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.     

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.     

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.     

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.     

Refractive index measurements of ammonia and hydrocarbon ices at 632.8 nm

Optical constants in a broad temperature and wavelength range are important input parameters in radiative transfer models used in studies of planetary atmospheres. In the laboratory, the refractive index values of ices at the HeNe laser wavelength (632.8 nm) are often used to monitor the growth rate and thickness of ice films. In this report we present laboratory measurements determining the refractive index at 632.8 nm of ammonia and hydrocarbon ices in the temperature range 80-100 K. Thin ice films are vapor-deposited on a cryogenically cooled mirror located inside a high-vacuum apparatus. The real component of the refractive index of these ice films is determined by a two-angle interferometric technique. Optical modeling calculations of the transmittance and reflectance through the thin ice films assist in the interpretation of the experimental results. We discuss our results and compare them with other measurements available in the literature. The results reported here are relevant to the spectroscopy of icy objects in the solar system; they are needed to perform laboratory characterization of ices, derive optical constants, and model spectra.     

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.     

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.     

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.     

Cassini CIRS update on stratospheric ices at Titan's winter pole

A strong, broad spectral emission feature at 85° N latitude centered at 221 cm⁻¹ remains unidentified after candidate ices of H₂O and pure crystalline CH₃CH₂CN are unambiguously ruled out. A much shallower weak emission feature starts at 160 cm⁻¹ and blends into the strong feature at ∼190 cm⁻¹. This feature is consistent with one formed by an HCN ice cloud composed of ?5 μm radius particles that resides in the lower stratosphere somewhere below an altitude of 160 km. Titan's stratospheric aerosol appears to have a spectral emission feature at about 148 cm⁻¹. The aerosol abundance at 85° N is about a factor 2.2 greater than at 55° S.     

Eclipse reappearances of Io: Time-resolved spectroscopy (1.9-4.2 μm)

We obtained time-resolved, near-infrared spectra of Io during the 60-90 min following its reappearance from eclipse by Jupiter on five occasions in 2004. The purpose was to search for spectral changes, particularly in the well-known SO₂ frost absorption bands, that would indicate surface-atmosphere exchange of gaseous SO₂ induced by temperature changes during eclipse. These observations were a follow-on to eclipse spectroscopy observations in which Bellucci et al. [Bellucci et al., 2004. Icarus 172, 141-148] reported significant changes in the strengths of two strong SO₂ bands in data acquired with the VIMS instrument aboard the Cassini spacecraft. One of the bands (4.07 μm [ν₁ + ν₃]) observed by Bellucci et al. is visible from ground-based observatories and is included in our data. We detected no changes in Io’s spectrum at any of the five observed events during the approximately 60-90 min during which spectra were obtained following Io’s emergence from Jupiter’s shadow. The areas of the three strongest SO₂ bands in the region 3.5-4.15 μm were measured for each spectrum; the variation of the band areas with time does not exceed that which can be explained by the Io’s few degrees of axial rotation during the intervals of observation, and in no case does the change in band strength approach that seen in the Cassini VIMS data. Our data are of sufficient quality and resolution to show the weak 2.198 μm (4549.6 cm⁻¹) 4ν₁ band of SO₂ frost on Io for what we believe is the first time. At one of the events (June 22, 2004), we began the acquisition of spectra ∼6 min before Io reappeared from Jupiter’s shadow, during which time it was detected through its own thermal emission. No SO₂ bands were superimposed on the purely thermal spectrum on this occasion, suggesting that the upper limit to condensed SO₂ in the vertical column above Io’s surface was ∼4 × 10⁻⁵ g cm⁻².     

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.     

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.     

Water ice crystallinity and grain sizes on Dione

Saturn’s satellite Dione is becoming an increasingly important object in the outer Solar System, as evidence for its current activity accumulates. Infrared observations of the surface can provide clues to the history of the body and currently active processes. Using data from the Cassini Visual and Infrared Mapping Spectrometer (VIMS), we perform three sets of analyses that are sensitive to the ice state, temperature, thermal history, grain size and composition of surface ice. These are calculation of a “crystallinity factor”, spectral ratios and water ice band depths. In our analysis, we focus on the dichotomy between the wispy and dark terrain on Dione’s trailing hemisphere, to better understand the source of the different materials and their current properties. Our results suggest two different scenarios: (1) the ice from the wispy region has a higher crystallinity and water ice content than the dark region or (2) the wispy region contains larger grains. Both of these models imply recent geologic activity on Dione.     

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.     

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.     

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.     

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.     

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.     

Radiolysis of sulfuric acid, sulfuric acid monohydrate, and sulfuric acid tetrahydrate and its relevance to Europa

We report laboratory studies on the 0.8 MeV proton irradiation of ices composed of sulfuric acid (H₂SO₄), sulfuric acid monohydrate (H₂SO₄·H₂O), and sulfuric acid tetrahydrate (H₂SO₄·4H₂O) between 10 and 180 K. Using infrared spectroscopy, we identify the main radiation products as H₂O, SO₂, (S₂O₃)_x, H₃O⁺, , and . At high radiation doses, we find that H₂SO₄ molecules are destroyed completely and that H₂SO₄·H₂O is formed on subsequent warming. This hydrate is significantly more stable to radiolytic destruction than pure H₂SO₄, falling to an equilibrium relative abundance of 50% of its original value on prolonged irradiation. Unlike either pure H₂SO₄ or H₂SO₄·H₂O, the loss of H₂SO₄·4H₂O exhibits a strong temperature dependence, as the tetrahydrate is essentially unchanged at the highest irradiation temperatures and completely destroyed at the lowest ones, which we speculate is due to a combination of radiolytic destruction and amorphization. Furthermore, at the lower temperatures it is clear that irradiation causes the tetrahydrate spectrum to transition to one that closely resembles the monohydrate spectrum. Extrapolating our results to Europa’s surface, we speculate that the variations in SO₂ concentrations observed in the chaotic terrains are a result of radiation processing of lower hydration states of sulfuric acid and that the monohydrate will remain stable on the surface over geological times, while the tetrahydrate will remain stable in the warmer regions but be destroyed in the colder regions, unless it can be reformed by other processes, such as thermal reactions induced by diurnal cycling.     

Optical constants of amorphous and crystalline H2O-ice in the near infrared from 1.1 to 2.6 μm

Using new laboratory spectra, we have calculated the real and imaginary parts of the index of refraction of amorphous and crystalline H₂O-ice from 20 to 150 K in the frequency range 9000-3800 cm⁻¹ (1.1-2.6 μm) at a spectral resolution of 1 cm⁻¹. These optical constants can be used to create model spectra for comparison to spectra from Solar System objects. We also analyzed the differences between the amorphous and crystalline H₂O-ice spectra, including weakening of bands and shifting of bands to shorter wavelength in amorphous H₂O-ice spectra. We have also observed two spectrally distinct phases of amorphous H₂O-ice.