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- Genre: Masters Thesis
- Member of: ASU Electronic Theses and Dissertations
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 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
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
Description
Volcanoes can experience multiple eruption styles throughout their eruptive histories. Among the most complex and most common are eruptions of intermediate explosivity, such as Vulcanian and sub-Plinian eruptions. Vulcanian eruptions are characterized by small-scale, short-lived, ash-rich eruptions initiated by the failure of a dense magma plug or overlying dome that had sealed an overpressured conduit. Sub-Plinian eruptions are characterized by sustained columns that reach tens of kilometers in height.
Multiple eruption styles can be observed in a single eruptive sequence. In recent decades, transitions in eruption style during well-documented eruptions have been described in detail, with some workers proposing explanatory mechanisms for the transitions. These proposed mechanisms may be broadly classified into processes at depth, processes in the conduit, or some combination of both.
The present study is focused on the Pietre Cotte sequence because it may have encompassed up to three different eruptive cycles, each representing different degrees of explosivity. The first deposits are composed of repeated layers of fine ash and lapilli composed of latite and rhyolite endmembers, efficiently mixed at sub-cm scales. The thin layers and bubble/crystal textures indicate that the magma underwent numerous decompressions and open-system degassing, and that the eruptions waned with time. The second phase of the sequence appears to have been initiated by cm-scale mixing between a volatile-rich, mafic magma from deeper in the system and a shallow silicic body. Textures indicate that the magma ascended rapidly and experienced little to no open-system degassing. The final phase of the sequence again produced repeated layers of fine ash and lapilli, of uniform trachyte composition, and waned with time. The first and last phases were likely produced in Vulcanian eruptions, while the pumice-rich layers were likely produced in Vulcanian to sub-Plinian eruptions.
In summary, the Pietre Cotte sequence is characterized by up to three magma recharge events in ~200 years. The differences in eruptive style appear to have been controlled by variations in the volatile content of the recharge magma, as well as the efficiency and scale of magma mixing and resulting overpressures.
Multiple eruption styles can be observed in a single eruptive sequence. In recent decades, transitions in eruption style during well-documented eruptions have been described in detail, with some workers proposing explanatory mechanisms for the transitions. These proposed mechanisms may be broadly classified into processes at depth, processes in the conduit, or some combination of both.
The present study is focused on the Pietre Cotte sequence because it may have encompassed up to three different eruptive cycles, each representing different degrees of explosivity. The first deposits are composed of repeated layers of fine ash and lapilli composed of latite and rhyolite endmembers, efficiently mixed at sub-cm scales. The thin layers and bubble/crystal textures indicate that the magma underwent numerous decompressions and open-system degassing, and that the eruptions waned with time. The second phase of the sequence appears to have been initiated by cm-scale mixing between a volatile-rich, mafic magma from deeper in the system and a shallow silicic body. Textures indicate that the magma ascended rapidly and experienced little to no open-system degassing. The final phase of the sequence again produced repeated layers of fine ash and lapilli, of uniform trachyte composition, and waned with time. The first and last phases were likely produced in Vulcanian eruptions, while the pumice-rich layers were likely produced in Vulcanian to sub-Plinian eruptions.
In summary, the Pietre Cotte sequence is characterized by up to three magma recharge events in ~200 years. The differences in eruptive style appear to have been controlled by variations in the volatile content of the recharge magma, as well as the efficiency and scale of magma mixing and resulting overpressures.
