Comparison of Nitrogen Incorporation in Tholins Produced by FUV Irradiation and Spark Discharge

The discovery of very heavy ions (Coates et al., 2007) in Titan's thermosphere has dramatically altered our understanding of the processes involved in the formation of the complex organic aerosols that comprise Titan's characteristic haze. Before Cassini's arrival, it was believed that aerosol production began in the stratosphere where the chemical processes were predominantly initiated by FUV radiation. This understanding guided the design of Titan atmosphere simulation experiments. However, the energy environment of the thermosphere is significantly different than the stratosphere; in particular there is a greater flux of EUV photons and energetic particles available to initiate chemical reactions, including the destruction of N2. in the upper atmosphere. Using a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS), we have obtained in situ composition measurements of aerosol particles (so'called "tholins") produced in CH4/N2 gas mixtures subjected to either FUV radiation (deuterium lamp, 115-400 nm) (Trainer et al., 2012) or a spark discharge. A comparison of the composition of tholins produced using the two different energy sources will be presented, in particular with regard to the variation in nitrogen content of the two types of tholin. Titan's aerosols are known to contain significant amounts of nitrogen (Israel et al., 2005) and therefore understanding the role of nitrogen in the aerosol chemistry is important to further our knowledge of the formation and evolution of aerosols in Titan's atmosphere

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)

Aromatic Structure in Simulates Titan Aerosol

Observations of Titan by the Cassini Composite Infrared Spectrometer (CIRS) between 560 and 20 per centimeter (approximately 18 to 500 micrometers) have been used to infer the vertical variations of Titan's ice abundances, as well as those of the aerosol from the surface to an altitude of 300 km [1]. The aerosol has a broad emission feature centered approximately at 140 per centimeter (71 micrometers). As seen in Figure 1, this feature cannot be reproduced using currently available optical constants from laboratory-generated Titan aerosol analogs [2]. The far-IR is uniquely qualified for investigating low-energy vibrational motions within the lattice structures of COITIDlex aerosol. The feature observed by CIRS is broad, and does not likely arise from individual molecules, but rather is representative of the skeletal movements of macromolecules. Since Cassini's arrival at Titan, benzene (C6H6) has been detected in the atmosphere at ppm levels as well as ions that may be polycyclic aromatic hydrocarbons (PAHs) [3]. We speculate that the feature may be a blended composite that can be identified with low-energy vibrations of two-dimensional lattice structures of large molecules, such as PAHs or nitrogenated aromatics. Such structures do not dominate the composition of analog materials generated from CH4 and N2 irradiation. We are performing studies forming aerosol analog via UV irradiation of aromatic precursors - specifically C6H6 - to understand how the unique chemical architecture of the products will influence the observable aerosol characteristics. The optical and chemical properties of the aromatic analog will be compared to those formed from CH4/N2 mixtures, with a focus on the as-yet unidentified far-IR absorbance feature. Preliminary results indicate that the photochemically-formed aromatic aerosol has distinct chemical composition, and may incorporate nitrogen either into the ring structure or adjoined chemical groups. These compositional differences are demonstrated in the aerosol mass spectra shown in Figure 2. The aromatic aerosol also demonstrates strong chemical reactivity when exposed to laboratory air, indicating substantial stored chemical potential. Oxidatoin and solubility studies wil be presented and implicatoins for prebiotic chemistry o nTitan will be discussed

Investigating the Origin and Evolution of Venus with In Situ Mass Spectrometry

The exploration of Venus continues to be a top priority of planetary science. The Planetary Decadal Survey goals for inner-planet exploration seek to discern the origin and diversity of terrestrial planets, understand how the evolution of terrestrial planets relates to the evolution of life, and explore the processes that control climate on Earth-like planets [1]. These goals can only be realized through continued and extensive exploration of Venus, the most mysterious of the terrestrial planets, remarkably different from the Earth despite the gross similarities between these twin planets. It is unknown if this apparent divergence was intrinsic, programmed during accretion from distinct nebular reservoirs, or a consequence of either measured or catastrophic processes during planetary evolution. Even if the atmosphere of Venus is a more recent development, its relationship to the resurfacing of the planets enigmatic surface is not well understood. Resolving such uncertainties directly addresses the hypothesis of a more clement, possibly water-rich era in Venus past as well as whether Earth could become more Venus-like in the future

