Molecular hydrogen in Titan’s atmosphere: Implications of the measured tropospheric and thermospheric mole fractions

The third most abundant species in Titan’s atmosphere is molecular hydrogen with a tropospheric/lower stratospheric mole fraction of 0.001 derived from Voyager and Cassini infrared measurements. The globally averaged thermospheric H₂ mole fraction profile from the Cassini Ion Neutral Mass Spectrometer (INMS) measurements implies a small positive gradient in the H₂ mixing ratio from the tropopause region to the lower thermosphere (∼950-1000 km), which drives a downward H₂ flux into Titan’s surface comparable to the H₂ escape flux out of the atmosphere (∼2 × 10¹⁰ cm⁻² s⁻¹ referenced to the surface) and requires larger photochemical production rates of H₂ than obtained by previous photochemical models. From detailed model calculations based on known photochemistry with eddy, molecular, and thermal diffusion, the tropospheric and thermospheric H₂ mole fractions are incompatible by a factor of ∼2. The measurements imply that the downward H₂ surface flux is in substantial excess of the speculative threshold value for methanogenic life consumption of H₂ (McKay, C.P., Smith, H.D. [2005], Icarus 178, 274-276. doi:10.1016/j.icarus.2005.05.018), but without the extreme reduction in the surface H₂ mixing ratio.     

Carbon Monoxide on Jupiter: Evidence for Both Internal and External Sources

Thirteen lines of the CO band near 4.7 μm have been observed on a jovian hot spot at a resolution of 0.045 cm⁻¹. The measured line profiles indicate that the CO mole fraction is 1.0±0.2 ppb around the 6-bar level and is larger in the upper troposphere and/or stratosphere. An external source of CO providing an abundance of 4⁺³₋₂×10¹⁶ molecules cm⁻² is implied by the observations in addition to the amount deposited at high altitude by the Shoemaker-Levy 9 collision. From a simple diffusion model, we estimate that the CO production rate is (1.5-10)×10⁶ molecules cm⁻² s⁻¹ assuming an eddy diffusion coefficient around the tropopause between 300 and 1500 cm² s⁻¹. Precipitation of oxygen atoms from the jovian magnetosphere or photochemistry of water vapor from meteoroidal material can only provide a negligible contribution to this amount. A significant fraction of the CO in Jupiter's upper atmosphere may be formed by shock chemistry due to the infall of kilometer- to subkilometer-size Jupiter family comets. Using the impact rate from Levison et al. (2000, Icarus143, 415-420) rescaled by Bottke et al. (2002, Icarus156, 399-433), this source can provide the observed stratospheric CO only if the eddy diffusion coefficient around the tropopause is 100-300 cm² s⁻¹. Higher values, ∼700 cm² s⁻¹, would require an impact rate larger by a factor of 5-10, which cannot be excluded considering uncertainties in the distribution of Jupiter family comets. Such a large rate is indeed consistent with the observed cratering record of the Galilean satellites (Zahnle et al. 1998, Icarus136, 202-222). On the other hand, the ∼1 ppb concentration in the lower troposphere requires an internal source. Revisiting the disequilibrium chemistry of CO in Jupiter, we conclude that rapid vertical mixing can provide the required amount of CO at ∼6 bar for a global oxygen abundance of 0.2-9 times the solar value considering the uncertainties in the convective mixing rate and in the chemical constants.     

Chemical budgets of the stratosphere

A review is given of the stratospheric budgets of odd oxygen, odd nitrogen, nitrous oxide, methane and carbonyl sulfide. The stratospheric column production rate of NO by the reaction N₂O + O(¹D) → 2 NO is 1.1–1.9 × 10⁸ molecules cm^?2 s^?1. The stratospheric loss rates for N₂O, CH₄ and COS are equal to 0.9–1.4 × 10⁹, 1 × 10¹⁰ and 0.5 × 10⁷ molecules cm^?2 s^?1, respectively. From currently available information on the global distributions of N₂O and CH₄ there are some indications of about two times smaller OH concentrations below 35 km than those which are calculated based on the latest compilation of kinetic data.Most significantly, however, it is shown that photochemical models and available ozone observations cannot be reconciled and that there may be particularly severe problems in the 25–35 km region. This issue is thoroughly discussed.Volcanic emissions of SO₂ to the stratosphere may locally lead to much enhanced ozone concentrations and heating rates. These may influence the dynamic behaviour of volcanic plumes before their dispersion over large volumes of the stratosphere.     

