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NASA NTRS2011

An Icy Kuiper-Belt Around the Young Solar-Type Star HD 181327

HD 181327 is a young Main Sequence F5/F6 V star belonging to the Beta Pictoris moving group (age approx 12 Myr). It harbors an optically thin belt of circumstellar material at approx90 AU, presumed to result from collisions in a populat.ion of unseen planetesimals. Aims. We aim to study the dust properties in the belt in great details, and to constrain the gas-to-dust ratio. Methods. We obtained far-IR photometric observations of HD 181327 with the PACS instrument onboard the Herschel Space Observatory, complemented by new 3.2 nun observations carried with the ATCA array. The geometry of the belt is constrained with newly reduced HST /NICMOS scattered light images that break the degeneracy between the disk geometry and the dust properties. We then use the radiative transfer code GRaTer to compute a large grid of dust models, and we apply a Bayesian inference method to identify the grain models that best reproduce the SED. We attempt to detect the oxygen and ionized carbon fine-structure lines with Herschel/PACS spectroscopy, providing observables to our photochemical code ProDiMo. Results. The HST observations confirm that the dust is confined in a narrow belt. The continuum is detected with Herschel/PACS completing nicely the SED in the far-infrared. The disk is marginally resolved with both PACS and ATCA. A medium integration of the gas spectral lines only provides upper limits on the [OI] and [CII] line fluxes. We show that the HD 181327 dust disk consists of micron-sized grains of porous amorphous silicates and carbonaceous material surrounded by an import.ant layer of ice for a total dust mass of approx 0.05 stellar Mass. We discuss evidences that the grains consists of fluffy aggregates. The upper limits on the gas atomic lines do not provide unambiguous constraints: only if the PAH abundance is high, the gas mass must be lower than approx 17 Stellar Mass Conclusions. Despite the weak constraints on the gas disk, the age of HD 181327 and the properties of the dust disk suggest that it has passed the stage of gaseous planets formation. The dust reveals a population of icy planetesimals, similar to the primitive Edgeworth-Kuiper Belt, that may be a source for the future delivery of water and volatiles onto forming terrestrial planets.

Lebreton, J.↗
NASA NTRS2011

Gas Modelling in the Disc of HD 163296

We present detailed model fits to observations of the disc around the Herbig Ae star HD 163296. This well-studied object has an age of approx. 4Myr, with evidence of a circumstellar disc extending out to approx. 540AU. We use the radiation thermo-chemical disc code ProDiMo to model the gas and dust in the circumstellar disc of HD 163296, and attempt to determine the disc properties by fitting to observational line and continuum data. These include new Herschel/PACS observations obtained as part of the open-time key program GASPS (Gas in Protoplanetary Systems), consisting of a detection of the [Oi] 63 m line and upper limits for several other far infrared lines. We complement this with continuum data and ground-based observations of the CO-12 3-2, 2-1 and CO-13 J=1-0 line transitions, as well as the H2 S(1) transition. We explore the effects of stellar ultraviolet variability and dust settling on the line emission, and on the derived disc properties. Our fitting efforts lead to derived gas/dust ratios in the range 9-100, depending on the assumptions made. We note that the line fluxes are sensitive in general to the degree of dust settling in the disc, with an increase in line flux for settled models. This is most pronounced in lines which are formed in the warm gas in the inner disc, but the low excitation molecular lines are also affected. This has serious implications for attempts to derive the disc gas mass from line observations. We derive fractional PAH abundances between 0.007 and 0.04 relative to ISM levels. Using a stellar and UV excess input spectrum based on a detailed analysis of observations, we find that the all observations are consistent with the previously assumed disc geometry

Tilling, I.↗
NASA NTRS2012

Titan Aerosol Analogs from Aromatic Precursors: Comparisons to Cassini CIRS Observations in the Thermal Infrared

Since Cassini's arrival at Titan, ppm levels of benzene (C6H6) as well as large positive ions, which may be polycyclic aromatic hydrocarbons (PAHs). have been detected in the atmosphere. Aromatic molecules. photolytically active in the ultraviolet, may be important in the formation of the organic aerosol comprising the Titan haze layer even when present at low mixing ratios. Yet there have not been laboratory simulations exploring the impact of these molecules as precursors to Titan's organic aerosol. Observations of Titan by the Cassini Composite Infrared Spectrometer (CIRS) in the far-infrared (far-IR) between 560 and 20/cm (approx. 18 to 500 microns) and in the mid-infrared (mid-IR) between 1500 and 600/cm (approx. 7 to 17 microns) have been used to infer the vertical variations of Titan's aerosol from the surface to an altitude of 300 km in the far-IR and between 150 and 350 km in the mid-IR. Titan's aerosol has several observed emission features which cannot be reproduced using currently available optical constants from laboratory-generated Titan aerosol analogs, including a broad far-IR feature centered approximately at 140/cm (71 microns).

