Robert Hodyss

Titan tholins: simulating Titan organic chemistry in the Cassini-Huygens era.

Titan Tholins: Simulating Titan Organic Chemistry in the Cassini-Huygens Era Morgan L. Cable, Sarah M. H€orst, Robert Hodyss, Patricia M. Beauchamp, Mark A. Smith, and Peter A. Willis* NASA Jet Propulsion Laboratory, California Institute of Technology, Pasadena, California 91109, United States Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado 80309, United States Department of Chemistry, University of Arizona, Tucson, Arizona 85721, United States College of Natural Sciences and Mathematics, University of Houston, Houston, Texas 77004, United States

HYDROGEN–DEUTERIUM EXCHANGE IN PHOTOLYZED METHANE–WATER ICES

Previous work has concluded that H-D exchange occurs readily in polycyclic aromatic hydrocarbons frozen in deuterated water (D2O) irradiated with ultraviolet light. Here, we examine H-D exchange in methane-water ices following exposure to ultraviolet radiation and analyze the products formed as a result. We find that H-D exchange also occurs in methane-water ices by means of ultraviolet photolysis. Exchange proceeds through a radical mechanism that implies that almost all organic species will undergo significant H-D exchange with the matrix in water ices exposed to ultraviolet radiation. Given sufficient energetic processing of the ice, the H/D ratio of an ice matrix may be transferred to the organic species in the ice.

Methanol on Enceladus

Near infrared spectra of the surface of Enceladus returned by Cassini show the presence of an absorption feature at 3.53 μm, ascribed by Brown et al. (2006) to “short chain organics,” and by Newman et al. (2007) to hydrogen peroxide. We assign this feature tentatively to methanol. Variations in the peak position of the feature suggest that methanol in the “tiger stripes” region may be segregated from the water ice, and not homogeneously distributed in the ice matrix. The photolytic destruction of methanol implies that methane or methanol itself must be continually deposited on the surface. On Enceladus, methanol may be generated photochemically from a mixed methane/water ice, or deposited from the plume itself. The variation in the concentration of methanol over the surface could be used to distinguish between these two processes.

Formation of a New Benzene–Ethane Co-Crystalline Structure Under Cryogenic Conditions

We report the first experimental finding of a solid molecular complex between benzene and ethane, two small apolar hydrocarbons, at atmospheric pressure and cryogenic temperatures. Considerable amounts of ethane are found to be incorporated inside the benzene lattice upon the addition of liquid ethane onto solid benzene at 90-150 K, resulting in formation of a distinctive co-crystalline structure that can be detected via micro-Raman spectroscopy. Two new features characteristic of these co-crystals are observed in the Raman spectra at 2873 and 1455 cm(-1), which are red-shifted by 12 cm(-1) from the υ1 (a1g) and υ11 (eg) stretching modes of liquid ethane, respectively. Analysis of benzene and ethane vibrational bands combined with quantum mechanical modeling of isolated molecular dimers reveal an interaction between the aromatic ring of benzene and the hydrogen atoms of ethane in a C-H···π fashion. The most favored configuration for the benzene-ethane dimer is the monodentate-contact structure, with a calculated interaction energy of 9.33 kJ/mol and an equilibrium bonding distance of 2.66 Å. These parameters are comparable to those for a T-shaped co-crystalline complex between benzene and acetylene that has been previously reported in the literature. These results are relevant for understanding the hydrocarbon cycle of Titan, where benzene and similar organics may act as potential hydrocarbon reservoirs due to this incorporation mechanism.

CHEMISTRY OF FROZEN SODIUM–MAGNESIUM–SULFATE–CHLORIDE BRINES: IMPLICATIONS FOR SURFACE EXPRESSION OF EUROPA’S OCEAN COMPOSITION

The composition of Europas subsurface ocean is a critical determinant of its habitability. However, our current understanding of the ocean composition is limited to its expression on the surface. This work investigates experimentally the composition of mixed sodium–magnesium–sulfate–chloride solutions when frozen to 100 K, simulating conditions that likely occur as ocean fluids are emplaced onto Europas surface. Micro-Raman spectroscopy is used to characterize phase composition of the frozen brines at 100 K. Our results show that solutions containing Na+, Cl−, Mg2+, and preferentially crystallize into Na2SO4 and MgCl2 hydrated minerals upon freezing, even at elevated [Mg2+]/[Na+] ratios. The detection of epsomite (MgSO4•7H2O) on Europas surface, if confirmed, may thus imply a relatively sodium-poor ocean composition or a radiolytic process that converts MgCl2 to MgSO4 as suggested by Brown & Hand. The formation of NaCl on the surface, while dependent upon a number of factors such as freezing rate, may indicate an ocean significantly more concentrated in sodium than in magnesium.

Experimental determination of the kinetics of formation of the benzene-ethane co-crystal and implications for Titan

Benzene is found on Titan and is a likely constituent of the putative evaporite deposits formed around the hydrocarbon lakes. We have recently demonstrated the formation of a benzene-ethane co-crystal under Titan-like surface conditions. Here we investigate the kinetics of formation of this new structure as a function of temperature. We show that the formation process would reach completion under Titan surface conditions in ~18 h and that benzene precipitates from liquid ethane as the co-crystal. This suggests that benzene-rich evaporite basins around ethane/methane lakes and seas may not contain pure crystalline benzene, but instead benzene-ethane co-crystals. This co-crystalline form of benzene with ethane represents a new class of materials for Titans surface, analogous to hydrated minerals on Earth. This new structure may also influence evaporite characteristics such as particle size, dissolution rate, and infrared spectral properties.

Ultraviolet-stimulated fluorescence and phosphorescence of aromatic hydrocarbons in water ice.

A principal goal of astrobiology is to detect and inventory the population of organic compounds on extraterrestrial bodies. Targets of specific interest include the wealth of icy worlds that populate our Solar System. One potential technique for in situ detection of organics trapped in water ice matrices involves ultraviolet-stimulated emission from these compounds. Here, we report a preliminary investigation into the feasibility of this concept. Specifically, fluorescence and phosphorescence of pure benzene ice and 1% mixtures of benzene, toluene, p-xylene, m-xylene, and o-xylene in water ice, respectively, were studied at temperatures ranging from ∼17 K up to 160 K. Spectra were measured from 200-500 nm (50,000-20,000 cm(-1)) while ice mixtures were excited at 248.6 nm. The temperature dependence of the fluorescence and phosphorescence intensities was found to be independent of the thermal history and phase of the ice matrix in all cases examined. All phosphorescent emissions were found to decrease in intensity with increasing temperature. Similar behavior was observed for fluorescence in pure benzene, while the observed fluorescence intensity in water ices was independent of temperature.

Prospects for mineralogy on Titan

Abstract Saturn’s moon Titan has a surface that is dominated by molecular materials, much of which are photochemically produced in the moon’s atmosphere. This outlook reviews the potential minerals that would be expected to form on the surface and subsurface of Titan from these molecular solids. We seek to classify them and look toward how the future study of these minerals will enhance our understanding of this planetary body. The classification uses the basis of intermolecular interactions, with the materials grouped into “Molecular solids,” “Molecular co-crystals,” and “Hydrates” classes alongside speculation on other possible classes of potential Titan minerals.