Stable Isotope Fractionation in Titan Aerosol Formation

Stable isotope ratio measurements are a powerful tool used to understand both ancient and modern planetary processes. Instruments on the Cassini- Huygens spacecraft along with ground-based observations have measured several isotope pairs, including C-13/C-12 and N-15/N-14, in Titan's atmosphere. This includes isotopic measurements of the major atmospheric species, CH4 and N2, along with HCN, HC3N, C2H2. C2H6 and C4H2. However, the isotopic fractionation of Titan's organic aerosol has not conclusively been measured and therefore the effect of aerosol formation as an isotopic fractionation pathway in Titan's atmosphere has not been considered. Laboratory studies have measured the carbon and/or nitrogen isotopic fractionation of Titan aerosol analogs. [18] found that the carbon fractionation of photochemical organic aerosol analogs are more enriched in C-13. This enrichment in the aerosol analogs is opposite of what is predicted for photochemical products by the kinetic isotope effect. Additionally, both [16] and [18] found that the nitrogen fractionation in the organic aerosol analogs are opposite of what is observed in Titan's atmospheric N2 and HCN, with the aerosol analogs being a light nitrogen sink. Here we monitor the gas phase during photochemical aerosol analog production as a function of reaction time. In a recirculation experiment, the isotopic fractionation of carbon within the gas-phase products is measured as the CH4 reservoir is depleted. This allows us to monitor the isotopic fractionation pathway during photochemical aerosol analog formation

Laboratory Simulations of the Titan Surface to Elucidate the Huygens Probe GCMS Observations

The Cassini/Huygens mission has vastly increased the information we have available to stndy Satnro's moon Titan. The complete mission has included an array of observational methods including remote sensing techniques, upper atmosphere in-situ saropling, and the descent of the Huygens probe directly through the atmosphere to the surface [1,2]. The instruments on the Huygens probe remain the ouly source of in-situ measurements at the surface of Titan, and work evaluating these measurements to create a pict.rre of the surface environment is ongoing. In particular, the Gas Chromatograph Mass Spectrometer (GCMS) experiment on Huygens found that although there were no heavy hydrocarbons detected in the lower atmosphere, a rich spectrum of mass peaks arose once the probe landed on the surface [3,4], However, to date it has not been possible to extract the identity and abundances of the many minor components of the spectra due to a lack of temperatnre- and instrumentappropriate data for the relevant species. We are performing laboratory stndies designed to elucidate the spectrum collected on Titan's surface, utilizing a cryogenic charober maintained at appropriate temperature and pressure conditions. The experiments will simulate the temperatnre rise experienced by the surface, which led to an enhanced signal of volatiles detected by the Huygens GCMS. The objective of this study is to exaroine the characteristics of various surface analogs as measured by the Huygens GCMS flight spare instrument, which is currently housed in our laboratory at NASA Goddard Space Flight Center (GSFC). This identification cannot be adequately accomplished through theoretical work alone since the thermodynamic properties of many species at these temperatnres (94 K, HASI measurement [5]) are not known

Calibration of the Quadrupole Mass Spectrometer of the Sample Analysis at Mars Instrument Suite

The SAM suite of instruments on the "Curiosity" Rover of the Mars Science Laboratory (MSL) is designed to provide chemical and isotopic analysis of organic and inorganic volatiles for both atmospheric and solid samples. The mission of the MSL investigations is to advance beyond the successful search for aqueous transformation in surface environments at Mars toward a quantitative assessment of habitability and preservation through a series of chemical and geological measurements. The SAM suite was delivered in December 2010 (Figure 1) to the Jet Propulsion Laboratory for integration into the Curiosity Rover. We previously outlined the range of SAM solid and gas calibrations implemented or planned and here we discuss a specific set of calibration experiments to establish the response of the SAM Quadrupole Mass Spectrometer (QMS) to the four most abundant gases in the Martian atmosphere CO2, N2, Ar, and O2, A full SAM instrument description and calibration report is presently in preparation

Seasonal Variations in Atmospheric Composition as Measured in Gale Crater, Mars

The atmosphere of Mars is made up of primarily carbon dioxide, and during the Martian year, the barometric pressure is known to cycle up and down substantially as this carbon dioxide freezes out and then is rereleased from polar caps. The Mars Science Laboratory Curiosity rover has now acquired atmospheric composition measurements at the ground over multiple years, capturing the variations in the major gases over several seasonal cycles for the first time. With the Sample Analysis at Mars instrument, the annual average composition in Gale Crater was measured as 95.1% carbon dioxide, 2.59% nitrogen, 1.94% argon, 0.161% oxygen, and 0.058% carbon monoxide. However, the abundances of some of these gases were observed to vary up to 40% throughout the year due to the seasonal cycle.Melissa G. Trainer; Michael H. Wong; Timothy H. McConnochie; Heather B. Franz; Sushil K. Atreya; Pamela G. Conrad; Franck Lefèvre; Paul R. Mahaffy; Charles A. Malespin; Heidi L.K. Manning; Javier Martín‐Torres; Germán M. Martínez; Christopher P. McKay; Rafael Navarro‐González; Álvaro Vicente‐Retortillo; Christopher R. Webster; María‐Paz Zorzan