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At least 127 records · Page 7

Simulating the Effect of Space Vehicle Environments on Directional Solidification of a Binary Alloy

Space microgravity missions are designed to provide a microgravity environment for scientific experiments, but these missions cannot provide a perfect environment, due to vibrations caused by crew activity, on-board experiments, support systems (pumps, fans, etc.), periodic orbital maneuvers, and water dumps. Therefore, it is necessary to predict the impact of these vibrations on space experiments, prior to performing them. Simulations were conducted to study the effect of the vibrations on the directional solidification of a dendritic alloy. Finite element ca!cu!attie?ls were dme with a simd2titcr based on a continuum model of dendritic solidification, using the Fractional Step Method (FSM). The FSM splits the solution of the momentum equation into two steps: the viscous intermediate step, which does not enforce continuity; and the inviscid projection step, which calculates the pressure and enforces continuity. The FSM provides significant computational benefits for predicting flows in a directionally solidified alloy, compared to other methods presently employed, because of the efficiency gains in the uncoupled solution of velocity and pressure. finite differences, arises when the interdendritic liquid reaches the eutectic temperature and concentration. When a node reaches eutectic temperature, it is assumed that the solidification of the eutectic liquid continues at constant temperature until all the eutectic is solidified. With this approach, solidification is not achieved continuously across an element; rather, the element is not considered solidified until the eutectic isotherm overtakes the top nodes. For microgravity simulations, where the convection is driven by shrinkage, it introduces large variations in the fluid velocity. When the eutectic isotherm reaches a node, all the eutectic must be solidified in a short period, causing an abrupt increase in velocity. To overcome this difficulty, we employed a scheme to numerically predict a more accurate value for the rate of change of fraction of liquid as the liquid in an element solidifies. The new method enables us to contrast results of simulations in which the alloy is subjected to no gravity or a steady-state acceleration versus simulations when the alloy is subjected to vibration disturbances; therefore, the effect of vibration disturbances can be assessed more accurately. To assess the impact of these vibration-perturbations, transient accelerometer data from a space shuttle mission are used as inputs for the simulation model. These on-orbit acceleration data were obtained from the Microgravity Science Division at Glenn Research Center (GRC- MSD) and are applied to the buoyancy term of the momentum equation in a simulation of a Pb-5.8 wt. % Sb alloy that solidifies in a thermal gradient of 4000 K/m and a translation velocity of 3 p d s . Figure 2 shows the vertical velocity of a node that begins in the all-liquid region and subsequently solidifies; the vibrations are applied at 5000 seconds in this simulation. An important difficulty, common to all solidification models based on finite elements or 2 The magnitudes of the velocity oscillations that are vibration-induced are very small and acceptable. The biggest concern is whether the concentration of the liquid near the dendrite tips is distorted because of the vibration-induced perturbations. Results for this case show no concentration oscillations present in the all-liquid region.

Westra, D. G.↗

Effects of Ice Particle Size Vertical Inhomogeneity on the Passive Remote Sensing of Ice Clouds

The solar reflectance bi-spectral (SRBS) and infrared split-window (IRSpW) methods are two of the most popular techniques for passive ice cloud property retrievals from multispectral imagers. Ice clouds are usually assumed to be vertically homogeneous in global operational algorithms based on these methods, although significant vertical variations of ice particle size are typically observed in ice clouds. In this Study we investigate uncertainties in retrieved optical thickness, effective particle size, and ice water path introduced by a homogeneous cloud assumption in both the SRBS and IRSpW methods, and focus on whether the assumption can lead to significant discrepancies between the two methods. The study simulates the upwelling spectral radiance associated with vertically structured clouds and passes the results through representative SRBS and IRSpW retrieval algorithms. Cloud optical thickness is limited to values for which IRSpW retrievals are possible (optical thickness less than about 7). When the ice cloud is optically thin and yet has a significant ice particle size vertical variation, it is found that both methods tend to underestimate the effective radius and ice water path. The reason for the underestimation is the nonlinear dependence of ice particle scattering properties (extinction and single scattering albedo) on the effective radius. Because the nonlinearity effect is stronger in the IRSpW than the SRBS method, the IRSpW-based IWP tends to be smaller than the SRBS counterpart. When the ice cloud is moderately optically thick, the IRSpW method is relatively insensitive to cloud vertical structure and effective radius retrieval is weighted toward smaller ice particle size, while the weighting function makes the SRBS method more sensitive to the ice particle size in the upper portion of the cloud. As a result, when ice particle size increases monotonically toward cloud base, the two methods are in qualitative agreement; in the event that ice particle size decreases toward cloud base, the effective radius and ice water path retrievals based on the SRBS method are substantially larger than those from the IRSpW. The main findings of this Study Suggest that the homogenous cloud assumption can affect the SRBS and IRSpW methods to different extents and, consequently, can lead to significantly different retrievals. Therefore caution should be taken when comparing and combining the ice cloud property retrievals from these two methods.

