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Nitric Oxide and Oxygen Air-Contamination Effects on Extinction Limits of Non-Premixed Hydrocarbon-Air Flames for a HIFiRE Scramjet

Unique nitric oxide (NO) and oxygen air-contamination effects on the extinction Flame Strength (FS) of non-premixed hydrocarbon (HC) vs. air flames are characterized for 7 gaseous HCs, using a new idealized 9.3 mm straight-tube Opposed Jet Burner (OJB) at 1 atm. FS represents a laminar strain-induced extinction limit based on cross-section-average air jet velocity, Uair, that sustains combustion of a counter jet of gaseous fuel just before extinction. Besides ethane, propane, butane, and propylene, the HCs include ethylene, methane, and a 64 mole-% ethylene / 36 % methane mixture, the writer s previously recommended gaseous surrogate fuel for HIFiRE scramjet tests. The HC vs. clean air part of the work is an extension of a May 2008 JANNAF paper that characterized surrogates for the HIFiRE project that should mimic the flameholding of reformed (thermally- or catalytically-cracked) endothermic JP-like fuels. The new FS data for 7 HCs vs. clean air are thus consolidated with the previously validated data, normalized to absolute (local) axial-input strain rates, and co-plotted on a dual kinetically dominated reactivity scale. Excellent agreement with the prior data is obtained for all 7 fuels. Detailed comparisons are also made with recently published (Univ. Va) numerical results for ethylene extinction. A 2009-revised ethylene kinetic model (Univ. Southern Cal) led to predicted limits within approx. 5 % (compared to 45 %, earlier) of this writer s 2008 (and present) ethylene FSs, and also with recent independent data (Univ. Va) obtained on a new OJB system. These +/- 5 % agreements, and a hoped-for "near-identically-performing" reduced kinetics model, would greatly enhance the capability for accurate numerical simulations of surrogate HC flameholding in scramjets. The measured air-contamination effects on normalized FS extinction limits are projected to assess ongoing Arc-Heater-induced "facility test effects" of NO production (e.g., 3 mole-%) and resultant oxygen depletion (from 21 to 19.5 %), for testing the "64/36" surrogate fuel in Langley s Arc-Heated Scramjet Test Facility for HIFiRE engine designs. The FS results show a generally small (< 4 %) "nitric oxide enhancement" effect, relative to clean air, for up to 3 % NO (freestream Mach number up to 7 in Arc Jet testing). However, a progressively large "oxygendeficiency weakening" effect develops. For 3 % NO, a net weakening of 26 % in FS is derived for the "64/36" fuel vs. air. The corresponding net weakening for pure ethylene is 20 %. A number of practical recommendations regarding facility test effects are offered.

Pellett, Gerald L.↗

Operation of a Third Generation JPL Electronic Nose in the Regenerative ECLSS Module Simulator at MSFC

An electronic nose has been developed at the Jet Propulsion Laboratory (JPL) to monitor spacecraft cabin air for anomalous events such as leaks and spills of solvents, coolants or other fluids with near-real-time analysis. It is designed to operate in the environment of the US Lab on ISS and was deployed on the International Space Station for a seven-month experiment in 2008-2009. In order improve understanding of ENose response to crew activities, an ENose was installed in the Regenerative ECLSS Module Simulator (REMS) at Marshall Space Flight Center (MSFC) for several months. The REMS chamber is operated with continuous analysis of the air for presence and concentration of CO, CO2, ethane, ethanol and methane. ENose responses were analyzed and correlated with logged activities and air analyses in the REMS.

