Microanalysis for Oxygen Fugacity by Secondary Ion Mass Spectrometry

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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.…

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.
Date Created
2019
Agent

Solubility of Nitrogen in Stishovite: A Possible Storage Mechanism for Nitrogen in Earth's Deep Interior

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Description
Though large amounts of nitrogen are allocated to the Earth's mantle, not much is known concerning how it is stored and transported. In this study, stishovite is proposed as a host for nitrogen within the Earth's deep interior. Stishovite was…

Though large amounts of nitrogen are allocated to the Earth's mantle, not much is known concerning how it is stored and transported. In this study, stishovite is proposed as a host for nitrogen within the Earth's deep interior. Stishovite was synthesized and heated under nitrogen rich conditions using diamond-anvil cell equipment and double-sided laser heating. Synthesis pressures ranged from 16 to 44 GPa and temperatures centered at ~1800 K. Experimental products were removed from diamond anvil cells and analyzed for nitrogen content via SIMS and SEM/EDX analysis. Unit cell parameters were obtained through XRD analysis. N solubility in stishovite was calculated to be up to 1.54 wt % from SIMS data through the use of an ion implant and a relative sensitivity factor. XRD data indicated a decrease in unit cell volume at higher pressures, with the c-axis length showing larger compressibility than the a-axis length. Through SEM and EDX analysis, a uniformly low level of N was observed throughout the sample indicating that N was uniformly incorporated into the crystal structure of stishovite. The data suggests that, rather than existing separately from stishovite as a silicon or carbon nitride, N has substituted into the crystal structure of stishovite. Both O and N have largely similar atomic radii, with N being slightly smaller, indicating that N can substitute for O. With the levels of N observed in the experiment, it is implicated that the mantle has an extremely large storage capacity for N. Further experimentation, with the addition of TEM analysis, should be conducted in order to determine the effects of pressure and temperature on the solubility of N in stishovite. Additionally, substitution of N as HN into stishovite should be investigated as HN accounts for the charge imbalance seen when substituting N for O.
Date Created
2016-05
Agent

Amorphous weathering products: evidence for basalt-water interactions and the relevance to paleo-environments on Mars

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Description
Amorphous phases are detected over large regions of the Martian surface from orbit and in more localized deposits by rovers on the surface. Amorphous silicates can be primary or secondary in origin, both having formed through very different processes, so…

Amorphous phases are detected over large regions of the Martian surface from orbit and in more localized deposits by rovers on the surface. Amorphous silicates can be primary or secondary in origin, both having formed through very different processes, so the unambiguous identification of these phases is important for understanding the geologic history of Mars. Secondary amorphous silicates are poorly understood and underrepresented in spectral libraries because they lack the long-range structural order that makes their crystalline counterparts identifiable in most analytical techniques. Fortunately, even amorphous materials have some degree of short-range order so that distinctions can be made with careful characterization.

Two sets of laboratory experiments were used to produce and characterize amorphous weathering products under probable conditions for the Martian surface, and one global spectral analysis using thermal-infrared (TIR) data from the Thermal Emission Spectrometer (TES) instrument was used to constrain variations in amorphous silicates across the Martian surface. The first set of experiments altered crystalline and glassy basalt samples in an open system under strong (pH 1) and moderate (pH 3) acidic conditions. The second set of experiments simulated a current-day Martian weathering scenario involving transient liquid water where basalt glass weathering solutions, formed in circumneutral (pH ~5.5 and 7) conditions, were rapidly evaporated, precipitating amorphous silicates. The samples were characterized using visible and near-infrared (VNIR) spectroscopy, TIR spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD).

All experiments formed amorphous silicate phases that are new to spectral libraries. Moderately acidic alteration experiments produced no visible or spectral evidence of alteration products, whereas exposure of basalt glass to strongly acidic fluids produced silica-rich alteration layers that are spectrally consistent with VNIR and TIR spectra from the circum-polar region of Mars, indicating this region has undergone acidic weathering. Circum-netural pH basalt weathering solution precipitates are consistent with amorphous materials measured by rovers in soil and rock surface samples in Gale and Gusev Craters, suggesting transient water interactions over the last 3 billion years. Global spectral analyses determine that alteration conditions have varied across the Martian surface, and that alteration has been long lasting.
Date Created
2016
Agent

Using micro-scale observations to understand large-scale geophysical phenomena: examples from seismology and mineral physics

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…

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.
Date Created
2015
Agent

Thermochemical structure and dynamics of Earth's lowermost mantle

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Description
Seismic observations have revealed two large low shear velocity provinces (LLSVPs) in the lowermost mantle beneath Pacific and Africa. One hypothesis for the origin of LLSVPs is that they are caused by accumulation of subducted oceanic crust on the core-mantle…

Seismic observations have revealed two large low shear velocity provinces (LLSVPs) in the lowermost mantle beneath Pacific and Africa. One hypothesis for the origin of LLSVPs is that they are caused by accumulation of subducted oceanic crust on the core-mantle boundary (CMB). Here, I perform high resolution geodynamical calculations to test this hypothesis. The result shows that it is difficult for a thin (~ 6 km) subducted oceanic crust to accumulate on the CMB, and the major part of it is viscously stirred into the surrounding mantle. Another hypothesis for the origin of LLSVPs is that they are caused by thermochemical piles of more-primitive material which is remnant of Earth's early differentiation. In such case, a significant part of the subducted oceanic crust would enter the more-primitive reservoir, while other parts are either directly entrained into mantle plumes forming on top of the more-primitive reservoir or stirred into the background mantle. As a result, mantle plumes entrain a variable combination of compositional components including more-primitive material, old oceanic crust which first enters the more-primitive reservoir and is later entrained into mantle plumes with the more-primitive material, young oceanic crust which is directly entrained into mantle plumes without contacting the more-primitive reservoir, and depleted background mantle material. The result reconciles geochemical observation of multiple compositional components and varying ages of oceanic crust in the source of ocean-island basalts. Seismic studies have detected ultra-low velocity zones (ULVZs) in some localized regions on the CMB. Here, I present 3D thermochemical calculations to show that the distribution of ULVZs provides important information about their origin. ULVZs with a distinct composition tend to be located at the edges of LLSVPs, while ULVZs solely caused by partial melting tend to be located inboard from the edges of LLSVPs. This indicates that ULVZs at the edges of LLSVPs are best explained by distinct compositional heterogeneity, while ULVZs located insider of LLSVPs are better explained by partial melting. The results provide additional constraints for the origin of ULVZs.
Date Created
2015
Agent

