Isotopic evidence for a young lunar magma ocean Borg, Lars E.; Gaffney, Amy M.; Kruijer, Thomas S. ...
Earth and planetary science letters,
10/2019, Letnik:
523, Številka:
C
Journal Article
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Odprti dostop
Mare basalt sources and ferroan anorthosite suite cumulates define a linear array on a 146Sm/144Nd versus 142Nd/144Nd isochron plot demonstrating these materials were derived from a common reservoir ...at 4336+31/−32 Ma. The minimum proportion of the Moon that was in isotopic equilibrium at this time is estimated to be 1-3% of its entire volume based on the geographic extent from which the analyzed samples were collected and the calculated depths from which the samples were derived. Scenarios in which large portions of the Moon were molten to depths of many hundreds of kilometers are required to produce the observed Sm-Nd isotopic equilibrium between the mantle and crustal rocks at 4.34 Ga. This is a consequence of the fact that limited heating of a solid Moon above the blocking temperature of the Sm-Nd isotopic system is insufficient to diffusively homogenize radiogenic Nd throughout the mantle and crust. There are three scenarios that might account for global-scale isotopic equilibrium on the Moon relatively late in Solar System history including: (1) Sm-Nd re-equilibration of a solid Moon resulting from widespread melting in response to mantle overturn or a very large impact, (2) early accretion of the Moon followed by delayed cooling due to the presence of an additional heat source that kept a large portion of the Moon molten until 4.34 Ga, or (3) late accretion of the Moon followed by rapid cooling of the magma ocean late in Solar System history. Neither density-driven overturn of the mantle, nor a large impact, are likely to homogenize the mantle and crust to the extent required by the Sm-Nd isochron. Likewise, secondary heating mechanisms, such as tidal heating or radioactive decay, are not efficient enough to keep the Moon molten to the depth of the mare basalt source regions for many tens to hundreds of millions of years. Instead, the age of equilibrium between such a compositionally diverse set of rocks, produced on a global scale, likely records the time of primordial solidification of the Moon from a magma ocean. This scenario accounts for both the petrogenetic characteristics of lunar rock suites, as well as their Sm-Nd isotopic systematics. It is supported by the preponderance of ∼4.35 Ga ages obtained for other hypothetical magma ocean crystallization products, such as ferroan anorthosite suite rocks and K, REE, and P enriched cumulates that are thought to represent flotation cumulates of the magma ocean and the last vestiges of magma ocean solidification, respectively.
•Lunar mantle and crust in 146Sm-142Nd isotopic equilibrium at 4336+31/−32 Ma.•Mare basalts and ferroan anorthosites derived from same reservoir at same time.•The reservoir was likely a magma ocean, so the age defines when it differentiated.
The mantle of Mars probably differentiated through the crystallization of a magma ocean during the first tens of million years (Ma) of Solar System evolution. However, the exact timescale of ...large-scale silicate differentiation of the martian mantle is debated, and in particular, it remains unclear when differentiation commenced. Here we applied the short-lived 53Mn-53Cr system to martian meteorites in order to date the onset of large-scale mantle differentiation on Mars. The new Cr isotope data demonstrate that martian meteorites exhibit no resolvable radiogenic 53Cr variations, and instead have a uniform +20.2±1.2 (95% conf.) parts-per-million excess in 53Cr/52Cr relative to the terrestrial mantle. The investigated groups of martian meteorites are lithologically varied and derive from diverse mantle sources that probably had variable Mn/Cr. Hence, the lack of 53Cr variability among martian meteorites demonstrates that silicate differentiation on Mars occurred after the extinction of 53Mn. Provided that the sources of the martian meteorites have Mn/Cr variations that are typical of the terrestrial planets, this result implies that the onset of large-scale silicate differentiation must have occurred later than 20±5 Ma after Solar System formation. The onset of silicate differentiation on Mars inferred here is significantly later than time estimates for segregation of the martian core which conservatively occurred within <10 Ma after Solar System formation. Thus, the new Mn-Cr data imply that there was a small, but resolvable, time gap of at least 5 Ma between core formation and magma ocean solidification on Mars. If the age of core segregation is taken at face value, our results imply that the martian magma ocean remained mostly molten over several Ma. This inferred longevity of the magma ocean is inconsistent with thermal models predicting rapid (<1 Ma) solidification of the martian magma ocean. Although there is currently no unique solution to this conundrum, our results can potentially be explained by a protracted history of impact bombardment that delayed differentiation in a shallow magma ocean on Mars, or perhaps more readily, by the presence of an early and dense atmosphere that acted as an insulator and prevented the magma ocean from cooling quickly.
