Determination of the complex refractive indices of Titan haze analogs using photothermal deflection spectroscopy

The spectrometers of the Cassini mission to the Saturn system have detected haze layers reaching up to 800 km in Titan’s atmosphere. Knowledge of the complex refractive index (k) of the haze is important for modeling the surface and atmosphere of Titan and retrieving some information about the functional groups present in the aerosols. Plasma discharges or ultraviolet radiation are commonly used to drive the formation of solid organics assumed to be good analogs of the Titan aerosols. [Tran, B.N., Ferris, J.P., Chera, J.J., 2003a. The photochemical formation of a Titan haze analog. Structural analysis by X-ray photoelectron and infrared spectroscopy. Icarus 162, 114-124; Tran, B.N., Force, M., Briggs, R., Ferris J.P., Persans, P., Chera, J.J., 2008. Photochemical processes on Titan: Irradiation of mixtures of gases that simulate Titan’s atmosphere. Icarus 177, 106-115] reported the index of refraction of analogs synthesized by far ultraviolet irradiation of various gas mixtures. k was determined in the 200-800 nm wavelength range from transmission and reflection spectroscopy. However, this technique is limited by (i) uncertainties in the absorption values because of the small amounts of organics available, (ii) light scattering by the surface roughness and particulates in the sample. These limitations prompted us to perform new measurements using photothermal deflection spectroscopy (PDS), a technique based on the conversion of absorbed light into heat in the material of interest. By combining traditional spectroscopy (λ < 500 nm) and PDS (λ > 500 nm), we determined values of k over the 375-1550 nm range. k values as low as 10⁻⁴ above 1000 nm were determined. This is one order of magnitude lower than the measurements generally used as a reference for Titan’s aerosols analogs [Khare, B.N., Sagan, C., Arakawa, E.T., Suits, F., Callicott, T.A., Williams, M.W., 1984. Optical-constants of organic Tholins produced in a simulated Titanian atmosphere—from soft-X-ray to microwave-frequencies. Icarus 60(1), 127-137]. We recommend that these results were used in models to describe the optical properties of the aerosols produced in Titan’s stratosphere.     

Characterization of zonal winds in the stratosphere of Titan with UVES

Titan has been observed with UVES, the UV-Visual Echelle Spectrograph at the Very Large Telescope, with the aim of characterizing the zonal wind flow. We use a retrieval scheme originally developed for absolute stellar accelerometry [Connes, P., 1985. Astrophys. Space Sci., 110, 211-255] to extract the velocity signal by simultaneously taking into account all the lines present in the spectrum. The method allows to measure the Doppler shift induced at a given point by the zonal wind flow, with high precision. The short-wavelength channel (4200-5200 Å) probes one scale height higher than the long-wavelength one (5200-6200 Å), and we observe statistically significant evidence for stronger winds at higher altitudes. The results show a high dispersion. Globally, we detect prograde zonal winds, with lower limits of 62 and 50 m s⁻¹ at the regions centered at 200 and 170 km altitude, but approximately a quarter of the measurements indicates null or retrograde winds.     

Detection of CH3D on Titan

We report the detection of ¹³CH₃D in Titan's stratosphere from Cassini/CIRS infrared spectra near 8.7 μm. Fitting simultaneously the ν₆ bands of both ¹³CH₃D and ¹²CH₃D and the ν₄ band of CH₄, we derive a D/H ratio equal to and a ¹²C/¹³C ratio in deuterated methane of , consistent with that measured in normal methane.     

