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.     

H-implantation in SO2 and CO2 ices

Ices in the solar system are observed on the surface of planets, satellites, comets and asteroids where they are continuously subordinate at particle fluxes (cosmic ions, solar wind and charged particles caught in the magnetosphere of the planets) that deeply modify their physical and structural properties. Each incoming ion destroys molecular bonds producing fragments that, by recombination, form new molecules also different from the original ones. Moreover, if the incoming ion is reactive (H⁺, Oⁿ⁺, Sⁿ⁺, etc.), it can concur to the formation of new molecules.Those effects can be studied by laboratory experiments where, with some limitation, it is possible to reproduce the astrophysical environments of planetary ices.In this work, we describe some experiments of 15-100 keV H⁺ and He⁺ implantation in pure sulfur dioxide (SO₂) at 16 and 80 K and carbon dioxide (CO₂) at 16 K ices aimed to search for the formation of new molecules. Among other results we confirm that carbonic acid (H₂CO₃) is formed after H-implantation in CO₂, vice versa H-implantation in SO₂ at both temperatures does not produce measurable quantity of sulfurous acid (H₂SO₃). The results are discussed in the light of their relevance to the chemistry of some solar system objects, particularly of Io, the innermost of Jupiter's Galilean satellites, that exhibits a surface very rich in frost SO₂ and it is continuously bombarded with H⁺ ions caught in Jupiter's magnetosphere.     

Trapping of N2, CO and Ar in amorphous ice—Application to comets

Recent attempts using high resolution spectra to detect N⁺₂ in several comets were unsuccessful [Cochran, A.L., Cochran, W.D., Baker, E.S., 2000. Icarus 146, 583-593; Cochran, A.L., 2002. Astrophys. J. 576, L165-L168]. The upper limits on N⁺₂ in comparison with the positively detected CO⁺ for Comets C/1995 O1 Hale-Bopp, 122P/1995 S1 de Vico and 153P/2002 C1 Ikeya-Zhang range between . Ar was not detected in three recent comets [Weaver, H.A., Feldman, P.D., Combi, M.R., Krasnopolsky, V., Lisse, C.M., Shemansky, D.E., 2002. Astrophys. J. 576, L95-L98], with upper limits of Ar/CO<(3.4-7.8)×¹⁰⁻² for Comets C/1999 T1 McNaught-Hartley, C/2001 A2 LINEAR and C/2000 WM1 LINEAR. The Ar detected by Stern et al. [Stern, S.A., Slater, D.C., Festou, M.C., Parker, J.Wm., Gladstone, G.R., A'Hearn, M.F., Wilkinson, E., 2000. Astrophys. J. 544, L169-L172] for Comet C/1995 O1 Hale-Bopp, gives a ratio Ar/CO=7.25×¹⁰⁻², which was not confirmed by Cosmovici et al. [Cosmovici, C.B., Bratina, V., Schwarz, G., Tozzi, G., Mumma, M.J., Stalio, R., 2006. Astrophys. Space Sci. 301, 135-143]. Trying to solve the two problems, we studied experimentally the trapping of N₂+CO+Ar in amorphous water ice, at 24-30 K. CO was found to be trapped in the ice 20-70 times more efficiently than N₂ and with the same efficiency as Ar. The resulting Ar/CO ratio of 1.2×¹⁰⁻² is consistent with Weaver et al.'s [Weaver, H.A., Feldman, P.D., Combi, M.R., Krasnopolsky, V., Lisse, C.M., Shemansky, D.E., 2002. Astrophys. J. 576, L95-L98] non-detection of Ar. However, with an extreme starting value for N₂/CO = 0.22 in the region where the ice grains which agglomerated to produce comet nuclei were formed, the expected N₂/CO ratio in the cometary ice should be 6.6×¹⁰⁻³, much higher than its non-detection limit.     

