Detection of C2HD and the D/H ratio on Titan

We report here the first detection of mono-deuterated acetylene (acetylene-d1, C₂HD) in Titan's atmosphere from the presence of two of its emission bands at 678 and 519 cm⁻¹ as observed in CIRS spectral averages of nadir and limb observations taken between July 2004 and mid-2007. By using new laboratory spectra for this molecule, we were able to derive its abundance at different locations over Titan's disk. We find the C₂HD value () to be roughly constant with latitude from the South to about 45° N and then to increase slightly in the North, as is the case for C₂H₂. Fitting the 678 cm⁻¹ν₅ band simultaneously with the nearby C₂H₂ 729 cm⁻¹ν₅ band, allows us to infer a D/H ratio in acetylene on Titan with an average of the modal values of 2.09±0.45×¹⁰⁻⁴ from the nadir observations, the uncertainties being mainly due to the vertical profile used for the fit of the acetylene band. Although still subject to significant uncertainty, this D/H ratio appears to be significantly larger than the one derived in methane from the CH₃D band (upper limit of 1.5×¹⁰⁻⁴; Bézard, B., Nixon, C.A., Kleiner, I., Jennings, D.E., 2007. Icarus, 191, 397-400; Coustenis, A., Achterberg, R., Conrath, B., Jennings, D., Marten, A., Gautier, D., Bjoraker, G., Nixon, C., Romani, P., Carlson, R., Flasar, M., Samuelson, R.E., Teanby, N., Irwin, P., Bézard, B., Orton, G., Kunde, V., Abbas, M., Courtin, R., Fouchet, Th., Hubert, A., Lellouch, E., Mondellini, J., Taylor, F.W., Vinatier, S., 2007. Icarus 189, 35-62). From the analysis of limb data we infer D/H values of (at 54° S), (at 15° S), (at 54° N) and (at 80° N), which average to a mean value of 1.63±0.27×¹⁰⁻⁴.     

Removal of Titan's noble gases by their trapping in its haze

Titan's haze, formed by photolysis of C₂H₂, C₂H₄ and HCN, was found experimentally to trap Ar, Kr and Xe with efficiencies of 3.5 × 10⁻⁴, 1.9 × 10⁻³ and 6.5 × 10⁻² [noble gas atom]/[carbon atom] in the polymer, respectively. The rate of aerosol formation and settling down of 3 × 10⁻¹³ kg m⁻² s⁻¹, as inferred from our experiments on CH₄ photolysis in the far UV [Podolak, M., Bar-Nun, A., 1979. Icarus 39, 272-276], is sufficient to reduce the mixing ratios of ³⁶Ar and ⁴⁰Ar to their low values of (2.8 ± 0.3) × 10⁻⁷ and (4.3 ± 0.1) × 10⁻³, respectively, and those of Kr and Xe to below the detection limit of 10⁻⁸.     

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.     

Ground-based measurements of the methane distribution on Titan

Using spectra taken with NIRSPEC (Near Infrared Spectrometer) and adaptive optics on the Keck II telescope, we resolved the latitudinal variation of the 3ν₂ band of CH₃D at 1.56 μm. As CH₃D is less abundant than CH₄ by a factor of 50±10×10^-5, these CH₃D lines do not saturate in Titan’s atmosphere, and are well characterized by laboratory measurements. Thus they do not suffer from the large uncertainties of the CH₄ lines that are weak enough to be unsaturated in Titan. Our measurements of the methane abundance are confined to the latitude range of 32°S-18°N and longitudes sampled by a 0.04″ slit centered at ∼195°W. The methane abundance below 10 km is constant to within 20% in the tropical atmosphere sampled by our observations, consistent with the low surface insolation and lack of surface methane [Griffith, C.A., McKay, C.P., Ferri, F., 2008. Astrophys. J. 687, L41-L44].     

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.     