“Methane on Mars: A product of H2O photolysis in the presence of CO”: Response to V.A. Krasnopolsky

The detection of CH₄ in the martian atmosphere, at a mixing ratio of about 10 ppb, prompted Krasnopolsky et al. [Krasnopolsky, V.A., Maillard, J.P., Owen, T.C., 2004. Icarus 172, 537-547] and Krasnopolsky [Krasnopolsky, V.A., 2006. Icarus 180, 359-367] to propose that the CH₄ is of biogenic origin. Bar-Nun and Dimitrov [Bar-Nun, A., Dimitrov, V., 2006. Icarus 181, 320-322] proposed that CH₄ can be formed in the martian atmosphere by photolysis of H₂O in the presence of CO. We based our arguments on a clear demonstration that CH₄ is formed in our experiments, and on thermodynamic equilibrium calculations, which show that CH₄ formation is favored even in the presence of oxygen at a mixing ratio 1.3×¹⁰⁻³, as observed on Mars. In the present comment, Krasnopolsky [Krasnopolsky, V.A., 2007. Icarus, in press (this issue)] presents his arguments against the suggestion of Bar-Nun and Dimitrov [Bar-Nun, A., Dimitrov, V., 2006. Icarus 181, 320-322], based on the effect of O₂ on CH₄ formation, the absence of kinetic pathways for CH₄ formation and on the inadequacy of thermodynamic equilibrium calculations to describe the martian atmosphere. In this rebuttal we demonstrate that experiments with molecular oxygen at a ratio of O₂/CO₂=(8.9-17)×¹⁰⁻³, exceeding the martian ratio, still form CH₄. Thermodynamic equilibrium calculations replicate the experimental CH₄ mixing ratio to within a factor of 1.9 and demonstrate that CH₄ production is favored in the martian atmosphere, which is obviously not in thermodynamic equilibrium. Consequently, we do not find the presence of methane to be a sign of biological activity on Mars.     

The D/H Ratio in Methane in Titan: Origin and History

We propose a new interpretation of the D/H ratio in CH₄ observed in the atmosphere of Titan. Using a turbulent evolutionary model of the subnebula of Saturn (O. Mousis et al. 2002, Icarus156, 162-175), we show that in contrast to the current scenario, the deuterium enrichment with respect to the solar value observed in Titan cannot have occurred in the subnebula. Instead, we argue that values of the D/H ratio measured in Titan were obtained in the cooling solar nebula by isotopic thermal exchange of hydrogen with CH₃D originating from interstellar methane D-enriched ices that vaporized in the nebula. The rate of the isotopic exchange decreased with temperature and became fully inhibited around 200 K. Methane was subsequently trapped in crystalline ices around 10 AU in the form of clathrate hydrates formed at 60 K, and incorporated into planetesimals that formed the core of Titan. The nitrogen-methane atmosphere was subsequently outgassed from the decomposition of the hydrates (Mousis et al. 2002). By use of a turbulent evolutionary model of the solar nebula (O. Mousis et al. 2000, Icarus148, 513-525), we have reconstructed the entire story of D/H in CH₄, from its high value in the early solar nebula (acquired in the presolar cloud) down to the value measured in Titan's atmosphere today. Considering the two last determinations of the D/H ratio in Titan—D/H=(7.75±2.25)×10⁻⁵ obtained from ground-based observations (Orton 1992, In: Symposium on Titan, ESA SP-338, pp. 81-85), and D/H=(8.75^+3.25_−2.25)×10⁻⁵, obtained from ISO observations (Coustenis et al. 2002, submitted for publication)—we inferred an upper limit of the D/H ratio in methane in the early outer solar nebula of about 3×10⁻⁴. Our approach is consistent with the scenario advocated by several authors in which the atmospheric methane of Titan is continuously replenished from a reservoir of clathrate hydrates of CH₄ at high pressures, located in the interior of Titan. If this scenario is correct, observations of the satellite to be performed by the radar, the imaging system, and other remote sensing instruments aboard the spacecraft of the Cassini-Huygens mission from 2004 to 2008 should reveal local disruptions of the surface and other signatures of the predicted outgassing.     

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.     

