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. Rocks and dust from the asteroid Bennu contain some of the molecular building blocks of life on Earth, such as amino acids and nucleobases. They also carry ammonia that formed billions of years ago in cold, distant regions of our Solar System.
The search for organic molecules on Mars is central to understanding the planet's past habitability and potential for ancient life. Although organic molecules have previously been detected on Mars, their nature, origin and preservation mechanisms remain debated. On the floor of the Jezero crater-an ancient delta-lake system on Mars-the Perseverance rover detected Raman features that may be due to organic compounds spatially associated with sulfates, although their origin is uncertain. Here we report the detection of similar Raman features in the Jezero fan top and attribute them to polycyclic aromatic hydrocarbons based on comparisons with laboratory data. We propose that these polycyclic aromatic hydrocarbons may have formed through endogenous igneous processes and were subsequently preserved by sulfate precipitation. These findings align with previous studies on Martian meteorites and at Gale crater, underscoring the role of sulfates in preserving organic matter on Mars. Returning these samples to Earth would be key to assess their astrobiological relevance.
The Perseverance rover landed at Jezero Crater, Mars, on 18 February 2021, with a payload of scientific instruments to examine Mars' past habitability, look for signs of past life, and process samples for future return to Earth. The instrument payload includes the Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) deep ultraviolet Raman and fluorescence imaging spectrometer designed to detect, characterize, and map the presence of organics and minerals on the Martian surface. Operation and engineering constraints sometimes result in the acquisition of spectra with features near the detection limit. It is therefore important to separate instrumental (background) spectral components and spectral components inherent to Martian surface materials. For SHERLOC, the instrumental background is assessed by collecting spectra in the stowed-arm configuration where the instrument is pointed at the Martian nighttime sky with no surface sample present in its optical path. These measurements reveal weak Raman and fluorescence background spectral signatures as well as charged-coupled device pixels prone to erroneous intensity spikes separate from cosmic rays. We quantitatively describe these features and provide a subtraction procedure to remove the spectral background from surface spectra. By identifying and accounting for the SHERLOC Raman background features within the median Raman spectra of Martian target scans, we find that the undefined silicate spectral feature interpreted to be either amorphous silicate or plagioclase feldspar is ubiquitously found in every Mars target Raman scan collected through Sol 751.
This study analyzed samples of the Murchison and Sutter's Mill carbonaceous chondrite meteorites in support of the future analysis of samples returned from the asteroid (10155) Bennu by the OSIRIS-REx (Origins, Spectral Interpretation, Resource Identification, and Security-Regolith Explorer) mission. Focusing specifically on the insoluble organic matter (IOM), this study establishes that a total of 1.3 g of bulk sample from a single chondritic meteorite are sufficient to obtain a wide range of cosmochemical information, including light element analysis (H, C, and N), isotopic analysis (D/H, 13C/12C, and 15N/14N), and x-ray fluorescence spectroscopy for major elemental abundances. IOM isolated from the bulk meteorite samples was analyzed by light element and isotopic analysis as described above, 1H and 13C solid-state nuclear magnetic resonance spectroscopy, Raman spectroscopy, and complete noble gas analyses (abundances and isotopes). The samples studied included a pair from Murchison (CM2), one of which had been irradiated with high-energy x-rays in the course of computed tomographic imaging. No differences between the irradiated and non-irradiated Murchison samples were observed in the many different chemical and spectroscopic analyses, indicating that any x-ray-derived sample damage is below levels of detection. Elemental, isotopic, and molecular spectroscopic data derived from IOM isolated from the Sutter's Mill sample reveals evidence that this meteorite falls into the class of heated CM chondrites.
