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.     

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.     

Latitudinal variations of HCN, HC3N, and C2N2 in Titan's stratosphere derived from Cassini CIRS data

Mid- and far-infrared spectra from the Composite InfraRed Spectrometer (CIRS) have been used to determine volume mixing ratios of nitriles in Titan's atmosphere. HCN, HC₃N, C₂H₂, and temperature were derived from 2.5 cm⁻¹ spectral resolution mid-IR mapping sequences taken during three flybys, which provide almost complete global coverage of Titan for latitudes south of 60° N. Three 0.5 cm⁻¹ spectral resolution far-IR observations were used to retrieve C₂N₂ and act as a check on the mid-IR results for HCN. Contribution functions peak at around 0.5-5 mbar for temperature and 0.1-10 mbar for the chemical species, well into the stratosphere. The retrieved mixing ratios of HCN, HC₃N, and C₂N₂ show a marked increase in abundance towards the north, whereas C₂H₂ remains relatively constant. Variations with longitude were much smaller and are consistent with high zonal wind speeds. For 90°-20° S the retrieved HCN abundance is fairly constant with a volume mixing ratio of around 1 × 10⁻⁷ at 3 mbar. More northerly latitudes indicate a steady increase, reaching around 4 × 10⁻⁷ at 60° N, where the data coverage stops. This variation is consistent with previous measurements and suggests subsidence over the northern (winter) pole at approximately 2 × 10⁻⁴ m s⁻¹. HC₃N displays a very sharp increase towards the north pole, where it has a mixing ratio of around 4 × 10⁻⁸ at 60° N at the 0.1-mbar level. The difference in gradient for the HCN and HC₃N latitude variations can be explained by HC₃N's much shorter photochemical lifetime, which prevents it from mixing with air at lower latitude. It is also consistent with a polar vortex which inhibits mixing of volatile rich air inside the vortex with that at lower latitudes. Only one observation was far enough north to detect significant amounts of C₂N₂, giving a value of around 9 × 10⁻¹⁰ at 50° N at the 3-mbar level.     

The deep water abundance on Jupiter: New constraints from thermochemical kinetics and diffusion modeling

We have developed a one-dimensional thermochemical kinetics and diffusion model for Jupiter’s atmosphere that accurately describes the transition from the thermochemical regime in the deep troposphere (where chemical equilibrium is established) to the quenched regime in the upper troposphere (where chemical equilibrium is disrupted). The model is used to calculate chemical abundances of tropospheric constituents and to identify important chemical pathways for CO-CH₄ interconversion in hydrogen-dominated atmospheres. In particular, the observed mole fraction and chemical behavior of CO is used to indirectly constrain the jovian water inventory. Our model can reproduce the observed tropospheric CO abundance provided that the water mole fraction lies in the range (0.25-6.0) × 10⁻³ in Jupiter’s deep troposphere, corresponding to an enrichment of 0.3-7.3 times the protosolar abundance (assumed to be H₂O/H₂ = 9.61 × 10⁻⁴). Our results suggest that Jupiter’s oxygen enrichment is roughly similar to that for carbon, nitrogen, and other heavy elements, and we conclude that formation scenarios that require very large (>8× solar) enrichments in water can be ruled out. We also evaluate and refine the simple time-constant arguments currently used to predict the quenched CO abundance on Jupiter, other giant planets, and brown dwarfs.     

The density and temperature structure near the exobase of Saturn from Cassini UVIS solar occultations

We analyzed 15 solar occultations observed by the Cassini UVIS instrument to constrain the density and temperature structure near the exobase of Saturn. We retrieved the density of H₂ and thus the temperature at altitudes higher than 1900 km above the 1 bar level by analyzing the ionization continuum of H₂ at wavelengths shorter than 804 Å. We find that the exospheric temperature ranges from 370 K to 540 K, with a typical uncertainty of less than 20 K. According to our data the temperature increases with latitude from the equator to the poles by 100–150 K. At similar latitudes, the temperature varies by 20–50 K at different times with no evidence for any systematic diurnal trend so far. Based on our data, the exobase of Saturn is 2700–3000 km above the 1 bar level and the thermal escape parameter near the exobase ranges from 260 to 340, implying that thermal escape from Saturn is firmly in the Jeans regime. The mixing ratio of H₂ is close to unity at all altitudes below the exobase. We find that the pressure levels in the thermosphere deviate significantly from a simple spheroid predicted by potential theory. This is consistent with significant meridional temperature variations in the lower thermosphere. A global analysis of the temperature structure at different depths in the atmosphere is required to constrain both the shape and the deposition and redistribution of energy in the upper atmosphere further.     

