Table Mesa and Rattlesnake Fields are located on the Four Corners Platform, New Mexico, between the Paradox Basin to the north and San Juan Basin to the south. Diagenesis is extensive and includes partial dissolution and replacement of ooids, partial silicification of allochems and matrix, and filling of pore space with large, blocky calcite. Pore types include interparticle, intraparticle, and vuggy, with much porosity lost to late cementation. Porosity is greatest in cycles interpreted as regressive deposits with meteoric and burial diagenesis being most significant to porosity enhancement. Sea level and depositional history are shown to be significantly useful in predicting patterns of porosity development and destruction. These results are directly applicable to other economically important carbonate platforms.

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Heavy metals like cadmium, lead and zinc pose a significant threat to human health and environment. Several factors such as pH, EH, organic matter and clay content of the soil affect the bioavailability of such heavy metals in the environment. The presence of several naturally occurring minerals such as calcite (calcium carbonate, CaCO3) and calcium oxalate (CaC2O4.) in the environment significantly influence the fate and transport of some of the heavy metal cations. Sequestration of heavy metals such as cadmium (Cd) and zinc (Zn) from solution by calcite has been clearly demonstrated in the literature. However, studies on heavy metal sequestration by calcite and calcium oxalate from a multi-metal environmental that represents real world situations are rare. In this contribution, column flow studies of Cd and Zn sequestration by calcite exposed to influent solutions saturated or non-saturated with calcite and containing either 1 mg/L of Cd, 1 mg/L of Zn or combined 1 mg/L of Zn and Cd, followed by desorption of the sequestered metals were conducted. Complementary scanning electron microscopy (SEM) coupled with electron dispersive x-ray spectroscopy (EDS) data were generated. Kinetic studies show that reaction rates of Cd and Zn with calcite are governed by a simple rate law with reaction orders of less than 1 (0.02 - 0.07) indicating at least mathematically, the occurrence of reactions that went to completion if the reaction orders did not change. When the influent solution contains a single cation, the rate of Zn removal from solution by calcite and calcium oxalate is greater than Cd removal rate. However in a multi-cation environment, cadmium removal rate was greater than zinc removal rate. MINTEQA2 a geochemical equilibrium speciation model was used to compute the equilibrium between the various species in the cation-calcite environment. Complimentary desorption studies and surface SEM/EDS analysis indicate that the removal of Cd and Zn from solution by calcite and calcium oxalate is probably due to precipitation/complexation reaction. The SEM and EDS results appear to confirm the presence of a precipitate on the mineral surface in the case of the influent solution containing Zn. The current research also examines the effect of citrate, a commonly present urinary tract species on calcium oxalate dissolution. The dissolution studies indicate that citrate solution is capable of dissolving sodium oxalate at high pH. The dissolution of calcium oxalate results in the release of heavy metals that were previously sequestered within the mineral. Results show that a greater percentage of zinc was removed than cadmium, from calcium oxalate due to its dissolution by citrate. / Engineering

