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.

Elevated water contents in various lunar materials have invigorated the discussion on the volatile content of the lunar interior and on the extent to which the volatile element inventory of lunar magmatic rocks is controlled by volatility and degassing. Abundances of moderately volatile and siderophile elements can reveal insights into lunar processes such as core formation, late accretion and volatile depletion. However, previous assessments relied on incomplete data sets and data of variable quality. Here we report mass fractions of the siderophile volatile elements Cu, Se, Ag, S, Te, Cd, In, and Tl in lunar magmatic rocks, analyzed by state-of-the-art isotope dilution-inductively coupled plasma mass spectrometry. The new data enable us to disentangle distribution processes during the formation of different magmatic rock suites and to constrain mantle source compositions. Mass fractions of Cu, S, and Se in mare basalts and magnesian suite norites clearly correlate with indicators of fractional crystallization. Similar mass fractions and fractional crystallization trends in mafic volcanic and plutonic rocks indicate that the latter elements are less prone to degassing during magma ascent and effusion than proposed previously. The latter processes predominate only for specific elements (e.g., Tl, Cd) and complementary enrichments of these elements also occur in some brecciated highland rocks. A detailed comparison of elements with different affinities to metal or sulfide and gas phase reveals systematic differences between lunar magmatic rock suites. The latter observation suggests a predominant control of the variations of S, Se, Cu, and Ag by mantle source composition instead of late-stage magmatic degassing. New estimates of mantle source compositions of two low-Ti mare basalt suites support the notion of a lunar mantle that is strongly depleted in siderophile volatile elements compared to the terrestrial mantle.(C) 2022 Elsevier B.V. All rights reserved.

The formation of the Moon is thought to be the result of a giant impact between a Mercury-to-proto-Earth-sized body and the proto-Earth. However, the initial thermal state of the Moon following its accretion is not well constrained by geochemical data. Here, we provide geochemical evidence that supports a high-temperature origin of the Moon by performing high-temperature (1973-2873 K) metal-silicate partitioning experiments, simulating core formation in the newly-formed Moon. Results indicate that the observed lunar mantle depletions of Ni and Co record extreme temperatures (>2600-3700 K depending on assumptions about the composition of the lunar core) during lunar core formation. This temperature range is within range of the modeled silicate evaporation buffer in a synestia-type environment. Our results provide independent geochemical support for a giant-impact origin of the Moon and show that lunar thermal models should start with a fully molten Moon. Our results also provide quantitative constraints on the effects of high-temperature lunar differentiation on the lunar mantle geochemistry of volatile, and potentially siderophile elements Cu, Zn, Ga, Ge, Se, Sn, Cd, In, Te and Pb. At the extreme temperatures recorded by Ni and Co, many of these elements behave insufficiently siderophile to explain their depletions by core formation only, consistent with the inferred volatility related loss of Cr, Cu, Zn, Ga and Sn during the Moon-forming event and/or subsequent magma-ocean degassing. (C) 2020 Elsevier B.V. All rights reserved.

