Valences of Ti, Cr, and V in Apollo 17 high-Ti and very low-Ti basalts and implications for their formation

To assess the variability of redox states among mare basalt source regions, investigation of the valence of Ti, Cr, and V and the coordination environment of Ti in pyroxene and olivine in lunar rocks via XANES (X-ray absorption near-edge structure) spectroscopy has been extended to Apollo 17 basalts: two high-Ti (70017 and 74275) hand samples, and three very low-Ti (70006,371, 70007,289B, and 70007,296) basalt fragments from the Apollo 17 deep drill core. Valences of Ti in pyroxene of both suites range from 3.6 to 4, or from 40% to 0% Ti3+, averaging 15-20% Ti3+. Assuming Ti3+ is more compatible in pyroxene than Ti4+, then even lower Ti3+ proportions are indicated for the parental melts. The VLT pyroxene exhibits a slightly wider range of V valences (2.57-2.96) than the high-Ti pyroxene (2.65-2.86) and a much wider range of Cr valences (2.32-2.80 versus 2.68-2.86); Cr is generally reduced in VLT pyroxene compared to high-Ti pyroxene. Valences of Ti and Cr in VLT pyroxene become less reduced with increasing FeO contents, possibly indicating change in oxygen fugacity during crystallization. Olivine in all samples has very low (<20%) proportions of Ti3+, with no Ti3+ and higher proportions of Ti in tetrahedral coordination in the VLTs than in the high-Ti basalts. Olivine in 74275, including that in a dunite clast, has much higher proportions of Cr2+ than the pyroxene in that sample, consistent with previous studies indicating that the olivine grains in this sample are xenocrysts and possibly indicating oxidation just prior to pyroxene crystallization. Results for this sample, the VLTs, and previously studied Apollo 14 and 15 basalts all indicate that mare magmas were in reducing environments at depth, as recorded in early crystallization products, and that later, presumably shallower environments, were relatively oxidizing; single, characteristic fO(2)s of formation cannot be assigned to these samples. A process likely to account for this feature seen in multiple samples is loss by degassing of a reducing, H-rich vapor (probably H-2) during ascent and/or eruption, causing oxidation of the residual melt, recorded in relatively late-crystallized pyroxene.