Modeling chemical growth processes in Titan's atmosphere 2. Theoretical study of reactions between C2H and ethene, propene, 1-butene, 2-butene, isobutene, trimethylethene, and tetramethylethene

Barrierless reactions between unsaturated hydrocarbons and the ethynyl radical (C₂H) can contribute to the growth of organic particulates in the haze-forming regions of Titan's atmosphere as well as in the gas giants and in the interstellar medium. We employed a combination of quantum chemistry and statistical rate theories to characterize reactions between ground state C₂H and seven alkenes of the general structure R₁R₂C^′C^″R₃R₄ containing up to six carbons. The alkenes included ethene (C₂H₄); propene (C₃H₆); 1-butene, 2-butene, and isobutene (C₄H₈); trimethylethene (C₅H₁₀); and tetramethylethene (C₆H₁₂). Density functional theory calculations at the B3LYP/6-31 + G^∗∗ level were used to characterize the adducts, isomers, products, and the intervening transition states for the addition-elimination reactions of all seven species. A multiple-well treatment was then employed to determine the outcome distributions for the range of temperatures and pressures relevant to Titan's atmosphere, the interstellar medium, and the outer atmospheres of the gas giants. Finally, trajectory calculations using an ROMP2 potential energy surface were used to calculate kinetic rates for the ethene + C₂H reaction, where the agreement between the computed and measured values is very good. At low pressure and temperature, vinyl acetylene is a dominant product of several of the reactions, and all of the reactions yield at least one dominant product with both a double and a triple CC bond.     

Estimation of the escape of photoelectrons from Mars in 2004 liberated by the ionization of carbon dioxide and atomic oxygen

Photoelectron peaks in the atmosphere of Mars caused by the ionization of carbon dioxide and atomic oxygen by solar 30.4 nm photons have been observed by the Electron Spectrometer (ELS), a component of the Mars Express (MEx) Analyzer of Space Plasmas and Energetic Atoms (ASPERA-3) experiment. Ionization mostly occurs at the Mars exobase with the majority of the photoionized electron flux trapped in the remanent and induced magnetic field, with a portion of that flux escaping the planet down its tail. Since Mars is overall charge neutral, the number of electrons must be identical to the number of ion charges which escape the planet. An estimate of the fraction of the total number of escaping electrons is obtained for the year 2004, specifically those produced by the ionization of carbon dioxide and atomic oxygen by solar 30.4 nm photons. In achieving this process, an illustrative example pass is used to show how the electron spectrum is adjusted for the potential on the spacecraft; then the region of the electron spectrum which shows photoelectron peaks is integrated over energy, yielding a flux of 5.74 × 10⁶ electrons/(cm² s sr). This technique is then applied to a subset of 22 sample averaged spectra from the 2004 data (5 January 2004 through 25 January 2005), yielding an average result of 4.15 × 10⁶ electrons/(cm² s sr) for the 22 cases. The observation cone of 33.75° is used to integrate over solid angle (assuming the flux is constant), giving 4.39 × 10⁶ electrons/(cm² s). This average value was taken as representative of the full data interval. Frequency of occurrence statistics showing about a 6.2% occurrence rate for the 2004 data is applied to give an average escape flux from Mars of 2.72 × 10⁵ electrons/(cm² s) during 2004. By estimating the outflow area as 1.16 × 10¹⁸ cm² at X = −1.5 R_Mars the electron escape rate of 3.14 × 10²³ electrons/s is obtained. Thus about 9.92 × 10³⁰ electrons or 16.5 Mmole of electrons escaped Mars during 2004 due to the ionization of carbon dioxide and atomic oxygen by the He 30.4 nm line. Due to the caveats of the analysis, these derived escape rates should be considered lower limits on the total electron escape rate from Mars.     

