Alkali and Chlorine Photochemistry in a Volcanically Driven Atmosphere on Io

Observations of the Io plasma torus and neutral clouds indicate that the extended ionian atmosphere must contain sodium, potassium, and chlorine in atomic and/or molecular form. Models that consider sublimation of pure sulfur dioxide frost as the sole mechanism for generating an atmosphere on Io cannot explain the presence of alkali and halogen species in the atmosphere—active volcanoes or surface sputtering must also be considered, or the alkali and halide species must be discharged along with the SO₂ as the frost sublimates. To determine how volcanic outgassing can affect the chemistry of Io's atmosphere, we have developed a one-dimensional photochemical model in which active volcanoes release a rich suite of S-, O-, Na-, K-, and Cl-bearing vapor and in which photolysis, chemical reactions, condensation, and vertical eddy and molecular diffusion affect the subsequent evolution of the volcanic gases. Observations of Pele plume constituents, along with thermochemical equilibrium calculations of the composition of volcanic gases exsolved from high-temperature silicate magmas on Io, are used to constrain the composition of the volcanic vapor. We find that NaCl, Na, Cl, KCl, and K will be the dominant alkali and chlorine gases in atmospheres generated from Pele-like plume eruptions on Io. Although the relative abundances of these species will depend on uncertain model parameters and initial conditions, these five species remain dominant for a wide variety of realistic conditions. Other sodium and chlorine molecules such as NaS, NaO, Na₂, NaS₂, NaO₂, NaOS, NaSO₂, SCl, ClO, Cl₂, S₂Cl, and SO₂Cl₂ will be only minor constituents in the ionian atmosphere because of their low volcanic emission rates and their efficient photochemical destruction mechanisms. Our modeling has implications for the general appearance, properties, and variability of the neutral sodium clouds and jets observed near Io. The neutral NaCl molecules present at high altitudes in atmosph eres generated by active volcanoes might provide the NaX⁺ ion needed to help explain the morphology of the high-velocity sodium “stream” feature observed near Io.     

Photochemistry of a Volcanically Driven Atmosphere on Io: Sulfur and Oxygen Species from a Pele-Type Eruption

To determine how active volcanism might affect the standard picture of sulfur dioxide photochemistry on Io, we have developed a one-dimensional atmospheric model in which a variety of sulfur-, oxygen-, sodium-, potassium-, and chlorine-bearing volatiles are volcanically outgassed at Io's surface and then evolve due to photolysis, chemical kinetics, and diffusion. Thermochemical equilibrium calculations in combination with recent observations of gases in the Pele plume are used to help constrain the composition and physical properties of the exsolved volcanic vapors. Both thermochemical equilibrium calculations (Zolotov and Fegley 1999, Icarus141, 40-52) and the Pele plume observations of Spencer et al. (2000; Science288, 1208-1210) suggest that S₂ may be a common gas emitted in volcanic eruptions on Io. If so, our photochemical models indicate that the composition of Io's atmosphere could differ significantly from the case of an atmosphere in equilibrium with SO₂ frost. The major differences as they relate to oxygen and sulfur species are an increased abundance of S, S₂, S₃, S₄, SO, and S₂O and a decreased abundance of O and O₂ in the Pele-type volcanic models as compared with frost sublimation models. The high observed SO/SO₂ ratio on Io might reflect the importance of a contribution from volcanic SO rather than indicate low eddy diffusion coefficients in Io's atmosphere or low SO “sticking” probabilities at Io's surface; in that case, the SO/SO₂ ratio could be temporally and/or spatially variable as volcanic activity fluctuates. Many of the interesting volcanic species (e.g., S₂, S₃, S₄, and S₂O) are short lived and will be rapidly destroyed once the volcanic plumes shut off; condensation of these species near the source vent is also likely. The diffuse red deposits associated with active volcanic centers on Io may be caused by S₄ radicals that are created and temporarily preserved when sulfur vapor (predominantly S₂) condenses around the volcanic vent. Condensation of SO across the surface and, in particular, in the polar regions might also affect the surface spectral properties. We predict that the S/O ratio in the torus and neutral clouds might be correlated with volcanic activity—during periods when volcanic outgassing of S₂ (or other molecular sulfur vapors) is prevalent, we would expect the escape of sulfur to be enhanced relative to that of oxygen, and the S/O ratio in the torus and neutral clouds could be correspondingly increased.     