Coastal karst aquifers are important water resources, often providing the only source of freshwater to coastal communities for agriculture, industrial usage and human consumption. In order to implement management strategies and preventative measures for future perseveration of this resource, it is imperative to understand how coastal groundwater conditions are controlled by the interaction of freshwater/seawater on local and regional scales, but also over recent and past time periods. However, there is a limited resource of published hydrological data on recent aquifer conditions. In the Yucatán Peninsula and other anchialine environments, this lack of information inhibits the understanding of the spatial and temporal interaction of the meteoric and marine water masses. Documenting how the aquifer is responding to forcing mechanisms such as large precipitation events, seasonal cycles and short-term sea level rise (e.g. storm surge) will assist in understanding modern aquifer condition but also the interpretation of paleo-records. Utilization of water level and salinity sensors in strategic positions in the aquifer demonstrate that meteoric water mass salinity varies over wet and dry seasons with the movement of the halocline, but also on a short-term basis though large rainfall events. Salinity in the meteoric water mass is influenced by mixing with the marine water mass during intense precipitation events associated with Hurricane Ingrid (2013), Tropical Storm Hanna (2014) and a series of unnamed events in 2015. During wet periods, induced flow from increase precipitation causes turbulent mixing with the marine water mass, increasing salinity in the upper meteoric lens. On the contrary, during dry periods, mixing is reduced, therefore making the meteoric lens less saline. This contemporary understanding of meteoric/marine water mass dynamics can be applied to developing and calibrating the geochemical record of calcite rafts, calcite precipitation at the air-water interface of cave pools, as a hydrological proxy for aquifer conditions. Our monitoring of calcite raft formation, deposition and geochemistry shows that raft accumulations (e.g., raft piles/cones) can offer a good paleoenvironmental archive of changing hydrological conditions. Based on a 2-year observational record, results indicate that calcite raft precipitation/formation occurs continuously but with only minor biases with intense rainfall events altering supersaturation conditions in the surface waters. Testing the use of calcite rafts in sediment cores from Hoyo Negro show that geochemical analyses (87Sr/86Sr, δ18O, δ13C, Sr/Ca and Cl/Ca) show that meteoric water mass salinity varied during the Holocene (~ 8.5 Ka – present) likely due to changing rainfall and or cave passage geomorphology, which is coherent with other independent climate records. Prior to this study, calcite rafts have never been considered a paleo-hydrological archive for aquifer conditions, however, the consistency and cross-validation with independent records demonstrates great potential for future paleohydrological reconstructions. / Thesis / Doctor of Philosophy (PhD)

Calcite c-axes and e-twin plane orientations were measured in both matrix cements and younger fracture fills from late Cambrian to Middle Ordovician age limestone samples taken from the NW and SE limbs of the Massanutten Syncline, located within the North Mountain thrust sheet. Paleostress magnitude estimates using the Rowe and Rutter (1990) twin density technique indicate a differential stress of 240±31 MPa for samples collected from both limbs of the syncline. Three distinct patterns of paleostress orientations (compression directions) have been detected in the samples; each pattern is observed on both the NW and SE limbs of the syncline. The first pattern, exhibited by calcite grains cementing late fractures, is characterized by a maximum of compression axes oriented sub-perpendicular to bedding possibly indicating either thrust sheet loading or stress refraction associated with folding. Samples in which calcite grains from both fracture fills and earlier matrix cements were measured are characterized by a bimodal distribution of compression axes—the first point maximum being oriented sub-perpendicular to bedding, the second maximum placing compression directions at low to moderate angles to bedding. Restoration of bedding to horizontal results in this second set of compression axes plunging to either the SE or NW, sub-parallel to the regional thrust transport direction. The third pattern, originating from early cements, places compression directions plunging to the NE-SW at angles which are sub-parallel to bedding. These compression directions do not seem to correlate with major tectonic movements or thrust sheet loading and may reflect stresses associated with either movement over lateral ramps or oblique thrusting. / Master of Science

Fossils recovered from limestones of the lower Cambrian (Stage 2-3) Yanjiahe Formation in Hubei Province, South China, recovered using acetic acid maceration, fracturing, and thin sectioning techniques were examined using a combination of analytical techniques, including energy dispersive spectroscopic (EDS) elemental mapping and micro-focus X-ray computed tomography (micro-CT). One important fossil recovered and analyzed with these techniques is a fossilized embryo. Fossilized animal embryos from lower Cambrian rocks provide a rare opportunity to study the ontogeny and developmental biology of early animals during the Cambrian explosion. The fossil embryos in this study exhibit a phosphatized outer envelope (interpreted as the chorion) that encloses a multicelled blastula-like embryo or a calcitized embryo marked by sets of grooves on its surface. The arrangement of these grooves resembles annulations found on the surface of the Cambrian-Ordovician fossil embryo Markuelia. Previously described late-stage Markuelia embryos exhibit annulations and an introvert ornamented by scalids, suggesting a scalidophoran affinity. In the Yanjiahe fossils illustrated herein, however, the phosphatized chorions and blastulas are not taxonomically or phylogenetically diagnostic, and the late-stage embryo is secondarily calcitized and thus poorly preserved, with only vague grooves indicative of Markuelia-type annulations. Consequently, their taxonomic assignment to the genus Markuelia is uncertain. If they indeed belong to the genus Markuelia, they are the oldest known Markuelia fossils from China, and represent both a new occurrence and possibly a new species. / Master of Science

