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At least 271 records · Page 15

Identification and Quantitative Measurements of Chemical Species by Mass Spectrometry

The development of a miniature gas chromatograph/mass spectrometer system for the measurement of chemical species of interest to combustion is described. The completed system is a fully-contained, automated instrument consisting of a sampling inlet, a small-scale gas chromatograph, a miniature, quadrupole mass spectrometer, vacuum pumps, and software. A pair of computer-driven valves controls the gas sampling and introduction to the chromatographic column. The column has a stainless steel exterior and a silica interior, and contains an adsorbent of that is used to separate organic species. The detection system is based on a quadrupole mass spectrometer consisting of a micropole array, electrometer, and a computer interface. The vacuum system has two miniature pumps to maintain the low pressure needed for the mass spectrometer. A laptop computer uses custom software to control the entire system and collect the data. In a laboratory demonstration, the system separated calibration mixtures containing 1000 ppm of alkanes and alkenes.

Zondlo, Mark A.↗

Sensor arrays for detecting analytes in fluids

A sensor array for detecting an analyte in a fluid, comprising at least first and second chemically sensitive resistors electrically connected to an electrical measuring apparatus, wherein each of the chemically sensitive resistors comprises a mixture of nonconductive material and a conductive material. Each resistor provides an electrical path through the mixture of nonconductive material and the conductive material. The resistors also provide a difference in resistance between the conductive elements when contacted with a fluid comprising an analyte at a first concentration, than when contacted with an analyte at a second different concentration. A broad range of analytes can be detected using the sensors of the present invention. Examples of such analytes include, but are not limited to, alkanes, alkenes, alkynes, dienes, alicyclic hydrocarbons, arenes, alcohols, ethers, ketones, aldehydes, carbonyls, carbanions, polynuclear aromatics, organic derivatives, biomolecules, sugars, isoprenes, isoprenoids and fatty acids. Moreover, applications for the sensors of the present invention include, but are not limited to, environmental toxicology, remediation, biomedicine, material quality control, food monitoring and agricultural monitoring.

Lewis, Nathan S.↗

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↗

Experimental Study of Abiotic Organic Synthesis at High Temperature and Pressure Conditions: Carbon Isotope and Mineral Surface Characterizations

Abiotic organic synthesis processes have been proposed as potential mechanisms for methane generation in subseafloor hydrothermal systems on Earth, and on other planets. To better understand the detailed reaction pathways and carbon isotope fractionations in this process under a wide range of physical and chemical conditions, hydrothermal experiments at high temperature (750 C) and pressure (0.55 GPa) were performed using piston cylinder apparatus. Formic acid was used as the source of CO2 and H2, and magnetite was the mineral catalyst. The chemical and carbon isotopic compositions of dissolved organic products were determined by GC-C-MS-IRMS, while organic intermediaries on the mineral catalyst were characterized by Pyrolysis-GC-MS. Among experimental products, dissolved CO2 was the dominant carbon species with a relative abundance of 88 mol%. Dissolved CH4 and C2H6 were also identified with a mole ratio of CH4 over C2H6 of 15:1. No dissolved CO was detected in the experiment, which might be attributable to the loss of H2 through the Au capsule used in the experiments at high temperature and pressure conditions and corresponding conversion of CO to CO2 by the water-gas shift reaction. Carbon isotope results showed that the 13C values of CH4 and C2H6 were -50.3% and -39.3% (V-PDB), respectively. CO2 derived from decarboxylation of formic acid had a (sigma)C-13 value of -19.2%, which was 3.2% heavier than its source, formic acid. The (sigma)C-13 difference between CO2 and CH4 was 31.1%, which was higher than the value of 9.4% calculated from theoretical isotopic equilibrium predictions at experimental conditions, suggesting the presence of a kinetic isotope effect. This number was also higher than the values (4.6 to 27.1%) observed in similar experiments previously performed at 400 C and 50 MPa with longer reaction times. CH4 is 11.0% less enriched in C-13 than C2H6. Alcohols were observed as carbon compounds on magnetite surfaces by Pyrolysis-GC-MS, which confirms the hypothesis regarding the reaction pathways of hydrothermal abiotic organic synthesis proposed by Fu et al. (2007, 2008). In this proposed pathway, hydroxymethylene (-CHOH) groups serve as organic intermediaries on mineral surfaces while dissolved H2 serves as a chain terminator/breaker to generate short chain hydrocarbons and oxygenated compounds. This pathway is different from the carbide polymerization theory of Fischer- Tropsch-type (FTT) synthesis in a gas phase. The observed increase of (sigma)C-13 values of C1 and C2 alkanes with carbon number in our hydrothermal experiments can be readily interpreted by hydroxymethylene pathway, and might be used to differentiate between hydroxymethylene and carbide polymerization pathways. Carbon isotope analysis of alcohols on mineral catalyst surfaces is under way to provide further constraints on formation of organic compounds by FTT in hydrothermal systems.

