Lunar Magma Ocean Research Articles

Crystals stirred up: 2. Numerical insights into the formation of the earliest crust on the Moon

This is the second paper in a two‐part series examining the fluid dynamics of crystal settling and flotation in the lunar magma ocean. In the first paper, we develop a direct numerical method for resolving the hydrodynamic interactions between crystals and their feedback on the flow field in magmatic liquid. In this paper, we use this computational technique to test the leading model for the formation of the earliest crust on the Moon. The anorthositic lithology of the lunar crust is thought to have been formed by the flotation of buoyant plagioclase crystals at a time when the lunar mantle was still wholly or largely molten. This model is appealing from an observational point of view, but its fluid dynamical validity is not obvious, because (1) plagioclase probably started crystallizing very late (i.e., when the magma ocean was already 80% solidified) and (2) a significant portion of the shallow lunar crust consists of almost pure plagioclase (>90 vol. %), requiring very efficient plagioclase segregation. The goal of this study is to better understand the fluid dynamical conditions that hinder or facilitate crystal settling or flotation. Our approach complements earlier studies by explicitly linking the petrological and fluid dynamical evolution and by focusing on the effect of increasing crystal fraction. We find that crystal settling was probably possible throughout the entire solidification history of the lunar magma ocean as long as crystal sizes were sufficiently large (r > 1 mm) and crystal fraction sufficiently low (ϕ < 13%).

Massive layer of pure anorthosite on the Moon

We present a new global survey of the purest anorthosite (PAN) rock using the Spectral Profiler onboard Kaguya. We found that PAN rocks are widely distributed over the Moon, including the Feldspathic Highland Terrain and the south and north polar regions. All PAN sites are associated with huge impact structures with diameters larger than 100 km. Based on the global distributions of PAN and olivine‐rich sites, we propose the existence of a massive PAN layer with a thickness of ∼50 km below an uppermost mafic‐rich mixed layer with a thickness of ∼10 km. Below the PAN layer, a lower crustal layer with olivine‐rich materials may be present on the nearside, but not on the far side of the Moon. The existence of a PAN layer with a thickness of ∼50 km suggests an Al2O3 abundance of 33 to 34 wt.% in the lunar crust, which is higher than previous estimates of <32 wt.%. Our data indicate the massive production event of PAN during the early stage of the formation of the Moon, supporting the lunar magma ocean scenario.

Lunar farside Th distribution measured by Kaguya gamma-ray spectrometer

Kaguya gamma-ray spectrometer measured thorium (Th) distribution on the lunar farside with the highest sensitivity among past gamma-ray remote sensing missions. The newly obtained Th map has revealed that two regions near the equator on the farside have the lowest Th abundances. We found that the variation of the Th abundance perfectly correlates with the crustal thickness in the farside and the southern nearside, and it could be a result of the crystallization of the lunar magma ocean.

Geochemical and mineralogical analysis of Gruithuisen region on Moon using M3 and DIVINER images

Spectral information from the Moon Mineralogy Mapper (M3) onboard Chandrayaan-1 and DIVINER Lunar Radiometer onboard LRO have been used for geochemical and mineralogical characterisation of the Gruithuisen region on Moon along with morphometrical information from LOLA Digital elevation model. The apparent reflectance of M3 on global mode is used for (1) spectral characterisation (2) estimating the abundance of Ti and Fe using Lucey's method and (3) discriminating non-mare region from mare regions by means of Minimum Noise Fraction (MNF) transform and Integrated Band Depth (IBD) parameters. Christensen frequency (CF) value derived from DIVINER data is used to delineate the silica saturated lithology from the undersaturated rocks as well as to delineate their spatial spread. Low values of FeO, TiO2, and IBD indicate non-mare nature of the domes and highland material, also supplemented by CF values. The highland rocks represent signatures of sodic plagioclase, the end result of plagioclase crystallisation from Lunar Magma Ocean. Compositional variations are observed among the domes. NW dome has highest silica concentration than the other two domes and in turn higher viscosity. It is most likely that the three domes tapped residual liquid from different locations of the residual magma chamber which is in constant mixing. The extrusion is probably a localised phenomenon, where urKREEP welled out along the zone of crustal weakness formed by Imbrium Impact. It is likely that δ dome has extruded over a larger time span than other two features.

