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.     

Near-infrared spectra of laboratory H2O-CH4 ice mixtures

We present 1.25-19 μm infrared spectra of pure solid CH₄ and H₂O/CH₄=87, 20, and 3 solid mixtures at temperatures from 15 to 150 K. We compare and contrast the absorptions of CH₄ in solid H₂O with those of pure CH₄. Changes in selected peak positions, profiles, and relative strength with temperature are presented, and absolute strengths for absorptions of CH₄ in solid H₂O are estimated. Using the two largest (ν₃+ν₄) and (ν₁+ν₄) near-IR absorptions of CH₄ at 2.324 and 2.377 μm (4303 and 4207 cm⁻¹), respectively, as examples, we show that peaks of CH₄ in solid H₂O are at slightly shorter wavelength (higher frequency) and broader than those of pure solid CH₄. With increasing temperature, these peaks shift to higher frequency and become increasingly broad, but this trend is reversible on re-cooling, even though the phase transitions of H₂O are irreversible. It is to be hoped that these observations of changes in the positions, profiles, and relative intensities of CH₄ absorptions with concentration and temperature will be of use in understanding spectra of icy outer Solar System bodies.     

Ejecta fragmentation in impacts into gypsum and water ice

Using the light gas gun at the Open University’s Hypervelocity Impact facility, a series of impact experiments exploring impacts into water ice and gypsum have been performed. Fragmentation of solid ejecta was recorded using two different methods, analysed and compared with the total ejecta. Preliminary results show that the size distribution of the ejecta fragments from water ice is very similar to those from gypsum. These results also represent a step towards a better understanding of ejecta fragmentation in geological materials, including icy surfaces in the Solar System.     

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.     

Cratering of icy targets by different impactors: Laboratory experiments and implications for cratering in the Solar System

Studies of impacts (impactor velocity about 5 km s⁻¹) on icy targets were performed. The prime goal was to study the response of solid CO₂ targets to impacts and to find the differences between the results of impacts on CO₂ targets with those on H₂O ice targets. The crater dimensions in CO₂ ice were found to scale with impact energy, with little dependence on projectile density (which ranged from nylon to copper, i.e., 1150-8930 kg m⁻³). At equal temperatures, craters in CO₂ ice were the same diameter as those in water ice, but were shallower and smaller in volume. In addition, the shape of the radial profiles of the craters was found to depend strongly on the type of ice and to change with impact energy. The impact speed of the data is comparable to that for impacts on many types of icy bodies in the outer Solar System (e.g., the satellites of the giant planets, the cometary nuclei and the Kuiper Belt objects), but the size and thus energy of the impactors is lower. Scaling with impact energy is demonstrated for the impacts on CO₂ ice. The issue of impact disruption (rather than cratering) is discussed by analogy with that on water ice. Expressions for the critical energy density for the onset of disruption rather than cratering are established for water ice as a function of porosity and silicate content. Although the critical energy density for disruption of CO₂ ice is not established, it is argued that the critical energy to disrupt a CO₂ ice body will be greater than that for a (non-porous) water ice body of the similar mass.     

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.     

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.     

Mechanistic studies on the decomposition of carbon suboxide in a cometary ice analog

A cometary ice analog sample consisting primarily of carbon suboxide ice (C₃O₂) was produced from the irradiation of its precursor, carbon monoxide. This carbon suboxide sample was subjected to irradiation with energetic electrons at 10 K to simulate the interaction of carbon suboxide-rich cometary analog ices with ionizing radiation. The destruction of carbon suboxide as well as the production of the primary degradation products, dicarbon monoxide (C₂O), and carbon monoxide (CO), were monitored quantitatively by infrared spectroscopy in situ; the gas phase was simultaneously sampled via quadrupole mass spectrometry. A kinetic model was produced to help explain the decomposition kinetics of carbon suboxide in cometary ices and to infer the underlying reaction mechanisms.     

Ultraviolet photolysis and proton irradiation of astrophysical ice analogs containing hydrogen cyanide

Hydrogen cyanide (HCN) has been identified in the gas phase of the interstellar medium as well as in the comae of several comets. Terrestrially, HCN is a key component in the synthesis of biologically important molecules such as amino acids. In this paper, we report the results of low-temperature (18 K) ice energetic processing experiments involving pure HCN and mixtures of HCN with H₂O and NH₃. Ice films, 0.1 to several microns in thickness, were exposed to either ultraviolet photons (110-250 nm) or 0.8-MeV protons to simulate the effects of space environments. Observed products include HCNO (isocyanic acid), NH₄⁺ (ammonium ion), CN⁻ (cyanide ion), OCN⁻ (cyanate ion), HCONH₂ (formamide), and species spectrally similar to HCN polymers. Product formation rates and HCN destruction rates were determined where possible. Results are discussed in terms of astrophysical situations in the ISM and the Solar System where HCN would likely play an important role in prebiotic chemistry. These results imply that if HCN is present in icy mixtures representative of the ISM or in comets, it will be quickly converted into other species in energetic environments; pure HCN seems to be polymerized by incident radiation.     

