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Abstract The lunar surface and interior are highly reducing, resulting in the virtually absence of ferric ion. However, recent studies suggest the presence of ferric iron in lunar samples, and in most cases they were found in amorphous silicates (e.g., glass beads) measured by TEM–EELS. In this work, we conducted a systematic TEM–EELS analysis on the iron valence states of Chang’e-5 impact glass beads. The Fe3+/ΣFe ratio of each silicate glass sample was determined from integral intensity of Fe L3 and L2 edge. The measurements show a positive correlation between the dwell time and Fe3+/ΣFe ratio, which reveals that ferric iron can be significantly produced by electron beam bombardment under routine analytical condition. The calculated Fe3+/ΣFe with short dwell times (≤ 20 ms) in our Chang’e-5 impact glass beads show no detectable inherent ferric iron, suggesting that the ferric iron is not ubiquitous as previously reported. It is obvious that a careful control of experiment conditions is critical to determine the inherent redox state of other beam-sensitive terrestrial and extraterrestrial samples. Graphical Abstract

Upper: Giant impact (Courtesy NASA/JPL-Caltech); chondrule, majorite in shocked enstatite (Courtesy Miyahara); Lower: Collision of planetesimals (Courtesy NASA/JPL-Caltech); Raman mapping of wadsleyite and ringwoodite in Peace River L6 (Courtesy Miyahara and El Goresy).

Abstract Enstatite chondrites are a small clan of meteorites, only ~ 1% out of all meteorite collection. However, they are the most reduced meteorites and have almost identical isotopic compositions to those of the Earth, suggestive of significant contributions to the latter and other terrestrial planets. Enstatite chondrites contain a unique mineral inventory of sulfides of typical lithophile elements, Si-bearing metal, silicide and phosphide, which record the nebular processes and the thermal metamorphism in asteroidal bodies under extremely reducing environments. EH group is mainly characteristic of the higher Si content of metallic Fe–Ni and the higher MnS contents of sulfides than EL group, indicative of a more reducing condition than the latter. However, the fugacity pH2S could be the same in both EH and EL regions, because it was buffered by kamacite and troilite. The majority of sulfides condensed from the nebula, partially enclosing schreibersite micron-spherules formed probably by early melting. Another part of troilite, sphalerite and djerfisherite, intergrown with perryite, were produced via sulfidation of metallic Fe–Ni. Minor exotic components were also found in enstatite chondrites, including Ca-, Al-rich inclusions and FeO-rich silicate clasts. The Ca-, Al-rich inclusions are identical to those in carbonaceous chondrites except for the alteration under reducing environments, and the FeO-rich silicate clasts show reduction reactions, both suggestive of migration of dust in the protoplanetary disk. The highly reducing conditions (as C/O ratios) might be established via repeating evaporation and condensation of water ice and organic matter across the snow line along the protoplanetary disk, but need to find evidence. Another issue is the preservation of submicron-to-micron-sized presolar grains during high-temperature condensation of the major constituent minerals. After accretion, the parent bodies of EH and EL chondrites probably experienced distinct thermal histories, indicated by their distinct petrologic-type distributions and different correlations with the closure temperatures determined by the FeS contents of sulfides in contact with troilite. The composition of (Mg, Mn, Fe)S, a key indicator for condensation and metamorphism of enstatite chondrites.

