Near-IR methane absorption in outer planet atmospheres: Improved models of temperature dependence and implications for Uranus cloud structure

Near-IR absorption of methane in the 2000-9500 cm⁻¹ spectral region plays a major role in outer planet atmospheres. However, the theoretical basis for modeling the observations of reflectivity and emission in these regions has had serious uncertainties at temperatures needed for interpreting observations of the colder outer planets. A lack of line parameter information, including ground-state energies and the absence of weak lines, limit the applicability of line-by-line calculations at low temperatures and for long path lengths, requiring the use of band models. However, prior band models have parameterized the temperature dependence in a way that cannot be accurately extrapolated to low temperatures. Here we use simulations to show how a new parameterization of temperature dependence can greatly improve band model accuracy and allow extension of band models to the much lower temperatures that are needed to interpret observations of Uranus, Neptune, Titan, and Saturn. Use of this new parameterization by Irwin et al. [Irwin, P.G.J., Sromovsky, L.A., Strong, E.K., Sihra, K., Bowles, N., Calcutt, S.B., 2005b. Icarus. In press] has verified improved fits to laboratory observations of Strong et al. [Strong, K., Taylor, F.W., Calcutt, S.B., Remedios, J.J., Ballard, J., 1993. J. Quant. Spectrosc. Radiat. Trans. 50, 363-429] and Sihra [1998. Ph.D. Thesis, Univ. of Oxford], which cover the temperature range from 100 to 340 K. Here we compare model predictions to 77 K laboratory observations and to Uranus spectra, which show much improved agreement between observed and modeled spectral features, allowing tighter constraints on pressure levels of Uranus cloud particles, implying that most scattering contributions arise from pressures near 2 bars and 6 bars rather than expected pressures near 1.25 and 3.1 bars. Between visible and near-IR wavelengths, both cloud layers exhibit strong decreases in reflectivity that are indicative of low opacity and submicron particle sizes.     

The methane abundance and structure of Uranus' cloud bands inferred from spatially resolved 2006 Keck grism spectra

Grism spectra of Uranus obtained at the Keck Observatory in 2006, using the NIRC2 instrument and adaptive optics, provide new constraints on the vertical structure of Uranus' cloud bands and on the volume mixing ratio of methane. The best model fits to H-band spectra (1.49-1.635 μm) are found for a methane volume mixing ratio of 1.0 ± 0.25% for latitudes near 43° S and 1-1.6% for latitudes of 12° S and 33° N. Analysis of the J-band spectra are confused by discrepancies between short-wave and long-wave sides of the 1.28 μm window region. The short-wave side of the window (1.23-1.30 μm) is best fit with 1.6% CH₄, but if the fitted spectral range is extended to include the long-wave side of the window (1.2-1.34 μm), the best fit CH₄ mixing ratio is 4% or more, although many small scale spectral features are poorly fit over this range even at high methane mixing ratios, suggesting that models of methane opacity may be inconsistent in this spectral region. Most of the latitudinal variability of the H-band spectra can be fit with clouds near 2-3 and 6-8 bar, with cloud reflectivity of the deeper layer increasing from ∼2% at 33° N to 3-4% in the southern hemisphere. This layer is most likely made of H₂S particles and appears weakly reflective because it is optically thin and possibly also contaminated by absorbing materials. The reflectivity of the 2-3-bar cloud increases from 0.5% at 33° N to ∼1% at the bright band centered near 43° S, where the upper cloud is a little higher (pressure is 10% lower) and ∼25% more reflective than at nearby latitudes. The bright band is also associated with lowering of the deep cloud pressure, by ∼1.4 bar. The bright band parameters are roughly consistent with those obtained from 1975 disk-averaged spectra, obtained when the southern hemisphere was more exposed to the Sun. The lack of significant cloud particle contributions near 1.2 bar, where occultation results suggested a methane cloud, is confirmed by both spectra and HST imaging observations.     

