The C/C isotopic ratio in Titan hydrocarbons from Cassini/CIRS infrared spectra

We have analyzed infrared spectra of Titan recorded by the Cassini Composite Infrared Spectrometer (CIRS) to measure the isotopic ratio ¹²C/¹³C in each of three chemical species in Titan's stratosphere: CH₄, C₂H₂ and C₂H₆. This is the first measurement of ¹²C/¹³C in any C₂ molecule on Titan, and the first measurement of ¹²CH₄/¹³CH₄ (non-deuterated) on Titan by remote sensing. Our spectra cover five widely-spaced latitudes, 65° S to 71° N and we have searched for both latitude variability of ¹²C/¹³C within a given species, and also for differences between the ¹²C/¹³C in the three gases. For CH₄ alone, we find (1-σ), essentially in agreement with the ¹²CH₄/¹³CH₄ measured by the Huygens Gas Chromatograph/Mass Spectrometer instrument (GCMS) [Niemann, H.B., and 17 colleagues, 2005. Nature 438, 779-784]: 82.3±1.0, and also with measured values in H¹³CN and ¹³CH₃D by CIRS at lower precision [Bézard, B., Nixon, C., Kleiner, I., Jennings, D., 2007. Icarus 191, 397-400; Vinatier, S., Bézard, B., Nixon, C., 2007. Icarus 191, 712-721]. For the C₂ species, we find in C₂H₂ and 89.8±7.3 in C₂H₆, a possible trend of increasingly value with molecular mass, although these values are both compatible with the Huygens GCMS value to within error bars. There are no convincing trends in latitude. Combining all fifteen measurements, we obtain a value of , also compatible with GCMS. Therefore, the evidence is mounting that ¹²C/¹³C is some 8% lower on Titan than on the Earth (88.9, inorganic standard), and lower than typical for the outer planets (88±7 [Sada, P.V., McCabe, G.H., Bjoraker, G.L., Jennings, D.E., Reuter, D.C., 1996. Astrophys. J. 472, 903-907]). There is no current model for this enrichment, and we discuss several mechanisms that may be at work.     

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.     

High-resolution spectroscopy of Venus: Detection of OCS, upper limit to H2S, and latitudinal variations of CO and HF in the upper cloud layer

Venus was observed at 2.4 and 3.7 μm with a resolving power of 4×¹⁰⁴ using the long-slit high-resolution spectrograph CSHELL at NASA IRTF. The observations were made along a chord that covered a latitude range of ± 60° at a local time near 8:00. The continuous reflectivity and limb brightening at 2.4 μm are fitted by the clouds with a single scattering albedo 1−a=0.01 and a pure absorbing layer with τ=0.09 above the clouds. The value of 1−a agrees with the refractive index of H₂SO₄ (85%) and the particle radius of 1 μm. The absorbing layer is similar to that observed by the UV spectrometer at the Pioneer Venus orbiter. However, its nature is puzzling. CO₂ was measured using its R32 and R34 lines. The retrieved product of the CO₂ abundance and airmass is constant at 1.9 km-atm along the instrument slit in the latitude range of ± 60°. The CO mixing ratio (measured using the P21 line) is rather constant at 70 ppm, and its variations of ∼10% may be caused by atmospheric dynamics. The observed value is higher than the 50 ppm retrieved previously from a spectrum of the full disk, possibly, because of some downward extension of the mesospheric morningside bulge of CO. The observations of the HF R3 line reveal a constant HF mixing ratio of 3.5±0.5 ppb within ± 60° of latitude, which is within the scatter in the previous measurements of HF. OCS has been detected for the first time at the cloud tops by summing 17 lines of the P-branch. The previous detections of OCS refer to the lower atmosphere at 30-35 km. The retrieved OCS mixing ratio varies with a scale height of 1 to 3 km. The mean OCS mixing ratio is ∼2 ppb at 70 km and ∼14 ppb at 64 km. Vertical motions in the atmosphere may change the OCS abundance. The detected OCS should significantly affect Venus' photochemistry. A sensitive search for H₂S using its line at 2688.93 cm⁻¹ results in a 3 sigma upper limit of 23 ppb, which is more restrictive than the previous limit of 100 ppb.     

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.     

