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.     

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.     

Experimental and theoretical study of hydrocarbon photochemistry applied to Titan stratosphere

None of the Titan photochemical models currently available have been able to reproduce the full set of stratospheric molecular mixing ratios inferred from observations. In order to assess how well reaction sets describe hydrocarbon chemistry, theoretical modeling predictions were compared to the results of a laboratory experiment. A CH₄-C₂H₂ mixture was irradiated at 185 nm in an atmospheric simulation chamber and the evolution of the gas mixture was followed in situ and in real time by infrared spectroscopy. In parallel, a 0D theoretical model of the laboratory experiment was developed. A new reaction set describing Titan's chemistry was built and incorporated in the model. Lebonnois et al. [Lebonnois, S., Toublanc, D., Hourdin, F., Rannou, P., 2001. Icarus 152, 384-406] reaction set was also used for comparison. The presence of small amounts of atmospheric O₂ in the experiment was properly accounted for and led us to suggest that oxygenated chemistry might be a source of C₂H₄ in Titan's atmosphere. With Lebonnois et al. [Lebonnois, S., Toublanc, D., Hourdin, F., Rannou, P., 2001. Icarus 152, 384-406] reaction set, the model could not fit at all the experimental evolution of the compounds. This is explained by some of the choices made for crucial kinetic parameters such as the quantum yield of photolysis of C₂H₂. Also, the absence of some reactions led to the enhancement of pathways that would otherwise be negligible. For example, the lack of reactions between C₄H₄ and radicals induced an erroneously high photolysis rate for this species. With the reaction set built in this study, the model much better fits the experiment, especially when the “soot,” which includes C₄H₄, is recycled into C₂H₂. This shows that photochemistry of the larger species has a role in determining the lighter species concentrations and that considering that they are simply lost from the system is not a valid assumption. Including even an abridged set of C₄ + hydrocarbon reactions will be required in future photochemical models. Especially, photolysis rates and yields for C₂H₂, C₄H₂, and C₄H₄, are important parameters in need of a better determination.     

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.     

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.     

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.     

Temperature-dependent photoabsorption cross-sections of cyanoacetylene and diacetylene in the mid- and vacuum-UV: Application to Titan's atmosphere

Cyanoacetylene (HC₃N) and diacetylene (C₄H₂) play an important role in the photochemistry of Titan's atmosphere, in part because of their strong absorption between 110 and 180 nm. Accurate photoabsorption cross-sections at temperatures representative of Titan's atmosphere are required to interprete Cassini observations and to calculate photolysis rates used in photochemical models. Using synchrotron radiation as a tunable vacuum ultraviolet (VUV) light source, we have measured absolute photoabsorption cross-sections of C₄H₂ and HC₃N with a spectral resolution of 0.05 nm in the region between 80 and 225 nm and at different temperatures between 173 and 295 K. The measured cross-sections are used to model transmission spectra of Titan atmosphere in the VUV.     

Analysis of Cassini/CIRS limb spectra of Titan acquired during the nominal mission: I. Hydrocarbons, nitriles and CO2 vertical mixing ratio profiles

Observations of the Composite InfraRed Spectrometer (CIRS) during the entire nominal Cassini mission (2004-2008) provide us with an accurate global view of composition and temperature in the middle atmosphere of Titan (between 100 and 500 km). We investigated limb spectra acquired at resolution at nine different latitudes between 56°S and 80°N, with a better sampling in the northern hemisphere where molecular abundances and temperature present strong latitudinal variations. From this limb data acquired between February 2005 and May 2008, we retrieved the vertical mixing ratio profiles of C₂H₂, C₂H₄, C₂H₆, C₃H₈, CH₃C₂H, C₄H₂, C₆H₆, HCN, HC₃N and CO₂. We present here for the first time, the latitudinal variations of the C₂H₆, C₃H₈, CO₂, C₂H₄ and C₆H₆ vertical mixing ratios profiles. Some molecules, such as C₂H₆ or C₃H₈ present little variations above their condensation level. The other molecules (except CO₂) show a significant enhancement of their mixing ratios poleward of 50°N. C₂H₄ is the only molecule whose mixing ratio decreases with height at latitudes below 46°N. Regions depleted in C₂H₂, HCN and C₄H₂ are observed around 400 km (0.01 mbar) and 55°N. We also inferred a region enriched in CO₂ located between 30 and 40°N in the 2-0.7 mbar pressure range. At 80°N, almost all molecules studied here present a local minimum of their mixing ratio profiles near 300 km (∼0.07 mbar), which is in contradiction with Global Circulation Models that predict constant-with-height vertical profiles due to subsidence at the north pole.     

