Chemical and isotopic kinship of iron in the Earth and Moon deduced from the lunar Mg-Suite

1Paolo A. Sossi, 2Frédéric Moynier
Earth and Planetary Science Letters (in Press) Link to Article []
1Institut de Physique du Globe de Paris, Université Paris Diderot, Université Sorbonne Paris Cité, CNRS UMR 7154, 1 rue Jussieu, 75238 Paris Cedex 05, France
2Institut Universitaire de France, Paris, France
Copyright Elsevier

The Moon and the Earth’s mantle share many chemical and isotopic traits, leading to the prevailing theory that they were formed from similar material. Iron is one element that shows apparent differences between the two bodies, with models for the composition of the Moon having ≈1.5 times more FeO (12–14 wt.%), relative to the Earth’s mantle (8 wt.%). This difference is mirrored in their isotope compositions, where lunar mare basalts have δ57Fe (per mille deviation of the 57Fe/54Fe ratio from the IRMM-014 standard) 0.1–0.2‰ higher than peridotitic rocks representative of Earth’s mantle, a feature initially attributed to loss of isotopically light Fe following a giant impact. However, whether basaltic rocks are suitable analogues for the Moon’s composition is debatable in the light of their distinct source regions that reflect the extensive lithological stratification of the lunar mantle. Here, we evaluate the iron isotope composition of the bulk Moon through the study of igneous cumulate rocks of the lunar highlands Magnesium Suite (Mg Suite). The δ57Fe of Mg Suite rocks spans a limited range, from 0.05‰ to 0.10‰, with an average (+0.07±0.02‰+0.07±0.02‰) that overlaps with Earth’s mantle (+0.05±0.01‰+0.05±0.01‰), similarities that extend to their Mg#s, where both reach 0.9. Numerical modelling of iron isotope fractionation during lunar magma ocean crystallisation shows that the Mg Suite should accurately reflect the composition of the bulk Moon, which is therefore +0.07±0.02‰+0.07±0.02‰, indistinguishable from Earth’s mantle but heavier than chondrites (−0.01±0.01‰−0.01±0.01‰). Iron thus behaves coherently with other elements that condense at temperatures higher than Li in showing no isotopic difference between the Earth and Moon, suggesting element depletion on the Moon affected only the more volatile elements. Therefore, there is no cosmochemical basis for iron enrichment or depletion in the bulk Moon relative to the Earth’s mantle, whose composition is an analogue for that of the Moon.

Silver contents and Cu/Ag ratios in Martian meteorites and the implications for planetary differentiation

1Zaicong Wang, 1Harry Becker
Geochimica et Cosmochimica Acta (in Press) Link to Article []
1Freie Universität Berlin, Institut für Geologische Wissenschaften, Malteserstrasse 74-100, 12249, Berlin, Germany
Copyright Elsevier

Silver and Cu show very similar partitioning behavior in sulfide melt-silicate melt and metal-silicate systems at low and high pressure-temperature (P-T) experimental conditions, implying that mantle melting, fractional crystallization and core-mantle differentiation have at most modest (within a factor of 3) effects on Cu/Ag ratios. For this reason, it is likely that Cu/Ag ratios in mantle-derived magmatic products of planetary bodies reflect that of the mantle and, in some circumstances, also the bulk planet composition. To test this hypothesis, new Ag mass fractions and Cu/Ag ratios in different groups of Martian meteorites are presented and compared with data from chondrites and samples from the Earth’s mantle.

Silver contents in lherzolitic, olivine-phyric and basaltic shergottites and nakhlites range between 1.9 and 12.3 ng/g. The data display a negative trend with MgO content and correlate positively with Cu contents. In spite of displaying variable initial Ɛ143Nd values and representing a diverse spectrum of magmatic evolution and physiochemical conditions, shergottites and nakhlites display limited variations of Cu/Ag ratios (1080±320, 1s, n=14). The relatively constant Cu/Ag suggests limited fractionation of Ag from Cu during the formation and evolution of the parent magmas, irrespectively of whether sulfide saturation was attained or not. The mean Cu/Ag ratio of Martian meteorites thus reflects that of the Martian mantle and constrains its Ag content to 1.9±0.7 ng/g (1s).

