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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
Description
Earthquake faulting and the dynamics of subducting lithosphere are among the frontiers of geophysics. Exploring the nature, cause, and implications of geophysical phenomena requires multidisciplinary investigations focused at a range of spatial scales. Within this dissertation, I present studies of micro-scale processes using observational seismology and experimental mineral physics to

Earthquake faulting and the dynamics of subducting lithosphere are among the frontiers of geophysics. Exploring the nature, cause, and implications of geophysical phenomena requires multidisciplinary investigations focused at a range of spatial scales. Within this dissertation, I present studies of micro-scale processes using observational seismology and experimental mineral physics to provide important constraints on models for a range of large-scale geophysical phenomena within the crust and mantle.

The Great Basin (GB) in the western U.S. is part of the diffuse North American-Pacific plate boundary. The interior of the GB occasionally produces large earthquakes, yet the current distribution of regional seismic networks poorly samples it. The EarthScope USArray Transportable Array provides unprecedented station density and data quality for the central GB. I use this dataset to develop an earthquake catalog for the region that is complete to M 1.5. The catalog contains small-magnitude seismicity throughout the interior of the GB. The spatial distribution of earthquakes is consistent with recent regional geodetic studies, confirming that the interior of the GB is actively deforming everywhere and all the time. Additionally, improved event detection thresholds reveal that swarms of temporally-clustered repeating earthquakes occur throughout the GB. The swarms are not associated with active volcanism or other swarm triggering mechanisms, and therefore, may represent a common fault behavior.

Enstatite (Mg,Fe)SiO3 is the second most abundant mineral within subducting lithosphere. Previous studies suggest that metastable enstatite within subducting slabs may persist to the base of the mantle transition zone (MTZ) before transforming to high-pressure polymorphs. The metastable persistence of enstatite has been proposed as a potential cause for both deep-focus earthquakes and the stagnation of slabs at the base of the MTZ. I show that natural Al- and Fe-bearing enstatite reacts more readily than previous studies and by multiple transformation mechanisms at conditions as low as 1200°C and 18 GPa. Metastable enstatite is thus unlikely to survive to the base of the MTZ. Additionally, coherent growth of akimotoite and other high-pressure phases along polysynthetic twin boundaries provides a mechanism for the inheritance of crystallographic preferred orientation from previously deformed enstatite-bearing rocks within subducting slabs.
ContributorsLockridge, Jeffrey Steven (Author) / Sharp, Thomas (Thesis advisor) / Arrowsmith, Ramon (Thesis advisor) / Shim, Sang-Heon (Committee member) / Garnero, Edward (Committee member) / Leinenweber, Kurt (Committee member) / Arizona State University (Publisher)
Created2015
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Description
The present work covers two distinct microanalytical studies that address issues in planetary materials: (1) Genesis Na and K solar wind (SW) measurements, and (2) the effect of water on high-pressure olivine phase transformations.

NASA’s Genesis mission collected SW samples for terrestrial analysis to create a baseline of solar chemical abundances

The present work covers two distinct microanalytical studies that address issues in planetary materials: (1) Genesis Na and K solar wind (SW) measurements, and (2) the effect of water on high-pressure olivine phase transformations.

NASA’s Genesis mission collected SW samples for terrestrial analysis to create a baseline of solar chemical abundances based on direct measurement of solar material. Traditionally, solar abundances are estimated using spectroscopic or meteoritic data. This study measured bulk SW Na and K in two different Genesis SW collector materials (diamond-like carbon (DlC) and silicon) for comparison with these other solar references. Novel techniques were developed for Genesis DlC analysis. Solar wind Na fluence measurements derived from backside depth profiling are generally lower in DlC than Si, despite the use of internal standards. Nevertheless, relative to Mg, the average SW Na and K abundances measured in Genesis wafers are in agreement with solar photospheric and CI chondrite abundances, and with other SW elements with low first ionization potential (within error). The average Genesis SW Na and K fluences are 1.01e11 (+9e09, -2e10) atoms/cm2 and 5.1e09 (+8e08, -8e08) atoms/cm2, respectively. The errors reflect average systematic errors. Results have implications for (1) SW formation models, (2) cosmochemistry based on solar material rather than photospheric measurements or meteorites, and (3) the accurate measurement of solar wind ion abundances in Genesis collectors, particularly DlC and Si.

