Ion chemistry in the cometary atmosphere

Dirty ice of a second kind (major components, H₂O, CO, and N₂; minor components less than several percents, NH₃, CH₄, and other organic substances such as HCN, CH₃CN etc.) is assumed for the composition of volatiles in the cometary nucleus. The consistency with the observations of molecular ions and daughter molecules in the cometary atmosphere is argued by taking into account various ion-molecular reactions and dissociative recombinations. There is a satisfactory agreement for the second kind of dirty-ice model, but the presence of large amounts of CH₄ and NH₃ is found to be rather in contradiction with observational evidence. A velocity of 8 km s^?1 for the hydrogen atoms, derived from analysis of the hydrogen Lyman-alpha corona around comets, is found from the dissociative recombination of H₃O⁺, the dominant constituent of cometary ionosphere, in accordance with H₃O⁺+e ^?→OH+H+H.     

The influence of grain mantles on the formation of hydrogen molecules on grain surfaces

The physical adsorption energy,E, of hydrogen molecules on various substrates at temperatures between 5 and 30 K and at the lowest practicable gas densities has been measured. Values ofE/k are for condensed CO 340 K, CO₂ 800 K, H₂O 850 K and for ‘dirty’ graphite 980 K and ‘dirty’ copper 800 K. From these measurements temperature ranges in which H atoms might combine on the surface to form H₂ molecules are estimated. Duley has discussed the formation and composition of condensed gas mantles on interstellar grains. The effects of such mantles in promoting and poisoning hydrogen molecule formation are discussed.     

Surface materials on unusual planetary object chiron

We present the first JHK near-infrared colorimetry giving some indication of the surface materials on the peculiar object 2060 Chiron. The colors appear to exclude relatively clean bright ice surfaces, such as those of Europa, Ganymede, Rhea, Dione, and theoretically studied micronscale clean ice particles. The colors are consistent with those of numerous outer solar system asteroids, which in all measured cases have: albedos of only a few percent, C?, RD?, or DM-type spectra, and no known H₂O ice absorption features. The colors are also consistent with theoretical colors for certain size distributions of dirty ice grains. These and additional VJHK colorimetric data suggest that the spectrally dominant surface is C-type material, probably dark carbonaceous-like silicate dust, with a possible admixture of ice grains on a microscale. If Chiron has the low albedo common to such material on known interplanetary bodies, its diameter would be about 310 to 400 km, placing Chiron among the eight largest “asteroids”. Relationships to comet observations are discussed.     

The astronomical theory of climatic change on Mars

We examine the response of Martian climate to changes in solar energy deposition caused by variations of the Martian orbit and obliquity. We systematically investigate the seasonal cycles of carbon dioxide, water, and dust to provide a complete picture of the climate for various orbital configurations. We find that at low obliquity (15°) the atmospheric pressure will fall below 1 mbar; dust storms will cease; thick permanent CO₂ caps will form; the regolith will release CO₂; and H₂O polar ice sheets will develop as the permafrost boundaries move poleward. At high obliquity (35°) the annual average polar temperature will increase by about 10°K, slightly desorbing the polar regolith and causing the atmospheric pressure to increase by not more than 10 to 20 mbar. Summer polar ground temperatures as high as 273°K will occur. Water ice caps will be unstable and may disappear as the equilibrium permafrost boundary moves equatorward. However, at high eccentricity, polar ice sheets will be favored at one pole over the other. At high obliquity dust storms may occur during summers in both hemispheres, independent of the eccentricity cycle. Eccentricity and longitude of perihelion are most significant at modest obliquity (25°). At high eccentricity and when the longitude of perihelion is close to the location of solstice hemispherical asymmetry in dust-storm generation and in polar ice extent and albedo will occur.The systematic examination of the relation of climate and planetary orbit provides a new theory for the formation of the polar laminae. The terraced structure of the polar laminae originates when eccentricity and/or obliquity variations begin to drive water ice off the dusty permanent H₂O polar caps. Then a thin (meters) layer of consolidated dust forms on top of a dirty, slightly thicker (tens of meters) ice sheet and the composite is preserved as a layer of laminae composed predominately of water ice. Because of insolation variation on slopes, a series of poleward- and equatorward-facing scarps are formed where the edges of the laminae are exposed. Independently of orbital variations, these scarps propagate poleward both by erosion of the equatorward slopes and by deposition on the poleward slopes. Scarp propagation resurfaces and recycles the laminae forming the distinctive spiral bands of terraces observed and provides a supply of water to form new permanent ice caps. The polar laminae boundary marks the furthest eqautorward extension of the permanent H₂O caps as the orbit varies. The polar debris boundary marks the furthest equatorward extension of the annual CO₂ caps as the orbit varies.The Martian regolith is now a significant geochemical sink for carbon dioxide. CO₂ has been irreversibly removed from the atmosphere by carbonate formation. CO₂ has also benn removed by regolith adsorption. Polar temperature increases caused by orbital variations are not great enough     

