Condensed species in Titan's stratosphere: Confirmation of crystalline cyanoacetylene (HC3N) and evidence for crystalline acetylene (C2H2) on Titan

Infrared spectra of crystalline HC₃N and C₂H₂ were investigated at several temperatures between 15 and 150 K. The characteristics of the 505 and 753 cm⁻¹ bands of HC₃N are in complete agreement with the emission spectral data on Titan obtained by the Voyager IRIS instrument, thus confirming the identification of crystalline HC₃N on Titan. A composite spectrum in the 720-800 cm⁻¹ region, with contributions from HC₃N and C₂H₂ in crystalline phases, reproduces the Voyager emission data in that region, thus providing a suggestion for the identification of crystalline C₂H₂ on Titan.     

The composition of Titan's stratosphere from Cassini/CIRS mid-infrared spectra

We have analyzed data recorded by the Composite Infrared Spectrometer (CIRS) aboard the Cassini spacecraft during the Titan flybys T0-T10 (July 2004-January 2006). The spectra characterize various regions on Titan from 70° S to 70° N with a variety of emission angles. We study the molecular signatures observed in the mid-infrared CIRS detector arrays (FP3 and FP4, covering roughly the 600-1500 cm⁻¹ spectral range with apodized resolutions of 2.54 or 0.53 cm⁻¹). The composite spectrum shows several molecular signatures: hydrocarbons, nitriles and CO₂. A firm detection of benzene (C₆H₆) is provided by CIRS at levels of about 3.5×¹⁰⁻⁹ around 70° N. We have used temperature profiles retrieved from the inversion of the emission observed in the methane ν₄ band at 1304 cm⁻¹ and a line-by-line radiative transfer code to infer the abundances of the trace constituents and some of their isotopes in Titan's stratosphere. No longitudinal variations were found for these gases. Little or no change is observed generally in their abundances from the south to the equator. On the other hand, meridional variations retrieved for these trace constituents from the equator to the North ranged from almost zero (no or very little meridional variations) for C₂H₂, C₂H₆, C₃H₈, C₂H₄ and CO₂ to a significant enhancement at high northern (early winter) latitudes for HCN, HC₃N, C₄H₂, C₃H₄ and C₆H₆. For the more important increases in the northern latitudes, the transition occurs roughly between 30 and 50 degrees north latitude, depending on the molecule. Note however that the very high-northern latitude results from tours TB-T10 bear large uncertainties due to few available data and problems with latitude smearing effects. The observed variations are consistent with some, but not all, of the predictions from dynamical-photochemical models. Constraints are set on the vertical distribution of C₂H₂, found to be compatible with 2-D equatorial predictions by global circulation models. The D/H ratio in the methane on Titan has been determined from the CH₃D band at 1156 cm⁻¹ and found to be . Implications of this deuterium enrichment, with respect to the protosolar abundance on the origin of Titan, are discussed. We compare our results with values retrieved by Voyager IRIS observations taken in 1980, as well as with more recent (1997) disk-averaged Infrared Space Observatory (ISO) results and with the latest Cassini-Huygens inferences from other instruments in an attempt to better comprehend the physical phenomena on Titan.     

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.     

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.     

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.     

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.     

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.     

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.     

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

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

An experimental study of the reaction kinetics of C2(XΣg) with hydrocarbons (CH4, C2H2, C2H4, C2H6 and C3H8) over the temperature range 24-300 K: Implications for the atmospheres of Titan and the Giant Planets

The reactivity of C₂(X¹Σ⁺_g) with simple saturated (CH₄, C₂H₆ and C₃H₈) and unsaturated (C₂H₂ and C₂H₄) hydrocarbons has been studied in the gas phase over the temperature range 24-300 K using the CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in a Uniform Supersonic Flow) technique. All reactions have been found to be very rapid in this temperature range and the rate coefficients are typically ?10⁻¹⁰ cm³ molecule⁻¹ s⁻¹ with the exception of methane for which the rate coefficient is one order of magnitude lower: ∼10⁻¹¹ cm³ molecule⁻¹ s⁻¹. These results have been analyzed in terms of potential destruction sources of C₂(X¹Σ⁺_g) in the atmospheres of Titan and the Giant Planets. It appears that the rate coefficient of the reaction ¹C₂ + CH₄ should be updated with our new data and that reactions with C₂H₂, C₂H₄ and C₂H₆ should also be included in the existing photochemical models.     

