Evidence for diverse lunar melt compositions and mixing of the pre-3.9 Ga crust from zircon chemistry

Lunar samples collected during Apollo missions are typically impact-related breccias or regolith that contain amalgamations of rocks and minerals with various origins (e.g., products of igneous differentiation, mantle melting, and/or impact events). The largest intact pre-Nectarian (∼≥3.92 Ga) fragments of igneous rock contained within the breccia and regolith rarely exceed 1 cm in size, and they often show evidence for impact recrystallization. This widespread mixing of disparate materials makes unraveling the magmatic history of pre-Nectarian period fraught with challenges. To address this issue, we combine U-Pb geochronology of Apollo 14 zircons (²⁰⁷Pb–²⁰⁶Pb ages from 3.93 to 4.36 Ga) with zircon trace element chemistry and thermodynamic models. Zircon crystallization temperatures are calculated with Ti-in-zircon thermometry after presenting new titania and silica activity models for lunar melts. We also present rare earth element (REE), P, actinide, and Mg + Fe + Al concentrations. While REE patterns and P yield little information about the parent melt origins of these out-of-context grains, U and Th concentrations are highly variable among pre-4.2 Ga zircons when compared to younger grains. Thus, the distribution of heat-producing radioactive elements in melt sources pervading the early lunar crust was heterogenous. Melt composition variation is confirmed by zircon Al concentrations and thermodynamic modeling that reveal at least two dominant magma signatures in the pre-4.0 Ga zircon population. One inferred magma type has a high alumina activity. This magma likely assimilated anorthosite-rich rocks (e.g., Feldspathic Highlands Terrane; FHT), though impact-generated melts of an alumina-rich target rock is a viable alternative. The other magma signature bears more similarities to KREEP basalts from the Procellarum KREEP Terrane (PKT), reflecting lower apparent alumina activities. Melt diversity seems to disappear after 4.0 Ga, with zircon recording magma compositions that largely fall in-between the two main groups found for pre-4.0 Ga samples. We interpret <4 Ga zircons to have formed from a mixture of KREEP basalts and FHT-like rocks, consistent with the upper ∼15 km of the crust being thoroughly mixed and re-melted by basin-forming impacts during the pre-Nectarian period.