Production, ionization and redistribution of O2 in Saturn's ring atmosphere

Molecular oxygen produced by the decomposition of icy surfaces is ubiquitous in Saturn's magnetosphere. A model is described for the toroidal O₂ atmosphere indicated by the detection of and O⁺ over the main rings. The O₂ ring atmosphere is produced primarily by UV photon-induced decomposition of ice on the sunlit side of the ring. Because O₂ has a long lifetime and interacts frequently with the ring particles, equivalent columns of O₂ exist above and below the ring plane with the scale height determined by the local ring temperature. Energetic particles also decompose ice, but estimates of their contribution over the main rings appear to be very low. In steady state, the O₂ column density over the rings also depends on the relative efficiency of hydrogen to oxygen loss from the ring/atmosphere system with oxygen being recycled on the grain surfaces. Unlike the neutral density, the ion densities can differ on the sunlit and shaded sides due to differences in the ionization rate, the quenching of ions by the interaction with the ring particles, and the northward shift of the magnetic equator relative to the ring plane. Although O⁺ is produced with a significant excess energy, is not. Therefore, should mirror well below those altitudes at which ions were detected. However, scattering by ion-molecule collisions results in much larger mirror altitudes, in ion temperatures that go through a minimum over the B-ring, and in the redistribution of both molecular hydrogen and oxygen throughout the magnetosphere. The proposed model is used to describe the measured oxygen ion densities in Saturn's toroidal ring atmosphere and its hydrogen content. The oxygen ion densities over the B-ring appear to require either significant levels of UV light scattering or ion transmission through the ring plane.     

Synthesis of hydrogen peroxide in water ice by ion irradiation

We present infrared absorption studies on the effects of 50-100 keV Ar⁺ and 100 keV H⁺ ion irradiation of water ice films at 20-120 K. The results support the view that energetic ions can produce hydrogen peroxide on the surface of icy satellites and rings in the outer Solar System, and on ice mantles on interstellar grains. The ion energies are characteristic of magnetospheric ions at Jupiter, and therefore the results support the idea that radiolysis by ion impact is the source of the H₂O₂ detected on Europa by the Galileo infrared spectrometer. We found that Ar⁺ ions, used to mimic S⁺ impacts, are roughly as efficient as H⁺ ions in producing H₂O₂, and that 100 keV H⁺ ions can produce hydrogen peroxide at 120 K. The synthesized hydrogen peroxide remained stable while warming the ice film after irradiation; the column density of the formed H₂O₂ is constant until the ice film begins to desorb, but the concentration of H₂O₂ increases with time during desorption because the water sublimes at a faster rate. Comparing the shape of the 3.5-μm absorption feature of H₂O₂ to the one measured on Europa shows excellent agreement in both shape and position, further indicating that the H₂O₂ detected on Europa is likely caused by radiolysis of water ice.     

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.     

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.     

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.     

Formation of radical species in photolyzed CH4:N2 ices

We report photochemical studies of thin cryogenic ice films composed of N₂, CH₄ and CO in ratios analogous to those on the surfaces of Neptune’s largest satellite, Triton, and on Pluto. Experiments were performed using a hydrogen discharge lamp, which provides an intense source of ultraviolet light to simulate the sunlight-induced photochemistry on these icy bodies. Characterization via infrared spectroscopy showed that C₂H₆ and C₂H₂, and HCO are formed by the dissociation of CH₄ into H, CH₂ and CH₃ and the subsequent reaction of these radicals within the ice. Other radical species, such as C₂, , CN, and CNN, are observed in the visible and ultraviolet regions of the spectrum. These species imply a rich chemistry based on formation of radicals from methane and their subsequent reaction with the N₂ matrix. We discuss the implications of the formation of these radicals for the chemical evolution of Triton and Pluto. Ultimately, this work suggests that , CN, HCO, and CNN may be found in significant quantities on the surfaces of Triton and Pluto and that new observations of these objects in the appropriate wavelength regions are warranted.     

Mass composition of the escaping plasma at Mars

Data from the Ion Mass Analyzer (IMA) sensor of the ASPERA-3 instrument suite on Mars Express have been analyzed to determine the mass composition of the escaping ion species at Mars. We have examined 77 different ion-beam events and we present the results in terms of flux ratios between the following ion species: CO⁺₂/O⁺ and O⁺₂/O⁺. The following ratios averaged over all events and energies were identified: CO⁺₂/O⁺ = 0.2 and O⁺₂/O⁺ = 0.9. The values measured are significantly higher, by a factor of 10 for O⁺₂/O⁺, than a contemporary modeled ratio for the maximum fluxes which the martian ionosphere can supply. The most abundant ion species was found to be O⁺, followed by O⁺₂ and CO⁺₂. We estimate the loss of CO⁺₂ to be by using the previous measurements of Phobos-2 in our calculations. The dependence of the ion ratios in relation to their energy ranges we studied, 0.3-3.0 keV, indicated that no clear correlation was found.     

