¹Shichun Huang, ²Stein B. Jacobsen
Geochimica et Cosmochmica Acta (in Press) Link to Article [http://dx.doi.org/10.1016/j.gca.2016.09.039]
¹Department of Geoscience, University of Nevada, Las Vegas
²Department of Earth and Planetary Sciences, Harvard University
Copyright Elsevier

We report mass-dependent and mass-independent Ca isotopic variations in nine chondrites from three groups: carbonaceous, ordinary and enstatite chondrites. There is about 0.25‰ per amu, i.e., ∼1‰ in 44Ca/40Ca, variation in chondrites: carbonaceous chondrites have the lightest Ca isotopes, enstatite chondrites have modeled bulk Earth like Ca isotopes, and ordinary chondrites are in between. The correlations between mass-dependent Ca isotopic variation and chemical variations in chondrites may reflect variable contributions from different endmembers, including refractory inclusions, in different chondrite groups. In detail, enstatite chondrites and the Earth share similar isotopic characteristics, but are very different in chemical compositions.

At the ±1 and ±2 ε-unit levels, respectively, there is no measurable 40Ca or 43Ca anomaly in bulk chondrites. Carbonaceous chondrites show several ε-units of 48Ca excess. That is, Ca exhibits both mass-dependent and mass-independent isotopic variations in chondrites, similar to O isotopes. The 48Ca anomaly in bulk chondrites is positively correlated with 50Ti anomaly, but does not form simple correlation with 54Cr anomaly, implying multiple supernova sources for these neutron-rich isotopes in the Solar System. Finally, all meteorites with negative Δ17O have either 48Ca deficits (differentiated meteorites) or 48Ca excess (carbonaceous chondrites), implying that the Sun with a very negative Δ17O is probably also characterized by 48Ca anomaly compared to the Earth. CAIs cannot be taken as representative of the initial isotopic compositions of refractory elements like Ca for the Earth-Moon system.

¹Glenn J. MacPherson, ²Kazuhide Nagashima, ²Alexander N. Krot, ³Patricia M. Doyle, ¹Marina A. Ivanova
Geochmica et Cosmochmica Acta (in Press) Link to Article [http://dx.doi.org/10.1016/j.gca.2016.09.032]
¹US National Museum of Natural History, Smithsonian Institution, Washington, D.C., 20560, USA
²Hawai‘i Institute of Geophysics and Planetology, University of Hawai‘i at Mānoa, Honolulu, HI 96822, USA
³Department of Geological Sciences, University of Cape Town, Rondebosch, 7701, RS91
Copyright Elsevier

High precision secondary ion mass-spectrometry (SIMS) analyses of kirschsteinite (CaFeSiO4) in the reduced CV3 chondrites Vigarano and Efremovka yield well resolved 53Cr excesses that correlate with 55Mn/52Cr, demonstrating in situ decay of the extinct short-lived radionuclide 53Mn. To ensure proper correction for relative sensitivities between 55Mn+ and 52Cr+ ions, we synthesized kirschsteinite doped with Mn and Cr to measure the relative sensitivity factor. The inferred initial ratio (53Mn/55Mn)0 in chondritic kirschsteinite is (3.71±0.50)×10–6. When anchored to 53Mn-53Cr relative and U-corrected 207Pb-206Pb absolute ages of the D’Orbigny angrite, this ratio corresponds to kirschsteinite formation View the MathML source3.2-0.7+08 Ma after CV Ca-, Al-rich inclusions. The kirschsteinite data are consistent within error with the data for aqueously-formed fayalite from the Asuka 881317 CV3 chondrite as reported by Doyle et al. (2015), supporting the idea that Ca-Fe silicates in CV3 chondrites are cogenetic with fayalite (and magnetite) and formed during metasomatic alteration on the CV3 parent body. Concentrically-zoned crystals of kirschsteinite and hedenbergite indicate that they initially formed as near end-member compositions that became more Mg-rich with time, possibly as a result of an increase in temperature.

¹J. Labidi, ²J. Farquhar, ³C.M.O’D. Alexander, ²D.L. Eldridge, ⁴H. Oduro
Geochimica et Cosmochimica Acta (in Press) Link to Article [http://dx.doi.org/10.1016/j.gca.2016.09.036]
¹Geophysical Laboratory, Carnegie Institution of Washington, Washington, D.C. 20015, USA
²Department of Geology, University of Maryland, College Park MD, 20740, USA
³Department of Terrestrial Magnetism, Carnegie Institution of Washington, Washington, D.C. 20015, USA
⁴Department of Earth and Environmental Sciences, St Andrews University, Fife KY16 9AJ, United Kingdom
Copyright Elsevier

