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- All Subjects: Geochemistry
- Genre: Academic theses
- Genre: Masters Thesis
- Creators: Wadhwa, Meenakshi
- Creators: Hervig, Richard L
- Member of: ASU Electronic Theses and Dissertations
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 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
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 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
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 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
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 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
Description
Molybdenum and uranium isotope variations are potentially powerful tools for reconstructing the paleoredox history of seawater. Reliable application and interpretation of these proxies requires not only detailed knowledge about the fractionation factors that control the distribution of molybdenum and uranium isotopes in the marine system, but also a thorough understanding of the diagenetic processes that may affect molybdenum and uranium isotopes entering the rock record. Using samples from the Black Sea water column, the first water column profile of 238U/235U variations from a modern euxinic basin has been measured. This profile allows the direct determination of the 238U/235U fractionation factor in a euxinic marine setting. More importantly however, these data demonstrate the extent of Rayleigh fractionation of U isotopes that can occur in euxinic restricted basins. Because of this effect, the offset of 238U/235U between global average seawater and coeval black shales deposited in restricted basins is expected to depend on the degree of local uranium drawdown from the water column, potentially complicating the interpretation 238U/235U paleorecords. As an alternative to the black shales typically used for paleoredox reconstructions, molybdenum and uranium isotope variations in bulk carbonate sediments from the Bahamas are examined. The focus of this work was to determine what processes, if any, fractionate molybdenum and uranium isotopes during incorporation into bulk carbonate sediments and their subsequent diagenesis. The results demonstrate that authigenic accumulation of molybdenum and uranium from anoxic and sulfidic pore waters is a dominant process controlling the concentration and isotopic composition of these sediments during early diagenesis. Examination of ODP drill core samples from the Bahamas reveals similar behavior for sediments during the first ~780ka of burial, but provides important examples where isolated cores and samples occasionally demonstrate additional fractionation, the cause of which remains poorly understood.
ContributorsRomaniello, Stephen J. (Author) / Anbar, Ariel (Thesis advisor) / Hartnett, Hilairy (Committee member) / Herrmann, Achim (Committee member) / Shock, Everett (Committee member) / Wadhwa, Meenakshi (Committee member) / Arizona State University (Publisher)
Created2012
Description
The isotopic compositions of meteorites provide valuable insights into the earliest history of the Solar System and, in some cases, provide constraints on presolar components that contributed to the solar nebula. In the past decade or so, mass-independent isotope anomalies in titanium have become particularly important geochemical tracers to study the distinct isotopic reservoirs in the early Solar System. In particular, mass-independent anomalies in the most neutron-rich isotope of titanium (50Ti) have been used to distinguish between carbonaceous chondritic (CC) and non-carbonaceous chondritic (NC) materials. These two groupings likely represent distinct isotopic reservoirs in the inner (NC) and outer (CC) Solar System. However, while the titanium isotope compositions of CC and NC materials are distinct, each group's full range of compositional variability is poorly characterized. For example, only one CK carbonaceous chondrite group member has been analyzed thus far for its bulk Ti isotope composition. This work aims to characterize better the range of mass-independent Ti isotope compositions within and among the carbonaceous chondrites, which has implications for the degree and potential sources of Ti isotope heterogeneity in the early Solar System. Methods utilized in this study include column chromatography to purify Ti and high-precision multi-collector inductively coupled plasma mass spectrometry for measuring Ti isotope compositions. The Ti isotope compositions of bulk samples of nine carbonaceous chondrites are reported here. In addition, the bulk fractions of the meteorites used in this study were taken from homogenized powders of relatively large (~200 mg each) samples. This was done to assess whether variability in mass-independent Ti isotope compositions previously reported within some meteorites could be a sampling artifact.
Results from this work show that the various CM2 chondrites and ungrouped carbonaceous chondrites have ε50Ti values that are similar, suggesting that the Ti in these samples was likely sourced from a common isotopic reservoir. On the other hand, the ε50Ti values reported for CI1 and CH/CBb bulk samples suggest that the parent bodies of these carbonaceous chondrite groups were formed in isotopic reservoir(s) distinct from that of the other CC groups in the early Solar System.
ContributorsPhelan, Nicole Danielle (Author) / Wadhwa, Meenakshi (Thesis advisor) / Young, Patrick (Committee member) / Nittler, Larry R. (Committee member) / Arizona State University (Publisher)
Created2023
Description
Studying natural variations in the isotopic composition of oxygen-sensitive elements in ancient marine sediments is a powerful way to study the geochemical evolution of Earth’s environments in the past. My dissertation focused on two broad aspects of isotope geochemistry: 1) the development of rhenium (Re) isotopes as a paleoredox and nuclear forensics tool, and 2) the application of mercury (Hg) isotopes as a tool to trace Hg mobility in the environment and what this movement means for isotopic changes in sedimentary rocks used to study Earth’s past. Chapter 2 is the first examination of Re isotopes in sedimentary rocks that formed ~2.5 billion years ago during a period of ocean and atmospheric oxygenation prior to the Great Oxidation Event. The data show variations in Re isotope ratios coincide with evidence for changes in oceanic and atmospheric oxygenation, supporting the use of Re isotopes as a tool to track paleoredox conditions throughout Earth's history. Another application of rhenium isotopes is explored in the third chapter on nuclear forensics. Rhenium isotopes in uranium ore concentrates (UOC) from known production locations revealed more than double the range of isotope fractionation previously reported for any natural geologic samples so far. These first Re isotope ratio data indicate that Re is a promising new tool for provenance assessment of UOCs. Chapter 4 focuses on geochemical applications of Hg isotopes. Mercury isotopes in shales are a geochemical tool that can be utilized to study the prevalence of global volcanism and detect oxygen-depleted conditions in the photic zone of ancient oceans. I measured Hg isotope ratio data from a Devonian shale bed in a road cut with varying degrees of weathering that has been well characterized for variations in elemental concentrations and other isotopic ratios. I found significant variation in mass-dependent and mass-independent Hg isotope fractionation in weathered samples. Surprisingly, however, I observed both loss and gain of Hg, when only significant loss was expected based on prior weathering studies. These findings improve the understanding of Hg mobility in nature and indicate that mass-independent fractionation can be modified after deposition in surprising ways.