Thermal stability of water and hydroxyl on the surface of the Moon from temperature-programmed desorption measurements of lunar analog materials

The adsorption of molecular water onto lunar analog materials was investigated under ultra-high vacuum with the goal to better understand the thermal stability and evolution of water on the lunar surface. Temperature-programmed desorption (TPD) experiments show that lunar-analog basaltic-composition glass is hydrophobic, with water-water interactions dominating over surface chemisorption. This suggests that lunar agglutinates will tend not to adsorb water at temperatures above where water clusters and multilayer ice forms. The basalt JSC-1A lunar mare analog, which is a complex mixture of minerals and glass, adsorbs water above 180 K with an adsorption profile that extends to 400 K, showing evidence for a continuum of water adsorption sites. Bancroft albite adsorbs more water, more strongly, than JSC-1A, with a well-defined desorption peak near 225 K. This suggests that mineral surfaces will adsorb more water than mare or mature (glassy, agglutinate rich) surfaces and may explain the association of water with fresh feldspathic craters at high latitudes. The activation energies for the thermal desorption of water from these materials were determined, and along with values from the literature, used to model the grain-to-grain migration of water within the lunar regolith. These models suggest that a combination of recombinative desorption of hydroxyl along with molecular desorption of water and its subsequent migration within and out of the regolith may explain observed diurnal variations in the distribution of water and hydroxyl on the illuminated Moon.     

Radiation-induced amorphization of crystalline ice

We study radiation-induced amorphization of crystalline ice, analyzing the results of three decades of experiments with a variety of projectiles, irradiation energy, and ice temperature, finding a similar trend of increasing resistance of amorphization with temperature and inconsistencies in results from different laboratories. We discuss the temperature dependence of amorphization in terms of the ‘thermal spike’ model. We then discuss the common use of the 1.65 μm infrared absorption band of water as a measure of degree of crystallinity, an increasingly common procedure to analyze remote sensing data of astronomical icy bodies. The discussion is based on new, high quality near-infrared reflectance absorption spectra measured between 1.4 and 2.2 μm for amorphous and crystalline ices irradiated with 225 keV protons at 80 K. We found that, after irradiation with 10¹⁵ protons cm⁻², crystalline ice films thinner than the ion range become fully amorphous, and that the infrared absorption spectra show no significant changes upon further irradiation. The complete amorphization suggests that crystalline ice observed in the outer Solar System, including trans-neptunian objects, may results from heat from internal sources or from the impact of icy meteorites or comets.     

Distribution of hydrate on Europa: Further evidence for sulfuric acid hydrate

Sulfuric acid hydrate has been proposed as an important species on Europa's surface, the acid being produced by radiolysis of surficial sulfur compounds. We investigated the spectral properties of disordered and crystalline forms of sulfuric acid and suggest that the hydration properties of Europa's hypothesized sulfuric acid lie between two end members: liquid sulfuric acid and its higher crystalline hydrates. The spectra of these end members are similar except for spectral shifts at the band edges. We measured the optical constants of sulfuric acid octahydrate and used these with simple radiative transfer calculations to fit Europa spectra obtained by Galileo's Near Infrared Mapping Spectrometer (NIMS). The global distribution of the hydrate that we associate here with hydrated sulfuric acid shows a strong trailing-side enhancement with a maximum fractional hydrate abundance of 90% by volume, corresponding to a sulfur atom to water molecule ratio of 10%. The hydrate concentration spatially correlates with the ultraviolet and visible absorption of the surface and with the sulfur dioxide concentration. The asymmetric global distribution is consistent with Iogenic plasma ion implantation as the source of the sulfur, possibly modified by electron irradiation and sputtering effects. The variegated distribution also correlates with geologic forms. A high spatial resolution image shows resolved lineae with less hydrate appearing within the lineae than in nearby crustal material. The low concentration of hydrated material in these lineae argues against their conveying sulfurous material to the surface from the putative ocean.     

