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Description
The present understanding of the formation and evolution of the earliest bodies in the Solar System is based in large part on geochemical and isotopic evidences contained within meteorites. The differentiated meteorites (meteorites originating from bodies that have experienced partial to complete melting) are particularly useful for deciphering magmatic processes

The present understanding of the formation and evolution of the earliest bodies in the Solar System is based in large part on geochemical and isotopic evidences contained within meteorites. The differentiated meteorites (meteorites originating from bodies that have experienced partial to complete melting) are particularly useful for deciphering magmatic processes occurring in the early Solar System. A rare group of differentiated meteorites, the angrites, are uniquely suited for such work. The angrites have ancient crystallization ages, lack secondary processing, and have been minimally affected by shock metamorphism, thus allowing them to retain their initial geochemical and isotopic characteristics at the time of formation. The scarcity of angrite samples made it difficult to conduct comprehensive investigations into the formation history of this unique meteorite group. However, a dramatic increase in the number of angrites recovered in recent years presents the opportunity to expand our understanding of their petrogenesis, as well as further refine our knowledge of the initial isotopic abundances in the early Solar System as recorded by their isotopic systematics. Using a combination of geochemical tools (radiogenic isotope chronometers and trace element chemistry), I have investigated the petrogenetic history of a group of four angrites that sample a range of formation conditions (cooling histories) and crystallization ages. Through isotope ratio measurements, I have examined a comprehensive set of long- and short-lived radiogenic isotope systems (26Al-26Mg, 87Rb-87Sr, 146Sm-142Nd, 147Sm-143Nd, and 176Lu-176Hf) within these four angrites. The results of these measurements provide information regarding crystallization ages, as well as revised estimates for the initial isotopic abundances of several key elements in the early Solar System. The determination of trace element concentrations in individual mineral phases, as well as bulk rock samples, provides important constraints on magmatic processes occurring on the angrite parent body. The measured trace element abundances are used to estimate the composition of the parent melts of individual angrites, examine crystallization conditions, and investigate possible geochemical affinities between various angrites. The new geochemical and isotopic measurements presented here significantly expand our understanding of the geochemical conditions found on the angrite parent body and the environment in which these meteorites formed.
ContributorsSanborn, Matthew E (Author) / Wadhwa, Meenakshi (Thesis advisor) / Hervig, Richard (Committee member) / Sharp, Thomas (Committee member) / Clarke, Amanda (Committee member) / Williams, Lynda (Committee member) / Carlson, Richard (Committee member) / Arizona State University (Publisher)
Created2012
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Description
The presence of a number of extinct radionuclides in the early Solar System (SS) is known from geochemical and isotopic studies of meteorites and their components. The half-lives of these isotopes are short relative to the age of the SS, such that they have now decayed to undetectable levels. They

The presence of a number of extinct radionuclides in the early Solar System (SS) is known from geochemical and isotopic studies of meteorites and their components. The half-lives of these isotopes are short relative to the age of the SS, such that they have now decayed to undetectable levels. They can be inferred to exist in the early SS from the presence of their daughter nuclides in meteoritic materials that formed while they were still extant. The extinct radionuclides are particularly useful as fine-scale chronometers for events in the early SS. They can also be used to help constrain the astrophysical setting of the formation of the SS because their short half-lives and unique formation environments yield information about the sources and timing of delivery of material to the protoplanetary disk. Some extinct radionuclides are considered evidence that the Sun interacted with a massive star (supernova) early in its history. The abundance of 60Fe in the early SS is particularly useful for constraining the astrophysical environment of the Sun's formation because, if present in sufficient abundance, its only likely source is injection from a nearby supernova. The initial SS abundance of 60Fe is poorly constrained at the present time, with estimates varying by 1-2 orders of magnitude. I have determined the 60Fe-60Ni isotope systematics of ancient, well-preserved meteorites using high-precision mass spectrometry to better constrain the initial SS abundance of 60Fe. I find identical estimates of the initial 60Fe abundance from both differentiated basaltic meteorites and from components of primitive chondrites formed in the Solar nebula, which suggest a lower 60Fe abundance than other recent estimates. With recent improved meteorite collection efforts there are more rare ungrouped meteorites being found that hold interesting clues to the origin and evolution of early SS objects. I use the 26Al-26Mg extinct radionuclide chronometer to constrain the ages of several recently recovered meteorites that sample previously unknown asteroid lithologies, including the only know felsic meteorite from an asteroid and two other ungrouped basaltic achondrites. These results help broaden our understanding of the timescales involved in igneous differentiation processes in the early SS.
ContributorsSpivak-Birndorf, Lev (Author) / Wadhwa, Meenakshi (Thesis advisor) / Hervig, Richard (Committee member) / Timmes, Francis (Committee member) / Williams, Lynda (Committee member) / Anbar, Ariel (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Boron concentrations and isotopic composition of phlogopite mica, amphibole, and selected coexisting anhydrous phases in mantle-derived xenoliths from the Kaapvaal Craton were measured by secondary ion mass spectrometry in an effort to better understand the B isotope geochemistry of the subcontinental lithospheric mantle (SCLM) and its implications for the global

