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Dworkin, J. P.

Publications and source records attributed to Dworkin, J. P..

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS2015

Amino Acid Stability in the Early Oceans

It is likely that a variety of amino acids existed in the early oceans of the Earth at the time of the origin and early evolution of life. "Primordial soup", hydrothermal vent, and meteorite based processes could have contributed to such an inventory. Several "protein" amino acids were likely present, however, based on prebiotic synthesis experiments and carbonaceous meteorite studies, non-protein amino acids, which are rare on Earth today, were likely the most abundant. An important uncertainty is the length of time these amino acids could have persisted before their destruction by abiotic and biotic processes. Prior to life, amino acid concentrations in the oceans were likely regulated by circulation through hydro-thermal vents. Today, the entire ocean circulates through vent systems every 10(exp 7) years. On the early Earth, this value was likely smaller due to higher heat flow and thus marine amino acid life-time would have been shorter. After life, amino acids in the oceans could have been assimilated by primitive organisms.

prebiotic synthesis↗
NASA NTRS2015

Distribution and Origin of Amino Acids in Lunar Regolith Samples

The existence of organic compounds on the lunar surface has been a question of interest from the Apollo era to the present. Investigations of amino acids immediately after collection of lunar samples yielded inconclusive identifications, in part due to analytical limitations including insensitivity to certain compounds, an inability to separate enantiomers, and lack of compound-specific isotopic measurements. It was not possible to determine if the detected amino acids were indigenous to the lunar samples or the result of terrestrial contamination. Recently, we presented initial data from the analysis of amino acid abundances in 12 lunar regolith samples and discussed those results in the context of four potential amino acid sources [5]. Here, we expand on our previous work, focusing on amino acid abundances and distributions in seven regolith samples and presenting the first compound-specific carbon isotopic ratios measured for amino acids in a lunar sample.

Elsila, J. E.↗
NASA NTRS2014

Liquid Chromatography-Mass Spectrometry Interface for Detection of Extraterrestrial Organics

The OASIS (Organics Analyzer for Sampling Icy surfaces) microchip enables electrospray or thermospray of analyte for subsequent analysis by the OASIS time-of-flight mass spectrometer. Electrospray of buffer solution containing the nucleobase adenine was performed using the microchip and detected by a commercial time-of-flight mass spectrometer. Future testing of thermospray and electrospray capability will be performed using a test fixture and vacuum chamber developed especially for optimization of ion spray at atmosphere and in low pressure environments.

extraterrestrial organics↗
NASA NTRS2014

The Effects of Thermal Metamorphism on the Amino Acid Content of the CI-Like Chondrite Y-86029

Carbonaceous chondrites con-tain a diverse suite of amino acids that varies in abundance and structural diversity depending on the degree of aqueous alteration and thermal histo-ry that the parent body experienced [1 - 3]. We recently determined the amino acid contents of several fragments of the Sutter's Mill CM2 chon-drite [4]. In contrast with most other CM2 chon-drites, the Sutter's Mill meteorites showed minimal evidence for the presence of indigenous amino acids. A notable difference between the Sutter's Mill meteorites and other CM2 chondrites are that the Sutter's Mill stones were heated to tempera-tures of 150 - 400 C [4], whereas most other CM2 chondrites do not show evidence for thermal met-amorphism [5]. Because empirical studies have shown that amino acids rapidly degrade in aqueous solutions above 150 C and the presence of miner-als accelerates this degradation [6], a plausible explanation for the lack of amino acids observed in the Sutter's Mill meteorites is that they were destroyed during metamorphic alteration. Fewer CI chondrites have been analyzed for amino acids because only a small number of these meteorites have been recovered. Nevertheless, indigenous amino acids have been reported in the CI chondrites Ivuna and Orgueil [7]. Here we report on the amino acid analysis of the CI-like chondrite, Yamato 86029 (Y-86029; sample size of 110 mg). Just as the Sutter's Mill meteorites were thermally metamporphosed CM2 chondrites, Y-86029 has experienced thermal metamorphism at higher temperatures than Orgueil and Ivuna (normal CI chondrites) experienced, possibly up to 600 C [8].

