Lunar Melt Research Articles

Review of melt inclusions in lunar rocks: constraints on melt and mantle composition and magmatic processes

Abstract. Mineral-hosted melt inclusions provide a window into magmatic processes and pre-eruptive liquid compositions. Because melt inclusions are small (typically < 100 µm), the study of lunar melt inclusions is enabled by advancements of microbeam instrumental techniques. In the 1970s immediately following the Apollo and Luna missions, major and minor oxide concentrations of lunar melt inclusions were measured using electron microprobes. The data were used to understand magma evolution, and they revealed the immiscibility of two silicate liquids in the late stage of lunar magma evolution. More recently, the development of secondary ion mass spectrometry as well as laser ablation–inductively coupled plasma–mass spectrometry has enabled the measurement of key volatile elements and other trace elements in lunar melt inclusions, down to about the 0.1 ppm level. The applications of these instruments have ushered in a new wave of lunar melt inclusion studies. Recent advances have gone hand in hand with improved understanding of post-entrapment loss of volatiles. These studies have provided deep insights into pre-eruptive volatiles in lunar basalts, the abundance of volatiles in the lunar mantle, the isotopic ratios of some volatile elements, and the partition of trace elements between host olivine and melt inclusions. The recent studies of lunar melt inclusions have played a critical role in establishing a new paradigm of a fairly wet Moon with about 100 ppm H2O in the bulk silicate Moon (rather than a “bone-dry” Moon) and have been instrumental in developing an improved understanding of the origin and evolution of the Moon.

Titanium-rich basaltic melts on the Moon modulated by reactive flow processes

The origin of titanium-rich basaltic magmatism on the Moon remains enigmatic. Ilmenite-bearing cumulates in the lunar mantle are often credited as the source, but their partial melts are not a compositional match and are too dense to enable eruption. Here we use petrological reaction experiments to show that partial melts of ilmenite-bearing cumulates react with olivine and orthopyroxene in the lunar mantle, shifting the melt composition to that of the high-Ti suite. New high-precision Mg isotope data confirm that high-Ti basalts have variable and isotopically light Mg isotope compositions that are inconsistent with equilibrium partial melting. We employ a diffusion model to demonstrate that kinetic isotope fractionation during reactive flow of partial melts derived from ilmenite-bearing cumulates can explain these anomalously light Mg isotope compositions, as well as the isotope composition of other elements such as Fe, Ca and Ti. Although this model does not fully replicate lunar melt–solid interaction, we suggest that titanium-rich magmas erupted on the surface of the Moon can be derived through partial melting of ilmenite-bearing cumulates, but melts undergo extensive modification of their elemental and isotopic composition through reactive flow in the lunar mantle. Reactive flow may therefore be the critical process that decreases melt density and allows high-Ti melts to erupt on the lunar surface.

Experimental Evidence Supporting an Overturned Iron‐Titanium‐Rich Melt Layer in the Deep Lunar Interior

AbstractDense Fe‐Ti‐rich cumulates, formed as the last dregs of the lunar magma ocean, are thought to have driven a large‐scale overturn of the lunar mantle over 4 Ga ago. Analysis of lunar seismic data has implied that some of the overturned bodies may have reached the lunar core‐mantle boundary and remained there until the present day as a partially molten layer. However, whether such a molten layer could be stable during >4 Ga of post‐magma‐ocean lunar history and explain lunar seismic observations remains poorly constrained. Here, we report the first sound velocity measurements on a Fe‐Ti‐rich lunar melt up to conditions of the lowermost lunar mantle. Our results suggest that a partial melt layer with at least 20% overturned Fe‐Ti‐rich melt can be trapped atop the lunar core‐mantle boundary until the present day, strongly influencing the thermochemical evolution of the lunar interior.

