Io's dayside SO2 atmosphere

An extensive set of HI Lyman-α images obtained with the Hubble Space Telescope (HST) Space Telescope Imaging Spectrograph (STIS) from 1997-2001 has been analyzed to provide information about the spatial and temporal character of Io's SO₂ atmosphere. An atmospheric distribution map derived from the observations reveals that the sunlit SO₂ atmosphere is temporally stable on a global scale, with only small local changes. An anti-/sub-jovian asymmetry in the SO₂ distribution is present in all 5 years of the observations. The average daytime atmosphere is densest on the anti-jovian hemisphere in the equatorial regions, with a maximum equatorial column density of 5.0×¹⁰¹⁶ cm−2 at 140° longitude. The SO₂ atmosphere also has greater latitudinal extent on the anti-jovian hemisphere as compared to the sub-jovian. The atmospheric distribution appears to be best correlated with the location of hot spots and known volcanic plumes, although small number statistics for the plumes limits the correlation.     

Observations of C2H6 and C2H2 in the stratosphere of Saturn

We have performed high-resolution spectral observations at mid-infrared wavelengths of C₂H₆ (12.16 μm), and C₂H₂ (13.45 μm) on Saturn. These emission features probe the stratosphere of the planet and provide information on the hydrocarbon photochemical processes taking place in that region of the atmosphere. The observations were performed using our cryogenic echelle spectrometer Celeste, in conjunction with the McMath-Pierce 1.5-m solar telescope in November and December 1994. We used Voyager IRIS CH₄ observations (7.67 μm) to derive a temperature profile on the saturnian atmosphere for the region of the stratosphere. This profile was then used in conjunction with height-dependent volume mixing ratios of each hydrocarbon to determine global abundances for ethane and acetylene. Our ground-based measurements indicate abundances of for C₂H₆ (1.0 mbar pressure level), and for C₂H₂ (1.6 mbar pressure level). We also derived new mixing ratios from the Voyager mid-latitude IRIS observations; 8.6±0.9×¹⁰⁻⁶ for C₂H₆ (0.1-3.0 mbar pressure level), and 1.6±0.2×¹⁰⁻⁷ for C₂H₂ (2.0 mbar pressure level).     

Saturn's latitudinal C2H2 and C2H6 abundance profiles from Cassini/CIRS and ground-based observations

Hydrocarbons in the upper atmosphere of Saturn are known, from Voyager, ground-based, and early Cassini results, to vary in emission intensity with latitude. Of particular interest is the marked increase in hydrocarbon line intensity near the south pole during southern summer, as the increased line intensity cannot be simply explained by the increased temperatures observed in that region since the variations between C₂H₂ and C₂H₆ emission in the south pole region are different. In order to measure the latitudinal variations of hydrocarbons in Saturn's southern hemisphere we have used 3 cm⁻¹ resolution Cassini CIRS data from 2006 and combined this with measurements from the ground in October 2006 at NASA's IRTF using Celeste, an infrared high-resolution cryogenic grating spectrometer. These two data sets have been used to infer the molecular abundances of C₂H₂ and C₂H₆ across the southern hemisphere in the 1-10 mbar altitude region. We find that the latitudinal acetylene profile follows the yearly average mean daily insolation except at the southern pole where it peaks in abundance. Near the equator (5° S) the C₂H₂ abundance at the 1.2 mbar level is (1.6±0.19)×¹⁰−7 and it decreases by a factor of 2.7 from the equator toward the pole. However, at the pole (∼87° S) the C₂H₂ abundance jumps to (1.8±0.3)×¹⁰−7, approximately the equatorial value. The C₂H₆ abundance near the equator at the 2 mbar level is (0.7±0.1)×¹⁰−5 and stays approximately constant until mid-latitudes where it increases gradually toward the pole, attaining a value of (1.4±0.4)×¹⁰−5 there. The increase in ethane toward the pole with the corresponding decrease in acetylene is consistent with southern hemisphere meridional winds [Greathouse, T.K., Lacy, J.H., Bézard, B., Moses, J.I., Griffith, C.A., Richter, M.J., 2005. Icarus 177, 18-31]. The localized increase in acetylene at the pole provides evidence that there is dynamical transport of hydrocarbons from the equator to the southern pole.     

