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Evolution of the Earth and Origin of Life: The Role of Gas/Fluid Interactions with Rocks

The work under the Cooperative Agreement will be centered on questions of the evolution of Life on the early Earth and possibly on Mars. It is still hotly debated whether the essential organic molecules were delivered to the early Earth from space (by comets, meteorites or interplanetary dust particles) or were generated in situ on Earth. Prior work that has shown that the matrix of igneous minerals is a medium in which progenitors of organic molecules assemble from H2O, C02 and N2 incorporated as minority "impurities" in minerals of igneous rocks during crystallization from H2O/CO2/N2-laden magmas. The underlying processes involve a redox. conversion whereby C, H, and N become chemically reduced, while 0 becomes oxidized to the peroxy state. During Year 02 the work will be divided into three tasks. Task 1: After carboxylic (fatty) acids and N-bearing compounds have been identified, other extractable organic molecules including lipids, oily substances and amino acids will be studied. Dedicated lipid analysis will be combined with gas chromatographic-mass spectroscopic (GCMS) analysis of organic compounds extracted from minerals and rocks. Task 2: Using infrared (IR) spectroscopy, C-H entities that are indicators for the organic progenitors in mineral matrices will be studied. A preliminary heating experiment with MgO single crystals has shown that the C-H entities can be pyrolyzed, causing the IR bands to disappear, but at room temperature the IR bands reappear in a matter of days to weeks. This work will be expanded, both by studying synthetic MgO crystals and olivine crystals from the Earth's upper mantle. The C-H bands will be compared to the published "organic" IR feature of dust in the interstellar medium (ISM) and interplanetary dust particles (IDP). Task 3: A paradox marks the evolution of early Life: Oxygen is highly toxic to primitive life, yet early organisms "learned" to detoxify reactive oxygen species, to utilize oxygen, and even produce it. Why would organisms on the early anaerobic Earth be under evolutionary pressure to evolve defenses against reactive oxygen species? Minerals in igneous rocks are now known to contain peroxy. When such minerals weather, the peroxy hydrolyzes to H2O2. The hypothesis will be tested whether organisms living in intimate contact with rock surfaces are subjected to a constant trickle of H202 and thus under stress to develop strategies to either detoxify the reactive oxygen species or repair the molecular damage that they cause. Understanding these processes is central to the Astrobiology mission. It opens new avenues toward understanding the evolution of early life on Earth, and the potential for aerobic life elsewhere. This Cooperative Agreement also has a strong educational and public outreach component involving high school, undergraduate students, and high school teachers.

Freund, Friedemann↗

High Resolution UV Emission Spectroscopy of Molecules Excited by Electron Impact

Photodissociation via discrete line absorption into predissociating Rydberg and valence states is the dominant destruction mechanism of CO and other molecules in the interstellar medium and molecular clouds. Accurate values for the rovibronic oscillator strengths of these transitions and predissociation yields of the excited states are required for input into the photochemical models that attempt to reproduce observed abundances. We report here on our latest experimental results of the electron collisional properties of CO and N2 obtained using the 3-meter high resolution single-scattering spectroscopic facility at JPL.

