Analysis of Cation Composition in Dolomites on the Intact Particles Sampled from Asteroid Ryugu.

Characterization of the elemental distribution of samples with rough surfaces has been strongly desired for the analysis of various natural and artificial materials. Particularly for pristine and rare analytes with micrometer sizes embedded on specimen surfaces, non-invasive and matrix effect-free analysis is required without surface polishing treatment. To satisfy these requirements, we proposed a new method employing the sequential combination of two imaging modalities, i.e., microenergy-dispersive X-ray fluorescence (micro-XRF) and Raman micro-spectroscopy. The applicability of the developed method is tested by the quantitative analysis of cation composition in micrometer-sized carbonate grains on the surfaces of intact particles sampled directly from the asteroid Ryugu. The first step of micro-XRF imaging enabled a quick search for the sparsely scattered and micrometer-sized carbonates by the codistributions of Ca2+ and Mn2+ on the Mg2+- and Fe2+-rich phyllosilicate matrix. The following step of Raman micro-spectroscopy probed the carbonate grains and analyzed their cation composition (Ca2+, Mg2+, and Fe2+ + Mn2+) in a matrix effect-free manner via the systematic Raman shifts of the lattice modes. The carbonates were basically assigned to ferroan dolomite bearing a considerable amount of Fe2+ + Mn2+ at around 10 atom %. These results are in good accordance with the assignments reported by scanning electron microscopy-energy-dispersive X-ray spectroscopy, where the thin-sectioned and surface-polished Ryugu particles were applicable. The proposed method requires neither sectioning nor surface polishing; hence, it can be applied to the remote sensing apparatus on spacecrafts and planetary rovers. Furthermore, the non-invasive and matrix effect-free characterization will provide a reliable analytical tool for quantitative analysis of the elemental distribution on the samples with surface roughness and chemical heterogeneity at a micrometer scale, such as art paintings, traditional crafts with decorated shapes, as well as sands and rocks with complex morphologies in nature.

Water circulation in Ryugu asteroid affected the distribution of nucleosynthetic isotope anomalies in returned sample.

Studies of material returned from Cb asteroid Ryugu have revealed considerable mineralogical and chemical heterogeneity, stemming primarily from brecciation and aqueous alteration. Isotopic anomalies could have also been affected by delivery of exogenous clasts and aqueous mobilization of soluble elements. Here, we show that isotopic anomalies for mildly soluble Cr are highly variable in Ryugu and CI chondrites, whereas those of Ti are relatively uniform. This variation in Cr isotope ratios is most likely due to physicochemical fractionation between 54Cr-rich presolar nanoparticles and Cr-bearing secondary minerals at the millimeter-scale in the bulk samples, likely due to extensive aqueous alteration in their parent bodies that occurred [Formula: see text] after Solar System birth. In contrast, Ti isotopes were marginally affected by this process. Our results show that isotopic heterogeneities in asteroids are not all nebular or accretionary in nature but can also reflect element redistribution by water.

Abundant presolar grains and primordial organics preserved in carbon-rich exogenous clasts in asteroid Ryugu.

Preliminary analyses of asteroid Ryugu samples show kinship to aqueously altered CI (Ivuna-type) chondrites, suggesting similar origins. We report identification of C-rich, particularly primitive clasts in Ryugu samples that contain preserved presolar silicate grains and exceptional abundances of presolar SiC and isotopically anomalous organic matter. The high presolar silicate abundance (104 ppm) indicates that the clast escaped extensive alteration. The 5 to 10 times higher abundances of presolar SiC (~235 ppm), N-rich organic matter, organics with N isotopic anomalies (1.2%), and organics with C isotopic anomalies (0.2%) in the primitive clasts compared to bulk Ryugu suggest that the clasts formed in a unique part of the protoplanetary disk enriched in presolar materials. These clasts likely represent previously unsampled outer solar system material that accreted onto Ryugu after aqueous alteration ceased, consistent with Ryugu's rubble pile origin.

Macromolecular organic matter in samples of the asteroid (162173) Ryugu.

