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 V 0. 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 V 0. 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 - Hibonite
KW - native vanadium
KW - grossite
KW - krotite
KW - super-reduced conditions
KW - mantle methane
KW - Mt Carmel
KW - Volatile Elements in Differentiated Planetary Interiors
UR - http://www.scopus.com/inward/record.url?scp=85059402700&partnerID=8YFLogxK
U2 - 10.2138/am-2019-6733
DO - 10.2138/am-2019-6733
M3 - Article
VL - 104
SP - 207
EP - 219
JO - American Mineralogist
JF - American Mineralogist
SN - 0003-004X
IS - 2
ER -