Trainer, Melissa G.↗
NASA NTRS2012

Hydrocarbons on Phoebe, Iapetus, and Hyperion: Quantitative Analysis

We present a quantitative analysis of the hydrocarbon spectral bands measured on three of Saturn's satellites, Phoebe, Iaperus, and Hyperion. These bands, measured with the Cassini Visible-Infrared Mapping Spectrometer on close fly-by's of these satellites, are the C-H stretching modes of aromatic hydrocarbons at approximately 3.28 micrometers (approximately 3050 per centimeter), and the are four blended bands of aliphatic -CH2- and -CH3 in the range approximately 3.36-3.52 micrometers (approximately 2980- 2840 per centimeter) bably indicating the presence of polycyclic aromatic hydrocarbons (PAH), is unusually strong in comparison to the aliphatic bands, resulting in a unique signarure among Solar System bodies measured so far, and as such offers a means of comparison among the three satellites. The ratio of the C-H bands in aromatic molecules to those in aliphatic molecules in the surface materials of Phoebe, NAro:NAliph approximately 24; for Hyperion the value is approximately 12, while laperus shows an intermediate value. In view of the trend of the evolution (dehydrogenation by heat and radiation) of aliphatic complexes toward more compact molecules and eventually to aromatics, the relative abundances of aliphatic -CH2- and -CH3- is an indication of the lengths of the molecular chain structures, hence the degree of modification of the original material. We derive CH2:CH3 approximately 2.2 in the spectrum of low-albedo material on laperus; this value is the same within measurement errors to the ratio in the diffuse interstellar medium. The similarity in the spectral signatures of the three satellites, plus the apparent weak trend of aromatic/aliphatic abundance from Phoebe to Hyperion, is consistent with, and effectively confirms that the source of the hydrocarbon-bearing material is Phoebe, and that the appearance of that material on the other two satellites arises from the deposition of the inward-spiraling dust that populates the Phoebe ring.

Cruikshank, Dale P.↗
NASA NTRS2013

The Impact and Oxidation Survival of Selected Meteoritic Compounds: Signatures of Asteroid Organic Material on Planetary Surfaces

Polar, non-volatile organic compounds may be present on the surfaces (or near surfaces) of multiple Solar System bodies. If found, by current or future missions, it would be desirable to determine the origin(s) of such compounds, e.g., asteroidal or in situ. To test the possible survival of meteoritic compounds both during impacts with planetary surfaces and under subsequent (possibly) harsh ambient conditions, we subjected known meteoritic compounds to relatively high impact-shock pressures and/or to varying oxidizing/corrosive conditions. Tested compounds include sulfonic and phosphonic acids (S&P), polyaromatic hydrocarbons (PAHs) amino acids, keto acids, dicarboxylic acids, deoxy sugar acids, and hydroxy tricarboxylic acids (Table 1). Meteoritic sulfonic acids were found to be relatively abundant in the Murchison meteorite and to possess unusual S-33 isotope anomalies (non mass-dependent isotope fractionations). Combined with distinctive C-S and C-P bonds, the S&P are potential signatures of asteroidal organic material.

Cooper, George↗
NASA NTRS2012

Compact Two-step Laser Time-of-Flight Mass Spectrometer for in Situ Analyses of Aromatic Organics on Planetary Missions