Samples of the carbonaceous asteroid (162173) Ryugu were collected and brought to Earth by the Hayabusa2 spacecraft. We investigated the macromolecular organic matter in Ryugu samples and found that it contains aromatic and aliphatic carbon, ketone, and carboxyl functional groups. The spectroscopic features of the organic matter are consistent with those in chemically primitive carbonaceous chondrite meteorites that experienced parent-body aqueous alteration (reactions with liquid water). The morphology of the organic carbon includes nanoglobules and diffuse carbon associated with phyllosilicate and carbonate minerals. Deuterium and/or nitrogen-15 enrichments indicate that the organic matter formed in a cold molecular cloud or the presolar nebula. The diversity of the organic matter indicates variable levels of aqueous alteration on Ryugu's parent body.

Samples returned from the asteroid Ryugu are similar to Ivuna-type carbonaceous meteorites.

Carbonaceous meteorites are thought to be fragments of C-type (carbonaceous) asteroids. Samples of the C-type asteroid (162173) Ryugu were retrieved by the Hayabusa2 spacecraft. We measured the mineralogy and bulk chemical and isotopic compositions of Ryugu samples. The samples are mainly composed of materials similar to those of carbonaceous chondrite meteorites, particularly the CI (Ivuna-type) group. The samples consist predominantly of minerals formed in aqueous fluid on a parent planetesimal. The primary minerals were altered by fluids at a temperature of 37° ± 10°C, about [Formula: see text] million (statistical) or [Formula: see text] million (systematic) years after the formation of the first solids in the Solar System. After aqueous alteration, the Ryugu samples were likely never heated above ~100°C. The samples have a chemical composition that more closely resembles that of the Sun's photosphere than other natural samples do.

Ryugu's nucleosynthetic heritage from the outskirts of the Solar System.

Little is known about the origin of the spectral diversity of asteroids and what it says about conditions in the protoplanetary disk. Here, we show that samples returned from Cb-type asteroid Ryugu have Fe isotopic anomalies indistinguishable from Ivuna-type (CI) chondrites, which are distinct from all other carbonaceous chondrites. Iron isotopes, therefore, demonstrate that Ryugu and CI chondrites formed in a reservoir that was different from the source regions of other carbonaceous asteroids. Growth and migration of the giant planets destabilized nearby planetesimals and ejected some inward to be implanted into the Main Belt. In this framework, most carbonaceous chondrites may have originated from regions around the birthplaces of Jupiter and Saturn, while the distinct isotopic composition of CI chondrites and Ryugu may reflect their formation further away in the disk, owing their presence in the inner Solar System to excitation by Uranus and Neptune.

Cluster Analysis of Presolar Silicon Carbide Grains: Evaluation of Their Classification and Astrophysical Implications.

Cluster analysis of presolar silicon carbide grains based on literature data for 12C/13C, 14N/15N, δ 30Si/28Si, and δ 29Si/28Si including or not inferred initial 26Al/27Al data, reveals nine clusters agreeing with previously defined grain types but also highlighting new divisions. Mainstream grains reside in three clusters probably representing different parent star metallicities. One of these clusters has a compact core, with a narrow range of composition, pointing to an enhanced production of SiC grains in asymptotic giant branch (AGB) stars with a narrow range of masses and metallicities. The addition of 26Al/27Al data highlights a cluster of mainstream grains, enriched in 15N and 26Al, which cannot be explained by current AGB models. We defined two AB grain clusters, one with 15N and 26Al excesses, and the other with 14N and smaller 26Al excesses, in agreement with recent studies. Their definition does not use the solar N isotopic ratio as a divider, and the contour of the 26Al-rich AB cluster identified in this study is in better agreement with core-collapse supernova models. We also found a cluster with a mixture of putative nova and AB grains, which may have formed in supernova or nova environments. X grains make up two clusters, having either strongly correlated Si isotopic ratios or deviating from the 2/3 slope line in the Si 3-isotope plot. Finally, most Y and Z grains are jointly clustered, suggesting that the previous use of 12C/13C = 100 as a divider for Y grains was arbitrary. Our results show that cluster analysis is a powerful tool to interpret the data in light of stellar evolution and nucleosynthesis modeling and highlight the need of more multi-element isotopic data for better classification.

Presolar stardust in highly pristine CM chondrites Asuka 12169 and Asuka 12236.

