津田 雄一

Abstract The surface morphology of regolith grains from the C‐type asteroid Ryugu was studied in search of evidence of impact events on the asteroid. Scanning electron microscopy revealed that ~8% of C0105‐042 Ryugu grains have a smooth surface on one side of the grains. One of these grains has striated linear grooves (striations) on its smooth surface. Transmission electron microscopy of the grain showed that a porous fine‐grained Mg‐Fe phyllosilicate assemblage, which is the main component of Ryugu grains, is compacted near the smooth surface. The smooth surface with striations closely resembles a slickenside, a characteristic texture found in terrestrial fault rocks formed by shear deformation. There is no evidence of melting/decomposition in the Mg‐Fe phyllosilicates near the smooth surface, indicating that the shear heating temperature is less than ~1100 K. Assuming that the average length of the striations corresponds to the minimum displacement of the micro‐fault, the shock pressure recorded in the C0105‐042 Ryugu grain is estimated to be <~4.5 GPa by a fault mechanics calculation. The shock pressures of C0105‐042, together with those of C0014 (~2 GPa) and C0055 (>~3.9 GPa) in previous studies suggest that the impact velocities recorded in these grains are < ~0.89–1.63 km s⁻¹. Based on the impact velocities, these grains may record an impact event that occurred when asteroid Ryugu was in the orbit in Main Belt.

Abstract Primordial carbon delivered to the early earth by asteroids and meteorites provided a diverse source of extraterrestrial organics from pre-existing simple organic compounds, complex solar-irradiated macromolecules, and macromolecules from extended hydrothermal processing. Surface regolith collected by the Hayabusa2 spacecraft from the carbon-rich asteroid 162173 Ryugu present a unique opportunity to untangle the sources and processing history of carbonaceous matter. Here we show carbonaceous grains in Ryugu can be classified into three main populations defined by spectral shape: Highly aromatic (HA), Alkyl-Aromatic (AA), and IOM-like (IL). These carbon populations may be related to primordial chemistry, since C and N isotopic compositions vary between the three groups. Diffuse carbon is occasionally dominated by molecular carbonate preferentially associated with coarse-grained phyllosilicate minerals. Compared to related carbonaceous meteorites, the greater diversity of organic functional chemistry in Ryugu indicate the pristine condition of these asteroid samples.

Abstract We report primordial aqueous alteration signatures in water-soluble organic molecules from the carbonaceous asteroid (162173) Ryugu by the Hayabusa2 spacecraft of JAXA. Newly identified low-molecular-weight hydroxy acids (HO-R-COOH) and dicarboxylic acids (HOOC-R-COOH), such as glycolic acid, lactic acid, glyceric acid, oxalic acid, and succinic acid, are predominant in samples from the two touchdown locations at Ryugu. The quantitative and qualitative profiles for the hydrophilic molecules between the two sampling locations shows similar trends within the order of ppb (parts per billion) to ppm (parts per million). A wide variety of structural isomers, including α- and β-hydroxy acids, are observed among the hydrophilic molecules. We also identify pyruvic acid and dihydroxy and tricarboxylic acids, which are biochemically important intermediates relevant to molecular evolution, such as the primordial TCA (tricarboxylic acid) cycle. Here, we find evidence that the asteroid Ryugu samples underwent substantial aqueous alteration, as revealed by the presence of malonic acid during keto–enol tautomerism in the dicarboxylic acid profile. The comprehensive data suggest the presence of a series for water-soluble organic molecules in the regolith of Ryugu and evidence of signatures in coevolutionary aqueous alteration between water and organics in this carbonaceous asteroid.

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 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.

C-type asteroids are the presumed home to carbonaceous chondrites, some of which contain abundant life-forming volatiles and organics. For the first time, samples from a C-type asteroid (162173 Ryugu) were successfully returned to Earth by JAXA's Hayabusa2 mission. These pristine samples, uncontaminated by the terrestrial environment, allow a direct comparison with carbonaceous chondrites. This study reports the stable K isotopic compositions (expressed as δ41K) of Ryugu samples and seven carbonaceous chondrites to constrain the origin of K isotopic variations in the early Solar System. Three aliquots of Ryugu particles collected at two touchdown sites have identical δ41K values, averaged at −0.194 ± 0.038‰ (2SD). The K isotopic composition of Ryugu falls within the range of δ41K values measured on representative CI chondrites, and together, they define an average δ41K value of −0.185 ± 0.078‰ (2SE), which provides the current best estimate of the K isotopic composition of the bulk Solar System. Samples of CI chondrites with δ41K values that deviate from this range likely reflect terrestrial contaminations or compositional heterogeneities at sampled sizes. In addition to CI chondrites, substantial K isotopic variability is observed in other carbonaceous chondrites and within individual chondritic groups, with δ41K values inversely correlated with K abundances in many cases. These observations indicate widespread fluid activity occurred in chondrite parent bodies, which significantly altered the original K abundances and isotopic compositions of chondrules and matrices established at their accretion.

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.

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.

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 (Fe1−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.

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.

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.

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 Large amounts of nitrogen compounds, such as ammonium salts, may be stored in icy bodies and comets, but the transport of these nitrogen-bearing solids into the near-Earth region is not well understood. Here, we report the discovery of iron nitride on magnetite grains from the surface of the near-Earth C-type carbonaceous asteroid Ryugu, suggesting inorganic nitrogen fixation. Micrometeoroid impacts and solar wind irradiation may have caused the selective loss of volatile species from major iron-bearing minerals to form the metallic iron. Iron nitride is a product of nitridation of the iron metal by impacts of micrometeoroids that have higher nitrogen contents than the CI chondrites. The impactors are probably primitive materials with origins in the nitrogen-rich reservoirs in the outer Solar System. Our observation implies that the amount of nitrogen available for planetary formation and prebiotic reactions in the inner Solar System is greater than previously recognized.