Alkali and halogen chemistry in volcanic gases on Io

We use chemical equilibrium calculations to model the speciation of alkalis and halogens in volcanic gases emitted on Io. The calculations cover wide temperature (500-2000 K) and pressure (10⁻⁶ to 10⁺¹ bars) ranges, which overlap the nominal conditions at Pele (T=1760 K, P=0.01 bars). About 230 compounds of 11 elements (O, S, Li, Na, K, Rb, Cs, F, Cl, Br, I) are considered. The elemental abundances for O, S, Na, K, and Cl are based upon observations. CI chondritic elemental abundances relative to sulfur are used for the other alkalis and halogens (as yet unobserved on Io). We predict the major alkali species in Pele-like volcanic gases and the percentage distribution of each alkali are LiCl (73%), LiF (27%); NaCl (81%), Na (16%), NaF (3%); KCl (91%), K (5%), KF (4%); RbCl (93%), Rb (4%), RbF (3%); CsCl (92%), CsF (6%), Cs (2%). Likewise the major halogen species and the percentage distribution of each halogen are NaF (88%), KF (10%), LiF (2%); NaCl (89%), KCl (11%); NaBr (89%), KBr (10%), Br (1%); NaI (61%), I (30%), KI (9%). We predict the major halogen condensates and their condensation temperatures at P=0.01 bar are NaF (1115 K), LiF (970 K); NaCl (1050 K), KCl (950 K); KBr (750 K), RbBr (730 K), CsBr (645 K); and solid I₂ (200 K). We also model disequilibrium chemistry of the alkalis and halogens in the volcanic plume. Based on this work and our prior modeling for Na, K, and Cl in a volcanic plume, we predict the major loss processes for the alkali halide gases are photolysis and/or condensation onto grains. Their estimated photochemical lifetimes range from a few minutes for alkali iodides to a few hours for alkali fluorides. Condensation is apparently the only loss process for elemental iodine. On the basis of elemental abundances and photochemical lifetimes, we recommend searching for gaseous KCl, NaF, LiF, LiCl, RbF, RbCl, CsF, and CsCl around volcanic vents during eruptions. Based on abundance considerations and observations of brown dwarfs we also recommend a search of Io's extended atmosphere and the Io plasma torus for neutral and ionized Li, Cs, Rb, and F.     

Evolution of Io's volatile inventory

Using Voyager results, we have made crude estimates of the rate at which Io loses volatiles by a variety of processes to the surrounding magnetosphere for both the current SO₂-dominated atmosphere as well as hypothetical paleoatmospheres in which other gases, such as N₂, may have been the dominant constituent. Loss rates are strongly influenced by the surface pressure on the night side, the relationship between the exobase and the Jovian magnetospheric boundary, the exospheric temperature, and the peak altitudes reached by volcanic plumes. Several mechanisms make significant contributions to the prodigious rate at which Io is currently losing volatiles. These include: interaction of the magnetospheric plasma with volcanic plume particles and the background atmosphere; sputtering of ices on the surface, if the nightside atmospheric pressure is low enough; and Jeans' escape of O, a dissociation product of SO₂ gas. For paleoatmospheres, only the first two of these mechanisms would have been effective. However, they are capable of eliminating large amounts of N₂ and other volatiles from Io over the satellite's lifetime. Io could have also lost large amounts of water over its lifetime due to the extensive recycling of water between its upper and lower crust, with the partial dissociation of water vapor in silicate magma chambers initiating this loss process. Significant amounts of water may also have been lost as a result of the interaction of the magnetospheric plasma with water ice particles in volcanic plumes. Once an SO₂-dominated atmosphere becomes established, much water may have also been lost through the sputtering of surface water ice.     