Boron concentrations and isotopic composition of phlogopite mica, amphibole, and selected coexisting anhydrous phases in mantle-derived xenoliths from the Kaapvaal Craton were measured by secondary ion mass spectrometry in an effort to better understand the B isotope geochemistry of the subcontinental lithospheric mantle (SCLM) and its implications for the global geochemical cycle of B in the mantle. These samples display a wide, and previously unrecognized, range in their boron contents and isotopic compositions reflecting a complex history involving melt depletion and metasomatism by subduction- and plume-derived components, as well as late stage isotopic exchange related to kimberlite emplacements. Micas from ancient lithospheric harzburgite metasomatized by slab-derived fluids suggest extensive B-depletion during subduction, resulting in low-B, isotopically light compositions whereas kimberlite-related metasomatic products and a sample from the 2 Ga Palabora carbonatite have boron isotopic compositions similar to proposed primitive mantle. The results suggest that subduction of oceanic lithosphere plays a limited role in the B geochemistry of the convecting mantle.
ContributorsGuild, Meghan R (Author) / Hervig, Richard L (Thesis advisor) / Bell, David R. (Committee member) / Mcnamara, Allen (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Historically, uranium has received intense study of its chemical and isotopic properties for use in the nuclear industry, but has been largely ignored by geoscientists despite properties that make it an intriguing target for geochemists and cosmochemists alike. Uranium was long thought to have an invariant 238U/235U ratio in natural

Historically, uranium has received intense study of its chemical and isotopic properties for use in the nuclear industry, but has been largely ignored by geoscientists despite properties that make it an intriguing target for geochemists and cosmochemists alike. Uranium was long thought to have an invariant 238U/235U ratio in natural samples, making it uninteresting for isotopic work. However, recent advances in mass spectrometry have made it possible to detect slight differences in the 238U/235U ratio, creating many exciting new opportunities for U isotopic research. Using uranium ore samples from diverse depositional settings from around the world, it is shown that the low-temperature redox transition of uranium (U6+ to U4+) causes measurable fractionation of the 238U/235U ratio. Moreover, it is shown experimentally that a coordination change of U can also cause measurable fractionation in the 238U/235U ratio. This improved understanding of the fractionation mechanisms of U allows for the use of the 238U/235U ratio as a paleoredox proxy. The 238U/235U ratios of carbonates deposited spanning the end-Permian extinction horizon provide evidence of pronounced and persistent widespread ocean anoxia at, or immediately preceding, the extinction boundary. Variable 238U/235U ratios correlated with proxies for initial Cm/U in the Solar System's earliest objects demonstrates the existence of 247Cm in the early Solar System. Proof of variable 238U/235U ratios in meteoritic material forces a substantive change in the previously established procedures of Pb-Pb dating, which assumed an invariant 238U/235U ratio. This advancement improves the accuracy of not only the Pb-Pb chronometer that directly utilizes the 238U/235U ratio, but also for short-lived radiometric dating techniques that indirectly use the 238U/235U ratio to calculate ages of Solar System material.
ContributorsBrennecka, Gregory A (Author) / Anbar, Ariel D (Thesis advisor) / Wadhwa, Meenakshi (Thesis advisor) / Herrmann, Achim D (Committee member) / Hervig, Richard (Committee member) / Young, Patrick (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Chemical and mineralogical data from Mars shows that the surface has been chemically weathered on local to regional scales. Chemical trends and the types of chemical weathering products present on the surface and their abundances can elucidate information about past aqueous processes. Thermal-infrared (TIR) data and their respective models are

