The H2O concentration and H2O/Ce ratio in olivine-hosted melt inclusions are high in lunar pyroclastic sample 74220 (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 74220 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 74220 and other lunar samples. Two explanations have been advanced. One is that volcanic product in sample 74220 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 74220 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 79135 regolith breccia (unknown cooling rate but with glassy MIs similar in texture with those in 74220), and pyroxene-hosted melt inclusions (PHMIs) in 15597 pigeonite basalts (known high cooling rate, second only to 74220 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 74220 and other studied lunar samples should have preserved intermediate H2O concentrations and H2O/Ce ratios. Our results show that melt inclusions in 79135 and 15597 contain high H2O concentrations (up to 969 ppmw in 79135 and up to 793 ppmw in 15597) and high H2O/Ce ratios (up to 21 in 79135 and up to 13 in 15997), bridging the big gap in H2O/Ce ratio among 74220 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+67 33 ppmw, respectively.

Earth's Moon was thought to be highly depleted in volatiles due to its formation by a giant impact. Over the last decade, however, evidence has been found in apatites, lunar volcanic glass beads, nominally anhydrous minerals and olivine-hosted melt inclusions, to support a relatively wet Moon. In particular, based on H2O/Ce, F/Nd, and S/Dy ratios, recent melt inclusion (MI) work estimated volatile (H2O, F, and S) abundances in lunar rocks to be similar to or slightly lower than the terrestrial depleted mantle. Uncertainties still occur, however, in whether the limited numbers of lunar samples studied are representative of the primitive lunar mantle, and whether the high H2O/Ce ratio for pyroclastic sample 74220 is due to local heterogeneity. In this paper, we report major element, trace element, volatile, and transition metal data in MIs for 5 mare basalt samples (10020, 12040, 15016, 15647 and 74235) and a pyroclastic deposit (74220). With our new lunar MI data, H2O/Ce ratios are still found to vary significantly among different lunar samples, from similar to 50 for 74220, to similar to 9 for 10020, similar to 3 for 74235, 1.7 to 0.9 for 12008, 15016, and 15647, and 0.5 for 12040. H2O/Ce ratios for these samples show positive correlation with their cooling rates, indicating a possible effect of post-eruptive loss of H on their H2O/ Ce variations. It is evident that most other lab and lunar processes, including loss of H2O during homogenization, mantle partial melting, magma evolution, and ingassing during or post eruption are unlikely the causes of high H2O/Ce variations among different lunar samples. By comparing ratios of F/Nd, S/Dy, Zn/Fe, Pb/Ce, Cs/Rb, Rb/Ba, Cl/K, Na/Sr, Ga/Lu, K/Ba, and Li/Yb between 74220 and other lunar samples, the possibility of 74220 originating from a volatile-enriched heterogeneity in the lunar mantle can also be excluded. With all the above considerations, we think that the H2O/Ce ratio for 74220 best represents the pre-degassing lunar basaltic melt and primitive lunar mantle, either because it was formed by a rapid eruption process, or it was sourced from a deeper part of the lunar mantle that experienced less degassing H2O loss during lunar magma ocean crystallization. With an H2O/Ce ratio of similar to 50, the primitive lunar mantle is estimated to contain similar to 84 ppm H2O. Comparing volatile abundances in melt inclusions, glassy embayments, and glass beads in 74220 yields the following volatility trend for volcanic eruptions on the lunar surface: H2O >> Cl >> Zn approximate to Cu approximate to F > S approximate to Ga approximate to Cs > Rb approximate to Pb > Na > K approximate to Li. Using the melt inclusion data obtained thus far, the volatile depletion trend for the Moon from a MI perspective is estimated. Our results show that most of the volatile elements in the lunar mantle are depleted relative to the bulk silicate Earth by a factor of 2 to 20, however, a good correlation between half condensation temperature and the volatile depletion trend is not observed. The relatively flat pattern for the lunar volatile depletion trend requires a lunar formation model that can reconcile the abundances of these volatiles in the lunar mantle. (C) 2018 Elsevier Ltd. All rights reserved.

