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Kebukawa, Yoko

Publications and source records attributed to Kebukawa, Yoko.

Chemistry in Retrieved Ryugu Asteroid Samples Revealed by Non-Invasive X-ray Microanalyses: Pink-Beam Fluorescence CT and Tender-Energy Absorption Spectroscopy

The Hayabusa2 space mission recently retrieved 5.4 g of material from asteroid Ryugu, providing the first direct access to pristine material from a carbonaceous asteroid. This study employs a novel combination of non-invasive synchrotron X-ray techniques to examine microscale chemistry (elemental distributions and element-specific chemical speciation and local structure) inside Ryugu grains without physically cutting the samples. Manganese primarily occurs in carbonate: Mn-bearing dolomite with minor earlier ankerite. Iron sulfides present as large single grains and as smaller particles in the finer-grained matrix are both predominantly pyrrhotite. At the 5 μm scale, Fe sulfides do not show the mineralogical heterogeneity seen in many carbonaceous meteorites but exhibit some heterogeneous localized oxidation. Iron is present often as intergrowths of oxide and sulfide, indicating incomplete replacement. Trace selenium substitutes for S in pyrrhotite. Copper is present as Fe-poor Cu sulfide. These results demonstrate multiple episodes of fluid alteration on the parent body, including partial oxidation, and help constrain the sequence or evolution of fluids and processes that resulted in the current grain-scale mineralogical composition of Ryugu materials.

36 MATERIALS SCIENCE↗

Organic matter in carbonaceous chondrite lithologies of Almahata Sitta: Incorporation of previously unsampled carbonaceous chondrite lithologies into ureilitic regolith

The Almahata Sitta (AhS) meteorite is a unique polymict ureilite. Recently, carbonaceous chondritic lithologies were identified in AhS. Organic matter (OM) is ubiquitously found in primitive carbonaceous chondrites. The molecular and isotopic characteristics of this OM reflect its origin and parent body processes, and are particularly sensitive to heating. The C1 lithologies AhS 671 and AhS 91A were investigated, focusing mainly on the OM. We found that the OM in these lithologies is unique and contains primitive isotopic signatures, but experienced slight heating possibly by short-term heating event(s). These characteristics support the idea that one or more carbonaceous chondritic bodies were incorporated into the ureilitic parent body. Here, the uniqueness of the OM in the AhS samples implies that there were large variations in primitive carbonaceous chondritic materials in the solar system other than known primitive carbonaceous chondrite groups such as CI, CM, and CR chondrites.

58 GEOSCIENCES↗

STXM-XANES analyses of Murchison meteorite samples captured by aerogel after hypervelocity impacts: A potential implication of organic matter degradation for micrometeoroid collection experiments

The Tanpopo mission is an astrobiology space experiment at the Japanese Experiment Module (JEM) 'Kibo' on the International Space Station (ISS). One of the sub-divided themes of the Tanpopo mission is for the intact capture of organic bearing micrometeoroids in low Earth orbit using ultralow density silica aerogel (0.01 g/cm 3 ). In order to evaluate damage to organic matter in micrometeoroids during hyper velocity impacts into the aerogel, Murchison meteorite powdered samples, analogs of organic bearing micrometeoroids, were fired into flight-grade silica aerogel (0.01 g/cm 3 ) using a two-stage light-gas gun with velocities of 4.4 and 5.9 km/s. The recovered Murchison grains were analyzed using scanning transmission X-ray microscopy/X-ray absorption near edge structure (STXM/XANES), transmission electron microscopy (TEM) and nanoscale secondary ion mass spectrometry (NanoSIMS). TEM observation did not show significant modifications of the recovered Murchison grains. Carbon-XANES spectra, however, showed a large depletion of the organic matter after the 5.9 km/s impact, but no such effects nor any significant hydrogen isotopic fractionation were observed after the 4.4 km/s impact.

