In the last decade, several studies have reported enrichments of the heavy isotopes of moderately volatile elements in lunar mare basalts. However, the mechanisms controlling the isotope fractionation are still debated and may differ for elements with variable geochemical behaviour. Here, we present a new comprehensive dataset of mass-dependent copper isotope compositions (delta 65Cu) of 30 mare basalts sampled during the Apollo missions. The new delta 65Cu data range from +0.14 %o to +1.28 %o (with the exception of two samples at 0.01 %o and -1.42 %o), significantly heavier than chondrites and the bulk silicate Earth. A comparison with mass fractions of major and trace elements and thermodynamic constraints reveals that Cu isotopic variations within different mare basalt suites are mostly unrelated to fractional crystallisation of silicates or oxides and late-stage magmatic degassing. Instead, we propose that the delta 65Cu average of each suite is representative of the composition of its respective mantle source. The observed differences across geographically and temporally distinct mare basalt suites, suggest that this variation relates to large-scale processes that formed isotopically distinct mantle sources. Based on a Cu isotope fractionation model during metal melt saturation in crystal mush zones of the lunar magma ocean, we propose that distinct delta 65Cu compositions and Cu abundances of mare basalt mantle sources reflect local metal melt-silicate melt equilibration and trapping of metal in mantle cumulates during lunar magma ocean solidification. Differences in delta 65Cu and mass fractions and ratios of siderophile elements between low- and high-Ti mare basalt sources reflect the evolving compositions of both metal and silicate melt during the late cooling stages of the lunar magma ocean.

Chang'E-5 samples provide unique insights into the composition of the lunar interior similar to 2 billion years ago, but geochemical models of their formation show a significant degree of discrepancy. Trace element abundance measurements in olivine grains in Chang'E-5 sub-sample CE5C0600YJFM002GP provide additional constraints on the basalt source. Geochemical modeling indicates that low-degree (4 %) batch melting of an olivine-pyroxenite lunar magma ocean cumulate, incorporating high levels of trapped lunar magma ocean liquid and plagioclase, can reproduce the rare earth element, Sr, Rb, Sc, Co and Ni abundances in our and previously reported Chang'E-5 samples, as well as observed Rb-Sr and Sm-Nd isotope systematics. Overall, these results strengthen the direct geochemical links between lunar magma ocean evolution and basaltic volcanism occurring similar to 2.5 billion years later. Additionally, Chang'E-5 high-Fo olivine is enriched in the volatile element Ge (1.38-3.94 mu g/g) by similar to 2 orders of magnitude compared to modeled results (< 0.02 mu g/g). As Ge is a mildly compatible element with bulk Ge partition coefficients close to 1, a Ge-depleted initial LMO proposed by previous research cannot yield a high-Ge mantle source for Chang'E-5 basalt, even when invoking assimilation of high-Ge LMO cumulates. The overabundance of Ge requires either a high-Ge, volatile rich initial bulk Moon with chondritic composition or a late Ge chloride vapor-phase metasomatism.

Due to the lack of rock samples directly from the deep part of the Moon, experiments and numerical simulation are effective methods to understand the early evolution of the Moon. Since the 1970s, the Lunar Magma Ocean (LMO) evolution model has been verified and modified by a large number of experimental petrology and geochemical work. However, the original composition of the Moon and the depth of its magma ocean, which are the two most critical parameters of LMO models remain controversial. The different lunar crust thickness estimated from lunar seismic data compared to that estimated from gravity data, the volatile content of lunar samples, and the widespread of Mg and Al-rich spinet (Cr (#) <5) discovered from interpreting the new remote sensing data affect our assessment on the starting composition and the depth of LMO, and the fractional crystallization process thereafter. In this paper, we review a series of high temperature and high pressure experimental petrology and experimental geochemistry results on the Moon's early evolution by focusing on: (1) The influence of refractory elements and volatile content of LMO's composition and its depth on the thickness of lunar crust and the Moon's mineral constitution formed through early differentiation. (2) The rationality of stability of high pressure mineral garnet deep inside lunar mantle and it effect on the distribution of trace elements during the evolution of lunar. (3) The petrogenesis of the Moon's special components, including volcanic glasses and Mg-suite, and their indication on the composition of the Moon's deep interior. (4) The constraint of lunar core composition on the Moon's material source, especially the abundance of trace elements. Based on the latest observation and the new analysis results of lunar samples, we evaluate the existing LMO evolution models and propose a LMO model with garnet as an important constituent mineral inside the Moon. We also discuss the necessary work need to be done to improve the new LMO model.

