Near-infrared spectrophotometry of Titan

Detailed analysis of the R(5) manifold of Titan's 3ν₃ CH₄ band confirms that the column abundance of Titan's spectroscopically visible atmosphere is greater than 1.6 kmamagats. This agrees with the value estimated from the strength of Titan's 3ν₃ CH₄Q branch and is at least 25 times the value for the column abundance of Mars' atmosphere. Moreover, the enhanced strength of the weaker CH₄ lines in Titan's spectrum relative to Saturn's spectrum suggests that CH₄ constitutes a significant fraction of this bulk.Recently discovered strong, unidentified absorptions in Titan's spectrum at 1.05–1.06 μm have been compared with laboratory spectra of a number of gases including CH₄, C₂H₄, C₂H₆, and C₃H₈ with negative results. These comparisons, however, have not excluded the possibility that these features arise from a very large quantity of CH₄ or from an isotope of CH₄. The fundamental transition of the responsible molecule may affect the interpretation of Titan's 8–14 μm spectrum since its wavelength may lie in this window. Comparison with Uranus' spectrum suggests that the visible abundance of this molecule in Titan's atmosphere may be much greater than in Uranus' relatively clear, deep atmosphere.Spectra of features at λ8150.7 and λ8272.7 attributed possibly to H₂ have been obtained at high resolution also during the apparitions of 1971, 1972, and 1973. These are presented for comparison with the results of the 1970 apparition. The existence of the λ8150.7 feature is established definitively but further observations are needed to establish whether the λ8272.7 feature exists beyond doubt.     

Chemical reactions in the Titan’s troposphere during lightning

In the lower troposphere of the Titan the temperature is about 90 K, therefore the chemical production of compounds in the CH₄/N₂ atmosphere is extremely slow. However, atmospheric electricity could provide conditions at which chemical reactions are fast. This paper is based on the assumption that there are lightning discharges in the Titan’s lower atmosphere. The temporal temperature profile of a gas parcel after lightning was calculated at the conditions of 10 km above the Titan’s surface. Using this temperature profile, composition of the after-lightning atmosphere was simulated using a detailed chemical kinetic mechanism consisting of 1829 reactions of 185 species. The main reaction paths leading to the products were investigated. The main products of lighting discharges in the Titan’s atmosphere are H₂, HCN, C₂N₂, C₂H₂, C₂H₄, C₂H₆, NH₃ and H₂CN. The annual production of these compounds was estimated in the Titan’s atmosphere.     

On inhomogeneous scattering models of Titan's atmosphere

The spectrum of Titan from 4800 to 11 000 Å has many CH₄ absorption bands which cover a range of intensities of several orders of magnitude. Yet even the strongest of these bands in Titan's spectrum has considerable residual central intensity. Some investigators have concluded that these strong CH₄ bands must be highly saturated, but recent laboratory measurements of the bands made at room temperature show that curve-of-growth saturation is very small. At the presumed low pressures and temperatures in Titan's atmosphere, we show that saturation is very dependent on the band model parameters. However, in either a simple reflecting layer model or in a homogeneous scattering model saturation cannot be the principal cause of the filling in of these strong CH₄ bands if our best estimates of the band model parameters are correct. We find that an inhomogeneous scattering model atmosphere with fine “Axel dust” above most ot the CH₄ gas is needed to fill in the band centers. The calculated spectrum of one particular model of this class is compared to observations of Titan. Our essential conclusion is that Titan does have most of its scattering particles above most of the CH₄ gas which has an abundance of at least 2 km-am. This large abundance of CH₄ is necessary to produce the 6420-Å feature recently discovered in Titan's spectrum.     

