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.     

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.     

Ethane ices in the outer Solar System: Spectroscopy and chemistry

We report recent experiments on ethane ices made at temperatures applicable to the outer Solar System. New near- and mid-infrared data for crystalline and amorphous ethane, including new spectra for a seldom-studied solid phase that exists at 35-55 K, are presented along with radiation-chemical experiments showing the formation of more-complex hydrocarbons.     

Thermal evolution of Kuiper belt objects, with implications for cryovolcanism

We investigate the internal thermal evolution of Kuiper belt objects (KBOs), small (radii <1000 km), icy (mean densities ) bodies orbiting beyond Neptune, focusing on Pluto's moon Charon in particular. Our calculations are time-dependent and account for differentiation. We review evidence for ammonia hydrates in the ices of KBOs, and include their effects on the thermal evolution. A key finding is that the production of the first melt, at the melting point of ammonia dihydrate, ≈176 K, triggers differentiation of rock and ice. The resulting structure comprises a rocky core surrounded by liquids and ice, enclosed within a >100-km thick undifferentiated crust of rock and ice. This structure is especially conducive to the retention of subsurface liquid, and bodies the size of Charon or larger (radii >600 km) are predicted to retain some subsurface liquid to the present day. We discuss the possibility that this liquid can be brought to the surface rapidly via self-propagating cracks. We conclude that cryovolcanism is a viable process expected to affect the surfaces of large KBOs including Charon.     

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.     

Chemical and physical properties of the variegated Pluto and Charon surfaces

We present new photometric and spectroscopic observations of the Pluto–Charon system carried out at the VLT-ESO (Chile) with two 8-m telescopes equipped with the FORS2, ISAAC and SINFONI instruments. The spectra were obtained in the 0.6–2.45 μm range with a spectral resolution from 300 to 1500. The SINFONI data were obtained using adaptive optics, allowing a complete separation of the two bodies. We derive both objects’ magnitudes in the near infrared and convert them into albedo values. These first near infrared photometric data allow to adjust the different parts of Pluto’s spectrum, provided by the three instruments. We run spectral models in order to give chemical and physical constraints on the surface of Pluto and Charon. We discuss the dilution properties of the methane ice and its implications on Pluto’s surface. The heterogeneities of the pure and diluted methane ice on Pluto’s surface is also investigated. The high signal-to-noise level of the data and our analyses may support the presence of ethane ice on the surface of Pluto, which is one of the main products of the methane irradiation and photolysis. The analyses of the spectra of Charon suggest that the water ice is almost completely in its crystalline form and that the ammonia compound is hydrated on the surface of this satellite.     

The formation and stability of carbonic acid on outer Solar System bodies

The radiation chemistry, thermal stability, and vapor pressure of solid-phase carbonic acid (H₂CO₃) have been studied with mid-infrared spectroscopy. A new procedure for measuring this molecule’s radiation stability has been used to obtain intrinsic IR band strengths and half-lives for radiolytic destruction. We report, for the first time, measurements of carbonic acid’s vapor pressure (0.290-2.33 × 10⁻¹¹ bar for 240-255 K) and its enthalpy of sublimation (71 ± 9 kJ mol⁻¹). We also report the first observation of a chemical reaction involving solid-phase carbonic acid. Possible applications of these findings are discussed, with an emphasis on the outer Solar System icy surfaces.     

Evidence of N2-ice on the surface of the icy dwarf Planet 136472 (2005 FY9)

We present high signal precision optical reflectance spectra of 2005 FY9 taken with the Red Channel Spectrograph and the 6.5-m MMT telescope on 2006 March 4 UT (5000-9500 Å; 6.33 Å pixel⁻¹) and 2007 February 12 UT (6600-8500 Å; 1.93 Å pixel⁻¹). From cross-correlation experiments between the 2006 March 4 spectrum and a pure CH₄-ice Hapke model, we find the CH₄-ice bands in the MMT spectrum are blueshifted by 3 ± 4 Å relative to bands in the pure CH₄-ice Hapke spectrum. The higher resolution MMT spectrum of 2007 February 12 UT enabled us to measure shifts of individual CH₄-ice bands. We find the 7296, 7862, and 7993 Å CH₄-ice bands are blueshifted by 4 ± 2, 4 ± 4, and 6 ± 5 Å. From four measurements we report here and one of our previously published measurements, we find the CH₄-ice bands are shifted by 4 ± 1 Å. This small shift is important because it suggest the presence of another ice component on the surface of 2005 FY9. Laboratory experiments show that CH₄-ice bands in spectra of CH₄ mixed with other ices are blueshifted relative to bands in spectra of pure CH₄-ice. A likely candidate for the other component is N₂-ice because its weak 2.15 μm band and blueshifted CH₄ bands are seen in spectra of Triton and Pluto. Assuming the shift is due to the presence of N₂, spectra taken on two consecutive nights show no difference in CH₄/N₂. In addition, we find no measurable difference in CH₄/N₂ at different depths into the surface of 2005 FY9.     