Abstract Zirconolite is a common Zr-rich accessary mineral in mafic rocks. It is also an ideal U–Pb/Pb–Pb chronometer because it commonly contains high U content (mostly 0.1–10 wt%) and negligible initial Pb. However, zirconolite is usually very small (e.g., ~ 1 μm in width) in lunar rocks, requiring a high spatial resolution analysis. We analyzed a single, large (25 μm × 20 μm) grain of zirconolite in lunar meteorite NWA 4485 using Pb–Pb dating by NanoSIMS and U–Th–Pb dating by EPMA. The resultant U–Th–Pb age is 4540 ± 340 Ma (2σ) with a spatial resolution of 1.3 μm. The Pb–Pb age by NanoSIMS is 4348.5 ± 4.8 Ma (2σ) with a spatial resolution of ~ 2 μm, consistent with the age of 4352 ± 10 Ma and 4344 ± 14 Ma reported in the same meteorite and its paired meteorite NWA 4472. Although U–Th–Pb age is somewhat older, it still includes the NanoSIMS results within the analytical uncertainty. This work demonstrates the potential application of the combined EPMA dating and REE analysis of lunar zirconolite, with the benefits of high spatial resolution, non-destructive, and readily accessibility of the instrument. The precision of the EPMA dating (7.6%, 2σ) can be improved by increasing the counting time for Pb, U and Th. We expect to apply this EPMA technique for a quick and non-destructive age survey and geochemical study of zirconolite grains from the lunar mare basalts newly returned by Chang’E-5 mission which landed on a very young (1.2–2.0 Ga by crater-counting chronology) basalt unit in Procellarum KREEP Terrain.

Abstract Ringwoodite and wadsleyite are the high-pressure polymorphs of olivine, which are common in shocked meteorites. They are the major constituent minerals in the terrestrial mantle. NWA 8705, an olivine-phyric shergottite, was heavily shocked, producing shock-induced melt veins and pockets associated with four occurrences of ringwoodite: (1) the lamellae intergrown with the host olivine adjacent to a shock-induced melt pocket; (2) polycrystalline assemblages preserving the shapes and compositions of the pre-existing olivine within a shock-induced melt vein (60 μm in width); (3) the rod-like grains coexisting with wadsleyite and clinopyroxene within a shock-induced melt vein; (4) the microlite clusters embedded in silicate glass within a very thin shock-induced melt vein (20 μm in width). The first two occurrences of ringwoodite likely formed via solid-state transformation from olivine, supported by their morphological features and homogeneous compositions (Mg# 64–62) similar to the host olivine (Mg# 66–64). The third occurrence of ringwoodite might fractionally crystallize from the shock-induced melt, based on its heterogeneous and more FeO-enriched compositions (Mg# 76–51) than those of the coexisting wadsleyite (Mg# 77–67) and the host olivine (Mg# 66–64) of this meteorite. The coexistence of ringwoodite, wadsleyite, and clinopyroxene suggests a post-shock pressure of 14–16 GPa and a temperature of 1650–1750 °C. The fourth occurrence of ringwoodite with compositional variation (Mg# 72–58) likely crystallized from melt at 16–18 GPa and 1750–1850 °C. The presence of the four occurrences of ringwoodite was probably due to their very fast cooling rates in and/or adjacent to the thin shock-induced melt veins and small pockets. In addition, the higher Fa-contents of the host olivine (Fa35–39) in NWA 8705 than those in ordinary chondrites (Fa16–32) makes the olivine–ringwoodite transformation prolong to a lower pressure.

Abstract There are growing demands for integrated study of isotopes, trace elements and crystallography of micron-sized grains observed on polished sections or scattered on surface of sample holders. However, transmission electron microscopy (TEM) observation is largely restricted by the challenges associated with the preparation of ultrathin sections from given micron-sized grains after chemical and isotopic analyses. Here, we report a new method of combining focused ion beam (FIB) and microtome techniques. This method is demonstrated by the successful preparation of several ultrathin slices from a presolar graphite grain. The presolar graphite grain was a spherule with a diameter of 5 μm. It was found by nanoscale secondary ion mass spectrometry (NanoSIMS) mapping of a carbonaceous acid residue from the Qingzhen enstatite chondrite (EH3), deposited on a gold foil mount. The spherule showed isotope anomalies in C and Si, with 12C/13C = 99 ± 2 and δ29Si/28Si = 172 ± 36‰, and likely originated in an asymptotic branch giant (AGB) star. After NanoSIMS analysis, this spherule was transported and fixed on a pre-cut top surface of an epoxy stub, using FIB. The fixed spherule was then embedded entirely in resin, and cut into ~ 70 nm slices with a microtome. TEM observation of these ultrathin sections revealed a turbostratic structure free of any subgrains. The morphology, Raman spectrum, C and Si isotopic compositions, internal texture and crystallography of this graphite spherule suggest that it condensed from a carbon-rich outflow of an AGB star.