RATIONALE A miniature time-of-flight mass spectrometer has been adapted to demonstrate two-step laser desorption-ionization (LOI) in a compact instrument package for enhanced organics detection. Two-step LDI decouples the desorption and ionization processes, relative to traditional laser ionization-desorption, in order to produce low-fragmentation conditions for complex organic analytes. Tuning UV ionization laser energy allowed control ofthe degree of fragmentation, which may enable better identification of constituent species. METHODS A reflectron time-of-flight mass spectrometer prototype measuring 20 cm in length was adapted to a two-laser configuration, with IR (1064 nm) desorption followed by UV (266 nm) postionization. A relatively low ion extraction voltage of 5 kV was applied at the sample inlet. Instrument capabilities and performance were demonstrated with analysis of a model polycyclic aromatic hydrocarbon, representing a class of compounds important to the fields of Earth and planetary science. RESULTS L2MS analysis of a model PAH standard, pyrene, has been demonstrated, including parent mass identification and the onset o(tunable fragmentation as a function of ionizing laser energy. Mass resolution m/llm = 380 at full width at half-maximum was achieved which is notable for gas-phase ionization of desorbed neutrals in a highly-compact mass analyzer. CONCLUSIONS Achieving two-step laser mass spectrometry (L2MS) in a highly-miniature instrument enables a powerful approach to the detection and characterization of aromatic organics in remote terrestrial and planetary applications. Tunable detection of parent and fragment ions with high mass resolution, diagnostic of molecular structure, is possible on such a compact L2MS instrument. Selectivity of L2MS against low-mass inorganic salt interferences is a key advantage when working with unprocessed, natural samples, and a mechanism for the observed selectivity is presented.

Getty, Stephanie↗
NASA NTRS2014

Organic Analysis of Catalytic Fischer-Tropsch Synthesis Products and Ordinary Chondrite Meteorites by Stepwise Pyrolysis-GCMS: Organics in the Early Solar Nebula

Abiotic generation of complex organic compounds, in the early solar nebula that formed our solar system, is hypothesized by some to occur via Fischer-Tropsch (FT) synthesis. In its simplest form, FT synthesis involves the low temperature (<300degC) catalytic reaction of hydrogen and carbon monoxide gases to form more complex hydrocarbon compounds, primarily n-alkanes, via reactive nano-particulate iron, nickel, or cobalt, for example. Industrially, this type of synthesis has been utilized in the gas-to-liquid process to convert syngas, produced from coal, natural gas, or biomass, into paraffin waxes that can be cracked to produce liquid diesel fuels. In general, the effect of increasing reaction temperature (>300degC) produces FT products that include lesser amounts of n-alkanes and greater alkene, alcohol, and polycyclic aromatic hydrocarbon (PAH) compounds. We have begun to experimentally investigate FT synthesis in the context of abiotic generation of organic compounds in the early solar nebula. It is generally thought that the early solar nebula included abundant hydrogen and carbon monoxide gases and nano-particulate matter such as iron and metal silicates that could have catalyzed the FT reaction. The effect of FT reaction temperature, catalyst type, and experiment duration on the resulting products is being investigated. These solid organic products are analyzed by thermal-stepwise pyrolysis-GCMS and yield the types and distribution of hydrocarbon compounds released as a function of temperature. We show how the FT products vary by reaction temperature, catalyst type, and experimental duration and compare these products to organic compounds found to be indigenous to ordinary chondrite meteorites. We hypothesize that the origin of organics in some chondritic meteorites, that represent an aggregation of materials from the early solar system, may at least in part be from FT synthesis that occurred in the early solar nebula.

Locke, Darren R.↗
NASA NTRS2012

An Icy Kuiper Belt Around the Young Solar-type Star HD 181327

Context. HD 181327 is a young main sequence F5/F6 V star belonging to the Beta Pictoris moving group (age approx.. 12 Myr). It harbors an optically thin belt of circumstellar material at radius approx.. 90 AU, presumed to result from collisions in a population of unseen planetesimals. Aims. We aim to study the dust properties in the belt in details, and to constrain the gas-to-dust ratio. Methods. We obtained far-infrared photometric observations of HD 181327 with the PACS instrument onboard the Herschel Space Observatory, complemented by new 3.2 mm observations carried with the ATCA array. The geometry of the belt is constrained with newly reduced HST/NICMOS scattered light images that allow the degeneracy between the disk geometry and the dust properties to be broken. We then use the radiative transfer code GRaTeR to compute a large grid of models, and we identify the grain models that best reproduce the spectral energy distribution (SED) through a Bayesian analysis. We attempt to detect the oxygen and ionized carbon fine-structure lines with Herschel/PACS spectroscopy, providing observables to our photochemical code ProDiMo. Results. The HST observations confirm that the dust is confined in a narrow belt. The continuum is detected with Herschel/PACS completing nicely the SED in the far-infrared. The disk is marginally resolved with both PACS and ATCA. A medium integration of the gas spectral lines only provides upper limits on the [OI] and [CII] line fluxes.We show that the HD 181327 dust disk consists of micron-sized grains of porous amorphous silicates and carbonaceous material surrounded by an important layer of ice, for a total dust mass of approx.. 0.05 Solar Mass (in grains up to 1 mm). We discuss evidences that the grains consists of fluffy aggregates. The upper limits on the gas atomic lines do not provide unambiguous constraints: only if the PAH abundance is high, the gas mass must be lower than approx. 17 Solar Mass. Conclusions. Despite the weak constraints on the gas disk, the age of HD 181327 and the properties of the dust disk suggest that it has passed the stage of gaseous planets formation. The dust reveals a population of icy planetesimals, similar to the primitive Edgeworth-Kuiper belt, that may be a source for the future delivery of water and volatiles onto forming terrestrial planets.