James, G. K.↗

Sensor for Monitoring Nanodevice-Fabrication Plasmas

The term plasma process diagnostics (PPD) refers to a spectroscopic technique and sensing hardware that have been proposed for monitoring plasma processes used to fabricate electronic devices that feature sizes as small as several nanometers. Nanometer dimensions are characteristic of the quantum level of miniaturization, where single impurity atoms or molecules can drastically change the local properties of the nanostructures. Such changes may be purposely used in nanoscale design but may also be extremely damaging or cause improper operation of the fabricated devices. Determination of temperature and densities of reactants near the developing features is important, since the structural synthesis is affected by characteristics of the local microenvironment. Consequently, sensors capable of nonintrusive monitoring with high sensitivity and high resolution are essential for real-time atomistic control of reaction kinetics and minimizing trace contamination in plasma processes used to fabricate electronic nanodevices. Such process-monitoring sensors are required to be compact, multiparametric, and immune to the harsh environments of processing plasmas. PPD is intended to satisfy these requirements. The specific technique used to implement plasma diagnostics with a PPD sensor would be an advanced version of continuous-wave cavity-ringdown spectroscopy (CW-CRDS) capable of profiling spectral line broadenings in order to derive both Doppler and Stark components. CRDS is based on measurements of the rate of absorption of laser light in an optical resonator. The ultimate sensitivity results from a very long absorption path length within the cavity and immunity to variations in incident laser intensity. The proposed version of this technique would involve the use of multiplexing tunable laser diodes and an actively modulated high-reflectivity optical resonator, thus offering a synergistic combination of simplicity, compactness, high sensitivity, and high resolution. The multiplexing capabilities of diode lasers could be utilized to make the PPD sensor a single, simple, compact, and inexpensive tool for the acquisition of multiparametric data. A PPD sensor would be capable of continuous measurement of such physical parameters as gas temperature, gas velocity, electron number density, and absolute densities of reacting chemical species. A laser beam can be easily adjusted to analyze the immediate vicinity of the growing nanostructures (or features etched down) in real time. The absorption enhancement in an optical cavity would afford the sensitivity needed for measurement of the temperature and densities of species at concentrations significantly lower than measurable by other nonintrusive techniques. It is anticipated that fully developed PPD sensors would enable simultaneous measurement of local temperature and determination of plasma species responsible for the synthesis and functionalization of nanodevices. These sensors would also enable tracking the pathways and origins of damaging contaminants, thereby providing feedback for adjustment of processes to optimize them and reduce contamination. The PPD sensors should also be useful for optimization of conventional microelectronics manufacturing plasma processes. Going beyond plasma processes for fabrication of electronic devices, PPD sensors could be used for monitoring of atoms, molecules, ions, radicals, clusters, and particles in a variety of other settings, including outer space. Because of their high sensitivity, such sensors could also prove useful for detecting traces of illegal drugs and explosives.

Bolshakov, Alexander↗

Grism Performance for Mid-IR (5-40 microns) Spectroscopy

Grisms provide a straightforward method to transform an imager into a spectrometer with little change to the original imaging optics. This paper addresses the performance of a suite of grisms as part of an Astrobiology Science and Instrument Development (ASTID) Program to implement a moderate resolution spectroscopic capability to the mid/far-IR facility instrument FORCAST for the Stratospheric Observatory For Infrared Astronomy (SOFIA) [see accompanying abstract by Adams et al.]. A moderate resolution mid-IR spectrometer on SOFIA will offer advantages not available to either ground or space-based instruments after the Spitzer Space Telescope ceases operation in approx. 2007. SOFIA will begin operations in 2007 and will have an operational lifetime of approx. 20 years. From aircraft altitudes, it will be possible to cover a range of wavelengths, particularly in the critical 5-9 micron band, where detection of astrobiologically interesting molecules have key spectral signatures, that are not accessible from the ground. This grism suite consists of six grisms: four monolithic Si grisms [see accompanying abstract by Mar et al.] and two KRS-5 grisms. These devices will allow long slit low-resolution and short slit, cross-dispersed high-resolution spectroscopic modes selectable by simply moving the camera filter wheels. This configuration will enable observing programs to gather images and spectra in a single SOFIA flight. The four silicon grisms, whose performance is highlighted in this paper, will operate in the following wavelength ranges: 5-8, 17-28, and 28-37 microns. In the 5-8 micron range, R=1200 is achievable for a 2 arcsecond slit using the grism as a cross-disperser. For the 17-28 and 28-37 micron ranges, the resolving powers are R approx. 130, 250 when used in low orders with a slit of 3 arcseconds. The silicon grisms demonstrate a new family of dispersive elements with good optical performance for spectroscopy from 1.2-8 micron and beyond 18 microns. Furthermore, the FORCAST grism modes are close in wavelength coverage and resolving power to the Spitzer Infrared Spectrograph (IRS), so that among other possible observations, SOFIA can now enable follow-up studies of the brighter objects that Spitzer has observed and enable studies of sources that were too bright for observation with Spitzer.