Titan's hydrodynamically escaping atmosphere: Escape rates and the structure of the exobase region

In Strobel [Strobel, D.F., 2008. Icarus, 193, 588-594] a mass loss rate from Titan's upper atmosphere, , was calculated for a single constituent, N₂ atmosphere by hydrodynamic escape as a high density, slow outward expansion driven principally by solar UV heating due to CH₄ absorption. It was estimated, but not proven, that the hydrodynamic mass loss is essentially CH₄ and H₂ escape. Here the individual conservation of momentum equations for the three major components of the upper atmosphere (N₂, CH₄, H₂) are solved in the low Mach number limit and compared with Cassini Ion Neutral Mass Spectrometer (INMS) measurements to demonstrate that light gases (CH₄, H₂) preferentially escape over the heavy gas (N₂). The lightest gas (H₂) escapes with a flux 99% of its limiting flux, whereas CH₄ is restricted to ?75% of its limiting flux because there is insufficient solar power to support escape at the limiting rate. The respective calculated H₂ and CH₄ escape rates are 9.2×¹⁰²⁷ and 1.7×¹⁰²⁷ s−1, for a total of . From the calculated densities, mean free paths of N₂, CH₄, H₂, and macroscopic length scales, an extended region above the classic exobase is inferred where frequent collisions are still occurring and thermal heat conduction can deliver power to lift the escaping gas out of the gravitational potential well. In this region rapid acceleration of CH₄ outflow occurs. With the thermal structure of Titan's thermosphere inferred from INMS data by Müller-Wodarg et al. [Müller-Wodarg, I.C.F., Yelle, R.V., Cui, J., Waite Jr., J.H., 2008. J. Geophys. Res. 113, doi:10.1029/2007JE003033. E10005], in combination with calculated temperature profiles that include sputter induced plasma heating at the exobase, it is concluded that on average that the integrated, globally average, orbit-averaged, plasma heating rate during the Cassini epoch does not exceed ().     

Meridional distribution of CH3C2H and C4H2 in Saturn’s stratosphere from CIRS/Cassini limb and nadir observations

Limb and nadir spectra acquired by Cassini/CIRS (Composite InfraRed Spectrometer) are analyzed in order to derive, for the first time, the meridional variations of diacetylene (C₄H₂) and methylacetylene (CH₃C₂H) mixing ratios in Saturn’s stratosphere, from 5 hPa up to 0.05 hPa and 80°S to 45°N. We find that the C₄H₂ and CH₃C₂H meridional distributions mimic that of acetylene (C₂H₂), exhibiting small-scale variations that are not present in photochemical model predictions. The most striking feature of the meridional distribution of both molecules is an asymmetry between mid-southern and mid-northern latitudes. The mid-southern latitudes are found depleted in hydrocarbons relative to their northern counterparts. In contrast, photochemical models predict similar abundances at north and south mid-latitudes. We favor a dynamical explanation for this asymmetry, with upwelling in the south and downwelling in the north, the latter coinciding with the region undergoing ring shadowing. The depletion in hydrocarbons at mid-southern latitudes could also result from chemical reactions with oxygen-bearing molecules.Poleward of 60°S, at 0.1 and 0.05 hPa, we find that the CH₃C₂H and C₄H₂ abundances increase dramatically. This behavior is in sharp contradiction with photochemical model predictions, which exhibit a strong decrease towards the south pole. Several processes could explain our observations, such as subsidence, a large vertical eddy diffusion coefficient at high altitudes, auroral chemistry that enhances CH₃C₂H and C₄H₂ production, or shielding from photolysis by aerosols or molecules produced from auroral chemistry. However, problems remain with all these hypotheses, including the lack of similar behavior at lower altitudes.Our derived mean mixing ratios at 0.5 hPa of (2.4 ± 0.3) × 10⁻¹⁰ for C₄H₂ and of (1.1 ± 0.3) × 10⁻⁹ for CH₃C₂H are compatible with the analysis of global-average ISO observations performed by Moses et al. (Moses, J.I., Bézard, B., Lellouch, E., Gladstone, G.R., Feuchtgruber, H., Allen, M. [2000a]. Icarus 143, 244-298). Finally, we provide values for the ratios [CH₃C₂H]/[C₂H₂] and [C₄H₂]/[C₂H₂] that can constrain the coupled chemistry of these hydrocarbons.     

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.     

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.     

Prebiotic organic synthesis in early Earth and Mars atmospheres: Laboratory experiments with quantitative determination of products formed in a cold plasma flow reactor

