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.     

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.     

A spatially resolved high spectral resolution study of Neptune’s stratosphere

Using TEXES, the Texas Echelon cross Echelle Spectrograph, mounted on the Gemini North 8-m telescope we have mapped the spatial variation of H₂, CH₄, C₂H₂ and C₂H₆ thermal-infrared emission of Neptune. These high-spectral-resolution, spatially resolved, thermal-infrared observations of Neptune offer a unique glimpse into the state of Neptune’s stratosphere in October 2007, L_S = 275.4° just past Neptune’s southern summer solstice (L_S = 270°). We use observations of the S(1) pure rotational line of molecular hydrogen and a portion of the ν₄ band of methane to retrieve detailed information on Neptune’s stratospheric vertical and meridional thermal structure. We find global-average temperatures of 163.8 ± 0.8, 155.0 ± 0.9, and 123.8 ± 0.8 K at the 7.0 × 10⁻³-, 0.12-, and 2.1-mbar levels with no meridional variations within the errors. We then use the inferred temperatures to model the emission of C₂H₂ and C₂H₆ in order to derive stratospheric volume mixing ratios (hence forth, VMR) as a function of pressure and latitude. There is a subtle meridional variation of the C₂H₂ VMR at the 0.5-mbar level with the peak abundance found at −28° latitude, falling off to the north and south. However, the observations are consistent within error to a meridionally constant C₂H₂ VMR of at 0.5 mbar. We find that the VMR of C₂H₆ at 1-mbar peaks at the equator and falls by a factor of 1.6 at −70° latitude. However, a meridionally constant VMR of at the 1-mbar level for C₂H₆ is also statistically consistent with the retrievals. Temperature predictions from a radiative-seasonal climate model of Neptune that assumes the hydrocarbon abundances inferred in this paper are lower than the measured temperatures by 40 K at 7 × 10⁻³ mbar, 30 K at 0.12 mbar and 25 K at 2.1 mbar. The radiative-seasonal model also predicts meridional temperature variations on the order of 10 K from equator to pole, which are not observed. Assuming higher stratospheric CH₄ abundance at the equator relative to the south pole would bring the meridional trends of the inferred temperatures and radiative-seasonal model into closer agreement.We have also retrieved observations of C₂H₄ emission from Neptune’s stratosphere using TEXES on the NASA Infrared Telescope Facility (IRTF) in June 2003, L_S = 266°. Using the observations from the middle of the planet and an average of the middle three latitude temperature profiles from the 2007 observations (9.5° of L_S later, the seasonal equivalent of 9.5 Earth days within Earth’s seasonal cycle), we infer a C₂H₄ VMR of at 1.5 × 10⁻³ mbar, a value that is 3.25 times that predicted by global-average photochemical models.     

Clouds, haze, and CH4, CH3D, HCN, and C2H2 in the atmosphere of Titan probed via 3 μm spectroscopy

Using synthetic spectra derived from an updated model atmosphere together with a continuum model that includes contributions from haze, cloud and ground, we have re-analyzed the recently published (Geballe et al., 2003, Astrophys. J. 583, L39-L42) high-resolution 3 μm spectrum of Titan which contains newly-detected bands of HCN (in emission) and C₂H₂ and CH₃D (in absorption), in addition to previously detected bands of CH₄. In the 3.10-3.54 μm interval the analysis yields strong evidence for the existence of a cloud deck or optically thick haze layer at about the 10 mbar (∼ 100 km) level. The haze must extend well above this altitude in order to mask the strong CH₄ lines at 3.20-3.50 μm. These cloud and haze components must be transparent at 2.87-2.92 μm, where analysis of the CH₃D spectrum demonstrates that Titan's surface is glimpsed through a second cloud deck at about the 100 mbar (∼ 50 km) level. Through a combination of areal distribution and optical depth this cloud deck has an effective transmittance of ∼ 20%. The spectral shape of Titan's continuum indicates that the higher altitude cloud and haze particles responsible for suppressing the CH₄ absorptions have a largely organic make-up. The rotational temperature of the HCN ranges from 140 to 180 K, indicating that the HCN emission occurs over a wide range of altitudes. This emission, remodeled using an improved collisional deactivation rate, implies mesospheric mixing ratio curves that are consistent with previously predictions. The stratospheric and mesospheric C₂H₂ mixing ratios are ∼¹⁰⁻⁵, considerably less than previous model predictions (Yung et al., 1984), but approximately consistent with recent observational results. Upper limits to mixing ratios of HC₃N and C₄H₂ are derived from non-detections of those species near 3.0 μm.     

