Volatiles in melt inclusions from lunar mare basalts: Bridging the gap in the H2O/Ce ratio between melt Inclusions in lunar pyroclastic sample 74220 and other mare samples

Abstract

The H2O concentration and H2O/Ce ratio in olivine-hosted melt inclusions are high in lunar pyroclastic sample 74,220 (H2O up to 1410 ppmw; H2O/Ce up to 77) but lower (H2O 10 to 430 ppmw; H2O/Ce 0.3 to 9.4) in all other lunar samples studied before this work. The difference in H2O concentration and in H2O/Ce ratio is absent for other volatile elements (F, S, and Cl) in melt inclusions in 74,220 and other lunar samples. Because H2O (or H) is a critical volatile component with significant ramifications on the origin and evolution of the Moon, it is important to understand what causes such a large gap in H2O/Ce ratio between 74,220 and other lunar samples. Two explanations have been advanced. One is that volcanic product in sample 74,220 has the highest cooling rate and thus best preserved H2O in melt inclusions compared to melt inclusions in other samples. The other explanation is that sample 74,220 comes from a localized heterogeneity enriched in some volatiles. To distinguish these two possibilities, here we present new data from two rapidly cooled lunar samples with glassy melt inclusions: olivine-hosted melt inclusions (OHMIs) in 79,135 regolith breccia (unknown cooling rate but with glassy MIs similar in texture with those in 74220), and pyroxene-hosted melt inclusions (PHMIs) in 15,597 pigeonite basalts (known high cooling rate, second only to 74,220 and 15421). In addition, we also investigated new OHMIs in sample 74220. If the gap is due to the difference in cooling rates, samples with cooling rates between those of 74,220 and other studied lunar samples should have preserved intermediate H2O concentrations and H2O/Ce ratios. Our results show that melt inclusions in 79,135 and 15,597 contain high H2O concentrations (up to 969 ppmw in 79,135 and up to 793 ppmw in 15597) and high H2O/Ce ratios (up to 21 in 79,135 and up to 13 in 15997), bridging the big gap in H2O/Ce ratio among 74,220 and other lunar samples. Combined with literature data, we confirm that H2O/Ce ratios of different lunar samples are positively correlated to the cooling rates and independent of the type of mare basalts. We hence reinforce the interpretation that the lunar sample with the highest cooling rate best represents pre-eruptive volatiles in lunar basalts due to the least degassing. Based on Ce concentration in the primitive lunar mantle, we estimate that H2O concentration in the primitive lunar mantle (meaning bulk silicate Moon) is 121 ± 15 ppmw. Our new data also further constrain F/P, S/Dy and Cl/Ba ratios in lunar basalts and the lunar mantle. Estimated F, P, and S concentrations in the lunar primitive mantle are 4.4 ± 1.1 ppmw, 22 ± 8 ppmw, and 67-33+67 ppmw, respectively.