安部 正真

Abstract Understanding the processes of aqueous alteration within primitive bodies is crucial for unraveling the complex history of early planetesimals. To better identify the signs of this process and its consequences, we have studied the heterogeneity at a micrometric scale of the structure of the aliphatic organic compounds and its relationship to its mineralogical environment. Here, we report an analysis performed on two micrometric grains of Ryugu (C0002‐FC027 and C0002‐FC028). The samples were crushed in a diamond compression cell and analyzed using high‐spatial resolution Fourier Transform InfraRed (FT‐IR) hyperspectral imaging measurements conducted in transmission mode. We showed here the spatial distributions of the main components and the structural heterogeneity of the aliphatic organic matter highlighting a micrometer‐scale variability in the methylene‐to‐methyl ratio. Moreover, we connected this heterogeneity to the one of the phyllosilicate band positions. Our findings indicate that the organic matter within Ryugu's micrometric grains underwent varying degrees of aqueous alteration in distinct microenvironments resulting in an elongation of the length of their aliphatic chains, and/or a reduction in their branching and/or cross‐linking.

Abstract Nucleosynthetic isotope variations are powerful tracers to determine genetic relationships between meteorites and planetary bodies. They can help to link material collected by space missions to known meteorite groups. The Hayabusa 2 mission returned samples from the Cb‐type asteroid (162173) Ryugu. The mineralogical, chemical, and isotopic characteristics of these samples show strong similarities to carbonaceous chondrites and in particular CI chondrites. The nucleosynthetic isotope compositions of Ryugu overlap with CI chondrites for several elements (e.g., Cr, Ti, Fe, and Zn). In contrast to these isotopes, which are of predominately supernovae origin, s‐process variations in Mo isotope data are similar to those of carbonaceous chondrites, but even more s‐process depleted. To further constrain the origin of this depletion and test whether this signature is also present for other s‐process elements, we report Zr isotope compositions for three bulk Ryugu samples (A0106, A0106‐A0107, C0108) collected from the Hayabusa 2 mission. The data are complemented with that of terrestrial rock reference materials, eucrites, and carbonaceous chondrites. The Ryugu samples are characterized by distinct ⁹⁶Zr enrichment relative to Earth, indicative of a s‐process depletion. Such depletion is also observed for carbonaceous chondrites and eucrites, in line with previous Zr isotope work, but it is more extreme in Ryugu, as observed for Mo isotopes. Since s‐process Zr and Mo are coupled in mainstream SiC grains, these distinct s‐process variations might be due to SiC grain depletion in the analyzed materials, potentially caused by incomplete sample digestion, because the Ryugu samples were dissolved on a hotplate only to avoid high blank levels for other elements (e.g., Cr). However, local depletion of SiC grains cannot be excluded. An alternative, equally possible scenario is that aqueous alteration redistributed anomalous, s‐process‐depleted, Zr on a local scale, for example, into Ca‐phosphates or phyllosilicates.

Abstract Regolith samples returned from asteroid 162173 Ryugu by the Hayabusa2 mission provide direct means to study how space weathering operates on the surfaces of hydrous asteroids. The mechanisms of space weathering, its effects on mineral surfaces, and the characteristic time scales on which alteration occurs are central to understanding the spectroscopic properties and the taxonomy of asteroids in the solar system. Here, we investigate the behavior of the iron monosulfides mineral pyrrhotite (Fe_1−xS) at the earliest stages of space weathering. Using electron microscopy methods, we identified a partially exposed pyrrhotite crystal that morphologically shows evidence for mass loss due to exposure to solar wind ion irradiation. We find that crystallographic changes to the pyrrhotite can be related to sulfur loss from its space‐exposed surface and the diffusive redistribution of resulting excess iron into the interior of the crystal. Diffusion profiles allow us to estimate an order of magnitude of the exposure time of a few thousand years consistent with previous estimates of space exposure. During this interval, the adjacent phyllosilicates did not acquire discernable damage, suggesting that they are less susceptible to alteration by ion irradiation than pyrrhotite.

Abstract Apatite is present as an accessory phase in many meteorites and is often formed as a secondary product of aqueous alteration. Its propensity to incorporate rare earth elements (REE) results in apatite usually being the main REE‐bearing phase in hydrously altered meteorites. Asteroid Ryugu is thought to have experienced pervasive aqueous alteration and material collected from the surface of Ryugu is expected to provide insight into asteroidal aqueous alteration processes without influence by terrestrial weathering. Morphologies and mineral associations of apatite grains from five rock fragments collected from the asteroid Ryugu by the Hayabusa2 spacecraft were examined and their REE concentrations were measured by synchrotron X‐ray fluorescence (SXRF) spectroscopy. The main minerals associated with apatite are dolomite, magnetite, and pyrrhotite. Grain boundary corrosion of the interfaces between apatite assemblages and the surrounding matrix suggest that paragenetic formation on the asteroid was followed by a later episode of hydrous alteration. Light REE (LREE) concentration levels recorded at 20–150 times those of bulk CI levels together with a steady increase from LREE toward enrichment of medium REE (MREE, up to Er) at 50–400 times bulk CI levels may suggest postgenetic removal of LREE from Ryugu apatite grains by late‐stage circulation of a hydrothermal fluid.