Low oxygen fugacity (f(O2)) in the lunar interior (one log unit below the iron-wustite buffer inverted right perpendicular IW-1 inverted left perpendicular) offers the possibility that stable Fe-metal and sulfide phases exist as restites within lunar mare basalt source regions. Metal and sulfide phases have high metal-melt and sulfide-melt partition coefficients for chalcophile, siderophile (> 100), and highly siderophile elements (>> 100 000; HSE: Os, Ir, Ru, Rh, Pt, Pd, Re, Au). If these phases are residual after mare basalt extraction, they would be expected to retain significant quantities of these elements, likely generating non-chondritic HSE inter-element ratios, including Re/Os in the silicate magma. If such phases were present, then the estimated HSE abundances of the bulk silicate moon (BSM) would be proportionally higher than current estimates (0.00023 +/- 2 x CI chondrite), and perhaps closer to the bulk silicate earth (BSE) estimate (0.009 +/- 2 x CI chondrite). Here I show that relationships between elements of similar incompatibility but with siderophile (W), chalcophile (Cu), and lithophile tendencies (Th, U, Yb) do not deviate from expected trends generated by magmatic differentiation during cooling and crystallization of mare basalts. These results, combined with chondrite-relative HSE abundances and near-chondritic measured Os-187/Os-188 compositions of primitive high-MgO mare basalts, imply that lunar mantle melts were generated from residual metal-and sulfide-free sources, or experienced complete exhaustion of metal and sulfides during partial melt extraction. Evidence for the loss of moderately volatile elements during lunar formation and early differentiation indicates that the BSM is >4 to 10 times more depleted in S than BSE. Because of an S-depleted BSM, mare basalt melts are unlikely to have reached S saturation, even if sulfide concentration at sulfide saturation (SCSS) was lowered relative to terrestrial values due to low lunar f(O2). In the absence of residual sulfide or metal, resultant partial melt models indicate that a lunar mantle source with 25 to 75 mu g/g S and high sulfide-melt partition coefficients can account for the chondritic-relative abundances of the HSE in mare basalts from a BSM that experienced <0.02% by mass of late accretion.

Geophysical and geochemical observations point to the presence of a light element in the lunar core, but the exact abundance and type of light element are poorly constrained. Accurate constraints on lunar core composition are vital for models of lunar core dynamo onset and demise, core formation conditions (e.g., depth of the lunar magma ocean or LMO) and therefore formation conditions, as well as the volatile inventory of the Moon. A wide range of previous studies considered S as the dominant light element in the lunar core. Here, we present new constraints on the composition of the lunar core, using mass-balance calculations, combined with previously published models that predict the metal silicate partitioning behavior of C, S, Ni, and recently proposed new bulk silicate Moon (BSM) abundances of S and C. We also use the bulk Moon abundance of C and S to assess the extent of their devolatilization. We observe that the Ni content of the lunar core becomes unrealistically high if shallow (3 GPa) LMO scenarios are considered for S and C. The moderately siderophile metal silicate partitioning behavior of S during lunar core formation, combined with the low BSM abundance of S, yields only <0.16 wt% S in the core, virtually independent of the pressure (P) and temperature (7) conditions during core formation. Instead, our analysis suggests that C is the dominant light element in the lunar core. The siderophile behavior of C during lunar core formation results in a core C content of similar to 0.6-4.8 wt%, with the exact amount depending on the core formation conditions. A C-rich lunar core could explain (1) the existence of a present-day molten outer core, (2) the estimated density of the lunar outer core, and (3) the existence of an early lunar core dynamo driven by compositional buoyancy due to core crystallization. Finally, our calculations suggest the C content of the bulk Moon is close to its estimated abundance in the bulk silicate Earth (BSE), suggesting more limited volatile loss during the Moon-forming event than previously thought.

We re-examine the conditions at which core formation in the Moon may have occurred by linking the observed lunar mantle depletions of 15 siderophile elements, including volatile siderophile elements (VSE) to predictive equations derived from a database compilation of metal-silicate partition coefficients obtained at lunar-relevant pressure-temperature-oxygen fugacity (P-T-fO(2)) conditions. Our results suggest that at mantle temperatures between the solidus and liquidus the depletions for all elements considered can be satisfied, but only if the Moon was essentially fully molten at the time of core formation while assuming a S-rich (>8 wt%) core comprising 2.5 wt% of the mass of the Moon. However, we observe that at temperatures exceeding the mantle liquidus, with increasing temperature the core S content required to satisfy the element depletions is reduced. As a S-poor core is likely from recent lunar mantle estimates of S abundance, this suggests much higher temperatures during lunar core formation than previously proposed. We conclude that the VSE depletions in the lunar mantle can be solely explained by core formation depletion, suggesting that no significant devolatilization has occurred in later periods of lunar evolution. This is in agreement with the discovery of significant amounts of other volatiles in the lunar interior, but hard to reconcile with current lunar formation models. (C) 2016 Elsevier B.V. All rights reserved.