Fluorescence spectra of Titan tholins: in-situ detection of astrobiologically interesting areas on Titan's surface

We report the three-dimensional fluorescence spectra of Titan tholins in water and acetonitrile, and separate some of the fluorescent components of tholins using two-dimensional thin layer chromatography. In acetonitrile, tholins exhibit a broad fluorescence with a maximum at 471 nm, and an excitation maximum at 410 nm. The fluorescence spectrum of a water extraction displays a more complicated spectrum with multiple peaks. TLC results indicate the presence of at least three distinct fluorescent species. In addition, we obtained the two-dimensional fluorescence spectrum of tholins in water ice at 77 K, close to the surface temperature of Titan. The fluorescence of tholins in a 77 K ice matrix is red-shifted in comparison to a water solution, and undergoes a further red-shift when the water solution is heated prior to freezing. These results suggest that a simple fluorescence probe could be used on the surface of Titan to identify sites where tholins have been mixed with water, and possibly reveal information about the extent of heating the tholin-water mixture has undergone. This would be useful for a future mission with the goal of examining the organic chemistry of Titan.     

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.     

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.     

Reflectance spectra of hydrated Titan tholins at cryogenic temperatures and implications for compositional interpretation of red objects in the outer Solar System

We report the visible and near-infrared (0.4-2.5 μm) laboratory bidirectional reflectance of hydrated Titan tholin at cryogenic temperatures (∼100-300 K). When compared with room temperature measurements, the visible and near-infrared color of hydrated Titan tholin becomes bluer by ∼14% at low temperatures in the 0.7-1.0 μm region. Assuming the observed color changes are representative of tholin-like materials we estimate the influence of such color changes on the interpretation of the Centaur Pholus and find that the modest color changes will not significantly alter existing interpretations.     

Mapping of Titan: Results from the first Titan radar passes

The first two swaths collected by Cassini's Titan Radar Mapper were obtained in October of 2004 (Ta) and February of 2005 (T3). The Ta swath provides evidence for cryovolcanic processes, the possible occurrence of fluvial channels and lakes, and some tectonic activity. The T3 swath has extensive areas of dunes and two large impact craters. We interpret the brightness variations in much of the swaths to result from roughness variations caused by fracturing and erosion of Titan's icy surface, with additional contributions from a combination of volume scattering and compositional variations. Despite the small amount of Titan mapped to date, the significant differences between the terrains of the two swaths suggest that Titan is geologically complex. The overall scarcity of impact craters provides evidence that the surface imaged to date is relatively young, with resurfacing by cryovolcanism, fluvial erosion, aeolian erosion, and likely atmospheric deposition of materials. Future radar swaths will help to further define the nature of and extent to which internal and external processes have shaped Titan's surface.     

Amino acids in the Tagish Lake meteorite

Abstract— High‐performance liquid chromatography (HPLC) based amino acid analysis of a Tagish Lake meteorite sample recovered 3 months after the meteorite fell to Earth have revealed that the amino acid composition of Tagish Lake is strikingly different from that of the CM and CI carbonaceous chondrites. We found that the Tagish Lake meteorite contains only trace levels of amino acids (total abundance = 880 ppb), which is much lower than the total abundance of amino acids in the CI Orgueil (4100 ppb) and the CM Murchison (16 900 ppb). Because most of the same amino acids found in the Tagish Lake meteorite are also present in the Tagish Lake ice melt water, we conclude that the amino acids detected in the meteorite are terrestrial contamination. We found that the exposure of a sample of Murchison to cold water lead to a substantial reduction over a period of several weeks in the amount of amino acids that are not strongly bound to the meteorite matrix. However, strongly bound amino acids that are extracted by direct HCl hydrolysis are not affected by the leaching process. Thus even if there had been leaching of amino acids from our Tagish Lake meteorite sample during its 3 month residence in Tagish Lake ice and melt water, a Murchison type abundance of endogenous amino acids in the meteorite would have still been readily detectable. The low amino acid content of Tagish Lake indicates that this meteorite originated from a different type of parent body than the CM and CI chondrites. The parent body was apparently devoid of the reagents such as aldehyldes/ketones, HCN and ammonia needed for the effective abiotic synthesis of amino acids. Based on reflectance spectral measurements, Tagish Lake has been associated with P‐ or D‐type asteroids. If the Tagish Lake meteorite was indeed derived from these types of parent bodies, our understanding of these primitive asteroids needs to be reevaluated with respect to their potential inventory of biologically important organic compounds.     

