APPLICATION OF STABLE ISOTOPES OF OXYGEN, HYDROGEN, AND CARBON TO HYDROGEOCHEMICAL STUDIES, WITH SPECIAL REFERENCE TO CANADA DEL ORO VALLEY AND THE TUCSON BASIN (GEOCHEMISTRY, ISOTOPE, CARBON-14).
KeywordsGeochemistry -- Data processing.
Geochemistry -- Arizona -- Tucson Region -- Data processing.
Geochemistry -- Arizona -- Pima County -- Data processing.
Hydrogeology -- Data processing.
Isotope geology -- Data processing.
Isotope geology -- Arizona -- Tucson Region -- Data processing.
Isotope geology -- Arizona -- Pima County -- Data processing.
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PublisherThe University of Arizona.
RightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
AbstractHydrogeochemical studies are generally qualitative in nature. The goal of this study is to investigate the possibility of quantitative interpretation of hydrogeochemistry by considering the chemical characteristics and the isotopic compositions of oxygen, hydrogen, and carbon of the water. This study examines ephemeral stream and well waters from Canada del Oro valley, southern Arizona. By chemical and isotopic considerations, this study finds that the change of chemical composition of the wash water was mainly due to water-rock interaction. The concentrations of dissolved constituents increase between 10 to 50% from upstream to downstream samples, while the evaporation loss of water is less than 3%. By chemical and isotopic considerations of the well waters, this study identifies three recharge waters in the CDO ground-water system. The chemical and water isotopic compositions of the well waters are results of mixing between these three recharge waters and subsequent dissolution of the aquifer. By thermodynamic consideration, albite, kaolinite, montmorillonite, and calcite are the main phases that influence the chemical characteristics of this ground-water system. Simulations with the computer program PHREEQE verifies the above conclusions. The mechanisms that influence the chemical and carbon isotopic compositions of the water are quite different in a system open to a CO2 gas reservoir than in a closed system. Deines, Langmuir, and Harmon (1974) derived a set of chemical-isotopic equations to calculate the carbon isotopic composition of water under open system condition. Wigley, Plummer, and Pearson (1978) formulated a mass transfer equation to calculate the change of carbon isotopic composition of natural water in closed system environment. This study implements these two type of equations as a subroutine--CSOTOP to the computer program PHREEQE. With this PHREEQE-CSOTOP package, the evolution of carbon chemical and isotopic composition of natural water can be conveniently modeled from open to closed system conditions. This study also uses this package to date water samples from the Tucson basin, and finds that choice of reaction path may cause a difference in carbon-14 age of up to a few thousand years. This study concludes that it is possible to rigorously interpret hydrogeochemistry in a quantitative way. With sufficient measurements to define the reaction path, followed by thermodynamic consideration, chemical-isotopic evaluation, and computer modeling, one should be able to achieve this goal.
Degree GrantorUniversity of Arizona
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Elemental and Isotope Geochemistry of Appalachian Fluids: Constraints on Basin-Scale Brine Migration, Water-Rock Reactions, Microbial Processes, and Natural Gas GenerationOsborn, Stephen (The University of Arizona., 2010)This study utilizes new geochemical analyses of fluids (formation water and gas) collected predominately from Devonian organic-rich shales and reservoir sandstones from the northern Appalachian Basin margin to investigate basin scale hydrologic processes, water-rock reactions, microbial activity, and natural gas generation. Elemental and isotopic composition of co-produced formation waters and natural gas show that the majority of methane in Devonian organic-rich shales and reservoir sandstones is thermogenic in origin with localized accumulations of microbial gas. Microbial methanogenesis appears to be primarily limited by redox buffered conditions favoring microbial sulfate reduction. Thermal maturity (bioavailability) of shale organic matter and the paucity of formation waters may also explain the lack of extensive microbial methane accumulations. Iodine and strontium isotopes, coupled to elemental chemistry demonstrate basin scale fluid flow and clay mineral diagenesis. Evidence for this is based on anomalously high ¹²⁹I/I values sourced from uranium deposits (fissiogenic production of ¹²⁹I) at the structural front of the Appalachian Basin. Radiogenic ⁸⁷Sr/⁸⁶Sr (up to 0.7220), and depleted boron and potassium concentrations support smectite clay diagenesis at temperatures greater than 120 °C. The development of fissiogenic ¹²⁹I as a tracer of basin scale fluid flow is a novel application of iodine isotopes provided that the sources of cosmogenic and anthropogenic ¹²⁹I are reasonably well constrained. The anomalously high ¹²⁹I/I in Appalachian Basin brines may be alternatively explained by microbial fractionation based on a correlation with decreasing δ¹³C-DIC values and decreasing sulfate concentrations in the range of sulfate reduction. These results demonstrate that the microbial fractionation of iodine isotopes may be possible and an important consideration when interpreting ¹²⁹I/I, regardless of the source of ¹²⁹I. Results from this study have important implications for understanding the controls on and origins of natural gas production in sedimentary basins; tectonically and topographically driven basin scale fluid flow, including diagenetically induced waterrock reactions and mineral ore deposition related to orogenesis; and an improvement of the use of iodine isotopes for understanding large scale fluid flow, and possibly its use as a tracer of organic matter diagenesis and the distribution of radionuclides in the environment.
Behavior of lutetium-hafnium, samarium-neodymium and rubidium-strontium isotopic systems during processes affecting continental crust.Barovich, Karin Marie. (The University of Arizona., 1991)Combined Lu-Hf, Sm-Nd and Rb-Sr isotopic studies of continental crustal rocks were undertaken to assess the relative effects of secondary crustal processes on isotopic systematics of whole-rock systems. The processes studied include ductile deformation, and three cases of hydrothermal alteration, involving fluids of varying composition. The Rb-Sr system proved to be easily disturbed during all secondary processes, while Sm-Nd and Lu-Hf systems were, for the most part, resilient. These results show that Nd or Hf isotopic information obtained from old rocks that have undergone typical crustal deformational and alteration events can be counted on to be equally reliable. Nd and Hf isotopic analyses were performed on four suites of Early Archean felsic gneiss complexes from Greenland, Labrador, Swaziland, and Michigan to explore questions associated with Early Archean crustal growth. The Sm-Nd isotopic data yield initial ∊(Nd) values that are mostly consistent with published age data for the suites. Calculations show limited scatter may be attributed to subtle changes in the Sm/Nd ratio or Nd isotopic composition. The Hf isotopic results are more variable and complex than the Nd results. The relevance of the studies on isotopic mobility in the first part of this work is that they have demonstrated that Nd and Hf isotopes are equally resilient during a range of secondary crustal processes. Given the robustness of the Nd isotopic data from the Archean samples, however, it seems unreasonable to attribute the much wider variation in Hf isotopic data to post-Archean isotopic disturbances. Differences in initial Hf isotopic ratios from differing magma sources seem called for. Nd and Hf whole-rock analyses of a Late Archean pristine garnet-bearing granitoid complex from northern Canada point out the importance of garnet in fractionating Lu/Hf ratios, and in developing anomalous ∊(Hf) signatures in potential source regions. Calculations show that even short-lived upper mantle/lower crustal heterogeneities, products of previous partial melting events involving garnet fractionation, can develop the range of positive and negative ∊(Hf) values seen in the Early Archean samples.
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