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Licensed Unlicensed Requires Authentication Published by De Gruyter January 23, 2019

A terrestrial magmatic hibonite-grossite-vanadium assemblage: Desilication and extreme reduction in a volcanic plumbing system, Mount Carmel, Israel

  • William L. Griffin EMAIL logo , Sarah E.M. Gain , Jin-Xiang Huang , Martin Saunders , Jeremy Shaw , Vered Toledo and Suzanne Y. O’Reilly
From the journal American Mineralogist

Abstract

Hibonite (CaAl12O19) is a constituent of some refractory calcium-aluminum inclusions (CAIs) in carbonaceous meteorites, commonly accompanied by grossite (CaAl4O7) and spinel. These phases are usually interpreted as having condensed, or crystallized from silicate melts, early in the evolution of the solar nebula. Both Ca-Al oxides are commonly found on Earth, but as products of high-temperature metamorphism of pelitic carbonate rocks. We report here a unique occurrence of magmatic hibonitegrossite-spinel assemblages, crystallized from Ca-Al-rich silicate melts under conditions [high-temperature, very low oxygen fugacity (fO2)] comparable to those of their meteoritic counterparts. Ejecta from Cretaceous pyroclastic deposits on Mt Carmel, N. Israel, include aggregates of hopper/skeletal Ti-rich corundum, which have trapped melts that crystallized at fO2 extending from 7 log units below the iron-wustite buffer (ΔIW = –7; SiC, Ti2O3, Fe-Ti silicide melts) to ΔIW ≤ –9 (native V, TiC, and TiN). The assemblage hibonite + grossite + spinel + TiN first crystallized late in the evolution of the melt pockets; this hibonite contains percentage levels of Zr, Ti, and REE that reflect the concentration of incompatible elements in the residual melts as corundum continued to crystallize. A still later stage appears to be represented by coarse-grained (centimeter-size crystals) ejecta that show the crystallization sequence: corundum + Liq → (low-REE) hibonite → grossite + spinel ± krotite → Ca4Al6F2O12 + fluorite. V0 appears as spheroidal droplets, with balls up to millimeter size and spectacular dendritic intergrowths, included in hibonite, grossite, and spinel. Texturally late V0 averages 12 wt% Al and 2 wt% Mn. Spinels contain 10–16 wt% V in V0-free samples, and <0.5 wt% V in samples with abundant V0. Ongoing paragenetic studies suggest that the fO2 evolution of the Mt Carmel magmatic system reflects the interaction between OIB-type mafic magmas and mantle-derived CH4+H2 fluids near the crust-mantle boundary. Temperatures estimated by comparison with 1 atm phase-equilibrium studies range from ca. 1500 °C down to 1200–1150 °C. When fO2 reached ca. ΔIW = –7, the immiscible segregation of Fe,Ti-silicide melts and the crystallization of SiC and TiC effectively desilicated the magma, leading to supersaturation in Al2O3 and the rapid crystallization of corundum, preceding the development of the hibonite-bearing assemblages. Reports of Ti-rich corundum and SiC from other areas of explosive volcanism suggest that these phenomena may be more widespread than presently realized, and the hibonite-grossite assemblage may serve as another indicator to track such activity.

This is the first reported terrestrial occurrence of krotite (CaAl2O4), and of at least two unknown Zr-Ti oxides.

Acknowledgments

We thank E. Sass and Oded Navon for useful discussions on the geology of Mt Carmel and the volcanism of Israel in general. The project benefitted greatly from the skill and dedication of the Shefa Yamim operational staff at Akko and especially the mineral sorters. Paul Asimov, David Mittlefelhdt, and handling editor E.B. Watson provided constructive reviews and advice. This study used instrumentation funded by ARC LIEF and DEST Systemic Infrastructure Grants, Macquarie University and industry. This is contribution 1209 from the ARC Centre of Excellence for Core to Crust Fluid Systems (www.ccfs.mq.edu.au) and 1256 from the GEMOC Key Centre (www.gemoc.mq.edu.au).

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Received: 2018-07-15
Accepted: 2018-10-13
Published Online: 2019-01-23
Published in Print: 2019-02-25

© 2019 Walter de Gruyter GmbH, Berlin/Boston

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