A thermodynamic model of high temperature lava vaporization on Io

We modified the MAGMA chemical equilibrium code developed by Fegley and Cameron (1987, Earth Planet. Sci. Lett. 82, 207-222) and used it to model vaporization of high temperature silicate lavas on Io. The MAGMA code computes chemical equilibria in a melt, between melt and its equilibrium vapor, and in the gas phase. The good agreement of MAGMA code results with experimental data and with other computer codes is demonstrated. The temperature-dependent pressure and composition of vapor in equilibrium with lava is calculated from 1700 to 2400 K for 109 different silicate lavas in the ONaKFeSiMgCaAlTi system. Results for five lavas (tholeiitic basalt, alkali basalt, Barberton komatiite, dunite, and a molten type B1 Ca, Al-rich inclusion) are discussed in detail. The effects of continuous fractional vaporization on chemistry of these lavas and their equilibrium vapor are presented. The predicted abundances (relative to Na) of K, Fe, Si, Al, Ca, and Ti in the vapor equilibrated with lavas at 1900 K are lower than published upper limits for Io's atmosphere (which do not include Mg). We predict evaporative loss of alkalis, Fe, and Si during volcanic eruptions. Sodium is more volatile than K, and the Na/K ratio in the gas is decreased by fractional vaporization. This process can match Io's atmospheric Na/K ratio of 10±3 reported by Brown (2001, Icarus 151, 190-195). Silicon monoxide is an abundant species in the vapor above lavas. Spectroscopic searches are recommended for SiO at IR and mm wavelengths. Reactions of metallic vapors with S- and Cl-bearing volcanic gases may form other unusual gases including MgCl₂, MgS, MgCl, FeCl₂, FeS, FeCl, and SiS.     

S2O, polysulfuroxide and sulfur polymer on Io's surface?

To settle the question of disulfur monoxide and sulfur monoxide deposition and occurrence on Io's surface, we performed series of laboratory experiments reproducing the condensation of S₂O at low temperature. Its polymerization has been monitored by recording infrared spectra under conditions of temperature, pressure, mixing with SO₂ and UV-visible radiation simulating that of Io's surface. Our experiments show that S₂O condensates are not chemically stable under ionian conditions. We also demonstrate that SO and S₂O outgassed by Io's volcanoes and condensing on Io's surface should lead to yellow polysulfuroxide deposits or to white deposits of S₂O diluted in sulfur dioxide frost (i.e., S₂O/SO₂ < 0.1%). Thus S₂O condensation cannot be responsible for the red volcanic deposits on Io. Comparison of the laboratory infrared spectra of S₂O and polysulfuroxide with NIMS/Galileo infrared spectra of Io's surface leads us to discuss the possible identification of polysulfuroxide. We also recorded the visible transmission spectra of sulfur samples resulting from polysulfuroxide decomposition. These samples consist in a mixture of sulfur polymer and orthorhombic sulfur. Using the optical constants extracted from these measurements, we show that a linear combination of the reflectance spectra of our samples, the reflectance spectrum of orthorhombic S₈ sulfur and SO₂ reflectance spectrum, leads to a very good matching of Io's visible spectrum between 330 and 520 nm. We conclude then that Io's surface is probably mainly composed of sulfur dioxide and a mixture of sulfur S₈ and sulfur polymer. Some polysulfuroxide could also co-exist with these dominant components, but is probably restricted to some volcanic areas.     

Galileo observations of volcanic plumes on Io

Io's volcanic plumes erupt in a dazzling variety of sizes, shapes, colors and opacities. In general, the plumes fall into two classes, representing distinct source gas temperatures. Most of the Galileo imaging observations were of the smaller, more numerous Prometheus-type plumes that are produced when hot flows of silicate lava impinge on volatile surface ices of SO₂. Few detections were made of the giant, Pele-type plumes that vent high temperature, sulfur-rich gases from the interior of Io; this was partly because of the insensitivity of Galileo's camera to ultraviolet wavelengths. Both gas and dust spout from plumes of each class. Favorably located gas plumes were detected during eclipse, when Io was in Jupiter's shadow. Dense dust columns were imaged in daylight above several Prometheus-type eruptions, reaching heights typically less than 100 km. Comparisons between eclipse observations, sunlit images, and the record of surface changes show that these optically thick dust columns are much smaller in stature than the corresponding gas plumes but are adequate to produce the observed surface deposits. Mie scattering calculations suggest that these conspicuous dust plumes are made up of coarse grained “ash” particles with radii on the order of 100 nm, and total masses on the order of 10⁶ kg per plume. Long exposure images of Thor in sunlight show a faint outer envelope apparently populated by particles small enough to be carried along with the gas flow, perhaps formed by condensation of sulfurous “snowflakes” as suggested by the plasma instrumentation aboard Galileo as it flew through Thor's plume [Frank, L.A., Paterson, W.R., 2002. J. Geophys. Res. (Space Phys.) 107, doi:10.1029/2002JA009240. 31-1]. If so, the total mass of these fine, nearly invisible particles may be comparable to the mass of the gas, and could account for much of Io's rapid resurfacing.     

