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NASA NTRS2017

A Library of ATMO Forward Model Transmission Spectra for Hot Jupiter Exoplanets

We present a grid of forward model transmission spectra, adopting an isothermal temperature-pressure profile, alongside corresponding equilibrium chemical abundances for 117 observationally significant hot exoplanets (equilibrium temperatures of 547-2710 K). This model grid has been developed using a 1D radiative-convective-chemical equilibrium model termed ATMO, with up-to-date high-temperature opacities. We present an interpretation of observations of 10 exoplanets, including best-fitting parameters and X(exp 2) maps. In agreement with previous works, we find a continuum from clear to hazy/cloudy atmospheres for this sample of hot Jupiters. The data for all the 10 planets are consistent with subsolar to solar C/O ratio, 0.005 to 10 times solar metallicity and water rather than methane-dominated infrared spectra. We then explore the range of simulated atmospheric spectra for different exoplanets, based on characteristics such as temperature, metallicity, C/O ratio, haziness and cloudiness. We find a transition value for the metallicity between 10 and 50 times solar, which leads to substantial changes in the transmission spectra. We also find a transition value of C/O ratio, from water to carbon species dominated infrared spectra, as found by previous works, revealing a temperature dependence of this transition point ranging from approximately 0.56 to approximately 1-1.3 for equilibrium temperatures from approximately 900 to approximately 2600 K. We highlight the potential of the spectral features of HCN and C2H2 to constrain the metallicities and C/O ratios of planets, using James Webb Space Telescope (JWST) observations. Finally, our entire grid (approximately 460 000 simulations) is publicly available and can be used directly with the JWST simulator PandExo for planning observations.

techniques: spectroscopic – planets and satellit↗
NASA NTRS2012

The Formation Heritage of Jupiter Family Comet 10P/Tempel 2 as Revealed by Infrared Spectroscopy

We present spectral and spatial information for major volatile species in Comet 10P/Tempel 2, based on high-dispersion infrared spectra acquired on UT 2010 July 26 (heliocentric distance R h = 1.44 AU) and September 18 (R h = 1.62 AU), following the comet’s perihelion passage on UT 2010 July 04. The total production rate for water on July 26 was (1.90 ± 0.12) × 10 28 molecules s −1 , and abundances of six trace gases (relative to water) were: CH 3 OH (1.58% ± 0.23%), C 2 H 6 (0.39% ± 0.04%), NH 3 (0.83% ± 0.20%), and HCN (0.13% ± 0.02%). A detailed analysis of intensities for water emission lines provided a rotational temperature of 35 ± 3 K. The mean OPR is consistent with nuclear spin populations in statistical equilibrium (OPR = 3.01 ± 0.18), and the (1σ) lower bound corresponds to a spin temperature >38 K. Our measurements were contemporaneous with a jet-like feature observed at optical wavelengths. The spatial profiles of four primary volatiles display strong enhancements in the jet direction, which favors release from a localized vent on the nucleus. The measured IR continuum is much more sharply peaked and is consistent with a dominant contribution from the nucleus itself. The peak intensities for H 2 O, CH 3 OH, and C 2 H 6 are offset by ∼200 km in the jet direction, suggesting the possible existence of a distributed source, such as the release of icy grains that subsequently sublimed in the coma. On UT September 18, no obvious emission lines were present in our spectra, nevertheless we obtained a 3σ upper limit Q(H 2 O) < 2.86 × 10 27 molecules s −1 .

Organic Chemistry↗
NASA NTRS2017

Revised Models of Interstellar Nitrogen Isotopic Fractionation

Nitrogen-bearing molecules in cold molecular clouds exhibit a range of isotopic fractionation ratios and these molecules may be the precursors of 15N enrichments found in comets and meteorites. Chemical model calculations indicate that atom-molecular ion and ion-molecule reactions could account for most of the fractionation patterns observed. However, recent quantum-chemical computations demonstrate that several of the key processes are unlikely to occur in dense clouds. Related model calculations of dense cloud chemistry show that the revised 15N enrichments fail to match observed values. We have investigated the effects of these reaction rate modifications on the chemical model of Wirstrom et al. (2012) for which there are significant physical and chemical differences with respect to other models. We have included 15N fractionation of CN in neutral-neutral reactions and also updated rate coefficients for key reactions in the nitrogen chemistry. We find that the revised fractionation rates have the effect of suppressing 15N enrichment in ammonia at all times, while the depletion is even more pronounced, reaching 14N/15N ratios of >2000. Taking the updated nitrogen chemistry into account, no significant enrichment occurs in HCN or HNC, contrary to observational evidence in dark clouds and comets, although the 14N/15N ratio can still be below 100 in CN itself. However, such low CN abundances are predicted that the updated model falls short of explaining the bulk 15N enhancements observed in primitive materials. It is clear that alternative fractionating reactions are necessary to reproduce observations, so further laboratory and theoretical studies are urgently needed.