A spectroscopic study of the surfaces of Saturn's large satellites: H2O ice, tholins, and minor constituents

We present spectra of Saturn's icy satellites Mimas, Enceladus, Tethys, Dione, Rhea, and Hyperion, 1.0-2.5 μm, with data extending to shorter (Mimas and Enceladus) and longer (Rhea and Dione) wavelengths for certain objects. The spectral resolution (R=λ/Δλ) of the data shown here is in the range 800-1000, depending on the specific instrument and configuration used; this is higher than the resolution (R=225 at 3 μm) afforded by the Visual-Infrared Mapping Spectrometer on the Cassini spacecraft. All of the spectra are dominated by water ice absorption bands and no other features are clearly identified. Spectra of all of these satellites show the characteristic signature of hexagonal H₂O ice at 1.65 μm. We model the leading hemisphere of Rhea in the wavelength range 0.3-3.6 μm with the Hapke and the Shkuratov radiative transfer codes and discuss the relative merits of the two approaches to fitting the spectrum. In calculations with both codes, the only components used are H₂O ice, which is the dominant constituent, and a small amount of tholin (Ice Tholin II). Tholin in small quantities (few percent, depending on the mixing mechanism) appears to be an essential component to give the basic red color of the satellite in the region 0.3-1.0 μm. The quantity and mode of mixing of tholin that can produce the intense coloration of Rhea and other icy satellites has bearing on its likely presence in many other icy bodies of the outer Solar System, both of high and low geometric albedos. Using the modeling codes, we also establish detection limits for the ices of CO₂ (a few weight percent, depending on particle size and mixing), CH₄ (same), and NH₄OH (0.5 weight percent) in our globally averaged spectra of Rhea's leading hemisphere. New laboratory spectral data for NH₄OH are presented for the purpose of detection on icy bodies. These limits for CO₂, CH₄, and NH₄OH on Rhea are also applicable to the other icy satellites for which spectra are presented here. The reflectance spectrum of Hyperion shows evidence for a broad, unidentified absorption band centered at 1.75 μm.     

Spatially resolved SO2 ice on Io, observed in the near IR

We present equivalent width maps of the 1.98 and 2.13 μm SO₂ ice absorption bands on the surface of Io. The data were taken on 17 April 2006 with the near-infrared mapping spectrometer, OSIRIS at the W.M. Keck Observatory, Hawaii. The maps show significant regional enhancements of SO₂ ice over the Bosphoros, Media, Tarsus and Chalybes Regiones.     

Ultraviolet photolysis of amino acids in a 100 K water ice matrix: Application to the outer Solar System bodies

We report the rates of decomposition by ultraviolet (UV) photolysis of four amino acids in millimeter-thick crystalline water ice matrices at 100 K to constrain the survivability of these important organic molecules within ice lying near the surfaces of outer Solar System bodies. We UV-irradiated crystalline ice samples containing known concentrations of the amino acids glycine, aspartic acid, glutamic acid, and phenylalanine, then we measured the surviving concentrations using high performance liquid chromatography (HPLC) with fluorescence detection. From these experiments, we determine photolytic decomposition rates and half-lives. The half-life varies linearly with the ice thickness for all acids studied here. For example, glycine is the most resistant to photolytic destruction with a half-life of 50, 12, and 3.7 h in 1.6, 0.28, and 0.14 mm thick ices, respectively. We explain this linear variation of half-life with thickness as a consequence of extinction, mostly due to scattering, within these macroscopically thick ice samples. Applied to low latitude surface ice on Jupiter's satellite Europa, this analysis indicates that the concentration of any of these amino acids within the top meter of similar ice will be halved within a ∼10 year timescale.     

Experimental study on the rheological properties of polycrystalline solid nitrogen and methane: Implications for tectonic processes on Triton

To investigate the evolution of any processes on planetary surfaces in the outer Solar System, the rheological properties of non-water ices were studied by means of a sound velocity measurement system and a uniaxial deformation apparatus. A pulse transmission method was used to obtain longitudinal (V_p) and transverse (V_s) wave velocities through solid nitrogen and methane at temperatures ranging from 5 to 64 K and from 5 to 90 K, respectively. The measured velocities confirmed that the solid methane and solid nitrogen samples were non-porous polycrystalline samples without any cracks and bubbles inside. Compression tests at constant strain-rate were performed for solid nitrogen and methane at temperatures of 5-56 K and 5-77 K, respectively, at strain-rates of 10⁻⁴-10⁻² s⁻¹. Both brittle and ductile behavior was observed for solid nitrogen and methane under these conditions. The maximum strength of solid nitrogen was observed to be 9 MPa in the brittle failure mode, and that of solid methane was 10 MPa. These low strengths cannot support cantaloupe structures with the topographic undulation larger than several kilometers found on Triton’s surface, suggesting that other materials such as H₂O ice could underlay solid methane and nitrogen and support these structures.     

