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Abstract 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 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 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 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.

The chirality of amino acids in extraterrestrial materials may provide an insight into the origin of the essential l-enantiopure amino acids in the terrestrial biosphere. In 2020, the Hayabusa2 mission succeeded in bringing back surface materials from the C-type asteroid (162173) Ryugu to the Earth. Amino acids were one of the targeted organic molecules to be studied in the Ryugu samples. To analyze the various structural isomers of amino acids, which were expected to be present, from the limited amount of the returned samples, the development of a highly-sensitive and selective analytical method was necessary. In the present study, a three-dimensional high-performance liquid chromatography (3D-HPLC) system has been developed for the enantioselective determination of five proteinogenic and three non-proteinogenic amino acids in the Ryugu samples, in which amino acids in the sample were separated by reversed-phase, anion-exchange and enantioselective columns after the fluorescence derivatization with 4-fluoro-7-nitro-2,1,3-benzoxadiozole. The applicability of the analytical system to the extraterrestrial samples was evaluated by analyzing several types of carbonaceous meteorites before applying the system to the Ryugu samples. In the analysis of the Ryugu samples, all of the target amino acids were successfully determined quantitatively. Non-proteinogenic amino acids including 2-amino-n-butyric acid, isovaline and norvaline, rarely present in the terrestrial environment, were found as almost racemic mixtures with 47.1 to 55.2%l.

Abstract 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 SO4 2− > Cl− > S2O3 2− > NO3 − > NH4 +. The salt fraction extracts contain anionic soluble sulfur-bearing species such as S n -polythionic acids (n

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.

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.

Abstract We performed in-situ analysis on a ~ 1 mm-sized grain A0080 returned by the Hayabusa2 spacecraft from near-Earth asteroid (162173) Ryugu to investigate the relationship of soluble organic matter (SOM) to minerals. Desorption electrospray ionization-high resolution mass spectrometry (DESI-HRMS) imaging mapped more than 200 CHN, CHO, CHO–Na (sodium adducted), and CHNO soluble organic compounds. A heterogeneous spatial distribution was observed for different compound classes of SOM as well as among alkylated homologues on the sample surface. The A0080 sample showed mineralogy more like an Ivuna-type (CI) carbonaceous chondrite than other meteorites. It contained two different lithologies, which are either rich (lithology 1) or poor (lithology 2) in magnetite, pyrrhotite, and dolomite. CHN compounds were more concentrated in lithology 1 than in lithology 2; on the other hand, CHO, CHO–Na, and CHNO compounds were distributed in both lithologies. Such different spatial distribution of SOM is likely the result of interaction of the SOM with minerals, during precipitation of the SOM via fluid activity, or could be due to difference in transportation efficiencies of SOMs in aqueous fluid. Organic-related ions measured by time-of-flight secondary ion mass spectrometry (ToF–SIMS) did not coincide with the spatial distribution revealed by DESI-HRMS imaging. This result may be because the different ionization mechanism between DESI and SIMS, or indicate that the ToF–SIMS data would be mainly derived from methanol-insoluble organic matter in A0080. In the Orgueil meteorite, such relationship between altered minerals and SOM distributions was not observed by DESI-HRMS analysis and field-emission scanning electron microscopy, which would result from differences of SOM formation processes and sequent alteration process on the parent bodies or even on the Earth. Alkylated homologues of CHN compounds were identified in A0080 by DESI-HRMS imaging as observed in the Murchison meteorite, but not from the Orgueil meteorite. These compounds with a large C number were enriched in Murchison fragments with abundant carbonate grains. In contrast, such relationship was not observed in A0080, implying different formation or growth mechanisms for the alkylated CHN compounds by interaction with fluid and minerals on the Murchison parent body and asteroid Ryugu. Graphical Abstract

Uracil was identified in the sample returned from the asteroid Ryugu. Having been provided to the early Earth as a component in such asteroidal materials, these molecules might have played a role for prebiotic chemical evolution on the early Earth

Amino acid concentrations from 2 particles returned from different touchdown sites on the surface of Ryugu are reported. Differences in chemistry suggest different levels of aqueous alteration are recorded at the 2 sampled locations.

