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Soluble Organic Matter (SOM) analysis of the Hayabusa2 samples: The first results

The Hayabusa2 spacecraft successfully collected the surface and possible sub-surface materials of the asteroid 162173 Ryugu. Ryugu is a C-type asteroid characterized by a low-albedo surface probably consisting of hydrous minerals and carbonaceous materials. [1] The direct optical and spectral analysis of the returned samples indicates that Ryugu material is dominated by hydrous carbonaceous chondrite-like matter (similar to CI chondrites) [2]. Since carbonaceous chondrites have generally yielded various types of organic matter, the collected Ryugu grains are expected to contain diverse types of organic compounds including bio-related molecules. The occurrence of organic compounds in the Ryugu surface will provide clues to the evolution of prebiotic molecules and their preservations associated with aqueous alteration of the primitive asteroid. The initial analysis of soluble organic matter (SOM) of the Hayabusa2-returned samples has been performed by an international team consisting of 32 members. Because the sample amount available for comprehensive SOM analyses is limited, and because the SOM is expected to be present as a complex mixture of various types of organic compounds with very small concentrations of each compound, high-sensitivity and high-resolution analytical techniques have been developed using carbonaceous meteorites [e.g. 3]. Two aggregate samples of the Ryugu grains (A106 and C107) were allocated for the solvent extractions and bulk carbon (C), hydrogen (H), nitrogen (N), sulfur (S) and oxygen (O) measurements. The A106 sample was collected during the 1st sampling in February 2019 and the C107 sample was collected during the 2nd sampling in July 2019 after the Small Carry Impactor (SCI) operation. They consist mainly of particles smaller than 1 mm in diameter, and each sample mass was 38-39 mg. They were firstly investigated spectroscopically in the near infrared wavelength range by the Stone Team prior to the solvent extractions. Other small grains (A0080 and C0057) were also allocated for this study to investigate the spatial distribution of organic compounds on the sample surface. The extraction and analytical measurements implemented by the SOM Team are summarized in Figure 1. Each powder sample was extracted sequentially with non-polar to polar solvents, i.e., hexane, dichloromethane (DCM), methanol (MeOH) and H2O, for non-targeted analysis to reveal the compound composition. Each solvent extract was analyzed by solution state nuclear magnetic resonance (NMR) spectroscopy [4], Fourier transform- ion cyclotron resonance/mass spectrometry (FT-ICR/MS) with ESI and APPI ionization [5] and by high-resolution mass spectroscopy using Orbitrap MS coupled with nano-liquid chromatography (nanoLC/Orbitrap MS) [6], and using two dimensional gas chromatography/mass spectrometry (GC×GC/MS). The extracted residues were passed to the Chemistry Team for further inorganic element analysis. The other powder sample was subjected to the hot water extraction for amino acid analyses including chiral isomer separation, which was performed by three-dimensional (3D) high-performance liquid chromatography (HPLC) with high-sensitivity fluorescence detection (FD) [7] and by HPLC/FD coupled with quadrupole-time of flight/mass spectrometry (QToF/MS) [8]. After the hot water extraction, the residue was split into two halves. One half was further extracted with hydrochloric acid (HCl) to analyze for amino acids in bound-form. The other half was sequentially extracted with DCM/MeOH (1/1) to analyze semi-polar compounds such as polycyclic aromatic hydrocarbons (PAHs) by GC/MS, followed by further extraction with formic acid to analyze polar heterocyclic compounds, and subsequent extraction with HCl to detect bound-form polar compounds. The extracted residues were passed to the IOM Team for the analysis of insoluble organic matter (IOM). Compound-specific stable isotope analyses will be performed using GC/combustion/isotope ratio mass spectrometry (GC/C/IRMS) if the compound concentration is high enough to enable such an isotopic measurement. All extraction procedures were performed on an ISO 6 (Class 100) clean bench inside an ISO 5 (Class 1000) clean room. Baked serpentine powder was also analyzed as a procedural blank. In situ organic compound analysis with the molecular imaging was performed using desorption electrospray ionization (DESI) equipped with Orbitrap MS [9, 10], followed by spatial imaging of organic compounds using ToF/secondary ion mass spectrometry (ToF/SIMS) [11]. The bulk chemical and isotopic compositions of CNS and HO were determined using nano-elemental analysis/isotope ratio mass spectrometry (nanoEA/IRMS) [12] and EA/pyrolysis/IRMS, respectively. We have identified a variety of indigenous organic compounds in the extracts of both A106 and C107 samples. The Ryugu grains host organic molecules under the high-vacuum and cosmic-ray irradiation environment of the asteroid surface. The analysis of extracted molecules is in progress, and the first results will be presented at the symposium.

