A Cl stable isotope fractionation factor between amphibole and fluid has been determined at 700 °C and 0.2 GPa. Rates of isotope exchange between pargasite and water at 600-800 °C were slow; therefore synthesis of amphibole in the presence of a fluid was necessary to facilitate the incorporation of Cl into amphibole. Hastingsite was synthesized from an oxide mixture and reacted with a NaCl-bearing supercritical fluid for periods of 3 to 14 days, approximately at the wüstite-magnetite buffer. Based on these synthesis-reaction experiments, the fractionation between hastingsite and a NaCl-bearing solution (~20000 ppm Cl) at 700 °C is 103lnαamphibole-fluid = 0.19‰ ± 0.23‰. These data display near zero fractionation at 700 °C, but suggest that amphibole is slightly enriched in 37Cl relative to the fluid, in agreement with empirical and theoretical results. / text

Uranium-series isotopes are an emerging tool to characterize weathering and soil forming processes in the Critical Zone, the dynamic region of earth's surface where bedrock, water, soil, and life chemically and physically interact to support ecosystems. Understanding controls on the U-series composition of soils across a range of lithologies and climate is critical to applying existing mass balance models of U-series isotopes to calculate soil formation rates in these systems. This study seeks to understand the behavior of U-series isotopes in soil profiles in the semi-arid complex volcanic terrain of the Valles Caldera, NM. (²³⁴U/²³⁸U) measured in soils ranged from 0.90 to 1.56 and (²³⁰Th/²³⁸U) values ranged from 0.48 to 1.39. Significant ²³⁰Th enrichment in upper soil profiles was interpreted as evidence of mixing with ²³⁰Th-enriched volcanic ash and significant ²³⁴U enrichment in one soil profile was interpreted as evidence of addition of U to soils from ²³⁴U-enriched soil solutions. A simple U isotope mass balance model was applied to estimate soil residence time based on U addition, which yielded a minimum residence time of ~10ka. Evidence of past episodic mixing of volcanic ash in these soils suggests modeling soil formation using a mass balance approach is problematic, and future applications of existing models in other heterogeneous volcanic soils should be applied cautiously. U-series isotopes have also shown promise as a tracer of residence time in shallow groundwater and streams. In this study, (²³⁴U/²³⁸U) in dissolved U is used to trace seasonal variation in source water contributions to streamflow in a small (3.29km²), headwater catchment in the Jemez River Basin Critical Zone Observatory within the Valles Caldera. Systematically lower (²³⁴U/²³⁸U) values in dissolved U were observed in spring and stream waters in conjunction with greater contributions of longer residence time waters during snowmelt ((²³⁴U/²³⁸U) ranged 1.7 to 2.8) vs. dry seasons ((²³⁴U/²³⁸U) ranged 1.9 to 3.1). The lower (²³⁴U/²³⁸U) values in longer residence time waters were attributed to progressive depletion of easily-weathered ²³⁴U with increasing duration of water rock interaction. Further studies with more quantitative age tracers, such as ³H, could help to establish (²³⁴U/²³⁸U) values as a powerful tracer of water sources and residence time in streamwaters at the catchment scale.

The Nopal I uranium deposit located in northern Chihuahua Mexico has been the focus of study for the past 40 years. Information regarding to its formation and evolution through time demonstrate that it has a very complex history. Uranium mineralization occurs in two different styles: uranium oxide uraninite and a secondary phases of silicates (uranophane, soddyite) and oxyhydroxides (schoepite and ianthinite). Petrographic studies have revealed that uraninite is found encapsulated within the host rock (ignimbrites) as fine grains while secondary uranium minerals are filling fractures and micro-veins. Chemical dates from the uranium minerals give a wide range from 0 to 611 Ma; many of the ages may be overestimated since the host rock is 44 Ma. U/Pb isotopic studies demonstrate the presence of common Pb, and after a correction was applied, a new range of dates from 1< to 7 Ma was obtained.

