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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
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
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
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
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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
Impact cratering has played a key role in the evolution of the solid surfaces of Solar System bodies. While much of Earth’s impact record has been erased, its Moon preserves an extensive history of bombardment. Quantifying the timing of lunar impact events is crucial to understanding how impacts have shaped

Impact cratering has played a key role in the evolution of the solid surfaces of Solar System bodies. While much of Earth’s impact record has been erased, its Moon preserves an extensive history of bombardment. Quantifying the timing of lunar impact events is crucial to understanding how impacts have shaped the evolution of early Earth, and provides the basis for estimating the ages of other cratered surfaces in the Solar System.

Many lunar impact melt rocks are complex mixtures of glassy and crystalline “melt” materials and inherited clasts of pre-impact minerals and rocks. If analyzed in bulk, these samples can yield complicated incremental release 40Ar/39Ar spectra, making it challenging to uniquely interpret impact ages. Here, I have used a combination of high-spatial resolution 40Ar/39Ar geochronology and thermal-kinetic modeling to gain new insights into the impact histories recorded by such lunar samples.

To compare my data to those of previous studies, I developed a software tool to account for differences in the decay, isotopic, and monitor age parameters used for different published 40Ar/39Ar datasets. Using an ultraviolet laser ablation microprobe (UVLAMP) system I selectively dated melt and clast components of impact melt rocks collected during the Apollo 16 and 17 missions. UVLAMP 40Ar/39Ar data for samples 77135, 60315, 61015, and 63355 show evidence of open-system behavior, and provide new insights into how to interpret some complexities of published incremental heating 40Ar/39Ar spectra. Samples 77115, 63525, 63549, and 65015 have relatively simple thermal histories, and UVLAMP 40Ar/39Ar data for the melt components of these rocks indicate the timing of impact events—spanning hundreds of millions of years—that influenced the Apollo 16 and 17 sites. My modeling and UVLAMP 40Ar/39Ar data for sample 73217 indicate that some impact melt rocks can quantitatively retain evidence for multiple melt-producing impact events, and imply that such polygenetic rocks should be regarded as high-value sampling opportunities during future exploration missions to cratered planetary surfaces. Collectively, my results complement previous incremental heating 40Ar/39Ar studies, and support interpretations that the Moon experienced a prolonged period of heavy bombardment early in its history.
ContributorsMercer, Cameron Mark (Author) / Hodges, Kip V (Thesis advisor) / Robinson, Mark S (Committee member) / Wadhwa, Meenakshi (Committee member) / Desch, Steven J (Committee member) / Hervig, Richard L (Committee member) / Arizona State University (Publisher)
Created2017
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Description
Establishing the timing of impact crater formation is essential to exploring the relationship between bolide impact and biological evolution, and constraining the tempo of planetary surface evolution. Unfortunately, precise and accurate impact geochronology can be challenging. Many of the rock products of impact (impactites) contain relict, pre-impact phases that may

Establishing the timing of impact crater formation is essential to exploring the relationship between bolide impact and biological evolution, and constraining the tempo of planetary surface evolution. Unfortunately, precise and accurate impact geochronology can be challenging. Many of the rock products of impact (impactites) contain relict, pre-impact phases that may have had their isotopic systematics completely reset during the impact event, only partially reset, or not reset at all. Of the many isotopic chronometers that have been used to date impactites, the U/Pb zircon chronometer (ZrnPb) seems least susceptible to post-impact disturbances, and ZrnPb dates are typically much more precise than those obtained using other chronometers. However, the ZrnPb system is so resistant to resetting that relict zircons in impactites often yield dates that reflect the igneous or metamorphic ages of the target rocks rather than the age of the impact itself. The present study was designed to answer a simple question: is there a straightforward sample collection and analysis strategy for high-accuracy ZrnPb dating of an impact structure if the impactites collected from it may contain inherited zircons? To study this, ZrnPb dates were determined for impactites from a single crater with a well-constrained impact age: the West Clearwater Lake impact structure, located at Lake Wiyâshâkimî, Québec, Canada.

