The radiolysis of SO2 and H2S in water ice: Implications for the icy jovian satellites

Spectra of Europa, Ganymede, and Callisto reveal surfaces dominated by frozen water, hydrated materials, and minor amounts of SO₂, CO₂, and H₂O₂. These icy moons undergo significant bombardment by jovian magnetospheric radiation (protons, electrons, and sulfur and oxygen ions) which alters their surface compositions. In order to understand radiation-induced changes on icy moons, we have measured the mid-infrared spectra of 0.8 MeV proton-irradiated SO₂, H₂S, and H₂O-ice mixtures containing either SO₂ or H₂S. Samples with H₂O/SO₂ or H₂O/H₂S ratios in the 3-30 range have been irradiated at 86, 110, and 132 K, and the radiation half-lives of SO₂ and H₂S have been determined. New radiation products include the H₂S₂ molecule and HSO⁻₃, HSO⁻₄, and SO²⁻₄ ions, all with spectral features that make them candidates for future laboratory work and, perhaps, astronomical observations. Spectra of both unirradiated and irradiated ices have been recorded as a function of temperature, to examine thermal stability and phase changes. The formation of hydrated sulfuric acid in irradiated ice mixtures has been observed, along with the thermal evolution of hydrates to form pure sulfuric acid. These laboratory studies provide fundamental information on likely processes affecting the outer icy shells of Europa, Ganymede, and Callisto.     

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.     

Near-infrared laboratory spectra of solid H2O/CO2 and CH3OH/CO2 ice mixtures

We present near-IR spectra of solid CO₂ in H₂O and CH₃OH, and find they are significantly different from that of pure solid CO₂. Peaks not present in either pure H₂O or pure CO₂ spectra become evident when the two are mixed. First, the putative theoretically forbidden CO₂ (2ν₃) overtone near 2.134 μm (4685 cm⁻¹), that is absent from our spectrum of pure solid CO₂, is prominent in the spectra of H₂O/CO₂=5 and 25 mixtures. Second, a 2.74-μm (3650 cm⁻¹) dangling OH feature of H₂O (and a potentially related peak at 1.89 μm) appear in the spectra of CO₂-H₂O ice mixtures, but are probably not diagnostic of the presence of CO₂. Other CO₂ peaks display shifts in position and increased width because of intermolecular interactions with H₂O. Warming causes some peak positions and profiles in the spectrum of a H₂O/CO₂=5 mixture to take on the appearance of pure CO₂. Absolute strengths for absorptions of CO₂ in solid H₂O are estimated. Similar results are observed for CO₂ in solid CH₃OH. Since the CO₂ (2ν₃) overtone near 2.134 μm (4685 cm⁻¹) is not present in pure CO₂ but prominent in mixtures, it may be a good observational (spectral) indicator of whether solid CO₂ is a pure material or intimately mixed with other molecules. These observations may be applicable to Mars polar caps as well as outer Solar System bodies.     

CO2 production by ion irradiation of H2O ice on top of carbonaceous materials and its relevance to the Galilean satellites

In this work we report on new experiments of ion irradiation of water ice deposited on top of solid carbonaceous materials to study the production of CO₂ at the interface ice/refractory material and discuss the possibility that this mechanism accounts for the quantity of CO₂ ice detected on the surfaces of the Galilean satellites. The used experimental technique has been in situ infrared spectroscopy. We have irradiated thin films of H₂O frost on carbonaceous layers with 200 keV of He⁺ and Ar⁺, and 30 keV of He⁺ at 16 and 80 K. The used carbonaceous layers have been asphaltite, a natural bitumen, and solid organic residues obtained by irradiation of frozen benzene. In both cases the results show that CO₂ is produced very efficiently after irradiation obtaining a maximum quantity of the order of . These results are, also quantitatively similar, to those recently obtained for water ice deposited on amorphous carbon films [Mennella, V., Palumbo, M.E., Baratta, G.A., 2004. Formation of CO and CO₂ molecules by ion irradiation of water ice covered hydrogenated carbon grains. Astrophys. J. 615, 1073-1080]. Thus we suggest that, whatever is the carbonaceous residue, CO₂ will be produced efficiently by the studied process. These results have interest in the context of the surfaces of the icy Galilean satellites in which CO₂ has been detected mainly trapped in the non-ice material, not in the pure water ice. We suggest that radiolysis of mixtures of water ice and refractory carbonaceous materials is the primary formation mechanism responsible for the CO₂ formation on the surfaces of the Galilean satellites.     