Methane in Martian atmosphere: Average spatial, diurnal, and seasonal behaviour

A large number of spectra measured by the planetary Fourier spectrometer aboard the European Mars Express mission have been studied to identify the average properties of methane in the Martian atmosphere. Using the line at 3018 cm⁻¹, we have studied the seasonal, diurnal, and spatial variations of methane through the analysis of large averages of spectra (more than 1000 measurements). Methane mixing ratio has been obtained simultaneously with water vapour mixing ratio and water ice content, by best fitting (minimising the χ²) the computed averages with synthetic spectra. These spectra were computed for different values of the three parameters (methane and water vapour mixing ratio, and water ice optical depth).The methane mixing ratio shows a slow decrease from northern spring to southern summer with an average value of 14±5 ppbv (part per billion by volume) and it does not show a particular trend with latitude. The methane mixing ratio seems not to be uniform in longitude in the Martian atmosphere, as already reported by Formisano et al. [2004. Detection of methane in the atmosphere of Mars. Science 306, 1758-1761]. Two maxima are present at −40°E and +70°E longitude. In local time, the methane mixing ratio seems to follow the water vapour diurnal cycle. The most important point for future understanding is, however, that there are special orbits in which methane mixing ratio has a very high value.     

Vertical profile of H2SO4 vapor at 70-110 km on Venus and some related problems

The vertical profile of H₂SO₄ vapor is calculated using current atmospheric and thermodynamic data. The atmospheric data include the H₂O profiles observed at 70-112 km by the SOIR solar occultations, the SPICAV-UV profiles of the haze extinction at 220 nm, the VeRa temperature profiles, and a typical profile of eddy diffusion. The thermodynamic data are the saturated vapor pressures of H₂O and H₂SO₄ and chemical potentials of these species in sulfuric acid solutions. The calculated concentration of sulfuric acid in the cloud droplets varies from 85% at 70 km to a minimum of 70% at 90 km and then gradually increasing to 90-100% at 110 km. The H₂SO₄ vapor mixing ratio is ∼10⁻¹² at 70 and 110 km with a deep minimum of 3 × 10⁻¹⁸ at 88 km. The H₂O-H₂SO₄ system matches the local thermodynamic equilibrium conditions up to 87 km. The column photolysis rate of H₂SO₄ is 1.6 × 10⁵ cm⁻² s⁻¹ at 70 km and 23 cm⁻² s⁻¹ at 90 km. The calculated abundance of H₂SO₄ vapor at 90-110 km and its photolysis rate are smaller than those presented in the recent model by Zhang et al. (Zhang, X., Liang, M.C., Montmessin, F., Bertaux, J.L., Parkinson, C., Yung, Y.L. [2010]. Nat. Geosci. 3, 834-837) by factors of 10⁶ and 10⁹, respectively. Assumptions of 100% sulfuric acid, local thermodynamic equilibrium, too warm atmosphere, supersaturation of H₂SO₄ (impossible for a source of SO_X), and cross sections for H₂SO₄·H₂O (impossible above the pure H₂SO₄) are the main reasons of this huge difference. Significant differences and contradictions between the SPICAV-UV, SOIR, and ground-based submillimeter observations of SO_X at 70-110 km are briefly discussed and some weaknesses are outlined. The possible source of high altitude SO_X on Venus remains unclear and probably does not exist.     

Condensation in Titan's stratosphere during polar winter

In Titan's north polar region stratospheric clouds are expected to form due to a combination of low temperatures and downward motion of volatile-enriched air. Here we investigate possible sources of stratospheric clouds at Titan's pole using data from the Cassini Composite Infrared Spectrometer and a simple condensation model. An upper limit for C₄N₂ gas was determined to be 9×¹⁰⁻⁹, which is less than required to make the C₄N₂ cloud at the Voyager epoch. Hence, the presence of this cloud after equinox remains a mystery. The largest cloud seen in far-infrared spectra has a feature around 220 cm⁻¹ and is located around an altitude of 140 km. The upper limit for propionitrile (C₂H₅CN) gas shows that the feature around 220 cm⁻¹ is probably not due to pure propionitrile ice. Instead, our model calculations show that HCN should cause by far the largest cloud around 140 km. We therefore propose that HCN ice plays an important role in the formation of the massive polar cloud, because of the unavailability of sufficient condensable gas other than HCN to produce a strong enough condensate feature. However, the signature at 220 cm⁻¹ is not consistent with that of pure HCN ice at 172 cm⁻¹ and mixing of HCN ice with other ices, or chemical alteration of HCN ice might mask the HCN ice signature.     

