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NASA NTRS2017

Multi-Wavelength Laser Transmitter for the Two-Step Laser Time-of-Flight Mass Spectrometer

Missions to diverse Outer Solar System bodies will require investigations that can detect a wide range of organics in complex mixtures, determine the structure of selected molecules, and provide powerful insights into their origin and evolution. Previous studies from remote spectroscopy of the Outer Solar System showed a diverse population of macromolecular species that are likely to include aromatic and conjugated hydrocarbons with varying degrees of methylation and nitrile incorporation. In situ exploration of Titan's upper atmosphere via mass and plasma spectrometry has revealed a complex mixture of organics. Similar material is expected on the Ice Giants, their moons, and other Outer Solar System bodies, where it may subsequently be deposited onto surface ices. It is evident that the detection of organics on other planetary surfaces provides insight into the chemical and geological evolution of a Solar System body of interest and can inform our understanding of its potential habitability. We have developed a prototype two-step laser desorption/ionization time-of-flight mass spectrometer (L2MS) instrument by exploiting the resonance-enhanced desorption of analyte. We have successfully demonstrated the ability of the L2MS to detect hydrocarbons in organically-doped analog minerals, including cryogenic Ocean World-relevant ices and mixtures. The L2MS instrument operates by generating a neutral plume of desorbed analyte with an IR desorption laser pulse, followed at a delay by a ultraviolet (UV) laser pulse, ionizing the plume. Desorption of the analyte, including trace organic species, may be enhanced by selecting the wavelength of the IR desorption laser to coincide with IR absorption features associated with vibration transitions of minerals or organic functional groups. In this effort, a preliminary laser developed for the instrument uses a breadboard mid-infrared (MIR) desorption laser operating at a discrete 3.475 μm wavelength, and a breadboard UV ionization laser operating at a wavelength of 266 nm. The MIR wavelength was selected to overlap the C-H stretch vibrational transition of certain aromatic hydrocarbons, and the UV wavelength provides additional selectivity to aromatic species via UV resonance-enhanced multiphoton ionization effects. The use of distinct laser wavelengths allows efficient coupling to the vibrational and electronic spectra of the analyte in independent desorption and ionization steps, mitigating excess energy that can lead to fragmentation during the ionization process and leading to selectivity that can aid in data interpretation.

Yu, Anthony W.↗
NASA NTRS2017

The Chemistry of Pluto and its Satellites

Pluto's bulk composition and the composition of the surface layers hold clues to the origin and evolution of a number of other Solar System bodies of comparable size in the region beyond Neptune. The July 14, 2015 flyby of the Pluto system with the New Horizons spacecraft afforded the opportunity to corroborate and greatly improve discoveries about the planet and its satellites derived Earth-based studies. It also revealed extraordinary details of the surface and atmosphere of Pluto, as well as the geology and composition of Charon and two smaller satellites. With a mean density of 1.86 g/sq cm, the bulk composition of Pluto is about two-thirds anhydrous solar composition rocky material and one-third volatiles (primarily H2O in liquid and solid states) by mass, the surface is a veneer of ices dominated by N2, with smaller amounts of CH4 and CO, as well as limited exposures of H2O ice (considered to be "bedrock"). N2, CH4, and CO occur as solid solutions at temperature-dependent mutual concentrations, each component being soluble in the others. Frozen C2H6 as a minor component has also been identified. Sublimation and recondensation of N2, CH4, and CO over seasonal (248 y) and Milankovich-type megaseasons (approx. 3 My) result in the redistribution of these ices over time and with latitude control. Solid N2 is found in glaciers originating in higher elevations and flowing at the present time into a basin structure larger than the State of Texas, forming a convecting lens of N2 that overturns on a timescale of order 10 My. The varied colors of Pluto's landscape arise from the energetic processing of the surface ices in processes that break the simple molecules and reassemble complex organic structures consisting of groups of aromatic rings connected by aliphatic chains. When synthesized in the laboratory by UV or electron irradiation of a Pluto mix of ice, this material, called tholin, has colors closely similar to Pluto. The Pluto ice tholin analog contains carboxylic acids, urea, ketones, aldehydes, amines, and some nitriles. The largest satellite, Charon has density 1.70 g/sq cm and it is about 3/5 anhydrous solar composition rock, with the remainder in H2O ice. The surface H2O ice is infused in some way with NH3, probably as a hydrate, distributed nonuniformly, but to some degree related to geological structures. Pluto's atmosphere is N2, CH4, with CO, C2-hydrocarbons, HCN, and other molecules in trace but detectable amounts. The atmosphere supports a complex haze structure with about 20 discrete layers, and suspected clouds. The haze is presumed to be made of aggregates of complex hydrocarbons (tholins) produced by photolysis of the atmospheric gases, and with similar composition to the ice tholins made on the planet's surface. Urea and a suite of carboxylic acids are of interest for prebiotic and biological chemistries.

