A model of Titan's aerosols based on measurements made inside the atmosphere

The descent imager/spectral radiometer (DISR) instrument aboard the Huygens probe into the atmosphere of Titan measured the brightness of sunlight using a complement of spectrometers, photometers, and cameras that covered the spectral range from 350 to 1600 nm, looked both upward and downward, and made measurements at altitudes from 150 km to the surface. Measurements from the upward-looking visible and infrared spectrometers are described in Tomasko et al. [2008a. Measurements of methane absorption by the descent imager/spectral radiometer (DISR) during its descent through Titan's atmosphere. Planet. Space Sci., this volume]. Here, we very briefly review the measurements by the violet photometers, the downward-looking visible and infrared spectrometers, and the upward-looking solar aureole (SA) camera. Taken together, the DISR measurements constrain the vertical distribution and wavelength dependence of opacity, single-scattering albedo, and phase function of the aerosols in Titan's atmosphere.Comparison of the inferred aerosol properties with computations of scattering from fractal aggregate particles indicates the size and shape of the aerosols. We find that the aggregates require monomers of radius 0.05 μm or smaller and that the number of monomers in the loose aggregates is roughly 3000 above 60 km. The single-scattering albedo of the aerosols above 140 km altitude is similar to that predicted for some tholins measured in laboratory experiments, although we find that the single-scattering albedo of the aerosols increases with depth into the atmosphere between 140 and 80 km altitude, possibly due to condensation of other gases on the haze particles. The number density of aerosols is about 5/cm³ at 80 km altitude, and decreases with a scale height of 65 km to higher altitudes. The aerosol opacity above 80 km varies as the wavelength to the −2.34 power between 350 and 1600 nm.Between 80 and 30 km the cumulative aerosol opacity increases linearly with increasing depth in the atmosphere. The total aerosol opacity in this altitude range varies as the wavelength to the −1.41 power. The single-scattering phase function of the aerosols in this region is also consistent with the fractal particles found above 60 km.In the lower 30 km of the atmosphere, the wavelength dependence of the aerosol opacity varies as the wavelength to the −0.97 power, much less than at higher altitudes. This suggests that the aerosols here grow to still larger sizes, possibly by incorporation of methane into the aerosols. Here the cumulative opacity also increases linearly with depth, but at some wavelengths the rate is slightly different than above 30 km altitude.For purely fractal particles in the lowest few km, the intensity looking upward opposite to the azimuth of the sun decreases with increasing zenith angle faster than the observations in red light if the single-scattering albedo is assumed constant with altitude at these low altitudes. This discrepancy can be decreased if the single-scattering albedo decreases with altitude in this region. A possible explanation is that the brightest aerosols near 30 km altitude contain significant amounts of methane, and that the decreasing albedo at lower altitudes may reflect the evaporation of some of the methane as the aerosols fall into dryer layers of the atmosphere. An alternative explanation is that there may be spherical particles in the bottom few kilometers of the atmosphere.     

Influence of high abundances of aerosols on the electrical conductivity of the Titan atmosphere

Observations of optical depth and scattering by instrumentation onboard the Huygens probe have been used by Tomasko et al. [Tomasko et al., 2005. Rain, winds and haze during Huygens probe's descent to Titan's surface. Nature 438 (8), 765-778] to deduce that the size and abundance of Titan aerosols could be nearly independent of altitude. Here we show that by assuming a constant mass flux with altitude and using the measured optical depth as a constraint, we obtain more realistic size and abundance distributions. In particular, the calculated abundance decreases from 3.5×10⁷ m⁻³ at 100 km to 8×10⁶ m⁻³ near the surface while the particle radius varies from 0.25 μm at 150 km to 1.1 μm at the surface. These distributions are consistent with the reported measurements for these quantities. Our results are then employed to compute electron and ion densities and conductivities for various solar UV photoelectron emission thresholds. Our model shows that to get agreement with the published (preliminary) conductivity measurements, photoemission cannot be an important source of electrons and ions. To get agreement with the electron and ion conductivity observations, both an additional population of aerosol embryos above 50 km and a trace amount of an electrophillic molecular species below 50 km are needed.     

