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NASA NTRS2012

The Sample Analysis at Mars Investigation and Instrument Suite

The Sample Analysis at Mars (SAM) investigation of the Mars Science Laboratory (MSL) addresses the chemical and isotopic composition of the atmosphere and volatiles extracted from solid samples. The SAM investigation is designed to contribute substantially to the mission goal of quantitatively assessing the habitability of Mars as an essential step in the search for past or present life on Mars. SAM is a 40 kg instrument suite located in the interior of MSL's Curiosity rover. The SAM instruments are a quadrupole mass spectrometer, a tunable laser spectrometer, and a 6-column gas chromatograph all coupled through solid and gas processing systems to provide complementary information on the same samples. The SAM suite is able to measure a suite of light isotopes and to analyze volatiles directly from the atmosphere or thermally released from solid samples. In addition to measurements of simple inorganic compounds and noble gases SAM will conduct a sensitive search for organic compounds with either thermal or chemical extraction from sieved samples delivered by the sample processing system on the Curiosity rover's robotic arm,

Mahaffy, Paul↗
NASA NTRS2017

Distribution of Aliphatic Amines in CO, CV, and CK Carbonaceous Chondrites and Relation to Mineralogy and Processing History

The analysis of water-soluble organic compounds in meteorites provides valuable insights into the prebiotic synthesis of organic matter and the processes that occurred during the formation of the solar system. We investigated the concentration of aliphatic monoamines present in hot acid water extracts of the unaltered Antarctic carbonaceous chondrites, Dominion Range (DOM) 08006 (CO3) and Miller Range (MIL) 05013 (CO3), and the thermally altered meteorites, Allende (CV3), LAP 02206 (CV3), GRA 06101 (CV3), Allan Hills (ALH) 85002 (CK4), and EET 92002 (CK5). We have also reviewed and assessed the petrologic characteristics of the meteorites studied here to evaluate the effects of asteroidal processing on the abundance and molecular distributions of monoamines. The CO3, CV3, CK4, and CK5 meteorites studied here contain total concentrations of amines ranging from 1.2 to 4.0 nmol/g of meteorite; these amounts are 1-3 orders of magnitude below those observed in carbonaceous chondrites from the CI, CM, and CR groups. The low-amine abundances for CV and CK chondrites may be related to their extensive degree of thermal metamorphism and/or to their low original amine content. Although the CO3 meteorites, DOM 08006 and MIL 05013, do not show signs of thermal and aqueous alteration, their monoamine contents are comparable to those observed in moderately/extensively thermally altered CV3, CK4, and CK5 carbonaceous chondrites. The low content of monoamines in pristine CO carbonaceous chondrites suggests that the initial amounts, and not asteroidal processes, play a dominant role in the content of monoamines in carbonaceous chondrites. The primary monoamines, methylamine, ethylamine, and n-propylamine constitute the most abundant amines in the CO3, CV3, CK4, and CK5 meteorites studied here. Contrary to the predominance of n-x-amino acid isomers in CO3 and thermally altered meteorites, there appears to be no preference for the larger n-amines.

mineralogy↗
NASA NTRSDate not supplied

A Cold Wet Mars: A Testable Hypothesis for Ancient Mars Ocean Freezing Point Depression Via Low Molecular Weight Organics

Mars exhibits widespread evidence of surface water in the distant past, but global modeling has had difficulty producing climatological conditions conducive to a wet surface. The hypothesis discussed here examines a different way of approaching the problem rather than focusing on climate, instead an examination of the nature of the surface liquid itself. Previous work has largely assumed that martian surface water was a brine analogous to terrestrial ocean water, but recent discoveries suggest that significant amounts of light organic compounds may have been present via abiogenic native production of light organics on Mars [1]. Light organics such as methanol and formaldehyde have an approximate order-of-magnitude greater freezing point depression than brine, potentially lowering the freezing point of martian surface fluids sufficiently to remain liquid even if the mean surface temperature is below zero Centigrade. As Mars evolved and the surface transitioned to the strongly oxidized conditions seen today, the light organics would have oxidized to carbon dioxide and may be a constituent of the atmosphere today. Considerable work must be done to constrain the freezing points of Mars-relevant organic/water and organic/salt/water mixtures, but this investigation might explain the presence of surface fluid on a cold early Mars – a cold, wet Mars as opposed to a warm, wet Mars. Additionally, this approach may work in conjunction with climatological modeling to better describe early conditions conducive which adequately explain observations. This hypothesis can be tested by examination of ancient fluid inclusions (either in situ or via Mars Sample Return) such as those commonly found in halite, preserving samples of ancient martian surface fluid.