Burton, A. S.↗
NASA NTRS2014

Distribution of Amino Acids in Lunar Regolith

One of the most eagerly studied questions upon initial return of lunar samples was whether significant amounts of organic compounds, including amino acids, were present. Analyses during the 1970s produced only tentative and inconclusive identifications of indigenous amino acids. Those analyses were hampered by analytical difficulties including relative insensitivity to certain compounds, the inability to separate chiral enantiomers, and the lack of compound-specific isotopic measurements, which made it impossible to determine whether the detected amino acids were indigenous to the lunar samples or the results of contamination. Numerous advances have been made in instrumentation and methodology for amino acid characterization in extraterrestrial samples in the intervening years, yet the origin of amino acids in lunar regolith samples has been revisited only once for a single lunar sample, (3) and remains unclear. Here, we present initial data from the analyses of amino acid abundances in 12 lunar regolith samples. We discuss these abundances in the context of four potential amino acid sources: (1) terrestrial biological contamination; (2) contamination from lunar module (LM) exhaust; (3) derivation from solar windimplanted precursors; and (4) exogenous delivery from meteorites.

Elsila, J. E.↗
NASA NTRS2013

Does Aspartic Acid Racemization Constrain the Depth Limit of the Subsurface Biosphere?

Previous studies of the subsurface biosphere have deduced average cellular doubling times of hundreds to thousands of years based upon geochemical models. We have directly constrained the in situ average cellular protein turnover or doubling times for metabolically active micro-organisms based on cellular amino acid abundances, D/L values of cellular aspartic acid, and the in vivo aspartic acid racemization rate. Application of this method to planktonic microbial communities collected from deep fractures in South Africa yielded maximum cellular amino acid turnover times of approximately 89 years for 1 km depth and 27 C and 1-2 years for 3 km depth and 54 C. The latter turnover times are much shorter than previously estimated cellular turnover times based upon geochemical arguments. The aspartic acid racemization rate at higher temperatures yields cellular protein doubling times that are consistent with the survival times of hyperthermophilic strains and predicts that at temperatures of 85 C, cells must replace proteins every couple of days to maintain enzymatic activity. Such a high maintenance requirement may be the principal limit on the abundance of living micro-organisms in the deep, hot subsurface biosphere, as well as a potential limit on their activity. The measurement of the D/L of aspartic acid in biological samples is a potentially powerful tool for deep, fractured continental and oceanic crustal settings where geochemical models of carbon turnover times are poorly constrained. Experimental observations on the racemization rates of aspartic acid in living thermophiles and hyperthermophiles could test this hypothesis. The development of corrections for cell wall peptides and spores will be required, however, to improve the accuracy of these estimates for environmental samples.

cellular↗
NASA NTRS2013

Curiosity's Sample Analysis at Mars (SAM) Investigation: Overview of Results from the First 120 Sols on Mars

During the first 120 sols of Curiosity s landed mission on Mars (8/6/2012 to 12/7/2012) SAM sampled the atmosphere 9 times and an eolian bedform named Rocknest 4 times. The atmospheric experiments utilized SAM s quadrupole mass spectrometer (QMS) and tunable laser spectrometer (TLS) while the solid sample experiments also utilized the gas chromatograph (GC). Although a number of core experiments were pre-programmed and stored in EEProm, a high level SAM scripting language enabled the team to optimize experiments based on prior runs.

Mahaffy, P. R.↗
NASA NTRS2012

OASIS: Organics Analyzer for Sampling Icy Surfaces

Liquid chromatography mass spectrometry (LC-MS) is a well established laboratory technique for detecting and analyzing organic molecules. This approach has been especially fruitful in the analysis of nucleobases, amino acids, and establishing chirol ratios [1 -3]. We are developing OASIS, Organics Analyzer for Sampling Icy Surfaces, for future in situ landed missions to astrochemically important icy bodies, such as asteroids, comets, and icy moons. The OASIS design employs a microfabricated, on-chip analytical column to chromatographically separate liquid ana1ytes using known LC stationary phase chemistries. The elution products are then interfaced through electrospray ionization (ESI) and analyzed by a time-of-flight mass spectrometer (TOF-MS). A particular advantage of this design is its suitability for microgravity environments, such as for a primitive small body.

Getty, S. A.↗
NASA NTRS2012

The Amino Acid Composition of the Sutter's Mill Carbonaceous Chondrite

In contrast to the Murchison meteorite which had a complex distribution of amino acids with a total C2 to Cs amino acid abundance of approx.14,000 parts-per-billion (ppb) [2], the Sutters Mill meteorite was found to be highly depleted in amino acids. Much lower abundances (approx.30 to 180 ppb) of glycine, beta-alanine, L-alanine and L-serine were detected in SM2 above procedural blank levels indicating that this meteorite sample experienced only minimal terrestrial amino acid contamination after its fall to Earth. Carbon isotope measurements will be necessary to establish the origin of glycine and beta-alanine in SM2. Other non-protein amino acids that are rare on Earth, yet commonly found in other CM meteorites such as aaminoisobutyric acid (alpha-AIB) and isovaline, were not identified in SM2. However, traces of beta-AIB (approx.1 ppb) were detected in SM2 and could be" extraterrestrial in origin. The low abundances of amino acids in the Sutter's Mill meteorite is consistent with mineralogical evidence that at least some parts of the Sutter's Mill meteorite parent body experienced extensive aqueous and/or thermal alteration.

