Coupling photochemistry with haze formation in Titan's atmosphere, Part II: Results and validation with Cassini/Huygens data

The new one-dimensional radiative-convective/photochemical/microphysical model described in Part I is applied to the study of Titan's atmospheric processes that lead to haze formation. Our model generates the haze structure from the gaseous species photochemistry. Model results are presented for the species vertical concentration profiles, haze formation and its radiative properties, vertical temperature/density profiles and geometric albedo. These are validated against Cassini/Huygens observations and other ground-based and space-borne measurements. The model reproduces well most of the latest measurements from the Cassini/Huygens instruments for the chemical composition of Titan's atmosphere and the vertical profiles of the observed species. For the haze production we have included pathways that are based on pure hydrocarbons, pure nitriles and hydrocarbon/nitrile copolymers. From these, the nitrile and copolymer pathways provide the stronger contribution, in agreement with the results from the ACP instrument, which support the incorporation of nitrogen in the pyrolized haze structures. Our haze model reveals a new second major peak in the vertical profile of haze production rate between 500 and 900 km. This peak is produced by the copolymer family used and has important ramifications for the vertical atmospheric temperature profile and geometric albedo. In particular, the existence of this second peak determines the vertical profile of haze extinction. Our model results have been compared with the DISR retrieved haze extinction profiles and are found to be in very good agreement. We have also incorporated in our model heterogeneous chemistry on the haze particles that converts atomic hydrogen to molecular hydrogen. The resultant H₂ profile is closer to the INMS measurements, while the vertical profile of the diacetylene formed is found to be closer to that of the CIRS profile when this heterogenous chemistry is included.     

Chemical sources of haze formation in Titan's atmosphere

A prominent feature of Titan's atmosphere is a thick haze region that acts as the end product of hydrocarbon and nitrile chemistry. Using a one-dimensional photochemical model, an investigation into the chemical mechanisms responsible for the formation of this haze region is conducted. The model derives profiles for Titan's atmospheric constituents that are consistent with observations. Included is an updated benzene profile that matches more closely with—recent ISO observations (Icarus 161 (2003) 383), replacing the profile given in the benzene study of Wilson et al. (J. Geophys. Res. 108 (2003) 5014). Using these profiles, pathways from polyynes, aromatics, and nitriles are considered, as well as possible copolymerization among the pathways. The model demonstrates that the growth of polycyclic aromatic hydrocarbons throughout the lower stratosphere plays an important role in furnishing the main haze layer, with nitriles playing a secondary role. The peak chemical production of haze layer ranges from 140 to 300 km peaking at an altitude of 220 km, with a production rate of 3.2×10⁻¹⁴ gcm⁻² s⁻¹. Possible mechanisms for polymerization and copolymerization and suggestions for further kinetic study are discussed, along with the implications for the distribution of haze in Titan's atmosphere.     

Removal of Titan's noble gases by their trapping in its haze

Titan's haze, formed by photolysis of C₂H₂, C₂H₄ and HCN, was found experimentally to trap Ar, Kr and Xe with efficiencies of 3.5 × 10⁻⁴, 1.9 × 10⁻³ and 6.5 × 10⁻² [noble gas atom]/[carbon atom] in the polymer, respectively. The rate of aerosol formation and settling down of 3 × 10⁻¹³ kg m⁻² s⁻¹, as inferred from our experiments on CH₄ photolysis in the far UV [Podolak, M., Bar-Nun, A., 1979. Icarus 39, 272-276], is sufficient to reduce the mixing ratios of ³⁶Ar and ⁴⁰Ar to their low values of (2.8 ± 0.3) × 10⁻⁷ and (4.3 ± 0.1) × 10⁻³, respectively, and those of Kr and Xe to below the detection limit of 10⁻⁸.     

