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Glavin, D. P.

Publications and source records attributed to Glavin, D. P..

At least 19 records

Analysis of Volatile Organic Compounds in the Apollo Next Generation Sample Analysis (ANGSA) 73002 Core Sample

Understanding the organic content of lunar regolith was an early priority upon the return of Apollo samples, with amino acids being of special interest because of their importance to life on Earth and their astrobiological relevance. Many initial studies focused on the detection of amino acids in these samples and attempts to determine the origin of those compounds. Although no consensus on the origin of the amino acids was reached in those early studies, more recent work determined that the detected amino acids originated from both terrestrial contamination and meteoritic or cometary in fall to the lunar surface. A majority of the amino acids in the Apollo samples studied originated from precursor molecules, either indigenous to the lunar samples or contaminants, that reacted during the water extraction and acid hydrolysis process for analysis in the laboratory, but the identities of the amino acid precursors still remain poorly understood. Such precursors could include hydrogen cyanide (HCN) and other volatile organic compounds such as amines, carboxylic acids, or aldehydes and ketones. The identities of these compounds, as well as the effects of years of curation on their abundances in lunar regolith samples stored at ambient temperature under nitrogen gas purge, are not clear. The specially curated samples available through the Apollo Next Generation Sample Analysis (ANGSA) program provide a unique opportunity to use state-of- the-art analytical techniques to examine previously unstudied lunar materials. The ANGSA samples include three types of samples: 1) samples stored frozen since <1 month after Earth arrival; 2) samples stored under helium; and 3) a double drive tube collected by Apollo 17 astronauts, with the bottom portion of the drive tube sealed under vacuum on the Moon and never opened. In contrast to the typically curated Apollo samples that have been kept for decades at room temperature under flowing nitrogen purge that may have significantly reduced the abundance of volatiles, the vacuum-sealed and frozen samples may have enhanced preservation of these volatiles. Our initial investigation examines amino acids and their potential volatile precursors, including hydrogen cyanide (HCN), aldehydes, ketones, amines, and mono-carboxylic acids, in a sample from the top portion of the Apollo 17 double drive tube. These results will aid in understanding the lunar abundances of these molecules and will also be compared to future analyses of other drive tube and frozen ANGSA samples.

Elsila, J. E.

Episodes of Particle Ejection from the Surface of the Active Asteroid (101955) Bennu

Active asteroids are those that show evidence of ongoing mass loss. We report repeated instances of particle ejection from the surface of (101955) Bennu, demonstrating that it is an active asteroid. The ejection events were imaged by the OSIRIS-REx (Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer) spacecraft. For the three largest observed events, we estimated the ejected particle velocities and sizes, event times, source regions, and energies. We also determined the trajectories and photometric properties of several gravitationally bound particles that orbited temporarily in the Bennu environment. We consider multiple hypotheses for the mechanisms that lead to particle ejection for the largest events, including rotational disruption, electrostatic lofting, ice sublimation, phyllosilicate dehydration, meteoroid impacts, thermal stress fracturing, and secondary impacts.

Lauretta, D. S.

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.

The CAESAR New Frontiers Mission: 1. Expected Nature of the Returned Comet Sample

Comets are time capsules from the birth of our Solar System that record pre-solar history, the initial stages of planet formation, and the sources of prebiotic organics and volatiles for the origin of life. These capsules can only be opened in laboratories on Earth. CAESAR (Comet Astrobiology Exploration Sample Return)’s sample analysis objectives are to understand the nature of Solar System starting materials and how these components came together to form planets and give rise to life. Examination of these comet nucleus surface samples in laboratories around the world will also provide ground truth to remote observations of the innumerable icy bodies of the Solar System.

Lauretta, D. S.

Oxychlorine Detection in Gale Crater, Mars and Implications for Past Environmental Conditions

The Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) rover Curiosity has analyzed 3 scooped samples and 15 drilled samples since landing in 2012. Oxychlorine compounds (perchlorate/chlorate) were detected in the first 9 drilled samples but have not been detected in the last 6, starting with the Oudam sample in the Hartmann’s Valley member of the Murray formation (Table 1). Scooped samples have all contained detectable oxychlorine. These results suggest that oxychlorine formation and preservation spans the geologic record on Mars but has not been uniform spatially or temporally.

Archer, P. D., Jr.