Glavin, D. P.↗
NASA NTRS2012

The Osiris-Rex Mission - Sample Acquisitions Strategy and Evidence for the Nature of Regolith on Asteroid (101955) 1999 RQ36

NASA selected the OSIRIS-REx Asteroid Sample Return Mission as the third New Frontiers mission in May 2011 [I]. The mission name is an acronym that captures the scientific objectives: Origins, Spectral Interpretation, Resource Identification, and Security-Regolith Explorer. OSIRIS-REx will characterize near-Earth asteroid (101955) 1999 RQ36, which is both the most accessible carbonaceous asteroid [2,3] and one of the most potentially hazardous asteroids known [4]. The primary objective of the mission is to return a pristine sample from this bod, to advance our understanding of the generation, evolution, and maturation of regolith on small bodies.

Lauretta, D. S.↗
NASA NTRS2012

The Influence of Mineralogy on Recovering Organic Acids from Mars Analogue Materials Using the One-Pot Derivatization Experiment on the Sample Analysis at Mars(SAM) Instrument Suite

The search for complex organic molecules on Mars, including important biomolecules such as amino acids and carboxylic acids, will require a chemical extraction and a derivatization step to transform these organic compounds into species that are sufficiently volatile to be detected by gas chromatography mass spectrometry (GCMS). We have developed a ''one-pot'' extraction and chemical derivatization protocol using N-methyl-N-(tert-butyldimethylsilyl) trifluoroacetamide (MTBSTFA) and dimethylformamide (DMF) for the Sample Analysis at Mars (SAM) experiment instrument suite on NASA's the Mars Science Laboratory (MSL) mission. The temperature and duration of the derivatization reaction, pre-concentration of chemical derivatives, and gas chromatographic separation parameters have been optimized under SAM instrument design constraints. MTBSTFA/DMF extraction and derivatization at 300 1C for several minutes of a variety of terrestrial Mars analog materials facilitated the detection of amino acids and carboxylic acids in a surface soil sample collected from the Atacama Desert and a carbonate-rich stromatolite sample from Svalbard. However, the rapid reaction of MTBSTFA with water in several analog materials that contained high abundances of hydrated minerals, and the possible deactivation of derivatized compounds by iron oxides, as detected by XRD/XRF using the CheMin field unit Terra, proved to be highly problematic for the direct extraction of organics using MTBSTFA. The combination of pyrolysis and two different wet-chemical derivatization methods employed by SAM should enable a wide range of organic compounds to be detected by GCMS if present on Mars.

MSL↗
NASA NTRS2012

The Importance of Meteorite Collections to Sample Return Missions: Past, Present, and Future Considerations

While much of the scientific community s current attention is drawn to sample return missions, it is the existing meteorite and cosmic dust collections that both provide the paradigms to be tested by these missions and the context for interpreting the results. Recent sample returns from the Stardust and Hayabusa missions provided us with new materials and insights about our Solar System history and processes. As an example, Stardust sampled CAIs among the population of cometary grains, requiring extensive and unexpected radial mixing in the early solar nebula. This finding would not have been possible, however, without extensive studies of meteoritic CAIs that established their high-temperature, inner Solar System formation. Samples returned by Stardust also revealed the first evidence of a cometary amino acid, a discovery that would not have been possible with current in situ flight instrument technology. The Hayabusa mission provided the final evidence linking ordinary chondrites and S asteroids, a hypothesis that developed from centuries of collection and laboratory and ground-based telescopic studies. In addition to these scientific findings, studies of existing meteorite collections have defined and refined the analytical techniques essential to studying returned samples. As an example, the fortuitous fall of the Allende CV3 and Murchison CM2 chondrites within months before the return of Apollo samples allowed testing of new state-of-the-art analytical facilities. The results of those studies not only prepared us to better study lunar materials, but unanticipated discoveries changed many of our concepts about the earliest history and processes of the solar nebula. This synergy between existing collections and future space exploration is certainly not limited to sample return missions. Laboratory studies confirmed the existence of meteorites from Mars and raised the provocative possibility of preservation of ancient microbial life. The laboratory studies in turn led to a new wave of Mars exploration that ultimately could lead to sample return focused on evidence for past or present life. This partnership between collections and missions will be increasingly important in the coming decades as we discover new questions to be addressed and identify targets for for both robotic and human exploration . Nowhere is this more true than in the ultimate search for the abiotic and biotic processes that produced life. Existing collections also provide the essential materials for developing and testing new analytical schemes to detect the rare markers of life and distinguish them from abiotic processes. Large collections of meteorites and the new types being identified within these collections, which come to us at a fraction of the cost of a sample return mission, will continue to shape the objectives of future missions and provide new ways of interpreting returned samples.