Results from the Huygens probe on Titan

The Cassini–Huygens mission, comprising the NASA Saturn Orbiter and the ESA Huygens Probe, arrived at Saturn in late June 2004. The Huygens probe descended under parachute in Titan’s atmosphere on 14 January 2005, 3 weeks after separation from the Orbiter. We discuss here the breakthroughs that the Huygens probe, in conjunction with the Cassini spacecraft, brought to Titan science. We review the achievements ESA’s Huygens probe put forward and the context in which it operated. The findings include new localized information on several aspects of Titan science: the atmospheric structure and chemical composition; the aerosols distribution and content; the surface morphology and composition at the probe’s landing site; the winds, the electrical properties, and the implications on the origin and evolution of the satellite.     

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.     

Determining Titan surface topography from Cassini SAR data

A technique, referred to as SARTopo, has been developed for obtaining surface height estimates with 10 km horizontal resolution and 75 m vertical resolution of the surface of Titan along each Cassini Synthetic Aperture Radar (SAR) swath. We describe the technique and present maps of the co-located data sets. A global map and regional maps of Xanadu and the northern hemisphere hydrocarbon lakes district are included in the results. A strength of the technique is that it provides topographic information co-located with SAR imagery. Having a topographic context vastly improves the interpretability of the SAR imagery and is essential for understanding Titan.SARTopo is capable of estimating surface heights for most of the SAR-imaged surface of Titan. Currently nearly 30% of the surface is within 100 km of a SARTopo height profile. Other competing techniques provide orders of magnitude less coverage.We validate the SARTopo technique through comparison with known geomorphological features such as mountain ranges and craters, and by comparison with co-located nadir altimetry, including a 3000 km strip that had been observed by SAR a month earlier. In this area, the SARTopo and nadir altimetry data sets are co-located tightly (within 5-10 km for one 500 km section), have similar resolution, and as expected agree closely in surface height. Furthermore the region contains prominent high spatial resolution topography, so it provides an excellent test of the resolution and precision of both techniques.     

Hypsometry of Titan

Cassini RADAR topography data are used to evaluate Titan’s hypsometric profile, and to make comparisons with other planetary bodies. Titan’s hypsogram is unimodal and strikingly narrow compared with the terrestrial planets. To investigate topographic extremes, a novel variant on the classic hypsogram is introduced, with a logarithmic abscissa to highlight mountainous terrain. In such a plot, the top of the terrestrial hypsogram is quite distinct from those of Mars and Venus due to the ‘glacial buzz-saw’ that clips terrestrial topography above the snowline. In contrast to the positive skew seen in other hypsograms, with a long tail of positive relief due to mountains, there is an indication (weak, given the limited data for Titan so far) that the Titan hypsogram appears slightly negatively skewed, suggesting a significant population of unfilled depressions. Limited data permit only a simplistic comparison of Titan topography with other icy satellites but we find that the standard deviation of terrain height (albeit at different scales) is similar to those of Ganymede and Europa.     