Spectral reflectance of solid sulfur trioxide (0.25–5.2 μm): Implications for Jupiter's satellite Io

We have measured the reflection spectrum of solid sulfur trioxide and we have compared this spectrum to the spectral geometric albedo of Jupiter's satellite Io. We find that the laboratory spectrum of solid SO₃ has very strong absorption features at 3.38, and 4.08 μm. The 3.38- and 3.70-μm absorptions are present very weakly (if indeed at all) in the spectral geometric albedo of Io. This suggests that solid SO₃, if present at all, could exist only as a very minor component of Io's surface. We note that studies involving particle bombardment of SO₂ (a known Io surface constituent) produce SO₃ (Moore, 1984, Icarus 31, 40–80). Sulfur trioxide, once formed on Io's surface, would be extremely stable; however, it would not be expected to accumulate to levels detectable from Earth-based instruments. While it may be possible that the constant resurfacing of Io by volcanic ejecta may cover any SO₃ formed, the area subject to such extensive resurfacing on short time scales (∼ 1 year) is at best ∼10%. Therefore, we would expect that condensed SO₂ remote from volcanos should develop a small but significant SO₃ concentration that could be detected by instruments such as the near-infrared mapping spectrometer on the Galileo spacecraft.     

The SO2 atmosphere and ionosphere of Io: Ion chemistry,atmospheric escape,and models corresponding to the Pioneer 10 radio occultation measurements

Models of Io's ionosphere at the time of the Pioneer 10 encounter are constructed in the presence of an SO₂Na atmosphere on Io. The formation of the observed ionosphere on the downstream side requires precipitation of electrons; solar EUV alone is inadequate. Electron impact in the range 500–800 eV on an SO₂ atmosphere with a surface density of 14 × 10¹⁰ cm^?3 provides the best fit to the Pioneer 10 radio occultation entry data. The SO₂⁺, the major ion produced, is converted rapidly to SO⁺ and in turn to S⁺ by reactions with the dissociation products of SO₂. Ion chemistry leads to the formation of S⁺ as the dominant ion at and above the ionospheric peak. Na⁺ would dominate the ion composition near the surface, and it provides important constraints on the amount of Na allowed in the atmosphere. The relatively narrow energy range and flux required for incident electrons suggests that a fraction of torus plasma is accelerated in the wake region and penetrates deep into the atmosphere. On the upstream side the torus plasma compresses the ionosphere. These characteristics support the possible presence of a weak magnetic field associated with Io. S⁺ ions would escape from Io in the wake region at a rate of up to 10²⁶ sec^?1.     

Unsteady flows in Io’s atmosphere caused by condensation and sublimation during and after eclipse: Numerical study based on a model Boltzmann equation