HD 181327↗
NASA NTRS2013

Tomographic Sounding of Protoplanetary and Transitional Disks: Using Inner Disk Variability at Near to Mid-IR Wavelengths to Probe Conditions in the Outer Disk

Spitzer synoptic monitoring of young stellar associations has demonstrated that variability among young stars and their disks is ubiquitous. The Spitzer studies have been limited by target visibility windows and cover only a short temporal baseline in years. A complementary approach is to focus on stars chosen for high-value observations (e.g. high-contrast imaging, interferometry, or access to wavelengths which are difficult to achieve from the ground) where the synoptic data can augment the imagery or interferometry as well as probing disk structure. In this talk, we discuss how synoptic data for two protoplanetary disks, MWC 480 and HD 163296, constrain the dust disk scale height, account for variable disk illumination, and can be used to locate emission features, such as the IR bands commonly associated with PAHs in the disk, as part of our SOFIA cycle 1 study. Similar variability is now known for several pre-transitional disks, where synoptic data can be used to identify inner disks which are not coplanar with the outer disk, and which may be relicts of giant planet-giant planet scattering events. Despite the logistical difficulties in arranging supporting, coordinated observations in tandem with high-value observations, such data have allowed us to place imagery in context, constrained structures in inner disks not accessible to direct imagery, and may be a tool for identifying systems where planet scattering events have occurred.

target visibility windows↗
NASA NTRS2015

Pyrolysis-GCMS Analysis of Solid Organic Products from Catalytic Fischer-Tropsch Synthesis Experiments

Abiotic synthesis of complex organic compounds in the early solar nebula that formed our solar system is hypothesized to occur via a Fischer-Tropsch type (FTT) synthesis involving the reaction of hydrogen and carbon monoxide gases over metal and metal oxide catalysts. In general, at low temperatures (less than 200 C), FTT synthesis is expected to form abundant alkane compounds while at higher temperatures (greater than 200 C) it is expected to product lesser amounts of n-alkanes and greater amounts of alkene, alcohol, and polycyclic aromatic hydrocarbons (PAHs). Experiments utilizing a closed-gas circulation system to study the effects of FTT reaction temperature, catalysts, and number of experimental cycles on the resulting solid insoluble organic products are being performed in the laboratory at NASA Goddard Space Flight Center. These experiments aim to determine whether or not FTT reactions on grain surfaces in the protosolar nebula could be the source of the insoluble organic matter observed in meteorites. The resulting solid organic products are being analyzed at NASA Johnson Space Center by pyrolysis gas chromatography mass spectrometry (PY-GCMS). PY-GCMS yields the types and distribution of organic compounds released from the insoluble organic matter generated from the FTT reactions. Previously, exploratory work utilizing PY-GCMS to characterize the deposited organic materials from these reactions has been reported. Presented here are new organic analyses using magnetite catalyst to produce solid insoluble organic FTT products with varying reaction temperatures and number of experimental cycles.

Locke, Darren R.↗
NASA NTRS2015

Survival of Organic Materials in Ancient Cryovolcanically-Produced Halite Crystals