Analysis of Titan's neutral upper atmosphere from Cassini Ion Neutral Mass Spectrometer measurements

In this paper we present an in-depth study of the distributions of various neutral species in Titan's upper atmosphere, between 950 and 1500 km for abundant species (N₂, CH₄, H₂) and between 950 and 1200 km for other minor species. Our analysis is based on a large sample of Cassini/INMS (Ion Neutral Mass Spectrometer) measurements in the CSN (Closed Source Neutral) mode, obtained during 15 close flybys of Titan. To untangle the overlapping cracking patterns, we adopt Singular Value Decomposition (SVD) to determine simultaneously the densities of different species. Except for N₂, CH₄, H₂ and ⁴⁰Ar (as well as their isotopes), all species present density enhancements measured during the outbound legs. This can be interpreted as a result of wall effects, which could be either adsorption/desorption of these molecules or heterogeneous surface chemistry of the associated radicals on the chamber walls. In this paper, we provide both direct inbound measurements assuming ram pressure enhancement only and abundances corrected for wall adsorption/desorption based on a simple model to reproduce the observed time behavior. Among all minor species of photochemical interest, we have firm detections of C₂H₂, C₂H₄, C₂H₆, CH₃C₂H, C₄H₂, C₆H₆, CH₃CN, HC₃N, C₂N₂ and NH₃ in Titan's upper atmosphere. Upper limits are given for other minor species.The globally averaged distributions of N₂, CH₄ and H₂ are each modeled with the diffusion approximation. The N₂ profile suggests an average thermospheric temperature of 151 K. The CH₄ and H₂ profiles constrain their fluxes to be and , referred to Titan's surface. Both fluxes are significantly higher than the Jeans escape values. The INMS data also suggest horizontal/diurnal variations of temperature and neutral gas distribution in Titan's thermosphere. The equatorial region, the ramside, as well as the nightside hemisphere of Titan appear to be warmer and present some evidence for the depletion of light species such as CH₄. Meridional variations of some heavy species are also observed, with a trend of depletion toward the north pole. Though some of the above variations might be interpreted by either the solar-driven models or auroral-driven models, a physical scenario that reconciles all the observed horizontal/diurnal variations in a consistent way is still missing. With a careful evaluation of the effect of restricted sampling, some of the features shown in the INMS data are more likely to be observational biases.     

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).     

Chemical reactions in the Titan’s troposphere during lightning

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

Latitudinal variation of Saturn photochemistry deduced from spatially-resolved ultraviolet spectra

We obtained spatially-resolved ultraviolet spectra of Saturn in 1994 with the Faint Object Spectrometer and Goddard High Resolution Spectrograph of the Hubble Space Telescope. We observed four areas on the planet at 15° N, 33° S, 41° S, and 52° S, with a field-of-view of less than 2 × 2 arcsec², compared to the 16-arcsec planet diameter. The wavelength range, 1550-2300 Å, encompasses absorption from major hydrocarbons (C₂H₆, C₂H₄, C₂H₂, CH₃C₂H, C₄H₂) and water. We find global hydrocarbon abundances and a C₂H₂ vertical distribution compatible with infrared observations, in contrast with previous analyses of ultraviolet spectra. The stratospheric haze opacity decreases from polar region to the equator. Saturn mid-latitudes are photochemically distinct from the rest of the planet. At 33° S, the spectrum requires either (1) a distinctly different C₂H₂ vertical distribution or (2) a locally enhanced water abundance. At 41° S, the hydrocarbon abundance exhibits a local minimum, within a global trend of increasing abundance from equator to pole. This global trend may result from an increased abundance of short-lived hydrocarbons such as C₄H₂. Photochemical models predict a depletion of hydrocarbon molecules in the presence of stratospheric water [Moses et al., 2000. Icarus 143, 166-202]. These results are consistent with a localized influx of water, in the form of high charge to mass ratio particles, flowing into Saturn's atmosphere at latitudes magnetically linked to the rings.     