The Nopal I uranium deposit located in northern Chihuahua Mexico has been the focus of study for the past 40 years. Information regarding to its formation and evolution through time demonstrate that it has a very complex history. Uranium mineralization occurs in two different styles: uranium oxide uraninite and a secondary phases of silicates (uranophane, soddyite) and oxyhydroxides (schoepite and ianthinite). Petrographic studies have revealed that uraninite is found encapsulated within the host rock (ignimbrites) as fine grains while secondary uranium minerals are filling fractures and micro-veins. Chemical dates from the uranium minerals give a wide range from 0 to 611 Ma; many of the ages may be overestimated since the host rock is 44 Ma. U/Pb isotopic studies demonstrate the presence of common Pb, and after a correction was applied, a new range of dates from 1< to 7 Ma was obtained.

The Gawler Craton, South Australia, consists of late Archaean to early Mesoproterozoic igneous and supracrustal lithologies which preserve a deformation history lasting the duration of the Palaeoproterozoic. Understanding the evolution of the Gawler Craton is of significance in global supercontient reconstructions as it preserves evidence for earliest Palaeoproterozoic collisional orogenesis (c. 2460-2430 Ma) and, in conjunction with the North Australian Craton and Antarctica, has often been correlated to the western margin of Laurentia. In addition, the Gawler Craton is also host to the world-class Olympic Dam Fe-oxide-Cu-Au-U type-deposit (world's fourth largest Cu and largest U deposit) and related Fe-oxide-Cu-Au-U and Cu-Au mineralising systems. Despite the various geologically and economically important characteristics of the Gawler Craton there has traditionally been a poor understanding of the tectonothermal evolution of the Gawler Craton, in particular for the Palaeoproterozoic. This study addresses and refines the Palaeo-to Mesoproterozoic tectonothermal evolution of the Gawler Craton. This is done using geochemical, geochronological and isotopic analytical techniques to better understand selected supracrustal and igneous lithologies in the Gawler Craton and the orogenic events which have affected them. Largely unexposed metasedimentary lithologies of the northern Gawler Craton record multiple deformation events but have previously been virtually unconstrained with respect to their timing of protolith deposition and the age of deformation/metamorphism. New geochronological data demonstrate these metasedimentary lithologies were deposited during the time period -1750-1730 Ma before being metamorphosed and deformed during the Kimban (1730-1690 Ma) and Kararan (1570-1545 Ma) Orogenies. Detrital zircon geochronology and isotopic and geochemical characteristics of the sampled metasedimentary lithologies suggest a relatively similar protolith sedimentary succession was deposited across a large extent of the northern Gawler Craton. Detritus for the sedimentary protolith does not appear to have been sourced from the Gawler Craton. Instead the protolith it is more consistent with a North Australian Craton provenance suggesting a proximity between the northern Gawler Craton and North Australian Craton at the time of protolith deposition. The newly defined presence of the Palaeoproterozoic Kimban Orogeny in the northern Gawler Craton demonstrates the Kimban Orogeny to be a major, high-grade, craton-wide orogenic event. This finding contradicts previous suggestions that the northern Gawler Craton was accreted to the proto-Gawler Craton during the later Mesoproterozoic Kararan Orogeny. In addition, previous reconstruction models for the Palaeo-to early Mesoproterozoic often cite the felsic Tunkillia Suite (1690-1670 Ma), western and central Gawler Craton, as representing arc magmatism prior to the subsequent amalgamation of the Gawler Craton during the Kararan Orogeny. New geochemical and isotopic data for the Tunkillia Suite have allowed for re-examination of the tectonic setting for the petrogenesis of the Tunkillia Suite. Contrary to previous suggestions (based upon discrimination diagrams), the mineralogy, geochemistry and isotopic characteristics of the Tunkillia Suite are not consistent with arc-magmatism. Instead the Tunkillia Suite is interpreted to represent a late-to post-tectonic magmatic suite generated during the waning stages of the Kimban Orogeny. This petrogenesis further highlights the importance of the Kimban Orogeny as a fundamental tectonothermal event in the evolution of the Gawler Craton. Subsequent to the Kimban Orogeny, the Gawler Craton was thought to undergo a period of subduction-related magmatism (St Peter Suite) prior to the anorogenic magmatism of the voluminous felsic Gawler Range Volcanic (GRV) and Hiltaba Suite magmatism (1595-1575 Ma). New geochronological data for the ms-bi-gt-bearing peraluminous Munjeela Suite (1590-1580 Ma) have demonstrated the Hiltaba/GRV event was accompanied by significant crustal anatexis not associated with the Hiltaba/GRV magmatism. The Munjeela Suite and metasedimentary enclaves within it demonstrate that the Gawler Craton was likely to be undergoing compressive deformation and crustal thickening sometime during the petrogenesis of the Hiltaba/GRV magmatism. This suggests the Hiltaba/GRV magmatism did not occur in an anorogenic setting as previously proposed. The findings of this study are incorporated into a revised tectonothermal evolution of the Gawler Craton. This is used to discuss previous reconstruction models for Proterozoic Australia and provide a new reconstruction model of Australia and Antarctica during the Palaeoproterozoic. Important facets of the proposed model are links to the Archaean-Early Palaeoproterozoic Sask Craton in the Trans-Hudson Orogen, Laurentia, and the joint evolution of the North Australian and Gawler Cratons throughout the entire Palaeoproterozoic. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1330862 / Thesis (Ph.D.) - University of Adelaide, School of Earth and Environmental Sciences, 2008

