Titanium oxynitrides (Ti(N,O,C)) are abundant in xenolithic corundum aggregates in pyroclastic ejecta of Cretaceous volcanoes on Mount Carmel, northern Israel. Petrographic observations indicate that most of these nitrides existed as melts, immiscible with coexisting silicate and Fe-Ti-C silicide melts; some nitrides may also have crystallized directly from the silicide melts. The TiN phase shows a wide range of solid solution, taking up 0–10 wt% carbon and 1.7–17 wt% oxygen; these have crystallized in the halite (fcc) structure common to synthetic and natural TiN. Nitrides coexisting with silicide melts have higher C/O than those coexisting with silicate melts. Analyses with no carbon fall along the TiN–TiO join in the Ti–N–O phase space, implying that their Ti is a mixture of Ti3+ and Ti2+, while those with 1–3 at.% C appear to be solid solutions between TiN and Ti0.75O. Analyses with >10 at% C have higher Ti2+/Ti3+, reflecting a decrease in fO2. Oxygen fugacity was 6 to 8 log units below the iron–wüstite buffer, at or below the Ti2O3–TiO buffer. These relationships and coexisting silicide phases indicate temperatures of 1400–1100 °C. Ti oxynitrides are probably locally abundant in the upper mantle, especially in the presence of CH4–H2 fluids derived from the deeper metal-saturated mantle.
Oxygen fugacity and the fluid C-H-O phase in the Earth’s mantle