Low temperature hydrolysis of laboratory tholins in ammonia-water solutions: Implications for prebiotic chemistry on Titan

Laboratory tholins react rapidly in 13 wt% ammonia-water at low temperature, producing complex organic molecules containing both oxygen and altered nitrogen functional groups. These reactions display first-order kinetics with half-lives between 0.3 and 14 days at 253 K. The reaction timescales are much shorter than the freezing timescales of impact melts and volcanic sites on Titan, providing ample time for the formation of oxygenated, possibly prebiotic, molecules on its surface. Comparing the rates of the hydrolysis reactions in ammonia-water to those measured in pure water [Neish, C.D, Somogyi, A., Imanaka, H., Lunine, J.I., Smith, M.A., 2008a. Astrobiology 8, 273-287], we find that incorporation of oxygen into the tholins is faster in the presence of ammonia. The rate increases could be due to the increased pH of the solution, or to the availability of new reaction pathways made possible by the presence of ammonia. Using labeled ¹⁵NH₃ water, we find that ammonia does incorporate into some products, and that the reactions with ammonia are largely independent of those with water. A related study in confirms water as the source of the oxygen incorporated into the oxygen containing products.     

Numerical calculations of the longevity of impact oases on Titan

A promising setting for the formation of interesting prebiotic molecules on Titan is the transient liquid water environment formed by a comet impact, as originally suggested by Thompson and Sagan (1992, in: Symposium on Titan, ESA SP, vol. 338, p. 167). The impact melt (water or a water-ammonia mixture) generated in such an event can react with the abundant photochemical hydrocarbons and nitriles deposited on the surface of Titan to form more complex molecules such as purines and amino acids. We use a finite-difference thermal conduction code to calculate how long it takes for realistic liquid deposits in crater floors to freeze in the Titan environment. Our results suggest that 15 km diameter craters can sustain liquid water or water-ammonia environments for ∼¹⁰²-10³ yr and 150 km craters can sustain them for ∼¹⁰³-10⁴ yr. We discuss the implications of these timescales for organic chemistry on Titan.     

Polycyclic aromatic hydrocarbons in the atmospheres of Titan and Jupiter

Polycyclic aromatic hydrocarbons (PAHs) are important components of the interstellar medium and carbonaceous chondrites, but have never been identified in the reducing atmospheres of the outer solar system. Incompletely characterized complex organic solids (tholins) produced by irradiating simulated Titan atmospheres reproduce well the observed UV/visible/IR optical constants of the Titan stratospheric haze. Titan tholin and a tholin generated in a crude simulation of the atmosphere of Jupiter are examined by two-step laser desorption/multiphoton ionization mass spectrometry. A range of two- to four-ring PAHs, some with one to four alkylation sites are identified, with net abundance approximately 10(-4) g g-1 (grams per gram) of tholins produced. Synchronous fluorescence techniques confirm this detection. Titan tholins have proportionately more one- and two-ring PAHs than do Jupiter tholins, which in turn have more four-ring and larger PAHs. The four-ringed PAH chrysene, prominent in some discussions of interstellar grains, is found in Jupiter tholins. Solid state 13C NMR spectroscopy suggests approximately equal to 25% of the total C in both tholins is tied up in aromatic and/or aliphatic alkenes. IR spectra indicate an upper limit in both tholins of approximately equal to 6% by mass in benzenes, heterocyclics, and PAHs with more than four rings. Condensed PAHs may contribute at most approximately 10% to the observed detached limb haze layers on Titan. As with interstellar PAHs, the synthesis route of planetary PAHs is likely to be via acetylene addition reactions.     

