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Corundum-quartz metastability: the influence of a nanometer-sized phase on mineral equilibria in the system Al2O3–SiO2–H2O

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Abstract

The metastable paragenesis of corundum and quartz is rare in nature but common in laboratory experiments where according to thermodynamic predictions aluminum–silicate polymorphs should form. We demonstrate here that the existence of a hydrous, silicon-bearing, nanometer-thick layer (called “HSNL”) on the corundum surface can explain this metastability in experimental studies without invoking unspecific kinetic inhibition. We investigated experimentally formed corundum reaction products synthesized during hydrothermal and piston–cylinder experiments at 500–800 °C and 0.25–1.8 GPa and found that this HSNL formed inside and on the corundum crystals, thereby controlling the growth behavior of its host. The HSNL represents a substitution of Al with Si and H along the basal plane of corundum. Along the interface of corundum and quartz, the HSNL effectively isolates the bulk phases corundum and quartz from each other, thus apparently preventing their reaction to the stable aluminum silicate. High temperatures and prolonged experimental duration lead to recrystallization of corundum including the HSNL and to the formation of quartz + fluid inclusions inside the host crystal. This process reduces the phase boundary area between the bulk phases, thereby providing further opportunity to expand their coexistence. In addition to its small size, its transient nature makes it difficult to detect the HSNL in experiments and even more so in natural samples. Our findings emphasize the potential impact of nanometer-sized phases on geochemical reaction pathways and kinetics under metamorphic conditions in one of the most important chemical systems of the Earth’s crust.

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All data and material used and discussed in the text are included as Figures and Tables in the main text or in the Electronic Supplementary Material.

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Perplex_X (Connolly 2009, see References) was used to calculating and illustrate Fig. 1a.

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Acknowledgements

Special thanks to Anja Schreiber (GFZ Potsdam), Iryna Driehorst and Jörg Nissen (ZELMI at Technische Universität Berlin) for their support.

Funding

This work was supported by the Deutsche Forschungsgemeinschaft in the research group FOR 741 “Nanoscale Processes and Geomaterials Properties” [Grant No. FR 557/26].

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According to CRediT (Contributor Roles Taxonomy) author statement:

DS investigation, conceptualization, methodology, writing—original draft preparation, visualization. RW investigation, visualization, data curation, writing—reviewing and editing. BW investigation, resources, writing- reviewing and editing. AL writing—reviewing and editing. MW writing- reviewing and editing. GF supervision, funding acquisition, writing—reviewing and editing.

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Correspondence to Dina S. Schultze.

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The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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Communicated by Timothy L. Grove.

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Schultze, D.S., Wirth, R., Wunder, B. et al. Corundum-quartz metastability: the influence of a nanometer-sized phase on mineral equilibria in the system Al2O3–SiO2–H2O. Contrib Mineral Petrol 176, 27 (2021). https://doi.org/10.1007/s00410-021-01786-5

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  • DOI: https://doi.org/10.1007/s00410-021-01786-5

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