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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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Searching for Life Underground: An Analysis of Remote Sensing Observations of a Drill Core from Rio Tinto, Spain for Mineralogical Indications of Biological Activity

Water is unstable on the surface of Mars, and therefore the Martian surface is not likely to support life. It is possible, however, that liquid water exists beneath the surface of Mars, and thus life might also be found in the subsurface. Subsurface life would most likely be microbial, anaerobic, and chemoautotrophic; these types of biospheres on Earth are rare, and not well understood. Finding water and life are high priorities for Mars exploration, and therefore it is important that we learn to explore the subsurface robotically, by drilling. The Mars Analog Rio Tinto Experiment (MARTE), has searched successfully for a subsurface biosphere at Rio Tinto, Spain [1,2,3,4]. The Rio Tinto study site was selected to search for a subsurface biosphere because the extremely low pH and high concentrations of elements such as iron and copper in the Tinto River suggest the presence of a chemoautotrophic biosphere in the subsurface beneath the river. The Rio Tinto has been recognized as an important mineralogical analog to the Sinus Meridiani site on Mars [5].

Battler, M.↗

Nanoflow Separation of Amino Acids for the Analysis of Cosmic Dust

The delivery of amino acids to the early Earth by interplanetary dust particles, comets, and carbonaceous meteorites could have been a significant source of the early Earth's prebiotic organic inventory. Amino acids are central to modern terrestrial biochemistry as major components of proteins and enzymes and were probably vital in the origin of life. A variety of amino acids have been detected in the CM carbonaceous meteorite Murchison, many of which are exceptionally rare in the terrestrial biosphere including a-aminoisobutyric acid (AIB) and isovaline. AIB has also been detected in a small percentage of Antarctic micrometeorite grains believed to be related to the CM meteorites We report on progress in optimizing a nanoflow liquid chromatography separation system with dual detection via laser-induced-fluorescence time of flight mass spectrometry (nLC-LIF/ToF-MS) for the analysis of o-phthaldialdehydelN-acetyl-L-cysteine (OPA/NAC) labeled amino acids in cosmic dust grains. The very low flow rates (<3 micro-L/min) of nLC over analytical LC (>0.1 ml/min) combined with <2 micron column bead sizes has the potential to produce efficient analyte ionizations andchromatograms with very sharp peaks; both increase sensitivity. The combination of the selectivity (only primary amines are derivatized), sensitivity (>4 orders of magnitude lower than traditional GC-MS techniques), and specificity (compounds identities are determined by both retention time and exact mass) makes this a compelling technique. However, the development of an analytical method to achieve separation of compounds as structurally similar as amino acid monomers and produce the sharp peaks required for maximum sensitivity is challenging.

Martin, M. P.↗

Fungal Peptaibiotics: Assessing Potential Meteoritic Amino Acid Contamination

The presence of non-protein alpha-dialkyl-amino acids such as alpha-aminoisobutyric acid (alpha-A1B) and isovaline (Iva), which are relatively rare in the terrestrial biosphere, has long been used as an indication of the indigeneity of meteoritic amino acids, however, the discovery of alpha-AIB in peptides producers by a widespread group of filamentous fungi indicates the possibility of a terrestrial biotic source for the alpha-AIB observed in some meteorites. The alpha-AIB-containing peptides produced by these fungi are dubbed peptaibiotics. We measured the molecular distribution and stable carbon and nitrogen isotopic ratios for amino acids found in the total hydrolysates of four biologically synthesized peptaibiotics. We compared these aneasurenetts with those from the CM2 carbonaceous chondrite Murchison and from three Antarctic CR2 carbonaceous chondrites in order to understand the peptaibiotics as a potential source of meteoritic contamination.

Elsila, J. E.↗

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.↗

Extraterrestrial Amino Acids in the C2 Ungrouped Carbonaceous Chondrite Tarda: A Unique Distribution

