Dune-forming winds on Titan and the influence of topography

Numerous extended dunes on Saturn's moon Titan detected by the Cassini RADAR constrain the long-term pattern of surface winds. We analyse the statistics of surface wind speed and direction and their spatial and temporal variability predicted by a general circulation model (GCM) in order to constrain surface wind predictions of this GCM by dune observations. The model shows that modern winds are sufficient for saltation and dune formation at low latitudes, in agreement with the presence of dunes there. The best condition for the dune-forming wind occurs with a threshold friction speed of 0.02 m s⁻¹ or slightly less. The equatorial region is conducive to longitudinal dunes because of a combined effect of a high sand drift potential and obtuse bimodal wind pattern oblique to the equator caused by the seasonal reversal of the Hadley circulation. The cross-equatorial wind is steady, and is characterised by a high Weibull shape parameter (k∼4). The wind pattern at higher latitudes is more complex and gusty, and neither longitudinal nor transversal dunes would be able to form. Putative large-scale topography is found to have a profound influence on the near-surface wind pattern. Generally mountains cause a convergence and speeding up on the flank, while basins weaken the wind and cause a divergent flow. Longitudinal dunes can be deflected on the foot of mountains by up to 90°. If Xanadu is a hypothetical large mountain, a wind pattern converging in Xanadu that entirely disagrees with the dune observations is predicted. If instead Xanadu is a large basin, the wind arcs clockwise north of Xanadu and anti-clockwise west and southwest of Xanadu, in agreement with the dune orientations in the vicinity of Xanadu. The albedo pattern has comparatively little influence on the wind field. Isolated mountain chains cause only local-scale change in the wind pattern. However, the persistent surface easterlies in Belet, which are in conflict with the dune orientations, do not disappear by any combination of large-scale topography.     

Laboratory kinetics of C2H radical reactions with ethane, propane, and n-butane at T = 96-296 K: implications for Titan

The kinetics of the reactions of C₂H radical with ethane (k₁), propane (k₂), and n-butane (k₃) are studied over the temperature range of T = 96-296 K with a pulsed Laval nozzle apparatus that utilizes a pulsed laser photolysis-chemiluminescence technique. The C₂H decay profiles in the presence of both the alkane reactant and O₂ are monitored by the CH(A²Δ) chemiluminescence tracer method. The results, together with available literature data, yield the following Arrhenius expressions: k₁(T) = (0.51 ± 0.06) × 10⁻¹⁰ exp[(−76 ± 30)K/T] cm³ molecule⁻¹ s⁻¹ (T = 96-800 K), k₂(T) = (0.98 ± 0.32) × 10⁻¹⁰exp[(−71 ± 60)K/T] cm³ molecule⁻¹ s⁻¹ (T = 96-361 K), and k₃(T) = (1.23 ± 0.26) × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹ (T = 96-297 K). At T = 296 K, k₁ is measured as a function of total pressure and has little or no pressure dependence. The results from this work support a direct hydrogen abstraction mechanism for the title reactions. Implications to the atmospheric chemistry of Titan are discussed.     

Ground-based measurements of the methane distribution on Titan

Using spectra taken with NIRSPEC (Near Infrared Spectrometer) and adaptive optics on the Keck II telescope, we resolved the latitudinal variation of the 3ν₂ band of CH₃D at 1.56 μm. As CH₃D is less abundant than CH₄ by a factor of 50±10×10^-5, these CH₃D lines do not saturate in Titan’s atmosphere, and are well characterized by laboratory measurements. Thus they do not suffer from the large uncertainties of the CH₄ lines that are weak enough to be unsaturated in Titan. Our measurements of the methane abundance are confined to the latitude range of 32°S-18°N and longitudes sampled by a 0.04″ slit centered at ∼195°W. The methane abundance below 10 km is constant to within 20% in the tropical atmosphere sampled by our observations, consistent with the low surface insolation and lack of surface methane [Griffith, C.A., McKay, C.P., Ferri, F., 2008. Astrophys. J. 687, L41-L44].     