M D Fries↗
NASA NTRS2003

Sample Analysis at Mars

The next landed missions to Mars, such as the planned Mars Science Laboratory and ExoMars, will require sample analysis capabilities refined well beyond what has been flown to date. A key science objective driving this requirement is the determination of the carbon inventory of Mars, and particularly the detection of organic compounds. While the gas chromatograph mass spectrometers (GC/MS) on the Viking landers did not detect any indigenous organics in near surface fines, it is possible that these measurements were not representative of Mars on the whole. That is, those compounds to which the GC/MS was sensitive would likely not have survived the strong oxidative decomposition in the regolith at the landing sites in question. The near surface fines could very well contain a significant quantity of refractory compounds that would not have been volatilized in the sample ovens on Viking. It is also possible that volatile organics exist on Mars in sedimentary, subsurface, or polar niches.

W B Brinckerhoff↗
NASA NTRS2003

Sample Analysis At Mars

The next landed missions to Mars, such as the planned Mars Science Laboratory and ExoMars, will require sample analysis capabilities refined well beyond what has been flown to date. A key science objective driving this requirement is the determination of the carbon inventory of Mars, and particularly the detection of organic compounds. While the gas chromatograph mass spectrometers (GCMS) on the Viking landers did not detect any indigenous organics in near surface fines, it is possible that these measurements were not representative of Mars on the whole. That is, those compounds to which the GC/MS was sensitive would likely not have survived the strong oxidative decomposition in the regolith at the landing sites in question. The near surface fines could very well contain a significant quantity of refractory compounds that would not have been volatilized in the sample ovens on Viking. It is also possible that volatile organics exist on Mars in sedimentary, subsurface, or polar niches.

Brinckerhoff, W. B.↗
NASA NTRS2020

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.

Aaron B. Regberg↗
NASA NTRS2006

Flight Data Update on Long-Term Compound Stability in Dual Sorbent Tubes

Dual Sorbent Tubes (DSTs) are currently the primary method for collecting volatile organic compounds in the cabin air of the International Space Station (ISS). Data from groundbased analysis of these archival air samplers provide a major component of the assessment of ISS air quality by the NASA toxicologist. At the 2005 ICES conference data from the positive control DSTs, returned on Soyuz 7S and 8S, were presented. Positive control tubes are dosed, preflight, with known concentrations of representative contaminant compounds and they are launched to ISS in the DST kit as trip controls. Upon return of the DST kit to the ground, results from analysis of the trip (positive) and laboratory control tubes are used to determine the recoveries: concentration of dosed compounds retained in the tube. Results from positive controls, returned on 7S and 8S showed substantial losses of some compounds dosed into the tubes 156 to 240 days prior to the analysis. Low recoveries are expected for spacecraft air contaminants with similar properties to the poorly recovered dosed compounds. It was shown that compound losses in the control tubes were consistent, which led to the generation of acceptable correction factors for spacecraft air contaminants. Correction factors decrease the accuracy of derived compound concentrations and substantial error could arise under some conditions. An investigation into the mechanism for compound loss is necessary before design modifications can be implemented to improve the DST performance. This paper will update results from the DSTs returned on Soyuz 9S and 10S missions during the latter part of 2005. The data acquired from these returned DSTs will be compared to the 7S and 8S data presented last year. Discussion will focus on the reliability of correction factors and identify any trends in the data. This paper will describe the experimental design and plans to identify the compound loss mechanism.

