Aging of Titan's Aerosols

Titan's haze is composed of aerosols containing long chain polymers of acetylene with some hydrogen cyanide. These polymers have alternating double/single and triple/single bonds, which can open spontaneously or under the action of UV radiation or particle impact. Once opened, they can induce the opening of a double or triple bond in an adjacent chain and link to it. This cross-linking and chain elongation hardens or “ages” the polymer particles, making them less sticky. As observed experimentally and calculated theoretically, newly formed polymer particles grow by collecting other polymer chains and by complete merging into symmetrical spheres. However, when aged, they merely adhere to each other and do not merge. Eventually, when hard enough, they do not even adhere to each other. In this paper we calculate the spontaneous aging process as applied to Titan's atmospheric conditions and find that the surface tension and viscosity of the aerosols below H∼570 km are one order of magnitude harder than when the aerosols formed. Furthermore, UV irradiation and particle impacts reduce both viscosity and surface tension by an additional factor of 10-100. Thus, the aerosol particles expected to be encountered by the descending Huygens probe will, most likely, be quite hard.     

Laboratory light-scattering measurements with Titan's aerosols analogues produced by a dusty plasma

The chemistry leading to the formation of solid aerosols (tholins) in Titan's atmosphere is simulated by a capacitively coupled plasma in a N₂-CH₄ gas mixture. The solid grains are produced in volume directly in the gas phase and studied ex-situ by SEM imaging and by light scattering on clouds of particles. The scattered light properties depend on the physical properties of the particles (morphologies, size distribution), as well as on the phase angle and the wavelength of the light. The particles may be aggregated or agglomerated grains. The grains size distribution is studied as a function of plasma parameters such as initial methane concentration introduced into the discharge, gas flow, absorbed RF power and plasma duration. The average grain size increases when the amount of CH₄ increases, when the gas flow decreases, and when the plasma duration increases up to a limit for each production condition.For all the samples, the absorption decreases with increasing wavelength in the visible domain. As usually found for irregular particles, the polarization phase curves have a bell-shaped positive branch and a shallow negative branch. The maximum of polarization (P_max) increases when the average grain size decreases (sub-μm-sized grains). To obtain P_max values within the range of those measured in Titan's atmosphere; the average grains diameter has to be smaller than 100 nm, in agreement with the space observations results. In the light-scattering experiment, the size of the agglomerates in the clouds is in the 40-80 μm range in equivalent diameter. As a consequence P_max increases with decreasing wavelength due to the increasing absorption, in agreement with observations of Titan from outside the atmosphere.     

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.     

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 from 0 to 400 km. Ionization due to both galactic cosmic rays and electron precipitation from the Saturnian magnetosphere is considered. This ionization results in free electrons and the primary ions N₂⁺ and N⁺ which are then rapidly converted into secondary ions such as H₂CN⁺ and NH₄⁺ which in turn form ion clusters such as H₂CN⁺(HCN)_n and NH₄⁺(NH₃)_m. In contrast to the atmospheres of Venus and Earth, we find no species in the Titan atmosphere that lead to the formation of appreciable concentrations of negative ions. Consequently, the predicted conductivity is quite different in that a substantial concentration of electrons exists all the way to the surface of Titan. The ubiquitous aerosols observed in the Titan atmosphere also play an important role in determining the charge distribution in the atmosphere. At altitudes above 100 km and for aerosol concentrations above approximately 10/cc, the recombination of electrons and positive ions is controlled by the recombination on the surface of the aerosols rather than by the gas-kinetic recombination rate. For small aerosol concentrations, the ratio of the number of charges per particle to the radius of the particle is approximately 30, for radii in microns. This value is similar to that obtained by previous investigators for terrestrial noctilucent clouds. Because the aerosol particles are highly charged, coagulation is inhibited, particle sizes are smaller, and their settling rates are reduced. As a consequence, the optical depth of the atmosphere is much higher than it would be if the particles were uncharged.     