Products of meteoric metal ion chemistry within planetary atmospheres. 1. Mg at Titan

We report results of quantum chemical calculations of Mg⁺/ligand bond dissociation energies involving ligands identified as major constituents of Titan's upper atmosphere. Trends identified in these results allow elucidation of the important bimolecular and termolecular reactions of Mg⁺, and of simple molecular ions containing Mg⁺, arising from meteoric infall into Titan's atmosphere. Our study highlights, and includes calculated rate coefficients for, crucial ligand-switching and ligand-stripping reactions which ensure that a dynamic equilibrium exists between atomic and molecular ions of Mg⁺. Neutralization of ionized meteoric Mg is expected to produce the radical MgNC in high yield. The highly polar MgNC radical should provide an excellent nucleation site for condensation of polar (e.g., HCN, CH₃CN, and HC₃N) and highly unsaturated (e.g., C₂H₂, C₄H₂, and C₂N₂) neutrals at comparatively high altitude, leading to precipitation of Mg-doped tholin-like material. The implications for Titan's prebiotic chemical evolution, of the surface deposition of such material (which may feasibly contain magnesium porphyrins, or other bioactive Mg-containing complexes) remain to be assessed.     

The role of organic haze in Titan's atmospheric chemistry: I. Laboratory investigation on heterogeneous reaction of atomic hydrogen with Titan tholin

In Titan's atmosphere consisting of N₂ and CH₄, large amounts of atomic hydrogen are produced by photochemical reactions during the formation of complex organics. This atomic hydrogen may undergo heterogeneous reactions with organic aerosol in the stratosphere and mesosphere of Titan. In order to investigate both the mechanisms and kinetics of the heterogeneous reactions, atomic deuterium is irradiated onto Titan tholin formed from N₂ and CH₄ gas mixtures at various surface-temperatures of the tholin ranging from 160 to 310 K. The combined analyses of the gas species and the exposed tholin indicate that the interaction mechanisms of atomic deuterium with the tholin are composed of three reactions; (a) abstraction of hydrogen from tholin resulting in gaseous HD formation (HD recombination), (b) addition of D atom into tholin (hydrogenation), and (c) removal of carbon and/or nitrogen (chemical erosion). The reaction probabilities of HD recombination and hydrogenation are obtained as ηabst=1.9(±0.6)×¹⁰⁻³×exp(−300/T) and ηhydro=2.08(±0.64)×exp(−1000/T), respectively. The chemical erosion process is very inefficient under the conditions of temperature range of Titan's stratosphere and mesosphere. Under Titan conditions, the rates of hydrogenation > HD recombination ? chemical erosion. Our measured HD recombination rate is about 10 times (with an uncertainty of a factor of 3-5) the prediction of previous theoretical model. These results imply that organic aerosol can remove atomic hydrogen efficiently from Titan's atmosphere through the heterogeneous reactions and that the presence of aerosol may affect the subsequent organic chemistry.     

Clouds on Titan during the Cassini prime mission: A complete analysis of the VIMS data

We use data from the VIMS instrument on board the Cassini spacecraft to construct high sensitivity and high spatial-resolution maps of the locations of tropospheric clouds on Titan in the late northern winter season during which the Cassini prime mission took place. These observations show that, in this season, clouds on Titan are strongly hemispherically asymmetric. Mid-latitude clouds, in particular, occur only in the southern hemisphere and have not ever been observed in the north. Such an asymmetry is in general agreement with circulation models where sub-solar surface heating controls the locations of clouds and appears in conflict with models where perennial polar hazes prevent significant summertime polar heating from affecting the circulation. The southern mid-latitude clouds appear to be distributed uniformly in longitude, in contrast to some previous observations. Southern high-latitude clouds exhibit a significant concentration, however, between about 180° and 270°E longitude. A spatially and temporally uniform cloud always appears northward of ∼50°N latitude. This cloud appears unchanged over the course of the observations, consistent with the interpretation that it is caused by continuous ethane condensation as air subsides and radiatively cools through the tropopause. The location of this cloud likely provides a direct tracer of elements of north polar atmospheric circulation, potentially allowing continuous monitoring of circulation changes as Titan passes through equinox into north polar spring and summer. We show that a similar analysis of this dataset by Rodriguez et al. (2009) contains substantial errors and should not be used.     