The near-IR spectrum of Titan modeled with an improved methane line list

We have obtained spatially resolved spectra of Titan in the near-infrared J, H and K bands at a resolving power of ∼5000 using the near-infrared integral field spectrometer (NIFS) on the Gemini North 8 m telescope. Using recent data from the Cassini/Huygens mission on the atmospheric composition and surface and aerosol properties, we develop a multiple-scattering radiative transfer model for the Titan atmosphere. The Titan spectrum at these wavelengths is dominated by absorption due to methane with a series of strong absorption band systems separated by window regions where the surface of Titan can be seen. We use a line-by-line approach to derive the methane absorption coefficients. The methane spectrum is only accurately represented in standard line lists down to ∼2.1 μm. However, by making use of recent laboratory data and modeling of the methane spectrum we are able to construct a new line list that can be used down to 1.3 μm. The new line list allows us to generate spectra that are a good match to the observations at all wavelengths longer than 1.3 μm and allow us to model regions, such as the 1.55 μm window that could not be studied usefully with previous line lists such as HITRAN 2008. We point out the importance of the far-wing line shape of strong methane lines in determining the shape of the methane windows. Line shapes with Lorentzian, and sub-Lorentzian regions are needed to match the shape of the windows, but different shape parameters are needed for the 1.55 μm and 2 μm windows. After the methane lines are modeled our observations are sensitive to additional absorptions, and we use the data in the 1.55 μm region to determine a D/H ratio of 1.77 ± 0.20 × 10⁻⁴, and a CO mixing ratio of 50 ± 11 ppmv. In the 2 μm window we detect absorption features that can be identified with the ν₅ + 3ν₆ and 2ν₃ + 2ν₆ bands of CH₃D.     

Atomic and molecular hydrogen budget in Titan’s atmosphere

Using a one-dimensional model, we investigate the hydrogen budget and escape to space in Titan’s atmosphere. Our goal is to study in detail the distributions and fluxes of atomic and molecular hydrogen in the model, while identifying sources of qualitative and quantitative uncertainties. Our study confirms that the escape of atomic and molecular hydrogen to space is limited by the diffusion through the homopause level. The H distribution and flux inside the atmosphere are very sensitive to the eddy diffusion coefficient used above altitude 600 km. We chose a high value of this coefficient 1 × 10⁸ cm² s⁻¹ and a homopause level around altitude 900 km. We find that H flows down significantly from the production region above 500 km to the region [300-500] km, where it recombines into H₂. Production of both H and H₂ also occurs in the stratosphere, mostly from photodissociation of acetylene. The only available observational data to be compared are the escape rate of H deduced from Pioneer 11 and IUE observations of the H torus 1-3 × 10⁹ cm⁻² s⁻¹ and the latest retrieved value of the H₂ mole fraction in the stratosphere: (1.1 ± 0.1) × 10⁻³. Our results for both of these values are at least 50-100% higher, though the uncertainties within the chemical schemes and other aspects of the model are large. The chemical conversion from H to H₂ is essentially done through catalytic cycles using acetylene and diacetylene. We have studied the role of this diacetylene cycle, for which the associated reaction rates are poorly known. We find that it mostly affects C₄ species and benzene in the lower atmosphere, rather than the H profile and the hydrogen budget. We have introduced the heterogenous recombination of hydrogen on the surface of aerosol particles in the stratosphere, and this appears to be a significant process, comparable to the chemical processes. It has a major influence on the H distribution, and consequently on several other species, especially C₃H₄, C₄H₂ and C₆H₆. Therefore, this heterogenous process should be taken into account when trying to understand the stratospheric distribution of these hydrocarbons.     

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].     

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.     

