We have analyzed molybdenum, ruthenium, and barium isotopes simultaneously in 21 individual high-density presolar graphite grains from the Murchison CM2 meteorite using the Chicago Instrument for Laser Ionization (CHILI). While all grains clearly suffered from contamination with molybdenum of solar composition, probably from the parent asteroid of the host meteorite, six grains showed s-process enrichments in at least one of the elements analyzed, pointing toward an AGB star origin of these grains. For one of the grains, we found almost pure s-process ruthenium, challenging existing AGB star models that assume full homogenization of freshly produced s-process material in the convective AGB star envelope prior to grain condensation. Furthermore, our results indicate that these grains condensed before about half of the 99Tc decayed to 99Ru and that technetium did not condense into the grains.

Most carbonaceous chondrite (CC) meteorites contain abundant chondrules, millimeter-scale spherical inclusions of previously molten material. Ivuna-type carbonaceous chondrites (CIs) do not contain chondrules, nor do samples of the carbonaceous asteroid Ryugu. CIs and Ryugu share isotopic properties distinct from those of other CCs, implying that their parent bodies formed at a different time or place than those of other CCs. We applied manganese-chromium dating and oxygen isotope thermometry to Ryugu and Ivuna samples. The results indicate that the parent bodies of Ryugu and Ivuna formed less than 2 million years after the beginning of Solar System formation—before the majority of chondrules in CCs and the parent bodies of other CCs formed. This implies that Ryugu and CIs are remnants of an earlier generation of carbonaceous planetesimals.

Presolar graphite grains carry the isotopic signatures of their parent stars. A significant fraction of presolar graphites show isotopic abundance anomalies relative to solar for elements such as O, Si, Mg, and Ca, which are compatible with nucleosynthesis in core-collapse supernovae (CCSNe). Therefore, they must have condensed from CCSN ejecta before the formation of the Sun. Their most puzzling abundance signature is the ^22 Ne-enriched component Ne-E(L), interpreted as the effect of the radioactive decay of ^22 Na ( T _1/2 = 2.6 yr). Previous works have shown that if H is ingested into the He shell and not fully destroyed before the explosion, the CCSN shock in the He-shell material produces large amounts of ^22 Na. Here we focus on such CCSN models, showing a radioactive ^26 Al production compatible with grain measurements, and analyze the conditions of ^22 Na nucleosynthesis. In these models, ^22 Na is mostly made in the He shell, with a total ejected mass varying between 2.6 × 10 ^−3 M _⊙ and 1.9 × 10 ^−6 M _⊙ . We show that such ^22 Na may already impact the CCSN light curve 500 days after the explosion, and at later stages it can be the main source powering the CCSN light curve for up to a few years before ^44 Ti decay becomes dominant. Based on the CCSN yields above, the 1274.53 keV γ -ray flux due to ^22 Na decay could be observable for years after the first CCSN light is detected, depending on the distance. This makes CCSNe possible sites to detect a ^22 Na γ -ray signature consistently with the Ne-E(L) component found in presolar graphites. Finally, we discuss the potential contribution from ^22 Na decay to the Galactic positron annihilation rate.

This study reports detection of rare p -process isotopes within presolar grains. Presolar grains are relic dust grains from dying stars. These microscopic dust particles are found in primitive solar system materials. Their distinct isotopic compositions record the nucleosynthetic processes in their parent stars and the Galactic chemical environment in which these stars formed. We studied presolar graphite grains of high-density type from the Murchison meteorite and found five grains with subgrains that show enrichments in ^84 Sr compared to the solar abundance. ^84 Sr is the neutron-deficient isotope of strontium that can be produced in the deep oxygen-rich interior of high-mass stars that end their lives as core-collapse supernovae. The observed ^84 Sr excesses cannot be produced in low-mass asymptotic giant branch stars, the source of most high-density presolar graphites found in meteorites. High-density graphites with embedded ^84 Sr excesses are, instead, compatible with a core-collapse supernovae origin. The graphite subgrains condensed from carbon-rich materials in the outer layers of core-collapse supernovae, where ^84 Sr was destroyed by neutron captures during hydrostatic evolution of the stars and their final explosion. Based on current theoretical stellar models, a few percent of contribution from the inner regions of core-collapse supernovae, which are enriched in p -process nuclides, to the outer carbon-rich regions is the most likely explanation for the observed enrichment of ^84 Sr in the subgrains of the high-density graphites. In this study, we present the first observational evidence that core-collapse supernovae produce and eject isotopes made by the p -process.