The Origin of Water Vapor and Carbon Dioxide in Jupiter's Stratosphere

Observations of H₂O rotational lines from the Infrared Space Observatory (ISO) and the Submillimeter Wave Astronomy Satellite (SWAS) and of the CO₂ ν₂ band by ISO are analyzed jointly to determine the origin of water vapor and carbon dioxide in Jupiter's stratosphere. Simultaneous modelling of ISO/LWS and ISO/SWS observations acquired in 1997 indicates that most of the stratospheric jovian water is restricted to pressures less than 0.5±0.2 mbar, with a disk-averaged column density of (2.0±0.5)×10¹⁵ cm⁻². Disk-resolved observations of CO₂ by ISO/SWS reveal latitudinal variations of the CO₂ abundance, with a decrease of at least a factor of 7 from mid-southern to mid-northern latitudes, and a disk-center column density of (3.4±0.7)×10¹⁴ cm⁻². These results strongly suggest that the observed H₂O and CO₂ primarily result from the production, at midsouthern latitudes, of oxygenated material in the form of CO and H₂O by the Shoemaker-Levy 9 (SL9) impacts in July 1994 and subsequent chemical and transport evolution, rather than from a permanent interplanetary dust particle or satellite source. This conclusion is supported by quantitative evolution model calculations. Given the characteristic vertical mixing times in Jupiter's stratosphere, material deposited at ∼0.1 mbar by the SL9 impacts is indeed expected to diffuse down to the ∼0.5 mbar level after 3 years. A coupled chemical-horizontal transport model indicates that the stability of water vapor against photolysis and conversion to CO₂ is maintained over typically ∼50 years by the decrease of the local CO mixing ratio associated with horizontal spreading. A model with an initial (i.e., SL9-produced) H₂O/CO mass mixing ratio of 0.07, not inconsistent with immediate post-impact observations, matches the observed H₂O abunda nce and CO₂ horizontal distribution 3 years after the impacts. In contrast, the production of CO₂ from SL9-produced CO and a water component deriving from an interplanetary dust component is insufficient to account for the observed CO₂ amounts. The observations can further be used to place a stringent upper limit (8×10⁴ cm⁻² s⁻¹) on the permanent water influx into Jupiter. This may indicate that the much larger flux observed at Saturn derives dominantly from a ring source, or that the ablation of micrometeoroids leads dominantly to different species at Saturn (H₂O) and Jupiter (CO). Finally, the SWAS H₂O spectra do not appear fully consistent with the ISO data and should be confirmed by future ODIN and Herschel observations.     

New Millimeter Heterodyne Observations of Titan: Vertical Distributions of Nitriles HCN, HC3N, CH3CN, and the Isotopic Ratio N/N in Its Atmosphere

High sensitivity observations were performed at 1.2- and 3-mm wavelengths with the IRAM 30-m telescope (Spain) between April 1996 and December 1999 to investigate the nitrile composition of Titan's stratosphere. A part of our dataset consists of high resolution spectra of HC¹⁴N taken at 88.6 GHz as well as spectra of HC¹⁵N recorded at 258.16 GHz. From a thorough analysis of both lines and with the help of appropriate radiative transfer calculations we show that the isotopic ratio ¹⁵N/¹⁴N is strongly enhanced compared to the terrestrial value. We propose that the range 3.9-4.5 should be considered as a basis for the enrichment factor. Five individual lines of HC₃N were measured at 39-kHz resolution using a frequency-switched technique. Several CH₃CN features were recorded at 78-kHz resolution in two transitions around 147.6 and 220.7 GHz. The high spectral resolution and the good signal-to-noise ratio affecting the spectra permit us to retrieve disk-averaged vertical profiles for HCN up to 450 km and for HC₃N and CH₃CN up to 500 km. Comparison of our inferred vertical profiles with relevant results of presently published photochemical models is presented. We show that the profiles of HCN and HC₃N predicted by various authors below 450-km altitude appear inconsistent with our new observations. We find that the three distributions present very different gradients of abundance below 200-km altitude down to the condensation levels around 80 km. In the upper stratosphere HC₃N and CH₃CN have approximately the same mixing ratio of about 4×10⁻⁸ at 450 km, at least one order of magnitude lower than that of HCN. In the same time, another nitrile HC₅N has been searched for by observing four transitions located between 109 and 221 GHz. As no spectral features could be detected after several hours of integration time, we propose an upper limit for the mixing ratio equal to 4×10⁻¹⁰ assuming a uniform distribution of this compound in the lower stratosphere.     