New perspectives on Titan's upper atmosphere from a reanalysis of the Voyager 1 UVS solar occultations

We have reanalyzed the Voyager 1 UVS solar occultations by Titan to expand upon previous analyses and to resolve inconsistencies that have been noted in the scientific literature. To do so, we have developed a detailed model of the UVS detector and improved both the data reduction methods and retrieval techniques. In comparison to the values previously determined by Smith et al. (1982, J. Geophys. Res. 87, 1351-1359) we find N₂ densities that are 25-60% higher, CH₄ densities that are smaller by a factor of 3-7, and C₂H₂ densities that are roughly two orders of magnitude smaller. Our values for the thermospheric temperature are 153-158 K, which are approximately 20-40 K colder than previous estimates. We also report the first-ever determination from Voyager UVS data of density profile information for C₂H₄, HCN, and HC₃N. Finally, we present a simple engineering model that is consistent with our new results in the upper atmosphere and merges smoothly with the model of Yelle et al. (1997, in: HUYGENS Science, Payload and Mission, in: ESA SP, vol. 1177, pp. 243-256) in the lower atmosphere. Our results provide improved constraints for photochemical models and offer scientists a better understanding of Titan's upper atmosphere as we head into the Cassini era in the exploration of the saturnian system.     

Abundances of Jupiter's trace hydrocarbons from Voyager and Cassini

The flybys of Jupiter by the Voyager spacecraft in 1979, and over two decades later by Cassini in 2000, have provided us with unique datasets from two different epochs, allowing the investigation of seasonal change in the atmosphere. In this paper we model zonal averages of thermal infrared spectra from the two instruments, Voyager 1 IRIS and Cassini CIRS, to retrieve the vertical and meridional profiles of temperature, and the abundances of the two minor hydrocarbons, acetylene (C₂H₂) and ethane (C₂H₆). The spatial variation of these gases is controlled by both chemistry and dynamics, and therefore their observed distribution gives us an insight into both processes. We find that the two gases paint quite different pictures of seasonal change. Whilst the 2-D cross-section of C₂H₆ abundance is slightly increased and more symmetric in 2000 (northern summer solstice) compared to 1979 (northern fall equinox), the major trend of equator to pole increase remains. For C₂H₂ on the other hand, the Voyager epoch exhibits almost no latitudinal variation, whilst the Cassini era shows a marked decrease polewards in both hemispheres. At the present time, these experimental findings are in advance of interpretation, as there are no published models of 2-D Jovian seasonal chemical variation available for comparison.     

Cyanopolyyne chemistry in TMC-1

Using pseudo-time-dependent models and three different reaction networks, a detailed study of the dominant reaction pathways for the formation of cyanopolyynes and their abundances in TMC-1 is presented. The analysis of the chemical reactions show that for the formation of cyanopolyynes there are two major chemical regimes. First, early times of less than ～10⁴ yrs when ion-molecule reactions are dominant, the main chemical route for the formation of larger cyanopolyynes is $$C_n H^ + \xrightarrow{N}C_n N^ + \xrightarrow{{H_2 }}HC_n N^ + \xrightarrow{{H_2 }}H_2 C_n N^ + \xrightarrow{{e^ - }}HC_n N$$ wheren=5, 7, and 9. Second, at times greater than 10⁴ yrs, when neutral-neutral reactions become dominant, two major reaction routes for the formation of cyanopolyynes are (a), $$HCN\xrightarrow{{C_2 H}}HC_3 N\xrightarrow{{C_2 H}}HC_5 N\xrightarrow{{C_2 H}}HC_7 N\xrightarrow{{C_2 H}}HC_9 N$$ and (b) $$C_n H_2 + CN \to HC_{n + 1} N + H,{\text{ }}n = 4,6, and 8$$ depending on the reaction network used. The results indicate that for route (a) large abundances ofC ₂ H (fractional abundances of ～10^?7), and for route (b) large abundances ofC ₂ H ₂ are required in order to reproduce the observed abundances of cyanopolyynes. The calculated abundances of cyanopolyynes show great sensitivity to the value of extinction particularly att?5×10⁵ yrs (i.e. photochemical timescale). The effect of other physical parameters, such as the cosmic-ray ionization abundances are also examined. In general, the model calculations show that the observed abundances of cyanopolyynes can be achieved by pseudo-time-dependent models at late times of several million years.     