Significant science at Titan and Neptune from aerocaptured missions

In 2001, NASA began assembling the Aerocapture Systems Analysis Team, a team of scientists and engineers from multiple NASA centers. Their charter is to perform high-fidelity analyses of delivering scientifically compelling orbital missions that use aerocapture for orbit insertion at their destinations. After establishing scientific credibility, studies focus on aerocapture systems design and performance, including approach navigation, flight mechanics, aerothermodynamics, and thermal protection. The team's October 2001-September 2002 study examined a mission to explore the organic environment of Titan and its chemical, geological, and dynamical context. Its architecture includes a Titan polar orbiter that would complete and extend Cassini's soon-to-begin global mapping, aiding global extrapolation of findings from a mobile in situ element (rover, blimp, etc.). The in situ element would perform remote sensing and in situ investigations, for analysis and characterization of Titan's surface, shallow subsurface, atmosphere, processes occurring there, and energy sources driving it all. The study concentrated on the orbiter and orbit insertion, largely treating the in situ element as a black box with data relay requirements. October 2002-September 2003 the team studied a mission to perform Cassini/Huygens-level exploration of the Neptune system. Before aerocapture this mission would deploy and support multiple Neptune atmospheric entry probes. After aerocapture the orbiter uses Triton as a “tour engine”, in much the same manner as Cassini uses Titan, to provide many Triton flybys and orbit evolution for detailed investigation of Neptune's interior, atmosphere, magnetosphere, rings, and satellites.This presentation summarizes the missions’ science objectives, instrumentation, and data requirements that served as the foundations for the studies, and describes mission design requirements and constraints that affect the science investigations.     

Radiocarbon on Titan

Abstract— We explore the likely production and fate of ¹⁴C in the thick nitrogen atmosphere of Saturn's moon Titan and investigate the constraints that measurements of ¹⁴C might place on Titan's photochemical, atmospheric transport and surface‐atmosphere interaction processes. Titan's atmosphere is thick enough that cosmic‐ray flux limits the production of ¹⁴C: absence of a strong magnetic field and the increased distance from the Sun suggest production rates of ?9 atom/cm²/s, ?4x higher than Earth. The fate and detectability of ¹⁴C depends on the chemical species into which it is incorporated: as methane it would be hopelessly diluted even in only the atmosphere. However, in the more likely case that the ¹⁴C attaches to the haze that rains out onto the surface (as tholin, HCN or acetylene and their polymers), haze in the atmosphere or recently deposited on the surface would be quite radioactive. Such radioactivity may lead to a significant enhancement in the electrical conductivity of the atmosphere which will be measured by the Huygens probe. Measurements with simple detectors on future missions could place useful constraints on the mass deposition rates of photochemical material on the surface and identify locations where surface deposits of such material are “freshest”.     

Electron conductivity and density profiles derived from the mutual impedance probe measurements performed during the descent of Huygens through the atmosphere of Titan

During the descent of the Huygens probe through the atmosphere of Titan, on January 14th, 2005, the permittivity, waves and altimetry (PWA) subsystem, a component of the Huygens atmospheric structure instrument (HASI), detected an ionized layer at altitudes around 63 km with two different instruments, the relaxation probe (RP) and the mutual impedance probe (MIP). A very detailed analysis of both data sets is required, in order to correct for environmental effects and compare the two independent estimates of the electrical conductivity. The present work is dedicated to the MIP data analysis. New laboratory tests have been performed to validate or improve the available calibration results. Temperature effects have been included and numerical models of the MIP sensors and electric circuitry have been developed to take into account the proximity of the Huygens probe body. The effect of the vertical motion of the vessel in the ionized atmosphere is estimated in both analytical and numerical ways. The peculiar performance of the instrument in the altitude range 100–140 km is scrutinized. The existence of a prominent ionized layer, and of enhancements in the conductivity and electron density profiles at 63 km, are discussed in the light of previous theoretical predictions.     