IRAS 22036+5306: an Al2O3 oxide-dominated post-AGB star

Radiative transfer modelling of the Infrared Space Observatory ( ISO ) spectrum of IRAS 22036+5306 has shown that its unusual 11-μm band can be suitably modelled with an alumina-olivine mixture substantially dominated by the former. The results of this work add further credence to recent findings that significant amounts of Al  ₂O₃  dust grains are present in the dust shells of stars near or beyond the tip of the asymptotic giant branch. Indeed, in the case of IRAS 22036+5306, Al  ₂O₃  dominates the dust composition to the extent that it shifts the 9.8-μm band due to amorphous silicates to 11 μm. IRAS 22036+5306 may be an unusual case in that the inner dust torus is maintained at a sufficiently high temperature for Al  ₂O₃  condensation, but not silicate.     

H-implantation in SO2 and CO2 ices

Ices in the solar system are observed on the surface of planets, satellites, comets and asteroids where they are continuously subordinate at particle fluxes (cosmic ions, solar wind and charged particles caught in the magnetosphere of the planets) that deeply modify their physical and structural properties. Each incoming ion destroys molecular bonds producing fragments that, by recombination, form new molecules also different from the original ones. Moreover, if the incoming ion is reactive (H⁺, Oⁿ⁺, Sⁿ⁺, etc.), it can concur to the formation of new molecules.Those effects can be studied by laboratory experiments where, with some limitation, it is possible to reproduce the astrophysical environments of planetary ices.In this work, we describe some experiments of 15-100 keV H⁺ and He⁺ implantation in pure sulfur dioxide (SO₂) at 16 and 80 K and carbon dioxide (CO₂) at 16 K ices aimed to search for the formation of new molecules. Among other results we confirm that carbonic acid (H₂CO₃) is formed after H-implantation in CO₂, vice versa H-implantation in SO₂ at both temperatures does not produce measurable quantity of sulfurous acid (H₂SO₃). The results are discussed in the light of their relevance to the chemistry of some solar system objects, particularly of Io, the innermost of Jupiter's Galilean satellites, that exhibits a surface very rich in frost SO₂ and it is continuously bombarded with H⁺ ions caught in Jupiter's magnetosphere.     

Meridional variations of C2H2 and C2H6 in Jupiter's atmosphere from Cassini CIRS infrared spectra