Experimental impact shock chemistry on planetary icy satellites

We present new experimental results on impact shock chemistry into icy satellites of the outer planets. Icy mixtures of pure water ice with CO₂, Na₂CO₃, CH₃OH, and CH₃OH/(NH₄)₂SO₄ at 77 K were ablated with a powerful pulsed laser—a new technique used to simulate shock processes which can occur during impacts. New products were identified by GC-MS and FTIR analyses after laser ablation. Our results show that hydrogen peroxide is formed in irradiated H₂O/CO₂ ices with a final concentration of 0.23%. CO and CH₃OH were also detected as main products. The laser ablation of frozen H₂O/Na₂CO₃ generates only CO and CO₂ as destruction products from the salt. Pulsed irradiation of water ice containing methanol leads also to the formation of CO and CO₂, generates methane and more complex molecules containing carbonyl groups like acetaldehyde, acetone, methyl formate, and a diether, dimethyl formal. The last three compounds are also produced when adding ammonium sulfate to H₂O/CH₃OH ice, but acetone is more abundant. The formation of two hydrocarbons, CH₄ and C₂H₆ is observed as well as the production of three nitrogen compounds, nitrous oxide, hydrogen cyanide, and acetonitrile.     

Composition of Titan''s surface from Cassini VIMS

Titan's bulk density along with Solar System formation models indicates considerable water as well as silicates as its major constituents. This satellite's dense atmosphere of nitrogen with methane is unique. Deposits or even oceans of organic compounds have been suggested to exist on Titan's solid surface due to UV-induced photochemistry in the atmosphere. Thus, the composition of the surface is a major piece of evidence needed to determine Titan's history. However, studies of the surface are hindered by the thick, absorbing, hazy and in some places cloudy atmosphere. Ground-based telescope investigations of the integral disk of Titan attempted to observe the surface albedo in spectral windows between methane absorptions by calculating and removing the haze effects. Their results were reported to be consistent with water ice on the surface that is contaminated with a small amount of dark material, perhaps organic material like tholin. We analyze here the recent Cassini Mission's visual and infrared mapping spectrometer (VIMS) observations that resolve regions on Titan. VIMS is able to see surface features and shows that there are spectral and therefore likely compositional units. By several methods, spectral albedo estimates within methane absorption windows between 0.75 and 5 μm were obtained for different surface units using VIMS image cubes from the Cassini-Huygens Titan T_a encounter. Of the spots studied, there appears to be two compositional classes present that are associated with the lower albedo and the higher albedo materials, with some variety among the brighter regions. These were compared with spectra of several different candidate materials. Our results show that the spectrum of water ice contaminated with a darker material matches the reflectance of the lower albedo Titan regions if the spectral slope from 2.71 to 2.79 μm in the poorly understood 2.8-μm methane window is ignored. The spectra for brighter regions are not matched by the spectrum of water ice or unoxidized tholin, in pure form or in mixtures with sufficient ice or tholin present to allow the water ice or tholin spectral features to be discerned. We find that the 2.8-μm methane absorption window is complex and seems to consist of two weak subwindows at 2.7 and 2.8 μm that have unknown opacities. A ratio image at these two wavelengths reveals an anomalous region on Titan that has a reflectance unlike any material so far identified, but it is unclear how much the reflectances in these two subwindows pertain to the surface.     

Discharge experiments simulating chemical evolution on the surface of Titan

Saturn's moon Titan has been considered as one of the few places in our Solar System, where atmospheric and surface conditions could have produced organic compounds essential as precursors for an evolution of life. The Cassini-Huygens mission has provided new data on Titan's atmosphere and surface, which enabled us to simulate the chemical processes occurring under these conditions. Possible lightning events on Titan cannot only produce higher hydrocarbons, but also allow surface water ice to participate in the reaction scenario, resulting in CHO, CHN, and CHON compounds including several molecules relevant for the formation of amino acids and nucleic acids.     