New experimental constraints on the composition and structure of tholins

Powdered samples of carbon-nitrogen-hydrogen “tholins” that mimic Titan's atmosphere aerosols were produced under levitation conditions in the laboratory with a dusty plasma (PAMPRE experiment) using different initial N₂:CH₄ gas mixtures and studied using UV Raman and infrared spectroscopy, X-ray diffraction and high resolution transmission electron microscopy (HRTEM). Comparison between the tholins produced in the PAMPRE experiments and samples prepared by other techniques reveal that they form a fairly homogeneous family of hydrogenated carbon nitride materials. Wall effects during the PAMPRE deposition experiments and other were found to have little effect on the chemical structure of tholins. The first-order UV Raman bands of the disordered carbonaceous materials point to a large contribution of sp² clusters present compared with olefinic CN or CC groupings, whereas features at 690 and 980 cm⁻¹ suggest C₃N₃ rings are present as a species inserted in the macromolecular network. Diffraction techniques do not indicate the presence of large polyaromatic species in any of the tholins studied, whatever their nitrogen concentration, in disagreement with certain previous observations. This precludes the idea that the nature and degree of absorption in the visible range is controlled by the size of polyaromatic species, as has been observed in series of carbon-based materials obtained via thermal processing. Infrared spectroscopy analysis of the tholins has confirmed earlier identifications of chemical groups present including primary amines, nitriles, and alkyl moieties such as CH₂/CH₃, but has ruled out CH₂/CH₃ branches appearing on secondary or tertiary amines. Similar analyses were also performed on a polymeric (HCN)_x material, which was found to present several similarities with the tholins, hence suggesting similar polymerization processes.     

Carbon isotopic enrichment in Titan's tholins? Implications for Titan's aerosols

Since the discovery of the main composition of Titan's atmosphere, many laboratory experiments have been carried out to reproduce its chemical evolution, particularly the formation of organic haze particles found throughout this atmosphere. Some of these simulations have produced solid products—referred to as Titan's tholins—that are assumed to have properties similar to those of Titan's aerosols. In the present work, we focus on the possible isotopic fractionation of carbon during the processes involved in the formation of Titan's tholins. Initial ¹²C/¹³C isotopic ratios measured on tholins made in the laboratory using cold plasma discharges are presented. Measurements of isotopic enhancement in ¹³C (δ¹³C), both on tholins and on the initial gas mixture (N₂:CH₄ (98:2)) used to produce them do not show any clear deficit or enrichment in ¹³C relative to ¹²C in the lab-made tholins compared to the initial gas mixture. Preliminary data recovered from the Aerosol Collector Pyrolyzer (ACP) experiment of the Huygens probe suggests that Titan's aerosols may also be exempt of carbon isotopic enrichment. This observation creates possibilities for deeper analysis of ACP experiment data.     

Titan haze distribution and optical properties retrieved from recent observations

The VIMS instrument onboard Cassini observed the north polar region of Titan at 113° phase angle, 28 December 2006. On this spectral image, a vast polar cloud can be seen northward to 62°N, and elsewhere, the haze appears as the dominant source of scattering. Because the surface does not appear in the wavelength range between 0.3 and , this spectro-image is ideal to study airborn scatterers both in methane bands and windows. In this work, we study this image, along with another image taken at 13° phase angle. This image probe both the atmosphere and the surface from pole to pole. First, we characterise the spatial distribution of the haze layer above 100 km between 80°S and 70°N. We find a north south asymmetry with a haze opacity increasing by a factor 3 from the south pole to the equator, then a constant value up to about 30°N and a decrease of a factor 2 between 30°N and about 60°N. Beyond 60°N, we can see the influence of the north polar cloud, even in the band, but no polar haze accumulation. The fact that the north polar region is still in the polar night is a possible explanation. No haze accumulation is observed in the southern polar region. Secondly, we partly identify the origin of spectral features in the 2.8-μm methane window, which are found to be due to deuterated methane (CH₃D). This allows the analyse of this window and to retrieve the opacity of scatterers layer below 80 km (presumably made of aerosols and condensate droplets) between 35°N and 60°N. Finally, we constrained the values and the spectral behaviour of the imaginary part of the aerosol refractive index in the range between 0.3 and . To do so, we studied the 2.8-μm window with the image taken at 113° phase angle. To complete the analysis, we studied the transmission through the haze layer in the 3.4-μm band observed in solar occultation mode with VIMS, and we analysed the single scattering albedo retrieved with DISR instrument between 0.4 and . The imaginary part of the refractive index that we find for Titan aerosols follows Khare et al. (Khare, B.N. et al. [1984]. Icarus 60, 127-137) optical constant up to and becomes constant beyond this wavelength at least up to . It also has a prominent peak at and a secondary peak at , which indicates material rich in C-H bonds, with much less N-H bonds than in Khare et al. (1984) tholins.     