Hiroshi Naraoka↗

Heating and Sampling Efficiency Evaluation for the Nephele Venus Cloud Sampling Mission Concept

Nephele is a descent probe concept with a unique combination of entry (3D-CC+HEEET), sampling (flow-through passive impactors), and optics (laser-induced breakdown spectroscopy, or LIBS, and surface-enhanced Raman spectroscopy, or SERS), technologies with two key innovations. The first is the integration of the aerosol sampling inlet into the aeroshell body, allowing the possibility of sampling during passive descent without separation. The second is the use of the aerosol capture surface as an optical analysis substrate, allowing fast-cadence aerosol analysis via a dual optical spectrometer instead of mass spectrometry. Although this concept shares some features with other efforts such as Cupid’s Arrow (single-body sample capture system), DAVINCI and Venera-D (use of an optical spectrometer), Nephele is unique in its physical integration of the sonde body, aerosol and gas sampler, and analysis instrumentation. This innovation is designed to eliminate the need for a controlled descent to achieve a detailed atmospheric aerosol transect, which offers in situ planetary science in a small spacecraft envelope. Aeroshell designs with inlets for free-falling sondes are well-understood, though not yet assessed for aerosol capture efficiency. A HEEET aeroshell with a specialized nose inlet material comprised of Carbon-Carbon is proposed for this mission concept.

Venus↗

Heating and Sampling Efficiency Evaluation for the Nephele Venus Cloud Sampling Mission Concept

Nephele [1] is a descent probe concept with a unique combination of entry (3D-CC+HEEET), sampling (flow-through passive impactors), and optics (laser-induced breakdown spectroscopy, or LIBS, and surface-enhanced Raman spectroscopy, or SERS), technologies with two key innovations (Figure 1). The first is the integration of the aerosol sampling inlet into the aeroshell body, allowing the possibility of sampling during passive descent without separation. The second is the use of the aerosol capture surface as an optical analysis substrate, allowing fast-cadence aerosol analysis via a dual optical spectrometer instead of mass spectrometry. Although this concept shares some features with other efforts such as Cupid’s Arrow [1] (single-body sample capture system), DAVINCI [2] and Venera-D [3] (use of an optical spectrometer), Nephele is unique in its physical integration of the sonde body, aerosol and gas sampler, and analysis instrumentation. This innovation is designed to eliminate the need for a controlled descent to achieve a detailed atmospheric aerosol transect, which offers in situ planetary science in a small spacecraft envelope. Aeroshell designs with inlets for free-falling sondes are well-understood, though not yet assessed for aerosol capture efficiency. A HEEET aeroshell with a specialized nose inlet material comprised of Carbon-Carbon is proposed for this mission concept.