SOLAR SYSTEMS↗
NASA NTRS2018

Retrieval of H2O Abundance in Titan's Stratosphere: A (Re)Analysis of CIRS/Cassini and PACS/Herschel Observations

Since its first measurement 20 years ago by the Infrared Space Observatory (ISO), the water (H2O) mole fraction in Titan’s stratosphere remains uncertain due to large differences between the determinations from available measurements. More particularly, the recent measurements made from the Herschel observatory (PACS (Photodetector Array Camera and Spectrometer) and HIFI (Heterodyne Instrument for the Far Infrared)) estimated the H2O mole fraction to be 0.023 parts per billion at 12.1 millibars. A mixing ratio of 0.14 parts per billion at 10.7 millibars was, however, retrieved from nadir spatially-resolved observations of Cassini/CIRS (Composite Infrared Spectrometer). At the same pressure level (10.7 millibars), this makes a difference of a factor of 5.5 between PACS and CIRS measurements, and this has notably prevented current models from fully constraining the oxygen flux flowing into Titan’s atmosphere. In this work, we try to understand the differences between the H2O mole fractions estimated from Herschel/PACS and Cassini/CIRS observations. The strategy for this is to 1) analyse recent disc-averaged observations of CIRS to investigate if the observation geometry could explain the previous observed differences, and 2) (re)analyse the three types of observation with the same retrieval scheme to assess if previous differences in retrieval codes/methodology could be responsible for the previous discrepancies. With this analysis, we show that using the same retrieval method better reconcile the previous measurements of these instruments. However, the addition of the disc-averaged CIRS observations, instead of confirming the consistency between the different datasets, reveals discrepancies between one of the CIRS disc-averaged set of observations and PACS measurements. This raises new questions regarding the possibility of latitudinal variations of H2O, which could be triggered by seasonal changes of the meridional circulation. As it has already been shown for nitriles and hydrocarbons, this circulation could potentially impact the latitudinal distribution of H2O through the subsidence or up- welling of air rich in H2O. The possible influence of spatial/time variations of the OH/H2O input flux in Titan’s atmosphere is also discussed. The analysis of more observations will be needed in future work to address the questions arising from this work and to improve the understanding of the sources of H2O in Titan’s atmosphere.

Bauduin, S.↗
NASA NTRS2019

Titan's Neutral Atmosphere Seasonal Variations up to the End of the Cassini Mission