Role of H2O and CO2 Ices in Martian Climate Changes

In order to study the stability of martian climate, we constructed a two-dimensional (horizontal-vertical) energy balance model. The long-term CO₂ mass exchange process between the atmosphere and CO₂ ice caps is investigated with particular attention to the effect of planetary ice distribution on the climate stability. Our model calculation suggests that high atmospheric pressure presumed for past Mars would be unstabilized if H₂O ice widely prevailed. As a result, a cold climate state might have been achieved by the condensation of atmospheric CO₂ onto ice caps. On the other hand, the low atmospheric pressure, which is buffered by the CO₂ ice cap and likely close to the present pressure, would be unstabilized if the CO₂ ice albedo decreased. This may have led the climate into a warm state with high atmospheric pressure owing to complete evaporation of CO₂ ice cap. Through the albedo feedback mechanisms of H₂O and CO₂ ices in the atmosphere-ice cap system, Mars may have experienced warm and cold climates episodically in its history.     

Remote comets and related bodies: VJHK colorimetry and surface materials

Spectrophotometric data show that major compositional groups among outer solar system (OSS) surfaces include bright ices and at least two distinct classes of blackish carbonaceous-like materials, called C-type and RD-type. VJHK colorimetry of asteroids, satellites, and laboratory samples shows that these three classes can be distinguished by VJHK colors. We define an “α index” that denotes the position of objects in VJHK color - color diagrams; it empirically increases with albedo and ice/dirt ratio. We use the above data to define color fields that may be useful in interpreting our observations of eight comets (1980–1981). All eight comets have colors generally resembling RD asteroids and are inconsistent with reflection off clean ice surfaces. The observations suggest that these comets' halos contain RD dirt or dirty ice grains colored by RD dirt, supporting J. Gradie and J. Veverka's [Nature283, 840–842 (1980)] prediction of RD, rather than C, material in comets. Remote Comet P/Schwassmann-Wachmann 1 was observed both during outburst and quiescence and had the highest α index of any observed comet. Comet α indices appear to be correlated with solar distance. Further work will be needed to clarify possible coloring effects due to particle size, dispersal, and composition. We suggest a number of physical interpretations based on a single two-component mixing model, which assumes that all OSS planetesimals formed primarily from bright ices and dark carboneceous-like dirt, consistent with condensation theory. We discuss differentiation processes that concentrated one component or the other at the surface. All measured OSS interplanetary bodies have surfaces of dark dirt or dark dirty ice colored by the dirt component. Comets, consistent with the Whipple dirty iceberg model, are such objects close enough to the Sun for volatilization to throw dirty ice grains into the coma. In remote comets, the ice component of the grains remains stable, and we see dirty ice grains; in near comets, the ice component vaporizes, and we see dirt grains. A volatile-depleted dusty regolith on P/Schwassmann-Wachmann 1 and other remote comets could explain their eruptive behavior by means of gas pressure buildup in the porous, weakly bonded dust.     

Radiation chemistry of H2O + O2 ices

The chemistry and spectroscopy of proton-irradiated H₂O + O₂ ices have been investigated in relation to the production of oxidants in icy satellite surfaces. Hydrogen peroxide (H₂O₂), ozone (O₃), and the hydroperoxy (HO₂) and hydrogen trioxide (HO₃) radicals have all been observed, and their temperature and dose dependent production trends have been measured. We find that O₂ aggregates form during the growth of H₂O + O₂ ice films, and the presence of these aggregates greatly affects the HO₂ and H₂O₂ yields. In addition, we have found that the position of the spectral maximum of the ν₃ vibration of O₃ shifts with ice composition, giving an indication of the degree of dispersion of O₃ molecules within the ice. We discuss the relevance of these measurements to icy satellite surfaces.     

