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

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

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

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

Carbon monoxide fluorescence from Titan's atmosphere

We report on the discovery of emissions due to carbon monoxide from Titan's atmosphere, from mid-infrared observations with the ISAAC spectrometer at the Very Large Telescope and covering the 4.50-4.85 μm range. We detected about 45 emission lines coinciding with CO ro-vibrational lines, including CO(1-0) (P18 to R11) and CO(2-1) (P11 to R11). We show that these emissions cannot be generated thermally but occur in non-LTE conditions, due to radiative de-excitation from the v=1 and v=2 CO levels after excitation at 4.7 and 2.3 μm by solar radiation. A complete fluorescence model is then developed, allowing to compute the state populations of the two most abundant CO isotopes and N₂(1). It includes absorption by CO and CH₄, and vibrational-thermal and vibrational-vibrational collisional exchanges with CO, N₂, CH₄, and H₂. Emerging radiances at the top of the atmosphere are evaluated with a line-by-line code and compared to observations. Contribution functions show that the CO emissions sound Titan's stratosphere: while the (1-0) lines generally probe two layers, located respectively at 100-250 km and 300-550 km, the (2-1) lines are sensitive to the intermediate layer at 150-300 km. A sensitivity study is performed to establish the effect of the main model parameters (temperature profile, collisional scenario, and CO stratospheric abundance) on the results. Models reproduce the essential structure of the observed emissions. The (1-0) fundamental band is generally well fit with a nominal CO mixing ratio of 32 ppm—as inferred in the troposphere from observations at 4.80-5.10 μm (Lellouch et al., 2003, Icarus 162, 126-143). However, this band is only weakly dependent on the CO abundance, and given temperature and collisional scenario uncertainties, it constrains the CO stratospheric mixing ratio only to within a factor of ∼3. In addition, the nominal model with 32 ppm CO underestimates the first hot (2-1) transition by approximately a factor of 2. This discrepancy can be resolved by a combined adjustment of collisional rates and an increased CO stratospheric ratio of 60 ppm, consistent with the determination of Gurwell and Muhleman (2000, Icarus 145, 653-656). In contrast, the CO vertical profile suggested by Hidayat et al. (1998, Icarus 133, 109-133), strongly depleted above 200 km, cannot match the data for any realistic collisional scenario, and is therefore not supported by our results.     

Simulation of Titan haze formation using a photochemical flow reactor: The optical constants of the polymer

Solar UV is the principal energy source impinging the atmosphere of Titan while the energy from the electrons in Saturn's magnetosphere is less than 0.5% of the UV light. Titan haze analogs were prepared by the photolysis of a mixture of gases that simulate the composition of its atmosphere (nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene). The real (n) and imaginary (k) parts of the complex refractive index of haze analogs formed from four different gas mixtures were calculated from the spectral properties of the solid polymer in UV-visible, near infrared and infrared wavelength spectral regions. The value of n was constant at 1.6±0.1 throughout the 0.2-2.5 μm region. The variation of k with wavelength for the values derived for Titan has a lower error than the absolute values of k so the more significant comparisons are with the slopes of the k(λ) plots in the UV-VIS region. Three of the photochemical Titan haze analogs had slopes comparable to those derived for Titan from the Voyager data (Rages and Pollack, 1980, Icarus 41, 119-130; McKay and Toon, 1992, in: Proceedings of the Symposium on Titan, in: ESA SP, Vol. 338, pp. 185-190). The slopes of the k(λ) plots for haze analogs prepared by spark discharge (Khare et al., 1984, Icarus 60, 127-137) and plasma discharge (Ramirez et al., 2002, Icarus 156, 515-529) were also comparable to Titan's. These finding show that the k(λ) plots do not differentiate between different laboratory simulations of atmospheric chemistry on Titan in the UV-VIS near IR region (0.2-2.5 microns). There is a large difference between the k(λ) in the infrared between the haze analogs prepared photochemically and analogs prepared using a plasma discharges (Khare et al., 1984, Icarus 60, 127-137; Coll et al., 1999, Planet. Space Sci. 47, 1331-1340; Khare et al., 2002, Icarus 160, 172-182). The C/N ratio in the haze analog prepared by discharges is in the 2-11 range while that of the photochemical analogs is in the 18-24 range. The use of discharges and UV light for initiating the chemistry in Titan's atmosphere is discussed.     