Venus↗

The effects of ultraviolet light on the degradation of organic compounds - A possible explanation for the absence of organic matter on Mars

The analysis of the top layer of the Martian regolith at the two Viking landing sites did not reveal any indigenous organic compounds. However, the existence of such compounds at deeper layers cannot be ruled out. Cosmochemical considerations indicate various potential sources for organic matter on Mars, such as comets and meteorites. The study tested the stability of a sample of the Murchison meteorite and various organic substances which have been detected in carbonaceous chondrites, such as glycine, adenine and naphthalene, to the action of ultraviolet light. The compounds were adsorbed on powdered quartz and on California desert soil and were irradiated in the presence or absence of oxygen. The organic content, before and after irradiation, was measured by carbon elementary analysis, UV-absorption, amino acid analysis or pyrolysis-gas chromatography-mass spectrometry. In the absence of oxygen, adenine and glycine appear to be stable over the given part of irradiation. A definite degradation was noticed in the case of naphtalene and the Murchison meteorite. In the presence of oxygen in amounts comparable to those on Mars all compounds were degraded. The degree of degradation was influenced by the irradiation time, temperature and oxygen content.

Oro, J.↗

Isolation, characterization, and primary structure of rubredoxin from the photosynthetic bacterium, Heliobacillus mobilis

Rubredoxin is a small nonheme iron protein that serves as an electron carrier in bacterial systems. Rubredoxin has now been isolated and characterized from the strictly anaerobic phototroph, Heliobacillus mobilis. THe molecular mass (5671.3 Da from the amino acid sequence) was confirmed and partial formylation of the N-terminal methionyl residue was established by matrix-assisted laser desorption mass spectroscopy. The complete 52-amino-acid sequence was determined by a combination of N-terminal sequencing by Edman degradation and C-terminal sequencing by a novel method using carboxypeptidase treatment in conjunction with amino acid analysis and laser desorption time of flight mass spectrometry. The molar absorption coefficient of Hc. mobilis rubredoxin at 490 nm is 6.9 mM-1 cm-1 and the midpoint redox potential at pH 8.0 is -46 mV. The EPR spectrum of the oxidized form shows resonances at g = 9.66 and 4.30 due to a high-spin ferric iron. The amino acid sequence is homologous to those of rubredoxins from other species, in particular, the gram-positive bacteria, and the phototrophic green sulfur bacteria, and the evolutionary implications of this are discussed.

NASA Discipline Number 52-30↗

Chlorine Isotopic Compositions of Apatite in Apollo 14 Rocks: Evidence for Widespread Vapor-Phase Metasomatism on the Lunar Nearside ~4 Billion Years Ago

Compared to most other planetary materials in the Solar System, some lunar rocks display high delta (sup 37) Cl signatures. Loss of Cl in a H<<Cl environment has been invoked to explain the heavy signatures observed in lunar samples, either during volcanic eruptions onto the lunar surface or during large scale degassing of the lunar magma ocean. To explore the conditions under which Cl isotope fractionation occurred in lunar basaltic melts, five Apollo 14 crystalline samples were selected (14053,19, 14072,13, 14073,9, 14310,171 along with basaltic clast 14321,1482) for in situ analysis of Cl isotopes using secondary ion mass spectrometry. Cl isotopes were measured within the mineral apatite, with delta (sup 37) Cl values ranging from +14.6 ± 1.6 per mille to +40.0 ± 2.9 per mille. These values expand the range previously reported for apatite in lunar rocks, and include some of the heaviest Cl isotope compositions measured in lunar samples to date. The data here do not display a trend between increasing rare earth elements contents and delta (sup 37) Cl values, reported in previous studies. Other processes that can explain the wide inter- and intra-sample variability of delta (sup 37) Cl values are explored. Magmatic degassing is suggested to have potentially played a role in fractionating Cl isotope in these samples. Degassing alone, however, could not create the wide variability in isotopic signatures. Our favored hypothesis, to explain small scale heterogeneity, is late-stage interaction with a volatile-rich gas phase, originating from devolatilization of lunar surface regolith rocks ~4 billion years ago. This period coincides with vapor-induced metasomastism recorded in other lunar samples collected at the Apollo 16 and 17 landing sites, pointing to the possibility of widespread volatile-induced metasomatism on the lunar nearside at that time, potentially attributed to the Imbrium formation event.

