Large enantiomeric excesses in primitive meteorites and the diverse effects of water in cosmochemical evolution.

Carbonaceous chondrites are meteoritic fragments of asteroids that avoided the geological reprocessing of larger planets and allow laboratory probing of early solar-nebula materials. Among these, Renazzo-type (CR) chondrites found in Antarctica appear remarkably pristine and are distinguished by abundant organic materials and water-soluble molecules such as amino acids and ammonia. We present a comprehensive analysis of the organic composition of selected CR meteorites of different petrographic classification and compare compounds' abundance and distribution as they may relate to asteroidal aqueous processing and concomitant evolution of the mineral phases. We found that several CR compounds such as amino acids and sugar alcohols are fully represented in stones with no or minimal water exposure indicating a formation that, if solar, preceded parent body processes. The most pristine CRs also revealed natal enantiomeric excesses (ee) of up to 60%, much larger than ever recorded. However, aqueous alteration appears to affect CR soluble organic composition and abundances, in particular some diastereomeric amino acids may gauge its extent by the consequent racemization of their ee.

Petrography, stable isotope compositions, microRaman spectroscopy, and presolar components of Roberts Massif 04133: A reduced CV3 carbonaceous chondrite.

Here, we report the mineralogy, petrography, C-N-O-stable isotope compositions, degree of disorder of organic matter, and abundances of presolar components of the chondrite Roberts Massif (RBT) 04133 using a coordinated, multitechnique approach. The results of this study are inconsistent with its initial classification as a Renazzo-like carbonaceous chondrite, and strongly support RBT 04133 being a brecciated, reduced petrologic type >3.3 Vigarano-like carbonaceous (CV) chondrite. RBT 04133 shows no evidence for aqueous alteration. However, it is mildly thermally altered (up to approximately 440 °C); which is apparent in its whole-rock C and N isotopic compositions, the degree of disorder of C in insoluble organic matter, low presolar grain abundances, minor element compositions of Fe,Ni metal, chromite compositions and morphologies, and the presence of unequilibrated silicates. Sulfides within type I chondrules from RBT 04133 appear to be pre-accretionary (i.e., did not form via aqueous alteration), providing further evidence that some sulfide minerals formed prior to accretion of the CV chondrite parent body. The thin section studied contains two reduced CV3 lithologies, one of which appears to be more thermally metamorphosed, indicating that RBT 04133, like several other CV chondrites, is a breccia and thus experienced impact processing. Linear foliation of chondrules was not observed implying that RBT 04133 did not experience high velocity impacts that could lead to extensive thermal metamorphism. Presolar silicates are still present in RBT 04133, although presolar SiC grain abundances are very low, indicating that the progressive destruction or modification of presolar SiC grains begins before presolar silicate grains are completely unidentifiable.

Order of amino acid recruitment into the genetic code resolved by Last Universal Common Ancestor's protein domains.

The current "consensus" order in which amino acids were added to the genetic code is based on potentially biased criteria such as absence of sulfur-containing amino acids from the Urey-Miller experiment which lacked sulfur. Even if inferred perfectly, abiotic abundance might not reflect abundance in the organisms in which the genetic code evolved. Here, we instead exploit the fact that proteins that emerged prior to the genetic code's completion are likely enriched in early amino acids and depleted in late amino acids. We identify the most ancient protein-coding sequences born prior to the archaeal-bacterial split. Amino acid usage in protein sequences whose ancestors date back to a single homolog in the Last Universal Common Ancestor (LUCA) largely matches the consensus order. However, our findings indicate that metal-binding (cysteine and histidine) and sulfur-containing (cysteine and methionine) amino acids were added to the genetic code much earlier than previously thought. Surprisingly, even more ancient protein sequences - those that had already diversified into multiple distinct copies in LUCA - show a different pattern to single copy LUCA sequences: significantly less depleted in the late amino acids tryptophan and tyrosine, and enriched rather than depleted in phenylalanine. This is compatible with at least some of these sequences predating the current genetic code. Their distinct enrichment patterns thus provide hints about earlier, alternative genetic codes.

Macromolecular organic matter in samples of the asteroid (162173) Ryugu.