Spectral properties of lunar impact melt deposits from Moon Mineralogy Mapper (M3) data

Lunar impact melt deposits have unusual surface properties, unlike any measured terrestrial lava flow. Radar observations suggest that they are incredibly rough at decimeter scales, but they appear smooth in high-resolution, meter-scale optical images. The cause of their unusual surface roughness is unknown. In this work, we investigate the properties of impact melt deposits from seven lunar craters, ranging in size from 7.5 to 96 km in diameter, in an effort to understand the cause of their unique surface texture. We use data from the Lunar Reconnaissance Orbiter's (LRO) Mini-RF instrument to characterize the small-scale roughness of the deposits, data from the LRO Camera (LROC) to characterize their meter-scale morphology, and data from Chandrayaan-1's Moon Mineralogy Mapper (M3) to characterize their composition. This represents the most comprehensive study of the composition of lunar melt deposits completed to date. In particular, we applied a customized spectral unmixing model to the M3 data using laboratory spectra acquired from a range of possible lunar endmembers: pyroxene, olivine, fast-quenched lunar glass simulants, and impact melts and breccias (both synthetic and natural). We found that spectra derived from lunar melt deposits are typically modeled as a mix of the pyroxene and/or impact melts and breccias endmembers. Our modeled results suggest that lunar melt deposits are either crystalline deposits of pyroxene-rich rocks, or a mixture of glassy material and pyroxene minerals. The latter interpretation could explain the roughness observed in the Mini-RF data, if the melt deposits have a glassy surficial layer that shatters during impact gardening to produce decimeter scale blocks.

Metal grains in lunar rocks as indicators of igneous and impact processes

AbstractAnhedral metal grains of >micrometer size occur in many lunar rock types, including mare basalts, magnesian suite rocks (MGS), ferroan anorthosites (FAN), and impact melt rocks and breccias. Some metal grains are inherited from, or modified by, impactors striking the Moon into crustal materials. These grains have high Ni/Co resulting from the addition of chondritic or iron impactors. Metal grains in mare basalts, FAN, and MGS have Ni/Co ranging from >20 to <1, being generally distinct from impactor compositions. Nickel and Co behave as compatible elements in lunar melts, with parental melts having between ~40–50 ppm Co, ~40–60 ppm Ni, and Ni/Co ~1. These compositions suggest a bulk silicate Moon (BSM) with Ni some three times lower than in bulk silicate Earth. Modeling of Ni and Co during fractional crystallization of mafic mare basalt parental melts originating from a BSM source predicts high Ni/Co metals form during early olivine fractionation. The combined effects of pyroxene ± plagioclase crystallization and increasing but variable compatibility of Ni and Co during basaltic melt evolution can explain the generation of low Ni/Co metals in more differentiated mare basalts. High‐Ti mare basalts have metal with low Ni/Co, but the crystallization of ilmenite and armalcoite restricts the range of Ni and Co in metal. Collectively, these results are consistent with metal grains in mare basalts forming solely through endogenous processes. Measurement of metal grains represents a rapid way for determining endogenous (e.g., lunar interior melts) versus exogenous (e.g., impact contamination) processes acting on lunar samples. In turn, the presence of low Ni/Co metal grains in mare basalts supports their origin as uncontaminated partial melts originating from lunar mantle sources that may have experienced loss of Ni to a small lunar core.

The hydrogen isotopic composition of lunar melt inclusions: An interplay of complex magmatic and secondary processes

Since the discovery of water (a term collectively used for the total H, OH and H2O) in samples derived from the lunar interior, heterogeneity in both water concentration and its hydrogen isotopic ratio has been documented for various lunar phases. However, most previous studies have focused on measurements of hydrogen in apatite, which typically forms during the final stages of melt crystallisation. To better constrain the abundance and isotopic composition of water in the lunar interior, we have targeted melt inclusions (MIs), in mare basalts, that are trapped during the earliest stages of melt crystallisation. Melt inclusions are expected to have suffered minimal syn- or post-eruption modification processes, and, therefore, should provide more accurate information about the history of H in the lunar interior. Here, we report H−/18O− measurements as calibrated water concentrations, and hydrogen isotope ratios obtained by secondary ion mass spectrometry (SIMS) in a large set of basaltic MIs from Apollo mare basalts 10020, 10058, 12002, 12004, 12008, 12020, 12040, 14072 and 15016. Our results demonstrate that partially crystallised MIs from lunar basalts and their parental melts were influenced by a variety of processes such as hydrogen diffusion, degassing and assimilation of material affected by solar-wind implantation. Deconvolution of these processes show that lunar basaltic parental magmas were heterogeneous and had a broadly chondritic hydrogen isotopic composition with δD values varying between −200 and +200‰.

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.