James, John T.↗
NASA NTRS1999

Lipid synthesis under hydrothermal conditions by Fischer-Tropsch-type reactions

Ever since their discovery in the late 1970's, mid-ocean-ridge hydrothermal systems have received a great deal of attention as a possible site for the origin of life on Earth (and environments analogous to mid-ocean-ridge hydrothermal systems are postulated to have been sites where life could have originated or Mars and elsewhere as well). Because no modern-day terrestrial hydrothermal systems are free from the influence of organic compounds derived from biologic processes, laboratory experiments provide the best opportunity for confirmation of the potential for organic synthesis in hydrothermal systems. Here we report on the formation of lipid compounds during Fischer-Tropsch-type synthesis from aqueous solutions of formic acid or oxalic acid. Optimum synthesis occurs in stainless steel vessels by heating at 175 degrees C for 2-3 days and produces lipid compounds ranging from C2 to > C35 which consist of n-alkanols, n-alkanoic acids, n-alkenes, n-alkanes and alkanones. The precursor carbon sources used are either formic acid or oxalic acid, which disproportionate to H2, CO2 and probably CO. Both carbon sources yield the same lipid classes with essentially the same ranges of compounds. The synthesis reactions were confirmed by using 13C labeled precursor acids.

Non-NASA Center↗
NASA NTRS1979

Simulation of the Viking biology experiments - An overview

In the present paper, ground-based investigations of the Viking Martian biology data, which have resulted in reasonable simulations of these data, are reviewed. These simulations, which in strong oxidants, UV-treated materials, iron-containing clays, or iron salts were used as Martian analogs, are capable of explaining the ambiguity between the GCMS (gas-chromatography mass-spectrometry) experiments, in which no organic compounds were found on Mars, and the Labeled Release experiments, in which added organics were decomposed.

Klein, H. P.↗
NASA NTRS1986

What can meteorites tell us about comets?

Cometary silicates, carbon, and volatiles are reviewed using data from the Halley probes, interplanetary dust particles, and cometary spectra. The origins of anhydrous Fe(2+)-bearing silicates; whether hydrated silicates, if present, were made by gaseous or liquid H2O3; sources of organic compounds: ion-molecule reactions, photochemistry, grain catalysis; sources of CO2 and of organic polymers; and interstellar molecules and grains in comets are discussed.

Anders, Edward↗
NASA NTRS1994

An exobiology science strategy for Mars exploration

Of all the other planets in the solar system, Mars remains the most promising for further elucidating concepts about chemical evolution and the origin of life. Exobiological objectives for Mars exploration include: determining the abundance and distribution of the biogenic elements and organic compounds, detecting evidence of an ancient biota on Mars, and determining whether indigenous organisms exist anywhere on the planet. Both approved and planned missions to Mars were evaluated for their potential to contribute to the understanding of these exobiology science objectives and an exploration strategy was developed for each objective.

Klein, H. P.↗
NASA NTRS1995

Exobiological exploration of Mars

Of all the other planets in the solar system, Mars remains the most promising for further elucidating concepts about chemical evolution and the origin of life. Strategies were developed to pursue three exobiological objectives for Mars exploration: determining the abundance and distribution of the biogenic elements and organic compounds, detecting evidence of an ancient biota on Mars, and determining whether indigenous organisms exist anywhere on the planet. The three strategies are quite similar and, in fact, share the same sequence of phases. In the first phase, each requires global reconnaissance and remote sensing by orbiters to select sites of interest for detailed in situ analyses. In the second phase, lander missions are conducted to characterize the chemical and physical properties of the selected sites. The third phase involves conducting 'critical' experiments at sites whose properties make them particularly attractive for exobiology. These critical experiments would include, for example, identification of organics, detection of fossils, and detection of extant life. The fourth phase is the detailed analysis of samples returned from these sites in Earth-based laboratories to confirm and extend previous discoveries. Finally, in the fifth phase, human exploration is needed to establish the geological settings for the earlier findings or to discover and explore sites that are not accessible to robotic spacecraft.

