Magma Ocean Crystallization Research Articles

Composition and age constraints on a Hadean enriched mantle source revealed by the Paleoarchean São Tomé layered intrusion, NE Brazil

Evidence for Hadean depleted mantle reservoir(s) is well-established by mantle-derived rocks from multiple Archean complexes showing excesses in 142Nd compared to the modern mantle. Yet, the existence of an early enriched mantle source, which should have concomitantly formed during these Hadean silicate differentiation event(s), has only been recently confirmed by well-resolved 142Nd deficits measured in Paleoarchean mafic amphibolites from the São José do Campestre massif of the Borborema Province, NE Brazil. To investigate the nature and extent of this early-formed enriched reservoir, a series of samples from the Seridó belt, NE Brazil, have been investigated for their geochemical and coupled 147,146Sm-143,142Nd isotopic compositions, focusing on the Paleoarchean São Tomé layered intrusion. The São Tomé intrusion is composed of layers of metamorphosed mafic and ultramafic rocks with whole-rock trace element compositions and high olivine crystal Ni contents consistent with an incompatible trace element enriched pyroxenitic mantle source. Most analyzed samples from the Seridó belt yielded negative µ142Nd, as low as ∼ -20 (representing the lowest 142Nd/144Nd ratio ever measured in terrestrial rocks), with an average µ142Nd for the São Tomé intrusion of -9.6 ± 1.4. The São Tomé samples interpreted as the least isotopically disturbed yielded an 147Sm-143Nd isochron age of 3551 ± 368 Ma, consistent with previous zircon U-Pb ages, with an initial ε143Nd = -1.7 ± 1.2. Coupling the long-lived 147Sm-143Nd and the short-lived 146Sm-142Nd systems for the São Tomé rocks suggests a Hadean enriched mantle source formed at ∼4.44 Ga with a 147Sm/144Nd of ∼0.18, which may be complementary to the early depleted mantle recorded by Eoarchean rocks from the North Atlantic Craton, possibly formed during magma ocean crystallization. These results also imply that the record of this Hadean enriched mantle source is not restricted to the São José do Campestre massif but extends to a larger portion of the Borborema Province.

The fate of nitrogen during early silicate differentiation of rocky bodies constrained by experimental mineral-melt partitioning

Nitrogen (N) is an essential element for life. Yet the processes of planet formation and early planetary evolution through which rocky planets like Earth obtained their atmospheric and surface nitrogen inventory are poorly understood. In order to understand the effect of early silicate differentiation of the rocky bodies on N inventory, here we study the elemental partitioning of N between the silicate minerals and melts. We conducted laboratory experiments using tholeiitic basalts and Fe + Si alloy mixtures at 1.5 – 4.0 GPa and 1300 to 1550 °C under graphite saturation at an oxygen fugacity range of IW–1.1 to IW–3.0. The experiments yielded an assemblage of Fe-rich alloy melt (am) + silicate melt (sm) + clinopyroxene (cpx) ± garnet (grt) ± orthopyroxene (opx) ± plagioclase (plag). Using electron microprobe, we determine that under the experimental conditions, N act as an incompatible element with DNcpx/sm (0.11 – 0.47) >DNplag/sm (0.41) >DNopx/sm (0.25) >DNgrt/sm(0.06 – 0.21). The DNmineral/sm do not show any strong dependence on temperature, pressure, and melt composition. However, through comparison with previous estimates, it appears that with decreasing fO2, N becomes less incompatible. Under our experimental conditions of alloy melt-mineral equilibria, N behaves as a siderophile element (DNam/mineral ranging from 4.1 to 60.6) with fO2 playing the strongest control on DNam/mineral. Our data suggest that under reducing conditions, in the early stages of a magma ocean (MO) and/or deeper mantle, silicate minerals would hold a non-negligible fraction of N as N becomes less atmophile and siderophile. Therefore, reduced parent bodies could also retain substantial N in the residual mantle during partial melting. The extraction of N from an internal MO or a solid planetary mantle is thus enhanced only as the system becomes more oxidizing, enriching the surficial reservoirs in N. Thus, Earth’s N2-rich atmosphere may be intrinsically linked to its mantle oxidation, whereas other rocky planets of the Solar System, such as Mars and Mercury, may have retained a significant portion of their N inventory in nominally N-free mantle silicates through episodes of MO crystallization and mantle melting.

Chandrayaan-3 APXS elemental abundance measurements at lunar high latitude.