Lunar zirconology

Compared with zircons found in a variety of rocks on Earth, lunar zircons have received relatively little attention over the last four decades since samples were delivered by the Apollo missions. Nevertheless, the comparatively small number of studies carried out following these missions and in particular made over the last five years has demonstrated enormous potential of zircon research for understanding of lunar magmatism, impact history and provenance of lunar breccias. These studies have identified zircon age patterns that shed new light on the history of the Moon and raise new questions related to our understanding of lunar evolution. In particular, (i) the youngest limit for Lunar Magma Ocean (LMO) crystallisation was determined as 4417 ± 6 Ma; (ii) several periods of intensified magmatic activity at about 4.34, 4.20 and 4.00 Ga were identified in the post-LMO history of the Moon; and (iii) several pre-3.9 Ga impacts have been identified on the Moon. Here we discuss some of these results, questions and new directions, and propose an approach for further lunar zircon research.

Very high-K KREEP-rich clasts in the impact melt breccia of the lunar meteorite SaU 169: New constraints on the last residue of the Lunar Magma Ocean

In the impact melt breccia (IMB) of Sayh al Uhaymir (SaU) 169, the most KREEP-rich lunar meteorite to date (Gnos et al., 2004), clasts of a new type of lithologies were discovered, consisting of Ca-poor and Ca-rich pyroxenes (60.8vol.%), Ba-rich K-feldspar (27.9vol.%), phosphates (5.6vol.%), Nb-rich ilmenite (4.0vol.%), zircon (1.2vol.%) and minor sulfide (0.6vol.%). These mafic lithic clasts are more enriched in KREEP component (∼1500×CI) than the host meteorite and are highly enriched in potassium. They are referred to as very high-K (VHK) KREEP lithology, and probably most close to the last residual liquid of the Lunar Magma Ocean without significant dilution by other Mg-rich magmas. The fine-grained matrix of the SaU 169 IMB has very similar mineral chemistry to the VHK KREEP lithology, but contains abundant plagioclase with trace K-feldspar. The matrix shows decoupling of K from the REEP-like component; however, it cannot be simply interpreted by mixing the VHK KREEP lithology with anorthosites, which should have diluted the REEP-like component with the same proportion.SIMS Pb–Pb dating was conducted on zircons in various petrographic settings and with different crystal habits. All analyses show a main age peak at 3921±3Ma and a smaller one at 4016±6Ma. The main age peak is identical to the previous Pb–Pb age by Gnos et al. (2006) and U–Pb age by Liu et al. (2009), dating the catastrophic shock event contributed to the formation of SaU 169 IMB. The older ages are consistent with the previous report of an older bulk U–Pb age by Kramers et al. (2007), suggestive of presence of relict crystals in a few large zircon grains. The VHK KREEP clasts predated the fine-grained matrix, but have the same zircon Pb–Pb ages as the latter within the analytical uncertainties. Plagioclase was converted to maskelynite whereas zircon was shocked to diaplectic glass, probably by a second event at ∼2.8Ga. However, the identical zircon Pb–Pb ages of the amorphous parts and the remained crystalline areas indicate no resetting of Pb–Pb isotopes by the later shock metamorphism, or there was another severe impact event postdated solidification of the fine-grained matrix within a few million years.

Characterization of multiple lithologies within the lunar feldspathic regolith breccia meteorite Northeast Africa 001

Abstract– Lunar meteorite Northeast Africa (NEA) 001 is a feldspathic regolith breccia. This study presents the results of electron microprobe and LA‐ICP‐MS analyses of a section of NEA 001. We identify a range of lunar lithologies including feldspathic impact melt, ferroan noritic anorthosite and magnesian feldspathic clasts, and several very‐low titanium (VLT) basalt clasts. The largest of these basalt clasts has a rare earth element (REE) pattern with light‐REE (LREE) depletion and a positive Euanomaly. This clast also exhibits low incompatible trace element (ITE) concentrations (e.g., <0.1 ppm Th, <0.5 ppm Sm), indicating that it has originated from a parent melt that did not assimilate KREEP material. Positive Eu‐anomalies and such low‐ITE concentrations are uncharacteristic of most basalts returned by the Apollo and Luna missions, and basaltic lunar meteorite samples. We suggest that these features are consistent with the VLT clasts crystallizing from a parent melt which was derived from early mantle cumulates that formed prior to the separation of plagioclase in the lunar magma ocean, as has previously been proposed for some other lunar VLT basalts. Feldspathic impact melts within the sample are found to be more mafic than estimations for the composition of the upper feldspathic lunar crust, suggesting that they may have melted and incorporated material from the lower lunar crust (possibly in large basin‐forming events). The generally feldspathic nature of the impact melt clasts, lack of a KREEP component, and the compositions of the basaltic clasts, leads us to suggest that the meteorite has been sourced from the Outer‐Feldspathic Highlands Terrane (FHT‐O), probably on the lunar farside and within about 1000 km of sources of both Low‐Ti and VLT basalts, the latter possibly existing as cryptomaria deposits.