Impact History and Regolith Evolution on the Moon: Geochemistry and Ages of Glasses from the Apollo 16 Site

AbstractLunar impact glasses are quenched droplets of melt that carry geochemical records of their target compositions, formation ages, and time‐integrated exposure in the upper layers of the lunar regolith. Here we present the first study to obtain major element, trace element, and Ar isotopic data for impact glasses from the Apollo 16 regolith sample 66031. Thirty particles were analysed with 27 of them yielding useable age information. The glasses have a wide range of major and trace element compositions, similar to that observed in lunar meteorites. Half of these glasses have compositions similar to Apollo 16 soils and are considered to be “locally derived”, whereas the others represent diverse source regions and are considered to be “exotic” particles that were delivered from a considerable distance to the landing site.Almost 40% of the samples analysed for this study have formation ages younger than 500 Ma. Duplicate particles produced in single impact events contribute minimally to the age distribution, and diurnal or transient heating of the regolith does not appear to have had a significant effect on the 40Ar/39Ar ages. Rather, the ages reflect primarily the formation of these glasses by impact melting, with the distribution modified to some degree by preservation bias. As most of these glasses are likely formed by relatively small impactors, their age distribution cannot be compared directly with the crystalline lunar melt rocks to constrain the impact mass flux through time.

Effects of pH2O, pH2 and fO2 on the diffusion of H-bearing species in lunar basaltic liquid and an iron-free basaltic analog at 1 atm

Abstract We have experimentally determined the diffusivity of water in a representative lunar basaltic liquid composition (LG) and in an iron-free analog of a basaltic liquid (AD) at the low water concentrations and low oxygen fugacities (fO2) relevant to the eruption of lunar basalts. Experiments were conducted at 1 atm and 1350 °C over a range of pH2/pH2O from near zero to ∼10 and a range in fO2 spanning ∼9 orders of magnitude (from 2.2 log units below the iron-wustite buffer, IW−2.2, to IW+6.7). The water concentrations measured in our quenched experimental glasses by secondary ion mass spectrometry (SIMS) and Fourier transform infrared spectroscopy (FTIR) vary from a few ppm to ∼430 ppm. Water concentration gradients in the majority of our AD experiments are well described by models in which the diffusivity of water ( D w a t e r ∗ ) has a constant value of ∼2 × 10−10 m2/s, while our LG results indicate that D w a t e r ∗ in LG melt has a constant value of ∼6 × 10−10 m2/s under the conditions of our experiments. Water concentration gradients in hydration and dehydration experiments that were run simultaneously in H2/CO2 gas mixtures are well described by the same D w a t e r ∗ , and water concentrations measured near the melt-vapor interfaces of these experiment pairs are approximately the same. These observations strongly support an equilibrium boundary condition for our experiments containing >70 ppm H2O. However, dehydration experiments into nominally anhydrous CO2, N2, and CO/CO2 gas mixtures leave some scope for the importance of kinetics during dehydration of melts containing less than a few 10′s of ppm H2O. Comparison of our results with the modified speciation model (Ni et al., 2013) in which both molecular water and hydroxyl are allowed to diffuse suggests that we have resolved the diffusivity of hydroxyl ( D O H ) in AD and LG melts. Our results support a positive correlation between D O H and melt depolymerization. Best-fit values of D w a t e r ∗ for our LG experiments vary within a factor of ∼2 over a range of pH2/pH2O from 0.007 to 9.7 and a range of logfO2 from IW−2.2 to IW+4.9. The relative insensitivity of our best-fit values of D w a t e r ∗ to variations in pH2 suggests that H2 diffusion did not control the rate of degassing of H-bearing species from the lunar glasses of Saal et al. (2008); however, we cannot rule out a role for molecular H2 diffusion under lower-temperature and/or higher-pressure conditions than explored in our experiments. The value of D w a t e r ∗ chosen by Saal et al. (2008) for modeling the diffusive degassing of the lunar volcanic glasses is within a factor of ∼2 of our measured value in LG melt at 1350 °C. By coupling our LG results at 1350 °C with an activation energy of 220 kJ/mol (Zhang et al., 2017), we obtain the following Arrhenius relationship, which can be used to model syneruptive diffusive water loss from lunar melt beads: D w a t e r ∗ ( m 2 / s ) = 7.2 × 1 0 - 3 e x p - 2.6 × 1 0 4 T ( K ) .