Electronic Nose (ENose)↗

Single Spatial-Mode Room-Temperature-Operated 3.0 to 3.4 micrometer Diode Lasers

Compact, highly efficient, 3.0 to 3.4 m light emitters are in demand for spectroscopic analysis and identification of chemical substances (including methane and formaldehyde), infrared countermeasures technologies, and development of advanced infrared scene projectors. The need for these light emitters can be currently addressed either by bulky solid-state light emitters with limited power conversion efficiency, or cooled Interband Cascade (IC) semiconductor lasers. Researchers here have developed a breakthrough approach to fabrication of diode mid-IR lasers that have several advantages over IC lasers used for the Mars 2009 mission. This breakthrough is due to a novel design utilizing the strain-engineered quantum-well (QW) active region and quinternary barriers, and due to optimization of device material composition and growth conditions (growth temperatures and rates). However, in their present form, these GaSb-based laser diodes cannot be directly used as a part of sensor systems. The device spectrum is too broad to perform spectroscopic analysis of gas species, and operating currents and voltages are too high. In the current work, the emitters were fabricated as narrow-ridge waveguide index-guided lasers rather than broad stripe-gain guided multimode Fabry-Perot (FP) lasers as was done previously. These narrow-ridge waveguide mid-IR lasers exhibit much lower power consumptions, and can operate in a single spatial mode that is necessary for demonstration of single-mode distributed feedback (DBF) devices for spectroscopic applications. These lasers will enable a new generation of compact, tunable diode laser spectrometers with lower power consumption, reduced complexity, and significantly reduced development costs. These lasers can be used for the detection of HCN, C2H2, methane, and ethane.

Frez, Clifford F.↗

Diffusion Flame Stabilization

Diffusion flames are commonly used for industrial burners in furnaces and flares. Oxygen/fuel burners are usually diffusion burners, primarily for safety reasons, to prevent flashback and explosion in a potentially dangerous system. Furthermore, in most fires, condensed materials pyrolyze, vaporize, and burn in air as diffusion flames. As a result of the interaction of a diffusion flame with burner or condensed-fuel surfaces, a quenched space is formed, thus leaving a diffusion flame edge, which plays an important role in flame holding in combustion systems and fire spread through condensed fuels. Despite a long history of jet diffusion flame studies, lifting/blowoff mechanisms have not yet been fully understood, compared to those of premixed flames. In this study, the structure and stability of diffusion flames of gaseous hydrocarbon fuels in coflowing air at normal earth gravity have been investigated experimentally and computationally. Measurements of the critical mean jet velocity (U(sub jc)) of methane, ethane, or propane at lifting or blowoff were made as a function of the coflowing air velocity (U(sub a)) using a tube burner (i.d.: 2.87 mm). By using a computational fluid dynamics code with 33 species and 112 elementary reaction steps, the internal chemical-kinetic structures of the stabilizing region of methane and propane flames were investigated. A peak reactivity spot, i.e., reaction kernel, is formed in the flame stabilizing region due to back-diffusion of heat and radical species against an oxygen-rich incoming flow, thus holding the trailing diffusion flame. The simulated flame base moved downstream under flow conditions close to the measured stability limit.

Takahashi, Fumiaki↗

Cloud Condensation in Titan's Lower Stratosphere

A 1-D condensation model is developed for the purpose of reproducing ice clouds in Titan's lower stratosphere observed by the Composite Infrared Spectrometer (CIRS) onboard Cassini. Hydrogen cyanide (HCN), cyanoacetylene (HC3N), and ethane (C2H6) vapors are treated as chemically inert gas species that flow from an upper boundary at 500 km to a condensation sink near Titan's tropopause (-45 km). Gas vertical profiles are determined from eddy mixing and a downward flux at the upper boundary. The condensation sink is based upon diffusive growth of the cloud particles and is proportional to the degree of supersaturation in the cloud formation regIOn. Observations of the vapor phase abundances above the condensation levels and the locations and properties of the ice clouds provide constraints on the free parameters in the model. Vapor phase abundances are determined from CIRS mid-IR observations, whereas cloud particle sizes, altitudes, and latitudinal distributions are derived from analyses of CIRS far-IR observations of Titan. Specific cloud constraints include: I) mean particle radii of2-3 J.lm inferred from the V6 506 cm- band of HC3N, 2) latitudinal abundance distributions of condensed nitriles, inferred from a composite emission feature that peaks at 160/cm , and 3) a possible hydrocarbon cloud layer at high latitudes, located near an altitude of 60 km, which peaks between 60 and 80 cm l . Nitrile abundances appear to diminish substantially at high northern latitudes over the time period 2005 to 2010 (northern mid winter to early spring). Use of multiple gas species provides a consistency check on the eddy mixing coefficient profile. The flux at the upper boundary is the net column chemical production from the upper atmosphere and provides a constraint on chemical pathways leading to the production of these compounds. Comparison of the differing lifetimes, vapor phase transport, vapor phase loss rate, and particle sedimentation, sheds light on temporal stability of the clouds.