Introduction: Meteorites provide a record of the chemical processes that occurred in the early solar sys-tem. The delivery of organic matter by carbonaceous chondrites to the early Earth could have been an im-portant source of amino acids and other prebiotic or-ganic molecules required for the emergence of life [1]. To date, 96 amino acids have been named in meteor-ites, most of which are rare or absent in the biosphere [2]. The variability in amino acid concentrations and isomer distributions measured in carbonaceous chon-drites can be explained by differences in parent body chemistry and alteration conditions [3]. In addition, aqueous alteration was likely important in the amplifi-cation of some left-handed amino acids over their right-handed forms (L-excesses up to ~60%) in the Tagish Lake meteorite [3], suggesting that the origin of life on Earth and possibly elsewhere in the solar sys-tem was biased towards L-amino acids. On August 25, 2020, a fireball was witnessed in southern Morocco and the first pieces of the meteorite fall were recovered the following day near the town of Tarda [4]. Thousands of individual fragments were recovered from the strewn field totaling ~4 kg [4]. Based on petrographic observations, bulk mineralogy, and chemical and O-isotopic analyses, Tarda has been classified as a C2 ungrouped carbonaceous chondrite with similarities to Tagish Lake (though more primi-tive), as well as CI, CY, and CR chondrites [4,5]. The fall and rapid recovery of the Tarda stones provide an important opportunity to investigate a C-rich meteorite using the state-of-the-art techniques that will also be used to study the samples returned from asteroids Ryugu and Bennu by the Hayabusa2 and OSIRIS-REx missions, respectively. Here, we report the first amino acid analyses of the Tarda meteorite. The total concentrations, enantio-meric ratios and relative distributions of amino acids were determined using ultrahigh performance liquid chromatography with UV fluorescence and time-of-flight mass spectrometry (LC-FD/ToF-MS) at NASA GSFC. This analytical technique was employed on extracts from two different pre-rain Tarda meteorite fragments and a sample of sand collected from the Tarda fall site for the purpose of assessing potential terrestrial contamination. Bulk H, C, and N elemental and isotopic analyses were also conducted at the Car-negie Institution for Science (CIS) to assist with petro-logic type classification using elemental analysis iso-tope ratio mass spectrometry (EA-IRMS).

D P Glavin↗

Carbon exchange between the mantle and the crust and its effect upon the atmosphere: Today compared to Archean time

Paleobiologists now recognize that the Earth's biosphere has been profoundly affected by geologic processes. One very important process is the dissipation of heat which has been generated by radioactivity and/or stored within the earth. Heat flow is responsible for crustal movements and therefore it is the principal architect for constructing the environments (e.g. shallow marine, continental, etc.) wherein life developed and flourished. Heat flow has also influenced the movements of volatile elements (e.g. C, N, H, S, rare gases, etc.) both within the Earth's crust and between the crust and mantle. The inventory of these elements in the Earth's crust is important, not just because some of them constitute the building blocks of organic matter, but also because they influence the biosphere's climate. The purpose of this work is to evaluate how the decline of heat flow over the course of the Earth's history has influenced the carbon inventory in the Earth's crust. Such an evaluation must first consider whether the rate at which carbon is presently being exchanged between the mantle and crust is sufficient to play an important role in controlling the crustal inventory. Secondly, this exchange of carbon must be reevaluated in the context of the Precambrian Earth's environment. One very important consideration is that the upper mantle was perhaps 300 C hotter 3 b.y. ago than it is today.

Desmarais, D.↗

The role of extinction in evolution

The extinction of species is not normally considered an important element of neodarwinian theory, in contrast to the opposite phenomenon, speciation. This is surprising in view of the special importance Darwin attached to extinction, and because the number of species extinctions in the history of life is almost the same as the number of originations; present-day biodiversity is the result of a trivial surplus of originations, cumulated over millions of years. For an evolutionary biologist to ignore extinction is probably as foolhardy as for a demographer to ignore mortality. The past decade has seen a resurgence of interest in extinction, yet research on the topic is still at a reconnaissance level, and our present understanding of its role in evolution is weak. Despite uncertainties, extinction probably contains three important elements. (i) For geographically widespread species, extinction is likely only if the killing stress is one so rare as to be beyond the experience of the species, and thus outside the reach of natural selection. (ii) The largest mass extinctions produce major restructuring of the biosphere wherein some successful groups are eliminated, allowing previously minor groups to expand and diversify. (iii) Except for a few cases, there is little evidence that extinction is selective in the positive sense argued by Darwin. It has generally been impossible to predict, before the fact, which species will be victims of an extinction event.

Review, Tutorial↗

Kara and Ust-Kara impact structures (USSR) and their relevance to the K/T boundary event

Ample evidence exists for at least one major meteorite impact event at the time of the Cretaceous/Tertiary (K/T) boundary, and it is therefore important to establish if any recognized terrestrial impact craters are K/T in age. The Kara, USSR, impact structure consists of two adjacent large impact craters (a rare and interesting geologic phenomenon), and it has been suggested that this twin impact structure might be related to the K/T boundary event. However, newly determined (Ar-40)/(Ar-39) and K-Ar ages presented here suggest that these structures are slightly older than 70 Ma, and may thus be too old for a 66 Ma K/T boundary event. Still, these two craters represent a substantial impact event that could have initiated regional, if not global, degradation of the biosphere. Their age suggests a possible relation with the Campanian/Maastrichtian boundary.