A physical model of Titan's aerosols

Microphysical simulations of Titan's stratospheric haze show that aerosol microphysics is linked to organized dynamical processes. The detached haze layer may be a manifestation of 1 cm sec-1 vertical velocities at altitudes above 300 km. The hemispherical asymmetry in the visible albedo may be caused by 0.05 cm sec-1 vertical velocities at altitudes of 150 to 200 km, we predict contrast reversal beyond 0.6 micrometer. Tomasko and Smith's (1982, Icarus 51, 65-95) model, in which a layer of large particles above 220 km altitude is responsible for the high forward scattering observed by Rages and Pollack (1983, Icarus 55, 50-62), is a natural outcome of the detached haze layer being produced by rising motions if aerosol mass production occurs primarily below the detached haze layer. The aerosol's electrical charge is critical for the particle size and optical depth of the haze. The geometric albedo, particularly in the ultraviolet and near infrared, requires that the particle size be near 0.15 micrometer down to altitudes below 100 km, which is consistent with polarization observations (Tomasko and Smith 1982, West and Smith 1991, Icarus 90, 330-333). Above about 400 km and below about 150 km Yung et al.'s (1984, Astrophys. J. Suppl. Ser. 55, 465-506) diffusion coefficients are too small. Dynamical processes control the haze particles below about 150 km. The relatively large eddy diffusion coefficients in the lower stratosphere result in a vertically extensive region with nonuniform mixing ratios of condensable gases, so that most hydrocarbons may condense very near the tropopause rather than tens of kilometers above it. The optical depths of hydrocarbon clouds are probably less than one, requiring that abundant gases such as ethane condense on a subset of the haze particles to create relatively large, rapidly removed particles. The wavelength dependence of the optical radius is calculated for use in analyzing observations of the geometric albedo. The lower atmosphere and surface should be visible outside of regions of methane absorption in the near infrared. Limb scans at 2.0 micrometers wavelength should be possible down to about 75 km altitude.     

Optical properties of aerosols in Titan's atmosphere

In the frame of fractal modeling of tholin aggregates we made a systematic analysis of their optical properties. Ballistic particle-cluster aggregation (BPCA) and diffusion-limited aggregation (DLA) of spherical primary particles (monomers) identical in material composition were considered. Aggregates composed of identical particles (monodisperse cluster), as well as of size-distributed particles (polydisperse cluster), were simulated. To calculate the light-scattering models, the code based on the superposition T-matrix method is used. Orientationally averaged properties of light scattering by model particles were extracted, and the normalized phase function and the degree of linear polarization were calculated as functions of scattering angle. We concluded that: (a) aggregation mechanism as well as specific internal structure of the clusters play only a minor role, and for the future it is not necessary to investigate aggregates of different types; (b) the intensity is very sensitive both to the size parameter of forming particles x and to the size parameter of the aggregates X; (c) characterization of the aggregates by the number of monomers is insufficient to retrieve physical properties of aggregates from optical measurement; and (d) it is very desirable to include into the analysis polarization data calculated for the different clusters.     

Effect of charging of aerosols in the lower atmosphere of Mars during the dust storm of 2001

Aerosols are very important in the Martian climate system. Aerosols get charged by the attachment of ions in the atmosphere. Charging of aerosols reduces the conductivity of the atmosphere as the very mobile ions are lost during the ion-aerosol attachment. During a dust storm the dust opacity increases and more ion-aerosol attachment process occurs and consequently conductivity reduces further. It was found that with the background aerosols (dust opacity ∼0.2), the conductivity close to the surface of Mars was reduced by a factor of 5, but during the dust storm (opacity ∼5) of 2001 the conductivity decreased by about 2 orders of magnitude.     