The behavior of Io’s atmosphere during and after eclipse is investigated on the basis of kinetic theory. The atmosphere is mainly composed of sulfur dioxide (SO₂) gas, which condenses to or sublimates from the frost of SO₂ on the surface depending on the variation of surface temperature (～90–114 K). The atmosphere may also contain a noncondensable gas, such as sulfur monoxide (SO) or oxygen (O₂), as a minor component. In the present study, an accurate numerical analysis for a model Boltzmann equation by a finite-difference method is performed for a one-dimensional atmosphere, and the detailed structure of unsteady gas flows caused by the phase transition of SO₂ is clarified. For instance, the following scenario is obtained. The condensation of SO₂ on the surface, starting when eclipse begins, gives rise to a downward flow of the atmosphere. The falling atmosphere then bounces upward when colliding with the lower atmosphere but soon falls again. This process of falling and bounce back of the atmosphere repeats during the eclipse, resulting in a temporal oscillation of the macroscopic quantities, such as the velocity and temperature, at a fixed altitude. For a pure SO₂ atmosphere, the amplitude of the oscillation is large because of a fast downward flow, but the oscillation decays rapidly. In contrast, for a mixture, the downward flow is slow because the noncondensable gas adjacent to the surface hinders the condensation of SO₂. The oscillation in this case is weak but lasts much longer than in the case of pure SO₂. The present paper is complementary to the work by Moore et al. (Moore, C.H., Goldstein, D.B., Varghese, P.L., Trafton, L.M., Stewart, B. [2009]. Icarus 201, 585–597) using the direct simulation Monte Carlo (DSMC) method.     

A sensitive search for SO2 in the martian atmosphere: Implications for seepage and origin of methane

Mars was observed near the peak of the strongest SO₂ band at 1364-1373 cm⁻¹ with resolving power of 77,000 using the Texas Echelon Cross Echelle Spectrograph on the NASA Infrared Telescope Facility. The observation covered the Tharsis volcano region which may be preferable to search for SO₂. The spectrum shows absorption lines of three CO₂ isotopomers and three H₂O isotopomers. The water vapor abundance derived from the HDO lines assuming D/H = 5.5 times the terrestrial value is 12±1.0 pr. μm, in agreement with the simultaneous MGS/TES observations of 14 pr. μm at the latitudes (50° S to 10° N) of our observation. Summing of spectral intervals at the expected positions of sixteen SO₂ lines puts a 2σ upper limit on SO₂ of 1 ppb. SO₂ may be emitted into the martian atmosphere by seepage and is removed by three-body reactions with OH and O. The SO₂ lifetime, 2 years, is longer than the global mixing time 0.5 year, so SO₂ should be rather uniformly distributed across Mars. Seepage of SO₂ is less than 15,000 tons per year on Mars which is smaller than the volcanic production of SO₂ on the Earth by a factor of 700. Because CH₄/SO₂ is typically 10⁻⁴-10⁻³ in volcanic gases on the Earth, our results show seepage is unlikely to be the source of the recently discovered methane on Mars and therefore strengthen its biogenic origin.     

Geology and activity around volcanoes on Io from the analysis of NIMS spectral images

The last two successful flybys of Io by Galileo in 2001 (orbits I31, I32) allowed the Near Infrared Mapping Spectrometer to enrich its collection of IR spectral image cubes of the satellite. These data cover hemispheric portions of Io, several volcanic centers as well as their surroundings with a spatial resolution ranging from 2 to 93 km pixel⁻¹. They map thermal emission from the hot-spots and the distribution of solid SO₂ in the 1.0-4.7 μm spectral range. We obtain maps of SO₂ abundance and granularity from the NIMS data using the method of Douté et al. (2002, Icarus 158, 460-482). The maps are correlated to distinguish four different physical units that indicate zones of SO₂ condensation, metamorphism and sublimation. We relate these information with visible images from Galileo's Solid State Imaging System and with detailed mapping of the thermal emission produced by Io's surface. Our principal goal is to understand the mechanisms controlling how lava, pyroclastics and gas are emitted by different types of volcanoes and how these products evolve. The 800 km diameter white ring of fallout created by a violent “Pillanian” eruption during summer of 2001 is at least partly composed of solid SO₂ and has enriched preexisting regional deposits. Orange materials have been recently or are currently emplaced 240 km south from the main eruption site, possibly as sulfur flows. A similar event may have taken place in the past at Ababinili Patera (12.5° N, 142° W). Carefull study of SO₂ maps covering the Emakong region also suggests that sulfur forms the bright channel-fed flow emerging from the south eastern side of the caldera. Within the main caldera of Tvashtar Catena completely cooled patches of crust exist. Elsewhere, the caldera is still cooling from previous episodes of flooding. We confirm that Amirani emits constantly large amount of SO₂ gas by interaction of fresh lava with the volatiles of the underlying plains. Nevertheless SO₂ frost is not the major component of the bright white ring seen in the SSI images. Over the whole Gish Bar region, SO₂ frost seems barely stable and is constantly regenerated. The stability increases along gray filamentary structures which could be faults filled with materials having peculiar thermal properties. Northwest of Gish Bar Patera, a localized bright deposit shows an unusual spectral signature potentially indicative of H₂O molecules forming ice crystals or being trapped in a nonidentified matrix. The Chaac region may present a thickened old crust reducing the geothermal flux to levels lower than 0.5 W m⁻² and thus creating a cold trap for SO₂. Looking at the abundance and degree of metamorphose of SO₂, we establish the relative age of different flows and ejecta for the Sobo Fluctus. Finally the assumption that the white patches in visible images indicate SO₂ rich deposits is once again challenged. In the Camaxtli region we identify a topographically controlled compact white deposit showing only moderate SO₂ abundance. In contrast, we detect two spots of quite pure SO₂ ice on the gray flanks of Emakong. Furthermore, the close association of fumarolic SO₂ and red S₂ already noted for several volcanic centers is observed at Tupan.     