Reflectance spectra of hydrated Titan tholins at cryogenic temperatures and implications for compositional interpretation of red objects in the outer Solar System

We report the visible and near-infrared (0.4-2.5 μm) laboratory bidirectional reflectance of hydrated Titan tholin at cryogenic temperatures (∼100-300 K). When compared with room temperature measurements, the visible and near-infrared color of hydrated Titan tholin becomes bluer by ∼14% at low temperatures in the 0.7-1.0 μm region. Assuming the observed color changes are representative of tholin-like materials we estimate the influence of such color changes on the interpretation of the Centaur Pholus and find that the modest color changes will not significantly alter existing interpretations.     

Vertical cloud structure of Uranus from UKIRT/UIST observations and changes seen during Uranus’ northern spring equinox from 2006 to 2008

Long-slit spectroscopy observations of Uranus by the United Kingdom Infrared Telescope UIST instrument in 2006, 2007 and 2008 have been used to monitor the change in Uranus’ vertical and latitudinal cloud structure through the planet’s northern spring equinox in December 2007.The observed reflectance spectra in the Long J (1.17-1.31 μm) and H (1.45-1.65 μm) bands, obtained with the slit aligned along Uranus’ central meridian, have been fitted with an optimal estimation retrieval model to determine the vertical cloud profile from 0.1 to 6-8 bar over a wide range of latitudes. Context images in a number of spectral bands were used to discriminate general zonal cloud structural changes from passing discrete clouds. From 2006 to 2007 reflection from deep clouds at pressures between 2 and 6-8 bar increased at all latitudes, although there is some systematic uncertainty in the absolute pressure levels resulting from extrapolating the methane coefficients of Irwin et al. (Irwin, P.G.J., Sromovsky, L.A., Strong, E.K., Sihra, K., Teanby, N.A., Bowles, N., Calcutt, S.B., Remedios, J.J. [2006] Icarus, 181, 309-319) at pressures greater than 1 bar, as noted by Tomasko et al. and Karkoschka and Tomasko (Tomasko, M.G., Bezard, B., Doose, L., Engel, S., Karkoschka, E. [2008] Planet. Space Sci., 56, 624-647; Karkoschka, E., Tomasko, M. [2009] Icarus). However, from 2007 to 2008 reflection from these clouds throughout the southern hemisphere and from both northern and southern mid-latitudes (30° N,S) diminished. As a result, the southern polar collar at 45°S has diminished in brightness relative to mid-latitudes, a similar collar at 45°N has become more prominent (e.g. Rages, K.A., Hammel, H.B., Sromovsky, L. [2007] Bull. Am. Astron. Soc., 39, 425; Sromovsky, L.A., Fry, P.M., Ahue, W.M., Hammel, H.B., de Pater, I., Rages, K.A., Showalter, M.R., van Dam, M.A. [2008] vol. 40 of AAS/Division for Planetary Sciences Meeting Abstracts, pp. 488-489; Sromovsky, L.A., Ahue, W.K.M., Fry, P.M., Hammel, H.B., de Pater, I., Rages, K.A., Showalter, M.R. [2009] Icarus), and the lowering reflectivity from mid-latitudes has left a noticeable brighter cloud zone at the equator (e.g. Sromovsky, L.A., Fry, P.M. [2007] Icarus, 192, 527-557;Karkoschka, E., Tomasko, M. [2009] Icarus). For such substantial cloud changes to have occurred in just two years suggests that the circulation of Uranus’ atmosphere is much more vigorous and/or efficient than is commonly thought. The composition of the main observed cloud decks between 2 and 6-8 bar is unclear, but the absence of the expected methane cloud at 1.2-1.3 bar (Lindal, G.F., Lyons, J.R., Sweetnam, D.N., Eshleman, V.R., Hinson, D.P. [1987] J. Geophys. Res., 92, 14987-15001) is striking (as previously noted by, among others, Sromovsky, L.A., Irwin, P.G.J., Fry, P.M. [2006] Icarus, 182, 577-593; Sromovsky, L.A., Fry, P.M. [2007] Icarus, 192, 527-557; Sromovsky, L.A., Fry, P.M. [2008] Icarus, 193, 252-266; Karkoschka, E., Tomasko, M. [2009] Icarus) and suggests that cloud particles may be considerably different from pure condensates and may be linked with stratospheric haze particles drizzling down from above, or that tropospheric hazes are generated near the methane condensation level and then drizzle down to deep pressures as suggested by Karkoschka and Tomasko (Karkoschka, E., Tomasko, M. [2009] Icarus).The retrieved cloud structures were also tested for different assumptions of the deep methane mole fraction, which Karkoschka and Tomasko (Karkoschka, E., Tomasko, M. [2009] Icarus) find may vary from ∼1-2% in polar regions to perhaps as much as 4% equatorwards of 45°N,S. We found that such variations did not significantly affect our conclusions.     