Wirstrom, E. S.↗
NASA NTRS2018

The Volatile Composition of Comet C/2017 E4 (Lovejoy) before its Disruption, as Revealed by High-Resolution Infrared Spectroscopy with iSHELL at the NASA/IRTF

In 2017 April, we acquired comprehensive high-resolution spectra of newly discovered comet C/2017 E4 (Lovejoy) as it approached perihelion, and before its disintegration. We detected many cometary emission lines in the range (2.8-5.3) μm, in four customized instrument settings (L1-c, L3, Lp1-c, and M1) of iSHELL-the new near-IR high-resolution immersion echelle spectrograph at NASA/IRTF (Maunakea, Hawaii). We identified 12 molecular species: nine primary volatiles (H2O, HCN, NH3, CO, C2H2, C2H6, CH4, CH3OH, H2CO) and three product species (CN, NH2, OH). We detected 85 H2O emission lines from 12 water vibrational bands across L1-c and M1 settings. The many detected water emission lines enabled retrieval of accurate measures for ortho- and para-H2O independently, thereby reducing systematic uncertainty in the derived ortho-para ratio and nuclear spin temperature. Excitation analyses and emission profile analyses were performed for all species, and molecular abundance ratios relative to water are compared with values found for other Oort Cloud comets in our infrared database. Abundance ratios are consistent for most species, with the exception of underabundant methanol and overabundant ammonia in E4.

Faggi, S.↗
NASA NTRS2018

Compound-Specific Carbon Isotope Compositions of Aldehydes and Ketones in the Murchison Meteorite

Compound-specific carbon isotope analysis (delta(exp 13)C) of meteoritic organic compounds can be used to elucidate the abiotic chemical reactions involved in their synthesis. The soluble organic content of the Murchison carbonaceous chondrite has been extensively investigated over the years, with a focus on the origins of amino acids and the potential role of Strecker-cyanohydrin synthesis in the early solar system. Previous delta(exp 13)C investigations have targeted alpha-amino acid and alpha-hydroxy acid Strecker products and reactant HCN; however, delta(exp 13)C values for meteoritic aldehydes and ketones (Strecker precursors) have not yet been reported. As such, the distribution of aldehydes and ketones in the cosmos and their role in prebiotic reactions have not been fully investigated. Here, we have applied an optimized O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) derivatization procedure to the extraction, identification, and delta(exp 13)C analysis of carbonyl compounds in the Murchison meteorite. A suite of aldehydes and ketones, dominated by acetaldehyde, propionaldehyde, and acetone, were detected in the sample. delta(exp 13)C values, ranging from -10.0(0/00) to +66.4(0/00), were more (exp 13)C-depleted than would be expected for aldehydes and ketones derived from the interstellar medium, based on interstellar (exp 12)C/(exp 13)C ratios. These relatively (exp 13)C-depleted values suggest that chemical processes taking place in asteroid parent bodies (e.g., oxidation of the IOM) may provide a secondary source of aldehydes and ketones in the solar system. Comparisons between delta(exp 13)C compositions of meteoritic aldehydes and ketones and other organic compound classes were used to evaluate potential structural relationships and associated reactions, including Strecker synthesis and alteration-driven chemical pathways.

meteoritic organic compounds↗
NASA NTRS2018

Impact of August 2017 British Columbia Pyrocumulonimbus Injection Events on Lower Stratospheric Composition