New laboratory measurements of CH4 in Titan's conditions and a reanalysis of the DISR near-surface spectra at the Huygens landing site

Laboratory spectra of methane-nitrogen mixtures have been recorded in the near-infrared range (1.0-1.65 μm) in conditions similar to Titan's near surface, to facilitate the interpretation of the DISR/DLIS (DISR—Descent Imager/Spectral Radiometer) spectra taken during the last phase of the descent of the Huygens Probe, when the surface was illuminated by a surface-science lamp. We used a 0.03 cm⁻¹ spectral resolution, adequate to resolve the lines at high pressure (p_N2∼1.5 bar). By comparing the laboratory spectra with synthetic calculations in the well-studied ν₂+2ν₃ band (7515-7620 cm⁻¹), we determine a methane absorption column density of 178±20 cm atm and a temperature of 118±10 K in our experiment. From this, we derive the methane absorption coefficients over 1.0-1.65 μm with a 0.03 cm⁻¹ sampling, allowing for the extrapolation of the results to any other methane column density under the relevant pressure and temperature conditions. We then revisit the calibration and analysis of the Titan “lamp-on” DLIS spectra. We infer a 5.1±0.8% methane-mixing ratio in the first 25 m of Titan's atmosphere. The CH₄ mixing ratio measured 90 s after landing from a distance of 45 cm is found to be 0.92±0.25 times this value, thus showing no post-landing outgassing of methane in excess of ∼20%. Finally, we determine the surface reflectivity as seen between 25 m and 45 cm and find that the 1500 nm absorption band is deeper in the post-landing spectrum as compared to pre-landing.     

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.     

Calculations of the thermochemistry of six reactions leading to ammonia formation in Titan's atmosphere

The thermochemical properties of the six reactions: (1) N₂+hν (solar EUV) → N⁺ + N(⁴S) + e⁻, (2) N⁺ + H₂ → NH⁺ + H, (3) NH⁺ + H₂ → NH⁺₂ + H, (4) NH⁺₂ + H₂ → NH⁺₃ + H, (5) NH⁺₃ + H₂ → NH⁺₄ + H, and (6) NH⁺₄ + e⁻ → NH₃ + H, were theoretically proposed by Atreya in 1986 and were cited in 2003 by Bernard who assumed that this chain reaction would lead to ammonia formation in Titan's atmosphere. The thermochemical properties of these six reactions have been calculated by means of the coupled cluster singles and doubles (CCSD) at the CCSD/cc-pvdz level, and the CCSD/6-311++g(3df,3pd) level, and G2 method. The geometries of the reactants and products of reactions have been optimized, the energies of reactions have been computed. The analysis of the results shows that: (I) The free energies of four reactions among these six reactions are negative. It means that these reactions, namely reactions (1)-(6) except reaction (2), can react spontaneously in Titan's low temperature environment. The converted temperatures of reactions (3) and (5) are 11881.7 and 4596.9 K, respectively. (II) Reaction (2) is an endothermic reaction, its converted temperature is 1797.6 K. When T<1797.6 K, reaction (2) cannot react forward spontaneously. The barrier of reaction (2) is 26.154 kcal mol⁻¹, which is probably too high to allow it to occur in the atmosphere of Titan. The rate for this reaction at 300 K has been calculated, and the value is k=4.16×¹⁰⁻⁷ s⁻¹. (III) The results of the three methods are more or less the same. So it is concluded that this chain reaction cannot be a pathway to lead to ammonia (gas phase) formation in Titan's atmosphere.     