Koeberl, Christian↗

Exobiochemistry

Exobiochemistry is the putative biochemistry of extraterrestrial life. It suggests the possible energy and material bases of extraterrestrial life and could help detect it. The diverse biochemistry of Earth indicates that a wide range of exobiochemistry is possible on other planets. An exobiochemistry will probably use the same energy sources as Earths ecology, light, biological organic material, and more rarely abiotic chemicals. Extraterrestrial life will be based on familiar chemical principles and probably capture, store, and release energy using oxidation-reduction reactions. Extraterrestrial life will give chemical indications of its existence. Key elements will be concentrated, stored, and recycled, altering their availability and isotopic composition. Any significant departure from chemical equilibrium would be good evidence for exobiochemistry, but an integrated system of departures from the expected equilibrium would be better. Exobiochemistry can be expected to include closed biogeochemical cycles of the major life supporting elements and may well show the complex dynamic close-coupled interactions that characterize the terrestrial biosphere. Terrestrial biochemistry provides a basis for generalization and extrapolation but it does not set bounds on exobiochemistry. In exobiochemistry we can expect: 1. closed chemical cycles that recycle materials, nutrients, and catalysts, 2. organisms with complementary metabolisms that cooperate to close the chemical cycles, 3. a high probability of a carbon and water chemistry, but some possibility of a non-carbon or non-water chemistry in extreme environments, and, 4. life similar to bacteria more prevalent than higher plants and animals.

Jones, Harry↗

The Containment Assurance Risk Framework of the Mars Sample Return Program

The Mars Sample Return campaign aims at bringing rock and atmospheric samples from Mars to Earth through a series of robotic missions. These missions would collect the samples being cached and deposited on Martian soil by the Perseverance rover, place them in a container, and launch them into Martian orbit for subsequent capture by an orbiter that would bring them back. Given there exists a non-zero probability that the samples contain biological material, precautions are being taken to design systems that would break the chain of contact between Mars and Earth. These include techniques such as sterilization of Martian particles, redundant containment vessels, and a robust reentry capsule capable of accurate landings without a parachute. Requirements exist that the probability of containment not assured of Martian-contaminated material into Earth’s biosphere be less than one in a million. To demonstrate compliance with this strict requirement, a statistical framework was developed to assess the likelihood of containment loss during each sample return phase and make a statement about the total combined mission probability of containment not assured. The work presented here describes this framework, which considers failure modes or fault conditions that can initiate failure sequences ultimately leading to containment not assured. Reliability estimates are generated from databases, design heritage, component specifications, or expert opinion in the form of probability density functions or point estimates and provided as inputs to the mathematical models that simulate the different failure sequences. The probabilistic outputs are then combined following the logic of several fault trees to compute the ultimate probability of containment not assured. Given the multidisciplinary nature of the problem and the different types of mathematical models used, the statistical tools needed for analysis are required to be computationally efficient. While standard Monte Carlo approaches are used for fast models, a multi-fidelity approach to rare event probabilities is proposed for expensive models. In this paradigm, inexpensive low-fidelity models are developed for computational acceleration purposes while the expensive high-fidelity model is kept in the loop to retain accuracy in the results. This work presents an example of end-to-end application of this framework highlighting the computational benefits of a multi-fidelity approach.

Giuseppe Cataldo↗

Enantioselective Three-Dimensional High-Performance Liquid Chromatographic Determination of Amino Acids in the Hayabusa2 Returned Samples from the Asteroid Ryugu

The chirality of amino acids in extraterrestrial materials may provide an insight into the origin of the essential L-enantiopure amino acids in the terrestrial biosphere. In 2020, the Hayabusa2 mission succeeded in bringing back surface materials from the C-type asteroid (162173) Ryugu to the Earth. Amino acids were one of the targeted organic molecules to be studied in the Ryugu samples. To analyze the various structural isomers of amino acids, which were expected to be present, from the limited amount of the returned samples, the development of a highly-sensitive and selective analytical method was necessary. In the present study, a three-dimensional high-performance liquid chromatography (3D-HPLC) system has been developed for the enantioselective determination of five proteinogenic and three non-proteinogenic amino acids in the Ryugu samples, in which amino acids in the sample were separated by reversed-phase, anion-exchange and enantioselective columns after the fluorescence derivatization with 4-fluoro-7-nitro-2,1,3-benzoxadiozole. The applicability of the analytical system to the extraterrestrial samples was evaluated by analyzing several types of carbonaceous meteorites before applying the system to the Ryugu samples. In the analysis of the Ryugu samples, all of the target amino acids were successfully determined quantitatively. Non-proteinogenic amino acids including 2-amino-n-butyric acid, isovaline and norvaline, rarely present in the terrestrial environment, were found as almost racemic mixtures with 47.1 to 55.2%L.

Amino acids↗