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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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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
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 NTRS2013

A Search for Amino Acids and Nucleobases in the Martian Meteorite Roberts Massif 04262 Using Liquid Chromatography-Mass Spectrometry

The investigation into whether Mars contains signatures of past or present life is of great interest to science and society. Amino acids and nucleobases are compounds that are essential for all known life on Earth and are excellent target molecules in the search for potential Martian biomarkers or prebiotic chemistry. Martian meteorites represent the only samples from Mars that can be studied directly in the laboratory on Earth. Here, we analyzed the amino acid and nucleobase content of the shergottite Roberts Massif (RBT) 04262 using liquid chromatography-mass spectrometry. We did not detect any nucleobases above our detection limit in formic acid extracts; however, we did measure a suite of protein and nonprotein amino acids in hot-water extracts with high relative abundances of beta-alanine and gamma-amino-eta-butyric acid. The presence of only low (to absent) levels of several proteinogenic amino acids and a lack of nucleobases suggest that this meteorite fragment is fairly uncontaminated with respect to these common biological compounds. The distribution of straight-chained amine-terminal eta-omega-amino acids in RBT 04262 resembled those previously measured in thermally altered carbonaceous meteorites. A carbon isotope ratio of -24(0/00) +/- 6(0/00) for beta-alanine in RBT 04262 is in the range of reduced organic carbon previously measured in Martian meteorites (Steele et al. 2012). The presence of eta-omega-amino acids may be due to a high temperature Fischer-Tropschtype synthesis during igneous processing on Mars or impact ejection of the meteorites from Mars, but more experimental data are needed to support these hypotheses.

Laboratory analysis↗
NASA NTRS2014

Vaporization Studies of Olivine via Knudsen Effusion Mass Spectrometry

Olivine is the major mineral in the Earth's upper mantle occurring predominantly in igneous rocks and has been identified in meteorites, asteroids, the Moon and Mars. Among many other important applications in planetary and materials sciences, the thermodynamic properties of vapor species from olivine are crucial as input parameters in computational modelling of the atmospheres of hot, rocky exoplanets (lava planets). There are several weight loss studies of olivine vaporization in the literature and one Knudsen Effusion Mass Spectrometry (KEMS) study. In this study, we examine a forsterite-rich olivine (93% forsterite and 7% fayalite, Fo93Fa7) with KEMS to further understand its vaporization and thermodynamic properties.

Planetary atmospheres↗
NASA NTRS2017

Analysis of Mixed Aryl/Alkyl Esters by Pyrolysis Gas Chromatography-Mass Spectrometry in the Presence of Perchlorate

Mars is an important target for Astrobiology. A key goal of the MSL mission was to determine whether Mars was habitable in the past, a que-tion that has now been definitely determined to be yes. Another key goal for Mars exploration is to understand the origin and distribution of organic material on Mars; this question is being addressed by the SAM instrument on MSL, and will also be informed by two upcoming Mars exploration missions, ExoMars and Mars 2020. These latter two missions have instrumentation capable of detecting and characterize organic molecules. Over the next decade, these missions will analyze organics in surface, near-surface and sub-surface samples. Each mission has the capability to analyze organics by different methods (pyrolysis gas chromatography-mass spectrometry [py-GC-MS]; laser desorption and thermal volatilization GC-MS; and Raman spectroscopy). Plausibly extraterrestrial organics were recently discovered by the Mars Science Laboratory (MSL), providing an important first step towards understanding the organic inventory on Mars [1]. The compounds detected were chlorobenzenes and chloroalkanes, but it was argued that chlorination of these compounds occurred during pyrolysis of samples containing unchlorinated organics in the presence of perchlorate. A recent report analyzed a suite of aromatic (benzene, toluene, benzoic acid, phthalic acid, and mellitic acid) and aliphatic (acetic acid, propane, propanol, and hexane) by pyrolysis under SAM-like conditions in the presence of perchlorate to attempt to constrain possible precursor molecules for the organic molecules detected on Mars. For aromatic compounds, the aromatic acids all readily produced SAM-relevant chlorobenzes, whereas benzene and toluene did not. This observation suggests that the chlorobenzene detected on Mars could have derived from compounds like mellitic acid, consistent with the previous hypothesis by Benner et al. [3]. Among the aliphatic molecules, it was shown that pyrolysis of alkanes and alcohols in the presence of perchlorates produced polychlorine containing chloro-alkanes similar to what was observed on Mars. Surpris-ingly, however, similar treatment of acetic acid pro-duced chloroketones, instead, and no chloroalkanes were reported. This suggests that the chloroalkanes detected in the Sheepbed mudstone were not derived from aliphatic carboxylic acids, but instead were from more reduced alcohols or even alkanes, or perhaps were degradation products of more complicated organic material. Because organics analyses on mars will rely heavily on py-GC-MS of perchlorate-containing samples over the next decade, it is important to understand the fate of organic molecules of biotic and abiotic origin under such conditions. In this work we begin a series of experiments to improve our understanding of products generated during py-GC-MS of increasingly complex organic molecules (esters, amides, peptides, nucleic acids, fatty acids) in the presence of perchlorate.