Measurements of methane absorption by the descent imager/spectral radiometer (DISR) during its descent through Titan's atmosphere

New low-temperature methane absorption coefficients pertinent to the Titan environment are presented as derived from the Huygens DISR spectral measurements combined with the in-situ measurements of the methane gas abundance profile measured by the Huygens Gas Chromatograph/Mass Spectrometer (GCMS). The visible and near-infrared spectrometers of the descent imager/spectral radiometer (DISR) instrument on the Huygens probe looked upward and downward covering wavelengths from 480 to 1620 nm at altitudes from 150 km to the surface during the descent to Titan's surface. The measurements at continuum wavelengths were used to determine the vertical distribution, single-scattering albedos, and phase functions of the aerosols. The gas chromatograph/mass spectrometer (GCMS) instrument on the probe measured the methane mixing ratio throughout the descent. The DISR measurements are the first direct measurements of the absorbing properties of methane gas made in the atmosphere of Titan at the pathlengths, pressures, and temperatures that occur there. Here we use the DISR spectral measurements to determine the relative methane absorptions at different wavelengths along the path from the probe to the sun throughout the descent. These transmissions as functions of methane path length are fit by exponential sums and used in a haze radiative transfer model to compare the results to the spectra measured by DISR. We also compare the recent laboratory measurements of methane absorption at low temperatures [Irwin et al., 2006. Improved near-infrared methane band models and k-distribution parameters from 2000 to 9500 cm⁻¹ and implications for interpretation of outer planet spectra. Icarus 181, 309-319] with the DISR measurements. We find that the strong bands formed at low pressures on Titan act as if they have roughly half the absorption predicted by the laboratory measurements, while the weak absorption regions absorb considerably more than suggested by some extrapolations of warm measurements to the cold Titan temperatures. We give factors as a function of wavelength that can be used with the published methane coefficients between 830 and 1620 nm to give agreement with the DISR measurements. We also give exponential sum coefficients for methane absorptions that fit the DISR observations. We find the DISR observations of the weaker methane bands shortward of 830 nm agree with the methane coefficients given by Karkoschka [1994. Spectrophotometry of the jovian planets and Titan at 300- to 1000-nm wavelength: the methane spectrum. Icarus 111, 174-192]. Finally, we discuss the implications of our results for computations of methane absorption in the atmospheres of the outer planets.     

Complex Refractive Index of Titan's Aerosol Analogues in the 200-900 nm Domain

The main gas-phase constituents of Titan's upper atmosphere, N₂ and CH₄, are photolyzed and radiolyzed by solar photons and magnetospheric electrons, respectively. The primary products of these chemical interactions evolve to heavier organic compounds that are likely to associate into the particles of haze layers that hide Titan's surface. The different theories and models that have been put forward to explain the characteristics and properties of the haze composites require a knowledge of their optical properties, which are determined by the complex refractive index. We present a new set of values for refractive index n and extinction coefficient k calculated directly from the transmittance and reflectance curves exhibited by a laboratory analogue of Titan's aerosols in the 200-900 nm range. Improvements in the aerosol analogue quality have been made. The effects of variables such as the uncertainty in sample thickness, aerosol porosity, and amount of scattered light on the final n and k values are assessed and discussed. Within the studied wavelength domain, n varies from 1.53 to 1.68 and k varies from 2.62×10⁻⁴ to 2.87×10⁻². These final n and k values should be considered as a new reference to modelers who compute the properties of Titan's aerosols in trying to explain the atmospheric dynamics and surface characteristics.     

Condensate clouds in Titan's north polar stratosphere

Analysis of the 250-560 cm⁻¹ spectral continuum of Titan's north polar hood just after spring equinox reveals, in addition to the ubiquitous aerosol, a tenuous but relatively uniform cloud of small particles permeating the lower stratosphere at altitudes between 58 and 90 km. Voyager 1 IRIS data suggest the particles are highly scattering, almost certainly condensed organics, with radii between 1 and 5 μm. Mole fractions for the condensed material range between 4×¹⁰⁻⁸ and 4×¹⁰⁻⁶, depending upon particle size. Vapor pressure arguments imply condensed nitriles near 90 km, the most likely being HCN, with condensed hydrocarbons such as C₂H₆ restricted to regions considerably nearer the tropopause. No direct chemical identification is possible. Negligible methane supersaturation in the troposphere at 67.4° N latitude, when compared with degrees of supersaturation at other latitudes, hints at precipitation fluxes of north polar stratospheric condensates during the previous northern winter that were perhaps three orders of magnitude greater than those at low latitudes during that time. A scale height of 1.5 times the density scale height above 160 km is reaffirmed for the photochemical aerosol of the north polar hood. There appears to be a depletion of aerosol somewhere below 160 km. An aerosol mole fraction ∼8×¹⁰⁻⁸ at 160 km is inferred, about 33% greater than the value derived in a previous study. The Cassini CIRS instrument, with its expanded spectral range and higher spectral resolution, should be able to provide highly complementary information for the time period covering most of the northern winter season.     