The albedo of Titan

The irradiance of Titan has been measured from 0.50 to 1.08μ in 30 Å band-passes spaced 0.01–0.02μ apart. Geometric albedos have been computed at the wavelenghts of measurement using a standard solar flux distribution after Labs and Neckel. The maximum value of p_λ(0) is 0.37 at 0.68, 0.75, and 0.834μ, the minimum value, in the centers of the strongest methane absorption bands, is 0.10 at 0.887 and 1.012μ.The brightness of Titan at the time of the present measurements has been compared with that of previous modern photoelectric measurements. Within the apparent consistency of the different photoelectric systems, the brightness of Titan appears to undergo changes with time.A provisional curve of the geometric albedo from 0.30 to 4.0μ has been made by combining the present results with those of other authors, i.e., relative measurements of Titan from 0.30 to 0.50μ, and measurements of Jupiter and Saturn from 1.08 to 4.00μ. The latter are used to estimate the strengths of the methane absorption bands of Titan in that spectral range. The bolometric geometric albedo, $\text{p}{}^1\text{(0)}$, is computed to be 0.21. A variety of current measurements of Titan indicate a substantial atmosphere, suggesting a value of the phase integral $\text{q}\text{= 1.30 ± 0.20}$. The bolometric Bond albedo, $\text{A}{}^1$, is then 0.27 ± 0.04, giving an effective radiative temperature T_e= 84 ± 2°K.The absorption band contours of Titan have been compared with those of Jupiter and Saturn at the same resolution. The bands of the planets are known to be due primarily to methane, and they show a very regular relationship, with those of Saturn being consistently deeper and wider. For Titan, the strengths of the bands are equal or less than those of Jupiter in the band centers, while the wings are stronger than those of Saturn.Previous photoelectric and photographic spectra have been examined for evidence of temporal variation of the methane path length in the atmosphere of Titan. Differences in measurement techniques prohibit detection of small differences. The only potential differences beyond experimental uncertainties are those of Kuiper (1944) and Harris (mid-fifties). Taking Kuiper's results at face value, Titan appears to have a shorter methane path length in 1972. Harris's results can be reconciled only by the doubtful hypothesis of an almost complete absence of methane at that time.     

Radar-bright channels on Titan

During Cassini’s T44 flyby of Titan (May 28, 2008), the Cassini SAR (synthetic aperture radar) revealed sinuous channels in the Southwest of Xanadu. These channels feature very large radar cross-sections, up to 5 dB, whereas the angle of incidence was relatively high, ∼20°. This backscatter is larger than allowed by the coherent backscatter model considered to explain the unusual reflective and polarization properties of the icy satellites and only a few radar scattering mechanisms can be responsible for such high radar returns. The presence of rounded (icy) pebbles with size larger than the radar wavelength (2.18 cm) is proposed to explain the large radar cross-sections measured in these units. The radar-bright channels are thus interpreted as riverbeds, where debris, likely shaped and transported by fluvial activity, have been deposited. Similar debris were observed in the landing site of the Huygens probe. This work may point the way to an explanation for the enhanced brightness of other fluvial regions of Titan.