Romani, Paul N.↗

The Composition of Titan's Lower Atmosphere and Simple Surface Volatiles as Measured by the Cassini-Huygens Probe Gas Chromatograph Mass Spectrometer Experiment

The Cassini-Huygens Probe Gas Chromatograph Mass Spectrometer (GCMS) determined the composition of the Titan atmosphere from ~140km altitude to the surface. After landing, it returned composition data of gases evaporated from the surface. Height profiles of molecular nitrogen (N2), methane (CH4) and molecular hydrogen (H2) were determined. Traces were detected on the surface of evaporating methane, ethane (C2H6), acetylene (C2H2), cyanogen (C2N2) and carbon dioxide (CO2). The methane data showed evidence that methane precipitation occurred recently. The methane mole fraction was (1.48+/-0.09) x 10(exp -2) in the lower stratosphere (139.8 km to 75.5 km) and (5.65+/-0.18) x 10(exp -2) near the surface (6.7 km to the surface). The molecular hydrogen mole fraction was (1.01+/-0.16) x 10(exp -3) in the atmosphere and (9.90+/-0.17) x 10(exp -4) on the surface. Isotope ratios were 167.7+/-0.6 for N-14/N-15 in molecular nitrogen, 91.1+/-1.4 for C-12/C-13 in methane and (1.35+/-0.30) x 10(exp -4) for D/H in molecular hydrogen. The mole fractions of Ar-36 and radiogenic Ar-40 are (2.1+/-0.8) x 10(exp -7) and (3.39 +/-0.12) x 10(exp -5) respectively. Ne-22 has been tentatively identified at a mole fraction of (2.8+/-2.1) x 10(exp -7) Krypton and xenon were below the detection threshold of 1 x 10(exp -8) mole fraction. Science data were not retrieved from the gas chromatograph subsystem as the abundance of the organic trace gases in the atmosphere and on the ground did not reach the detection threshold. Results previously published from the GCMS experiment are superseded by this publication.

Niemann, H. B.↗

Titan's Aerosol and Condensation Cloud Properties in the Far-IR Between 2005 and 2010

Analyses of far-IR spectra between 20 and 560 cm(exp -1) (500 to 18 micron) recorded by the Cassini Composite Infrared Spectrometer (CIRS) yield the spectral dependence and the vertical distribution of Titan's photochemical aerosol and ice clouds. Titan's aerosol appears to be well mixed between the surface and an altitude of 300 km, with a spectral shape that does not change with latitude or time. The aerosol exhibits an extremely broad emission feature with a spectral peak at 140 cm(exp -1) (71 micron), which is not evident in laboratory simulated Titan aerosols (tholin). This low- energy aerosol emission feature may arise from low-energy molecules such as polycyclic aromatic hydrocarbons and/or nitrogenated aromatics. Unlike the vertically well-mixed aerosol, Titan's condensate clouds are located in highly restricted altitudes in the lower stratosphere, ranging between 60 and 100 km at low and moderate latitudes, to between 150 and 165 km at high northern latitudes during northern winter. Such clouds are located at altitudes where nitrile vapors are expected to condense and appear to be dominated by HCN and HC3N, which are the two most abundant nitriles in Titan's atmosphere. Associated with this ice cloud is a broad emission feature that spectrally peaks near 160 cm(exp -1) (62.5 micron). This ice composite appears to chemically change with altitude and latitude, probably as a result of differences in vapor abundance and condensation temperature, and the ice cloud appears to be global in extent. Both CIRS and the Huygens Descent Imager and Spectral Radiometer (DISR) show evidence of cloud layering in Titan's lower stratosphere. The 15 km difference in cloud altitude indicated by the two instruments suggests a difference in ice composition. CIRS also indicates a second ice cloud that exists at isolated latitudes and is consistent with hydrocarbon condensation above the tropopause. This cloud exhibits an emission feature that spectrally peaks near 80 cm(exp -1) (125 micron), possibly due to C2H6 ice or dominated by an ethane-acetylene composite ice, given that CzH6 then C2H2 are the two most abundant hydrocarbons next to methane in Titan's atmosphere.

