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NASA NTRS2011

Laboratory Spectroscopy of Ices of Astrophysical Interest

Ongoing and future NASA and ESA astronomy missions need detailed information on the spectra of a variety of molecular ices to help establish the identity and abundances of molecules observed in astronomical data. Examples of condensed-phase molecules already detected on cold surfaces include H2O, CO, CO2, N2, NH3, CH4, SO2, O2, and O3. In addition, strong evidence exists for the solid-phase nitriles HCN, HC3N, and C2N2 in Titan's atmosphere. The wavelength region over which these identifications have been made is roughly 0.5 to 100 micron. Searches for additional features of complex carbon-containing species are in progress. Existing and future observations often impose special requirements on the information that comes from the laboratory. For example, the measurement of spectra, determination of integrated band strengths, and extraction of complex refractive indices of ices (and icy mixtures) in both amorphous and crystalline phases at relevant temperatures are all important tasks. In addition, the determination of the index of refraction of amorphous and crystalline ices in the visible region is essential for the extraction of infrared optical constants. Similarly, the measurement of spectra of ions and molecules embedded in relevant ices is important. This laboratory review will examine some of the existing experimental work and capabilities in these areas along with what more may be needed to meet current and future NASA and ESA planetary needs.

Hudson, Reggie↗
NASA NTRS2011

Qualification Status of Non-Asbestos Internal Insulation in the Reusable Solid Rocket Motor Program

This paper provides a status of the qualification efforts associated with NASA's RSRMV non-asbestos internal insulation program. For many years, NASA has been actively engaged in removal of asbestos from the shuttle RSRM motors due to occupation health concerns where technicians are working with an EPA banned material. Careful laboratory and subscale testing has lead to the downselect of a organic fiber known as Polybenzimidazol to replace the asbestos fiber filler in the existing synthetic rubber copolymer Nitrile Butadiene - now named PBI/NBR. Manufacturing, processing, and layup of the new material has been a challenge due to the differences in the baseline shuttle RSRM internal insulator properties and PBI/NBR material properties. For this study, data gathering and reduction procedures for thermal and chemical property characterization for the new candidate material are discussed. Difficulties with test procedures, implementation of properties into the Charring Material Ablator (CMA) codes, and results correlation with static motor fire data are provided. After two successful five segment motor firings using the PBI/NBR insulator, performance results for the new material look good and the material should eventually be qualified for man rated use in large solid rocket motor applications.

Clayton, Louie↗
NASA NTRS2012

Nitrogen Incorporation in CH4-N2 Photochemical Aerosol Produced by Far UV Irradiation

Nitrile incorporation into Titan aerosol accompanying hydrocarbon chemistry is thought to be driven by extreme UV wavelengths (lambda < 120 nm) or magnetospheric electrons in the outer reaches of the atmosphere. Far UV radiation (120 - 200 nm), which is transmitted down to the stratosphere of Titan, is expected to affect hydrocarbon chemistry only and not initiate the formation of nitrogenated species. We have examined the chemical properties of photochemical aerosol produced at far UV wavelengths using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS), which allows for elemental analysis of particle-phase products. Our results show that aerosol formed from CH4/N2 photochemistry contains a surprising amount of nitrogen, up to 16% by mass, a result of photolysis in the far UV. The proportion of nitrogenated organics to hydrocarbon species is shown to be correlated with that of N2 in the irradiated gas. The aerosol mass greatly decreases when N2 is removed, indicating that N2 plays a major role in aerosol production. Because direct dissociation of N2 is highly improbable given the immeasurably low cross-section at the wavelengths studied, the chemical activation of N2 must occur via another pathway. Any chemical activation of N2 at wavelengths > 120 nm is presently unaccounted for in atmospheric photochemical models. We suggest that reaction with CH radicals produced from CH4 photolysis may provide a mechanism for incorporating N into the molecular structure of the aerosol. Further work is needed to understand the chemistry involved, as these processes may have significant implications for prebiotic chemistry on the early Earth and similar planets.

