Ti3+ in corundum traces crystal growth in a highly reduced magma.

Aggregates of corundum crystals with skeletal to hopper morphology occur in pyroclastic rocks erupted from Cretaceous basaltic volcanoes on Mt Carmel, N. Israel. The rapid growth of the crystals trapped volumes of the parental Al2O3-supersaturated melt; phenocrysts of tistarite (Ti2O3) in the trapped melts indicate crystallization at oxygen fugacities 6-7 log units below the Iron-Wüstite buffer (fO2 = ΔIW - 6 to - 7), induced by fluxes of mantle-derived CH4-H2 fluids. Cathodoluminescence images reveal growth zoning within the individual crystals of the aggregates, related to the substitution of Ti3+ in the corundum structure. Ti contents are < 0.3 wt% initially, then increase first linearly, then exponentially, toward adjacent melt pockets to reach values > 2 wt%. Numerical modelling indicates that the first skeletal crystals grew in an open system, from a moving magma. The subsequent linear increase in Ti reflects growth in a partially closed system, with decreasing porosity; the exponential increase in Ti close to melt pockets reflects closed-system growth, leading to dramatic increases in incompatible-element concentrations in the residual melts. We suggest that the corundum aggregates grew in melt/fluid conduits; diffusion modelling implies timescales of days to years before crystallization was terminated by explosive eruption. These processes probably operate in explosive volcanic systems in several tectonic settings.

Immiscible metallic melts in the deep Earth: clues from moissanite (SiC) in volcanic rocks.

The occurrence of moissanite (SiC), as xenocrysts in mantle-derived basaltic and kimberlitic rocks sheds light on the interplay between carbon, hydrogen and oxygen in the lithospheric and sublithospheric mantle. SiC is stable only at ƒO2 < ΔIW-6, while the lithospheric mantle and related melts commonly are considered to be much more oxidized. SiC grains from both basaltic volcanoclastic rocks and kimberlites contain metallic inclusions whose shapes suggest they were entrapped as melts. The inclusions consist of Si0 + Fe3Si7 ± FeSi2Ti ± CaSi2Al2 ± FeSi2Al3 ± CaSi2, and some of the phases show euhedral shapes toward Si0. Crystallographically-oriented cavities are common in SiC, suggesting the former presence of volatile phase(s), and the volatiles extracted from crushed SiC grains contain H2 + CH4 ± CO2 ± CO. Our observations suggest that SiC crystalized from metallic melts (Si-Fe-Ti-C ± Al ± Ca), with dissolved H2 + CH4 ± CO2 ± CO derived from the sublithospheric mantle and concentrated around interfaces such as the lithosphere-asthenosphere and crust-mantle boundaries. When mafic/ultramafic magmas are continuously fluxed with H2 + CH4 they can be progressively reduced, to a point where silicide melts become immiscible, and crystallize phases such as SiC. The occurrence of SiC in explosive volcanic rocks from different tectonic settings indicates that the delivery of H2 + CH4 from depth may commonly accompany explosive volcanism and modify the redox condition of some lithospheric mantle volumes. The heterogeneity of redox states further influences geochemical reactions such as melting and geophysical properties such as seismic velocity and the viscosity of mantle rocks.

GZ7 and GZ8 - Two Zircon Reference Materials for SIMS U-Pb Geochronology.

Here, we document a detailed characterisation of two zircon gemstones, GZ7 and GZ8. Both stones had the same mass at 19.2 carats (3.84 g) each; both came from placer deposits in the Ratnapura district, Sri Lanka. The U-Pb data are in both cases concordant within the uncertainties of decay constants and yield weighted mean 206Pb/238U ages (95% confidence uncertainty) of 530.26 Ma ± 0.05 Ma (GZ7) and 543.92 Ma ± 0.06 Ma (GZ8). Neither GZ7 nor GZ8 have been subjected to any gem enhancement by heating. Structure-related parameters correspond well with the calculated alpha doses of 1.48 × 1018 g-1 (GZ7) and 2.53 × 1018 g-1 (GZ8), respectively, and the (U-Th)/He ages of 438 Ma ± 3 Ma (2s) for GZ7 and 426 Ma ± 9 Ma (2s) for GZ8 are typical of unheated zircon from Sri Lanka. The mean U mass fractions are 680 µg g-1 (GZ7) and 1305 µg g-1 (GZ8). The two zircon samples are proposed as reference materials for SIMS (secondary ion mass spectrometry) U-Pb geochronology. In addition, GZ7 (Ti mass fractions 25.08 µg g-1 ± 0.18 µg g-1; 95% confidence uncertainty) may prove useful as reference material for Ti-in-zircon temperature estimates.