Chemical and mineralogical data from Mars shows that the surface has been chemically weathered on local to regional scales. Chemical trends and the types of chemical weathering products present on the surface and their abundances can elucidate information about past aqueous processes. Thermal-infrared (TIR) data and their respective models are essential for interpreting Martian mineralogy and geologic history. However, previous studies have shown that chemical weathering and the precipitation of fine-grained secondary silicates can adversely affect the accuracy of TIR spectral models. Furthermore, spectral libraries used to identify minerals on the Martian surface lack some important weathering products, including poorly-crystalline aluminosilicates like allophane, thus eliminating their identification in TIR spectral models. It is essential to accurately interpret TIR spectral data from chemically weathered surfaces to understand the evolution of aqueous processes on Mars. Laboratory experiments were performed to improve interpretations of TIR data from weathered surfaces. To test the accuracy of deriving chemistry of weathered rocks from TIR spectroscopy, chemistry was derived from TIR models of weathered basalts from Baynton, Australia and compared to actual weathering rind chemistry. To determine how specific secondary silicates affect the TIR spectroscopy of weathered basalts, mixtures of basaltic minerals and small amounts of secondary silicates were modeled. Poorly-crystalline aluminosilicates were synthesized and their TIR spectra were added to spectral libraries. Regional Thermal Emission Spectrometer (TES) data were modeled using libraries containing these poorly-crystalline aluminosilicates to test for their presence on the Mars. Chemistry derived from models of weathered Baynton basalts is not accurate, but broad chemical weathering trends can be interpreted from the data. TIR models of mineral mixtures show that small amounts of crystalline and amorphous silicate weathering products (2.5-5 wt.%) can be detected in TIR models and can adversely affect modeled plagioclase abundances. Poorly-crystalline aluminosilicates are identified in Northern Acidalia, Solis Planum, and Meridiani. Previous studies have suggested that acid sulfate weathering was the dominant surface alteration process for the past 3.5 billion years; however, the identification of allophane indicates that alteration at near-neutral pH occurred on regional scales and that acid sulfate weathering is not the only weathering process on Mars.
ContributorsRampe, Elizabeth Barger (Author) / Sharp, Thomas G (Thesis advisor) / Christensen, Phillip (Committee member) / Hervig, Richard (Committee member) / Shock, Everett (Committee member) / Williams, Lynda (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Fluorine (F) is a volatile constituent of magmas and hydrous mantle minerals. Compared to other volatile species, F is highly soluble in silicate melts, allowing F to remain in the melt during magma differentiation and rendering F less subject to disturbance during degassing upon magma ascent. Hence, the association between