Hydrocarbons such as acetylene (C₂H₂) and ethane (C₂H₆) are important tracers in Jupiter's atmosphere, constraining our models of the chemical and dynamical processes. However, our knowledge of the vertical and meridional variations of their abundances has remained sparse. During the flyby of the Cassini spacecraft in December 2000, the Composite Infrared Spectrometer (CIRS) instrument was used to map the spatial variation of emissions from 10 to 1400 cm⁻¹ (1000-7 μm). In this paper we analyze a zonally averaged set of CIRS spectra taken at the highest (0.48 cm⁻¹) resolution, firstly to infer atmospheric temperatures in the stratosphere at 0.5-20 mbar via the ν₄ band of CH₄, and in the troposphere at 150-400 mbar, via the H₂ absorption at 600-800 cm⁻¹. Stratospheric temperatures at 5 mbar are generally warmer in the north than the south by 7-8 K, while tropospheric temperatures show no such asymmetry. Both latitudinal temperature profiles however do show a pattern of maxima and minima which are largely anti-correlated between the two levels. We then use the derived temperature profiles to infer the vertical abundances of C₂H₂ and C₂H₆ by modeling tropospheric absorption (∼200 mbar) and stratospheric emission (∼5 mbar) in the C₂H₂ν₅ and C₂H₆ν₉ bands, and also emission of the acetylene (ν₄+ν₅)−ν₄ hotband (∼0.1 mbar). Acetylene shows a distinct north-south asymmetry in the stratosphere, with 5 mbar abundances greatest close to 20° N and decreasing from there towards both poles by a factor of ∼4. At 200 mbar in contrast, acetylene is nearly flat at a level of ∼3×¹⁰⁻⁹. Additionally, the abundance gradient of C₂H₂ between 10 and 0.1 mbar is derived, based on interpolated temperatures at 0.1 mbar, and is found to be positive and uniform with latitude to within errors. Ethane at both 5 and 200 mbar shows increasing VMR towards polar regions of ∼1.75 towards 70° N and ∼2.0 towards 70° S. An explanation for the meridional trends is proposed in terms of a combination of photochemistry and dynamics. Poleward, the decreasing UV flux is predicted to decrease the abundances of C₂H₂ and C₂H₆ by factors of 2.7 and 3.5, respectively, at latitude 70°. However, the lifetime of C₂H₆ in the stratosphere (3×¹⁰¹⁰ s at 5 mbar) is much longer than the dynamical timescale for meridional mixing inferred from Comet SL-9 debris (5-50×¹⁰⁸ s), and therefore the rising abundance towards high latitudes likely indicates that meridional mixing dominates over photochemical effects. For C₂H₂, the opposite occurs, with the relatively short photochemical lifetime (3×¹⁰⁷ s), compared to meridional mixing times, ensuring that the expected photochemical trends are visible.     

Sulfurous acid (H2SO3) on Io?

Sulfurous acid (H₂SO₃) has never been characterized or isolated on Earth. This is caused by the unfavorable conditions for H₂SO₃ within Earth's atmosphere due to the high temperatures, the high water content and the oxidizing environment. Kinetic investigations by means of transition state theory showed that the half-life of H₂SO₃ at 300 K is 1 day but at 100 K it is increased to 2.7 billion years. Natural conditions to form H₂SO₃ presumably require cryogenic SO₂ or SO₂/H₂O mixtures and high energy proton irradiation at temperatures around 100 K. Such conditions can be found on the Jupiter moons Io and Europa. Therefore, we calculated IR-spectra of H₂SO₃ which we compared with Galileo's spectra of Io and Europa. From the available data we surmise that H₂SO₃ is present on Io and probably but to a smaller extent on Europa.     

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.     

Brightness fluctuations of the Sun and p‐mode oscillations: The inverse problem and nonadiabatic waves in the photosphere

Using photometric observations of the Sun as a star (DIFOS, SoHO) we were able to solve the inverse heloiseismic problem and determine the global time‐dependent relative temperature fluctuations as functions of the geometric height. This was done under the adiabatic assumption. A mathematical tool was developed to solve the inverse problem, which is ill‐posed. The calculations were done using the numerical software Matlab 7. The adiabatic solution shows signs of temperature waves in the lower photosphere, which agrees with calculations done by Rodríguez Hidalgo et al. (2001) and Stodilka (2011). (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The spatial morphology of Europa's near-surface O2 atmosphere

Results from a three-dimensional ballistic model of Europa's O₂ atmosphere are presented. Hubble Space Telescope (HST) ultraviolet observations show spatially non-uniform O₂ airglow from Europa. One explanation for this is that the O₂ atmosphere is spatially non-uniform. We show that non-uniform ejection of O₂ alone cannot reproduce the required morphology, but that a non-uniform distribution of reactive species in Europa's porous regolith can result in a non-uniform O₂ atmosphere. By allowing O₂ molecules to react with Europa's visibly dark surface material, we produced a spatially non-uniform atmosphere which, assuming uniform electron excitation of O₂ over the trailing hemisphere, compares favorably with the morphology suggested by the HST observations. This model, which requires a larger source of O₂ than has previously been estimated, can in principal be tested by the New Horizons observations of Europa's O₂ atmosphere.     