Meridional variations of temperature, C2H2 and C2H6 abundances in Saturn's stratosphere at southern summer solstice

Measurements of the vertical and latitudinal variations of temperature and C₂H₂ and C₂H₆ abundances in the stratosphere of Saturn can be used as stringent constraints on seasonal climate models, photochemical models, and dynamics. The summertime photochemical loss timescale for C₂H₆ in Saturn's middle and lower stratosphere (∼40-10,000 years, depending on altitude and latitude) is much greater than the atmospheric transport timescale; ethane observations may therefore be used to trace stratospheric dynamics. The shorter chemical lifetime for C₂H₂ (∼1-7 years depending on altitude and latitude) makes the acetylene abundance less sensitive to transport effects and more sensitive to insolation and seasonal effects. To obtain information on the temperature and hydrocarbon abundance distributions in Saturn's stratosphere, high-resolution spectral observations were obtained on September 13-14, 2002 UT at NASA's IRTF using the mid-infrared TEXES grating spectrograph. At the time of the observations, Saturn was at a LS≈270°, corresponding to Saturn's southern summer solstice. The observed spectra exhibit a strong increase in the strength of methane emission at 1230 cm⁻¹ with increasing southern latitude. Line-by-line radiative transfer calculations indicate that a temperature increase in the stratosphere of ≈10 K from the equator to the south pole between 10 and 0.01 mbar is implied. Similar observations of acetylene and ethane were also recorded. We find the 1.16 mbar mixing ratio of C₂H₂ at −1° and −83° planetocentric latitude to be and , respectively. The C₂H₂ mixing ratio at 0.12 mbar is found to be at −1° planetocentric latitude and at −83° planetocentric latitude. The 2.3 mbar mixing ratio of C₂H₆ inferred from the data is and at −1° and −83° planetocentric latitude, respectively. Further observations, creating a time baseline, will be required to completely resolve the question of how much the latitudinal variations of C₂H₂ and C₂H₆ are affected by seasonal forcing and/or stratospheric circulation.     

High-resolution 3-μm spectra of Jupiter: Latitudinal spectral variations influenced by molecules, clouds, and haze

We present latitudinally-resolved high-resolution (R = 37,000) pole-to-pole spectra of Jupiter in various narrow longitudinal ranges, in spectral intervals covering roughly half of the spectral range 2.86-3.53 μm. We have analyzed the data with the aid of synthetic spectra generated from a model jovian atmosphere that included lines of CH₄, CH₃D, NH₃, C₂H₂, C₂H₆, PH₃, and HCN, as well as clouds and haze. Numerous spectral features of many of these molecular species are present and are individually identified for the first time, as are many lines of and a few unidentified spectral features. In both polar regions the 2.86-3.10-μm continuum is more than 10 times weaker than in spectra at lower latitudes, implying that in this wavelength range the single-scattering albedos of polar haze particles are very low. In contrast, the 3.24-3.53 μm the weak polar and equatorial continua are of comparable intensity. We derive vertical distributions of NH₃, C₂H₂ and C₂H₆, and find that the mixing ratios of NH₃ and C₂H₆ show little variation between equatorial and polar regions. However, the mixing ratios of C₂H₂ in the northern and southern polar regions are ∼6 and ∼3 times, respectively, less than those in the equatorial regions. The derived mixing ratio curves of C₂H₂ and C₂H₆ extend up to the 10⁻⁶ bar level, a significantly higher altitude than most previous results in the literature. Further ground-based observations covering other longitudes are needed to test if these mixing ratios are representative values for the equatorial and polar regions.     