Optical constants from 370 nm to 900 nm of Titan tholins produced in a low pressure RF plasma discharge

Determining the optical constants of Titan aerosol analogues, or tholins, has been a major concern for the last three decades because they are essential to constrain the numerical models used to analyze Titan’s observational data (albedo, radiative transfer, haze vertical profile, surface contribution, etc.). Here we present the optical constant characterization of tholins produced with an RF plasma discharge in a (95%N₂–5%CH₄) gas mixture simulating Titan’s main atmospheric composition, and deposited as a thin film on an Al–SiO₂ substrate. The real and imaginary parts, n and k, of the tholin complex refractive index have been determined from 370 nm to 900 nm wavelength using spectroscopic ellipsometry. The values of n decrease from n = 1.64 (at 370 nm) to n = 1.57 (at 900 nm) as well as the values of k which feature two behaviors: an exponential decay from 370 nm to 500 nm, with k = 12.4 × e^?0.018λ (where λ is expressed in nm), followed by a plateau, with k = (1.8 ± 0.2) × 10^?3. The trends observed for the PAMPRE tholins optical constants are compared to those determined for other Titan tholins, as well as to the optical constants of Titan’s aerosols retrieved from observational data.     

Evidence from scanning electron microscopy ofexperimental influences on the morphology of Triton andTitan tholins

To simulate experimentally the production of aerosols in the atmospheres of Titan andTriton, we have studied organic material (tholins) obtained by inductively coupled plasma fromCH₄ : N₂ gas mixtures, with ratios 10 : 90 for Titan simulations and 0.1 : 99.9 for Tritonsimulations. Observation of tholins by high performance scanning electron microscopy showsthat tholin morphology varies with the chemical composition of the initial gas mixture. Althoughthe role of the experimental design (especially the diameter of the discharge chamber) and theflux of matter were not fully investigated, it appears that they have a significant effect not on theoverall morphology of the tholins but on the size distribution of the particles.     

Influence of methane concentration on the optical indices of Titan’s aerosols analogues

This work deals with the optical constant characterization of Titan aerosol analogues or “tholins” produced with the PAMPRE experimental setup and deposited as thin films onto a silicon substrate. Tholins were produced in different N₂–CH₄ gaseous mixtures to study the effect of the initial methane concentration on their optical constants. The real (n) and imaginary (k) parts of the complex refractive index were determined using the spectroscopic ellipsometry technique in the 370–1000 nm wavelength range. We found that optical constants depend strongly on the methane concentrations of the gas phase in which tholins are produced: imaginary optical index (k) decreases with initial CH₄ concentration from 2.3 × 10^?2 down to 2.7 × 10^?3 at 1000 nm wavelength, while the real optical index (n) increases from 1.48 up to 1.58 at 1000 nm wavelength. The larger absorption in the visible range of tholins produced at lower methane percentage is explained by an increase of the secondary and primary amines signature in the mid-IR absorption. Comparison with results of other tholins and data from Titan observations are presented. We found an agreement between our values obtained with 10% methane concentration, and Imanaka et al. (Imanaka, H., Khare, B.N., Elsila, J.E., Bakes, E.L.O., McKay, C.P., Cruikshank, D.P., Sugita, S., Matsui, T., Zare, R.N. [2004]. Icarus, 168, 344–366) values, in spite of the difference in the analytical method. This confirms a reliability of the optical properties of tholins prepared with various setups but with similar plasma conditions. Our comparison with Titan’s observations also raises a possible inconsistency between the mid-IR aerosol signature by VIMS and CIRS Cassini instruments and the visible Huygens-DISR derived data. The mid-IR VIMS and CIRS signatures are in agreement with an aerosol dominated by an aliphatic carbon content, whereas the important visible absorption derived from the DISR measurement seems to be incompatible with such an important aliphatic content, but more compatible with an amine-rich aerosol.     

Optical constants of Titan tholins at mid-infrared wavelengths (2.5–25 μm) and the possible chemical nature of Titan’s haze particles

Complex organic materials may exist as haze layers in the atmosphere of Titan and as dark coloring agents on icy satellite surfaces. Laboratory measurements of optical constants of plausible complex organic materials are necessary for quantitative evaluation from remote sensing observations, and to document the existence of complex organic materials in the extraterrestrial environments. The recent Cassini VIMS and CIRS observations provide new constraints on Titan’s haze properties in the mid-infrared wavelength region. Here, we present the optical constants (2.5–25 μm) of Titan tholins generated with cold plasma irradiation of a N₂/CH₄ (90/10) gas mixture at pressures of 0.26 mbar, 1.6 mbar, and 23 mbar. Our new optical constants of three types of Titan tholins suggest that no single Titan tholin in this study fulfills all the observational constraints of the Titan haze material. The discrepancy remains a challenge for future modeling and laboratory efforts that aim toward a better understanding of Titan’s haze material.     