Volatile abundances in lunar mantle are critical factors to consider for constraining the model of Moon formation. Recently, the earlier understanding of a dry Moon has shifted to a fairly wet Moon due to the detection of measurable amount of H2O in lunar volcanic glass beads, mineral grains, and olivine-hosted melt inclusions. The ongoing debate on a dry or wet Moon requires further studies on lunar melt inclusions to obtain a broader understanding of volatile abundances in the lunar mantle. One important uncertainty for lunar melt inclusion studies, however, is whether the homogenization of melt inclusions would cause volatile loss. In this study, a series of homogenization experiments were conducted on olivine-hosted melt inclusions from the sample 74220 to evaluate the possible loss of volatiles during homogenization of lunar melt inclusions. Our results suggest that significant loss of H2O could occur even during minutes of homogenization, while F, Cl and S in the inclusions remain unaffected. We model the trend of H2O loss in homogenized melt inclusions by a diffusive hydrogen loss model. The model can reconcile the observed experimental data well, with a best-fit H diffusivity in accordance with diffusion data explained by the slow mechanism for hydrogen diffusion in olivine. Surprisingly, no significant effect for the low oxygen fugacity on the Moon is observed on the diffusive loss of hydrogen during homogenization of lunar melt inclusions under reducing conditions. Our experimental and modeling results show that diffusive H loss is negligible for melt inclusions of >25 mu m radius. As our results mitigate the concern of H2O loss during homogenization for crystalline lunar melt inclusions, we found that H2O/Ce ratios in melt inclusions from different lunar samples vary with degree of crystallization. Such a variation is more likely due to H2O loss on the lunar surface, while heterogeneity in their lunar mantle source is also a possibility, A similar size-dependence trend of H2O concentrations was also observed in natural unheated melt inclusions in 742204 By comparing the trend of diffusive H loss in the natural MIs and in our homogenized MIs, the cooling rate for 74220 was estimated to be similar to 1 degrees C/s or slower. (C) 2017 Elsevier B.V. All rights reserved.

While it is now recognized that the Moon has indigenous water and volatiles, their total abundances are unclear, with current literature estimates ranging from nearly absent to Earth-like levels. Similarly unconstrained is the source of the Moon's water, which could be cometary, chondritic, or the primordial nebula. Here we measure H2O and D/H in olivine-hosted melt inclusions in lunar mare basalts 12018, 12035, and 12040, part of the consanguineous suite of Apollo 12 olivine basalts that differ primarily because of cooling rate (Walker et al., 1976). We find that the water contents are higher in the more rapidly cooled 12018 (62-740 ppm H2O) compared to the more slowly cooled basalts 12035 (28-156 ppm H2O) and 12040 (27-90 ppm H2O), suggesting that lunar basalts may have been dehydrating during slow cooling. D/H is similar in the olivine-hosted melt inclusions in all three samples, and indistinguishable from terrestrial water (dD = -183 +/- 212% to + 138 +/- 61%). When we compare the D/H of olivine-hosted melt inclusions to D/H of apatite in the same samples, the evolution of dD and water content can be better constrained. We propose that lunar magmas first exchange hydrogen with a low D/H reservoir during cooling, and then ultimately lose their water during extended subsolidus cooling. Due to high diffusion rates of hydrogen in olivine, it is likely that all basaltic olivine-hosted melt inclusions from the Moon exchanged hydrogen with a low D/H reservoir in near-surface magma chambers or lava flows. The most likely source of the low D/H reservoir on the Moon is the lunar regolith, which is known to have a significant solar wind hydrogen component.

The concentrations of volatile elements in the moon have important implications for the formation of the earth-moon system. There is currently a debate regarding the water content of the lunar mantle: Authors studying H2O in lunar pyroclastic glass beads and in olivine-hosted melt inclusions in such pyroclastic samples and in plagioclase crystals in lunar highland anorthosites infer hundreds of ppm H2O in the lunar mantle. In contrast, authors studying Zn/Fe ratios infer that the H2O concentration in the lunar mantle is <= 1 ppm, and they argue that the glassy lunar basalts are a local anomaly. We contribute to a resolution of the debate by a broader examination of the concentrations of H2O and other volatile components in olivine-hosted melt inclusions in a wider range of lunar mare basalts, including crystalline melt inclusions that are homogenized by melting in the laboratory. We find that F, Cl, and S concentrations in various lunar melt inclusions (including those in glassy lunar basalts) are similar to one another, and previously studied glassy lunar basalts are not a local anomaly in terms of these volatile concentrations. Furthermore, we estimate the pre-degassing H2O/Ce, F/Nd, and S/Dy ratios of mare basaltic magmas to be at least 64, 4.0 and 100 respectively. These ratios are lower than those of primitive earth mantle by a factor of 3, 5, and 4 respectively. The depletion factors of these volatile elements relative to the earth's primitive mantle do not correlate strongly with volatility or bonding energy, and indeed they are roughly constant and similar to those of other volatile elements such as Li, Cs, Rb and K. This approximate constancy of volatile depletion in the moon relative to the earth can be explained by assuming that both the earth and the moon acquired volatiles from a similar source or by a similar mechanism but the earth was more efficient in acquiring the volatiles. We estimate the H2O, F and S concentrations in the primitive lunar mantle source to be at least 110, 5.3, and 70 Pim. respectively - similar to or slightly lower than those in terrestrial MORB mantle. (C) 2015 Elsevier B.V. All rights reserved.