On August 12-13, 2017 large wildfires in the Cariboo region of British Columbia, Canada sparked a series of pyrocumulonimbus events lifting carbonaceous aerosol and other trace gases to the tropopause region (~10-11 km). Over the subsequent days, this plume of trace gas and aerosol species was observed from numerous NASA satellite instruments to rise to over 22 km due to the strong shortwave heating of the carbonaceous aerosol. We will show observations of CO and H2O from the Microwave Limb Sounder (MLS) instrument on Aura satellite demonstrating the clear rise and spread of the plume which can be coherently tracked for at least 2 months. Enhancements in HCN, CH3CN, and methanol (CH3OH) are also evident in MLS measurements with the former two having low vertical resolution. We have also detected a significantly lower concentration of O3 and HNO3 in the plume compared to the surrounding environment, which is consistent with a dynamical perturbation from the rapid diabatic rise of the heated plume from the tropopause through the lower stratosphere. In the weeks and months that followed this plume spread over much of the Northern Hemisphere and the aerosol was observed to be slowly removed by transport back into the troposphere. We will compare and contrast the Aug. 2017 event with the other large event in the MLS record, the Feb. 2009 Australian "Black Saturday" event, and use the Goddard Earth Observing System Chemistry-Climate Model (GEOSCCM) replayed to observed meteorology to understand the effect of the British Columbia event on trace gas species. GEOSCCM helps us to separate the relative roles of dynamics and chemistry on lower stratospheric trace gas composition changes, not only in the rising plume but also the impact of its eventual spread over the Northern Hemisphere during fall and winter of 2017-2018.

Oman, Luke D.↗
NASA NTRS2018

A Tale of "Two" Comets: The Primary Volatile Composition of Comet 2P/Encke Across Apparitions and Implications for Cometary Science

The highly favorable 2017 apparition of 2P/Encke allowed the first comprehensive comparison of primary volatile abundances in a given comet across multiple apparitions. This apparition offered opportunities to address pressing questions in cometary science, including investigating evolutionary and/or heliocentric distance (R(sub h)) effects on volatile production, sampling the hypervolatiles CO and CH4 in an ecliptic comet, and measuring volatile release at small R(sub h). The faintness and frequently low geocentric velocity of ecliptic comets during most apparitions make our near-infrared observations of these hypervolatiles rare and of high scientific impact. We characterized the volatile composition of 2P/Encke on three post-perihelion dates using the iSHELL spectrograph at the NASA Infrared Telescope Facility on Maunakea, HI. We detected fluorescent emission from nine primary volatiles (H2O, CO, C2H6, CH3OH, CH4, H2CO, NH3, OCS, and HCN) and three fragment species (OH*, NH2, and CN), and obtained a sensitive upper limit for C2H2. We report rotational temperatures, production rates, and mixing ratios (abundances relative to H2O). Compared to mean abundances in comets observed to date in the near-infrared, mixing ratios of trace gases in 2P/Encke were depleted for all species except H2CO and NH3, which were “normal.” The detection of the hypervolatiles CO and CH4 is particularly notable given the paucity of measurements in ecliptic comets. We observed significant differences in primary volatile composition compared to published pre-perihelion results from 2003 at larger R(sub h). We discuss possible mechanisms for these differences and discuss these results in the context of findings from the Rosetta mission and ground-based studies of comets.

Roth, Nathan X.↗
NASA NTRS2018

Comet C/2013 V5 (Oukaimeden): Evidence for Depleted Organic Volatiles and Compositional Heterogeneity as Revealed through Infrared Spectroscopy

We obtained high-resolution (lambda divided by delta times lambda equals approximately 25,000) pre-perihelion spectra of Comet C/2013 V5 (Oukaimeden) using NIRSPEC at Keck II on UT 2014 September 5-6, and CSHELL (Cryogenic Echelle Spectrograph) at the NASA-Infrared Telescope Facility on September 11-13, altogether spanning a range in heliocentric distance R (sub h) equals 0.789-0.698 astronomical units. We report water production rates, and production rates and abundance ratios relative to co-measured H2O for eight trace molecules: CO, H2CO, CH3OH, CH4, C2H2, C2H6, HCN, and NH3. Our measured water production rates from NIRSPEC ( Near Infra-Red Spectrograph) and CSHELL observations remained relatively constant and were close to those from SOHO (Solar and Heliospheric Observatory) / Solar Wind Anisotropies observations that encompassed our dates, suggesting H2O production dominated by release directly from or within approximately 2000 kilometers of the nucleus. All trace volatiles were depleted relative to their respective median abundances among comets, excepting NH3, which was consistent with its median abundance. Most surprising were pronounced increases in abundance ratios for CH3OH (by 51 percent relative to simultaneously measured H2O) and especially C2H6 (by 87 percent) between September 5 and 6. On September 5, C2H6 was severely depleted, consistent with its lowest abundance yet measured for any comet. It also tracked the spatial profile of H2O, suggesting C2H6 was associated with a polar ice phase dominating gas production. On September 6, C2H6 was only moderately depleted and was spatially distinct from H2O, suggesting both polar- and nonpolar-dominated ice phases contributed to the activity then. Our results are consistent with a nonhomogeneous volatile composition for C/2013V5, implying differential processing of its constituent ices.