The first detection of propane on Saturn

We report the first detection of propane, C₃H₈, in Saturn's stratosphere. Observations taken on September 8, 2002 UT at NASA's IRTF using TEXES, show multiple emission lines due to the 748 cm⁻¹ν₂₁ band of C₃H₈. Using a line-by-line radiative transfer code, we are able to fit the data by scaling the propane vertical mixing ratio profile from the photochemical model of Moses et al. [2000. Icarus 143, 244-298]. Multiplicative factors of 0.7 and 0.65 are required to fit the −20° and −80° planetocentric latitude spectra. The resultant profiles are characterized by a 5 mbar mixing ratio of 2.7±0.8×¹⁰⁻⁸ at −20° and at −80° latitude. These results suggest that the time scale for meridional circulation lies between the net photochemical lifetimes of C₂H₂ and C₃H₈, ≈30-600 years.     

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.     

On the HCN and CO2 abundance and distribution in Jupiter's stratosphere

Observations of Jupiter by Cassini/CIRS, acquired during the December 2000 flyby, provide the latitudinal distribution of HCN and CO₂ in Jupiter's stratosphere with unprecedented spatial resolution and coverage. Following up on a preliminary study by Kunde et al. [Kunde, V.G., and 41 colleagues, 2004. Science 305, 1582-1587], the analysis of these observations leads to two unexpected results (i) the total HCN mass in Jupiter's stratosphere in 2000 was (6.0±1.5)×¹⁰¹³ g, i.e., at least three times larger than measured immediately after the Shoemaker-Levy 9 (SL9) impacts in July 1994 and (ii) the latitudinal distributions of HCN and CO₂ are strikingly different: while HCN exhibits a maximum at 45° S and a sharp decrease towards high Southern latitudes, the CO₂ column densities peak over the South Pole. The total CO₂ mass is (2.9±1.2)×¹⁰¹³ g. A possible cause for the HCN mass increase is its production from the photolysis of NH₃, although a problem remains because, while millimeter-wave observations clearly indicate that HCN is currently restricted to submillibar (∼0.3 mbar) levels, immediate post-impact infrared observations have suggested that most of the ammonia was present in the lower stratosphere near 20 mbar. HCN appears to be a good atmospheric tracer, with negligible chemical losses. Based on 1-dimensional (latitude) transport models, the HCN distribution is best interpreted as resulting from the combination of a sharp decrease (over an order of magnitude in Kyy) of wave-induced eddy mixing poleward of 40° and an equatorward transport with velocity. The CO₂ distribution was investigated by coupling the transport model with an elementary chemical model, in which CO₂ is produced from the conversion of water originating either from SL9 or from auroral input. The auroral source does not appear adequate to reproduce the CO₂ peak over the South Pole, as required fluxes are unrealistically high and the shape of the CO₂ bulge is not properly matched. In contrast, the CO₂ distribution can be fit by invoking poleward transport with a velocity and vigorous eddy mixing (). While the vertical distribution of CO₂ is not measured, the combined HCN and CO₂ results imply that the two species reside at different stratospheric levels. Comparing with the circulation regimes predicted by earlier radiative-dynamical models of Jupiter's stratosphere, and with inferences from the ethane and acetylene stratospheric latitudinal distribution, we suggest that CO₂ lies in the middle stratosphere near or below the 5-mbar level.     

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.     

Observations of C2H6 and C2H2 in the stratosphere of Saturn

We have performed high-resolution spectral observations at mid-infrared wavelengths of C₂H₆ (12.16 μm), and C₂H₂ (13.45 μm) on Saturn. These emission features probe the stratosphere of the planet and provide information on the hydrocarbon photochemical processes taking place in that region of the atmosphere. The observations were performed using our cryogenic echelle spectrometer Celeste, in conjunction with the McMath-Pierce 1.5-m solar telescope in November and December 1994. We used Voyager IRIS CH₄ observations (7.67 μm) to derive a temperature profile on the saturnian atmosphere for the region of the stratosphere. This profile was then used in conjunction with height-dependent volume mixing ratios of each hydrocarbon to determine global abundances for ethane and acetylene. Our ground-based measurements indicate abundances of for C₂H₆ (1.0 mbar pressure level), and for C₂H₂ (1.6 mbar pressure level). We also derived new mixing ratios from the Voyager mid-latitude IRIS observations; 8.6±0.9×¹⁰⁻⁶ for C₂H₆ (0.1-3.0 mbar pressure level), and 1.6±0.2×¹⁰⁻⁷ for C₂H₂ (2.0 mbar pressure level).     