Ennico, K. A.↗

Synthesis and Characterization of Chalcopyrite (CuInS2 and CuhInSe2) Colloidal Nanoparticles for Optoelectronic Applications via Low-Temperature Pyrolysis of Single-Source Precursors

Nanocrystalline (or quantum dot) materials hold potential as components of next-generation photovoltaic (PV) devices. The inclusion of quantum dots in PV devices has been proposed as a means to improve the efficiency of photon conversion (quantum dot solar cell), enable low-cost deposition of thin-films, provide sites for exciton dissociation, and pathways for electron transport. Quantum dots are also expected to be more resistant to degradation from electron, proton, and alpha particle radiation than the corresponding bulk material, a requirement for use in space solar ~sells. Chalcopyrite nanocrystals can be produced by low-temperature thermal decomposition of single-source precursors such as (PR3)2CuIn(ER')4 (R = Ph, R' = Et, E = S; R = R' = Ph, E = Se). Single-source precursors are molecules which contain all the necessary elements for synthesis of a desired material. Thermal decomposition of the precursor results in the formation of material with the correct stoichiometry as a nanocrystalline powder or a thin film, often at significantly lower temperatures than those typically employed for thin-film deposition by multi-source evaporation techniques, typically less than 500 C. We show that CuInSz and CuInSe2 nanocrystals can be synthesized from the precursors at temperatures as low as 250 C. The nanocrystals are characterized by optical spectroscopy, X-ray diffraction, and electron microscopy.

Castro, S. L.↗

Theoretical Study of the Electric Dipole Moment Function of the CIO Molecule

The potential energy function and electric dipole moment function (EDMF) are computed for CIO Chi(sup 2)Pi using several different techniques to include electron correlation. The EDMF is used to compute Einstein coefficients, vibrational lifetimes, and dipole moments in higher vibrational levels. Remaining questions concerning the position of the maximum of the EDMF may be resolved through experimental measurement of dipole moments of higher vibrational levels. The band strength of the 1-0 fundamental transition is computed to be 12 +/- 2 /sq cm atm in good agreement with three experimental values, but larger than a recent value of 5 /sq cm atm determined from infrared heterodyne spectroscopy. The theoretical methods used include SCF, CASSCF, multireference singles plus doubles configuration interaction (MRCI) and contracted CI, coupled pair functional (CPF), and a modified version of the CPF method. The results obtained using the different methods are critically compared.

Pettersson, Lars G. M.↗

The Structure of Young Stellar Systems: Establishing the Initial Conditions for Planet Formation

FYO1-FY03 Origins support to the PI had been as part of an effort involving Profs. Blake, van Dishoeck and L.G. Mundy of the University of Maryland. As outlined below, the merging of BIMA+OVRO into the Combined Array for Research in Millimeter Astronomy (CARMA) and our mutual involvement in the Spitzer Legacy Science program now provides a more natural means of continuing the Caltech/Maryland collaboration. In addition, the spectroscopy/radiative transfer programs led by Profs. Blake, Hogerheijde, and van Dishoeck form a more cohesive basis for a single proposal. Students supported by our previous Origins grant have been involved in making some of the first sub-arcsecond resolution images of the morphology and chemistry of individual YSOs at OVRO and BIMA, in the analysis of IR spectra taken by ISO, and in continuing exploratory IR diffraction-limited imaging and spectroscopy at the Keck and VLT observatories. Notable scientific accomplishments in the past grant period include: 1) detecting high density and temperature hot cores in the dynamically accreting envelopes of low mass protostars that contain significant quantities of complex, prebioitc molecules, 2) imaging chemical and isotopic zonation in the outer regions of T Tauri star accretion disks, particularly fractional ionization and D/H studies, 3) acquiring and modeling the first extensive CO v = 1 approaches 0 spectroscopy survey of the terrestrial planet-forming region of circumstellar accretion disks, and 4) optimizing detailed radiative transfer modeling of the molecular and dust emission from YSO envelopes and from comets, including a new parallelized implementation.