Climate forced atmospheric CO2 variability in the early Holocene: A stomatal frequency reconstruction

The dynamic climate in the Northern Hemisphere during the early Holocene could be expected to have impacted on the global carbon cycle. Ice core studies however, show little variability in atmospheric CO₂. Resolving any possible centennial to decadal CO₂ changes is limited by gas diffusion through the firn layer during bubble enclosure. Here we apply the inverse relationship between stomatal index (measured on sub-fossil leaves) and atmospheric CO₂ to complement ice core records between 11,230 and 10,330 cal. yr BP. High-resolution sampling and radiocarbon dating of lake sediments from the Faroe Islands reconstruct a distinct CO₂ decrease centred on ca. 11,050 cal. yr BP, a consistent and steady decline between ca. 10,900 and 10,600 cal. yr BP and an increased instability after ca. 10,550 cal. yr BP. The earliest decline lasting ca. 150 yr is probably associated with the Preboreal Oscillation, an abrupt climatic cooling affecting much of the Northern Hemisphere a few hundred years after the end of the Younger Dryas. In the absence of known global climatic instability, the decline to ca. 10,600 cal. yr BP is possibly due to expanding vegetation in the Northern Hemisphere. The increasing instability in CO₂ after 10,600 cal. yr BP occurs during a period of increasing cooling of surface waters in the North Atlantic and some increased variability in proxy climate indicators in the region.The reconstructed CO₂ changes also show a distinct similarity to indicators of changing solar activity. This may suggest that at least the Northern Hemisphere was particularly sensitive to changes in solar activity during this time and that atmospheric CO₂ concentrations fluctuated via rapid responses in climate.     

Long-term spectroscopic observations of Mars using IRTF/CSHELL: Mapping of O2 dayglow, CO, and search for CH4

Long-term spectroscopic observations of the O₂ dayglow at 1.27 μm result in a map of the latitudinal and seasonal behavior of the dayglow intensity for the full martian year. The O₂ dayglow is a sensitive tracer of Mars' photochemistry, and this map reflects variations of Mars' photochemistry at low and middle latitudes. It may be used to test photochemical models. Long-term observations of the CO mixing ratio have been also combined into the seasonal-latitudinal map. Seasonal and latitudinal variations of the mixing ratios of CO and the other incondensable gases (N₂, Ar, O₂, and H₂) discovered in our previous work are caused by condensation and sublimation of CO₂ to and from the polar regions. They reflect dynamics of the atmosphere and polar processes. The observed map may be used to test global circulation models of the martian atmosphere. The observed global abundances of CO are in reasonable agreement with the predicted variations with the 11-year solar cycle. Despite the perfect observing conditions, methane has not been detected using the IRTF/CSHELL with a 3σ upper limit of 14 ppb. This upper limit does not rule out the value of 10 ppb observed using the Canada-France-Hawaii Telescope and the Mars Express Planetary Fourier Spectrometer.     