apatit↗

NASA Tech Briefs, November 2010

Topics covered include: Portable Handheld Optical Window Inspection Device; Salience Assignment for Multiple-Instance Data and Its Application to Crop Yield Prediction; Speech Acquisition and Automatic Speech Recognition for Integrated Spacesuit Audio Systems ; Predicting Long-Range Traversability from Short-Range Stereo-Derived Geometry; Browser-Based Application for Telemetry Monitoring of Robotic Assets; Miniature Low-Noise G-Band I-Q Receiver; Methods of Using a Magnetic Field Response Sensor Within Closed, Electrically Conductive Containers; Differential Resonant Ring YIG Tuned Oscillator; Microfabricated Segmented-Involute-Foil Regenerator for Stirling Engines; Reducing Seal Adhesion in Low Impact Docking Systems; Optimal Flow Control Design; Corrosion-Resistant Container for Molten-Material Processing; Reusable Hot-Wire Cable Cutter; Deployment of a Curved Truss; High-Volume Airborne Fluids Handling Technologies to Fight Wildfires; Modeling of Alkane Oxidation Using Constituents and Species; Fabrication of Lanthanum Telluride 14-1-11 Zintl High-Temperature Thermoelectric Couple; A Computer Model for Analyzing Volatile Removal Assembly; Analysis of Nozzle Jet Plume Effects on Sonic Boom Signature; Optical Sidebands Multiplier; Single Spatial-Mode Room-Temperature-Operated 3.0 to 3.4 micrometer Diode Lasers; Self-Nulling Beam Combiner Using No External Phase Inverter; Portable Dew Point Mass Spectrometry System for Real-Time Gas and Moisture Analysis; Maximum Likelihood Time-of-Arrival Estimation of Optical Pulses via Photon-Counting Photodetectors; Handheld White Light Interferometer for Measuring Defect Depth in Windows; Decomposition Algorithm for Global Reachability on a Time-Varying Graph; Autonomous GN and C for Spacecraft Exploration of Comets and Asteroids; Efficient Web Services Policy Combination; Using CTX Image Features to Predict HiRISE-Equivalent Rock Density; Isolation of the Paenibacillus phoenicis, a Spore-Forming Bacterium; Monolithically Integrated, Mechanically Resilient Carbon-Based Probes for Scanning Probe Microscopy; Cell Radiation Experiment System; Process to Produce Iron Nanoparticle Lunar Dust Simulant Composite; Inversion Method for Early Detection of ARES-1 Case Breach Failure; Use of ILTV Control Laws for LaNCETS Flight Research;and Evaluating Descent and Ascent Trajectories Near Non-Spherical Bodies.

Source record↗

Detection of Cometary Amines in Samples Returned by the Stardust Spacecraft

The delivery of amino acids to the early Earth by comets and their fragments could have been a significant source of the early Earth's prebiotic organic inventory that led to the emergence of life (Chyba and Sagan, 1992). Over 20 organic molecules including methane, ethane, ammonia, cyanic acid, formaldehyde, formamide, acetaldehyde, acetonitrile, and methanol have been identified by radio spectroscopic observations of the comae of comets Hale-Bopp and Hyakutake (Crovisier et al. 2004). These simple molecules could have provided the organic reservoir to allow the formation of more complex prebiotic organic compounds such as amino acids. After a 7-year mission, the Stardust spacecraft returned to Earth samples from comet Wild 2 on January 15, 2006 providing the opportunity to analyze the organic composition and isotopic distribution of cometary material with state-of-the-art laboratory instrumentation. The Preliminary Examination Team analyses of organics in samples returned by Stardust were largely focused on particles that impacted the collector aerogel and aluminum foil (Sandford et al. 2006). However, it is also possible that Stardust returned a "diffuse" sample of gas-phase organic molecules that struck the aerogel directly or diffused away from the grains after impact. To test this possibility, samples of Stardust flight aerogel and foil were carried through a hot water extraction and acid hydrolysis procedure to see if primary amine compounds were present in excess of those seen in controls. Here we report highly sensitive liquid chromatography time-of-flight mass spectrometry measurements of amino acids and amines in samples returned from a comet (Glavin et al. 2008). A suite of amino acids and amines including glycine, L-alanine, methylamine (MA), and ethylamine (EA) were identified in the Stardust bulk aerogel. With the exception of MA and EA, all other primary amines detected in comet-exposed aerogels were also present in the aerogel witness tile that was not exposed to Wild 2, suggesting that most amines are terrestrial in origin. However, the enhanced abundances of MA, EA, and possibly glycine in comet-exposed aerogel compared to controls, coupled with MA to EA ratios (1 to 2) that are distinct from preflight aerogels (7 to 10), suggest that these amines were captured from Wild 2. It is possible that MA and EA were formed on energetically processed icy grains containing methane, ethane, and ammonia. The presence of cometary amines in Stardust material supports the hypothesis that comets were an important source of prebiotic organics on the early Earth. To better understand their origin, a systematic compound specific carbon isotopic analysis (C-CSIA) via gas chromatography quadrupole mass spectrometry in with parallel with combustion isotope ratio mass spectrometry (GCQMS/ IRMS) is being conducted. We will discuss our latest C-CSIA measurements and what they indicate about the origin of amino acids extracted from Stardust samples.