Zhang, Zhibo↗

NASA Tech Briefs, November 2013

Topics include: Cryogenic Liquid Sample Acquisition System for Remote Space Applications; 5 Spatial Statistical Data Fusion (SSDF); GPS Estimates of Integrated Precipitable Water Aid Weather Forecasters; Integrating a Microwave Radiometer into Radar Hardware for Simultaneous Data Collection Between the Instruments; Rapid Detection of Herpes Viruses for Clinical Applications; High-Speed Data Recorder for Space, Geodesy, and Other High-Speed Recording Applications; Datacasting V3.0; An All-Solid-State, Room-Temperature, Heterodyne Receiver for Atmospheric Spectroscopy at 1.2 THz; Stacked Transformer for Driver Gain and Receive Signal Splitting; Wireless Integrated Microelectronic Vacuum Sensor System; Fabrication Method for LOBSTER-Eye Optics in <110> Silicon; Compact Focal Plane Assembly for Planetary Science; Fabrication Methods for Adaptive Deformable Mirrors; Visiting Vehicle Ground Trajectory Tool; Workflow-Based Software Development Environment; Mobile Thread Task Manager; A Kinematic Calibration Process for Flight Robotic Arms; Magnetostrictive Alternator; Bulk Metallic Glasses and Composites for Optical and Compliant Mechanisms; Detection of Only Viable Bacterial Spores Using a Live/Dead Indicator in Mixed Populations; and Intravenous Fluid Generation System.

Source record↗

On Dynamical Impacts on Stratospheric Water Vapor Trends Above Boulder, Colorado

Long-term stratospheric water vapor (SWV) trends above Boulder, CO, (40°N, 255°E) are generally positive and slightly larger than those for zonal average SWV. This study finds a slight enhancement for SWV at 31.6 hPa above Boulder from middle February through March 1979, as seen in the satellite dataset from the LIMS instrument. That excess of SWV correlates well with air in the polar vortex that underwent an elongation and splitting in middle February following a final stratospheric warming event. Zonal wave-2 events tend to occur in late winter, but not every year. Such aperiodic variations in data time series of SWV may affect the fitting of its linear trend term.

Ellis Remsberg↗

On Dynamical Impacts on Stratospheric Water Vapor Trends Above Boulder, Colorado

Long-term stratospheric water vapor (SWV) trends above Boulder, CO, (40°N, 255°E) are generally positive and slightly larger than those for zonal average SWV. This study finds a slight enhancement for SWV at 31.6 hPa above Boulder from middle February through March 1979, as seen in the satellite dataset from the LIMS instrument. That excess of SWV correlates well with air in the polar vortex that underwent an elongation and splitting in middle February following a final stratospheric warming event. Zonal wave-2 events tend to occur in late winter, but not every year. Such aperiodic variations in data time series of SWV may affect the fitting of its linear trend term.

