The atmosphere of Titan

A summary is given of our current knowledge of Titan's atmosphere, based on the report of the 1973 Titan Atmosphere Workshop.     

An inversion in the atmosphere of Titan

It is proposed that a large temperature inversion exists in the atmosphere of Titan due to absorption of solar radiation by small “dust” particles. A very simplified preliminary analysis indicates that this inversion model can expain the high infrared brightness temperatures in the absence of a greenhouse effect.     

An update of nitrile photochemistry on Titan

New chemical schemes leading to the formation of cyanogen (C2N2) and dicyanoacetylene (C4N2) in the upper atmosphere of Titan are proposed and examined in light of recent laboratory kinetics experiments and Voyager observations.     

Phosphine photochemistry in the atmosphere of Saturn

A model is presented for the photochemistry of PH₃ in the upper troposphere and lower stratosphere of Saturn that includes the effects of coupling with NH₃ and hydrocarbon photochemistry, specifically the C₂H₂ catalyzed photodissociation of CH₄. PH₃ is rapidly depleted with altitude (scale height ～35 km) in the upper troposphere when K～10⁴cm²sec^?1; an upper limit for K at the tropopause is estimated at ～10⁵cm²sec^?1. If there is no gas phase P₂H₄ because of sublimation, P₂ and P₄ formation is unlikely unless the rate of the spin-forbidden recombination reaction PH + H₂ + M → PH₃ + M is exceedingly slow. An upper limit P₄ column density of ～2×10¹⁵cm^?2 is estimated in the limit of no recombination. If sublimation does not remove all gas phase P₂H₄, P₂ and P₄ may be produced in potentially larger quantities, although they would be restricted almost entirely to the lowest levels of our model, where T?100°K. Potentially observable amounts of the organophosphorus compounds CH₃P₂H₂ and HCP are predicted, with column densities of >10¹⁷ cm^?2 and production rates of ～2×10⁸cm^?2sec^?1. The possible importance of electronically excited states of PH_x and additional PH₃/hydrocarbon photochemical coupling paths are also considered.     

High-altitude charged aerosols in the atmosphere of Titan

Observations by several instruments onboard the Cassini spacecraft revealed the existence of heavy hydrocarbon and nitrile species with masses of several thousand atomic mass units in the ionosphere of Titan. These very large molecules are in fact aerosols. The goal of this paper is to compute the concentrations of the charged aerosols in the upper atmosphere (950-1200 km) of Titan. The charging of these aerosols has been studied using the charge balance equations, where positive ions, negative ions, electrons, neutral and charged aerosols are included. Number concentrations of charged aerosols are compared with those observed by the Cassini instruments. The present work estimates the aerosol mass density as 1-10 kg/m³, which is within the predicted range. The results show that the aerosols must be smaller than 10 nm in order to have reasonable agreement with observations by the Cassini Plasma Spectrometer.     

Hydrocarbon photochemistry in the upper atmosphere of Jupiter

The hydrocarbon photochemistry in the upper atmosphere of Jupiter is investigated using a one-dimensional, photochemical-diffusive, and diurnally averaged model. The important chemical cycles and pathways among the major species are outlined and a standard model for the North Equatorial Belt region is examined in detail. It is found that several traditionally dominant chemical pathways among the C and C2 species are replaced in importance by cycles involving C-C4 species. The pressure and altitude profiles of mixing ratios for several observable hydrocarbon species are compared with available ultraviolet- and infrared-derived abundances. The results of sensitivity studies on the standard model with respect to variations in eddy diffusion profile, solar flux, atomic hydrogen influx, latitude, temperature, and important chemical reaction rates are presented. Measured and calculated airglow emissions of He at 584 angstroms and H at 1216 angstroms are also used to provide some constraints on the range of model parameters. The relevance of the model results to the upcoming Galileo mission is briefly discussed. The model is subject to considerable improvement; there is a great need for laboratory measurements of basic reaction rates and photodissociation quantum yields, even for such simple species as methylacetylene and allene. Until such laboratory measurements exist there will be considerable uncertainty in the understanding of the C3 and higher hydrocarbons in the atmospheres of the jovian planets.     