Titan’s atomic hydrogen corona

Based on measurements performed by the Hydrogen Deuterium Absorption Cell (HDAC) aboard the Cassini orbiter, Titan’s atomic hydrogen exosphere is investigated. Data obtained during the T9 encounter are used to infer the distribution of atomic hydrogen throughout Titan’s exosphere, as well as the exospheric temperature.The measurements performed during the flyby are modeled by performing Monte Carlo radiative transfer calculations of solar Lyman-α radiation, which is resonantly scattered on atomic hydrogen in Titan’s exosphere. Two different atomic hydrogen distribution models are applied to determine the best fitting density profile. One model is a static model that uses the Chamberlain formalism to calculate the distribution of atomic hydrogen throughout the exosphere, whereas the second model is a Particle model, which can also be applied to non-Maxwellian velocity distributions.The density distributions provided by both models are able to fit the measurements although both models differ at the exobase: best fitting exobase atomic hydrogen densities of n_H = (1.5 ± 0.5) × 10⁴ cm⁻³ and n_H = (7 ± 1) × 10⁴ cm⁻³ were found using the density distribution provided by both models, respectively. This is based on the fact that during the encounter, HDAC was sensitive to altitudes above about 3000 km, hence well above the exobase at about 1500 km. Above 3000 km, both models produce densities which are comparable, when taking into account the measurement uncertainty.The inferred exobase density using the Chamberlain profile is a factor of about 2.6 lower than the density obtained from Voyager 1 measurements and much lower than the values inferred from current photochemical models. However, when taking into account the higher solar activity during the Voyager flyby, this is consistent with the Voyager measurements. When using the density profile provided by the particle model, the best fitting exobase density is in perfect agreement with the densities inferred by current photochemical models.Furthermore, a best fitting exospheric temperature of atomic hydrogen in the range of T_H = (150-175) ± 25 K was obtained when assuming an isothermal exosphere for the calculations. The required exospheric temperature depends on the density distribution chosen. This result is within the temperature range determined by different instruments aboard Cassini. The inferred temperature is close to the critical temperature for atomic hydrogen, above which it can escape hydrodynamically after it diffused through the heavier background gas.     

Impact-induced N2 production from ammonium sulfate: Implications for the origin and evolution of N2 in Titan’s atmosphere

Chemical reactions and volatile supply through hypervelocity impacts may have played a key role for the origin and evolution of both planetary and satellite atmospheres. In this study, we evaluate the role of impact-induced N₂ production from reduced nitrogen-bearing solids proposed to be contained in Titan’s crust, ammonium sulfate ((NH₄)₂SO₄), for the replenishment of N₂ to the atmosphere in Titan’s history. To investigate the conversion of (NH₄)₂SO₄ into N₂ by hypervelocity impacts, we measured gases released from (NH₄)₂SO₄ that was exposed to hypervelocity impacts created by a laser gun. The sensitivity and accuracy of the measurements were enhanced by using an isotope labeling technique for the target. We obtained the efficiency of N₂ production from (NH₄)₂SO₄ as a function of peak shock pressure ranging from ∼8 to ∼45 GPa. Our results indicate that the initial and complete shock pressures for N₂ degassing from (NH₄)₂SO₄ are ∼10 and ∼25 GPa, respectively. These results suggest that cometary impacts on Titan (i.e., impact velocity v_i > ∼8 km/s) produce N₂ efficiently; whereas satellitesimal impacts during the accretion (i.e., v_i < 4 km/s) produce N₂ only inefficiently. Even when using the proposed small amount of (NH₄)₂SO₄ content in the crust (∼4 wt.%) (Fortes, A.D. et al., 2007. Icarus 188, 139-153), the total amount of N₂ provided through cometary impacts over 4.5 Ga reaches ∼2-6 times the present atmospheric N₂ (i.e., ∼7 × 10²⁰-2 × 10²¹ [mol]) based on the measured production efficiency and results of a hydrodynamic simulation of cometary impacts onto Titan. This implies that cometary impacts onto Titan’s crust have the potential to account for a large part of the present N₂ through the atmospheric replenishment after the accretion.     

A sensitive search for SO2 in the martian atmosphere: Implications for seepage and origin of methane

Mars was observed near the peak of the strongest SO₂ band at 1364-1373 cm⁻¹ with resolving power of 77,000 using the Texas Echelon Cross Echelle Spectrograph on the NASA Infrared Telescope Facility. The observation covered the Tharsis volcano region which may be preferable to search for SO₂. The spectrum shows absorption lines of three CO₂ isotopomers and three H₂O isotopomers. The water vapor abundance derived from the HDO lines assuming D/H = 5.5 times the terrestrial value is 12±1.0 pr. μm, in agreement with the simultaneous MGS/TES observations of 14 pr. μm at the latitudes (50° S to 10° N) of our observation. Summing of spectral intervals at the expected positions of sixteen SO₂ lines puts a 2σ upper limit on SO₂ of 1 ppb. SO₂ may be emitted into the martian atmosphere by seepage and is removed by three-body reactions with OH and O. The SO₂ lifetime, 2 years, is longer than the global mixing time 0.5 year, so SO₂ should be rather uniformly distributed across Mars. Seepage of SO₂ is less than 15,000 tons per year on Mars which is smaller than the volcanic production of SO₂ on the Earth by a factor of 700. Because CH₄/SO₂ is typically 10⁻⁴-10⁻³ in volcanic gases on the Earth, our results show seepage is unlikely to be the source of the recently discovered methane on Mars and therefore strengthen its biogenic origin.     