Revised vertical cloud structure of Uranus from UKIRT/UIST observations and changes seen during Uranus’ Northern Spring Equinox from 2006 to 2008: Application of new methane absorption data and comparison with Neptune

Long-slit spectroscopy observations of Uranus by the United Kingdom InfraRed Telescope UIST instrument in 2006, 2007 and 2008 have been used to monitor the change in Uranus’ vertical and latitudinal cloud structure through the planet’s Northern Spring Equinox in December 2007.These spectra were analysed and presented by Irwin et al. (Irwin, P.G.J., Teanby, N.A., Davis, G.R. [2009]. Icarus 203, 287-302), but since publication, a new set of methane absorption data has become available (Karkoschka, E., Tomasko, M. [2010]. Methane absorption coefficients for the jovian planets from laboratory, Huygens, and HST data. Icarus 205, 674-694.), which appears to be more reliable at the cold temperatures and high pressures of Uranus’ deep atmosphere. We have fitted k-coefficients to these new methane absorption data and we find that although the latitudinal variation and inter-annual changes reported by Irwin et al. (2009) stand, the new k-data place the main cloud deck at lower pressures (2-3 bars) than derived previously in the H-band of ∼3-4 bars and ∼3 bars compared with ∼6 bars in the J-band. Indeed, we find that using the new k-data it is possible to reproduce satisfactorily the entire observed centre-of-disc Uranus spectrum from 1 to 1.75 μm with a single cloud at 2-3 bars provided that we make the particles more back-scattering at wavelengths less than 1.2 μm by, for example, increasing the assumed single-scattering albedo from 0.75 (assumed in the J and H-bands) to near 1.0. In addition, we find that using a deep methane mole fraction of 4% in combination with the associated warm ‘F’ temperature profile of Lindal et al. (Lindal, G.F., Lyons, J.R., Sweetnam, D.N., Eshleman, V.R., Hinson, D.P. [1987]. J. Geophys. Res. 92, 14987-15001), the retrieved cloud deck using the new (Karkoschka and Tomasko, 2010) methane absorption data moves to between 1 and 2 bars.The same methane absorption data and retrieval algorithm were applied to observations of Neptune made during the same programme and we find that we can again fit the entire 1-1.75 μm centre-of-disc spectrum with a single cloud model, providing that we make the stratospheric haze particles (of much greater opacity than for Uranus) conservatively scattering (i.e. ω = 1) and we also make the deeper cloud particles, again at around the 2 bar level more reflective for wavelengths less than 1.2 μm. Hence, apart from the increased opacity of stratospheric hazes in Neptune’s atmosphere, the deeper cloud structure and cloud composition of Uranus and Neptune would appear to be very similar.     

Methane absorption in the atmosphere of Jupiter from 1800 to 9500 cm and implications for vertical cloud structure

