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.     

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.     

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 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.     

Combined experimental and theoretical studies on methane photolysis at 121.6 and 248 nm—implications on a program of laboratory simulations of Titan’s atmosphere

Methane is, together with N₂, the main precursor of Titan’s atmospheric chemistry. In our laboratory, we are currently developing a program of laboratory simulations of Titan’s atmosphere, where methane is intended to be dissociated by multiphotonic photolysis at 248 nm. A preliminary study has shown that multiphotonic absorption of methane at 248 nm is efficient and leads to the production of hydrocarbons such as C₂H₂ (Romanzin et al., 2008). Yet, at this wavelength, little is known about the branching ratios of the hydrocarbon radicals (CH₃, CH₂ and CH) and their following photochemistry. This paper thus aims at investigating methane photochemistry at 248 nm by comparing the chemical evolution observed after irradiation of CH₄ at 248 and at 121.6 nm (Ly-α). It is indeed important to see if the chemistry is driven the same way at both wavelengths in particular because, on Titan, methane photolysis mainly involves Ly-α photons. An approach combining experiments and theoretical analysis by means of a specifically adapted 0-D model has thus been developed and is presented in this paper. The results obtained clearly indicate that the chemistry is different depending on the wavelength. They also suggest that at 248 nm, methane dissociation is in competition with ionisation, which could occur through a three-photon absorption process. As a consequence, 248 nm photolysis appears to be unsuitable to study methane neutral photochemistry alone. The implications of this result on our laboratory simulation program and new experimental developments are discussed. Additional information on methane photochemistry at 121.6 nm are also obtained.     

High spectral resolution infrared studies of Titan: Winds, temperature, and composition

The Cassini Huygens mission provides a unique opportunity to combine ground-based and spacecraft investigations to increase our understanding of chemical and dynamical processes in Titan’s atmosphere. Spectroscopic measurements from both vantage points enable retrieving global wind structure, temperature structure, and atmospheric composition. An updated analysis of Titan data obtained with the NASA Goddard Space Flight Center’s Infrared Heterodyne Spectrometer (IRHS) and Heterodyne Instrument for Planetary Wind and Composition (HIPWAC) prior to and during the Cassini Huygens mission is compared to retrievals from measurements with the Cassini Composite Infrared Spectrometer (CIRS). IRHS/HIPWAC results include the first direct stratospheric wind measurements on Titan, constraints on stratospheric temperature, and the study of atmospheric molecular composition. These results are compared to CIRS retrievals of wind and temperature profile from thermal mapping data and ethane abundance at 10-15° South latitude, near the equatorial region. IRHS/HIPWAC wind results are combined with other direct techniques, stellar occultation measurements, and CIRS results to explore seasonal variability over nearly one Titan year and to provide an empirical altitude profile of stratospheric winds, varying from ∼50 to 210 m/s prograde. The advantage of fully resolved line spectra in species abundance measurements is illustrated by comparing the possible effect on retrieved ethane abundance by blended spectral features of other molecular constituents, e.g., acetylene (C₂H₂), ethylene (C₂H₄), allene (C₃H₄), and propane (C₃H₈), which overlap the ν₉ band of ethane, and are not resolved at lower spectral resolution. IR heterodyne spectral resolution can discriminate weak spectral features that overlap the ν₉ band of ethane, enabling ethane lines alone to be used to retrieve abundance. Titan’s stratospheric mean ethane mole fraction (8.6±3 ppmv) retrieved from IRHS/HIPWAC emission line profiles (resolving power λ?Δλ∼10⁶) is compared to past values obtained from lower resolution spectra and from CIRS measurements (resolving power λ?Δλ∼2×10³) and more compatible recent analysis. Results illustrate how high spectral resolution ground-based studies complement the spectral and spatial coverage and resolution of moderate spectral resolution space-borne spectrometers.     

Molecular hydrogen in Titan’s atmosphere: Implications of the measured tropospheric and thermospheric mole fractions

The third most abundant species in Titan’s atmosphere is molecular hydrogen with a tropospheric/lower stratospheric mole fraction of 0.001 derived from Voyager and Cassini infrared measurements. The globally averaged thermospheric H₂ mole fraction profile from the Cassini Ion Neutral Mass Spectrometer (INMS) measurements implies a small positive gradient in the H₂ mixing ratio from the tropopause region to the lower thermosphere (∼950-1000 km), which drives a downward H₂ flux into Titan’s surface comparable to the H₂ escape flux out of the atmosphere (∼2 × 10¹⁰ cm⁻² s⁻¹ referenced to the surface) and requires larger photochemical production rates of H₂ than obtained by previous photochemical models. From detailed model calculations based on known photochemistry with eddy, molecular, and thermal diffusion, the tropospheric and thermospheric H₂ mole fractions are incompatible by a factor of ∼2. The measurements imply that the downward H₂ surface flux is in substantial excess of the speculative threshold value for methanogenic life consumption of H₂ (McKay, C.P., Smith, H.D. [2005], Icarus 178, 274-276. doi:10.1016/j.icarus.2005.05.018), but without the extreme reduction in the surface H₂ mixing ratio.     