The 2.9-4.2 micron spectrum of Saturn: Clouds and CH4, PH3, and NH3

We have used synthetic spectra to analyze a medium resolution 2.9-4.2 μm spectrum of Saturn's temperate region observed at UKIRT using CGS4. The synthetic spectra include CH₄, PH₃, and NH₃ lines, for which mixing ratios were adopted from recent Cassini results. The observed absorption features in the spectrum are well accounted for by lines of these molecular species formed 22 +/− 8 km above the 1 bar pressure level at ∼610 mbar. The influence of optically thin haze particles at higher altitudes on the spectrum is not pronounced, with higher spectral resolution probably required to constrain the effects of haze in this wavelength region. Fluorescent line emission by CH₄ in its ν₃ and ν₃+ν₄−ν₄ bands, detected in the 3.2-3.5 μm region, originates between 400 km (∼0.06 mbar) and 800 km (∼0.01 μbar) above the 1 bar level, with peak contributions from the two major contributing bands at 550 km (∼3 μbar) and 700 km (∼0.1 μbar), respectively.     

The role of organic haze in Titan's atmospheric chemistry: II. Effect of heterogeneous reaction to the hydrogen budget and chemical composition of the atmosphere

One of the key components controlling the chemical composition and climatology of Titan's atmosphere is the removal of reactive atomic hydrogen from the atmosphere. A proposed process of the removal of atomic hydrogen is the heterogeneous reaction with organic aerosol. In this study, we investigate the effect of heterogeneous reactions in Titan's atmospheric chemistry using new measurements of the heterogeneous reaction rate [Sekine, Y., Imanaka, H., Matsui, T., Khare, B.N., Bakes, E.L.O., McKay, C.P., Sugita, S., 2008. Icarus 194, 186-200] in a one-dimensional photochemical model. Our results indicate that 60-75% of the atomic hydrogen in the stratosphere and mesosphere are consumed by the heterogeneous reactions. This result implies that the heterogeneous reactions on the aerosol surface may predominantly remove atomic hydrogen in Titan's stratosphere and mesosphere. The results of our calculation also indicate that a low concentration of atomic hydrogen enhances the concentrations of unsaturated complex organics, such as C₄H₂ and phenyl radical, by more than two orders in magnitude around 400 km in altitude. Such an increase in unsaturated species may induce efficient haze production in Titan's mesosphere and upper stratosphere. These results imply a positive feedback mechanism in haze production in Titan's atmosphere. The increase in haze production would affect the chemical composition of the atmosphere, which might induce further haze production. Such a positive feedback could tend to dampen the loss and supply cycles of CH₄ due to an episodic CH₄ release into Titan's atmosphere.     

