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.     

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.     

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.     

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.     

The composition and origin of Titan's atmosphere

The discovery that Titan had an atmosphere was made by the identification of methane in the satellite's spectrum in 1944. But the abundance of this gas and the identification of other major constituents required the 1980 encounter by the Voyager 1 spacecraft. In the intervening years, traces of C₂H₂, C₂H₄, C₂H₆ and CH₃D had been posited to interpret emission bands in Titan's i.r. spectrum. The Voyager Infra-red Spectrometer confirmed that these gases were present and added seven more. The atmosphere is now known to be composed primarily of molecular nitrogen. But the derived mean molecular weight suggests the presence of a significant amount of some heavier gas, most probably argon. It is shown that this argon must be primordial, and that one can understand the evolution of Titan's atmosphere in terms of degassing of a mixed hydrate dominated by CH₄, N₂ and ³⁶Ar. This model satisfactorily explains the absence of neon and makes no special requirements on the satellite's surface temperature.     

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.     

Photochemical aerosols in Titan's atmosphere

The optical properties of polymers, produced photolytically from ethylene, which was detected in Titan's atmosphere and from acetylene or hydrogen cyanide which may be present there, were studied experimentally. It is shown that an aerosol consisting of polyethylene provides an excellent fit to the variation of Titan's albedo with wavelength, while polymers of acetylene or hydrogen cyanide do not. This fit seems to remove the requirement of nitrogen-bearing polymers, which was proposed earlier to account for Titan's red coloration. Therefore, Titan's coloration does not necessarily imply the presence of nitrogen in its atmosphere. It is also proposed that above the layer of larger aerosol particles, whose scattering determines the phase function, there are smaller particles of the same material, which act as an absorbing haze to darken and slightly redden the underlying aerosol. This high-altitude haze also causes the observed strong limb-darkening.     

Titan aerosols: Optical properties and vertical distribution

An analysis of Titan's solar phase variation as a function of wavelength together with the continuum geometric albedo makes it possible to set limits on the real part of the refractive index and on the average particle size of the aerosol component of Titan's atmosphere: $\text{1.5 ?n}{}_{\mathrm{r}}\text{< 2.0}\text{and}\text{0.20 μm <}\text{r}\text{?0.35 μm}$. If n_ris known $\text{r}$ can be determined to within a few percent, and varies inversely with n_r. Using this information in a two-layer model of a methane-aerosol atmosphere and comparing the result with Titan's visible and near-infrared methane spectrum leads to the conclusion that the top layer of Titan's atmosphere contains 0.01 km atm of methane and 2.5 extinction optical depths of aerosol, while the data are consistent with a bottom layer containing 2.2 km atm of methane and about 7.5 aerosol optical depths for $\text{n}{}_{\mathrm{<mtext>r</mtext>}}\text{= 1.7,}\text{r}\text{= 0.25 μ}\text{m}$.     

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.     

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.     

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.     

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.     

A primordial origin for the atmospheric methane of Saturn’s moon Titan

The origin of Titan’s atmospheric methane is a key issue for understanding the origin of the saturnian satellite system. It has been proposed that serpentinization reactions in Titan’s interior could lead to the formation of the observed methane. Meanwhile, alternative scenarios suggest that methane was incorporated in Titan’s planetesimals before its formation. Here, we point out that serpentinization reactions in Titan’s interior are not able to reproduce the deuterium over hydrogen (D/H) ratio observed at present in methane in its atmosphere, and would require a maximum D/H ratio in Titan’s water ice 30% lower than the value likely acquired by the satellite during its formation, based on Cassini observations at Enceladus. Alternatively, production of methane in Titan’s interior via radiolytic reactions with water can be envisaged but the associated production rates remain uncertain. On the other hand, a mechanism that easily explains the presence of large amounts of methane trapped in Titan in a way consistent with its measured atmospheric D/H ratio is its direct capture in the satellite’s planetesimals at the time of their formation in the solar nebula. In this case, the mass of methane trapped in Titan’s interior can be up to ∼1300 times the current mass of atmospheric methane.     