The aftermath of the July 2009 impact on Jupiter: Ammonia, temperatures and particulates from Gemini thermal infrared spectroscopy

We obtained longitudinally resolved thermal infrared spectra (8-13 μm and 17-25 μm) of Jupiter’s impact debris at the Gemini South Telescope on July 24, 2009; five days after the July 19th collision. These were used to study the mechanisms responsible for the redistribution of thermal energy and material (ammonia and stratospheric particulates) following the impact. Upwelling of (8.5 ± 4.1) × 10¹⁴ g of tropospheric air was sufficient to deposit (6.7 ± 4.1) × 10¹² g of NH₃ over a 6° longitude range above the impact core. The NH₃ was distributed over the 20-80 mbar region with a peak abundance of 1.0 ± 0.6 ppm at 45 mbar. Only a 10th of this abundance was observed over the western ejecta, and it is unlikely that these observations were sensitive to NH₃ entrained in the ballistic plume itself. The pattern of excess thermal energy was markedly different from that of Shoemaker-Levy 9 (SL9), with a localized tropospheric perturbation of 2.0 ± 1.0 K at 200-300 mbar and a broader stratospheric warming of up to 3.5 ± 2.0 K at 10-30 mbar. We find no evidence of residual warmth at p < 1 mbar five days after the impact. The excess thermal energy places lower limits on the total energy of the impact (1.8-15.7 × 10²⁶ ergs), which limits the impactor diameter to 70-510 m (depending on the bulk density chosen for the material).The models of the Gemini spectra required three distinct aerosol features, indicative of the mineralogy of the dark particulate debris, centred at 9.1, 10.0 and 18.5 μm. The retrieved opacities for each of these features were distributed over a larger area (9-10° longitude) and at higher altitudes (above the 10-mbar level) than the stratospheric NH₃, and they are more spatially inhomogeneous. This implies the particulates were either entrained with the rising hot plume or created upon plume re-entry and are subsequently redistributed by stratospheric winds. The three particulate features were consistent with a mixture of amorphous iron and magnesium-rich silicates and silicas in the debris field. A broad 10-μm signature was coincident with peaks expected from material rich in amorphous olivines (but poor in pyroxenes), and similar to silicate features observed during SL9. A narrow 9.1-μm signature was interpreted as a combination of amorphous and crystalline silica. Finally, a broad 18.5-μm emitter was not adequately reproduced by a mixture of simple olivines and pyroxenes and remains to be identified.     

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.     

Kinetic studies at room temperature of the cyanide anion CN with cyanoacetylene (HC3N) reaction

Rate coefficient of the cyanide anion (CN⁻) with cyanoacetylene (HC₃N) reaction, has been studied in gas phase at room temperature using a Flowing Afterglow Langmuir Probe - Mass Spectrometer (FALP-MS) apparatus. The rate constant for the CN⁻ + HC₃N reaction is k = 4.8 × 10⁻⁹ cm³/s with an uncertainty of 30%.     

The lunar exosphere: The sputtering contribution

We have extended our Monte Carlo model of exospheres [Wurz, P., Lammer, H., 2003. Icarus 164 (1), 1-13] by treating the ion-induced sputtering process from a known surface in a self-consistent way. The comparison of the calculated exospheric densities with experimental data, which are mostly upper limits, shows that all of our calculated densities are within the measurement limits. The total calculated exospheric density at the lunar surface of about 1×¹⁰⁷ m⁻³ as result of solar wind sputtering we find is much less than the experimental total exospheric density of about ¹⁰¹² m⁻³. We conclude that sputtering contributes only a small fraction of the total exosphere, at least close to the surface. Because of the considerably larger scale height of atoms released via sputtering into the exosphere, sputtered atoms start to dominate the exosphere at altitudes exceeding a few 1000 km, with the exception of some light and abundant species released thermally, e.g. H₂, He, CH₄, and OH. Furthermore, for more refractory species such as calcium, our model indicates that sputtering may well be the dominant mechanism responsible for the lunar atmospheric inventory, but observational data does not yet allow firm conclusions to be drawn.     