Sulfur dioxide on Io: Spatial distribution and physical state

Observations of the 4-μm SO₂ band on Jupiter's satellite Io and laboratory measurements of SO₂ frost are presented. The observations confirm the existence of a large longitudinal variation in band strength but show no evidence of temporal changes. Comparison of the band position and shape in Io's spectrum with those in the laboratory frost's suggests that the bulk of the absorption on Io is due to frost, not adsorbed gas. The derived SO₂ coverage is large enough to require that SO₂ be present in most terrain types on Io and not just in the white plains unit. To reconcile the infrared observations that indicate large amounts of SO₂ with the ultraviolet observations of Voyager and IUE that show little, the SO₂ must be mixed intimately with the sulfur (or other material) so that at each wavelength the darker component dominates the spectrum.     

Observational tests for sulfur allotropes on Io

One of the intrinsic properties of particulate sulfur allotropes is a change in UV-visible reflectivity with temperature change of the material. The surface of Io experiences temperature changes during eclipse which are sufficient to cause a detectable change in the spectral reflectivity of sulfur; thus, if the surface of Io is composed primarily of sulfur allotropes, a change in reflectivity at certain wavelengths should be observable shortly after eclipse reappearance. We observed four eclipse reappearances during July and August of 1983 and saw no posteclipse brightening effects in filter bands selected for sensitivity to color changes in sulfur. Our model of the brightness change for S₈ (“yellow” sulfur) implies that this material covers less than 50% of Io's surface. Negative posteclipse brightening observations were also obtained with a filter chosen for the high contrast between SO₂ frost and the average albedo of the surface of Io at that wavelength. We conclude that no significant condensation of optically thick SO₂ occurred on the surface of Io during these eclipses.     

The atmospheric signature of Io's Prometheus plume and anti-jovian hemisphere: evidence for a sublimation atmosphere