ContributorsKim, Jisoo (Author) / Clarke, Amanda B (Thesis advisor) / Roggensack, Kurt (Thesis advisor) / Barboni, Melanie (Committee member) / Arizona State University (Publisher)
Created2020
Description
A novel technique for measuring heavy trace elements in geologic materials with secondary ion mass spectrometry (SIMS) is presented. This technique combines moderate levels of mass resolving power (MRP) with energy filtering in order to remove molecular ion interferences while maintaining enough sensitivity to measure trace elements. The technique was evaluated by measuring a set of heavy chalcophilic elements in two sets of doped glasses similar in composition to rhyolites and basalts, respectively. The normalized count rates of Cu, As, Se, Br, and Te were plotted against concentrations to test that the signal increased linearly with concentration. The signal from any residual molecular ion interferences (e.g. ²⁹Si³⁰Si¹⁶O on ⁷⁵As) represented apparent concentrations ≤ 1 μg/g for most of the chalcophiles in rhyolitic matrices and between 1 and 10 μg/g in basaltic compositions. This technique was then applied to two suites of melt inclusions from the Bandelier Tuff: Ti-rich, primitive and Ti-poor, evolved rhyolitic compositions. The results showed that Ti-rich inclusions contained ~30 μg/g Cu and ~3 μg/g As while the Ti-poor inclusions contained near background Cu and ~6 μg/g As. Additionally, two of the Ti-rich inclusions contained > 5 μg/g of Sb and Te, well above background. Other elements were at or near background. This suggests certain chalcophilic elements may be helpful in unraveling processes relating to diversity of magma sources in large eruptions. Additionally, an unrelated experiment is presented demonstrating changes in the matrix effect on SIMS counts when normalizing against ³⁰Si⁺ versus ²⁸Si²⁺. If one uses doubly charged silicon as a reference, (common when using large-geometry SIMS instruments to study the light elements Li - C) it is important that the standards closely match the major element chemistry of the unknown.
ContributorsCarlson, Eric Norton (Author) / Hervig, Richard L (Thesis advisor) / Roggensack, Kurt (Committee member) / Burt, Donald M (Committee member) / Arizona State University (Publisher)
Created2021
Description
Among the deadliest of explosive volcanic hazards are pyroclastic surges – fast-moving, hot, dilute ground-hugging currents that overtop topography and leave complex deposits. Understanding the link between surge dynamics and their deposits is crucial for forecasting the impacts of future eruptions. To investigate surges, two sets of scaled laboratory experiments were conducted. Set 1 released fluid pulses into less-dense ambient water (3-m flume). Pulse fluids were saline solutions with and without particles, and alcohol-water-particle mixtures. Non-dimensional numbers are calculated using both input parameters and measured outcomes. Inputs - fluid density, particle size and concentration, and volume of fluid released - were varied to explore a range of conditions. Key output parameters obtained by video analysis are flow thickness and propagation velocity. Propagation velocity, Re, and Ri increased with increasing pulse density, while Pn decreased. Lab Re values indicate fully turbulent flows, consistent with natural flows. Lab Ri closely matched nature and flow propagation was largely controlled by negative buoyancy, with entrainment playing a minor role. All flows began as subcritical (Fr<1). Alcohol-water-particle runs exhibited buoyancy reversals caused by particle sedimentation, characterized by gradual deceleration and late-stage formation of buoyant plumes. Saline runs maintained nearly constant velocities. In the second set of experiments, alcohol-water-particle mixtures were pulsed over particle bed. Various substrate topographies were tested (flat, mound-trough sequences, steps, wedges). Deposits thickened in troughs and thinned on peaks. Progressive climbing dunes formed on the lee side of the second peak of double peaks and peak-trough combinations, and in step-up topographies. Regressive climbing dunes formed on the stoss side of the first peak of peak-trough combinations and step-down topographies, and on the stoss side of mounds. Climb angles were 16 to 36°, consistent with those documented in pyroclastic surge deposits. The occurrence of both regressive and progressive climbing dunes suggests localized transitions between subcritical and supercritical flow. No cross-beds formed on flat substrates, suggesting that complex substrate topography is required for bedforms to occur in nature. A code benchmarking effort is underway in which targeted model runs will be compared to both sets of experiments in order to develop comprehensive hazards prediction tool.
ContributorsRagavan, Rupa (Author) / Clarke, Amanda (Thesis advisor) / Semken, Steven (Committee member) / Roggensack, Kurt (Committee member) / de'Michieli Vitturi, Mattia (Committee member) / Arizona State University (Publisher)
Created2023