Chronological evidence that the Moon is either young or did not have a global magma ocean

Chemical evolution of planetary bodies, ranging from asteroids to the large rocky planets, is thought to begin with differentiation through solidification of magma oceans many hundreds of kilometres in depth. The Earth's Moon is the archetypical example of this type of differentiation. Evidence for a lunar magma ocean is derived largely from the widespread distribution, compositional and mineralogical characteristics, and ancient ages inferred for the ferroan anorthosite (FAN) suite of lunar crustal rocks. The FANs are considered to be primary lunar flotation-cumulate crust that crystallized in the latter stages of magma ocean solidification. According to this theory, FANs represent the oldest lunar crustal rock type. Attempts to date this rock suite have yielded ambiguous results, however, because individual isochron measurements are typically incompatible with the geochemical make-up of the samples, and have not been confirmed by additional isotopic systems. By making improvements to the standard isotopic techniques, we report here the age of crystallization of FAN 60025 using the (207)Pb-(206)Pb, (147)Sm-(143)Nd and (146)Sm-(142)Nd isotopic systems to be 4,360 ± 3 million years. This extraordinarily young age requires that either the Moon solidified significantly later than most previous estimates or the long-held assumption that FANs are flotation cumulates of a primordial magma ocean is incorrect. If the latter is correct, then much of the lunar crust may have been produced by non-magma-ocean processes, such as serial magmatism.

Anorthosite formation by plagioclase flotation in ferrobasalt and implications for the lunar crust

The Sept Iles layered intrusion (Quebec, Canada) is dominated by a basal Layered Series made up of troctolites and gabbros, and by anorthosites occurring (1) at the roof of the magma chamber (100–500 m-thick) and (2) as cm- to m-size blocks in gabbros of the Layered Series. Anorthosite rocks are made up of plagioclase, with minor clinopyroxene, olivine and Fe–Ti oxide minerals. Plagioclase displays a very restricted range of compositions for major elements (An 68–An 60), trace elements (Sr: 1023–1071 ppm; Ba: 132–172 ppm) and Sr isotopic ratios ( 87Sr/ 86Sr i : 0.70356–0.70379). This compositional range is identical to that observed in troctolites, the most primitive cumulates of the Layered Series, whereas plagioclase in layered gabbros is more evolved (An 60–An 38). The origin of Sept Iles anorthosites has been investigated by calculating the density of plagioclase and that of the evolving melts. The density of the FeO-rich tholeiitic basalt parent magma first increased from 2.70 to 2.75 g/cm 3 during early fractionation of troctolites and then decreased continuously to 2.16 g/cm 3 with fractionation of Fe–Ti oxide-bearing gabbros. Plagioclase (An 69–An 60) was initially positively buoyant and partly accumulated at the top of the magma chamber to form the roof anorthosite. With further differentiation, plagioclase (<An 60) became negatively buoyant and anorthosite stopped forming. Blocks of anorthosite (autoliths) even fell downward to the basal cumulate pile. The presence of positively buoyant plagioclase in basal troctolites is explained by the low efficiency of plagioclase flotation due to crystallization at the floor and/or minor plagioclase nucleation within the main magma body. Dense mafic minerals of the roof anorthosite are shown to have crystallized from the interstitial liquid. The processes related to floating and sinking of plagioclase in a large and shallow layered intrusion serve as a proxy to refine the crystallization model of the lunar magma ocean and explain the vertically stratified structure of the lunar crust, with (gabbro-)noritic rocks at the base and anorthositic rocks at the top. We propose that the lunar crust mainly crystallized bottom-up. This basal crystallization formed a mafic lower crust that might have a geochemical signature similar to the magnesian-suite without KREEP contamination, while flotation of some plagioclase grains produced ferroan anorthosites in the upper crust.