The CAESAR New Frontiers Mission: Comet Surface Sample Acquisition and Preservation

NASA recently selected the Comet Astrobiology Exploration Sample Return (CAESAR) mission for Phase A study in the New Frontiers Program. This mission will acquire and return to Earth for laboratory analysis at least 80 g of surface material from the nucleus of comet 67P/Churyumov-Gerasimenko (hereafter 67P). CAESAR will characterize the surface region sampled, preserve the sample in a pristine state, and return evolved volatiles by capturing them in a separate gas reservoir. The system protects both volatile and non-volatile components from contamination or alteration thatwould hamper their scientific analysis. Laboratory analyses of comet samples provide unparalleled knowledge about the presolar history through the initial stages of planet formation to the origin of life.

CAESAR

The Origin and Evolution of Organic Matter in Carbonaceous Chondrites and Links to Their Parent Bodies

The nature of organic matter in meteorites reveals information about early solar system chemistry and the histories of parent bodies as recorded in the effects of physical and chemical processes that occurred over the past 4.5 billion years. Asteroids and their fragments impact the Earth with approximately 40 million kg of material each year and contributed to the inventory of organics available for the origin of life. Analyses of primitive carbonaceous chondrites over the last five decades have revealed a major insoluble organic component, as well as a complex and highly diverse suite of soluble organic molecules that includes aliphatic and aromatic hydrocarbons, carboxylic acids, hydroxy acids, N-heterocycles, polyols, amino acids, amines, and many other molecules that have not yet been identified. Thermal and aqueous alteration in primitive asteroids played an important role in the formation and destruction organics, including amplification of L-amino acid and D-sugar acid enantiomeric excesses that may have contributed to the origin of homochirality in life on Earth.

Chondrites

Seeking Signs of Life on Mars: A Strategy for Selecting and Analyzing Returned Samples from Hydrothermal Deposits

Highly promising locales for biosignature prospecting on Mars are ancient hydrothermal deposits, formed by the interaction of surface water with heat from volcanism or impacts. On Earth, they occur throughout the geological record (to at least approx. 3.5 Ga), preserving robust mineralogical, textural and compositional evidence of thermophilic microbial activity. Hydrothermal systems were likely present early in Mars' history, including at two of the three finalist candidate landing sites for M2020, Columbia Hills and NE Syrtis Major. Hydrothermal environments on Earth's surface are varied, constituting subaerial hot spring aprons, mounds and fumaroles; shallow to deep-sea hydrothermal vents (black and white smokers); and vent mounds and hot-spring discharges in lacustrine and fluvial settings. Biological information can be preserved by rapid, spring-sourced mineral precipitation, but also could be altered or destroyed by postdepositional events. Thus, field observations need to be followed by detailed laboratory analysis to verify potential biosignatures. See Attachment

Campbell, K. A.

Seeking Signs of Life on Mars: the Importance of Sedimentary Suites as Part of a Mars Sample Return Campaign

Seeking the signs of life on Mars is often considered the "first among equal" objectives for any potential Mars Sample Return (MSR) campaign. Among the geological settings considered to have the greatest potential for recording evidence of ancient life or its pre-biotic chemistry on Mars are lacustrine (and marine, if ever present) sedimentary depositional environments. This potential, and the possibility of returning samples that could meaningfully address this objective, have been greatly enhanced by investigations of an ancient redox stratified lake system in Gale crater by the Curiosity rover.

Mangold, N.

Indigenous Amino Acids in Iron Meteorites

Understanding the organic content of meteorites and the potential delivery of molecules relevant to the origin of life on Earth is an important area of study in astrobiology. There have been many studies of meteoritic organics, with much focus on amino acids as monomers of proteins and enzymes essential to terrestrial life. The majority of these studies have involved analysis of carbonaceous chondrites, primitive meteorites containing approx. 3-5 wt% carbon. Amino acids have been observed in varying abundances and distributions in representatives of all eight carbonaceous chondrite groups, as well as in ungrouped carbonaceous chondrites, ordinary and R chondrites, ureilites, and planetary achondrites [1 and references therein].

carbonaceous chondrites

OSIRIS-REx Contamination Control Strategy and Implementation

OSIRIS-REx will return pristine samples of carbonaceous asteroid Bennu. This article describes how pristine was defined based on expectations of Bennu and on a realistic understanding of what is achievable with a constrained schedule and budget, and how that definition flowed to requirements and implementation. To return a pristine sample, the OSIRIS-REx spacecraft sampling hardware was maintained at level 100 A/2 and less than 180 ng/cm(exp 2) of amino acids and hydrazine on the sampler head through precision cleaning, control of materials, and vigilance. Contamination is further characterized via witness material exposed to the spacecraft assembly and testing environment as well as in space. This characterization provided knowledge of the expected background and will be used in conjunction with archived spacecraft components for comparison with the samples when they are delivered to Earth for analysis. Most of all, the cleanliness of the OSIRIS-REx spacecraft was achieved through communication among scientists, engineers, managers, and technicians.