On the chemical composition of Titan’s dry lakebed evaporites

Titan, the main satellite of Saturn, has an active cycle of methane in its troposphere. Among other evidence for a mechanism of evaporation at work on the ground, dry lakebeds have been discovered. Recent Cassini infrared observations of these empty lakes have revealed a surface composition poor in water ice compared to that of the surrounding terrains—suggesting the existence of organic evaporites deposits. The chemical composition of these possible evaporites is unknown. In this paper, we study evaporite composition using a model that treats both organic solids dissolution and solvent evaporation. Our results suggest the possibility of large abundances of butane and acetylene in the lake evaporites. However, due to uncertainties of the employed theory, these determinations have to be confirmed by laboratory experiments.     

The reflectance spectrum of Titan's surface at the Huygens landing site determined by the descent imager/spectral radiometer

The descent imager/spectral radiometer aboard the Huygens probe successfully acquired images and spectra of the surface of Titan. To counter the effects of haze and atmospheric methane absorption it carried a surface science lamp to illuminate the surface just before landing. We reconstruct the reflectance spectrum of the landing site in the 500-1500 nm range from downward looking visual and infrared spectrometers data that show evidence of lamp light. Our reconstruction is a followup to the analysis by Tomasko et al. [2005. Rain, winds and haze during the Huygens probe's descent to Titan's surface. Nature 438, 765-778], who scaled their result to the ratio of the up- and down flux measured just before landing. Instead, we use the lamp flux from the calibration experiment, and find a significantly higher overall reflectance. We attribute this to a phase angle dependance, possibly representing the opposition surge commonly encountered on solar system bodies. The reconstruction in the visible wavelength range is greatly improved. Here, the reflectance spectrum features a red slope, consistent with the presence of organic material. We confirm the blue slope in the near-IR, featureless apart from a single shallow absorption feature at 1500 nm. We agree with Tomasko et al. that the evidence for water ice is inconclusive. By modeling of absorption bands we find a methane mixing ratio of 4.5±0.5% just above the surface. There is no evidence for the presence of liquid methane, but the data do not rule out a wet soil at a depth of several centimeters.     

Ultraviolet photolysis of amino acids in a 100 K water ice matrix: Application to the outer Solar System bodies

We report the rates of decomposition by ultraviolet (UV) photolysis of four amino acids in millimeter-thick crystalline water ice matrices at 100 K to constrain the survivability of these important organic molecules within ice lying near the surfaces of outer Solar System bodies. We UV-irradiated crystalline ice samples containing known concentrations of the amino acids glycine, aspartic acid, glutamic acid, and phenylalanine, then we measured the surviving concentrations using high performance liquid chromatography (HPLC) with fluorescence detection. From these experiments, we determine photolytic decomposition rates and half-lives. The half-life varies linearly with the ice thickness for all acids studied here. For example, glycine is the most resistant to photolytic destruction with a half-life of 50, 12, and 3.7 h in 1.6, 0.28, and 0.14 mm thick ices, respectively. We explain this linear variation of half-life with thickness as a consequence of extinction, mostly due to scattering, within these macroscopically thick ice samples. Applied to low latitude surface ice on Jupiter's satellite Europa, this analysis indicates that the concentration of any of these amino acids within the top meter of similar ice will be halved within a ∼10 year timescale.     