Carbonaceous and enstatite chondrites display a limited range of Cu/Ag ratios of mostly 500-2400. Ordinary chondrites show a larger scatter of Cu/Ag up to 4500, which may have been caused by Ag redistribution during parent body metamorphism. The majority of chondrites have Cu/Ag ratios indistinguishable from the Martian mantle value, indicating that Martian core formation strongly depleted Cu and Ag contents, but probably did not significantly change the Cu/Ag ratio of the mantle compared to bulk Mars. Bulk Mars is richer in moderately volatile elements than Earth, however, the Martian mantle displays a much stronger depletion of the moderately volatile elements Cu and Ag, e.g., by a factor of 15 for Cu. This observation is consistent with experimental studies suggesting that core formation at low P-T conditions on Mars led to more siderophile behavior of Cu and Ag than at high P-T conditions as proposed for Earth. In contrast, Cu/Ag ratios of the mantles of Mars and Earth (Cu/AgEarth=3500±1000) display only a difference by a factor of 3, which implies restricted fractionation of Cu and Ag even at high P-T conditions. The concentration data support the notion that siderophile element partitioning during planetary core formation scales with the size of the planetary body, which is particularly important for the differentiation of large terrestrial planets such as Earth. Collectively, the Ag and Cu data on magmatic products from the mantles of Mars and Earth and the data on chondrites confirm experimental predictions and support the limited fractionation of Cu and Ag during planetary core formation and high-temperature magmatic evolution, and probably also in early solar nebular processes.

Experimental constraints on the solidification of a nominally dry lunar magma ocean

1Yanhao Lin, 1Elodie J. Tronche, 1Edgar S. Steenstra, 1Wim van Westrenen
Earth and Planetary Science Letters (in Press) Link to Article []
1Faculty of Earth and Life Sciences, VU Amsterdam, De Boelelaan 1085, 1081 HV Amsterdam, The Netherlands
Copyright Elsevier

The lunar magma ocean (LMO) concept has been used extensively for lunar evolution models for decades, but to date the full cooling and crystallization path of the LMO has not been studied experimentally. Here we present results of a high-pressure, high-temperature experimental study of the mineralogical and geochemical evolution accompanying the full solidification of a nominally dry LMO. Experiments used a bulk composition based on geophysical data, and assumed an initial LMO depth of 700 km. The effect of pressure within a deep magma ocean on solidification at different levels in the ocean was explicitly taken into account, by performing experiments at multiple pressures and constant temperature during each solidification step. Results show formation of a deep harzburgite (olivine + low-Ca pyroxene) layer in the first ∼50% of equilibrium crystallization. The crystallising mineral assemblage does not change until plagioclase and clinopyroxene appear at 68 PCS (per cent solid by volume), while low-Ca pyroxene stops forming. Olivine disappears at 83 PCS, and ilmenite and β-quartz start crystallizing at 91 and 96 PCS, respectively. At 99 PCS, we observe an extremely iron-rich (26.5 wt.% FeO) residual LMO liquid. Our results differ substantially from the oft-cited LMO solidification study of Snyder et al. (1992), which was based on a limited number of experiments at a single pressure. Differences include the mineralogy of the deepest sections of the solidified LMO (harzburgitic instead of dunitic), the formation of SiO2 in the lunar interior, and the development of extreme iron enrichment in the last remaining dregs of the LMO. Our findings shed new light on several aspects of lunar petrology, including the formation of felsic and iron-rich magmas in the Moon. Finally, based on our experiments the lunar crust, consisting of the light minerals plagioclase and quartz, would reach a thickness of ∼67.5 km. This is far greater than crustal thickness estimates from recent GRAIL mission gravitational data (34–43 km, Wieczorek et al., 2013). Although the initial depth of the LMO has an effect on the thickness of crust produced, this effect is not large enough to explain this discrepancy. Inefficient plagioclase segregation, trapping of magma in cumulate reservoirs, and Al sequestration in spinel cannot explain the discrepancy either. As plagioclase crystallization can be suppressed by the presence of H2O, this implies that the lunar magma ocean was water-bearing.

Osmium isotopic homogeneity in the CK carbonaceous chondrites

1,2,3Steven Goderis, 1Alan D. Brandon, 4Bernhard Mayer, 4Munir Humayun
Geochimica et Cosmochimica Acta (in Press) Link to Article []
1Dept. of Earth and Atmospheric Sciences, University of Houston, Science and Research Building 1, Houston, TX 77204, USA
2Earth System Science, Vrije Universiteit Brussel, BE-1050 Brussels, Belgium
3Dept. of Analytical Chemistry, Ghent University, Krijgslaan 281 – S12, BE-9000 Ghent, Belgium
4National High Magnetic Field Laboratory and Dept. of Earth, Ocean & Atmospheric Science, Florida State University, Tallahassee, FL 32310, USA
Copyright Elsevier