DiSanti, Michael A.↗
NASA NTRS2016

Compact Multi-Channel Infrared Laser Absorption Spectrometer for Spacecraft Fire Safety Monitoring

We report on the design of a six-channel tunable laser absorption spectroscopy instrument for measuring ambient gas-phase concentrations of CO, HCl, HCN, HF, CO2, and O2 in spacecraft environments. Monitoring of these compounds can provide early warning detection of fire events while also indicating what materials have been exposed to heating. Continued post-fire monitoring of these hazardous gases can also facilitate safe and effective cleanup. The sensor is a miniaturized version of a five-channel prototype that was previously validated in ground-based oxidative pyrolysis tests. Here, we describe absorption line selection and theoretical detection limits for a sensor with reduced absorption pathlengths for each detection channel, which allows for a substantial reduction in overall instrument footprint. Ultimately, the new instrument is designed to be used in fire safety tests conducted by NASA, where various materials will undergo oxidative pyrolysis in an unmanned spacecraft returning from low Earth orbit.

Briggs, Ryan M.↗
NASA NTRS2019

Detailed Infrared Study of Amorphous to Crystalline Propionitrile Ices Relevant to Observed Spectra of Titan's Stratospheric Ice Clouds

We have conducted a comprehensive study of propionitrile (C2H5CN) ice from the amorphous to crystalline phase in order to provide detailed information on this specific cyanide, which may potentially contribute to the chemical composition of the Haystack ice cloud observed in Titan's stratosphere by the Cassini Composite InfraRed Spectrometer (CIRS). Infrared transmission spectra of thin films of pure propionitrile ices deposited at low temperature (30-160 K) were collected from 50 cm1 to 11,700 cm1 (200-0.85 m). The far-infrared spectral region was specifically targeted to compare with CIRS far-infrared limb spectra. The temperature and time evolution of C2H5CN ice was thoroughly investigated to better understand discrepancies reported in pre- viously published laboratory studies on the crystalline phase of C2H5CN. Specifically, we observe peculiar temperature and time-driven ice phase transitions, revealed by significant spectral variations in the ice, which stabilizes once a complete crystalline phase is achieved. From these results, the crystalline phase of propionitrile ice was identified at deposition temperatures greater than or equal to 135 K and < 140 K. Our findings corro- borate previous studies that ruled out pure propionitrile ice as the sole chemical identity of Titan's observed Haystack emission feature. In order to understand and identify the Haystack cloud, we have initiated co-de- position experiments that incorporate mixtures of Titan-relevant organics, many of which have corresponding vapors that are abundantly present in Titan's stratosphere. In this paper, we present the result of one example of a co-deposited ternary ice mixture containing 16% hydrogen cyanide (HCN), 23% C2H5CN, and 61% benzene (C6H6). Although this co-condensed ice mixture is the best fit thus far obtained to match the broad width of the Haystack, it is still not the appropriate chemical candidate. However, it reveals an intriguing result: the strong lattice mode of pure C2H5CN ice is drastically altered by the surrounding molecules as a result of mixing in a co- condensed phase. The laboratory results reported here on propionitrile ice may help to further constrain the chemical identification of Titan's stratospheric Haystack ice cloud, as well as improve on the current state of knowledge of Titan's stratospheric ice cloud chemistry.