Coupled ion and neutral rotating model of Titan's upper atmosphere

A one-dimensional composition model of Titan's upper atmosphere is constructed, coupling 36 neutral species and 47 ions. Energy inputs from the Sun and from Saturn's magnetosphere and updated temperature and eddy coefficient parameters are taken into account. A rotating technique at constant latitude and varying local-time is proposed to account for the diurnal variation of solar inputs. The contributions of photodissocation, neutral chemistry, ion-neutral chemistry, and electron recombination to neutral production are presented as a function of altitude and local time. Local time-dependent mixing ratio and density profiles are presented in the context of the TA and T₅ Cassini data and are compared in detail to previous models. An independent and simplified ion and neutral scheme (19-species) is also proposed for future 3D-purposes. The model results demonstrate that a complete understanding of the chemistry of Titan's upper atmosphere requires an understanding of the coupled ion and neutral chemistry. In particular, the ionospheric chemistry makes significant contributions to production rates of several important neutral species.     

A photochemical model of Titan's atmosphere and ionosphere

A global-mean model of coupled neutral and ion chemistry on Titan has been developed. Unlike the previous coupled models, the model involves ambipolar diffusion and escape of ions, hydrodynamic escape of light species, and calculates the H₂ and CO densities near the surface that were assigned in some previous models. We tried to reduce the numbers of species and reactions in the model and remove all species and reactions that weakly affect the observed species. Hydrocarbon chemistry is extended to C₁₂H₁₀ for neutrals and C₁₀H⁺₁₁ for ions but does not include PAHs. The model involves 415 reactions of 83 neutrals and 33 ions, effects of magnetospheric electrons, protons, and cosmic rays. UV absorption by Titan's haze was calculated using the Huygens observations and a code for the aggregate particles. Hydrocarbon, nitrile, and ion chemistries are strongly coupled on Titan, and attempt to calculate them separately (e.g., in models of ionospheric composition) may result in significant error. The model densities of various species are typically in good agreement with the observations except vertical profiles in the stratosphere that are steeper than the CIRS limb data. (A model with eddy diffusion that facilitates fitting to the CIRS limb data is considered as well.) The CO densities are supported by the O⁺ flux from Saturn's magnetosphere. The ionosphere includes a peak at 80 km formed by the cosmic rays, steplike layers at 500-700 and 700-900 km and a peak at 1060 km (SZA = 60°). Nighttime densities of major ions agree with the INMS data. Ion chemistry dominates in the production of bicyclic aromatic hydrocarbons above 600 km. The model estimates of heavy positive and negative ions are in reasonable agreement with the Cassini results. The major haze production is in the reactions C₆H + C₄H₂, C₃N + C₄H₂, and condensation of hydrocarbons below 100 km. Overall, precipitation rate of the photochemical products is equal to 4-7 kg cm⁻² Byr⁻¹ (50-90 m Byr⁻¹ while the global-mean depth of the organic sediments is ∼3 m). Escape rates of methane and hydrogen are 2.9 and 1.4 kg cm⁻² Byr⁻¹, respectively. The model does not support the low C/N ratio observed by the Huygens ACP in Titan's haze.     

The detached haze layer in Titan's mesosphere

By comparing observations from the Cassini imaging system, UV spectrometer, and Huygens atmospheric structure instrument, we determine an apparent radius of ∼40 nm, an imaginary index <0.3 at 187.5 nm and a number density of ∼30 particles cm⁻³ for the detached haze layer at 520 km in Titan's mesosphere. We point out that the detached haze layer is coincident with a local maximum in the measured temperature profile and show that the temperature maximum is caused by absorption of sunlight in the detached haze layer. This rules out condensation as the source of the layer. The derived particle size is in good agreement with that estimated for the size of the monomers in the aggregate particles that make up the main haze layer. Calculations of the sedimentation velocity of the haze particles coupled with the derived number density imply a mass flux , which is approximately equal to the mass flux required to explain the main haze layer. Because the aerosol size and mass flux derived for the detached layer agree with those determined for the main layer, we suggest that the main haze layer in Titan's stratosphere is formed primarily by sedimentation and coagulation of particles in the detached layer. This implies that high-energy radical and ion chemistry in the thermosphere is the main source of haze on Titan.     