Ellis Remsberg↗

The Slope Imaging Multi-Polarization Photon-Counting Lidar: Development and Performance Results

The Slope Imaging Multi-polarization Photon-counting Lidar is an airborne instrument developed to demonstrate laser altimetry measurement methods that will enable more efficient observations of topography and surface properties from space. The instrument was developed through the NASA Earth Science Technology Office Instrument Incubator Program with a focus on cryosphere remote sensing. The SIMPL transmitter is an 11 KHz, 1064 nm, plane-polarized micropulse laser transmitter that is frequency doubled to 532 nm and split into four push-broom beams. The receiver employs single-photon, polarimetric ranging at 532 and 1064 nm using Single Photon Counting Modules in order to achieve simultaneous sampling of surface elevation, slope, roughness and depolarizing scattering properties, the latter used to differentiate surface types. Data acquired over ice-covered Lake Erie in February, 2009 are documenting SIMPL s measurement performance and capabilities, demonstrating differentiation of open water and several ice cover types. ICESat-2 will employ several of the technologies advanced by SIMPL, including micropulse, single photon ranging in a multi-beam, push-broom configuration operating at 532 nm.

Dabney, Phillip↗

Landsat Data Continuity Mission

The Landsat Data Continuity Mission (LDCM) is currently under development and is on schedule to launch the 8th satellite in the Landsat series in December of 2012. LDCM is a joint project between the National Aeronautics and Space Administration (NASA) and the United States Geological Survey (USGS). NASA is responsible for developing and launching the flight hardware and on-orbit commissioning and USGS is responsible for developing the ground system and operating the system onorbit after commissioning. Key components of the flight hardware are the Operational Land Imager (OLI), nearing completion by Ball Aerospace & Technologies Corp in Boulder, CO, the Thermal Infrared Sensor (TIRS), being built by NASA's Goddard Space Flight Center and the spacecraft, undergoing integration at Orbital Sciences Corp in Gilbert, Arizona. The launch vehicle will be an Atlas-5 with launch services provided by NASA's Kennedy Space Center. Key ground systems elements are the Mission Operations Element, being developed by the Hammers Corporation, and the Collection Activity Planning Element, Ground Network Element, and Data Processing and Archive System, being developed internally by the USGS Earth Resources Observations and Science (EROS) Center. The primary measurement goal of LDCM is to continue the global coverage of moderate spatial resolution imagery providing continuity with the existing Landsat record. The science goal for this imagery is to monitor land use and land cover, particularly as it relates to global climate change. Together the OLI and TIRS instruments on LDCM replace the ETM+ instrument on Landsat-7 with significant enhancements. The OLI is a pushbroom design instrument where the scanning mechanism of the ETM+ is effectively replaced by a long line of detectors. The OLI has 9 spectral bands with similar spatial resolution to ETM+: 7 of them similar to the reflective spectral bands on ETM+ and two new bands. The two new bands cover (1) the shorter wavelength blue part of the spectrum to help with coastal studies and aerosol analyses/atmospheric correction and (2) an atmospheric water absorption band, where the Earth surface is generally not visible, but Cirrus clouds are, to aid in cloud detection and screening. The radiometry of OLI benefits from improved SNR, dynamic range and quantization. OLI is undergoing system testing with a delivery scheduled for Spring 2011. The TIRS is also a pushbroom design and used QWIPS detectors that require cooling to 43K using a cryocooler. It.has two spectral bands, effectively splitting the ETM+ band 6 in half, that can be used as a split window to aid in atmospheric correction. It has nominally 100 m spatial resolution as opposed to the 60 m of Landsat-7 ETM+: TIRS has commenced integration and test, with a delivery to the spacecraft vendor scheduled for Winter 2011-2012. The Orbital spacecraft currently being integrated for LDCM will have improved capabilities for pointing over previous missions. These capabilities will allow the OLI and TIRS instruments to point off-nadir the equivalent of one WRS-2 path to increase the chances of coverage for high priority targets, particularly in the event of natural disasters. Also, the pointing capability will allow the calibration of the OLI using the sun (roughly weekly), the moon (monthly), stars (during commissioning) and the Earth (at 90 deg from normal orientation, a.k.a., side slither) quarterly. The solar calibration will be used for OLI absolute and relative calibration, the moon for trending the stability of the OLI response, the stars will be used for Line of Sight determination and the side slither will be an alternate OLI and relative gain determination methodology. The spacecraft is scheduled to begin integration with the OLI instrument in Summer 2011. The LDCM data processing and archive system (DPAS), located at USGS EROS, generates the products for distribution to users. Like Landsat-7 this includes an image assessment system for characrizing instrument performance and updating calibration parameters. Products will be generated that include the spectral bands from both instruments, terrain corrected and registered to the geoid. Also, like Landsat-7, data products will be distributed at no charge to the user. The current status and plans of the space and ground segments of the LDCM project will be presented along with performance predictions as available. More detailed information on the two instruments is intended to be presented in separate papers.