We report a NanoSIMS search for presolar grains in the CM chondrites Asuka (A) 12169 and A12236. We found 90 presolar O-rich grains and 25 SiC grains in A12169, giving matrix-normalized abundances of 275 (+55/-50, 1σ) ppm or, excluding an unusually large grain, 236 (+37/-34) ppm for O-rich grains and 62 (+15/-12) ppm for SiC grains. For A12236, 18 presolar silicates and 6 SiCs indicate abundances of 58 (+18/-12) and 20 (+12/-8) ppm, respectively. The SiC abundances are in the typical range of primitive chondrites. The abundance of presolar O-rich grains in A12169 is essentially identical to that in CO3.0 Dominion Range 08006, higher than in any other chondrites, while in A12236, it is higher than found in other CMs. These abundances provide further strong support that A12169 and A12236 are the least-altered CMs as indicated by petrographic investigations. The similar abundances, isotopic distributions, silicate/oxide ratios, and grain sizes of the presolar O-rich grains found here to those of presolar grains in highly primitive CO, CR, and ungrouped carbonaceous chondrites (CCs) indicate that the CM parent body(ies) accreted a similar population of presolar oxides and silicates in their matrices to those accreted by the parent bodies of the other CC groups. The lower abundances and larger grain sizes seen in some other CMs are thus most likely a result of parent-body alteration and not heterogeneity in nebular precursors. Presolar silicates are unlikely to be present in high abundances in returned samples from asteroids Ryugu and Bennu since remote-sensing data indicate that they have experienced substantial aqueous alteration.

High Abundances of Presolar Grains and 15N-rich Organic Matter in CO3.0 Chondrite Dominion Range 08006.

NanoSIMS C-, N-, and O-isotopic mapping of matrix in CO3.0 chondrite Dominion Range (DOM) 08006 revealed it to have in its matrix the highest abundance of presolar O-rich grains (257 +76/-96 ppm, 2σ) of any meteorite. It also has a matrix abundance of presolar SiC of 35 (+25/-17, 2σ) ppm, similar to that seen across primitive chondrite classes. This provides additional support to bulk isotopic and petrologic evidence that DOM 08006 is the most primitive known CO meteorite. Transmission electron microscopy of five presolar silicate grains revealed one to have a composite mineralogy similar to larger amoeboid olivine aggregates and consistent with equilibrium condensation, two non-stoichiometric amorphous grains and two olivine grains, though one is identified as such solely based on its composition. We also found insoluble organic matter (IOM) to be present primarily as sub-micron inclusions with ranges of C- and N-isotopic anomalies similar to those seen in primitive CR chondrites and interplanetary dust particles. In contrast to other primitive extraterrestrial materials, H isotopic imaging showed normal and homogeneous D/H. Most likely, DOM 08006 and other CO chondrites accreted a similar complement of primitive and isotopically anomalous organic matter to that found in other chondrite classes and IDPs, but the very limited amount of thermal metamorphism experienced by DOM 08006 has caused loss of D-rich organic moieties, while not substantially affecting either the molecular carriers of C and N anomalies or most inorganic phases in the meteorite. One C-rich grain that was highly depleted in 13C and 15N was identified; we propose it originated in the Sun's parental molecular cloud.

Late formation of silicon carbide in type II supernovae.

We have found that individual presolar silicon carbide (SiC) dust grains from supernovae show a positive correlation between 49Ti and 28Si excesses, which is attributed to the radioactive decay of the short-lived (t½ = 330 days) 49V to 49Ti in the inner highly 28Si-rich Si/S zone. The 49V-49Ti chronometer shows that these supernova SiC dust grains formed at least 2 years after their parent stars exploded. This result supports recent dust condensation calculations that predict a delayed formation of carbonaceous and SiC grains in supernovae. The astronomical observation of continuous buildup of dust in supernovae over several years can, therefore, be interpreted as a growing addition of C-rich dust to the dust reservoir in supernovae.

Extremely 54Cr- and 50Ti-rich presolar oxide grains in a primitive meteorite: Formation in rare types of supernovae and implications for the astrophysical context of solar system birth.