Release of N2, CH4, CO2, and H2O from surface ices on Enceladus

We vapor deposit at 20 K a mixture of gases with the specific Enceladus plume composition measured in situ by the Cassini INMS [Waite, J.H., Combi, M.R., Ip, W.H., Cravens, T.E., McNutt, R.L., Kasprzak, W., Yelle, R., Luhmann, J., Niemann, H., Gell, D., Magee, B., Fletcher, G., Lunine, J., Tseng, W.L., 2006. Science 311, 1419-1422] to form a mixed molecular ice. As the sample is slowly warmed, we monitor the escaping gas quantity and composition with a mass spectrometer. Pioneering studies [Schmitt, B., Klinger, J., 1987. Different trapping mechanisms of gases by water ice and their relevance for comet nuclei. In: Rolfe, E.J., Battrick, B. (Eds.), Diversity and Similarity of Comets. SP-278. ESA, Noordwijk, The Netherlands, pp. 613-619; Bar-Nun, A., Kleinfeld, I., Kochavi, E., 1988. Phys. Rev. B 38, 7749-7754; Bar-Nun, A., Kleinfeld, I., 1989. Icarus 80, 243-253] have shown that significant quantities of volatile gases can be trapped in a water ice matrix well above the temperature at which the pure volatile ice would sublime. For our Enceladus ice mixture, a composition of escaping gases similar to that detected by Cassini in the Enceladus plume can be generated by the sublimation of the H₂O:CO₂:CH₄:N₂ mixture at temperatures between 135 and 155 K, comparable to the high temperatures inferred from the CIRS measurements [Spencer, J.R., Pearl, J.C., Segura, M., Flasar, F.M., Mamoutkine, A., Romani, P., Buratti, B.J., Hendrix, A.R., Spilker, L.J., Lopes, R.M.C., 2006. Science 311, 1401-1405] of the Enceladus “tiger stripes.” This suggests that the gas escape phenomena that we measure in our experiments are an important process contributing to the gases emitted from Enceladus. A similar experiment for ice deposited at 70 K shows that both the processes of volatile trapping and release are temperature dependent over the temperature range relevant to Enceladus.     

Martian glaciation and the flow of solid CO2

The flow law determined experimentally for solid CO₂ establishes that a hypothesis of glacial flow of CO₂ at the Martian poles is not physically unrealistic. Compression experiments carried out under 1 atm pressure and constant strain rate demonstrate that the strength of CO₂ near its sublimation point is considerably less than the strength of water ice near its melting point. The data fit a power law “creep” equation of the form

$\text{?}\text{?}\text{= (4 × 10}{}^6\text{) σ}{}^{3.9}\text{exp}\text{(}\text{?12 200}\text{RT}\text{)}$

, where ? is compressive strain rate (sec^?1), σ is compressive stress (bars), R is the gas constant in calories per mole, and T is absolute temperature. The exponent of σ of 3.9 contrasts with a value near 3.1 for water ice, and indicates that the strain rate is somewhat more sensitive to stress for CO₂ than for water. Likewise, the low activation energy for creep, 12 200 cal mole^?1, illustrates that CO₂ is not highly sensitive to temperature and is thus likely to flow over a broad range of temperatures below its melting point. Strength values for CO₂ are of the order of one-tenth to one-third the strength of ice under equivalent conditions.A plausible glacial model for the Martian polar caps can be constructed and is helpful in explaining the unique character of the polar regions. CO₂-rich layers deposited near the pole would have flowed outward laterally to relieve high internal shear stresses. The topography of the polar caps, the uniform layering of the layered deposits, and the general extent of the polar “sediments” could all be explained using this model. Flow of CO₂ rather than water ice greatly reduces the problems with Martian glaciation. Nevertheless, problems do remain, in particular the large amounts of CO₂ necessary, the need to increase vapor pressure and temperature with depth in the polar deposits, and the lack of good observational evidence of flor features. Within the limits of the present knowledge of surface conditions of Mars, CO₂ glaciation appears to be a realistic alternate working hypothesis for the origin of the polar features.     

Sublimation kinetics of CO2 ice on Mars

Dynamic models of the martian polar caps are in abundance, but most rely on the assumption that the rate of sublimation of CO₂ ice can be calculated from heat transfer and lack experimental verification. We experimentally measured the sublimation rate of pure CO₂ ice under simulated martian conditions as a test of this assumption, developed a model based on our experimental results, and compared our model's predictions with observations from several martian missions (MRO, MGS, Viking). We show that sun irradiance is the primary control for the sublimation of CO₂ ice on the martian poles with the amount of radiation penetrating the surface being controlled by variations in the optical depth, ensuring the formation and sublimation of the seasonal cap. Our model confirmed by comparison of MGS-MOC and MRO-HiRISE images, separated by 2-3 martian years, shows that ∼0.4 m are currently being lost from the south perennial cap per martian year. At this rate, the ∼2.4-m-thick south CO₂ perennial cap will disappear in about 6-7 martian years, unless a short-scale climatic cycle alters this rate of retreat.