Glavin, Daniel P.↗

Extraterrestrial Molecular Indicators of Life Investigation (EMILI)

Future missions to Enceladus, Europa, Mars, and beyond may seek the molecular signs of extraterrestrial life through chemical analysis of acquired samples. Particularly on ocean worlds such as Enceladus and Europa, samples may contain trace ocean-borne molecular biosignatures of extant life that may or may not share similarities to those of terrestrial life. In situ analyses must be prepared to detect and characterize a wide range of possible molecular species, structures, and patterns, typically with exquisite sensitivity and within a complex, poorly-characterized planetary environment. The Extraterrestrial Molecular Indicators of Life Investigation (EMILI) is designed to meet or exceed the requirements of such missions for organic molecular analysis through a powerful combination of dual chemical separation and both optical and mass spectrometry detection techniques, realized in an integrated, compact instrument package fully compatible with anticipated flight resources and conditions. The full EMILI instrument combines two sample analysis subsystems to provide wide-ranging and complementary detection of organic compounds and inorganic salts. The Gas Analysis Processing System (GAPS) uses a chemical derivatization protocol with gas chromatography (GC) separation prior to detection in an ion trap mass spectrometer (ITMS) to enable full characterization of lower-polarity, volatile and semi-volatile molecules such as fatty acids and hydrocarbons. The Organic Capillary Electrophoresis ANalysis System (OCEANS) uses a liquid-based extraction protocol with CE separation to enable precise analysis of more water-soluble/polar compounds. OCEANS features a laser-induced fluorescence detection mode to perform ultra-sensitive quantitative analysis of chiral amino acids. In EMILI, OCEANS is additionally coupled to the same ITMS through a novel electrospray ionization interface. The common ITMS allows EMILI to identify and cross-correlate molecular species and patterns, detected through either or both protocols, of molecular weights to over 1000 u, potentially even revealing complex biosignatures such as alien oligopeptides and informational polymers.

Europa↗

A Fly-Through Mission Strategy Targeting Peptide as a Signature of Chemical Evolution and Possible Life in Enceladus Plumes