Spectroscopic evidence supports the presence of Mg-Na-K salts derived from cryovolcanism on the surface of Europa. Halite (NaCl) is effective at very long-term preservation of organic phases and structures. Collection of salt crystals from Europan plumes would provide solid inclusions of organics, potentially also biomaterials, all suitable for analysis. Two thermally-metamorphosed ordinary chondrite regolith breccias (Monahans 1998 (H5) and Zag (H3-6)) contain fluid and solid inclusion-bearing halite crystals, dated to approximately 4.5 billion years, and thus the trapped aqueous fluids and solids are at least as old. Heating/freezing studies of the aqueous fluid inclusions in these halites demonstrated that they were trapped near 25 degrees Centigrade, and their continued presence in the halite grains requires that their incorporation into the H chondrite asteroid occurred after that body's metamorphism ended, since heating would have dessicated the halite. O and H isotopes of the trapped fluids are consistent with mixing of asteroidal and cometary water. Cryovolcanic Origin of the Halite: We hypothesize that these meteoritic halites derive from ancient cryovolcanism based on the following points. (1) Salts crystals are observed as products of current cryovolcanism on Enceladus. (2) In-situ spacecraft analysis of some of the icy grains associated with the Enceladus salt found minor organic or siliceous components, including methane, also found in the Monahans halite. (3) Cryovolcanic fluids are observed to be in chemical disequilibrium, reflecting incomplete reactions between interior volatiles and rocky materials. The coexistence of N2 and HCN in Enceladus' cryovolcanic fluids requires that the plume consists of a mixture of materials whose sources experienced different degrees of aqueous processing, including primordial material trapped in ice that has not been in contact with liquid water. The observed mineral assemblage within the Monahans and Zag halites is also far from equilibrium. Cryovolcanoes on Ceres are a potential source of our halite, however the processes that form halite should also be operating within Europa. Dissolution of Monahans halite grains has revealed a remarkable variety of organics, which dominate the population of solid inclusions. Thermal alteration of this macromolecular carbon (measured by Raman spectroscopy) shows remarkable diversity. We have identified highly-condensed aromatics, diamond, carbonates and chloromethane. Light organic compounds like methane tend to be water soluble and require cold formation temperatures at high hydrogen fugacity - i.e. require water ice. Another indication that these halites have not been heated is that light organics readily volatilize or aromaticize into PAHs. We are currently analyzing the organics by Raman and C-XANES, and measuring the content and exploring the potential chirality of amino acids in the halite. Implications for Europa Plumes: Organic materials and structures erupted by a Europa cryovolcano should be similarly preserved within halite, and other salts, which will be a convenient form for capture and analysis, since halite will serve to encapsulate and protect the organics from spacecraft contamination. Also, being transparent at many wavelengths halite will permit analysis by spacecraft-mounted spectroscopic techniques. In addition, halite is readily dissolved, permitting further analysis of entrained organics.

Zolensky, M.↗
NASA NTRS2015

Organics in Space: Results from Space Exposure Platforms and Nanosatellites

A series of successful laboratory astrophysics experiments performed on International Space Station(ISS) external platforms such as EXPOSE have provided insights into the evolution of organic and biological materials in space and planetary environments. The study of the reactions, destruction, and longevity of organics in the space environment is of fundamental interest. To provide an accurate outer space environment for extended durations, exposure experiments in low Earth orbit have been conducted in the last decades in order to examine the consequences of actual space conditions including combinations of solar and cosmic radiation, space vacuum, and microgravity. The OOREOS (OrganismORganic Exposure to Orbital Stresses) nanosatellite studied in situ during the 6-month primary and 1-year extended mission the photochemical processing of selected PAHs in low Earth orbit (650 km altitude); results were autonomously telemetered to Earth. We report on the methods and flight preparation of samples for space exposure platforms and results on the stability of organic thin-films. The UV-vis degradation process of thin-films was recorded over time, which revealed intriguing and counter-intuitive photolytic kinetics that will be re-investigated on the ISS in a space environment.

Space weathering↗
NASA NTRS2013

Organic Nano-Grains in Comet 103P/Hartley 2: The Organic Glue of Porous Aggregate Grains?