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

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

Titan’s 5-μm window: observations with the Very Large Telescope

We report on mid-resolution (R∼2000) spectroscopic observations of Titan, acquired in November 2000 with the Very Large Telescope and covering the range 4.75-5.07 μm. These observations provide a detailed characterization of the CO (1-0) vibrational band, clearly separating for the first time individual CO lines (P10 to P19 lines of ¹³CO). They indicate that the CO/N₂ mixing ratio in Titan’s troposphere is 32±10 ppm. Comparison with photochemical models indicates that CO is not in a steady state in Titan’s atmosphere. The observations confirm that Titan’s 5-μm continuum geometric albedo is ∼0.06, and further indicates a ∼20% albedo decrease over 4.98-5.07 μm. Nonzero flux is detected at the 0.01 geometric albedo level in the saturated core of the ¹²CO (1-0) band, at 4.75-4.85 μm, providing evidence for backscattering on the stratospheric haze. Finally, emission lines are detected at 4.75-4.835 μm, coinciding in position with lines from the CO(1-0) and/or CO(2-1) bands. Matching them by thermal emission would require Titan’s stratosphere to be much warmer (by ∼ 25 K at 0.1 mbar) than indicated by the methane 7.7-μm emission and the Voyager radio-occultation. We show instead that a nonthermal mechanism, namely solar-excited fluorescence, is a more plausible source for these emissions. Improved observations and laboratory measurements on the vibrational-translational relaxation of CO are needed for further interpretation of these emissions in terms of a CO stratospheric mixing ratio.     

Spatially-resolved high-resolution spectroscopy of Venus 1. Variations of CO2, CO, HF, and HCl at the cloud tops

Variations of the upper cloud boundary and the CO, HF, and HCl mixing ratios were observed using the CSHELL spectrograph at NASA IRTF. The observations were made in three sessions (October 2007, January 2009, and June 2009) at early morning and late afternoon on Venus in the latitude range of ±60°. CO₂ lines at 2.25 μm reveal variations of the cloud aerosol density (∼25%) and scale height near 65 km. The measured reflectivity of Venus at low latitudes is 0.7 at 2.25 μm and 0.028 at 3.66 μm, and the effective CO₂ column density is smaller at 3.66 μm than those at 2.25 μm by a factor of 4. This agrees with the almost conservative multiple scattering at 2.25 μm and single scattering in the almost black aerosol at 3.66 μm. The expected difference is just a factor of (1 − g)⁻¹ = 4, where g = 0.75 is the scattering asymmetry factor for Venus’ clouds. The observed CO mixing ratio is 52 ± 4 ppm near 08:00 and 40 ± 4 ppm near 16:30 at 68 km, and the higher ratio in the morning may be caused by extension of the CO morningside bulge to the cloud tops. The observed weak limb brightening in CO indicates an increase of the CO mixing ratio with altitude. HF is constant at 3.5 ± 0.2 ppb at 68 km in both morningside and afternoon observations and in the latitude range ±60°. Therefore the observations do not favor a bulge of HF, though HF is lighter than CO. Probably a source in the upper atmosphere facilitates the bulge formation. The recent measurements of HCl near 70 km are controversial (0.1 and 0.74 ppm) and require either a strong sink or a strong source of HCl in the clouds. The HCl lines of the (2-0) band are blended by the solar and telluric lines. Therefore we observed the P8 lines of the (1-0) band at 3.44 μm. These lines are spectrally clean and result in the HCl mixing ratio of 0.40 ± 0.03 ppm at 74 km. HCl does not vary with latitude within ±60°. Our observations support a uniformly mixed HCl throughout the Venus atmosphere.     

The structure and microphysical properties of the Venus clouds: Venera 9, 10, and 11 data

