Published papers

Deliveries of organic molecules from space, such as those found in carbonaceous meteorites, have long been hypothesized as a source of the inventory of the first life on Earth. This hypothesis is strengthened by detections of two of life’s fundamental building blocks—nucleobases and protein-building amino acids—in pristine samples returned by spacecraft from the carbonaceous asteroids Bennu and Ryugu. However, life also requires sugars, which cannot be searched for in Ryugu samples due to limited available mass, and their presence in some meteorites is equivocal owing to terrestrial exposure. Here we analyse an extract from a sample of asteroid (101955) Bennu collected by the OSIRIS-REx spacecraft and identify several bio-essential sugars, including ribose (RNA sugar) and glucose (metabolism substrate). These sugars complete the inventory of ingredients crucial to life. Their distribution is consistent with that in the condensation products of formaldehyde solution. Given that Bennu contains formaldehyde and originates from an ancient parent asteroid that underwent long-term alteration by aqueous fluids, we postulate that the detected sugars formed in the parent asteroid from brines containing formaldehyde. This indicates that material with all three components necessary to life could have been dispersed to prebiotic Earth and other inner planets.

Organic matter in meteorites reveals clues about early Solar System chemistry and the origin of molecules important to life, but terrestrial exposure complicates interpretation. Samples returned from the B-type asteroid Bennu by the Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer mission enabled us to study pristine carbonaceous astromaterial without uncontrolled exposure to Earth’s biosphere. Here we show that Bennu samples are volatile rich, with more carbon, nitrogen and ammonia than samples from asteroid Ryugu and most meteorites. Nitrogen-15 isotopic enrichments indicate that ammonia and other N-containing soluble molecules formed in a cold molecular cloud or the outer protoplanetary disk. We detected amino acids (including 14 of the 20 used in terrestrial biology), amines, formaldehyde, carboxylic acids, polycyclic aromatic hydrocarbons and N-heterocycles (including all five nucleobases found in DNA and RNA), along with ~10,000 N-bearing chemical species. All chiral non-protein amino acids were racemic or nearly so, implying that terrestrial life’s left-handed chirality may not be due to bias in prebiotic molecules delivered by impacts. The relative abundances of amino acids and other soluble organics suggest formation and alteration by low-temperature reactions, possibly in NH3-rich fluids. Bennu’s parent asteroid developed in or accreted ices from a reservoir in the outer Solar System where ammonia ice was stable.

Polycyclic aromatic hydrocarbons (PAHs) contain ≲20% of the carbon in the interstellar medium. They are potentially produced in circumstellar environments (at temperatures ≳1000 kelvin), by reactions within cold (~10 kelvin) interstellar clouds, or by processing of carbon-rich dust grains. We report isotopic properties of PAHs extracted from samples of the asteroid Ryugu and the meteorite Murchison. The doubly-13C substituted compositions (D2×13C values) of the PAHs naphthalene, fluoranthene, and pyrene are 9 to 51% higher than values expected for a stochastic distribution of isotopes. The D2×13C values are higher than expected if the PAHs formed in a circumstellar environment, but consistent with formation in the interstellar medium. By contrast, the PAHs phenanthrene and anthracene in Ryugu samples have D2×13C values consistent with formation by higher-temperature reactions.

Microbiological activities can be detected in various extreme environments on Earth, which suggest that extraterrestrial environments, such as on Mars, could host life. There have been proposed a number of biomarkers to detect extant life mostly based on specific molecules. Because terrestrial organisms have catalytic proteins (enzymes), enzymatic activity may also be a good indicator to evaluate biological activities in extreme environments. Phosphatases are essential for all terrestrial organisms because phosphate esters are ubiquitously used in genetic molecules (DNA/RNA) and membranes. In this study, we evaluated microbial activity in soils of the Atacama Desert, Chile, by analysing several biomarkers, including phosphatase activity. Phosphatases extracted with Tris buffer were assayed fluorometrically using 4-methylumbelliferyl phosphate as a substrate. The horizontal distribution of phosphatase activity and other parameters in soils from the Atacama Desert showed that phosphatase activity was positively correlated with amino acid concentration and colony-forming units and negatively correlated with precipitation amount. We found consistent that biochemical indicators including phosphatase significantly decreased in the extreme hyper-arid zone where rainfall of <25 mm year-1. The results were compared with phosphatase activities detected in extreme environments, such as submarine hydrothermal systems and Antarctic soils, as well as soils from ordinary environments. Overall, our results suggested that phosphatase activity could be a good indicator for evaluating biological activities in extreme environments.