Titan trace gaseous composition from CIRS at the end of the Cassini-Huygens prime mission

This paper reports on the results from an extensive study of all nadir-looking spectra acquired by Cassini/CIRS during the 44 flybys performed in the course of the nominal mission (2004-2008). With respect to the previous study (Coustenis, A., and 24 colleagues [2007]. Icarus 189, 35-62, on flybys TB-T10) we present here a significantly richer dataset with, in particular, more data at high northern and southern latitudes so that the abundances inferred here at these regions are more reliable. Our enhanced high-resolution dataset allows us to infer more precisely the chemical composition of Titan all over the disk. We also include improved spectroscopic data for some molecules and updated temperature profiles. The latitudinal distributions of all of the gaseous species are inferred. We furthermore test vertical distributions essentially for acetylene (C₂H₂) from CIRS limb-inferred data and from current General Circulation Models for Titan and compare our results on all the gaseous abundances with predictions from 1-D photochemical-radiative models to check the reliability of the chemical reactions and pathways.     

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.     

Reflectance spectra and chemical structure of Titan's tholins: Application to the analysis of Cassini-Huygens observations

Titan's tholins are used as analogs of Titan's aerosols and N-rich organic solids present on many icy surfaces. However, it is not clear whether or not they are relevant analogs, and which kind of tholins should be used among a wide set available in literature. This paper presents reflectance spectral data of two tholins selected as end-members of a series of samples covering a very wide range of continuous chemical and optical properties. These samples were formed under experimental conditions fairly consistent with Titan's stratosphere. A general framework for using these laboratory data to the analysis of spectral observation of Titan's surface or other objects is suggested. Furthermore, the study reports the first in situ unambiguous identification of aromatics compounds and evidences variations in the sp² carbon structure, which controls the absorption properties in the visible/NIR. These results also point out it is very unlikely to derive quantitative chemical information (e.g., N content, sp²/sp³ ratio) from remote sensing reflectance data.     

Dunes on Titan observed by Cassini Radar

Thousands of longitudinal dunes have recently been discovered by the Titan Radar Mapper on the surface of Titan. These are found mainly within ±30° of the equator in optically-, near-infrared-, and radar-dark regions, indicating a strong proportion of organics, and cover well over 5% of Titan's surface. Their longitudinal duneform, interactions with topography, and correlation with other aeolian forms indicate a single, dominant wind direction aligned with the dune axis plus lesser, off-axis or seasonally alternating winds. Global compilations of dune orientations reveal the mean wind direction is dominantly eastwards, with regional and local variations where winds are diverted around topographically high features, such as mountain blocks or broad landforms. Global winds may carry sediments from high latitude regions to equatorial regions, where relatively drier conditions prevail, and the particles are reworked into dunes, perhaps on timescales of thousands to tens of thousands of years. On Titan, adequate sediment supply, sufficient wind, and the absence of sediment carriage and trapping by fluids are the dominant factors in the presence of dunes.     

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.     

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.     

The role of organic haze in Titan's atmospheric chemistry: II. Effect of heterogeneous reaction to the hydrogen budget and chemical composition of the atmosphere

One of the key components controlling the chemical composition and climatology of Titan's atmosphere is the removal of reactive atomic hydrogen from the atmosphere. A proposed process of the removal of atomic hydrogen is the heterogeneous reaction with organic aerosol. In this study, we investigate the effect of heterogeneous reactions in Titan's atmospheric chemistry using new measurements of the heterogeneous reaction rate [Sekine, Y., Imanaka, H., Matsui, T., Khare, B.N., Bakes, E.L.O., McKay, C.P., Sugita, S., 2008. Icarus 194, 186-200] in a one-dimensional photochemical model. Our results indicate that 60-75% of the atomic hydrogen in the stratosphere and mesosphere are consumed by the heterogeneous reactions. This result implies that the heterogeneous reactions on the aerosol surface may predominantly remove atomic hydrogen in Titan's stratosphere and mesosphere. The results of our calculation also indicate that a low concentration of atomic hydrogen enhances the concentrations of unsaturated complex organics, such as C₄H₂ and phenyl radical, by more than two orders in magnitude around 400 km in altitude. Such an increase in unsaturated species may induce efficient haze production in Titan's mesosphere and upper stratosphere. These results imply a positive feedback mechanism in haze production in Titan's atmosphere. The increase in haze production would affect the chemical composition of the atmosphere, which might induce further haze production. Such a positive feedback could tend to dampen the loss and supply cycles of CH₄ due to an episodic CH₄ release into Titan's atmosphere.     