Using the Hubble Space Telescope's Space Telescope Imaging Spectrograph we have obtained for the first time spatially resolved 2000-3000 Å spectra of Io's Prometheus plume and adjoining regions on Io's anti-jovian hemisphere in the latitude range 60° N-60° S, using a 0.1″ slit centered on Prometheus and tilted roughly 45° to the spin axis. The SO₂ column density peaked at 1.25×10¹⁷ cm⁻² near the equator, with an additional 5×10¹⁶ cm⁻² enhancement over Prometheus corresponding to a model volcanic SO₂ output of 10⁵ kg s⁻¹. Apart from the Prometheus peak, the SO₂ column density dropped fairly smoothly away from the subsolar point, even over regions that included potential volcanic sources. At latitudes less than ±30°, the dropoff rate was consistent with control by vapor pressure equilibrium with surface frost with subsolar temperature 117.3±0.6 K, though SO₂ abundance was higher than predicted by vapor pressure control at mid-latitudes, especially in the northern hemisphere. We conclude that, at least at low latitudes on the anti-jovian hemisphere where there are extensive deposits of optically-thick SO₂ frost, the atmosphere is probably primarily supported by sublimation of surface frost. Although the 45° tilt of our slit prevents us from separating the dependence of atmospheric density on solar zenith angle from its dependence on latitude, the pattern is consistent with a sublimation atmosphere regardless of which parameter is the dominant control. The observed drop in gas abundance towards higher latitudes is consistent with the interpretation of previous Lyman alpha images of Io as indicating an atmosphere concentrated at low latitudes. Comparison with previous disk-resolved UV spectroscopy, Lyman-alpha images, and mid-infrared spectroscopy suggests that Io's atmosphere is denser and more widespread on the anti-jovian hemisphere than at other longitudes. SO₂ gas temperatures were in the range of 150-250 K over the majority of the anti-jovian hemisphere, consistent with previous observations. SO was not definitively detected in our spectra, with upper limits to the SO/SO₂ ratio in the range 1-10%, roughly consistent with previous observations. S₂ gas was not seen anywhere, with an upper limit of 7.5×10¹⁴ cm⁻² for the Prometheus plume, confirming that this plume is significantly poorer in S₂ than the Pele plume (S₂ /SO₂<0.005, compared to 0.08-0.3 at Pele). In addition to the gas absorption signatures, we have observed continuum emission in the near ultraviolet (near 2800 Å) for the first time. The brightness of the observed emission was directly correlated with the SO₂ abundance, strongly peaking in the equatorial region over Prometheus. Emission brightness was modestly anti-correlated with the jovian magnetic latitude, decreasing when Io intersected the torus centrifugal equator.     

Io’s atmosphere: Constraints on sublimation support from density variations on seasonal timescales using NASA IRTF/TEXES observations from 2001 to 2010

We present an analysis of 19 μm spectra of Io’s SO₂ atmosphere from the TEXES mid-infrared high spectral resolution spectrograph on NASA’s Infrared Telescope Facility, incorporating new data taken between January 2005 and June 2010 and a re-analysis of earlier data taken from November 2001 to January 2004. This is the longest set of contiguous observations of Io’s atmosphere using the same instrument and technique thus far. We have fitted all 16 detected blended absorption lines of the ν₂ SO₂ vibrational band to retrieve the subsolar values of SO₂ column abundance and the gas kinetic temperature. By incorporating an existing model of Io’s surface temperatures and atmosphere, we retrieve sub-solar column densities from the disk-integrated data. Spectra from all years are best fit by atmospheric temperatures <150 K. Best-fit gas kinetic temperatures on the anti-Jupiter hemisphere, where SO₂ gas abundance is highest, are low and stable, with a mean of 108 (±18) K. The sub-solar SO₂ column density between longitudes of 90–220° varies from a low of 0.61 (±0.145) × 10^?17 cm^?2, near aphelion in 2004, to a high of 1.51 (±0.215) × 10¹⁷ cm^?2 in 2010 when Jupiter was approaching its early 2011 perihelion. No correlation in the gas temperature was seen with the increasing SO₂ column densities outside the errors.Assuming that any volcanic component of the atmosphere is constant with time, the correlation of increasing SO₂ abundance with decreasing heliocentric distance provides good evidence that the atmosphere is at least partially supported by frost sublimation. The SO₂ frost thermal inertias and albedos that fit the variation in atmospheric density best are between 150–1250 W m^?2 s^?1/2 K^?1 and 0.613–0.425 respectively. Photometric evidence favors albedos near the upper end of this range, corresponding to thermal inertias near the lower end. This relatively low frost thermal inertia produces larger amplitude seasonal variations than are observed, which in turn implies a substantial additional volcanic atmospheric component to moderate the amplitude of the seasonal variations of the total atmosphere on the anti-Jupiter hemisphere. The seasonal thermal inertia we measure is unique both because it refers exclusively to the SO₂ frost surface component, and also because it refers to relatively deep subsurface layers (few meters) due to the timescales of many years, while previous studies have determined thermal inertias at shallower levels (few centimeters), relevant for timescales of ～2 h (eclipse) or ～2 days (diurnal curves).     