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.     

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.     

Stability of methane clathrate hydrates under pressure: Influence on outgassing processes of methane on Titan

We have conducted high-pressure experiments in the H₂O-CH₄ and H₂O-CH₄-NH₃ systems in order to investigate the stability of methane clathrate hydrates, with an optical sapphire-anvil cell coupled to a Raman spectrometer for sample characterization. The results obtained confirm that three factors determine the stability of methane clathrate hydrates: (1) the bulk methane content of the samples; (2) the presence of additional gas compounds such as nitrogen; (3) the concentration of ammonia in the aqueous solution. We show that ammonia has a strong effect on the stability of methane clathrates. For example, a 10 wt.% NH₃ solution decreases the dissociation temperature of methane clathrates by 14-25 K at pressures above 5 MPa. Then, we apply these new results to Titan’s conditions. Dissociation of methane clathrate hydrates and subsequent outgassing can only occur in Titan’s icy crust, in presence of locally large amounts of ammonia and in a warm context. We propose a model of cryomagma chamber within the crust that provides the required conditions for methane outgassing: emplacement of an ice plume triggers the melting (if solid) or heating (if liquid) of large ammonia-water pockets trapped at shallow depth, and the generated cryomagmas dissociate surrounding methane clathrate hydrates. We show that this model may allow for the outgassing of significant amounts of methane, which would be sufficient to maintain the presence of methane in Titan’s atmosphere for several tens of thousands of years after a large cryovolcanic event.     

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.     

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.     

A study of the propagation of electromagnetic waves in Titan’s atmosphere with the TLM numerical method

A numerical modeling of the electromagnetic characteristics of Titan’s atmosphere is carried out by means of the TLM numerical method, with the aim of calculating the Schumann resonant frequencies of Saturn’s satellite. The detection and measurement of these resonances by the Huygens probe, which will enter Titan’s atmosphere at the beginning of 2005, is expected to show the existence of electric activity with lightning discharges in the atmosphere of this satellite. As happens with the Schumann frequencies on Earth, losses associated with electric conductivity will make these frequencies lower than theoretically expected, the fundamental frequency being located between 11 and 15 Hz. This numerical study also shows that the strong losses associated to the high conductivity make it impossible for an electromagnetic wave with a frequency of 10 MHz or lower, generated near the surface, to reach the outer part of Titan’s atmosphere.     

The photochemical formation of a titan haze analog. Structural analysis by x-ray photoelectron and infrared spectroscopy

The photochemical flow reactor (D.W. Clarke et al., 2000, Icarus 147, 282-291) has been modified to minimize the incorporation of oxygen and other impurities in the photoproducts. A mixture of gases that approximate their mixing ratios on Titan (N₂, CH₄, H₂, C₂H₂, C₂H₄, and HC₃N) (0.98, 0.018, 0.002, 3.5 × 10⁻⁴, 3 × 10⁻⁴, 1.7 × 10⁻⁵, respectively) was irradiated in the flow photochemical reactor using a 185-nm source to give a Titan haze analog as a solid product. X-ray photoelectron spectroscopy (XPS) gave a composition of 93.3% C, 5.3% N, and 1.4% O. Of the 93.3% carbon, high-resolution XPS revealed that 81.2% was present as CH, CC, and CC groups, 12.1% may be CO, CN, CN, CN, and/or CN groups, 5.3% as a CN group. The peak for N was symmetrical and was assigned to the CN while that for oxygen was assigned to the CO and/or the CO group. Some of these assignments were confirmed by FTIR spectroscopy. The polymeric product had a C:N ratio of 17.6, which is significantly greater than that for Titan haze analogs prepared in discharge reactions. When the polymer was exposed to air for seven days the oxygen content increased by 6% along with an increase in the infrared absorption at 1710 cm⁻¹ assigned to the CO group of a ketone. The oxidation is attributed to the reaction of oxygen with free radicals trapped in the polymer matrix. It is proposed that the photochemical initiation of Titan haze formation from compounds formed from starting materials formed high in Titan’s atmosphere is a more plausible model than haze formed in reactions initiated by solely by discharges. These data will be helpful in the interpretation of the data returned from the Huygens probe of the Cassini mission.     