The GNIRS instrument on the Gemini 8-­‐m telescope observed comet 103P/Hartley on 2010-­‐ Dec-­‐04UT, a month after the EPOXI Mission encounter, and detected the 3.3 and 3.4 um bands in emission. The 3.3/3.4 ratio and the broad band widths are consistent with experiments of heated (approximately 600 K) aliphatic carbon (-CH3, -CH2) thin films. For the 3.4 micron band to be in emission, the aliphatic bonds must be attached to a carrier possessing the strongly UV-­‐absorbing C=C aromatic rings, and these rings have to be less than 50-­‐100 carbon atoms (4-6 Angstrom) for attached -CH bonds to also generate a 3.3 micron-band in emission. Slightly larger (≥10Å) Very Small Grains (VSGs) can absorb single UV photons comparable to or exceeding their heat capacity, thermally fluctuate and release IR photon(s). The 3.3 micron and 3.4 micron bands observed by GNIRS suggest that organic macromolecules/ nano-­‐grains with both aliphatic and aromatic bonds are fluorescing/thermally fluctuating in the coma. Aliphatic and aromatic materials have been seen in Stardust samples and the primitive carbonaceous chondrite 'Tagish Lake'. The larger the ratio of the -CH2/-CH3 components of the aliphatic 3.4 micron band, the more 'primitive' the organic material. In a Stardust organic globule, some aliphatic bonds were transformed into aromatic bonds during the low dosage of Transmission Electron Microscope imaging. Conversely, lab experiments show irradiation of ices containing small PAHs generates aliphatic organics. Photo-­‐processing of ices also likely forms the ubiquitous aliphatic coatings that appear on the surfaces of all silicate subgrains constituting nine cometary interplanetary dust particles. The aliphatic coatings, dominated by -CH2, likely were important in sticking the aggregates together, and existed prior to incorporation of dust aggregates into comet nuclei. These comet aliphatics may be some of the sought-­‐after precursors to the more robust and complex organics studied as Insoluble Organic Matter in carbonaceous chondrites. Aliphatic coatings on submicron grains, however, will not be observable in absorption because they are fairly transparent, nor do the aliphatic carbonaceous coatings produce the 3.4 micron emission band because the particles they are attached to are too large (too many vibration modes). We must probe the nano-­‐sized organic carriers that undergo substantive thermal fluctuations in cometary comae and emit at 3.3 3.4 micron. Observations of the 3.3 and 3.4 micron emission features contribute to characterizing the evolution of organics prior to their incorporation into cometary nuclei as well as their rapid evolution in cometary comae, which in turn contributes to deepening our understanding of the evolution of organics on the surfaces of asteroids and outer icy bodies in our solar system. Studying organics in comets contributes to understanding the formation and evolution pathways of ISM organics through to the formation of the robust insoluble organic matter in meteorites. A'Hearn, M.F., et al. 2011, Science, 332, 1396; Bockelee-­‐Morvan, D. et al. 1995, Icarus, 116, 18; De Gregorio, B.T., et al. 2010, GCA, 74, 4454; Dello Russo, N., et al. 2011, ApJ, 734, L8; Dischler et al. 1983, Solid State Communications, 48, 105; Flynn, G., et al. 2010a, LPSC, 41, #1079; Flynn, G., et al. 2010b, COSPAR, 38, F31-­‐0012-­‐10; Flynn, G., Wirick, S. 2011, LPSC, 42, #1856; Fomenkova, et al. 1994, GCA 58, 4503; Matrajt, G., et al. 2013, ApJ, 765, 145; Schutte, et al. 1993, ApJ, 415, 397; Wooden, D.H. et al. 2011, EPSC-­‐DPS, 1557; Wooden, D.H. et al. 2013, submitted.

Stardust samples↗
NASA NTRS2016

Two-Step Resonance-Enhanced Desorption Laser Mass Spectrometry for In Situ Analysis of Organic-Rich Environments

A wide diversity of planetary surfaces in the solar system represent high priority targets for in situ compositional and contextual analysis as part of future missions. The planned mission portfolio will inform our knowledge of the chemistry at play on Mars, icy moons, comets, and primitive asteroids, which can lead to advances in our understanding of the interplay between inorganic and organic building blocks that led to the evolution of habitable environments on Earth and beyond. In many of these environments, the presence of water or aqueously altered mineralogy is an important indicator of habitable environments that are present or may have been present in the past. As a result, the search for complex organic chemistry that may imply the presence of a feedstock, if not an inventory of biosignatures, is naturally aligned with targeted analyses of water-rich surface materials. Here we describe the two-step laser mass spectrometry (L2MS) analytical technique that has seen broad application in the study of organics in meteoritic samples, now demonstrated to be compatible with an in situ investigation with technique improvements to target high priority planetary environments as part of a future scientific payload. An ultraviolet (UV) pulsed laser is used in previous and current embodiments of laser desorption/ionization mass spectrometry (LDMS) to produce ionized species traceable to the mineral and organic composition of a planetary surface sample. L2MS, an advanced technique in laser mass spectrometry, is selective to the aromatic organic fraction of a complex sample, which can provide additional sensitivity and confidence in the detection of specific compound structures. Use of a compact two-step laser mass spectrometer prototype has been previously reported to provide specificity to key aromatic species, such as PAHs, nucleobases, and certain amino acids. Recent improvements in this technique have focused on the interaction between the mineral matrix and the organic analyte. The majority of planetary targets of astrobiological interest are characterized by the presence of water or hydrated mineral phases. Water signatures can indicate a history of available liquid water that may have played an important role in the chemical environment of these planetary surfaces and subsurfaces. The studies we report here investigate the influence of water content on the detectability of organics by L2MS in planetary analog samples.

