Usui Tomohiro

Abstract Organic matter found in early Martian sediment may yield clues to the planet’s environmental conditions, prebiotic chemistry and habitability, but its origin remains unclear. Strong ¹³C depletion in sedimentary organic matter at Gale crater was recently detected by the Curiosity rover. Although this enigmatic depletion remains debated, if correct, a mechanism to cause such strong ¹³C depletion is required. Here we show from CO₂ photolysis experiments and theoretical considerations that solar ultraviolet photolysis of CO₂ in a reducing atmosphere can yield strongly ¹³C-depleted CO. We suggest that atmospheric synthesis of organic compounds from photolysis-produced CO is a plausible mechanism to explain the source of isotopically depleted organic matter in early Martian sediments. Furthermore, this mechanism could explain ¹³C enrichment of early Martian CO₂ without requiring long-term carbon escape into space. A mass balance model calculation using our estimated isotopic fractionation factor indicates the conversion of approximately 20% of volcanic CO₂ emissions on early Mars into organics via CO, consistent with the available data for carbon isotopes of carbonate. Although alternative pathways for organic compound production have been proposed, our findings suggest that considerable amounts of organic matter may have been synthesized from CO in a reducing early Martian atmosphere and deposited in sediments.

Abstract Oxygen 3‐isotope ratios of magnetite and carbonates in aqueously altered carbonaceous chondrites provide important clues to understanding the evolution of the fluid in the asteroidal parent bodies. We conducted oxygen 3‐isotope analyses of magnetite, dolomite, and breunnerite in two sections of asteroid Ryugu returned samples, A0058 and C0002, using a secondary ion mass spectrometer (SIMS). Magnetite was analyzed by using a lower primary ion energy that reduced instrumental biases due to the crystal orientation effect. We found two groups of magnetite data identified from the SIMS pit morphologies: (1) higher δ¹⁸O (from 3‰ to 7‰) and ∆¹⁷O (~2‰) with porous SIMS pits mostly from spherulitic magnetite, and (2) lower δ¹⁸O (~ −3‰) and variable ∆¹⁷O (0‰–2‰) mostly from euhedral magnetite. Dolomite and breunnerite analyses were conducted using multi‐collection Faraday cup detectors with precisions ≤0.3‰. The instrumental bias correction was applied based on carbonate compositions in two ways, using Fe and (Fe + Mn) contents, respectively, because Ryugu dolomite contains higher amounts of Mn than the terrestrial standard. Results of dolomite and breunnerite analyses show a narrow range of ∆¹⁷O; 0.0‰–0.3‰ for dolomite in A0058 and 0.2‰–0.8‰ for dolomite and breunnerite in C0002. The majority of breunnerite, including large ≥100 μm grains, show systematically lower δ¹⁸O (~21‰) than dolomite (25‰–30‰ and 23‰–27‰ depending on the instrumental bias corrections). The equilibrium temperatures between magnetite and dolomite from the coarse‐grained lithology in A0058 are calculated to be 51 ± 11°C and 78 ± 14°C, depending on the instrumental bias correction scheme for dolomite; a reliable temperature estimate would require a Mn‐bearing dolomite standard to evaluate the instrumental bias corrections, which is not currently available. These results indicate that the oxygen isotope ratios of aqueous fluids in the Ryugu parent asteroid were isotopically heterogeneous, either spatially, or temporary. Initial water ice accreted to the Ryugu parent body might have ∆¹⁷O > 2‰ that was melted and interacted with anhydrous solids with the initial ∆¹⁷O < 0‰. In the early stage of aqueous alteration, spherulitic magnetite and calcite formed from aqueous fluid with ∆¹⁷O ~ 2‰ that was produced by isotope exchange between water (∆¹⁷O > 2‰) and anhydrous solids (∆¹⁷O < 0‰). Dolomite and breunnerite, along with some magnetite, formed at the later stage of aqueous alteration under higher water‐to‐rock ratios where the oxygen isotope ratios were nearly at equilibrium between fluid and solid phases. Including literature data, δ¹⁸O of carbonates decreased in the order calcite, dolomite, and breunnerite, suggesting that the temperature of alteration might have increased with the degree of aqueous alteration.