The elemental composition of the lunar surface provides insights into mechanisms of the formation and evolution of the Moon1,2. The chemical composition of lunar regolith have so far been precisely measured using the samples collected by the Apollo, Luna and Chang'e 5 missions, which are from equatorial to mid-latitude regions3,4; lunar meteorites, whose location of origin on the Moon is unknown5,6; and the in situ measurement from the Chang'e 3 and Chang'e 4 missions7-9, which are from the mid-latitude regions of the Moon. Here we report the first in situ measurements of the elemental abundances in the lunar southern high-latitude regions by the Alpha Particle X-ray Spectrometer (APXS) experiment10 aboard the Pragyan rover of India's Chandrayaan-3 mission. The 23 measurements in the vicinity of the Chandrayaan-3 landing site show that the local lunar terrain in this region is fairly uniform and primarily composed of ferroan anorthosite (FAN), a product of the lunar magma ocean (LMO) crystallization. However, observation of relatively higher magnesium abundance with respect to calcium in APXS measurements suggests the mixing of further mafic material. The compositional uniformity over a few tens of metres around the Chandrayaan-3 landing site provides an excellent ground truth for remote-sensing observations.

Sound velocities in lunar mantle aggregates at simultaneous high pressures and temperatures: Implications for the presence of garnet in the deep lunar interior

Recent experimental and theoretical studies on lunar magma ocean crystallisation have suggested the presence of significant proportions of garnet in the deep lunar interior. While phase relation studies indicate a deep lunar mantle consisting of olivine, pyroxene, and garnet, the compatibility of such an assemblage with seismic models of the lunar interior is yet untested. In this study we report compressional and shear wave velocities in an iron-rich assemblage consisting of olivine, orthopyroxene, clinopyroxene, and garnet up to ∼8 GPa and 1300 K, by means of ultrasonic interferometry measurements combined with synchrotron techniques using the multi-anvil press apparatus. Sound velocity and density models of lunar mantle rocks along a selenotherm based on our experimental results find good agreement with the seismic and density profiles at lunar interior depths of 740–1260 km. Further models are constructed, allowing for the variation of chemical composition, phase proportion, and temperature; these suggest that a garnet-rich deep lunar mantle is compatible with present-day lower lunar mantle temperatures of between 1400–1800 K. Our results show that lunar mantle rocks with up to 33 wt.% garnet may provide an explanation for the observed high velocities of the lower lunar mantle. The presence of garnet in the lowermost part of the Moon's mantle has significant implications for the depth and temperature of the Moon's magma ocean as well as the composition, structure and internal dynamics of the solid Moon.

Copper and zinc isotope compositions of pristine eucrites as analogues for differentiated planetary feedstocks

Preferential enrichment of the heavier isotopes of moderately volatile elements (MVE) in samples from asteroids and the Moon have been attributed to volatile loss during the formation and differentiation of their parent bodies. Analogs for planetary feedstocks include the howardite-eucrite-diogenite meteorites, which originate from a differentiated planetesimal or planetesimals, likely including (4) Vesta. Complications arise in the interpretation of volatile depletion in these meteorites, however, due to post-crystallization processes including metamorphism and later impacts that acted upon them. We present new coupled Cu and Zn isotope data for a suite of eucrites that, when combined with published data, show significant ranges (δ65Cu = -1.6 to +0.9‰; δ66Zn = -7.8 to +13.5‰). Exclusion of eucrites that have been affected by metamorphism, impact contamination or surface condensation of isotopically light Zn and Cu leads to a range of ‘pristine’ compositions (δ66Zn = +1.1 ± 2.3‰; δ65Cu = +0.5 ± 0.5‰; 2 St. Dev.), implying inherent MVE variability within the eucrite parent body. As low-mass differentiated bodies, Vesta and the Moon represent endmembers in planet evolution. For the Moon, extensive volatile loss can be explained by a cataclysmic giant impact origin and later magma ocean crystallization. In contrast the parent body of eucrite meteorites likely heterogeneously lost volatile elements and compounds during differentiation. Vesta as the potential source of eucrite meteorites offers an important endmember composition for likely feedstocks to planets, representing the remaining vestige of what was likely to have been a larger population of differentiated objects in the inner Solar System shortly after nebula accretion. Mixing contributions of non-carbonaceous and carbonaceous chondrites constrained by nucleosynthetic Zn isotope anomalies suggests a significant fraction of Earth's accretion could have come from volatile-poor and differentiated planetary feedstocks that would have had limited effects on the bulk silicate Earth (BSE) Zn isotope composition. Furthermore, volatile-poor feedstocks cannot explain the BSE Cu isotope composition, which instead may have been modified by terrestrial core formation. Pristine eucrites offer key insights into early planetesimal differentiation and the role of volatile loss on small mass bodies within nascent solar systems.