Burton, A. S.↗
NASA NTRS2016

Tandem Mass Spectrometry on a Miniaturized Laser Desorption Time-of-Flight Mass Spectrometer

Tandem mass spectrometry (MSMS) is a powerful and widely-used technique for identifying the molecular structure of organic constituents of a complex sample. Application of MSMS to the study of unknown planetary samples on a remote space mission would contribute to our understanding of the origin, evolution, and distribution of extraterrestrial organics in our solar system. Here we report on the realization of MSMS on a miniaturized laser desorption time-of-flight mass spectrometer (LD-TOF-MS), which is one of the most promising instrument types for future planetary missions. This achievement relies on two critical components: a curved-field reflectron and a pulsed-pin ion gate. These enable use of the complementary post-source decay (PSD) and laser-assisted collision induced dissociation (L-CID) MSMS methods on diverse measurement targets with only modest investment in instrument resources such as volume and weight. MSMS spectra of selected molecular targets in various organic standards exhibit excellent agreement when compared with results from a commercial, laboratory-scale TOF instrument, demonstrating the potential of this powerful technique in space and planetary environments.

Li, Xiang↗
NASA NTRS2020

Creepy (not KREEPy) Gold-Indium Intermetallic Compounds on Secondary Ion Mass Spectrometry Samples

A series of Secondary Ion Mass Spectrometry (SIMS) sessions to measure hydrogen (H) in Martian meteorite minerals was completed using the Cameca 6f SIMS and NanoSIMS 50L at Arizona State University (ASU). During these sessions, a “creeping” phenomenon has occurred, where the edges of samples pressed in indium are covered by a metal alloy. We summarize these observations herein, present a collection of preliminary data, and discuss explanations and concerns for future SIMS work. We conclude the report with a research plan for further study.

Dudley, J. M.↗
NASA NTRS2020

A Sensitive Quantitative Analysis of Abiotically Synthesized Short Homopeptides using Ultraperformance Liquid Chromatography and Time-of-Flight Mass Spectrometry

In the origins of life field understanding the abiotic polymerization of simple organic monomers (e.g., amino acids) into larger biomolecules (e.g., oligopeptides), remains a seminal challenge. Recently, preliminary observations showed a limited set of peptides formed in the presence of the plausible prebiotic phosphorylating agent, diamidophosphate (DAP), highlighting the need for an analytical tool to critically evaluate the ability of DAP to induce oligomerization of simple organics under aqueous conditions. However, performing accurate and precise, targeted analyses of short oligopeptides remains a distinct challenge in the analytical chemistry field. Here, we developed a new technique to detect and quantitate amino acids and their homopeptides in a single run using ultraperformance liquid chromatography-fluorescence detection/time of flight mass spectrometry. Over an 8-minute retention time window, 18 target analytes were identified and quantitated, 16 of which were chromatographically separated at, or near baseline resolution. Compound identity was confirmed by accurate mass analysis using a 10 ppm mass tolerance window. This method featured limits of detection < 5 nM (< 1 fmol on column) and limits of quantitation (LOQs) <15 nM (< 3 fmol on column). The LODs and LOQs were upwards of ∼28x and ∼788x lower, respectively, than previous methods for the same analytes, highlighting the quantifiable advantages of this new method. Both detectors provided good quantitative linearity (R(exp 2) > 0.985) for all analytes spanning concentration ranges ∼3 - 4 orders of magnitude. We performed a series of laboratory experiments to investigate DAP-mediated oligomerization of amino acids and peptides and analyzed experimental products with the new method. DAP readily polymerized amino acids and peptides under a range of simulated environmental conditions. This research underscores the potential of DAP to have generated oligopeptides on the primordial Earth, enhancing prebiotic chemical diversity and complexity at or near the origin of life.