Transition from Gaseous Compounds to Aerosols in Titan's Atmosphere

We investigate the chemical transition of simple molecules like C₂H₂ and HCN into aerosol particles in the context of Titan's atmosphere. Experiments that synthesize analogs (tholins) for these aerosols can help illuminate and constrain these polymerization mechanisms. Using information available from these experiments, we suggest chemical pathways that can link simple molecules to macromolecules, which will be the precursors to aerosol particles: polymers of acetylene and cyanoacetylene, polycyclic aromatics, polymers of HCN and other nitriles, and polyynes. Although our goal here is not to build a detailed kinetic model for this transition, we propose parameterizations to estimate the production rates of these macromolecules, their C/N and C/H ratios, and the loss of parent molecules (C₂H₂, HCN, HC₃N and other nitriles, and C₆H₆) from the gas phase to the haze. We use a one-dimensional photochemical model of Titan's atmosphere to estimate the formation rate of precursor macromolecules. We find a production zone slightly lower than 200 km altitude with a total production rate of 4×10⁻¹⁴ g cm⁻² s⁻¹ and a C/N?4. These results are compared with experimental data, and to microphysical model requirements. The Cassini/Huygens mission will bring a detailed picture of the haze distribution and properties, which will be a great challenge for our understanding of these chemical processes.     

Saturn's magnetospheric interaction with Titan as defined by Cassini encounters T9 and T18: New results

We present new results of Cassini's T9 flyby with complementary observations from T18. Based on Cassini plasma spectrometer (CAPS) and Cassini magnetometer (MAG), compositional evidence shows the upstream flow for both T9 and T18 appears composed of light ions (H⁺ and H₂⁺), with external pressures ∼30 times lower than that for the earlier TA flyby where heavy ions dominated the magnetospheric plasma. When describing the plasma heating and sputtering of Titan's atmosphere, T9 and T18 can be considered interactions of low magnetospheric energy input. On the other hand, T5, when heavy ion fluxes are observed to be higher than typical (i.e., TA), represents the limiting case of high magnetospheric energy input to Titan's upper atmosphere. Anisotropy estimates of the upstream flow are 1<T_⊥/T_‖<3 and the flow is perpendicular to B, indicative of local picked up ions from Titan's H and H₂ coronae extending to Titan's Hill sphere radius. Beyond this distance the corona forms a neutral torus that surrounds Saturn. The T9 flyby unexpectedly resulted in observation of two “wake” crossings referred to as Events 1 and 2. Event 2 was evidently caused by draped magnetosphere field lines, which are scavenging pickup ions from Titan's induced magnetopause boundary with outward flux ∼2×10⁶ ions/cm²/s. The composition of this out flow is dominated by H₂⁺ and H⁺ ions. Ionospheric flow away from Titan with ion flux ∼7×10⁶ ion/cm²/s is observed for Event 1. In between Events 1 and 2 are high energy field aligned flows of magnetosphere protons that may have been accelerated by the convective electric field across Titan's topside ionosphere. T18 observations are much closer to Titan than T9, allowing one to probe this type of interaction down to altitudes ∼950 km. Comparisons with previously reported hybrid simulations are made.     