Fu, Qi↗

NASA Tech Briefs, February 2011

Topics covered include: Multi-Segment Radius Measurement Using an Absolute Distance Meter Through a Null Assembly; Fiber-Optic Magnetic-Field-Strength Measurement System for Lightning Detection; Photocatalytic Active Radiation Measurements and Use; Computer Generated Hologram System for Wavefront Measurement System Calibration; Non-Contact Thermal Properties Measurement with Low-Power Laser and IR Camera System; SpaceCube 2.0: An Advanced Hybrid Onboard Data Processor; CMOS Imager Has Better Cross-Talk and Full-Well Performance; High-Performance Wireless Telemetry; Telemetry-Based Ranging; JWST Wavefront Control Toolbox; Java Image I/O for VICAR, PDS, and ISIS; X-Band Acquisition Aid Software; Antimicrobial-Coated Granules for Disinfecting Water; Range 7 Scanner Integration with PaR Robot Scanning System; Methods of Antimicrobial Coating of Diverse Materials; High-Operating-Temperature Barrier Infrared Detector with Tailorable Cutoff Wavelength; A Model of Reduced Kinetics for Alkane Oxidation Using Constituents and Species for N-Heptane; Thermally Conductive Tape Based on Carbon Nanotube Arrays; Two Catalysts for Selective Oxidation of Contaminant Gases; Nanoscale Metal Oxide Semiconductors for Gas Sensing; Lightweight, Ultra-High-Temperature, CMC-Lined Carbon/Carbon Structures; Sample Acquisition and Handling System from a Remote Platform; Improved Rare-Earth Emitter Hollow Cathode; High-Temperature Smart Structures for Engine Noise Reduction and Performance Enhancement; Cryogenic Scan Mechanism for Fourier Transform Spectrometer; Piezoelectric Rotary Tube Motor; Thermoelectric Energy Conversion Technology for High-Altitude Airships; Combustor Computations for CO2-Neutral Aviation; Use of Dynamic Distortion to Predict and Alleviate Loss of Control; Cycle Time Reduction in Trapped Mercury Ion Atomic Frequency Standards; and A (201)Hg+ Comagnetometer for (199)Hg+ Trapped Ion Space Atomic Clocks.

Source record↗

Search for Chemical Biomarkers on Mars Using the Sample Analysis at Mars Instrument Suite on the Mars Science Laboratory

One key goal for the future exploration of Mars is the search for chemical biomarkers including complex organic compounds important in life on Earth. The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) will provide the most sensitive measurements of the organic composition of rocks and regolith samples ever carried out in situ on Mars. SAM consists of a gas chromatograph (GC), quadrupole mass spectrometer (QMS), and tunable laser spectrometer to measure volatiles in the atmosphere and released from rock powders heated up to 1000 C. The measurement of organics in solid samples will be accomplished by three experiments: (1) pyrolysis QMS to identify alkane fragments and simple aromatic compounds; pyrolysis GCMS to separate and identify complex mixtures of larger hydrocarbons; and (3) chemical derivatization and GCMS extract less volatile compounds including amino and carboxylic acids that are not detectable by the other two experiments.