58 GEOSCIENCES↗

Aqueous Alteration

A secondary process whereby liquid water modified the nature of anhydrous primary nebular components. In general, this process induced decomposition and changed the structures and compositions of primary minerals and formed secondary minerals in their place. This process occurred in the early history of meteorite parent bodies that contained water ice. The most effective heat source is considered to be the decay of short-lived radioactive nuclide such as Aluminium-26, but other causes have been suggested. The degree of aqueous alteration of meteorites is categorized as type 1 (most altered) to type 3 (least altered), according to mineralogy and petrology.

Kebukawa, Yoko↗

Heating experiments of the Tagish Lake meteorite: Investigation of the effects of short-term heating on chondritic organics

We present in this study the effects of short-term heating on organics in the Tagish Lake meteorite and how the difference in the heating conditions can modify the organic matter (OM) in a way that complicates the interpretation of a parent body's heating extent with common cosmothermometers. The kinetics of short-term heating and its influence on the organic structure are not well understood, and any study of OM is further complicated by the complex alteration processes of the thermally metamorphosed carbonaceous chondrites—potential analogues of the target asteroid Ryugu of the Hayabusa2 mission—which had experienced posthydration, short-duration local heating. In an attempt to understand the effects of short-term heating on chondritic OM, we investigated the change in the OM contents of the experimentally heated Tagish Lake meteorite samples using Raman spectroscopy, scanning transmission X-ray microscopy utilizing X-ray absorption near edge structure spectroscopy, and ultraperformance liquid chromatography fluorescence detection and quadrupole time of flight hybrid mass spectrometry. Our experiment suggests that graphitization of OM did not take place despite the samples being heated to 900 °C for 96 h, as the OM maturity trend was influenced by the heating conditions, kinetics, and the nature of the OM precursor, such as the presence of abundant oxygenated moieties. Although both the intensity of the 1s-σ* exciton cannot be used to accurately interpret the peak metamorphic temperature of the experimentally heated Tagish Lake sample, the Raman graphite band widths of the heated products significantly differ from that of chondritic OM modified by long-term internal heating.

Chan, Queenie H. S.↗

Fluid Inclusions in Astromaterials: Direct Samples of Early Solar System Aqueous Fluids

We have become increasingly aware of the fundamental importance of water, and aqueous alteration, on primitive solar-system bodies. All classes of astromaterials studied show some degree of interaction with aqueous fluids. We have direct observations of cryovolcanism of several small solar system bodies (e.g. Saturnian and Jovian moons), and indirect evidence for this process on the moons Europa, Titan, Ganymede, and Miranda, and the Kuiper Belt object Charon, and so are certain of the continuing and widespread importance of aqueous processes across the solar system. Nevertheless, we are still lacking fundamental information such as the location and timing of the aqueous alteration and the detailed nature of the aqueous fluid itself.

Zolensky, Michael↗

Organic matter in extraterrestrial water-bearing salt crystals

Direct evidence of complex prebiotic chemistry from a water-rich world in the outer solar system is provided by the 4.5-billion-year-old halite crystals hosted in the Zag and Monahans (1998) meteorites. This study offers the first comprehensive organic analysis of the soluble and insoluble organic compounds found in the millimeter-sized halite crystals containing brine inclusions and sheds light on the nature and activity of aqueous fluids on a primitive parent body. Associated with these trapped brines are organic compounds exhibiting wide chemical variations representing organic precursors, intermediates, and reaction products that make up life’s precursor molecules such as amino acids. The organic compounds also contain a mixture of C-, O-, and N-bearing macromolecular carbon materials exhibiting a wide range of structural order, as well as aromatic, ketone, imine, and/or imidazole compounds. The enrichment in 15 N is comparable to the organic matter in pristine Renazzo-type carbonaceous chondrites, which reflects the sources of interstellar 15 N, such as ammonia and amino acids. The amino acid content of the Zag halite deviates from the meteorite matrix, supporting an exogenic origin of the halite, and therefore, the Zag meteorite contains organics synthesized on two distinct parent bodies. Lastly, our study suggests that the asteroidal parent body where the halite precipitated, potentially asteroid 1 Ceres, shows evidence for a complex combination of biologically and prebiologically relevant molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A D- and N-15-Rich Micrometer-Sized Aggregate of Organic Matter in a Xenolithic Clast from the Zag Ordinary Chondrite