Markham, Brian↗

Circulation in the Chesapeake Bay entrance region: Estuary-shelf interaction

Current meters and temperature-salinity recorders confirm the assumption that the upper layers of the continental shelf waters off Chesapeake Bay can be banded in summer, such that the coastal boundary layer (consisting of the Bay outflow) and the outer shelf flow southward while the inner shelf flows to the north, driven by the prevailing southerly winds. These measurements show that the estuary itself may also be banded in its lower reaches such that the inflow is confined primarily to the deep channel, while the upper layer outflow is split into two flow maxima on either side of this channel.

Boicourt, W. C.↗

Convective dynamics

In addressing meteorological processes, including convection, it is convenient to separate these processes into their kinematic, dynamic, and microphysical components. Dynamic processes deal with the forces that initiate and sustain or alter motion, while kinematic processes describe the motion field. Microphysical processes address the distribution of water substance. This review of convective dynamics is organized along the following lines. First is an assessment of radar capability, particularly the use of one or more Doppler radars, to portray the wind field. Then various types of precipitating moist convection are reviewed. Each type or mode of convection results from a distinct environment. The principal interest of dynamics here is its role in the convection's evolution, structure, and movement. Thus, the important processes of storm rotation, splitting and propagation, including tornadogenesis, are examined.

Ray, Peter S.↗

Carbon distribution profiles in lunar fines

Radial distribution profiles of elemental carbon in lunar soils consisting of particles in the size range of 50 to 150 microns were investigated. Initial experiments on specimen preparation and the analysis of prepared specimens by Auger electron spectrometry (AES) and scanning electron microscopy (SEM) are described. Results from splits of samples 61501,84 and 64421,11, which were mounted various ways in several specimen holders, are presented. A low carbon content was observed in AES spectra from soil particles that were subjected to sputter-ion cleaning with 960eV argon ions for periods of time up to a total exposure for one hour. This ion charge was sufficient to remove approximately 70 nm of material from the surface. All of the physically adsorbed carbon (as well as water vapor, etc.) would normally be removed in the first few minutes, leaving only carbon in the specimen, and metal support structure, to be detected thereafter.

Hart, R. K.↗

Optimized retrievals of precipitable water fields from combinations of VAS satellite and conventional surface observations

VISSR (visible and infrared spin-scan radiometer) atmospheric sounder (VAS) radiances and conventional surface temperature and dewpoint data are used in several combinations within a regression approach to determine the optimum resolution and accuracy of precipitable water (PW) fields retrieved from satellite observations. Point retrievals at radiosonde stations are used to determine the numerical accuracy of each retrieval technique, and image sequences of the retrieved PW fields are used to determine the temporal stability and spatial coherence of mesoscale PW features. VAS channels 5, 6, 7, and 8 and the surface dewpoint contribute the most information to regression-based retrievals of PW. The most accurate PW retrievals are obtained when radiances are averaged to a resolution of 15 to 60 km. A physical 'split-window' approach provides better PW estimates than regression when only the 11- and 12-micron VAS channels are available or when radiosonde-based training is limited to only one time period.