Trainer, Melissa G.↗
NASA NTRS2012

Update from the Analysis of High Resolution Propane Spectra and the Interpretation of Titan's Infrared Spectra

Titan has an extremely thick atmosphere dominated by nitrogen, but includes a range of trace species such as hydrocarbons and nitriles. One such hydrocarbon is propane (C3H8). Propane has 21 active IR bands covering broad regions of the mid-infrared. Therefore, its ubiquitous signature may potentially mask weaker signatures of other undetected species with important roles in Titan's chemistry. Cassini's Composite Infrared Spectrometer (CIRS) observations of Titan's atmosphere hint at the presence of such molecules. Unfortunately, C3H8 line atlases for the vibration bands V(sub 8), V(sub 21), V(sub 20), and V(sub 7) (869, 922, 1054, and 1157 per centimeter, respectively) are not currently available for subtracting the C3H8 signal to reveal, or constrain, the signature of underlying chemical species. Using spectra previously obtained by Jennings, D. E., et al. at the McMath-Pierce FTIR at Kitt Peak, AZ, as the source and automated analysis utilities developed for this application, we are compiling an atlas of spectroscopic parameters for propane that characterize the ro-vibrational transitions in the above bands. In this paper, we will discuss our efforts for inspecting and fitting the aforementioned bands, present updated results for spectroscopic parameters including absolute line intensities and transition frequencies in HITRAN and GEISA formats, and show how these optical constants will be used in searching for other trace chemical species in Titan's atmosphere. Our line atlas for the V(sub 21) band contains a total number of 2971 lines. The band integrated strength calculated for the V(sub 21) band is 1.003 per centimeter per (centimeter-atm).

Klavans, V.↗
NASA NTRS2011

XANES Analysis of Organic Residues Produced from the UV Irradiation of Astrophysical Ice Analogs

Organic residues formed in the laboratory from the ultraviolet (UV) photo-irradiation or ion bombardment of astrophysical ice analogs have been extensively studied for the last 15 years with a broad suite of techniques, including infrared (IR) and UV spectroscopies, as well as mass spectrometry. Analyses of these materials show that they consist of complex mixtures of organic compounds stable at room temperature, mostly soluble, that have not been fully characterized. However, the hydrolysis products of these residues have been partly identified using chromatography techniques, which indicate that they contain molecular precursors of prebiotic interest such as amino acids, nitrile-bearing compounds, and amphiphilic compounds. In this study, we present the first X-ray absorption near-edge structure (XANES) spectroscopy measurements of three organic residues made from the UV irradiation of ices having different starting compositions. XANES spectra confirm the presence of different chemical functions in these residues, and indicate that they are rich in nitrogenand oxygen-bearing species. These data can be compared with XANES measurements of extraterrestrial materials. Finally, this study also shows how soft X rays can alter the chemical composition of samples.

XANES(X-RAY ABSORPTION NEAR-EDGE STRUCTURE)↗
NASA NTRS2012

Detecting Organic Compounds Released from Iron Oxidizing Bacteria using Sample Analysis at Mars (SAM) Like Instrument Protocols

Mars is a planet of great interest for Astrobiology since its past environmental conditions are thought to have been favourable for the emergence life. At present, the Red Planet is extremely cold and dry and the surface is exposed to intense UV and ionizing radiation, conditions generally considered to be incompatible with life as we know it on Earth. It was proposed that the shallow subsurface of Mars, where temperatures can be above freezing and liquid water can exist on rock surfaces, could harbor chemolithoautotrophic bacteria such as the iron oxidizing microorganism Pseudomonas sp. HerB. The Mars Science Laboratory (MSL) mission will provide the next opportunity to carry out in situ measurements for organic compounds of possible biological origin on Mars. One instrument onboard MSL, called the Sample Analysis at Mars (SAM) instrument suite, will carry out a broad and sensitive search for organic compounds in surface samples using either high temperature pyrolysis or chemical extraction followed by gas chromatography mass spectrometry. We present gas chromatograph mass spectrometer (GC/MS) data on crushed olivine rock powders that have been inoculated with Pseudomonas sp. HerB at different concentrations ranging from approx 10(exp 2) to 10(exp 7) cells per gram. The inoculated olivine samples were heated under helium carrier gas flow at 500 C and the pyrolysis products concentrated using a SAM-like hydrocarbon trap set at -20 C followed by trap heating and analysis by GC/Ms. In addition, the samples were also extracted using a low temperature "one-pot" chemical extraction technique using N-methyl, N-(tert-butyldimethylsilyl) trifluoroacetamide (MTBSTFA) as the silylating agent prior to GC/MS analysis. We identified several aldehydes, thiols, and alkene nitriles after pyrolysis GC/MS analysis of the bacteria that were not found in the olivine control samples that had not been inoculated with bacteria. The distribution of pyrolysis products extracted from the bacteria was clearly distinct from similar GC/MS analyses of the carbonaceous meteorite Murchison that was dominated by sulfur containing aromatic compounds. A similar comparison, if organic compounds are detected by SAM on Mars, could be useful to help discriminate between meteoritic or biological origins.