The role of organic haze in Titan's atmospheric chemistry: I. Laboratory investigation on heterogeneous reaction of atomic hydrogen with Titan tholin

In Titan's atmosphere consisting of N₂ and CH₄, large amounts of atomic hydrogen are produced by photochemical reactions during the formation of complex organics. This atomic hydrogen may undergo heterogeneous reactions with organic aerosol in the stratosphere and mesosphere of Titan. In order to investigate both the mechanisms and kinetics of the heterogeneous reactions, atomic deuterium is irradiated onto Titan tholin formed from N₂ and CH₄ gas mixtures at various surface-temperatures of the tholin ranging from 160 to 310 K. The combined analyses of the gas species and the exposed tholin indicate that the interaction mechanisms of atomic deuterium with the tholin are composed of three reactions; (a) abstraction of hydrogen from tholin resulting in gaseous HD formation (HD recombination), (b) addition of D atom into tholin (hydrogenation), and (c) removal of carbon and/or nitrogen (chemical erosion). The reaction probabilities of HD recombination and hydrogenation are obtained as ηabst=1.9(±0.6)×¹⁰⁻³×exp(−300/T) and ηhydro=2.08(±0.64)×exp(−1000/T), respectively. The chemical erosion process is very inefficient under the conditions of temperature range of Titan's stratosphere and mesosphere. Under Titan conditions, the rates of hydrogenation > HD recombination ? chemical erosion. Our measured HD recombination rate is about 10 times (with an uncertainty of a factor of 3-5) the prediction of previous theoretical model. These results imply that organic aerosol can remove atomic hydrogen efficiently from Titan's atmosphere through the heterogeneous reactions and that the presence of aerosol may affect the subsequent organic chemistry.     

Maintenance of equatorial superrotation in the atmospheres of Venus and Titan

This paper extends Leovy's theory on Venus’ equatorial superrotation by analytically examining additional terms in the mean zonal momentum equation that stably balances the momentum source of pumping by thermal tides. The general analytical solution is applied to the atmospheres of both Venus and Saturn's moon Titan. The main results are: (i) Venus’ equatorial superrotation of 118 m s⁻¹ results primarily from a balance between the momentum source of pumping by thermal tides and the momentum sink of meridional advection of wind shear by horizontal branches of the Hadley circulation; (ii) no solution is found for Titan's stratospheric equatorial superrotation centered at the 1-hPa level; (iii) however, if the main solar radiation absorption layer in Titan's stratosphere is lifted from 1 hPa (∼185 km) to 0.1 hPa (∼288 km), an equatorial superrotation of ∼110 m s⁻¹ centered at 0.1-hPa could be maintained. Titan's equatorial superrotation results mainly from a balance between the momentum source of tidal pumping and the momentum sink of frictional drag.     

Characteristics of Titan's stratospheric aerosols and condensate clouds from Cassini CIRS far-infrared spectra

Four broad spectral features were identified in far-infrared limb spectra from the Cassini Composite Infrared Spectrometer (CIRS), two of which have not been identified before. The features are broader than the spectral resolution, which suggests that they are caused by particulates in Titan's stratosphere. We derive here the spectral properties and variations with altitude for these four features for six latitudes between 65° S and 85° N. Titan's main aerosol is called Haze 0 here. It is present at all wavenumbers in the far-infrared and is found to have a fractional scale height (i.e., the aerosol density scale height divided by the atmospheric density scale height) between 1.5 and 1.7 with a small increase in opacity in the north. A second feature around 140 cm⁻¹ (Haze A) has similar spatial properties to Haze 0, but has a smaller fractional scale height of 1.2-1.3. Both Haze 0 and Haze A show an increase in retrieved abundance below 100 km. Two other features (Haze B around 220 cm⁻¹ and Haze C around 190 cm⁻¹) have a large maximum in their density profiles at 140 and 90 km, respectively. Haze B is much more abundant in the northern hemisphere compared to the southern hemisphere. Haze C also shows a large increase towards the north, but then disappears at 85° N.     