Fluorine (F) is a volatile constituent of magmas and hydrous mantle minerals. Compared to other volatile species, F is highly soluble in silicate melts, allowing F to remain in the melt during magma differentiation and rendering F less subject to disturbance during degassing upon magma ascent. Hence, the association between fluorine in basalts and fluorine in the mantle source region is more robust than for other volatile species. The ionic radius of F- is similar to that of OH- and O2-, and F may substitute for hydroxyl and oxygen in silicate minerals and melt. Fluorine is also incorporated at trace levels within nominally anhydrous minerals (NAMs) such as olivine, clinopyroxene, and plagioclase. Investigating the geochemical behavior of F in NAMs provides a means to estimate the pre-eruptive F contents of degassed magmas and to better understand the degassing behavior of H. The partition coefficients of F were determined for clinopyroxene, olivine, plagioclase, and hornblende within melts of olivine-minette, augite-minette, basaltic andesite, and latite compositions. The samples analyzed were run products from previously-published phase-equilibria experiments. Fluorine was measured by secondary ion mass spectrometry (SIMS) using an 16O- primary beam and detection of negative secondary ions (19F-, 18O-, 28Si-). SIMS ion intensities are converted to concentrations by analyzing matrix-matched microanalytical reference materials and constructing calibration curves. For robust F calibration standards, five basaltic glasses (termed Fba glasses) were synthesized in-house using a natural tholeiite mixed with variable amounts of CaF2. The Fba glasses were characterized for F content and homogeneity, using both SIMS and electron-probe microanalysis (EPMA), and used as F standards. The partition coefficients for clinopyroxene (0.04-028) and olivine (0.01-0.16) varied with melt composition such that DF (olivine-minette) < DF (augite-minette) < DF (basaltic andesite) < DF (latite). Crystal chemical controls were found to influence the incorporation of F into clinopyroxene, but none were found that affected olivine. Fluorine partitioning was compared with that of OH within clinopyroxenes, and the alumina content of clinopyroxene was shown to be a strong influence on the incorporation of both anions. Fluorine substitution into both olivine and clinopyroxene was found to be strongly controlled by melt viscosity and degree of melt polymerization.
ContributorsGuggino, Steve (Author) / Hervig, Richard L (Thesis advisor) / Donald, Burt M (Committee member) / Amanda, Clarke B (Committee member) / Lynda, Williams B (Committee member) / Stanley, Williams N (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Variations of 238U/235U in sedimentary carbonate rocks are being explored as a tool for reconstructing oceanic anoxia through time. However, the fidelity of this novel paleoredox proxy relies on characterization of uranium isotope geochemistry via laboratory experimental studies and field work in modern analog environmental settings. This dissertation systematically examines

Variations of 238U/235U in sedimentary carbonate rocks are being explored as a tool for reconstructing oceanic anoxia through time. However, the fidelity of this novel paleoredox proxy relies on characterization of uranium isotope geochemistry via laboratory experimental studies and field work in modern analog environmental settings. This dissertation systematically examines the fidelity of 238U/235U in sedimentary carbonate rocks as a paleoredox proxy focusing on the following issues: (1) U isotope fractionation during U incorporation into primary abiotic and biogenic calcium carbonates; (2) diagenetic effects on U isotope fractionation in modern shallow-water carbonate sediments; (3) the effects of anoxic depositional environments on 238U/235U in carbonate sediments.

Variable and positive shifts of 238U/235U were observed during U uptake by primary abiotic and biotic calcium carbonates, carbonate diagenesis, and anoxic deposition of carbonates. Previous CaCO3 coprecipitation experiments demonstrated a small but measurable U isotope fractionation of ~0.10 ‰ during U(VI) incorporation into abiotic calcium carbonates, with 238U preferentially incorporated into the precipitates (Chen et al., 2016). The magnitude of U isotope fractionation depended on aqueous U speciation, which is controlled by water chemistry, including pH, ionic strength, carbonate, and Ca2+ and Mg2+ concentrations. Based on this speciation-dependent isotope fractionation model, the estimated U isotope fractionation in abiotic calcium carbonates induced by secular changes in seawater chemistry through the Phanerozoic was predicted to be 0.11–0.23 ‰. A smaller and variable U isotope fractionation (0–0.09 ‰) was observed in primary biogenic calcium carbonates, which fractionated U isotopes in the same direction as abiotic calcium carbonates. Early diagenesis of modern shallow-water carbonate sediments from the Bahamas shifted δ238U values to be 0.270.14 ‰ (1 SD) higher than contemporaneous seawater. Also, carbonate sediments deposited under anoxic conditions in a redox-stratified lake—Fayetteville Green Lake, New York, USA— exhibited elevated δ238U values by 0.160.12 ‰ (1 SD) relative to surface water carbonates with significant enrichments in U.