•There are no resolvable radiogenic 53Cr variations among martian meteorites.•Mantle differentiation on Mars occurred >20 Ma after Solar System formation.•Mantle solidification on Mars started >5 Ma after core formation.•Inferred longevity of the martian magma ocean is inconsistent with thermal models.•An insulating early atmosphere on Mars may solve this discrepancy.
We present new high precision iron isotope data (δ56Fe vs. IRMM-014 in per mil) for four groups of achondrites: one lunar meteorite, 11 martian meteorites, 32 howardite–eucrite–diogenite meteorites ...(HEDs), and eight angrites. Angrite meteorites are the only planetary materials, other than Earth/Moon system, significantly enriched in the heavy isotopes of Fe compared to chondrites (by an average of +0.12‰ in δ56Fe). While the reason for such fractionation is not completely understood, it might be related to isotopic fractionation by volatilization during accretion or more likely magmatic differentiation in the angrite parent-body. We also report precise data on martian and HED meteorites, yielding an average δ56Fe of 0.00±0.01‰. Stannern-trend eucrites are isotopically heavier by +0.05‰ in δ56Fe than other eucrites. We show that this difference can be ascribed to the enrichment of heavy iron isotopes in ilmenite during igneous differentiation. Preferential dissolution of isotopically heavy ilmenite during remelting of eucritic crust could have generated the heavy iron isotope composition of Stannern-trend eucrites. This supports the view that Stannern-trend eucrites are derived from main-group eucrite source magma by assimilation of previously formed asteroidal crust.
These new results show that iron isotopes are not only fractionated in terrestrial and lunar basalts, but also in two other differentiated planetary crusts. We suggest that igneous processes might be responsible for the iron isotope variations documented in planetary crusts.
Magnesium isotopic compositions are reported for twenty‐four international geological reference materials including igneous, metamorphic and sedimentary rocks, as well as phlogopite and serpentine ...minerals. The long‐term reproducibility of Mg isotopic determination, based on 4‐year analyses of olivine and seawater samples, was ≤ 0.07‰ (2s) for δ26Mg and ≤ 0.05‰ (2s) for δ25Mg. Accuracy was tested by analysis of synthetic reference materials down to the quoted long‐term reproducibility. This comprehensive dataset, plus seawater data produced in the same laboratory, serves as a reference for quality assurance and inter‐laboratory comparison of high‐precision Mg isotopic data.
Les compositions isotopiques du magnésium sont fournies pour vingt‐quatre matériaux géologiques de référence internationaux, comprenant des roches ignées, métamorphiques et sédimentaires, ainsi qu'une phlogopite et des serpentines. La reproductibilité à long terme de la détermination isotopique du Mg, basée des analyses sur quatre ans d’échantillons d'olivine et d'eau de mer, était ≤ 0.07% (2s) pour δ26Mg et ≤ 0.05% (2s) pour δ25Mg. La précision a été testée par l'analyse de matériaux de référence synthétiques jusqu’à la reproductibilité à long terme indiquée. Cette base de données complète, ainsi que des données d'eau de mer produites dans le même laboratoire, servent de référence pour l'assurance qualité et la comparaison inter‐laboratoires de haute précision des données isotopiques du Mg.
Rationale
The microanalytical community has an outstanding need for platinum group element (PGE) reference materials, particularly for trace element analysis by laser ablation inductively coupled ...plasma mass spectrometry (LA‐ICPMS). National Institute of Standards and Technology (NIST) glasses contain Rh, Pd, and Pt, but lack Ru, Os, and Ir. Synthesis of silicate PGE standards has proven difficult due the tendency of PGEs to form metallic nuggets.
Methods
Additive manufacturing methods were used to produce PGE standards with a silica matrix. Monodispersed submicron PGE‐doped Stöber particles were used as feedstock materials for electrophoretic deposition (EPD). Two‐cm‐sized samples produced by EPD were subsequently densified by thermal processing. The homogeneity of PGEs was tested using LA‐ICPMS and concentrations were measured by laser ablation and solution ICPMS.
Results
The PGE concentrations ranged from 0.5 to 3 μg/g. The inhomogeneity was at the 3% RSD level for Ru, Rh, Ir, and Os throughout and 5% for Pt and Pd in the interior of the samples. Based on LA‐ICPMS analyses, the interiors of the two samples have near identical concentrations in PGEs.
Conclusions
The samples fabricated in this study represent the most complete and homogeneous PGE standards produced with a silicate matrix. The ability to produce multiple samples with the same composition provides opportunities for validating methods, monitoring long‐term reproducibility, and facilitating interlaboratory comparisons.