Scattering particles in nightside limb observations of Venus’ upper atmosphere by Venus Express VIRTIS

Nightside infrared limb spectra of the Venus upper atmosphere, obtained by Venus Express VIRTIS, show strong scattering of thermal radiation. This scattering of upward-going radiation into the line-of-sight is dominant below 82.5 km even at a wavelength of 5 μm, which is indicative of relatively large particles. We show that 1 μm-sized sulfuric acid particles (also known as mode 2 particles) provide a good fit to the VIRTIS limb data at high altitudes. We retrieve vertical profiles of the mode 2 number density between 75 and 90 km at two latitude ranges: 20-30°N and 47-50°N. Between 20 and 30°N, scattering by mode 2 particles is the main source of radiance for altitudes between 80 and 85 km. Above altitudes of 85 km smaller particles can also be used to fit the spectra. Between 47 and 50°N mode 2 number densities are generally lower than between 20 and 30°N and the profiles show more variability. This is consistent with the 47-50° latitude region being at the boundary between the low latitudes and high latitudes, with the latter showing lower cloud tops and higher ultraviolet brightness (Titov, D.V., Taylor, F.W., Svedhem, H., Ignatiev, N.I., Markiewicz, W.J., Piccioni, G., Drossart, P. [2008]. Nature 456, 620-623).     

Evidence for temporal change at Uranus' south pole

Analysis of Hubble Space Telescope images of Uranus taken between 1994 and 2002 shows evidence for temporal changes in zonal brightness patterns in the south polar region. Between 1994 and 2002, a relatively bright ring developed near 70° S. The pole itself, which was the brightest area of the southern hemisphere in 1994, has become relatively dark. The polar collar at 45° S has also become brighter relative to the rest of the southern polar region. Comparison of images through different filters suggests that the change is occurring at pressures of 2-4 bars in the atmosphere. A change at this depth is consistent with radio measurements which indicate seasonal variability in Uranus' deep atmosphere. Disk-integrated photometry at visible wavelengths also exhibits variability on seasonal (∼?decades) timescales. The observed changes are not predicted by existing dynamical models of Uranus' atmosphere.     

Latitudinal variations of CO and OCS in the lower atmosphere of Venus from near-infrared nightside spectro-imaging

Spectro-imaging of Venus' nightside in the 2.3-μm window provides a powerful means of probing the lower atmosphere in the 25-40 km altitude range. We present observations recorded at the NASA/IRTF in February 2003 and August 2004, using the SpeX spectro-imager in the 2.1-2.5-μm region. Abundances of CO and OCS have been derived as a function of latitude for different longitudes. The CO abundance increases by about 15% between the equatorial region and higher latitudes (±40°). No longitudinal or temporal variations are observed. The OCS abundance shows the opposite variation in observational sets with sufficient S/N. These variations and anticorrelation are consistent with upwelling motions in the equatorial region and downwelling at higher latitudes.     

Long-term variations in the microwave brightness temperature of the Uranus atmosphere

We present a self-consistent, 36-year record of the disk-averaged radio brightness of Uranus at wavelengths near 3.5 cm. It covers nearly half a uranian year, and includes both equatorial and polar viewing geometries (corresponding to equinox and solstice, respectively). We find large (greater than 30 K) changes over this time span. In agreement with analyses made of more limited microwave data sets, our observations suggest the changes are not caused by geometric effects alone, and that temporal variations may exist in the deep uranian troposphere down to pressures of tens of bars. Our data also support an earlier suggestion that a rapid, planetary-scale change may have occurred in late 1993 and early 1994. The seasonal record presented here will be useful for constraining dynamical models of the deep atmosphere, and for interpreting observations made during Uranus' 2007 equinox passage. As part of a multi-wavelength observing campaign for this event, the Goldstone-Apple Valley Radio Telescope (GAVRT) project will continue to make frequent, single-dish observations near 3.5 cm.     

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.     

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.     

Investigation of water vapor on Mars with PFS/SW of Mars Express

New insight into the seasonal, diurnal and spatial distribution of water vapor on Mars has been obtained from analyzing the spectra of the short-wavelength channel (SW) of the Planetary Fourier Spectrometer (PFS) onboard Mars Express. The processed dataset, recorded between January 2004 and April 2005, covers the seasons from LS=331° of Mars Year 26 to LS=196° of the following year. In this period the mean column density around vernal equinox was 8.2 pr. μm. The maximum values during northern summer were about 65 pr. μm, located around 75° N latitude with a longitudinally inhomogeneous distribution. Regarding the atmospheric transport, the majority of polar water vapor remains in the north polar region while only about a quarter is transported southward. Geographically there are two water vapor maxima visible, over Arabia Terra and the Tharsis plateau, that are most likely caused both by atmosphere-ground interaction and by atmospheric circulation. A comparison with other instruments generally shows a good agreement, only the SPICAM results are systematically lower. Compared to the results from the PFS long-wavelength channel the results of this work are slightly higher. A strong discrepancy is visible northward of about 50° N during the northern summer that is possibly explained by a non-uniform vertical H₂O mixing. In particular, a confinement of the water to the lower few kilometers yields a much better agreement between the retrieved column densities of the two PFS channels.     