Data processing and interpretation of the nephelometer measurements made in the Venus atmosphere aboard the Venera 9, 10 and 11 landers in the sunlit hemisphere near the equator are discussed. These results were used to obtain the aerosol distribution and its microphysical properties from 62 km to the surface. The main aerosol content is found in the altitude range between 62 km (where measurements began) and 48 km, the location of the cloud region. Three prominent layers labeled as I (between 62 and 57 km), II (between 57 and 51 km) and III (between 51 and 48 km), each with different particle characteristics are discovered within the clouds. The measured light-scattering patterns can be intrepreted as having been produced by particles with effective radii from 1 to 2 μm depending on height and indices of refractivity from 1.45 in layer I to 1.42 in layer III. These values do not contradict the idea that the droplets are made of sulfuric acid. In layers II and III the particle size distribution is at least bimodal rather than uni-modal. The index of refraction is found to decrease to 1.33 in the lower part of layer II, suggesting a predominant abundance of larger particles of different chemical origin, and chlorine compounds are assumed to be relevant to this effect. In the entire heightrange of the Venera 9–11 craft descents, the clouds are rather rarefied and are characterized by a mean volume scattering coefficient σ ～ 2 × 10^?5 cm^?1 that corresponds to the mean meteorological range of visibility of about 2 km. The average mass content of condensate is estimated to be equal to 4 × 10^?9 g/cm³, and the total optical depth of clouds to τ ～ 35. Near the bottom of layer III clouds are strongly variable. In the subcloud atmosphere a haze was observed between 48 and 32 km; that haze is mainly made of submicron particles, r_eff ～ 0.1μm. The atmosphere below that is totally transparent but separate (sometimes possibly disappearing) layers may be present up to a height of 8 km above the surface. A model of this region with a very low particle density (N ? 2–3 cm^?3) strongly refractive large particles (r_eff ? 2.5 μm; 1.7 < n < 2.0) provided satisfactory agreement. The optical depth of aerosol in the atmosphere below the subcloud haze does not exceed 2.5.     

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.     

Retrieval and tentative indentification of the 3 μm spectral feature in Titan's haze

Recently, an unidentified 3.3-3.4 μm feature found in the solar occultation spectra of the atmosphere of Titan observed by Cassini/VIMS was tentatively attributed to the C-H stretching mode of aliphatic hydrocarbon chains attached to large organic molecules, but without properly extracting the feature from adjacent influences of strong CH₄ and weak C₂H₆ absorptions (Bellucci et al., 2009). In this work, we retrieve the detailed spectral feature using a radiative transfer program including absorption and fluorescent emission of both molecules, as well as absorption and scattering by haze particles. The spectral features of the haze retrieved from the VIMS data at various altitudes are similar to each other, indicating relatively uniform spectral properties of the haze with altitude. However, slight deviations observed near 127 km and above 300 km suggest inhomogeneity at these altitudes. We find that the positions of the major spectral peaks occur at 3.33-3.37 μm, which are somewhat different from the typical 3.3 μm aromatic or 3.4 μm aliphatic C-H stretches usually seen in the spectra of dust particles of the interstellar medium and comets. The peaks, however, coincide with those of the solid state spectra of C₂H₆, CH₄, and CH₃CN; and a broad shoulder from 3.37 to 3.50 μm coincides with those of C₅H₁₂ and C₆H₁₂ as well as those of typical aliphatic C-H stretches. This result combined with high-altitude (∼1000 km) haze formation process recently reported by Waite et al. (2007) opens a new question on the chemical composition of the haze particles. We discuss the possibility that the 3 μm feature may be due to the solid state absorption bands of these molecules (or some other molecules) and we advocate additional laboratory measurements for the ices of hydrocarbon and nitrogen-bearing molecules present in Titan's atmosphere for the identification of this 3 μm feature.     

Simultaneous measurements of No and No2 in the stratosphere

Simultaneous measurements of NO and NO₂ in the stratosphere leading to an NO_x determination have been performed by means of i.r. absorption spectrometry using the Sun as a source in the 5·2 μm band of NO and in the 6·2 μm band of NO₂. The observed abundance of NO_P peaks at 26 km where it is equal to (4·2 ± 1) × 10⁹ cm^?3. The volume mixing ratio of NO_p was observed to vary from 1·3 × 10^?9 at 20 km to 1·3 × 10^?8 at 34 km.     

Heavy ion formation in Titan's ionosphere: Magnetospheric introduction of free oxygen and a source of Titan's aerosols?