The Titan N/N and C/C isotopic ratios in HCN from Cassini/CIRS

We report the detection of H¹³CN and HC¹⁵N in mid-infrared spectra recorded by the Composite Infrared Spectrometer (CIRS) aboard Cassini, along with the determination of the ¹²C/¹³C and ¹⁴N/¹⁵N isotopic ratios. We analyzed two sets of limb spectra recorded near 13-15° S (Tb flyby) and 83° N (T4 flyby) at 0.5 cm⁻¹ resolution. The spectral range 1210-1310 cm⁻¹ was used to retrieve the temperature profile in the range 145-490 km at 13° S and 165-300 km at 83° N. These two temperature profiles were then incorporated in the atmospheric model to retrieve the abundance profile of H¹²C¹⁴N, H¹³CN and HC¹⁵N from their bands at 713, 706 and 711 cm⁻¹, respectively. The HCN abundance profile was retrieved in the range 90-460 km at 15° S and 165-305 km at 83° N. There is no evidence for vertical variations of the isotopic ratios. Constraining the isotopic abundance profiles to be proportional to the HCN one, we find at 15° S, and at 83° N, two values that are statistically consistent. A combination of these results yields a ¹²C/¹³C value equal to 75±12. This global result, as well as the 15° S one, envelop the value in Titan's methane (82.3±1) [Niemann, H.B., and 17 colleagues, 2005. Nature 438, 779-784] measured at 10° S and is slightly lower than the terrestrial inorganic standard value (89). The ¹⁴N/¹⁵N isotopic ratio is found equal to at 15° S and at 83° N. Combining the two values yields ¹⁴N/¹⁵N = 56 ± 8, which corresponds to an enrichment in ¹⁵N of about 4.9 compared with the terrestrial ratio. These results agree with the values obtained from previous ground-based millimeter observations [Hidayat, T., Marten, A., Bézard, B., Gautier, D., Owen, T., Matthews, H.E., Paubert, G., 1997. Icarus 126, 170-182; Marten, A., Hidayat, T., Biraud, Y., Moreno, R., 2002. Icarus 158, 532-544]. The ¹⁵N/¹⁴N ratio found in HCN is ∼3 times higher than in N₂ [Niemann, H.B., and 17 colleagues, 2005. Nature 438, 779-784], which implies a large fractionation process in the HCN photochemistry.     

Vertical and meridional distribution of ethane, acetylene and propane in Saturn’s stratosphere from CIRS/Cassini limb observations

Measuring the spatial distribution of chemical compounds in Saturn’s stratosphere is critical to better understand the planet’s photochemistry and dynamics. Here we present an analysis of infrared spectra in the range 600-1400 cm⁻¹ acquired in limb geometry by the Cassini spacecraft between March 2005 and January 2008. We first determine the vertical temperature profiles from 3 to 0.01 hPa, at latitudes ranging from 70°N to 80°S. We infer a similar meridional temperature gradient at 1-2 hPa as in recent previous studies [Fletcher, L.N., Irwin, P.G.J., Teanby, N.A., Orton, G.S., Parrish, P.D., de Kok, R., Howett, C., Calcutt, S.B., Bowles, N., Taylor, F.W., 2007. Icarus 189, 457-478; Howett, C.J.A., Irwin, P.G.J., Teanby, N.A., Simon-Miller, A., Calcutt, S.B., Fletcher, L.N., de Kok, R., 2007. Icarus 190, 556-572]. We then retrieve the vertical profiles of C₂H₆ and C₂H₂ from 3 to 0.01 hPa and of C₃H₈ around 1 hPa. At 1 hPa, the meridional variation of C₂H₂ is found to follow the yearly averaged solar insolation, except for a strong equatorial mole fraction of 8×10^-7, nearly two times higher than expected. This enhancement in abundance can be explained by the descent of hydrocarbon-rich air, with a vertical wind speed at the equator of 0.25±0.1 mm/s at 1 hPa and 0.4±0.15 mm/s at 0.1 hPa. The ethane distribution is relatively uniform at 1 hPa, with only a moderate 25% increase from 35°S to 80°S. Propane is found to increase from north to south by a factor of 1.9, suggesting that its lifetime may be shorter than Saturn’s year at 1 hPa. At high altitudes (1 Pa), C₂H₂ and C₂H₆ abundances depart significantly from the photochemical model predictions of Moses and Greathouse [Moses, J.I., Greathouse, T.K., 2005. J. Geophys. Res. 110, 9007], except at high southern latitudes (62, 70 and 80°S) and near the equator. The observed abundances are found strongly depleted in the 20-40°S region and enhanced in the 20-30°N region, the latter coinciding with the ring’s shadow. We favor a dynamical explanation for these anomalies.     