Fractionation of iron and titanium isotopes by ilmenite and the isotopic compositions of lunar magma ocean cumulates

Basaltic volcanism on the Moon produced low- and high-Ti mare basalt suites that are also distinct with respect to their iron, titanium, and magnesium isotopic compositions. Here, the equilibrium fractionation of Fe and Ti isotopes between ilmenite and melt was experimentally investigated in order to evaluate the role of ilmenite in generating the isotopic compositional variability among the lunar mare basalts. Ilmenite crystallization experiments were conducted using two bulk compositions: an ilmenite-saturated basaltic andesite and an ilmenite-saturated Apollo 14 black glass, and the Fe and Ti isotopic compositions of the experimental ilmenites and glass (quenched melt) were analyzed using solution MC-ICPMS after hand-picking. Additionally, Nuclear Resonant Inelastic X-ray Scattering (NRIXS) measurements on synthetic ilmenite were conducted and compared to previous NRIXS measurements on synthetic lunar glasses in order to derive temperature-dependent equilibrium ilmenite-melt Fe isotopic fractionations. Experimentally determined ilmenite-melt fractionations were then incorporated into a lunar magma ocean crystallization model that tracks the major element and isotopic compositional evolution of lunar magma ocean cumulates and residual liquid. There is good agreement between the Fe equilibrium isotopic fractionation measured by NRIXS and the laboratory equilibration experiments, and we find that the isotopic fractionation is sensitive to ilmenite compositional differences (0 vs. 10% Fe3+). Further, the light Ti isotopic composition of ilmenite relative to the melt (Δ49Ti=ilmenite-melt−0.09±0.03‰ at 1100∘C) is consistent with the higher coordination of Ti in ilmenite relative to melts and results of previous studies. The modeled Ti isotopic compositions for lunar magma ocean cumulates display Ti isotopic variability sufficient to explain the low- and high-Ti mare basalt sources. However, the difference in Fe isotopic composition between the low- and high-Ti mare basalts cannot be attributed solely to ilmenite fractionation. Instead, Fe isotopic fractionation by additional products of lunar magma ocean crystallization, such as clinopyroxene, is required to generate the inferred Fe and Mg isotopic variability in the lunar mantle. Alternatively, the Fe and Mg isotopic compositions of the lunar mare basalts may indicate Fe-Mg interdiffusion has occurred in the Ti-rich component of the mare basalt source regions via reaction between ilmenite cumulates and the olivine- and pyroxene-rich lunar mantle.

Methodologies for 176Lu-176Hf Analysis of Zircon Grains from the Moon and Beyond.

Zircons are found in extraterrestrial rocks from the Moon, Mars, and some differentiated meteorite parent-bodies. These zircons are rare, often of small size, and have been affected by neutron capture induced by cosmic ray exposure. The application of the 176Lu-176Hf decay system to zircons from planetary bodies such as the Moon can help establish the chronology of large-scale differentiation processes such as the crystallization of the lunar magma ocean. Here, we present methods to measure the isotopic composition of Hf of extraterrestrial zircons dated using ID-TIMS U-Pb after chemical abrasion. We introduce a 2-stage elution scheme to separate Hf from Zr while preserving the unused Zr fraction for future isotopic analysis. The effect of neutron capture is also re-examined using the latest thermal neutron capture cross sections and epithermal resonance integrals. Our tests show that the precision of Hf isotopic analyses is close to what is theoretically attainable. We have tested this method to a limited set of zircon grains from lunar rocks returned by the Apollo missions (lunar soil 14163, fragmental polymict breccia 72275, and clast-rich breccia 14321). The model ages align with previously reported values, but further work is needed to assess the chronology of lunar magma ocean crystallization as only a handful of small zircons (5 zircons from 3 samples) were analyzed, and the precision of the analyses can be improved by measuring more and larger lunar zircon grains.