Variable proportions of isotopically diverse presolar components are known to account for nucleosynthetic isotopic anomalies for a variety of elements (e.g., Ca, Ti, Cr, Ni, Sr, Zr, Mo, Ru, Pd, Ba, Nd, and Sm) in both bulk chondrites and achondrites. However, although large Os isotopic anomalies have been measured in acid leachates and residues of unequilibrated chondrites, bulk chondrites of various groups, iron meteorites, and pallasites exhibit Os isotopic compositions that are indistinguishable from terrestrial or bulk solar isotopic abundances. Since the magnitude of nucleosynthetic anomalies is typically largest in the carbonaceous chondrites, this study reports high-precision Os isotopic compositions and highly siderophile element (HSE) concentrations for ten CK chondrites. The isotope dilution concentration data for HSE and high-precision Os isotope ratios were determined on the same digestion aliquots, to precisely correct for radiogenic contributions to 186Os and 187Os. While acid leached bulk unequilibrated carbonaceous chondrites show deficits of s-process Os components to the same extent as revealed by unequilibrated enstatite, ordinary, and Rumuruti chondrites, equilibrated bulk CK chondrites exhibit no resolvable Os isotopic anomalies. These observations support the idea that acid-resistant, carbon-rich presolar grains, such as silicon carbide (SiC) or graphite, are major carriers for nucleosynthetic isotopic anomalies of Os. The destruction of these presolar grains, which are omnipresent in unequilibrated meteorites, must have occurred during aqueous alteration and thermal metamorphism, early in the CK chondrite parent body history. The dispersal of CK chondrites along the IIIAB iron meteorite isochron on a 187Os/188Os versus 187Re/188Os diagram, with Re/Os ratios from 0.032 to 0.083, in combination with the observed redistribution of other HSE (e.g., Pt, Pd), highlights the influence of parent body processes, overprinted by effects of recent terrestrial alteration. Under the oxidizing conditions prevalent on the CK parent body, evident from high abundances of magnetite and limited Fe-Ni metal in CK chondrites, these parent body processes made all isotopically anomalous Os, originally hosted in reduced presolar grains, accessible. The absence of Os isotopic anomalies in ordinary, enstatite, and now also carbonaceous chondrites, implies that the carriers of s- and r-process Os must have been effectively homogenized across the region of chondrite formation, and possibly even the entire solar protoplanetary nebula, as suggested by the Os isotopic compositions of iron meteorites and non-anomalous ureilites. Except for a limited number of ureilites, the relative proportions of presolar s- and r-process carriers of Os (and other elements such as W) in chondrites, and most other planetary bodies, must have remained constant during all subsequent nebular and planetary processes, which appears not to have been the case for other siderophile elements, including Mo, Ru, and Pd. The existence of Mo, Ru, Pd and other siderophile element isotopic anomalies thus appears to be in part controlled by the chemical properties of these elements (e.g., volatility), their host phase(s) (e.g., SiC, graphite, metal, sulfides), and the nature of the nebular or planetary processes experienced in the early solar system.

Multiple stages of aqueous alteration along fractures in mudstone and sandstone strata in Gale Crater, Mars

1A.S.Yen et al. (>10)*
Earth and Planetary Science Letters (in Press) Link to Article []
1Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, United States
*Find the extensive, full author and affiliation list on the publishers website
Copyright Elsevier

The Mars rover Curiosity in Gale crater conducted the first-ever direct chemical and mineralogical comparisons of samples that have clear parent (unaltered) and daughter (altered) relationships. The mineralogy and chemistry of samples within and adjacent to alteration halos in a sandstone formation were established by the Chemistry and Mineralogy (CheMin) X-ray diffraction (XRD) instrument and the Alpha Particle X-ray Spectrometer (APXS), respectively. The Stimson formation sandstones unconformably overlie the Murray mudstone formation and represent the youngest stratigraphic unit explored by Curiosity to date. Aqueous alteration of the parent sandstone resulted in a loss of half of the original crystalline mineral phases and a three-fold increase in X-ray amorphous material. Aqueous fluids extensively leached Mg, Al, Mn, Fe, Ni, Zn and other elements from the parent material, decreased the pyroxene to feldspar ratio by a factor of two, introduced Ca and mixed-cation sulfates, and both passively and actively enriched the silica content. Leaching of Mg, Al, Mn, Fe, Ni and Zn and enrichment of Si and S are also observed in alteration halos in the underlying mudstone. These observations are consistent with infiltration of subsurface fluids, initially acidic and then alkaline, propagating along fractures crosscutting the Stimson sandstone and Murray mudstone. The geochemistry and mineralogy suggest a complicated diagenetic history with multiple stages of aqueous alteration under a variety of environmental conditions (e.g. both low and moderate pH). The formation of these alteration halos post-dates lithification of the sandstones and mudstones and represents one of the youngest hydrogeologic events presently known to have occurred in Gale crater.