No / Small-scale heterogeneity of biogenic carbonate elemental composition can be a significant source of error in the accurate use of element/Ca ratios as geochemical proxies. In this study ion microprobe (SIMS) profiles showed significant small-scale variability of Mg/Ca, Sr/Ca and Mn/Ca ratios in new shell calcite of the marine bivalves Pecten maximus and Mytilus edulis that was precipitated during a constant-temperature culturing experiment. Elevated Mg/Ca, Sr/Ca and Mn/Ca ratios were found to be associated with the deposition of elaborate shell features, i.e. a shell surface stria in P. maximus and surface shell disturbance marks in both species, the latter a common occurrence in bivalve shells. In both species the observed small-scale elemental heterogeneity most likely was not controlled by variable transport of ions to the extra-pallial fluid, but by factors such as the influence of shell organic content and/or crystal size and orientation, the latter reflecting conditions at the shell crystalsolution interface. In the mid and innermost regions of the P. maximus shell the lack of significant small-scale variation of Mg/Ca ratios, which is consistent with growth at constant temperature, suggest a potential application as a palaeotemperature proxy. Cross-growth band element/Ca ratio profiles in the interior of bivalve shells may provide more promising palaeo-environmental tools than sampling from the outer region of bivalve shells.

<p> Speleothems are calcium carbonate deposits, such as stalagmites, stalactites and flowstones, formed in a cave environment by loss of carbon dioxide from saturated groundwaters. Variations in the 18o/16o ratio of calcite are related to changes in depositional temperature provided that the speleothem formed in isotopic equilibrium with its seepage water (conditions characterised by slow coloss and no evaporation of seepage water). Variations in 18o/16o of the seepage water will also be reproduced in the calcite but allowance for this effect can be made if 18o/16o ratio of the source (ocean water) can be estimated (from deep sea sediment cores) and if the influence of temperature on 18o/16o ratio of precipitation at the site can be determined. Because cave temperatures closely approximate mean annual surface temperature, the axial 18o/16o record of a speleothem is therefore an indication of paleoclimate and of temperature change over the period of its growth. </p> <p> The frequency distribution of age measurements for several speleothems from an area may also be used as a paleoclimatic indicator because cold or glacial conditions above the cave will inhibit speleothem growth by freezing water at the surface and removing vegetation and soil cover, the main source of CO2 for the limestone dissolution-reprecipitation process. </p> <p> Pure, non-porous calcite speleothems from several limestone regions have been dated in this study by the 230Th/234U method, and in cases of uranium-rich speleothems, by the 231Pa/230Th method also. For ten such cases, examined, good agreement of ages determined by both dating methods was found. </p> <p> Relatively few deposits however, have shown deposition under isotopic equilibriwn conditions, due probably to the well-ventilated nature of the caves studied. </p> <p> The age distribution for speleothem from Cascade Cave on Vancouver Island, B.C., indicates growth during the mid-Wisconsin interstadial dated as 65 -30,000 yrs. B.P. Stable isotope profiles for two speleothems which grew over this period both show values of 18o/16o ratios of calcite which are significantly lower than calcite growing in the cave today. This is the first clearly-defined record of such an occurence (in previous work, 18o/16o of fossil speleothem was generally greater than modern). Using estimates of the change in 18o/16o of ocean water from a Pacific deep sea core, and the value determined by Dansgaard (1964) for the temperature dependence of 18o/16o of precipitation for oceanic sites, a realistic paleotemperature record is derived. The results indicate that temperatures at the Cascade Cave site were about 4.0°C , 64,000 yrs. ago· and gradually declined to 0°c by 35,000 yrs. ago. These data are consistent with the findings of Canadian workers from 14c and palynological studies of fossil organic matter in the area, and do not support the proposal by some American workers of a major glaciation occurring between 35 - 40,000 yrs. B.P. </p> <p> The age distribution for 140 analyses of 82 speleothems collected from caves in north-west England show abundant deposition during the periods 130 -90,000 yrs. B.P. and 13,000 yrs. B.P. to present, with limited growth over the periods > 350 -170,000 yrs. B.P. and 70 -35,000 yrs. B.P. No ages were found to lie within the periods 170 -140,000 yrs. B.P. and 35-15,000 yrs. B.P. These intervals are correlated to the Wolstonian and Devensian glaciations respectively. </p> <p> Only four speleothems were found to have grown in isotopic equilibrium with their seepage waters, and one of these showed periods of non-equilibrium deposition. In contrast to the Vancouver Island results, 18o/16o all ratios were found to be greater than or equal to modern, indicating that the apparent oceanic location of this site is not expressed in the on the value for temperature dependence of 18o/16o precipitation. </p> <p> An oxygen isotope profile for a flowstone dated between 126,000 and 109, 000 yrs. B.P. shows 18o/16o ratios commencing at values slightly lower than for modern calcite and shifting to still lower values at about 112, 000 yrs. B.P. This shift may indicate a cooling event perhaps carrelative with the isotope stage 5e-5d transition seen in the deep sea core record. A profile for a flowstone over the period 290 -190,000 yrs. B.P. shows excellent correlation to interglacial stages 9e and 7c seen in the deep sea core record, and a pronounced growth hiatus dated at about 250 210,000 yrs. B.P. correlates with glacial stage 8. These are the first speleothem results to show a climatic record beyond 200,000 yrs. B.P. </p> <p> The differences in 18o/16o behaviour for speleothems from the two locations (N .E. Pacific and ..E. Atlantic) are interpreted in terms of their relative proximity to the ocean, potential for exchange of water vapour and 'rainout' by airmasses moving towards the cave sites, and possibility of change in meteorological conditions (principally storm track) over the periods studied. </p> <p> In a subsidiary study, evidence for major sea level lowering during the Illinoian glaciation is recognised by age determinations on the calcite core of speleothems collected at 45m below present sea level from a 'blue hole' near Andros Island in the Bahamas. </p> <p> The possibility of applying the 234U/238U dating method to speleothem is also investigated in this work, by the analysis of modern calci tes and their seepage waters, using a new method for uranium extraction from groundwater. However the variations in 234U/238U ratios observed over short distances in the same cave demonstrate that estimation of initial fossil 234U/238U in the speleothem cannot simply be made by averaging modern ratios for the cave. </p> <p> Consideration is also given to the temperature dependent distribution of trace elements in calcite, particularly magnesium and strontium. Analyses of modern calcites and waters show that Mg incorporation is strongly temperature dependent whereas Sr is not. The possibility of using Mg variations in fossil speleothem as indication of temperature change is briefly examined but the results for one sample are found to be inconclusive. </p> / Thesis / Doctor of Philosophy (PhD)