The goal of this study was to explore prebiotic chemistry in a range of plausible early Earth and Mars atmospheres. To achieve this laboratory continuous flow plasma irradiation experiments were performed on N₂/H₂/CO/CO₂ gas mixtures chosen to represent mildly reducing early Earth and Mars atmospheres derived from a secondary volcanic outgassing of volatiles in chemical equilibrium with magmas near present day oxidation state. Under mildly reducing conditions (91.79% N₂, 5.89% H₂, 2.21% CO, and 0.11% CO₂), simple nitriles are produced in the gas phase with yield (G in molecules per 100 eV), for the key prebiotic marker molecule HCN at G∼1×¹⁰⁻³ (0.1 nmol J⁻¹). In this atmosphere localized HCN concentrations possibly could approach the 10⁻² M needed for HCN oligomerization. Yields under mildly oxidizing conditions (45.5% N₂, 0.1% H₂, 27.2% CO, 27.2% CO₂) are significantly less as expected, with HCN at G∼3×¹⁰⁻⁵ (). Yields in a Triton atmosphere which can be plausibly extrapolated to represent what might be produced in trace CH₄ conditions (99.9% N₂, 0.1% CH₄) are significant with HCN at G∼1×¹⁰⁻² (1 nmol J⁻¹) and tholins produced. Recently higher methane abundance atmospheres have been examined for their greenhouse warming potential, and higher abundance hydrogen atmospheres have been proposed based on a low early Earth exosphere temperature. A reducing (64.04% N₂, 28.8% H₂, 3.60% CO₂, and 3.56% CH₄), representing a high CH₄ and H₂ abundance early Earth atmosphere had HCN yields of G∼5×¹⁰⁻³ (0.5 nmol J⁻¹). Tholins generated in high methane hydrogen gas mixtures is much less than in a similar mixture without hydrogen. The same mixture with the oxidizing component CO₂ removed (66.43% N₂, 29.88% H₂, 0% CO₂, and 3.69% CH₄) had HCN yields of G∼1×¹⁰⁻³ (0.1 nmol J⁻¹) but more significant tholin yields.     

“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.     

Detection of CH3D on Titan

We report the detection of ¹³CH₃D in Titan's stratosphere from Cassini/CIRS infrared spectra near 8.7 μm. Fitting simultaneously the ν₆ bands of both ¹³CH₃D and ¹²CH₃D and the ν₄ band of CH₄, we derive a D/H ratio equal to and a ¹²C/¹³C ratio in deuterated methane of , consistent with that measured in normal methane.     

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 1.10- and 1.18-μm nightside windows of Venus observed by SPICAV-IR aboard Venus Express

Observations of the 1.10- and 1.18-μm nightside windows by the SPICAV-IR instrument aboard Venus Express were analyzed to characterize the various sources of gaseous opacity and determine the H₂O mole fraction in the lower atmosphere of Venus. We showed that the line profile model of Afanasenko and Rodin (Afanasenko, T.S., Rodin, A.V. [2007]. Astron. Lett. 33, 203–210) underestimates the CO₂ absorption in the high-wavelength wing of the 1.18-μm window and we derived an empirical lineshape that matches this wing well. An additional continuum opacity is required to reproduce the variation of the 1.10- and 1.18-μm radiances with surface elevation as observed by the VIRTIS-M instrument aboard Venus Express. A constant absorption coefficient of 0.7 ± 0.2 × 10⁻⁹ cm⁻¹ am⁻² best reproduces the observed variation. We compared spectra calculated with different CO₂ and H₂O line lists. We found that the CDSD line list lacks the 5ν₁ + ν₃ series of CO₂ bands, which provide significant opacity in Venus’ deep atmosphere, and we have constructed a composite line list that best reproduces the observations. We also showed for the first time that HDO brings significant absorption at 1140–1190 nm. Using the best representation of the atmospheric opacity we could reach, we retrieved a water vapor mole fraction of ppmv, pertaining to the altitude range 5–25 km. Combined with previous measurements in the 1.74- and 2.3-μm windows, this result provides strong evidence for a uniform H₂O profile below 40 km, in agreement with chemical models.     

Search for spatial variation in the jovian N/N ratio from Cassini/CIRS observations

We have used the spectra obtained by the Composite Infrared Spectrometer (CIRS) onboard the Cassini spacecraft to search for latitudinal variation in the ¹⁵N/¹⁴N ratio on Jupiter. We found no variations statistically significant given the observational and model uncertainties. The absence of latitudinal variations demonstrates that ¹⁵NH₃ is not fractionated in Jupiter's atmosphere, and that the measured ¹⁵N/¹⁴N represents Jupiter's global value. Our mean value for the global jovian ¹⁵N/¹⁴N ratio of (2.22±0.52)×10⁻³ agrees with previous measurements made by Fouchet et al. (2000, Icarus 143, 223-243) and Owen et al. (2001, Astrophys. J. 553, L77-L79). We argue that the jovian isotopic ¹⁵N/¹⁴N ratio must represent the solar nitrogen isotopic composition. The solar ¹⁵N/¹⁴N ratio hence significantly differs from the terrestrial value: (¹⁵N/¹⁴N)_⊕=3.68×10⁻³. This supports the proposition that terrestrial nitrogen originates from a nitrogen reservoir isolated from the main nitrogen reservoir in the proto-solar nebula. The origin and carrier of this isolated reservoir are still unknown.     