Optical properties of Titan and early Earth haze laboratory analogs in the mid-visible

Scattering and absorption of sunlight by aerosols are integral to understanding the radiative balance of any planetary atmosphere covered in a haze, such as Titan and possibly the early Earth. One key optical parameter of an aerosol is its refractive index. We have simulated both Titan and early Earth organic haze aerosols in the laboratory and measured the real and imaginary portion of their refractive index at λ = 532 nm using cavity ringdown aerosol extinction spectroscopy. This novel technique allows analysis on freely-floating particles minutes after formation. For our Titan analog particles, we find a real refractive index of n = 1.35 ± 0.01 and an imaginary refractive index k = 0.023 ± 0.007, and for the early Earth analog particles we find n = 1.81 ± 0.02 and k = 0.055 ± 0.020. The Titan analog refractive index has a smaller real and similar imaginary refractive index compared to most previous laboratory measurements of Titan analog films, including values from Khare et al. (Khare, B.N., Sagan, C., Arakawa, E.T., Suits, F., Callcott, T.A., Williams, M.W. [1984]. Icarus 60, 127-137). These newly measured Titan analog values have implications for spacecraft retrievals of aerosol properties on Titan. The early Earth analog has a significantly higher real and imaginary refractive index than Titan analogs reported in the literature. These differences suggest that, for a given amount of aerosol, the early Earth analog would act as a stronger anti-greenhouse agent than the Titan analog.     

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.     

Global and temporal variations in hydrocarbons and nitriles in Titan's stratosphere for northern winter observed by Cassini/CIRS

Mid-infrared spectra measured by Cassini's Composite InfraRed Spectrometer (CIRS) between July 2004 and January 2007 (Ls=293°-328°) have been used to determine stratospheric temperature and abundances of C₂H₂, C₃H₄, C₄H₂, HCN, and HC₃N. Over 65,000 nadir spectra with spectral resolutions of 0.5 and 2.5 cm⁻¹ were used to probe spatial and temporal composition variations in Titan's stratosphere. Cassini's 180° orbital transfer in mid-2006 allowed low emission angle observations of the north polar region for the first time in the mission and allowed us to probe the full latitude range. We present the first measurements of composition variations within the polar vortex, which display increasing abundances right up to 90° N. The lack of a homogeneous abundance-latitude variation within the vortex indicates limited horizontal mixing and suggests that subsidence is greatest at the vortex core. Contrary to numerical model predictions and tropospheric cloud observations, we do not see any evidence for a secondary circulation cell near the south pole, which suggests a single Hadley-type circulation in the stratosphere at this epoch. This difference can be reconciled if the secondary cell is restricted to altitudes below 100 km, where there is no sensitivity in our data. Temporal variations in composition were observed in the south, with volatile species becoming less abundant as the season progressed. The observed variations are compared to numerical model predictions and observations from Voyager.     

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.     

Condensation in Titan's stratosphere during polar winter

In Titan's north polar region stratospheric clouds are expected to form due to a combination of low temperatures and downward motion of volatile-enriched air. Here we investigate possible sources of stratospheric clouds at Titan's pole using data from the Cassini Composite Infrared Spectrometer and a simple condensation model. An upper limit for C₄N₂ gas was determined to be 9×¹⁰⁻⁹, which is less than required to make the C₄N₂ cloud at the Voyager epoch. Hence, the presence of this cloud after equinox remains a mystery. The largest cloud seen in far-infrared spectra has a feature around 220 cm⁻¹ and is located around an altitude of 140 km. The upper limit for propionitrile (C₂H₅CN) gas shows that the feature around 220 cm⁻¹ is probably not due to pure propionitrile ice. Instead, our model calculations show that HCN should cause by far the largest cloud around 140 km. We therefore propose that HCN ice plays an important role in the formation of the massive polar cloud, because of the unavailability of sufficient condensable gas other than HCN to produce a strong enough condensate feature. However, the signature at 220 cm⁻¹ is not consistent with that of pure HCN ice at 172 cm⁻¹ and mixing of HCN ice with other ices, or chemical alteration of HCN ice might mask the HCN ice signature.     

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.     