Abstract Hayabusa2 spacecraft successfully collected rock samples from the surface of C-type near-Earth asteroid 162173 Ryugu through two touchdowns and brought them back to Earth in 2020. At the Extraterrestrial Sample Curation Center in JAXA, we performed initial description of all samples to obtain fundamental information and prepare the database for sample allocation. We propose morphological classifications for the returned samples based on the initial description of 205 grains described in the first 6 months. The returned samples can be distinguished by four morphological characteristics: dark, glossy, bright, and white. According to coordinated study to provide an initial description and detailed investigation by scanning electron microscopy and X-ray diffraction analysis in this study, these features reflect the differences in the degree of space weathering and mineral assemblages. The degree of space weathering of the four studied grain types is heterogeneous: weak for A0042 (dark group) and C0041 (white group); moderate for C0094 (glossy); and severe for A0017 (bright). The white phase, which is the mineral characteristic of the white group grains, is identified as large carbonate minerals. This is the first effort to classify Ryugu returned samples into distinct categories. Based on these results, researchers can estimate sample characteristics only from the information on the JAXA curation public database. It will be an important reference for sample selection for further investigation. Graphical Abstract

Abstract 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

Chondrule-like objects and CAIs in the Ryugu samples are early generations of chondrules and possibly oldest solids in the Solar System. They were transported from the inner solar nebula to the formation location of the Ryugu original parent body.

Abstract A fundamental parameter-based quantification scheme for confocal XRF was applied to sub-micron synchrotron radiation X-ray fluorescence (SR-XRF) data obtained at the beamline P06 of the Deutsches Elektronen-Synchrotron (DESY, Hamburg, Germany) from two sections C0033-01 and C0033-04 that were wet cut from rock fragment C0033 collected from Cb-type asteroid (162173) Ryugu by JAXA’s Hayabusa2 mission. Trace-element quantifications show that C0033 bulk matrix is CI-like, whereas individual mineral grains (i.e., magnetite, pyrrhotite, dolomite, apatite and breunnerite) show, depending on the respective phase, minor to strong deviations. The non-destructive nature of SR-XRF coupled with a new PyMca (a Python toolkit for XRF data analysis)-based quantification approach, performed in parallel with the synchrotron experiments, proves to be an attractive tool for the initial analysis of samples from return missions, such as Hayabusa2 and OSIRIS-REx, the latter returning material from a B-type asteroid (101955) Bennu in 2023. Graphical Abstract

Abstract Millimetre-sized primordial rock fragments originating from asteroid Ryugu were investigated using high energy X-ray fluorescence spectroscopy, providing 2D and 3D elemental distribution and quantitative composition information on the microscopic level. Samples were collected in two phases from two sites on asteroid Ryugu and safely returned to Earth by JAXA’s asteroid explorer Hayabusa2, during which time the collected material was stored and maintained free from terrestrial influences, including exposure to Earth’s atmosphere. Several grains of interest were identified and further characterised to obtain quantitative information on the rare earth element (REE) content within said grains, following a reference-based and computed-tomography-assisted fundamental parameters quantification approach. Several orders of magnitude REE enrichments compared to the mean CI chondrite composition were found within grains that could be identified as apatite phase. Small enrichment of LREE was found for dolomite grains and slight enrichment or depletion for the general matrices within the Ryugu rock fragments A0055 and C0076, respectively. Graphical 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 ^55 Mn/ ^52 Cr, ε ^54 Cr, and initial ε ^53 Cr 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 ^54 Cr and initial ε ^53 Cr values of Ryugu and NWA 6704/6693 are also identical, while they show distinct Δ' ^17 O 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 Martian moons exploration, MMX, is the new sample return mission planned by the Japan Aerospace Exploration Agency (JAXA) targeting the two Martian moons with the scheduled launch in 2024 and return to the Earth in 2029. The major scientific objectives of this mission are to determine the origin of Phobos and Deimos, to elucidate the early Solar System evolution in terms of volatile delivery across the snow line to the terrestrial planets having habitable surface environments, and to explore the evolutionary processes of both moons and Mars surface environment. To achieve these objectives, during a stay in circum-Martian space over about 3 years MMX will collect samples from Phobos along with close-up observations of this inner moon and carry out multiple flybys of Deimos to make comparative observations of this outer moon. Simultaneously, successive observations of the Martian atmosphere will also be made by utilizing the advantage of quasi-equatorial spacecraft orbits along the moons’ orbits. Graphical Abstract