The photochemistry and dynamics of a dusty cometary atmosphere

A self-consistent solution of the dynamical and thermal structure of an H₂O-dominated, two-phase, dusty-gas cometary atmosphere has been obtained by solving the simultaneous set of differential equations representing conservation of number density, momentum and energy together with the transfer of solar radiation in the streams responsible for the major photolytic processes and the heating of the nucleus. The validity of the model is restricted to the collision-dominated region where all the gas species are assumed to attain a common velocity and common temperature. Two models are considered for the transfer of solar radiation through the circum-nuclear dust halo. In the first only the direct extinction by the dust is considered. In the second, the finding of some recent models, that the diffuse radiation field due to multiple scattering by the dust halo more or less compensates for radiation removed by direct absorption when the optical depth is near unity, is approximated by neglecting the attenuation of the radiation by the dust altogether.As has been shown earlier, the presence of dust results in a transonic solution, and it is obtained by a two-step iterative procedure which makes use of the asymptotic behaviour of the radiation fields sufficiently far from the nucleus and a regularity condition at the sonic point.The calculations were performed for a medium sized comet (R _n =2.5 km) having a dust to gas production rate ratio of unity, at a heliocentric distance of 1 AU. The dust grains were assumed to be of the same radius (1), of low density (1g cm^–3) and be strongly absorbing (having the optical properties of magnetite).The main effect of the dust on the cometary atmosphere is dynamic. While the dust-gas coupling persists to about 20R _n , the strong throat effect of the dust friction on the gas causes the latter to go supersonic quite rapidly. Consequently the sub-sonic region around the nucleus is very thin, varying between 45 and 85m in the two models considered. On the other hand, while this highly absorbing dust has a temperature substantially above that of the gas in the inner coma, heat exchange between them does not significantly change the temperature profile of the gas. This is because of the predominance of the expansion cooling, and even more importantly, the IR-cooling by H₂O, in the inner coma. Consequently, the gas temperature goes through a strong inversion, as in the dust-free case, achieving a temperature as low as about 6K within about 50km of the nucleus, before increasing to about 700K atr=10⁴km, due to the high efficiency of photolytic heating over the cooling process in the outer coma. The Mach number achieves a maximum value of about 10 at the distance of the temperature minimum, thereafter steadily decreasing to a value of about 2.5 atr10⁴km.It is shown that while the dust attenuation has a strong effect on the production rate of H₂O, it also has an interesting effect on the electron density profile. It increases the electron density in the inner coma over the unattenuated case, while at the same time, decreasing it in the outer coma. In conclusion, the limitations of the present model and the necessity to extend it using a multi-fluid approach are discussed.     

Ozone and photochemistry of the Martian lower atmosphere

The calculation of number densities of CO₂, H₂O and N₂ photolysis products was carried out for the Martian atmosphere at heights up to 60 km. The ozone distributed in the atmosphere as a layer of 10 km width with [O₃] max = 2.5 × 10⁹ cm³ at height of 35 km which agree well with the results of u.v. observations on the evening terminator from the Mars-5 satellite. The calculated densities of O₂, CO and H₂O are also in good agreement with the measured data. The eddy diffusion coefficient is equal to 3 × 10⁶ in the troposphere (h ? 30 km) and 10⁸ cm² s^?1 above 40 km. The dependence of the total ozone content on water vapour amount in the atmosphere is considered; the hypothesis about the influence of water ice aerosol on the ozone formation is proposed to explain the high concentrations of ozone in the morning.     

Key reactions in the photochemistry of hydrocarbons in Neptune's stratosphere

We studied the propagation of uncertainties carried by the reaction rate coefficients in the photochemistry of Neptune's stratosphere. We showed that the uncertainties on the mole fractions of main hydrocarbons are equal to or larger than the estimated uncertainties on abundances gathered from observations. From a global sensitivity analysis study, we determined a list of 26 key reactions and discussed the 7 main key reactions that should be studied in priority to lower the uncertainties in the mole fractions computed from a photochemical model. This methodology is essential to improve the predictivity of photochemical models and, consequently, to better understand the physical and chemical processes that govern the composition of giant planet atmospheres.     