Monte Carlo modeling of Io’s [OI] 6300 Å and [SII] 6716 Å auroral emission in eclipse

We present a Monte Carlo (MC) model of [OI] 6300 Å and [SII] 6716 Å emission from Io entering eclipse. The simulation accounts for the 3-D distribution of SO₂, O, SO, S, and O₂ in Io’s atmosphere, several volcanic plumes, and the magnetic field around Io. Thermal electrons from the jovian plasma torus are input along the simulation domain boundaries and move along the magnetic field lines distorted by Io, occasionally participating in collisions with neutrals. We find that the atmospheric asymmetry resulting from varying degrees of atmospheric collapse across Io (due to eclipse ingress) and the presence of volcanoes contributes significantly to the unique morphology of the [OI] 6300 Å emission. The [OI] radiation lifetime of ∼134 s limits the emission to regions that have a sufficiently low neutral density so that intermolecular collisions are rare. We find that at low altitudes (typically <40 km) and in volcanic plumes (Pele, Prometheus, etc.) the number density is large enough (>4 × 10⁹ cm⁻³) to collisionally quench nearly all (>95%) of the excited oxygen for reasonable quenching efficiencies. Upstream (relative to the plasma flow), Io’s perturbation of the jovian magnetic field mirrors electrons with high pitch angles, while downstream collisions can trap the electrons. This magnetic field perturbation is one of the main physical mechanisms that results in the upstream/downstream brightness asymmetry in [OI] emission seen in the observation by Trauger et al. (Trauger, J.T., Stapelfeldt, K.R., Ballester, G.E., Clarke, J.I., 1997. HST observations of [OI] emissions from Io in eclipse. AAS-DPS Abstract (1997DPS29.1802T)). There are two other main causes for the observed brightness asymmetry. First, the observation’s viewing geometry of the wake spot crosses the dayside atmosphere and therefore the wake’s observational field of view includes higher oxygen column density than the upstream side. Second, the phased entry into eclipse results in less atmospheric collapse and thus higher collisional quenching on the upstream side relative to the wake. We compute a location (both in altitude and latitude) for the intense wake emission feature that agrees reasonably well with this observation. Furthermore, the peak intensity of the simulated wake feature is less than that observed by a factor of ∼3, most likely because our model does not include direct dissociation-excitation of SO₂ and SO. We find that the latitudinal location of the emission feature depends not so much on the tilt of the magnetic field as on the relative north/south flux tube depletion that occurs due to Io’s changing magnetic latitude in the plasma torus. From 1-D simulations, we also find that the intensity of [SII] 6716 and 6731 Å emission is much weaker than that of [OI] even if the [SII] excitation cross section is 10³ times larger than excitation to [OI]. This is because the density of S⁺ is much less than that of O and because the Einstein-A coefficient of the [SII] emission is a factor of ∼10 smaller than that of [OI].     

Orbital effects on Mercury’s escaping sodium exosphere

We present results from coronagraphic imaging of Mercury’s sodium tail over a 7° field of view. Several sets of observations made at the McDonald Observatory since May 2007 show a tail of neutral sodium atoms stretching more than 1000 Mercury radii (R_m) in length, or a full degree of sky. However, no tail was observed extending beyond 120 R_m during the January 2008 MESSENGER fly-by period, or during a similar orbital phase of Mercury in July 2008. Large changes in Mercury’s heliocentric radial velocity cause Doppler shifts about the Fraunhofer absorption features; the resultant change in solar flux and radiation pressure is the primary cause of the observed variation in tail brightness. Smaller fluctuations in brightness may exist due to changing source rates at the surface, but we have no explicit evidence for such changes in this data set. The effects of radiation pressure on Mercury’s escaping atmosphere are investigated using seven observations spanning different orbital phases. Total escape rates of atmospheric sodium are estimated to be between 5 and 13 × 10²³ atoms/s and show a correlation to radiation pressure. Candidate sources of Mercury’s sodium exosphere include desorption by UV sunlight, thermal desorption, solar wind channeled along Mercury’s magnetic field lines, and micro-meteor impacts. Wide-angle observations of the full extent of Mercury’s sodium tail offer opportunities to enhance our understanding of the time histories of these source rates.