The temperature of nonspherical circumstellar dust grains

The temperatures of prolate and oblate spheroidal dust grains in the envelopes of stars of various spectral types are calculated. Homogeneous particles with aspect ratios a/b≤10 composed of amorphous carbon, iron, dirty ice, various silicates, and other materials are considered. The temperatures of spherical and spheroidal particles were found to vary similarly with particle size, distance to the star, and stellar temperature. The temperature ratio T _d(spheroid)/T _d(sphere) depends most strongly on the grain chemical composition and shape. Spheroidal grains are generally colder than spherical particles of the same volume; only iron spheroids can be slightly hotter than iron spheres. At a/b≈2, the temperature differences do not exceed 10%. If a/b≥4, the temperatures can differ by 30–40%. For a fixed dust mass in the medium, the fluxes at wavelengths λ≥100 are higher if the grains are nonspherical, which gives overestimated dust masses from millimeter observations. The effect of grain shape should also be taken into account when modeling Galactic-dust emission properties, which are calculated when searching for fluctuations of the cosmic microwave background radiation in its Wien wing.     

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.     

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.     

Enhanced CO2 trapping in water ice via atmospheric deposition with relevance to Mars

It has been suggested that inclusions of CO₂ or CO₂ clathrate hydrates may comprise a portion of the polar deposits on Mars. Here we present results from an experimental study in which CO₂ molecules were trapped in water ice deposited from CO₂/H₂O atmospheres at temperatures relevant for the polar regions of Mars. Fourier-Transform Infrared spectroscopy was used to monitor the phase of the condensed ice, and temperature programmed desorption was used to quantify the ratio of species in the generated ice films. Our results show that when H₂O ice is deposited at 140-165 K, CO₂ is trapped in large quantities, greater than expected based on lower temperature studies in amorphous ice. The trapping occurs at pressures well below the condensation point for pure CO₂ ice, and therefore this mechanism may allow for CO₂ deposition at the poles during warmer periods. The amount of trapped CO₂ varied from 3% to 16% by mass at 160 K, depending on the substrate studied. Substrates studied were a tetrahydrofuran (C₄H₈O) base clathrate and Fe-montmorillonite clay, an analog for Mars soil. Experimental evidence indicates that the ice structures are likely CO₂ clathrate hydrates. These results have implications for the CO₂ content, overall composition, and density of the polar deposits on Mars.     

Spatial variability,composition and thickness of the seasonal north polar cap of Mars in mid-spring

The planetary fourier spectrometer (PFS) for the Mars express mission (MEX) is an infrared spectrometer operating in the wavelength range from 1.2 to 45 μm by means of two spectral channels, called SWC (short wavelength channel) and LWC (long wavelength channel), covering, respectively, 1.2–5.5 and 5.5–45 μm.The middle-spring Martian north polar cap (Ls∼40°) has been observed by PFS/MEX in illuminated conditions during orbit 452. The SWC spectra are here used to study the cap composition in terms of CO₂ ice, H₂O ice and dust content. Significant spectral variation is noted in the cap interior, and regions of varying CO₂ ice grain sizes, water frost abundance, CO₂ ice cover and dust contamination can be distinguished. In addition, we correlate the infrared spectra with an image acquired during the same orbit by the OMEGA imaging spectrometer and with the altimetry from MOLA data. Many of the spectra variations correlate with heterogeneities noted in the image, although significant spectral variations are not discernible in the visible. The data have been divided into five regions with different latitude ranges and strong similarities in the spectra, and then averaged. Bi-directional reflectance models have been run with the appropriate lighting geometry and used to fit the observed data, allowing for CO₂ ice and H₂O ice grain sizes, dust and H₂O ice contaminations in the form of intimate granular mixtures and spatial mixtures.A wide annulus of dusty water ice surrounds the recessing CO₂ seasonal cap. The inner cap exhibits a layered structure with a thin CO₂ layer with varying concentrations of dark dust, on top of an H₂O ice underneath ground. In the best-fits, the ices beneath the top layer have been considered as spatial mixtures. The results are still very good everywhere in the spectral range, except where the CO₂ ice absorption coefficients are such that even a thin layer is enough to totally absorb the incoming radiation (i.e. the band is saturated). This only happens around 3800 cm⁻¹, inside the strong 2.7-μm CO₂ ice absorption band. The effect of finite snow depth has been investigated through a layered albedo model. The thickness of the CO₂ ice deposits increases with latitude, ranging from 0.5–1 g cm⁻² within region II to 60–80 g cm⁻² within the highest-latitude (up to 84°N) region V.Region I is at the cap edge and extends from 65°N to 72°N latitude. No CO₂ ice is present in this region, which consists of relatively large grains of water ice (20 μm), highly contaminated by dust (0.15 wt%). The adjacent region II is a narrow region [76–79°N] right at the edge of the north residual polar cap. This region is very distinct in the OMEGA image, where it appears to surround the whole residual cap. The CO₂ ice features are barely visible in these spectra, except for the strong saturated 2.7 μm band. It basically consists of a thin layer of 5-mm CO₂ ice on top of an H₂O ice layer with the same composition as region I. A third interesting region III is found all along the shoulder of the residual cap [79–81°N]. It extends over 1.5 km in altitude and over only 2° of latitude and consists of CO₂ ice with a large dust content. It is an admixture of CO₂ ice (3–4 mm), with several tens of ppm by mass of water ice and more than 2 ppt by mass of dust. The surface temperatures have been retrieved from the LWC spectra for each observation. We found an increase in the surface temperature in this region, indicating a spatial mixture of cold CO₂ ice and warmer dust/H₂O ice. Region IV is close to the top of the residual cap [81–84°N]; it is much brighter than region III, with a dust content 10 times lower than the latter. The CO₂ grain size is 3 mm and strong CO₂ ice features are present in the data, indicating a thicker CO₂ ice layer than in region II (1–2 g cm⁻²). The final region V is right at the top of the residual cap (⩾84°N). It is “pure” CO₂ ice (no dust) of 5 mm grain sizes, with 30 ppm by weight of water ice. The CO₂ ice features are very pronounced and the 2.7 μm band is saturated. The optical thickness is close to the semi-infinite limit (30–40 g cm⁻²). Assuming a snowpack density of 0.5 g cm⁻³, we get a minimum thickness of 1–2 cm for the top-layer of regions II and III, 4–10 cm for region IV, and ⩾60–80 cm thickness for region V. These values are in close agreement with several recent results for the south seasonal polar cap.These results should provide new, useful constraints in models of the Martian climate system and volatile cycles.     