In this paper we report new results concerning the seasonal atmospheric evolution near Titan's poles and equator using the Cassini Composite Infrared Spectrometer (CIRS). In previous papers (Coustenis et al. 2016 and 2018), after the 2010 equinox, we have monitored Titan's stratosphere since the beginning of the mission and reported recently on the observed strong temperature decrease and compositional enhancement above Titan's southern polar latitudes since 2012 of several trace species such as complex hydrocarbons and nitriles, which were previously observed only at high northern latitudes. This effect followed the transition of Titan's seasons from northern winter in 2002 to northern summer in 2017, while at that latter time, the southern hemisphere was entering winter. From 2013 until 2016, the northern polar region has shown a temperature increase of 10 K, while the south has shown a more significant decrease (up to 25 K) in a similar period of time. The stratosphere over the south pole of Titan shows a change in shape with a steeper positive slope and an increase in temperature in 2017 with respect to 2014, by 10-50 K in the 0.5 mbar-0.05 mbar pressure range, the larger 2017 temperatures observed in the higher atmospheric levels around 0.05 mbar, while in average the 70°S values return closer to the warmer ones found in 2012. While the south polar region is continuously enhanced since 2012, the chemical content in the north is showing a clear depletion for all molecules only since 2015 (Coustenis et al., 2018). We present here a complementary analysis of nadir spectra acquired by Cassini/CIRS at high resolution during the last year of the Cassini mission in 2017 and describe the temperature and composition variations near Titan's poles and at the equator over almost two Titan seasons. The 2017 data we have acquired and analyzed here are important because they are the only nadir ones afforded since 2014 close to the south pole at high resolution. They show no significant changes in the north with respect to 2016, but a large temperature increase in the southern polar stratosphere and a change in the temperature profiles shape while the South is also finally showing a related significant decrease in most of the abundances.

Coustenis, A.↗
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

Preliminary XANES Analysis of Laboratory Analogs of Titan Tholins

Titan, the largest moon of Saturn, is a fascinating object. It is the only other object in the Solar System, besides Earth, with a dense (1.5 bar at the surface) atmosphere whose composition is dominated by N2, with CH4 as the second most abundant gas. A complex organic chemistry between N2 and CH4, induced by solar UV photons and energetic particles, results in the formation of a large variety of organic compounds, including hydrocarbons (e.g., C2H2, C2H4, C2H6, C3H4, C6H6), nitriles (e.g., HCN, HNC, HC3N, CH3CN, C2N2), as well as larger molecules that include aromatic and heteroaromatic compounds [1]. This complex organic chemistry also leads to the formation of aerosols that play an important role in Titan’s atmospheric dynamics, climate, as well as surface composition and processes. Because of its N2-based dense atmosphere, and its CH4 cycle that resembles the hydrological cycle on Earth, Titan is often considered to be an analog of early Earth. In recent years, Titan’s atmosphere and surface were monitored in detail by the NASA Cassini mission, which orbited the Saturnian system from 2004 to 2017, as well as the ESA Huygens probe, which plunged into Titan’s atmosphere and landed on its surface in 2005.

Titan↗
NASA NTRS2019

Titan's Neutral Atmosphere Seasonal Variations up to the End of the Cassini Mission

In this paper we report new results concerning the seasonal atmospheric evolution near Titan's poles and equator in terms of temperature and composition using nadir spectra acquired by the Cassini Composite Infrared Spectrometer (CIRS) at high spectral resolution during the last year of the Cassini mission in 2017 complementing previous investigations covering almost two Titan seasons. In recent previous papers (Coustenis et al., 2016, 2018), we have reported on monitoring of Titan's stratosphere near the poles after the mid-2009 northern spring equinox. In particular we have reported on the observed strong temperature decrease and compositional enhancement above Titan's southern polar latitudes since 2012 and until 2014 of several trace species, such as complex hydrocarbons and nitriles, which were previously observed only at high northern latitudes. This effect accompanied the transition of Titan's seasons from northern winter in 2002 to northern summer in 2017, while at that latter time, the southern hemisphere was entering winter. Our new data, acquired in 2017 and analyzed here, are important because they are the only ones recorded since 2014 close to the south pole in the mid-infrared nadir mode at high resolution. A large temperature increase in the southern polar stratosphere (by 10–50 K in the 0.1 mbar–0.01 mbar pressure range) is found associated with a change in the temperature profile's shape. The 2017 observations also show a related significant decrease in most of the southern abundances which must have started sometime between 2014 and 2017. For the north, the spectra indicate a continuation of the decrease of the abundances which we first reported to have started in 2015 and small temperature variations. We discuss comparisons with other results and with current photochemical and dynamical models which could be updated and improved by the new constraints set by the findings presented here.