Samples of the carbonaceous asteroid (162173) Ryugu were collected and brought to Earth by the Hayabusa2 spacecraft. We investigated the macromolecular organic matter in Ryugu samples and found that it contains aromatic and aliphatic carbon, ketone, and carboxyl functional groups. The spectroscopic features of the organic matter are consistent with those in chemically primitive carbonaceous chondrite meteorites that experienced parent-body aqueous alteration (reactions with liquid water). The morphology of the organic carbon includes nanoglobules and diffuse carbon associated with phyllosilicate and carbonate minerals. Deuterium and/or nitrogen-15 enrichments indicate that the organic matter formed in a cold molecular cloud or the presolar nebula. The diversity of the organic matter indicates variable levels of aqueous alteration on Ryugu's parent body.

Soluble organic molecules in samples of the carbonaceous asteroid (162173) Ryugu.

The Hayabusa2 spacecraft collected samples from the surface of the carbonaceous near-Earth asteroid (162173) Ryugu and brought them to Earth. The samples were expected to contain organic molecules, which record processes that occurred in the early Solar System. We analyzed organic molecules extracted from the Ryugu surface samples. We identified a variety of molecules containing the atoms CHNOS, formed by methylation, hydration, hydroxylation, and sulfurization reactions. Amino acids, aliphatic amines, carboxylic acids, polycyclic aromatic hydrocarbons, and nitrogen-heterocyclic compounds were detected, which had properties consistent with an abiotic origin. These compounds likely arose from an aqueous reaction on Ryugu's parent body and are similar to the organics in Ivuna-type meteorites. These molecules can survive on the surfaces of asteroids and be transported throughout the Solar System.

Inferring interiors and structural history of top-shaped asteroids from external properties of asteroid (101955) Bennu.

Asteroid interiors play a key role in our understanding of asteroid formation and evolution. As no direct interior probing has been done yet, characterisation of asteroids' interiors relies on interpretations of external properties. Here we show, by numerical simulations, that the top-shaped rubble-pile asteroid (101955) Bennu's geophysical response to spinup is highly sensitive to its material strength. This allows us to infer Bennu's interior properties and provide general implications for top-shaped rubble piles' structural evolution. We find that low-cohesion (≲0.78 Pa at surface and ≲1.3 Pa inside) and low-friction (friction angle ≲ 35∘) structures with several high-cohesion internal zones can consistently account for all the known geophysical characteristics of Bennu and explain the absence of moons. Furthermore, we reveal the underlying mechanisms that lead to different failure behaviours and identify the reconfiguration pathways of top-shaped asteroids as functions of their structural properties that either facilitate or prevent the formation of moons.

Near-zero cohesion and loose packing of Bennu's near subsurface revealed by spacecraft contact.

When the OSIRIS-REx spacecraft pressed its sample collection mechanism into the surface of Bennu, it provided a direct test of the poorly understood near-subsurface physical properties of rubble-pile asteroids, which consist of rock fragments at rest in microgravity. Here, we find that the forces measured by the spacecraft are best modeled as a granular bed with near-zero cohesion that is half as dense as the bulk asteroid. The low gravity of a small rubble-pile asteroid such as Bennu effectively weakens its near subsurface by not compressing the upper layers, thereby minimizing the influence of interparticle cohesion on surface geology. The underdensity and weak near subsurface should be global properties of Bennu and not localized to the contact point.

Assessing the Sampleability of Bennu's Surface for the OSIRIS-REx Asteroid Sample Return Mission.