Diagnostics of Titan's stratospheric dynamics using Cassini/CIRS data and the 2-dimensional IPSL circulation model

The dynamics of Titan's stratosphere is discussed in this study, based on a comparison between observations by the CIRS instrument on board the Cassini spacecraft, and results of the 2-dimensional circulation model developed at the Institute Pierre-Simon Laplace, available at http://www.lmd.jussieu.fr/titanDbase [Rannou, P., Lebonnois, S., Hourdin, F., Luz, D., 2005. Adv. Space Res. 36, 2194-2198]. The comparison aims at both evaluating the model's capabilities and interpreting the observations concerning: (1) dynamical and thermal structure using temperature retrievals from Cassini/CIRS and the vertical profile of zonal wind at the Huygens landing site obtained by Huygens/DWE; and (2) vertical and latitudinal profiles of stratospheric gases deduced from Cassini/CIRS data. The modeled thermal structure is similar to that inferred from observations (Cassini/CIRS and Earth-based observations). However, the upper stratosphere (above 0.05 mbar) is systematically too hot in the 2D-CM, and therefore the stratopause region is not well represented. This bias may be related to the haze structure and to misrepresented radiative effects in this region, such as the cooling effect of hydrogen cyanide (HCN). The 2D-CM produces a strong atmospheric superrotation, with zonal winds reaching 200 m s⁻¹ at high winter latitudes between 200 and 300 km altitude (0.1-1 mbar). The modeled zonal winds are in good agreement with retrieved wind fields from occultation observations, Cassini/CIRS and Huygens/DWE. Changes to the thermal structure are coupled to changes in the meridional circulation and polar vortex extension, and therefore affect chemical distributions, especially in winter polar regions. When a higher altitude haze production source is used, the resulting modeled meridional circulation is weaker and the vertical and horizontal mixing due to the polar vortex is less extended in latitude. There is an overall good agreement between modeled chemical distributions and observations in equatorial regions. The difference in observed vertical gradients of C₂H₂ and HCN may be an indicator of the relative strength of circulation and chemical loss of HCN. The negative vertical gradient of ethylene in the low stratosphere at 15° S, cannot be modeled with simple 1-dimensional models, where a strong photochemical sink in the middle stratosphere would be necessary. It is explained here by dynamical advection from the winter pole towards the equator in the low stratosphere and by the fact that ethylene does not condense. Near the winter pole (80° N), some compounds (C₄H₂, C₃H₄) exhibit an (interior) minimum in the observed abundance vertical profiles, whereas 2D-CM profiles are well mixed all along the atmospheric column. This minimum can be a diagnostic of the strength of the meridional circulation, and of the spatial extension of the winter polar vortex where strong descending motions are present. In the summer hemisphere, observed stratospheric abundances are uniform in latitude, whereas the model maintains a residual enrichment over the summer pole from the spring cell due to a secondary meridional overturning between 1 and 50 mbar, at latitudes south of 40-50° S. The strength, as well as spatial and temporal extensions of this structure are a difficulty, that may be linked to possible misrepresentation of horizontally mixing processes, due to the restricted 2-dimensional nature of the model. This restriction should also be kept in mind as a possible source of other discrepancies.     