A spherical model for computing polarized radiation in Titan's atmosphere

The Huygens descent through Titan's atmosphere in January 2005 will provide invaluable information about Titan's atmospheric composition and aerosol properties. The Descent Imager/Spectral Radiometer (DISR) will perform upward and downward looking radiation observations at various spectral ranges and spatial resolutions. To prepare the DISR data interpretation we have developed a new model for radiation transfer in Titan's atmosphere. The model solves for the full three-dimensional polarized radiation field in spherical geometry. However, the atmosphere itself is assumed to be spherically symmetric. The model is initialized with a fast-to-compute plane–parallel solution based on the doubling and adding algorithm that incorporates a spherical correction for the incoming direct solar beam. The full three-dimensional problem is then solved using the characteristics method combined with the Picard iterative approximation as described in Rozanov et al. (J. Quant. Spectrosc. Radiat. Transfer 69 (2001) 491). Aerosol scattering properties are calculated with a new microphysical model. In this formulation, aerosols are assumed to be fractal aggregates and include methane gas absorption embedded into the extinction coefficient. The resulting radiance of the model atmosphere's internal field is presented for two prescribed DISR wavelengths.     

Particle size and abundance of HC3N ice in Titan’s lower stratosphere at high northern latitudes

Up to now, there has been no corroboration from Cassini CIRS of the Voyager IRIS-discovery of cyanoacetylene (HC₃N) ice in Titan’s thermal infrared spectrum. We report the first compelling spectral evidence from CIRS for the ν₆ HC₃N ice feature at 506 cm⁻¹ at latitudes 62°N and 70°N, from which we derive particle sizes and column abundances in Titan’s lower stratosphere. We find mean particle radii of 3.0 μm and 2.3 μm for condensed HC₃N at 62°N and 70°N, respectively, and corresponding ice phase molecular column abundances in the range 1-10 × 10¹⁶ mol cm⁻². Only upper limits for cloud abundances can be established at latitudes of 85°N, 55°N, 30°N, 10°N, and 15°S. Under the assumption that cloud tops coincide with the uppermost levels at which HC₃N vapor saturates, we infer geometric thicknesses for the clouds equivalent to 10-20 km or so, with tops at 165 km and 150 km at 70°N and 62°N, respectively.     

Kinetic studies at room temperature of the cyanide anion CN with cyanoacetylene (HC3N) reaction

Rate coefficient of the cyanide anion (CN⁻) with cyanoacetylene (HC₃N) reaction, has been studied in gas phase at room temperature using a Flowing Afterglow Langmuir Probe - Mass Spectrometer (FALP-MS) apparatus. The rate constant for the CN⁻ + HC₃N reaction is k = 4.8 × 10⁻⁹ cm³/s with an uncertainty of 30%.     

Cassini CIRS update on stratospheric ices at Titan's winter pole

A strong, broad spectral emission feature at 85° N latitude centered at 221 cm⁻¹ remains unidentified after candidate ices of H₂O and pure crystalline CH₃CH₂CN are unambiguously ruled out. A much shallower weak emission feature starts at 160 cm⁻¹ and blends into the strong feature at ∼190 cm⁻¹. This feature is consistent with one formed by an HCN ice cloud composed of ?5 μm radius particles that resides in the lower stratosphere somewhere below an altitude of 160 km. Titan's stratospheric aerosol appears to have a spectral emission feature at about 148 cm⁻¹. The aerosol abundance at 85° N is about a factor 2.2 greater than at 55° S.     

Titan's stratospheric C2N2, C3H4, and C4H2 abundances from Cassini/CIRS far-infrared spectra

Far-IR (25-50 μm, 200-400 cm⁻¹) nadir and limb spectra measured during Cassini's four year prime mission by the Composite InfraRed Spectrometer (CIRS) instrument have been used to determine the abundances of cyanogen (C₂N₂), methylacetylene (C₃H₄), and diacetylene (C₄H₂) in Titan's stratosphere as a function of latitude. All three gases are enriched at northern latitudes, consistent with north polar subsidence. C₄H₂ abundances agree with those derived previously from mid-IR data, but C₃H₄ abundances are about 2 times lower, suggesting a vertical gradient or incorrect band intensities in the C₃H₄ spectroscopic data. For the first time C₂N₂ was detected at southern and equatorial latitudes with an average volume mixing ratio of 5.5±1.4×¹⁰−11 derived from limb data (>3-σ significance). This limb result is also corroborated by nadir data, which give a C₂N₂ volume mixing ratio of 6±3×¹⁰−11 (2-σ significance) or alternatively a 3-σ upper limit of 17×¹⁰−11. Comparing these figures with photochemical models suggests that galactic cosmic rays may be an important source of N₂ dissociation in Titan's stratosphere. Like other nitriles (HCN, HC₃N), C₂N₂ displays greater north polar relative enrichment than hydrocarbons with similar photochemical lifetimes, suggesting an additional loss mechanism for all three of Titan's main nitrile species. Previous studies have suggested that HCN requires an additional sink process such as incorporation into hazes. This study suggests that such a sink may also be required for Titan's other nitrile species.     