The significant U isotope fractionation observed in these studies suggests the need to correct for the U isotopic offset between carbonate sediments and coeval seawater when using δ238U variations in ancient carbonate rocks to reconstruct changes in ocean anoxia. The U isotope fractionation in abiotic and biogenic primary carbonate precipitates, during carbonate diagenesis, and under anoxic depositional environments provide a preliminary guideline to calibrate 238U/235U in sedimentary carbonate rocks as a paleoredox proxy.
ContributorsChen, Xinming (Author) / Anbar, Ariel D (Thesis advisor) / Williams, Lynda B (Committee member) / Sharp, Thomas (Committee member) / Hervig, Richard (Committee member) / Romaniello, Stephen (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Oxygen fugacity (ƒO2) is a thermodynamic variable used to represent the redox state of a material or a system. It is equivalent to the partial pressure of oxygen in a particular environment corrected for the non-ideal behavior of the gas. ƒO2 is often used to indicate the potential for iron

Oxygen fugacity (ƒO2) is a thermodynamic variable used to represent the redox state of a material or a system. It is equivalent to the partial pressure of oxygen in a particular environment corrected for the non-ideal behavior of the gas. ƒO2 is often used to indicate the potential for iron to occur in a more oxidized or reduced state at a particular temperature and pressure in a natural system. Secondary ion mass spectrometry (SIMS) is a powerful analytical instrument that can be used to analyze elemental and isotopic compositional information about microscopic features within solid materials. SIMS analyses of the secondary ion energy distribution of semi-pure metals demonstrate that the energy spectrum of individual mass lines can provide information about alterations in its surface environment.

The application of high-resolution (see Appendix C) energy spectrum calibrations to natural ilmenite led to the investigation of zirconium (90Zr+) and niobium (93Nb+) as potential indicators of sample ƒO2. Energy spectrum measurements were performed on an array of ilmenite crystals from the earth’s upper mantle retrieved from kimberlites and from a reduced meteorite. In all studied materials, variability in the peak shape and width of the energy spectra has been correlated with inferred sample ƒO2. The best descriptor of this relationship is the full-width at half-maximum (FWHM; see Appendix C) of the energy spectra for each sample. It has been estimated that a 1eV change in the FWHM of 93Nb+ energy spectra is roughly equivalent to 1 log unit ƒO2. Simple estimates of precision suggest the FWHM values can be trusted to  1eV and sample ƒO2 can be predicted to ±1 log unit, assuming the temperature of formation is known.

The work of this thesis also explores the applicability of this technique beyond analysis of semi-pure metals and ilmenite crystals from kimberlites. This technique was applied to titanium oxides experimentally formed at known ƒO2 as well as an ilmenite crystal that showed compositional variations across the grain (i.e., core to rim chemical variations). Analyses of titanium oxides formed at known ƒO2 agree with the estimation that 1 eV change in the FWHM of 93Nb+ is equivalent to ~1 log unit ƒO2 (in all cases but one); this is also true for analyses of a natural ilmenite crystal with compositional variations across the grain.
ContributorsDillon, Sarah Marie (Author) / Hervig, Richard L (Thesis advisor) / Shim, Sang-Heon (Committee member) / Williams, Peter (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Hydrogen isotope compositions of the martian atmosphere and crustal materials can provide unique insights into the hydrological and geological evolution of Mars. While the present-day deuterium-to-hydrogen ratio (D/H) of the Mars atmosphere is well constrained (~6 times that of terrestrial ocean water), that of its deep silicate interior (specifically, the

Hydrogen isotope compositions of the martian atmosphere and crustal materials can provide unique insights into the hydrological and geological evolution of Mars. While the present-day deuterium-to-hydrogen ratio (D/H) of the Mars atmosphere is well constrained (~6 times that of terrestrial ocean water), that of its deep silicate interior (specifically, the mantle) is less so. In fact, the hydrogen isotope composition of the primordial martian mantle is of great interest since it has implications for the origin and abundance of water on that planet. Martian meteorites could provide key constraints in this regard, since they crystallized from melts originating from the martian mantle and contain phases that potentially record the evolution of the H2O content and isotopic composition of the interior of the planet over time. Examined here are the hydrogen isotopic compositions of Nominally Anhydrous Phases (NAPs) in eight martian meteorites (five shergottites and three nakhlites) using Secondary Ion Mass Spectrometry (SIMS).