In situ detection of organic molecules in the extraterrestrial environment provides a key step towards better understanding the variety and the distribution of building blocks of life and it may ultimately lead to finding extraterrestrial life within the Solar System. Here we present combined results of two separate experiments that enable us to realize such in situ life signature detection from the deep habitats of the "Ocean World": a hydrothermal reactor experiment simulating complex organic synthesis and a simulated fly-through capture experiment of organic-bearing microparticles using silica aerogels, followed by subsequent analysis. Both experiments employ peptide as a plausible organics existing in Encleadus plume particles produced in its subsurface ocean. Recent laboratory hydrothermal experiments and a theoretical model on silica saturation indicated an on going hydrothermal reactions in subsurface Enceladus ocean. Given the porous chondritic origin of the core, it is likely that organic compounds originated by radiation chemistry such as amino acid precursors could have been provided, leached, and altered through widespread water-rock interactions. By using the same laboratory experimental setup from the latest water-rock interaction study, we performed amino acid polymerization experiments for 144 days and monitored the organic complexity changing over time. So far over 3,000 peaks up to the size of greater than 600 MW were observed through the analysis of capillary electrophoresis time-of-flight mass spectrometry (CE-TOF-MS) with an indication of amino acid derivatives and short peptides. Generally abiotic polymerization of enantiomeric amino acids results in forming stereoisomeric peptides with identical molecular weight and formula as opposed to homochiral biopolymers. Assuming Enceladus plume particles may contain a mixture of stereoisomeric peptides, we were able to distinguish 16 of the 17 stereoisomeric tripeptides as a test sample using capillary electrophoresis (CE) under optimized conditions. We further conducted Enceladus plume fly-through capture experiment by accelerating peptides soaked in rock particles up to a speed of 5.7 km/s and capturing with originally developed hydrophobic silica aerogels. Direct peptide extraction with acetonitrile-water followed by CE analysis led to detection of only but two stereoisomeric acidic peptide peaks, presenting the first run-through hypervelocuty impact sample analysis targeting peptides as key molecule to to understand the ongoing astrobiology on Enceladus.

organic molecules↗

Extraterrestrial Amino Acids in the Almahata Sitta Meteorite

Amino acid analysis of a meteorite fragment of asteroid 2008 TC3 called Almahata Sitta was carried out using reverse-phase liquid chromatography coupled with UV fluorescence detection and time-of-flight mass spectrometry (LC-FD/ToF-MS) as part of a sample analysis consortium. LC-FD/ToF-MS analyses of hot-water extracts from the meteorite revealed a complex distribution of two- to seven-carbon aliphatic amino acids and one- to three-carbon amines with abundances ranging from 0.5 to 149 parts-per-billion (ppb). The enantiomeric ratios of the amino acids alanine, R-amino-n-butyric acid (beta-ABA), 2-amino-2-methylbutanoic acid (isovaline), and 2-aminopentanoic acid (norvaline) in the meteorite were racemic (D/L approximately 1), indicating that these amino acids are indigenous to the meteorite and not terrestrial contaminants. Several other non-protein amino acids were also identified in the meteorite above background levels including alpha-aminoisobutyric acid (alpha-AIB), 4-amino-2- methylbutanoic acid, 4-amino-3-methylbutanoic acid, and 3-, 4-, and 5-aminopentanoic acid. The total abundances of isovaline and alpha-AIB in Almahata Sitta are 1000 times lower than the abundances of these amino acids found in the CM carbonaceous chondrite Murchison. The extremely low abundances and unusual distribution of five carbon amino acids in Almahata Sitta compared to Cl, CM, and CR carbonaceous chondrites may reflect extensive thermal alteration of amino acids on the parent asteroid by partial melting during formation or subsequent impact shock heating. It is also possible that amino acids were synthesized by catalytic reactions on the parent body after asteroid 2008 TC3 cooled to lower temperatures.

Glavin, Daniel P.↗

In-Situ Reaction Monitoring for Lunar Applications Utilizing a Single Quadrupole Residual Gas Analyzer

