Detection of new hydrocarbons in Uranus' atmosphere by infrared spectroscopy

Ethane (C₂H₆), methylacetylene (CH₃C₂H or C₃H₄) and diacetylene (C₄H₂) have been discovered in Spitzer 10-20 μm spectra of Uranus, with 0.1-mbar volume mixing ratios of (1.0±0.1)×¹⁰⁻⁸, (2.5±0.3)×¹⁰⁻¹⁰, and (1.6±0.2)×¹⁰⁻¹⁰, respectively. These hydrocarbons complement previously detected methane (CH₄) and acetylene (C₂H₂). Carbon dioxide (CO₂) was also detected at the 7-σ level with a 0.1-mbar volume mixing ratio of (4±0.5)×¹⁰⁻¹¹. Although the reactions producing hydrocarbons in the atmospheres of giant planets start from radicals, the methyl radical (CH₃) was not found in the spectra, implying much lower abundances than in the atmospheres of Saturn or Neptune where it has been detected. This finding underlines the fact that Uranus' atmosphere occupies a special position among the giant planets, and our results shed light on the chemical reactions happening in the absence of a substantial internal energy source.     

Laboratory kinetics of C2H radical reactions with ethane, propane, and n-butane at T = 96-296 K: implications for Titan

The kinetics of the reactions of C₂H radical with ethane (k₁), propane (k₂), and n-butane (k₃) are studied over the temperature range of T = 96-296 K with a pulsed Laval nozzle apparatus that utilizes a pulsed laser photolysis-chemiluminescence technique. The C₂H decay profiles in the presence of both the alkane reactant and O₂ are monitored by the CH(A²Δ) chemiluminescence tracer method. The results, together with available literature data, yield the following Arrhenius expressions: k₁(T) = (0.51 ± 0.06) × 10⁻¹⁰ exp[(−76 ± 30)K/T] cm³ molecule⁻¹ s⁻¹ (T = 96-800 K), k₂(T) = (0.98 ± 0.32) × 10⁻¹⁰exp[(−71 ± 60)K/T] cm³ molecule⁻¹ s⁻¹ (T = 96-361 K), and k₃(T) = (1.23 ± 0.26) × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹ (T = 96-297 K). At T = 296 K, k₁ is measured as a function of total pressure and has little or no pressure dependence. The results from this work support a direct hydrogen abstraction mechanism for the title reactions. Implications to the atmospheric chemistry of Titan are discussed.     

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.     

Removal of Titan's noble gases by their trapping in its haze

Titan's haze, formed by photolysis of C₂H₂, C₂H₄ and HCN, was found experimentally to trap Ar, Kr and Xe with efficiencies of 3.5 × 10⁻⁴, 1.9 × 10⁻³ and 6.5 × 10⁻² [noble gas atom]/[carbon atom] in the polymer, respectively. The rate of aerosol formation and settling down of 3 × 10⁻¹³ kg m⁻² s⁻¹, as inferred from our experiments on CH₄ photolysis in the far UV [Podolak, M., Bar-Nun, A., 1979. Icarus 39, 272-276], is sufficient to reduce the mixing ratios of ³⁶Ar and ⁴⁰Ar to their low values of (2.8 ± 0.3) × 10⁻⁷ and (4.3 ± 0.1) × 10⁻³, respectively, and those of Kr and Xe to below the detection limit of 10⁻⁸.     

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.     

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.     

Flowing afterglow studies of temperature dependencies for electron dissociative recombination of HCNH, CH3CNH and CH3CH2CNH and their symmetrical proton-bound dimers

A study has been made using a variable temperature flowing afterglow Langmuir probe technique (VT-FALP) to determine the equilibrium temperature dependencies of the dissociative electron-ion recombination of the protonated cyanide ions (RCNH⁺, where R=H, CH₃ and C₂H₅) and their symmetrical proton-bound dimers (RCNH⁺NCR). The power law temperature dependencies of the recombination coefficients, α_e, over the temperature range 180 to 600 K for the protonated ions are α_e(T)(cm³ s⁻¹)=3.5±0.5×10⁻⁷ (300/T)^1.38 for HCNH⁺, α_e(T)=3.4±0.5×10⁻⁷ (300/T)^1.03 for CH₃CNH⁺, and α_e(T)=4.6±0.7×10⁻⁷ (300/T)^0.81 for CH₃CH₂CNH⁺. The equivalent values for the proton-bound dimers are α_e(T)(cm³ s⁻¹)=2.4±0.4×10⁻⁶(300/T)^0.5 for (HCN)₂H⁺ to α_e(T)=2.8±0.4×10⁻⁶(300/T)^0.5 for (CH₃CN)₂H⁺, and α_e(T)=2.3±0.3×10⁻⁶(300/T)^0.5 for (CH₃CH₂CN)₂H⁺. The relevance of these data to molecular synthesis in the interstellar medium and the Titan ionosphere are discussed.     