Abstract Although CI chondrites are susceptible to terrestrial weathering on Earth, the specific processes are unknown. To elucidate the weathering mechanism, we conduct a laboratory experiment using pristine particles from asteroid Ryugu. Air‐exposed particles predominantly develop small‐sized euhedral Ca‐S‐rich grains (0.5–1 μm) on the particle surface and along open cracks. Both transmission electron microscopy and synchrotron‐based computed tomography combined with XRD reveal that the grains are hydrous Ca‐sulfate. Notably, this phase does not form in vacuum‐ or nitrogen‐stored particles, suggesting this result is due to laboratory weathering. We also compare the Orgueil CI chondrite with the altered Ryugu particles. Due to the weathering of pyrrhotite and dolomite, Orgueil contains a significant amount of gypsum and ferrihydrite. We suggest that mineralogical changes due to terrestrial weathering of particles returned directly from asteroid occur even after a short‐time air exposure. Consequently, conducting prompt analyses and ensuring proper storage conditions are crucial, especially to preserve the primordial features of organics and volatiles.

Abstract The nitrogen isotope compositions of two samples returned from the asteroid Ryugu were determined using a stepwise combustion method, along with Ivuna (CI) and Y‐980115, a CI‐like Antarctic meteorite, as references. The two Ryugu samples A0105‐07 and C0106‐07 showed bulk δ¹⁵N values of +1.7 ± 0.5‰ and +0.2 ± 0.6‰, respectively, significantly lower than Ivuna with +36.4 ± 0.4‰, but close to Y‐980115 with +4.0 ± 0.3‰. The Ryugu samples are further characterized by C/N and ³⁶Ar/N ratios up to 3.4× and 4.9× the value of Ivuna, respectively. Among all Ryugu samples and CI chondrites, a positive correlation was observed between nitrogen concentrations and δ¹⁵N values, with samples with lower nitrogen concentrations exhibiting lower δ¹⁵N. This trend is explained by a two‐component mixing model. One component is present at a constant abundance among all CI‐related samples, with a δ¹⁵N value around 0‰ or lower. The other varies in abundance between different samples, and exhibits a δ¹⁵N value of +56 ± 4‰. The first ¹⁵N‐poor endmember is seemingly tightly incorporated into a carbonaceous host phase, whereas the ¹⁵N‐rich endmember can be mobilized and decoupled from carbon, potentially because it is in the form of ammonia. Asteroid materials with volatile compositions that are similar to those reported here for the Ryugu samples are attractive candidates for the volatile sources among Earth's building blocks.

Abstract Extraterrestrial minerals on the surface of airless Solar System bodies undergo gradual alteration processes known as space weathering over long periods of time. The signatures of space weathering help us understand the phenomena occurring in the Solar System. However, meteorites rarely retain the signatures, making it impossible to study the space weathering processes precisely. Here, we examine samples retrieved from the asteroid Ryugu by the Hayabusa2 spacecraft and discover the presence of nonmagnetic framboids through electron holography measurements that can visualize magnetic flux. Magnetite particles, which normally provide a record of the nebular magnetic field, have lost their magnetic properties by reduction via a high-velocity (>5 km s^–1) impact of a micrometeoroid with a diameter ranging from 2 to 20 μm after destruction of the parent body of Ryugu. Around these particles, thousands of metallic-iron nanoparticles with a vortex magnetic domain structure, which could have recorded a magnetic field in the impact event, are found. Through measuring the remanent magnetization of the iron nanoparticles, future studies are expected to elucidate the nature of the nebular/interplanetary magnetic fields after the termination of aqueous alteration in an asteroid.

Abstract We analyzed an asteroid Ryugu sample returned to Earth by JAXA's Hayabusa2 mission using nanoIR, SEM, and TEM microscopy. We identified multiple distinct carbon reservoirs within the phyllosilicate matrix and demonstrate infrared spectral affinities for some of the carbon to insoluble organic matter (IOM). TEM studies of Ryugu samples have allowed us to better understand the interrelationship between the crystallographic orientations of phyllosilicates and the secondary minerals such as carbonate, sulfide, and apatite. Transport of elements provides a unifying theme for understanding these interrelationships.