Sulfur plays a major role in martian geochemistry and sulfate minerals are important repositories of water. However, their hydration states on Mars are poorly constrained. Therefore, understanding the hydration and distribution of sulfate minerals on Mars is important for understanding its geologic, hydrologic, and atmospheric evolution as well as its habitability potential. NASA's Perseverance rover is currently exploring the Noachian-age Jezero crater, which hosts a fan-delta system associated with a paleolake. The crater floor includes two igneous units (the Seitah and Maaz formations), both of which contain evidence of later alteration by fluids including sulfate minerals. Results from the rover instruments Scanning Habitable Environments with Raman and Luminescence for Organics and Chemistry and Planetary Instrument for X-ray Lithochemistry reveal the presence of a mix of crystalline and amorphous hydrated Mg-sulfate minerals (both MgSO4 center dot[3-5]H2O and possible MgSO4 center dot H2O), and anhydrous Ca-sulfate minerals. The sulfate phases within each outcrop may have formed from single or multiple episodes of water activity, although several depositional events seem likely for the different units in the crater floor. Textural and chemical evidence suggest that the sulfate minerals most likely precipitated from a low temperature sulfate-rich fluid of moderate pH. The identification of approximately four waters puts a lower constraint on the hydration state of sulfate minerals in the shallow subsurface, which has implications for the martian hydrological budget. These sulfate minerals are key samples for future Mars sample return. The history of water on Mars is a puzzle that is of interest to scientists as well as the general public. Mars currently has water in the form of ice at the poles, trace amounts of gas in the atmosphere, and an unknown amount beneath the surface as ground water, bound in minerals, and in ice. However, there is strong evidence that ancient Mars may have had long-lived streams, rivers, and lakes. There is still much to learn about what Mars was like and how it transformed over time. One approach is to study the inventory of water at different times. In this work, we report the presence of hydrated magnesium sulfate (similar to Epsom salts) and dehydrated calcium sulfate that were formed by water flowing through cracks in volcanic rocks at the bottom of the 3.8-billion-year-old Jezero crater. These hydrated minerals trap water within themselves and record the history of how and when they formed. Returning samples of these minerals to Earth would allow researchers to explore the history of Mars' water and climate, and possibly evidence of ancient life with the most sensitive instruments possible. Sulfate phases detected by Scanning Habitable Environments with Raman and Luminescence for Organics and Chemistry and PIXL in igneous units consists of crystalline/amorphous Mg-sulfate minerals with 3-5 waters and anhydrous Ca-sulfate minerals Hydration of sulfate minerals sets a lower constraint on how much subsurface water is stored in sulfate minerals The sulfate minerals of Jezero crater floor were deposited in moderate pH, likely at low temperature, and during several episodes
X-ray computed tomography (XCT) is a valuable reconnaissance tool for three-dimensional imaging and identification of distinct lithologies in extraterrestrial samples. It will be used as part of the preliminary examination of samples returned from asteroid (101955) Bennu by the Origins, Spectral Interpretation, Resource Identification, and Security-Regolith Explorer (OSIRIS-REx) mission. However, it must first be established whether x-rays generated during XCT could degrade or alter the organic composition of the returned samples by radiolysis. To test this, we split a crushed sample of the Murchison CM2 meteorite, kept one portion as a control, and irradiated the other portion up to the maximum x-ray dosage (similar to 180 Gy) that a Bennu sample would experience during an XCT imaging experiment. We then extracted organic compounds from both splits and conducted (i) nontargeted soluble organic analyses to compare the chemical distributions of C-, H-, O-, N-, and S-bearing species and (ii) targeted measurements to quantify the abundances of 96 individual soluble organic molecules that included protein amino acids, amines, carboxylic acids, hydroxy acids, carbonyl compounds, polycyclic aromatic hydrocarbons, alcohols, sugars, and N-heterocycles. We found that XCT imaging of the Murchison meteorite had no measurable impact on the relative abundances or enantiomeric compositions of most of the soluble organic compounds targeted in this study. Elevated total abundances of several soluble organic compound classes were observed in the XCT-scanned Murchison sample relative to the control. This is likely related to particle size heterogeneity and specific surface area differences between the sample aliquots used for the extractions, rather than a result of the x-ray exposure. Assuming the samples returned from asteroid Bennu by OSIRIS-REx have a similar composition to carbonaceous chondrites, these data provide confidence that XCT will not significantly alter their soluble organic compositions.