Predicting sulfide precipitation in magma oceans on Earth, Mars and the Moon using machine learning

The sulfur content at sulfide saturation (SCSS) of a silicate melt can regulate the stability of sulfides and, therefore, chalcophile elements’ behaviors in planetary magma oceans. Many studies have reported high-pressure experiments to determine SCSS using either linear or exponential regressions to parameterize the thermodynamics of the system. Although these empirical equations describe the effects of different parameters on SCSS, they perform poorly when predicting laboratory measurements. Here, we compiled 542 published analyses of experiments performed on a range of sulfide and silicate compositions at varying P-T conditions (<24 GPa, <2673 K). Using empirical equations, linear regression, Random Forest algorithms, and a hybrid algorithm employing empirical fits to P-T conditions and the Random Forest algorithm for compositions, we developed several SCSS models and compared them to laboratory measurements. The Random Forest and hybrid models (R2 = 0.82–0.91, mean average error [MAE] < 746 ppmw S, residual mean standard error [RMSE] < 972 ppmw S), significantly outperform previous empirical models (R2 = 0.28–0.69, MAE = 622–1,170 ppmw S, RMSE = 1,070–1,744 ppmw S), whereas linear regression performs moderately well, i.e., between the classic and machine learning models. We applied our hybrid model to predict SCSS during magma ocean solidification on Earth, Mars, and the Moon, and we compared our model results to expected S contents in the residual magma oceans calculated by mass balance. Our results confirm that during early accretion, sulfides precipitated from magma oceans and into the outer cores of Earth and Mars, but not the Moon. Subsequently, once the respective magma oceans began precipitating minerals with increasingly FeO-rich and SiO2-, Al2O3-, and MgO-depleted compositions, the increasing S concentration in the residual magma was offset by temperature and compositional effects on SCSS, preventing sulfide precipitation during intermediate stages of crystallization. Sulfides precipitated late during magma ocean crystallization, but failed to percolate through the underlying crystalline mantle, significantly contributing to the modern bulk-silicate sulfur abundances of Earth, Mars, and the Moon. Our calculations suggest that late-stage sulfide precipitation occurred at shallow depths of 120–220 km, 40–320 km, and < 10 km in the magma oceans of Earth, Mars, and the Moon, respectively.

Fluorine abundance of the lunar magma ocean constrained by experimentally determined mineral-melt F partitioning

To quantify fluorine (F) evolution during lunar magma ocean (LMO) crystallization, high-pressure, high-temperature experiments have been conducted to determine mineral-melt partitioning of F for lunar minerals (plagioclase, orthopyroxene and ilmenite). Results constrain the F abundance in the magma ocean to 21–41 ppm at the time crust-forming plagioclase started crystallizing. Forward modeling shows that 352–703 ppm F would remain in the final 1 % of magma toward the end of magma ocean solidification. This range overlaps that inferred for the urKREEP reservoir (660 ppm). Taking into account model uncertainties, from the perspective of F abundances the urKREEP reservoir can be formed at 98.9–99.5% LMO solidification, with negligible loss of F from the Moon since the onset of crust formation. Backward modeling from initial crust-forming plagioclase, an initial LMO would contain 4.2–8.5 ppm F, which is consistent with estimates of the lunar primitive mantle F content derived from melt inclusions in Apollo samples. This finding is consistent with previous suggestions that the bulk silicate Moon is depleted in F relative to the bulk silicate Earth (which contains ∼25 ppm F). A BSE-like initial LMO would yield a magma containing 122 ppm F at the onset of crust formation, significantly higher than our calculated 21–41 ppm F. Fluorine depletion could have occurred by degassing during the early LMO stages (between the onset of LMO crystallization and first crust formation), and/or prior to the LMO stage (e.g., depletion during the giant impact or vapor drainage in the protolunar disk), but seems to have ended by the time the crust started forming.

Moon’s high-energy giant-impact origin and differentiation timeline inferred from Ca and Mg stable isotopes

Mass-dependent stable isotopic variations recorded in lunar samples provide novel resolution to the formation and differentiation history of the Moon. In this study, we report new high-precision Ca-isotope measurements for lunar rocks and minerals. Ca-isotope data and modeling of the lunar magma ocean together demonstrate indistinguishable mass-dependent Ca isotopic compositions of the bulk silicate Earth and Moon. This implied Earth-Moon isotope equilibration is consistent with the Moon’s high-energy giant-impact (Synestia) origin and not readily compatible with the traditional giant-impact models. Moreover, a cross-comparison between Ca and Mg isotopic data for an important anorthosite sample (60025) consistently clarifies its formation near the completion of the lunar magma ocean crystallization. Therefore, the various existing radiometric dating for 60025 sets the lunar magma ocean to have fully solidified by either 4.51 or 4.38 billion years ago, constraining the two respective lunar differentiation timescales to <30 (short-lived) or ~130–150 (long-lived) million years.

