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.     

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.     

Trapping and adsorption of CO2 in amorphous ice: A FTIR study

The interaction of carbon dioxide and amorphous water ice at 95 K is studied using transmission infrared spectroscopy. Samples are prepared in two ways: co-deposition of the gases admitted simultaneously or sequential deposition, in which amorphous water ice (ASW) is grown first and CO₂ vapor is added subsequently. In either case, a fraction of the CO₂ molecules is found to interact with water in a way that gives rise to shifts and splittings in the infrared bands with respect to those of a pure CO₂ solid. In co-deposition experiments, a larger amount of carbon dioxide is trapped within the amorphous water than in sequential deposition samples, where a substantial proportion of molecules appears to be trapped in macropores of the ASW. The specific surface area of sequential samples is evaluated and compared to previous literature results. When the sequential samples are heated to 140 K, beyond the onset temperature at which water ice undergoes a phase transition, the CO₂ molecules at the pores relocate inside the bulk in a structure similar to that found in co-deposited samples, as deduced by changes in the shape of the CO₂ infrared bands.     

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.     

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.     

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.     

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.     

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.     

The high-pressure phase relation of the MgSO4-H2O system and its implication for the internal structure of Ganymede

We have determined the phase relation of the MgSO₄-H₂O binary system using an externally heated diamond anvil cell in the compositional range of 0-30 wt.% MgSO₄, and under temperature and pressure conditions from 298 to 500 K and up to 4.5 GPa. Using our experimental results, we were able to estimate the composition of the ice mantle of the large icy satellites of Jupiter, such as Ganymede.In our experiments, we identified the following phases in the MgSO₄-H₂O system up to 4 GPa at 298 K: Ices VI and VII, magnesium heptahydrate, MgSO₄·7H₂O, and a liquid phase. The present phase relations suggest that there may be a deep internal ocean down to a depth about 800 km in the interior of Ganymede.     

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.     

Iapetus surface variability revealed from statistical clustering of a VIMS mosaic: The distribution of CO2

We present a detailed study of an Iapetus mosaic of VIMS data with high spatial resolution (0.5 × 0.5° or ∼6.4 km/pixel). The spectra were taken in August 2007 and provide the highest VIMS spatial resolution data for this object during Cassini’s primary mission. We analyze this set of data using a statistical clustering approach to reduce the analysis of a large number of data (∼10⁴ spectra from 0.35 to 5.10 μm) to the study of seven representative groups accounting for 99.6% of the surface covered by the original sample. We analyze the spectral absorption bands in the spectra of the different clusters indicative of different composition over the observed surface. We find coherence between the distribution of the clusters and the geographical features on the surface. We give special attention to the study of the water ice and CO₂ bands. We find that CO₂ is widespread over the entire surface being studied, including the bright and dark areas on Iapetus’ surface, and is probably trapped at the molecular level with other materials. The strength of the CO₂ band in the areas where both, H₂O- and carbon-bearing materials exist, gives support to the hypothesis that this volatile is formed on the surface of Iapetus as a product of irradiation of these two components. Finally, we also compare the Iapetus CO₂ with that on other satellites confirming, that there are evident differences on the center, depth and width of the band on Iapetus and Phoebe, where CO₂ has been suggested to be endogenous.     

Ion irradiation of crystalline H2O-ice: Effect on the 1.65-μm band

We have found that 0.8 MeV proton irradiation of crystalline H₂O-ice results in temperature dependent amorphization. The H₂O-ice's phase was determined using the near infrared spectrum from 1.0 μm (10,000 cm⁻¹) to 2.5 μm (4000 cm⁻¹). In crystalline H₂O-ice, the 1.65-μm (6061 cm⁻¹) band is strong while it is nearly absent in the amorphous spectrum [Schmitt, B., Quirico, E., Trotta, F., Grundy, W.M., 1998. In: Schmitt, B., de Bergh, C., Festou, M. (Eds.), Solar System Ices. Kluwer Academic, Norwell, MA, 1998, pp. 199-240]. In this experiment, at low temperatures (9, 25, and 40 K), irradiation of crystalline H₂O-ice produced the amorphous H₂O-ice's spectrum. However, at 50 K, some crystalline absorptions persisted after irradiation and at 70 and 100 K the crystalline spectrum showed only slight changes after irradiation. Our results agree with previous H₂O-ice irradiation studies examining the crystalline peaks near 44 and 62 μm by Moore and Hudson [Moore, M.H., Hudson, R.L., 1992. Astrophys. J. 401, 353-360] and near 3.07 μm by Strazzulla et al. [Strazzulla, G., Baratta, G.A., Leto, G., Foti, G., 1992. Europhys. Lett. 18, 517-522] and by Leto and Baratta [Leto, G., Baratta, G.A., 2003. Astron. Astrophys. 397, 7-13]. We present a method of measuring band areas to quantify the phase and radiation dose of icy Solar System surfaces.     