Cassini CIRS update on stratospheric ices at Titan's winter pole

A strong, broad spectral emission feature at 85° N latitude centered at 221 cm⁻¹ remains unidentified after candidate ices of H₂O and pure crystalline CH₃CH₂CN are unambiguously ruled out. A much shallower weak emission feature starts at 160 cm⁻¹ and blends into the strong feature at ∼190 cm⁻¹. This feature is consistent with one formed by an HCN ice cloud composed of ?5 μm radius particles that resides in the lower stratosphere somewhere below an altitude of 160 km. Titan's stratospheric aerosol appears to have a spectral emission feature at about 148 cm⁻¹. The aerosol abundance at 85° N is about a factor 2.2 greater than at 55° S.     

Detection of new hydrocarbons in Uranus' atmosphere by infrared spectroscopy

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

Updated Galileo probe mass spectrometer measurements of carbon, oxygen, nitrogen, and sulfur on Jupiter

The in situ measurements of the Galileo Probe Mass Spectrometer (GPMS) were expected to constrain the abundances of the cloud-forming condensible volatile gases: H₂O, H₂S, and NH₃. However, since the probe entry site (PES) was an unusually dry meteorological system—a 5-μm hotspot—the measured condensible volatile abundances did not follow the canonical condensation-limited vertical profiles of equilibrium cloud condensation models (ECCMs) such as Weidenschilling and Lewis (1973, Icarus 20, 465-476). Instead, the mixing ratios of H₂S and NH₃ increased with depth, finally reaching well-mixed equilibration levels at pressures far greater than the lifting condensation levels, whereas the mixing ratio of H₂O in the deep well-mixed atmosphere could not be measured. The deep NH₃ mixing ratio (with respect to H₂) of (6.64±2.54)×10⁻⁴ from 8.9-11.7 bar GPMS data is consistent with the NH₃ profile from probe-to-orbiter signal attenuation (Folkner et al., 1998, J. Geophys. Res. 103, 22847-22856), which had an equilibration level of about 8 bar. The GPMS deep atmosphere H₂S mixing ratio of (8.9±2.1)×10⁻⁵ is the only measurement of Jupiter's sulfur abundance, with a PES equilibration level somewhere between 12 and 15.5 bar. The deepest water mixing ratio measurement is (4.9±1.6)×10⁻⁴ (corresponding to only about 30% of the solar abundance) at 17.6-20.9 bar, a value that is probably much smaller than Jupiter's bulk water abundance. The ¹⁵N/¹⁴N ratio in jovian NH₃ was measured at (2.3±0.3)×10⁻³ and may provide the best estimate of the protosolar nitrogen isotopic ratio. The GPMS methane mixing ratio is (2.37±0.57)×10⁻³; although methane does not condense on Jupiter, we include its updated analysis in this report because like the condensible volatiles, it was presumably brought to Jupiter in icy planetesimals. Our detailed discussion of calibration and error analysis supplements previously reported GPMS measurements of condensible volatile mixing ratios (Niemann et al., 1998, J. Geophys. Res. 103, 22831-22846; Atreya et al., 1999, Planet. Space Sci. 47, 1243-1262; Atreya et al., 2003, Planet. Space Sci. 51, 105-112) and the nitrogen isotopic ratio (Owen et al., 2001b, Astrophys. J. Lett. 553, L77-L79). The approximately three times solar abundance of NH₃ (along with CH₄ and H₂S) is consistent with enrichment of Jupiter's atmosphere by icy planetesimals formed at temperatures <40 K (Owen et al., 1999, Nature 402 (6759), 269-270), but would imply that H₂O should be at least 3×solar as well. An alternate model, using clathrate hydrates to deliver the nitrogen component to Jupiter, predicts O/H?9×solar (Gautier et al., 2001, Astrophys. J. 550 (2), L227-L230). Finally we show that the measured condensible volatile vertical profiles in the PES are consistent with column-stretching or entraining downdraft scenarios only if the basic state (the pre-stretched column or the entrainment source region) is described by condensible volatile vertical profiles that are drier than those in the equilibrium cloud condensation models. This dryness is supported by numerous remote sensing results but seems to disagree with observations of widespread clouds on Jupiter at pressure levels predicted by equilibrium cloud condensation models for ammonia and H₂S.     

