吉川 真

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.

Returned samples from the carbonaceous asteroid (162173) Ryugu provide pristine information on the original aqueous alteration history of the Solar System. Secondary precipitates, such as carbonates and phyllosilicates, reveal elemental partitioning of the major component ions linked to the primordial brine composition of the asteroid. Here, we report on the elemental partitioning and Mg isotopic composition (25Mg/24Mg) of breunnerite [(Mg, Fe, Mn)CO3] from the Ryugu C0002 sample and the A0106 and C0107 aggregates by sequential leaching extraction of salts, exchangeable ions, carbonates, and silicates. Breunnerite was the sample most enriched in light Mg isotopes, and the 25Mg/24Mg value of the fluid had shifted lower by ~0.38‰ than the initial value (set to 0‰) before dolomite precipitation. As a simple model, the Mg2+ first precipitated in phyllosilicates, followed by dolomite precipitation, at which time ~76-87% of Mg2+ had been removed from the primordial brine. A minor amount of phyllosilicate precipitation continued after dolomite precipitation. The element composition profiles of the latest solution that interacted with the cation exchange pool of Ryugu were predominantly Na-rich. Na+ acts as a bulk electrolyte and contributes to the stabilization of the negative surface charge of phyllosilicates and organic matter on Ryugu.

Abstract We present an analysis of a stellar occultation event caused by a near-Earth asteroid (98943) 2001 CC21, an upcoming flyby target in the Hayabusa2 extended mission, on 2023 March 5. To determine the asteroid’s shape from diffraction-affected light curves accurately, we developed a novel data-reduction technique named the Diffracted Occultation’s United Simulator for Highly Informative Transient Explorations (DOUSHITE). Using DOUSHITE-generated synthetic models, we derived constraints on (98943) 2001 CC21’s shadow shape from the single-chord occultation data. Our results suggest a significant elongation of the shadow with an axis ratio of $b/a = 0.37\pm 0.09$. This shape could be crucial for planning Hayabusa2’s high-speed flyby to optimise the limited imaging opportunities.

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 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.

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.

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.

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.

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.

Abstract We report Nd and Sm isotopic compositions of four samples of Ryugu returned by the Hayabusa2 mission, including “A” (first touchdown) and “C” (second touchdown) samples, and several carbonaceous chondrites to evaluate potential genetic relationships between Ryugu and known chondrite groups and track the cosmic ray exposure history of Ryugu. We resolved Nd and Sm isotopic anomalies in small (<20 ng Nd and Sm) sample sizes via thermal ionization mass spectrometer using 10¹³ Ω amplifiers. Ryugu samples exhibit resolvable negative μ¹⁴²Nd values consistent with carbonaceous chondrite values, suggesting that Ryugu is related to the parent bodies of carbonaceous chondrites. Ryugu's negative μ¹⁴⁹Sm values are the result of exposure to galactic cosmic rays, as demonstrated by the correlation between ¹⁵⁰Sm/¹⁵²Sm and ¹⁴⁹Sm/¹⁵²Sm ratios that fall along the expected neutron capture correlation line. The neutron fluence calculated in the “A” samples (2.75 ± 1.94 × 10¹⁵ n cm⁻²) is slightly higher compared to the “C” samples (0.95 ± 2.04 × 10¹⁵ n cm⁻²), though overlapping within measurement uncertainty. The Sm results for Ryugu, at this level of precision, thus are consistent with a well‐mixed surface layer at least to the depths from which the “A” and “C” samples derive.

Ryugu is the C-type asteroid from which material was brought to Earth by the Hayabusa2 mission. A number of individual grains and fine-grained samples analysed so far for noble gases have indicated that solar wind and planetary (known as P1) noble gases are present in Ryugu samples with concentrations higher than those observed in CIs, suggesting the former to be more primitive compared to the latter. Here we present results of analyses of three fine-grained samples from Ryugu, in one of which Xe concentration is an order of magnitude higher than determined so far in other samples from Ryugu. Isotopically, this Xe resembles P1, but with a much stronger isotopic fractionation relative to solar wind and significantly lower 36Ar/132Xe ratio than in P1. This previously unknown primordial noble gas component (here termed P7) provides clues to constrain how the solar composition was fractionated to form the planetary components.