The orbit, mass, size, albedo, and density of (65489) Ceto/Phorcys: A tidally-evolved binary Centaur

Hubble Space Telescope observations of Uranus- and Neptune-crossing object (65489) Ceto/Phorcys (provisionally designated 2003 FX₁₂₈) reveal it to be a close binary system. The mutual orbit has a period of 9.554±0.011 days and a semimajor axis of 1840±48 km. These values enable computation of a system mass of (5.41±0.42)×¹⁰¹⁸ kg. Spitzer Space Telescope observations of thermal emission at 24 and 70 μm are combined with visible photometry to constrain the system's effective radius and geometric albedo . We estimate the average bulk density to be , consistent with ice plus rocky and/or carbonaceous materials. This density contrasts with lower densities recently measured with the same technique for three other comparably-sized outer Solar System binaries (617) Patroclus, (26308) 1998 SM₁₆₅, and (47171) 1999 TC₃₆, and is closer to the density of the saturnian irregular satellite Phoebe. The mutual orbit of Ceto and Phorcys is nearly circular, with an eccentricity ?0.015. This observation is consistent with calculations suggesting that the system should tidally evolve on a timescale shorter than the age of the Solar System.     

Rotation and cometary activity of KBO (29981) 1999 TD10

We describe observations of the scattered Kuiper Belt object (29981) 1999 TD₁₀ performed during five observing runs at two observatories, over 370 days from 2000 September to 2001 September. They show significant brightness variations that fit a double-peaked lightcurve with period 15.448±0.012 h in V and R bands. The phase effect in V band, 0.09±0.01 mag deg⁻¹, is smaller than that of Pluto but larger than that of several KBOs, while in R band it is 0.030±0.005 mag deg⁻¹. We find color variation between the two bands, which implies a non-homogeneous albedo distribution on the surface. Evidence of surface activity near perihelion in the form of a coma/tail is presented using radial image profiles and a 2D contour map.     

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.     

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.     

The coating hypothesis for ammonia ice particles in Jupiter: Laboratory experiments and optical modeling

We report laboratory experiments and modeling calculations investigating the effect of a hydrocarbon coating on ammonia ice spectral signatures. Observational evidence and thermochemical models indicate an abundance of ammonia ice clouds in Jupiter's atmosphere. However, spectrally identifiable ammonia ice clouds are found covering less than 1% of Jupiter's atmosphere, notably in areas of strong vertical transport, indicating a short lifetime for the signature of ammonia absorption on condensed ammonia particles [Baines, K.H., Carlson, R.W., Kamp, L.W., 2002. Icarus 159, 74-94]. Current literature has suggested coating of ammonia ice particles by a hydrocarbon haze as a possible explanation for this paradox. The work presented here supports the inference of a coating effect that can alter or suppress ammonia absorption features. In the experiments, thin films of ammonia ices are deposited in a cryogenic apparatus, coated with hydrocarbons, and characterized by reflection-absorption infrared spectroscopy. We have observed the effects on the ammonia ice absorption features near 3 and 9 μm with coverage by thin layers of hydrocarbons. Modeling calculations of these multilayer thin films assist in the interpretation of the experimental results and reveal the important role of optical interference in altering the aforementioned ammonia spectral features. Mie and T-matrix scattering calculations demonstrate analogous effects for ammonia ice particles and investigate the relative effects of ammonia ice particle size, shape, and coating layer thickness on the ice particle spectral signatures.     