Axel dust on Saturn and Titan

The scattering and absorption properties of Axel dust were investigated by means of Mie theory. We find that a flat distribution of particle radii between 0 and 0.1 μm, and an imaginary part of the index of refraction which varies as λ^?2.5 produce a good fit to the variation of Titan's geometric albedo with wavelength (λ) provided that τ_ext, the extinction optical depth of Titan's atmosphere at 5000 Å, is about 10. The real part of the complex index is taken to be 2.0. The model assumes that the mixing ratio of Axel dust to gas is uniform above the surface of Titan. The same set of physical properties for Axel dust also produces a good fit to Saturn's albedo if τ_ext = 0.7 at 5000 Å. To match the increase in albedo shortward of 3500 Å, a clear layer (containing about 7 km-am H₂) is required above the Axel dust. Such a layer is also required to explain the limb brightening in the ultraviolet. These models can be used to analyze the observed equivalent widths of the visible methane bands. The analysis yields an abundance of the order of 1000 m-am CH₄ in Titan's atmosphere. The derived CH₄/H₂ mixing ratio for Saturn is about 3.5 × 10^?3 or an enhancement of about 5 over the solar ratio.     

The abundance of CH3D in the atmosphere of Titan,derived from 8- to 14-μm thermal emission

The 8.6-μm emission feature of Titan's infrared spectrum was analyzed using the Voyager temperature-pressure profile. Although both C₃H₈ and CH₃D have bands at that wavelength, we show that CH₃D dominates the observed emission on Titan. We derived a CH₃D/CH₄ mixing ratio using this band and the strong CH₄ band at 7.7 μm. The corresponding D/H ratio is 4.2_?1.5⁺² × 10^?4, neglecting deuterium fractionation with other molecules. The main uncertainty in this value comes from the continuum emission characteristics. The D/H ratio is apparently significantly enhanced on Titan with respect to published values for Saturn.     

Titan: Far-infrared and microwave remote sensing of methane clouds and organic haze

It is shown that Titan's surface and plausible atmospheric thermal opacity sources—gaseous N₂, CH₄, and H₂, CH₄ cloud, and organic haze—are sufficient to match available Earth-based and Voyager observations of Titan's thermal emission spectrum. Dominant sources of thermal emission are the surface for wavelenghts λ ? 1 cm, atmospheric N₂ for 1 cm ? λ ? 200 μm,, condensed and gaseous CH₄ for 200 μm ? λ ? 20 μm, and molecular bands and organic haze for λ ? 20 μm. Matching computed spectra to the observed Voyager IRIS spectra at 7.3 and 52.7° emission angles yields the following abundances and locations of opacity sources: CH₄ clouds: 0.1 g cm^? at a planetocentric radius of 2610–2625 km, 0.3 g cm^?2 at 2590–2610 km, total 0.4 ± 0.1 g cm^–2 above 2590 km; organic haze: $\text{4 ± 2 × 10}{}^{\mathrm{?6}}\text{,}\text{g cm}\text{,}{}^{\mathrm{?2}}$ above 2750 km; tropospheric H₂: 0.3 ± 0.1 mol%. This is the first quantitative estimate of the column density of condensed methane (or CH₄/C₂H₆) on Titan. Maximum transparency in the middle to far IR occurs at 19 μm where the atmospheric vertical absorption optical depth is $\text{?0.6}$ A particle radius $\text{r}\text{? 2 μ}\text{m}$ in the upper portion of the CH₄ cloud is indicated by the apparent absence of scattering effects.     

Chemistry and evolution of Titan's atmosphere

The chemistry and evolution of Titan's atmosphere is reviewed in the light of the scientific findings from the Voyager mission. It is argued that the present N₂ atmosphere may be Titan's initial atmosphere rather than photochemically derived from an original NH₃ atmosphere. The escape rate of hydrogen from Titan is controlled by photochemical production from hydrocarbons. CH₄ is irreversibly converted to less hydrogen rich hydrocarbons, which over geologic time accumulate on the surface to a layer thickness of ～0.5 km. Magnetospheric electrons interacting with Titan's exosphere may dissociate enough N₂ into hot, escaping N atoms to remove ～0.2 of Titan's present atmosphere over geologic time. The energy dissipation of magnetospheric electrons exceeds solar e.u.v. energy deposition in Titan's atmosphere by an order of magnitude and is the principal driver of nitrogen photochemistry. The environmental conditions in Titan's upper atmosphere are favorable to building up complex molecules, particularly in the north polar cap region.     