Extreme Ultraviolet Photon-Induced Chemical Reactions in the C2H2-H2O Mixed Ices at 10 K

Experimental results on the spectral identification of new infrared absorption features and the changes of their absorbances produced through vacuum ultraviolet-extreme ultraviolet (VUV-EUV) photon-induced chemical reactions in the C₂H₂-H₂O mixed ices at 10 K are obtained. To the best of our knowledge, this is the first time that EUV photons have been employed in the study of the photolysis of ice analogues. Two different compositions, i.e., C₂H₂:H₂O=1:4 and 1:1, were investigated in this work. A tunable intense synchrotron radiation light source available at the Synchrotron Radiation Research Center, Hsinchu, Taiwan, was employed to provide the required VUV-EUV photons. In this study, the photon wavelengths selected to irradiate the icy samples corresponded to the prominent solar hydrogen, helium, and helium ion lines at 121.6 nm, 58.4 nm, and 30.4 nm, respectively. The photon dosages used were typically in the range of 1×10¹⁵ to 2×10¹⁷ photons. Molecular species produced and identified in the ice samples at 10 K resulting from VUV-EUV photon irradiation are mainly CO, CO₂, CH₄, C₂H₆, CH₃OH, and H₂CO. In addition to several unidentified features, we have tentatively assigned several absorption features to HCO, C₃H₈, and C₂H₅OH. While new molecular species were formed, the original reactants, i.e., H₂O and C₂H₂, were detectably depleted due to their conversion to other species. The new chemical species produced by irradiation of photons at 30.4 nm and 58.4 nm can be different from those produced by the 121.6-nm photolysis. In general, the product column density of CO reaches saturation at a lower photon dosage than that of CO₂. Furthermore, the production yield of CO is higher than that of CO₂ in the photon irradiation. In the present study, we also observe that the photon-induced chemical reaction yields are high using photons at 30.4 and 58.4 nm. The results presented in this work are essential to our understanding of chemical synthesis in ice analogues, e.g., the cometary-type ices and icy satellites of planetary systems.     

An experimental study of the reaction kinetics of C2(XΣg) with hydrocarbons (CH4, C2H2, C2H4, C2H6 and C3H8) over the temperature range 24-300 K: Implications for the atmospheres of Titan and the Giant Planets

The reactivity of C₂(X¹Σ⁺_g) with simple saturated (CH₄, C₂H₆ and C₃H₈) and unsaturated (C₂H₂ and C₂H₄) hydrocarbons has been studied in the gas phase over the temperature range 24-300 K using the CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in a Uniform Supersonic Flow) technique. All reactions have been found to be very rapid in this temperature range and the rate coefficients are typically ?10⁻¹⁰ cm³ molecule⁻¹ s⁻¹ with the exception of methane for which the rate coefficient is one order of magnitude lower: ∼10⁻¹¹ cm³ molecule⁻¹ s⁻¹. These results have been analyzed in terms of potential destruction sources of C₂(X¹Σ⁺_g) in the atmospheres of Titan and the Giant Planets. It appears that the rate coefficient of the reaction ¹C₂ + CH₄ should be updated with our new data and that reactions with C₂H₂, C₂H₄ and C₂H₆ should also be included in the existing photochemical models.     

Spatially-resolved high-resolution spectroscopy of Venus 2. Variations of HDO, OCS, and SO2 at the cloud tops

While CO, HCl, and HF, that were considered in the first part of this work, have distinct absorption lines in high-resolution spectra and were detected four decades ago, the lines of HDO, OCS, and SO₂ are either very weak or blended by the telluric lines and have not been observed previously by ground-based infrared spectroscopy at the Venus cloud tops. The H₂O abundance above the Venus clouds is typically below the detection limit of ground-based IR spectroscopy. However, the large D/H ratio on Venus facilitates observations of HDO. Converted to H₂O with D/H ≈ 200, our observations at 2722 cm⁻¹ in the Venus afternoon show a H₂O mixing ratio of ∼1.2 ppm at latitudes between ±40° increasing to ±60° by a factor of 2. The observations in the early morning reveal the H₂O mixing ratio that is almost constant at 2.9 ppm within latitudes of ±75°. The measured H₂O mixing ratios refer to 74 km. The observed increase in H₂O is explained by the lack of photochemical production of sulfuric acid in the night time. The recent observations at the P-branch of OCS at 4094 cm⁻¹ confirm our detection of OCS. Four distributions of OCS along the disk of Venus at various latitudes and local times have been retrieved. Both regular and irregular components are present in the variations of OCS. The observed OCS mixing ratio at 65 km varies from ∼0.3 to 9 ppb with the mean value of ∼3 ppb. The OCS scale height is retrieved from the observed limb darkening and varies from 1 to 4 km with a mean value of half the atmospheric scale height. SO₂ at the cloud tops has been detected for the first time by means of ground-based infrared spectroscopy. The SO₂ lines look irregular in the observed spectra at 2476 cm⁻¹. The SO₂ abundances are retrieved by fitting by synthetic spectra, and two methods have been applied to determine uncertainties and detection limits in this fitting. The retrieved mean SO₂ mixing ratio of 350 ± 50 ppb at 72 km favors a significant increase in SO₂ above the clouds since the period of 1980-1995 that was observed by the SOIR occultations at Venus Express. Scale heights of OCS and SO₂ may be similar, and the SO₂/OCS ratio is ∼500 and may be rather stable at 65-70 km under varying conditions on Venus.     