Robinson, W. D.↗

Intensity-dependent circular polarization and circumstellar magnetic fields from the observation of SiO masers

A new aspect of the propagation of astrophysical maser radiation in the presence of a magnetic field is described in which circular polarization is created. The resulting antisymmetric spectral line profile for this circular polarization resembles that produced by the ordinary Zeeman effect when the Zeeman splittings are much less than the spectral line breadth. It is caused by the change, with increasing maser intensity, in the axis of symmetry for the molecular quantum states from a direction that is parallel to the magnetic field to a direction that is parallel to the direction of propagation. When the maser is radiatively saturated, and the rate for stimulated emission is within an order of magnitude of the Zeeman splitting in frequency units, this 'intensity-dependent circular polarization' is greater than that due to the ordinary Zeeman effect by factors as large as 1000. The circular polarization that is observed in the spectra of circumstellar SiO (J = 1-0) masers associated with late-type giants and supergiants may then be caused by magnetic fields as weak as about 10 mG. With the standard Zeeman interpretation of the observations, magnetic fields of 10-100 G are indicated. The lower fields are similar to the limits obtained from the observation of the 22 GHz water masers which are typically somewhat further from the central star. The observed tendency for the fractional linear polarization of SiO masers to increase with increasing angular momentum of the molecular state is shown to be a likely result of anisotropic pumping. Errors are identified that invalidate a recent conflicting claim in the literature about the basic theory of maser polarization in the regime that is relevant here.

Nedoluha, Gerald E.↗

Acid Sulfate Alteration in Gusev Crater, Mars

The Mars Exploration Rover (MER) Spirit landed on the Gusev Crater plains west of the Columbia Hills in January, 2004, during the Martian summer (sol 0; sol = 1 Martian day = 24 hr 40 min). Spirit explored the Columbia Hills of Gusev Crater in the vicinity of Home Plate at the onset on its second winter (sol approximately 900) until the onset of its fourth winter (sol approximately 2170). At that time, Spirit became mired in a deposit of fined-grained and sulfate-rich soil with dust-covered solar panels and unfavorable pointing of the solar arrays toward the sun. Spirit has not communicated with the Earth since sol 2210 (January, 2011). Like its twin rover Opportunity, which landed on the opposite side of Mars at Meridiani Planum, Spirit has an Alpha Particle X-Ray Spectrometer (APXS) instrument for chemical analyses and a Moessbauer spectrometer (MB) for measurement of iron redox state, mineralogical speciation, and quantitative distribution among oxidation (Fe(3+)/sigma Fe) and coordination (octahedral versus tetrahedral) states and mineralogical speciation (e.g., olivine, pyroxene, ilmenite, carbonate, and sulfate). The concentration of SO3 in Gusev rocks and soils varies from approximately 1 to approximately 34 wt%. Because the APXS instrument does not detect low atomic number elements (e.g., H and C), major-element oxide concentrations are normalized to sum to 100 wt%, i.e., contributions of H2O, CO2, NO2, etc. to the bulk composition care not considered. The majority of Gusev samples have approximately 6 plus or minus 5 wt% SO3, but there is a group of samples with high SO3 concentrations (approximately 30 wt%) and high total iron concentrations (approximately 20 wt%). There is also a group with low total Fe and SO3 concentrations that is also characterized by high SiO2 concentrations (greater than 70 wt%). The trend labeled "Basaltic Soil" is interpreted as mixtures in variable proportions between unaltered igneous material and oxidized and SO3-rich basaltic dust. The Moessbauer parameters are not definitive for mineralogical speciation (other than octahedrally-coordinated Fe(3+) but are consistent with a schwertmannite-like phase (i.e., a nanophase ferric oxide). The high oxidation state and values of Moessbauer parameters (center shift and quadrupole splitting) for the high-SO3 samples imply ferric sulfate (i.e., oxidized sulfur), although the hydration state cannot be constrained. In no case is there an excess of SO3 over available cations (i.e., no evidence for elemental sulfur), and Fe sulfide (pyrite) has been detected in only one Gusev sample. The presence of both high-SiO2 (and low total iron and SO3) and high SO3 (and high total iron as ferric sulfate) can be accommodated by a two-step geochemical model developed with the Geochemist's Workbench. (1) Step 1 is anoxic acid sulfate leaching of Martian basalt at high water-to rock ratios (greater than 70). The result is a high-SiO2 residue0, and anoxic conditions are required to solubilize Fe as Fe(2+). (2) Step 2 is the oxic precipitation of sulfate salts from the leachate. Oxic conditions are required to produce the high concentrations of ferric sulfate with minor Mg-sulfates and no detectable Fe(2+)-sulfates.