Anderson, Carrie↗

Temporal and Spatial Aspects of Gas Release During the 2010 Apparition of Comet 103P/Hartley-2

We report measurements of eight primary volatiles (H2O, HCN, CH4, C2H6, CH3OH, C2H2, H2CO, and NH3) and two product species (OH and NH2) in comet lO3P/Hartley-2 using high dispersion infrared spectroscopy. We quantified the long- and short-term behavior of volatile release over a three-month interval that encompassed the comet's close approach to Earth, its perihelion passage, and flyby of the comet by the Deep Impact spacecraft during the EPOXI mission. We present production rates for individual species, their mixing ratios relative to water, and their spatial distributions in the coma on multiple dates. The production rates for water, ethane, HCN, and methanol vary in a manner consistent with independent measures of nucleus rotation, but mixing ratios for HCN, C2H6, & CH3OH are independent of rotational phase. Our results demonstrate that the ensemble average composition of gas released from the nucleus is well defined, and relatively constant over the three-month interval (September 18 through December 1,7). If individual vents vary in composition, enough diverse vents must be active simultaneously to approximate (in sum) the bulk composition of the nucleus. The released primary volatiles exhibit diverse spatial properties which favor the presence of separate polar and apolar ice phases in the nucleus, establish dust and gas release from icy clumps, and from the nucleus, and provide insights into the driver for the cyanogen (CN) polar jet. The spatial distributions of C2H6 & HCN along the near-polar jet (UT 19.5 October) and nearly orthogonal to it (UT 22.5 October) are discussed relative to the origin of CN. The ortho-para ratio (OPR) of water was 2.85 +/- 0.20; the lower bound (2.65) defines T(sub spin) > 32 K. These values are consistent with results returned from ISO in 1997 .

Mumma, M. J.↗

Rotating-Pump Design Code

Pump Design (PUMPDES) is a computer program for designing a rotating pump for liquid hydrogen, liquid oxygen, liquid nitrogen, water, methane, or ethane. Using realistic properties of these fluids provided by another program called GASPAK, this code performs a station-by-station, mean-line analysis along the pump flow path, obtaining thermodynamic properties of the pumped fluid at each station and evaluating hydraulic losses along the flow path. The variables at each station are obtained under constraints that are consistent with the underlying physical principles. The code evaluates the performance of each stage and the overall pump. In addition, by judiciously choosing the givens and the unknowns, the code can perform a geometric inverse design function: that is, it can compute a pump geometry that yields a closest approximation of given design point. The code contains two major parts: one for an axial-rotor/inducer and one for a multistage centrifugal pump. The inducer and the centrifugal pump are functionally integrated. The code can be used in designing and/or evaluating the inducer/centrifugal-pump combination or the centrifugal pump alone. The code is written in standard Fortran 77.

Walker, James F.↗

Abundances of Jupiter's Trace Hydrocarbons from Voyager and Cassini

The flybys of Jupiter by the Voyager spacecraft in 1979, and over two decades later by Cassini in 2000, have provided us with unique datasets from two different epochs, allowing the investigation of seasonal change in the atmosphere. In this paper we model zonal averages of thermal infrared spectra from the two instruments, Voyager 1 IRIS and Cassini CIRS, to retrieve the vertical and meridional profiles of temperature, and the abundances of the two minor hydrocarbons, acetylene (C2H2) and ethane (C2H6). The spatial variation of these gases is controlled by both chemistry and dynamics, and therefore their observed distribution gives us an insight into both processes, We find that the two gases paint quite different pictures of seasonal change. Whilst the 2-D cross-section of C2H6 abundance is slightly increased and more symmetric in 2000 (northern summer solstice) compared to 1979 (northern fall equinox), the major trend of equator to pole increase remains. For C2H2 on tile other hand, the Voyager epoch exhibits almost no latitudinal variation, whilst the Cassini era shows a marked decrease polewards in both hemispheres. At the present time, these experimental findings are in advance of interpretation, as there are no published models of 2-D Jovian seasonal chemical variation available for comparison.