Deep focus earthquakes have been attributed to rapid transformation of metastable olivine within the mantle transition zone (MTZ). However, the presence of H2O acts to overcome metastability, promoting phase transformation in olivine, so olivine must be relatively anhydrous (<75 ppmw) to remain metastable to depth. A microtextural analysis of olivine phase transformation products was conducted to test the feasibility for subducting olivine to persist metastably to the MTZ. Transformation (as intracrystalline or rim nucleation) shifts from ringwoodite to ringwoodite-wadsleyite nucleation with decreasing H2O content within olivine grains. To provide accurate predictions for olivine metastability at depth, olivine transformation models must reflect how changing H2O distributions lead to complex changes in strain and reaction rates within different parts of a transforming olivine grain.
ContributorsRieck, Karen Dianne (Author) / Hervig, Richard L (Thesis advisor) / Sharp, Thomas G (Thesis advisor) / Jurewicz, Amy J G (Committee member) / Wadhwa, Meenakshi (Committee member) / Williams, Peter (Committee member) / Young, Patrick A (Committee member) / Arizona State University (Publisher)
Created2015
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Description
Shock metamorphism in meteorites constrains the impact histories of asteroids and planets. Shock-induced high-pressure (HP) minerals can provide more precise estimates of shock conditions than shock-induced deformation effects. In this research, I use shock features, particularly HP minerals, in ordinary-chondrite samples to constrain not only shock pressures but also the

Shock metamorphism in meteorites constrains the impact histories of asteroids and planets. Shock-induced high-pressure (HP) minerals can provide more precise estimates of shock conditions than shock-induced deformation effects. In this research, I use shock features, particularly HP minerals, in ordinary-chondrite samples to constrain not only shock pressures but also the pressure-temperature-time (P-T-t) paths they experienced.

Highly shocked L5/6 chondrites Acfer 040, Mbale, NWA 091 and Chico and LL6 chondrite NWA 757 were used to investigate a variety of shock pressures and post-shock annealing histories. NWA 757 is the only highly shocked LL chondrite that includes abundant HP minerals. The assemblage of ringwoodite and majoritic garnet indicates an equilibration shock pressure of ~20 GPa, similar to many strongly shocked L chondrites. Acfer 040 is one of the only two chondrite samples with bridgmanite (silicate perovskite), suggesting equilibration pressure >25 GPa. The bridgmanite, which is unstable at low-pressure, was mostly vitrified during post-shock cooling. Mbale demonstrates an example of elevated post-shock temperature resulting in back-transformation of ringwoodite to olivine. In contrast, majoritic garnet in Mbale survives as unambiguous evidence of strong shock. In these two samples, HP minerals are exclusively associated with shock melt, indicating that elevated shock temperatures are required for rapid mineral transformations during the transient shock pulse. However, elevated post-shock temperatures can destroy HP minerals: in temperature sequence from bridgmanite to ringwoodite then garnet. NWA 091 and Chico are impact melt breccias with pervasive melting, blackening of silicates, recrystallization of host rock but no HP minerals. These features indicate near whole-rock-melting conditions. However, the elevated post-shock temperatures of these samples has annealed out HP signatures. The observed shock features result from a complex P-T-t path and may not directly reflect the peak shock pressure. Although HP minerals provide robust evidence of high pressure, their occurrence also requires high shock temperatures and rapid cooling during the shock pulse. The most highly shocked samples lack HP signatures but have abundant high-temperature features formed after pressure release.
ContributorsHu, Jinping (Author) / Sharp, Thomas G. (Thesis advisor) / Tyburczy, James A. (Committee member) / Leinenweber, Kurt (Committee member) / Wadhwa, Meenakshi (Committee member) / Zolotov, Mikhail (Committee member) / Arizona State University (Publisher)
Created2016
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Description
The redox conditions of Earth have been changing since proto-Earth’s accretion from the solar nebula. These changes have influenced the distribution and partitioning of volatile elements between the atmosphere and the mantle (Righter et al., 2020; Stagno and Fei, 2020. Though oxygen fugacity fO2 is arguably not the main

