Engineering topics

Seiichiro Watanabe

Publications and source records attributed to Seiichiro Watanabe.

2 records

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↗