Nixon, C. A.↗

Application of Emulsified Zero-Valent Iron to Marine Environments

Contamination of marine waters and sediments with heavy metals and dense non-aqueous phase liquids (DNAPLs) including chlorinated solvents, pesticides and PCBs pose ecological and human health risks through the contaminant's potential bioaccumulation in fish, shellfish and avian populations. The contaminants enter marine environments through improper disposal techniques and storm water run-off. Current remediation technologies for application to marine environments include costly dredging and off-site treatment of the contaminated media. Emulsified zero-valent iron (EZVI) has been proven to effectively degrade dissolved-phase and DNAPL-phase contaminants in freshwater environments on both the laboratory and field-scale level. However, the application to marine environments is only just being explored. This paper discusses the potential use of EZVI in brackish and saltwater environments, with supporting laboratory data detailed. Laboratory studies were performed in 2005 to establish the effectiveness of EZVI to degrade trichloroethylene (TCE) in saltwater. Headspace vials were setup to determine the kinetic rate of TCE degradation using EZVI in seawater. The reaction vials were analyzed by Gas Chromatographic/Flame Ionization Detection (GC/FID) for ethene production after a 48 day period using a GC/FID Purge and Trap system. Analytical results showed that EZVI was very effective at degrading TCE. The reaction by-products (ethene, acetylene and ethane) were produced at 71% of the rate in seawater as in the fresh water controls. Additionally, iron within the EZVI particles was protected from oxidation of the corrosive seawater, allowing EZVI to perform in an environment where zero-valent iron alone could not compete. Laboratory studies were also performed to establish the effectiveness of emulsified zero-valent metal (EZVM) to remove dissolved-phase cadmium and lead found in seawater. EZVM is comprised of a combination of magnesium and iron metal surrounded by the same oil/surfactant membrane used in EZVI. The removal of cadmium and lead from a seawater matrix is a unique challenge. It requires a system that is resistant to the corrosive nature of seawater while removing specific ions that are in a relatively low concentration compared to naturally occurring seawater salts. Laboratory studies conducted show greater than 99% removal of lead and 96% removal of cadmium from a seawater solution spiked at 5 mg/L that was treated with an Emulsified Zero-Valent Metal (EZVM). The cadmium and lead are removed from the solution as they transport across the emulsion membrane and plate out onto the zero-valent metal surface.

Brooks, Kathleen B.↗

Primary Volatile Abundances in Comets from Infrared Spectroscopy: Implications for Reactions on Grain Surfaces in the Interstellar/Nebular Environment

Comets retain relatively primitive icy material remaining from the epoch of Solar System formation, however the extent to which they are modified from their initial state remains a key question in cometary science. High-resolution lR spectroscopy has emerged as a powerful tool for measuring vibrational emissions from primary volatiles (i.e., those contained in the nuclei of comets). With modern instrumentation, most notably NIRSPEC at the Keck II 10-m telescope, we can quantify species of astrobiological importance (e.g., H20, C2H2, CH4, C2H6, CO, H2CO, CH30H, HCN, NH3). In space environments, compounds of keen interest to astrobiology could originate from HCN and NH3 (leading to amino acids), H2CO (leading to sugars), or C2H6 and CH4 (suggested precursors of ethyl- and methylamine). Measuring the abundances of these precursor molecules (and their variability among comets) is a feasible task that contributes to understanding their delivery to Earth's early biosphere and to the synthesis of more complex pre biotic compounds. Over 20 comets have now been measured with IR spectroscopy, and this sample reveals significant diversity in primary volatile compositions. From this, a taxonomic classification scheme is emerging, presumably reflecting the diverse conditions experienced by pre-cometary grains in interstellar and subsequent nebular environs. The importance of H-atom addition to C2H2 on the surfaces of interstellar grains to produce C2H6 was validated by the discovery of abundant ethane in comet C/1996 B2 (Hyakutake) with C2H6/CH4 well above that achievable by gas-phase chemistry , and then in irradiation experiments on laboratory ices at 10 - 50 K. The large abundance ratios C2H6/CH4 observed universally in comets establish H-atom addition as an important and likely ubiquitous process, and comparing C2H6/C2H2 among comets can provide information on its efficiency. The IR is uniquely capable since symmetric hydrocarbons (e.g., C2H2, CH4, C2H6) have no electric dipole moment and thus no allowed pure rotational transitions. CO should also be hydrogenated on grain surfaces. Irradiation experiments on interstellar ice analogs show this to require very low temperatures, the resulting yields of H2CO and CH30H being highly dependent on temperature in the range approx 10 - 25 K. The relative abundances of these chemically-related molecules in comets provide one measure of the efficiency of H-atom addition to CO Oxidation of CO is also important on grain mantles, as evidenced by the widespread presence of C02 ice towards interstellar sources observed with ISO and in a survey of 17 comets observed with AKARI. H-atom addition to C2H2 produces the vinyl radical, and through subsequent oxidation1reduction reactions can lead to vinyl alcohol, acetaldehyde, and ethanol This may have implications for interpreting observed abundance ratios CO/C2H2. We will discuss possible implications regarding formation conditions in the context of measured primary volatile compositions, emphasizing recently observed comets and published results. These are continually providing new insights regarding our taxonomic scheme and also delivery of pre-biological material to the young Earth.