Blake, Geoffrey A.↗

Utilization of O4 Slant Column Density to Derive Aerosol Layer Height from a Space-Borne UV-Visible Hyperspectral Sensor: Sensitivity and Case Study

The sensitivities of oxygen-dimer (O4) slant column densities (SCDs) to changes in aerosol layer height are investigated using the simulated radiances by a radiative transfer model, the linearized pseudo-spherical vector discrete ordinate radiative transfer (VLIDORT), and the differential optical absorption spectroscopy (DOAS) technique. The sensitivities of the O4 index (O4I), which is defined as dividing O4 SCD by 10(sup 40) molecules (sup 2) per centimeters(sup -5), to aerosol types and optical properties are also evaluated and compared. Among the O4 absorption bands at 340, 360, 380, and 477 nanometers, the O4 absorption band at 477 nanometers is found to be the most suitable to retrieve the aerosol effective height. However, the O4I at 477 nanometers is significantly influenced not only by the aerosol layer effective height but also by aerosol vertical profiles, optical properties including single scattering albedo (SSA), aerosol optical depth (AOD), particle size, and surface albedo. Overall, the error of the retrieved aerosol effective height is estimated to be 1276, 846, and 739 meters for dust, non-absorbing, and absorbing aerosol, respectively, assuming knowledge on the aerosol vertical distribution shape. Using radiance data from the Ozone Monitoring Instrument (OMI), a new algorithm is developed to derive the aerosol effective height over East Asia after the determination of the aerosol type and AOD from the MODerate resolution Imaging Spectroradiometer (MODIS). About 80 percent of retrieved aerosol effective heights are within the error range of 1 kilometer compared to those obtained from the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) measurements on thick aerosol layer cases.

Air Pollution↗

NASA Tech Briefs, July 2009

Topics covered include: Dual Cryogenic Capacitive Density Sensor; Hail Monitor Sensor; Miniature Six-Axis Load Sensor for Robotic Fingertip; Improved Blackbody Temperature Sensors for a Vacuum Furnace; Wrap-Around Out-the-Window Sensor Fusion System; Wide-Range Temperature Sensors with High-Level Pulse Train Output; Terminal Descent Sensor Simulation; A Robust Mechanical Sensing System for Unmanned Sea Surface Vehicles; Additive for Low-Temperature Operation of Li-(CF)n Cells; Li/CFx Cells Optimized for Low-Temperature Operation; Number Codes Readable by Magnetic-Field-Response Recorders; Determining Locations by Use of Networks of Passive Beacons; Superconducting Hot-Electron Submillimeter-Wave Detector; Large-Aperture Membrane Active Phased-Array Antennas; Optical Injection Locking of a VCSEL in an OEO; Measuring Multiple Resistances Using Single-Point Excitation; Improved-Bandwidth Transimpedance Amplifier; Inter-Symbol Guard Time for Synchronizing Optical PPM; Novel Materials Containing Single-Wall Carbon Nanotubes Wrapped in Polymer Molecules; Light-Curing Adhesive Repair Tapes; Thin-Film Solid Oxide Fuel Cells; Zinc Alloys for the Fabrication of Semiconductor Devices; Small, Lightweight, Collapsible Glove Box; Radial Halbach Magnetic Bearings; Aerial Deployment and Inflation System for Mars Helium Balloons; Steel Primer Chamber Assemblies for Dual Initiated Pyrovalves; Voice Coil Percussive Mechanism Concept for Hammer Drill; Inherently Ducted Propfans and Bi-Props; Silicon Nanowire Growth at Chosen Positions and Orientations; Detecting Airborne Mercury by Use of Gold Nanowires; Detecting Airborne Mercury by Use of Palladium Chloride; Micro Electron MicroProbe and Sample Analyzer; Nanowire Electron Scattering Spectroscopy; Electron-Spin Filters Would Offer Spin Polarization Greater than 1; Subcritical-Water Extraction of Organics from Solid Matrices; A Model for Predicting Thermoelectric Properties of Bi2Te3; Integrated Miniature Arrays of Optical Biomolecule Detectors; A Software Rejuvenation Framework for Distributed Computing; Kurtosis Approach to Solution of a Nonlinear ICA Problem; Robust Software Architecture for Robots; R4SA for Controlling Robots; Bio-Inspired Neural Model for Learning Dynamic Models; Evolutionary Computing Methods for Spectral Retrieval; Monitoring Disasters by Use of Instrumented Robotic Aircraft; Complexity for Survival of Living Systems; Using Drained Spacecraft Propellant Tanks for Habitation; Connecting Node; and Electrolytes for Low-Temperature Operation of Li-CFx Cells.