Abstract Oxygen 3‐isotope ratios of magnetite and carbonates in aqueously altered carbonaceous chondrites provide important clues to understanding the evolution of the fluid in the asteroidal parent bodies. We conducted oxygen 3‐isotope analyses of magnetite, dolomite, and breunnerite in two sections of asteroid Ryugu returned samples, A0058 and C0002, using a secondary ion mass spectrometer (SIMS). Magnetite was analyzed by using a lower primary ion energy that reduced instrumental biases due to the crystal orientation effect. We found two groups of magnetite data identified from the SIMS pit morphologies: (1) higher δ¹⁸O (from 3‰ to 7‰) and ∆¹⁷O (~2‰) with porous SIMS pits mostly from spherulitic magnetite, and (2) lower δ¹⁸O (~ −3‰) and variable ∆¹⁷O (0‰–2‰) mostly from euhedral magnetite. Dolomite and breunnerite analyses were conducted using multi‐collection Faraday cup detectors with precisions ≤0.3‰. The instrumental bias correction was applied based on carbonate compositions in two ways, using Fe and (Fe + Mn) contents, respectively, because Ryugu dolomite contains higher amounts of Mn than the terrestrial standard. Results of dolomite and breunnerite analyses show a narrow range of ∆¹⁷O; 0.0‰–0.3‰ for dolomite in A0058 and 0.2‰–0.8‰ for dolomite and breunnerite in C0002. The majority of breunnerite, including large ≥100 μm grains, show systematically lower δ¹⁸O (~21‰) than dolomite (25‰–30‰ and 23‰–27‰ depending on the instrumental bias corrections). The equilibrium temperatures between magnetite and dolomite from the coarse‐grained lithology in A0058 are calculated to be 51 ± 11°C and 78 ± 14°C, depending on the instrumental bias correction scheme for dolomite; a reliable temperature estimate would require a Mn‐bearing dolomite standard to evaluate the instrumental bias corrections, which is not currently available. These results indicate that the oxygen isotope ratios of aqueous fluids in the Ryugu parent asteroid were isotopically heterogeneous, either spatially, or temporary. Initial water ice accreted to the Ryugu parent body might have ∆¹⁷O > 2‰ that was melted and interacted with anhydrous solids with the initial ∆¹⁷O < 0‰. In the early stage of aqueous alteration, spherulitic magnetite and calcite formed from aqueous fluid with ∆¹⁷O ~ 2‰ that was produced by isotope exchange between water (∆¹⁷O > 2‰) and anhydrous solids (∆¹⁷O < 0‰). Dolomite and breunnerite, along with some magnetite, formed at the later stage of aqueous alteration under higher water‐to‐rock ratios where the oxygen isotope ratios were nearly at equilibrium between fluid and solid phases. Including literature data, δ¹⁸O of carbonates decreased in the order calcite, dolomite, and breunnerite, suggesting that the temperature of alteration might have increased with the degree of aqueous alteration.

Abstract The analysis of samples returned from the C-type asteroid Ryugu has drastically advanced our knowledge of the evolution of early solar system materials. However, no consensus has been obtained on the chronological data, which is important for understanding the evolution of the asteroid Ryugu. Here, the aqueous alteration age of Ryugu particles was determined by the Mn–Cr method using bulk samples, yielding an age of 4.13 + 0.62/−0.55 Myr after the formation of Ca–Al-rich inclusions (CAI). The age corresponds to 4563.17 + 0.60/−0.67 Myr ago. The higher ⁵⁵Mn/⁵²Cr, ε ⁵⁴Cr, and initial ε ⁵³Cr values of the Ryugu samples relative to any carbonaceous chondrite samples implies that its progenitor body formed from the least thermally processed precursors in the outermost region of the protoplanetary disk. Despite accreting at different distances from the Sun, the hydrous asteroids (Ryugu and the parent bodies of CI, CM, CR, and ungrouped C2 meteorites) underwent aqueous alteration during a period of limited duration (3.8 ± 1.8 Myr after CAI). These ages are identical to the crystallization age of the carbonaceous achondirtes NWA 6704/6693 within the error. The ε ⁵⁴Cr and initial ε ⁵³Cr values of Ryugu and NWA 6704/6693 are also identical, while they show distinct Δ'¹⁷O values. This suggests that the precursors that formed the progenitor bodies of Ryugu and NWA 6703/6693 were formed in close proximity and experienced a similar degree of thermal processing in the protosolar nebula. However, the progenitor body of Ryugu was formed by a higher ice/dust ratio, than NWA6703/6693, in the outer region of the protoplanetary disk.

The JAXA Hayabusa2 mission returned well-preserved samples collected from the carbonaceous asteroid Ryugu, providing unique non-terrestrially weathered samples from a known parent body. This work aims to provide a better understanding of the formation and evolution of primitive asteroidal matter by studying the fine scale association of organic matter and minerals in Ryugu samples. We characterized the samples by IR nanospectroscopy using the AFM-IR technique. This technique overcomes the diffraction limit (of several microns) of conventional infrared microspectroscopy (µ-FTIR). The samples were mapped in the mid-IR range at a lateral spatial resolution about a hundred times better than with µ-FTIR. This provided us with unique in situ access to the distribution of the different infrared signatures of organic components at the sub-micron scale present in the Ryugu whole-rock samples as well as to the characterization of the compositional variability of Ryugu in the insoluble organic matter (IOM) chemically extracted from the Ryugu samples. The AFM-IR maps of whole-rock particles and IOM residues from Ryugu samples were recorded with a lateral resolution of tens of nanometers. Spectra were recorded in the 1900-900 cm$^−1$ spectral range by AFM-IR (Icon-IR) for all samples, and additional spectra were recorded from 2700 to 4000 cm$^−1$ for one IOM sample by an optical photothermal IR (O-PTIR) technique using a mIRage$^ textregistered $ IR microscope. Organic matter is present in two forms in the whole-rock samples: as a diffuse phase intermixed with the phyllosilicate matrix and as individual organic nanoparticles. We identify the Ryugu organic nanoparticles as nanoglobule-like inclusions texturally resembling nanoglobules present in primitive meteorites. Using AFM-IR, we record for the first time the infrared spectra of Ryugu organic nanoparticles that clearly show enhanced carbonyl (C=O) and CH contributions with respect to the diffuse organic matter in Ryugu whole-rock and IOM residue.

