Seasonal variation of Titan's stratospheric ethylene (C2H4) observed

All previous observations of seasonal change on Titan have been of physical phenomena such as clouds and haze. We present here the first observational evidence of chemical change in Titan's atmosphere. Images taken during 1999-2002 (late southern spring on Titan) with the W.M. Keck I 10-meter telescope at 8-13 μm show a significant accumulation of ethylene (C₂H₄) in the south polar stratosphere as well as north-south stratospheric temperature variation (colder at poles). Our observations restrict this newly discovered south polar ethylene accumulation to latitudes south of 60° S. The only other observations of the spatial distribution of C₂H₄ were those of Voyager I, which found a significant north polar accumulation in early northern spring. We see no build-up in the north, although the highest northern latitudes are obstructed from view in the current season. Our observations constrain any unobserved north polar accumulation of C₂H₄ to north of 50° N latitude. Comparison of the Voyager I results with our new results show seasonal chemical change has occurred in Titan's atmosphere.     

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.     

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.     

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.     

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.     

Condensed species in Titan's atmosphere: Identification of crystalline propionitrile (C2H5CN, CH3CH2CN) based on laboratory infrared data

We report the results of infrared studies of crystalline C₂H₅CN at several temperatures between 15 and 160 K. A case is made for the identification of crystalline C₂H₅CN in the stratosphere from the Voyager IRIS spectrum of Titan.     

Improved Determination of Ethane (C2H6) Abundance in Titan's Stratosphere

Ethane spectral lines were observed in emission from Titan in August 1993, October 1995, and September 1996, at a spectral resolution of λ/Δλ≈10⁶, at wavelength 11.7−11.9 μm using the Goddard Infrared Heterodyne Spectrometer at the NASA Infrared Telescope Facility on Mauna Kea, Hawaii. The ethane mole fraction is determined to be (8.8±2.2)×10⁻⁶ (68.3% confidence limits, “1σ”), averaging the retrievals from each observing run obtained using the “recommended” thermal profile of R. V. Yelle, D. Strobel, E. Lellouch, and D. Gautier (1997, in Huygens: Science, Payload, and Mission (J.-P. Lebreton, Ed.), pp. 243-256, European Space Agency SP-1177).     

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.     

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.     

Crossed molecular beam study of gas phase reactions relevant to the chemistry of planetary atmospheres: The case of C2+C2H2

The reaction between dicarbon (C₂) and acetylene was recently suggested as a possible competitive reaction in the atmospheres of Titan, Saturn and Uranus by rate constant measurements at very low temperatures [see Canosa, A., Páramo, A., Le Picard, S.D., Sims, I.R., 2007. An experimental study of the reaction kinetics of C₂(X¹Σ_g⁺) 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. Icarus 187, 558-568]. We have investigated the reaction of the two low lying electron states of C₂ and acetylene by the crossed molecular beam (CMB) technique with mass spectrometric detection. C₄H, already identified as a primary product in previous CMB experiments, is confirmed as such, even though the mechanism of formation is inferred to be partly different with respect to the previous study. An experimental setup has been devised to characterize the internal population of C₂ and refine the interpretation of the scattering results. The implications for the modelling of the atmospheres of Giant Planets and Titan, as well as cometary comae and the interstellar medium, are discussed.     

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).     

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

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

High-resolution spectroscopy of Saturn at 3 microns: CH4, CH3D, C2H2, C2H6, PH3, clouds, and haze

We report observation and analysis of a high-resolution 2.87-3.54 μm spectrum of the southern temperate region of Saturn obtained with NIRSPEC at Keck II. The spectrum reveals absorption and emission lines of five molecular species as well as spectral features of haze particles. The ν₂+ν₃ band of CH₃D is detected in absorption between 2.87 and 2.92 μm; and we derived from it a mixing ratio approximately consistent with the Infrared Space Observatory result. The ν₃ band of C₂H₂ also is detected in absorption between 2.95 and 3.05 μm; analysis indicates a sudden drop in the C₂H₂ mixing ratio at 15 mbar (130 km above the 1 bar level), probably due to condensation in the low stratosphere. The presence of the ν₃+ν₉+ν₁₁ band of C₂H₆ near 3.07 μm, first reported by Bjoraker et al. [Bjoraker, G.L., Larson, H.P., Fink, U., 1981. Astrophys. J. 248, 856-862], is confirmed, and a C₂H₆ condensation altitude of 10 mbar (140 km) in the low stratosphere is determined. We assign weak emission lines within the 3.3 μm band of CH₄ to the ν₇ band of C₂H₆, and derive a mixing ratio of 9±4×¹⁰⁻⁶ for this species. Most of the C₂H₆ 3.3 μm line emission arises in the altitude range 460-620 km (at ∼μbar pressure levels), much higher than the 160-370 km range where the 12 μm thermal molecular line emission of this species arises. At 2.87-2.90 μm the major absorber is tropospheric PH₃. The cloud level determined here and at 3.22-3.54 is 390-460 mbar (∼30 km), somewhat higher than found by Kim and Geballe [Kim, S.J., Geballe, T.R., 2005. Icarus 179, 449-458] from analysis of a low resolution spectrum. A broad absorption feature at 2.96 μm, which might be due to NH₃ ice particles in saturnian clouds, is also present. The effect of a haze layer at about 125 km (∼12 mbar level) on the 3.20-3.54 μm spectrum, which was not apparent in the low resolution spectrum, is clearly evident in the high resolution data, and the spectral properties of the haze particles suggest that they are composed of hydrocarbons.     