The 2-week, virtual Future of the Search for Life science and engineering workshop brought together more than 100 scientists, engineers, and technologists in March and April 2022 to provide their expert opinion on the interconnections between life-detection science and technology. Participants identified the advances in measurement and sampling technologies they believed to be necessary to perform in situ searches for life elsewhere in our Solar System, 20 years or more in the future. Among suggested measurements for these searches, those pertaining to three potential indicators of life termed "dynamic disequilibrium," "catalysis," and "informational polymers" were identified as particularly promising avenues for further exploration. For these three indicators, small breakout groups of participants identified measurement needs and knowledge gaps, along with corresponding constraints on sample handling (acquisition and processing) approaches for a variety of environments on Enceladus, Europa, Mars, and Titan. Despite the diversity of these environments, sample processing approaches all tend to be more complex than those that have been implemented on missions or envisioned for mission concepts to date. The approaches considered by workshop breakout groups progress from nondestructive to destructive measurement techniques, and most involve the need for fluid (especially liquid) sample processing. Sample processing needs were identified as technology gaps. These gaps include technology and associated sampling strategies that allow the preservation of the thermal, mechanical, and chemical integrity of the samples upon acquisition; and to optimize the sample information obtained by operating suites of instruments on common samples. Crucially, the interplay between science-driven life-detection strategies and their technological implementation highlights the need for an unprecedented level of payload integration and extensive collaboration between scientists and engineers, starting from concept formulation through mission deployment of life-detection instruments and sample processing systems.
The salt-induced peptide formation (SIPF) reaction is a prebiotically plausible mechanism for the spontaneous polymerization of amino acids into peptides on early Earth. Experimental investigations of the SIPF reaction have found that in certain conditions, the l enantiomer is more reactive than the d enantiomer, indicating its potential role in the rise of biohomochirality. Previous work hypothesized that the distortion of the CuCl active complex toward a tetrahedral-like structure increases the central chirality on the Cu ion, which amplifies the inherent parity-violating energy differences between l- and d-amino acid enantiomers, leading to stereoselectivity. Computational evaluations of this theory have been limited to the protonated–neutral l + l forms of the CuCl active complex. Here, density functional theory methods were used to compare the energies and geometries of the homochiral (l + l and d + d) and heterochiral (l + d) CuCl–amino acid complexes for both the positive–neutral and neutral–neutral forms for alanine, valine, and proline. Significant energy differences were not observed between different chiral active complexes (i.e., d + d, l + l vs. l + d), and the distortions of active complexes between stereoselective systems and non-selective systems were not consistent, indicating that the geometry of the active complex is not the primary driver of the observed stereoselectivity of the SIPF reaction.
The presence and distribution of preserved organic matter on the surface of Mars can provide key information about the Martian carbon cycle and the potential of the planet to host life throughout its history. Several types of organic molecules have been previously detected in Martian meteorites 1 and at Gale crater, Mars 2 – 4 . Evaluating the diversity and detectability of organic matter elsewhere on Mars is important for understanding the extent and diversity of Martian surface processes and the potential availability of carbon sources 1 , 5 , 6 . Here we report the detection of Raman and fluorescence spectra consistent with several species of aromatic organic molecules in the Máaz and Séítah formations within the Crater Floor sequences of Jezero crater, Mars. We report specific fluorescence-mineral associations consistent with many classes of organic molecules occurring in different spatial patterns within these compositionally distinct formations, potentially indicating different fates of carbon across environments. Our findings suggest there may be a diversity of aromatic molecules prevalent on the Martian surface, and these materials persist despite exposure to surface conditions. These potential organic molecules are largely found within minerals linked to aqueous processes, indicating that these processes may have had a key role in organic synthesis, transport or preservation.