Analysis of Cassini/CIRS limb spectra of Titan acquired during the nominal mission II: Aerosol extinction profiles in the 600–1420 cm spectral range

We have analyzed the continuum emission of limb spectra acquired by the Cassini/CIRS infrared spectrometer in order to derive information on haze extinction in the 3–0.02 mbar range (∼150–350 km). We focused on the 600–1420 cm⁻¹ spectral range and studied nine different limb observations acquired during the Cassini nominal mission at 55°S, 20°S, 5°N, 30°N, 40°N, 45°N, 55°N, 70°N and 80°N. By means of an inversion algorithm solving the radiative transfer equation, we derived the vertical profiles of haze extinction coefficients from 17 spectral ranges of 20-cm⁻¹ wide at each of the nine latitudes. At a given latitude, all extinction vertical profiles retrieved from various spectral intervals between 600 and 1120 cm⁻¹ display similar vertical slopes implying similar spectral characteristics of the material at all altitudes. We calculated a mean vertical extinction profile for each latitude and derived the ratio of the haze scale height (H_haze) to the pressure scale height (H_gas) as a function of altitude. We inferred H_haze/H_gas values varying from 0.8 to 2.4. The aerosol scale height varies with altitude and also with latitude. Overall, the haze extinction does not show strong latitudinal variations but, at 1 mbar, an increase by a factor of 1.5 is observed at the north pole compared to high southern latitudes. The vertical optical depths at 0.5 and 1.7 mbar increase from 55°S to 5°N, remain constant between 5°N and 30°N and display little variation at higher latitudes, except the presence of a slight local maximum at 45°N. The spectral dependence of the haze vertical optical depth is uniform with latitude and displays three main spectral features centered at 630 cm⁻¹, 745 cm⁻¹ and 1390 cm⁻¹, the latter showing a wide tail extending down to ∼1000 cm⁻¹. From 600 to 750 cm⁻¹, the optical depth increases by a factor of 3 in contrast with the absorbance of laboratory tholins, which is generally constant. We derived the mass mixing ratio profiles of haze at the nine latitudes. Below the 0.4-mbar level all mass mixing ratio profiles increase with height. Above this pressure level, the profiles at 40°N, 45°N, 55°N, at the edge of the polar vortex, display a decrease-with-height whereas the other profiles increase. The global increase with height of the haze mass mixing ratio suggest a source at high altitudes and a sink at low altitudes. An enrichment of haze is observed at 0.1 mbar around the equator, which could be due to a more efficient photochemistry because of the strongest insolation there or an accumulation of haze due to a balance between sedimentation and upward vertical drag.     

Solar infrared occultation observations by SPICAM experiment on Mars-Express: Simultaneous measurements of the vertical distributions of H2O, CO2 and aerosol

The infrared AOTF spectrometer is a part of the SPICAM experiment onboard the Mars-Express ESA mission. The instrument has a capability of solar occultations and operates in the spectral range of 1-1.7 μm with a spectral resolution of ∼3.5 cm⁻¹. We report results from 24 orbits obtained during MY28 at Ls 130°-160°, and the latitude range of 40°-55° N. For these orbits the atmospheric density from 1.43 μm CO₂ band, water vapor mixing ratio based on 1.38 μm absorption, and aerosol opacities were retrieved simultaneously. The vertical resolution of measurements is better than 3.5 km. Aerosol vertical extinction profiles were obtained at 10 wavelengths in the altitude range from 10 to 60 km. The interpretation using Mie scattering theory with adopted refraction indices of dust and H₂O ice allows to retrieve particle size (reff∼0.5-1 μm) and number density (∼1 cm⁻³ at 15-30 km) profiles. The haze top is generally below 40 km, except the longitude range of 320°-50° E, where high-altitude clouds at 50-60 km were detected. Optical properties of these clouds are compatible with ice particles (effective radius reff=0.1-0.3 μm, number density N∼10 cm−3) distributed with variance νeff=0.1-0.2 μm. The vertical optical depth of the clouds is below 0.001 at 1 μm. The atmospheric density profiles are retrieved from CO₂ band in the altitude range of 10-90 km, and H₂O mixing ratio is determined at 15-50 km. Unless a supersaturation of the water vapor occurs in the martian atmosphere, the H₂O mixing ratio indicates ∼5 K warmer atmosphere at 25-45 km than predicted by models.     