Negligible fractionation between fluorine and chlorine during magma ocean crystallization and implications for the origin of Earth’s volatiles

Halogens are powerful tracers for the accretion of Earth’s volatiles. Their sensitivity to Earth’s differentiation, such as core formation, magma ocean crystallization, and planetary evaporation allows us to track such major events and the origin of Earth’s building blocks. Here we examine the role of magma ocean crystallization in fractionating F/Cl ratio of the BSE by experimentally determining the partitioning behavior of F and Cl between silicate melt and crystallized minerals. Previous experimental data, due to technical challenges, are only available at pressures <25 GPa. To simulate relevant conditions for deep magma oceans, we perform laser-heated diamond anvil cell experiments to determine partition coefficients of F and Cl between bridgmanite and silicate melt at temperatures of ∼4000–4500 K and pressures of 33–55 GPa. Our data show that F and Cl are both strongly favored in silicate melt, with partition coefficients of F and Cl in the range of 0.12–0.16 and 0.007–0.017, respectively. Given plausible magma ocean scenarios, our results indicate that F and Cl are not significantly fractionated during crystallization of a deep magma ocean. Neglecting other potential processes that may fractionate F and Cl, the F/Cl ratio in the BSE should reflect that of Earth’s building blocks. It indicates Earth’s volatiles may be largely derived from inner solar system, in alignment with other isotopic systems such as nitrogen and hydrogen.

Partitioning of Fe2+ and Fe3+ between bridgmanite and silicate melt: Implications for redox evolution of the Earth's mantle

Crystallization of deep magma oceans would have created the chemical heterogeneity of the Earth's mantle. Previous geophysical studies have suggested a possible existence of the Fe3+-rich lower mantle relative to the upper mantle because the seismic profile of the Earth's lower mantle is well explained by the presence of Fe3+-rich bridgmanite. Such a contrasting distribution of Fe3+/ΣFe ratios between the upper mantle and the lower mantle could have triggered the gradual oxidation of the upper mantle by upwelling Fe3+-rich lower mantle in the early Archean around 3 billion years ago (Ga). However, whether Fe3+-rich lower mantle and Fe3+-poor upper mantle could have been formed or not in the early Earth is still poorly understood. Here we report experimental constraints on the partitioning of Fe2+ and Fe3+ between bridgmanite and silicate melt at 23–27 GPa to investigate the solid-liquid fractionation of Fe2+ and Fe3+ in the deep magma ocean. Our results show negligible fractionation of Fe2+ and Fe3+ between bridgmanite and silicate melt at the uppermost lower mantle conditions, suggesting that preferential incorporation of Fe3+ into bridgmanite during magma ocean crystallization is unlikely. If the lower mantle had become enriched in Fe3+ during the formation of the Earth, another mechanism, such as the redox disproportionation of Fe2+, may have played a more important role in controlling the Fe3+/ΣFe ratio of the mantle.

Calcium isotope constraints on the origin of eucrites and diogenites: The role of magma ocean and magmatism

Howardite-Eucrite-Diogenite (HED) meteorites represent a large suit of crustal and sub-crustal rocks from the Vesta. This work presents systematic examination of the Ca isotope data on multiple varieties of HED meteorites for a better understanding of the magmatic evolution of the Vesta. Falls and finds possess similar Ca isotope compositions, and no correlation is observed between δ44/40Ca and (Sr/Eu*)n, indicating that terrestrial weathering effect on Ca isotopes is insubstantial. According to the data in literature, the inner solar system may have a homogeneous δ44/40Ca and the average of inner solar system bodies (0.97±0.03‰) can approximate the composition of bulk silicate Vesta (BSV). Basaltic eucrites define a cluster in δ44/40Ca (0.95±0.07‰, 2SD, N=15) that is higher than the terrestrial mid-ocean ridge basalts (∼0.85‰). Combined with partial melting and magma ocean differentiation modeling, the Ca isotope signatures suggest that eucrites represent the residual melts evolved from a magma ocean formed by primordial Vesta's moderate-to-high degree melting (20-100%). Diogenites have distinguishingly higher δ44/40Ca (1.18±0.15‰, 2SD, N=7) than the basaltic eucrites, which displays a negative correlation with the 1000×Lu/Ti ratio and a positive correlation with 1/Ca. However, magma ocean crystallization can only explain diogenites with δ44/40Ca higher than 1.17‰, suggesting that diogenites have complicated petrogenesis and are not necessarily cogenetic with eucrites. Diogenites with δ44/40Ca<1.17‰ may result from magma-ocean-cumulate partial melts intruding the eucritic crust. Mixing models suggest that the eucritic component in these diogenites may be less than 10%. Two howardites have lower δ44/40Ca of 0.80±0.04‰ and 0.86±0.05‰ than eucrites and diogenites. This signature may reflect the addition of carbonaceous chondritic materials due to impact brecciation.