Analysis of Cassini/CIRS limb spectra of Titan acquired during the nominal mission II: Aerosol extinction profiles in the 600–1420 cm spectral range

We have analyzed the continuum emission of limb spectra acquired by the Cassini/CIRS infrared spectrometer in order to derive information on haze extinction in the 3–0.02 mbar range (∼150–350 km). We focused on the 600–1420 cm⁻¹ spectral range and studied nine different limb observations acquired during the Cassini nominal mission at 55°S, 20°S, 5°N, 30°N, 40°N, 45°N, 55°N, 70°N and 80°N. By means of an inversion algorithm solving the radiative transfer equation, we derived the vertical profiles of haze extinction coefficients from 17 spectral ranges of 20-cm⁻¹ wide at each of the nine latitudes. At a given latitude, all extinction vertical profiles retrieved from various spectral intervals between 600 and 1120 cm⁻¹ display similar vertical slopes implying similar spectral characteristics of the material at all altitudes. We calculated a mean vertical extinction profile for each latitude and derived the ratio of the haze scale height (H_haze) to the pressure scale height (H_gas) as a function of altitude. We inferred H_haze/H_gas values varying from 0.8 to 2.4. The aerosol scale height varies with altitude and also with latitude. Overall, the haze extinction does not show strong latitudinal variations but, at 1 mbar, an increase by a factor of 1.5 is observed at the north pole compared to high southern latitudes. The vertical optical depths at 0.5 and 1.7 mbar increase from 55°S to 5°N, remain constant between 5°N and 30°N and display little variation at higher latitudes, except the presence of a slight local maximum at 45°N. The spectral dependence of the haze vertical optical depth is uniform with latitude and displays three main spectral features centered at 630 cm⁻¹, 745 cm⁻¹ and 1390 cm⁻¹, the latter showing a wide tail extending down to ∼1000 cm⁻¹. From 600 to 750 cm⁻¹, the optical depth increases by a factor of 3 in contrast with the absorbance of laboratory tholins, which is generally constant. We derived the mass mixing ratio profiles of haze at the nine latitudes. Below the 0.4-mbar level all mass mixing ratio profiles increase with height. Above this pressure level, the profiles at 40°N, 45°N, 55°N, at the edge of the polar vortex, display a decrease-with-height whereas the other profiles increase. The global increase with height of the haze mass mixing ratio suggest a source at high altitudes and a sink at low altitudes. An enrichment of haze is observed at 0.1 mbar around the equator, which could be due to a more efficient photochemistry because of the strongest insolation there or an accumulation of haze due to a balance between sedimentation and upward vertical drag.     

The first detection of propane on Saturn

We report the first detection of propane, C₃H₈, in Saturn's stratosphere. Observations taken on September 8, 2002 UT at NASA's IRTF using TEXES, show multiple emission lines due to the 748 cm⁻¹ν₂₁ band of C₃H₈. Using a line-by-line radiative transfer code, we are able to fit the data by scaling the propane vertical mixing ratio profile from the photochemical model of Moses et al. [2000. Icarus 143, 244-298]. Multiplicative factors of 0.7 and 0.65 are required to fit the −20° and −80° planetocentric latitude spectra. The resultant profiles are characterized by a 5 mbar mixing ratio of 2.7±0.8×¹⁰⁻⁸ at −20° and at −80° latitude. These results suggest that the time scale for meridional circulation lies between the net photochemical lifetimes of C₂H₂ and C₃H₈, ≈30-600 years.     

Laboratory measurements of the microwave opacity of hydrochloric acid vapor in a carbon dioxide atmosphere

Laboratory measurements of the microwave opacity of HCl in a CO₂ atmosphere have been conducted in the S (13.3 cm), X (3.6 cm), and K (1.4 cm) microwave bands at a pressure of 7.2 bar and at two different mixing ratios. The results are consistent with an opacity model employing the Van Vleck-Weisskopf lineshape applied to the published submillimeter line intensities of HCl (JPL Catalog [Pickett et al., 1998, J. Quant. Spectrosc. Rad. Trans. 60, 883-890]) and empirically fitted with a modeled parameter for CO₂ broadening. Based on the deep atmospheric abundance of HCl inferred from near-infrared measurements [Dalton et al., 2000, Bull. Am. Astron. Soc. 32, 1120], the resulting modeled HCl opacity is constrained to have a small effect on the overall microwave absorption spectrum of Venus, but can be used in developing a more accurate radiative transfer model.     