Measured ion-molecule reaction rates for modelling Titan's atmosphere

Rate coefficients for several two- and three-body ion-molecule reactions involving hydrocarbons have been determined at thermal energies and above using drift tube-mass spectrometer techniques. The measured rates for clustering and breakup reactions involving CH₅⁺ and C₂H₅⁺ ions in methane are found to be strongly temperature dependent in the range from 80 to 240 K. The equilibrium constants determined for these reactions differ somewhat from those of Hiraoka and Kebarle. Rate coefficients for two-body reactions of CH₅⁺, C₂H₅⁺, N⁺, H⁺ and D⁺ ions with methane and/or ethane have been measured. The results indicate that the product yields of several of the fast ion-molecule reactions depend strongly on ion energy (temperature), and therefore previous room-temperature results may be of limited value for model calculations of Titan's atmosphere.     

Sounding of Titan’s atmosphere at submillimeter wavelengths from an orbiting spacecraft

An investigation of the capabilities and science goals of a submillimeter-wave heterodyne sounder onboard a Titan orbiter is presented. Based on a model of Titan’s submillimeter spectrum, and including realistic instrumental performances, we show that passive limb observations of Titan’s submillimeter radiation would bring novel and unique information on the dynamical and chemical state of Titan’s atmosphere, particularly in the so far poorly probed 500-900 km region. The 300-360, 540-660 and 1080-1280 GHz spectral ranges appear especially promising, and could be explored with an instrument equipped with a tunable local oscillator system. Vertical temperature profiles can be determined up to ∼1200 km using rotational lines of CH₄, CO, and HCN. Winds can be measured over the 200-1200 km altitude range with an accuracy of 3-5 m/s from Doppler shift measurements of any strong optically thin line. Numerous molecular species are accessible, including H₂O, NH₃, CH₃C₂H, CH₂NH, and several nitriles (HC₃N, HC₅N, CH₃CN, and C₂H₃CN). Many of them are expected to be detectable in a large fraction of the atmosphere and in some cases at all levels, providing an observational link between stratospheric and thermospheric chemistry. Isotopic variants of some of these species can also be measured, providing new measurements of H, C, N, and O isotopic ratios. Mapping of the thermal, wind, and composition fields, best achieved from a polar orbit and with an articulated antenna, would provide a new view of the couplings between chemistry and dynamics over an extended altitude range of Titan’s atmosphere. Additional science goals at Saturn and Enceladus are briefly discussed.     

The spectrum of titan in the far-infrared and microwave regions

The pressure-induced absorptions of gaseous nitrogen (N₂) and methane (CH₄) are computed on the basis of the collisional lineshape theory of G. Birnhaum and E.R. Cohen [Canad. J. Phys.54, 593–602 (1976)]. Laboratory data at 300 and 124°K for N₂ and at 296 and 195°K for CH₄ are used to determine the collisional time constant and their temperature dependence. The spectrum of Titan from the microwave to the far-infrared region (0.1–600 cm^?1) is then modeled using these opacities and a temperature profile of Titan's atmosphere derived from the Voyager 1 radio occultation experiment. The model atmosphere is composed of N₂ and CH₄, their relative proportions being determined by the vapor pressure law of CH₄. A model with gaseous opacity alone is ruled out by the far-infrared observations. An additional opacity, thought to be associated with a methane cloud, is confirmed. The effective temperature of Titan is estimated at T_e = 83.2 ± 1.4°K.     

Infrared polar brightening on Jupiter: III. Spectrometry from the Voyager 1 IRIS experiment

Spectra from the Voyager 1 IRIS experiment confirm the existence of enhanced infrared emission near Jupiter's north magnetic pole in March 1979. The spectral characteristics of the enhanced emission are consistent with a Planck source function. A temperature-pressure profile is derived for the region near the north magnetic pole, from which quantitative abundance estimates of minor species are made. Some species previously detected on Jupiter, including CH₃D, C₂H₂ and C₂H₆, have been observed again near the pole. Newly discovered species, not previously observed on Jupiter, include C₂H₄, C₃H₄, and C₆H₆. All of these species except CH₃D appear to have enhanced abundances at the north polar region with respect to midlatitudes. Upper limits are determined for C₄H₂ and C₃H₈. The quantitative results are compared with model calculations based on ultraviolet results from the IUE satellite. The plausibility of the C₆H₆ identification in discussed in terms of the literature on C₂H₂ polymerization. The relation of C₆H₆ to cuprene is also discussed.     