Methane, ethane, and mixed clouds in Titan's atmosphere: Properties derived from microphysical modeling

Theoretical arguments point to and recent observations confirm the existence of clouds in Titan's atmosphere, yet we possess very little data on their particle size, composition and formation mechanism. A time-dependent microphysical model is used to study the evolution of ice clouds in Titan's atmosphere. The model simulates nucleation, condensational growth, evaporation, coagulation, and transport of particles in a column of atmosphere. A variety of cloud compositions are studied, including pure ethane clouds, pure methane clouds, and mixed methane-ethane clouds (all with tholin cores). The abundance of methane cloud particles may be limited by the number of ethane coated tholin nuclei rather than the number of tholins with hydrocarbon coatings. However, even the condensation of methane onto these relatively sparse ethane/tholin cloud particles is sufficient to keep the methane close to saturation. Typical methane supersaturations are of order 0.06 on the average. For simulations which take into account recent lab measurements indicating it is relatively easy for methane to nucleate onto tholin particles without an ethane-layer present, the three types of clouds (methane, ethane, and mixed) exist simultaneously. Pure methane clouds are the most abundant cloud type and serve to lower the supersaturation to about 0.04. Cloud production does not require a continuous surface source of methane. However, clouds produced by mean motions are not the visible methane clouds seen in recent Cassini and ground-based observations. Ethane clouds in the troposphere almost instantaneously nucleate methane to form mixed clouds. However, a thin ethane ‘haze’ remains just above the tropopause for some scenarios and the mixed clouds at the tropopause remain ?50% ethane by mass. Also, evaporation of methane from the mixed cloud particles near the surface leaves a thicker layer of ethane cloud particles at ∼10 km. Nevertheless, the precipitation rate of methane to Titan's surface is between 0.001 and 0.5 cm/terrestrial-year, depending on various initial conditions such as critical saturation, size and abundance of cloud condensation nuclei, surface sources and eddy diffusion.     

Titan's corona: The contribution of exothermic chemistry

The contribution of exothermic ion and neutral chemistry to Titan's corona is studied. The production rates for fast neutrals N₂, CH₄, H, H₂, ³CH₂, CH₃, C₂H₄, C₂H₅, C₂H₆, N(⁴S), NH, and HCN are determined using a coupled ion and neutral model of Titan's upper atmosphere. After production, the formation of the suprathermal particles is modeled using a two-stream simulation, as they travel simultaneously through a thermal mixture of N₂, CH₄, and H₂. The resulting suprathermal fluxes, hot density profiles, and energy distributions are compared to the N₂ and CH₄ INMS exospheric data presented in [De La Haye, V., Waite Jr., J.H., Johnson, R.E., Yelle, R.V., Cravens, T.E., Luhmann, J.G., Kasprzak, W.T., Gell, D.A., Magee, B., Leblanc, F., Michael, M., Jurac, S., Robertson, I.P., 2007. J. Geophys. Res., doi:10.1029/2006JA012222, in press], and are found insufficient for producing the suprathermal populations measured. Global losses of nitrogen atoms and carbon atoms in all forms due to exothermic chemistry are estimated to be and .     

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.     

Negative ion chemistry in Titan's upper atmosphere

The Electron Spectrometer (ELS), one of the sensors making up the Cassini Plasma Spectrometer (CAPS) revealed the existence of numerous negative ions in Titan's upper atmosphere. The observations at closest approach (∼1000 km) show evidence for negatively charged ions up to ∼10,000 amu/q, as well as two distinct peaks at 22±4 and 44±8 amu/q, and maybe a third one at 82±14 amu/q. We present the first ionospheric model of Titan including negative ion chemistry. We find that dissociative electron attachment to neutral molecules (mostly HCN) initiates the formation of negative ions. The negative charge is then transferred to more acidic molecules such as HC₃N, HC₅N or C₄H₂. Loss occurs through associative detachment with radicals (H and CH₃). We attribute the three low mass peaks observed by ELS to CN⁻, C₃N⁻/C₄H⁻ and C₅N⁻. These species are the first intermediates in the formation of the even larger negative ions observed by ELS, which are most likely the precursors to the aerosols observed at lower altitudes.     