In situ Viscometry of Primitive Lunar Magmas at High Pressure and High Temperature

Understanding the dynamics of the magmatic evolution of the interior of the Moon requires accurate knowledge of the viscosity () of lunar magmas at high pressure (P) and high temperature (T) conditions. Although the viscosities of terrestrial magmas are relatively well documented, and their relation to magma composition well studied, the viscosities of lunar titano-silicate melts are not well known. Here, we present an experimentally measured viscosity dataset for three end member compositions, characterized by a wide range of titanium contents, at lunar-relevant pressure-temperature range of 1.1 – 2.4 GPa and 1830 - 2090 K. In-situ viscometry using the falling sphere technique shows that the viscosity of lunar melts varies between  0.13 and 0.87 Pa-s depending on temperature, pressure and composition. Viscosity decreases with increasing temperature with activation energies for viscous flow of Ea = 201 kJ/mol and Ea = 106 kJ/mol for low-titanium (Ti) and high-Ti melts, respectively. Pressure is found to mildly increase the viscosity of these intermediate polymerized melts by a factor of  1.5 between 1.1 and 2.4 GPa. Viscosities of low-Ti and high-Ti magmas at their respective melting temperatures are very close. However at identical P-T conditions ( 1.3 GPa,  1840 K) low-Ti magmas are about a factor of three more viscous than high-Ti magmas, reflecting structural effects of Si and Ti on melt viscosity. Measured viscosities differ significantly from empirical models based on measurements of the viscosity of terrestrial basalts, with largest deviations observed for the most Ti-rich and Si-poor composition. Viscosity coefficients for these primitive lunar melts are found to be lower than those of common terrestrial basalts, giving them a high mobility throughout the lunar mantle and onto the surface of the Moon despite their Fe and Ti-rich compositions.

Upwards migration phenomenon on molten lunar regolith: New challenges and prospects for ISRU

As part of our research on the feasibility of producing commodities from lunar regolith by thermal-driven processes with minimal terrestrial precursors we need to characterize, reproduce, and understand thermophysical properties of the molten regolith still unforeseen under the lunar vacuum conditions at a scalable sample size. Two unanticipated phenomena, apparently caused by lunar melt’s surface tension under vacuum, have been revealed in our research work, vacuum void formation and upwards migration. In this paper we present our findings and thinkable explanation on the upwards migration phenomenon experimentally observed and consistently replicated as JSC-1A lunar regolith simulant melted at high vacuum. Upwards migration of molten lunar regolith will make future lunar ISRU’s melting processes both challenging as molten bulk material would migrate upwards along the container’s walls, and also promising on new opportunities for alternative ISRU’s sustainable processes as regolith’s upwards migration takes place in uniformed thin-film pattern. Among the potential ISRU’s processes that might use controlled thermal thin-film-based migration without the necessity of terrestrial precursors are production of feedstock for 3D printing, fractional separation of regolith’s component’s (O2, metals, and alloys) via pyrolysis, film coating, purification of valuables solid crystals including silicon, and fabrication of key elements for microfluidic, and MEMS devices. Thermal upwards migration phenomenon on JSC-1A’s melt is formulated and explained by the authors as due to thermal Marangoni effect (also known as thermo-capillarity) in which temperature gradients within the melt’s bulk and along the crucible’s wall yield the surface tension large enough to supersede the gravitational force and yield the experimentally observed upwards thin-film migration. As far as the authors know, upwards thermal migration of molten JSC-1A (or other lunar simulant regolith) under vacuum has not been reported in the literature. A thermal mathematical model accounting for thermal Marangoni effect on molten JSC-1A agrees with what experimentally was observed, the formation of the meniscus on the melt-wall surface interface along with an incipient upwards migration in thin-film pattern along the crucible wall that, according to the model, experiences large temperature gradient, an important factor to trigger the thermal Marangoni effect along with the fact that surface tension of the molten lunar regolith material is temperature dependent.