Morris, R. V.↗

Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS: Application to Analysis of Experimentally Derived Hydrothermal Mineral-Catalyzed Organic Products

We report results of experiments to measure the H isotope composition of organic acids and alcohols. These experiments make use of a pyroprobe interfaced with a GC and high temperature extraction furnace to make quantitative H isotope measurements. This work compliments our previous work that focused on the extraction and analysis of C isotopes from the same compounds [1]. Together with our carbon isotope analyses our experiments serve as a "proof of concept" for making C and H isotope measurements on more complex mixtures of organic compounds on mineral surfaces in abiotic hydrocarbon formation processes at elevated temperatures and pressures. Our motivation for undertaking this work stems from observations of methane detected within the Martian atmosphere [2-5], coupled with evidence showing extensive water-rock interaction during Mars history [6-8]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization [9,10]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [11-13]. Our H isotope measurements utilize an analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). This technique is designed to carry a split of the pyrolyzed GC-separated product to a Thermo DSQII quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

Socki, Richard A.↗

Air Launch: Examining Performance Potential of Various Configurations and Growth Options

The Advanced Concepts Office at NASA's George C. Marshall Space Flight Center conducted a high-level analysis of various air launch vehicle configurations, objectively determining maximum launch vehicle payload while considering carrier aircraft capabilities and given dimensional constraints. With the renewed interest in aerial launch of low-earth orbit payloads, referenced by programs such as Stratolaunch and Spaceship2, there exists a need to qualify the boundaries of the trade space, identify performance envelopes, and understand advantages and limiting factors of designing for maximum payload capability. Using the NASA/DARPA Horizontal Launch Study (HLS) Point Design 2 (PD-2) as a pointof- departure configuration, two independent design actions were undertaken. Both designs utilized a Boeing 747-400F as the carrier aircraft, LOX/RP-1 first stage and LOX/LH2 second stage. Each design was sized to meet dimensional and mass constraints while optimizing propellant loads and stage delta V splits. All concepts, when fully loaded, exceeded the allowable Gross Takeoff Weight (GTOW) of the aircraft platform. This excess mass was evaluated as propellant/fuel offload available for a potential in-flight propellant loading scenario. Results indicate many advantages such as payload delivery of approximately 47,000 lbm and significant mission flexibility including variable launch site inclination and launch window. However, in-flight cryogenic fluid transfer and carrier aircraft platform integration are substantial technical hurdles to the realization of such a system configuration.

Waters, Eric D.↗

Air Launch: Examining Performance Potential of Various Configurations and Growth Options

The Advanced Concepts Office at NASA's George C. Marshall Space Flight Center conducted a high-level analysis of various air launch vehicle configurations, objectively determining maximum launch vehicle payload while considering carrier aircraft capabilities and given dimensional constraints. With the renewed interest in aerial launch of low-earth orbit payloads, referenced by programs such as Stratolaunch and Spaceship2, there existed a need to qualify the boundaries of the trade space, identify performance envelopes, and understand advantages and limiting factors of designing for maximum payload capability. Using the NASA/DARPA Horizontal Launch Study (HLS) Point Design 2 (PD-2) as a point-of-departure configuration, two independent design actions were undertaken. Both configurations utilized a Boeing 747-400F as the carrier aircraft, LOX/RP-1 first stage and LOX/LH2 second stage. Each design was sized to meet dimensional and mass constraints while optimizing propellant loads and stage delta V (ΔV) splits. All concepts, when fully loaded, exceeded the allowable Gross Takeoff Weight (GTOW) of the aircraft platform. This excess mass was evaluated as propellant/fuel offload available for a potential in-flight refueling scenario. Results indicate many advantages such as large, relative payload delivery of approximately 47,000 lbm and significant mission flexibility, such as variable launch site inclination and launch window; however, in-flight cryogenic fluid transfer and carrier aircraft platform integration are substantial technical hurdles to the realization of such a system configuration.