Polycyclic aromatic hydrocarbons in the atmospheres of Titan and Jupiter

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

Ionization by cosmic rays of the atmosphere of Titan

Cosmic ray radiation is the main mechanism for ionizing the lower atmosphere of Titan. Their higher penetration power, in comparison with solar photons, allows cosmic rays to penetrate deep into the atmosphere of Titan, ionizing the neutral molecules and generating an ionosphere with an electron density peak, placed at around 90 km, similar in magnitude to the ionospheric peak produced by solar radiation in the upper atmosphere. In the lower atmosphere, the electron density profile, in the absence of a magnetic field, depends mainly on the modulation of cosmic rays by the solar wind and on the nature of the ionizable particles. We present here the first results of a new numerical model developed to calculate the concentration of electrons and most abundant ions in the Titan lower atmosphere. The present knowledge of Titan’s atmosphere permits us to include new neutral and ionic species, such as oxygen derivates, in a more detailed ion-chemistry calculation than previous lower ionospheric models of Titan. The electron density peaks at 90 km with a magnitude of 2150 cm⁻³. The ion distribution obtained predicts that cluster cations and hydrocarbon cations are the most abundant ions below and above the electron density peak, respectively. We also discuss the effect of solar activity at the distance of the Saturn orbit on the spectrum of the cosmic particles. We obtain that from solar minimum to solar maximum the ionization rate at the energy deposition peak changes by a factor of 1.2 at 70 km, and by a factor of 2.6 at altitudes as high as 400 km. The electron density at the concentration peak changes by a factor of 1.1 at 90 km, and by a factor of 1.6 at 400 km.     

Infrared observations of the surface and atmosphere of Titan

Infrared photometry of Titan, Saturn, and Saturn's Rings at 3.5, 4.9, 17.8, and 18.4 μm is reported. Comparison of the albedo of Titan in the 4.9 μm “window” with the albedo of the rings and with laboratory spectra suggests that frost, possibly water ice, could be a major constituent. If thick clouds are present they must be very dark at 4.9 μm. The 17.8 and 18.4 μm data are not consistent with a clear, dense molecular hydrogen atmosphere.     

Estimates of quasipolar absorption by methane in the atmosphere of Titan

The basis for “quasipolar” absorption (QPA) by CH₄ is the existence of a small electric dipole moment in its ground state. The integrated intensity α_QPA at a temperature of 90K is calculated to be between 4.8 × 10^?5 and 1.9 × 10^?2 cm^?2 atm^?1. With an assumed mean pressure of 0.1 atm and a relative abundance of $\text{[}\text{CH}{}_4\text{]}\text{[}\text{H}{}_2\text{]}\text{= 1}$, it is estimated that the ratio of quasipolar to pressure-induced absorption (PIA) is 0.05 ? α_QPA/α_PIA ? 18 for the spectral range from 0 to 300 cm^?1. This result suggests that quasipolar absorption may contribute to a weak, CH₄-induced greenhouse in the atmosphere of Titan.     