Dependence of the effective rate constants for the hydrogenation of CO on the temperature and composition of the surface

Experiments on the hydrogenation of CO on pure CO and CO-H₂O mixed ice have been performed at temperatures between 8 and 20 K. We obtained temperature and compositional dependence of the effective reaction rate constants. Results indicate that hydrogenation proceeds efficiently on pure solid CO and CO-H₂O mixed ice at temperatures below 10 and 20 K, respectively. Rate constants for pure CO decreased significantly at 12 K compared to those obtained with CO-H₂O mixed ice. Hydrogenation of CO at temperatures greater than 12 K were catalyzed by the H₂O adjacent to the CO. The importance of the experimental results for some relevant astrophysical environments has also been outlined.     

Studies of proton-irradiated SO2 at low temperatures: Implications for lo

The infrared absorption spectrum from 3.3 to 27 μm (3030-370 cm^?) of SO₂ ice films has been measured at 20 and 88°K before and after 1-MeV proton irradiation. The radiation flux was chosen to simulate the estimated flux of Jovian magnetospheric 1-MeV protons incident on Io. After irradiation, SO₃ is identified as the dominant molecule synthesized in the SO₂ ice. This is also the case after irradiation of composite samples of SO₂ with sulfur, or disulfites. Darkening was observed in irradiated SO₂ ice and in irradiated S₈ pellets. Photometric and spectral measurements of the thermoluminescence of irradiated SO₂ have been made during warming. The spectrum appears as a broad band with a maximum at 4450 Å. Analysis of the luminescence data suggests that, at Ionian temperatures, irradiated SO₂ ice would not be a dominant contributor to posteclipse brightening phenomena. After warming to room temperature, a form of SO₃ remains along with a sulfate and S₈. Based on these experiments, it is reasonable to propose that small amounts of SO₃ may exist on the surface of Io as a result of irradiation synthesis in SO₂ frosts.     