Prebiotic Chemistry and Analytical Chemistry↗
NASA NTRS2021

In Situ Mg/Ca Measurements on Foraminifera: Comparison Between Laser Ablation Inductively Coupled Plasma Mass Spectrometry and Wavelength-Dispersive X-Ray Spectroscopy by Electron Probe Microanalyzer

We present a comparison of two different techniques: Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) and wavelength-dispersive X-Ray Spectroscopy by electron probe microanalyzer (EPMA) for obtaining Mg/Ca ratios in individual foraminifera shells. The goal is to assess the use of EPMA as an alternative technique for Mg/Ca analyses of single foraminiferal calcite shells. Foraminifera obtained from sediments (benthic, Uvigerina spp.) and from plankton tows (planktonic, Orbulina universa) were analyzed. All specimens were prepared in epoxy mounts and exposed in cross-section such that multiple high-resolution analyses could be completed on the shells using both techniques. We examined our data using statistical methods designed for the assessment and comparison of measurement techniques. In the case of Uvigerina, the mean difference for ratios obtained using EPMA and LA-ICP-MS is very small (−0.046 mmol mol−1) and scale independent. The Limits of Agreement (LoA, the standard deviation of the bias plus the mean bias) is [−0.315, 0.223] mmol mol−1. For samples with ratios lower than 13 mmol mol−1, we found a mean EPMA–LA-ICP-MS bias of −2.44 mmol mol−1 and a corresponding LoA of [−3.85, −1.04] mmol mol−1. For ratios higher than 13 mmol mol−1, there appears to be a scale dependent bias, meaning that the EPMA measured ratios become progressively larger than those of LA-ICP-MS as the Mg/Ca ratio increases, so the mean bias and LoA metrics are not meaningful. Results indicate that it is possible to use EPMA to collect Mg/Ca data, if the ratios are lower than ∼13 mmol mol−1.

EPMA↗
NASA NTRS2021

Identifying molecules as biosignatures with assembly theory and mass spectrometry

The search for alien life is hard because we do not know what signatures are unique to life. We show why complex molecules found in high abundance are universal biosignatures and demonstrate the first intrinsic experimentally tractable measure of molecular complexity, called the molecular assembly index (MA). To do this we calculate the complexity of several million molecules and validate that their complexity can be experimentally determined by mass spectrometry. This approach allows us to identify molecular biosignatures from a set of diverse samples from around the world, outer space, and the laboratory, demonstrating it is possible to build a life detection experiment based on MA that could be deployed to extraterrestrial locations, and used as a complexity scale to quantify constraints needed to direct prebiotically plausible processes in the laboratory. Such an approach is vital for finding life elsewhere in the universe or creating de-novo life in the lab.

Stuart M. Marshall↗
NASA NTRSDate not supplied

Nearest-Neighbor Machine Learning Feature Selection for Interpretation of Microbial Molecular Signatures from Isotope Ratio Mass Spectrometry Data

Mass spectrometry (MS) promises to be a powerful tool for potential biosignature detection during astrobiological missions on ocean worlds in our solar system. Accurate and generalizable machine learning methods could enhance science return on investment by predicting seawater chemistry and classifying isotopic biosignatures, either as a signature consistent with microbial life (biotic) or as a novelty (unclassified/unique). However, machine learning models are likely to be complex and involve interactions between MS features, making biosignatures difficult to interpret. Feature selection methods provide biological and chemical context that help interpret the mechanisms of machine learning models, but these methods also need the ability to detect complex interactions. Previously, we developed a machine learning feature selection algorithm called nearest-neighbor projected distance regression (NPDR) that has the ability to identify important model features that involve complex interactions and automatically reduce correlation and the dimensionality in a high-dimensional variable space. The standard distance metrics used in NPDR – Manhattan and Euclidean – assume the multivariate data are isotropic, which is often violated in real data due to differences in the covariance between variables. Thus, we extend NPDR to include a random forest distance, and other anisotropic distance metrics, for computing nearest neighbors. We also augment the isotope-ratio MS data with time-series features from the raw MS signal to improve biotic classification. We test NPDR on our novel experimental ocean world seawater analog MS data. We measure isotope fractionations of volatile CO 2 that could be measured in exospheres or plumes. Samples include baseline abiotic conditions using a range of possible seawater chemistry consistent with Europa and Enceladus, and biotic samples that include microbes in these seawaters. We use penalized NPDR with random forest proximity to identify interpretable microbial molecular signatures. We compare features with random forest importance, and we train a classifier that discriminates between biotic and abiotic samples with high accuracy. These ML-trained ocean-world analog MS data could be used to assist in identifying biosignatures during future missions.

geochemistry↗
NASA NTRSDate not supplied

Development and Airborne Demonstration of the Concurrent Artificially-Intelligent Spectrometry and Adaptive Lidar System: Advancing Lidar Capabilities for the STV Observing System

