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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.

Although hydrogen is the most abundant element in the solar system, the mechanisms of exchange of this element between the deep interior and surface of Earth are still uncertain. Hydrogen has profound effects on properties and processes on microscopic-to-global scales. Here we report the discovery of the first hydride (VH2) ever reported in nature. This phase has been found in the ejecta of Cretaceous pyroclastic volcanoes on Mt Carmel, N. Israel, which include abundant xenoliths containing highly reduced mineral assemblages. These xenoliths were sampled by their host magmas at different stages of their evolution but are not genetically related to them. The xenoliths are interpreted as the products of extended interaction between originally mafic magmas and CH4+H2 fluids, derived from a deeper, metal-saturated mantle. The last stages of melt evolution are recorded by coarse-grained aggregates of hibonite (CaAl12O19) + grossite (CaAl4O7) + V-rich spinels ± spheroidal to dendritic inclusions of metallic vanadium (V0), apparently trapped as immiscible metallic melts. The presence of V0 implies low oxygen fugacities and suggests crystallization of the aggregates in a hydrogen-rich atmosphere. The presence of such reducing conditions in the upper mantle has major implications for the transport of carbon, hydrogen and other volatile species from the deep mantle to the surface.