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Hikaru Yabuta

Publications and source records attributed to Hikaru Yabuta.

16 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2024

Primordial Aqueous Alteration Recorded in Water-Soluble Organic Molecules from the Carbonaceous Asteroid (162173) Ryugu

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.

Asteroids, comets and Kuiper belt↗
NASA NTRS2024

Raman spectroscopy of Ryugu particles and their extracted residues: Fluorescence background characteristics and similarities to CI chondrites

We present here an investigation of Ryugu particles recovered by the Hayabusa2 space mission and their extracted carbonaceous acid residues using Raman spectroscopy. Raman parameters of Ryugu intact grains and their acid residues are characterized by broad D (defect induced) and G (graphite) band widths, indicating the presence of polyaromatic carbonaceous matter with low thermal maturity. Raman spectra of Ryugu particles and CI (type 1) chondrites exhibit stronger laser-induced fluorescence backgrounds compared to Type 2 and Type 3 carbonaceous chondrites. The high fluorescence signatures and wide bandwidths of the D and G bands of Ryugu intact grains are similar to the Raman spectra observed in CI chondrites, reflecting the low structural order of their aromatic carbonaceous matter, and strengthening the link between Ryugu particles and CI chondrites. The high fluorescence background intensity of the Ryugu particles is due to multiple causes, but it is likely that the relative abundance of geometry-bearing macromolecular organic matter in total organic carbon contents makes a large contribution to the fluorescence intensities. Locally observed high fluorescence in the acid-extracted residues of Ryugu is due to nitrogen-bearing outlier phase. The high fluorescence signature is one consequence of the low degree of thermal maturity of the organic matter and supports evidence that the Ryugu particles have escaped significant parent body thermal metamorphism.

Ryugu particles↗
NASA NTRS2023

The Magnesium Isotope Composition of Samples Returned From Asteroid Ryugu

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.

Solar system evolution↗
NASA NTRS2023

Pervasive aqueous alteration in the early Solar System revealed by potassium isotopic variations in Ryugu samples and carbonaceous chondrites

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 δ 41 K) 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 δ 41 K values, averaged at -0.194 ± 0.038‰ (2SD). The K isotopic composition of Ryugu falls within the range of δ 41 K values measured on representative CI chondrites, and together, they define an average δ 41 K 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 δ 41 K 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 δ 41 K 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.

Asteroid Ryugu↗
NASA NTRS2023

Soluble Organic Matter Molecular Atlas of Ryugu Reveals Cold Hydrothermalism on C-Type Asteroid Parent Body

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.

Asteroids, comets and Kuiper belt↗
NASA NTRS2023

PAHs, Hydrocarbons, and Dimethylsulfides in Asteroid Ryugu Samples A0106 and C0107 and the Orgueil (CI1) Meteorite

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 like 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.

Hayabusa2↗
NASA NTRS2023

Soluble Organic Molecules in Samples of the Carbonaceous Asteroid (162173) Ryugu

The Hayabusa2 spacecraft collected samples from the surface of the carbonaceous near-Earth asteroid (162173) Ryugu, and brought them to Earth. The samples were expected to contain organic molecules, which record processes that occurred in the early Solar System. We analyzed organic molecules extracted from the Ryugu surface samples. We identify a variety of molecules containing the atoms CHNOS, formed by methylation, hydration, hydroxylation, and sulfurization reactions. Amino acids, aliphatic amines, carboxylic acids, polycyclic aromatic hydrocarbons, and nitrogen-heterocyclic compounds were detected, with properties consistent with an abiotic origin. These compounds likely arose from aqueous reaction on Ryugu’s parent body and are similar to organics in Ivuna-type meteorites. These molecules can survive on the surfaces of asteroids and be transported throughout the Solar System.

Hiroshi Naraoka↗
NASA NTRS2023

Extraterrestrial Amino Acids and Amines Identified in Asteroid Ryugu Samples Returned By the Hayabusa2 Mission