We report the identification of 19 presolar oxide grains from the Orgueil CI meteorite with substantial enrichments in 54Cr, with 54Cr/52Cr ratios ranging from 1.2 to 56 times the solar value. The most enriched grains also exhibit enrichments at mass 50, most likely due in part to 50Ti, but close-to-normal or depleted 53Cr/52Cr ratios. There is a strong inverse relationship between 54Cr enrichment and grain size; the most extreme grains are all <80 nm in diameter. Comparison of the isotopic data with predictions of nucleosynthesis calculations indicate that these grains most likely originated in either rare, high-density Type Ia supernovae (SNIa), or in electron-capture supernovae (ECSN) which may occur as the end stage of evolution for stars of mass 8-10 M ⊙. This is the first evidence for preserved presolar grains from either type of supernova. An ECSN origin is attractive since these likely occur much more frequently than high-density SNIa, and their evolutionary timescales (~20 Myr) are comparable to those of molecular clouds. Self-pollution of the Sun's parent cloud from an ECSN may explain the heterogeneous distribution of n-rich isotopic anomalies in planetary materials, including a recently reported dichotomy in Mo isotopes in the solar system. The stellar origins of three grains with solar 54Cr/52Cr, but anomalies in 50Cr or 53Cr, as well as of a grain enriched in 57Fe, are unclear.

Hydrogen and major element concentrations on 433 Eros: Evidence for an L- or LL-chondrite-like surface composition.

A reanalysis of NEAR X-ray/gamma-ray spectrometer (XGRS) data provides robust evidence that the elemental composition of the near-Earth asteroid 433 Eros is consistent with the L and LL ordinary chondrites. These results facilitated the use of the gamma-ray measurements to produce the first in situ measurement of hydrogen concentrations on an asteroid. The measured value, 1100-700+1600 ppm, is consistent with hydrogen concentrations measured in L and LL chondrite meteorite falls. Gamma-ray derived abundances of hydrogen and potassium show no evidence for depletion of volatiles relative to ordinary chondrites, suggesting that the sulfur depletion observed in X-ray data is a surficial effect, consistent with a space-weathering origin. The newfound agreement between the X-ray, gamma-ray, and spectral data suggests that the NEAR landing site, a ponded regolith deposit, has an elemental composition that is indistinguishable from the mean surface. This observation argues against a pond formation process that segregates metals from silicates, and instead suggests that the differences observed in reflectance spectra between the ponds and bulk Eros are due to grain size differences resulting from granular sorting of ponded material.

Fluid-induced organic synthesis in the solar nebula recorded in extraterrestrial dust from meteorites.

Isotopically anomalous carbonaceous grains in extraterrestrial samples represent the most pristine organics that were delivered to the early Earth. Here we report on gentle aberration-corrected scanning transmission electron microscopy investigations of eight (15)N-rich or D-rich organic grains within two carbonaceous Renazzo-type (CR) chondrites and two interplanetary dust particles (IDPs) originating from comets. Organic matter in the IDP samples is less aromatic than that in the CR chondrites, and its functional group chemistry is mainly characterized by C-O bonding and aliphatic C. Organic grains in CR chondrites are associated with carbonates and elemental Ca, which originate either from aqueous fluids or possibly an indigenous organic source. One distinct grain from the CR chondrite NWA 852 exhibits a rim structure only visible in chemical maps. The outer part is nanoglobular in shape, highly aromatic, and enriched in anomalous nitrogen. Functional group chemistry of the inner part is similar to spectra from IDP organic grains and less aromatic with nitrogen below the detection limit. The boundary between these two areas is very sharp. The direct association of both IDP-like organic matter with dominant C-O bonding environments and nanoglobular organics with dominant aromatic and C-N functionality within one unique grain provides for the first time to our knowledge strong evidence for organic synthesis in the early solar system activated by an anomalous nitrogen-containing parent body fluid.

Interstellar dust. Evidence for interstellar origin of seven dust particles collected by the Stardust spacecraft.

Seven particles captured by the Stardust Interstellar Dust Collector and returned to Earth for laboratory analysis have features consistent with an origin in the contemporary interstellar dust stream. More than 50 spacecraft debris particles were also identified. The interstellar dust candidates are readily distinguished from debris impacts on the basis of elemental composition and/or impact trajectory. The seven candidate interstellar particles are diverse in elemental composition, crystal structure, and size. The presence of crystalline grains and multiple iron-bearing phases, including sulfide, in some particles indicates that individual interstellar particles diverge from any one representative model of interstellar dust inferred from astronomical observations and theory.

Evidence for water ice near Mercury's north pole from MESSENGER Neutron Spectrometer measurements.