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.     

Gravitational tidal waves in Titan's upper atmosphere

Tidal waves driven by Titan's orbital eccentricity through the time-dependent component of Saturn's gravitational potential attain nonlinear, saturation amplitudes (|T^′|>10 K, , and ) in the upper atmosphere (?500 km) due to the approximate exponential growth as the inverse square root of pressure. The gravitational tides, with vertical wavelengths of ∼100-150 km above 500 km altitude, carry energy fluxes sufficient in magnitude to affect the energy balance of the upper atmosphere with heating rates in the altitude range of 500-900 km.     

Titan's hydrodynamically escaping atmosphere: Escape rates and the structure of the exobase region

In Strobel [Strobel, D.F., 2008. Icarus, 193, 588-594] a mass loss rate from Titan's upper atmosphere, , was calculated for a single constituent, N₂ atmosphere by hydrodynamic escape as a high density, slow outward expansion driven principally by solar UV heating due to CH₄ absorption. It was estimated, but not proven, that the hydrodynamic mass loss is essentially CH₄ and H₂ escape. Here the individual conservation of momentum equations for the three major components of the upper atmosphere (N₂, CH₄, H₂) are solved in the low Mach number limit and compared with Cassini Ion Neutral Mass Spectrometer (INMS) measurements to demonstrate that light gases (CH₄, H₂) preferentially escape over the heavy gas (N₂). The lightest gas (H₂) escapes with a flux 99% of its limiting flux, whereas CH₄ is restricted to ?75% of its limiting flux because there is insufficient solar power to support escape at the limiting rate. The respective calculated H₂ and CH₄ escape rates are 9.2×¹⁰²⁷ and 1.7×¹⁰²⁷ s−1, for a total of . From the calculated densities, mean free paths of N₂, CH₄, H₂, and macroscopic length scales, an extended region above the classic exobase is inferred where frequent collisions are still occurring and thermal heat conduction can deliver power to lift the escaping gas out of the gravitational potential well. In this region rapid acceleration of CH₄ outflow occurs. With the thermal structure of Titan's thermosphere inferred from INMS data by Müller-Wodarg et al. [Müller-Wodarg, I.C.F., Yelle, R.V., Cui, J., Waite Jr., J.H., 2008. J. Geophys. Res. 113, doi:10.1029/2007JE003033. E10005], in combination with calculated temperature profiles that include sputter induced plasma heating at the exobase, it is concluded that on average that the integrated, globally average, orbit-averaged, plasma heating rate during the Cassini epoch does not exceed ().     

Simulation of Titan haze formation using a photochemical flow reactor: The optical constants of the polymer

Solar UV is the principal energy source impinging the atmosphere of Titan while the energy from the electrons in Saturn's magnetosphere is less than 0.5% of the UV light. Titan haze analogs were prepared by the photolysis of a mixture of gases that simulate the composition of its atmosphere (nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene). The real (n) and imaginary (k) parts of the complex refractive index of haze analogs formed from four different gas mixtures were calculated from the spectral properties of the solid polymer in UV-visible, near infrared and infrared wavelength spectral regions. The value of n was constant at 1.6±0.1 throughout the 0.2-2.5 μm region. The variation of k with wavelength for the values derived for Titan has a lower error than the absolute values of k so the more significant comparisons are with the slopes of the k(λ) plots in the UV-VIS region. Three of the photochemical Titan haze analogs had slopes comparable to those derived for Titan from the Voyager data (Rages and Pollack, 1980, Icarus 41, 119-130; McKay and Toon, 1992, in: Proceedings of the Symposium on Titan, in: ESA SP, Vol. 338, pp. 185-190). The slopes of the k(λ) plots for haze analogs prepared by spark discharge (Khare et al., 1984, Icarus 60, 127-137) and plasma discharge (Ramirez et al., 2002, Icarus 156, 515-529) were also comparable to Titan's. These finding show that the k(λ) plots do not differentiate between different laboratory simulations of atmospheric chemistry on Titan in the UV-VIS near IR region (0.2-2.5 microns). There is a large difference between the k(λ) in the infrared between the haze analogs prepared photochemically and analogs prepared using a plasma discharges (Khare et al., 1984, Icarus 60, 127-137; Coll et al., 1999, Planet. Space Sci. 47, 1331-1340; Khare et al., 2002, Icarus 160, 172-182). The C/N ratio in the haze analog prepared by discharges is in the 2-11 range while that of the photochemical analogs is in the 18-24 range. The use of discharges and UV light for initiating the chemistry in Titan's atmosphere is discussed.     