ContributorsSullivan, Daniel Louis (Author) / Anbar, Ariel D (Thesis advisor) / Gordon, Gwyneth W (Committee member) / Hartnett, Hilairy E (Committee member) / Hervig, Richard L (Committee member) / Zheng, Wang (Committee member) / Arizona State University (Publisher)
Created2023
Description
There is a growing body of evidence that the evolving redox structure of the oceans has been an important influence on the evolutionary trajectory of animals. However, current understanding of connections between marine redox conditions and marine extinctions and recoveries is hampered by limited detailed knowledge of the timing, duration, and extent of marine redox changes.
The recent development of U isotopes (δ238U) in carbonates as a global ocean redox proxy has provided new insight into this problem. Reliable application and interpretation of the δ238U paleoproxy in geological records requires a thorough understanding of the reliability of δ238U recorded by bulk carbonate sediments. In this dissertation, I evaluate the robustness of δ238U paleoproxy by examining δ238U variations in marine carbonates across Permian-Triassic boundary (PTB) sections from different paleogeographic locations. Close agreement of δ238U profiles from coeval carbonate sections thousands of kilometers apart, in different ocean basins, and with different diagenetic histories, strongly suggests that bulk carbonate sediments can reliably preserve primary marine δ238U signals, validating the carbonate U-isotope proxy for global-ocean redox analysis.
To improve understanding of the role of marine redox in shaping the evolutionary trajectory of animals, high-resolution δ238U records were generated across several key evolutionary periods, including the Ediacaran-to-Early Cambrian Explosion of complex life (635-541 Ma) and the delayed Early Triassic Earth system recovery from the PTB extinction (252-246 Ma). Based on U isotope variations in the Ediacaran-to-the Early Cambrian ocean, the initial diversification of the Ediacara biota immediately postdates an episode of pervasive ocean oxygenation across the Shuram event. The subsequent decline and extinction of the Ediacara biota is coincident with an episode of extensive anoxic conditions during the latest Ediacaran Period. These findings suggest that global marine redox changes drove the rise and fall of the Ediacara biota. Based on U isotope variations, the Early Triassic ocean was characterized by multiple episodes of extensive marine anoxia. By comparing the high-resolution δ238U record with the sub-stage ammonoid extinction rate curve, it appears that multiple oscillations in marine anoxia modulated the recovery of marine ecosystems following the latest Permian mass extinction.
The recent development of U isotopes (δ238U) in carbonates as a global ocean redox proxy has provided new insight into this problem. Reliable application and interpretation of the δ238U paleoproxy in geological records requires a thorough understanding of the reliability of δ238U recorded by bulk carbonate sediments. In this dissertation, I evaluate the robustness of δ238U paleoproxy by examining δ238U variations in marine carbonates across Permian-Triassic boundary (PTB) sections from different paleogeographic locations. Close agreement of δ238U profiles from coeval carbonate sections thousands of kilometers apart, in different ocean basins, and with different diagenetic histories, strongly suggests that bulk carbonate sediments can reliably preserve primary marine δ238U signals, validating the carbonate U-isotope proxy for global-ocean redox analysis.
To improve understanding of the role of marine redox in shaping the evolutionary trajectory of animals, high-resolution δ238U records were generated across several key evolutionary periods, including the Ediacaran-to-Early Cambrian Explosion of complex life (635-541 Ma) and the delayed Early Triassic Earth system recovery from the PTB extinction (252-246 Ma). Based on U isotope variations in the Ediacaran-to-the Early Cambrian ocean, the initial diversification of the Ediacara biota immediately postdates an episode of pervasive ocean oxygenation across the Shuram event. The subsequent decline and extinction of the Ediacara biota is coincident with an episode of extensive anoxic conditions during the latest Ediacaran Period. These findings suggest that global marine redox changes drove the rise and fall of the Ediacara biota. Based on U isotope variations, the Early Triassic ocean was characterized by multiple episodes of extensive marine anoxia. By comparing the high-resolution δ238U record with the sub-stage ammonoid extinction rate curve, it appears that multiple oscillations in marine anoxia modulated the recovery of marine ecosystems following the latest Permian mass extinction.
ContributorsZhang, Feifei (Author) / Anbar, Ariel (Thesis advisor) / Gordon, Gwyneth (Committee member) / Hartnett, Hilairy (Committee member) / Wadhwa, Meenakshi (Committee member) / Ruff, Steven (Committee member) / Arizona State University (Publisher)
Created2018
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 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.
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
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 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