Waters, Eric D.↗

Classifying Agnostic Biosignatures using Raman, VNIR, and Elemental Data

How can we use our current wealth of terrestrial data, encompassing biogenic and abiogenic systems, to determine the distinguishing properties of life? SCOBI (Statistical Classification of Biosignature Information) uses machine learning techniques to algorithmically identify combinations of measurements that are “indicative of life”. A set of ~1000 observations, comprising elemental abundance, isotopic fractionation, VNIR reflectance, and (in progress) Raman spectra, have been assembled from existing literature and databases. The observations cover systems classified as “indicative alive” (e.g., cells, vegetation), “indicative non-alive” (e.g., fossils, teeth), “mixed indicative” (e.g., soil, pond water), or “non-indicative” (e.g., rocks, meteorites). VNIR data was preprocessed by linear interpolation from 400-2100 nm and smoothed with a Savitzky-Golay filter. To limit the amount of Earth-biochemistry-specific (non-agnostic) information included, the first five spectral features extracted were number of peaks, number of troughs, mean reflectance, mean peak width, and broadest peak width. To help further emphasize agnostic biosignatures, Earth-specific features such as chlorophylls have been manually flagged so that feature importance with and without them can be compared. Classifiers including k-nearest neighbors (KNN), Gaussian Naïve Bayes (GNB), logistic regression (LR), random forest (RF), and support vector machine (SVM) were implemented, as was a combination voting classifier. Performance metrics included false positive rates, false negative rates, and AUC with 50-50 test/train splits (Monte Carlo simulations). Key takeaways from this stage, prior to the inclusion of Raman spectra, are (1) the overall success rate of 0.933 AUC was most heavily influenced by the elemental abundance data; and (2) VNIR reflectance had the lowest classification performance with 0.52 AUC (58% of objects correctly classified). The next steps are to complete integration of Raman spectral data and to improve the approach to pre-processing and feature extraction for both types of spectral data, such as automated baseline removal, whole spectrum matching, and dimensionality reduction.

Biosignatures↗

Compound Specific Hydrogen Isotope Composition of Type II and III Kerogen Extracted by Pyrolysis-GC-MS-IRMS

The use of Hydrogen (H) isotopes in understanding oil and gas resource plays is in its infancy. Described here is a technique for H isotope analysis of organic compounds pyrolyzed from oil and gas shale-derived kerogen. Application of this technique will progress our understanding. This work complements that of Pernia et al. (2013, this meeting) by providing a novel method for the H isotope analysis of specific compounds in the characterization of kerogen extracted by analytically diverse techniques. Hydrogen isotope analyses were carried out entirely "on-line" utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC Ultra interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make semi-quantitative compositional measurements of the extracted compounds. Kerogen samples from five different basins (type II and III) were dehydrated (heated to 80 C overnight in vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C) which quantitatively forms H2, following a modified method of Burgoyne and Hayes, (1998, Anal. Chem., 70, 5136-5141). Samples ranging from approximately 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. Compounds were separated on a Poraplot Q GC column. Hydrogen isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight compounds. Water (H2O) average deltaD = -215.2 (V-SMOW), ranging from -271.8 for the Marcellus Shale to -51.9 for the Polish Shale. Higher molecular weight compounds like toluene (C7H8) have an average deltaD of -89.7 0/00, ranging from -156.0 for the Barnett Shale to -50.0 for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during formation within each basin. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas-water or oil-water interaction in resource plays, and further as a possible indicator of paleo-environmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analysis. More experiments are planned to discern these two or other possible scenarios.

Socki, Richard A.↗