Glavin, D. P.↗

Transformation of Air Quality Monitor Data from the International Space Station into Toxicological Effect Groups

The primary reason for monitoring air quality aboard the International Space Station (ISS) is to determine whether air pollutants have collectively reached a concentration where the crew could experience adverse health effects. These effects could be near-real-time (e.g. headache, respiratory irritation) or occur late in the mission or even years later (e.g. cancer, liver toxicity). Secondary purposes for monitoring include discovery that a potentially harmful compound has leaked into the atmosphere or that air revitalization system performance has diminished. Typical ISS atmospheric trace pollutants consist of alcohols, aldehydes, aromatic compounds, halo-carbons, siloxanes, and silanols. Rarely, sulfur-containing compounds and alkanes are found at trace levels. Spacecraft Maximum Allowable Concentrations (SMACs) have been set in cooperation with a subcommittee of the National Research Council Committee on Toxicology. For each compound and time of exposure, the limiting adverse effect(s) has been identified. By factoring the analytical data from the Air Quality Monitor (AQM), which is in use as a prototype instrument aboard the ISS, through the array of compounds and SMACs, the risk of 16 specific adverse effects can be estimated. Within each adverse-effect group, we have used an additive model proportioned to each applicable 180-day SMAC to estimate risk. In the recent past this conversion has been performed using archival data, which can be delayed for months after an air sample is taken because it must be returned to earth for analysis. But with the AQM gathering in situ data each week, NASA is in a position to follow toxic-effect groups and correlate these with any reported crew symptoms. The AQM data are supplemented with data from real-time CO2 instruments aboard the ISS and from archival measurements of formaldehyde, which the AQM cannot detect.

James, John T.↗

Landscape Evolution of Titan

Titan may have acquired its massive atmosphere relatively recently in solar system history. The warming sun may have been key to generating Titan's atmosphere over time, starting from a thin atmosphere with condensed surface volatiles like Triton, with increased luminosity releasing methane, and then large amounts of nitrogen (perhaps suddenly), into the atmosphere. This thick atmosphere, initially with much more methane than at present, resulted in global fluvial erosion that has over time retreated towards the poles with the removal of methane from the atmosphere. Basement rock, as manifested by bright, rough, ridges, scarps, crenulated blocks, or aligned massifs, mostly appears within 30 degrees of the equator. This landscape was intensely eroded by fluvial processes as evidenced by numerous valley systems, fan-like depositional features and regularly-spaced ridges (crenulated terrain). Much of this bedrock landscape, however, is mantled by dunes, suggesting that fluvial erosion no longer dominates in equatorial regions. High midlatitude regions on Titan exhibit dissected sedimentary plains at a number of localities, suggesting deposition (perhaps by sediment eroded from equatorial regions) followed by erosion. The polar regions are mainly dominated by deposits of fluvial and lacustrine sediment. Fluvial processes are active in polar areas as evidenced by alkane lakes and occasional cloud cover.

Moore, Jeffrey↗

Microbial Lipid and C Isotopic Biosignatures of a Unique Community at Grand Prismatic Spring, Yellowstone National Park

The microbial communities found in modern hot springs are considered analogs to ones that may have existed in hydrothermal systems on the early Earth and possibly Mars. Our goal was to characterize the microbial biosignatures and to assess the preservation of organic matter in the silica-depositing Grand Prismatic Spring in Yellowstone National Park. This study combines 16S rRNA surveys, lipid biomarkers, and C isotopes to query, "Who's there and what are they doing?" On the edge of the approximately 90 m diameter blue vent pool (56.1 C, pH 8.5), a floating green streamer community grew over a benthic pink community. The membrane lipids in the green streamers and pink mat were composed of unusual ester-linked fatty acids, indicating the presence of novel bacterial groups. In particular, we discovered a series of 2-methyl and 2,X-dimethyl phospholipid fatty acids (C18-22). We are attempting to use the 16S rRNA surveys to link these compounds to source organisms. Wax esters, biomarkers for Chloroflexi, were present in both communities, but displayed different profiles. A higher proportion of branched wax esters were found in the green streamers, and were associated with a relatively high concentration of long-chain di- and trienes (C29-31). This suggests that Chloroflexus primarily grew in the green streamers, while a pink mat of Roseiflexus grew on the sinter substrate underneath. Cyanobacterial alkanes were found in the green streamers (n-C17, 7-, 6- and 5-monomethyl-C17, 7,11-dimethyl-C17, n-C19, n-C19:1). We also detected a series of monoalkylglycerylethers and geologically relevant hopanoids in both communities. Carbon isotope analyses indicated that Chloroflexus was growing photoheterotrophically using cyanobacterial photosynthate. Roseiflexus also traditionally grows photoheterotrophically, but the C isotopic signatures of the lipids in the pink mat were approximately 10 %0 lighter than the cyanobacterial and Chloroflexus lipids, indicating a potentially novel metabolic mechanism or prior secondary reworking of substrates before reaching Roseiflexus. This arrangement of Synechococcus-Chloroflexus green streamers floating over a benthic pink community of Roseiflexus is different from the classical laminated Synechococcus-Chloroflexi mats at Octopus Hot Spring.