Cerium-Nd isotope evidence for an incompatible element depleted Moon

The Moon is a key example of a planetary body that originated from a giant impact collisional event. By better understanding its bulk composition, we gain critical constraints on the building blocks of the Earth-Moon system. Combined measurements of long-lived 147Sm-143Nd and short-lived 146Sm-142Nd isotope compositions of Earth and Moon have lead to controversial interpretations in the past and it remains ambiguous, whether or not the Moon is similar to primitive chondrites in its refractory lithophile element composition. We investigated coupled 138La-138Ce and 147Sm-143Nd isotope and trace element compositions across a wide range of lunar rock types to provide an independent assessment of the bulk Moon composition. All measured lunar rocks define a tight array in 138Ce-143Nd space, intersecting initial εNd=0 at an initial εCe =−0.26±0.04, significantly lower than the currently accepted chondritic 138Ce reference value. The results of combined modeling of 138Ce-143Nd-176Hf isotope and trace element behavior during lunar magma ocean (LMO) crystallization are in good agreement with the bulk silicate Moon having a slight depletion in its highly incompatible trace element inventory. Our calculated composition of the silicate Moon evolves towards εCe=−0.26 and εNd =+1.4 at 3.30 Ga, the approximate age of most lunar samples investigated here. This proposed lunar isotope composition at 3.30 Ga agrees well with the intersection of the 3.30±0.25 Ga lunar array and the terrestrial array defined by rocks from the Archean Pilbara and the Kaapvaal Cratons. We take this as evidence that accessible silicate Earth and the Moon may share a common reservoir slightly depleted in highly incompatible trace elements, named here Slightly Depleted Earth-Moon reservoir (SDEM). The SDEM reservoir proposed here is generally in line with previous models claiming a depleted composition of the accessible silicate Earth, but the degree of depletion is significantly smaller than previously proposed.

The Eoarchean Muzidian gneiss complex: Long-lived Hadean crustal components in the building of Archean continents

The nature of Earth's first crust and the processes that formed it are poorly constrained due to limited exposures of >3.7 billion-year-old (Ga) rocks. Here we report the discovery of a new Eoarchean terrane named the Muzidian gneiss complex in the Yangtze craton of central China where rocks as old as 3.81 Ga are preserved. In this study, we characterized six samples (including five TTGs and an amphibolite) through zircon U-Pb age, Hf isotope and bulk-rock 146,147Sm-142,143Nd isotope compositions. The subchondritic zircon initial Hf isotope compositions and the negative μ142Nd values for the 3.81 – 3.65 Ga samples reveal that these rocks were most likely reworked from >4.3 Ga mafic crust. The 2.5 – 2.4 Ga rocks in the same complex are the youngest felsic rocks on Earth with deficits in 142Nd, highlighting the long-lived role of Hadean crustal components in the building of a stable continent. The 147Sm-143Nd isotopic systematics of these rocks are disturbed. The currently available data for global Eoarchean rocks suggest two distinct lineages for > 3.6 Ga Eoarchean crustal blocks, one produced by reworking of Hadean mafic crust with the isotopic signature of coupled negative εHf(t) and μ142Nd, and the other by melting of incompatible-element-depleted mantle sources residual to Hadean crust formation characterized by positive μ142Nd and near chondritic εHf(t). The Eoarchean samples of the Muzidian gneiss complex in the present study, along with >3.6 Ga rocks in the Acasta, Napier and Nuvvuagittuq regions imply a Hadean crustal source distinct from the products expected for magma ocean crystallization.