The goals of NASA's Mars 2020 mission include searching for evidence of ancient life on Mars, studying the geology of Jezero crater, understanding Mars' current and past climate, and preparing for human exploration of Mars. During the mission's first science campaign, the Perseverance rover's SHERLOC deep UV Raman and fluorescence instrument collected microscale, two-dimensional Raman and fluorescence images on 10 natural (unabraded) and abraded targets on two different Jezero crater floor units: Seitah and Maaz. We report SHERLOC Raman measurements collected during the Crater Floor Campaign and discuss their implications regarding the origin and history of Seitah and Maaz. The data support the conclusion that Seitah and Maaz are mineralogically distinct igneous units with complex aqueous alteration histories and suggest that the Jezero crater floor once hosted an environment capable of supporting microbial life and preserving evidence of that life, if it existed.
The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) is a robotic arm-mounted instrument onboard NASA's Perseverance rover. SHERLOC combines imaging via two cameras with both Raman and fluorescence spectroscopy to investigate geological materials at the rover's Jezero crater field site. SHERLOC requires in situ calibration to monitor the health and performance of the instrument. These calibration data are critically important to ensure the veracity of data interpretation, especially considering the extreme martian environmental conditions where the instrument operates. The SHERLOC Calibration Target (SCT) is located at the front of the rover and is exposed to the same atmospheric conditions as the instrument. The SCT includes 10 individual targets designed to meet all instrument calibration requirements. An additional calibration target is mounted inside the instrument's dust cover. The targets include polymers, rock, synthetic material, and optical pattern targets. Their primary function is calibration of parameters within the SHERLOC instrument so that the data can be interpreted correctly. The SCT was also designed to take advantage of opportunities for supplemental science investigations and includes targets intended for public engagement. The exposure of materials to martian atmospheric conditions allows for opportunistic science on extravehicular suit (i.e., "spacesuit") materials. These samples will be used in an extended study to produce direct measurements of the expected service lifetimes of these materials on the martian surface, thus helping NASA facilitate human exploration of the planet. Other targets include a martian meteorite and the first geocache target to reside on another planet, both of which increase the outreach and potential of the mission to foster interest in, and enthusiasm for, planetary exploration. During the first 200 sols (martian days) of operation on Mars, the SCT has been analyzed three times and has proven to be vital in the calibration of the instrument and in assisting the SHERLOC team with interpretation of in situ data.
Using high-resolution atomic force microscopy (AFM) with CO-functionalized tips, we atomically resolved individual molecules from Murchison meteorite samples. We analyzed powdered Murchison meteorite material directly, as well as processed extracts that we prepared to facilitate characterization by AFM. From the untreated Murchison sample, we resolved very few molecules, as the sample contained mostly small molecules that could not be identified by AFM. By contrast, using a procedure based on several trituration and extraction steps with organic solvents, we isolated a fraction enriched in larger organic compounds. The treatment increased the fraction of molecules that could be resolved by AFM, allowing us to identify organic constituents and molecular moieties, such as polycyclic aromatic hydrocarbons and aliphatic chains. The AFM measurements are complemented by high-resolution mass spectrometry analysis of Murchison fractions. We provide a proof of principle that AFM can be used to image and identify individual organic molecules from meteorites and propose a method for extracting and preparing meteorite samples for their investigation by AFM. We discuss the challenges and prospects of this approach to study extraterrestrial samples based on single-molecule identification.