The hot water and acid extracts of two different Ryugu samples collected by the Hayabusa2 mission were analyzed for the presence of aliphatic amines and amino acids. The abundances and relative distributions of both classes of molecules were determined, as well as the enantiomeric compositions of the chiral amino acids. The Ryugu samples studied here were recovered from sample chambers A and C, which were composed of surface material, and a combination of surface and possible subsurface material, respectively. A total of thirteen amino acids were detected and quantitated in these samples, with an additional five amino acids that were tentatively identified but not quantitated. The abundances of four aliphatic amines identified in the Ryugu samples were also determined in the current work. Amino acids were observed in the acid hydrolyzed and unhydrolyzed hot water extracts of asteroid Ryugu regolith using liquid chromatography with UV fluorescence detection and high-resolution mass spectrometry. Conversely, aliphatic amines were only analyzed in the unhydrolyzed hot water Ryugu extracts. Two- to six-carbon (C 2 -C 6 ) amino acids with individual abundances ranging from 0.02 to 15.8 nmol g −1 , and one- to three-carbon (C 1 -C 3 ) aliphatic amines with individual abundances from 0.05 to 34.14 nmol g −1 , were found in the hot water extracts. Several non-protein amino acids that are rare in biology, including β-amino-n-butyric acid (β-ABA) and β-aminoisobuytric acid (β-AIB), were racemic or very nearly racemic, thus indicating their likely abiotic origins. Trace amounts of select protein amino acids that were enriched in the ւ-enantiomer may indicate low levels of terrestrial amino acid contamination in the samples. However, the presence of elevated abundances of free and racemic alanine, a common protein amino acid in terrestrial biology, and elevated abundances of the predominately free and racemic non-protein amino acids, β-ABA and β-AIB, indicate that many of the amino acids detected in the Ryugu water extracts were indigenous to the samples. Although the Ryugu samples have been found to be chemically similar to CI type carbonaceous chondrites, the measured concentrations and relative distributions of amino acids and aliphatic amines in Ryugu samples were notably different from those previously observed for the CI1.1 carbonaceous chondrite, Orgueil. This discrepancy could be the result of differences in the original chemical compositions of the parent bodies and/or alteration conditions, such as space weathering. In addition to α-amino acids that could have been formed by Strecker cyanohydrin synthesis during a low temperature aqueous alteration phase, β-, γ-, and δ-amino acids, including C 3 – C 5 straight-chain n-ω-amino acids that are not formed by Strecker synthesis, were also observed in the Ryugu extracts. The suite of amino acids measured in the Ryugu samples indicates that multiple amino acid formation mechanisms were active on the Ryugu parent body. The analytical techniques used here are well-suited to search for similar analytes in asteroid Bennu material collected by the NASA OSIRIS-REx mission scheduled for Earth return in September 2023.

Hayabusa2↗
NASA NTRS2022

Oxygen Isotopes of Anhydrous Primary Minerals Show Kinship Between Asteroid Ryugu and Comet 81P/Wild2

The extraterrestrial materials returned from asteroid (162173) Ryugu consist predominantly of low-temperature aqueously formed secondary minerals and are chemically and mineralogically similar to CI (Ivuna-type) carbonaceous chondrites. Here we show that high-temperature anhydrous primary minerals in Ryugu and CI chondrites exhibit a bimodal distribution of oxygen isotopic compositions: 16 O-rich (associated with refractory inclusions) and 16 O-poor (associated with chondrules). Both the 16 O-rich and 16 O-poor minerals probably formed in the inner solar protoplanetary disk and were subsequently transported outwards. The abundance ratios of the 16 O-rich to 16 O-poor minerals in Ryugu and CI chondrites are higher than in other carbonaceous chondrite groups, but are similar to that of comet 81P/Wild2, suggesting that Ryugu and CI chondrites accreted in the outer Solar System closer to the accretion region of comets.

Noriyuki Kawasaki↗
NASA NTRSDate not supplied

Initial Analysis of Volatile Components in the Hayabusa2 Samples

The major objectives of the Hayabusa2-initial-analysis volatile team are (1) to determine the pristine volatile components in the parental materials of the returned Ryugu samples, and (2) to elucidate the origin and chronological history of the asteroid Ryugu, as well as the evolution of the solar system through determination of volatile carrier phases and abundances of volatile components (e.g., presolar grain abundances). Our analytical data will be linked with remote sensing (NIRS3, ONCs, TIR, and LIDAR) data and theoretical modeling [e.g., 1-5]. For example, the erosion rate and the degree of gardening of the surface layer of the asteroid Ryugu can be estimated based on trapped solar wind (SW) and cosmic ray produced (cosmogenic) nuclides, which will be discussed in conjunction with the results based on the remote sensing data [3-5]. Taken together, these will provide characteristics of the surface materials, such as the degree and duration of the alteration by SW/cosmic ray irradiation and micrometeorite bombardments.

volatiles↗
NASA NTRSDate not supplied

Soluble Organic Matter (SOM) analysis of the Hayabusa2 samples: The first results