We conducted a petrologic study of apatite within eight unbrecciated, non-cumulate eucrites and two monomict, non-cumulate eucrites. These data were combined with previously published data to quantify the abundances of F, Cl, and H2O in the bulk silicate portion of asteroid 4 Vesta (BSV). Using a combination of apatite-based melt hygrometry/chlorometry and appropriately paired volatile/refractory element ratios, we determined that BSV has 3.0-7.2 ppm F, 0.39-1.8 ppm Cl, and 3.6-22 ppm H2O. The abundances of F and H2O are depleted in BSV relative to CI chondrites to a similar degree as F and H2O in the bulk silicate portion of the Moon. This degree of volatile depletion in BSV is similar to what has been determined previously for many moderately volatile elements in 4 Vesta (e.g., Na, K, Zn, Rb, Cs, and Pb). In contrast, Cl is depleted in 4 Vesta by a greater degree than what is recorded in samples from Earth or the Moon. Based on the Clisotopic compositions of eucrites and the bulk rock Cl-/F ratios determined in this study, the eucrites likely formed through serial magmatism of a mantle with heterogeneous delta Cl-37 and Cl/F, not as extracts from a partially crystallized global magma ocean. Furthermore, the volatile depletion and Cl-isotopic heterogeneity recorded in eucrites is likely inherited, at least in part, from the precursor materials that accreted to form 4 Vesta and is unlikely to have resulted solely from degassing of a global magma ocean, magmatic degassing of eucrite melts, and/or volatile loss during thermal metamorphism. Although our results can be reconciled with the past presence of wide-scale melting on 4 Vesta (i.e., a partial magma ocean), any future models for eucrite petrogenesis involving a global magma ocean would need to account for the preservation of a heterogeneous eucrite source with respect to Cl/F ratios and Cl isotopes. Published by Elsevier Ltd.

The Moon is not volcanically active at present, therefore, we rely on data from lunar samples, remote sensing, and numerical modeling to understand past lunar volcanism. The role of different volatile species in propelling lunar magma ascent and eruption remains unclear. We adapt a terrestrial magma ascent model for lunar magma ascent, considering different compositions of picritic magmas and various abundances of H-2, H2O, and CO (measured and estimated) for these magmas. We also conduct a sensitivity analysis to investigate the relationship between selected input parameters (pre-eruptive pressure, temperature, conduit radius, and volatile content) and given outputs (exit gas volume fraction, velocity, pressure, and mass eruption rate). We find that, for the model simulations containing H2O and CO, CO was more significant than H2O in driving lunar magma ascent, for the range of volatile contents considered here. For the simulations containing H-2 and CO, H-2 had a similar or slightly greater control than CO on magma ascent dynamics. Our results showed that initial H-2 and CO content has a strong control on exit velocity and pressure, two factors that strongly influence the formation of an eruption plume, pyroclast ejection, and overall deposit morphology. Our results highlight the importance of (a) quantifying and determining the origin of CO, and (b) understanding the abundance of different H-species present within the lunar mantle. Quantifying the role of volatiles in driving lunar volcanism provides an important link between the interior volatile content of the Moon and the formation of volcanic deposits on the lunar surface.