Klein, H. P.↗
NASA NTRS2000

Meteors: A Delivery Mechanism of Organic Matter to The Early Earth

All potential exogenous pre-biotic matter arrived to Earth by ways of our atmosphere, where much material was ablated during a luminous phase called 1. meteors" in rarefied flows of high (up to 270) Mach number. The recent Leonid showers offered a first glimpse into the elusive physical conditions of the ablation process and atmospheric chemistry associated with high-speed meteors. Molecular emissions were detected that trace a meteor's brilliant light to a 4,300 K warm wake rather than to the meteor's head. A new theoretical approach using the direct simulation by Monte Carlo technique identified the source-region and demonstrated that the ablation process is critical in the heating of the meteor's wake. In the head of the meteor, organic carbon appears to survive flash heating and rapid cooling. The temperatures in the wake of the meteor are just right for dissociation of CO and the formation of more complex organic compounds. The resulting materials could account for the bulk of pre-biotic organic carbon on the early Earth at the time of the origin of life.

Jenniskens, Peter↗
NASA NTRS2004

Atmospheric Tar Balls: Particles from Biomass and Biofuel Burning

Tar balls are amorphous, carbonaceous spherules that occur in the tropospheric aerosol as a result of biomass and biofuel burning. They form a distinct group of particles with diameters typically between 30 and 500 nm and readily identifiable with electron microscopy. Their lack of a turbostratic microstructure distinguishes them from soot, and their morphology and composition (approximately 90 mol% carbon) renders them distinct from other carbonaceous particles. Tar balls are particularly abundant in slightly aged (minutes to hours old) biomass smoke, indicating that they likely form by gas-to-particle conversion within smoke plumes. The material of tar balls is initially hygroscopic; however, the particles become largely insoluble as a result of free radical polymerization of their organic molecules. Consequently, tar balls are primarily externally mixed with other particle types, and they do not appreciably increase in size during aging. When tar balls coagulate with water-bearing particles, their material may partly dissolve and no longer be recognizable as distinct particles. Tar balls may contain organic compounds that absorb sunlight. They are an important, previously unrecognized type of carbonaceous (organic) atmospheric particle.

Posfai, Mihaly↗
NASA NTRS2012

Global Air Quality and Climate

Emissions of air pollutants and their precursors determine regional air quality and can alter climate. Climate change can perturb the long-range transport, chemical processing, and local meteorology that influence air pollution. We review the implications of projected changes in methane (CH4), ozone precursors (O3), and aerosols for climate (expressed in terms of the radiative forcing metric or changes in global surface temperature) and hemispheric-to-continental scale air quality. Reducing the O3 precursor CH4 would slow near-term warming by decreasing both CH4 and tropospheric O3. Uncertainty remains as to the net climate forcing from anthropogenic nitrogen oxide (NOx) emissions, which increase tropospheric O3 (warming) but also increase aerosols and decrease CH4 (both cooling). Anthropogenic emissions of carbon monoxide (CO) and non-CH4 volatile organic compounds (NMVOC) warm by increasing both O3 and CH4. Radiative impacts from secondary organic aerosols (SOA) are poorly understood. Black carbon emission controls, by reducing the absorption of sunlight in the atmosphere and on snow and ice, have the potential to slow near-term warming, but uncertainties in coincident emissions of reflective (cooling) aerosols and poorly constrained cloud indirect effects confound robust estimates of net climate impacts. Reducing sulfate and nitrate aerosols would improve air quality and lessen interference with the hydrologic cycle, but lead to warming. A holistic and balanced view is thus needed to assess how air pollution controls influence climate; a first step towards this goal involves estimating net climate impacts from individual emission sectors. Modeling and observational analyses suggest a warming climate degrades air quality (increasing surface O3 and particulate matter) in many populated regions, including during pollution episodes. Prior Intergovernmental Panel on Climate Change (IPCC) scenarios (SRES) allowed unconstrained growth, whereas the Representative Concentration Pathway (RCP) scenarios assume uniformly an aggressive reduction, of air pollutant emissions. New estimates from the current generation of chemistry-climate models with RCP emissions thus project improved air quality over the next century relative to those using the IPCC SRES scenarios. These two sets of projections likely bracket possible futures. We find that uncertainty in emission-driven changes in air quality is generally greater than uncertainty in climate-driven changes. Confidence in air quality projections is limited by the reliability of anthropogenic emission trajectories and the uncertainties in regional climate responses, feedbacks with the terrestrial biosphere, and oxidation pathways affecting O3 and SOA.