A model of Titan's haze of fractal aerosols constrained by multiple observations

We use Titan's geometric albedo to constrain the vertical distribution of the haze. Microphysical models incorporating fractal aggregates do not readily fit the methane features at 0.62 μm band and the dark 0.88 μm of the albedo spectrum simultaneously. We take advantage of this apparent discrepancy to constrain the haze vertical profile.We used the geometric albedo and several results and constraints from other works to better constrain the vertical haze extinction profile, especially in the low stratosphere. The objective of this model is to give a solution that simultaneously fits the main constraints known to apply to the haze.We find that the haze extinction increases with decreasing altitude with a scale height about equal to the atmospheric scale height down to 100 km. Below this altitude, extinction must decrease down to 30 km. This is necessary in order to have enough haze to sustain a relatively high albedo (0.076) in the dark 0.88 μm methane band and to show the 0.62 μm band in the haze continuum. We set the haze production rate around 7×10⁻¹⁴ kgm⁻² s⁻¹, and the aerosols production altitude around 400 km (or at pressure 1.5 Pa).The physical processes which generate such a profile are not clear. However, purely one-dimensional effects such as condensation, sedimentation, and rainout can be ruled out, and we believe that this relative clearing in Titan's troposphere and lower stratosphere is due to particle horizontal transport by the mean circulation.     

Laboratory simulations of Titan's atmosphere: organic gases and aerosols

Titan, the main satellite of Saturn, has been observed by remote sensing for many years, both from interplanetary probes (Pioneer and Voyager's flybys) and from the Earth. Its N2 atmosphere, containing a small fraction of CH4 (approximately 2%), with T approximately 90 K and P approximately 1.5 bar at the ground level, is irradiated by solar UV photons and deeply bombarded by energetic particles, i.e. Saturn mangetospheric electrons and protons, interplanetary electrons and cosmic rays. The resulting energy deposition, which takes place mainly below 1000 km, initiates chemical reactions which yield gaseous hydrocarbons and nitriles and, through polymerisation processes, solid aerosol particles which grow by coagulation and settle down to the ground. At the present time, photochemical models strongly require the results of specific laboratory studies. Chemical rate constants are not well known at low temperatures, charged-particle-induced reactions are difficult to model and laboratory simulations of atmospheric processes are therefore of great interest. Moreover, the synthesis of organic compounds which have not been detected to date provides valuable information for future observations. The origin and chemical composition of aerosols depend on the nature of chemical and energy sources. Their production from gaseous species may be monitored in laboratory chambers and their optical or microphysical properties compared to those deduced from the observations of Titan's atmosphere. The development of simulation chambers of Titan's extreme conditions is necessary for a better understanding of past and future observations. Space probes will sound Titan's atmosphere by remote sensing and in situ analysis in the near future (Cassini-Huygens mission). It appears necessary, as a preliminary step to test on-board experiments in such chambers, and as a final step, when new space data have been acquired, to use them for more general scientific purposes.     

Titan's aerosols: Comparison between our model and DISR findings

Our model [Dimitrov, V., Bar-Nun, A., 1999. A model of energy dependent agglomeration of hydrocarbon aerosol particles and implication to Titan's aerosol. J. Aerosol. Sci. 30(1), 35-49] describes the experimentally found polymerization of C₂H₂ and HCN to form aerosol embryos, their growth and adherence to form various aerosols objects [Bar-Nun, A., Kleinfeld, I., Ganor, E., 1988. Shape and optical properties of aerosols formed by photolysis of C₂H₂, C₂H₄ and HCN. J. Geophys. Res. 93, 8383-8387]. These loose fractal objects describe well the findings of DISR on the Huygens probe [Tomasko, M.G., Bézard, B., Doose, L., Engel, S., Karkoschka, E., 2008. Measurements of methane absorption by the descent imager/spectral radiometer (DISR) during its descent through Titan's atmosphere. Planet. Space Sci., this issue, doi:10.1016/j.pss.2007]. These include (1) various regular objects of R=(0.035-0.064)×10⁻⁶ m, as compared with DISR's 0.05×10⁻⁶ m; (2) diverse low and high fractal structures composed of random combinations of various regular and irregular objects; (3) the number density of fractal particles is 6.9×10⁶ m⁻³ at Z=100 km, as compared with DISR's finding of 5.0×10⁶ m⁻³ at Z=80 km; (4) the number of structural units per higher fractals in the atmosphere at Z∼100 km is (2400-2700), as compared with DISR's 3000, and their size being of R=(5.4-6.4)×10⁻⁶ m will satisfy this value and (5) condensation of CH₄ on the highly fractal structures could begin at the altitude where thin methane clouds were observed, filling somewhat the new open fractal structures.     