Ion chemistry and N-containing molecules in Titan's upper atmosphere

High-energy photons, electrons, and ions initiate ion-neutral chemistry in Titan's upper atmosphere by ionizing the major neutral species (nitrogen and methane). The Ion and Neutral Mass Spectrometer (INMS) onboard the Cassini spacecraft performed the first composition measurements of Titan's ionosphere. INMS revealed that Titan has the most compositionally complex ionosphere in the Solar System, with roughly 50 ions at or above the detection threshold. Modeling of the ionospheric composition constrains the density of minor neutral constituents, most of which cannot be measured with any other technique. The species identified with this approach include the most complex molecules identified so far on Titan. This confirms the long-thought idea that a very rich chemistry is actually taking place in this atmosphere. However, it appears that much of the interesting chemistry occurs in the upper atmosphere rather than at lower altitudes. The species observed by INMS are probably the first intermediates in the formation of even larger molecules. As a consequence, they affect the composition of the bulk atmosphere, the composition and optical properties of the aerosols and the flux of condensable material to the surface. In this paper, we discuss the production and loss reactions for the ions and how this affects the neutral densities. We compare our results to neutral densities measured in the stratosphere by other instruments, to production yields obtained in laboratory experiments simulating Titan's chemistry and to predictions of photochemical models. We suggest neutral formation mechanisms and highlight needs for new experimental and theoretical data.     

Ethane aerosol phase evolution in Titan's atmosphere

Strong experimental evidence is presented that the northern polar cloud observed in Titan's atmosphere by the Cassini orbiter (VIMS) was indeed composed of ethane aerosol as proposed by Griffith et al. [2006. Science 313, 1620-1622]. We report on the condensation and phase behavior of ethane aerosol under atmospheric conditions of Titan (145 hPa, 40 km altitude, 70-90 K, 10-30 ppm ethane in nitrogen). The results were obtained in an in-situ collisional cooling experiment combined with Fourier-transform infrared (FTIR) spectroscopy. Apart from the liquid phase, three crystalline phases (solid I, solid II, metastable) and the transitions into each other have been observed in the ethane aerosol. The phases were found to have a significant effect on the particles' IR spectra, their growth dynamics and the final size of the aerosols which varies between 0.5 and 4 μm (compared to 1-3 μm observed on Titan). This has strong implications on the ethane vapor pressure, precipitation and optical aerosol detection.     

Predictions of the electrical conductivity and charging of the aerosols in Titan's atmosphere