Compositional mapping of Saturn's satellite Dione with Cassini VIMS and implications of dark material in the Saturn system

Cassini VIMS has obtained spatially resolved imaging spectroscopy data on numerous satellites of Saturn. A very close fly-by of Dione provided key information for solving the riddle of the origin of the dark material in the Saturn system. The Dione VIMS data show a pattern of bombardment of fine, sub-0.5-μm diameter particles impacting the satellite from the trailing side direction. Multiple lines of evidence point to an external origin for the dark material on Dione, including the global spatial pattern of dark material, local patterns including crater and cliff walls shielding implantation on slopes facing away from the trailing side, exposing clean ice, and slopes facing the trailing direction which show higher abundances of dark material. Multiple spectral features of the dark material match those seen on Phoebe, Iapetus, Hyperion, Epimetheus and the F-ring, implying the material has a common composition throughout the Saturn system. However, the exact composition of the dark material remains a mystery, except that bound water and, tentatively, ammonia are detected, and there is evidence both for and against cyanide compounds. Exact identification of composition requires additional laboratory work. A blue scattering peak with a strong UV-visible absorption is observed in spectra of all satellites which contain dark material, and the cause is Rayleigh scattering, again pointing to a common origin. The Rayleigh scattering effect is confirmed with laboratory experiments using ice and 0.2-μm diameter carbon grains when the carbon abundance is less than about 2% by weight. Rayleigh scattering in solids is also confirmed in naturally occurring terrestrial rocks, and in previously published reflectance studies. The spatial pattern, Rayleigh scattering effect, and spectral properties argue that the dark material is only a thin coating on Dione's surface, and by extension is only a thin coating on Phoebe, Hyperion, and Iapetus, although the dark material abundance appears higher on Iapetus, and may be locally thick. As previously concluded for Phoebe, the dark material appears to be external to the Saturn system and may be cometary in origin. We also report a possible detection of material around Dione which may indicate Dione is active and contributes material to the E-ring, but this observation must be confirmed.     

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.     

Saturn’s icy satellites investigated by Cassini-VIMS: II. Results at the end of nominal mission

We report the detailed analysis of the spectrophotometric properties of Saturn’s icy satellites as derived by full-disk observations obtained by visual and infrared mapping spectrometer (VIMS) experiment aboard Cassini. In this paper, we have extended the coverage until the end of the Cassini’s nominal mission (June 1st 2008), while a previous paper (Filacchione, G., and 28 colleagues [2007]. Icarus 186, 259-290, hereby referred to as Paper I) reported the preliminary results of this study.During the four years of nominal mission, VIMS has observed the entire population of Saturn’s icy satellites allowing us to make a comparative analysis of the VIS-NIR spectral properties of the major satellites (Mimas, Enceladus, Tethys, Dione, Rhea, Hyperion, Iapetus) and irregular moons (Atlas, Prometheus, Pandora, Janus, Epimetheus, Telesto, Calypso, Phoebe). The results we discuss here are derived from the entire dataset available at June 2008 which consists of 1417 full-disk observations acquired from a variety of distances and inclinations from the equatorial plane, with different phase angles and hemispheric coverage. The most important spectrophotometric indicators (as defined in Paper I: I/F continua at 0.55 μm, 1.822 μm and 3.547 μm, visible spectral slopes, water and carbon dioxide bands depths and positions) are calculated for each observation in order to investigate the disk-integrated composition of the satellites, the distribution of water ice respect to “contaminants” abundances and typical regolith grain properties. These quantities vary from the almost pure water ice surfaces of Enceladus and Calypso to the organic and carbon dioxide rich Hyperion, Iapetus and Phoebe. Janus visible colors are intermediate between these two classes having a slightly positive spectral slope. These results could help to decipher the origins and evolutionary history of the minor moons of the Saturn’s system. We introduce a polar representation of the spectrophotometric parameters as function of the solar phase angle (along radial distance) and of the effective longitude interval illuminated by the Sun and covered by VIMS during the observation (in azimuth) to better investigate the spatial distribution of the spectrophotometric quantities across the regular satellites hemispheres. Finally, we report the observed spectral positions of the 4.26 μm band of the carbon dioxide present in the surface material of three outermost moons Hyperion, Iapetus and Phoebe.