Makoto YOSHIKAWA

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.

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 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.