Latitudinal variations of HCN, HC3N, and C2N2 in Titan's stratosphere derived from Cassini CIRS data

Mid- and far-infrared spectra from the Composite InfraRed Spectrometer (CIRS) have been used to determine volume mixing ratios of nitriles in Titan's atmosphere. HCN, HC₃N, C₂H₂, and temperature were derived from 2.5 cm⁻¹ spectral resolution mid-IR mapping sequences taken during three flybys, which provide almost complete global coverage of Titan for latitudes south of 60° N. Three 0.5 cm⁻¹ spectral resolution far-IR observations were used to retrieve C₂N₂ and act as a check on the mid-IR results for HCN. Contribution functions peak at around 0.5-5 mbar for temperature and 0.1-10 mbar for the chemical species, well into the stratosphere. The retrieved mixing ratios of HCN, HC₃N, and C₂N₂ show a marked increase in abundance towards the north, whereas C₂H₂ remains relatively constant. Variations with longitude were much smaller and are consistent with high zonal wind speeds. For 90°-20° S the retrieved HCN abundance is fairly constant with a volume mixing ratio of around 1 × 10⁻⁷ at 3 mbar. More northerly latitudes indicate a steady increase, reaching around 4 × 10⁻⁷ at 60° N, where the data coverage stops. This variation is consistent with previous measurements and suggests subsidence over the northern (winter) pole at approximately 2 × 10⁻⁴ m s⁻¹. HC₃N displays a very sharp increase towards the north pole, where it has a mixing ratio of around 4 × 10⁻⁸ at 60° N at the 0.1-mbar level. The difference in gradient for the HCN and HC₃N latitude variations can be explained by HC₃N's much shorter photochemical lifetime, which prevents it from mixing with air at lower latitude. It is also consistent with a polar vortex which inhibits mixing of volatile rich air inside the vortex with that at lower latitudes. Only one observation was far enough north to detect significant amounts of C₂N₂, giving a value of around 9 × 10⁻¹⁰ at 50° N at the 3-mbar level.     

Hardening of Titan's aerosols by their charging

Titan's haze consists of long chain polymers of pure and N-mixed hydrocarbons (Coustenis et al., 1989, Icarus 80, 54-76, 1991, Icarus 89, 152-167). These polymers have regularly alternating (i.e., conjugated) double/single and triple/single bonds, which open either spontaneously (free aging) or under the action of some external factors (forced aging), the latter being very diverse, e.g., charging, photolysis, radiolysis, thermolysis, chemical effect of environment, etc. An essential of free aging was examined previously (Dimitrov and Bar-Nun, 2002, Icarus 156, 530-538). The main distinction between free and any forced aging is that both of them possess the same thermodynamics while different kinetics, the forced aging in any case being faster, proceeding in different pathways than the free aging. The more extensive is the list of the external effects and the more intensive they are, the faster and more variably the forced aging proceeds. In this paper we quantified the kinetics of forced aging, considering charging of Titan's aerosol population. It was found that forced aging proceeds approximately hundred times faster as compared to the free aging. Various physico-chemical properties of Titan's aerosol material, including coagulation coefficients, depending on particle size and medium conditions, were defined. The comparison of the aging rate, rate of sedimentation and rate of the particle increase proves that Titan's aerosol domain can be subdivided conditionally into two big subdomains. The upper one contains minor portion (<5%) of the total aerosol bulk, unannealed aerosol particles being fine and sticky. The lower subdomain contains the major portion (>95%) of aerosol bulk, which is completely aged, coarsely dispersed particles. We established the border between these subdomains at the altitude Z∼620 km.