Nna-Mvondo, Delphine↗
NASA NTRS2019

Hazardous Product Detection and Environmental Clean-up Removal in Spacecraft Vehicles from Fire Induced Li-Ion Fires

A fire on-board the International Space Station (ISS) resulting from a commercial Surface Pro tablet Lithium-Ion (Li-ion) battery can be detrimental to the spacercraft and the astronauts. The Spacecraft Fire Safety Demonstration (Saffire) program is focused on identifying and quantifying the risks that potentially arise inside a space vehicle by conducting large fire experiments inside the Cygnus cargo vehicle upon re-entry to Earth. The potential candidate that will be flown on the ISS is a 4- cell Li-ion battery pack Surface Pro tablet (42 Wh). The tablets were tested at the White Sands Test Facility (WSTF) using a localized heating method to emulate the failing mechanism that leads the unit into thermal runaway. Measurements inside the test chamber were performed on aerosol mass concentrations and for specific toxic products (i.e. from CO, HCN, HCl and CO2). These toxic products depend on the size of the fire and energy content of the tablet. Comparisons will be made with the Dell XPS (97 Wh). The concentrations are then used to extrapolate to laptop fires on a vehicle at the approximate volumetric size of the Orion spacecraft. The presentation provides an analysis on the detection capability and the response time to trigger fire alarms aboard a vehicle by using the mass concentration levels. These results will consider the rate at which the life support system is able to filter the atmosphere in order to provide a hazardous free environment.

Padilla, Rosa E.↗
NASA NTRS2019

Earth's Early Reduced Atmospheres

Earth’s early atmosphere evolved in response to cosmic impacts, photochemistry generated by the copious extreme ultraviolet radiation emitted by the young Sun, hydrogen escape, mineral redox buffering, the evolution of iron in the mantle, and the character of crustal weathering and subduction. No single chemical composition, surface pressure, or temperature was typical. After the biggest impacts the temperature likely rose above 3000 K and the atmosphere held rock vapor. As the atmosphere cooled its constituents rained out: first the silicates, then the geochemical volatiles (such as salt), and last the water. Depending on the size of the impact, cooling took thousands to millions of years. Between impacts the atmosphere was thick with gases like CO2, H2, and CH4 that do not condense at Earth but provide greenhouse warming that could easily have maintained surface temperatures in excess of 500 K. At some point the early atmosphere must have been conducive to the evolution of organic chemistry and the origin of life. It was therefore --- at times --- dominated by reduced gases like hydrogen and methane. Hydrogen-methane atmospheres are easily formed thermochemically after major impacts if H2O and CO2 were present on Earth in quantities consistent with their inventories on Earth today – the key is high pressure. Hydrogen-methane atmospheres slowly break down over millions of years by hydrogen escape and photochemistry. At first methane decomposes into tars and nitriles that precipitate, but later as the atmosphere grows more oxidized from hydrogen escape the methane oxidizes to CO and CO2, with a small fraction going to HCN. Impacts can also produce NH3 directly from N2 and H2O, which is expected to rain out with the H2O. As impacts grew infrequent the climate cooled in response to the fixing of CO2 as carbonate and carbonate subduction. Eventually the CO2 was mostly removed to the mantle and the surface mostly frozen.

Zahnle, Kevin↗
NASA NTRSDate not supplied

Integrated laboratory, modeling and observational investigations of the condensation of benzene on Titan's stratospheric aerosols

Aerosols in Titan’s atmosphere play an important role in determining its thermal structure and can act as condensation nuclei for the formation of clouds. The global circulation of Titan’s atmosphere reversed within the two years following the northern spring equinox in August 2009, increasing the mixing ratios of benzene (C6H6) and other species at the South pole. A simultaneous strong cooling above the south pole (dropping temperatures below 120 K) resulted in conditions where molecules could condense at unusually high altitudes (>250 km). C6H6 and HCN ices have been detected by the Composite Infrared Spectrometer (CIRS) and the Visible and Infrared Mapping Spectrometer (VIMS), respectively, in the South polar cloud system, but the existing laboratory data is insufficient to allow models to reproduce the formation of the observed cloud system. We will present the preliminary results and the overall scope of a newly funded NASA SMD Cassini Data Analysis Program (CDAP) project which proposes to combine laboratory, modeling and observational studies to investigate the condensation of benzene on Titan’s aerosol as an important component of the cloud system that appeared during the autumn at 300 km above Titan’s South pole.