Mountains on Titan observed by Cassini Radar

The Cassini Titan Radar mapper has observed elevated blocks and ridge-forming block chains on Saturn's moon Titan demonstrating high topography we term “mountains.” Summit flanks measured from the T3 (February 2005) and T8 (October 2005) flybys have a mean maximum slope of 37° and total elevations up to 1930 m as derived from a shape-from-shading model corrected for the probable effects of image resolution. Mountain peak morphologies and surrounding, diffuse blankets give evidence that erosion has acted upon these features, perhaps in the form of fluvial runoff. Possible formation mechanisms for these mountains include crustal compressional tectonism and upthrusting of blocks, extensional tectonism and formation of horst-and-graben, deposition as blocks of impact ejecta, or dissection and erosion of a preexisting layer of material. All above processes may be at work, given the diversity of geology evident across Titan's surface. Comparisons of mountain and blanket volumes and erosion rate estimates for Titan provide a typical mountain age as young as 20-100 million years.     

Detection of C2HD and the D/H ratio on Titan

We report here the first detection of mono-deuterated acetylene (acetylene-d1, C₂HD) in Titan's atmosphere from the presence of two of its emission bands at 678 and 519 cm⁻¹ as observed in CIRS spectral averages of nadir and limb observations taken between July 2004 and mid-2007. By using new laboratory spectra for this molecule, we were able to derive its abundance at different locations over Titan's disk. We find the C₂HD value () to be roughly constant with latitude from the South to about 45° N and then to increase slightly in the North, as is the case for C₂H₂. Fitting the 678 cm⁻¹ν₅ band simultaneously with the nearby C₂H₂ 729 cm⁻¹ν₅ band, allows us to infer a D/H ratio in acetylene on Titan with an average of the modal values of 2.09±0.45×¹⁰⁻⁴ from the nadir observations, the uncertainties being mainly due to the vertical profile used for the fit of the acetylene band. Although still subject to significant uncertainty, this D/H ratio appears to be significantly larger than the one derived in methane from the CH₃D band (upper limit of 1.5×¹⁰⁻⁴; Bézard, B., Nixon, C.A., Kleiner, I., Jennings, D.E., 2007. Icarus, 191, 397-400; Coustenis, A., Achterberg, R., Conrath, B., Jennings, D., Marten, A., Gautier, D., Bjoraker, G., Nixon, C., Romani, P., Carlson, R., Flasar, M., Samuelson, R.E., Teanby, N., Irwin, P., Bézard, B., Orton, G., Kunde, V., Abbas, M., Courtin, R., Fouchet, Th., Hubert, A., Lellouch, E., Mondellini, J., Taylor, F.W., Vinatier, S., 2007. Icarus 189, 35-62). From the analysis of limb data we infer D/H values of (at 54° S), (at 15° S), (at 54° N) and (at 80° N), which average to a mean value of 1.63±0.27×¹⁰⁻⁴.     

The near-IR spectrum of Titan modeled with an improved methane line list

We have obtained spatially resolved spectra of Titan in the near-infrared J, H and K bands at a resolving power of ∼5000 using the near-infrared integral field spectrometer (NIFS) on the Gemini North 8 m telescope. Using recent data from the Cassini/Huygens mission on the atmospheric composition and surface and aerosol properties, we develop a multiple-scattering radiative transfer model for the Titan atmosphere. The Titan spectrum at these wavelengths is dominated by absorption due to methane with a series of strong absorption band systems separated by window regions where the surface of Titan can be seen. We use a line-by-line approach to derive the methane absorption coefficients. The methane spectrum is only accurately represented in standard line lists down to ∼2.1 μm. However, by making use of recent laboratory data and modeling of the methane spectrum we are able to construct a new line list that can be used down to 1.3 μm. The new line list allows us to generate spectra that are a good match to the observations at all wavelengths longer than 1.3 μm and allow us to model regions, such as the 1.55 μm window that could not be studied usefully with previous line lists such as HITRAN 2008. We point out the importance of the far-wing line shape of strong methane lines in determining the shape of the methane windows. Line shapes with Lorentzian, and sub-Lorentzian regions are needed to match the shape of the windows, but different shape parameters are needed for the 1.55 μm and 2 μm windows. After the methane lines are modeled our observations are sensitive to additional absorptions, and we use the data in the 1.55 μm region to determine a D/H ratio of 1.77 ± 0.20 × 10⁻⁴, and a CO mixing ratio of 50 ± 11 ppmv. In the 2 μm window we detect absorption features that can be identified with the ν₅ + 3ν₆ and 2ν₃ + 2ν₆ bands of CH₃D.     