Distributions of H2O and CO2 ices on Ariel, Umbriel, Titania, and Oberon from IRTF/SpeX observations

We present 0.8-2.4 μm spectral observations of uranian satellites, obtained at IRTF/SpeX on 17 nights during 2001-2005. The spectra reveal for the first time the presence of CO₂ ice on the surfaces of Umbriel and Titania, by means of 3 narrow absorption bands near 2 μm. Several additional, weaker CO₂ ice absorptions have also been detected. No CO₂ absorption is seen in Oberon spectra, and the strengths of the CO₂ ice bands decline with planetocentric distance from Ariel through Titania. We use the CO₂ absorptions to map the longitudinal distribution of CO₂ ice on Ariel, Umbriel, and Titania, showing that it is most abundant on their trailing hemispheres. We also examine H₂O ice absorptions in the spectra, finding deeper H₂O bands on the leading hemispheres of Ariel, Umbriel, and Titania, but the opposite pattern on Oberon. Potential mechanisms to produce the observed longitudinal and planetocentric distributions of the two ices are considered.     

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.     

Implications of the Galilean satellites ice envelope explosions II. The origin of the irregular satellites

The problem of the origin of the irregular satellites is solved readily in the context of a hypothesis involving explosion of the massive ice envelopes of the Galilean satellites saturated by electrolysis products. The thrown-off unexploded (primary) ice fragments of the outermost cold layers of the envelopes are also saturated by electrolysis products. In the course of explosive ejection their internal energy increases due to shock wave heating, as a result of which they will be able to detonate in subsequent sufficiently energetic collisions. The secondary fragments from new explosions may acquire additional velocity up to a few km s^–1 without breakup into small pieces.Gravitational perturbations by the parent satellites can eject the primary fragments moving near their orbits into the periphery of or beyond Jupiter's sphere of action. If such a fragment explodes in the outer zone of the sphere, then secondary fragments may become irregular satellites resulting in the so-called internal capture (the possibilities of capture considered earlier involved only bodies entering the sphere of action from outside).The mass of the primary fragment responsible for the inner (direct) group of Jupiter's irregular satellites is estimated as 10¹⁹ kg, and the additional velocity acquired by secondary fragments as 1.3 km s^–1; evaluation of the mass of the fragment responsible for the outer (retrograde) group yields 10¹⁸ kg, and that of the additional velocity of secondary fragments, 2 km s^–1.The ice envelopes of the Galilean and similar moonlike satellites should contain impurities corresponding to the composition of type C1 carbonaceous chondrites; therefore after sublimation of water ice the irregular satellites (just as type C asteroids, the Trojans and comets) exhibit spectro-photometric properties similar to those of C-type objects.     

Asymmetries in the distribution of H2O and CO2 in the inner coma of Comet 9P/Tempel 1 as observed by Deep Impact

Prior to the impact event, Deep Impact monitored the ambient inner coma of Comet 9P/Tempel 1 at high spatial resolution in July 2005. Gaseous H₂O and CO₂ are unambiguously detected in the infrared spectra collected with the HRI-IR spectrometer aboard Deep Impact. Detailed distribution maps of these volatiles in the inner coma, within 60 km from the nucleus, are produced from the integrated emission bands of H₂O (2.66 μm) and CO₂ (4.26 μm). Uncorrelated asymmetries are determined in the spatial distribution of both species indicating chemical heterogeneities within the nucleus. Although present at some abundance surrounding the entire nucleus, H₂O has a pronounced enhancement in abundance in the sunward direction rotational phases, evidence that the dominant process of subliming water ice from the nucleus is solar heating. In contrast, CO₂ is enhanced in the regions near the negative rotational pole of the nucleus, suggesting localized outgassing there. Both species show an increase in radiance above the limb of the nucleus toward Ecliptic North. The distribution maps also suggest that the process of dust removal from the nucleus is strongly connected to the outgassing of volatiles. Detailed study of these coma asymmetries gives insight to the relative abundances of the dominant molecular components of the inner coma, source regions of the native volatiles, anisotropic outgassing of the nucleus, and the formation and evolution of the nucleus. A quiescent water production rate for Tempel 1 on July 4, 2005, is estimated to be .     

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.     