We report on the design, build and planned airborne demonstration of a spaceflight-prototype Concurrent Artificially-intelligent Spectrometry and Adaptive Lidar System (CASALS). The CASALS lidar is an Adaptive Wavelength Scanning Lidar (AWSL) operating in push broom mode. The demonstration has three major goals: advance the Technical Readiness Level of the AWSL hardware, validate its measurement performance and mature algorithms and methods needed for the Surface Topography and Vegetation (STV) observing system. AWSL acquires parallel tracks of surface heights by rapidly steering a laser beam across a swath. A 1040nm-centered laser is tuned across 30nm and carved into 2-ns pulses, the pulse energy is fiber amplified and the pulses are dispersed cross-track using a non-mechanical wavelength-to-angle grating. For the spaceflight system the beam will be pointable to 1200 10m footprints across a 7km swath. For the airborne demonstration there will be 256 0.7m footprints across a 110m swath. In both cases the footprints overlap across- and along-track for uniform target illumination. For the airborne demonstration a steering mirror will increase the accessible swath width to 4km. At the receiver, solar radiation is filtered with a narrow-slit grating-spectrometer and the footprints are imaged onto a linear-mode, photon-sensitive HgCdTe APD-array. The received pulses are time-division-multiplexed to a few high-speed analog-to-digital converters to record waveforms. Spaceflight and airborne CASALS are designed to nominally detect 20 photons per pulse and, by averaging 27 overlapping footprints, achieve 2cm flat target range precision and high-quality vegetation structure waveforms The AWSL will be flown in the summer of 2024, along with a Headwall VNIR-SWIR hyperspectral sensor imaging a 4km wide swath, at NEON eddy covariance flux towers in the U.S. mid-Atlantic where high resolution hyperspectral and lidar data, acquired annually, are available for validation.

Guangning Yang↗
NASA NTRSDate not supplied

Development of Concurrent Artificially-Intelligent Spectrometry and Adaptive Lidar System (CASALS) for Swath Mapping From Space

We present the design and performance of a Concurrent Artificially-intelligent Spectrometry and Adaptive Lidar System (CASALS) for 3D imaging from Space. With a single fast wavelength tuning laser, CASALS accomplishes a 1,200 resolvable spots swath mapping by grating dispersion wavelength steering. Any subset of these 1,200 spots can be selected by wavelength switching. The validation operating principle was accomplished and reported in IGASS-2022. With configurable base design, we report the designs and progress of the CASALS airplane campaign with 256 contiguous ground spots. It is accomplished with a single fast tuning lase at 1040-nm, 1.152MHz tuning rate, and pulse modulated 2-ns on each wavelength. Return pulses are mapped to an eight-pixel detector array with single-photon sensitivity. The lidar returns are time-multiplexed to two outputs that are digitized with two 1-GSPS-digitizer. A grating spectrometer rejects solar background noise spatially and spectrally. We are developing a 1040-nm CASALS intended for multiple LEO orbit missions: Earth Venture Mission on ESPA Grande, STV Mission on ESPA Grande SmallSat, STV Mission on spacecraft equivalent to ICESat power (SWaP,) and splitting the laser beam requires higher laser pulse energy.

ranging lidar↗
NASA NTRS1966

Mass spectrometry without ions.

Molecular flow mass spectrometer analysis of porous metal membranes for gases of different molecular weights

POROUS MATERIAL↗
NASA NTRS2005

Simultaneous quantification of poly-dispersed anionic, amphoteric and nonionic surfactants in simulated wastewater samples using C18 high-performance liquid chromatography-quadrupole ion-trap mass spectrometry

This paper describes the development of a guantitative method for direct and simultaneous determination of three frequently encountered surfactants, amphoteric (cocoamphoacetate, CAA), anionic (sodium laureth sulfate, SLES), and nonionic (alcohol ethoxylate, AE) using a reversed-phase C18 HPLC coupled with an ESI ion-trap mass spectrometer (MS). Chemical composition, ionization characteristics and fragmentation pathways of the surfactants are presented. Positive ESI was effective for all three surfactants in agueous methanol buffered with ammonium acetate. The method enables rapid determinations in small sample volumes containing inorganic salts (up to 3.5 g L(-1)) and multiple classes of surfactants with high specificity by applying surfactant specific tandem mass spectrometric strategies. It has dynamic linear ranges of 2-60, 1.5-40, 0.8-56 mg L(-1) with R2 egual or greater than 0.999, 0.98 and 0.999 (10 microL injection) for CAA, SLES, and AE, respectively.

Chromatography, High Pressure Liquid/methods↗