Volatile loss following cooling and accretion of the Moon revealed by chromium isotopes

Terrestrial and lunar rocks share chemical and isotopic similarities in refractory elements, suggestive of a common precursor. By contrast, the marked depletion of volatile elements in lunar rocks together with their enrichment in heavy isotopes compared with Earth's mantle suggests that the Moon underwent evaporative loss of volatiles. However, whether equilibrium prevailed during evaporation and, if so, at what conditions (temperature, pressure, and oxygen fugacity) remain unconstrained. Chromium may shed light on this question, as it has several thermodynamically stable, oxidized gas species that can distinguish between kinetic and equilibrium regimes. Here, we present high-precision Cr isotope measurements in terrestrial and lunar rocks that reveal an enrichment in the lighter isotopes of Cr in the Moon compared with Earth's mantle by 100 ± 40 ppm per atomic mass unit. This observation is consistent with Cr partitioning into an oxygen-rich vapor phase in equilibrium with the proto-Moon, thereby stabilizing the CrO2 species that is isotopically heavy compared with CrO in a lunar melt. Temperatures of 1,600-1,800 K and oxygen fugacities near the fayalite-magnetite-quartz buffer are required to explain the elemental and isotopic difference of Cr between Earth's mantle and the Moon. These temperatures are far lower than modeled in the aftermath of a giant impact, implying that volatile loss did not occur contemporaneously with impact but following cooling and accretion of the Moon.

P-bearing Olivines from the “Luna-20” Soil Samples, Their Sources and Possible Phosphorus Substitution Mechanisms in Lunar Olivine

Rocks with P-bearing olivine were found in soil samples delivered by the “Luna-20” automated station. They are ascribed to the highland anorthosite–norite (more rarely, gabbro-norite)–troctolite rock series enriched in phosphorus and other incompatible elements, but are not related to typical KREEP rocks enriched in incompatible elements. Their source is presumably of hybrid origin and related to primary high- Mg suite (HMS) rocks. The occurrence of high- and low-Cr populations of P-bearing olivine in different structural rock types can be attributed to the annealing-related more rapid chromium diffusion (relative to that of phosphorus) in olivine from metamorphosed rocks. This assumption is supported by stoichiometric formula calculations of these olivines. An alternative explanation for these olivine populations is their derivation from at least two different sources. Disequilibrium crystallization of the P-bearing olivines, which is confirmed by an intricate phosphorus zoning, excludes the existence of P-rich melts, which is consistent with previous observations. At the same time, olivine fractionation can be responsible for the phosphorus content in lunar melts. The incorporation of phosphorus in olivine of the “Luna-20” anorthosite troctolites is presumably controlled by a coupled substitution mechanism of divalent cations and silicon for phosphorus and chromium in the tetrahedral and octahedral sites (Milman-Barris et al., 2008). Another possible mechanism is the substitution of divalent cations in octahedral sites by phosphorus and chromium, which provides the possible presence of P3+.

Evidence for a sulfur-undersaturated lunar interior from the solubility of sulfur in lunar melts and sulfide-silicate partitioning of siderophile elements

Sulfur concentrations at sulfide saturation (SCSS) were determined for a range of low- to high-Ti lunar melt compositions (synthetic equivalents of Apollo 14 black and yellow glass, Apollo 15 green glass, Apollo 17 orange glass and a late-stage lunar magma ocean melt, containing between 0.2 and 25 wt.% TiO2) as a function of pressure (1–2.5 GPa) and temperature (1683–1883 K). For the same experiments, sulfide-silicate partition coefficients were derived for elements V, Cr, Mn, Co, Cu, Zn, Ga, Ge, As, Se, Mo, Sn, Sb, Te, W and Pb. The SCSS is a strong function of silicate melt composition, most notably FeO content. An increase in temperature increases the SCSS and an increase in pressure decreases the SCSS, both in agreement with previous work on terrestrial, lunar and martian compositions. Previously reported SCSS values for high-FeO melts were combined with the experimental data reported here to obtain a new predictive equation to calculate the SCSS for high-FeO lunar melt compositions. Calculated SCSS values, combined with previously estimated S contents of lunar low-Ti basalts and primitive pyroclastic glasses, suggest their source regions were not sulfide saturated. Even when correcting for the currently inferred maximum extent of S degassing during or after eruption, sample S abundances are still > 700 ppm lower than the calculated SCSS values for these compositions. To achieve sulfide saturation in the source regions of low-Ti basalts and lunar pyroclastic glasses, the extent of degassing of S in lunar magma would have to be orders of magnitude higher than currently thought, inconsistent with S isotopic and core-to-rim S diffusion profile data. The only lunar samples that could have experienced sulfide saturation are some of the more evolved A17 high-Ti basalts, if sulfides are Ni- and/or Cu rich.Sulfide saturation in the source regions of lunar melts is also inconsistent with the sulfide-silicate partitioning systematics of Ni, Co and Cu. Segregation of significant quantities of (non)-stoichiometric sulfides during fractional crystallization would result in far larger depletions of Ni, Co and Cu than observed, whereas trends in their abundances are more likely explained by olivine fractionation. The sulfide exhaustion of the lunar magma source regions agrees with previously proposed low S abundances in the lunar core and mantle, and by extension with relatively minor degassing of S during the Moon-forming event. Our results support the hypothesis that refractory chalcophile and highly siderophile element systematics of low-Ti basalts and pyroclastic glasses reflect the geochemical characteristics of their source regions, instead of indicating the presence of residual sulfides in the lunar interior.