Glavin, D. P.↗
NASA NTRS2012

Titan's Tropopause Temperatures from CIRS: Implications for Stratospheric Methane Cloud Formation

Analysis of Cassini Composite Infrared Spectrometer (CIRS) far-IR spectra enable the construction of Titan's temperature profile in the altitude region containing the tropopause. Whereas the methane V4 band at 1306/cm (7.7 microns) is the primary opacity source for deducing thermal structure between 100 km and 500 km, N2-N2 collision-induced absorption between 70 and 140/cm (143 microns and 71 microns) is utilized to determine temperatures at Titan's tropopause. Additional opacity due to aerosol and nitrile ices must also be taken into account in this part of the far-IR spectral region. The spectral characteristics of these particulate opacities have been deduced from CIRS limb data at 58degS, 15degS, 15degN, and 85degN. Empirically, the spectral shapes of these opacities appear to be independent of both latitude and altitude below 300 km (Anderson and Samuelson, 2011, Icarus 212, 762-778), justifying the extension of these spectral properties to all latitudes. We find that Titan's tropopause temperature is cooler than the HAS! value of 70.5K by approx. 6K. This leads to the possibility that subsidence at high northern latitudes can cause methane condensation in the winter polar stratosphere. A search for methane clouds in this region is in progress.

Anderson, C. M.↗
NASA NTRS2012

Seasonal Disappearance of Far-Infrared Haze in Titan's Stratosphere

A far-infrared emission band attributed to volatile or refractory haze in Titan's stratosphere has been decreasing in intensity since Cassini's arrival in 2004. The 220 cm(sup -1) feature, first seen by the Voyager Infrared Interferometer Spectrometer, has only been found in Titan's winter polar region. The emission peaks at about 140 km altitude near the winter stratospheric temperature minimum. Observations recorded over the period 2004-2012 by the Composite Infrared Spectrometer on Cassini show a decrease in the intensity of this feature by about a factor of four. Possible seasonal causes of this decline are an increase in photolytic destruction of source chemicals at high altitude, a lessening of condensation as solar heating increased, or a weakening of downwelling of vapors. As of early 2012, the 220 cm(sup -1) haze has not yet been detected in the south. The haze composition is unknown, but its decrease is similar to that of HC3N gas in Titan's polar stratosphere, pointing to a nitrile origin.

Jennings, Donald E.↗
NASA NTRS2013

The Search for Ammonia in Martian Soils with Curiosity's SAM Instrument

Nitrogen is the second or third most abundant constituent of the Martian atmosphere [1,2]. It is a bioessential element, a component of all amino acids and nucleic acids that make up proteins, DNA and RNA, so assessing its availability is a key part of Curiosity's mission to characterize Martian habitability. In oxidizing desert environments it is found in nitrate salts that co-occur with perchlorates [e.g., 3], inferred to be widespread in Mars soils [4-6]. A Mars nitrogen cycle has been proposed [7], yet prior missions have not constrained the state of surface N. Here we explore Curiosity's ability to detect N compounds using data from the rover's first solid sample. Companion abstracts describe evidence for nitrates [8] and for nitriles (C(triple bond)N) [9]; we focus here on nonnitrile, reduced-N compounds as inferred from bonded N-H. The simplest such compound is ammonia (NH3), found in many carbonaceous chondrite meteorites in NH4(+) salts and organic compounds [e.g., 10].