NASA's first asteroid sample return mission, OSIRIS-REx, collected a sample from the surface of near-Earth asteroid Bennu in October 2020 and will deliver it to Earth in September 2023. Selecting a sample collection site on Bennu's surface was challenging due to the surprising lack of large ponded deposits of regolith particles exclusively fine enough ( ≤ 2 cm diameter) to be ingested by the spacecraft's Touch-and-Go Sample Acquisition Mechanism (TAGSAM). Here we describe the Sampleability Map of Bennu, which was constructed to aid in the selection of candidate sampling sites and to estimate the probability of collecting sufficient sample. "Sampleability" is a numeric score that expresses the compatibility of a given area's surface properties with the sampling mechanism. The algorithm that determines sampleability is a best fit functional form to an extensive suite of laboratory testing outcomes tracking the TAGSAM performance as a function of four observable properties of the target asteroid. The algorithm and testing were designed to measure and subsequently predict TAGSAM collection amounts as a function of the minimum particle size, maximum particle size, particle size frequency distribution, and the tilt of the TAGSAM head off the surface. The sampleability algorithm operated at two general scales, consistent with the resolution and coverage of data collected during the mission. The first scale was global and evaluated nearly the full surface. Due to Bennu's unexpected boulder coverage and lack of ponded regolith deposits, the global sampleability efforts relied heavily on additional strategies to find and characterize regions of interest based on quantifying and avoiding areas heavily covered by material too large to be collected. The second scale was site-specific and used higher-resolution data to predict collected mass at a given contact location. The rigorous sampleability assessments gave the mission confidence to select the best possible sample collection site and directly enabled successful collection of hundreds of grams of material.

Reconstruction of Bennu Particle Events From Sparse Data.

OSIRIS-REx began observing particle ejection events shortly after entering orbit around near-Earth asteroid (101955) Bennu in January 2019. For some of these events, the only observations of the ejected particles come from the first two images taken immediately after the event by OSIRIS-REx's NavCam 1 imager. Without three or more observations of each particle, traditional orbit determination is not possible. However, by assuming that the particles all ejected at the same time and location for a given event, and approximating that their velocities remained constant after ejection (a reasonable approximation for fast-moving particles, i.e., with velocities on the order of 10 cm/s or greater, given Bennu's weak gravity), we show that it is possible to estimate the particles' states from only two observations each. We applied this newly developed technique to reconstruct the particle ejection events observed by the OSIRIS-REx spacecraft during orbit about Bennu. Particles were estimated to have ejected with inertial velocities ranging from 7 cm/s to 3.3 m/s, leading to a variety of trajectory types. Most (>80%) of the analyzed events were estimated to have originated from midlatitude regions and to have occurred after noon (local solar time), between 12:44 and 18:52. Comparison with higher-fidelity orbit determination solutions for the events with sufficient observations demonstrates the validity of our approach and also sheds light on its biases. Our technique offers the capacity to meaningfully constrain the properties of particle ejection events from limited data.

Widespread carbon-bearing materials on near-Earth asteroid (101955) Bennu.

Asteroid (101955) Bennu is a dark asteroid on an Earth-crossing orbit that is thought to have assembled from the fragments of an ancient collision. We use spatially resolved visible and near-infrared spectra of Bennu to investigate its surface properties and composition. In addition to a hydrated phyllosilicate band, we detect a ubiquitous 3.4-micrometer absorption feature, which we attribute to a mix of organic and carbonate materials. The shape and depth of this absorption feature vary across Bennu's surface, spanning the range seen among similar main-belt asteroids. The distribution of the absorption feature does not correlate with temperature, reflectance, spectral slope, or hydrated minerals, although some of those characteristics correlate with each other. The deepest 3.4-micrometer absorptions occur on individual boulders. The variations may be due to differences in abundance, recent exposure, or space weathering.

Prokaryotic and Fungal Characterization of the Facilities Used to Assemble, Test, and Launch the OSIRIS-REx Spacecraft.