Impact of the seasonal variations of composition on the temperature field of Titan’s stratosphere

We investigate the role of seasonal variations of Titan’s stratospheric composition on the temperature. We use a general circulation model coupled with idealized chemical tracers that reproduce variations of ethane (C₂H₆), acetylene (C₂H₂), and hydrogen cyanide (HCN). Enhancement of the mole fractions of these compounds, at high latitudes in the winter hemisphere relative to their equatorial values, induces a relative decrease in temperature above approximately 0.2 mbar, with a peak amplitude around −20 K, and a relative increase in temperature below, around 1 mbar, with a peak amplitude around +7 K. These thermal effects are mainly due to the variations of the cooling to space induced by the varying distributions. The ethane, acetylene, and hydrogen cyanide variations affect the cooling rates in a similar way, with the dominant effect being due to ethane, though its latitudinal variations are small.     

A methodology to construct a reduced chemical scheme for 2D-3D photochemical models: Application to Saturn

We present a methodology to build a reduced chemical scheme adapted to the study of hydrocarbons in the atmospheres of giant planets and Titan. As an example, we have built a reduced chemical scheme, containing only 25 compounds and 46 reactions (including photolysis), which is well adapted to compute the abundance of the main hydrocarbons observed so far in the atmosphere of Saturn (CH₃, CH₄, C₂H₂, C₂H₄, C₂H₆, CH₃C₂H, C₃H₈ and C₄H₂). This scheme gives similar results, within the error bars of the model, as a 1D photochemical model using an initial chemical scheme containing 90 compounds and more than 600 reactions. As a consequence, such a methodology can be used to build a reduced scheme well adapted to future 2D (or 3D) photochemical models and GCMs.     

Impact-induced N2 production from ammonium sulfate: Implications for the origin and evolution of N2 in Titan’s atmosphere

Chemical reactions and volatile supply through hypervelocity impacts may have played a key role for the origin and evolution of both planetary and satellite atmospheres. In this study, we evaluate the role of impact-induced N₂ production from reduced nitrogen-bearing solids proposed to be contained in Titan’s crust, ammonium sulfate ((NH₄)₂SO₄), for the replenishment of N₂ to the atmosphere in Titan’s history. To investigate the conversion of (NH₄)₂SO₄ into N₂ by hypervelocity impacts, we measured gases released from (NH₄)₂SO₄ that was exposed to hypervelocity impacts created by a laser gun. The sensitivity and accuracy of the measurements were enhanced by using an isotope labeling technique for the target. We obtained the efficiency of N₂ production from (NH₄)₂SO₄ as a function of peak shock pressure ranging from ∼8 to ∼45 GPa. Our results indicate that the initial and complete shock pressures for N₂ degassing from (NH₄)₂SO₄ are ∼10 and ∼25 GPa, respectively. These results suggest that cometary impacts on Titan (i.e., impact velocity v_i > ∼8 km/s) produce N₂ efficiently; whereas satellitesimal impacts during the accretion (i.e., v_i < 4 km/s) produce N₂ only inefficiently. Even when using the proposed small amount of (NH₄)₂SO₄ content in the crust (∼4 wt.%) (Fortes, A.D. et al., 2007. Icarus 188, 139-153), the total amount of N₂ provided through cometary impacts over 4.5 Ga reaches ∼2-6 times the present atmospheric N₂ (i.e., ∼7 × 10²⁰-2 × 10²¹ [mol]) based on the measured production efficiency and results of a hydrodynamic simulation of cometary impacts onto Titan. This implies that cometary impacts onto Titan’s crust have the potential to account for a large part of the present N₂ through the atmospheric replenishment after the accretion.     