Hydrogen from Jupiter's atmosphere in the Jovian magnetosphere

The passage of Ulysses through Jupiter's magnetosphere presents a new opportunity to investigate the contribution to the Jovian magnetosphere of ions of atmospheric origin. A determination of the magnetospheric H⁺/He²⁺ flux ratio allows an estimate of the relative abundance of ionospheric material in the Jovian magnetosphere. We find that the H⁺/He²⁺ flux ratio, measured in the energy/charge range between 0.65 and 60 keV/e, steadily increases from a solar wind level of 25 at the magnetopause to a value of 700 at the point of closest approach, and then steadily decreases whilst approaching the magnetopause on the outbound path. We conclude from this that: (1) there is a significant solar wind component throughout the outer and middle magnetosphere; and (2) a significant fraction of the protons in the middle magnetosphere are of nonsolar origin.     

The role of ion-molecule reactions in the conversion of N2O5 to HNO3 in the stratosphere

We have investigated the role of several ion-molecule reactions in the conversion of N₂O₅ to HNO₃. In the proposed conversion, an N₂O₅ molecule would react with an H₂O molecule clustered to an inert ion to produce two HNO₃ molecules. Subsequent clustering of an H₂O molecule to the inert ion would make the reaction catalytic. If such an ion-catalysed conversion of N₂O₅ to HNO₃ occurs, it would probably play a role in the stratospheric chemistry at high latitudes in winter. In this paper we present reaction rate constant measurements made in a flowing afterglow apparatus for hydrated H₃O⁺, H⁺(CH₃CN)_m (m = 1, 2, 3), and several negative ions reacting with N₂O₅. Slow rate constants were found for these ions for hydration levels that are predominant in the stratosphere. With the known stratospheric ion density, these slow rate constants preclude significant N₂O₅ conversion by ion-molecule reactions.     

Experimental impact shock chemistry on planetary icy satellites

We present new experimental results on impact shock chemistry into icy satellites of the outer planets. Icy mixtures of pure water ice with CO₂, Na₂CO₃, CH₃OH, and CH₃OH/(NH₄)₂SO₄ at 77 K were ablated with a powerful pulsed laser—a new technique used to simulate shock processes which can occur during impacts. New products were identified by GC-MS and FTIR analyses after laser ablation. Our results show that hydrogen peroxide is formed in irradiated H₂O/CO₂ ices with a final concentration of 0.23%. CO and CH₃OH were also detected as main products. The laser ablation of frozen H₂O/Na₂CO₃ generates only CO and CO₂ as destruction products from the salt. Pulsed irradiation of water ice containing methanol leads also to the formation of CO and CO₂, generates methane and more complex molecules containing carbonyl groups like acetaldehyde, acetone, methyl formate, and a diether, dimethyl formal. The last three compounds are also produced when adding ammonium sulfate to H₂O/CH₃OH ice, but acetone is more abundant. The formation of two hydrocarbons, CH₄ and C₂H₆ is observed as well as the production of three nitrogen compounds, nitrous oxide, hydrogen cyanide, and acetonitrile.     

Meridional variations of C2H2 and C2H6 in Jupiter's atmosphere from Cassini CIRS infrared spectra