High-altitude charged aerosols in the atmosphere of Titan

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

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.     

Impact of aerosols present in Titan's atmosphere on the CASSINI radar experiment

Simulations of Titan's atmospheric transmission and surface reflectivity have been developed in order to estimate how Titan's atmosphere and surface properties could affect performances of the Cassini radar experiment. In this paper we present a selection of models for Titan's haze, vertical rain distribution, and surface composition implemented in our simulations. We collected dielectric constant values for the Cassini radar wavelength (∼2.2 cm) for materials of interest for Titan: liquid methane, liquid mixture of methane-ethane, water ice, and light hydrocarbon ices. Due to the lack of permittivity values for Titan's haze particles in the microwave range, we performed dielectric constant (ε_r) measurements around 2.2 cm on tholins synthesized in laboratory. We obtained a real part of ε_r in the range of 2-2.5 and a loss tangent between 10⁻³ and 5×10⁻². By combining aerosol distribution models (with hypothetical condensation at low altitudes) to surface models, we find the following results: (1) Aerosol-only atmospheres should cause no loss and are essentially transparent for Cassini radar, as expected by former analysis. (2) However, if clouds are present, some atmospheric models generate significant attenuation that can reach −50 dB, well below the sensitivity threshold of the receiver. In such cases, a 13.78 GHz radar would not be able to measure echoes coming from the surface. We thus warn about possible risks of misinterpretation if a “wet atmosphere” is not taken into account. (3) Rough surface scattering leads to a typical response of ∼−17 dB. These results will have important implications on future Cassini radar data analysis.     

An investigation of Titan's aerosols using microwave analog measurements and radiative transfer modeling

A combination of laboratory experiments, theoretical modeling, and spacecraft observations is employed to characterize the aerosols in the atmosphere of Titan. The scattering properties of model aerosols were measured using the Microwave Analog Light Scattering Facility at the University of Florida and complemented with theoretical modeling of single scattering characteristics and radiative transfer in Titan's atmosphere. This study compares these modeling results with photopolarimetric observations made over a range of phase angles by the Pioneer 11 and Voyagers 1 and 2 spacecraft. Important results of this work include a survey of the scattering properties of different particle morphologies and compositions necessary to accurately interpret these observations without introducing non-physical assumptions about the particles or requiring additional free parameters to the radiative transfer models. Previous studies use calculation methods which, due to computing memory and processing time requirements, a priori exclude much of the parameter space that the microwave analog laboratory is ideal for exploring. The goal of the present work, to directly constrain aerosol physical characteristics, is addressed by studying in a consistent manner how a variety of particle morphologies and refractive indices affect the polarization and intensity reflected by Titan's atmosphere. Based on comparisons of model results to spacecraft observations, many model morphologies are excluded from further consideration. The most plausible physical particle models suggest that a combination of Rayleigh-like single particles and aggregates that are larger than those previously suggested and investigated [West, R.A., Smith, P.H., 1991. Evidence for aggregate particles in the atmospheres of Titan and Jupiter. Icarus 90, 330-333; Rannou, P., Cabane, M., Botet, R., Chassefière, E., 1997. A new interpretation of scattered light measurements at Titan's limb. J. Geophys. Res. 102, 10997-11013] provide the best fit to the existing data. Additional laboratory experiments and more refined modeling awaits the results of the new rich observational dataset from the Cassini/Huygens encounter with Titan.     

