus, Aphelaspis, and Elvinia zones. In addition, two subzones had been defined. Cedaria eurycheilos Subzone recognized in the upper part of Cedaria Zone and Coosella helena Subzone recognized in the upper part of Crepicephalus Zone. The stratigraphic succession was divided into six distinct phases associated with large-scale relative sea-level fluctuations. An initial flooding over the Bolsa Quartzite forming the transgressive systems tract was terminated by maximum flooding, and a subsequent highstand systems tract developed during Bolaspidella Biozone time. The second sequence starts with another transgressive systems tract, and is overlain by a final highstand systems tract during the Cedaria and Crepicephalus biozones. The uppermost part of the second sequence represents a falling stage systems tract that developed during Aphelaspis Biozone time. The presence of Elvinia Biozone trilobites near the base of the highest sandstone unit suggests that delivery and deposition of these sands took place during the lowstand that followed the protracted and widespread Sauk II–Sauk III hiatus. Sedimentary dynamics were controlled by storm-induced wave action and offshore flows. There are two carbonate factories that operated simultaneously in this Cambrian inner shelf region. Dominance of carbonate versus siliciclastic strata in the offshore transition setting is interpreted to reflect periods when siliciclastic input was depleted, such that increasing accommodation and reduction of clay and possibly nutrients promoted carbonate production. Clay and silt bypassed the nearshore carbonate-depositing zone. Siliciclastic sediment input and dispersal were not only restricted to the falls in sea level, but appear to have dominated the transgressive systems tract and late phase of the highstand. Thus, carbonate sedimentation does not dominate the entire highstand systems tract as is commonly held but, rather, only during the late phase of the transgressive and early highstand phase. The comparison of this Cambrian model with younger mixed carbonate-siliciclastic units will help reveal the subtleties of the carbonate factory and how it operated in response to biotic evolution.

Within this dissertation, I document how—and hypothesize why—the quirks and qualities of the Cambrian Period demarcate this interval as fundamentally different from the preceding Proterozoic Eon and succeeding periods of the Phanerozoic Eon. To begin, I focus on the anomalous marine deposition of the mineral apatite. Sedimentary sequestration of phosphorus modulates the capacity for marine primary productivity and, thus, the redox state of the Earth system. Moreover, sedimentary apatite minerals may entomb and replicate skeletal and soft-tissue organisms, creating key aspects of the fossil record from which paleontologists deduce the trajectory of animal evolution. I ask what geochemical redox regime promoted the delivery of phosphorus to Cambrian seafloors and conclude that, for the case of the Thorntonia Limestone, apatite nucleation occurred under anoxic, ferruginous subsurface water masses. Moreover, I infer that phosphorus bound to iron minerals precipitated from the water column and organic-bound phosphorus were both important sources of phosphorus to the seafloor. Petrographic observations allow me to reconstruct the early diagenetic pathways that decoupled phosphorus from these delivery shuttles and promoted the precipitation of apatite within the skeletons of small animals. Together, mechanistic understandings of phosphorus delivery to, and retention within, seafloor sediment allow us to constrain hypotheses for the fleeting occurrence of widespread apatite deposition and exquisite fossil preservation within Cambrian sedimentary successions. Next, I describe and quantify the nature of carbonate production on a marine platform deposited at the hypothesized peak of Cambrian skeletal carbonate production. I find that fossils represent conspicuous, but volumetrically subordinate components of early Cambrian carbonate reef ecosystems and that despite the evolution of mineralized skeletons, Cambrian carbonate platforms appear similar to their Neoproterozoic counterparts, primarily reflecting abiotic and microbial deposition. Finally, I investigate the geodynamic mechanism responsible for rapid, oscillatory true polar wander (TPW) events proposed for the Neoproterozoic and Phanerozoic Earth on the basis of paleomagnetic data. Using geodynamic models, I demonstrate that elastic strength in the lithosphere and stable excess ellipticity of Earth’s figure provided sufficient stabilization to return the pole to its original state subsequent to convectively-driven TPW. / Earth and Planetary Sciences

Highly fractured carbonate reservoirs are a class of reservoirs characterized by high conductivity fractures surrounding low permeability matrix blocks. In these reservoirs, wettability alteration is a key method for recovering oil. Water imbibes into the matrix blocks upon water flooding if the reservoir rock is water-wet. However, many carbonate reservoirs are oil-wet. Surfactant solution was used to enhance spontaneous imbibition between the fractures and the matrix by both wettability alteration and ultra-low interfacial tensions. The first part of this study was devoted to determining the wettability of reservoir rocks using Amott-Harvey Index method, and also evaluating the performance of surfactants on wettability alteration, based on the contact angle measurement and spontaneous imbibition rate and ultimate oil recovery on oil-wet reservoir cores. The reservoir rocks have been found to be slightly oil-wet. One cationic surfactant BTC8358, one anionic surfactant and one ultra-low IFT surfactant formulation AKL-207 are all found to alter the wettability towards more water-wet and promote oil recovery through spontaneous imbibition. The second part of the study focused on the parameters that affect wettability alteration by surfactants. Some factors such as core dimension, permeability and heterogeneity of porous medium are evaluated in the spontaneous imbibition tests. Higher permeability leads to higher imbibition rate and higher ultimate oil recovery. Heterogeneity of core samples slows down the imbibition process if other properties are similar. Core dimension is critical in upscaling from laboratory conditions to field matrix blocks. The imbibition rate is slower in larger dimension of core. Further, we investigated the effects of EDTA in surfactant-mediated spontaneous imbibition. Since high concentration of cationic divalent ions in the aqueous solution markedly suppresses the surfactant-mediated wettability alteration, EDTA improved the performance of surfactant in the spontaneous imbibition tests. It is proposed in the thesis that surfactant/EDTA-enhanced imbibition may involve the dissolution mechanism. More experiments should be conducted to verify this mechanism. The benefits of using EDTA in the surfactant solution include but not limited to: altering the surface charge of carbonate to negative, producing the in-situ soap, reducing the brine hardness, decreasing the surfactant adsorption, and creating the water-wet area by dissolving the dolomite mineral. / text