Methane evolution from UV-irradiated spacecraft materials under simulated martian conditions: Implications for the Mars Science Laboratory (MSL) mission

Fifteen organic and three inorganic compounds were tested for methane (CH₄) evolution under simulated martian conditions of 6.9 mbar; UVC (200-280 nm) flux of 4 W m⁻²; 20 °C; simulated optical depth of 0.1; and a Mars gas composition of CO₂ (95.3%), N₂ (2.7%), Ar (1.7%), O₂ (0.13%), and water vapor (0.03%). All three inorganic compounds (i.e., NaCl, CaCO₃, graphite) failed to evolve methane at the minimum detection level 0.5 ppm, or above. In contrast, all organic compounds evolved methane when exposed to UV irradiation under simulated martian conditions. The polycyclic aromatic hydrocarbon, pyrene, released the most methane per unit of time at 0.175 nmol CH₄ g⁻¹ h⁻¹, and a spectral reflectance target material used for the MER rovers and Phoenix lander released the least methane at 0.00065 nmol CH₄ cm⁻² h⁻¹. Methane was also released from UV-killed bacterial endospores of Bacillus subtilis. Although all organic compounds evolved methane when irradiated with UV photons under martian conditions, the concentrations of residual organics, biogenic signature molecules, and dead microbial cells should be relatively low on the exterior surfaces of the MSL rover, and, thus, not significant sources of methane contamination. In contrast, kapton tape was found to evolve methane at the rate of 0.00165 nmol CH₄ cm⁻² h⁻¹ (16.5 nmol m⁻² h⁻¹) under the UV and martian conditions tested. Although the evolution of methane from kapton tape was found to decline over time, the large amount of kapton tape used on the MSL rover (lower bound estimated at 3 m²) is likely to create a significant source of terrestrial methane contamination during the early part of the mission.     

New laboratory measurements of CH4 in Titan's conditions and a reanalysis of the DISR near-surface spectra at the Huygens landing site

Laboratory spectra of methane-nitrogen mixtures have been recorded in the near-infrared range (1.0-1.65 μm) in conditions similar to Titan's near surface, to facilitate the interpretation of the DISR/DLIS (DISR—Descent Imager/Spectral Radiometer) spectra taken during the last phase of the descent of the Huygens Probe, when the surface was illuminated by a surface-science lamp. We used a 0.03 cm⁻¹ spectral resolution, adequate to resolve the lines at high pressure (p_N2∼1.5 bar). By comparing the laboratory spectra with synthetic calculations in the well-studied ν₂+2ν₃ band (7515-7620 cm⁻¹), we determine a methane absorption column density of 178±20 cm atm and a temperature of 118±10 K in our experiment. From this, we derive the methane absorption coefficients over 1.0-1.65 μm with a 0.03 cm⁻¹ sampling, allowing for the extrapolation of the results to any other methane column density under the relevant pressure and temperature conditions. We then revisit the calibration and analysis of the Titan “lamp-on” DLIS spectra. We infer a 5.1±0.8% methane-mixing ratio in the first 25 m of Titan's atmosphere. The CH₄ mixing ratio measured 90 s after landing from a distance of 45 cm is found to be 0.92±0.25 times this value, thus showing no post-landing outgassing of methane in excess of ∼20%. Finally, we determine the surface reflectivity as seen between 25 m and 45 cm and find that the 1500 nm absorption band is deeper in the post-landing spectrum as compared to pre-landing.     

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.     

The spectra of Uranus and Neptune at 8–14 and 17–23 μm

An array spectrometer was used on the nights of 1985 May 30–June 1 to observe the disks of Uranus and Neptune in the spectral regions 7–14 and 17–23 μm with effective resolution elements ranging from 0.23 to 0.87 μm. In the long-wavelength region, the spectra are relatively smooth with the broad S(1) H₂ collision-induced rotation line showing strong emission for Neptune. In the short-wavelength spectrum of Uranus, an emission feature attributable to C₂H₂ with a maximum stratospheric mixing ratio of 9 × 10⁻⁹ is apparent. An upper limit of 2 × 10⁻⁸ is placed on the maximum stratospheric mixing ratio of C₂H₆. The spectrum of Uranus is otherwise smooth and quantitatively consistent with the opacity provided by H₂ collision-induced absorption and spectrally continuous stratospheric emission, as would be produced by aerosols. Upper limits to detecting the planet near 8 μm indicate a CH₄ stratospheric mixing ratio of 1 × 10⁻⁵ or less, below a value consistent with saturation equilibrium at the temperature minimum. In the short-wavelength spectrum of Neptune, strong emission features of CH₄ and C₂H₆ are evident and are consistent with local saturation equilibrium with maximum stratospheric mixing ratios of 0.02 and 6 × 10⁻⁶, respectively. Emission at 8–10 μm is most consistent with a [CH₃D]/[CH₄] volume abundance ratio of 5 × 10⁻⁵. The spectrum of Neptune near 13.5 μm is consistent with emission by stratospheric C₂H₂ in local saturation equilibrium and a maximum mixing ratio of 9 × 10⁻⁷. Radiance detected near 10.5 μm could be attributed to stratospheric C₂H₄ emission for a maximum mixing ratio of approximately 3 × 10⁻⁹. Quantitative results are considered preliminary, as some absolute radiance differences are noted with respect to earlier observations with discrete filters.     

