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Yoko Kebukawa

Publications and source records attributed to Yoko Kebukawa.

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↗

STXM-C-XANES, IR Microspectroscopy, and Raman Microspectroscopy Analysis of Organic Matter in the Chwichiya 002 C3.00-Ungrouped Chondrite

Chwichiya 002 is a C3.00-ungrouped carbonaceous chondrite discovered in Western Sahara in 2018. The presence of hydrated phases in Chwichiya 002 was not confirmed by XRD analysis, and only a faint water and Si-O band attributed to phyllosilicate were observed by infrared transmission spectroscopy, indicating a very low degree of aqueous alteration (Meteoritical Bulletin, 2020). The structural order of polycyclic aromatic hydrocarbons evaluated by Raman spectroscopy indicates that the effect of thermal metamorphism is less severe than in the Semarkona meteorite, an LL3.00 ordinary chondrite (Meteoritical Bulletin, 2020). Chiwichiya 002 is a very primitive carbonaceous chondrite and an important information source for the early stage of the evolution of organic matter in the solar system. In this study, we investigated the molecular structure and distribution of organic matter in Chiwichiya 002 by Carbon X-ray Absorption Near Edge Structure (C-XANES) analysis using a Scanning Transmission X-ray Microscope (STXM). The STXM-C-XANES analysis has a spatial resolution of 20~100 nm and can observe the spatial distribution of organic materials in microstructures. In addition, to investigate the degree of thermal metamorphism of the organic matter, micro-IR, and micro-Raman spectroscopic analyses were performed. In addition, the Murchison CM2 chondrite was also analyzed for comparison. To evaluate contamination during analytical procedures, antigorite, which was heated in air at 500°C for 5 hours to eliminate organic matter was also analyzed in the same manner. The samples were milled into 100 nm-thick, thin sections using a Focused Ion Beam (FIB), and C-XANES spectra were obtained using the STXM at the High Energy Accelerator Research Organization, Photon Factory (PF), BL-19B. The obtained C-XANES spectra were smoothed and then fitted with Gaussian functions using the method of Le Guillou et al. (2018). The C-XANES showed that the ratio of oxygenated functional group (ketone, phenolic) carbons in Chwichiya 002 was lower than in Murchison, whereas the ratio of aliphatic carbons was almost the same. This may reflect the low degree of aqueous alteration of Chwichiya 002. In addition, contamination peaks were detected at 287.3-287.7 eV and 288.3-288.7 eV in the C-XANES spectra of some of the antigorite samples. The source of these peaks is under investigation. Raman spectroscopic analysis showed that the intensity ratio of the D band to the G band of Chwichiya 002 was slightly higher than that of Murchison. IR absorption spectra showed aromatic absorption at 1630 cm -1 , but there was little absorption due to aliphatic C-H around 2900 cm -1 . These results suggest that the organic matter in Chwichiya 002 may be more heated than in Murchison.

Chwichiya 002↗

Formation of Amino Acids and Carboxylic Acids in Weakly Reducing Planetary Atmospheres by Solar Energetic Particles from the Young Sun

Life most likely started during the Hadean Eon; however, the environmental conditions which contributed to the complexity of its chemistry are poorly known. A better understanding of various environmental conditions, including global (heliospheric) and local (atmospheric, surface, and oceanic), along with the internal dynamic conditions of the early Earth, are required to understand the onset of abiogenesis. Herein, we examine the contributions of galactic cosmic rays (GCRs) and solar energetic particles (SEPs) associated with superflares from the young Sun to the formation of amino acids and carboxylic acids in weakly reduced gas mixtures representing the early Earth’s atmosphere. We also compare the products with those introduced by lightning events and solar ultraviolet light (UV). In a series of laboratory experiments, we detected and characterized the formation of amino acids and carboxylic acids via proton irradiation of a mixture of carbon dioxide, methane, nitrogen, and water in various mixing ratios. These experiments show the detection of amino acids after acid hydrolysis when 0.5% (v/v) of initial methane was introduced to the gas mixture. In the set of experiments with spark discharges (simulation of lightning flashes) performed for the same gas mixture, we found that at least 15% methane was required to detect the formation of amino acids, and no amino acids were detected in experiments via UV irradiation, even when 50% methane was used. Carboxylic acids were formed in non-reducing gas mixtures (0% methane) by proton irradiation and spark discharges. Hence, we suggest that GCRs and SEP events from the young Sun represent the most effective energy sources for the prebiotic formation of biologically important organic compounds from weakly reducing atmospheres. Since the energy flux of space weather, which generated frequent SEPs from the young Sun in the first 600 million years after the birth of the solar system, was expected to be much greater than that of GCRs, we conclude that SEP-driven energetic protons are the most promising energy sources for the prebiotic production of bioorganic compounds in the atmosphere of the Hadean Earth.