We have investigated the quadruple sulfur isotopic composition of inorganic sulfur-bearing phases from 13 carbonaceous chondrites of CM type. Our samples include 4 falls and 9 Antarctic finds. We extracted sulfur from sulfides, sulfates, and elemental sulfur (S0) from all samples. On average, we recover a bulk sulfur (S) content of 2.11±0.39 wt.% S (1σ). The recovered sulfate, S0 and sulfide contents represent 25±12%, 10±7% and 65±15% of the bulk S, respectively (all 1σ). There is no evidence for differences in the bulk S content between falls and finds, and there is no correlation between the S speciation and the extent of aqueous alteration. We report ranges of Δ33S and Δ36S values in CMs that are significantly larger than previously observed. The largest variations are exhibited by S0, with Δ33S values ranging between -0.104±0.012‰ and +0.256±0.018‰ (2σ). The Δ36S/View the MathML sourceω¯33S ratios of S0 are on average -3.1±1.0 (2σ). Two CMs show distinct Δ36S/View the MathML sourceω¯33S ratios, of +1.3±0.1 and +0.9±0.1. We suggest that these mass independent S isotopic compositions record H2S photodissociation in the nebula. The varying ΔΔ36S/Δ33S ratios are interpreted to reflect photodissociation that occurred at different UV wavelengths. The preservation of these isotopic features requires that the S-bearing phases were heterogeneously accreted to the CM parent body. Non-zero Δ33S values are also preserved in sulfide and sulfate, and are positively correlated with S0 values. This indicates a genetic relationship between the S-bearing phases: We argue that sulfates were produced by the direct oxidation of S0 (not sulfide) in the parent body. We describe two types of models that, although imperfect, can explain the major features of the CM S isotope compositions, and can be tested in future studies. Sulfide and S0 could both be condensates from the nebula, as the residue and product, respectively, of incomplete H2S photodissociation by UV light (wavelength < 150 nm). This idea requires that FeS formation and the S0 condensation co-occur. As an alternative, ice accretion to the CM parent body could allow the delivery of S-MIF in CMs. In that case, sulfides would have been the only S-bearing condensate in CM precursors, and S0 would have been derived from the oxidation of H2S trapped in ices, after its photodissociation at low temperature (< 500 K) in the nebula. In our models, the observations of H2S UV photodissociation is required to occur at the disk surface, and allowed in nebular environments with canonical C/O ratios. Vertical motions in the disk would redistribute phases that condensed at high altitude to the midplane, where they accreted in the phases that make up the chondritic matrix.

¹Amber L. Gullikson, ²Justin J. Hagerty, ¹Mary R. Reid, ³Jennifer F. Rapp, ⁴David S. Draper
American Mineralogist 101, 2312-2321 Link to Article [DOI: 10.2138/am-2016-5619]
¹Northern Arizona University, Flagstaff, Arizona 86011, U.S.A.
²U.S. Geological Survey, Astrogeology Science Center, Flagstaff, Arizona 86001, U.S.A.
³Jacobs, NASA Johnson Space Center, Mail Code JE20, Houston, Texas 77058, U.S.A.
⁴Astromaterials Research office, ARES directorate, NASA Johnson Space Center, Houston, Texas, U.S.A.
Copyright: The Mineralogical Society of America

Lunar silicic rocks were first identified by granitic fragments found in samples brought to Earth by the Apollo missions, followed by the discovery of silicic domes on the lunar surface through remote sensing. Although these silicic lithologies are thought to make up a small portion of the lunar crust, their presence indicates that lunar crustal evolution is more complex than originally thought. Models currently used to describe the formation of silicic lithologies on the Moon include in situ differentiation of a magma, magma differentiation with silicate liquid immiscibility, and partial melting of the crust. This study focuses on testing a crustal melting model through partial melting experiments on compositions representing lithologies spatially associated with the silicic domes. The experiments were guided by the results of modeling melting temperatures and residual melt compositions of possible protoliths for lunar silicic rocks using the thermodynamic modeling software, rhyolite-MELTS.

Rhyolite-MELTS simulations predict liquidus temperatures of 950–1040 °C for lunar granites under anhydrous conditions, which guided the temperature range for the experiments. Monzogabbro, alkali gabbronorite, and KREEP basalt were identified as potential protoliths due to their ages, locations on the Moon (i.e., located near observed silicic domes), chemically evolved compositions, and the results from rhyolite-MELTS modeling. Partial melting experiments, using mixtures of reagent grade oxide powders representing bulk rock compositions of these rock types, were carried out at atmospheric pressure over the temperature range of 900–1100 °C. Because all lunar granite samples and remotely sensed domes have an elevated abundance of Th, some of the mixtures were doped with Th to observe its partitioning behavior.

Run products show that at temperatures of 1050 and 1100 °C, melts of the three protoliths are not silicic in nature (i.e., they have <63 wt% SiO₂). By 1000 °C, melts of both monzogabbro and alkali gabbronorite approach the composition of granite, but are also characterized by immiscible Si-rich and Fe-rich liquids. Furthermore, Th strongly partitions into the Fe-rich, and not the Si-rich glass in all experimental runs.

Our work provides important constraints on the mechanism of silicic melt formation on the Moon. The observed high-Th content of lunar granite is difficult to explain by silicate liquid immiscibility, because through this process, Th is not fractionated into the Si-rich phase. Results of our experiments and modeling suggests that silicic lunar rocks could be produced from monzogabbro and alkali gabbronorite protoliths by partial melting at T < 1000 °C. Additionally, we speculate that at higher pressures (P ≥ 0.005 GPa), the observed immiscibility in the partial melting experiments would be suppressed.