To characterize the ATLO (Assembly, Test, and Launch Operations) environment of the OSIRIS-REx spacecraft, we analyzed 17 aluminum witness foils and two blanks for bacterial, archaeal, fungal, and arthropod DNA. Under NASA's Planetary Protection guidelines, OSIRIS-REx is a Category II outbound, Category V unrestricted sample return mission. As a result, it has no bioburden restrictions. However, the mission does have strict organic contamination requirements to achieve its primary objective of returning pristine carbonaceous asteroid regolith to Earth. Its target, near-Earth asteroid (101955) Bennu, is likely to contain organic compounds that are biologically available. Therefore, it is useful to understand what organisms were present during ATLO as part of the larger contamination knowledge effort-even though it is unlikely that any of the organisms will survive the multi-year deep space journey. Even though these samples of opportunity were not collected or preserved for DNA analysis, we successfully amplified bacterial and archaeal DNA (16S rRNA gene) from 16 of the 17 witness foils containing as few as 7 ± 3 cells per sample. Fungal DNA (ITS1) was detected in 12 of the 17 witness foils. Despite observing arthropods in some of the ATLO facilities, arthropod DNA (COI gene) was not detected. We observed 1,009 bacterial and archaeal sOTUs (sub-operational taxonomic units, 100% unique) and 167 fungal sOTUs across all of our samples (25-84 sOTUs per sample). The most abundant bacterial sOTU belonged to the genus Bacillus. This sOTU was present in blanks and may represent contamination during sample handling or storage. The sample collected from inside the fairing just prior to launch contained several unique bacterial and fungal sOTUs that describe previously uncharacterized potential for contamination during the final phase of ATLO. Additionally, fungal richness (number of sOTUs) negatively correlates with the number of carbon-bearing particles detected on samples. The total number of fungal sequences positively correlates with total amino acid concentration. These results demonstrate that it is possible to use samples of opportunity to characterize the microbiology of low-biomass environments while also revealing the limitations imposed by sample collection and preservation methods not specifically designed with biology in mind.

Aqueous corrosion of phosphide minerals from iron meteorites: a highly reactive source of prebiotic phosphorus on the surface of the early Earth.

We present the results of an experimental study of aqueous corrosion of Fe-phosphide under conditions relevant to the early Earth. The results strongly suggest that iron meteorites were an important source of reactive phosphorus (P), a requirement for the formation of P-based life. We further demonstrate that iron meteorites were an abundant source of phosphide minerals early in Earth history. Phosphide corrosion was studied in five different solutions: deionized water, deionized water buffered with sodium bicarbonate, deionized water with dissolved magnesium and calcium chlorides, deionized water containing ethanol and acetic acid, and deionized water containing the chlorides, ethanol, and acetic acid. Experiments were performed in the presence of both air and pure Ar gas to evaluate the effect of atmospheric chemistry. Phosphide corrosion in deionized water results in a metastable mixture of mixed-valence, P-bearing ions including pyrophosphate and triphosphate, key components for metabolism in modern life. In a pH-buffered solution of NaHCO(3), the condensed and reduced species diphosphonate is an abundant corrosion product. Corrosion in ethanol- and acetic acid-containing solutions yields additional P-bearing organic molecules, including acetyl phosphonate and a cyclic triphosphorus molecule. Phosphonate is a major corrosion product of all experiments and is the only P-bearing molecule that persists in solutions with high concentrations of magnesium and calcium chlorides, which suggests that phosphonate may have been a primitive oceanic source of P. The stability and reactivity of phosphonate and hypophosphite in solution were investigated to elucidate reaction mechanisms and the role of mineral catalysts on P-solution chemistry. Phosphonate oxidation is rapid in the presence of Fe metal but negligible in the presence of magnetite and in the control sample. The rate of hypophosphite oxidation is independent of reaction substrate.

Supernova olivine from cometary dust.

An interplanetary dust particle contains a submicrometer crystalline silicate aggregate of probable supernova origin. The grain has a pronounced enrichment in 18O/16O (13 times the solar value) and depletions in 17O/16O (one-third solar) and 29Si/28Si (<0.8 times solar), indicative of formation from a type II supernova. The aggregate contains olivine (forsterite 83) grains <100 nanometers in size, with microstructures that are consistent with minimal thermal alteration. This unusually iron-rich olivine grain could have formed by equilibrium condensation from cooling supernova ejecta if several different nucleosynthetic zones mixed in the proper proportions. The supernova grain is also partially encased in nitrogen-15-rich organic matter that likely formed in a presolar cold molecular cloud.

A nebular origin for chondritic fine-grained phyllosilicates.

Hydrated minerals occur in accretionary rims around chondrules in CM chondrites. Previous models suggested that these phyllosilicates did not form by gas-solid reactions in the canonical solar nebula. We propose that chondrule-forming shock waves in icy regions of the nebula produced conditions that allowed rapid mineral hydration. The time scales for phyllosilicate formation are similar to the time it takes for a shocked system to cool from the temperature of phyllosilicate stability to that of water ice condensation. This scenario allows for simultaneous formation of chondrules and their fine-grained accretionary rims.