The electrical conductivity and electrical charge on the aerosols in atmosphere of Titan are computed for altitudes between 0 and 400 km. Ionization of methane and nitrogen due to galactic cosmic rays (GCR) is important at night where these ions are converted to ion clusters such as CH⁺₅CH₄, C₇H⁺₇, C₄H⁺₇, and H₄C₇N⁺. The ubiquitous aerosols observed also play an important role in determining the charge distribution in the atmosphere. Because polycyclic aromatic hydrocarbons (PAHs) are expected in Titan's atmosphere and have been observed in the laboratory and found to be electrophilic, we consider the formation of negative ions. During the night, the very smallest molecular complexes accept free electrons to form negative ions. This results in a large reduction of the electron abundance both in the region between 150 and 350 km over that predicted when such aerosols are not considered. During the day time, ionization by photoemission from aerosols irradiated by solar ultraviolet (UV) radiation overwhelms the GCR-produced ionization. The presence of hydrocarbon and nitrile minor constituents substantially reduces the UV flux in the wavelength band from the cutoff of CH₄ at 155 to 200 nm. These aerosols have such a low ionization potential that the bulk of the solar radiation at longer wavelengths is energetic enough to produce a photoionization rate sufficient to create an ionosphere even without galactic cosmic ray (GCR) bombardment. At altitudes below 60 km, the electron and positive ion abundances are influenced by the three-body recombination of ions and electrons. The addition of this reaction significantly reduces the predicted electron abundance over that previously predicted. Our calculations for the dayside show that the peaks of the charge distributions move to larger values as the altitude increases. This variation is the result of the increased UV flux present at the highest altitudes. Clearly, the situation is quite different than that for the night where the peak of the distribution for a particular size is nearly constant with altitude when negative ions are not present. The presence of very small aerosol particles (embryos) may cause the peak of the distribution to decrease from about 8 negative charges to as little as one negative charge or even zero charge. This dependence on altitude will require models of the aerosol formation to change their algorithms to better represent the effect of charged aerosols as a function of altitude. In particular, the charge state will be much higher than previously predicted and it will not be constant with altitude during the day time. Charging of aerosol particles, whether on the dayside or nightside, has a major influence on both the electron abundance and electrical conductivity. The predicted conductivities are within the measurement range of the HASI PWA instrument over most but not all, of the altitude range sampled.     

Epistemic bimodality and kinetic hypersensitivity in photochemical models of Titan's atmosphere

We show that photochemical models of Titan's atmosphere can give rise to bimodal distributions in the abundances of some major compounds, like C₂H₂ and C₂H₄. Sensitivity analysis enabled us to identify the causes and conditions of this bimodality. We propose several methods to control this behavior in photochemical models. In particular, we point out the importance of two key reactions and the needs for a critical evaluation of the kinetic data. We also show that the abundances of some compounds are hypersensitive to the ratio [CH₄]/[H], suggesting that a time-dependent variation of this ratio might lead to a real bistability in the high atmosphere of Titan.     

Vertical profiles of HCN, HC3N, and C2H2 in Titan's atmosphere derived from Cassini/CIRS data

Mid-infrared limb spectra in the range 600-1400 cm⁻¹ taken with the Composite InfraRed Spectrometer (CIRS) on-board the Cassini spacecraft were used to determine vertical profiles of HCN, HC₃N, C₂H₂, and temperature in Titan's atmosphere. Both high (0.5 cm⁻¹) and low (13.5 cm⁻¹) spectral resolution data were used. The 0.5 cm⁻¹ data gave profiles at four latitudes and the 13.5 cm⁻¹ data gave almost complete latitudinal coverage of the atmosphere. Both datasets were found to be consistent with each other. High temperatures in the upper stratosphere and mesosphere were observed at Titan's northern winter pole and were attributed to adiabatic heating in the subsiding branch of a meridional circulation cell. On the other hand, the lower stratosphere was much colder in the north than at the equator, which can be explained by the lack of solar radiation and increased IR emission from volatile enriched air. HC₃N had a vertical profile consistent with previous ground based observations at southern and equatorial latitudes, but was massively enriched near the north pole. This can also be explained in terms of subsidence at the winter pole. A boundary observed at 60° N between enriched and un-enriched air is consistent with a confining polar vortex at 60° N and HC₃N's short lifetime. In the far north, layers were observed in the HC₃N profile that were reminiscent of haze layers observed by Cassini's imaging cameras. HCN was also enriched over the north pole, which gives further evidence for subsidence. However, the atmospheric cross section obtained from 13.5 cm⁻¹ data indicated a HCN enriched layer at 200-250 km, extending into the southern hemisphere. This could be interpreted as advection of polar enriched air towards the south by a meridional circulation cell. This is observed for HCN but not for HC₃N due to HCN's longer photochemical lifetime. C₂H₂ appears to have a uniform abundance with altitude and is not significantly enriched in the north. This is consistent with observations from previous CIRS analysis that show increased abundances of nitriles and hydrocarbons but not C₂H₂ towards the north pole.