Abstract Samples from asteroid Ryugu, brought back by asteroid explorer Hayabusa2, are important for investigating the origin and evolution of the solar system. Here, we report the elemental compositions of a 123‐mg Ryugu sample determined with a nondestructive muon elemental analysis method. This method is a powerful tool for determining bulk chemical composition, including light elements such as C, N, and O. From the muonic x‐ray spectra with three carbonaceous chondrites, the relationship between the elemental composition and muonic x‐ray intensity was determined for each element. Calibration curves showed linearity, and the elemental composition of Ryugu was quantitatively determined. The results reflect the average bulk elemental composition of asteroid Ryugu owing to the large amount of samples. Ryugu has an elemental composition similar to that of Orgueil (CI1) and should be classified as CI1. However, the O/Si ratio of Ryugu is 25% lower than that of Orgueil, indicating that Orgueil may have been seriously contaminated by terrestrial materials after its fall to Earth. These results indicate that the Ryugu sample is more representative than the CI chondrites as a solid material of the solar system.

Abstract In order to gain insights on the conditions of aqueous alteration on asteroid Ryugu and the origin of water in the outer solar system, we developed the measurement of water content in magnetite at the micrometer scale by secondary ion mass spectrometry (NanoSIMS) and determined the H and Si content of coarse‐grained euhedral magnetite grains (polyhedral magnetite) and coarse‐grained fibrous (spherulitic) magnetite from the Ryugu polished section A0058‐C1001. The hydrogen content in magnetite ranges between ~900 and ~3300 wt ppm equivalent water and is correlated with the Si content. Polyhedral magnetite has low and homogenous silicon and water content, whereas fibrous magnetite shows correlated Si and water excesses. These excesses can be explained by the presence of hydrous Si‐rich amorphous nanoinclusions trapped during the precipitation of fibrous magnetite away from equilibrium and testify that fibrous magnetite formed from a hydrous gel with possibly more than 20 wt% water. An attempt to determine the water content in sub‐μm framboids indicates that additional calibration and contamination issues must be addressed before a safe conclusion can be drawn, but hints at elevated water content as well. The high water content in fibrous magnetite, expected to be among the first minerals to crystallize at low water–rock ratio, points to the control of water content by local conditions of magnetite precipitation rather than large‐scale alteration conditions. Systematic lithological variations associated with water‐rich and water‐poor magnetite suggest that the global context of alteration may be better understood if local water concentrations are compared with millimeter‐scale distribution of the various morphologies of magnetite. Finally, the high water content in the magnetite precursor gel indicates that the initial O isotopic composition in alteration water must not have been very different from that of the earliest magnetite crystals.

Abstract Transmission electron microscopy analyses of Hayabusa2 samples show that Ryugu organic matter exhibits a range of morphologies, elemental compositions, and carbon functional chemistries consistent with those of carbonaceous chondrites that have experienced low‐temperature aqueous alteration. Both nanoglobules and diffuse organic matter are abundant. Non‐globular organic particles are also present, and including some that contain nanodiamond clusters. Diffuse organic matter is finely distributed in and around phyllosilicates, forms coatings on other minerals, and is also preserved in vesicles in secondary minerals such as carbonate and pyrrhotite. The average elemental compositions determined by energy‐dispersive spectroscopy of extracted, demineralized insoluble organic matter samples A0107 and C0106 are C₁₀₀N₃O₉S₁ and C₁₀₀N₃O₇S₁, respectively, with the difference in O/C slightly outside the difference in the standard error of the mean. The functional chemistry of the nanoglobules varies from mostly aromatic C=C to mixtures of aromatic C=C, ketone C=O, aliphatic (CH_n), and carboxyl (COOH) groups. Diffuse organic matter associated with phyllosilicates has variable aromatic C, ketone and carboxyl groups, and some localized aliphatics, but is dominated by molecular carbonate (CO₃) absorption, comparable to prior observations of clay‐bound organic matter in CI meteorites.

The Hayabusa2 spacecraft delivered samples of the carbonaceous asteroid Ryugu to Earth. Some of the sample particles show evidence of micrometeoroid impacts, which occurred on the asteroid surface. Among those, particles A0067 and A0094 have flat surfaces on which a large number of microcraters and impact melt splashes are observed. Two impact melt splashes and one microcrater were analyzed to unveil the nature of the objects that impacted the asteroid surface. The melt splashes consist mainly of Mg-Fe–rich glassy silicates and Fe-Ni sulfides. The microcrater trapped an impact melt consisting mainly of Mg-Fe–rich glassy silicate, Fe-Ni sulfides, and minor silica-rich glass. These impact melts show a single compositional trend indicating mixing of Ryugu surface materials and impactors having chondritic chemical compositions. The relict impactor in one of the melt splashes shows mineralogical similarity with anhydrous chondritic interplanetary dust particles having a probable cometary origin. The chondritic micrometeoroids probably impacted the Ryugu surface during its residence in a near-Earth orbit.

This paper is focused on the characterization of the thermal history of C-type asteroid Ryugu through the structure of the polyaromatic carbonaceous matter in the returned samples determined by Raman spectroscopy. Both intact particles and extracted Insoluble Organic Matter (IOM) from the two sampling sites on Ryugu have been characterized. The main conclusions are that (i) there is no structural difference of the polyaromatic component probed by Raman spectroscopy between the two sampling sites, (ii) in a manner similar to type 1 and 2 chondrites, the characterized Ryugu particles did not experience significant long-duration thermal metamorphism related to the radioactive decay of elements such as 26Al; (iii) some structural variability is nevertheless observed within our particle set. It can be interpreted as some particles having experienced some short-duration and weak heating (R3 in the scale defined by Quirico et al. 2018 and TII or lower according to the scale defined by Nakamura, 2005).