Source record↗

X-ray photoelectron spectroscopy study of the stability of Fomblin Z25 on the native oxide of aluminum

Thin films of Fomblin Z25, a perfluoropolyalkylether lubricant, were vapor deposited onto clean, oxidized aluminum, and onto sapphire surfaces, and their behavior at different temperatures was studied using X-ray photoelectron spectroscopy and temperature desorption spectroscopy (TDS). The interfacial fluid molecules decompose on the native oxide at room temperature, and continue to decompose at elevated temperatures, as previous studies had shown to occur on the clean metal. TDS indicated that different degradation mechanisms were operative for clean and oxidized aluminum. On sapphire substrates, no reaction was observed at room temperature. The native oxide of aluminum is neither passive nor protective towards Fomblin Z25. At higher temperatures (150 C), degradation of the polymer on sapphire produced a debris layer at the interface with a chemical composition similar to the one formed on aluminum oxide. Rubbing a Fomblin film on a single crystal sapphire also induced the decomposition of the lubricant in contact with the interface and the formation of a debris layer.

Herrera-Fierro, Pilar↗

Infrared Band Strengths for Amorphous and Crystalline Methyl Propionate, a Candidate Interstellar Molecule

Mid-infrared spectra of amorphous and crystalline methyl propionate, CH3CH2COOCH3, are presented for the first time from a single laboratory, along with measurements of the refractive index of each solid form. Density estimates are made and IR band strengths and absorption coefficients are calculated. Vapor pressures of crystalline methyl propionate at 140-150 K are reported along with an enthalpy of sublimation. Spectroscopic results are compared to a recent study of this compound, and the phase of methyl propionate in that work is identified. Several applications are described.

Astrochemistry↗

An XPS study of the stability of Fomblin Z25 on the native oxide of aluminum

Thin films of Fomblin Z25, a perfluoropolyalkylether lubricant, were vapor deposited onto clean, oxidized aluminum and sapphire surfaces, and their behavior at different temperatures was studied using x ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS). It was found that the interfacial fluid molecules decompose on the native oxide at room temperature, and continue to decompose at elevated temperatures, as previous studies had shown to occur on clean metal. TDS indicated that different degradation mechanisms were operative for clean and oxidized aluminum. On sapphire substrates, no reaction was observed at room temperature. Our conclusion is that the native oxide of aluminum is neither passive nor protective towards Fomblin Z25. At high temperatures (150 C) degradation of the polymer on sapphire produced a debris layer at the interface with a chemical composition similar to the one formed on aluminum oxide. Rubbing a Fomblin film on a single crystal sapphire also induced the decomposition of the lubricant in contact with the interface and the formulation of a debris layer.