Lunar atmospheric H2 detections by the LAMP UV spectrograph on the Lunar Reconnaissance Orbiter

We report on the detection of H₂ as seen in our analysis of twilight observations of the lunar atmosphere observed by the LAMP instrument aboard NASA’s Lunar Reconnaissance Orbiter. Using a large amount of data collected on the lunar atmosphere between September 2009 and March 2013, we have detected and identified, the presence of H₂ in the native lunar atmosphere, for the first time. We derive a surface density for H₂ of 1.2 ± 0.4 × 10³ cm⁻³ at 120 K. This is about 10 times smaller than originally predicted, and several times smaller than previous upper limits from the Apollo era data.     

Analysis of Titan CH4 3.3 μm upper atmospheric emission as measured by Cassini/VIMS

After molecular nitrogen, methane is the most abundant species in Titan’s atmosphere and plays a major role in its energy budget and its chemistry. Methane has strong bands at 3.3 μm emitting mainly at daytime after absorption of solar radiation. This emission is strongly affected by non-local thermodynamic equilibrium (non-LTE) in Titan’s upper atmosphere and, hence, an accurate modeling of the non-LTE populations of the emitting vibrational levels is necessary for its analysis. We present a sophisticated and extensive non-LTE model which considers 22 CH₄ levels and takes into account all known excitation mechanisms in which they take part. Solar absorption is the major excitation process controlling the population of the v₃-quanta levels above 1000 km whereas the distribution of the vibrational energy within levels of similar energy through collisions with N₂ is also of importance below that altitude. CH₄-CH₄ vibrational exchange of v₄-quanta affects their population below 500 km. We found that the ν₃ → ground band dominates Titan’s 3.3 μm daytime limb radiance above 750 km whereas the ν₃ + ν₄ → ν₄ band does below that altitude and down to 300 km. The ν₃ + ν₂ → ν₂, the 2ν₃ → ν₃, and the ¹³CH₄ν₃ → ground bands each contribute from 5% to 8% at regions below 800 km. The ν₃ + 2ν₄ → 2ν₄and ν₂ + ν₃ + ν₄ → ν₂ + ν₄ bands each contribute from 2% to 5% below 650 km. Contributions from other CH₄ bands are negligible. We have used the non-LTE model to retrieve the CH₄ abundance from 500 to 1100 km in the southern hemisphere from Cassini-VIMS daytime measurements near 3.3 μm. Our retrievals show good agreement with previous measurements and model results, supporting a weak deviation from well mixed values from the lower atmosphere up to 1000 km.     

Methane on Uranus: The case for a compact CH4 cloud layer at low latitudes and a severe CH4 depletion at high-latitudes based on re-analysis of Voyager occultation measurements and STIS spectroscopy

Lindal et al. (Lindal, G.F., Lyons, J.R., Sweetnam, D.N., Eshleman, V.R., Hinson, D.P. [1987]. J. Geophys. Res. 92 (11), 14987-15001) presented a range of temperature and methane profiles for Uranus that were consistent with 1986 Voyager radio occultation measurements of refractivity versus altitude. A localized refractivity slope variation near 1.2 bars was interpreted to be the result of a condensed methane cloud layer. However, models fit to near-IR spectra found particle concentrations much deeper in the atmosphere, in the 1.5-3 bar range (Sromovsky, L.A., Irwin, P.G.J., Fry, P.M. [2006]. Icarus 182, 577-593; Sromovsky, L.A., Fry, P.M. [2010]. Icarus 210, 211-229; Irwin, P.G.J., Teanby, N.A., Davis, G.R. [2010]. Icarus 208, 913-926), and a recent analysis of STIS spectra argued for a model in which aerosol particles formed diffusely distributed hazes, with no compact condensation layer (Karkoschka, E., Tomasko, M. [2009]. Icarus 202, 287-309). To try to reconcile these results, we reanalyzed the occultation observations with the He volume mixing ratio reduced from 0.15 to 0.116, which is near the edge of the 0.033 uncertainty range given by Conrath et al. (Conrath, B., Hanel, R., Gautier, D., Marten, A., Lindal, G. [1987]. J. Geophys. Res. 92 (11), 15003-15010). This allowed us to obtain saturated mixing ratios within the putative cloud layer and to reach above-cloud and deep methane mixing ratios compatible with STIS spectral constraints. Using a 5-layer vertical aerosol model with two compact cloud layers in the 1-3 bar region, we find that the best fit pressure for the upper compact layer is virtually identical to the pressure range inferred from the occultation analysis for a methane mixing ratio near 4% at 5°S. This strongly argues that Uranus does indeed have a compact methane cloud layer. In addition, our cloud model can fit the latitudinal variations in spectra between 30°S and 20°N, using the same profiles of temperature and methane mixing ratio. But closer to the pole, the model fails to provide accurate fits without introducing an increasingly strong upper tropospheric depletion of methane at increased latitudes, in rough agreement with the trend identified by Karkoschka and Tomasko (Karkoschka, E., Tomasko, M. [2009]. Icarus 202, 287-309).     