Laboratory studies of methane and ethane adsorption and nucleation onto organic particles: Application to Titan's clouds

Titan, Saturn's largest moon, has a thick nitrogen/methane atmosphere. The temperature and pressure conditions in Titan's atmosphere are such that the methane vapor should condense near the tropopause to form clouds. Several ground-based measurements have observed sparse cloud-like features in Titan's atmosphere, while the Cassini mission to Saturn has provided large scale images of the clouds. However, Titan's cloud formation conditions remain poorly constrained. Heterogeneous nucleation (from the vapor phase onto a solid or liquid aerosol surface) greatly enhances cloud formation relative to homogeneous nucleation. In order to elucidate the cloud formation mechanism near the tropopause, we have performed laboratory measurements of the adsorption of methane and ethane onto solid organic particles (tholins) representative of Titan's photochemical haze. We find that monolayers of methane adsorb onto tholin particles at saturation ratios less than unity. We also find that solid methane nucleates onto the adsorbed methane at a saturation ratio of S=1.07±0.008. This implies that Titan's methane clouds should form easily. This is consistent with recent measurements of the column of methane ruling out excessive methane supersaturation. In addition, we find ethane adsorbs onto tholin particles in a metastable phase prior to nucleation. However, ethane nucleation onto the adsorbed ethane occurs at a relatively high saturation ratio of S=1.36±0.08. These findings are consistent with the recent report of polar ethane clouds in Titan's lower stratosphere.     

The history of titan,of Saturn's rings and magnetic field,and the nature of short-period comets

Titan in the past, just as Ganymede, had a massive ice envelope subjected to volumetric electrolysis under the action of unipolar electric current generated through the interaction of the satellite with Saturn's magnetosphere. The electrolysis products concentration required to cause explosion could become accumulated only under conditions of an exponential decay of Saturn's magnetic field in time (with τ_? ≈ 0.55 Gyr) which implies a relict nature of the field and agrees with the present ideas on the planet's structure. The explosion of the electrolysis products contained in the ice envelope resulted in Titan's having lost ～13% of its mass in the form of gas (mainly of water vapor) and solid ice fragments, as well as in the appearance on Titan of an atmosphere (of volatile products from incomplete combustion of hydrogen and hydrocarbons) and a deep (～1000 km) ocean of liquid water. The presence of liquid water on Titan's surface is confirmed by an analysis of the available microwave measurements of brightness temperature. The condensation of the water vapor lost by Titan produced the visible inner rings of Saturn while large solid fragments of the ice envelope govern their dynamics. These are also located in the gap between Rhea and Titan (the G ring?). Most of the ice fragments were swept out from Saturn's system through perturbations by Titan. They made up a reservoir of cometary nuclei beyond Jupiter's orbit. Arguments are presented in favor of a recent (3–10 thousand years ago) explosion of Titan. Some implications from these concepts, lending themselves to observational testing, are pointed out.     

Unveiling the nature of 10199 Chariklo: near-infrared observations and modeling

10199 Chariklo (1997 CU26) is the largest Centaur so far known. We carried out near-infrared observations of this object during two different runs separated by a year. Although no evidence for spectral variations has been found over short time scales, slight differences have been detected between the two observational runs. We interpret these findings as likely due to a heterogeneous composition of the surface of Chariklo. We suggest two different models comprising geographical mixtures of tholins, amorphous carbon, and water ice in slightly different percentages. Our observations confirm the presence of water ice on the surface of this Centaur, as already detected by Brown et al. (1998, Science 280, 1430-1432) and Brown and Koresko (1998, Astrophys. J. 505, L65-67).     

Laboratory experiments of Titan tholin formed in cold plasma at various pressures: implications for nitrogen-containing polycyclic aromatic compounds in Titan haze