Influence of neutral transport on ion chemistry uncertainties in Titan ionosphere

Models of Titan ionospheric chemistry have shown that ion densities depend strongly on the neutral composition. The turbulent diffusion transport conditions, as modeled by eddy coefficients, can spectacularly affect the uncertainty on predicted neutral densities. In order to evaluate the error budget on ion densities predicted by photochemical models, we perform uncertainty propagation of neutral densities by Monte Carlo sampling and assess their sensitivity to two turbulent diffusion profiles, corresponding to the extreme profiles at high altitudes described in the literature. A strong sensitivity of the ion density uncertainties to transport is observed, generally more important than to ion–molecule reaction parameters themselves. This highlights the necessity to constrain eddy diffusion profiles for Titan ionosphere, which should progressively be done thanks to the present and future measurements of the orbiter Cassini.     

Meteorological assessment of the surface temperatures on Titan: constraints on the surface type

The latitudinal profile of near-surface air temperature on Titan retrieved by Voyager 1 has been difficult to understand and raised several speculations about possible exotic processes that might be occurring near Titan's surface, while the thermal properties of the surface itself are unknown. This study systematically investigates the seasonal and spatial variation of the surface temperature and air temperature in the lower troposphere by a 3-dimensional general circulation model for different putative surface types (porous icy regolith, rock-ice mixture, hydrocarbon lakes). For any viable surface type the surface temperature is unlikely to be constant through the year and should more or less vary seasonally and even diurnally, most likely by a few K. Recent observations of tropospheric clouds may be evidence of seasonal variation of the surface temperature and the model predicts in the case of solid surface the development of a convective layer with superadiabatic lapse rates near the surface exactly at those latitudes and seasons where clouds have been identified. The latitudinal profile of the surface temperature retrieved from Voyager 1 infrared spectra can be explained without invoking exotic effects, provided the thermal inertia of the surface is relatively small and/or the surface albedo is low. A dominance of water ice (high thermal inertia and high albedo) at the surface is unfavorable to reproduce the observation. The latitudinal gradient of the surface temperature is particularly large at the hydrocarbon lake surface due to low albedo and small surface drag. Local anomalies of the surface albedo or surface thermal inertia are likely to cause substantial inhomogeneities of the surface temperature. Quasi-permanent accumulation of stratospheric haze at both poles would create a perennial equator-to-pole contrast of the surface temperature, but also a substantially lower global-mean surface temperature due to an enhanced anti-greenhouse effect in summer. The air temperature in the lower troposphere exhibits a tiny latitudinal gradient and a pole-to-pole gradient due to the presence of a pole-to-pole Hadley circulation, indicating that the temperature within the planetary boundary layer may exhibit a vertical profile characteristic of season, location and scenario. There may be a shallow near-surface inversion layer in cold seasons and a shallow convective layer in warm seasons.     

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.     

The absence of endogenic methane on Titan and its implications for the origin of atmospheric nitrogen

We calculate the D/H ratio of CH₄ from serpentinization on Titan to determine whether Titan’s atmospheric CH₄ was originally produced inside the giant satellite. This is done by performing equilibrium isotopic fractionation calculations in the CH₄-H₂O-H₂ system, with the assumption that the bulk D/H ratio of the system is equivalent to that of the H₂O in the plume of Enceladus. These calculations show that the D/H ratio of hydrothermally produced CH₄ would be markedly higher than that of atmospheric CH₄ on Titan. The implication is that Titan’s CH₄ is a primordial chemical species that was accreted by the moon during its formation. There are two evolutionary scenarios that are consistent with the apparent absence of endogenic CH₄ in Titan’s atmosphere. The first is that hydrothermal systems capable of making CH₄ never existed on Titan because Titan’s interior has always been too cold. The second is that hydrothermal systems on Titan were sufficiently oxidized so that C existed in them predominately in the form of CO₂. The latter scenario naturally predicts the formation of endogenic N₂, providing a new hypothesis for the origin of Titan’s atmospheric N₂: the hydrothermal oxidation of ¹⁵N-enriched NH₃. A primordial origin for CH₄ and an endogenic origin for N₂ are self-consistent, but both hypotheses need to be tested further by acquiring isotopic data, especially the D/H ratio of CH₄ in comets, and the ¹⁵N/¹⁴N ratio of NH₃ in comets and that of N₂ in one of Enceladus’ plumes.