Volatile loss during homogenization of lunar melt inclusions

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 μm 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 74220. 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 ∼1 °C/s or slower.

The Late Heavy Bombardment

Heavily cratered surfaces on the Moon, Mars, and Mercury show that the terrestrial planets were battered by an intense bombardment during their first billion years or more, but the timing, sources, and dynamical implications of these impacts are controversial. The Late Heavy Bombardment refers to impact events that occurred after stabilization of the planetary lithospheres such that they could be preserved as craters and basins. Lunar melt rocks and meteorite shock ages point toward a discrete episode of elevated impact flux between ∼3.5 and ∼4.0–4.2 Ga, and a relative quiescence between ∼4.0–4.2 and ∼4.4 Ga. Evidence from Precambrian impact spherule layers suggests that a long-lived tail of terrestrial impactors lasted to ∼2.0–2.5 Ga. Dynamical models that include populations residual from primary accretion and destabilized by giant planet migration can potentially account for the available observations, although all have pros and cons. The most parsimonious solution to match constraints is a hybrid model with discrete early, post-accretion and later, planetary instability–driven populations of impactors.

Volcanic gas composition, metal dispersion and deposition during explosive volcanic eruptions on the Moon

The transport of metals in volcanic gases on the Moon differs greatly from their transport on the Earth because metal speciation depends largely on gas composition, temperature, pressure and oxidation state. We present a new thermochemical model for the major and trace element composition of lunar volcanic gas during pyroclastic eruptions of picritic magmas calculated at 200–1500°C and over 10−9–103bar. Using published volatile component concentrations in picritic lunar glasses, we have calculated the speciation of major elements (H, O, C, Cl, S and F) in the coexisting volcanic gas as the eruption proceeds. The most abundant gases are CO, H2, H2S, COS and S2, with a transition from predominantly triatomic gases to diatomic gases with increasing temperatures and decreasing pressures. Hydrogen occurs as H2, H2S, H2S2, HCl, and HF, with H2 making up 0.5–0.8mol fractions of the total H. Water (H2O) concentrations are at trace levels, which implies that H-species other than H2O need to be considered in lunar melts and estimates of the bulk lunar composition. The Cl and S contents of the gas control metal chloride gas species, and sulfide gas and precipitated solid species. We calculate the speciation of trace metals (Zn, Ga, Cu, Pb, Ni, Fe) in the gas phase, and also the pressure and temperature conditions at which solids form from the gas. During initial stages of the eruption, elemental gases are the dominant metal species. As the gas loses heat, chloride and sulfide species become more abundant. Our chemical speciation model is applied to a lunar pyroclastic eruption model with isentropic gas decompression. The relative abundances of the deposited metal-bearing solids with distance from the vent are predicted for slow cooling rates (<5°C/s). Close to a volcanic vent we predict native metals are deposited, whereas metal sulfides dominate with increasing distance from the vent. Finally, the lunar gas speciation model is compared with the speciation of a H2O-, CO2- and Cl-rich volcanic gas from Erta Ale volcano (Ethiopia) as an analogy for more oxidized planetary eruptions. In the terrestrial Cl-rich gas the metals are predominantly transported as chlorides, as opposed to metallic vapors and sulfides in the lunar gas. Due to the presence of Cl-species, metal transport is more efficient in the volcanic gas from Erta Ale compared to the Moon.