primitive asteroids↗
NASA NTRS2015

The Formation of Complex Organic Compounds in Astrophysical Ices and their Implications for Astrobiology

Ices in astrophysical environments are generally dominated by very simple molecules like H2O, CH3OH, CH4, NH3, CO, CO2, etc, although they likely contain PAHs as well. These molecules, particularly H2O, are of direct interest to astrobiology in-and-of themselves since they represent some of the main carriers of the biogenic elements C, H, O, and N. In addition, these compounds are present in the dense interstellar clouds in which new stars and planetary systems are formed and may play a large role in the delivery of volatiles and organics to the surfaces of new planets. However, these molecules are all far simpler than the more complex organic compounds found in living systems.

UV Irradiation↗
NASA NTRS2017

Herschel Extreme Lensing Line Observations: [CII] Variations in Galaxies at Redshifts z=1-3*

We observed the [C II] line in 15 lensed galaxies at redshifts 1 less than z less than 3 using HIFI on the Herschel Space Observatory and detected 14/15 galaxies at 3sigma or better. High magnifications enable even modestly luminous galaxies to be detected in [C II] with Herschel. The [C II] luminosity in this sample ranges from 8 × 10(exp 7) solar luminosity to 3.7 × 10(exp 9) solar luminosity (after correcting for magnification), confirming that [C II] is a strong tracer of the ISM at high redshifts. The ratio of the [C II] line to the total far-infrared (FIR) luminosity serves as a measure of the ratio of gas to dust cooling and thus the efficiency of the grain photoelectric heating process. It varies between 3.3% and 0.09%. We compare the [C II]/FIR ratio to that of galaxies at z = 0 and at high redshifts and find that they follow similar trends. The [C II]/FIR ratio is lower for galaxies with higher dust temperatures. This is best explained if increased UV intensity leads to higher FIR luminosity and dust temperatures, but gas heating does not rise due to lower photoelectric heating efficiency. The [C II]/FIR ratio shows weaker correlation with FIR luminosity. At low redshifts highly luminous galaxies tend to have warm dust, so the effects of dust temperature and luminosity are degenerate. Luminous galaxies at high redshifts show a range of dust temperatures, showing that [C II]/FIR correlates most strongly with dust temperature. The [C II] to mid-IR ratio for the HELLO sample is similar to the values seen for low-redshift galaxies, indicating that small grains and PAHs dominate the heating in the neutral ISM, although some of the high [CII]/FIR ratios may be due to turbulent heating.

Malhotra, Sangeeta↗
NASA NTRS2020

Titan's Ionospheric Chemistry, Fullerenes, Oxygen, Galactic Cosmic Rays and the Formation of Exobiological Molecules on and Within Its Surfaces and Lakes

