Grossite

Abstract: Krotite, CaAl_2O_4, occurs as the dominant phase in an unusual Ca-,Al-rich refractory inclusion from the NWA 1934 CV3 carbonaceous chondrite. Krotite occupies the central and mantle portions of the inclusion along with minor perovskite, gehlenite, hercynite, and Cl-bearing mayenite, and trace hexamolybdenum. A layered rim surrounds the krotite-bearing regions, consisting from inside to outside of grossite, mixed hibonite, and spinel, then gehlenite with an outermost layer composed of Al-rich diopside. Krotite was identified by XRD, SEM-EBSD, micro-Raman, and electron microprobe. The mean chemical composition determined by electron microprobe analysis of krotite is (wt%) Al_2O_3 63.50, CaO 35.73, sum 99.23, with an empirical formula calculated on the basis of 4 O atoms of Ca_(1.02)Al_(1.99)O_4. Single-crystal XRD reveals that krotite is monoclinic, P2_1/n; a = 8.6996(3), b = 8.0994(3), c = 15.217(1) A, β = 90.188(6), and Z = 12. It has a stuffed tridymite structure, which was refined from single-crystal data to R_1 = 0.0161 for 1014 F_o > 4σF reflections. Krotite is colorless and transparent with a vitreous luster and white streak. Mohs hardness is ~6½. The mineral is brittle, with a conchoidal fracture. The calculated density is 2.94 g/cm3. Krotite is biaxial (–), α = 1.608(2), β = 1.629(2), γ = 1.635(2) (white light), 2V_(meas) = 54.4(5)°, and 2V_(calc) = 55.6°. No dispersion was observed. The optical orientation is X = b; Y ≈ a; Z ≈ c. Pleochroism is colorless to very pale gray, X > Y = Z. Krotite is a low-pressure CaAl_2O_4 mineral, likely formed by condensation or crystallization from a melt in the solar nebula. This is the first reported occurrence of krotite in nature and it is one of the earliest minerals formed in the solar system.

Abstract: 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.