Wray, James J.↗
NASA NTRS2013

Titan's Far-Infrared 220 cm(exp -1) Cloud Seen for the First Time in the South

In 2012 an emission feature at 220 cm(exp -1) in Titan's far-infrared spectrum was seen for the first time in the south. Attributed to a stratosphere ice cloud formed at the winter pole, the 220 (exp -1) emission had previously been seen only at high northern latitudes where it bad been decreasing since the arrival of Cassini in 2004. Our far-infrared observations were performed With the Composite Infrared Spectrometer (CIRS) on Caasini. Although it bad been expected that the 220 cm(exp -1) emission would eventnal1y appear in the south, the emission appeared rather suddenly, increasing by a factor of at least four between February (when it was not detected) and July 2012. At the time of our observations, one Titan month after equinox, the 220 cm(exp -1) feature was present in both the north and south and showed a trend of continued slow decrease in the north and steep increase in the south. As has been the case in the north, the emission in the south was confined to high latitudes associated with winter polar shadowing. Our spectroscopic detection of the southern 220 cm(exp -1) ice cloud coincided with the rapid formation in 2012 of a haze hood and vortex at the south pole as seen in Cassini image. The 220 cm(exp -1) feature was first observed by the Infrared Interferometer Spectrometer (IRIS) on Voyager I and has been extensively studied in the north by CIRS. Until now the 220 cm(exp -1) emission, like the polar hood, has been associated solely with the north, owing to the fact that Voyager and Cassini have viewed Titan only during winter-spring. In 2012 we witnessed the start of a seasonal shift of this pattern to the south. The 220 cm(exp -1) emission arises from altitudes of 80-150 km and peaks sharply near 140 km. The material responsible for the spectral feature is not known, but indirect evidence hints at a condensate arising from complex nitriles, which also tend to be present only at high winter latitudes.

Jennings, Donald↗
NASA NTRS2014

Trash to Gas (TtG) Simulant Analysis

Space exploration in outer earths orbit is a long-term commitment, where the reuse of discarded materials is a critical component for its success. The Logistics Reduction and Repurposing (LRR) project under the NASA Advanced Exploration System Program is a project focused on technologies that reduce the amount of consumables that are needed to be sent into space, repurpose items sent to space, or convert wastes to commodities. In particular, Trash to Gas (TtG), part of the LRR project, is a novel space technology capable of converting raw elements from combustible waste including food waste and packaging, paper, wipes and towels, nitrile gloves, fecal matter, urine brine, maximum absorbency garments, and other organic wastes from human space exploration into useful gases. Trash to gas will ultimately reduce mission cost by producing a portion of important consumables in situ. This paper will discuss results of waste processing by steam reforming. Steam reforming is a thermochemical process developed as part of TtG, where waste is heated in the presence of oxygen and steam to produce carbon dioxide, carbon monoxide, hydrogen, methane and water. The aim of this experiment is to investigate the processing of different waste simulants and their gaseous products. This will lay a foundation for understating and optimizing the production of useful gases for propulsion and recovery of water for life support.

Trash to Gas↗
NASA NTRS2015

Probing Titan's Complex Atmospheric Chemistry Using the Atacama Large Millimeter/Submillimeter Array

Titan is Saturn's largest moon, with a thick (1.45 bar) atmosphere composed primarily of molecular nitrogen and methane. Atmospheric photochemistry results in the production of a wide range of complex organic molecules, including hydrocarbons, nitriles, aromatics and other species of possible pre-biotic relevance. Titan's carbon-rich atmosphere may be analogous to that of primitive terrestrial planets throughout the universe, yet its origin, evolution and complete chemical inventory are not well understood. Here we present spatially-resolved maps of emission from C2H5CN, HNC, HC3N, CH3CN and CH3CCH in Titan's atmosphere, observed using the Atacama Large Millimeter/submillimeter Array (ALMA) in 2012-2013. These data show previously-undetected spatial structures for the observed species and provide the first spectroscopic detection of C2H5CN on Titan. Our maps show spatially resolved peaks in Titan's northern and southern hemispheres, consistent with photochemical production and transport in the upper atmosphere followed by subsidence over the poles. The HNC emission peaks are offset from the polar axis, indicating that Titan's mesosphere may be more longitudinally variable than previously thought.