New measurements of the low-temperature near-infrared absorption of methane (Sihra, 1998, Laboratory measurements of near-infrared methane bands for remote sensing of the jovian atmosphere, Ph.D. thesis, University of Oxford) have been combined with existing, longer path-length, higher-temperature data of Strong et al. (1993, Spectral parameters of self- and hydrogen-broadened methane from 2000 to 9500 cm⁻¹ for remote sounding of the atmosphere of Jupiter, J. Quant. Spectrosc. Radiat. Trans. 50, 309-325) and fitted with band models. The combined data set is found to be more consistent with previous low-temperature methane absorption measurements than that of Strong et al. (1993, J. Quant. Spectrosc. Radiat. Trans. 50, 309-325) but covers the same wider wavelength range and accounts for both self- and hydrogen-broadening conditions. These data have been fitted with k-coefficients in the manner described by Irwin et al. (1996, Calculated k-distribution coefficients for hydrogen- and self-broadened methane in the range 2000-9500 cm⁻¹ from exponential sum fitting to band modelled spectra, J. Geophys. Res. 101, 26,137-26,154) and have been used in multiple-scattering radiative transfer models to assess their impact on our previous estimates of the jovian cloud structure obtained from Galileo Near-Infrared Mapping Spectrometer (NIMS) observations (Irwin et al., 1998, Cloud structure and atmospheric composition of Jupiter retrieved from Galileo NIMS real-time spectra, J. Geophys. Res. 103, 23,001-23,021; Irwin et al., 2001, The origin of belt/zone contrasts in the atmosphere of Jupiter and their correlation with 5-μm opacity, Icarus 149, 397-415; Irwin and Dyudina, 2002, The retrieval of cloud structure maps in the equatorial region of Jupiter using a principal component analysis of Galileo/NIMS data, Icarus 156, 52-63). Although significant differences in methane opacity are found at cooler temperatures, the difference in the optical depth of the atmosphere due to methane is found to diminish rapidly with increasing pressure and temperature and thus has negligible effect on the cloud structure inferred at deeper levels. Hence the main cloud opacity variation is still found to peak at around 1-2 bar using our previous analytical approach, and is thus still in disagreement with Galileo Solid State Imager (SSI) determinations (Banfield et al., 1998, Jupiter's cloud structure from Galileo imaging data, Icarus 135, 230-250; Simon-Miller et al., 2001, Color and the vertical structure in Jupiter's belts, zones and weather systems, Icarus 154, 459-474) which place the main cloud deck near 0.9 bar. Further analysis of our retrievals reveals that this discrepancy is probably due to the different assumptions of the two analyses. Our retrievals use a smooth vertically extended cloud profile while the SSI determinations assume a thin NH₃ cloud below an extended haze. When the main opacity in our model is similarly assumed to be due to a thin cloud below an extended haze, we find the main level of cloud opacity variation to be near the 1 bar level—close to that determined by SSI and moderately close to the expected condensation level of ammonia ice of 0.85 bar, assuming that the abundance of ammonia on Jupiter is (7±1)×¹⁰⁻⁴ (Folkner et al., 1998, Ammonia abundance in Jupiter's atmosphere derived from the attenuation of the Galileo probe's radio signal, J. Geophys. Res. 103, 22,847-22,855; Atreya et al., 1999, A comparison of the atmospheres of Jupiter and Saturn: deep atmospheric composition, cloud structure, vertical mixing, and origin, Planet. Space Sci. 47, 1243-1262). However our data in the 1-2.5 μm range have good height discrimination and our lowest estimate of the cloud base pressure of 1 bar is still too great to be consistent with the most recent estimates of the ammonia abundance of 3.5 × solar. Furthermore the observed limited spatial distribution of ammonia ice absorption features on Jupiter suggests that pure ammonia ice is only present in regions of localised vigorous uplift (Baines et al., 2002, Fresh ammonia ice clouds in Jupiter: spectroscopic identification, spatial distribution, and dynamical implications, Icarus 159, 74-94) and is subsequently rapidly modified in some way which masks its pure absorption features. Hence we conclude that the main cloud deck on Jupiter is unlikely to be composed of pure ammonia ice and instead find that it must be composed of either NH₄SH or some other unknown combination of ammonia, water, and hydrogen sulphide and exists at pressures of between 1 and 2 bar.     