Experimental laboratory simulation of Titan’s atmosphere: aerosols and gas phase

The discovery that Titan, the largest satellite of Saturn, has an atmosphere and that methane is a significant constituent of it, was the starting point for a systematic study of Titan’s atmospheric organic chemistry. Since then, the results from numerous ground-based observations and two flybys of Titan, by Voyager I and II, have led to experimental laboratory simulation studies and photochemical and physical modeling. All these works have provided a more detailed picture of Titan. We report here a continuation of such a study performing an experimental laboratory simulation of Titan’s atmospheric chemistry, and considering the two physical phases involved: gases and aerosols. Concerning the gaseous phase, we report the first detection of C₄N₂ and we propose possible atmospheric abundances for 70 organic compounds on Titan’s upper atmosphere. Concerning the solid phase, we have characterized aerosol analogues synthesized in conditions close to those of Titan’s environment, using elemental analysis, pyrolysis, solubility studies and infrared spectroscopy.     

Theoretical investigation of interstellar C–C–O and C–O–C bonding backbone molecules

There are numerous complex organic molecules containing carbon and oxygen atoms which show either C–C–O or C–O–C bonding backbone. This paper examines altogether 51 C–C–O and C–O–C bonding backbone molecules from ten different isomeric groups (C₂H₂O, C₃H₂O, C₂H₄O, C₂H₄O₂, C₃H₄O, C₂H₆O, C₂H₆O₂, C₃H₆O, C₃H₆O₂, C₃H₈O) to summarize the present astronomical status of these molecules. Accurate calculations of enthalpy of formation of these molecules show that the isomers with C–C–O backbone are more stable than the C–O–C backbone. Interestingly, a detailed analysis of relevant astromolecules indicates that most of the observed astromolecules have the C–C–O backbone. As a matter of fact, of all the molecules examined in this study, 80% of the astronomically observed species have the C–C–O backbone while only 20% have the C–O–C backbone. In general, interstellar abundance of a molecule is controlled by some factors such as kinetics, formation and destruction pathways,thermodynamics etc. A proper consideration of these factors could explain the observed abundances of these molecules. All these possible key factors are discussed in this paper.     

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.     

Long-term spectroscopic observations of Mars using IRTF/CSHELL: Mapping of O2 dayglow, CO, and search for CH4

Long-term spectroscopic observations of the O₂ dayglow at 1.27 μm result in a map of the latitudinal and seasonal behavior of the dayglow intensity for the full martian year. The O₂ dayglow is a sensitive tracer of Mars' photochemistry, and this map reflects variations of Mars' photochemistry at low and middle latitudes. It may be used to test photochemical models. Long-term observations of the CO mixing ratio have been also combined into the seasonal-latitudinal map. Seasonal and latitudinal variations of the mixing ratios of CO and the other incondensable gases (N₂, Ar, O₂, and H₂) discovered in our previous work are caused by condensation and sublimation of CO₂ to and from the polar regions. They reflect dynamics of the atmosphere and polar processes. The observed map may be used to test global circulation models of the martian atmosphere. The observed global abundances of CO are in reasonable agreement with the predicted variations with the 11-year solar cycle. Despite the perfect observing conditions, methane has not been detected using the IRTF/CSHELL with a 3σ upper limit of 14 ppb. This upper limit does not rule out the value of 10 ppb observed using the Canada-France-Hawaii Telescope and the Mars Express Planetary Fourier Spectrometer.     

The organic composition of Comet C/2001 A2 (LINEAR): I. Evidence for an unusual organic chemistry

We used the NIRSPEC instrument on the Keck-2 telescope atop Mauna Kea, HI to observe Comet C/2001 A2 (LINEAR) in a Target of Opportunity campaign on UT 2001 July 9.5, 10.5 August 4.4, 10.5. We measured seven organic parent volatiles (C₂H₆, C₂H₂, HCN, CH₄, CO, CH₃OH, H₂CO) simultaneously with H₂O. We obtained absolute production rates and relative abundances for parent volatiles, and also measured rotational temperatures for several of these species. The chemical composition of C/2001 A2 differs substantially from any comet we have observed to date. The abundances we measure (relative to H₂O) for C₂H₆, C₂H₂, HCN, and CH₃OH are enriched by a factor of ∼2 to 3 in C/2001 A2 compared with most comets in our database. Other molecular species were detected within the typical range of measured abundances. C/2001 A2 presented a unique opportunity to study the chemistry of a fragmenting comet where pristine areas are exposed to the Sun.