Titan↗
NASA NTRS2014

Gemini NorthNIRI Spectra of Pluto and Charon: Simultaneous Analysis of the Surface and Atmosphere

94035We report on our analysis of blended Pluto and Charon spectra over the wavelength range 1.4 to 2.5 m as obtained by the NIRI instrument on Gemini North on June 25-28, 2004. The data have a resolving power () around 1500 and a SNR around 200 per pixel. The observed blended spectra are compared to models that combine absorption from the solid ice on the surface using Hapke theory, and absorption from the gaseous atmosphere. We assume the spectrum is a combination of several spatially separate spectral units: a CH4-rich ice unit, a volatile unit (an intimate mixture of N2, CH4 and CO), and a Charon unit (H2O, ammonia hydrate and kaolinite). We test for the presence of hydrocarbons (i.e. C2H6) and nitriles (i.e. HCN) and examine cases where additional ices are present as either pure separate spatial units, mixed with the CH4-rich unit or part of the volatile unit. We conclude that 2-4 of Plutos surface is covered with pure-C2H6 and our identification of C2H6 is significantly strengthened when absorption due to gaseous CH4 is included. The inclusion of Plutos atmosphere demonstrates that low-resolution, high-SNR observations are capable of detecting Plutos atmosphere during a time when Plutos atmosphere may have been undergoing rapid changes (1988-2002) and no high-resolution spectra were obtained. In particular, we identify features at 1.665 and 2.317 m as the Q-branch of the 23 and 3+4 bands of gaseous CH4, respectively. The later band is also evident in many previously published spectra of Pluto. Our analysis finds it is unnecessary to include 13CO to explain the depth of the 2.405 m, which has been previously suggested to be a spectral blended with C2H6, but we cannot definitively rule out its presence. Funding for this work (Cook) has been provided by a NASA-PATM grant.

Charon↗
NASA NTRS2015

Evolution of the Far-Infrared Cloud at Titan's South Pole

A condensate cloud on Titan identified by its 220 cm−1 far-infrared signature continues to undergo seasonal changes at both the north and south poles. In the north, the cloud, which extends from 55 N to the pole, has been gradually decreasing in emission intensity since the beginning of the Cassini mission with a half-life of 3.8 years. The cloud in the south did not appear until 2012 but its intensity has increased rapidly, doubling every year. The shape of the cloud at the south pole is very different from that in the north. Mapping in 2013 December showed that the condensate emission was confined to a ring with a maximum at 80 S. The ring was centered 4deg from Titanʼs pole. The pattern of emission from stratospheric trace gases like nitriles and complex hydrocarbons (mapped in 2014 January) was also offset by 4deg, but had a central peak at the pole and a secondary maximum in a ring at about 70 S with a minimum at 80 S. The shape of the gas emission distribution can be explained by abundances that are high at the atmospheric pole and diminish toward the equator, combined with correspondingly increasing temperatures. We discuss possible causes for the condensate ring. The present rapid build up of the condensate cloud at the south pole is likely to transition to a gradual decline from 2015 to 2016. Key words: molecular processes - planets and satellites: atmospheres - planets and satellites: composition - planets and satellites: individual (Titan) - radiation mechanisms: thermal