Influence of neutral transport on ion chemistry uncertainties in Titan ionosphere

Models of Titan ionospheric chemistry have shown that ion densities depend strongly on the neutral composition. The turbulent diffusion transport conditions, as modeled by eddy coefficients, can spectacularly affect the uncertainty on predicted neutral densities. In order to evaluate the error budget on ion densities predicted by photochemical models, we perform uncertainty propagation of neutral densities by Monte Carlo sampling and assess their sensitivity to two turbulent diffusion profiles, corresponding to the extreme profiles at high altitudes described in the literature. A strong sensitivity of the ion density uncertainties to transport is observed, generally more important than to ion–molecule reaction parameters themselves. This highlights the necessity to constrain eddy diffusion profiles for Titan ionosphere, which should progressively be done thanks to the present and future measurements of the orbiter Cassini.     

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.     

Latitudinal transport by barotropic waves in Titan's stratosphere.: I. General properties from a horizontal shallow-water model

We present a numerical study of barotropic waves in Titan's stratosphere based on a shallow-water model. The forcing of the zonal flow by the mean meridional circulation is represented by a relaxation towards a barotropically unstable wind profile. The relaxation profile is consistent with observations and with previous results from a 3D general circulation model. The time constant of the forcing that best matches the northward eddy-transport of zonal momentum from the 3D model is τ∼5 Titan days. The eddy wind field is a zonal wavenumber-2 wave with a peak amplitude about 10% of the mean wind speed. The latitudinal transport of angular momentum by the wave tends to keep the flow close to marginal stability by carrying momentum upgradient, from the core of the jets into the low latitudes. Although the strongest eddy motions occur at the latitudes of the wind maxima, the strongest mixing takes place at the barotropically unstable regions, close to ±30° and spanning about 30° in latitude. An eddy-mixing time constant of the order of 1 Titan day is inferred within these regions, and of a few tens of days within regions of stable flow. Horizontal gradients in transient tracer fields are less than 10% of the latitudinal gradient of the meridional tracer profile. Cassini's detection of such waves could provide a direct observation of wind speeds at stratospheric levels.     

Local sensitivity analysis for observed hydrocarbons in a Jupiter photochemistry model

A box model sensitivity analysis was applied to output from a version of the 1-D JPL/Caltech KINETICS photochemistry-transport model of Jupiter's atmosphere. Results quantify the controlling chemical reaction parameters for the variety of observable hydrocarbons, and suggest changes to explore and new observations and rate measurements to pursue. High sensitivities are found to photolysis steps and to several hydrogen atom recombination steps and product branches. Complexity ranges from the relatively simple scheme seen for the methyl radical, to the rich variety of reactions tested by diacetylene.     

Latitudinal transport by barotropic waves in Titan's stratosphere.: II. Results from a coupled dynamics-microphysics-photochemistry GCM

We present a 2D general circulation model of Titan's atmosphere, coupling axisymmetric dynamics with haze microphysics, a simplified photochemistry and eddy mixing. We develop a parameterization of latitudinal eddy mixing by barotropic waves based on a shallow-water, longitude-latitude model. The parameterization acts locally and in real time both on passive tracers and momentum. The mixing coefficient varies exponentially with a measure of the barotropic instability of the mean zonal flow. The coupled GCM approximately reproduces the Voyager temperature measurements and the latitudinal contrasts in the distributions of HCN and C₂H₂, as well as the main features of the zonal wind retrieved from the 1989 stellar occultation. Wind velocities are consistent with the observed reversal time of the North-South albedo asymmetry of 5 terrestrial years. Model results support the hypothesis of a non-uniform distribution of infrared opacity as the cause of the Voyager temperature asymmetry. Transport by the mean meridional circulation, combined with polar vortex isolation may be at the origin of the latitudinal contrasts of trace species, with eddy mixing remaining restricted to low latitudes most of the Titan year. We interpret the contrasts as a signature of non-axisymmetric motions.     