The Postspinel Boundary in Pyrolitic Compositions Determined in the Laser-Heated Diamond Anvil Cell

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Description

In situ multianvil press (MAP) studies have reported that the depth and the Clapeyron slope of the postspinel boundary are significantly less than those of the 660 km discontinuity inferred from seismic studies. These results have raised questions about whether…

In situ multianvil press (MAP) studies have reported that the depth and the Clapeyron slope of the postspinel boundary are significantly less than those of the 660 km discontinuity inferred from seismic studies. These results have raised questions about whether the postspinel transition is associated with the discontinuity. We determined the postspinel transition in pyrolitic compositions in the laser-heated diamond anvil cell (LHDAC) combined with in situ synchrotron X-ray diffraction. The Clapeyron slope was determined to be −2.5 ± 0.4MPa/K and did not vary significantly with compositions and used pressure scales. Using Pt scales, our data indicate that the postspinel transition occurs in pyrolitic compositions at 23.6–24.5GPa (1850K). The transition pressure and slope are consistent with the depth and topography of the 660 km discontinuity. Our data reveal that inaccuracy in pressure scales alone cannot explain the discrepancy and technical differences between MAP and LHDAC contribute significantly to the discrepancy.

Date Created
2014-06-16
Agent

Astrobiological Stoichiometry

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Description

Chemical composition affects virtually all aspects of astrobiology, from stellar astrophysics to molecular biology. We present a synopsis of the research results presented at the “Stellar Stoichiometry” Workshop Without Walls hosted at Arizona State University April 11–12, 2013, under the…

Chemical composition affects virtually all aspects of astrobiology, from stellar astrophysics to molecular biology. We present a synopsis of the research results presented at the “Stellar Stoichiometry” Workshop Without Walls hosted at Arizona State University April 11–12, 2013, under the auspices of the NASA Astrobiology Institute. The results focus on the measurement of chemical abundances and the effects of composition on processes from stellar to planetary scales. Of particular interest were the scientific connections between processes in these normally disparate fields. Measuring the abundances of elements in stars and giant and terrestrial planets poses substantial difficulties in technique and interpretation. One of the motivations for this conference was the fact that determinations of the abundance of a given element in a single star by different groups can differ by more than their quoted errors.

The problems affecting the reliability of abundance estimations and their inherent limitations are discussed. When these problems are taken into consideration, self-consistent surveys of stellar abundances show that there is still substantial variation (factors of ∼2) in the ratios of common elements (e.g., C, O, Na, Al, Mg, Si, Ca) important in rock-forming minerals, atmospheres, and biology. We consider how abundance variations arise through injection of supernova nucleosynthesis products into star-forming material and through photoevaporation of protoplanetary disks. The effects of composition on stellar evolution are substantial, and coupled with planetary atmosphere models can result in predicted habitable zone extents that vary by many tens of percent. Variations in the bulk composition of planets can affect rates of radiogenic heating and substantially change the mineralogy of planetary interiors, affecting properties such as convection and energy transport.

Date Created
2014-07-01
Agent

Variability of elemental abundances in the local neighborhood and its effect on planetary systems

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Description
As the detection of planets become commonplace around our neighboring stars, scientists can now begin exploring their possible properties and habitability. Using statistical analysis I determine a true range of elemental compositions amongst local stars and how this variation could…

As the detection of planets become commonplace around our neighboring stars, scientists can now begin exploring their possible properties and habitability. Using statistical analysis I determine a true range of elemental compositions amongst local stars and how this variation could affect possible planetary systems. Through calculating and analyzing the variation in elemental abundances of nearby stars, the actual range in stellar abundances can be determined using statistical methods. This research emphasizes the diversity of stellar elemental abundances and how that could affect the environment from which planets form. An intrinsic variation has been found to exist for almost all of the elements studied by most abundance-finding groups. Specifically, this research determines abundances for a set of 458 F, G, and K stars from spectroscopic planet hunting surveys for 27 elements, including: C, O, Na, Mg, Al, Si, S, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo, Ba, La, Ce, Nd, Eu, and Hf. Abundances of the elements in many known exosolar planet host stars are calculated for the purpose investigating new ways to visualize how stellar abundances could affect planetary systems, planetary formation, and mineralogy. I explore the Mg/Si and C/O ratios as well as place these abundances on ternary diagrams with Fe. Lastly, I emphasize the unusual stellar abundance of τ Ceti. τ Ceti is measured to have 5 planets of Super-Earth masses orbiting in near habitable zone distances. Spectroscopic analysis finds that the Mg/Si ratio is extremely high (~2) for this star, which could lead to alterations in planetary properties. τ Ceti's low metallicity and oxygen abundance account for a change in the location of the traditional habitable zone, which helps clarify a new definition of habitable planets.
Date Created
2014
Agent
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