DiSanti, M. A.↗

Analyses of Cometary Silicate Crystals: DDA Spectral Modeling of Forsterite

Comets are the Solar System's deep freezers of gases, ices, and particulates that were present in the outer protoplanetary disk. Where comet nuclei accreted was so cold that CO ice (approximately 50K) and other supervolatile ices like ethane (C2H2) were preserved. However, comets also accreted high temperature minerals: silicate crystals that either condensed (greater than or equal to 1400 K) or that were annealed from amorphous (glassy) silicates (greater than 850-1000 K). By their rarity in the interstellar medium, cometary crystalline silicates are thought to be grains that formed in the inner disk and were then radially transported out to the cold and ice-rich regimes near Neptune. The questions that comets can potentially address are: How fast, how far, and over what duration were crystals that formed in the inner disk transported out to the comet-forming region(s)? In comets, the mass fractions of silicates that are crystalline, f_cryst, translate to benchmarks for protoplanetary disk radial transport models. The infamous comet Hale-Bopp has crystalline fractions of over 55%. The values for cometary crystalline mass fractions, however, are derived assuming that the mineralogy assessed for the submicron to micron-sized portion of the size distribution represents the compositional makeup of all larger grains in the coma. Models for fitting cometary SEDs make this assumption because models can only fit the observed features with submicron to micron-sized discrete crystals. On the other hand, larger (0.1-100 micrometer radii) porous grains composed of amorphous silicates and amorphous carbon can be easily computed with mixed medium theory wherein vacuum mixed into a spherical particle mimics a porous aggregate. If crystalline silicates are mixed in, the models completely fail to match the observations. Moreover, models for a size distribution of discrete crystalline forsterite grains commonly employs the CDE computational method for ellipsoidal platelets (c:a:b=8.14x8.14xl in shape with geometrical factors of x:y:z=1:1:10, Fabian et al. 2001; Harker et al. 2007). Alternatively, models for forsterite employ statistical methods like the Distribution of Hollow Spheres (Min et al. 2008; Oliveira et al. 2011) or Gaussian Random Spheres (GRS) or RGF (Gielen et al. 200S). Pancakes, hollow spheres, or GRS shapes similar to wheat sheaf crystal habit (e.g., Volten et al. 2001; Veihelmann et al. 2006), however, do not have the sharp edges, flat faces, and vertices seen in images of cometary crystals in interplanetary dust particles (IDPs) or in Stardust samples. Cometary forsterite crystals often have equant or tabular crystal habit (J. Bradley). To simulate cometary crystals, we have computed absorption efficiencies of forsterite using the Discrete Dipole Approximation (DDA) DDSCAT code on NAS supercomputers. We compute thermal models that employ a size distribution of discrete irregularly shaped forsterite crystals (nonspherical shapes with faces and vertices) to explore how crystal shape affects the shape and wavelength positions of the forsterite spectral features and to explore whether cometary crystal shapes support either condensation or annealing scenarios (Lindsay et al. 2012a, b). We find forsterite crystal shapes that best-fit comet Hale-Bopp are tetrahedron, bricks or brick platelets, essentially equant or tabular (Lindsay et al. 2012a,b), commensurate with high temperature condensation experiments (Kobatake et al. 2008). We also have computed porous aggregates with crystal monomers and find that the crystal resonances are amplified. i.e., the crystalline fraction is lower in the aggregate than is derived by fitting a linear mix of spectral features from discrete subcomponents, and the crystal resonances 'appear' to be from larger crystals (Wooden et al. 2012). These results may indicate that the crystalline mass fraction in comets with comae dominated by aggregates may be lower than deduced by popular methods that only emoy ensembles of discrete crystals.