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.     

Chemical reactions in the Titan’s troposphere during lightning

In the lower troposphere of the Titan the temperature is about 90 K, therefore the chemical production of compounds in the CH₄/N₂ atmosphere is extremely slow. However, atmospheric electricity could provide conditions at which chemical reactions are fast. This paper is based on the assumption that there are lightning discharges in the Titan’s lower atmosphere. The temporal temperature profile of a gas parcel after lightning was calculated at the conditions of 10 km above the Titan’s surface. Using this temperature profile, composition of the after-lightning atmosphere was simulated using a detailed chemical kinetic mechanism consisting of 1829 reactions of 185 species. The main reaction paths leading to the products were investigated. The main products of lighting discharges in the Titan’s atmosphere are H₂, HCN, C₂N₂, C₂H₂, C₂H₄, C₂H₆, NH₃ and H₂CN. The annual production of these compounds was estimated in the Titan’s atmosphere.     

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

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

Meridional variations of C2H2 and C2H6 in Jupiter's atmosphere from Cassini CIRS infrared spectra

Hydrocarbons such as acetylene (C₂H₂) and ethane (C₂H₆) are important tracers in Jupiter's atmosphere, constraining our models of the chemical and dynamical processes. However, our knowledge of the vertical and meridional variations of their abundances has remained sparse. During the flyby of the Cassini spacecraft in December 2000, the Composite Infrared Spectrometer (CIRS) instrument was used to map the spatial variation of emissions from 10 to 1400 cm⁻¹ (1000-7 μm). In this paper we analyze a zonally averaged set of CIRS spectra taken at the highest (0.48 cm⁻¹) resolution, firstly to infer atmospheric temperatures in the stratosphere at 0.5-20 mbar via the ν₄ band of CH₄, and in the troposphere at 150-400 mbar, via the H₂ absorption at 600-800 cm⁻¹. Stratospheric temperatures at 5 mbar are generally warmer in the north than the south by 7-8 K, while tropospheric temperatures show no such asymmetry. Both latitudinal temperature profiles however do show a pattern of maxima and minima which are largely anti-correlated between the two levels. We then use the derived temperature profiles to infer the vertical abundances of C₂H₂ and C₂H₆ by modeling tropospheric absorption (∼200 mbar) and stratospheric emission (∼5 mbar) in the C₂H₂ν₅ and C₂H₆ν₉ bands, and also emission of the acetylene (ν₄+ν₅)−ν₄ hotband (∼0.1 mbar). Acetylene shows a distinct north-south asymmetry in the stratosphere, with 5 mbar abundances greatest close to 20° N and decreasing from there towards both poles by a factor of ∼4. At 200 mbar in contrast, acetylene is nearly flat at a level of ∼3×¹⁰⁻⁹. Additionally, the abundance gradient of C₂H₂ between 10 and 0.1 mbar is derived, based on interpolated temperatures at 0.1 mbar, and is found to be positive and uniform with latitude to within errors. Ethane at both 5 and 200 mbar shows increasing VMR towards polar regions of ∼1.75 towards 70° N and ∼2.0 towards 70° S. An explanation for the meridional trends is proposed in terms of a combination of photochemistry and dynamics. Poleward, the decreasing UV flux is predicted to decrease the abundances of C₂H₂ and C₂H₆ by factors of 2.7 and 3.5, respectively, at latitude 70°. However, the lifetime of C₂H₆ in the stratosphere (3×¹⁰¹⁰ s at 5 mbar) is much longer than the dynamical timescale for meridional mixing inferred from Comet SL-9 debris (5-50×¹⁰⁸ s), and therefore the rising abundance towards high latitudes likely indicates that meridional mixing dominates over photochemical effects. For C₂H₂, the opposite occurs, with the relatively short photochemical lifetime (3×¹⁰⁷ s), compared to meridional mixing times, ensuring that the expected photochemical trends are visible.     