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.     

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.     

Simulations of Titan's brightness by a two-dimensional haze model

We have used a 2-D microphysics model to study the effects of atmospheric motions on the albedo of Titan's thick haze layer. We compare our results to the observed variations of Titan's brightness with season and latitude. We use two wind fields; the first is a simple pole-to-pole Hadley cell that reverses twice a year. The second is based on the results of a preliminary Titan GCM. Seasonally varying wind fields, with horizontal velocities of about 1 cm sec-1 at optical depth unity, are capable of producing the observed change in geometric albedo of about 10% over the Titan year. Neither of the two wind fields can adequately reproduce the latitudinal distribution of reflectivity seen by Voyager. At visible wavelengths, where only haze opacity is important, upwelling produces darkening by increasing the particle size at optical depth unity. This is due to the suspension of larger particles as well as the lateral removal of smaller particles from the top of the atmosphere. At UV wavelengths and at 0.89 micrometers the albedo is determined by the competing effects of the gas the haze material. Gas is bright in the UV and dark at 0.89 micrometers. Haze transport at high altitudes controls the UV albedo and transport at low altitude controls the 0.89 micrometers albedo. Comparisons between the hemispheric contrast at UV, visible, and IR wavelengths can be diagnostic of the vertical structure of the wind field on Titan.     

Oxygen compounds in Titan's stratosphere as observed by Cassini CIRS

We have investigated the abundances of Titan's stratospheric oxygen compounds using 0.5 cm⁻¹ resolution spectra from the Composite Infrared Spectrometer on the Cassini orbiter. The CO abundance was derived for several observations of far-infrared nadir spectra, taken at a range of latitudes (75° S-35° N) and emission angles (0°-60°), using rotational lines that have not been analysed before the arrival of Cassini at Saturn. The derived volume mixing ratios for the different observations are mutually consistent regardless of latitude. The weighted mean CO volume mixing ratio is 47±8 ppm if CO is assumed to be uniform with latitude. H₂O could not be detected and an upper limit of 0.9 ppb was determined. CO₂ abundances derived from mid-infrared nadir spectra show no significant latitudinal variations, with typical values of 16±2 ppb. Mid-infrared limb spectra at 55° S were used to constrain the vertical profile of CO₂ for the first time. A vertical CO₂ profile that is constant above the condensation level at a volume mixing ratio of 15 ppb reproduces the limb spectra very well below 200 km. This is consistent with the long chemical lifetime of CO₂ in Titan's stratosphere. Above 200 km the CO₂ volume mixing ratio is not well constrained and an increase with altitude cannot be ruled out there.     

Dissipation of Titan's south polar clouds

Nearly all adaptive optics images of Titan taken between December 2001 and November 2004 showed tropospheric clouds located within 30° of the south pole. We report here on a dissipation of Titan's south polar clouds observed in twenty-nine Keck and Gemini images taken between December 2004 and April 2005. The near complete lack of south polar cloud activity during this time, and subsequent resurgence months later at generally higher latitudes, may be the beginning of seasonal change in Titan's weather. The ∼5 month decrease in cloud activity may also have been caused by methane rainout from a large cloud event in October 2004. Understanding the seasonal evolution of Titan's clouds, and of any precipitation associated with them, is essential for interpreting the geological observations of fluid flow features observed over a wide range of Titan latitudes with the Cassini/Huygens spacecraft.     

Ejection of nitrogen from Titan's atmosphere by magnetospheric ions and pick-up ions

A 3-D Monte Carlo model is used to describe the ejection of N and N₂ from Titan due to the interaction of Saturn's magnetospheric N⁺ ions and molecular pick-up ions with its N₂ atmosphere. Based on estimates of the ion flux into Titan's corona, atmospheric sputtering is an important source of both atomic and molecular nitrogen for the neutral torus and plasma in Saturn's outer magnetosphere, a region now being studied by the Cassini spacecraft.