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The last several years have seen renewed interest in the origin of silicic magmas thanks to the developments of new microanalytical techniques allowing the measurement of the isotopic and trace element compositions of erupted magmas on sub-crystal length scales. Concurrently, there has been rapid improvement in the sophistication of computer modeling of igneous systems. This dissertation is an interdisciplinary study of the rhyolites of the Yellowstone hotspot track using both techniques. Chapters II-IV, which have all been published in existing journals, are a detailed study of the O and Hf isotopic compositions of zircon phenocrysts from large rhyolitic eruptions in the central Snake River Plain, and from rhyolites which erupted in Oregon, Idaho, and Nevada coeval with the Columbia River flood basalts. They show that rhyolites are derived from combinations of fractionates of mantle-derived basalts and of different crustal end-members which are identifiable by their distinct isotopic end-member compositions. In the Snake River Plain and Yellowstone, they recognize a common trend where early erupted rhyolites have a strong signature of melting of ancient Precambrian crust, whereas later erupted rhyolites more closely resemble the mantle in their radiogenic isotopes and are more likely to be depleted in oxygen isotopes. Diversity in zircon grain compositions also documents a batch mixing process in which multiple compositionally distinct magma bodies are assembled into a larger common magma body prior to eruption. In Chapters V and VI, the former of which has been published with the latter in preparation, a new series of magmatic-thermomechanical models is presented which assume that melts rising through the crust are arrested by strong rheological contrasts. The strongest such contrast occurs at the brittle-ductile transition at 5-10 km depth, leading to the formation of a 10-15 km thick mafic mid-crustal sill, which separates upper and lower-crustal zones of partial melt, corroborating previous geophysical imaging studies. In Chapter VI, the above isotopic trends are replicated in the modeling scheme, which shows that the source depth of crustal melts tends to shallow with time through a combination of crustal heating and repeated caldera collapses. This dissertation includes both previously published co-authored material.