Early differentiation processes on Mars inferred from silicon isotopes

Accretion of terrestrial planets involved partial or global melting events such as magma oceans or magma ponds. Mars experienced large-scale differentiation very early in its history, as shown by its 146Sm-142Nd and 182Hf-182W record. The broad variations in ε142Nd and ε142W of SNC meteorites highlight the presence of mantle sources that must have remained isolated, at least partly, after the crystallization of a global magma ocean. In this study, we have investigated whether the crystallization of the martian magma ocean could have generated mantle reservoirs characterized by different silicon isotope signatures, as the fractionation of Si isotopes between minerals and melts is known to depend on pressure. Thus, the goal of this study was to investigate whether there were any relationships between magma ocean crystallisation and possible variations in the Si isotope record of SNC meteorites. High resolution silicon isotope measurements were performed on twelve meteorites from the Shergottite, Nakhlite and Chassignite groups using a Neptune Plus MC-ICP-MS in dry plasma mode. The δ30Si values are in good agreement with previous studies but display a narrower range of variations with a mean value at −0.46 ‰ ± 0.07 (2SD). A magma ocean crystallization model shows that the range of δ30Si in SNCs is consistent with that generated by magma ocean crystallisation. In particular, there is a correlation between calculated 147Sm/144Nd for the moderately depleted mantle sources with δ30Si values; this correlation is consistent with the crystallization model if one includes trapped melt in the cumulates. In contrast, enriched shergottites displayed a very homogenous composition in Sm/Nd ratios, despite significant variability in δ30Si. This observation could be related to either fluid-rock interactions or redox effect during magma differentiation. Altogether, silicon isotope compositions of SNC provide new constraints about magma ocean crystallization processes in Mars.

A primordial atmospheric origin of hydrospheric deuterium enrichment on Mars

The deuterium-to-hydrogen (D/H or 2H/1H) ratio of Martian atmospheric water (∼6× standard mean ocean water, SMOW) is higher than that of known sources, requiring planetary enrichment. A recent measurement by NASA's Mars Science Laboratory rover Curiosity of Hesperian-era (>3 Ga) clays yields a D/H ratio ∼3×SMOW, demonstrating that most of the enrichment occurs early in Mars's history, reinforcing the conclusions of Martian meteorite studies. As on Venus, Mars's D/H enrichment is widely thought to reflect preferential loss to space of 1H (protium) relative to 2H (deuterium), but both the cause and the global environmental context of large and early hydrogen losses remain to be determined. Here, we apply a recent model of primordial atmosphere evolution to Mars, link the magma ocean of the accretion epoch with a subsequent water-ocean epoch, and calculate the behavior of deuterium for comparison with the observed record. In contrast to earlier works that consider Martian D/H fractionation in atmospheres in which hydrogen reservoirs are present exclusively as H2O or H2, here we consider 2-component (H2O-H2) outgassed atmospheres in which both condensing (H2O) and escaping (H2) components – and their interaction – are explicitly calculated. We find that a ≈2-3× hydrospheric deuterium-enrichment is produced rapidly if the Martian magma ocean is chemically reducing at last equilibration with the primordial atmosphere, making H2 and CO the initially dominant species, with minor abundances of H2O and CO2. Reducing gases – in particular H2 – can cause substantial greenhouse warming and prevent a water ocean from freezing immediately after the magma ocean epoch. We find that greenhouse warming due to plausible H2 inventories (pH=21−102 bars) yields surface temperatures high enough (T=s290−560 K) to stabilize a water ocean and produce an early hydrological cycle through which surface water can be circulated. Moreover, the pressure-temperature conditions are high enough to produce ocean-atmosphere H2O-H2 isotopic equilibrium through gas-phase deuterium exchange such that surface H2O strongly concentrates deuterium relative to H2, which preferentially takes up protium and escapes from the primordial atmosphere. The efficient physical separation of deuterium-rich (H2O) and deuterium-poor (H2) species via condensation permits equilibrium isotopic partitioning and early atmospheric escape to be recorded in modern crustal reservoirs. The proposed scenario of primordial H2-CO-rich outgassing and escape suggests significant durations (>Myr) of chemical conditions on the Martian surface conducive to prebiotic chemistry immediately following magma ocean crystallization.

Predictions for Observable Atmospheres of Trappist-1 Planets from a Fully Coupled Atmosphere–Interior Evolution Model