Fracture penetration in planetary ice shells

The proposed past eruption of liquid water on Europa and ongoing eruption of water vapor and ice on Enceladus have led to discussion about the feasibility of cracking a planetary ice shell. We use a boundary element method to model crack penetration in an ice shell subjected to tension and hydrostatic compression. We consider the presence of a region at the base of the ice shell in which the far-field extensional stresses vanish due to viscoelastic relaxation, impeding the penetration of fractures towards a subsurface ocean. The maximum extent of fracture penetration can be limited by hydrostatic pressure or by the presence of the unstressed basal layer, depending on its thickness. Our results indicate that Europa's ice shell is likely to be cracked under 1-3 MPa tension only if it is ?2.5 km thick. Enceladus' ice shell may be completely cracked if it is capable of supporting ∼1-3 MPa tension and is less than 25 km thick.     

Subsurface oceans and deep interiors of medium-sized outer planet satellites and large trans-neptunian objects

The detection of induced magnetic fields in the vicinity of the jovian satellites Europa, Ganymede, and Callisto is one of the most surprising findings of the Galileo mission to Jupiter. The observed magnetic signature cannot be generated in solid ice or in silicate rock. It rather suggests the existence of electrically conducting reservoirs of liquid water beneath the satellites' outermost icy shells that may contain even more water than all terrestrial oceans combined. The maintenance of liquid water layers is closely related to the internal structure, composition, and thermal state of the corresponding satellite interior. In this study we investigate the possibility of subsurface oceans in the medium-sized icy satellites and the largest trans-neptunian objects (TNO's). Controlling parameters for subsurface ocean formation are the radiogenic heating rate of the silicate component and the effectiveness of the heat transfer to the surface. Furthermore, the melting temperature of ice will be significantly reduced by small amounts of salts and/or incorporated volatiles such as methane and ammonia that are highly abundant in the outer Solar System. Based on the assumption that the satellites are differentiated and using an equilibrium condition between the heat production rate in the rocky cores and the heat loss through the ice shell, we find that subsurface oceans are possible on Rhea, Titania, Oberon, Triton, and Pluto and on the largest TNO's 2003 UB₃₁₃, Sedna, and 2004 DW. Subsurface oceans can even exist if only small amounts of ammonia are available. The liquid subsurface reservoirs are located deeply underneath an ice-I shell of more than 100 km thickness. However, they may be indirectly detectable by their interaction with the surrounding magnetic fields and charged particles and by the magnitude of a satellite's response to tides exerted by the primary. The latter is strongly dependent on the occurrence of a subsurface ocean which provides greater flexibility to a satellite's rigid outer ice shell.     

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

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

Carbon dioxide on planetary bodies: Theoretical and experimental studies of molecular complexes

An absorption band at ∼4.26 μm wavelength attributed to the asymmetric stretching mode of CO in CO₂ has been found on two satellites of Jupiter and several satellites of Saturn. The wavelength of pure CO₂ ice determined in the laboratory is 4.2675 μm, indicating that the CO₂ on the satellites occurs either trapped in a host material, or in a chemical or physical complex with other materials, resulting in a blue shift of the wavelength of the band. In frequency units, the shifts in the satellite spectra range from 3.7 to 11.3 cm⁻¹. We have performed ab initio quantum chemical calculations of CO₂ molecules chemically complexed with one, two, and more H₂O molecules and molecules of CH₃OH to explore the possibility that the blue shift of the band is caused by chemical complexing of CO₂ with other volatile materials. Our computations of the harmonic and anharmonic vibrational frequencies using high levels of theory show a frequency shift to the blue by 5 cm⁻¹ from pure CO₂ to CO-H₂O, and an additional 5 cm⁻¹ from CO₂-H₂O to CO₂-2H₂O. Complexing with more than two H₂O molecules does not increase the blue shift. Complexes of CO₂ with one molecule of CH₃OH and with one CH₃OH plus one H₂O molecule produce smaller shifts than the CO₂-2H₂O complex. Laboratory studies of CO₂:H₂O in a solid N₂ matrix also show a blue shift of the asymmetric stretching mode.     