Welzenbach, L. C.↗
NASA NTRS2012

Strategies for Distinguishing Abiotic Chemistry from Martian Biochemistry in Samples Returned from Mars

A key goal in the search for evidence of extinct or extant life on Mars will be the identification of chemical biosignatures including complex organic molecules common to all life on Earth. These include amino acids, the monomer building blocks of proteins and enzymes, and nucleobases, which serve as the structural basis of information storage in DNA and RNA. However, many of these organic compounds can also be formed abiotically as demonstrated by their prevalence in carbonaceous meteorites [1]. Therefore, an important challenge in the search for evidence of life on Mars will be distinguishing between abiotic chemistry of either meteoritic or martian origin from any chemical biosignatures from an extinct or extant martian biota. Although current robotic missions to Mars, including the 2011 Mars Science Laboratory (MSL) and the planned 2018 ExoMars rovers, will have the analytical capability needed to identify these key classes of organic molecules if present [2,3], return of a diverse suite of martian samples to Earth would allow for much more intensive laboratory studies using a broad array of extraction protocols and state-of-theart analytical techniques for bulk and spatially resolved characterization, molecular detection, and isotopic and enantiomeric compositions that may be required for unambiguous confirmation of martian life. Here we will describe current state-of-the-art laboratory analytical techniques that have been used to characterize the abundance and distribution of amino acids and nucleobases in meteorites, Apollo samples, and comet- exposed materials returned by the Stardust mission with an emphasis on their molecular characteristics that can be used to distinguish abiotic chemistry from biochemistry as we know it. The study of organic compounds in carbonaceous meteorites is highly relevant to Mars sample return analysis, since exogenous organic matter should have accumulated in the martian regolith over the last several billion years and the analytical techniques previously developed for the study of extraterrestrial materials can be applied to martian samples.

Glavin, D. P.↗
NASA NTRS2012

Detecting Organic Compounds Released from Iron Oxidizing Bacteria using Sample Analysis at Mars (SAM) Like Instrument Protocols

Mars is a planet of great interest for Astrobiology since its past environmental conditions are thought to have been favourable for the emergence life. At present, the Red Planet is extremely cold and dry and the surface is exposed to intense UV and ionizing radiation, conditions generally considered to be incompatible with life as we know it on Earth. It was proposed that the shallow subsurface of Mars, where temperatures can be above freezing and liquid water can exist on rock surfaces, could harbor chemolithoautotrophic bacteria such as the iron oxidizing microorganism Pseudomonas sp. HerB. The Mars Science Laboratory (MSL) mission will provide the next opportunity to carry out in situ measurements for organic compounds of possible biological origin on Mars. One instrument onboard MSL, called the Sample Analysis at Mars (SAM) instrument suite, will carry out a broad and sensitive search for organic compounds in surface samples using either high temperature pyrolysis or chemical extraction followed by gas chromatography mass spectrometry. We present gas chromatograph mass spectrometer (GC/MS) data on crushed olivine rock powders that have been inoculated with Pseudomonas sp. HerB at different concentrations ranging from approx 10(exp 2) to 10(exp 7) cells per gram. The inoculated olivine samples were heated under helium carrier gas flow at 500 C and the pyrolysis products concentrated using a SAM-like hydrocarbon trap set at -20 C followed by trap heating and analysis by GC/Ms. In addition, the samples were also extracted using a low temperature "one-pot" chemical extraction technique using N-methyl, N-(tert-butyldimethylsilyl) trifluoroacetamide (MTBSTFA) as the silylating agent prior to GC/MS analysis. We identified several aldehydes, thiols, and alkene nitriles after pyrolysis GC/MS analysis of the bacteria that were not found in the olivine control samples that had not been inoculated with bacteria. The distribution of pyrolysis products extracted from the bacteria was clearly distinct from similar GC/MS analyses of the carbonaceous meteorite Murchison that was dominated by sulfur containing aromatic compounds. A similar comparison, if organic compounds are detected by SAM on Mars, could be useful to help discriminate between meteoritic or biological origins.