Cette étude aborde la formation de gypse résultant de la neutralisation d'une solution d'acide sulfurique par ajout d'une suspension de calcite dans un réacteur semi-ouvert. La phénoménologie et l'impact des paramètres opératoires sont documentés par des prélèvements de solution et de solides analysés hors ligne, qui permettent d'évaluer les écarts à l'équilibre générés à divers stades du mélange et les caractéristiques géométriques du gypse précipité. La solubilité du gypse est évaluée en fonction de la température et de la concentration en sulfate via un modèle de spéciation. Selon les conditions opératoires utilisées, le gypse peut se former à la surface de la calcite par conversion partielle ou en solution par précipitation. La modélisation du procédé est conduite en deux étapes. La conversion est simulée à partir d'un modèle de grain à cœur rétrécissant, adapté pour représenter la dissolution de la calcite et la croissance d'une couche poreuse de gypse. La précipitation en solution est simulée par un bilan de population et résolu par une méthode des caractéristiques. Les paramètres des lois de germination et de croissance sont évalués par un algorithme d'optimisation. Le modèle de conversion rend compte de la sensibilité du processus à l'acidité de la solution et à la taille des particules de calcite. Le modèle de précipitation fournit des profils de sursaturation et de distribution granulométriques simulés cohérents avec les profils expérimentaux. Le contrôle du procédé repose surtout sur l'ajustement de la concentration en acide, qui détermine la vitesse de dissolution de la calcite et la proportion de gypse formé par remplacement.