The amount of ZrnPb resetting and the mechanisms responsible for resetting varied amongst the samples. Each sample characteristically contained either: newly crystallized zircons from the impact melt ("neocrystalline"), relict zircons ~50-100% reset, or, relict zircons ~0-50% reset. The variably reset relict zircons define a discordia line from ~2700 Ma to ~286 Ma – consistent with the ages of the target rock and the impact, respectively (Schmieder et al., 2015a; Simard, 2004). ZrnPb measurements from the neocrystalline zircons provided a new preferred impact age of 286.64 ± 0.35 Ma (2σ), a ~10x improvement in precision. The characteristics of the West Clearwater ZrnPb data vary between samples yet become easily interpretable as a whole, showing that efforts to measure robust, precise impact ages benefit from strategies that prioritize applying multiple analytical techniques to multiple types of impactite from the same crater.
ContributorsBrunner, Anna Elizabeth (Author) / Hodges, Kip V (Thesis advisor) / Barboni, Melanie (Committee member) / Van Soest, Matthijs C (Committee member) / Sharp, Thomas G (Committee member) / Arizona State University (Publisher)
Created2019
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Description
The hydrous alteration of ultramafic rocks, known as serpentinization, produces some of the most reduced (H2 >1 mmolal) and alkaline (pH >11) fluids on Earth. Serpentinization can proceed even at the low-temperature conditions (<50°C) characteristic of most of Earth’s continental aquifers, raising questions on the limits of life deep in

The hydrous alteration of ultramafic rocks, known as serpentinization, produces some of the most reduced (H2 >1 mmolal) and alkaline (pH >11) fluids on Earth. Serpentinization can proceed even at the low-temperature conditions (<50°C) characteristic of most of Earth’s continental aquifers, raising questions on the limits of life deep in the subsurface and the magnitude in the flux of reduced volatiles to the surface. In this work, I explored the compositions and consequences of fluids and volatiles found in three low-temperature serpentinizing environments: (1) active hyperalkaline springs in ophiolites, (2) modern shallow and deep peridotite aquifers, and (3) komatiitic aquifers during the Archean.

Around 140 fluids were sampled from the Oman ophiolite and analyzed for their compositions. Fluid compositions can be accounted for by thermodynamic simulations of reactions accompanying incipient to advanced stages of serpentinization, as well as by simulations of mass transport processes such as fluid mixing and mineral leaching. Thermodynamic calculations were also used to predict compositions of end-member fluids representative of the shallow and deep peridotite aquifers that were ultimately used to quantify energy available to various subsurface chemolithotrophs. Calculations showed that sufficient energy and power supply can be available to support deep-seated methanogens. An additional and a more diverse energy supply can be available when surfacing deep-seated fluids mix with shallow groundwater in discharge zones of the subsurface fluid pathway. Finally, the consequence of the evolving continental composition during the Archean for the global supply of H2 generated through komatiite serpentinization was quantified. Results show that the flux of serpentinization-generated H2 could have been a significant sink for O2 during most of the Archean. This O2 sink diminished greatly towards the end of the Archean as komatiites became less common and helped set the stage for the Great Oxidation Event. Overall, this study provides a framework for exploring the origins of fluid and volatile compositions, including their redox state, that can result from various low-temperature serpentinizing environments in the present and past Earth and in other rocky bodies in the solar system.
ContributorsLeong, James Andrew (Author) / Shock, Everett L (Thesis advisor) / Anbar, Ariel D (Committee member) / Hartnett, Hilairy E (Committee member) / Sharp, Thomas G (Committee member) / Till, Christy B. (Committee member) / Arizona State University (Publisher)
Created2020
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Description
My dissertation research broadly focuses on the geochemical and physical exchange of materials between the Earth’s crust and mantle at convergent margins, and how this drives the compositional diversity observed on the Earth’s surface. I combine traditional petrologic and geochemical studies of natural and experimental high-pressure mafic rocks, with thermodynamic

My dissertation research broadly focuses on the geochemical and physical exchange of materials between the Earth’s crust and mantle at convergent margins, and how this drives the compositional diversity observed on the Earth’s surface. I combine traditional petrologic and geochemical studies of natural and experimental high-pressure mafic rocks, with thermodynamic modeling of high-pressure aqueous fluids and mafic-ultramafic lithologies allowing for more complete understanding of fluid-melt-rock interactions. The results of the research that follows has important implications for: the role of lower crustal foundering in the geochemical origin and evolution of the modern continental crust (Chapter 2; Guild et al., under review), metasomatic processes involving aqueous metal-carbon complexes in high pressure-temperature subduction zone fluids (Chapter 3; Guild & Shock, 2020), natural hydrous mineral stability at the slab-mantle interface (Chapter 4; Guild, et al., in preparation) and water-undersaturated melting in the sub-arc (Chapter 5; Guild & Till, in preparation).
ContributorsGuild, Meghan Rose (Author) / Till, Christy B. (Thesis advisor) / Shock, Everett L (Committee member) / Hervig, Richard L (Committee member) / Hartnett, Hilairy (Committee member) / Clarke, Amanda (Committee member) / Arizona State University (Publisher)
Created2020