This study presents a total of 113 individual analyses of H2O contents and hydrogen isotopic compositions of NAPs in the shergottites Zagami, Los Angeles, QUE 94201, SaU 005, and Tissint, and the nakhlites Nakhla, Lafayette, and Yamato 000593. The hydrogen isotopic variation between and within meteorites may be due to one or more processes including: interaction with the martian atmosphere, magmatic degassing, subsolidus alteration (including shock), and/or terrestrial contamination. Taking into consideration the effects of these processes, the hydrogen isotope composition of the martian mantle may be similar to that of the Earth. Additionally, this study calculated upper limits on the H2O contents of the shergottite and nakhlite parent melts based on the measured minimum H2O abundances in their maskelynites and pyroxenes, respectively. These calculations, along with some petrogenetic assumptions based on previous studies, were subsequently used to infer the H2O contents of the mantle source reservoirs of the depleted shergottites (200-700 ppm) and the nakhlites (10-100 ppm). This suggests that mantle source of the nakhlites is systematically drier than that of the depleted shergottites, and the upper mantle of Mars may have preserved significant heterogeneity in its H2O content. Additionally, this range of H2O contents is not dissimilar to the range observed for the Earth’s upper mantle.
ContributorsTucker, Kera (Author) / Wadhwa, Meenakshi (Thesis advisor) / Hervig, Richard (Committee member) / Till, Christy (Committee member) / Arizona State University (Publisher)
Created2015
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Description
Volcanic devolatilization is one of the major processes in the global nitrogen cycle. Past studies have often estimated the magnitude of this flux using volcanic emission measurements, which are limited to currently active systems and sensitive to atmospheric contamination. A different methodological approach requires appropriate analytical parameters for nitrogen analysis

Volcanic devolatilization is one of the major processes in the global nitrogen cycle. Past studies have often estimated the magnitude of this flux using volcanic emission measurements, which are limited to currently active systems and sensitive to atmospheric contamination. A different methodological approach requires appropriate analytical parameters for nitrogen analysis in silicate glasses by secondary ion mass spectrometry (SIMS), which have not yet been established. To this end, we analyze various ion implanted basaltic and rhyolitic glasses by SIMS. We demonstrate that water content significantly affects the ion yields of 14N+ and 14N16O−, as well as the background intensity of 14N+ and 12C+. Application of implant-derived calibrations to natural samples provide the first reported concentrations of nitrogen in melt inclusions. These measurements are from samples from the Bishop Tuff in California, the Huckleberry Ridge Tuff of the Yellowstone Volcanic Center, and material from the Okaia and Oruanui eruptions in the Taupo Volcanic Center. In all studied material, we find maximum nitrogen contents of less than 45 ppm and that nitrogen concentration varies positively with CO2 concentration, which is interpreted to reflect partial degassing trend. Using the maximum measured nitrogen contents for each eruption, we find that the Bishop released >3.6 x 1013 g of nitrogen, the Huckleberry Ridge released >1.3 x 1014 g, the Okaia released >1.1 x 1011 g of nitrogen, the Oruanui released >4.7 x 1013 g of nitrogen. Simple calculations suggest that with concentrations such as these, rhyolitic eruptions may ephemerally increase the nitrogen flux to the atmosphere, but are insignificant compared to the 4 x 1021 g of nitrogen stored in the atmosphere.
ContributorsRegier, Margo Elaine (Author) / Hervig, Richard L (Thesis advisor) / Roggensack, Kurt (Committee member) / Till, Christy B. (Committee member) / Arizona State University (Publisher)
Created2016