Discovery by Cassini's plasma instrument of heavy positive and negative ions within Titan's upper atmosphere and ionosphere has advanced our understanding of ion neutral chemistry within Titan's upper atmosphere, primarily composed of molecular nitrogen, with ~2.5% methane. The external energy flux transforms Titan's upper atmosphere and ionosphere into a medium rich in complex hydrocarbons, nitriles and haze particles extending from the surface to 1200 km altitudes. The energy sources are solar UV, solar X-rays, Saturn's magnetospheric ions and electrons, solar wind and shocked magnetosheath ions and electrons, galactic cosmic rays (GCR) and the ablation of incident meteoritic dust from Enceladus’ E-ring and interplanetary medium. Here it is proposed that the heavy atmospheric ions detected in situ by Cassini for heights >950 km, are the likely seed particles for aerosols detected by the Huygens probe for altitudes <100 km. These seed particles may be in the form of polycyclic aromatic hydrocarbons (PAH) containing both carbon and hydrogen atoms C_nH_x. There could also be hollow shells of carbon atoms, such as C₆₀, called fullerenes which contain no hydrogen. The fullerenes may compose a significant fraction of the seed particles with PAHs contributing the rest. As shown by Cassini, the upper atmosphere is bombarded by magnetospheric plasma composed of protons, H₂⁺ and water group ions. The latter provide keV oxygen, hydroxyl and water ions to Titan's upper atmosphere and can become trapped within the fullerene molecules and ions. Pickup keV N₂⁺, N⁺ and CH₄⁺ can also be implanted inside of fullerenes. Attachment of oxygen ions to PAH molecules is uncertain, but following thermalization O+ can interact with abundant CH₄ contributing to the CO and CO₂ observed in Titan's atmosphere. If an exogenic keV O+ ion is implanted into the haze particles, it could become free oxygen within those aerosols that eventually fall onto Titan's surface. The process of freeing oxygen within aerosols could be driven by cosmic ray interactions with aerosols at all heights. This process could drive pre-biotic chemistry within the descending aerosols. Cosmic ray interactions with grains at the surface, including water frost depositing on grains from cryovolcanism, would further add to abundance of trapped free oxygen. Pre-biotic chemistry could arise within surface microcosms of the composite organic-ice grains, in part driven by free oxygen in the presence of organics and any heat sources, thereby raising the astrobiological potential for microscopic equivalents of Darwin's “warm ponds” on Titan.     

On the Vertical Thermal Structure of Pluto's Atmosphere

A radiative–conductive model for the vertical thermal structure of Pluto's atmosphere is developed with a non-LTE treatment of solar heating in the CH₄3.3 μm and 2.3 μm bands, non-LTE radiative exchange and cooling in the CH₄7.6 μm band, and LTE cooling by CO rotational line emission. The model includes the effects of opacity and vibrational energy transfer in the CH₄molecule. Partial thermalization of absorbed solar radiation in the CH₄3.3 and 2.3 μm bands by rapid vibrational energy transfer from the stretch modes to the bending modes generates high altitude heating at sub-microbar pressures. Heating in the 2.3 μm bands exceeds heating in 3.3 μm bands by approximately a factor of 6 and occurs predominantly at microbar pressures to generate steep temperature gradients ∼10–20 K km⁻¹forp> 2 μbar when the surface or tropopause pressure is ∼3 μbar and the CH₄mixing ratio is a constant 3%. This calculated structure may account for the “knee” in the stellar occultation lightcurve. The vertical temperature structure in the first 100 km above the surface is similar for atmospheres with Ar, CO, and N₂individually as the major constituent. If a steep temperature gradient ∼20 K km⁻¹is required near the surface or above the tropopause, then the preferred major constituent is Ar with 3% CH₄mixing ratio to attain a calculated ratio ofT/(= 3.5 K amu⁻¹) in agreement with inferred values from stellar occultation data. However, pure Ar and N₂ices at the same temperature yield an Ar vapor pressure of only ∼0.04 times the N₂vapor pressure. Alternative scenarios are discussed that may yield acceptable fits with N₂as the dominant constituent. One possibility is a 3 μbar N₂atmosphere with 0.3% CH₄that has 106 K isothermal region (T/= 3.8 K amu⁻¹) and ∼8 K km⁻¹surface/tropopause temperature gradient. Another possibility would be a higher surface pressure ∼10 μbar with a scattering haze forp> 2 μbar. Our model with appropriate adjustments in the CH₄density profile to Triton's inferred profile yields a temperature profile consistent with the UVS solar occultation data (Krasnopolsky, V. A., B. R. Sandel, and F. Herbert 1992.J. Geophys. Res.98, 3065–3078.) and ground-based stellar occultation data (Elliot, J. L., E. W. Dunham, and C. B. Olkin 1993.Bull. Am. Astron. Soc.25, 1106.).     

