abstract: The transport of hydrogen to the Earth’s deep interior remains uncertain. The upper mantle minerals have very low hydrogen solubilities (hundreds of ppm). The hydrogen storage capability in the transition zone minerals (2 wt%) is high compared to those of the upper mantle. The hydrogen storage in the lower mantle is not well known. The main minerals in the lower mantle bridgmanite and ferropericlase have very low hydrogen storage capacities (less than 20 ppm). In order to further understand the hydrogen storage in the lower mantle, a series of experiments had been conducted to simulate the environment similar to the Earth’s mantle. The experiments with hydrous Mg2SiO4 ringwoodite (Rw) show that it converts to crystalline dense hydrous silica, stishovite (Stv) or CaCl2-type SiO2(mStv), containing ∼1 wt% H2O together with bridgmanite (Brd) and MgO at the pressure-temperature conditions expected for lower mantle depths between approximately 660 to 1600 km. Brd would break down partially to dense hydrous silica (6–25 mol%) and(Mg,Fe)O in mid-mantle regions with 0.05–0.27 wt% H2O. The hydrous stishovite has a CaCl2 structure, which is common among hydrous minerals in the lower mantle. Based on this observation, I hypothesize the existence of hydrous phases in the lower mantle. The experiments found a new hexagonal iron hydroxide (η-Fe12O18+x/2Hx) between the stability fields of the epsilon and pyrite-type FeOOH at 60–80 GPa and high temperature. The new phase contains less H2O, limiting the H2O transport from the shallow to the deep mantle in the Fe–O–H system. Possible hydrogen storage in Ca-perovskite was studied. CaPv could contain 0.5–1 wt% water and the water in CaPv could distort the crystal structure of CaPv from cubic to tetragonal structure. In conclusion, hydrogen can be stored in hydrous stishovite in the shallower depth of the lower mantle. At greater depth, the new η phase and pyrite-type phase would take over the hydrogen storage. The role of CaPv in deep water storage needs to be considered in future studies. / Dissertation/Thesis / Doctoral Dissertation Natural Science 2019

abstract: 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. / Dissertation/Thesis / Ph.D. Geological Sciences 2012