Infrared imaging spectroscopy of Mars: H2O mapping and determination of CO2 isotopic ratios

High-resolution infrared imaging spectroscopy of Mars has been achieved at the NASA Infrared Telescope Facility (IRTF) on June 19-21, 2003, using the Texas Echelon Cross Echelle Spectrograph (TEXES). The areocentric longitude was 206°. Following the detection and mapping of hydrogen peroxide H₂O₂ [Encrenaz et al., 2004. Icarus 170, 424-429], we have derived, using the same data set, a map of the water vapor abundance. The results appear in good overall agreement with the TES results and with the predictions of the Global Circulation Model (GCM) developed at the Laboratory of Dynamical Meteorology (LMD), with a maximum abundance of water vapor of 3±1.5×¹⁰⁻⁴(17±9 pr-μm). We have searched for CH₄ over the martian disk, but were unable to detect it. Our upper limits are consistent with earlier reports on the methane abundance on Mars. Finally, we have obtained new measurements of CO₂ isotopic ratios in Mars. As compared to the terrestrial values, these values are: (¹⁸O/¹⁷O)[M/E] = 1.03 ± 0.09; (¹³C/¹²C)[M/E] = 1.00 ± 0.11. In conclusion, in contrast with the analysis of Krasnopolsky et al. [1996. Icarus 124, 553-568], we conclude that the derived martian isotopic ratios do not show evidence for a departure from their terrestrial values.     

Jupiter's hydrocarbon polar brightening: Discovery of 3-micron line emission from south polar CH4, C2H2, and C2H6

Jupiter exhibits bright H⁺₃ auroral arcs at 3-4 microns that cool the hot (>1000 K) ionosphere above the ∼¹⁰−7 bar level through the infrared bands of this trace constituent. Below the ¹⁰−7 bar level significant cooling proceeds through infrared active bands of CH₄, C₂H₂, and C₂H₆. We report the discovery of 3-micron line emission from these hydrocarbon species in spectra of the jovian south polar region obtained on April 18 and 20, 2006 (UT) with CGS4 on the United Kingdom Infrared Telescope. Estimated cooling rates through these molecules are 7.5×¹⁰−3, 1.4×¹⁰−3, and , respectively, for a total nearly half that of H⁺₃. We derive a temperature of 450 ± 50 K in the ¹⁰−7-¹⁰−5 bar region from the C₂H₂ lines.     

On the HCN and CO2 abundance and distribution in Jupiter's stratosphere

Observations of Jupiter by Cassini/CIRS, acquired during the December 2000 flyby, provide the latitudinal distribution of HCN and CO₂ in Jupiter's stratosphere with unprecedented spatial resolution and coverage. Following up on a preliminary study by Kunde et al. [Kunde, V.G., and 41 colleagues, 2004. Science 305, 1582-1587], the analysis of these observations leads to two unexpected results (i) the total HCN mass in Jupiter's stratosphere in 2000 was (6.0±1.5)×¹⁰¹³ g, i.e., at least three times larger than measured immediately after the Shoemaker-Levy 9 (SL9) impacts in July 1994 and (ii) the latitudinal distributions of HCN and CO₂ are strikingly different: while HCN exhibits a maximum at 45° S and a sharp decrease towards high Southern latitudes, the CO₂ column densities peak over the South Pole. The total CO₂ mass is (2.9±1.2)×¹⁰¹³ g. A possible cause for the HCN mass increase is its production from the photolysis of NH₃, although a problem remains because, while millimeter-wave observations clearly indicate that HCN is currently restricted to submillibar (∼0.3 mbar) levels, immediate post-impact infrared observations have suggested that most of the ammonia was present in the lower stratosphere near 20 mbar. HCN appears to be a good atmospheric tracer, with negligible chemical losses. Based on 1-dimensional (latitude) transport models, the HCN distribution is best interpreted as resulting from the combination of a sharp decrease (over an order of magnitude in Kyy) of wave-induced eddy mixing poleward of 40° and an equatorward transport with velocity. The CO₂ distribution was investigated by coupling the transport model with an elementary chemical model, in which CO₂ is produced from the conversion of water originating either from SL9 or from auroral input. The auroral source does not appear adequate to reproduce the CO₂ peak over the South Pole, as required fluxes are unrealistically high and the shape of the CO₂ bulge is not properly matched. In contrast, the CO₂ distribution can be fit by invoking poleward transport with a velocity and vigorous eddy mixing (). While the vertical distribution of CO₂ is not measured, the combined HCN and CO₂ results imply that the two species reside at different stratospheric levels. Comparing with the circulation regimes predicted by earlier radiative-dynamical models of Jupiter's stratosphere, and with inferences from the ethane and acetylene stratospheric latitudinal distribution, we suggest that CO₂ lies in the middle stratosphere near or below the 5-mbar level.     