The formation process of the two Martian moons, Phobos and Deimos, is still debated with two main competing hypotheses: the capture of an asteroid or a giant impact onto Mars. In order to reveal their origin, the Martian Moons eXploration (MMX) mission by Japan Aerospace Exploration Agency (JAXA) plans to measure Phobos’ elemental composition by a gamma-ray and neutron spectrometer called MEGANE. This study provides a model of Phobos’ bulk elemental composition, assuming the two formation hypotheses. Using the mixing model, we established a MEGANE data analysis flow to discriminate between the formation hypotheses by multivariate analysis. The mixing model expresses the composition of Phobos in 6 key lithophile elements that will be measured by MEGANE (Fe, Si, O, Ca, Mg, and Th) as a linear mixing of two mixing components: material from Mars and material from an asteroid as represented by primitive meteorite compositions. The inversion calculation includes consideration of MEGANE's measurement errors (EP) and derives the mixing ratio for a given Phobos composition, based on which the formation hypotheses are judged. For at least 65% of the modeled compositions, MEGANE measurements will determine the origin uniquely (EP = 30%), and this increases from 74 to 87% as EP decreases from 20 to 10%. Although the discrimination performance depends on EP, the current operation plan for MEGANE predicts an instrument performance for EP of 20—30%, resulting in 70% discrimination between the original hypotheses. MEGANE observations can also enable the determination of the asteroid type of the captured body or the impactor. The addition of other measurements, such as MEGANE's measurements of the volatile element K, as well as observations by other MMX remote sensing instruments, will also contribute to the MMX mission's goal to constrain the origin of Phobos.

Abstract Japan Aerospace Exploration Agency's Martian Moons eXploration (MMX) mission will launch a spacecraft in 2024 to return samples from Phobos in 2029. Curatorial work for the returned Phobos samples is critical for the sample allocation without degrading the sample integrity and subsequent sample analysis that will provide new constraints on the origin of Phobos and the evolution of the circum‐Mars environment. The Sample Analysis Working Team of the MMX is designing the sample curation protocol. The curation protocol consists of three phases: (1) quick analysis (extraction and mass spectrometry for gases), (2) pre‐basic characterization (bulk‐scale observation), and (3) basic characterization (grain‐by‐grain observation and allocation of the sample aliquots). Nondestructive analyses within the clean chamber (e.g., visible and near‐infrared spectral imaging) and outside the chamber (e.g., gas mass spectrometry) are incorporated into the curation flow in coordination with the MMX mission instrument teams for ground‐truthing the remote‐sensing data sets. The MMX curation/sample analysis flow enables the seamless integration between the sample and remote‐sensing data sets to maximize the scientific value of the collected Phobos samples.

The pristine sample from the near-Earth carbonaceous asteroid (162173) Ryugu collected by the Hayabusa2 spacecraft enabled us to analyze the pristine extraterrestrial material without uncontrolled exposure to the Earth’s atmosphere and biosphere. The initial analysis team for the soluble organic matter reported the detection of wide variety of organic molecules including racemic amino acids in the Ryugu samples. Here we report the detection of uracil, one of the four nucleobases in ribonucleic acid, in aqueous extracts from Ryugu samples. In addition, nicotinic acid (niacin, a B3 vitamer), its derivatives, and imidazoles were detected in search for nitrogen heterocyclic molecules. The observed difference in the concentration of uracil between A0106 and C0107 may be related to the possible differences in the degree of alteration induced by energetic particles such as ultraviolet photons and cosmic rays. The present study strongly suggests that such molecules of prebiotic interest commonly formed in carbonaceous asteroids including Ryugu and were delivered to the early Earth.