Water (hydrogen) in the lunar mantle: Results from petrology and magma ocean modeling

Measurements of hydroxyl or water in lunar materials are being used to suggest that melting source regions within the Moon contained tens to hundreds of ppm water. The compositions of magmatic source regions in the Moon can be calculated using magma ocean fractional solidification models, given an initial bulk composition. Our magma ocean models demonstrate that to make a source region with 10 to 200 ppm water, the bulk magma ocean must contain 100 to 1000 ppm water or more (and in a 1000-km deep lunar magma ocean, 1000 ppm water is equivalent to ~ 5% of an Earth ocean by weight). As solidification of the magma ocean continues water and other incompatible elements are progressively enriched in the evolving liquids. The final KREEP-like liquids would contain the greatest fraction of water. We suggest that a bulk magma ocean with over ~ 100 ppm water is prohibited by constraints on these KREEP-like final magma ocean liquids, and by the thermodynamic equilibrium requirement with metallic iron in mare basalts. We conclude that bulk lunar interior water contents must be at the low end of the range posited by recent observations (<~ 10 ppm), though some water from later impacts may have been assimilated into lunar magmas. Most importantly, given the oxygen fugacity of lunar rocks, hydrogen would be expected to be an important volatile species equal to or within an order of magnitude of the abundance of water in a lunar magma.

Trace element partitioning between ilmenite, armalcolite and anhydrous silicate melt: Implications for the formation of lunar high-Ti mare basalts

We performed a series of experiments at high pressures and temperatures to determine the partitioning of a wide range of trace elements between ilmenite (Ilm), armalcolite (Arm) and anhydrous lunar silicate melt, to constrain geochemical models of the formation of titanium-rich melts in the Moon. Experiments were performed in graphite-lined platinum capsules at pressures and temperatures ranging from 1.1 to 2.3 GPa and 1300–1400 °C using a synthetic Ti-enriched Apollo ‘black glass’ composition in the CaO–FeO–MgO–Al 2O 3–TiO 2–SiO 2 system. Ilmenite–melt and armalcolite–melt partition coefficients ( D) show highly incompatible values for the rare earth elements (REE) with the light REE more incompatible compared to the heavy REE ( D La Ilm – melt 0.0020 ± 0.0010 to D Lu Ilm – melt 0.069 ± 0.010 for ilmenite; D La Arm – melt 0.0048 ± 0.0023 to D Lu Arm – melt 0.041 ± 0.008 for armalcolite). D values for the high field strength elements vary from highly incompatible for Th, U and to a lesser extent W (for ilmenite: D Th Ilm – melt 0.0013 ± 0.0008, D U Ilm – melt 0.0035 ± 0.0015 and D W Ilm – melt 0.039 ± 0.005, and for armalcolite D Th Arm – melt 0.008 ± 0.003, D U Arm – melt 0.0048 ± 0.0022 and D W Arm – melt 0.062 ± 0.03), to mildly incompatible for Nb, Ta, Zr, and Hf (e.g. D Hf Ilm – melt 0.28 ± 0.05 and : D Hf Arm – melt 0.76 ± 0.07). Both minerals fractionate the high field strength elements with D Ta/ D Nb and D Hf/ D Zr between 1.3 and 1.6 for ilmenite and 1.3 and 1.4 for armalcolite. Armalcolite is slightly more efficient at fractionating Hf from W during lunar magma ocean crystallisation, with D Hf /D W = 12–13 compared to 6.7–7.5 for ilmenite. The transition metals vary from mildly incompatible to compatible, with the highest compatibilities for Cr in ilmenite ( D ∼ 7.5) and V in armalcolite ( D ∼ 8.1). D values show no clear variation with pressure in the small range covered. Crystal lattice strain modelling of D values for di-, tri- and tetravalent trace elements shows that in ilmenite, divalent elements prefer to substitute for Fe while armalcolite data suggest REE replacing Mg. Tetravalent cations appear to preferentially substitute for Ti in both minerals, with the exception of Th and U that likely substitute for the larger Fe or Mg cations. Crystal lattice strain modelling is also used to identify and correct for very small (∼0.3 wt.%) melt contamination of trace element concentration determinations in crystals. Our results are used to model the Lu–Hf–Ti concentrations of lunar high-Ti mare basalts. The combination of their subchondritic Lu/Hf ratios and high TiO 2 contents requires preferential dissolution of ilmenite or armalcolite from late-stage, lunar magma ocean cumulates into low-Ti partial melts of deeper pyroxene-rich cumulates.