Detection of methane in the martian atmosphere: evidence for life?

Using the Fourier Transform Spectrometer at the Canada-France-Hawaii Telescope, we observed a spectrum of Mars at the P-branch of the strongest CH₄ band at 3.3 μm with resolving power of 180,000 for the apodized spectrum. Summing up the spectral intervals at the expected positions of the 15 strongest Doppler-shifted martian lines, we detected the absorption by martian methane at a 3.7 sigma level which is exactly centered in the summed spectrum. The observed CH₄ mixing ratio is 10±3 ppb. Total photochemical loss of CH₄ in the martian atmosphere is equal to , the CH₄ lifetime is 340 years and methane should be uniformly mixed in the atmosphere. Heterogeneous loss of atmospheric methane is probably negligible, while the sink of CH₄ during its diffusion through the regolith may be significant. There are no processes of CH₄ formation in the atmosphere, so the photochemical loss must therefore be balanced by abiogenic and biogenic sources. Outgassing from Mars is weak, the latest volcanism is at least 10 million years old, and thermal emission imaging from the Mars Odyssey orbiter does not reveal any hot spots on Mars. Hydrothermal systems can hardly be warmer than the room temperature at which production of methane is very low in terrestrial waters. Therefore a significant production of hydrothermal and magmatic methane is not very likely on Mars. The calculated average production of CH₄ by cometary impacts is 2% of the methane loss. Production of methane by meteorites and interplanetary dust does not exceed 4% of the methane loss. Methane cannot originate from an extinct biosphere, as in the case of “natural gas” on Earth, given the exceedingly low limits on organic matter set by the Viking landers and the dry recent history which has been extremely hostile to the macroscopic life needed to generate the gas. Therefore, methanogenesis by living subterranean organisms is a plausible explanation for this discovery. Our estimates of the biomass and its production using the measured CH₄ abundance show that the martian biota may be extremely scarce and Mars may be generally sterile except for some oases.     

The role of organic haze in Titan's atmospheric chemistry: I. Laboratory investigation on heterogeneous reaction of atomic hydrogen with Titan tholin

In Titan's atmosphere consisting of N₂ and CH₄, large amounts of atomic hydrogen are produced by photochemical reactions during the formation of complex organics. This atomic hydrogen may undergo heterogeneous reactions with organic aerosol in the stratosphere and mesosphere of Titan. In order to investigate both the mechanisms and kinetics of the heterogeneous reactions, atomic deuterium is irradiated onto Titan tholin formed from N₂ and CH₄ gas mixtures at various surface-temperatures of the tholin ranging from 160 to 310 K. The combined analyses of the gas species and the exposed tholin indicate that the interaction mechanisms of atomic deuterium with the tholin are composed of three reactions; (a) abstraction of hydrogen from tholin resulting in gaseous HD formation (HD recombination), (b) addition of D atom into tholin (hydrogenation), and (c) removal of carbon and/or nitrogen (chemical erosion). The reaction probabilities of HD recombination and hydrogenation are obtained as ηabst=1.9(±0.6)×¹⁰⁻³×exp(−300/T) and ηhydro=2.08(±0.64)×exp(−1000/T), respectively. The chemical erosion process is very inefficient under the conditions of temperature range of Titan's stratosphere and mesosphere. Under Titan conditions, the rates of hydrogenation > HD recombination ? chemical erosion. Our measured HD recombination rate is about 10 times (with an uncertainty of a factor of 3-5) the prediction of previous theoretical model. These results imply that organic aerosol can remove atomic hydrogen efficiently from Titan's atmosphere through the heterogeneous reactions and that the presence of aerosol may affect the subsequent organic chemistry.