Measurements by the Neutron Spectrometer on the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft show decreases in the flux of epithermal and fast neutrons from Mercury's north polar region that are consistent with the presence of water ice in permanently shadowed regions. The neutron data indicate that Mercury's radar-bright polar deposits contain, on average, a hydrogen-rich layer more than tens of centimeters thick beneath a surficial layer 10 to 30 cm thick that is less rich in hydrogen. Combined neutron and radar data are best matched if the buried layer consists of nearly pure water ice. The upper layer contains less than 25 weight % water-equivalent hydrogen. The total mass of water at Mercury's poles is inferred to be 2 × 10(16) to 10(18) grams and is consistent with delivery by comets or volatile-rich asteroids.

The major-element composition of Mercury's surface from MESSENGER X-ray spectrometry.

X-ray fluorescence spectra obtained by the MESSENGER spacecraft orbiting Mercury indicate that the planet's surface differs in composition from those of other terrestrial planets. Relatively high Mg/Si and low Al/Si and Ca/Si ratios rule out a lunarlike feldspar-rich crust. The sulfur abundance is at least 10 times higher than that of the silicate portion of Earth or the Moon, and this observation, together with a low surface Fe abundance, supports the view that Mercury formed from highly reduced precursor materials, perhaps akin to enstatite chondrite meteorites or anhydrous cometary dust particles. Low Fe and Ti abundances do not support the proposal that opaque oxides of these elements contribute substantially to Mercury's low and variable surface reflectance.

Radioactive elements on Mercury's surface from MESSENGER: implications for the planet's formation and evolution.

The MESSENGER Gamma-Ray Spectrometer measured the average surface abundances of the radioactive elements potassium (K, 1150 ± 220 parts per million), thorium (Th, 220 ± 60 parts per billion), and uranium (U, 90 ± 20 parts per billion) in Mercury's northern hemisphere. The abundance of the moderately volatile element K, relative to Th and U, is inconsistent with physical models for the formation of Mercury requiring extreme heating of the planet or its precursor materials, and supports formation from volatile-containing material comparable to chondritic meteorites. Abundances of K, Th, and U indicate that internal heat production has declined substantially since Mercury's formation, consistent with widespread volcanism shortly after the end of late heavy bombardment 3.8 billion years ago and limited, isolated volcanic activity since.

Flood volcanism in the northern high latitudes of Mercury revealed by MESSENGER.

MESSENGER observations from Mercury orbit reveal that a large contiguous expanse of smooth plains covers much of Mercury's high northern latitudes and occupies more than 6% of the planet's surface area. These plains are smooth, embay other landforms, are distinct in color, show several flow features, and partially or completely bury impact craters, the sizes of which indicate plains thicknesses of more than 1 kilometer and multiple phases of emplacement. These characteristics, as well as associated features, interpreted to have formed by thermal erosion, indicate emplacement in a flood-basalt style, consistent with x-ray spectrometric data indicating surface compositions intermediate between those of basalts and komatiites. The plains formed after the Caloris impact basin, confirming that volcanism was a globally extensive process in Mercury's post-heavy bombardment era.

Hollows on Mercury: MESSENGER evidence for geologically recent volatile-related activity.

High-resolution images of Mercury's surface from orbit reveal that many bright deposits within impact craters exhibit fresh-appearing, irregular, shallow, rimless depressions. The depressions, or hollows, range from tens of meters to a few kilometers across, and many have high-reflectance interiors and halos. The host rocks, which are associated with crater central peaks, peak rings, floors, and walls, are interpreted to have been excavated from depth by the crater-forming process. The most likely formation mechanisms for the hollows involve recent loss of volatiles through some combination of sublimation, space weathering, outgassing, or pyroclastic volcanism. These features support the inference that Mercury's interior contains higher abundances of volatile materials than predicted by most scenarios for the formation of the solar system's innermost planet.

Origin and evolution of prebiotic organic matter as inferred from the Tagish Lake meteorite.

The complex suite of organic materials in carbonaceous chondrite meteorites probably originally formed in the interstellar medium and/or the solar protoplanetary disk, but was subsequently modified in the meteorites' asteroidal parent bodies. The mechanisms of formation and modification are still very poorly understood. We carried out a systematic study of variations in the mineralogy, petrology, and soluble and insoluble organic matter in distinct fragments of the Tagish Lake meteorite. The variations correlate with indicators of parent body aqueous alteration. At least some molecules of prebiotic importance formed during the alteration.