Abstract Japan Aerospace Exploration Agency's Martian Moons eXploration (MMX) mission will launch a spacecraft in 2024 to return samples from Phobos in 2029. Curatorial work for the returned Phobos samples is critical for the sample allocation without degrading the sample integrity and subsequent sample analysis that will provide new constraints on the origin of Phobos and the evolution of the circum‐Mars environment. The Sample Analysis Working Team of the MMX is designing the sample curation protocol. The curation protocol consists of three phases: (1) quick analysis (extraction and mass spectrometry for gases), (2) pre‐basic characterization (bulk‐scale observation), and (3) basic characterization (grain‐by‐grain observation and allocation of the sample aliquots). Nondestructive analyses within the clean chamber (e.g., visible and near‐infrared spectral imaging) and outside the chamber (e.g., gas mass spectrometry) are incorporated into the curation flow in coordination with the MMX mission instrument teams for ground‐truthing the remote‐sensing data sets. The MMX curation/sample analysis flow enables the seamless integration between the sample and remote‐sensing data sets to maximize the scientific value of the collected Phobos samples.

Abstract The Hayabusa2 mission from the Japan Aerospace Exploration Agency (JAXA) returned to the Earth samples of carbonaceous asteroid (162173) Ryugu. This mission offers a unique opportunity to investigate in the laboratory samples from a C‐type asteroid, without physical or chemical alteration by the terrestrial atmosphere. Here, we report on an investigation of the mineralogy and the organo‐chemistry of Hayabusa2 samples using a combination of micro‐ and nano‐infrared spectroscopy. Particles investigated with conventional FTIR spectroscopy have spectra dominated by phyllosilicate‐related absorption, as observed for samples of CI‐chondrites, selected ungrouped carbonaceous chondrites, and selected hydrated micrometeorites. Ryugu samples show smaller sulfate‐related absorption than CI‐chondrites. Our samples that were only briefly exposed to the Earth atmosphere show absorptions related to molecular water, revealing fast terrestrial contamination of the spectral signature at 3 μm. Overall, our FTIR data are in agreement with other work done on Ryugu samples, revealing a low degree of mineralogical variability across Ryugu samples. AFM‐IR mapping of the grains shows the presence of a micrometer‐sized organic globule in one of our analyzed grains. The AFM‐IR spectra obtained on this globule are similar to IR spectra obtained on IOM suggesting that it is constituted of refractory organic matter. This globule may host silicate in its interior, with a different mineralogy than bulk Ryugu phyllosilicate. The shape, presence of peculiar silicate, and the nature of organic constituting the globule point toward a pre‐accretionary origin of this globule and that at least part of Ryugu organics were inherited from the protosolar nebulae or the interstellar media. Altogether, our results show the similarities between Ryugu samples and CI chondrites.

Abstract Ryugu asteroid grains brought back to the Earth by the Hayabusa2 space mission are pristine samples containing hydrated minerals and organic compounds. Here, we investigate the mineralogy of their phyllosilicate‐rich matrix with four‐dimensional scanning transmission electron microscopy (4D‐STEM). We have identified and mapped the mineral phases at the nanometer scale (serpentine, smectite, pyrrhotite), observed the presence of Ni‐bearing pyrrhotite, and identified the serpentine polymorph as lizardite, in agreement with the reported aqueous alteration history of Ryugu. Furthermore, we have mapped the d‐spacings of smectite and observed a broad distribution of values, ranging from 1 to 2 nm, with an average d‐spacing of 1.24 nm, indicating significant heterogeneity within the sample. Such d‐spacing variability could be the result of either the presence of organic matter trapped in the interlayers or the influence of various geochemical conditions at the submicrometer scale, suggestive of a range of organic compounds and/or changes in smectite crystal chemistry.

Polycyclic aromatic hydrocarbons (PAHs) contain ≲20% of the carbon in the interstellar medium. They are potentially produced in circumstellar environments (at temperatures ≳1000 kelvin), by (~10 kelvin) interstellar clouds, or by processing of carbon-rich dust grains. We report isotopic properties of PAHs extracted from samples of the asteroid Ryugu and the meteorite Murchison. The doubly- ¹³ C substituted compositions (Δ2× ¹³ C values) of the PAHs naphthalene, fluoranthene, and pyrene are 9 to 51‰ higher than values expected for a stochastic distribution of isotopes. The Δ2× ¹³ C values are higher than expected if the PAHs formed in a circumstellar environment, but consistent with formation in the interstellar medium. By contrast, the PAHs phenanthrene and anthracene in Ryugu samples have Δ2× ¹³ C values consistent with formation by higher-temperature reactions.

The carbonaceous asteroid Ryugu has been explored by the Hayabusa2 spacecraft to elucidate the actual nature of hydrous asteroids. Laboratory analyses revealed that the samples from Ryugu are comparable to unheated CI carbonaceous chondrites; however, reflectance spectra of Ryugu samples and CIs do not coincide. Here, we demonstrate that Ryugu sample spectra are reproduced by heating Orgueil CI chondrite at 300°C under reducing conditions, which caused dehydration of terrestrial weathering products and reduction of iron in phyllosilicates. Terrestrial weathering of CIs accounts for the spectral differences between Ryugu sample and CIs, which is more severe than space weathering that likely explains those between asteroid Ryugu and the collected samples. Previous assignments of CI chondrite parent bodies, i.e., chemically most primitive objects in the solar system, are based on the spectra of CI chondrites. This study indicates that actual spectra of CI parent bodies are much darker and flatter at ultraviolet to visible wavelengths than the spectra of CI chondrites.