The loss and depth of CO2 ice in comet nuclei

An analytical model has been developed to simulate the chemical differentiation of a homogeneous, initially unmantled cometary nucleus composed of water ice, putative unclathrated CO₂ ice, and silicate dust in specified proportions. Selective sublimation of any free CO₂ ice present in a new comet should produce a surface layer of water ice and dust overlying the undifferentiated core. This surface layer modifies the temperature of buried CO₂ ice and restricts the outflow of gaseous CO₂. On each orbit, water sublimation closer to perihelion temporarily reduces the thickness of the water ice and dust layer and liberates dust. Most of the dust is blown off the nucleus, but a small amount of residual dust remains on the surface (cf. H. L. F. Houpis, W. H. Ip, and D. A. Mendis, 1986, Astrophys. J., in press). Our model includes the effects of nucleus rotation, arbitrary orientation of the rotation axis, latitude, heat conduction into the interior of the nucleus, restriction of CO₂ gas outflow by the water ice and dust layer, and the use of thermal conductivities for both amorphous and crystalline water ice as appropriate, featuresthat were not included in the Houpis et al. model. The model also accounts for the erosion of the water ice surface, which Houpis et al. appear to have accounted for and which is an important effect. Specifically, we investigate the effects of varying the permeability of the surface water ice layer, the mass fraction of CO₂, the orbit and the latitude, using the orbital parameters of Comets Halley and Tempel 2. It is found that CO₂ gas production should exceed H₂O gas production beyond ∼3 AU, and at 1 AU CO₂ gas production should be between 20 to 25% of H₂O gas production. The depth of CO₂ ice and the variation in the depth of CO₂ ice throughout an orbit are affected significantly by the perihelion of the orbit. The effects due to water ice permeability are significant but much less than expected on the basis of flow area. Latitude and CO₂ concentration produce relatively small effects. Under all conditions considered here, CO₂ ice should always be found within ∼1 m from the surface of comet nuclei if it is present as a free species to begin with. This result is probably generally valid for unmantled portions of most comets and qualitatively simulates the behavior of an abundant, highly volatile component in an H₂O/silicate matrix. Comparison of these and similar results with observations could yield information regarding the permeability and chemical composition of cometary material and suggest sampling strategies to minimize fractionation effects. The method is applicable to other nonwater ices.     

Oceans in the icy Galilean satellites of Jupiter?

Equilibrium models of heat transfer by heat conduction and thermal convection show that the three satellites of Jupiter—Europa, Ganymede, and Callisto—may have internal oceans underneath ice shells tens of kilometers to more than a hundred kilometers thick. A wide range of rheology and heat transfer parameter values and present-day heat production rates have been considered. The rheology was cast in terms of a reference viscosity ν₀ calculated at the melting temperature and the rate of change A of viscosity with inverse homologous temperature. The temperature dependence of the thermal conductivity k of ice I has been taken into account by calculating the average conductivity along the temperature profile. Heating rates are based on a chondritic radiogenic heating rate of 4.5 pW kg⁻¹ but have been varied around this value over a wide range. The phase diagrams of H₂O (ice I) and H₂O + 5 wt% NH₃ ice have been considered. The ice I models are worst-case scenarios for the existence of a subsurface liquid water ocean because ice I has the highest possible melting temperature and the highest thermal conductivity of candidate ices and the assumption of equilibrium ignores the contribution to ice shell heating from deep interior cooling. In the context of ice I models, we find that Europa is the satellite most likely to have a subsurface liquid ocean. Even with radiogenic heating alone the ocean is tens of kilometers thick in the nominal model. If tidal heating is invoked, the ocean will be much thicker and the ice shell will be a few tens of kilometers thick. Ganymede and Callisto have frozen their oceans in the nominal ice I models, but since these models represent the worst-case scenario, it is conceivable that these satellites also have oceans at the present time. The most important factor working against the existence of subsurface oceans is contamination of the outer ice shell by rock. Rock increases the density and the pressure gradient and shifts the triple point of ice I to shallower depths where the temperature is likely to be lower then the triple point temperature. According to present knowledge of ice phase diagrams, ammonia produces one of the largest reductions of the melting temperature. If we assume a bulk concentration of 5 wt% ammonia we find that all the satellites have substantial oceans. For a model of Europa heated only by radiogenic decay, the ice shell will be a few tens of kilometers thinner than in the ice I case. The underlying rock mantle will limit the depth of the ocean to 80-100 km. For Ganymede and Callisto, the ice I shell on top of the H₂O-NH₃ ocean will be around 60- to 80-km thick and the oceans may be 200- to 350-km deep. Previous models have suggested that efficient convection in the ice will freeze any existing ocean. The present conclusions are different mainly because they are based on a parameterization of convective heat transport in fluids with strongly temperature dependent viscosity rather than a parameterization derived from constant-viscosity convection models. The present parameterization introduces a conductive stagnant lid at the expense of the thickness of the convecting sublayer, if the latter exists at all. The stagnant lid causes the temperature in the sublayer to be warmer than in a comparable constant-viscosity convecting layer. We have further modified the parameterization to account for the strong increase in homologous temperature, and therefore decrease in viscosity, with depth along an adiabat. This modification causes even thicker stagnant lids and further elevated temperatures in the well-mixed sublayer. It is the stagnant lid and the comparatively large temperature in the sublayer that frustrates ocean freezing.     