Titan’s atmosphere from ISO mid-infrared spectroscopy

We have analyzed Titan observations performed by the Infrared Space Observatory (ISO) in the range 7-30 μm. The spectra obtained by three of the instruments on board the mission (the short wavelength spectrometer, the photometer, and the camera) were combined to provide new and more precise thermal and compositional knowledge of Titan’s stratosphere. With the high spectral resolution achieved by the SWS (much higher than that of the Voyager 1 IRIS spectrometer), we were able to detect and separate the contributions of most of the atmospheric gases present on Titan and to determine disk-averaged mole fractions. We have also tested existing vertical distributions for C₂H₂, HCN, C₂H₆, and CO₂ and inferred some information on the abundance of the first species as a function of altitude. From the CH₃D band at 1161 cm⁻¹ and for a CH₄ mole fraction assumed to be 1.9% in Titan’s stratosphere, we have obtained the monodeuterated methane-averaged abundance and retrieved a D/H isotopic ratio of 8.7−1.9+3.2 × 10⁻⁵. We discuss the implications of this value with respect to current evolutionary scenarios for Titan. The ν₅ band of HC₃N at 663 cm⁻¹ was observed for the first time in a disk-averaged spectrum. We have also obtained a first tentative detection of benzene at 674 cm⁻¹, where the fit of the ISO/SWS spectrum at R = 1980 is significantly improved when a constant mean mole fraction of 4 × 10⁻¹⁰ of C₆H₆ is incorporated into the atmospheric model. This corresponds to a column density of ∼ 2 × 10¹⁵ molecules cm⁻² above the 30-mbar level. We have also tested available vertical profiles for HC₃N and C₆H₆ and adjusted them to fit the data. Finally, we have inferred upper limits of a few 10⁻¹⁰ for a number of molecules proposed as likely candidates on Titan (such as allene, acetonitrile, propionitrile, and other more complex gases).     

Ultraviolet reflectivity and geometrical albedo of Titan

Intermediate resolution (6Å) photoelectric spectral scans of Titan, Saturn, Saturn's Rings and the Moon appear in two forms: ratio spectra of Titan vs the Rings and of Saturn vs the Rings, and relative reflectivities, which are compared to previously published results. Titan's geometrical albedo of 0.094 ± 0.012 was measured at 4255Å with a 50Å bandpass. From this and the spectral measurements, we derived the geometrical albedo as a function of wavelength. We find that the wavelength dependences of Titan's uv spectrum and the spectrum of Saturn's Rings are remarkably similar. No trace of any absorption bands is apparent. These results imply that uv gaseous absorption and Rayleigh scattering play a strongly subdued role in Titan's atmosphere. Any homogeneous atmospheric model implies that the absorber responsible for Titan's uv spectral albedo varies strongly with wavelength. On the other hand, we find that the uv observations can be satisfied by an absorber having a relatively weak dependence upon wavelength if an inhomogeneous atmospheric model is employed. In particular, a fine dust, which absorbs as 1/λ, can explain the uv observations provided that it is preferentially distributed high up in Titan's atmosphere where the optical depth from Rayleigh scattering is low. The likely presence of such a dust in Jupiter's atmosphere and the difficulty in explaining the nature of a continuous uv absorber which varies rapidly with wavelength suggest that the gas and aerosol in Titan's atmosphere are inhomogeneously distributed.     