Saturn's latitudinal C2H2 and C2H6 abundance profiles from Cassini/CIRS and ground-based observations

Hydrocarbons in the upper atmosphere of Saturn are known, from Voyager, ground-based, and early Cassini results, to vary in emission intensity with latitude. Of particular interest is the marked increase in hydrocarbon line intensity near the south pole during southern summer, as the increased line intensity cannot be simply explained by the increased temperatures observed in that region since the variations between C₂H₂ and C₂H₆ emission in the south pole region are different. In order to measure the latitudinal variations of hydrocarbons in Saturn's southern hemisphere we have used 3 cm⁻¹ resolution Cassini CIRS data from 2006 and combined this with measurements from the ground in October 2006 at NASA's IRTF using Celeste, an infrared high-resolution cryogenic grating spectrometer. These two data sets have been used to infer the molecular abundances of C₂H₂ and C₂H₆ across the southern hemisphere in the 1-10 mbar altitude region. We find that the latitudinal acetylene profile follows the yearly average mean daily insolation except at the southern pole where it peaks in abundance. Near the equator (5° S) the C₂H₂ abundance at the 1.2 mbar level is (1.6±0.19)×¹⁰−7 and it decreases by a factor of 2.7 from the equator toward the pole. However, at the pole (∼87° S) the C₂H₂ abundance jumps to (1.8±0.3)×¹⁰−7, approximately the equatorial value. The C₂H₆ abundance near the equator at the 2 mbar level is (0.7±0.1)×¹⁰−5 and stays approximately constant until mid-latitudes where it increases gradually toward the pole, attaining a value of (1.4±0.4)×¹⁰−5 there. The increase in ethane toward the pole with the corresponding decrease in acetylene is consistent with southern hemisphere meridional winds [Greathouse, T.K., Lacy, J.H., Bézard, B., Moses, J.I., Griffith, C.A., Richter, M.J., 2005. Icarus 177, 18-31]. The localized increase in acetylene at the pole provides evidence that there is dynamical transport of hydrocarbons from the equator to the southern pole.     

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.     

HST observation of the atmospheric composition of Jupiter’s equatorial region: evidence for tropospheric C2H2☆

This paper presents the first detailed analysis of acetylene absorption features observed longward of 190.0 nm in a jovian spectrum by the Faint Object Spectrograph on board the Hubble Space Telescope. The presence of two features located near 207.0 nm can only be explained by a substantial abundance of acetylene in the upper troposphere. Using a Rayleigh-Raman radiative transfer model, it was determined that the acetylene vertical profile is characterized by a decrease in the mole fraction with increasing pressure in the upper stratosphere, a minimum around 14 to 29 mbar, followed by an increase to about 1.5 × 10⁻⁷ in the upper troposphere. Longward of 220 nm, the relatively high contrast of Raman features to the continuum precludes the existence of an optically significant amount of clouds from 150 to 500 mbar unless they are highly reflective. Instead, the reflectivity at these long wavelengths is determined by stratospheric, not tropospheric, scatterers and absorbers. Analysis of the data also suggests that ammonia is extremely undersaturated at pressures below 700 mbar. However, no firm conclusions can be reached because of the uncertainties surrounding its cross section longward of 217.0 nm, which are due to vibrationally excited states.     

Jupiter's hydrocarbon polar brightening: Discovery of 3-micron line emission from south polar CH4, C2H2, and C2H6

Jupiter exhibits bright H⁺₃ auroral arcs at 3-4 microns that cool the hot (>1000 K) ionosphere above the ∼¹⁰−7 bar level through the infrared bands of this trace constituent. Below the ¹⁰−7 bar level significant cooling proceeds through infrared active bands of CH₄, C₂H₂, and C₂H₆. We report the discovery of 3-micron line emission from these hydrocarbon species in spectra of the jovian south polar region obtained on April 18 and 20, 2006 (UT) with CGS4 on the United Kingdom Infrared Telescope. Estimated cooling rates through these molecules are 7.5×¹⁰−3, 1.4×¹⁰−3, and , respectively, for a total nearly half that of H⁺₃. We derive a temperature of 450 ± 50 K in the ¹⁰−7-¹⁰−5 bar region from the C₂H₂ lines.