First Spitzer observations of Neptune: Detection of new hydrocarbons

We present the first spectra of Neptune taken with the Spitzer Space Telescope, highlighting the high-sensitivity, moderate-resolution 10-20 μm (500-1000 cm⁻¹) spectra. We report the discovery of methylacetylene (CH₃C₂H) and diacetylene (C₄H₂) with derived 0.1-mbar volume mixing ratios of (1.2±0.1)×¹⁰⁻¹⁰ and (3±1)×¹⁰⁻¹² respectively.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

A methodology to construct a reduced chemical scheme for 2D-3D photochemical models: Application to Saturn

We present a methodology to build a reduced chemical scheme adapted to the study of hydrocarbons in the atmospheres of giant planets and Titan. As an example, we have built a reduced chemical scheme, containing only 25 compounds and 46 reactions (including photolysis), which is well adapted to compute the abundance of the main hydrocarbons observed so far in the atmosphere of Saturn (CH₃, CH₄, C₂H₂, C₂H₄, C₂H₆, CH₃C₂H, C₃H₈ and C₄H₂). This scheme gives similar results, within the error bars of the model, as a 1D photochemical model using an initial chemical scheme containing 90 compounds and more than 600 reactions. As a consequence, such a methodology can be used to build a reduced scheme well adapted to future 2D (or 3D) photochemical models and GCMs.     

Titan’s atmosphere from ISO mid-infrared spectroscopy

We have analyzed Titan observations performed by the Infrared Space Observatory (ISO) in the range 7-30 μm. The spectra obtained by three of the instruments on board the mission (the short wavelength spectrometer, the photometer, and the camera) were combined to provide new and more precise thermal and compositional knowledge of Titan’s stratosphere. With the high spectral resolution achieved by the SWS (much higher than that of the Voyager 1 IRIS spectrometer), we were able to detect and separate the contributions of most of the atmospheric gases present on Titan and to determine disk-averaged mole fractions. We have also tested existing vertical distributions for C₂H₂, HCN, C₂H₆, and CO₂ and inferred some information on the abundance of the first species as a function of altitude. From the CH₃D band at 1161 cm⁻¹ and for a CH₄ mole fraction assumed to be 1.9% in Titan’s stratosphere, we have obtained the monodeuterated methane-averaged abundance and retrieved a D/H isotopic ratio of 8.7−1.9+3.2 × 10⁻⁵. We discuss the implications of this value with respect to current evolutionary scenarios for Titan. The ν₅ band of HC₃N at 663 cm⁻¹ was observed for the first time in a disk-averaged spectrum. We have also obtained a first tentative detection of benzene at 674 cm⁻¹, where the fit of the ISO/SWS spectrum at R = 1980 is significantly improved when a constant mean mole fraction of 4 × 10⁻¹⁰ of C₆H₆ is incorporated into the atmospheric model. This corresponds to a column density of ∼ 2 × 10¹⁵ molecules cm⁻² above the 30-mbar level. We have also tested available vertical profiles for HC₃N and C₆H₆ and adjusted them to fit the data. Finally, we have inferred upper limits of a few 10⁻¹⁰ for a number of molecules proposed as likely candidates on Titan (such as allene, acetonitrile, propionitrile, and other more complex gases).     

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.     

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.     

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.     

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.     

Upper limits for an atmosphere on Io

The 14 May 1971 occultation β Scorpi C by Io was successfully observed in ultraviolet light near Kingston, Jamaica. Within the limits established by time resolution and the signal-to-noise ratio, both the disappearance and reappearance were found to be instantaneous. Upper limits for the surface pressure for N₂, CH₄, and H₂ atmospheres are 0.09, 0.13, and 44.ubar, respectively. The corresponding number densities are 6.2 × 10¹², 9.4 × 10¹², and 3.2 × 10¹⁵ cm⁻³. An isothermal atmosphere at a temperature of 100°K was assumed.     

FT-IR measurements of cold C3H8 cross sections at 7–15 μm for Titan atmosphere

We present absorption cross sections of propane (C₃H₈) at temperatures from 145 K to 297 K in the 690–1550 cm⁻¹ region. Pure and N₂-broadened spectra were measured at pressures from 3 Torr to 742 Torr using a Bruker IFS125 FT-IR spectrometer at JPL. The gas absorption cell, developed at Connecticut College, was cooled by a closed-cycle helium refrigerator. The cross sections were measured and compiled for individual spectra recorded at various experimental conditions covering the planetary atmosphere and Titan. In addition to the cross sections, a propane pseudoline list with a frequency grid of 0.005 cm⁻¹, was fitted to the 34 laboratory spectra. Line intensities and lower state energies were retrieved for each line, assuming a constant width. Validation tests showed that the pseudoline list reproduces discrete absorption features and continuum, the latter contributed by numerous weak and hot band features, in most of the observed spectra within 3%. Based on the pseudoline list, the total intensity in the 690–1550 cm⁻¹ region was determined to be 52.93 (±3%) × 10⁻¹⁹ cm⁻¹/(molecule cm⁻²) at 296 K; this value is within 3% of the average from four earlier studies. Finally, the merit of the pseudoline approach is addressed for heavy polyatomic molecules in support of spectroscopic observation of atmospheres of Titan and other planets. The cold cross sections will be submitted to the HITRAN database (hitran.harvard.edu), and the list of C₃H₈ pseudolines will be available from a MK-IV website of JPL (http://mark4sun.jpl.nasa.gov/data/spec/Pseudo).     

The atmospheric composition and structure of Jupiter and Saturn from ISO observations: a preliminary review

Infrared spectra of Jupiter and Saturn have been recorded with the two spectrometers of the Infrared Space Observatory (ISO) in 1995–1998, in the 2.3–180 μm range. Both the grating modes (R=150–2000) and the Fabry-Pérot modes (R=8000–30,000) of the two instruments were used. The main results of these observations are (1) the detection of water vapour in the deep troposphere of Saturn; (2) the detection of new hydrocarbons (CH₃C₂H, C₄H₂, C₆H₆, CH₃) in Saturn’s stratosphere; (3) the detection of water vapour and carbon dioxide in the stratospheres of Jupiter and Saturn; (4) a new determination of the D/H ratio from the detection of HD rotational lines. The origin of the external oxygen source on Jupiter and Saturn (also found in the other giant planets and Titan in comparable amounts) may be either interplanetary (micrometeoritic flux) or local (rings and/or satellites). The D/H determination in Jupiter, comparable to Saturn’s result, is in agreement with the recent measurement by the Galileo probe (Mahaffy, P.R., Donahue, T.M., Atreya, S.K., Owen, T.C., Niemann, H.B., 1998. Galileo probe measurements of D/H and ³He/⁴He in Jupiters atmosphere. Space Science Rev. 84 251–263); the D/H values on Uranus and Neptune are significantly higher, as expected from current models of planetary formation.