Cassini↗
NASA NTRS2016

Tholins as Coloring Agents on Pluto and Other Icy Solar System Bodies

Tholins are refractory organic solids of complex structure and high molecular weight, with a wide range of color ranging from yellow and orange to dark red, and through tan to black. They are made in the laboratory by energy deposition (photons or charged particles) in gases and ices containing the simple molecules (e.g., N2, CH4, CO) found in planetary atmospheres or condensed on planetary surfaces. They are widely implicated in providing the colors and albedos, particularly in the region 0.3-1.0 microns, of several outer Solar System bodies, including Pluto, as well as aerosols in planetary atmospheres such as Titan. Recent color images of Pluto with the New Horizons spacecraft show concentrations of coloring agent(s) in some regions of the surface, and apparent near-absence in other regions. Tholins that may to some degree represent surface chemistry on Pluto have been synthesized in the laboratory by energetic processing of mixtures of the ices (N2, CH4, CO) known on Pluto's surface, or the same molecules in the gas phase. Details of the composition and yield vary with experimental conditions. Chemical analysis of Pluto ice tholins shows evidence of amides, carboxylic acids, urea, carbodiimides, and nitriles. Aromatic/olefinic, amide, and other functional groups are identified in XANES analysis. The ice tholins produced by e- irradiation have a higher concentration of N than UV ice tholins, with N/C approx. 0.9 (versus approx. 0.5 for UV tholins) and O/C approx.0.2. Raman spectra of the electron tholin show a high degree of structural disorder, while strong UV fluorescence indicates a large aromatic content. EUV photolysis of a Pluto gaseous atmosphere analog yields pale yellow solids relatively transparent in the visual, and with aliphatic CH bonds prominent in IR spectra. This or similar material may be responsible for Pluto's hazes.

Tholins↗
NASA NTRS2015

The THS Experiment: Simulating Titans Atmospheric Chemistry at Low Temperature (200K)

In Titan's atmosphere, composed mainly of N2 (95-98%) and CH4 (2-5%), a complex chemistry occurs at low temperature, and leads to the production of heavy organic molecules and subsequently solid aerosols. Here, we used the Titan Haze Simulation (THS) experiment, an experimental setup developed at the NASA Ames COSmIC simulation facility to study Titan's atmospheric chemistry at low temperature. In the THS, the chemistry is simulated by plasma in the stream of a supersonic expansion. With this unique design, the gas is cooled to Titan-like temperature ( approximately 150K) before inducing the chemistry by plasma, and remains at low temperature in the plasma discharge (approximately 200K). Different N2-CH4-based gas mixtures can be injected in the plasma, with or without the addition of heavier precursors present as trace elements on Titan, in order to monitor the evolution of the chemical growth. Both the gas- and solid phase products resulting from the plasma-induced chemistry can be monitored and analyzed using a combination of complementary in situ and ex situ diagnostics. A recent mass spectrometry[1] study of the gas phase has demonstrated that the THS is a unique tool to probe the first and intermediate steps of Titan's atmospheric chemistry at Titan-like temperature. In particular, the mass spectra obtained in a N2-CH4-C2H2-C6H6 mixture are relevant for comparison to Cassini's CAPS-IBS instrument. The results of a complementary study of the solid phase are consistent with the chemical growth evolution observed in the gas phase. Grains and aggregates form in the gas phase and can be jet deposited on various substrates for ex situ analysis. Scanning Electron Microscopy images show that more complex mixtures produce larger aggregates. A mass spectrometry analysis of the solid phase has detected the presence of aminoacetonitrile, a precursor of glycine, in the THS aerosols. X-ray Absorption Near Edge Structure (XANES) measurements also show the presence of imine and nitrile functional groups, showing evidence of nitrogen chemistry. These complementary studies show the high potential of THS to better understand Titan's chemistry and the origin of aerosol formation.

Laboratory↗
NASA NTRS2016

Alma Observations of HCN and its Isotopologues on Titan

We present sub-millimeter spectra of HCN isotopologues on Titan, derived from publicly available ALMA flux calibration observations of Titan taken in early 2014. We report the detection of a new HCN isotopologue on Titan, H13C15N, and confirm an earlier report of detection of DCN. We model high signal-to-noise observations of HCN, H13CN, HC15N, DCN, and H13C15N to derive abundances and infer the following isotopic ratios: 12C/13C = 89.8 +/- 2.8, 14N/15N = 72.3 +/- 2.2, D/H = (2.5 +/- 0.2) × 10−4, and HCN/H13C15N = 5800 +/- 270 (1sigma errors). The carbon and nitrogen ratios are consistent with and improve on the precision of previous results, confirming a factor of approximately 2.3 elevation in 14N/15N in HCN compared to N2 and a lack of fractionation in 12C/13C from the protosolar value. This is the first published measurement of D/H in a nitrile species on Titan, and we find evidence for a factor of approximately 2 deuterium enrichment in hydrogen cyanide compared to methane. The isotopic ratios we derive may be used as constraints for future models to better understand the fractionation processes occurring in Titan's atmosphere.

Molter, Edward M.↗
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.↗