Nitrile gas chemistry in Titan’s atmosphere

This work presents the first study of the gaseous products resulting from the partial dissociation of methane and nitrogen in the PAMPRE experimental setup simulating Titan’s atmospheric chemistry.Using cryogenic trapping, the gaseous products generated from the chemical reactions occurring in the reactor have been trapped. Analyses of these products by gas chromatography coupled to mass spectrometry have allowed the detection and identification of more than 30 reaction products. Most of them are identified as nitrile species, accompanied by aliphatic hydrocarbons and a few aromatics compounds. The observed species are in agreement with the data from the recent Cassini-Huygens mission as well as from other laboratory setups capable of dissociating nitrogen and methane. This work emphasizes the probable importance of nitrogen-bearing compounds in the chemistry taking place in Titan’s atmosphere.Furthermore, a quantification of mono-nitriles with saturated alkyl chains has been performed relatively to hydrogen cyanide and shows a power law dependence in their concentration. This dependence is consistent with the Cassini-INMS data and Titan’s photochemical models.An empirical relationship has been extracted from our experimental data: [C_xH_2x−1N] = 100x⁻⁵, where x is the number of carbon atoms in the nitrile molecule. This relationship can be directly used in order to foretell the concentration of heavier nitriles induced by chemistry in Titan’s atmosphere.     

A seasonal climate model of the atmospheres of the giant planets at the voyager encounter time: I. Saturn's stratosphere

A radiative seasonal model which incorporates a multilayer radiative transfer treatment at wave-lengths longward of 7 μm is presented and applied to Saturn's stratosphere. Opacities due to H₂-He, CH₄, C₂H₂, and C₂H₆ are included. Season-dependent insolation is shown to produce a strong hemispheric asymmetry decreasing with depth at the Voyager encounter times, and seasonal amplitudes of 30°K at the poles are predicted in the high stratosphere. The ring-modulated dependence of the insolation and the orbital eccentricity are shown to have a significant effect. Calculations agree closely with the Voyager 1 and 2 radio occultation ingress profiles recorded at 76°S and 36.5°S for CH₄/H₂ = 3.5 + 1.4/? 1.0 × 10^?3;the estimated errors include modeling systematic errors and uncertainties in the occultations profiles. The possible role of aerosols in the stratospheric heating is analyzed. The Voyager 2 egress profile recorded at 31°S cannot be reproduced by calculations. Some constraints on the C₂H₂ and C₂H₆ abundances are derived. The upper portion of the occultation profiles (p < 3mbar) can be matched for C₂H₂/H₂ = 1.0 + 1.3/?0.6 × 10^?7, C₂H₆/H₂ = 1.5 + 1.8/?0.9 × 10^?6 at 76°S and C₂H₂/H₂ = 4 + 6/?4 × 10^?8, C₂H₆/H₂ = 6 + 9/?6 × 10^?7 at 36.5°N. At the northern occultation latitude, the discrepancy with the concentrations derived from analysis of IRIS spectra by R. Courtin, D. Gautier, A. Marten, B. Bézard, and R. Hanel (1984, Astrophys. J.287) can be explained by a sharp variation of the mixing ratios of these gases with altitude in the upper stratosphere. Other interpretations are discussed.     

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.     

Condensed species in Titan's atmosphere: Identification of crystalline propionitrile (C2H5CN, CH3CH2CN) based on laboratory infrared data

We report the results of infrared studies of crystalline C₂H₅CN at several temperatures between 15 and 160 K. A case is made for the identification of crystalline C₂H₅CN in the stratosphere from the Voyager IRIS spectrum of Titan.     