New Horizons Alice ultraviolet observations of a stellar occultation by Jupiter’s atmosphere

The Alice ultraviolet spectrograph onboard the New Horizons spacecraft observed two occultations of the bright star χ Ophiucus by Jupiter’s atmosphere on February 22 and 23, 2007 during the approach phase of the Jupiter flyby. The ingress occultation probed the atmosphere at 32°N latitude near the dawn terminator, while egress probed 18°N latitude near the dusk terminator. A detailed analysis of both the ingress and egress occultations, including the effects of molecular hydrogen, methane, acetylene, ethylene, and ethane absorptions in the far ultraviolet (FUV), constrains the eddy diffusion coefficient at the homopause level to be  cm² s⁻¹, consistent with Voyager measurements and other analyses (Festou, M.C., Atreya, S.K., Donahue, T.M., Sandel, B.R., Shemansky, D.E., Broadfoot, A.L. [1981]. J. Geophys. Res. 86, 5717-5725; Vervack Jr., R.J., Sandel, B.R., Gladstone, G.R., McConnell, J.C., Parkinson, C.D. [1995]. Icarus 114, 163-173; Yelle, R.V., Young, L.A., Vervack Jr., R.J., Young, R., Pfister, L., Sandel, B.R. [1996]. J. Geophys. Res. 101 (E1), 2149-2162). However, the actual derived pressure level of the methane homopause for both occultations differs from that derived by [Festou et al., 1981] and [Yelle et al., 1996] from the Voyager ultraviolet occultations, suggesting possible changes in the strength of atmospheric mixing with time. We find that at 32°N latitude, the methane concentration is  cm⁻³ at 70,397 km, the methane concentration is  cm⁻³ at 70,383 km, the acetylene concentration is  cm⁻³ at 70,364 km, and the ethane concentration is  cm⁻³ at 70,360 km. At 18°N latitude, the methane concentration is  cm⁻³ at 71,345 km, the methane concentration is  cm⁻³ at 71,332 km, the acetylene concentration is cm⁻³ at 71,318 km, and the ethane concentration is  cm⁻³ at 71,315 km. We also find that the H₂ occultation light curve is best reproduced if the atmosphere remains cold in the microbar region such that the base of the thermosphere is located at a lower pressure level than that determined by in situ instruments aboard the Galileo probe (Seiff, A., Kirk, D.B., Knight, T.C.D., Young, R.E., Mihalov, J.D., Young, L.A., Milos, F.S., Schubert, G., Blanchard, R.C., Atkinson, D. [1998]. J. Geophys. Res. 103 (E10), 22857-22889) - the Sieff et al. temperature profile leads to too much absorption from H₂ at high altitudes. However, this result is highly model dependent and non-unique. The observations and analysis help constrain photochemical models of Jupiter’s atmosphere.     

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.     

Io's dayside SO2 atmosphere

An extensive set of HI Lyman-α images obtained with the Hubble Space Telescope (HST) Space Telescope Imaging Spectrograph (STIS) from 1997-2001 has been analyzed to provide information about the spatial and temporal character of Io's SO₂ atmosphere. An atmospheric distribution map derived from the observations reveals that the sunlit SO₂ atmosphere is temporally stable on a global scale, with only small local changes. An anti-/sub-jovian asymmetry in the SO₂ distribution is present in all 5 years of the observations. The average daytime atmosphere is densest on the anti-jovian hemisphere in the equatorial regions, with a maximum equatorial column density of 5.0×¹⁰¹⁶ cm−2 at 140° longitude. The SO₂ atmosphere also has greater latitudinal extent on the anti-jovian hemisphere as compared to the sub-jovian. The atmospheric distribution appears to be best correlated with the location of hot spots and known volcanic plumes, although small number statistics for the plumes limits the correlation.