The lunar magma ocean: Reconciling the solidification process with lunar petrology and geochronology

The Moon is thought to have originated with a magma ocean that produced a plagioclase flotation crust as solidification proceeded. Ages of anorthositic crust range over at least 200 million years. The model for solidification presented here integrates chemical and physical constraints of lunar magma ocean solidification to determine (1) the final thickness of flotation crust generated by a fractionally solidifying magma ocean, (2) the timescale of crystallization before plagioclase is a stable phase, (3) the timescale of solidification after the formation of the plagioclase flotation crust, and (4) the post-overturn lunar mantle composition and structure. We find that magma oceans of as much as 1000 km depth are consistent with creating an anorthositic crust 40 to 50 km in thickness. Solidification of the magma ocean prior to formation of the flotation crust may occur on the order of 1000 years, and complete solidification would require additional ten to tens of millions of years. Reconciling these short model timescales with radiometric dates of crustal samples requires either a very late-forming Moon combined with finding older crustal ages to be incorrect, or calling on tidal heating of the crust by the early Earth to prolong solidification. Gravitationally driven overturn of cumulates during tidal heating provides a mechanism for creating the compositions and ages of the lunar Mg suite of crustal rocks. Further, we find that upon crystallization, the Moon likely began with an azimuthally heterogeneous, gravitationally stable mantle, after magma ocean cumulate overturn. This result may help explain the experimentally determined origin of picritic glasses at similar depths but from different source materials.

On the elusive isotopic composition of lunar Pb

Highly radiogenic Pb isotope compositions determined for volcanic glass beads from the Apollo 14 soil sample 14163 are similar to those commonly determined for mare basalts and are correlated with chemical variations observed in the beads. This indicates that Pb unsupported by in-situ U decay has a similar origin in both glass beads and mare basalt samples and is likely to reflect variations of 238U/ 204Pb ( μ) in the lunar mantle. An alternative explanation that this Pb is a result of late equilibration with the radiogenic Pb present in soil is less likely as it would imply that all other characteristics of glass beads such as their chemistry must also be a consequence of equilibration near the lunar surface. Regardless of the origin of unsupported Pb, observed variations of Pb isotope compositions in the glass beads and mare basalts appear to be a result of two component mixing between a primitive reservoir with a μ-value similar to the Earth’s mantle and KREEP with a μ-value in excess of several thousand. This range cannot be explained by the fractionation of major rock forming minerals from the crystallising Lunar Magma Ocean and instead requires substantial extraction of sulphide late in the crystallisation sequence. The proportion of sulphide required to produce the inferred range places limits on the starting μ of the Moon prior to differentiation, demanding a relatively high value of about 100–200. Low μ indicated by several basalt samples and previously analysed volcanic glass beads can be explained by the preservation of an early (but post Ferroan Anorthosite) sulphide rich reservoir in the lunar mantle, while a complete range of Pb isotope compositions observed in the glass beads and mare basalts can be interpreted as mixing between this sulphide rich reservoir and KREEP.