Methane and its isotopologues on Saturn from Cassini/CIRS observations

High spectral resolution observations from the Cassini Composite Infrared Spectrometer [Flasar, F.M., and 44 colleagues, 2004. Space Sci. Rev. 115, 169-297] are analysed to derive new estimates for the mole fractions of CH₄, CH₃D and ¹³CH₄ of (4.7±0.2)×¹⁰⁻³, (3.0±0.2)×¹⁰⁻⁷ and (5.1±0.2)×¹⁰⁻⁵ respectively. The mole fractions show no hemispherical asymmetries or latitudinal variability. The analysis combines data from the far-IR methane rotational lines and the mid-IR features of methane and its isotopologues, using both the correlated-k retrieval algorithm of Irwin et al. [Irwin, P., and 9 colleagues, 2008. J. Quant. Spectrosc. Radiat. Trans. 109, 1136-1150] and a line-by-line approach to evaluate the reliability of the retrieved quantities. C/H was found to be enhanced by 10.9±0.5 times the solar composition of Grevesse et al. [Grevesse, N., Asplund, M., Sauval, A., 2007. Space Sci. Rev. 130 (1), 105-114], 2.25±0.55 times larger than the enrichment on Jupiter, and supporting the increasing fractional core mass with distance from the Sun predicted by the core accretion model of planetary formation. A comparison of the jovian and saturnian C/N, C/S and C/P ratios suggests different reservoirs of the trapped volatiles in a primordial solar nebula whose composition varies with distance from the Sun. This is supported by our derived D/H ratio in methane of (1.6±0.2)×¹⁰⁻⁵, which appears to be smaller than the jovian value of Lellouch et al. [Lellouch, E., Bézard, B., Fouchet, T., Feuchtgruber, H., Encrenaz, T., de Graauw, T., 2001. Astron. Astrophys. 370, 610-622]. Mid-IR emission features provided an estimate of , which is consistent with both the terrestrial ratio and jovian ratio, suggesting that carbon was accreted from a shared reservoir for all of the planets.     

Meridional transport of HCN from SL9 impacts on Jupiter

In July 1994, the Shoemaker-Levy 9 (SL9) impacts introduced hydrogen cyanide (HCN) to Jupiter at a well confined latitude band around −44°, over a range of specific longitudes corresponding to each of the 21 fragments (Bézard et al. 1997, Icarus 125, 94-120). This newcomer to Jupiter's stratosphere traces jovian dynamics. HCN rapidly mixed with longitude, so that observations recorded later than several months after impact witnessed primarily the meridional transport of HCN north and south of the impact latitude band. We report spatially resolved spectroscopy of HCN emission 10 months and 6 years following the impacts. We detect a total mass of HCN in Jupiter's stratosphere of 1.5±0.7×10¹³ g in 1995 and 1.7±0.4×10¹³ g in 2000, comparable to that observed several days following the impacts (Bézard et al. 1997, Icarus 125, 94-120). In 1995, 10 months after impact, HCN spread to −30° and −65° latitude (half column masses), consistent with a horizontal eddy diffusion coefficient of K_yy=2-3×10¹⁰ cm² s⁻¹. Six years following impact HCN is observed in the northern hemisphere, while still being concentrated at 44° south latitude. Our meridional distribution of HCN suggests that mixing occurred rapidly north of the equator, with K_yy=2-5×10¹¹ cm² s⁻¹, consistent with the findings of Moreno et al. (2003, Planet. Space Sci. 51, 591-611) and Lellouch et al. (2002, Icarus 159, 112-131). These inferred eddy diffusion coefficients for Jupiter's stratosphere at 0.1-0.5 mbar generally exceed those that characterize transport on Earth. The low abundance of HCN detected at high latitudes suggests that, like on Earth, polar regions are dynamically isolated from lower latitudes.     

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.     

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

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