Eucrite meteorites are early-formed (>4.5 Ga) basaltic rocks that are likely to derive from the asteroid 4 Vesta, or a similarly differentiated planetesimal. To understand trace element and moderately volatile element (MVE) behavior more fully within and between eucrites, a laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) study is reported for plagioclase and pyroxene, as well as fusion crust and vitrophyric materials for ten eucrites. These eucrites span from a cumulate eucrite (Northwest Africa [NWA] 1923) to samples corresponding to Main Group (Queen Alexandra Range 97053, Pecora Escarpment 91245, Cumulus Hills 04049, Bates Nunatak 00300, Lewis Cliff 85305, Graves Nunataks 98098) and Stannern Group (Allan Hills 81001, NWA 1000) compositions, in addition to Elephant Moraine 90020. Along with a range of refractory trace elements, focus was given to abundances of five MVE (K, Zn, Rb, Cs, Pb) to interrogate the volatile abundance distributions in eucrite mineral phases. Modal recombination analyses of the eucrites reveals the important role of accessory phases (zircon, apatite) in some of the incompatible trace element (ITE) distributions, but not for the MVE which, for the phases that were analyzed, are mostly sited within plagioclase (Cs, Rb, K) and pyroxene (Zn, Pb), and are in equilibrium with a parental melt composition for Main Group eucrites. The new data reveal a possible relationship with total refractory ITE enrichment and texture, with the most ITE enriched Stannern Group eucrites examined (NWA 1000, ALHA 81001) having acicular textures and, in the case of ALHA 81001 a young degassing age (-3.7 Ga). Collectively the results suggest that Stannern Group eucrites may be related to anatexis of the eucritic crust by thermal metamorphism, with the heat source possibly coming from impacts. Impact processes do not have a pronounced effect on the abundances of the MVE, where plagioclase, pyroxene, fusion crust, and whole rock compositions of eucrites are all significantly depleted in the MVE, with Zn/Fe, Rb/Ba and K/U similar to lunar rocks. Assessment of eucrite compositions, however, suggests that Vesta has a more heterogeneous distribution of volatile elements and is similarly to slightly less volatile-depleted than the Moon. Phase dependence of the MVE (e.g., Cl in apatite, Zn primarily into spinel and early formed phases, including pyroxene) is likely to influence comparison diagrams where MVE stable isotopes are shown. In the case of delta Cl-37 versus delta Zn-66, metamorphism and impact processes may lead to a decrease in the delta Cl-37 value for a given delta Zn-66 value in eucrites, raising the possibility that late-stage impact and metamorphism had a profound effect on volatile distributions in early planetesimal crusts.(C) 2021 Elsevier Ltd. All rights reserved.

It is believed that the Moon formed following collision of a large planetesimal with the early Earth. Over the similar to 4 Gyr since this event the Moon has been considerably less processed by geological activity than the Earth, and may provide a better record of processes and conditions in the early Earth-Moon system. There have been many studies of magmatic volatiles such as H, F, Cl, S and C in lunar materials. However, our ability to interpret variable volatile contents in the lunar sample suite is dependent on our understanding of volatile behaviour in lunar systems. This is currently constrained by limited experimental data. Here, we present the first experimental mineral-melt partitioning coefficients for F, Cl and H2O in a model lunar system under appropriately reduced conditions (log fO(2) to IW-2.1, i.e. oxygen fugacity down to 2.1 log units below the Fe-FeO buffer). Data are consistent with structural incorporation of F, Cl and OH - in silicate melt, olivine and pyroxene under conditions of the lunar mantle. Oxygen fugacity has a limited effect on H2O speciation, and partitioning of H2O, F and Cl is instead largely dependent on mineral chemistry and melt structure. Partition coefficients are broadly consistent with a mantle source region for lunar volcanic products that is significantly depleted in F, Cl and H2O, and depleted in Cl relative to F and H2O, compared to the terrestrial mantle. Partitioning data are also used to model volatile redistribution during lunar magma ocean (LMO) crystallisation. The volatile content of lunar mantle cumulates is dependent upon proportion of trapped liquid during LMO solidification. However, differences in mineral-melt partitioning during LMO solidification can result in significant enrichment on F relative to Cl, and F relative to H2O, in cumulate phases relative to original LMO composition. As such, Cl depletion in lunar volcanic products may in part be a result of LMO solidification. Crown Copyright (C) 2020 Published by Elsevier Ltd. All rights reserved.

Volatile-bearing lunar surface and interior, giant magmatic-intrusion-laden near and far side, globally distributed layer of purest anorthosite (PAN) and discovery of Mg-Spinel anorthosite, a new rock type, represent just a sample of the brand new perspectives gained in lunar science in the last decade. An armada of missions sent by multiple nations and sophisticated analyses of the precious lunar samples have led to rapid evolution in the understanding of the Moon, leading to major new findings, including evidence for water in the lunar interior. Fundamental insights have been obtained about impact cratering, the crystallization of the lunar magma ocean and conditions during the origin of the Moon. The implications of this understanding go beyond the Moon and are therefore of key importance in solar system science. These new views of the Moon have challenged the previous understanding in multiple ways and are setting a new paradigm for lunar exploration in the coming decade both for science and resource exploration. Missions from India, China, Japan, South Korea, Russia and several private ventures promise continued exploration of the Moon in the coming years, which will further enrich the understanding of our closest neighbor. The Moon remains a key scientific destination, an active testbed for in-situ resource utilization (ISRU) activities, an outpost to study the universe and a future spaceport for supporting planetary missions.