The Trappist-1 planets provide a unique opportunity to test the current understanding of rocky planet evolution. The James Webb Space Telescope is expected to characterize the atmospheres of these planets, potentially detecting CO2, CO, H2O, CH4, or abiotic O2 from water photodissociation and subsequent hydrogen escape. Here, we apply a coupled atmosphere–interior evolution model to the Trappist-1 planets to anticipate their modern atmospheres. This model, which has previously been validated for Earth and Venus, connects magma ocean crystallization to temperate geochemical cycling. Mantle convection, magmatic outgassing, atmospheric escape, crustal oxidation, a radiative-convective climate model, and deep volatile cycling are explicitly coupled to anticipate bulk atmospheres and planetary redox evolution over 8 Gyr. By adopting a Monte Carlo approach that samples a broad range of initial conditions and unknown parameters, we make some tentative predictions about current Trappist-1 atmospheres. We find that anoxic atmospheres are probable, but not guaranteed, for the outer planets; oxygen produced via hydrogen loss during the pre-main sequence is typically consumed by crustal sinks. In contrast, oxygen accumulation on the inner planets occurs in around half of all models runs. Complete atmospheric erosion is possible but not assured for the inner planets (occurs in 20%–50% of model runs), whereas the outer planets retain significant surface volatiles in virtually all model simulations. For all planets that retain substantial atmospheres, CO2-dominated or CO2–O2 atmospheres are expected; water vapor is unlikely to be a detectable atmospheric constituent in most cases. There are necessarily many caveats to these predictions, but the ways in which they misalign with upcoming observations will highlight gaps in terrestrial planet knowledge.

Retention of Water in Terrestrial Magma Oceans and Carbon-rich Early Atmospheres

Massive steam and CO2 atmospheres have been proposed for magma ocean outgassing of Earth and terrestrial planets. Yet formation of such atmospheres depends on volatile exchange with the molten interior, governed by volatile solubilities and redox reactions. We determine the evolution of magma ocean–atmosphere systems for a range of oxygen fugacities, C/H ratios, and hydrogen budgets that include redox reactions for hydrogen (H2–H2O), carbon (CO–CO2), methane (CH4), and solubility laws for H2O and CO2. We find that small initial budgets of hydrogen, high C/H ratios, and oxidizing conditions suppress outgassing of hydrogen until the late stage of magma ocean crystallization. Hence, early atmospheres in equilibrium with magma oceans are dominantly carbon-rich, and specifically CO-rich except at the most oxidizing conditions. The high solubility of H2O limits its outgassing to melt fractions below ∼30%, the fraction at which the mantle transitions from vigorous to sluggish convection with melt percolation. Sluggish melt percolation could enable a surface lid to form, trapping water in the interior and thereby maintaining a carbon-rich atmosphere (equilibrium crystallization). Alternatively, efficient crystal settling could maintain a molten surface, promoting a transition to a water-rich atmosphere (fractional crystallization). However, additional processes, including melt trapping and H dissolution in crystallizing minerals, further conspire to limit the extent of H outgassing, even for fractional crystallization. Hence, much of the water delivered to planets during their accretion can be safely harbored in their interiors during the magma ocean stage, particularly at oxidizing conditions.

Garnet stability in the deep lunar mantle: Constraints on the physics and chemistry of the interior of the Moon

High-pressure, high-temperature experiments have been conducted at deep lunar mantle conditions to constrain the garnet stability field. Using the Taylor Whole Moon composition, garnet is found to be stable at pressures above 3 GPa and temperatures below 1700°C, yielding a smaller stability field than previously suggested on the basis of thermodynamic calculations. Experimental data are used to model equilibrium crystallization in a ‘two-stage’ model of lunar magma ocean (LMO) crystallization starting from a fully molten Moon. In the first stage, isothermal (1600°C) equilibrium crystallization of the LMO would produce garnet-bearing lherzolite cumulates (containing up to ∼20 wt.% garnet) in the lowermost lunar mantle. Garnet in the deep lunar mantle would significantly decrease the Al2O3 content of the residual LMO and impact HREE/MREE fractionation. Numerical modeling of the second stage (residual LMO fractional crystallization) shows a delay in plagioclase saturation compared to models of single-stage fractional crystallization of a whole-Moon LMO of the Taylor Whole Moon composition, thinning the anorthositic crust from 95 km to 75 km. To reach the upper limit of current estimates of the average lunar crustal thickness (∼45 km), the two-stage scenario needs to be accompanied by a total of 10% liquid trapped in cumulates and 70% efficiency of plagioclase flotation. We also conduct trace element evolution modeling and reproduce a REE pattern identical to high K, REE, and P (KREEP) compositions after 99.8% solidification, when starting with a CI chondritic REE abundance. The density of a garnet-bearing deep lunar mantle is significantly higher than the density of olivine/orthopyroxene mixtures without garnet. The present-day lowest mantle in the Moon could therefore be characterized by chemical interactions between the earliest (garnet-bearing) and latest (ilmenite-bearing) products of LMO crystallization.