The redox conditions of Earth have been changing since proto-Earth’s accretion from the solar nebula. These changes have influenced the distribution and partitioning of volatile elements between the atmosphere and the mantle (Righter et al., 2020; Stagno and Fei, 2020. Though oxygen fugacity fO2 is arguably not the main factor for phase stability at certain pressure-temperature conditions (McCammon, 2005), it can influence which phases are stable, especially within a closed system such as the ones presented in this study. Despite the importance of controlling fO2 for interpreting the history of planetary bodies, there have been no methods to control the redox conditions in the laser-heated diamond anvil cell (LHDAC). This thesis has examined the feasibility for controlling redox conditions in the LHDAC using a mixture of Ar and H2 for insulation media. The experiments of this study were carried out at the GSECARS sector of the Advanced Photon Source at Argonne National Laboratory. In this study, α-Fe2O3 (hematite), ε-FeOOH (CaCl2-type), and Fe3O4 (magnetite) starting materials were used for probing changes of redox conditions. Experiments were also conducted with a pure Ar-medium for ε-FeOOH at the same pressure-temperature conditions of the hydrogen-bearing medium in order to provide a reference point for data which has uncontrolled redox conditions for an initially Fe(2+)-free material. The results for the ε-FeOOH starting material in Ar show transformation to ι-Fe2O3 (Rh2O3(II)-type) at 30.0 GPa and 1900 K, while in Ar + H2 it transformed to Fe5O7 with minor FeH (dhcp) at 30.0 GPa and 1850 K. For α-Fe2O3 in Ar + H2, it was found to convert to ε-FeOOH, Fe5O7, Fe5O6, and FeH (dhcp) at 36.5 GPa and 1800 K. For Fe3O4 in Ar + H2, it was found to convert to Fe4O5 (CaFe3O5-type), Fe5O6, and minor FeH (fcc) at 26.0 GPa and 1800 K. These results demonstrate that H in an Ar medium can promote the conversion of some Fe(3+) to Fe(2+) and Fe(0). However, the formation of ε-FeOOH in the α-Fe2O3 starting material suggests that H may participate in the chemical reaction of iron oxides.
ContributorsKulka, Britany Lynn (Author) / Shim, Sang-Heon (Thesis advisor) / Sharp, Thomas (Committee member) / Leinenweber, Kurt (Committee member) / Hervig, Richard (Committee member) / Arizona State University (Publisher)
Created2021
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Description
The mineralogy of the deep mantle is one of the key factors for the chemical evolution of the Earth. The constituent minerals of the mantle rock control the physical properties of the mantle, which have significant impacts on the large-scale processes occurring in the Earth's interior. In my PhD research,

The mineralogy of the deep mantle is one of the key factors for the chemical evolution of the Earth. The constituent minerals of the mantle rock control the physical properties of the mantle, which have significant impacts on the large-scale processes occurring in the Earth's interior. In my PhD research, I adopted experimental approaches to investigate the mineralogy and the physical properties of the Earth's materials in the deep mantle by using the diamond anvil cells (DACs) combined with in-situ X-ray diffraction techniques.

First, I found that Ca-bearing bridgmanite can be stable in the deeper part of the Earth's lower mantle where temperature is sufficiently high. The dissolution of calcium into bridgmanite can change the physical properties of the mantle, such as compressibility and viscosity. This study suggests a new mineralogical model for the lower mantle, which is composed of the two layers depending on whether calcium dissolves in bridgmanite or forms CaSiO3 perovskite as a separate phase.

Second, I investigated the mineralogy and density of the subducting materials in the Archean at the P-T conditions near 670 km-depth. The experiments suggest that the major phases of Archean volcanic crust is majoritic garnet and ringwoodite in the P-T conditions of the deep transition zone, which become bridgmanite with increasing pressure. The density model showed that Archean volcanic crust would have been denser than the surrounding mantle, promoting sinking into the lower mantle regardless of the style of the transportation in the Archean.

Lastly, I further investigated the mineralogies and densities of the ancient volcanic crusts for the Archean and Proterozoic at the P-T conditions of the lower mantle. The experiments suggest that the mineralogy of the ancient volcanic crusts is composed mostly of bridgmanite, which is systemically denser than the surrounding lower mantle. This implies that the ancient volcanic crusts would have accumulated at the base of the mantle because of their large density and thickness. Therefore, the distinctive chemistry of the ancient volcanic crusts from the surrounding mantle would have given a rise to the chemical heterogeneities in the region for billions of years.
ContributorsKo, Byeongkwan (Author) / Shim, Sang-Heon (Thesis advisor) / Garnero, Edward (Committee member) / Leinenweber, Kurt (Committee member) / Li, Mingming (Committee member) / Desch, Steven (Committee member) / Arizona State University (Publisher)
Created2020