Evaluating the molecular distribution of organic compounds in pristine extraterrestrial materials is cornerstone to understanding the abiotic synthesis of organics and allows us to better understand the molecular diversity available during the formation of our solar system and before the origins of life on Earth. In this work, we identify multiple organic compounds in solvent extracts of asteroid Ryugu samples A0106 and C0107 and the Orgueil meteorite using two-dimensional gas chromatography and time-of-flight high resolution mass spectrometry (GC×GC–HRMS). Our analyses found similarities between the molecular distribution of organic compounds in Ryugu and the CI carbonaceous chondrite Orgueil. Specifically, several PAHs and organosulfides were found in Ryugu and Orgueil suggesting an interstellar and parent body origin for these compounds. We also evaluated the common relationship between Ryugu, Orgueil, and comets, such as Wild-2; however, until comprehensive compound-specific isotopic analyses for these organic species are undertaken, and until the effects of parent body processes and Earth’s weathering processes on meteoritic organics are better understood, their parent–daughter relationships will remain unanswered. Finally, the study of organic compounds in Ryugu samples and the curation practices for the future preservation of these unvaluable materials are also of special interest for future sample return missions, including NASA’s OSIRIS-REx asteroid sample return mission. Graphical Abstract: [Figure not available: see fulltext.].

Abstract Samples returned from the carbonaceous asteroid (162173) Ryugu by the Hayabusa2 mission revealed that Ryugu is composed of materials consistent with CI chondrites and some types of space weathering. We report detailed mineralogy of the fine‐grained Ryugu samples allocated to our “Sand” team and report additional space weathering features found on the grains. The dominant mineralogy is composed of a fine‐grained mixture of Mg‐rich saponite and serpentine, magnetite, pyrrhotite, pentlandite, dolomite, and Fe‐bearing magnesite. These grains have mineralogy comparable to that of CI chondrites, showing severe aqueous alteration but lacking ferrihydrite and sulfate. These results are similar to previous works on large Ryugu grains. In addition to the major minerals, we also find many minerals that are rare or have not been reported among CI chondrites. Accessory minerals identified are hydroxyapatite, Mg‐Na phosphate, olivine, low‐Ca pyroxene, Mg‐Al spinel, chromite, manganochromite, eskolaite, ilmenite, cubanite, polydymite, transjordanite, schreibersite, calcite, moissanite, and poorly crystalline phyllosilicate. We also show scanning transmission electron microscope and scanning electron microscope compositional maps and images of some space‐weathered grains and severely heated and melted grains. Although our mineralogical results are consistent with that of millimeter‐sized grains, the fine‐grained fraction is best suited to investigate impact‐induced space weathering.

Abstract The Hayabusa2 mission sampled Ryugu, an asteroid that did not suffer extensive thermal metamorphism, and returned rocks to the Earth with no significant air exposure. It therefore offers a unique opportunity to study the redox state of carbonaceous Cb‐type asteroids and evaluate the overall redox state of the most primitive rocks of the solar system. An analytical framework was developed to investigate the iron mineralogy and valence state in extraterrestrial material at the micron scale by combining x‐ray diffraction, conventional Mössbauer (MS), and nuclear forward scattering (NFS) spectroscopies. An array of standard minerals was analyzed and cross‐calibrated between MS and NFS. Then, MS and NFS spectra on three Ryugu grains were collected at the bulk and the micron scales. In Ryugu samples, iron is essentially accommodated in magnetite, clay minerals (serpentine–smectite), and sulfides. Only a single set of Mössbauer parameters was necessary to account for the entire variability observed in MS and NFS spectra, at all spatial scales investigated. These parameters therefore make up a fully consistent iron mineralogical model for the Ryugu samples. As far as MS and NFS spectroscopies are concerned, Ryugu grains are overall similar to each other and share most of their mineralogical features with CI‐type chondrites. In detail however, no ferrihydrite is found in Ryugu particles even at the very sensitive scale of Mössbauer spectroscopy. The typical Fe³⁺/Fe_tot of clay minerals is much lower than typical redox ratios measured in CI chondrites (Fe³⁺/Fe_tot = 85%–90%). Furthermore, magnetite from Ryugu is stoichiometric with no significant maghemite component, whereas up to 12% of maghemite was previously identified in the Orgueil's so‐called magnetite. These differences suggest that most CI meteorites suffered terrestrial alteration and that the preterrestrial composition of these carbon‐rich samples was less oxidized than previously measured. However, it is not clear yet whether or not the parent bodies of CI chondrites were as reduced as Ryugu. Finally, the high spatial resolution of NFS allows to disentangle the redox state and the crystal chemistry of iron accommodated in serpentine and smectite. The most likely polytype of serpentine is lizardite, containing <35% of Fe³⁺, a fraction of which being tetrahedrally coordinated. Smectite is more oxidized (Fe³⁺/Fe_tot > 65%) and mainly contains octahedral ferric iron. This finding implies that these clays formed from highly alkaline fluids and the spatial variability highlighted here may suggest a temporal evolution or a spatial variability of the nature of this fluid.