Jahnke, Linda↗

Are the Basins of Tui Regio and Hotei Arcus Sites of Former Titanian Seas?

Features observed in the basins of Tui Regio and Hotei Arcus on Titan have attracted the attention of the Cassini-era investigators. At both locations, VIMS observed discrete 5-micron bright approx.500-km wide features described as lobate in shape. Several studies have proposed that these materials are cryo-volcanic flows; in the case of the Hotei Arcus feature this inference was buttressed with SAR RADAR images showing bright and dark patches with lobate margins. We propose an alternative explanation. First we note that all landforms on Titan that are unambiguously identifiable can be explained by exogenic processes (aeolian, fluvial, impact cratering, and mass wasting). Suggestions of endogenically produced cryovolcanic constructs and flows have, without exception, lacked conclusive diagnostic evidence. Recently published topographic profiles across Tui Regio and the lobate feature region north of Hotei Arcus indicate these features appear to occur in large regional basins, at least along the direction of the profiles. SAR images show that the terrains surrounding both 5-micron bright features exhibit fluvial networks that appear to converge and debauch into the probable basins. The 5-micron bright features themselves correspond to fields of discrete radar-bright depressions whose bounding edges are commonly rounded and cumulate in planform in SAR images. These fields of discrete radar-bright depressions strongly resemble fields of features seen at Titan s high latitudes usually attributed to be dry lakes. Thus the combination of (1) the resemblance to high-latitude dry lakes, (2) location in the centers of probable regional depressions, and (3) convergence of fluvial networks are inferred by us to best explain the 5-micron bright regions at Tui Regio and Hotei Arcus as sites of dry seas or at least paleolake clusters. Such equatorial seas, if real, may be evidence of substantially larger inventories of liquid alkanes in Titan s past.

Moore, Jeffrey Morgan↗

Methanol Droplet Combustion in Oxygen-Inert Environments in Microgravity

The Flame Extinguishment (FLEX) experiment that is currently underway in the Combustion Integrated Rack facility onboard the International Space Station is aimed at understanding the effects of inert diluents on the flammability of condensed phase fuels. To this end, droplets of various fuels, including alkanes and alcohols, are burned in a quiescent microgravity environment with varying amounts of oxygen and inert diluents to determine the limiting oxygen index (LOI) for these fuels. In this study we report experimental observations of methanol droplets burning in oxygen-nitrogen-carbon dioxide and oxygen-nitrogen-helium gas mixtures at 0.7 and 1 atmospheric pressures. The initial droplet size varied between approximately 1.5 mm and 4 mm to capture both diffusive extinction brought about by insufficient residence time at the flame and radiative extinction caused by excessive heat loss from the flame zone. The ambient oxygen concentration varied from a high value of 30% by volume to as low as 12%, approaching the limiting oxygen index for the fuel. The inert dilution by carbon dioxide and helium varied over a range of 0% to 70% by volume. In these experiments, both freely floated and tethered droplets were ignited using symmetrically opposed hot-wire igniters and the burning histories were recorded onboard using digital cameras, downlinked later to the ground for analysis. The digital images yielded droplet and flame diameters as functions of time and subsequently droplet burning rate, flame standoff ratio, and initial and extinction droplet diameters. Simplified theoretical models correlate the measured burning rate constant and the flame standoff ratio reasonably well. An activation energy asymptotic theory accounting for time-dependent water dissolution or evaporation from the droplet is shown to predict the measured diffusive extinction conditions well. The experiments also show that the limiting oxygen index for methanol in these diluent gases is around 12% to 13% oxygen by volume.