Production and condensation of organic gases in the atmosphere of Titan

The rates and altitudes for the dissociation of atmospheric constituents of Titan are calculated for solar UV, solar wind protons, interplanetary electrons, Saturn magnetospheric particles, and cosmic rays. The resulting integrated synthesis rates of organic products range from 10²–10³ g cm^?2 over 4.5 × 10⁹ years for high-energy particle sources to 1.3 × 10⁴ g cm^?2 for UV at $\text{λ < 1550}\text{A}\text{?}$, and to 5.0 × 10⁵ g cm^?2 if $\text{λ > 1550}\text{A}\text{?}$ (acting primarily on C₂H₂, C₂H₄, and C₄H₂) is included. The production rate curves show no localized maxima corresponding to observed altitudes of Titan's hazes and clouds. For simple to moderately complex organic gases in the Titanian atmosphere, condensation occurs below the top of the main cloud deck at 2825 km. Such condensates comprise the principal cloud mass, with molecules of greater complexity condensing at higher altitudes. The scattering optical depths of the condensates of molecules produced in the Titanian mesosphere are as great as ～ 10²/(particulate radius, μm) if column densities of condensed and gas phases are comparable. Visible condensation hazes of more complex organic compounds may occur at altitudes up to ～ 3060 km provided only that the abundance of organic products declines with molecular mass no faster than laboratory experiments indicate. Typical organics condensing at 2900 km have molecular masses = 100–150 Da. At current rates of production the integrated depth of precipitated organic liquids, ices, and tholins produced over 4.5 × 10⁹ years ranges from a minimum ～ 100 m to kilometers if UV at $\text{λ > 1550}\text{A}\text{?}$ is important. The organic nitrogen content of this layer is expected to be ～ 10^?1?10^?3 by mass.     

The effect of a dense atmosphere on the tidally induced potential of Titan

The effect of the dense atmosphere of Titan on the tidal variations of the external gravitational potential of degree two is quantified. The atmospheric tides perturb the external gravitational potential of Titan in two ways. First, the atmosphere itself contributes directly to the external gravitational potential with a period of 15.945 days. Second, the variable loading of the atmosphere induces mass redistribution within Titan, which also changes the external gravitational potential. It is shown that the relative atmospheric contributions to the tides are most likely less than 2% and vanish almost completely for the most plausible models with a subsurface ocean. This suggest that atmospheric tidal perturbations will contribute only negligibly to Cassini measurements of Titan's gravitational field so that the tidal Love numbers derived from these observations can be directly interpreted in terms of the satellite's interior.     

Experimental and theoretical study of hydrocarbon photochemistry applied to Titan stratosphere

None of the Titan photochemical models currently available have been able to reproduce the full set of stratospheric molecular mixing ratios inferred from observations. In order to assess how well reaction sets describe hydrocarbon chemistry, theoretical modeling predictions were compared to the results of a laboratory experiment. A CH₄-C₂H₂ mixture was irradiated at 185 nm in an atmospheric simulation chamber and the evolution of the gas mixture was followed in situ and in real time by infrared spectroscopy. In parallel, a 0D theoretical model of the laboratory experiment was developed. A new reaction set describing Titan's chemistry was built and incorporated in the model. Lebonnois et al. [Lebonnois, S., Toublanc, D., Hourdin, F., Rannou, P., 2001. Icarus 152, 384-406] reaction set was also used for comparison. The presence of small amounts of atmospheric O₂ in the experiment was properly accounted for and led us to suggest that oxygenated chemistry might be a source of C₂H₄ in Titan's atmosphere. With Lebonnois et al. [Lebonnois, S., Toublanc, D., Hourdin, F., Rannou, P., 2001. Icarus 152, 384-406] reaction set, the model could not fit at all the experimental evolution of the compounds. This is explained by some of the choices made for crucial kinetic parameters such as the quantum yield of photolysis of C₂H₂. Also, the absence of some reactions led to the enhancement of pathways that would otherwise be negligible. For example, the lack of reactions between C₄H₄ and radicals induced an erroneously high photolysis rate for this species. With the reaction set built in this study, the model much better fits the experiment, especially when the “soot,” which includes C₄H₄, is recycled into C₂H₂. This shows that photochemistry of the larger species has a role in determining the lighter species concentrations and that considering that they are simply lost from the system is not a valid assumption. Including even an abridged set of C₄ + hydrocarbon reactions will be required in future photochemical models. Especially, photolysis rates and yields for C₂H₂, C₄H₂, and C₄H₄, are important parameters in need of a better determination.     

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.     

