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

William L. Griffin, Sarah E.M. Gain, Jin Xiang Huang, Martin Saunders, Jeremy Shaw, Vered Toledo, Suzanne Y. O'Reilly

Research output: Contribution to journalArticle

4 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)207-219
Number of pages13
JournalAmerican Mineralogist
Volume104
Issue number2
DOIs
Publication statusPublished - 1 Feb 2019

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hibonite
Plumbing
Vanadium
Israel
Aluminum Oxide
vanadium
spinel
volcanology
corundum
aluminum oxides
Crystallization
melt
Silicates
ejecta
crystallization
Oxides
silicates
Earth mantle
Bearings (structural)
silicate melt

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@article{9b8f4af721f64017b30fca0ab71fbbca,
title = "A terrestrial magmatic hibonite-grossite-vanadium assemblage: Desilication and extreme reduction in a volcanic plumbing system, Mount Carmel, Israel",
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.",
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year = "2019",
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pages = "207--219",
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A terrestrial magmatic hibonite-grossite-vanadium assemblage : Desilication and extreme reduction in a volcanic plumbing system, Mount Carmel, Israel. / Griffin, William L.; Gain, Sarah E.M.; Huang, Jin Xiang; Saunders, Martin; Shaw, Jeremy; Toledo, Vered; O'Reilly, Suzanne Y.

In: American Mineralogist, Vol. 104, No. 2, 01.02.2019, p. 207-219.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A terrestrial magmatic hibonite-grossite-vanadium assemblage

T2 - Desilication and extreme reduction in a volcanic plumbing system, Mount Carmel, Israel

AU - Griffin, William L.

AU - Gain, Sarah E.M.

AU - Huang, Jin Xiang

AU - Saunders, Martin

AU - Shaw, Jeremy

AU - Toledo, Vered

AU - O'Reilly, Suzanne Y.

PY - 2019/2/1

Y1 - 2019/2/1

N2 - 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.

AB - 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.

KW - grossite

KW - Hibonite

KW - krotite

KW - mantle methane

KW - Mt Carmel

KW - native vanadium

KW - super-reduced conditions

KW - Volatile Elements in Differentiated Planetary Interiors

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