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.

The origin and evolution of solar system bodies, including water on the Earth, have been discussed based on the assumption that the relevant ingredients were simply silicates and ices. However, large amounts of organic matter have been found in cometary and interplanetary dust, which are recognized as remnants of interstellar/precometary grains. Precometary organic matter may therefore be a potential source of water; however, to date, there have been no experimental investigations into this possibility. Here, we experimentally demonstrate that abundant water and oil are formed via the heating of a precometary-organic-matter analog under conditions appropriate for the parent bodies of meteorites inside the snow line. This implies that H2O ice is not required as the sole source of water on planetary bodies inside the snow line. Further, we can explain the change in the oxidation state of the Earth from an initially reduced state to a final oxidized state. Our study also suggests that petroleum was present in the asteroids and is present in icy satellites and dwarf planets.

Evidence suggests that Saturns icy moon Enceladus has a subsurface ocean that sources plumes of water vapor and ice vented to space from its south pole. In situ analyses of this material by the Cassini spacecraft have shown that the ocean contains key ingredients for life (elements H, C, N, O and possibly S; simple and complex organic compounds; chemical disequilibria at water-rock interfaces; clement temperature, pressure, and pH). The Cassini discoveries make Enceladus interior a prime locale for life detection beyond Earth. Scant material exchange with the inner Solar System makes it likely that such life would have emerged independently of life on Earth. Thus, its discovery would illuminate lifes universal characteristics. The alternative result of an upper bound on a detectable biosphere in an otherwise habitable environment would likewise considerably advance our understanding of the prevalence of life beyond Earth. Here we outline the rationale for returning vented ocean samples, accessible from Enceladus surface or low altitudes, to Earth for life detection. Returning samples allows analyses using laboratory instruments that cannot be flown, with decades or more to adapt and repeat analyses. We describe an example set of measurements to estimate the amount of sample to be returned and discuss possible mission architectures and collection approaches. We then turn to the challenges of preserving sample integrity and implementing planetary protection policy. We conclude by placing such a mission in the broader context of Solar System exploration.

Chemical evolution is an abiotic reaction process in which complex organic molecules arise from a combination of simple inorganic and organic chemical compounds. To assess the possible ongoing chemical evolution in the subsurface ocean of Saturn's icy satellite Enceladus, we explored the water-rock aqueous reactions and the peptide formation capability under a hydrothermal environment similar to that on Enceladus. It has been suggested that the core of Enceladus has not experienced high temperatures from the time of satellite formation to the present. The major components of the core are assumed to be carbonaceous chondrites; thus, simple organic substances, including amino acids, are likely present in the alkaline seawater of Enceladus. In this study, we conducted a laboratory-based simulation experiment to describe the chemical alteration of six prebiotically abundant amino acids over 147 days under high pressure with thermal cycling (30 to 100 °C) to simulate the water-rock interface of the ocean on Enceladus. As a result, we detected 28 out of 36 possible dipeptide species during the entire reaction period. We propose that peptide-bond formation is coupled to rock surface chemisorption of amino acids under alkaline condition, which was further supported by the elemental analysis showing carbon and nitrogen signature on the rock surface only when amino acids are added. The above result suggests that ongoing chemical evolution on Enceladus is likely producing short abiotic peptides on the porous core surface.