Wooden, Diane↗

A Newly Developed Fluorescence Model for C2H6 v5 and Application to Cometary Spectra Acquired with NIRSPEC at Keck II

Accurate rotational temperatures are essential for extracting production rates for parent volatiles in comets. Two strong bands of ethane (v7 at 2985.39/cm and v5 at 2895.67/cm) are seen in infrared cometary spectra, but the Q-branches of v7 are not resolved by current instruments and cannot provide an accurate rotational temperature with current models.We developed a fluorescence model for the C2H6 v5 band that can be used to derive a rotational temperature.We applied our C2H6 5 model to high-resolution infrared spectra of the comets C/2004 Q2 Machholz and C/2000 WM1 (LINEAR), acquired with the Near-infrared Echelle Spectrograph on the Keck II telescope. We demonstrate agreement among the rotational temperatures derived from C2H6 v5 and other species, and between mixing ratios derived from C2H6 v5 and C2H6 v7. As a symmetric hydrocarbon, C2H6 is observed only in the infrared, and it is now the fifth molecule (along with H2O, HCN, CO, and H2CO) for which we can derive a reliable rotational temperature from cometary infrared spectra.

Radeva, Yana L.↗

The Evolution and Fate of Saturn's Stratospheric Vortex: Infrared Spectroscopy from Cassini

The planet-encircling springtime storm in Saturn's troposphere (December 2010-July 2011) produced dramatic perturbations to stratospheric temperatures, winds and composition at mbar pressures that persisted long after the tropospheric disturbance had abated. Observations from the Cassini Composite Infrared Spectrometer (CIRS), supported by ground-based imaging from the VISIR instrument on the Very Large Telescope,is used to track the evolution of a large, hot stratospheric anticyclone between January 2011 and the present day. The evolutionary sequence can be divided into three phases: (I) the formation and intensification of two distinct warm airmasses near 0.5 mbar between 25 and 35N (one residing directly above the convective storm head) between January-April 2011, moving westward with different zonal velocities; (II) the merging of the warm airmasses to form the large single 'stratospheric beacon' near 40N between April and June 2011, dissociated from the storm head and at a higher pressure (2 mbar) than the original beacons; and (III) the mature phase characterized by slow cooling and longitudinal shrinkage of the anticyclone since July 2011, moving west with a near-constant velocity of 2.70+/-0.04 deg/day (-24.5+/-0.4 m/s at 40N). Peak temperatures of 220 K at 2 mbar were measured on May 5th 2011 immediately after the merger, some 80 K warmer than the quiescent surroundings. Thermal winds hear calculations in August 2011 suggest clockwise peripheral velocities of 200400 mls at 2 mbar, defining a peripheral collar with a width of 65 degrees longitude (50,000 km in diameter) and 25 degrees latitude. Stratospheric acetylene (C2H2) was uniformly enhanced by a factor of three within the vortex, whereas ethane (C2H6) remained unaffected. We will discuss the thermal and chemical characteristics of Saturn's beacon in its mature phase, and implications for stratospheric vortices on other giant planets.

Fletcher, Leigh N.↗

Detecting Methane From Leaking Pipelines and as Greenhouse Gas in the Atmosphere

Laser remote sensing measurements of trace gases from orbit can provide unprecedented information about important planetary science and answer critical questions about planetary atmospheres. Methane (CH4) is the second most important anthropogenically produced greenhouse gas. Though its atmospheric abundance is much less than that of CO2 (1.78 ppm vs. 380 ppm), it has much larger greenhouse heating potential. CH4 also contributes to pollution in the lower atmosphere through chemical reactions, leading to ozone production. Atmospheric CH4 concentrations have been increasing as a result of increased fossil fuel production, rice farming, livestock, and landfills. Natural sources of CH4 include wetlands, wild fires, and termites, and perhaps other unknown sources. Important sinks for CH4 include non-saturated soils and oxidation by hydroxyl radicals in the atmosphere. Remotely measuring CH4 and other biogenic molecules (such as ethane and formaldehyde) on Mars also has important implications on the existence of life on Mars. Measuring CH4 at very low (ppb) concentrations from orbit will dramatically improve the sensitivity and spatial resolution in the search for CH4 vents and sub-surface life on other planets. A capability has been developed using lasers and spectroscopic detection techniques for the remote measurements of trace gases in open paths. Detection of CH4, CO2, H2O, and CO in absorption cells and in open paths, both in the mid- IR and near-IR region, has been demonstrated using an Optical Parametric Amplifier laser transmitter developed at GSFC. With this transmitter, it would be possible to develop a remote sensing methane instrument. CH4 detection also has very important commercial applications. Pipeline leak detection from an aircraft or a helicopter can significantly reduce cost, response time, and pinpoint the location. The main advantage is the ability to rapidly detect CH4 leaks remotely. This is extremely important for the petrochemical industry. This capability can be used in manned or unmanned airborne platforms for the detection of leaks in pipelines and other areas of interest where a CH4 leak is suspected.