•Planetary core formation causes a fractionation of Fe isotopes.•The mantles of the smaller terrestrial planets and asteroids are isotopically light.•Core-bound impurity elements cause shortening of ...nearest-neighbor distances.•Shorter, stiffer bonds increase the preference of Fe-alloys for heavy Fe isotopes.•Volatile depletion processes are not needed to explain Fe isotope variations.
We have conducted high-pressure, high-temperature isotope exchange experiments between molten silicate and molten Fe–Si–C-alloys to constrain the effect of Si on equilibrium Fe isotope fractionation during planetary core formation. The values of Δ57FeMetal-Silicate at 1850°C and 1 GPa determined by high-resolution MC-ICP-MS in this study range from −0.013±0.054‰ (2SE) to 0.072 ± 0.085‰ with 1.34–8.14 atom % Si in the alloy, respectively. These results, although not definitive on their own, are consistent with previous experimental results from our group and a model in which elements that substitute for Fe atoms in the alloy structure (i.e., Ni, S, and Si) induce a fractionation of Fe isotopes between molten silicate and molten Fe-alloys during planetary differentiation. Using in situ synchrotron X-ray diffraction data for molten Fe-rich alloys from the literature, we propose a model to explain this fractionation behavior in which impurity elements in Fe-alloys cause the nearest neighbor atomic distances to shorten, thereby stiffening metallic bonds and increasing the preference of the alloy for heavy Fe isotopes relative to the silicate melt. This fractionation results in the bulk silicate mantles of the smaller terrestrial planets and asteroids becoming isotopically light relative to chondrites, with an enrichment of heavy Fe isotopes in their cores, consistent with magmatic iron meteorite compositions. Our model predicts a bulk silicate mantle δ57Fe ranging from −0.01‰ to −0.12‰ for the Moon, −0.06‰ to −0.33‰ for Mars, and −0.08‰ to −0.33‰ for Vesta. Independent estimates of the δ57Fe of primitive mantle source regions that account for Fe isotope fractionation during partial melting agree well with these ranges for all three planetary bodies and suggest that Mars and Vesta have cores with impurity (i.e., Ni, S, Si) abundances near the low end of published ranges. Therefore, we favor a model in which core formation results in isotopically light bulk silicate mantles for the Moon, Mars, and Vesta. The processes of magma ocean crystallization, mantle partial melting, and fractional crystallization of mantle-derived melts are all likely to result in heavy Fe isotope enrichment in the melt phase, which can explain why basaltic samples from these planetary bodies have variable δ57Fe values consistently heavier than our bulk mantle estimates. Additionally, we find no clear evidence that Fe isotopes were fractionated to a detectable level by volatile depletion processes during or after planetary accretion, although it cannot be ruled out.
Eight spinel-group minerals were synthesized by a flux-growth method producing spinels with varying composition and Fe3+/Fetot ratios. The mean force constants of iron bonds in these minerals were ...determined by synchrotron nuclear resonant inelastic X-ray scattering (NRIXS) in order to determine the reduced isotopic partition function ratios (β-factors) of these spinels. The mean force constants are strongly dependent on the Fe3+/Fetot of the spinel but are independent, or weakly dependent on other structural and compositional parameters. From our spectroscopic data, it is found that a single redox-dependent calibration line accounts for the effects of Fe3+/Fetot on the β-factors of spinels. This calibration successfully describes the equilibrium Fe isotopes fractionation factors between spinels and silicates (olivine and pyroxenes). Our predictions are in excellent agreement with independent determinations for the equilibrium Fe isotopic fractionations for the magnetite–fayalite and the magnetite–hedenbergite couples. Our calibration applies to the entire range of Fe3+/Fetot ratios found in natural spinels and provides a basis for interpreting iron isotopic variations documented in mantle peridotites. Except for a few exceptions, most of the samples measured so far are in isotopic disequilibrium, reflecting metasomatism and partial melting processes.