Spectral characteristics of rocks: Effects of composition and texture and implications for the interpretation of planet surface compositions

In spectroscopic remote sensing for the exploration of the surface compositions of Earth and terrestrial planets, reflectance spectra with very low spectral contrast and even devoid of diagnostic absorption bands can be observed, which make the interpretation of the component minerals ambiguous. Using selected examples of terrestrial rock samples from intrusive and effusive geologic systems, we discuss compositional and textural properties related to these particular spectral shapes. We show that: (1) this spectral behaviour is common for coarse grains of multimineral rocks, where the optical coupling is expected to occur between welded mineral particles; (2) it is emphasised by the presence of opaque minerals with various compositions, such as ulvospinel, magnetite and chromite in effusive rock groundmass and in intrusive rocks; (3) it is controlled by the number of silicate phases within which the FeO is distributed, irrespective of the total iron content in the rock: a rock composition with a high number of iron-bearing minerals producing this kind of low contrast, almost featureless spectra is indicated here as “critical mode”; (4) it is also strongly intensified by aqueous alteration of silicates.These observations suggest unpredictable combinations of several different petrographic variables affecting the spectra of some compact rocks, and stimulate both targeted studies to quantitatively relate spectral and petrographic parameters, and the development of appropriate methods of spectral decomposition. Our ongoing work is at present focused on the spectroscopic effects of the FeO concentration in transparent neutral plagioclase, the different compositions of the opaque neutral minerals, and the iron bearing amorphous phases.We also discuss the analogy between the rocks used in the analysis reported here and the crustal rock compositions observed on Mars and inferred for Mercury as well as the compatibility of the factors responsible for the low spectral contrast of terrestrial rock samples with the factors expected for the two planets. We observe that a coarse-grained surface and a composition approaching a critical mode could explain the featureless Acidalia spectra on Mars, and suggest that the still open questions about Mercury’s surface regolith characteristics and composition do not exclude a priori the contribution of some of the factors examined in this paper to the peculiar surface properties of this planet.     

Spectroscopy, morphometry, and photoclinometry of Titan's dunefields from Cassini/VIMS

Fine-resolution (500 m/pixel) Cassini Visual and Infrared Mapping Spectrometer (VIMS) T20 observations of Titan resolve that moon's sand dunes. The spectral variability in some dune regions shows that there are sand-free interdune areas, wherein VIMS spectra reveal the exposed dune substrate. The interdunes from T20 are, variously, materials that correspond to the equatorial bright, 5-μm-bright, and dark blue spectral units. Our observations show that an enigmatic “dark red” spectral unit seen in T5 in fact represents a macroscopic mixture with 5-μm-bright material and dunes as its spectral endmembers. Looking more broadly, similar mixtures of varying amounts of dune and interdune units of varying composition can explain the spectral and albedo variability within the dark brown dune global spectral unit that is associated with dunes. The presence of interdunes indicates that Titan's dunefields are both mature and recently active. The spectrum of the dune endmember reveals the sand to be composed of less water ice than the rest of Titan; various organics are consistent with the dunes' measured reflectivity. We measure a mean dune spacing of 2.1 km, and find that the dunes are oriented on the average in an east-west direction, but angling up to 10° from parallel to the equator in specific cases. Where no interdunes are present, we determine the height of one set of dunes photoclinometrically to be between 30 and 70 m. These results pave the way for future exploration and interpretation of Titan's sand dunes.     

Distributions of H2O and CO2 ices on Ariel, Umbriel, Titania, and Oberon from IRTF/SpeX observations

We present 0.8-2.4 μm spectral observations of uranian satellites, obtained at IRTF/SpeX on 17 nights during 2001-2005. The spectra reveal for the first time the presence of CO₂ ice on the surfaces of Umbriel and Titania, by means of 3 narrow absorption bands near 2 μm. Several additional, weaker CO₂ ice absorptions have also been detected. No CO₂ absorption is seen in Oberon spectra, and the strengths of the CO₂ ice bands decline with planetocentric distance from Ariel through Titania. We use the CO₂ absorptions to map the longitudinal distribution of CO₂ ice on Ariel, Umbriel, and Titania, showing that it is most abundant on their trailing hemispheres. We also examine H₂O ice absorptions in the spectra, finding deeper H₂O bands on the leading hemispheres of Ariel, Umbriel, and Titania, but the opposite pattern on Oberon. Potential mechanisms to produce the observed longitudinal and planetocentric distributions of the two ices are considered.     