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 96 Zr 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.

Carbonaceous asteroids are the source of the most primitive meteorites1 and represent leftover planetesimals that formed from ice and dust in the outer Solar System and may have delivered volatiles to the terrestrial planets2-5. Understanding the aqueous activity of asteroids is key to deciphering their thermal, chemical and orbital evolution, with implications for the origin of water on the terrestrial planets. Analyses of the objects, in particular pristine samples returned from asteroid Ryugu, have provided detailed information on fluid-rock interactions within a few million years after parent-body formation6-11. However, the long-term fate of asteroidal water remains poorly understood. Here we present evidence for fluid flow in a carbonaceous asteroid more than 1 billion years after formation, based on the 176Lu-176Hf decay systematics of Ryugu samples, which reflect late lutetium mobilization. Such late fluid flow was probably triggered by an impact that generated heat for ice melting and opened rock fractures for fluid migration. This contrasts the early aqueous activity powered by short-lived radioactive decay, with limited fluid flow and little elemental fractionation12. Our results imply that carbonaceous planetesimals accreted by the terrestrial planets could have retained not only hydrous minerals but also aqueous water, leading to an upwards revision of the inventory of their water delivery by a factor of two to three.

Asymptotic giant branch (AGB) stars, which are evolved low- to intermediate-mass stars, rank among the most prolific producers of interstellar dust in the Galaxy. Presolar silicon carbide (SiC) grains in meteorites are mainly produced by AGB stars. These presolar grains contain abundant noble gases, believed to have been implanted by stellar winds from the central stars of planetary nebulae (CSPNe). Here we report 3-D maps of the helium distribution in individual presolar SiC grains. The maps reveal that the implantation energy of 4He for individual grains varies from about 2 to about 4 keV/nucleon, which falls within the range of the CSPN winds. The variation of 4He fluence (1×1012-2×1015 atom cm-2) shows that the SiC grains form during the last about 1 My period of the AGB star phase. Then, they migrate outwards and become exposed to CSPN winds at distances of 0.3-32 light-years from the CSPNe.

The isotopic compositions of samples returned from Cb-type asteroid Ryugu and Ivuna-type (CI) chondrites are distinct from other carbonaceous chondrites, which has led to the suggestion that Ryugu/CI chondrites formed in a different region of the accretion disk, possibly around the orbits of Uranus and Neptune. We show that, like for Fe, Ryugu and CI chondrites also have indistinguishable Ni isotope anomalies, which differ from those of other carbonaceous chondrites. We propose that this unique Fe and Ni isotopic composition reflects different accretion efficiencies of small FeNi metal grains among the carbonaceous chondrite parent bodies. The CI chondrites incorporated these grains more efficiently, possibly because they formed at the end of the disk's lifetime, when planetesimal formation was also triggered by photoevaporation of the disk. Isotopic variations among carbonaceous chondrites may thus reflect fractionation of distinct dust components from a common reservoir, implying CI chondrites/Ryugu may have formed in the same region of the accretion disk as other carbonaceous chondrites.

The surface chemistry of pyrrhotites from intact particles directly collected from asteroid (162173) Ryugu was investigated by micro-Raman spectroscopy. The Raman peak characteristic to pyrrhotite was observed at around 115 cm-1 in Ryugu pyrrhotites, similar to freshly cleaved surfaces of terrestrial pyrrhotites. Additional Raman bands centered at around 220, 275, and 313 cm-1 with broadened features were also detected from the Ryugu pyrrhotites. The set of Raman bands at 220 and 275 cm-1 was assigned to typical Fe-S stretching vibrations of nu 2 (225 cm-1 ) and nu 1 (275 cm-1 ). These bands are not clearly observed in bulk crystals of pyrrhotite but appear in its nanoparticulate phase. These bands are ordinarily seen in amorphous monosulfides that formed under low oxygen fugacity ( f O 2 ) conditions in nature, indicating that the structural alteration of pyrrhotite surfaces occurred heterogeneously on the nanoscale under low f O 2 conditions. Further, the Raman band at 313 cm-1 was attributed to a characteristic tetrahedral bonding of Fe(III) in the lattice of Fe II 1-3x Fe III 1-2x S, followed by the local breakdown of the crystal lattice structures from planar bonding with Fe(II). In addition, some areas of the Ryugu pyrrhotite grains showed corroded structures with iridescence. Furthermore, assemblages of magnetite particles were also preferentially observed on small areas of the likely-dissolved pyrrhotite crystals in phyllosilicate matrices. These characteristic features in the Raman spectra and in corroded structures of Ryugu pyrrhotites record changes in the local environmental conditions via aqueous alteration. The corrosion of pyrrhotite crystals followed by the preferential formation of magnetite particles by asteroidal water is the likely product of dissolution of Fe(II) from the pyrrhotite surface and its oxidative precipitation in microchemical environments on the Ryugu parent body.