ozone↗
NASA NTRS2019

Role of the Tenax® Adsorbent in the Interpretation of the EGA and GC‐MS Analyses Performed With the Sample Analysis at Mars in Gale Crater

The Sample Analysis at Mars (SAM) experiment on the National Aeronautics and Space Administration Curiosity rover seeks evidence of organic compounds on the surface of Mars. Since the beginning of the mission, various organic molecules have been detected and identified. While several have been demonstrated to be indigenous to the Martian soil and rocks analyzed, others appear to have been produced from sources internal to the experiment. The objective of this study is to build an exhaustive molecular database to support the interpretation of SAM results by identifying all the chemical species produced from Tenax® adsorbents, by determining (1) the thermal degradation by‐products of Tenax®, (2) the effect of Tenax® conditioning on the formation of Tenax® by‐products, (3) the impact of MTBSTFA or a mixture of MTBSTFA and DMF on Tenax® decomposition, and (4) the reaction between Tenax® and calcium perchlorate. Our results indicate that the by‐products of the SAM trap are due to the impact of trap heating, the impact of the derivatization reagent (MTBSTFA) and the presence of perchlorate in Martian soil. Some of these by‐products are observed in the SAM gas chromatograph mass spectrometer data from Mars.

Buch, A.↗
NASA NTRSDate not supplied

The Search for Chiral Asymmetry as a Potential Biosignature in Samples from Mars

The search for evidence of extraterrestrial life in our solar system is currently guided by our understanding of terrestrial biology and its associated biosignatures. The observed homochirality in all life on Earth, that is, the predominance of “left-handed” or L-amino acids and “right-handed” or D-sugars, is a unique property of life that is crucial for molecular recognition, enzymatic function, information storage and structure and is thought to be a prerequisite for the origin or early evolution of life. Therefore, the detection of L- or D-enantiomeric excesses of chiral amino acids and sugars could be a powerful indicator of extant or extinct life on Mars or other habitable environments in our solar system. The exploration of habitable environments on Mars, including an assessment of the preservation potential for complex organics of either abiotic or biological origin, remains a key goal of both current and future Mars missions. Now with the unambiguous detection of indigenous organic matter in sedimentary rocks on Mars [1-3], NASA’s Curiosity rover has significantly advanced our understanding of the preservation of potential chemical biosignatures in the martian near surface. Although amino acids have not yet been identified by in situ measurements on Mars, if they were present, it is expected that amino acid hydrolysis and racemization would be very slow and any chiral or isotopic signatures from an extinct martian biota could be preserved for billions of years, given the extremely cold and dry surface conditions [4]. One of ESA’s Rosalind Franklin rover payload instruments called the Mars Organic Molecule Analyzer (MOMA) includes a wet chemistry package capable of measuring the enantiomeric ratios of any chiral amino acids present at part-per-million concentrations or higher [5]. The complexity and limited duration of spaceflight operations and the known analytical challenges associated with in situ extraction and characterization of trace reduced organic compounds in ancient rocks make it challenging to determine the origins of martian organic matter found to date. Coordinated state-of-the-art laboratory measurements of returned samples from Mars that include spatially resolved chemical, mineralogical, and isotopic studies and molecule-specific isotopic and enantiomeric measurements will be required to firmly establish whether the complex organic matter detected on Mars comes from biotic or abiotic sources. Ultimately, sample return may be our best chance of identifying chemical biosignatures from a past or present martian biota, if one ever existed on Mars. NASA’s Perseverance rover will collect dozens of surface sample cores for possible future return to Earth by NASA and ESA. Here we review our current knowledge of the distributions and enantiomeric and isotopic compositions of non-biological amino acids found in meteorites compared to terrestrial biochemistry and propose a set of measurement criteria that should be used to help establish the origin of any chiral asymmetry detected in samples from Mars [6].

Daniel P Glavin↗