Glavin, D. P.↗
NASA NTRS2012

Analysis of Organic Molecules Extracted from Mars Analogues and Influence of Their Mineralogy Using N-Methyl-N-(tert-butyldimethylsilyl)Trifluoroacetamide Derivatization Coupled with Gas Chromatography Mass Spectrometry in Preparation for the Sample Analysis at Mars Derivatization Experiment on the Mars Science Laboratory Mission

The search for complex organic molecules on Mars, including important biomolecules such as amino acids and carboxylic acids will require a chemical extraction and derivatization step to transform these organic compounds into species that are sufficiently volatile to be detected by gas chromatography mass spectrometry (GCMS). We have developed, a one-pot extraction and chemical derivatization protocol using N-methyl-N-(tert-butyldimethylsilyl)trifluoroacetamide (MTBSTFA) and dimethylformamide (DMF) for the Sample Analysis at Mars (SAM) experiment on the Mars Science Laboratory (MSL). The temperature and duration the derivatization reaction, pre-concentration of chemical derivatives, and gas chromatographic separation parameters have been optimized under SAM instrument design constraints. MTBSTFA/DMF extraction and derivatization at 300 C for several minutes of a variety of terrestrial Mars analogue materials facilitated the detection of amino acids and carboxylic acids in a surface soil sample collected from the Atacama Desert and a carbonate-rich stromatolite sample from Svalbard. However, the rapid reaction of MTBSTFA with water in several analogue materials that contained high abundances of hydrated minerals and the possible deactivation of derivatized compounds by iron oxides, as detected by XRD/XRF using the CheMin field unit Terra, proved to be highly problematic for the direct extraction of organics using MTBSTFA, The combination of pyrolysis and two different chemical derivatization methods employed by SAM should enable a wide range of organic compounds to be detected by GCMS if present on Mars,

Stalport, F.↗
NASA NTRS2011

The Importance of Sample Return in Establishing Chemical Evidence for Life on Mars or Other Solar System Bodies

The search for evidence of life on Mars and elsewhere will continue to be one of the primary goals of NASA s robotic exploration program over the next decade. NASA and ESA are currently planning a series of robotic missions to Mars with the goal of understanding its climate, resources, and potential for harboring past or present life. One key goal will be the search for chemical biomarkers including complex organic compounds important in life on Earth. These include amino acids, the monomer building blocks of proteins and enzymes, nucleobases and sugars which form the backbone of DNA and RNA, and lipids, the structural components of cell membranes. Many of these organic compounds can also be formed abiotically as demonstrated by their prevalence in carbonaceous meteorites [1], though, their molecular characteristics may distinguish a biological source [2]. It is possible that in situ instruments may reveal such characteristics, however, return of the right sample (i.e. one with biosignatures or having a high probability of biosignatures) to Earth would allow for more intensive laboratory studies using a broad array of powerful instrumentation for bulk characterization, molecular detection, isotopic and enantiomeric compositions, and spatially resolved chemistry that may be required for confirmation of extant or extinct Martian life. Here we will discuss the current analytical capabilities and strategies for the detection of organics on the Mars Science Laboratory (MSL) using the Sample Analysis at Mars (SAM) instrument suite and how sample return missions from Mars and other targets of astrobiological interest will help advance our understanding of chemical biosignatures in the solar system.

Glavin, D. P.↗
NASA NTRS2011

Extraterrestrial Amino Acids in Ureilites Including Almahata Sitta

Ureilites are a class of meteorites that lack chondrules (achondrites) but have relatively high carbon abundances, averaging approx.3 wt %. Using highly sensitive liquid chromatography coupled with UV fluorescence and time-of-flight mass spectrometry (LC-FD/ToF-MS), it was recently determined that there are amino acids in. fragment 94 of the Almahata Sitta ureilite[l]. Based on the presence of amino acids that are rare in the Earth's biosphere, as well as the near-racemic enantiomeric ratios of marry of the more common amino acids, it was concluded that most of the detected amino acids were indigenous to the meteorite. Although the composition of the Almahata Sitta ureilite appears to be unlike other recovered ureilites, the discovery of amino acids in this meteorite raises the question of whether other ureilites rnav also contain amino acids. Herein we present the results of LC-FDlTo.F-MS analyses of: a sand sample from the Almahata Sitta strewn held, Almahata Sitta fragments 425 (an ordinary H5 chondrite) and 427 (ureilite), as well as an Antarctic ureilite (Allan lulls, ALHA 77257).

Burton, A. S.↗