A Saturnian gas ring and the recycling of Titan's atmosphere

Atoms which escape Titan's atmosphere are unlikely to possess escape velocity from Saturn, and can orbit the planet until lost by ionization or collision with Titan. It is predicted that a toroidal ring of between ～1 and ～10³ atoms or molecules cm^?3 exists around Saturn at a distance of about 10 times the radius of the visible rings. This torus may be detectable from Earth-orbit and detection of nondetection of it may provide some information about the presence or absence of a Saturnian magnetic field, and the exospheric temperature and atmospheric escape rate of Titan. It is estimated that, if Titan has a large exosphere, ～97% or more of the escaping atoms can be recaptured by Titan, thereby decreasing the effective net atmospheric loss rate by up to two orders of magnitude. With such a reduction in atmospheric loss rates, it becomes more plausible to suggest that satellites previously thought too small to retain an atmosphere may have one. It is suggested that Saturn be examined by Lyman-α and other observations to search for the gaseous torus of Titan. If successful, these could then be extended to other satellites.The effect of a hypothetical Saturnian magnetosphere on the atmosphere of Titan is investigated. It is shown that, if Saturn has a magnetic field comparable to Jupiter's (～10 G at the planetary surface), the magnetospheric plasma can supply Titan with hydrogen at a rate comparable to the loss rates in some of the models of Trafton (1972) and Sagan (1973). A major part of the Saturnian ionospheric escape flux (～ 10²⁷ photoelectrons sec^?1) could perhaps be captured by Titan. At the upper limit, this rate of hydrogen input to the satellite could total ～0.1 atm pressure over the lifetime of the solar system, an amount comparable to estimates of the present atmospheric pressure of Titan.     

Erratum

The hot Jovian plasma torus discovered by Voyager 1 is responsible for the periodic intensity variations of Io's sodium cloud, which are correlated with Io's magnetic latitude. The plasma torus must be a long-lived phenomenon in spite of its apparent absence at the time of the Pioneer flybys. The hot electrons (～10⁵°K) must be concentrated ～1 R_J from the magnetic equator in order to produce the observed variations. Electron impact ionization in the hot plasma torus is strong enough to form and to maintain Io's ionosphere; the hot plasma torus may be the dominant agent forming the ionosphere. Io's bound atmosphere is dense enough that the plasma torus electrons cannot cause a noticeable variation in its Na emission intensity.     

Germane in the atmosphere of Jupiter

High-altitude spectra of Jupiter obtained from the Kuiper Airborne Observatory are analyzed for the presence of germane (GeH₄) in Jupiter's atmosphere. Comparison with laboratory spectra shows that the strong Q branch of the ν₃ band of germane at 2111 cm^?1 is prominent in the Jovian spectra. The abundance of germane in Jupiter's atmosphere is 0.006 (±0.003) cm-am corresponding to a mixing ratio of 0.6 ppb. This trace amount of germane is consistent with chemical equilibrium calculations if the germane present at ～1000°K is carried up by convection to the spectroscopically observable region at ～300°K.     

Heavy ion formation in Titan's ionosphere: Magnetospheric introduction of free oxygen and a source of Titan's aerosols?