Riris, Haris↗

Impact-Induced Climate Change on Titan

Titan's thick atmosphere and volatile surface cause it to respond to big impacts like the one that produced the prominent Menrva impact basin in a somewhat Earth-like manner. Menrva was big enough to raise the surface temperature by 100 K. If methane in the regolith is generally as abundant as it was at the Huygens landing site, Menrva would have been big enough to double the amount of methane in the atmosphere. The extra methane would have drizzled out of the atmosphere over hundreds of years. Conditions may have been favorable for clathrating volatiles such as ethane. Impacts can also create local crater lakes set in warm ice but these quickly sink below the warm ice; whether the cryptic waters quickly freeze by mixing with the ice crust or whether they long endure under the ice remains a open question. Bigger impacts can create shallow liquid water oceans at the surface. If Titan's crust is made of water ice, the putative Hotei impact (a possible 800-1200 km diameter basin, Soderblom et al 2009) would have raised the average surface temperature to 350-400 K. Water rain would have fallen and global meltwaters would have averaged 50 m to as much as 500 m deep. The meltwaters may not have lasted more than a few decades or centuries at most, but are interesting to consider given Titan's organic wealth.

Zahnle, Kevin↗

Thermal Infrared Sensor (TIRS) Instrument Thermal Subsystem Design and Lessons Learned

The Thermal Infrared Sensor (TIRS) is one of two instruments on the Landsat Data Continuity Mission (LDCM), which is scheduled to launch in February of 2013. The TIRS instrument was officially added to the mission later in the flow, which led to a highly aggressive schedule that became one of the main drivers during instrument development. The thermal subsystem design of the TIRS Sensor Unit is comprised of five thermal zones which range in temperature from less than 43 Kelvin to 330 Kelvin. Most zones are proportional heater controlled, and all are within a volume of 35 cu.ft. A two-stage cryocooler is used to cool the "cold stage" including three QWIP detectors to less than 43 Kelvin, and cool the "warm stage" to 105 Kelvin. The excess power dissipation from the cryocooler is rejected via ammonia transport heat pipes to a dedicated Cryocooler Radiator with embedded ammonia heat pipes. The cryogenic subsystem includes a series of shells used to radiatively and conductively isolate the cold stage from the warmer surroundings. The Optical System (telescope) is passively cooled to 180-190 Kelvin using a "thermal link" (comprised of a Flexible Conductive Thermal Strap and an APG Bar) which couples the telescope stage to a dedicated radiator with embedded ethane heat pipes. The Scene Select Mechanism, which is responsible for moving the Scene Select Mirror to three distinct positions (including Nadir, Space, and On-board Black Body Calibrator pointing), runs nominally at 278 Kelvin and is thermally isolated from the cryogenic thermal zones. The On-board Black Body Calibrator requires a dedicated radiator which allows for a temperature range of 260-330 Kelvin at the Source. The detectors are powered by the FPE Box, which is mounted to the nadir external surface of the composite honeycomb structure. There are two additional electronics boxes which are wet-mounted directly to the spacecraft shear panel, the Main Electronics Box and Cryocooler Electronics Box; thermal control of these boxes is the responsibility of Orbital Sciences Corporation, the spacecraft developer. The TIRS thermal subsystem design was successfully verified during months of testing campaign, from component & subsystem level to two instrument-level thermal vacuum tests. The Instrument, despite an aggressive schedule, was delivered to the spacecraft vendor in February of 2012 and is currently undergoing the final stages of spacecraft environmental testing in preparation for launch.

Otero, Veronica↗