The nature and origin of extraterrestrial organic matter are still under debate despite the significant progress in the analyses and experimental approaches in this field over the last five decades. Xenolithic clasts are often found in a wide variety of meteorite groups, some of which contain exotic organic matter (OM). The Zag meteorite is a thermally-metamorphosed H ordinary chondrite. It contains a primitive xenolithic clast that has been proposed to have originated from Ceres, which was accreted to the Zag host asteroid after metamorphism. The cm-sized clast contains abundant large carbon-rich (mostly organic) grains or aggregates up to 20 microns. Such large OM grains are unique among astromaterials with respect to the size. Here we report organic and isotope analyses of a large (approx.10 microns) aggregate of solid OM in the Zag clast. The X-ray micro-spectroscopic technique revealed that the OM has sp2 bonded carbon with no other functional groups nor graphitic feature (1s-sigma exciton), and thus it is distinguished from most of the OM in carbonaceous meteorites. The apparent absence of functional groups in the OM suggests that it is composed of hydrocarbon networks with less heteroatoms, and therefore the OM aggregate is similar to hydrogenated amorphous carbon (HAC). The OM aggregate has high D/H and 15N/14N ratios, 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 survived the extensive late-stage aqueous processing. It is not in the case for OM in carbonaceous chondrites of which the D/H ratio was reduced by the alteration via the D-H exchange of water. It indicates that both the OM precursors and the water had high D/H ratios, similar to the water in Enceladus. Our results support the idea that the clast originated from Ceres, or at least, a hydrovolcanically active body similar to Ceres, and further imply that Ceres originally formed in the outer Solar System and migrated to the main belt asteroid region as suggested by the "Grand tack" scenario.

Kebukawa, Yoko↗

Heating Experiments of the Tagish Lake Meteorite: Investigation of the Effects of Short-Term Heating on Chondritic Organics

We present in this study the effects of short-term heating on organics in the Tagish Lake meteorite and how the difference in the heating conditions can modify the organic matter (OM) in a way that complicates the interpretation of a parent body's heating extent with common cosmo thermometers. The kinetics of short-term heating and its influence on the organic structure are not well understood, and any study of OM is further complicated by the complex alteration processes of the thermally metamorphosed carbonaceous chondrites - potential analogues of the target asteroid Ryugu of the Hayabusa2 mission - which had experienced post-hydration, short-duration local heating. In an attempt to understand the effects of short-term heating on chondritic OM, we investigated the change in the OM contents of the experimentally heated Tagish Lake meteorite samples using Raman spectroscopy, scanning transmission X-ray microscopy utilizing X-ray absorption near edge structure spectroscopy, and ultra-performance liquid chromatography fluorescence detection and quadrupole time of flight hybrid mass spectrometry. Our experiment suggests that graphitization of OM did not take place despite the samples being heated to 900 degrees Centigrade for 96 hours, as the OM maturity trend was influenced by the nature of the OM precursor, such as the presence of abundant oxygenated moieties. Although both the intensity of the 1s-sigma σ* exciton cannot be used to accurately interpret the peak metamorphic temperature of the experimentally heated Tagish Lake sample, the Raman graphite band widths of the heated products significantly differ from that of chondritic OM modified by long-term internal heating.