Herrera-Fierro, Pilar↗

The AstroBiology Explorer (ABE) MIDEX Mission Concept: Using Infrared Spectroscopy to Identify Organic Molecules in Space

One of the principal means by which organic compounds are detected and identified in space is by infrared spectroscopy. Past IR telescopic and laboratory studies have shown that much of the carbon in the interstellar medium (ISM) is in complex organic species but the distribution, abundance and evolutionary relationships of these materials are not well understood. The Astrobiology Explorer (ABE) is a MIDEX mission concept designed to conduct IR spectroscopic observations to detect and identify these materials and address outstanding problems in astrobiology, astrochemistry, and astrophysics. ABE's core science program includes observations of planetary nebulae and stellar outflows, protostellar objects, Solar System objects, and galaxies, and lines of sight through dense molecular clouds and the diffuse ISM. ABE is a cryogenically-cooled 60 cm diameter space telescope equipped with 3 cross-dispersed R-2000 spectrometers that share a single common slit. Each spectrometer measures one spectral octave and together cover the entire 2.5-20 micron region simultaneously. The spectrometers use state-of-the-art InSb and Si:As 1024x1024 pixel detectors. ABE would operate in a heliocentric, Earth drift-away orbit and have a core science mission lasting approximately 1.5 years. ABE is currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corp.

Sandford, Scott A.↗

Does UV instrumentation effectively measure ozone abundance?

Measurements of O3 on Mars provide significant information about the chemistry and composition of the atmosphere, including long-term changes. The most extensive and accurate data were inferred from the Mariner 9 UV spectrometer experiment. Mars O3 shows strong seasonal and latitudinal variation, with column abundances ranging from 0.2 microns at equatorial latitudes to 60 microns over the northern winter polar latitudes (1 micron-atm is a column abundance of 2.689 x 10(exp 15) molecules cm(exp-2)). The Mariner 9 UV spectrometer scanned from 2100 to 3500 Angstroms in one of its two spectral channels every 3 seconds with a spectral resolution of 15 Angstroms and an effective field-of-view of approximately 300 km(exp 2). Measurements were made for almost half a Martian year, with winter and spring in the Northern Hemisphere and summer and fall in the Southern Hemisphere. The detectability limit of the spectrometer was approximately 3 microns of ozone. The UV spectrometer on Mariner 9 was incapable of penetrating the dust during dust storms; the single-scattering albedo and phase function of airborne dust and cloud ice are not known to the degree required to extract the small UV signal reflected up from near the surface. The reflectance spectroscopy technique would also have difficulty detecting the total column abundance of O3 in cases where large dust abundances exist together with the polar hood, especially at high latitudes where large solar zenith angles magnify those optical depths; yet these cases would contain the maximum O3, based on theoretical results. It is quite possible that the maximum O3 column abundance observed by Mariner 9 of 60 microns is common. In fact, larger quantities may exist in some of the colder areas with optically thick clouds and dust. As the Viking period often had more atmospheric dust loading than did that of Mariner 9, the reflectance spectroscopy technique may even have been incapable of detecting the entire O3 column abundance during much of the Mars year that Viking observed, particularly at high latitudes.

Lindner, Bernhard Lee↗

Near-infrared observations of the proto-planetary nebula AFGL 618

Near-IR images and spectroscopy of the bipolar protoplanetary nebula AFGL 618 are presented. Emission from molecular hydrogen is detected in the 0.90-1.34-micron spectrum. A visual extinction of 3.4 +4.0/-2.0 mag to the H2-emitting region is derived from molecular hydrogen line ratios. Models of collisionally excited and fluorescent H2 emission are compared with the data: the near-IR H2 spectrum is found to be dominated by emission from collisionally excited molecules at Tex of about 2000 K, but a component of fluorescent emission is also present. It is shown that this type of near-IR spectrum is an excellent tool for discriminating relatively low levels of fluorescent H2 emission from a strong collisionally excited component. Images in the H- and K-bandpasses are analyzed using models which assume single scattering of photons from the central objects. The models indicate that the bipolar axis is inclined to the plane of the sky by about 45 deg. The emission in the H- and K-bands is found to be consistent with single scattering of photons by dust with a distribution such that the dust density increases with increasing stellar latitude and is nearly zero at the poles.