Lunar Magma Ocean crystallization revisited: Bulk composition, early cumulate mineralogy, and the source regions of the highlands Mg-suite

Crystallization of the Lunar Magma Ocean (LMO) has been numerically modeled and its products inferred from sample observations, but it has never been fully tested experimentally. This study is a reexamination of the LMO hypothesis by means of the first experimental simulation of lunar differentiation. Two end-member bulk Moon compositions are considered: one enriched in refractory lithophile elements relative to Earth and one with no such enrichment. A “two-stage” model of magma ocean crystallization based on geophysical constraints is simulated and features early crystal suspension and equilibrium crystallization followed by fractional crystallization of the residual magma ocean. An initially entirely molten Moon is assumed. Part 1 of this study, presented here, focuses on stage 1 of this model and considers the early cumulates formed by equilibrium crystallization, differences in mantle mineralogy resulting from different bulk Moon compositions, and implications for the source regions of the highlands Mg-suite. Refractory element enriched bulk Moon compositions produce a deep mantle that contains garnet and trace Cr-spinel in addition to low-Ca pyroxene and olivine. In contrast, compositions without refractory element enrichment produce a deep dunitic mantle with low-Ca pyroxene but without an aluminous phase. The differences in bulk composition are magnified in the residual melt; the residual LMO from the refractory element enriched composition will likely produce plagioclase and ilmenite earlier and in greater quantities. Both compositions produce Mg-rich early cumulate piles that extend from the core-mantle boundary to ∼355 km depth, if 50% equilibrium crystallization and whole Moon melting are assumed. These early LMO cumulates provide good fits for the source regions for a component of the high-Mg ∗, Ni- and Co-poor parental magmas of the Mg-suite cumulates, if certain conditions are called upon. The olivine in early LMO cumulates produced by either bulk Moon composition is far too rich in Cr to be reasonable for the source regions of the Mg-suite, meaning either core formation in the presence of S and/or C must be invoked to deplete the LMO and the crystallizing olivine in Cr, or that current estimates of the bulk lunar Cr content are too high. We infer that melts meeting the criteria of the Mg-suite parents could be produced from early LMO cumulates by solid state KREEP and plagioclase hybridization near the base of the crust and subsequent partial melting. Additionally, we propose a revised model for Mg-suite petrogenesis.

Water on the Moon

The Moon is not wet like Earth, and it doesn’t have frozen icecaps like those on Mars. But it might be just a tiny bit damp, both inside and on its surface.

Experimental study of trace element partitioning between lunar orthopyroxene and anhydrous silicate melt: Effects of lithium and iron

Orthopyroxene (Opx) was present during a significant portion of crystallisation of the lunar magma ocean, but its influence on co-existing melt trace element contents is not well quantified. We performed high-pressure ( P, 1.1 to 3.2 GPa), high-temperature ( T, 1400 to 1600 °C) experiments on synthetic Fe-rich compositions at reducing conditions relevant to the lunar mantle to constrain trace element partitioning between Opx and anhydrous silicate melts. Opx–melt partition coefficients ( D Opx-melt) for a wide range of trace elements (LILE: Li, Ba; REE: La, Ce, Nd, Sm, Dy, Eu, Er, Tm Y, Yb, Lu; HFSE: Zr, Nb, Hf, Ta, Th, U); and transition metals (Sc, V, Mn, Co, Mo) show only very minor variations across the considered P– T range. REE partition coefficients increase from D La opx-melt = 0.0014 ± 0.0008 to D Lu opx-melt = 0.051 ± 0.007. D values for highly charged elements vary from D Th opx-melt = 0.0013 ± 0.0008 through D Nb opx-melt = 0.0018 ± 0.0006 and D U opx-melt = 0.0015 ± 0.0006 to D Ti opx-melt = 0.068 ± 0.0010. D Lu opx-melt/ D Hf opx-melt values of 6.3 ± 2.4 are at the high end of reported values for minerals that played a role during crystallisation of the lunar magma ocean, and higher than previously reported for Opx under identical oxygen fugacity conditions, implying Opx-rich cumulates in the lunar mantle have highly superchondritic Lu–Hf ratios. Lattice strain modelling of our REE partitioning data suggests that varying the concentration of divalent Fe in Opx very slightly decreases the ideal cation radius for M 3+ elements entering the M2 site, r 0 M2 , whereas the partitioning of M 3+ elements entering the M1 site is unaffected. A subtle increase in the maximum partition coefficient for M 3+ elements entering both the M1 and M2 sites with decreasing T is identified, when experiments carried out at similar reducing oxygen fugacities are considered. The presence of Li at concentrations of up to ~ 350 ppm does not have a measureable effect on the Opx–melt partitioning behaviour of REE or any other element, showing that charge-balancing of M 3+, M 4+ and M 5+ elements in Opx is likely dominated by a vacancy mechanism.