Hydrocarbons such as acetylene (C₂H₂) and ethane (C₂H₆) are important tracers in Jupiter's atmosphere, constraining our models of the chemical and dynamical processes. However, our knowledge of the vertical and meridional variations of their abundances has remained sparse. During the flyby of the Cassini spacecraft in December 2000, the Composite Infrared Spectrometer (CIRS) instrument was used to map the spatial variation of emissions from 10 to 1400 cm⁻¹ (1000-7 μm). In this paper we analyze a zonally averaged set of CIRS spectra taken at the highest (0.48 cm⁻¹) resolution, firstly to infer atmospheric temperatures in the stratosphere at 0.5-20 mbar via the ν₄ band of CH₄, and in the troposphere at 150-400 mbar, via the H₂ absorption at 600-800 cm⁻¹. Stratospheric temperatures at 5 mbar are generally warmer in the north than the south by 7-8 K, while tropospheric temperatures show no such asymmetry. Both latitudinal temperature profiles however do show a pattern of maxima and minima which are largely anti-correlated between the two levels. We then use the derived temperature profiles to infer the vertical abundances of C₂H₂ and C₂H₆ by modeling tropospheric absorption (∼200 mbar) and stratospheric emission (∼5 mbar) in the C₂H₂ν₅ and C₂H₆ν₉ bands, and also emission of the acetylene (ν₄+ν₅)−ν₄ hotband (∼0.1 mbar). Acetylene shows a distinct north-south asymmetry in the stratosphere, with 5 mbar abundances greatest close to 20° N and decreasing from there towards both poles by a factor of ∼4. At 200 mbar in contrast, acetylene is nearly flat at a level of ∼3×¹⁰⁻⁹. Additionally, the abundance gradient of C₂H₂ between 10 and 0.1 mbar is derived, based on interpolated temperatures at 0.1 mbar, and is found to be positive and uniform with latitude to within errors. Ethane at both 5 and 200 mbar shows increasing VMR towards polar regions of ∼1.75 towards 70° N and ∼2.0 towards 70° S. An explanation for the meridional trends is proposed in terms of a combination of photochemistry and dynamics. Poleward, the decreasing UV flux is predicted to decrease the abundances of C₂H₂ and C₂H₆ by factors of 2.7 and 3.5, respectively, at latitude 70°. However, the lifetime of C₂H₆ in the stratosphere (3×¹⁰¹⁰ s at 5 mbar) is much longer than the dynamical timescale for meridional mixing inferred from Comet SL-9 debris (5-50×¹⁰⁸ s), and therefore the rising abundance towards high latitudes likely indicates that meridional mixing dominates over photochemical effects. For C₂H₂, the opposite occurs, with the relatively short photochemical lifetime (3×¹⁰⁷ s), compared to meridional mixing times, ensuring that the expected photochemical trends are visible.     

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.     

Sulfur chemistry in the Venus mesosphere from SO2 and SO microwave spectra

First measurements of SO₂ and SO in the Venus mesosphere (70-100 km) are reported. This altitude range is distinctly above the ∼60-70 km range to which nadir-sounding IR and UV investigations are sensitive. Since July 2004, use of ground-based sub-mm spectroscopy has yielded multiple discoveries. Abundance of each molecule varies strongly on many timescales over the entire sub-Earth Venus hemisphere. Diurnal behavior is evident, with more SO₂, and less SO, at night than during the day. Non-diurnal variability is also present, with measured SO₂ and SO abundances each changing by up to 2× or more between observations conducted on different dates, but at fixed phase, hence identical sub-Earth Venus local times. Change as large and rapid as a 5σ doubling of SO on a one-week timescale is seen. The sum of SO₂ and SO abundances varies by an order of magnitude or more, indicating at least one additional sulfur reservoir must be present, and that it must function as both a sink and source for these molecules. The ratio SO₂/SO varies by nearly two orders of magnitude, with both diurnal and non-diurnal components. In contrast to the strong time dependence of molecular abundances, their altitude distributions are temporally invariant, with far more SO₂ and SO at 85-100 km than at 70-85 km. The observed increase of SO₂ mixing ratio with altitude requires that the primary SO₂ source be upper mesospheric photochemistry, contrary to atmospheric models which assert upward transport as the only source of above-cloud SO₂. Abundance of upper mesospheric aerosol, with assumption that it is composed primarily of sulfuric acid, is at least sufficient to provide the maximum gas phase (SO + SO₂) sulfur reported in this study. Sulfate aerosol is thus a plausible source of upper mesospheric SO₂.     

Physisorption of CO2 on non-ice materials relevant to icy satellites

CO₂ is known to adsorb onto clay and other minerals when a significant atmospheric pressure is present. We have found that CO₂ can also adsorb onto some clays when the CO₂ partial pressure is effectively zero under ultra-high vacuum (UHV) if cooled to the surface temperatures of the icy satellites of Jupiter and Saturn. The strength of adsorption and the spectral characteristics of the adsorbed CO₂ infrared (IR) ν₃ absorption band near 4.25 μm depend on the composition and temperature of the adsorbent. CO₂ remains adsorbed onto the clay mineral montmorillonite for >10 s of min when exposed to a vacuum of ∼1×¹⁰⁻⁸ Torr at ∼125 K. CO₂ does not adsorb onto serpentine, goethite, or palagonite under these conditions. A small amount may adsorb onto kaolinite. When heated above 150 K under vacuum, the CO₂ desorbs from the montmorillonite within a few minutes. The ν₃ absorption band of CO₂ adsorbed onto montmorillonite at 125 K is similar to that of the CO₂ detected on the saturnian and Galilean satellites and is markedly different from CO₂ adsorbed onto montmorillonite at room temperature. We infer the adsorption process is physisorption and postulate that this mechanism may explain the presence and spectral characteristics of the CO₂ detected in the surfaces of these outer satellites.     