Chan, Queenie Hoi Shan↗

EXPLORING THE POTENTIAL FORMATION OF ORGANIC SOLIDS IN CHONDRITES AND COMETS THROUGH POLYMERIZATION OF INTERSTELLAR FORMALDEHYDE

Polymerization of interstellar formaldehyde, first through the formose reaction and then through subsequent condensation reactions, provides a plausible explanation for how abundant and highly chemically complex organic solids may have come to exist in primitive solar system objects. In order to gain better insight on the reaction, a systematic study of the relationship of synthesis temperature with resultant molecular structure was performed. In addition, the effect of the presence of ammonia on the reaction rate and molecular structure of the product was studied. The synthesized formaldehyde polymer is directly compared to chondritic insoluble organic matter (IOM) isolated from primitive meteorites using solid-state {sup 13}C nuclear magnetic resonance, Fourier transform infrared, and X-ray absorption near edge structure spectroscopy. The molecular structure of the formaldehyde polymer is shown to exhibit considerable similarity at the functional group level with primitive chondritic IOM. The addition of ammonia to the solution enhances the rate of polymerization reaction at lower temperatures and results in substantial incorporation of nitrogen into the polymer. Morphologically, the formaldehyde polymer exists as submicron to micron-sized spheroidal particles and spheroidal particle aggregates that bare considerable similarity to the organic nanoglobules commonly observed in chondritic IOM. These spectroscopic and morphological data support the hypothesis that IOM in chondrites and refractory organic carbon in comets may have formed through the polymerization of interstellar formaldehyde after planetesimal accretion, in the presence of liquid water, early in the history of the solar system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Origin and Evolution of Prebiotic Organic Matter as Inferred from the Tagish Lake Meteorite

The complex suite of organic materials in carbonaceous chondrite meteorites probably originally formed in the interstellar medium and/or the solar protoplanetary disk, but was subsequently modified in the meteorites' asteroidal parent bodies. The mechanisms of formation and modification are still very poorly understood. We carried out a systematic study of variations in the mineralogy, petrology, and soluble and insoluble organic matter in distinct fragments of the Tagish Lake meteorite. The variations correlate with indicators of parent body aqueous alteration and at least some molecules of pre-biotic importance formed during the alteration.

Herd, Christopher D.↗

Rapid Contamination During Storage of Carbonaceous Chondrites Prepared for Micro FTIR Measurements

The carbonaceous chondrites Tagish Lake and Murchison, which contain abundant hydrous minerals, when pressed on aluminum plates and analyzed by micro FTIR, were found to have been contaminated during brief (24 hours) storage. This contamination occurred when the samples were stored within containers which included silicone rubber, silicone grease or adhesive tape. Long-path gas cell FTIR measurements for silicone rubber revealed the presence of contaminant volatile molecules having 2970 cm(sup -1) (CH3) and 1265 cm(sup -1) (Si-CH3) peaks. These organic contaminants are found to be desorbed by in-situ heating infrared measurements from room temperature to 200-300 C. Careful preparation and storage are therefore needed for precious astronomical samples such as meteorites, IDPs and mission returned samples from comets, asteroids and Mars, if useful for FTIR measurements are to be made.

Kebukawa, Yoko↗

In-situ micro-FTIR Study of Thermal Changes of Organics in Tagish Lake Meteorite: Behavior of Aliphatic Oxygenated Functions and Effects of Minerals

Systematic in-situ FTIR heating experiments of Tagish Lake meteorite grains have been performed in order to study thermal stability of chondritic organics. Some aliphatic model organic substances have also been used to elucidate effects of hydrous phyllosilicate minerals on the thermal stability of organics. The experimental results indicated that organic matter in the Tagish Lake meteorite might contain oxygenated aliphatic hydrocarbons which are thermally stable carbonyls such as ester and/or C=O in ring compounds. The presence of hydrous phyllosilicate minerals has a pronounced effect on the increase of the thermal stability of aliphatic and oxygenated functions. These oxygenated aliphatic organics in Tagish Lake can be formed during the aqueous alteration in the parent body and the formation temperature condition might be less than 200 C, based especially on the thermal stability of C-O components. The hydrous phyllosilicates might provide sites for organic globule formation and protected some organic decomposition

Kebukawa, Yoko↗