Reactions between CO2-charged brines and reservoir minerals might either enhance the long-term storage of CO2 in geological reservoirs or facilitate leakage by corroding cap rocks and fault seals. Modelling the progress of such reactions is frustrated by uncertainties in the absolute mineral surface reaction rates and the significance of other rate limiting steps in natural systems. This study uses the chemical evolution of groundwater from the Jurassic Navajo Sandstone, part of a leaking natural accumulation of CO2 at Green River, Utah, in the Colorado Plateau, USA, to place constraints on the rates and potential controlling mechanisms of the mineral-fluid reactions,under elevated CO2 pressures, in a natural system. The progress of individual reactions, inferred from changes in groundwater chemistry is modelled using mass balance techniques. The mineral reactions are close to stoichiometric with plagioclase and K-feldspar dissolution largely balanced by precipitation of clay minerals and carbonate. Mineral modes, in conjunction with published surface area measurements and flow rates estimated from hydraulic head measurements, are then used to quantify the kinetics of feldspar dissolution. Maximum estimated dissolution rates for plagioclase and K-feldspar are 2x10-14 and 4x10-16 mol·m-2·s-1, respectively. Fluid ion-activity products are close to equilibrium (e.g. DGr for plagioclase between -2 and -10 kJ/mol) and lie in the region in which mineral surface reaction rates show a strong dependence on DGr. Local variation in DGr is attributed to the injection and disassociation of CO2 which initially depresses silicate mineral saturation in the fluid, promoting feldspar dissolution. With progressive flow through the aquifer, feldspar hydrolysis reactions consume H+ and liberate solutes to solution which increase mineral saturation in the fluid and rates slow as a consequence. The measured plagioclase dissolution rates at low DGr would be compatible with far-from-quilibrium rates of ~1x10-13 mol·m-2·s-1 as observed in some experimental studies. This suggests that the discrepancy between field and laboratory reaction rates may in part be explained by the differences in the thermodynamic state of natural and experimental fluids, with field-scale reactions occurring close to equilibrium whereas most laboratory experiments are run far-from-equilibrium. Surface carbonate deposits and cementation within the footwall of the local fault systems record multiple injections of CO2 into the Navajo Aquifer and leakage of CO2 from the site over ca. 400,000 years. The d18O, d13C and 87Sr/86Sr of these deposits record rapid rates of CO2 leakage (up to ~1000 tonnes/a) following injection of CO2, but rates differ by an order of magnitude between each fault, due to differences in the fault architecture. Elevated pCO2 enhances rates of feldspar dissolution in the host aquifer and carbonate precipitation in fracture conduits. Silicate mineral dissolution rates decline and carbonate precipitation rates increase as pH and the CO2 charge dissipate. The Sr/Ca of calcite cements record average precipitation rates of ~2x10-6 mol/m2/s, comparable to laboratory derived calcite precipitation rates in fluids with elevated Mn/Ca and Fe/Ca, at cc of ~1 to 3. This suggests that far-from-equilibrium carbonate precipitation, which blocks fracture conduits and causes the leaking system to self-seal, driven by CO2 degassing in the shallow subsurface, can be accurately modeled with laboratory derived rates. Sandstones altered in CO2 leakage conduits exhibit extensive dissolution of hematite grain coatings and are chemically bleached as a result. Measurements of Eh-pH conditions in the modern fluid, and modeling of paleo-Eh-pH conditions using calcite Fe and Mn concentrations, suggests that the CO2-charged groundwaters are reducing, due to their low dissolved O2 content and that pH suppression due to high pCO2 is capable of dissolving and transporting large concentrations of metals. Exhumed paleo-CO2 reservoirs along the crest of the Green River anticline have been identified using volatile hosting fluid inclusions. Paleo-CO2-charged fluids mobilized hydrocarbons and CH4 from deeper formations, enhancing the reductive dissolution of hematite, which produced spectacular km-scale bleached patterns in these sediment.

Calcium phosphates are important compounds as they exist in natural aqueous systems such as rivers, lakes, ocean, and soil. These calcium phosphates are widely used to provide information on paleotemperatures as well as many anthropological features, such as paleodiets. One of the most ubiquitous forms of calcium phosphate is hydroxyapatite (Ca10(PO4)6(OH)2) which is a major component of hard tissue such as bones, fossils, and tooth enamel. The oxygen isotope systematics in the hydroxyapatite associated with carbonate-water system will provide further information to allow for the reconstruction of terrestrial and marine environments. For example, Fricke et al. (1998) used oxygen isotope analysis of the carbonate components of hydroxyapatite in tooth enamel of mammals to investigate changes in terrestrial climate. Therefore, the purpose of this research study was to examine the oxygen isotope systematics in inorganic carbonate-bearing hydroxyapatite and water at low temperatures. This Master’s thesis followed and modified the methods described in Lécuyer et al. (2010) in an attempt to synthesize hydroxyapatite crystals and carbonate-bearing hydroxyapatite. The crystals synthesized were characterized in terms of several conditions (i.e., influence of mixing rate and maturations, pH, and concentrations of NaHCO3). Methods to produce hydroxyapatite were developed and analyzed using X-Ray diffraction analysis. The results demonstrated a strong dependence of pH in the hydroxyapatite solutions. Moreover, the effect of concentrations of NaHCO3 was deemed to be essential in order to obtain the desired amount of structural carbonates in the hydroxyapatite crystals. Furthermore, this research evaluated the temperature dependence of oxygen isotopic fractionation between HAP-bound carbonate and water at 10, 25, and 40 oC. Our study is the first to assess the two mixing-rates experiments with different maturations (7 and 14 days) on the oxygen isotope effects and fractionation behaviour between HAP-bound carbonate and water. Both maturation time and the effect of initial concentration of NaHCO3 were found to be the most important in determining the equilibrium conditions in our experiments. / Dissertation / Master of Science (MSc)

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