Nayagam, Vedha↗

The Search for Organic Compounds of Martian Origin in Gale Crater by the Sample Analysis at Mars (SAM) Instrument on Curiosity

One of the key objectives of the Mars Science Laboratory rover and the Sample Analysis at Mars (SAM) instrument suite is to determine the inventory of organic and inorganic volatiles in the atmosphere and surface regolith and rocks to help assess the habitability potential of Gale Crater. The SAM instrument on the Curiosity rover can detect volatile organic compounds thermally evolved from solid samples using a combination of evolved gas analysis (EGA) and gas chromatography mass spectrometry (GCMS) (Mahaffy et al. 2012). The first solid samples analyzed by SAM, a scoop of windblown dust and sand at Rocknest, revealed several chloromethanes and a C4-chlorinated hydrocarbon derived primarily from reactions between a martian oxychlorine phase (e.g. perchlorate) and terrestrial carbon from N-methyl-N-(tertbutyldimethylsilyl)- trifluoroacetamide (MTBSTFA) vapor present in the SAM instrument background (Glavin et al. 2013). After the analyses at Rocknest, Curiosity traveled to Yellowknife Bay and drilled two separate holes in a fluvio-lacustrine sediment (the Sheepbed unit) designated John Klein and Cumberland. Analyses of the drilled materials by both SAM and the CheMin X-Ray Diffraction instrument revealed a mudstone consisting of ~20 wt% smectite clays (Ming et al. 2013; Vaniman et al. 2013), which on Earth are known to aid the concentration and preservation of organic matter. Oxychlorine compounds were also detected in the Sheepbed mudstone during pyrolysis; however, in contrast to Rocknest, much higher levels of chloromethanes were released from the Sheepbed materials, suggesting an additional, possibly martian source of organic carbon (Ming et al. 2013). In addition, elevated abundances of chlorobenzene and a more diverse suite of chlorinated alkanes including dichloropropane and dichlorobutane detected in Cumberland compared to Rocknest suggest that martian or meteoritic organic carbon sources may be preserved in the mudstone (Freissinet et al. 2013). Chloromethane and dichloromethane were also identified after thermal volatilization of the surface soils by the GCMS instruments at the Viking landing sites, although no other chlorinated hydrocarbons were reported (Biemann et al. 1977). Here we focus on the origin of the chlorinated hydrocarbons detected in the Sheepbed mudstone by SAM and the implications for the preservation of organic matter in near-surface materials on Mars.

Mars Curiosity Rover↗

Preservation of Lipid Biomarkers Under Prolonged and Extreme Hyperaridity in Atacama Desert Soils

Molecular biomarkers are the most direct biosignatures of life on early Earth and a key target in the search for life on Mars. Lipid biomarkers are of particular interest given their ability to survive oxidative degradation and record microbial presence and activity of microorganisms that occurred billions of years ago (Eigenbrode, 2008). Environmental conditions that suspend biotic and abiotic degradative processes prior to lithification can lead to enhanced biomolecular preservation over geological time-scales. The hyperarid core of the Atacama Desert in northern Chile offers a unique environment to investigate lipid biomarker taphonomy under extreme and prolonged dryness. We investigated the accumulation and degree of preservation of lipid biomarkers in million-year-old hyperarid soils where primarily abiotic conditions influence their taphonomy. Soils were extracted and free and membrane bound lipids were analyzed across a vertical profile of 2.5 meters in the Yungay hyper-arid core of the Atacama Desert. Due to the extremely low inventory of biomass in Atacama soils, samples were collected by scientists wearing cleanroom suits to minimize anthropogenic contamination during sampling. Fatty acids were found to be well preserved in Yungay soils, and were most abundant in the clay-rich soils at approx.2 m depth (approx.750 ng of fatty acid methyl ester/g of soil). These buried clays layers were fluvially deposited approximately 2 million years ago, and have been excluded from exposure to rainwater and modern surficial processes since their emplacement (Ewing et al., 2008). Monocarboxylic fatty acid, monohydroxy fatty acid, glycerol tetraether, and n-alkane hydrocarbon content was found to change with depth. Lipid biomarker content in deeper soil layers is suggestive of soils having been formed at a time when environmental conditions were capable of supporting active microbial communities and plants. In short, total lipid extracts reveal a remarkable degree of lipid biomarker preservation even in the oldest soils analyzed (ca. 2 Myr) indicating that typical diagenetic processes of lipid destruction are arrested under extreme dryness. This result has implications for the search for molecular biomarkers on Mars, which could have experienced millions to billions of years of extreme hyperaridity.