A high field strength element perspective on early lunar differentiation

Lunar rocks are inferred to tap the different fossil cumulate layers formed during crystallisation of a lunar magma ocean (LMO). A coherent dataset, including Zr isotope data and high precision HFSE (W, Nb, Ta, Zr, Hf) and REE (Nd, Sm, Lu) data, all obtained by isotope dilution, can now provide new insights into the processes active during LMO crystallisation and during the petrogenesis of lunar magmas. Measured 92Zr and 91Zr abundances agree with the terrestrial value within 0.2 ε-units. Incompatible-trace-element enriched rocks from the Procellarum KREEP Terrane (PKT) display Nb/Ta and Zr/Hf above the bulk lunar value (ca. 17), and mare basalts display lower ratios, generally confirming the presence of complementary enriched and depleted mantle reservoirs on the Moon. The full compositional spectrum of lunar basalts, however, also requires interaction with ilmenite-rich layers in the lunar mantle. Notably, the high-Ti mare basalts analysed display the lowest Nb/Ta and Zr/Hf of all lunar rocks, and also higher Sm/Nd at similar Lu/Hf than low-Ti basalts. The high-Ti basalts also exhibit higher and strongly correlated Ta/W (up to 25) and Hf/W (up to 140), at similar W contents, which is difficult to reconcile with ortho- and clinopyroxene-controlled melting. Altogether, these patterns can be explained via assimilation of up to ca. 20% of ilmenite- and clinopyroxene-rich LMO cumulates by more depleted melts from the lower lunar mantle. Direct melting of ilmenite-rich cumulates or the possible presence of residual metals in the lunar mantle both cannot easily account for the observed Ta/W and Hf/W patterns. Cumulate assimilation is also a viable mechanism that can partially buffer the Lu/Hf of mare basalts at relatively low values while generating variable Sm/Nd. Thus, the dichotomy between low Lu/Hf of lunar basalts and high time integrated source Lu/Hf as inferred from Hf isotope compositions can potentially be explained. The proposed assimilation model also has important implications for the short-lived nuclide chronology of the Earth-Moon system. The new Hf/W and Ta/W data, together with a compilation of existing W-Th-U data for lunar rocks, indicate that the terrestrial and lunar mantles are indistinguishable in their Hf/W. Virtually identical εW and Hf/W in the terrestrial and lunar mantle suggest a strong link between final core-mantle equilibration on Earth and the Moon forming giant impact. Previously, linear arrays of lunar samples in 182W vs. Hf/W and 142Nd vs. Sm/Nd spaces have been interpreted as isochrons, arguing for LMO crystallisation as late as 250 Myrs after solar system formation. Based on the proposed assimilation model, the 182W and 142Nd in many lunar magmas can be shown to be decoupled from their ambient Hf/W and Sm/Nd source compositions. As a consequence, the 182W vs. Hf/W and 142Nd vs. Sm/Nd arrays would constitute mixing lines rather than isochrons. Hence, the lunar 182Hf– 182W and 146Sm– 142Nd data would be fully consistent with an “early” crystallisation age of the LMO, even as early as 50 Myrs after solar system formation when the Moon was probably formed.

REE characteristics and Nd isotopic compositions of Lunar pristine rocks: Implications for petrogenesis of pristine rocks and source regions

This paper compile the rare-earth elements and Nd isotope data for lunar pristine rocks from investigations in recent years. Using these data, we compared the REE characteristics of lunar pristine rocks and Nd isotopic compositions of their source regions. Based on the Lunar Magma Ocean model, we then studied their formation and petrogenetic correlations of Mg suite, alkali suite, and KREEP, with especial emphasis on the importance of assimilation during early magmatism. And Nd isotopic compositions of mare basalt samples suggest that mantle sources of mare basalts should be heterogeneous, which has not yet been explained by several current models.