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.     

Water ice in the dark dune spots of Richardson crater on Mars

Interfacial liquid water has been hypothesized to form during the seasonal evolution of the dark dune spots observed in the high latitudes of Mars. In this study we assess the presence, nature and properties of ices - in particular water ice - that occur within these spots using HIRISE and CRISM observations, as well as the LMD Global Climate Model. Our studies focus on Richardson crater (72°S, 179°E) and cover southern spring and summer (L_S=175-341°). Three units have been identified of these spots: dark core, gray ring and bright halo. Each unit show characteristic changes as the season progress. In winter, the whole area is covered by CO₂ ice with H₂O ice contamination. Dark spots form during late winter and early spring. During spring, the dark spots are located in a 10 cm thick depression compared to the surrounding bright ice-rich layer. They are spectrally characterized by weak CO₂ ice signatures that probably result from spatial mixing of CO₂ ice-rich and ice-free regions within pixels, and from mixing of surface signatures due to aerosols scattering. The bright halo shaped by winds shows stronger CO₂ absorptions than the average ice-covered terrain, which is consistent with a formation process involving CO₂ re-condensation. According to spectral, morphological and modeling considerations, the gray ring is composed of a thin layer of a few tens of μm of water ice. Two sources/processes could participate to the enrichment of water ice in the gray ring unit: (i) water ice condensation at the surface in early fall (prior to the condensation of a CO₂-rich winter layer) or during wintertime (due to cold trapping of the CO₂ layer) and (ii) ejection of dust grains surrounded by water ice by the geyser activity responsible for the dark spot. In any case, water ice remains longer in the gray ring unit after the complete sublimation of the CO₂. Finally, we also looked for liquid water in the near-IR CRISM spectra using linear unmixing modeling but found no conclusive evidence for it.     

Photochemistry of the martian atmosphere: Seasonal, latitudinal, and diurnal variations

There is a significant progress in the observational data relevant to Mars photochemistry in the current decade. These data are not covered by and sometimes disagree with the published models. Therefore we consider three types of models for Mars photochemistry. A steady-state model for global-mean conditions is currently the only way to calculate the abundances of long living species (H₂, O₂, and CO). However, our model does not fit the observed CO abundance using gas-phase chemistry and reasonable values of heterogeneous loss of odd hydrogen on the water ice aerosol. The second type of the calculated models is steady-state models for local conditions. The MGS/TES data on temperature profiles, H₂O, and dust are input parameters for these models. The calculations have been made for nine seasonal points spread over the martian year and for twelve latitudes with a step of 10° for each season. The only adopted heterogeneous reaction is a weak loss of H₂O₂ on water ice with probability of 5×¹⁰⁻⁴. The results are in good agreement with the recent observations of the O₂ dayglow at 1.27 μm and the O₃ and H₂O₂ abundances. Global maps of the seasonal and latitudinal behavior of these species have been made. The third type of models is a time-dependent model for local conditions. These models show that odd hydrogen quickly converts to H₂O₂ at the nighttime and the chemistry is switched off while the association of O, the heterogeneous loss of H₂O₂, and eddy diffusion continue. This requires significant changes in the global-mean and local steady-state models discussed above, and these changes have been properly done. The calculated diurnal variations of Mars photochemistry are discussed. The martian photochemistry at low and middle latitudes is significantly different in the aphelion period at LS=10°-130° from that in the remaining part of the year.     

Ultraviolet irradiation of naphthalene in H2O ice: Implications for meteorites and biogenesis

Abstract— The polycyclic aromatic hydrocarbon (PAH) naphthalene was exposed to ultraviolet radiation in H₂O ice under astrophysical conditions, and the products were analyzed using infrared spectroscopy and high‐performance liquid chromatography. As we found in our earlier studies on the photoprocessing of coronene in H₂O ice, aromatic alcohols and ketones (quinones) were formed. The regiochemistry of the reactions is described and leads to specific predictions of the relative abundances of various oxidized naphthalenes that should exist in meteorites if interstellar ice photochemistry influenced their aromatic inventory. Since oxidized PAHs are present in carbon‐rich meteorites and interplanetary dust particles (IDPs), and ubiquitous in and fundamental to biochemistry, the delivery of such extraterrestrial molecules to the early Earth may have played a role in the origin and evolution of life.