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.     

Keck NIRC2 photometry of Uranus, uranian satellites, and Triton in August 2004

On August 11, 2004, we made adaptive optics observations of the Uranus and Neptune systems with the Keck II Near Infrared Camera. Uranus and Triton were observed in three broadband filters (J, H, and K-prime) and four narrowband filters [Hcont, FeII, He1_B, and H2(v=1-0)]. Miranda, Ariel, Umbriel, and Oberon were observed in the four narrowband filters only. To achieve the highest possible photometric accuracy, and thus the tightest possible constraints on atmospheric aerosol models and gas mixing ratios, we used aperture photometry that accounted for the dependence of point-spread functions and growth curves on the adaptive optics reference object, and accounted for recently determined phase curves of each object. The satellite albedos we determined were compared with published relative spectra to verify the relative consistency of our observations, which were subsequently used to convert published relative spectra to absolute spectra. We used these absolute spectra and synthetic photometry methods to compare published values in dissimilar photometric systems to each other and to our observations. We find our satellite albedos in best agreement with photometry from Karkoschka [Karkoschka, E., 2001. Icarus 151, 51-68], which is the best characterized and most contemporaneous data set. Our estimated absolute accuracy of 5% to 8% is consistent with these intercomparisons. We obtained the following ring-subtracted and discrete feature-free albedos of Uranus: J: (1.66±0.07)×¹⁰⁻², H: (1.09±0.05)×¹⁰⁻², K^′: (2.08±0.15)×¹⁰⁻⁴, Hcont: (3.71±0.23)×¹⁰⁻², FeII: (1.14±0.07)×¹⁰⁻³, He1_B: (2.06±0.16)×¹⁰⁻⁴, and H2: (1.27±0.10)×¹⁰⁻⁴.     

Temporally varying ethylene emission on Jupiter

Ethylene (C₂H₄) emission has been measured in the poles and equator of Jupiter. The 949 cm⁻¹ spectra were recorded with a high resolution spectrometer at the McMath-Pierce telescope at Kitt Peak in October-November 1998 and at the Infrared Telescope Facility at Mauna Kea in June 2000. C₂H₄ is an important product of methane chemistry in the outer planets. Knowledge of its abundance can help discriminate among the various proposed sets of CH₄ photolysis branching ratios at Ly-α, and determine the relative importance of the reaction pathways that produce C₂H₂ and C₂H₆. In the equatorial region the C₂H₄ emission is weak, and we were only able to detect it at high air-mass, near the limb. We derive a peak equatorial molar abundance of C₂H₄ of 4.5×¹⁰⁻⁷-1.7×¹⁰⁻⁶ near 2.2×¹⁰⁻³ mbar, with a total column of 5.7×¹⁰¹⁴-2.2×¹⁰¹⁵ molecules cm⁻² above 10 mbar depending upon choice of thermal profile. We observed enhanced C₂H₄ emission from the poles in the regions where auroras are seen in X-ray, UV, and near infrared images. In 2000 we measured a short-term change in the distribution of polar C₂H₄ emission; the emission in the north IR auroral “hot spot” decreased by a factor of three over a two-day interval. This transient behavior and the sensitivity of C₂H₄ emission to temperature changes near its contribution peak at 5-10 microbar suggests that the polar enhancement is primarily a thermal effect coupled with vertical transport. Comparing our observations from Kitt Peak and Mauna Kea shows that the C₂H₄ emission of the northern non-“hot spot” auroral regions did not change over the three-year period while that in the southern polar regions decreased.     

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.     

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.     