Determining the distribution of porosity and permeability is one of the main challenges in carbonate petroleum reservoir characterization and requires a thorough understanding of pore type and origin, as well as their spatial distributions. Conventional studies of carbonate reservoirs require interpretation and analysis of cores to understand porosity. This study investigates the use of NMR logs in the determination of pore type and origin. This study is based on the analysis of both thin section petrographic and NMR data from a single well that cored the Lower Cretaceous (Aptian) shelf carbonates belonging to the Shuaiba Formation of the Middle East. Photographs of thin sections were used to determine pore type and origin according to Ahr's genetic classification of carbonate porosity. Descriptive statistics and modeling were used to analyze the NMR T2relaxation time distributions. Descriptive statistical analyses included estimating arithmetic average, standard deviation, skewness, median, mode and 90th percentile. T2modeling was performed by fitting multiple log-normal distributions to the measured T2distribution. Data from thin section petrography and from NMR measurements were then compared using conditional probabilities. As expected, thin section analysis revealed the predominance of mud-supported fabrics and micropores between matrix grains Vugs and dissolved rudistid fragments account for most of the macro porosity. Descriptive statistics showed that the mode and th percentile of the T2distribution had the greatest power to discriminate pores by origin. The first principal component (PC1) of the mode-90th percentile system was then used to compute the probabilities of having each pore origin, knowing that PC1 belongs to a given interval. Results were good, with each origin being predictable within a certain range of PC1. Decomposition of the T2distributions was performed using up to 3 log-normal component distributions. Samples of different pore origin behaved distinctively. Depositional porosity showed no increase in fit quality with increasing number of distributions whereas facies selective and diagenetic porosity did, with diagenetic porosity showing the greatest increase.

A one-kilometer-diameter carbonate/hydrate mound in Mississippi Canyon Block 118 has been chosen to be the site of a multi-sensor, multi-discipline sea-floor observatory. Several surveys have been carried out in preparation for installing the observatory. The resulting data set permits discussing the mound’s structure in some detail. Samples from the water column and intact hydrate outcrops show gas associated with the mound to be thermogenic. Lithologic and bio-geochemical studies have been done on sediment samples from gravity and box cores. Pore-fluid analyses carried out on these cores reveal that microbial sulfate reduction, anaerobic methane oxidation, and methanogenesis are important processes in the upper sediment. These microbial processes control the diffusive flux of methane into the overlying water column. The activity of microbes is also focused within patches near active vents. This is primarily dependent upon an active flux of hydrocarbon-rich fluids. The geochemical evidence suggests that the fluid flux waxes and wanes over time and that the microbial activity is sensitive to such change. Swath bathymetry by AUV combined with sea-floor video provides sub-meter resolution of features on the surface of the mound. Seismic reflection profiling with source-signature processing resolves layer thicknesses within the upper 200-300m of sediment to about a meter. Exploration-scale 3-D seismic imaging shows that a network of faults connects the mound to a salt diapir a few hundred meters below. Analyses of gases from fluid vents and hydrate outcrops imply that the faults act as migration conduits for hydrocarbons from a deep, hot reservoir. Source-signature-processed seismic traces provide normal-incidence reflection coefficients at 30,000 locations over the mound. Picking reflection horizons at each location allows a 3-D model of the mound’s interior to be constructed. This model provides a basis for understanding the movement of fluids within the mound.

Understanding the formation conditions of seep carbonate is crucial to better constrain the dynamic fluid flow and chemical fluxes associate with cold seeps on the seafloor. Rare earth element (REE) in seep carbonates collected from modern cold seeps of Gulf of Mexico, Black Sea, Congo Fan, ancient seeps of Beauvoisin (Oxfordian, J3, Southeastern France) and Marmorito (Miocene, Northern Italy) were studied. Our focus has been on 5% HNO3-treated solution (authigenic carbonate minerals) of carbonates. Several crystalline forms of carbonate minerals have been selected for analysis. Total REE (ΣREE) contents in seep carbonates varies widely, from 0.068 to 43.655 ppm, but the common trend is that the ΣREE in microcrystalline phases is highest and lowest of in sparite, suggesting that the ΣREE of seep carbonates may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates show varied Ce anomalies across several seep sites and even within one site, suggesting that the formation condition of seep carbonate is variable and complex. Overall, our results show that apart from anoxic, oxic formation condition is also common at hydrocarbon seep environments.