Revisiting the Petrogenesis of Pyroclastic Glass Bead Deposits at the Apollo 15 and 17 Sites

The Apollo 15 low-titanium and Apollo 17 high-titanium pyroclastic glass beads are among the most primitive magmatically derived samples obtained from the Moon. Two key samples, the low-Ti Apollo 15426 green glass clod and the high-Ti Apollo 74220 orange glass are morphologically distinct, where the Apollo 15 beads are larger (similar to 107 mu m along maximum axis) and more fractured, and the Apollo 17 are smaller (similar to 42 mu m) and less fractured. In this study, holohyaline beads as well as crystallized beads were examined from both samples using petrography, electron microprobe analysis, and laser-ablation inductively coupled plasma mass spectrometry. Crystallized beads show compositional variability in major, minor, and trace elements and enable examination of magmatic mineral fractionation processes during cooling of both deposits. The Apollo 15426 beads experienced variable olivine crystallization, whereas the Apollo 74220 beads experienced both olivine and ilmenite crystallization. Holohyaline beads from both deposits show more limited major, minor, and trace element variability than their crystallized counterparts. Trace element abundance data for individual holohyaline beads show that in Apollo 74220, they are tightly clustered at similar to 30x Carbonaceous Ivuna chondrite [CI] with negative Eu anomalies and subchondritic Nb/Ta, interpreted to reflect the presence of late-stage magma ocean cumulates overturned into an otherwise primitive mantle source. Incompatible trace element abundances for holohyaline beads in 15426 are supra-chondritic from similar to 8x CI, to >80x CI, with pronounced relative depletions in Sr and Eu for the most incompatible element enriched beads, which represent a distinct bead group within the deposit. Apollo 15426 beads have elevated Ni and Co abundances at the edges of the beads compared to their centers. These data are interpreted to reflect a more complex magmatic evolution of the 15426 deposit, beginning with (i) initial magma generation, storage, and assimilation within shallower low- and high-Ca pyroxene bearing magma ocean cumulates (15B,C); (ii) mobilization of the earlier magmas by more recently generated primitive magmas (15A); (iii) eruption and crystallization of some beads (15D,E); and (iv) later jumbling of the deposit, possible impact contamination and addition of exotic basaltic bead components (J Group). In contrast, the 74220 data show no discernable difference between Ni and Co abundances at the edges and centers supporting prior observations for limited melt fractionation and an absence of meteoritic components. Both deposits are likely to have been formed in the presence of a transient atmosphere. Using 74220 melt compositions from this study, post-entrapment crystallization abundances range from 266 to 1130 mu g/g for H2O, 36 to 68 mu g/g for F, 441 to 832 mu g/g for S, and 0 to 2.31 mu g/g for Cl, consistent with prior studies and suggesting up to similar to 0.1 wt % H2O in the melt, with considerably less in the source. The role that late-stage magma ocean cumulates rich in ilmenite and high-Ca pyroxene might play in modifying this volatile element estimate, however, casts remaining doubt on the volatile element abundance and evolution of the primitive Moon.