With a revived focus to create a permeant presence on the moon and in preparation for future Mars exploration, it is imperative that all re-sources are utilized to their fullest potential. In-Situ Resource Utilization (ISRU) will be critical for future mission success as it would enable independent operation of missions while minimally relying on the complex supply chain created between the Earth, moon and Mars. One of the most critical resources that have been identified for ISRU is the creation of liquid oxygen (O2) for not only breathable air, but also for rocket fuel. On the moon and potentially Mars, one of the most O2 rich resources is in the presence of regolith. Although there are numerous minerals within regolith and various processes to extract O2, this is not the scope of this paper. Since the O2 extraction method can vary, a critical standardized analytical method is needed to verify O2 (or oxygenated precursor compounds) for extraction efficiency and purity. Our group utilizes a modified consumer off-the-shelf (COTS), Residual Gas Analyzer (RGA) Single Quadrupole Mass Spectrometer (QMS). Due to the current field mission requirements, the gas analysis module will need to rely only on mass-to-charge ratios (m/z) and peak intensities to differentiate and quantitate targeted gas-phase reactants or products, i.e. carbon monoxide (CO), carbon dioxide (CO2), methane (CH4) and hydrogen (H2). However, due to solar wind implanted volatiles and various other compounds present in lunar regolith, such as nitrogen (N2), helium (He), and deuterium (D2), deconvolution and quantification of isobaric compounds becomes quite difficult. Specifically, the presence of N2 makes quantification of CO, an oxygenated precursor, difficult due to both compounds having a peak at m/z 28. Approaches to differentiate isobaric components: Initially, the solution to overcome isobaric overlap was to use isotopic ratios, particularly be-tween carbon-13 and nitrogen-15. Although limited literature discuss isotopic composition and attempt to quantify the ratios, variation is particularly high and limited to a few lunar regolith samples. The following were identified as potential approaches to quantify isobaric species, N2 and CO, using our RGA. Threshold Ionization. CO and N2 both have peaks at m/z 28, but only N2 is capable of producing a peak at m/z 7. While a N2 peak at m/z 7 is generally rare, instrument parameters can be optimized in order to maximize the peak intensity. Typically a standard ionization energy of 70 eV is used to monitor a batch process and would produce reliable results for a majority of the reactants or products that we are interested in quantifying. However, to analyze the rare molecular fragment of N2 (N2+ at m/z 7), a different ionization energy may be beneficial. Threshold Ionization Mass Spectrometry (TIMS) will be explored to optimize the N2+ peak at m/z 7 by varying parameters such as ionization energy and pressure. Therefore, a quantitative value at m/z 7 will be used to determine the product gas concentration of N2, which will be subtracted from the total concentration determined at m/z 28 enabling us to approximate the amount of CO. Secondary Detector (infrared gas detector, IR). Another approach to quantitate and differentiate be-tween isobaric components is to leverage alternative modes of detection. Unlike mass spectrometry, which generally uses a separation step prior to analysis (i.e. gas chromatography), IR produces energy that is specifically absorbed depending on the bond and configuration of the molecule. This technique could be leveraged since it is generally only active on non-symmetric molecules, i.e. CO. Utilizing concentrations of CO determined from another detector could help correct concentrations of CO obtained from the QMS. However, the inclusion of another detector adds additional mission requirements, such as power, software changes and avionics updates that add additional cost and schedule requirements.

mass spectrometry↗

Stable isotope analysis at the molecular level: A new approach for determining the origins of amino acids in the Murchison meteorite

A combined gas chromatography/isotope ratio mass spectrometry (GC/IRMS) method has been developed that permits the direct stable carbon isotope analysis of N(O)-trifluoroacetyl-isopropyl esters of individual amino acids and their respective enantiomers at nanomole abundances. Calculation of the original delta C-13 values of the amino acids is accomplished via a correction for the carbon introduced during the derivatization process. Previous GC/IRMS analyses of individual amino acids in the non-hydrolyzed water extract of an interior sample of a Murchison meteorite stone revealed an enrichment in C-13 relative to terrestrial organic matter, in agreement with previous findings for bulk extracts. The range of amino acid delta C-13 values (+5 to +30 per mill, PDB) suggests possible kinetic effects during synthesis. In this study, an apparent kinetic isotope effect was also observed for the amino acid products of a spark discharge experiment. These preliminary resutls are supportive of a similar mechanism for the abiotic synthesis of amino acids in the Murchison meteorite.

Engel, M. H.↗