Lipid Biomarkers↗

Detection of Propene in Titan's Stratosphere

The Voyager 1 flyby of Titan in 1980 gave a first glimpse of the chemical complexity of Titan's atmosphere, detecting many new molecules with the infrared interferometer spectrometer (IRIS). These included propane (C3H8) and propyne (CH3C2H), while the intermediate-sized C3Hx hydrocarbon (C3H6) was curiously absent. Using spectra from the Composite Infrared Spectrometer on Cassini, we show the first positive detection of propene (C3H6) in Titan's stratosphere (5(sigma) significance), finally filling the three-decade gap in the chemical sequence. We retrieve a vertical abundance profile from 100-250 km, that varies slowly with altitude from 2.0 +/- 0.8 ppbv at 125 km, to4.6 +/- 1.5 ppbv at 200 km. The abundance of C3H6 is less than both C3H8 and CH3C2H, and we remark on an emerging paradigm in Titans hydrocarbon abundances whereby alkanes greater than alkynes greater than alkenes within the C2Hx and C3Hx chemical families in the lower stratosphere. More generally, there appears to be much greater ubiquity and relative abundance of triple-bonded species than double-bonded, likely due to the greater resistance of triple bondsto photolysis and chemical attack.

Titan↗

Searching for Evidence of Life in Deep Time and Space

Cyanobacterial mats provide insights into ancient benthic microbial communities and their biosignatures. Thick mats occupy hypersaline saltern ponds at Guerrero Negro, Baja California, Mexico. Mat biota maintains rapid rates of biogeochemical processes under steep and rapidly changing environmental gradients. Cycling of C, O, and S all increased identically with temperature, indicating the tight coupling of these cycles. An enormous microbial diversity exhibits a highly structured spatial distribution of populations. Combined universal clone libraries from all mat layers indicated Bacteria/Archaea/Eukarya ratios of 57:7:1. More than 10,000 unique bacterial sequences were present. The relative abundance of Archaea increased with depth - below 10 cm, solvent-extractable archaeal lipids were twice as abundant as bacterial lipids. Only 15 species of Eukarya were found among 890 clones analyzed. Degradation of the mats’ insoluble macromolecular organic fraction (IMOM) by hydropyrolysis released a complex variety of linear, branched and polycyclic alkane structures, e.g., hopanes, methylhopanes and steranes. Covalent binding of these biosignatures into IMOM aids their long-term geological preservation. Mars rover missions revealed evidence of long-lived fluvial lacustrine systems and organics in associated mudstones. NASA’s Mars 2020 rover mission will examine sediments in Jezero crater, including a delta and shoreline carbonate deposits, environments that on Earth have sustained microbial mats.

Des Marais, David J.↗

Heterogeneity and Chemical Reactivity of the Remote Troposphere Defined By Aircraft Measurements - Corrected

The NASA Atmospheric Tomography (ATom) mission built a photochemical climatology of air parcels based on in situ measurements with the NASA DC-8 aircraft along objectively planned profiling transects through the middle of the Pacific and Atlantic oceans. In this paper we present and analyze a data set of 10 s (2 km) merged and gap-filled observations of the key reactive species driving the chemical budgets of O3 and CH4 (O3, CH4, CO, H2O, HCHO, H2O2, CH3OOH, C2H6, higher alkanes, alkenes, aromatics, NOx, HNO3, HNO4, peroxyacetyl nitrate, and other organic nitrates), consisting of 146 494 distinct air parcels from ATom deployments 1 through 4. Six models calculated the O3 and CH4 photochemical tendencies from this modeling data stream for ATom 1. We find that 80 %–90 % of the total reactivity lies in the top 50 % of the parcels and 25 %–35 % in the top 10 %, supporting previous model-only studies that tropospheric chemistry is driven by a fraction of all the air. Surprisingly, the probability densities of species and reactivities averaged on a model scale (100 km) differ only slightly from the 2 km ATom 10 s data, indicating that much of the heterogeneity in tropospheric chemistry can be captured with current global chemistry models. Comparing the ATom reactivities over the tropical oceans with climatological statistics from six global chemistry models, we find generally good agreement with the reactivity rates for O3 and CH4. Models distinctly underestimate O3 production below 2 km relative to the mid-troposphere, and this can be traced to lower NOx levels than observed. Attaching photochemical reactivities to measurements of chemical species allows for a richer, yet more constrained-to-what-matters, set of metrics for model evaluation.