Discovery by Cassini's plasma instrument of heavy positive and negative ions within Titan's upper atmosphere and ionosphere has advanced our understanding of ion neutral chemistry within Titan's upper atmosphere, primarily composed of molecular nitrogen, with ~2.5% methane. The external energy flux transforms Titan's upper atmosphere and ionosphere into a medium rich in complex hydrocarbons, nitriles and haze particles extending from the surface to 1200 km altitudes. The energy sources are solar UV, solar X-rays, Saturn's magnetospheric ions and electrons, solar wind and shocked magnetosheath ions and electrons, galactic cosmic rays (GCR) and the ablation of incident meteoritic dust from Enceladus’ E-ring and interplanetary medium. Here it is proposed that the heavy atmospheric ions detected in situ by Cassini for heights >950 km, are the likely seed particles for aerosols detected by the Huygens probe for altitudes <100 km. These seed particles may be in the form of polycyclic aromatic hydrocarbons (PAH) containing both carbon and hydrogen atoms C_nH_x. There could also be hollow shells of carbon atoms, such as C₆₀, called fullerenes which contain no hydrogen. The fullerenes may compose a significant fraction of the seed particles with PAHs contributing the rest. As shown by Cassini, the upper atmosphere is bombarded by magnetospheric plasma composed of protons, H₂⁺ and water group ions. The latter provide keV oxygen, hydroxyl and water ions to Titan's upper atmosphere and can become trapped within the fullerene molecules and ions. Pickup keV N₂⁺, N⁺ and CH₄⁺ can also be implanted inside of fullerenes. Attachment of oxygen ions to PAH molecules is uncertain, but following thermalization O+ can interact with abundant CH₄ contributing to the CO and CO₂ observed in Titan's atmosphere. If an exogenic keV O+ ion is implanted into the haze particles, it could become free oxygen within those aerosols that eventually fall onto Titan's surface. The process of freeing oxygen within aerosols could be driven by cosmic ray interactions with aerosols at all heights. This process could drive pre-biotic chemistry within the descending aerosols. Cosmic ray interactions with grains at the surface, including water frost depositing on grains from cryovolcanism, would further add to abundance of trapped free oxygen. Pre-biotic chemistry could arise within surface microcosms of the composite organic-ice grains, in part driven by free oxygen in the presence of organics and any heat sources, thereby raising the astrobiological potential for microscopic equivalents of Darwin's “warm ponds” on Titan.     

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.     

Far-infrared photometry of Titan and Iapetus

Titan was observed in four broad passbands between 35 and 150 μm. The brightness temperature in this interval is roughly constant at 76 ± 3°K. Integrating Titan's spectrum from 5 to 150 μm yields an effective temperature of 86 ± 3°K. Both the bright and dark hemispheres of Iapetus were observed in one broadband filter with λ_e ～ 66 μm. The brightness temperatures for these two sides of Iapetus are 96 ± 9°K and 114 ± 10°K, respectively. The bright-side Bond albedo is calculated to be 0.61_?0.22^+0.16.     

Titan’s atmosphere: An optimal gas mixture for aerosol production?

Here we present the first quantitative study of the gas to solid particle conversion in a Radio Frequency dusty plasma experiment simulating the complex atmospheric reactivity on Titan.Analogs of Titan’s aerosols have been produced in different N₂-CH₄ gas mixtures. Using in situ mass spectrometry, it has been found that, by varying the initial methane concentration, aerosols could be produced in methane steady state concentrations similar to Titan’s atmospheric conditions. In our experiment, an initial ∼5% methane concentration is necessary to ensure a ∼1.5% methane steady state concentration in the plasma.The tholin mass production rate has been quantified as a function of the initial methane concentration. A maximum was found for a steady state CH₄ concentration in agreement with Titan’s atmospheric CH₄ concentrations. At this maximum, the tholin C/N ratio is about 1.45 and the carbon gas to solid conversion yield is about 35%.We have modeled the mass production rate by a parabolic function, highlighting two competitive chemical regimes controlling the tholin production efficiency: an efficient growth process which is proportional to the methane consumption, and an inhibiting process which opposes the growth process and dominates it for initial methane concentrations higher than ∼5%. To explain these two opposite effects, we propose two mechanisms: one involving HCN patterns in the tholins for the growth process, and one involving the increasing amount of atomic hydrogen in the plasma as well as the increase in aliphatic contributions in the tholins for the inhibiting process. This study highlights new routes for understanding the chemical growth of the organic aerosols in Titan’s atmosphere.