Inhomogeneous models of the atmosphere of Saturn

Analyses of ultraviolet, visible, and near-infrared spectra of Saturn lead to an inhomogeneous atmospheric model, having a clear gas layer which lies above an absorbing particle layer which lies above an ammonia haze layer. The boundary between the clear layer and the absorbing particle layer is at a pressure of 0.2 atm in the equatorial region and 0.3 atm in the temperate region. The boundary between the absorbing particle layer and the haze layer is at the radiative-convective boundary. Observations of ammonia absorption lines indicate that sunlight penetrates the haze to the ammonia sublimation level at a depth of 1.1 atm. Absorbing particles cause the observed decrease in reflectivity from visible to ultraviolet wavelengths. Consideration of the wavelength variation of Mie scattering parameters leads to an upper limit of about 0.2 μm for the particle radii and a particle number density of 10³ cm^?3. Some possible particle compositions are discussed. Comparison of computed 3-0 and 4-0 band hydrogen quadropole line equivalent widths with observed values leads to a haze layer optical thickness above the ammonia sublimation level of approximately 10. Equivalent widths computed for an equilibrium distribution of states agree better with observed values than those computed for a normal distribution. Methane 3ν₃ band manifold equivalent widths are in best agreement with measured equivalent widths for a CH₄/H₂ abundance ratio of 2 × 10^?3, which is 4.5 times the solar C/H ratio.     

First observation of 628 CO2 isotopologue band at 3.3 μm in the atmosphere of Venus by solar occultation from Venus Express

The new ESA Venus Express orbiter is the first mission applying the probing technique of solar and stellar occultation to the atmosphere of Venus, with the SPICAV/SOIR instrument. SOIR is a new type of spectrometer used for solar occultations in the range 2.2-4.3 μm. Thanks to a high spectral resolving power R∼15,000-20,000 (unprecedented in planetary space exploration), a new gaseous absorption band was soon detected in the atmospheric transmission spectra around 2982 cm⁻¹, showing a structure resembling an unresolved Q branch and a number of isolated lines with a regular wave number pattern. This absorption could not be matched to any species contained in HITRAN or GEISA databases, but was found very similar to an absorption pattern observed by a US team in the spectrum of solar light reflected by the ground of Mars [Villanueva, G.L., Mumma, M.J., Novak, R.E., Hewagama, T., 2008. Icarus 195 (1), 34-44]. This team then suggested to us that the absorption was due to an uncatalogued transition of the ¹⁶O¹²C¹⁸O molecule. The possible existence of this band was soon confirmed from theoretical considerations by Perevalov and Tashkun. Some SOIR observations of the atmospheric transmission are presented around 2982 cm⁻¹, and rough calculations of line strengths of the Q branch are produced, based on the isotopic ratio measured earlier in the lower atmosphere of Venus. This discovery emphasizes the role of isotopologues of CO₂ (as well as H₂O and HDO) as important greenhouse gases in the atmosphere of Venus.     