Abstract The nucleosynthetic isotope composition of planetary materials provides a record of the heterogeneous distribution of stardust within the early solar system. In 2020 December, the Japan Aerospace Exploration Agency Hayabusa2 spacecraft returned to Earth the first samples of a primitive asteroid, namely, the Cb-type asteroid Ryugu. This provides a unique opportunity to explore the kinship between primitive asteroids and carbonaceous chondrites. We report high-precision μ²⁶Mg* and μ²⁵Mg values of Ryugu samples together with those of CI, CM, CV, and ungrouped carbonaceous chondrites. The stable Mg isotope composition of Ryugu aliquots defines μ²⁵Mg values ranging from –160 ± 20 ppm to –272 ± 30 ppm, which extends to lighter compositions relative to Ivuna-type (CI) and other carbonaceous chondrite groups. We interpret the μ²⁵Mg variability as reflecting heterogeneous sampling of a carbonate phase hosting isotopically light Mg (μ²⁵Mg ∼ –1400 ppm) formed by low temperature equilibrium processes. After correcting for this effect, Ryugu samples return homogeneous μ²⁶Mg* values corresponding to a weighted mean of 7.1 ± 0.8 ppm. Thus, Ryugu defines a μ²⁶Mg* excess relative to the CI and CR chondrite reservoirs corresponding to 3.8 ± 1.1 and 11.9 ± 0.8 ppm, respectively. These variations cannot be accounted for by in situ decay of ²⁶Al given their respective ²⁷Al/²⁴Mg ratios. Instead, it requires that Ryugu and the CI and CR parent bodies formed from material with a different initial ²⁶Al/²⁷Al ratio or that they are sourced from material with distinct Mg isotope compositions. Thus, our new Mg isotope data challenge the notion that Ryugu and CI chondrites share a common nucleosynthetic heritage.

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 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.

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 ⁵⁴ Cr-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 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.

Abstract Returned samples from Cb-type asteroid (162173) Ryugu exhibit very dark spectra in visible and near-infrared ranges, generally consistent with the Hayabusa2 observations. A critical difference is that a structural water absorption of hydrous silicates is around twice as deep in the returned samples compared with those of Ryugu’s surface, suggesting Ryugu surface is more dehydrated. Here we use laboratory experiments data to indicate the spectral differences between returned samples and asteroid surface are best explained if Ryugu surface has (1) higher porosity, (2) larger particle size, and (3) more space-weathered condition, with the last being the most effective. On Ryugu, space weathering by micrometeoroid bombardments promoting dehydration seem to be more effective than that by solar-wind implantation. Extremely homogeneous spectra of the Ryugu’s global surface is in contrast with the heterogeneous S-type asteroid (25143) Itokawa’s spectra, which suggests space weathering has proceeded more rapidly on Cb-type asteroids than S-type asteroids.

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 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.

The Hayabusa2 spacecraft explored asteroid Ryugu and brought its surface materials to Earth. Ryugu samples resemble Ivuna-type (CI) chondrites-the most chemically primitive meteorites-and contain secondary phyllosilicates and carbonates, which are indicative of aqueous alteration. Understanding the conditions (such as temperature, redox state and fluid composition) during aqueous alteration is crucial to elucidating how Ryugu evolved to its present state, but little is known about the temporal changes in these conditions. Here we show that calcium carbonate (calcite) grains in Ryugu and Ivuna samples have variable O-18/O-16 and C-13/C-12 ratios that are, respectively, 24-46 & PTSTHOUSND; and 65-108 & PTSTHOUSND; greater than terrestrial standard values, whereas those of calcium-magnesium carbonate (dolomite) grains are much more homogeneous, ranging within 31-36 & PTSTHOUSND; for oxygen and 67-75 & PTSTHOUSND; for carbon. We infer that the calcite precipitated first over a wide range of temperatures and oxygen partial pressures, and that the proportion of gaseous CO2/CO/CH4 molecules changed temporally. By contrast, the dolomite formed later in a more oxygen-rich and thus CO2-dominated environment when the system was approaching equilibrium. The characteristic isotopic compositions of secondary carbonates in Ryugu and Ivuna are not observed for other hydrous meteorites, suggesting a unique evolutionary pathway for their parent asteroid(s).The asteroid Ryugu experienced aqueous alteration under changing temperature and redox conditions, according to an isotopic analysis of secondary calcite and dolomite grains in samples from Ryugu obtained by the Hayabusa2 spacecraft.

We present oxygen isotopic analyses of fragments of the near-Earth C-b-type asteroid Ryugu returned by the Hayabusa2 spacecraft that reinforce the close correspondence between Ryugu and CI chondrites. Small differences between Ryugu samples and CI chondrites in Delta'O-17 can be explained at least in part by contamination of the latter by terrestrial water. The discovery that a randomly sampled C-complex asteroid is composed of CI-chondrite-like rock, combined with thermal models for formation prior to significant decay of the short-lived radioisotope Al-26, suggests that if lithified at the time of alteration, the parent body was small (<< 50 km radius). If the parent planetesimal was large (>50 km in radius), it was likely composed of high-permeability, poorly lithified sediment rather than consolidated rock.