Latter, William B.↗

The Star-Grazing Bodies in the HD 172555 System

Kiefer et al. reported the detection of infalling Ca II absorption in HD 172555, a member of the β Pictoris Moving Group (βPMG). We obtained HST Space Telescope Imaging Spectrograph and Cosmic Origins Spectrograph spectroscopy of this star at 2 epochs separated by a week, and we report the discovery of infalling gas in resonant transitions of Si III and IV, C II and IV, and neutral atomic oxygen. Variable absorption is seen in the C II transitions and is optically thick, with covering factors which range between 58% and 68%, similar to features seen in β Pictoris. The O I spectral profile resembles that of C II, showing a strong low-velocity absorption to +50 km/s in the single spectral segment obtained during orbital night, as well as what may be higher-velocity absorption. Studies of the mid-IR spectrum of this system have suggested the presence of silica. The O I absorption differs from that seen in Si III, suggesting that the neutral atomic oxygen does not originate in SiO dissociation products but in a more volatile parent molecule such as CO.

C. A. Grady↗

En Route to Destruction: the Evolution in Composition of Ices in Comet D 2012 S1 (ISON) Between 1.2 and 0.34 Au from the Sun as Revealed at Infrared Wavelengths

We report production rates for H2O and eight trace molecules (CO, C2H6, CH4, CH3OH, NH3, H2CO, HCN, C2H2) in the dynamically new, Sun-grazing Comet C2012 S1 (ISON), using high-resolution spectroscopy at Keck II and the NASA IRTF on 10pre-perihelion dates encompassing heliocentric distances Rh1.210.34 AU. Measured water production rates spanned two orders of magnitude, consistent with a long-term heliocentric power law Q(H2O) Rh-3.10.1). Abundance ratios for CO, C2H6, and CH4 with respect to H2O remained constant with Rh and below their corresponding mean values measured among a dominant sample of Oort Cloud comets. CH3OH was also depleted for Rh 0.5 AU, but was closer to its mean value for Rh0.5 AU. The remaining four molecules exhibited higher abundance ratios within 0.5 AU: for Rh 0.8 AU, NH3 and C2H2 were consistent with their mean values while H2CO and HCN were depleted. For Rh 0.5 AU, all four were enriched, with NH3, H2CO, and HCN increasing most. Spatial profiles of gas emission in ISON consistently peaked sunward of the dust continuum, which was asymmetric antisunward and remained singly peaked for all observations. NH3 within 0.5 AU showed a broad spatial distribution, possibly indicating its release in the coma provided that optical depth effects were unimportant. The column abundance ratio NH2H2O at 0.83 AU was close to the typical NHOH from optical wavelengths, but was higher within 0.5 AU. Establishing its production rate and testing its parentage (e.g., NH3) require modeling of coma outflow.

Disanti, M. A.↗

In-situ Measurements of the Radiolytic Destruction of Glycine in Ices: Applications to the Martian Subsurface

Amino acids and other organic molecules are thought to be easily destroyed on the surface of Mars by the high flux of incident ultraviolet rays or by chemical interactions with oxidizing substances in the soil. However, organic molecules may survive in the subsurface, where chemical processes are driven by penetrating galactic cosmic rays such as MeV protons. Models of the radiation dose as a function of depth on Mars have shown that the contribution of galactic cosmic rays dominates from about one centimeter to a few meters [1 J. Theoretical models have also been published to aid in understanding molecular destruction at these depths, but these usually are based on room-temperature laboratory data, studies of single-component samples, and ex-situ methods of chemical analysis. Recent studies of amino-acid survivability include those involving UV photolysis [2, 3J and gamma radiolysis [4], but nearly all chemical and kinetic analyses from such experiments involved room-temperature measurements on samples irradiated and then removed from sealed containers. We report new laboratory studies of the radiation-induced destruction of glycine-containing ices. In-situ infrared spectroscopy was used to study decay rates as a function of temperature and initial glycine concentrations. Our results indicate that glycine's destruction rate depends on temperature, the presence of H20-ice, and the initial relative abundance of glycine. These trends are not obvious in previous work, suggesting that room-temperature measurements on pure glycine's radiation stability are not directly applicable to Mars and other environments.

Gerakines, Perry A.↗