The Committee on Space Research (COSPAR) Sample Safety Assessment Framework (SSAF) has been developed by a COSPAR appointed Working Group. The objective of the sample safety assessment would be to evaluate whether samples returned from Mars could be harmful for Earth's systems (e.g., environment, biosphere, geochemical cycles). During the Working Group's deliberations, it became clear that a comprehensive assessment to predict the effects of introducing life in new environments or ecologies is difficult and practically impossible, even for terrestrial life and certainly more so for unknown extraterrestrial life. To manage expectations, the scope of the SSAF was adjusted to evaluate only whether the presence of martian life can be excluded in samples returned from Mars. If the presence of martian life cannot be excluded, a Hold & Critical Review must be established to evaluate the risk management measures and decide on the next steps. The SSAF starts from a positive hypothesis (there is martian life in the samples), which is complementary to the null-hypothesis (there is no martian life in the samples) typically used for science. Testing the positive hypothesis includes four elements: (1) Bayesian statistics, (2) subsampling strategy, (3) test sequence, and (4) decision criteria. The test sequence capability covers self-replicating and non-self-replicating biology and biologically active molecules. Most of the investigations associated with the SSAF would need to be carried out within biological containment. The SSAF is described in sufficient detail to support planning activities for a Sample Receiving Facility (SRF) and for preparing science announcements, while at the same time acknowledging that further work is required before a detailed Sample Safety Assessment Protocol (SSAP) can be developed. The three major open issues to be addressed to optimize and implement the SSAF are (1) setting a value for the level of assurance to effectively exclude the presence of martian life in the samples, (2) carrying out an analogue test program, and (3) acquiring relevant contamination knowledge from all Mars Sample Return (MSR) flight and ground elements. Although the SSAF was developed specifically for assessing samples from Mars in the context of the currently planned NASA-ESA MSR Campaign, this framework and the basic safety approach are applicable to any other Mars sample return mission concept, with minor adjustments in the execution part related to the specific nature of the samples to be returned. The SSAF is also considered a sound basis for other COSPAR Planetary Protection Category V, restricted Earth return missions beyond Mars. It is anticipated that the SSAF will be subject to future review by the various MSR stakeholders.
The Perseverance rover landed in Jezero crater, Mars, in February 2021. We used the Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument to perform deep-ultraviolet Raman and fluorescence spectroscopy of three rocks within the crater. We identify evidence for two distinct ancient aqueous environments at different times. Reactions with liquid water formed carbonates in an olivine-rich igneous rock. A sulfate-perchlorate mixture is present in the rocks, which probably formed by later modifications of the rocks by brine. Fluorescence signatures consistent with aromatic organic compounds occur throughout these rocks and are preserved in minerals related to both aqueous environments.
Chirality is a central feature in the evolution of biological systems, but the reason for biology’s strong preference for specific chiralities of amino acids, sugars, and other molecules remains a controversial and unanswered question in origins of life research. Biological polymers tend toward homochiral systems, which favor the incorporation of a single enantiomer (molecules with a specific chiral configuration) over the other. There have been numerous investigations into the processes that preferentially enrich one enantiomer to understand the evolution of an early, racemic, prebiotic organic world. Chirality can also be a property of minerals; their interaction with chiral organics is important for assessing how post-depositional alteration processes could affect the stereochemical configuration of simple and complex organic molecules. In this paper, we review the properties of organic compounds and minerals as well as the physical, chemical, and geological processes that affect organic and mineral chirality during the preservation and detection of organic compounds. We provide perspectives and discussions on the reactions and analytical techniques that can be performed in the laboratory, and comment on the state of knowledge of flight-capable technologies in current and future planetary missions, with a focus on organics analysis and life detection.