Abstract The bulk density of grains from a celestial body is a fundamental property related to its composition and structure, contributing to the understanding of its evolutionary history. In this study, we provide the bulk density of 637 grains returned from the C-type near-Earth asteroid 162173 Ryugu. This is the largest number of grains to date for the curation activity, corresponding to 38 wt.% of the total returned samples (approximately 5.4 g). Although several densities of the Ryugu grains were reported, the volume estimation of some samples showed uncertainties. Therefore, we applied a new volume estimation model calibrated by X-ray micro-computed tomography (XCT) to the Ryugu grains to more accurately estimate their bulk density. The obtained average bulk density of 637 Ryugu grains was 1.79 ± 0.31 g/cm³ (1σ variation) for weights of 0.5‒100 mg (sub-mm ‒to 10 mm) irrespective of their 3D shapes characterized by three axial length ratios, considered to be a representative of the returned samples. The bulk density distributions of the grains in Chambers A and C were statistically distinguishable, with mean values of 1.81 ± 0.30 and 1.76 ± 0.33 g/cm³ (1σ variations), respectively. Despite the small difference, bulk density may have differed by sampling site. The obtained average bulk density value of A + C samples was almost the same as that of 16 Ryugu grains estimated based on CT scanned data, and was consistent with the densities of CI chondrites (1.57–1.91 g/cm³). The axial ratios of the grains in Chambers A and C were similar and those of the 724 returned samples and the flying particles ejected during the sampling operations were also similar, suggesting that relatively small Ryugu materials (mm‒cm in size) are similar in shape. The minor difference between the Rygu grains and flying particles could be attributed to events such as scraping during sampling operations and transportation. Graphical Abstract

Abstract Developing a cleanroom and clean chambers (CCs) for Hayabusa2 returned samples has been discussed with the committee for Hayabusa2 sample curation facility since 2015. One major difference from the specifications of the CCs used for Itokawa samples is that a part of samples was decided to be handled and preserved in vacuum to avoid terrestrial nitrogen contamination with organics or unknown materials that might easily react with the samples. Thus, the CCs for Hayabusa2 samples were divided into two CCs for vacuum processes and three CCs for purified nitrogen conditions. The cleanroom was built in summer 2017, while the CCs were installed in the summer of 2018. After the installation of the CCs, instruments for initial descriptions, sample containers, handling tools for powder and particle samples, and jigs to assist handling samples were developed in parallel with functional checks and repeated rehearsals between the fall of 2018 and the fall of 2020. The curatorial works on Hayabusa2-retuned samples were conducted as previously planned. Simultaneously, contaminations and influences of inorganics, organics, microbial, and magnetic constructs have been assessed to evaluate their potential effects on the analysis of the returned samples. Additionally, the tools used to touch samples directly have been demagnetized to avoid sample magnetization during their handling and the tool magnetization was measured before and after their usages. The series of developments and experiences from the curatorial works of Hayabusa2-returned samples represent valuable implications for future sample return missions. Graphical Abstract

Abstract Samples were recently collected from the carbonaceous asteroid (162173) Ryugu, by the Japan Aerospace Exploration Agency (JAXA) Hayabusa2 mission. They resemble CI chondrites material, thus showing clear evidence of extensive aqueous alteration attested by the widespread presence of a mixture of serpentine and saponite. We present here a scanning transmission electron microscopy study of the Ryugu dominant lithology of the phyllosilicate matrix at the nanometer scale, which we compare with that of the Orgueil CI chondrite. In both objects, the phyllosilicates are of comparable nature and texture, consisting of a mixture of small‐sized crystallites of serpentine and saponite. At the micrometer scale or less, the texture is an alternation of fine and coarse domains. The fine‐grained regions are dominated by saponite. In Ryugu, they enclose numerous Fe,Ni nanosulfides, whereas in Orgueil, S‐ and Ni‐rich ferrihydrite is abundant. The coarse‐grained regions contain more serpentine and no or little Fe,Ni sulfides or ferrihydrite. Scanning transmission x‐ray microscopy at the Fe‐L₃ edge also reveals that iron valency of phyllosilicates is higher and more homogeneous in Orgueil (~70% Fe³⁺) than in Ryugu (<50% Fe³⁺). We interpret the observed textures as being mostly a consequence of aqueous alteration, likely resulting from the replacement by phyllosilicates of submicrometric components, initially agglomerated by a primary accretion. The fine‐grained domains may result from the replacement of GEMS (GEMS—glass with embedded metal and sulfides) objects or from other types of nanometric assemblages of silicate and Fe‐based nanophases. On the other hand, the coarse‐grained regions may correspond to the replacement of anhydrous crystalline silicates of the olivine and pyroxene type. The major difference is the presence of Fe,Ni sulfides in Ryugu and of ferrihydrite and higher iron valency of phyllosilicates in Orgueil. This might be due to long‐term terrestrial weathering that would have destabilized the nanosulfides. We also explore an alternative scenario involving more oxidizing hydrothermal conditions on the Orgueil parent body.

Abstract We report a Fourier transform infrared analysis of functional groups in insoluble organic matter (IOM) extracted from a series of 100–500 μm Ryugu grains collected during the two touchdowns of February 22 and July 11, 2019. IOM extracted from most of the samples is very similar to IOM in primitive CI, CM, and CR chondrites, and shows that the extent of thermal metamorphism in Ryugu regolith was, at best, very limited. One sample displays chemical signatures consistent with a very mild heating, likely due to asteroidal collision impacts. We also report a lower carbonyl abundance in Ryugu IOM samples compared to primitive chondrites, which could reflect the accretion of a less oxygenated precursor by Ryugu. The possible effects of hydrothermal alteration and terrestrial weathering are also discussed. Last, no firm conclusions could be drawn on the origin of the soluble outlier phases, observed along with IOM in this study and in the preliminary analysis of Ryugu samples. However, it is clear that the HF/HCl residues presented in this publication are a mix between IOM and the nitrogen‐rich outlier phase.