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.     

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.     

The mesosphere and lower thermosphere of Titan revealed by Cassini/UVIS stellar occultations

Stellar occultations observed by the Cassini/UVIS instrument provide unique data that probe the mesosphere and lower thermosphere of Titan at altitudes between 400 and 1400 km. This region is a site of complex photochemistry that forms hydrocarbon and nitrile species, and plays a crucial role in the formation of the organic hazes observed in the stratosphere, but has yet to be adequately characterized. We analyzed publicly available data obtained between flybys Tb in December 2004 and T58 in July 2009, with an emphasis on two stable occultations obtained during flybys T41 and T53. We derived detailed density profiles for CH₄, C₂H₂, C₂H₄, C₄H₂, HCN, HC₃N and C₆H₆ between ∼400 and 1200 km and extinction coefficients for aerosols between 400 and 900 km. Our analysis reveals the presence of extinction layers in the occultation data that are associated with large perturbations in the density profiles of the gaseous species and extinction profiles of the aerosols. These relatively stable features vary in appearance with location and change slowly over time. In particular, we identify a sharp extinction layer between 450 and 550 km that coincides with the detached haze layer. In line with recent images obtained by Cassini/ISS, the altitude of this layer changes rapidly around the equinox in 2009. Our results point to unexpected complexity that may have significant consequences for the dynamics and physical processes taking place in the upper atmosphere of Titan.     

Meridional distribution of CH3C2H and C4H2 in Saturn’s stratosphere from CIRS/Cassini limb and nadir observations

Limb and nadir spectra acquired by Cassini/CIRS (Composite InfraRed Spectrometer) are analyzed in order to derive, for the first time, the meridional variations of diacetylene (C₄H₂) and methylacetylene (CH₃C₂H) mixing ratios in Saturn’s stratosphere, from 5 hPa up to 0.05 hPa and 80°S to 45°N. We find that the C₄H₂ and CH₃C₂H meridional distributions mimic that of acetylene (C₂H₂), exhibiting small-scale variations that are not present in photochemical model predictions. The most striking feature of the meridional distribution of both molecules is an asymmetry between mid-southern and mid-northern latitudes. The mid-southern latitudes are found depleted in hydrocarbons relative to their northern counterparts. In contrast, photochemical models predict similar abundances at north and south mid-latitudes. We favor a dynamical explanation for this asymmetry, with upwelling in the south and downwelling in the north, the latter coinciding with the region undergoing ring shadowing. The depletion in hydrocarbons at mid-southern latitudes could also result from chemical reactions with oxygen-bearing molecules.Poleward of 60°S, at 0.1 and 0.05 hPa, we find that the CH₃C₂H and C₄H₂ abundances increase dramatically. This behavior is in sharp contradiction with photochemical model predictions, which exhibit a strong decrease towards the south pole. Several processes could explain our observations, such as subsidence, a large vertical eddy diffusion coefficient at high altitudes, auroral chemistry that enhances CH₃C₂H and C₄H₂ production, or shielding from photolysis by aerosols or molecules produced from auroral chemistry. However, problems remain with all these hypotheses, including the lack of similar behavior at lower altitudes.Our derived mean mixing ratios at 0.5 hPa of (2.4 ± 0.3) × 10⁻¹⁰ for C₄H₂ and of (1.1 ± 0.3) × 10⁻⁹ for CH₃C₂H are compatible with the analysis of global-average ISO observations performed by Moses et al. (Moses, J.I., Bézard, B., Lellouch, E., Gladstone, G.R., Feuchtgruber, H., Allen, M. [2000a]. Icarus 143, 244-298). Finally, we provide values for the ratios [CH₃C₂H]/[C₂H₂] and [C₄H₂]/[C₂H₂] that can constrain the coupled chemistry of these hydrocarbons.