E. Sciamma-O’Brien↗
NASA NTRS2019

Detailed Infrared Study of Amorphous to Crystalline Propionitrile Ices Relevant to Observed Spectra of Titan's Stratospheric Ice Clouds

We have conducted a comprehensive study of propionitrile (C2H5CN) ice from the amorphous to crystalline phase in order to provide detailed information on this specific cyanide, which may potentially contribute to the chemical composition of the Haystack ice cloud observed in Titan’s stratosphere by the Cassini Composite InfraRed Spectrometer (CIRS). Infrared transmission spectra of thin films of pure propionitrile ices deposited at low temperature (30 – 160 K) were collected from 50 cm(exp -1) to 11700 cm(exp -1) (200 – 0.85 μm). The far-infrared spectral region was specifically targeted to compare with CIRS far-infrared limb spectra. The temperature and time evolution of C2H5CN ice was thoroughly investigated to better understand discrepancies reported in previously published laboratory studies on the crystalline phase of C2H5CN. Specifically, we observe peculiar temperature and time-driven ice phase transitions, revealed by significant spectral variations in the ice, which stabilizes once a complete crystalline phase is achieved. From these results, the crystalline phase of propionitrile ice was identified at deposition temperatures greater than or equal to 135 K and less than 140 K. Our findings corroborate previous studies that ruled out pure propionitrile ice as the sole chemical identity of Titan’s observed Haystack emission feature. As a result, we have initiated co-deposition experiments that incorporate mixtures of Titan relevant organics, many of which have corresponding vapors that are abundantly present in Titan's stratosphere. In this paper, we present the result of one example of a co-deposited trinary ice mixture containing 16% hydrogen cyanide (HCN), 23% C2H5CN, and 61% benzene (C6H6). Although this co-condensed ice mixture is the best fit thus far obtained to match the broad width of the Haystack, it is still not the appropriate chemical candidate. However, it reveals an intriguing result: the strong lattice mode of pure C2H5CN ice is drastically altered by the surrounding molecules as a result of mixing in a co-condensed phase. The laboratory results reported here on propionitrile ice may help to further constrain the chemical identification of Titan’s stratospheric Haystack ice cloud, as well as improve on the current state of knowledge of Titan's stratospheric ice cloud chemistry.

Delphine Nna-Mvondo↗
NASA NTRS2019

Detailed Infrared Study of Amorphous to Crystalline Propionitrile Ices Relevant to Observed Spectra of Titan's Stratospheric Ice Clouds

We have conducted a comprehensive study of propionitrile (C2H5CN) ice from the amorphous to crystalline phase in order to provide detailed information on this specific cyanide, which may potentially contribute to the chemical composition of the Haystack ice cloud observed in Titan's stratosphere by the Cassini Composite InfraRed spectrometer (CIRS). Infrared transmission spectra of thin films of pure propionitrile ices deposited at low temperature (30–160 K) were collected from 50 cm(exp −1) to 11,700 cm(exp −1) (200–0.85 μm). The far-infrared spectral region was specifically targeted to compare with CIRS far-infrared limb spectra. The temperature and time evolution of C2H5CN ice was thoroughly investigated to better understand discrepancies reported in previously published laboratory studies on the crystalline phase of C2H5CN. Specifically, we observe peculiar temperature and time-driven ice phase transitions, revealed by significant spectral variations in the ice, which stabilizes once a complete crystalline phase is achieved. From these results, the crystalline phase of propionitrile ice was identified at deposition temperatures greater than or equal to 135 K and <140 K. Our findings corroborate previous studies that ruled out pure propionitrile ice as the sole chemical identity of Titan's observed Haystack emission feature. In order to understand and identify the Haystack cloud, we have initiated co-deposition experiments that incorporate mixtures of Titan-relevant organics, many of which have corresponding vapors that are abundantly present in Titan's stratosphere. In this paper, we present the result of one example of a co-deposited ternary ice mixture containing 16% hydrogen cyanide (HCN), 23% C2H5CN, and 61% benzene (C6H6). Although this co-condensed ice mixture is the best fit thus far obtained to match the broad width of the Haystack, it is still not the appropriate chemical candidate. However, it reveals an intriguing result: the strong lattice mode of pure C2H5CN ice is drastically altered by the surrounding molecules as a result of mixing in a co-condensed phase. The laboratory results reported here on propionitrile ice may help to further constrain the chemical identification of Titan's stratospheric Haystack ice cloud, as well as improve on the current state of knowledge of Titan's stratospheric ice cloud chemistry.