Stratospheric in situ measurements of H2SO4 and HSO3 vapors during a volcanically active period

In situ measurements of stratospheric H₂SO₄ and HSO₃vapors using passive chemical ionization mass spectrometry were made in October 1982 after the eruption of volcano El Chichon. Data were obtained between about 20 and 41 km showing [H₂SO₄ + HSO₃] sum concentrations between about 10⁴ and 2 × 10⁵ cm^?3 below 29 km and a steep rise above this altitude. Maximum [H₂SO₄ + HSO₃] values of about 3 × 10⁶ cm^?3 are reached above 35 km.Partial [HSO₃] concentrations increase above 34 km reaching about $\text{4 × 10}{}^5\text{cm}{}^{\mathrm{?3}}$ around 40 km. From the measurements it is concluded that H₂SO₄ and probably HSO₃photolysis have an important influence above 34 km leading to the observed increase of [HSO₃] and a depletion of H₂SO₄vapor.It also seems that the data support the view of heterogeneous HSO₃ removal. If correct, this would imply that stratospheric aerosols are formed primarily from HSO₃ rather than H₂SO₄vapor.     

Serpentinization and the inorganic synthesis of H2 in planetary surfaces

The near-surface inorganic synthesis of molecular hydrogen (H₂) is a fundamental process relevant to the origins and to the sustenance of early life on Earth and potentially other planets. Hydrogen production through the decomposition of water is thought to be a principal reaction that occurs during hydrothermal alteration of olivine, an iron-magnesium silicate abundant near planetary surfaces. We demonstrate that copious amounts of H₂ are produced only when the olivine undergoing alteration (serpentinization) contains 1 to 50 mol% iron over a variety of planetary surface P-T conditions. This suggests that extrasolar Earth-like planets that are hosted by a star with iron contents up to two times the solar value could support life provided they are hydrothermally active and fall within the habitable zone around the star.     

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.     

Ion irradiation of H2O ice on top of sulfurous solid residues and its relevance to the Galilean satellites

In this paper we present the results of new experiments of ion irradiation of water ice deposited on top of a solid sulfurous residue to study the potential formation of SO₂ at the interface ice/refractory material and discuss the possibility that this mechanism accounts for the sulfur dioxide ice detected on the surfaces of the Galilean satellites. In situ infrared spectroscopy was the used experimental technique. We have irradiated a thin film of H₂O frost on a sulfurous layer with 200 keV of He⁺ at 80 K. The used sulfurous residue was obtained by irradiation of frozen SO₂ at 16 K and it is used as a template of sulfur bearing solid materials. We have not found evidences of the efficient formation of SO₂ after irradiation of H₂O ice on top of the sulfurous residue. An upper limit to the production yield of SO₂, of interface area for each 100 eV of energy absorbed in 1 cm³ of ice-covered residue, has been estimated. These results have relevance in the context of the surfaces of the icy Galilean satellites in which SO₂ was detected. Our results show that radiolysis of mixtures of water ice and refractory sulfurous materials is not the primary formation mechanism responsible for the SO₂ present on the surfaces of the Galilean satellites.     

Carbon dioxide segregation in 1:4 and 1:9 CO2:H2O ices

The mid-infrared spectra of mixed vapor deposited ices of CO₂ and H₂O were studied as a function of both deposition temperature and warming from 15 to 100 K. The spectra of ices deposited at 15 K show marked changes on warming beginning at 60 K. These changes are consistent with CO₂ segregating within the ice matrix into pure CO₂ domains. Ices deposited at 60 and 70 K show a greater degree of segregation, as high as 90% for 1:4 CO₂:H₂O ice mixtures deposited at 70 K. As the ice is warmed above 80 K, preferential sublimation of the segregated CO₂ is observed. The kinetics of the segregation process is also examined. The segregation of the CO₂ as the ice is warmed corresponds to temperatures at which the structure of the water ice matrix changes from the high density amorphous phase to the low density amorphous phase. We show how these microstructural changes in the ice have a profound effect on the photochemistry induced by ultraviolet irradiation. These experimental results provide a framework in which observations of CO₂ on the icy bodies of the outer Solar System can be considered.     

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.