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Burton, A. S.

Publications and source records attributed to Burton, A. S..

31 records · Page 2
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NASA NTRS2015

Evidence from Meteorites for Multiple Possible Amino Acid Alphabets for the Origins of Life

A key question for the origins of life is understanding which amino acids made up the first proteins synthesized during the origins of life. The canonical set of 20 - 22 amino acids used in proteins are all alpha-amino, alpha-hydrogen isomers that, nevertheless, show considerable variability in properties including size, hydrophobicity, and ionizability. Abiotic amino acid synthesis experiments such as Miller-Urey spark discharge reactions produce a set of up to 23 amino acids, depending on starting materials and reaction conditions, with significant abundances of both alpha- and non-alpha-amino acid isomers. These two sets of amino acids do not completely overlap; of the 23 spark discharge amino acids, only 11 are used in modern proteins. Furthermore, because our understanding of conditions on the early Earth are limited, it is unclear which set(s) of conditions employed in spark discharge or hydrothermal reactions are correct, leaving us with significant uncertainty about the amino acid alphabet available for the origins of life on Earth. Meteorites, the surviving remnants of asteroids and comets that fall to the Earth, offer the potential to study authentic samples of naturally-occurring abiotic chemistry, and thus can provide an alternative approach to constraining the amino acid library during the origins of life.

Burton, A. S.↗
NASA NTRS2015

Analysis of Chiral Carboxylic Acids in Meteorites

Homochirality of amino acids in proteins and sugars in DNA and RNA is a critical feature of life on Earth. In the absence of a chiral driving force, however, reactions leading to the synthesis of amino acids and sugars result in racemic mixtures. It is currently unknown whether homochirality was necessary for the origins of life or if it was a product of early life. The observation of enantiomeric excesses of certain amino acids of extraterrestrial origins in meteorites provides evidence to support the hypothesis that there was a mechanism for the preferential synthesis or destruction of a particular amino acid enantiomer [e.g., 1-3]. The cause of the observed chiral excesses is un-clear, although at least in the case of the amino acid isovaline, the degree of aqueous alteration that occurred on the meteorite parent body is correlated to the isovaline L-enantiomeric excess [3, 4]. This suggests that chiral symmetry is broken and/or amplified within the meteorite parent bodies. Besides amino acids, there have been only a few reports of other meteoritic compounds found in enantiomeric excess: sugars and sugar acids [5, 6] and the hydroxy acid lactic acid [7]. Determining whether or not additional types of molecules in meteorites are also present in enantiomeric excesses of extraterrestrial information will provide insights into mechanisms for breaking chiral symmetry. Though the previous measurements (e.g., enantiomeric composition of lactic acid [7], and chiral carboxylic acids [8]) were made by gas chromatography-mass spectrometry, the potential for increased sensitivity of liquid chromatography-mass spectrometry (LC-MS) analyses is important because for many meteorite samples, only small sample masses are available for study. Furthermore, at least in the case of amino acids, many of the largest amino acid enantiomeric excesses were observed in samples that contained lower abundances (tens of ppb) of a given amino acid enantiomer. In the present work, we describe our efforts to develop highly sensitive LC-MS methods for the analysis of chiral carboxylic acids including hydroxy acids.

Burton, A. S.↗
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

Mineralogy, Petrology, Chronology, and Exposure History of the Chelyabinsk Meteorite and Parent Body

The Chelyabinsk meteorite fall on February 15, 2013 attracted much more attention worldwide than do most falls. A consortium led by JSC received 3 masses of Chelyabinsk (Chel-101, -102, -103) that were collected shortly after the fall and handled with care to minimize contamination. Initial studies were reported in 2013; we have studied these samples with a wide range of analytical techniques to better understand the mineralogy, petrology, chronology and exposure history of the Chelyabinsk parent body.

Righter, K.↗
NASA NTRS2014

The Mars 2020 Rover Mission: EISD Participation in Mission Science and Exploration

The Mars 2020 Rover mission will search for potential biosignatures on the martian surface, use new techniques to search for and identify tracelevel organics, and prepare a cache of samples for potential return to Earth. Identifying trace organic compounds is an important tenet of searching for potential biosignatures. Previous landed missions have experienced difficulty identifying unambiguously martian, unaltered organic compounds, possibly because any organic species have been destroyed on heating in the presence of martian perchlorates and/or other oxidants. The SHERLOC instrument on Mars 2020 will use ultraviolet (UV) fluorescence and Raman spectroscopy to identify trace organic compounds without heating the samples.

Fries, M.↗
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 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 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

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 NTRS2011

Meteorites, Organics and Fischer-Tropsch Type Reaction: Production and Destruction

There has been an ongoing debate about the relative importance about the various chemical reactions that fonned organics in the early solar system. One proposed method that has long been recognized as a potential source of organics is Fischer-Tropsch type (FTT) synthesis. This process is commonly used in industry to produce fuels (i.e., complex hydrocarbons) by catalytic hydrogenation of carbon monoxide. Hill and Nuth were the first to publish results of FTT experiments that also included Haber-Bosch (HB) processes (hydrogenation of nitrogen. Their findings included the production of nitrilebearing compounds as well as trace amounts of methyl amine. Previous experience with these reactions revealed that the organic coating deposited on the grains is also an efficient catalyst and that the coating is composed of insoluble organic matter (10M) and could be reminiscent of the organic matrix found in some meteorites. This current set of FTT-styled experiments tracks the evolution of a set of organics, amino acids, in detail.

Johnson, Natasha M.↗
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.↗