Delphine Nna-Mvondo↗
NASA NTRS2018

The Volatile Composition of Comet C/2017 E4 (Lovejoy) Before Its Disruption, as Revealed by High-Resolution Infrared Spectroscopy with iSHELL at the NASA-IRTF

In April 2017, we acquired comprehensive high-resolution spectra of newly-discovered comet C/2017 E4 (Lovejoy) as it approached perihelion, and before its disintegration. We detected many cometary emission lines in the (2.8–5.3)μm range, in four customized instrument settings (L1-c, L3, Lp1-cand M1) of iSHELL -the new near-IR high resolution immersion echelle spectrograph at NASA/IRTF (Maunakea, Hawaii). We identified twelve molecular species; nine primary volatiles (H2O, HCN, NH3, CO, C2H2, C2H6, CH4, CH3OH, H2CO) and three product species (CN, NH2,OH). We detected 85H2O emission lines from 12 water vibrational bands across L1-c and M1 settings. The many detected water emission lines enabled retrieval of accurate measures for ortho-and para-H2O independently, thereby reducing systematic uncertainty in the derived ortho-para ratio and nuclear spin temperature. Excitation analyses and emission profile analyses were performed for all species, and molecular abundance ratios relative to water are compared with values found for other Oort Cloud comets in our infrared database. Abundance ratios are consistent for most species, with the exception of under-abundant methanol and over-abundant ammonia in E4.

S. Faggi↗
NASA NTRS2017

Revised Models of Interstellar Nitrogen Isotopic Fractionation

Nitrogen-bearing molecules in cold molecular clouds exhibit a range of isotopic fractionation ratios and these molecules may be the precursors of 15N enrichments found in comets and meteorites. Chemical model calculations indicate that atom–molecular ion and ion–molecule reactions could account for most of the fractionation patterns observed. However, recent quantum-chemical computations demonstrate that several of the key processes are unlikely to occur in dense clouds. Related model calculations of dense cloud chemistry show that the revised 15N enrichments fail to match observed values. We have investigated the effects of these reaction rate modifications on the chemical model of Wirström et al. (2012) for which there are significant physical and chemical differences with respect to other models. We have included 15N fractionation of CN in neutral–neutral reactions and also updated rate coefficients for key reactions in the nitrogen chemistry. We find that the revised fractionation rates have the effect of suppressing 15N enrichment in ammonia at all times, while the depletion is even more pronounced, reaching 14N/15N ratios of >2000. Taking the updated nitrogen chemistry into account, no significant enrichment occurs in HCN or HNC, contrary to observational evidence in dark clouds and comets, although the 14N/15N ratio can still be below 100 in CN itself. However, such low CN abundances are predicted that the updated model falls short of explaining the bulk 15N enhancements observed in primitive materials. It is clear that alternative fractionating reactions are necessary to reproduce observations, so further laboratory and theoretical studies are urgently needed.

astrochemistry – molecular processes – comets: gen↗
NASA NTRS2017

Revised Models of Interstellar Nitrogen Isotopic Fractionation

Nitrogen-bearing molecules in cold molecular clouds exhibit a range of isotopic fractionation ratios and these molecules may be the precursors of 15N enrichments found in comets and meteorites. Chemical model calculations indicate that atom–molecular ion and ion–molecule reactions could account for most of the fractionation patterns observed. However, recent quantum-chemical computations demonstrate that several of the key processes are unlikely to occur in dense clouds. Related model calculations of dense cloud chemistry show that the revised 15N enrichments fail to match observed values. We have investigated the effects of these reaction rate modifications on the chemical model of Wirström et al. (2012) for which there are significant physical and chemical differences with respect to other models. We have included 15N fractionation of CN in neutral–neutral reactions and also updated rate coefficients for key reactions in the nitrogen chemistry. We find that the revised fractionation rates have the effect of suppressing 15N enrichment in ammonia at all times, while the depletion is even more pronounced, reaching 14N/15N ratios of >2000. Taking the updated nitrogen chemistry into account, no significant enrichment occurs in HCN or HNC, contrary to observational evidence in dark clouds and comets, although the 14N/15N ratio can still be below 100 in CN itself. However, such low CN abundances are predicted that the updated model falls short of explaining the bulk 15N enhancements observed in primitive materials. It is clear that alternative fractionating reactions are necessary to reproduce observations, so further laboratory and theoretical studies are urgently needed.

astrochemistry – molecular processes – comets: gen↗