The Hayabusa2 spacecraft successfully collected the surface and possible sub-surface materials of the asteroid 162173 Ryugu. Ryugu is a C-type asteroid characterized by a low-albedo surface probably consisting of hydrous minerals and carbonaceous materials. [1] The direct optical and spectral analysis of the returned samples indicates that Ryugu material is dominated by hydrous carbonaceous chondrite-like matter (similar to CI chondrites) [2]. Since carbonaceous chondrites have generally yielded various types of organic matter, the collected Ryugu grains are expected to contain diverse types of organic compounds including bio-related molecules. The occurrence of organic compounds in the Ryugu surface will provide clues to the evolution of prebiotic molecules and their preservations associated with aqueous alteration of the primitive asteroid. The initial analysis of soluble organic matter (SOM) of the Hayabusa2-returned samples has been performed by an international team consisting of 32 members. Because the sample amount available for comprehensive SOM analyses is limited, and because the SOM is expected to be present as a complex mixture of various types of organic compounds with very small concentrations of each compound, high-sensitivity and high-resolution analytical techniques have been developed using carbonaceous meteorites [e.g. 3]. Two aggregate samples of the Ryugu grains (A106 and C107) were allocated for the solvent extractions and bulk carbon (C), hydrogen (H), nitrogen (N), sulfur (S) and oxygen (O) measurements. The A106 sample was collected during the 1st sampling in February 2019 and the C107 sample was collected during the 2nd sampling in July 2019 after the Small Carry Impactor (SCI) operation. They consist mainly of particles smaller than 1 mm in diameter, and each sample mass was 38-39 mg. They were firstly investigated spectroscopically in the near infrared wavelength range by the Stone Team prior to the solvent extractions. Other small grains (A0080 and C0057) were also allocated for this study to investigate the spatial distribution of organic compounds on the sample surface. The extraction and analytical measurements implemented by the SOM Team are summarized in Figure 1. Each powder sample was extracted sequentially with non-polar to polar solvents, i.e., hexane, dichloromethane (DCM), methanol (MeOH) and H2O, for non-targeted analysis to reveal the compound composition. Each solvent extract was analyzed by solution state nuclear magnetic resonance (NMR) spectroscopy [4], Fourier transform- ion cyclotron resonance/mass spectrometry (FT-ICR/MS) with ESI and APPI ionization [5] and by high-resolution mass spectroscopy using Orbitrap MS coupled with nano-liquid chromatography (nanoLC/Orbitrap MS) [6], and using two dimensional gas chromatography/mass spectrometry (GC×GC/MS). The extracted residues were passed to the Chemistry Team for further inorganic element analysis. The other powder sample was subjected to the hot water extraction for amino acid analyses including chiral isomer separation, which was performed by three-dimensional (3D) high-performance liquid chromatography (HPLC) with high-sensitivity fluorescence detection (FD) [7] and by HPLC/FD coupled with quadrupole-time of flight/mass spectrometry (QToF/MS) [8]. After the hot water extraction, the residue was split into two halves. One half was further extracted with hydrochloric acid (HCl) to analyze for amino acids in bound-form. The other half was sequentially extracted with DCM/MeOH (1/1) to analyze semi-polar compounds such as polycyclic aromatic hydrocarbons (PAHs) by GC/MS, followed by further extraction with formic acid to analyze polar heterocyclic compounds, and subsequent extraction with HCl to detect bound-form polar compounds. The extracted residues were passed to the IOM Team for the analysis of insoluble organic matter (IOM). Compound-specific stable isotope analyses will be performed using GC/combustion/isotope ratio mass spectrometry (GC/C/IRMS) if the compound concentration is high enough to enable such an isotopic measurement. All extraction procedures were performed on an ISO 6 (Class 100) clean bench inside an ISO 5 (Class 1000) clean room. Baked serpentine powder was also analyzed as a procedural blank. In situ organic compound analysis with the molecular imaging was performed using desorption electrospray ionization (DESI) equipped with Orbitrap MS [9, 10], followed by spatial imaging of organic compounds using ToF/secondary ion mass spectrometry (ToF/SIMS) [11]. The bulk chemical and isotopic compositions of CNS and HO were determined using nano-elemental analysis/isotope ratio mass spectrometry (nanoEA/IRMS) [12] and EA/pyrolysis/IRMS, respectively. We have identified a variety of indigenous organic compounds in the extracts of both A106 and C107 samples. The Ryugu grains host organic molecules under the high-vacuum and cosmic-ray irradiation environment of the asteroid surface. The analysis of extracted molecules is in progress, and the first results will be presented at the symposium.