The role of photochemical processes in evolution of the isotopic composition of the atmosphere of Titan

Molecular nitrogen, the main component of the modern atmosphere of Titan, may have formed without significant changes in the nitrogen and hydrogen isotopic composition from the clathrate hydrate of ammonia NH₃ · H₂O_SLD, which is the main accreted form of nitrogen. The most preferable transformation mechanism of NH₃ · H₂O_SLD into atmospheric N₂ is its thermal decomposition in the interior of Titan rather than the photochemical decomposition of ammonia in the upper atmosphere of early Titan. The photolysis of ammonia does not lead to a change in the isotopic composition of nitrogen, as all the nitrogen remains in Titan’s atmosphere. The photolysis of NH does not lead to a change in the isotopic composition of nitrogen in Titan’s atmosphere. Fractionation of hydrogen and nitrogen isotopes during the impacts of comets with Titan does not seem to be significant either. It will be possible to determine the dissociative fractionation factor, the original ratio ¹⁴N/¹⁵N, and the mass of Titan’s original atmosphere when fractionation of nitrogen isotopes in Titan’s atmosphere is examined in additional theoretical and experimental studies that take into account processes occurring during the formation of a system of Saturn’s satellites.     

Constraints on bulk composition,seasonal variation,and global dynamics of Pluto's atmosphere

Cosmic abundance, vapor pressure, and molecular weight considerations restrict the likely gas candidates for Pluto's atmosphere to Ne, N₂, CO, O₂, and Ar, in addition to the already detected CH₄. The vapor pressures and cosmic abundances of these gases indicate that all except Ne should be saturated in Pluto's atmosphere. The vapor pressure of Ne is so high that the existence of solid or liquid Ne on Pluto's surface is very unlikely; cosmic abundance arguments imply that Ne cannot attain saturation in Pluto's atmosphere. At both perihelion, N₂ should dominate the saturated gases. CO₂ should have the next highest mixing ratio, followed by O₂ and Ar. CH₄ should have the smallest mixing ratio. Because vapor pressures of these gases vary with temperature at diverse rates, the bulk and constituent mixing ratios of Pluto's atmosphere should vary with season. Between perihelion and aphelion, the column abundance of CH₄ may change by a factor of 260 while that of N₂ changes by only a factor of 52. The potential seasonal variation of Pluto's atmosphere was investigated by considering the behavior of these gases when individually mixed with CH₄. The effects of diurnal and latitudinal variation of insolation and eclipses on the atmosphere also were investigated. Seasonal effects are shown to dominate. It was shown that the atmospheric bulk may not be a minimum near aphelion but rather at intermediate distances from the Sun during summer/winter inadequate ice deposits may allow the atmosphere to collapse by freezing out over winter latitudes. If the atmosphere does not collapse, its weight is sufficient to keep it distributed uniformly around Pluto's surface. In this case, the atmosphere tends to regulate the surface temperature to a seasonally dependent value which is uniform over the globe.Finally, the likely global circulation regimes for each model atmosphere as a function of temperature were investigated and it was concluded that if CH₄, O₂, or CO dominates the atmosphere, Pluto will exhibit cyclic variations between an axially symmetric circulation system at perihelion and a baroclinic wave regime at aphelion. However, if N₂ dominates, as is likely, the wave regime should hold continuously. If the atmosphere collapses to a thin halo during summer/winter seasons, only a weak, symmetric circulation should occur.     

CH4/N2/H2-spark hydrophobic tholins: A systematic approach to the characterisation of tholins. Part II

Two different simulation experiments of prebiotic synthesis were carried out in a CH₄/N₂/H₂ atmosphere with spark discharge activation of aqueous aerosols and liquid water. In both cases, a hydrophilic tholin and a hydrophobic tholin were obtained. The methodology developed by our group for the characterisation of hydrophilic tholins [Ruiz-Bermejo, M., Menor-Salván, C., Mateo-Martí, E., Osuna-Esteban, S., Martín-Gago, J.A., Veintemillas-Verdaguer, S., 2008. Icarus 198, 232-241] was used in order to study the hydrophobic tholins. The gas precursors of the tholins from mixtures containing CH₄, with and without H₂, were studied. We propose that the formation of the hydrophobic tholins involves the formation of unsaturated oligomeric hydrocarbon chains from vinyl and acetylene monomers, as well as allene derivatives formed in the gas phase after the incorporation of polar groups into these hydrocarbon chains. Finally, we compare our results concerning hydrophobic tholins with HCN polymers, since it is generally suggested that the polymeric material formed in spark experiments are possible oligomers of HCN, and that Titan’s tholins could be poly-HCN.