Titan, the largest satellite of Saturn, has a thick nitrogen/methane atmosphere with a thick global organic haze. A laboratory analogue of Titan's haze, called tholin, was formed in an inductively coupled plasma from nitrogen/methane=90/10 gas mixture at various pressures ranging from 13 to 2300 Pa. Chemical and optical properties of the resulting tholin depend on the deposition pressure in cold plasma. Structural analyses by IR and UV/VIS spectroscopy, microprobe laser desorption/ionization mass spectrometry, and Raman spectroscopy suggest that larger amounts of aromatic ring structures with larger cluster size are formed at lower pressures (13 and 26 Pa) than at higher pressures (160 and 2300 Pa). Nitrogen is more likely to incorporate into carbon networks in tholins formed at lower pressures, while nitrogen is bonded as terminal groups at higher pressures. Elemental analysis reveals that the carbon/nitrogen ratio in tholins increases from 1.5-2 at lower pressures to 3 at 2300 Pa. The increase in the aromatic compounds and the decrease in C/N ratio in tholin formed at low pressures indicate the presence of the nitrogen-containing polycyclic aromatic compounds in tholin formed at low pressures. Tholin formed at high pressure (2300 Pa) consists of a polymer-like branched chain structure terminated with CH₃, NH₂, and CN with few aromatic compounds. Reddish-brown tholin films formed at low pressures (13-26 Pa) shows stronger absorptions (almost 10 times larger k-value) in the UV/VIS range than the yellowish tholin films formed at high pressures (160 and 2300 Pa). The tholins formed at low pressures may be better representations of Titan's haze than those formed at high pressures, because the optical properties of tholin formed at low pressures agree well with that of Khare et al. (1984a, Icarus 60, 127-137), which have been shown to account for Titan's observed geometric albedo. Thus, the nitrogen-containing polycyclic aromatic compounds we find in tholin formed at low pressure may be present in Titan's haze. These aromatic compounds may have a significant influence on the thermal structure and complex organic chemistry in Titan's atmosphere, because they are efficient absorbers of UV radiation and efficient charge exchange intermediaries. Our results also indicate that the haze layers at various altitudes might have different chemical and optical properties.     

Titan's 5 micrometers spectral window: carbon monoxide and the albedo of the surface

We have measured the spectrum of Titan near 5 micrometers and have found it to be dominated by absorption from the carbon monoxide 1-0 vibration-rotation band. The position of the band edge allows us to constrain the abundance of CO in the atmosphere and/or the location of the reflecting layer in the atmosphere. In the most likely case, 5 micrometers radiation is reflected from the surface and the mole fraction of CO in the atmosphere is qCO=10(+10/-5) ppm, significantly lower than previous estimates for tropospheric CO. The albedo of the reflecting layer is approximately 0.07(+0.02/-0.01) in the 5 micrometers continuum outside the CO band. The 5 micrometers albedo is consistent with a surface of mixed ice and silicates similar to the icy Galilean satellites. Organic solids formed in simulated Titan conditions can also produce similar albedos at 5 micrometers.     

Reactions of nitriles in ices relevant to Titan, comets, and the interstellar medium: formation of cyanate ion, ketenimines, and isonitriles

Motivated by detections of nitriles in Titan's atmosphere, cometary comae, and the interstellar medium, we report laboratory investigations of the low-temperature chemistry of acetonitrile, propionitrile, acrylonitrile, cyanoacetylene, and cyanogen (CH₃CN, CH₃CH₂CN, CH₂CHCN, HCCCN, and NCCN, respectively). A few experiments were also done on isobutyronitrile and trimethylacetonitrile ((CH₃)₂CHCN and (CH₃)₃CCN, respectively). Trends were sought, and found, in the photo- and radiation chemical products of these molecules at 12-25 K. In the absence of water, all of these molecules isomerized to isonitriles, and CH₃CN, CH₃CH₂CN, and (CH₃)₂CHCN also formed ketenimines. In the presence of H₂O, no isonitriles were detected but rather the cyanate ion (OCN⁻) was seen in all cases. Although isonitriles, ketenimines, and OCN⁻ were the main focus of our work, we also describe cases of hydrogen loss, to make smaller nitriles, and hydrogen addition (reduction), to make larger nitriles. HCN formation also was seen in most experiments. The results are presented in terms of nitrile ice chemistry on Titan, in cometary ice, and in the interstellar medium. Possible connections to prebiotic chemistry are briefly discussed.