Secondary melting events in Semarkona chondrules revealed by compositional zoning in low-Ca pyroxene

1Bastian Baecker, 1Alan E. Rubin, 1,2John T. Wasson
Geochimica et Cosmochimica Acta (in Press) Link to Articl []
1Institute of Geophysics and Planetary Physics and Department of Earth, Planetary, and Space Sciences, University of California, Los Angeles, CA 90095-1567, USA
2Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095-1567, USA
Copyright Elsevier

It is well established that many chondrules contain relict grains formed in previous generations of chondrules. We here describe evidence that chondrules experienced multiple mesostasis melting events while remaining closed systems. Spheroidal chondrule shapes resulted from surface-tension effects following a primary heating event that caused substantial melting (≳40%) of the precursor assemblages. In some high-FeO chondrules in LL3.00 Semarkona, low-Ca pyroxene phenocrysts show multiple overgrowth layers produced by secondary melting events. We characterized these layers with the electron microprobe in terms of Fe, Ca and Cr in two Semarkona chondrules.

The first low-Ca pyroxene overgrowth that forms after a minor heating/melting event has low Ca and Fe; concentrations of these incompatibles gradually increase over the next 8±4 μm until falling temperatures and slowing diffusion caused growth to stop. The next melting event remelts and mixes the local mesostasis; cooling causes growth of a normal igneously zoned layer. In the simplest cases, the Ca concentrations at the minima gradually increase towards the edge of the phenocryst. Heat deposition during heating events varied over a wide range; the weakest events produced recognizable changes in slopes (that we call “inflections” rather than minima). Large fractions of the individual phenocrysts were formed by the process that produced the overgrowth layers. It appears that overgrowth formation stopped when the Ca content of the mesostasis became high enough to make high-Ca pyroxene a liquidus phase.

Both Semarkona chondrules include olivine phenocrysts similar in size and modal abundance to the low-Ca pyroxene phenocrysts. Olivine compositional profiles show symmetrical, apparently normal zoning except for asymmetries attributable to the presence of relict grains. Surface compositions of different olivine phenocrysts in the same chondrule are very similar to one another, consistent with growth from mesostasis in the present chondrule. Hence, these olivines must have experienced the same heating events as the pyroxenes with overgrowths.

As argued in earlier papers, the fraction of chondrules heated to low temperatures (sufficient to melt only mesostasis) during nebular heating and melting processes is much larger than the fraction heated sufficiently to melt half or more of the mafic minerals. Melting is expected to result from flash heating in which heat is transported into the chondrule by radiation.

A new high-precision 40Ar/39Ar age for the Rochechouart impact structure: At least 5 Ma older than the Triassic–Jurassic boundary

1,2Benjamin E. Cohen,1,3Darren F. Mark,2Martin R. Lee,2Sarah L. Simpson
Meteoritics & Planetary Science (in Press) Link to Article [DOI: 10.1111/maps.12880]
1NERC Argon Isotope Facility, Scottish Universities Environmental Research Centre, East Kilbride, UK
2School of Geographical and Earth Sciences, University of Glasgow, Glasgow, UK
3Department of Earth and Environmental Sciences, University of St Andrews, St Andrews, UK
Published by arrangement with John Wiley & Sons

The Rochechourt impact structure in south-central France, with maximum diameter of 40–50 km, has previously been dated to within 1% uncertainty of the Triassic–Jurassic boundary, at which time ~30% of global genera became extinct. To evaluate the temporal relationship between the impact and the Triassic–Jurassic boundary at high precision, we have re-examined the structure’s age using multicollector ARGUS-V 40Ar/39Ar mass spectrometry. Results from four aliquots of impact melt are highly reproducible, and yield an age of 206.92 ± 0.20/0.32 Ma (2σ, full analytical/external uncertainties). Thus, the Rochechouart impact structure predates the Triassic–Jurassic boundary by 5.6 ± 0.4 Ma and so is not temporally linked to the mass extinction. Rochechouart has formerly been proposed to be part of a multiple impact event, but when compared with new ages from the other purported “paired” structures, the results provide no evidence for synchronous impacts in the Late Triassic. The widespread Central Atlantic Magmatic Province flood basalts remain the most likely cause of the Triassic–Jurassic mass extinction.