The geothermal gradient of Io: Consequences for lithosphere structure and volcanic eruptive activity

We solve numerically the equations describing the transfer of heat through the lithosphere of Io by a mixture of conduction and volcanic advection as proposed by O’Reilly and Davies (O’Reilly, T.C., Davies, G.F. [1981]. Geophys. Res. Lett. 8, 313-316), removing the requirement that average material properties must be used. As expected, the dominance of advective heat transfer by volcanic eruptions means that Io’s geothermal gradient well away from volcanic centres is very small, of order 1 K km⁻¹. This result is independent of any reasonable assumptions about the radiogenic heating rate in the lithosphere. The lithosphere temperature does not increase greatly above the surface temperature until the base of the lithosphere is approached, except in limited areas around shallow magma bodies. As a consequence, solid volatile sulphur compounds mobilized by volcanic processes and re-deposited on the surface of Io commonly remain solid until they reach great depths as they are progressively buried by ongoing activity. For current estimates of the volcanic heat transfer rate, melting of SO₂ does not begin until a depth of ∼20 km and sulphur remains solid to a depth of ∼26 km in a 30 km thick lithosphere. Rising magmas can incorporate fluids from these deep sulphur compound aquifers, and we quantify the major influence that this can have on the bulk density of the magma and hence the resulting possible intrusion and eruption styles.     

The post-eclipse brightening of Io

We review the photometric work on eclipse reappearances of Io. New observations of eclipse reappearances of Io confirm the post-eclipse brightness anomaly reported by Binder and Cruikshank (1964) but testify to its intermittent nature. A post-eclipse anomaly of approximately 0.07 mag was observed on two occasions in 1972, while observations of Europa and Ganymede showed no brightness anomaly greater than 0.01 mag. The atmospheric condensation model for the anomaly on Io is reviewed in terms of the quantity of frost required to produce the effect and the corresponding amount of gas liberated to the atmosphere upon sublimation. The observational data and the results from a stellar occultation are in general accord with the theoretical predictions of the stability of heavy gases on Io, while both observational and theoretical criteria are satisfied by a tenuous atmosphere of a heavy gas such as methane or ammonia having a surface pressure ～10^?7 bar.     

Composition of jovian dust stream particles

The Cassini spacecraft encountered Jupiter in late 2000. Within more than 1 AU of the gas giant the Cosmic Dust Analyser onboard the spacecraft recorded the first ever mass spectra of jovian stream particles. To determine the chemical composition of particles, a comprehensive statistical analysis of the dataset was performed. Our results imply that the vast majority (>95%) of the observed stream particles originate from the volcanic active jovian satellite Io from where they are sprinkled out far into the Solar System. Sodium chloride (NaCl) was identified as the major particle constituent, accompanied by sulphurous as well as potassium bearing components. This is in contrast to observations of gas in the ionian atmosphere, its co-rotating plasma torus, and the neutral cloud, where sulphur species are dominant while alkali and chlorine species are only minor components. Io has the largest active volcanoes of the Solar System with plumes reaching heights of more than 400 km above the moons surface. Our in situ measurements indicate that alkaline salt condensation of volcanic gases inside those plumes could be the dominant formation process for particles reaching the ionian exosphere.     

Io's 4-μm band and the role of adsorbed SO2

The role of adsorbed SO₂ on Io's surface particles in producing the observed spectral absorption band near 4 μm in Io's reflectance spectrum is explored. Calculations show that a modest 50% monolayer coating of adsorbed SO₂ molecules on submicron grains of sulfur of alkali sulfide, assumed to make up Io's uppermost optical surface (“radialith”), will result in a ν₁ + ν₃ absorption band near 4 μm with depth ～30% below the adjacent continuum, consistent with the observed strength of the Io band. The precise wavelength position of the ν₁ + ν₃ band of SO₂ in different phase states such as frost, ice, adsorbate, and gas are summarized from the experimental literature and compared with the available telescopic measurements of the Io band position. The results suggest that the 4-μm band in Io's full disk spectrum can best be explained by the presence on Io's surface of widespread SO₂ in the form of adsorbate rather than ice or frost.