Characterization of mesostasis regions in lunar basalts: Understanding late‐stage melt evolution and its influence on apatite formation

AbstractRecent studies geared toward understanding the volatile abundances of the lunar interior have focused on the volatile‐bearing accessory mineral apatite. Translating measurements of volatile abundances in lunar apatite into the volatile inventory of the silicate melts from which they crystallized, and ultimately of the mantle source regions of lunar magmas, however, has proved more difficult than initially thought. In this contribution, we report a detailed characterization of mesostasis regions in four Apollo mare basalts (10044, 12064, 15058, and 70035) in order to ascertain the compositions of the melts from which apatite crystallized. The texture, modal mineralogy, and reconstructed bulk composition of these mesostasis regions vary greatly within and between samples. There is no clear relationship between bulk‐rock basaltic composition and that of bulk‐mesostasis regions, indicating that bulk‐rock composition may have little influence on mesostasis compositions. The development of individual melt pockets, combined with the occurrence of silicate liquid immiscibility, exerts greater control on the composition and texture of mesostasis regions. In general, the reconstructed late‐stage lunar melts have roughly andesitic to dacitic compositions with low alkali contents, displaying much higher SiO2 abundances than the bulk compositions of their host magmatic rocks. Relevant partition coefficients for apatite‐melt volatile partitioning under lunar conditions should, therefore, be derived from experiments conducted using intermediate compositions instead of compositions representing mare basalts.

Crystal accumulation in a 4.2 Ga lunar impact melt

The ages of lunar impact basins and the role of fractional crystallization in producing compositional heterogeneity of lunar melt sheets are long-standing problems with significant implications for solar system dynamics and the petrologic evolution of the lunar crust. Here we document the formation of a basin-scale impact on the Moon at 4.20±0.07Ga based on the 147Sm–143Nd isochron age of a magnesian, noritic anorthosite melt rock from lunar breccia 67955. Major element compositions of plagioclase and mafic silicates in the melt rock imply a substantial component of primary Mg-suite cumulates or related lithologies in the pre-impact crustal stratigraphy. Trace element compositions of the plagioclase, including diagnostic ratios such as Sr/Ba, are also mostly similar to those in plagioclase from Mg-suite cumulates, with a small number of grains trending toward compositions observed in ferroan anorthosites. Mineral-melt distribution coefficients applied to trace element compositions of the 67955 plagioclase and pyroxene predict parental melt compositions that contrast strongly with the bulk rock. Compared to the whole rock, parental melts calculated from the plagioclase are enriched in REE (ΣREELa–Yb=131–885, average 619ppm vs. 39.8ppm) and they have more fractionated REE patterns (La/Ybn=1.2–9.8, average 4.9 vs. 1.5) with deep negative Eu anomalies (Eu/Eu∗=0.09–0.40 vs. 1.36). Trace element data for the pyroxenes also imply incompatible-element enriched parental melts. Subsolidus equilibration between the plagioclase and the pyroxene apparently rotated the REE patterns, but the conclusion that the parental melt was highly enriched in REE relative to the whole rock appears robust. Quantitative modeling shows that fractional crystallization of the 67955 whole rock composition cannot reproduce the range of Ba, Sr, Ti, and La concentrations measured in the 67955 plagioclase. Rather, the models require an initial melt composition that was strongly enriched in these elements, and they suggest that fractional crystallization became less efficient as crystallization proceeded. The contrast between the inferred parental melt composition and the bulk rock implies formation of the 67955 noritic anorthosite as a crystal cumulate, and that the cogenetic residual melt was strongly enriched in incompatible elements. If so, this would be the first documented example of fractional crystallization in a lunar impact melt sheet. The petrological and geochemical characteristics of the 67955 noritic anorthosite suggest that it formed by an impact in the Procellarum-KREEP Terrane, and was transported to the Apollo 16 site as Imbrium ejecta. Inheritance of ejecta related to this pre-Imbrium basin may contribute to the common occurrence of ∼4.2Ga 40Ar–39Ar plateau ages in breccia clasts and regolith fragments from the rim of North Ray crater. In that case, those data may provide no constraints on the age of the Nectaris basin, despite its proximity to the Apollo 16 site.

Water, fluorine, and sulfur concentrations in the lunar mantle

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 ppm, respectively – similar to or slightly lower than those in terrestrial MORB mantle.