Moderately volatile elements (MVE) are key tracers of volatile depletion in planetary bodies. Zinc is an especially useful MVE because of its generally elevated abundances in planetary basalts, relative to other MVE, and limited evidence for mass-dependent isotopic fractionation under high-temperature igneous processes. Compared with terrestrial basalts, which have delta Zn-66 values (per mille deviation of the Zn-66/Zn-64 ratio from the JMC-Lyon standard) similar to some chondrite meteorites (similar to+0.3 parts per thousand), lunar mare basalts yield a mean delta Zn-66 value of +1.4 +/- 0.5 parts per thousand (2 st. dev.). Furthermore, mare basalts have average Zn concentrations similar to 50 times lower than in typical terrestrial basaltic rocks. Late-stage lunar magmatic products, including ferroan anorthosite, Mg- and Alkali-suite rocks have even higher delta Zn-66 values (+3 to +6 parts per thousand). Differences in Zn abundance and isotopic compositions between lunar and terrestrial rocks have previously been interpreted to reflect evaporative loss of Zn, either during the Earth-Moon forming Giant Impact, or in a lunar magma ocean (LMO) phase. To explore the mechanisms and processes under which volatile element loss may have occurred during a LMO phase, we developed models of Zn isotopic fractionation that are generally applicable to planetary magma oceans. Our objective was to identify conditions that would yield a delta Zn-66 signature of similar to+1.4%0 within the lunar mantle. For the sake of simplicity, we neglect possible Zn isotopic fractionation during the Giant Impact, and assumed a starting composition equal to the composition of the present-day terrestrial mantle, assuming both the Earth and Moon had zinc 'consanguinity' following their formation. We developed two models: the first simulates evaporative fractionation of Zn only prior to LMO mixing and crystallization; the second simulates continued evaporative fractionation of Zn that persists until similar to 75% LMO crystallization. The first model yields a relatively homogenous bulk solid LMO delta Zn-66 value, while the second results in a stratification of delta Zn-66 values within the LMO sequence. Loss and/or isolation mechanisms for volatiles are critical to these models; hydrodynamic escape was not a dominant process, but loss of a nascent lunar atmosphere or separation of condensates into a proto-lunar crust are possible mechanisms by which volatiles could be separated from the lunar interior. The results do not preclude models that suggest a lunar volatile depletion episode related to the Giant Impact. Conversely, LMO models for volatile loss do not require loss of volatiles prior to lunar formation. Outgassing during planetary magma ocean phases likely played a profound role in setting the volatile inventories of planets, particularly for low mass bodies that experienced the greatest volatile loss. In turn, our results suggest that the initial compositions of planets that accreted from smaller, highly differentiated planetesimals were likely to be severely volatile depleted. (C) 2017 Elsevier Inc. All rights reserved.

The abundance of volatile elements and compounds, such as zinc, potassium, chlorine, and water, provide key evidence for how Earth and the Moon formed and evolved. Currently, evidence exists for a Moon depleted in volatile elements, as well as reservoirs within the Moon with volatile abundances like Earth's depleted upper mantle. Volatile depletion is consistent with catastrophic formation, such as a giant impact, whereas a Moon with Earth-like volatile abundances suggests preservation of these volatiles, or addition through late accretion. We show, using the Rusty Rock impact melt breccia, 66095, that volatile enrichment on the lunar surface occurred through vapor condensation. Isotopically light Zn (delta Zn-66 = -13.7%), heavy CI (delta(CI)-C-37 = +15%), and high U/Pb supports the origin of condensates from a volatile-poor internal source formed during thermomagmatic evolution of the Moon, with long-term depletion in incompatible CI and Pb, and lesser depletion of more-compatible Zn. Leaching experiments on mare basalt 14053 demonstrate that isotopically light Zn condensates also occur on some mare basalts after their crystallization, confirming a volatile-depleted lunar interior source with homogeneous delta Zn-66 approximate to +1.4%. Our results show that much of the lunar interior must be significantly depleted in volatile elements and compounds and that volatile-rich rocks on the lunar surface formed through vapor condensation. Volatiles detected by remote sensing on the surface of the Moon likely have a partially condensate origin from its interior.