Abstract
Recent studies have shown that mineral end-member phases (δ-AlOOH phase, phase H, and stishovite) with rutile-type or modified rutile-type crystal structures and solid solutions between them in the MgO-Al2O3-SiO2 system can store large amounts of water and can be stable at high pressures and high temperatures relevant to the Earth’s lower mantle. The Al-H charge-coupled substitution (Si4+ → Al3+ + H+) has been proposed to explain the storage capacity found in some of these phases. However, the amount of H+ found in some recent examples does not match the expected value if such substitution is dominant, and it is difficult to explain the larger water storage in stishovite with such a mechanism alone. An octahedral version of the hydrogarnet-like substitution (Si4+ → 4H+) has been proposed to explain the incorporation of protons in Al-free, water-rich stishovite. Yet, the high-pressure structural behavior of OH in this phase has not yet been measured. In this study, we report high-pressure Raman spectroscopy measurements on Al-free hydrous stishovite with 3.2 ± 0.5 wt% water up to 55 GPa. At ambient pressure, we find that the OH stretching modes in this phase have frequencies lying in between those in low-water aluminous stishovite and those in δ-AlOOH, suggesting a strength of the hydrogen bonding intermediate between these two cases. After decompression to 1 bar, we observe modes that are similar to the IR-active modes of anhydrous and hydrous stishovite, suggesting that the existence of Si defects in the crystal structure can activate the inactive modes. For both lattice and OH-stretching modes, our data show a series of changes at pressures between 24 and 28 GPa suggesting a phase transition (likely to CaCl2-type). While some of the lattice mode behaviors are similar to what was predicted for the AlOOH polymorphs, the OH mode of our hydrous stishovite shows a positive frequency shift with pressure, which is different from δ-AlOOH. All our spectral observations suggest that water-rich pure dense silica has a distinct proton incorporation mechanism from aluminous low-water stishovite and δ-AlOOH, supporting the proposed direct substitution.
Special collection papers can be found online at http://www.minsocam.org/MSA/AmMin/special-collections.html.
Acknowledgments
We thank Ulrich Haussermann for providing TGA traces and valuable discussions on the water contents of hydrous stishovite samples. We thank the two anonymous reviewers and the associate editor for the discussion that greatly improved this paper. This work was supported by an NSF grant to K.L., S.H.S., and C.N. (EAR1321976). The results reported herein also benefitted from collaborations and/or information exchange within NASA’s Nexus for Exoplanet System Science (NExSS) research coordination network sponsored by NASA’s Science Mission Directorate.
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Artikel in diesem Heft
- Highlights and Breakthroughs
- Rutile: A novel recorder of high-fo2 fluids in subduction zones
- Highlights and Breakthroughs
- Granites and rhyolites: Messages from Hong Kong, courtesy of zircon
- Review
- Do Fe-Ti-oxide magmas exist? Probably not!
- Special Collection: Biomaterials—Mineralogy Meets Medicine
- Calcium (Ti,Zr) hexaorthophosphate bioceramics for electrically stimulated biomedical implant devices: A position paper
- Special Collection: Water in Nominally Hydrous and Anhydrous Minerals
- Raman spectroscopy of water-rich stishovite and dense high-pressure silica up to 55 GPa
- Tracking the evolution of Late Mesozoic arc-related magmatic systems in Hong Kong using in-situ U-Pb dating and trace element analyses in zircon
- Defect contributions to the heat capacities and stabilities of some chain, ring, and sheet silicates, with implications for mantle minerals
- Phase transition in SiC from zinc-blende to rock-salt structure and implications for carbon-rich extrasolar planets
- Non-destructive, multi-method, internal analysis of multiple inclusions in a single diamond: First occurrence of mackinawite (Fe,Ni)1+xS
- The fate of ammonium in phengite at high temperature
- Parameterized lattice strain models for REE partitioning between amphibole and silicate melt
- Unusual replacement of Fe-Ti oxides by rutile during retrogression in amphibolite-hosted veins (Dabie UHP terrane): A mineralogical record of fluid-induced oxidation processes in exhumed UHP slabs
- Crystallization experiments in rhyolitic systems: The effect of temperature cycling and starting material on crystal size distribution
- Dolomite dissociation indicates ultra-deep (>150 km) subduction of a garnet-bearing dunite block (the Sulu UHP terrane)
- Microscopic strain in a grossular-pyrope solution anti-correlates with excess volume through local Mg-Ca cation arrangement, more strongly at high Ca/Mg ratio
- Ferruginous seawater facilitates the transformation of glauconite to chamosite: An example from the Mesoproterozoic Xiamaling Formation of North China
- Charleshatchettite, CaNb4O10(OH)2·8H2O, a new mineral from Mont Saint-Hilaire, Québec, Canada: Description, crystal-structure determination, and origin
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