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 841K) 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 841K values, averaged at-0.194 +/- 0.038%o (2SD). The K isotopic composition of Ryugu falls within the range of 841K values measured on representative CI chondrites, and together, they define an average 841K value of-0.185 +/- 0.078%o (2SE), which provides the current best estimate of the K isotopic composition of the bulk Solar System. Samples of CI chondrites with 841K 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 841K 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.

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 similar to 900 and similar to 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-mu m 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 We report isotope data for C, N, Al, Si, and S of 33 presolar SiC and Si3N4 grains (0.3–1.6 $\mu$m) of Type X, C, D, and N from the Murchison CM2 meteorite of likely core-collapse supernova (CCSN) origin which we discuss together with data of six SiC X grains from an earlier study. The isotope data are discussed in the context of hydrogen ingestion supernova (SN) models. We have modified previously used ad-hoc mixing schemes in that we considered (i) heterogeneous H ingestion into the He shell of the pre-SN star, (ii) a variable C-N fractionation for the condensation of SiC grains in the SN ejecta, and (iii) smaller mass units for better fine-tuning. With our modified ad-hoc mixing approach over small scales (0.2–0.4 M⊙), with major contributions from the O-rich O/nova zone, we find remarkably good fits (within a few per cent) for 12C/13C, 26Al/27Al, and 29Si/28Si ratios. The 14N/15N ratio of SiC grains can be well matched if variable C-N fractionation is considered. However, the Si3N4 isotope data point to overproduction of 15N in hydrogen ingestion CCSN models and lower C-N fractionation during SiC condensation than applied here. Our ad-hoc mixing approach based on current CCSN models suggests that the O-rich O/nova zone, which uniquely combines explosive H- and He-burning signatures, is favourable for SiC and Si3N4 formation. The effective range of C/O abundance variations in the He shell triggered by H ingestion events in the massive star progenitor is currently not well constrained and needs further investigation.

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 delta O-18 (from 3 parts per thousand to 7 parts per thousand) and O-17 (similar to 2 parts per thousand) with porous SIMS pits mostly from spherulitic magnetite, and (2) lower delta O-18 (similar to -3 parts per thousand) and variable O-17 (0 parts per thousand-2 parts per thousand) mostly from euhedral magnetite. Dolomite and breunnerite analyses were conducted using multi-collection Faraday cup detectors with precisions <= 0.3 parts per thousand. 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 O-17; 0.0 parts per thousand-0.3 parts per thousand for dolomite in A0058 and 0.2 parts per thousand-0.8 parts per thousand for dolomite and breunnerite in C0002. The majority of breunnerite, including large >= 100 mu m grains, show systematically lower delta O-18 (similar to 21 parts per thousand) than dolomite (25 parts per thousand-30 parts per thousand and 23 parts per thousand-27 parts per thousand 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 degrees C and 78 +/- 14 degrees 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 O-17>2 parts per thousand that was melted and interacted with anhydrous solids with the initial O-17<0 parts per thousand. In the early stage of aqueous alteration, spherulitic magnetite and calcite formed from aqueous fluid with O-17 similar to 2 parts per thousand that was produced by isotope exchange between water (O-17>2 parts per thousand) and anhydrous solids (O-17<0 parts per thousand). 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, delta O-18 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.

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 10(13) Omega amplifiers. Ryugu samples exhibit resolvable negative mu Nd-142 values consistent with carbonaceous chondrite values, suggesting that Ryugu is related to the parent bodies of carbonaceous chondrites. Ryugu's negative mu Sm-149 values are the result of exposure to galactic cosmic rays, as demonstrated by the correlation between Sm-150/Sm-152 and Sm-149/Sm-152 ratios that fall along the expected neutron capture correlation line. The neutron fluence calculated in the "A" samples (2.75 +/- 1.94 x 10(15) n cm(-2)) is slightly higher compared to the "C" samples (0.95 +/- 2.04 x 10(15) 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.

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 Δ ′ 17 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.

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 5.2 − 1.4 + 1.8 Ma 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.

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.

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