OSIRIS-RE

Large Sulphur Isotope Fractionations in Martian Sediments at Gale Crater

Variability in the sulfur isotopic composition in sediments can reflect atmospheric, geologic and biological processes. Evidence for ancient fluvio-lacustrine environments at Gale crater on Mars and a lack of efficient crustal recycling mechanisms on the planet suggests a surface environment that was once warm enough to allow the presence of liquid water, at least for discrete periods of time, and implies a greenhouse effect that may have been influenced by sulfur-bearing volcanic gases. Here we report in situ analyses of the sulfur isotopic compositions of SO2 volatilized from ten sediment samples acquired by NASA's Curiosity rover along a 13 km traverse of Gale crater. We find large variations in sulfur isotopic composition that exceed those measured for Martian meteorites and show both depletion and enrichment in S-34. Measured values of δS-34 range from -47 +/- 14% to 28 +/- 7%, similar to the range typical of terrestrial environments. Although limited geochronological constraints on the stratigraphy traversed by Curiosity are available, we propose that the observed sulfur isotopic signatures at Gale crater can be explained by equilibrium fractionation between sulfate and sulfide in an impact-driven hydrothermal system and atmospheric processing of sulfur-bearing gases during transient warm periods.

Curiosity

OSIRIS-REx Contamination Control Strategy and Implementation

OSIRIS-REx will return pristine samples of carbonaceous asteroid Bennu. This manuscript describes how pristine was defined based on expectations of Bennu and on a realistic understanding of what is achievable with a constrained schedule and budget, and how that definition flowed to requirements and implementation. To return a pristine sample, the OSIRIS-REx spacecraft sampling hardware was maintained at Level 100 A/2 and less than 180 nanograms per square centimeter of amino acids and hydrazine on the sampler head through precision cleaning, control of materials, and vigilance. Contamination is further characterized via witness material exposed to the spacecraft assembly and testing environment as well as in space. This characterization provided knowledge of the expected background and will be used in conjunction with archived spacecraft components for comparison with the samples when they are delivered to Earth for analysis. Most of all, the cleanliness of the OSIRIS-REx spacecraft was achieved through communication between scientists, engineers, managers, and technicians.

Dworkin, J. P.

Evolved Gas Analyses of Sedimentary Rocks and Eolian Sediment in Gale Crater, Mars: Results of the Curiosity Rover's Sample Analysis at Mars Instrument from Yellowknife Bay to the Namib Dune

The sample analysis at Mars instrument evolved gas analyzer (SAM-EGA) has detected evolved water, H2, SO2, H2S, NO, CO2, CO, O2, and HCl from two eolian sediments and nine sedimentary rocks from Gale Crater, Mars. These evolved gas detections indicate nitrates, organics, oxychlorine phase, and sulfates are widespread with phyllosilicates and carbonates occurring in select Gale Crater materials. Coevolved CO2 (160 +/- 248-2373 +/- 820 μgC(CO2)/g) and CO (11 +/- 3-320 +/- 130 μgC(CO)/g) suggest that organic C is present in Gale Crater materials. Five samples evolved CO2 at temperatures consistent with carbonate (0.32 +/- 0.05-0.70 +/- 0.1 wt % CO3). Evolved NO amounts to 0.002 +/- 0.007-0.06 +/- 0.03 wt % NO3. Evolution of O2 suggests that oxychlorine phases (chlorate/perchlorate) (0.05 +/- 0.025-1.05 +/- 0.44 wt % ClO4) are present, while SO2 evolution indicates the presence of crystalline and/or poorly crystalline Fe and Mg sulfate and possibly sulfide. Evolved H2O (0.9 +/- 0.3-2.5 +/- 1.6 wt % H2O) is consistent with the presence of adsorbed water, hydrated salts, interlayer/structural water from phyllosilicates, and possible inclusion water in mineral/amorphous phases. Evolved H2 and H2S suggest that reduced phases occur despite the presence of oxidized phases (nitrate, oxychlorine, sulfate, and carbonate). SAM results coupled with CheMin mineralogical and Alpha-Particle X-ray Spectrometer elemental analyses indicate that Gale Crater sedimentary rocks have experienced a complex authigenetic/diagenetic history involving fluids with varying pH, redox, and salt composition. The inferred geochemical conditions were favorable for microbial habitability and if life ever existed, there was likely sufficient organic C to support a small microbial population.