Kensei Kobayashi↗

A Novel Organic-Rich Meteoritic Clast from the Outer Solar System

The Zag meteorite which is a thermally-metamorphosed H ordinary chondrite contains a primitive xenolithic clast that was accreted to the parent asteroid after metamorphism. The cm-sized clast contains abundant large organic grains or aggregates up to 20 μm in phyllosilicate-rich matrix. Here we report organic and isotope analyses of a large (~10 μm) OM aggregate in the Zag clast. The X-ray micro-spectroscopic technique revealed that the OM aggregate has sp2 dominated hydrocarbon networks with a lower abundance of heteroatoms than in IOM from primitive (CI,CM,CR) carbonaceous chondrites, and thus it is distinguished from most of the OM in carbonaceous meteorites. The OM aggregate has high D/H and (sup 15)N/(sup 14)N ratios (δD = 2,370 ± 74‰ and δ(sup 15)N = 696 ± 100‰), suggesting that it originated in a very cold environment such as the interstellar medium or outer region of the solar nebula, while the OM is embedded in carbonate-bearing matrix resulting from aqueous activities. Thus, the high D/H ratio must have been preserved during the extensive late-stage aqueous processing. It indicates that both the OM precursors and the water had high D/H ratios. Combined with (sup 16)O-poor nature of the clast, the OM aggregate and the clast are unique among known chondrite groups. We further propose that the clast possibly originated from D/P type asteroids or trans-Neptunian Objects.

Yoko Kebukawa↗

The Aguas Zarcas Breccia - Similarities to Surface Features of Asteroids Ryugu and Bennu

At 21:07 local time on 23rd April 2019, a meteorite fall occurred in Aguas Zarcas, San Carlos County, Alajuela province, Costa Rica. The rapid recovery of this brecciated carbonaceous chondrite after its fall provides an opportunity to investigate a freshly-fallen, relatively uncontaminated and highly-brecciated meteorite for comparison to the samples returned from C-group asteroids by the Hayabusa2 and OSIRIS-REx spacecraft. The study includes several pre-rain fragments. Our X-ray Computed Tomography(XCT) results show many different lithologies. In this study we describe the petrography and mineralogy of five different lithologies of the Aguas Zarcas meteorite. We also present bulk oxygen isotope data of some lithologies and results concerning the organic matter. We describe all the fragments in detail and attempt a classification of each lithology in order to understand the origin and the history of formation of the Aguas Zarcas' parent body. Our results show some lithologies of Aguas Zarcas similar to those in CM chondrites, but others are unique. The different lithologies [1] represent different levels of hydration and heating as well, which are good analogues for the types of materials returned from asteroids Bennu and Ryugu. Spectroscopic observations of the Ryugu and Bennu asteroids compared to laboratory measurements of meteorites suggest that the asteroids show some similarities to heated CM, heated CI or, CI chondrites [2-5]. Both asteroids are regarded to consist of materials altered by aqueous alteration (e.g., [5]) and formed by re-accretion after impact destruction and brecciation (e.g., [6-7]). Considering the various different lithologies in Aguas Zarcas [2] and other CM chondrites [8-9] these types of carbonaceous chondrites may be regarded as good analogues for samples from the Ryugu and Bennu asteroids. The presence of unique and rare lithologies in the Aguas Zarcas, that are distinct from typical CM chondrite lithologies, indicates a complex mixing of various materials in a highly dynamic environment.

Imene Kerraouch↗

Outer Solar System Carbon in the Laboratory

Samples of outer solar system carbon in various forms are available for analysis in the laboratory. The Stardust Mission returned organics and a few carbonate grains from Jupiter Class comet Wild-2 [1]. These complement similar phases available in chondritic interplanetary dust particles, some of which derive from comets, although it is not definitively known which have that origin. Carbonaceous chondrites probably derive from C-complex asteroids which may have outer solar system origins, though this origin is model dependent. There are rare carbonaceous xenoliths in, principally, ordinary chondrites and ureilites whose bulk isotopic and bulk chemical compositions suggest an origin farther from the Sun that the remainder of carbonaceous chondrites [2,3]. These contain abundant carbonaceous materials, including organic-bearing aqueous fluid inclusions [4]. The Hayabusa2 spacecraft recently returned samples of C-class asteroid Ryugu to Earth, now being analyzed in labs worldwide. These materials are expected to be dominated by materials similar to C1 and C2 carbonaceous chondrites [5].

Michael Zolensky↗