Titan’s atomic hydrogen corona

Based on measurements performed by the Hydrogen Deuterium Absorption Cell (HDAC) aboard the Cassini orbiter, Titan’s atomic hydrogen exosphere is investigated. Data obtained during the T9 encounter are used to infer the distribution of atomic hydrogen throughout Titan’s exosphere, as well as the exospheric temperature.The measurements performed during the flyby are modeled by performing Monte Carlo radiative transfer calculations of solar Lyman-α radiation, which is resonantly scattered on atomic hydrogen in Titan’s exosphere. Two different atomic hydrogen distribution models are applied to determine the best fitting density profile. One model is a static model that uses the Chamberlain formalism to calculate the distribution of atomic hydrogen throughout the exosphere, whereas the second model is a Particle model, which can also be applied to non-Maxwellian velocity distributions.The density distributions provided by both models are able to fit the measurements although both models differ at the exobase: best fitting exobase atomic hydrogen densities of n_H = (1.5 ± 0.5) × 10⁴ cm⁻³ and n_H = (7 ± 1) × 10⁴ cm⁻³ were found using the density distribution provided by both models, respectively. This is based on the fact that during the encounter, HDAC was sensitive to altitudes above about 3000 km, hence well above the exobase at about 1500 km. Above 3000 km, both models produce densities which are comparable, when taking into account the measurement uncertainty.The inferred exobase density using the Chamberlain profile is a factor of about 2.6 lower than the density obtained from Voyager 1 measurements and much lower than the values inferred from current photochemical models. However, when taking into account the higher solar activity during the Voyager flyby, this is consistent with the Voyager measurements. When using the density profile provided by the particle model, the best fitting exobase density is in perfect agreement with the densities inferred by current photochemical models.Furthermore, a best fitting exospheric temperature of atomic hydrogen in the range of T_H = (150-175) ± 25 K was obtained when assuming an isothermal exosphere for the calculations. The required exospheric temperature depends on the density distribution chosen. This result is within the temperature range determined by different instruments aboard Cassini. The inferred temperature is close to the critical temperature for atomic hydrogen, above which it can escape hydrodynamically after it diffused through the heavier background gas.     

The contribution by thunderstorms to the abundances of CO,C2H2, and HCN on Jupiter

The lightning energy dissipation rate on Jupiter from Voyager's observation is used, together with shock-tube experimental results and reasonable eddy diffusion coefficients for the various atmospheric layers, to compute the column abundances of lightning-produced CO, C₂H₂, and HCN. Shock-tube experiments on the hydrogenation of CO clearly rule out chemical “freezing” of CO at the 1064°K and 400-bar level and its subsequent upwelling to the upper atmosphere. Also, lightning in the water cloud cannot produce enough CO to meet its observed abundance. Hence, the CO is formed from an external source of oxygen or water. The production of acetylene both by lightning above the water cloud and by startospheric methane photolysis is required to maintain its observed abundance against destruction processes. This explains the decrease in the C₂H₂/C₂H₆ ratio from the equator to the pole, as observed in the IR. HCN production by lightning above the water cloud is sufficient to account for its observed abundance and meets the observational requirement of a tropospheric HCN source.     

Atomic and molecular hydrogen budget in Titan’s atmosphere

Using a one-dimensional model, we investigate the hydrogen budget and escape to space in Titan’s atmosphere. Our goal is to study in detail the distributions and fluxes of atomic and molecular hydrogen in the model, while identifying sources of qualitative and quantitative uncertainties. Our study confirms that the escape of atomic and molecular hydrogen to space is limited by the diffusion through the homopause level. The H distribution and flux inside the atmosphere are very sensitive to the eddy diffusion coefficient used above altitude 600 km. We chose a high value of this coefficient 1 × 10⁸ cm² s⁻¹ and a homopause level around altitude 900 km. We find that H flows down significantly from the production region above 500 km to the region [300-500] km, where it recombines into H₂. Production of both H and H₂ also occurs in the stratosphere, mostly from photodissociation of acetylene. The only available observational data to be compared are the escape rate of H deduced from Pioneer 11 and IUE observations of the H torus 1-3 × 10⁹ cm⁻² s⁻¹ and the latest retrieved value of the H₂ mole fraction in the stratosphere: (1.1 ± 0.1) × 10⁻³. Our results for both of these values are at least 50-100% higher, though the uncertainties within the chemical schemes and other aspects of the model are large. The chemical conversion from H to H₂ is essentially done through catalytic cycles using acetylene and diacetylene. We have studied the role of this diacetylene cycle, for which the associated reaction rates are poorly known. We find that it mostly affects C₄ species and benzene in the lower atmosphere, rather than the H profile and the hydrogen budget. We have introduced the heterogenous recombination of hydrogen on the surface of aerosol particles in the stratosphere, and this appears to be a significant process, comparable to the chemical processes. It has a major influence on the H distribution, and consequently on several other species, especially C₃H₄, C₄H₂ and C₆H₆. Therefore, this heterogenous process should be taken into account when trying to understand the stratospheric distribution of these hydrocarbons.