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.     

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.     

Sounding of Titan’s atmosphere at submillimeter wavelengths from an orbiting spacecraft

An investigation of the capabilities and science goals of a submillimeter-wave heterodyne sounder onboard a Titan orbiter is presented. Based on a model of Titan’s submillimeter spectrum, and including realistic instrumental performances, we show that passive limb observations of Titan’s submillimeter radiation would bring novel and unique information on the dynamical and chemical state of Titan’s atmosphere, particularly in the so far poorly probed 500-900 km region. The 300-360, 540-660 and 1080-1280 GHz spectral ranges appear especially promising, and could be explored with an instrument equipped with a tunable local oscillator system. Vertical temperature profiles can be determined up to ∼1200 km using rotational lines of CH₄, CO, and HCN. Winds can be measured over the 200-1200 km altitude range with an accuracy of 3-5 m/s from Doppler shift measurements of any strong optically thin line. Numerous molecular species are accessible, including H₂O, NH₃, CH₃C₂H, CH₂NH, and several nitriles (HC₃N, HC₅N, CH₃CN, and C₂H₃CN). Many of them are expected to be detectable in a large fraction of the atmosphere and in some cases at all levels, providing an observational link between stratospheric and thermospheric chemistry. Isotopic variants of some of these species can also be measured, providing new measurements of H, C, N, and O isotopic ratios. Mapping of the thermal, wind, and composition fields, best achieved from a polar orbit and with an articulated antenna, would provide a new view of the couplings between chemistry and dynamics over an extended altitude range of Titan’s atmosphere. Additional science goals at Saturn and Enceladus are briefly discussed.     

Vertical abundance profiles of hydrocarbons in Titan's atmosphere at 15° S and 80° N retrieved from Cassini/CIRS spectra

Limb spectra recorded by the Composite InfraRed Spectrometer (CIRS) on Cassini provide information on abundance vertical profiles of C₂H₂, C₂H₄, C₂H₆, CH₃C₂H, C₃H₈, C₄H₂, C₆H₆ and HCN, along with the temperature profiles in Titan's atmosphere. We analyzed two sets of spectra, one at 15° S (Tb flyby) and the other one at 80° N (T3 flyby). The spectral range 600-1400 cm⁻¹, recorded at a resolution of 0.5 cm⁻¹, was used to determine molecular abundances and temperatures in the stratosphere in the altitude range 100-460 km for Tb and 170-495 km for T3. Both temperature profiles show a well defined stratopause, at around 310 km (0.07 mbar) and 183 K at 13° S, and 380 km (0.01 mbar) with 207 K at 80° N. Near the north pole, stratospheric temperatures are colder and mesospheric temperatures are warmer than near the equator. C₂H₂, C₂H₆, C₃H₈ and HCN display vertical mixing ratio profiles that increase with height at 15° S and 80° N, consistent with their formation in the upper atmosphere, diffusion downwards and condensation in the lower stratosphere, as expected from photochemical models. The CH₃C₂H and C₄H₂ mixing ratios also increase with height at 15° S. But near the north pole, their profiles present an unexpected minimum around 300 km, observed for the first time thanks to the high vertical resolution of the CIRS limb data. C₂H₄ is the only molecule having a vertical abundance profile that decreases with height at 15° S. At 80° N, it also displays a minimum of its mixing ratio around the 0.1-mbar level. For C₆H₆, an upper limit of 1.1 ppb (in the 0.3-10 mbar range) is derived at 15° S, whereas a constant mixing ratio profile of is inferred near the north pole. At 15° S, the vertical profile of HCN exhibits a steeper gradient than other molecules, which suggests that a sink for this molecule exists in the stratosphere, possibly due to haze formation. All molecules display a more or less pronounced enrichment towards the north pole, probably due, in part, to subsidence of air at the north (winter) pole that brings air enriched in photochemical compounds from the upper atmosphere to lower levels.