Titan solar occultation observed by Cassini/VIMS: Gas absorption and constraints on aerosol composition

A solar occultation by Titan's atmosphere has been observed through the solar port of the Cassini/VIMS instrument on January 15th, 2006. Transmission spectra acquired during solar egress probe the atmosphere in the altitude range 70 to 900 km at the latitude of 71° S. Several molecular absorption bands of CH₄ and CO are visible in these data. A line-by-line radiative transfer calculation in spherical geometry is used to model three methane bands (1.7, 2.3, 3.3 μm) and the CO 4.7 μm band. Above 200 km, the methane 2.3 μm band is well fit with constant mixing ratio between 1.4 and 1.7%, in agreement with in situ and other Cassini measurements. Under 200 km, there are discrepancies between models and observations that are yet fully understood. Under 480 km, the 3.3 μm CH₄ band is mixed with a large and deep additional absorption. It corresponds to the C-H stretching mode of aliphatic hydrocarbon chains attached to large organic molecules. The CO 4.7 μm band is observed in the lower stratosphere (altitudes below 150 km) and is well fit with a model with constant mixing ratio of 33±10 ppm. The continuum level of the observed transmission spectra provides new constraints on the aerosol content of the atmosphere. A model using fractal aggregates and optical properties of tholins produced by Khare et al. [Khare, B.N., Sagan, C., Arakawa, E.T., Suits, F., Callcott, T.A., Williams, M.W., 1984. Icarus 60, 127-137] is developed. Fractal aggregates with more than 1000 spheres of radius 0.05 μm are needed to fit the data. Clear differences in the chemical composition are revealed between tholins and actual haze particles. Extinction and density profiles are also retrieved using an inversion of the continuum values. An exponential increase of the haze number density is observed under 420 km with a typical scale height of 60 km.     

Atmospheric acoustics of Titan, Mars, Venus, and Earth

Planetary atmospheres are complex dynamical systems whose structure, composition, and dynamics intimately affect the propagation of sound. Thus, acoustic waves, being coupled directly to the medium, can effectively probe planetary environments. Here we show how the acoustic absorption and speed of sound in the atmospheres of Venus, Mars, Titan, and Earth (as predicted by a recent molecular acoustics model) mirror the different environments. Starting at the surface, where the sound speed ranges from ∼200 m/s for Titan to ∼410 m/s for Venus, the vertical sound speed profiles reveal differences in the atmospheres' thermal layering and composition. The absorption profiles are relatively smooth for Mars, Titan, and Earth while Venus stands out with a noticeable attenuation dip occurring between 40 and 100 km. We also simulate a descent module sampling the sound field produced by a low-frequency “event” near the surface noting the occurrence of acoustic quiet zones.     

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

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

Latitudinal variation of Saturn photochemistry deduced from spatially-resolved ultraviolet spectra

We obtained spatially-resolved ultraviolet spectra of Saturn in 1994 with the Faint Object Spectrometer and Goddard High Resolution Spectrograph of the Hubble Space Telescope. We observed four areas on the planet at 15° N, 33° S, 41° S, and 52° S, with a field-of-view of less than 2 × 2 arcsec², compared to the 16-arcsec planet diameter. The wavelength range, 1550-2300 Å, encompasses absorption from major hydrocarbons (C₂H₆, C₂H₄, C₂H₂, CH₃C₂H, C₄H₂) and water. We find global hydrocarbon abundances and a C₂H₂ vertical distribution compatible with infrared observations, in contrast with previous analyses of ultraviolet spectra. The stratospheric haze opacity decreases from polar region to the equator. Saturn mid-latitudes are photochemically distinct from the rest of the planet. At 33° S, the spectrum requires either (1) a distinctly different C₂H₂ vertical distribution or (2) a locally enhanced water abundance. At 41° S, the hydrocarbon abundance exhibits a local minimum, within a global trend of increasing abundance from equator to pole. This global trend may result from an increased abundance of short-lived hydrocarbons such as C₄H₂. Photochemical models predict a depletion of hydrocarbon molecules in the presence of stratospheric water [Moses et al., 2000. Icarus 143, 166-202]. These results are consistent with a localized influx of water, in the form of high charge to mass ratio particles, flowing into Saturn's atmosphere at latitudes magnetically linked to the rings.     

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.