Tropospheric Chemistry↗

Organic Products of Fatty Acid and Magnesium Sulfate Mixtures after Gamma Radiolysis: Implications for Missions to Europa

If ocean-derived materials are present at Europa’s surface, they would represent accessible records of ocean chemistry and habitability, but such materials would be further processed by the moon’s harsh radiation environment. In this study, saturated fatty acids were precipitated onto a Europa-relevant hydrated magnesium sulfate and exposed to gamma radiation doses up to 2 MGy at -196° C. Alkane chains, with carbon numbers one less than those of the starting fatty acids, were the most abundant radiolysis products in solvent and thermal extracts analyzed by gas chromatography mass spectrometry. Detections of monounsaturated fatty acids and combined radiolysis products were attributed to the experiment’s Europa-like parameters. Additionally, elevated concentrations of shorter-chain saturated fatty acids suggest that gamma radiation induced charge remote fragmentation of the alkyl chains of some starting fatty acids under these experimental conditions. Quantitation of fatty acid concentrations in the irradiated samples enabled the calculation of a radiolysis constant that indicated exposure to a 5 MGy dose of gamma radiation would have resulted in a ~90% loss of the initial fatty acid population. The samples were further studied by Raman spectroscopy and laser desorption and ionization mass spectrometry, which characterized the distribution of fatty acids and their radiolysis products on sulfate surfaces. The substantial loss of starting fatty acids typically seen with increasing radiation dose, along with the remarkable diversity of radiolysis products identified, suggest that the detection of fatty acids in irradiated sulfate deposits on Europa will be challenged by rapid destruction of any initial fatty acid populations and scrambling of their residual signals by a myriad of organic radiolysis products. If missions to Europa encounter sulfate deposits, targeting minimally irradiated units may still enable the detection of surviving fatty acid signatures that could inform about Europa’s subsurface chemistry and habitability.

James M T Lewis↗

Molecular Inventory and Comparative Organic Profiling of A Homogenized Aggregate Sample From Asteroid (101955) Bennu

Evaluating the distribution and diversity of solvent-soluble organic molecules in extraterrestrial materials provide information about the physicochemical environments where prebiotic chemistry occurred and is essential for assessing the inventory of prebiotic compounds available to the early Earth. In this work, we conducted a comprehensive molecular characterization of solvent-soluble organic compounds in a homogenized aggregate sample (ID: OREX-800107-128) of unsorted regolith from asteroid (101955) Bennu returned by NASA’s OSIRIS-REx mission. Using two-dimensional gas chromatography coupled with high-resolution time-of-flight mass spectrometry (GC×GC-HRMS), we identified 87 organic compounds across several molecular classes, including alkanes, polycyclic aromatic hydrocarbons, and nitrogen-, oxygen-, and sulfur-bearing species. Comparison with the organic inventory of CI (Orgueil), C2-ungrouped (Tagish Lake and Tarda), and CM2 (Murchison) carbonaceous chondrites revealed that Bennu sample OREX-800107-128 is most similar to Tagish Lake and Tarda yet compositionally distinct from all of these meteorites. This Bennu sample exhibits a relatively high abundance of low-molecular-weight aromatics (e.g., toluene), pyridine derivatives, and sulfur species such as dimethyl sulfite, consistent with episodic low-temperature aqueous alteration. The presence of these organic compounds suggests that this material experienced chemically diverse processes in the parent body conducive to complex organic synthesis, including aldol condensation reactions responsible for N- and O-bearing compounds. We also compared the molecular distributions of this Bennu sample and previously analyzed samples from (162173) Ryugu to assess potential common origins between these two carbonaceous asteroids. Bennu shows more chemically diverse and nitrogen-rich organic materials than Ryugu. While both asteroids share broadly similar primitive compositions, the observed chemical differences indicate distinct evolutionary histories within a likely common formation environment though whether Bennu and Ryugu derive from a single compositionally heterogeneous parent body or from multiple closely related progenitors remains unresolved. Further detailed comparative analyses of material from Bennu, Ryugu, and specific carbonaceous meteorites (e.g., Tagish Lake and Tarda) will provide new insights into how the N-rich molecular profile observed in Bennu samples was formed and evolved in the outer Solar System.

sample return↗