A Coustenis↗
NASA NTRSDate not supplied

The Search for New Molecular Species in the Atmosphere of Titan

The atmosphere of Saturn’s moon, Titan, contains a vast array of minor molecular constituents originating from the dissociation of its primary compounds, N2and CH4. The extent of Titan’s photochemical network was revealed by ionospheric measurements from the Cassini orbiter, leaving substantial gaps in the corresponding neutral inventory typically probed through infrared spectroscopy. Utilizing the unprecedented sensitivity and high spectral resolution of the Atacama Large Millimeter/submillimeter Array (ALMA) at longer wavelengths, we searched for additional trace gases in Titan’s atmosphere during 2016, 2017,and 2019to further characterize Titan’s atmospheric and surface composition. These observations have resulted in the spectroscopic detections of the small cyclic molecule, cyclopropenylidene (c-C3H2), and the largest nitrile to date, methyl cyanoacetylene (CH3C3N), for the first time in Titan’s atmosphere –or anywhere else in the Solar System. We employed radiative transfer models to determine the volume mixing ratio of both species in Titan’s middle and upper atmosphere (altitudes > 350 km)and constrained the total column densities for the incorporation into future photochemical models of Titan’s atmosphere. Discrepancies between these results and current models necessitates the need for dedicated laboratory and modeling studies regarding the production pathways for trace complex organics in Titan’s atmosphere. Additionally, the measurement of previously undetected molecular species provides further incentive for the study of planetary atmospheres in the (sub)millimeter regime with facilities such as ALMA.

A E Thelen↗
NASA NTRS2021

Direct Measurements of Infrared Intensities of HCN and H2O + HCN Ices for Laboratory and Observational Astrochemistry

Hydrogen cyanide (HCN) is found in a wide variety of extraterrestrial environments within and beyond the solar system, and for that reason laboratory spectroscopists have studied this compound in many spectral regions, including the infrared (IR). However, one aspect that remains to be investigated is the intrinsic IR spectral intensities of solid HCN as opposed to relative band strengths, intrinsic intensities being needed to measure HCN abundances. Here we report measurements of IR absorption coefficients and band strengths, along with supporting refractive indices and densities, of both amorphous and crystalline HCN at two temperatures, one for interstellar work and one more relevant to the outer solar system. Spectra are presented at both temperatures, along with optical constants that can be used in numerical models. Despite widespread and longstanding interest in and investigations of solid HCN, this is the first time that the properties we are reporting have been measured in a single laboratory, avoiding the need for estimates or to combine results from various authors. We find that our measured band strength of ~1 × 1017 cm molecule1 for the CN vibration of HCN, in both amorphous HCN and in an H2O-rich ice, is substantially higher than an earlier estimate. Unless errors of 100% can be tolerated then our new value requires a rescaling of earlier work. Our results shed light on why HCN and other nitriles have been so difficult to identify in the solid state, in contrast to their many detections in the gas phase.

astrochemistry – methods: laboratory – solid state↗
NASA NTRS2021

Direct Measurements of Infrared Intensities of HCN and H2O + HCN Ices for Laboratory and Observational Astrochemistry

Hydrogen cyanide (HCN) is found in a wide variety of extraterrestrial environments within and beyond the solar system, and for that reason laboratory spectroscopists have studied this compound in many spectral regions, including the infrared (IR). However, one aspect that remains to be investigated is the intrinsic IR spectral intensities of solid HCN as opposed to relative band strengths, intrinsic intensities being needed to measure HCN abundances. Here we report measurements of IR absorption coefficients and band strengths, along with supporting refractive indices and densities, of both amorphous and crystalline HCN at two temperatures, one for interstellar work and one more relevant to the outer solar system. Spectra are presented at both temperatures, along with optical constants that can be used in numerical models. Despite widespread and longstanding interest in and investigations of solid HCN, this is the first time that the properties we are reporting have been measured in a single laboratory, avoiding the need for estimates or to combine results from various authors. We find that our measured band strength of ~1 × 1017 cm molecule1 for the CN vibration of HCN, in both amorphous HCN and in an H2O-rich ice, is substantially higher than an earlier estimate. Unless errors of 100% can be tolerated then our new value requires a rescaling of earlier work. Our results shed light on why HCN and other nitriles have been so difficult to identify in the solid state, in contrast to their many detections in the gas phase.