Sutter, B.

Influence of Oxychlorine Phases During the Pyrolysis of Organic Molecules: Implications for the Quest of Organics on Mars with the SAM Experiment Onboard the Curiosity Rover

One among the main objectives of the Sample Analysis at Mars (SAM) experiment is the in situ molecular analysis of gases evolving from solid samples heated up to approximately 850 degrees Centigrade, and collected by Curiosity on Mars surface/sub-surface in Gale crater. With this aim, SAM uses a gas-chromatograph coupled to a quadrupole mass spectrometer (GC-QMS) devoted to separate, detect and identify both volatile inorganic and organic compounds. SAM detected chlorinated organic molecules produced in evolved gas analysis (EGA) experiments. Several of these were also detected by the Viking experiments in 1976. SAM also detected oxychlorine compounds that were present at the Phoenix landing site. The oxychlorines may be prevelant over much of the martian surface. The C1 to C3 aliphatic chlorohydrocarbons (chloromethane and di- and trichloromethane) detected by SAM were attributed to reaction products occurring between the oxychlorines phases and the organic compounds coming from SAM instrument background. But SAM also showed the presence of a large excess of chlorobenzene and C2 to C4 dichloroalkanes among the volatile species released by the Cumberland sample of the Sheepbed mudstone. For the first time in the history of the Mars exploration, this proved the presence of Mars indigenous organic material at the Mars' surface. However, the identification of the precursor organic compounds of these chlorohydrocarbons is difficult due to the complexity of the reactions occurring during the sample pyrolysis. Laboratory pyrolysis experiments have demonstrated that oxychlorines phases such as perchlorates and chlorates, decomposed into dioxygen and volatile chlorine bearing molecules (HCl and/or Cl2) during the pyrolysis. These chemical species can then react with the organic molecules present in the martian solid samples through oxidation, chlorination and oxychlorination processes.

Millan, M.

Nitrogen on Mars: Insights from Curiosity

Recent detection of nitrate on Mars indicates that nitrogen fixation processes occurred in early martian history. Data collected by the Sample Analysis at Mars (SAM) instrument on the Curiosity Rover can be integrated with Mars analog work in order to better understand the fixation and mobility of nitrogen on Mars, and thus its availability to putative biology. In particular, the relationship between nitrate and other soluble salts may help reveal the timing of nitrogen fixation and post-depositional behavior of nitrate on Mars. In addition, in situ measurements of nitrogen abundance and isotopic composition may be used to model atmospheric conditions on early Mars.

Stern, J. C.

Effect of Tube-Based X-Ray Microtomography Imaging on the Amino Acid and Amine Content of the Murchison CM2 Chondrite

X-ray and synchrotron X-ray micro-computed tomography (micro-CT) are increasingly being used for three dimensional reconnaissance imaging of chondrites and returned extraterrestrial material prior to detailed chemical and mineralogical analyses. Although micro-CT imaging is generally considered to be a non-destructive technique since silicate and metallic minerals in chondrites are not affected by X-ray exposures at the intensities and wavelengths typically used, there are concerns that the use of micro-CT could be detrimental to the organics in carbonaceous chondrites. We recently conducted a synchrotron micro-CT experiment on a powdered sample of the Murchison CM2 carbonaceous chondrite exposed to a monochromatic high energy (approximately 48 kiloelectronvolts) total X-ray radiation dose of approximately 1 kilogray (kGy) using the Advanced Photon Source beamline 13-BMD (13-Bending Magnet-D Beamline) at Argonne National Laboratory and found that there were no detectable changes in the amino acid abundances or enantiomeric compositions in the chondrite after exposure relative to a Murchison control sample that was not exposed. However, lower energy bremsstrahlung X-rays could interact more with amino acids and other lower molecular weight amines in meteorites. To test for this possibility, three separate micro-CT imaging experiments of the Murchison meteorite using the GE Phoenix v/tome/x s 240 kilovolt microfocus high resolution tungsten target X-ray tube instrument at the American Museum of Natural History (AMNH) were conducted and the amino acid abundances and enantiomeric compositions were determined. We also investigated the abundances of the C1-C5 amines in Murchison which were not analyzed in the first study.

Microtomography Imaging