We discuss the formation of aerosols within Titan's thermosphere-ionosphere and the different chemical pathways. Negative ion measurements by the Cassini Plasma Spectrometer (CAPS) Electron Spectrometer (ELS) give evidence for formation of unsaturated anion carbon chains, while positive ion measurements of the Cassini Ion Neutral Mass Spectrometer (INMS) indicate formation of more aromatic cation hydrocarbons. There is presently no direct observational evidence for large neutral molecule growth in Titan's thermosphere-ionosphere. The hydrocarbon cations are expected to form Polycyclic Aromatic Hydrocarbons (PAHs), those with the addition of nitrogen being called PAHNs. We theorize anion carbon chains can eventually become long enough to fold into fullerene C60,70 carbon shells, of various charge states. Based on laboratory data the fullerenes can trap incoming O+ magnetospheric ions that have relatively high energy collisions with the fullerenes and, once trapped, protect the oxygen atom from Titan's reducing thermosphere-ionosphere. The fullerenes can form into larger onion fullerenes and condense into larger embryo aerosols (i.e., m/q (mass-to-charge ratio) greater than 10,000 amu/q (atomic mass unit-to-charge ratio) anions as observed by CAPS/ELS) eventually falling onto Titan's surface and precipitating to the bottom of its hydrocarbon lakes. Molecule production composed of H, C, N is known to occur in Titan's atmosphere with energy input from the magnetosphere, solar UV (ultraviolet), and deep-penetrating irradiation from galactic cosmic rays (GCR). Space radiation effects by GCR irradiation of Titan's surface and lakes can lead to the manufacture of exobiological molecules with oxygen as the new ingredient. We have developed a model of galactic cosmic ray irradiation of Titan's atmosphere, surface, subsurface and bottoms of Titan lakes. GCR would provide further energy for processing of the aerosols into more complex organic forms such as tholins and precursor molecules for amino acids. A second process called hydrolysis then converts the precursor molecules into amino acids. Hydrolysis is provided via meteor impacts with size greater than 10 kilometers and cryovolcanism both which can produce liquid water on Titan's surface for episodic periods more than several 100 to 1000 years. Our model shows that GCR secondary particles can penetrate ~100 meters below the ice surface (including the bottom of Titan's less dense hydrocarbon lakes ~150-meter depths) and produce chemically significant dosages over very long timescales ~450 million years. The GCR model is combined with laboratory data from experiments in which dry methyl ices were irradiated to doses producing prebiotic amino acids such as glycine. The model calculations show glycine can form to ~2.5 parts-per-billion levels near the surface after ~450 million years of GCR proton irradiation and potentially to 5 parts-per-billion if heavy-ion GCRs up through Fe are included. If such molecules were detected, this would not only confirm this model but indicate that life forms different from ours may not be required.

Edward C. Sittler Jr↗
NASA NTRS2019

Titan's Ionospheric Chemistry, Fullerenes, Oxygen, Galactic Cosmic Rays and the Formation of Exobiological Molecules on and within its Surfaces and Lakes

We discuss the formation of aerosols within Titan's thermosphere-ionosphere and the different chemical pathways. Negative ion measurements by the Cassini Plasma Spectrometer (CAPS) Electron Spectrometer (ELS) give evidence for formation of unsaturated anion carbon chains, while positive ion measurements of the Cassini Ion Neutral Mass Spectrometer (INMS) indicate formation of more aromatic cation hydrocarbons. There is presently no direct observational evidence for large neutral molecule growth in Titan's thermosphere-ionosphere. The hydrocarbon cations are expected to form Polycyclic Aromatic Hydrocarbons (PAH), those with the addition of nitrogen being called PAHNs. We theorize anion carbon chains can eventually become long enough to fold into fullerene C(60,70) carbon shells, of various charge states. Based on laboratory data the fullerenes can trap incoming O(sup +) magnetospheric ions that have relatively high energy collisions with the fullerenes and, once trapped, protect the oxygen atom from Titan's reducing thermosphere-ionosphere. The fullerenes can form into larger onion fullerenes and condense into larger embryo aerosols (i.e., m/q > 10,000 amu/q anions as observed by CAPS/ELS) eventually falling onto Titan's surface and precipitating to the bottom of its hydrocarbon lakes. Molecule production composed of H, C, N is known to occur in Titan's atmosphere with energy input from the magnetosphere, solar UV, and deeppenetrating irradiation from galactic cosmic rays (GCR). Space radiation effects by GCR irradiation of Titan's surface and lakes can lead to the manufacture of exobiological molecules with oxygen as the new ingredient. We have developed a model of galactic cosmic ray irradiation of Titan's atmosphere, surface, subsurface and bottoms of Titan lakes. GCR would provide further energy for processing of the aerosols into more complex organic forms such as tholins and precursor molecules for amino acids. A second process called hydrolysis then converts the precursor molecules into amino acids. Hydrolysis is provided via meteor impacts with size > 10 km and cryovolcanism both which can produce liquid water on Titan's surface for episodic periods > several 100 to 1000 years. Our model shows that GCR secondary particles can penetrate ~ 100 m below the ice surface (including the bottom of Titan's less dense hydrocarbon lakes ~ 150 m depths) and produce chemically significant dosages over very long timescales ~ 450 Myrs. The GCR model is combined with laboratory data from experiments in which dry methyl ices were irradiated to doses producing prebiotic amino acids such as glycine. The model calculations show glycine can form to ~ 2.5 ppb levels near the surface after ~450 Myrs of GCR proton irradiation and potentially to 5 ppb if heavy-ion GCRs up through Fe are included. If such molecules were detected, this would not only confirm this model but indicate that life forms different from ours may not be required.

Edward C. Sittler Jr↗