astrochemistry – methods: laboratory – solid state↗
NASA NTRSDate not supplied

A Search for Butane in Titan’s Atmosphere using Cassini CIRS Infrared Spectra

The atmosphere of Saturn’s moon, Titan, is unlike any other. Photochemistry and ion chemistry in the upper atmosphere process the major atmospheric constituents, molecular nitrogen (N2) and methane (CH4), into larger and more complex molecules including hydrocarbons and nitriles. To date there are ten hydrocarbons heavier than methane that have been detected, including large quantities of the saturated hydrocarbons (alkanes) ethane (C2H6) and propane (C3H8). In addition to being significant trace gases of the atmosphere, these species condense, rain out and add to the volume of Titan’s hydrocarbon lakes and seas. The fourth lightest alkane, butane (C4H10),comes in two structural forms: an unbranched carbon chain (n-butane) and a branched chain (i-butane). The relative production rates of both these isomers are presently unknown, although the circumstantial case for butane to be present in detectable amounts is strong, based on photochemical models and from Cassini low-resolution mass spectrometry of the ionosphere. Butane, like its lighter siblings ethane and propane, is thought to be present in Titan’s lakes and seas where it may be active in forming molecular ‘co-crystals’ with acetylene (C2H2). We report on our recent attempts to detect both forms of butane in Titan’s atmosphere by analysis of Cassini infrared spectra collected during 2004-2017 by the Composite Infrared Spectrometer(CIRS) instrument. This multi-year effort has encompassed the collection of new laboratory spectra of both isomers at several institutions, followed by a concerted attempt to find their signatures in CIRS spectra. We search for butane by high precision modeling and removal of overlying emissions due to other, already-known gases to reveal signatures that match those of the butane isomers. The current status of the search will be discussed, including improved upper limits for both isomers, and directions of future research to detect both species.

Conor Nixon↗
NASA NTRSDate not supplied

Designed Experiment Results for Constituent Effects on NBR Based Solid Rocket Motor Insulation Performance

Solid rocket motor internal insulations are facing serious issues with obsolescence of constituents and the need for improved performance. The design community is at a unique point with a large number of rocket motors requiring reformulation of insulation or design upgrades at the same time. Unfortunately, performance data related to component choice is not generally available to aid development. A study of insulation component materials, conducted at Marshall Space Flight Center over the last four years, used designed experiments to understand the contribution of each material to the performance of a formulation. This report covers work with Nitrile Butadiene Rubber (NBR) based formulations. In-house compounding provided modified formulations allowing for isolation of both individual and synergistic effects. All formulas were tested for mechanical, thermal and producibility properties to evaluate performance. This presentation will describe the methodology for, and results from, identifying the individual and combined effects of components used in our formulations. Specific properties investigated include, rheology, cure characteristics, density, tensile strength, along with erosion/ablation under various heat loads and flame chemistries. Scale up of several formulas from lab to production size batches was accomplished. We will discuss troubleshooting problems of scale and the new set of designed experiments with Ethylene Propylene Diene Monomer (EPDM) based formulations.

Insulation↗
NASA NTRS2017

IR Spectra and Properties of Solid Acetone, an Interstellar and Cometary Molecule

Mid-infrared spectra of amorphous and crystalline acetone are presented along with measurements of the refractive index and density for both forms of the compound. Infrared band strengths are reported for the first time for amorphous and crystalline acetone, along with IR optical constants. Vapor pressures and a sublimation enthalpy for crystalline acetone also are reported. Positions of (sup 13) C-labeled acetone are measured. Band strengths are compared to gas-phase values and to the results of a density-functional calculation. A 73 percent error in previous work is identified and corrected.

ethers↗