Observations of C2H6 and C2H2 in the stratosphere of Saturn

We have performed high-resolution spectral observations at mid-infrared wavelengths of C₂H₆ (12.16 μm), and C₂H₂ (13.45 μm) on Saturn. These emission features probe the stratosphere of the planet and provide information on the hydrocarbon photochemical processes taking place in that region of the atmosphere. The observations were performed using our cryogenic echelle spectrometer Celeste, in conjunction with the McMath-Pierce 1.5-m solar telescope in November and December 1994. We used Voyager IRIS CH₄ observations (7.67 μm) to derive a temperature profile on the saturnian atmosphere for the region of the stratosphere. This profile was then used in conjunction with height-dependent volume mixing ratios of each hydrocarbon to determine global abundances for ethane and acetylene. Our ground-based measurements indicate abundances of for C₂H₆ (1.0 mbar pressure level), and for C₂H₂ (1.6 mbar pressure level). We also derived new mixing ratios from the Voyager mid-latitude IRIS observations; 8.6±0.9×¹⁰⁻⁶ for C₂H₆ (0.1-3.0 mbar pressure level), and 1.6±0.2×¹⁰⁻⁷ for C₂H₂ (2.0 mbar pressure level).     

H2O2 production by high-energy electrons on icy satellites as a function of surface temperature and electron flux

Chemistry on the icy surface of Europa is heavily influenced by the incident energetic particle flux from the jovian magnetosphere. The majority (>75%) of this energy is in the form of high energy electrons (extending to >10 MeV). We have simulated the electron irradiation environment of Europa with a vacuum system containing a high-energy electron gun for irradiation of ice samples formed on a gold mirror cooled with a cryostat. Pure water films of ∼2.6 μm thickness were grown at 100 K and then either cooled (to 80 K), warmed (to 120 K) or left at 100 K and subsequently irradiated with 10 keV electrons. The production of hydrogen peroxide (H₂O₂) was monitored by observation of the 2850 cm⁻¹ (3.5 μm) band. Equilibrium concentrations of H₂O₂, in units of percent by number H₂O₂ relative to water, were found to be 0.043% (80 K), 0.029% (100 K), and 0.0063% (120 K). These values are 33%, 22%, and 5%, respectively, that of the reported surface concentration on the leading hemisphere of Europa (Carlson, R.W., Anderson, M.S., Johnson, R.E., Smythe, W.D., Hendrix, A.R., Barth, C.A., et al. [1999]. Science 283(5410), 2062-2064) and less than the equilibrium concentrations formed by ion irradiation. In addition to the ice film temperature, the current of electrons was varied between different experiments to determine the production and destruction of H₂O₂ as a function of both electron flux and ice temperature. Variation in current was found to have little effect on the results other than accelerating arrival at radiolytic equilibrium.     

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.     

Airglow on Mars: Some model expectations for the OH Meinel bands and the O2 IR atmospheric band

This work presents model calculations of the diurnal airglow emissions from the OH Meinel bands and the O₂ IR atmospheric band in the neutral atmosphere of Mars. A time-dependent photochemical model of the lower atmosphere below 80 km has been developed for this purpose. Special emphasis is placed on the nightglow emissions because of their potential to characterize the atomic oxygen profile in the 50-80 km region. Unlike on Earth, the OH Meinel emission rates are very sensitive to the details of the vibrational relaxation pathway. In the sudden death and collisional cascade limits, the maximum OH Meinel column intensities for emissions originating from a fixed upper vibrational level are calculated to be about 300 R, for transitions v^′=9→v^′?8, and 15,000 R, for transitions v^′=1→v^′=0, respectively. During the daytime the 1.27 μm emission from O₂(), primarily formed from ozone photodissociation, is of the order of MegaRayleighs (MR). Due to the long radiative lifetime of O₂(), a luminescent remnant of the dayglow extends to the dark side for about two hours. At night, excited molecular oxygen is expected to be produced through the three body reaction O + O + CO₂. The column emission of this nighttime component of the airglow is estimated to amount to 25 kR. Both nightglow emissions, from the OH Meinel bands and the O₂ IR atmospheric band, overlap in the 50-80 km region. Photodissociation of CO₂ in the upper atmosphere and the subsequent transport of the atomic oxygen produced to the emitting layer are revealed as key factors in the nightglow emissions from these systems. The Mars 5 upper constraint for the product [H][O₃] is revised on the basis of more recent values for the emission probabilities and collisional deactivation coefficients.