Influx of nitrogen-rich material from the outer Solar System indicated by iron nitride in Ryugu samples

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

Four‐dimensional‐STEM analysis of the phyllosilicate‐rich matrix of Ryugu samples

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

A dehydrated space-weathered skin cloaking the hydrated interior of Ryugu

Without a protective atmosphere, space-exposed surfaces of airless Solar System bodies gradually experience an alteration in composition, structure and optical properties through a collective process called space weathering. The return of samples from near-Earth asteroid (162173) Ryugu by Hayabusa2 provides the first opportunity for laboratory study of space-weathering signatures on the most abundant type of inner solar system body: a C-type asteroid, composed of materials largely unchanged since the formation of the Solar System. Weathered Ryugu grains show areas of surface amorphization and partial melting of phyllosilicates, in which reduction from Fe3+ to Fe2+ and dehydration developed. Space weathering probably contributed to dehydration by dehydroxylation of Ryugu surface phyllosilicates that had already lost interlayer water molecules and to weakening of the 2.7 µm hydroxyl (–OH) band in reflectance spectra. For C-type asteroids in general, this indicates that a weak 2.7 µm band can signify space-weathering-induced surface dehydration, rather than bulk volatile loss

Nonequilibrium spherulitic magnetite in the Ryugu samples

We have investigated several particles collected during each of two touchdowns of the Hayabusa2 spacecraft at the surface of the C-type asteroid 162173 Ryugu using various electron microscope techniques. Our detailed transmission electron microscopy study shows the presence of magnetite with various morphologies coexisting in close proximity. This is characteristic of CI chondrite-like materials and consistent with the mineral assemblages and compositions in the Ryugu parent body. We describe the microstructural characteristics of magnetite with different morphologies, which could have resulted from the chemical conditions (growth vs. diffusion rate) during their formation. Furthermore, we describe the presence of magnetites with a spherulitic structure composed of individual radiating fibers that are characterized by pervasive, homogeneously distributed euhedral to subhedral pores that have not been described in previous chondrite studies. This particular spherulitic structure is consistent with crystallization under nonequilibrium conditions. Additionally, the presence of a high density of defects within the magnetite fibers, the high surface/volume ratio of this morphology, and the presence of amorphous materials in several pores and at the edges of the acicular fibers further support their formation under nonequilibrium conditions. We suggest that the growth processes that lead to this structure result from the solution reaching a supersaturated state, resulting in an adjustment to a lower free energy condition via nucleation and rapid growth

In situ investigation of an organic micro‐globule and its mineralogical context within a Ryugu “sand” grain

International audienceThe 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

In situ investigation of an organic micro‐globule and its mineralogical context within a Ryugu “sand” grain

International audienceThe 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

Phyllosilicates with embedded Fe-based nanophases in Ryugu and Orgueil

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

Mineralogy and petrology of fine‐grained samples recovered from the asteroid (162173) Ryugu

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

Electron microscopy observations of the diversity of Ryugu organic matter and its relationship to minerals at the micro-to-nanoscale

International audienceTransmission 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 (CHn), 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