Numerical simulation of the general circulation of the atmosphere of Titan

The atmospheric circulation of Titan is investigated with a general circulation model. The representation of the large-scale dynamics is based on a grid point model developed and used at Laboratoire de Météorologie Dynamique for climate studies. The code also includes an accurate representation of radiative heating and cooling by molecular gases and haze as well as a parametrization of the vertical turbulent mixing of momentum and potential temperature. Long-term simulations of the atmospheric circulation are presented. Starting from a state of rest, the model spontaneously produces a strong superrotation with prograde equatorial winds (i.e., in the same sense as the assumed rotation of the solid body) increasing from the surface to reach 100 m sec-1 near the 1-mbar pressure level. Those equatorial winds are in very good agreement with some indirect observations, especially those of the 1989 occultation of Star 28-Sgr by Titan. On the other hand, the model simulates latitudinal temperature contrasts in the stratosphere that are significantly weaker than those observed by Voyager 1 which, we suggest, may be partly due to the nonrepresentation of the spatial and temporal variations of the abundances of molecular species and haze. We present diagnostics of the simulated atmospheric circulation underlying the importance of the seasonal cycle and a tentative explanation for the creation and maintenance of the atmospheric superrotation based on a careful angular momentum budget.     

Distribution of hydrogen and its Lyman-alpha intensity in the atmosphere of Titan

Several models of the Titan atmosphere are derived, and the corresponding vertical distribution of atomic hydrogen and its Lyman-alpha (1216 Å) emission are determined.     

The atmosphere of Titan: An analysis of the Voyager 1 radio occultation measurements

Two coherently related radio signals transmitted from Voyager 1 at wavelengths of 13 cm (S-band) and 3.6 cm (X-band) were used to probe the equatorial atmosphere of Titan. The measurements were conducted during the occultation of the spacecraft by the satellite on November 12, 1980. An analysis of the differential dispersive frequency measurements did not reveal any ionization layers in the upper atmosphere of Titan. The resolution was approximately 3 × 10³ and 5 × 10³ electrons/cm³ near the evening and morning terminators, respectively. Abrupt signal changes observed at ingress and egress indicated a surface radius of 2575.0 ± 0.5 km, leading to a mean density of 1.881 ± 0.002 g cm^?3 for the satellite. The nondispersive data were used to derive profiles in height of the gas refractivity and microwave absorption in Titan's troposphere and stratosphere. No absorption was detected; the resolution was about 0.01 dB/km at the 13-cm wavelength. The gas refractivity data, which extend from the surface to about 200 km altitude, were interpreted in two different ways. In the first, it is assumed that N₂ makes up essentially all of the atmosphere, but with very small amounts of CH₄ and other hydrocarbons also present. This approach yielded a temperature and pressure at the surface of 94.0 ± 0.7°K and 1496 ± 20 mbar, respectively. The tropopause, which was detected near 42 km altitude, had a temperature of 71.4 ± 0.5°K and a pressure of about 130 mbar. Above the tropopause, the temperature increased with height, reaching 170 ± 15°K near the 200-km level. The maximum temperature lapse rate observed near the surface (1.38 ± 0.10°K/km) corresponds to the adiabatic value expected for a dry N₂ atmosphere—indicating that methane saturation did not occur in tbis region. Above the 3.5-km altitude level the lapse rate dropped abruptly to 0.9 ± 0.1°K/km and then decreased slowly with increasing altitude, crossing zero at the tropopause. For the N₂ atmospheric model, the lapse rate transition at the 3.5-km level appears to mark the boundary between a convective region near the surface having the dry adiabatic lapse rate, and a higher stable region in radiative equilibrium. In the second interpretation of the refractivity data, it is assumed, instead, that the 3.5 km altitude level corresponds to the bottom of a CH₄ cloud layer, and that N₂ and CH₄ are perfectly mixed below this level. These assumptions lead to an atmospheric model which below the clouds contains about 10% CH₄ by number density. The temperature near the surface is about 95°K. Arguments concerning the temperature lapse rates computed from the radio measurements appear to favor models in which methane forms at most a limited haze layer high in the troposphere.