Global-scale surface spectral variations on Titan seen from Cassini/VIMS

We present global-scale maps of Titan from the Visual and Infrared Mapping Spectrometer (VIMS) instrument on Cassini. We map at 64 near-infrared wavelengths simultaneously, covering the atmospheric windows at 0.94, 1.08, 1.28, 1.6, 2.0, 2.8, and 5 μm with a typical resolution of 50 km/pixel or a typical total integration time of 1 s. Our maps have five to ten times the resolution of ground-based maps, better spectral resolution across most windows, coverage in multiple atmospheric windows, and represent the first spatially resolved maps of Titan at 5 μm. The VIMS maps provide context and surface spectral information in support of other Cassini instruments. We note a strong latitudinal dependence in the spectral character of Titan's surface, and partition the surface into 9 spectral units that we describe in terms of spectral and spatial characteristics.     

Chemical kinetic model for the lower atmosphere of Venus

A self-consistent chemical kinetic model of the Venus atmosphere at 0-47 km has been calculated for the first time. The model involves 82 reactions of 26 species. Chemical processes in the atmosphere below the clouds are initiated by photochemical products from the middle atmosphere (H₂SO₄, CO, S_x), thermochemistry in the lowest 10 km, and photolysis of S₃. The sulfur bonds in OCS and S_x are weaker than the bonds of other elements in the basic atmospheric species on Venus; therefore the chemistry is mostly sulfur-driven. Sulfur chemistry activates some H and Cl atoms and radicals, though their effect on the chemical composition is weak. The lack of kinetic data for many reactions presents a problem that has been solved using some similar reactions and thermodynamic calculations of inverse processes. Column rates of some reactions in the lower atmosphere exceed the highest rates in the middle atmosphere by two orders of magnitude. However, many reactions are balanced by the inverse processes, and their net rates are comparable to those in the middle atmosphere. The calculated profile of CO is in excellent agreement with the Pioneer Venus and Venera 12 gas chromatographic measurements and slightly above the values from the nightside spectroscopy at 2.3 μm. The OCS profile also agrees with the nightside spectroscopy which is the only source of data for this species. The abundance and vertical profile of gaseous H₂SO₄ are similar to those observed by the Mariner 10 and Magellan radio occultations and ground-based microwave telescopes. While the calculated mean S₃ abundance agrees with the Venera 11-14 observations, a steep decrease in S₃ from the surface to 20 km is not expected from the observations. The ClSO₂ and SO₂Cl₂ mixing ratios are ∼10⁻¹¹ in the lowest scale height. The existing concept of the atmospheric sulfur cycles is incompatible with the observations of the OCS profile. A scheme suggested in the current work involves the basic photochemical cycle, that transforms CO₂ and SO₂ into SO₃, CO, and S_x, and a minor photochemical cycle which forms CO and S_x from OCS. The net effect of thermochemistry in the lowest 10 km is formation of OCS from CO and S_x. Chemistry at 30-40 km removes the downward flux of SO₃ and the upward flux of OCS and increases the downward fluxes of CO and S_x. The geological cycle of sulfur remains unchanged.     

Titan at 3 microns: Newly identified spectral features and an improved analysis of haze opacity

We have reanalyzed the high-resolution spectrum of Titan between 2.87 and 3.12 μm observed with NIRSPEC/Keck II on 2001 Nov. 21 in southern summer, using updated CH₃D and C₂H₆ line-by-line models. From new synthetic spectra, we identify all but a few of the previously unidentified significant absorption spectral features in this wavelength range as due to these two species, both of which had been previously detected by Voyager and ground-based observations at other wavelengths. We also derive opacities and reflectivities of haze particles as functions of altitude for the 2.87-2.92 μm wavelength range, where Titan's atmosphere is partially transparent down to the surface. The extinction per unit altitude is observed to increase from 100 km (∼8 mbar) toward lower altitude. The derived total optical depth is approximately 1.1 for the 2.87-2.92 μm range. At wavelengths increasing beyond 2.92 μm the haze layers become much more optically thick, and the surface is rapidly hidden from view. These conclusions apply to equatorial and southern-temperate regions on Titan, excluding polar regions. We also find it unlikely that there is a large enhancement of the tropospheric CH₄ mole fraction over the value reported from analysis of the Huygens/GCMS observations.