Rock fragments of the Cb-type asteroid Ryugu returned to Earth by the JAXA Hayabusa2 mission share mineralogical, chemical, and isotopic properties with the Ivuna-type (CI) carbonaceous chondrites. Similar to CI chondrites, these fragments underwent extensive aqueous alteration and consist predominantly of hydrous minerals likely formed in the presence of liquid water on the Ryugu parent asteroid. Here we present an in situ analytical survey performed by secondary ion mass spectrometry from which we have estimated the D/H ratio of Ryugu’s hydrous minerals, D/H _Ryugu , to be [165 ± 19] × 10 ^−6 , which corresponds to δ D _Ryugu = +59 ± 121‰ (2 σ ). The hydrous mineral D/H _Ryugu ’s values for the two sampling sites on Ryugu are similar; they are also similar to the estimated D/H ratio of hydrous minerals in the CI chondrites Orgueil and Alais. This result reinforces a link between Ryugu and CI chondrites and an inference that Ryugu’s samples, which avoided terrestrial contamination, are our best proxy to estimate the composition of water at the origin of hydrous minerals in CI-like material. Based on this data and recent literature studies, the contribution of CI chondrites to the hydrogen of Earth’s surficial reservoirs is evaluated to be ∼3%. We conclude that the water responsible for the alteration of Ryugu’s rocks was derived from water ice precursors inherited from the interstellar medium; the ice partially re-equilibrated its hydrogen with the nebular H _2 before being accreted on the Ryugu’s parent asteroid.

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 μ ^26 Mg* and μ ^25 Mg values of Ryugu samples together with those of CI, CM, CV, and ungrouped carbonaceous chondrites. The stable Mg isotope composition of Ryugu aliquots defines μ ^25 Mg 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 μ ^25 Mg variability as reflecting heterogeneous sampling of a carbonate phase hosting isotopically light Mg ( μ ^25 Mg ∼ –1400 ppm) formed by low temperature equilibrium processes. After correcting for this effect, Ryugu samples return homogeneous μ ^26 Mg* values corresponding to a weighted mean of 7.1 ± 0.8 ppm. Thus, Ryugu defines a μ ^26 Mg* 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 ^26 Al given their respective ^27 Al/ ^24 Mg ratios. Instead, it requires that Ryugu and the CI and CR parent bodies formed from material with a different initial ^26 Al/ ^27 Al 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 In this study, we determined the alignment of the laser altimeter aboard Hayabusa2 with respect to the spacecraft using in-flight data. Since the laser altimeter data were used to estimate the trajectory of the Hayabusa2 spacecraft, the pointing direction of the altimeter needed to be accurately determined. The boresight direction of the receiving telescope was estimated by comparing elevations of the laser altimeter data and camera images, and was confirmed by identifying prominent terrains of other datasets. The estimated boresight direction obtained by the laser link experiment in the winter of 2015, during the Earth’s gravity assist operation period, differed from the direction estimated in this study, which fell on another part of the candidate direction; this was not selected in a previous study. Assuming that the uncertainty of alignment determination of the laser altimeter boresight was 4.6 pixels in the camera image, the trajectory error of the spacecraft in the cross- and/or along-track directions was determined to be 0.4, 2.1, or 8.6 m for altitudes of 1, 5, or 20 km, respectively.

Abstract The precise orbit of the Hayabusa2 spacecraft with respect to asteroid Ryugu is dynamically determined using the data sets collected by the spacecraft’s onboard laser altimeter (LIght Detection And Ranging, LIDAR) and automated image tracking (AIT). The LIDAR range data and the AIT angular data play complementary roles because LIDAR is sensitive to the line-of-sight direction from Hayabusa2 to Ryugu, while the AIT is sensitive to the directions perpendicular to it. Using LIDAR and AIT, all six components of the initial state vector can be derived stably, which is difficult to achieve using only LIDAR or AIT. The coefficient of solar radiation pressure (SRP) of the Hayabusa2 spacecraft and standard gravitational parameter (GM) of Ryugu can also be estimated in the orbit determination process, by combining multiple orbit arcs at various altitudes. In the process of orbit determination, the Ryugu-fixed coordinate of the center of the LIDAR spot is determined by fitting the range data geometrically to the topography of Ryugu using the Markov Chain Monte Carlo method. Such an approach is effective for realizing the rapid convergence of the solution. The root mean squares of the residuals of the observed minus computed values of the range and brightness-centroid direction of the image are 1.36 m and 0.0270°, respectively. The estimated values of the GM of Ryugu and a correction factor to our initial SRP model are 29.8 ± 0.3 m3/s2 and 1.13 ± 0.16, respectively.

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 ${{\rm{\Delta }}}^{{\prime} 17}{\rm{O}}$ 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 ^26 Al, 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.