Hiroshi Naraoka↗
NASA NTRSDate not supplied

Initial analysis of “stone” size Ryugu samples: current status

As a part of the initial analysis of the Ryugu samples, we perform a variety of analyses of millimeter-sized "stones". Our goals are to elucidate the entire formation process of C-type asteroid Ryugu from the viewpoint of petrology and mineralogy ande obtain necessary information by sample analysis, and then simulate the formation of Ryugu based on the evidencef obtained rom sample analysis. Eighteen stones (8 from Room A and 10 from Room C) were received from the ISAS curation facility on June 1, 2021, and brought into a fully nitrogen-displaced glove box at Tohoku University. At the same time, we also received the powder samples from Room A and Room C. To completely block the atmosphere from leaking into the container, all samples were put in the sample transport containers prepared by ISAS, transferred from the main chamber to the glovebox at ISAS, and then all containers were completely sealed in plastic bags with moisture and oxygen absorbers. No moisture or oxygen was detected when the bags were opened in the glove box at Tohoku University, so it was confirmed that there was no exposure to the atmosphere during transport. To date, a number of analyses have been carried out successfully and almost on schedule. The analysis started with the measurement of reflectance spectra, which are sensitive to atmospheric oxidation, hydroxylation, and adsorbed water. The visible, near-infrared, and mid-infrared reflectance spectra were measured while the samples were kept airtight. The spectra of powder samples and stone samples (as aggregates and as single stone) were successfully obtained. A major feature of the stone team's analysis is the use of synchrotron radiation facilities around the world. Since this analysis is non-destructive, stone samples whose reflectance spectra were measured were sent to KEK, SPring-8, ESRF (France), SOLEIL (France), DESY (Germany), and APS (USA). Using these synchrotron radiation facilities, high spatial resolution and sensitivity XRD, STXM, XANES, CT [1], IR-CT, FT-IR [2, 3], XRF, and Mössbauer analyses were performed. Most of the analyses were carried out under air-tight conditions on the stone samples and the particulates separated from the stone samples. These analyses allowed us to determine the three-dimensional distribution of minerals and elements, redox state, density and porosity of the stone samples. Furthermore, as a characteristic analysis of the stone team, light elemental analysis using negative Muon was performed at the MLF facility of J-PARC with an exceptionally long allocation of machine time. This is the only non-destructive method to measure the concentration of light elements in the whole (not the surface) of stone samples. Because the characteristic X-rays produced by muon irradiation are much higher in energy than the fluorescent X-rays produced by X-ray irradiation, there is little effect of self-absorption by the sample, and therefore, the concentration of light elements such as carbon, oxygen, and Na in the entire "stone" sample can be determined. Some stone samples are currently being measured for heat and strength physical properties in order to understand the physical properties of asteroid Ryugu. The data obtained from these measurements are useful for interpreting the remote-sensing data data taken from the surface layer of the asteroid Ryugu [4-7]. It is also important for understanding the behavior of the Ryugu material during impact events. The surfaces of many stone samples were observed by electron microscopy and other techniques, especially on natural “flat” surfaces formed on 5 stomes. As a result, characteristric mineral aggregates formed by the reactions with water and characteiristic impact features were observed on some of the samples. Based on the observations of surfaces and the synchrotron measurements of the whole stones, important objects such as characteristic structures and specific crystal aggregates for understanding the formation history of the asteroid were identified, and these parts were separated from the stone samples using an Xe beam (pFIB) and analyzed by various methods including transmission electron microscopy and synchrotron radiation analysis. Many stone samples, from which important objects have been separated, are embedded in epoxy resin and cut to produce many polished sections. Electron microscopy and spectroscopic measurements of the polished surfaces are being carried out to reveal the detailed mineralogical properties and elemental distribution inside the stone samples. In the fall, machine time for synchrotron radiation will begin, and we plan to analyze single crystals and characteristic objects separated from the stone samples.

Tomoki Nakamura↗
NASA NTRSDate not supplied

Space weathering features of anhydrous minerals in fine grains from the C-type asteroid Ryugu

Materials exposed to the space environment are expected to show optically and chemically modified properties. This process is called as space weathering and is caused mainly by micrometeoroid bombardments and solar wind implantation [1]. Thus far, the space weathering of carbonaceous asteroids has not been well understood. Regolith samples were successfully recovered from C-type asteroid Ryugu by the Hayabusa mission [2]. Ryugu samples will provide insights into the ongoing space weathering of Ryugu [3]. In this study, we investigated the space weathering of anhydrous minerals including iron sulfides, magnetite, and carbonates, which are major reservoirs of volatiles including carbon, oxygen, and sulfur in Ryugu materials. We performed scanning electron microscopy (SEM) and transmission/scanning transmission electron microscopy (TEM/STEM) analysis for Ryugu samples.

Toru Matsumoto↗
NASA NTRSDate not supplied

Characteristics of Mineralogy and Space Weathering Observed on the Grains in the Fine Fraction Samples Returned From the C-type Asteroid Ryugu.

Samples returned from near-Earth C-type asteroid Ryugu by the JAXA Hayabusa2 spacecraft have been investigated from June, 2021. Our Min-Pet Fine ("sand") sub-team have investigated mineralogy and petrology and space weathering of grains in the fine fraction of the samples. Space weathering is alteration induced mainly by solar wind irradiation and micrometeoroid impact. Here, we report mineralogy and microstructural and chemical features related to space weathering of Ryugu grains.

Takaaki Noguchi↗