Interplanetary dust is a scientifically important constituent of the Solar System that consists of material shed by asteroids, comets, and other airless bodies.As used here, the term "dust" includes interplanetary dust particles and micrometeoroids.Dust has been studied by missions such as Mariner, Pioneer, and Voyager in both interplanetary space and in the vicinity of most of the planets.To date, however, no dedicated interplanetary dust instrument has yet been employed for detailed analysis of the dust environment of Mars.Partial data on dust flux has been provided by the 1965 Mariner IV flyby, the MAVEN orbiter, and other missions, but a complete understanding of interplanetary dust abundance, composition, debris hazard, annual flux variation, and origins is lacking.These data are critical for understanding the effects of dust upon the martian system, including the carbonaceous input into the regolith of Mars and its moons, the chemical input into the martian atmosphere, potential effects upon remote sensing data, the hypothesized existence of a Phobos dust ring, and possible annual variations from meteor shower infall.These effects have direct ramifications for interpretation of Mars/Phobos/Deimos mission science and analysis of returned samples from those worlds.To remediate this shortfall, the authors recommend that a dedicated interplanetary dust analysis instrument should be included in the instrument package for an upcoming martian orbiter in the near term.Such an interplanetary dust analysis instrument should collect data over a time period of several martian years in order to generate a statistically robust data set on interplanetary dust concentration and flux over a wide range of mass, and to discern temporal variation over multiple martian years.
We describe the wavelength calibration of the spectrometer for the scanning of habitable environments with Raman and luminescence for organics and chemicals (SHERLOC) instrument onboard NASA’s Perseverance Rover. SHERLOC utilizes deep ultraviolet Raman and fluorescence (DUV R/F) spectroscopy to enable analysis of samples from the Martian surface. SHERLOC employs a 248.6 nm deep ultraviolet laser to generate Raman-scattered photons and native fluorescence emission photons from near-surface material to detect and classify chemical and mineralogical compositions. The collected photons are focused on a charge-coupled device and the data are returned to Earth for analysis. The compact DUV R/F spectrometer has a spectral range from 249.9 nm to 353.6 nm (∼200 cm −1 to 12, 000 cm −1 ) (with a spectral resolution of 0.296 nm (∼40 cm −1 )). The compact spectrometer uses a custom design to project a high-resolution Raman spectrum and a low-resolution fluorescence spectrum on a single charge-coupled device. The natural spectral separation enabled by deep ultraviolet excitation enables wavelength separation of the Raman/fluorescence spectra. The SHERLOC spectrometer was designed to optimize the resolution of the Raman spectral region and the wavelength range of the fluorescence region. The resulting illumination on the charge-coupled device is curved, requiring a segmented, nonlinear wavelength calibration in order to understand the mineralogy and chemistry of Martian materials.
For the past two decades, microbial monitoring of the International Space Station (ISS) has relied on culture-dependent methods that require return to Earth for analysis. This has a number of limitations, with the most significant being bias towards the detection of culturable organisms and the inherent delay between sample collection and ground-based analysis. In recent years, portable and easy-to-use molecular-based tools, such as Oxford Nanopore Technologies' MinION™ sequencer and miniPCR bio's miniPCR™ thermal cycler, have been validated onboard the ISS. Here, we report on the development, validation, and implementation of a swab-to-sequencer method that provides a culture-independent solution to real-time microbial profiling onboard the ISS. Method development focused on analysis of swabs collected in a low-biomass environment with limited facility resources and stringent controls on allowed processes and reagents. ISS-optimized procedures included enzymatic DNA extraction from a swab tip, bead-based purifications, altered buffers, and the use of miniPCR and the MinION. Validation was conducted through extensive ground-based assessments comparing current standard culture-dependent and newly developed culture-independent methods. Similar microbial distributions were observed between the two methods; however, as expected, the culture-independent data revealed microbial profiles with greater diversity. Protocol optimization and verification was established during NASA Extreme Environment Mission Operations (NEEMO) analog missions 21 and 22, respectively. Unique microbial profiles obtained from analog testing validated the swab-to-sequencer method in an extreme environment. Finally, four independent swab-to-sequencer experiments were conducted onboard the ISS by two crewmembers. Microorganisms identified from ISS swabs were consistent with historical culture-based data, and primarily consisted of commonly observed human-associated microbes. This simplified method has been streamlined for high ease-of-use for a non-trained crew to complete in an extreme environment, thereby enabling environmental and human health diagnostics in real-time as future missions take us beyond low-Earth orbit.