CN, C2 radicals and dust in Comets Shoemaker-Levy 1991 T2 and P/deVico 1995 S1

The results of the multiaperture photometry of Comet Shoemaker-Levy 1991 T2 in the pre-perihelion and P/deVico in the post-perihelion period with the narrowband CN, C₂ and Blue Continuum (BC) IHW filters are presented. A Haser model of the molecular coma was used for the determination of the parent and daughter scale-lengths and production rates of the radicals. The comets showed some substantial differences between their parent scale-lengths. The CN parent scale-length (at 1.0 AU) was 16×¹⁰³ km for Comet Shoemaker-Levy and 39×¹⁰³ for P/deVico, the C₂ parent scale-lengths were respectively 29×¹⁰³ and 54×¹⁰³ km. Such divergences could be interpreted in the frame of different scenarios of emission of cometary parents, either from a nucleus or from a volume source. The daughter scale-lengths for these comets were quite similar, namely: 306×¹⁰³ and 318×¹⁰³ km for CN and 69×¹⁰³ and 66×¹⁰³ km for C₂. We determined the Afρ parameter for apertures of different radii. A Monte Carlo model of the dust coma was used to obtain the dust ejection velocity. It was of the order of 0.1 km s⁻¹ for both comets. The power index of the distribution of the β-parameter of dust particles (ratio of light pressure to the solar gravitation) was of the order of 3 for C/Shoemaker-Levy and close to 2 for P/deVico. The dependence on heliocentric distance (rh) of the radical and dust production rates for P/deVico in the range of 0.7-1.0 AU was described by the power law function with a power index equal to: 5.55±0.14 for CN, 5.70±0.24 for C₂ and 5.22±0.19 for dust. Relative abundances of the dynamically new Comet Shoemaker-Levy and short-period P/deVico were quite similar with an enhancement of C₂ comparing with standard values taken from A'Hearn et al. (1995).     

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.     

Prebiotic organic synthesis in early Earth and Mars atmospheres: Laboratory experiments with quantitative determination of products formed in a cold plasma flow reactor

The goal of this study was to explore prebiotic chemistry in a range of plausible early Earth and Mars atmospheres. To achieve this laboratory continuous flow plasma irradiation experiments were performed on N₂/H₂/CO/CO₂ gas mixtures chosen to represent mildly reducing early Earth and Mars atmospheres derived from a secondary volcanic outgassing of volatiles in chemical equilibrium with magmas near present day oxidation state. Under mildly reducing conditions (91.79% N₂, 5.89% H₂, 2.21% CO, and 0.11% CO₂), simple nitriles are produced in the gas phase with yield (G in molecules per 100 eV), for the key prebiotic marker molecule HCN at G∼1×¹⁰⁻³ (0.1 nmol J⁻¹). In this atmosphere localized HCN concentrations possibly could approach the 10⁻² M needed for HCN oligomerization. Yields under mildly oxidizing conditions (45.5% N₂, 0.1% H₂, 27.2% CO, 27.2% CO₂) are significantly less as expected, with HCN at G∼3×¹⁰⁻⁵ (). Yields in a Triton atmosphere which can be plausibly extrapolated to represent what might be produced in trace CH₄ conditions (99.9% N₂, 0.1% CH₄) are significant with HCN at G∼1×¹⁰⁻² (1 nmol J⁻¹) and tholins produced. Recently higher methane abundance atmospheres have been examined for their greenhouse warming potential, and higher abundance hydrogen atmospheres have been proposed based on a low early Earth exosphere temperature. A reducing (64.04% N₂, 28.8% H₂, 3.60% CO₂, and 3.56% CH₄), representing a high CH₄ and H₂ abundance early Earth atmosphere had HCN yields of G∼5×¹⁰⁻³ (0.5 nmol J⁻¹). Tholins generated in high methane hydrogen gas mixtures is much less than in a similar mixture without hydrogen. The same mixture with the oxidizing component CO₂ removed (66.43% N₂, 29.88% H₂, 0% CO₂, and 3.69% CH₄) had HCN yields of G∼1×¹⁰⁻³ (0.1 nmol J⁻¹) but more significant tholin yields.     

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).     

Temporal Behavior of Stratospheric Ammonia Abundance and Temperature Following the SL9 Impacts