Oxygen and iron isotope constraints on near-surface fractionation effects and the composition of lunar mare basalt source regions

Oxygen and iron isotope analyses of low-Ti and high-Ti mare basalts are presented to constrain their petrogenesis and to assess stable isotope variations within lunar mantle sources. An internally-consistent dataset of oxygen isotope compositions of mare basalts encompasses five types of low-Ti basalts from the Apollo 12 and 15 missions and eight types of high-Ti basalts from the Apollo 11 and 17 missions. High-precision whole-rock δ 18O values (referenced to VSMOW) of low-Ti and high-Ti basalts correlate with major-element compositions (Mg#, TiO 2, Al 2O 3). The observed oxygen isotope variations within low-Ti and high-Ti basalts are consistent with crystal fractionation and match the results of mass-balance models assuming equilibrium crystallization. Whole-rock δ 56Fe values (referenced to IRMM-014) of high-Ti and low-Ti basalts range from 0.134‰ to 0.217‰ and 0.038‰ to 0.104‰, respectively. Iron isotope compositions of both low-Ti and high-Ti basalts do not correlate with indices of crystal fractionation, possibly owing to small mineral-melt iron fractionation factors anticipated under lunar reducing conditions. The δ 18O and δ 56Fe values of low-Ti and the least differentiated high-Ti mare basalts are negatively correlated, which reflects their different mantle source characteristics (e.g., the presence or absence of ilmenite). The average δ 56Fe values of low-Ti basalts (0.073 ± 0.018‰, n = 8) and high-Ti basalts (0.191 ± 0.020‰, n = 7) may directly record that of their parent mantle sources. Oxygen isotope compositions of mantle sources of low-Ti and high-Ti basalts are calculated using existing models of lunar magma ocean crystallization and mixing, the estimated equilibrium mantle olivine δ 18O value, and equilibrium oxygen-fractionation between olivine and other mineral phases. The differences between the calculated whole-rock δ 18O values for source regions, 5.57‰ for low-Ti and 5.30‰ for high-Ti mare basalt mantle source regions, are solely a function of the assumed source mineralogy. The oxygen and iron isotope compositions of lunar upper mantle can be approximated using these mantle source values. The δ 18O and δ 56Fe values of the lunar upper mantle are estimated to be 5.5 ± 0.2‰ (2 σ) and 0.085 ± 0.040‰ (2 σ), respectively. The oxygen isotope composition of lunar upper mantle is identical to the current estimate of Earth’s upper mantle (5.5 ± 0.2‰), and the iron isotope composition of the lunar upper mantle overlaps within uncertainty of estimates for the terrestrial upper mantle (0.044 ± 0.030‰).

Deep mantle storage of the Earth’s missing niobium in late-stage residual melts from a magma ocean

The origin of the observed niobium deficit in the bulk silicate Earth (BSE) compared to chondritic meteorites constitutes a long-standing problem in geochemistry. The deficit requires a large-scale process fractionating niobium from tantalum, and a super-chondritic Nb/Ta reservoir hidden in the deep silicate Earth and/or in the metallic core. The only voluminous super-chondritic Nb/Ta silicate reservoir analysed to date is found in lunar basalts that assimilated highly evolved Fe-rich rocks associated with anorthosites in the lunar crust. These Fe-rich rocks, enriched in incompatible elements, are thought to represent the last fractions of melt remaining at the end of lunar magma ocean crystallization. Here we report high-precision Nb–Ta data for a Fe-rich, late-stage rock suite associated with a terrestrial anorthosite from the Proterozoic Bolangir complex in India. The geochemical characteristics of this rock suite resemble those expected for late-stage residual melts from a terrestrial magma ocean. Samples show extreme, super-chondritic Nb/Ta up to 31.1 and highly elevated Nb concentrations up to 338 ppm. We argue that formation of an early enriched crustal reservoir (EECR) with these characteristics (high Fe, high Nb, superchondritic Nb/Ta) is likely in the course of Hadean late-stage terrestrial magma ocean solidification. Subduction and subsequent permanent deep mantle storage in the D′′ layer of a minor amount (∼0.5% of the BSE mass) of this EECR can readily explain the terrestrial Nb deficit, without the need to invoke core Nb storage. Our model is consistent with short-lived 142Nd and long-lived 176Hf– 143Nd isotope models for early differentiation of the Earth’s crust. In addition, the inferred Lu/Hf of this EECR implies that this reservoir can also balance the offset of terrestrial Hf isotope ratios compared to the chondritic reservoir. As such, late-stage magma ocean residual melts may constitute the enigmatic parental reservoir of Hadean zircons with low time-integrated Hf isotope compositions.