Isotopic fractionation associated with diffusion in crystals is the most reliable means of understanding the origin of mineral zoning in igneous and metamorphic rocks. We have experimentally ...determined the relative diffusivities of iron isotopes in olivine as a function of crystallographic orientation, composition, and temperature. For two isotopes i and j of an element, the isotope effect for diffusion is parameterized as Di/Dj = (mj/mi)β, where β is a dimensionless parameter, and D and m stand for diffusivity and mass, respectively. A series of single crystal diffusion couple experiments were conducted at an oxygen fugacity of QFM – 1.5 at temperatures of 1200, 1300, and 1400 °C. For the Fo83.4-Fo88.8 composition pair, βFe is isotropic and a value of 0.16 ± 0.09 can be used to describe diffusion along all major crystallographic axes in olivine. Based on our experiments and previously reported coupled Mg-Fe isotopic data, we also estimate βMg = 0.09 ± 0.05 for this range of olivine composition. For the Fo88.8-Fo100 composition pair, βFe becomes anisotropic with βFe 100 = 0.11 ± 0.03, βFe 010 = 0.14 ± 0.03 (both within error of the value measured for the Fo83.4-Fo88.8 pair), and βFe 001 = 0.03 ± 0.03. For Fo# between 83.4 and 100, βFe 100 and βFe 010 are thus independent of composition. The reason why βFe 001 transitions from ∼0.16 to ∼0.03 close to the Mg-endmember is unclear. Over the temperature range studied, a dependence of βFe on temperature was not resolved. General analytical expressions are introduced to calculate isotopic fractionation as a function of distance, time, β, and the concentration contrast between the diffusing media for spherical, cylindrical, and planar geometries.
Interpreting isotopic signatures documented in natural rocks requires knowledge of equilibrium isotopic fractionation factors. Here, we determine equilibrium Fe isotope fractionation factors between ...several common rock-forming minerals using a comparative approach involving three independent methods: (i) isotopic analyses of natural minerals from a metapelite from Mt. Moosilauke, New Hampshire, for which equilibration temperature and pressure are well constrained to be near the aluminosilicate triple point (T ≃ 500 °C, P ≃ 4 kbar), (ii) Nuclear Resonant Inelastic X-ray Scattering (NRIXS) measurements of Fe force constants of minerals, and (iii) Density Functional Theory (DFT) ab initio calculations of Fe force constants of minerals.
The minerals studied for Fe isotopes include, in increasing order of their β-factors: garnet < ilmenite ≈ fayalite < biotite < tourmaline < muscovite ≈ plagioclase. Some of this ordering is affected by the presence of Fe3+ in the minerals, which tends to form stiffer bonds and be associated with heavy Fe isotope enrichments relative to Fe2+. We are, however, able to assess the magnitude of the effect of the ratio Fe3+/ΣFe on equilibrium fractionation factors, notably on the ilmenite-hematite solid solution. Equilibrium Fe isotopic fractionation factors between garnet, ilmenite, biotite, tourmaline and fayalite are determined. We also report Mg and Ti isotopic compositions of selected Moosilauke minerals that allow us to better constrain the equilibrium fractionation factors for garnet-biotite-tourmaline (Mg isotopes) and biotite-ilmenite (Ti isotopes).
We show how the newly determined equilibrium fractionation factors can be used to address diverse problems in Earth and planetary sciences, notably (i) Fe and Mg isotopic fractionation during anatexis, (ii) Fe isotopic fractionation in lunar ilmenite, and (iii) Ti isotopic fractionation during fluvial transport of minerals.
The mantle of Mars probably differentiated through the crystallization of a magma ocean during the first tens of million years (Ma) of Solar System evolution. However, the exact timescale of ...large-scale silicate differentiation of the martian mantle is debated, and in particular, it remains unclear when differentiation commenced. In this paper, we applied the short-lived 53Mn-53Cr system to martian meteorites in order to date the onset of large-scale mantle differentiation on Mars. The new Cr isotope data demonstrate that martian meteorites exhibit no resolvable radiogenic 53Cr variations, and instead have a uniform +20.2±1.2 (95% conf.) parts-per-million excess in 53Cr/52Cr relative to the terrestrial mantle. The investigated groups of martian meteorites are lithologically varied and derive from diverse mantle sources that probably had variable Mn/Cr. Hence, the lack of 53Cr variability among martian meteorites demonstrates that silicate differentiation on Mars occurred after the extinction of 53Mn. Provided that the sources of the martian meteorites have Mn/Cr variations that are typical of the terrestrial planets, this result implies that the onset of large-scale silicate differentiation must have occurred later than 20±5 Ma after Solar System formation. The onset of silicate differentiation on Mars inferred here is significantly later than time estimates for segregation of the martian core which conservatively occurred within <10 Ma after Solar System formation. Thus, the new Mn-Cr data imply that there was a small, but resolvable, time gap of at least 5 Ma between core formation and magma ocean solidification on Mars. If the age of core segregation is taken at face value, our results imply that the martian magma ocean remained mostly molten over several Ma. This inferred longevity of the magma ocean is inconsistent with thermal models predicting rapid (<1 Ma) solidification of the martian magma ocean. Although there is currently no unique solution to this conundrum, our results can potentially be explained by a protracted history of impact bombardment that delayed differentiation in a shallow magma ocean on Mars, or perhaps more readily, by the presence of an early and dense atmosphere that acted as an insulator and prevented the magma ocean from cooling quickly.
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