Infrared emission lines of stratospheric ammonia (NH₃) were observed following the collisions of the fragments of Comet Shoemaker-Levy 9 with Jupiter in July of 1994 at the impact sites of fragments G and K. Infrared heterodyne spectra near 10.7 μm were obtained by A. Betz et al. (in Abstracts for Special Sessions on Comet Shoemaker-Levy 9, The 26th Meeting of the Division for Planetary Sciences, Washington DC, 31 Oct.-4 Nov. 1994, p. 25) using one of the Infrared Spatial Interferometer telescope systems on Mount Wilson. Lineshapes of up to three different NH₃ emission lines were measured at a resolving power of ∼10⁷ at multiple times following the impacts. We present here our radiative transfer analysis of the fully resolved spectral lineshapes of the multiple rovibrational lines. This analysis provides information on temperature structure and NH₃ abundance distributions and their temporal changes up to 18 days after impact. These results are compared to photochemical models to determine the role of photochemistry and other mechanisms in the destruction and dilution of NH₃ in the jovian stratosphere after the SL9 impacts.One day following the G impact, the inferred temperature above 0.001 mbar altitude is 283±13 K, consistent with a recent plume splashback model. Cooling of the upper stratosphere to 204 K by the fourth day and to quiescence after a week is consistent with a simple gray atmosphere radiative flux calculation and mixing with cold jovian air. During the first 4 days after impact, NH₃ was present primarily at altitudes above 1 mbar with a column density of (7.7±1.6)×10¹⁷ cm⁻² after 1 day and (3.7±0.8)×10¹⁷ cm⁻² after 4 days. (Errors represent precision.) We obtained >2.5 times more NH₃ than can be supplied by nitrogen from a large cometary fragment, suggesting a primarily jovian source for the NH₃. By 18 days postimpact, a return to quiescent upper stratospheric temperature is retrieved for the G region, with an NH₃ column density of 7.3×10¹⁷ cm⁻² or more in the lower stratosphere, possibly supplied by NH₃ upwelling across an impact-heated and turbulent tropopause, which may have been masked by initial dust and haze. Above the 1-mbar level, the maximum retrieved column density decreased to 6.5×10¹⁶ cm⁻². Comparison to photochemical models indicates that photolysis alone is not sufficient to account for the loss of NH₃ above 1 mbar by that time, even when chemical reformation of NH₃ is ignored. We speculate that the dispersion of plume material at high altitudes (above 1 mbar) is responsible for the change in the spectra observed a few days postimpact. Data on the K impact region provide qualitatively consistent results.     

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.     

Detection of the Forbidden SO aΔ→XΣ Rovibronic Transition on Io at 1.7 μm

We report the discovery of the forbidden electronic a¹Δ→X³Σ⁻ transition of the SO radical on Io at 1.7 μm with the W. M. Keck II telescope on 24 September 1999 (UT), while the satellite was eclipsed by Jupiter. The shape of the SO emission band suggests a rotational temperature of ∼1000 K; i.e., the gas is extremely hot. We interpret the observed emission rate of ∼2×10²⁷ photons s⁻¹ to be caused by SO molecules in the excited a¹Δ state being directly ejected from the vent at a thermodynamic quenching temperature of ∼1500 K, assuming a SO/SO₂ abundance ratio of ∼0.1 and a total venting rate of ∼10³¹ molecules s⁻¹ (Strobel and Wolven 2001, Astrophys. Space Sci. 277, 1-17). The shape of our complete (1.6-2.5 μm) spectrum suggests that the volcano Loki contains a small (∼2 km²) hot spot at 960±12 K, as well as a larger (∼50 km²) area at 640±5 K.     

Detection of C2HD and the D/H ratio on Titan

We report here the first detection of mono-deuterated acetylene (acetylene-d1, C₂HD) in Titan's atmosphere from the presence of two of its emission bands at 678 and 519 cm⁻¹ as observed in CIRS spectral averages of nadir and limb observations taken between July 2004 and mid-2007. By using new laboratory spectra for this molecule, we were able to derive its abundance at different locations over Titan's disk. We find the C₂HD value () to be roughly constant with latitude from the South to about 45° N and then to increase slightly in the North, as is the case for C₂H₂. Fitting the 678 cm⁻¹ν₅ band simultaneously with the nearby C₂H₂ 729 cm⁻¹ν₅ band, allows us to infer a D/H ratio in acetylene on Titan with an average of the modal values of 2.09±0.45×¹⁰⁻⁴ from the nadir observations, the uncertainties being mainly due to the vertical profile used for the fit of the acetylene band. Although still subject to significant uncertainty, this D/H ratio appears to be significantly larger than the one derived in methane from the CH₃D band (upper limit of 1.5×¹⁰⁻⁴; Bézard, B., Nixon, C.A., Kleiner, I., Jennings, D.E., 2007. Icarus, 191, 397-400; Coustenis, A., Achterberg, R., Conrath, B., Jennings, D., Marten, A., Gautier, D., Bjoraker, G., Nixon, C., Romani, P., Carlson, R., Flasar, M., Samuelson, R.E., Teanby, N., Irwin, P., Bézard, B., Orton, G., Kunde, V., Abbas, M., Courtin, R., Fouchet, Th., Hubert, A., Lellouch, E., Mondellini, J., Taylor, F.W., Vinatier, S., 2007. Icarus 189, 35-62). From the analysis of limb data we infer D/H values of (at 54° S), (at 15° S), (at 54° N) and (at 80° N), which average to a mean value of 1.63±0.27×¹⁰⁻⁴.