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- All Subjects: Mineralogy
- Creators: Hervig, Richard L
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
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.
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
Description
With the InSight mission deploying a seismometer , Martian bulk chemical compositional models are more important than ever. Three largely consistent models for the Martian mantle have been suggested over the past two decades. Of these three, two are fairly similar and one is dramatically different. Of these three, the EH70 (Sanloup et al., 1999) models have the systematically lower divalent cation to silicon ratios as compared to the other model, the DW85 (Dreibus and Wanke, 1985) model. However, impact of such a low (Mg+Fe+Ca)/Si ratio on mineralogy has not been experimentally investigated. Measurements have been made of the mineralogy of the EH70 bulk mantle composition (Sanloup et al., 1999)) through in-situ laser-heated diamond anvil cell (LHDAC) and large volume press (LVP). Majorite-garnet (Mj) dominated mineralogy has been observed up to 25 GPa. Bridgmanite (Bm) begins to appear from 25.2 GPa and continues in a mixed phase with Mj up to 27 GPa at which point only Bm and calcium perovskite (CaPv) remain. Akimotoite (Ak) is stable up to 1873 K, higher by ≈300 K compared to numerical calculations (Connolly, 2009). This may result in an Ak layer in the Martian mantle, something missing in Earth’s mantle. The overall ratio of pyroxene to olivine polymorphs by volume is high, approaching pure pyroxene. This agrees with numerical calculations. Additionally, ferropericlase (Fp) is stable at lower temperatures, suggesting a higher dependence on temperature for its stability, something that is different from Perple_X calculations which show a strong dependence on pressure. Furthermore, Mj, which make up a majority of the volume of EH70 mantles, was measured to increase in Fe content as pressure increases. The more oxidizing conditions coupled with the silicon-rich composition resulted in three times higher Fe3+ content in Mj as opposed to a pyrolite model. This increased Fe3+ meant our Mj composition approached that of skiagite (Ski,Fe2+ 3 Fe3+ 2 Si3O12) and this caused Mj to have a very low compressibility of only 152.8 GPa, lower than any other Mj compositions in literature. This result suggests that a mantle with EH70 bulk composition would have lower than predicted seismic wave velocities , lower than Perple_X predicts. The Al content of Mj was also found to suppress the first derivative of compressibility to 4.45, lower than that of Ski100 at 6.7. Such differences compared with pyrolitic composition are important to estimate the velocity profiles and to model the dynamics of the Martian mantle. This dataset of mineralogy and composition can also model terrestrial exoplanetary mantles. Current measurements of stellar abundances show a wide range of compositions, and especially compositions with (Mg+Fe+Ca)/Si ratios approaching 1 (Brewer and Fischer, 2016). This experimental study of EH70 composition can fill-in this gap.
ContributorsDolinschi, Jonathan David (Author) / Shim, Sang-Heon D. (Thesis advisor) / Desch, Steven (Committee member) / Lee, Mingming (Committee member) / Arizona State University (Publisher)
Created2019