Micrometeorite impact annealing of ice in the outer Solar System

The spectra of water ice on the surfaces of icy satellites and Kuiper Belt Objects (KBOs) indicate that the surface ice on these bodies is in a crystalline state. This conflicts with theoretical models, which predict that radiation (galactic cosmic rays and solar ultraviolet) should damage the crystalline structure of ice on geologically short timescales. Temperatures are too low in the outer Solar System for the ice to anneal, and reflectance spectra of these bodies should match those of amorphous solid water (ASW). We assess whether the kinetic energy deposited as heat by micrometeorite impacts on outer Solar System bodies is sufficient to anneal their surface ice down to a near-infrared optical depth . We calculate the kinetic energy flux from interplanetary micrometeorite impacts, including gravitational focusing. We also calculate the thermal diffusion of impact heat in various surfaces and the rate of annealing of ice. We conclude that the rate of annealing from micrometeorite impacts is sufficient to explain the crystallinity of ice on nearly all the surfaces of the saturnian, uranian and neptunian satellites. We discuss how the model can be used in conjunction with spectra of KBOs to probe dust fluxes in the Kuiper Belt.     

Remote sensing D/H ratios in methane ice: Temperature-dependent absorption coefficients of CH3D in methane ice and in nitrogen ice

The existence of strong absorption bands of singly deuterated methane (CH₃D) at wavelengths where normal methane (CH₄) absorbs comparatively weakly could enable remote measurement of D/H ratios in methane ice on outer Solar System bodies. We performed laboratory transmission spectroscopy experiments, recording spectra at wavelengths from 1 to 6 μm to study CH₃D bands at 2.47, 2.87, and 4.56 μm, wavelengths where ordinary methane absorption is weak. We report temperature-dependent absorption coefficients of these bands when the CH₃D is diluted in CH₄ ice and also when it is dissolved in N₂ ice, and describe how these absorption coefficients can be combined with data from the literature to simulate arbitrary D/H ratio absorption coefficients for CH₄ ice and for CH₄ in N₂ ice. We anticipate these results motivating new telescopic observations to measure D/H ratios in CH₄ ice on Triton, Pluto, Eris, and Makemake.     

Louth crater: Evolution of a layered water ice mound

We report on observations made of the ∼36 km diameter crater, Louth, in the north polar region of Mars (at 70° N, 103.2° E). High-resolution imagery from the instruments on the Mars Reconnaissance Orbiter (MRO) spacecraft has been used to map a 15 km diameter water ice deposit in the center of the crater. The water ice mound has surface features that include roughened ice textures and layering similar to that found in the North Polar Layered Deposits. Features we interpret as sastrugi and sand dunes show consistent wind patterns within Louth over recent time. CRISM spectra of the ice mound were modeled to derive quantitative estimates of water ice and contaminant abundance, and associated ice grain size information. These morphologic and spectral results are used to propose a stratigraphy for this deposit and adjoining sand dunes. Our results suggest the edge of the water ice mound is currently in retreat.     

The global distribution of sulfur dioxide ice on Io, observed with OSIRIS on the W.M. Keck telescope

We present ground based observations of Io taken with a high spatial resolution imaging spectrometer on 1 and 2 June 2006. We mapped the 1.98 and 2.12 μm absorptions of SO₂ frost, across Io's surface. We analyze these data with surface reflectance modeling using the Hapke method to determine the general frost distribution. This analysis also determined a lower limit of 700 μm on the grain size for the areas of strongest absorption. We incorporate our findings of a predominantly equatorial distribution of SO₂ frost, with the maps of Carlson et al. [Carlson, R.W., Smythe, W.D., Lopes-Gautier, R.M.C., Davies, A.G., Kamp, L.W., Mosher, J.A., Soderblom, L.A., Leader, F.E., Mehlman, R., Clark, R.N., Fanale, F.P., 1997. Geophys. Res. Lett. 24, 2479-2482], McEwen [McEwen, A.S., 1988. Icarus 73, 385-426] and Douté et al. [Douté, S., Schmitt, B., Lopes-Gautier, R., Carlson, R., Soderblom, L., Shirley, J., and The Galileo NIMS Team, 2001. Icarus 149, 107-132] to produce a self consistent explanation of the global distribution of SO₂. We propose that the differences between the above maps is attributable, in part, to the different bands that were studied by the investigators.