Abstract The sample from the near-Earth carbonaceous asteroid (162173) Ryugu is analyzed in the context of carbonaceous meteorites soluble organic matter. The analysis of soluble molecules of samples collected by the Hayabusa2 spacecraft shines light on an extremely high molecular diversity on the C-type asteroid. Sequential solvent extracts of increasing polarity of Ryugu samples are analyzed using mass spectrometry with complementary ionization methods and structural information confirmed by nuclear magnetic resonance spectroscopy. Here we show a continuum in the molecular size and polarity, and no organomagnesium molecules are detected, reflecting a low temperature and water-rich environment on the parent body approving earlier mineralogical and chemical data. High abundance of sulfidic and nitrogen rich compounds as well as high abundance of ammonium ions confirm the water processing. Polycyclic aromatic hydrocarbons are also detected in a structural continuum of carbon saturations and oxidations, implying multiple origins of the observed organic complexity, thus involving generic processes such as earlier carbonization and serpentinization with successive low temperature aqueous alteration.

Samples from the carbonaceous asteroid (162173) Ryugu provide information on the chemical evolution of organic molecules in the early solar system. Here we show the element partitioning of the major component ions by sequential extractions of salts, carbonates, and phyllosilicate-bearing fractions to reveal primordial brine composition of the primitive asteroid. Sodium is the dominant electrolyte of the salt fraction extract. Anions and NH4+ are more abundant in the salt fraction than in the carbonate and phyllosilicate fractions, with molar concentrations in the order SO42- > Cl- > S2O32- > NO3- > NH4+. The salt fraction extracts contain anionic soluble sulfur-bearing species such as Sn-polythionic acids (n < 6), Cn-alkylsulfonates, alkylthiosulfonates, hydroxyalkylsulfonates, and hydroxyalkylthiosulfonates (n < 7). The sulfur-bearing soluble compounds may have driven the molecular evolution of prebiotic organic material transforming simple organic molecules into hydrophilic, amphiphilic, and refractory S allotropes.

Abstract We report μm‐scale nondestructive infrared (IR) hyperspectral results (IR computed tomography, IR‐CT) in 3‐D and IR surface imaging, IR‐S) in 2‐D, at SOLEIL) combined with X‐ray nano‐computed tomography analyses (at SPring‐8) performed on eight small Ryugu fragments extracted from mm‐sized grains coming both from touchdown first and second sites. We describe the multiscale assembly of phyllosilicates, carbonates, sulfides, oxides, and organics. Two types of silicates, as well as diverse kinds of organic matter, were detected inside Ryugu material. Their spatial correlations are described to discuss the role of the mineralogical microenvironments in the formation/evolution of organic matter. In particular, we have shown that there is a redistribution of the organic matter diffuse component during aqueous alteration on the parent body, with a preferential circulation among fine‐grained phyllosilicates.

Abstract The JAXA Astromaterials Science Research Group developed a web-based database system for the Hayabusa2-returned samples from C-type asteroid Ryugu. The Ryugu Sample Database System database (RS-DBS) is designed as an online catalog for users of wide scientific communities to choose their preferred samples and propose the sample loan through the JAXA Ryugu Sample Announcement of Opportunity. Ryugu samples can be sorted and given identification numbers as individual particles larger than 1 mm and aggregate samples consisting of less than 1 mm particle through the Phase1 curation (i.e., the initial description). The RS-DBS lists all samples with analytical data such as a microscopy image, size, mass, spectroscopic data, and shape model obtained by the initial description at the JAXA curation facility. The list also includes research results conducted by previous projects (i.e., the Hayabusa2 initial analysis team and Phase2 curation teams). The RS-DBS, built with open-source technologies, archives the data securely and long-term on the Data Archives and Transmission System (DARTS) at ISAS/JAXA. Graphical Abstract

Abstract The infrared spectral characteristics of organic‐rich acid residues prepared from Ryugu samples returned by the JAXA Hayabusa2 mission generally match those from unheated carbonaceous chondrite meteorites, but the residues from Ryugu are richer in methyl and methylene functional groups and have higher CH₂/CH₃ ratios. Moreover, two distinct outlier carbonaceous phases are found; one with spectral characteristics of N‐H functional groups, likely amides, and a second phase containing less nitrogen. Such infrared characteristics of Ryugu organic matter might indicate the pristine nature of the freshly collected samples and reflect the near‐surface chemistry in the parent asteroid.

In the samples collected from the asteroid Ryugu, magnetite displays natural remanent magnetization due to nebular magnetic field, whereas contemporaneously grown iron sulfide does not display stable remanent magnetization. To clarify this counterintuitive feature, we observed their nanoscale magnetic domain structures using electron holography and found that framboidal magnetites have an external magnetic field of 300 A m(-1), similar to the bulk value, and its magnetic stability was enhanced by interactions with neighboring magnetites, permitting a disk magnetic field to be recorded. Micrometer-sized pyrrhotite showed a multidomain magnetic structure that was unable to retain natural remanent magnetization over a long time due to short relaxation time of magnetic-domain-wall movement, whereas submicron-sized sulfides formed a nonmagnetic phase. These results show that both magnetite and sulfide could have formed simultaneously during the aqueous alteration in the parent body of the asteroid Ryugu.