Surface composition and physical properties of several trans-neptunian objects from the Hapke scattering theory and Shkuratov model

Several different trans-neptunian objects have been studied in order to investigate their physical and chemical properties. New observations in the 1.1-1.4 μm range, obtained with the ISAAC instrument, are presented in order to complete previous observations carried out with FORS1 in the visible and SINFONI in the near infrared. All of the observations have been performed at the ESO/Very Large Telescope. We analyze the spectra of six different objects (2003 AZ₈₃, Echeclus, Ixion, 2002 AW₁₉₇, 1999 DE₉ and 2003 FY₁₂₈) in the 0.45-2.3 μm range with the model of Hapke (Hapke, B. [1981]. J. Geophys. Res. 86, 4571-4586) and the method of Shkuratov et al. (Shkuratov, Y., Starukhina, L., Hoffmann, H., Arnold, G. [1999]. Icarus 137, 235-246). Water ice is found on two objects, and in particular it is confirmed in its amorphous and crystalline states on 2003 AZ₈₄ surface. Upper limits on the water ice content are given for the other four TNOs investigated, confirming previous results (Barkume, K.M., Brown, M.E., Schaller, E.L. [2008]. Astron. J. 135, 55-67; Guilbert, A., Alvarez-Candal, A., Merlin, F., Barucci, M.A., Dumas, C., de Bergh, C., Delsanti, A. [2009]. Icarus 201, 272-283). Whatever the absorption features in the near infrared, all objects but one exhibit a moderate red slope in the visible, as most TNOs and Centaurs. We discuss the implications of the presence of water ice and the probable sources of the red slope.     

On convection in ice I shells of outer Solar System bodies, with detailed application to Callisto

It has been argued that the dominant non-Newtonian creep mechanisms of water ice make the ice shell above Callisto's ocean, and by inference all radiogenically heated ice I shells in the outer Solar System, stable against solid-state convective overturn. Conductive heat transport and internal melting (oceans) are therefore predicted to be, or have been, widespread among midsize and larger icy satellites and Kuiper Belt objects. Alternatively, at low stresses (where non-Newtonian viscosities can be arbitrarily large), convective instabilities may arise in the diffusional creep regime for arbitrarily small temperature perturbations. For Callisto, ice viscosities are low enough that convection is expected over most of geologic time above the internal liquid layer for plausible ice grain sizes (?a few mm); the alternative for early Callisto, a conducting shell over a very deep ocean (>450 km), is not compatible with Callisto's present partially differentiated state. Moreover, if convection is occurring today, the stagnant lid would be quite thick (∼100 km) and compatible with the lack of active geology. Nevertheless, Callisto's steady-state heat flow may have fallen below the convective minimum for its ice I shell late in Solar System history. In this case convection ends, the ice shell melts back at its base, and the internal ocean widens considerably. The presence of such an ocean, of order 200 km thick, is compatible with Callisto's moment-of-inertia, but its formation would have caused an ∼0.25% radial expansion. The tectonic effects of such a late, slow expansion are not observed, so convection likely persists in Callisto, possibly subcritically. Ganymede, due to its greater size, rock fraction and full differentiation, has a substantially higher heat flow than Callisto and has not reached this tectonic end state. Titan, if differentiated, and Triton should be more similar to Ganymede in this regard. Pluto, like Callisto, may be near the tipping point for convective shutdown, but uncertainties in its size and rock fraction prevent a more definitive assessment.     

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.     

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.     

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.     

Comment on “Mechanics of tidally driven fractures in Europa's ice shell” by S. Lee, R.T. Pappalardo, and N.C. Makris [2005. Icarus 177, 367-379]

We show Lee, Pappalardo, and Makris' [2005. Icarus 177, 367-379] argument that surface cracks in Europa's icy shell penetrate 3-10 times deeper in the presence of subsurface ocean is not correct. We use numerical calculations to demonstrate that there is at most 50% increase in penetration depth for a crack opening in a shell of finite thickness compared to a half-space. We also propose a simple equation based on force balances to estimate the maximum thickness of an ice shell that can be opened under tensile stress. Our calculations show that a crack can only penetrate 330-m-thick ice shell under 200 kPa far-field tensile stress and half of that if the stress is 100 kPa. But the presence of water would allow crack penetrate ∼4.0 km into the ice shell with zero porosity.     

Constraining the surface properties of Saturn's icy moons, using Cassini/CIRS emissivity spectra

We have conducted a search for emissivity features in the thermal infrared spectrum of the icy satellites of Saturn, Phoebe, Iapetus, Enceladus, Tethys, and Hyperion, observed by the Composite Infrared Spectrometer (CIRS) on board the Cassini spacecraft. Despite the heterogeneity of the composition of these bodies depicted by Earth-based and Cassini/VIMS observations, the CIRS spectra of all satellites are undistinguishable from black-body spectra, with no detectable emissivity feature. However, several materials, which have been detected on the surface of the same bodies, present emissivity features in the analyzed spectral range. In particular, water ice presents features with sufficient contrast to be detected by CIRS. Here we study the physical causes of the absence of features by simulating the effects of intimate mixtures using models of directional emissivity for optically thick surfaces for different particle sizes and abundances, and porosities. The simulations include a set of materials detected on the Phoebe's surface, like water ice, hydrated silicates, and organics. We find that featureless spectra can be produced in three scenarios: (1) ice particles with large sizes, (2) mixtures of ices dominated by dark contaminants, and (3) small particles with large porosity. Constraints imposed by the NIR spectra of the satellites favors the latter scenario as the more likely explanation to the absence of emissivity features on the icy satellites of Saturn.     

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.