Dust deposition at the Mars Pathfinder landing site: observations and modeling of visible/near-infrared spectra

Temporal variations in the visible/near-infrared reflectance spectra of the radiometric calibration targets on the Mars Pathfinder (MPF) lander obtained by the Imager for Mars Pathfinder (IMP) camera reveal the effects of aeolian dust deposition at the MPF site throughout the mission. Sky brightness models in combination with two-layer radiative transfer models were used with these data to track changes in dust opacity on the radiometric calibration targets (RCTs) to constrain the dust deposition rate and the spectral properties of the deposited dust. Two-layer models were run assuming both linear and nonlinear dust accumulation rates, and suggest that RCT dust optical depth at the end of the 83-sol mission was 0.08 to 0.16, or on the order of 5- to 10-μm thickness for plausible values for dust porosity and grain size. These values correspond to dust fall rates of about 20-45 μm per Earth year, consistent with previous studies of dust deposition on Mars. The single scattering albedos of the dust derived from the models fall between those previously determined for atmospheric dust and bright soils. Comparisons of relative reflectance spectra calibrated using observed RCT radiances from late in the mission versus using radiances from modeled (dust-free) RCTs also reveal distinct spectral differences consistent with dust on the RCTs. Temporal variations in RCT dust opacity are not clearly linked to known passages of vortices at the MPF site, but overall suggest that deposition of dust onto the targets by local dust devils may be favored over erosion. Analyses of temporal changes in visible/near-infrared spectra will provide valuable information for future missions by constraining how dust deposition affects landed spacecraft operability (e.g., solar power availability), instrument calibration, and interpretations of surface mineralogy and composition.     

The absence of endogenic methane on Titan and its implications for the origin of atmospheric nitrogen

We calculate the D/H ratio of CH₄ from serpentinization on Titan to determine whether Titan’s atmospheric CH₄ was originally produced inside the giant satellite. This is done by performing equilibrium isotopic fractionation calculations in the CH₄-H₂O-H₂ system, with the assumption that the bulk D/H ratio of the system is equivalent to that of the H₂O in the plume of Enceladus. These calculations show that the D/H ratio of hydrothermally produced CH₄ would be markedly higher than that of atmospheric CH₄ on Titan. The implication is that Titan’s CH₄ is a primordial chemical species that was accreted by the moon during its formation. There are two evolutionary scenarios that are consistent with the apparent absence of endogenic CH₄ in Titan’s atmosphere. The first is that hydrothermal systems capable of making CH₄ never existed on Titan because Titan’s interior has always been too cold. The second is that hydrothermal systems on Titan were sufficiently oxidized so that C existed in them predominately in the form of CO₂. The latter scenario naturally predicts the formation of endogenic N₂, providing a new hypothesis for the origin of Titan’s atmospheric N₂: the hydrothermal oxidation of ¹⁵N-enriched NH₃. A primordial origin for CH₄ and an endogenic origin for N₂ are self-consistent, but both hypotheses need to be tested further by acquiring isotopic data, especially the D/H ratio of CH₄ in comets, and the ¹⁵N/¹⁴N ratio of NH₃ in comets and that of N₂ in one of Enceladus’ plumes.     

Formation of methane in comet impacts: implications for Earth, Mars, and Titan

We calculate the amount of methane that may form via reactions catalyzed by metal-rich dust that condenses in the wake of large cometary impacts. Previous models of the gas-phase chemistry of impacts predicted that the terrestrial planets' atmospheres should be initially dominated by CO/CO₂, N₂, and H₂O. CH₄ was not predicted to form in impacts because gas-phase reactions in the explosion quench at temperatures ∼2000 K, at which point all of the carbon is locked in CO. We argue that the dust that condenses out in the wake of a large comet impact is likely to have very effective catalytic properties, opening up reaction pathways to convert CO and H₂ to CH₄ and CO₂, at temperatures of a few hundred K. Together with CO₂, CH₄ is an important greenhouse gas that has been invoked to compensate for the lower luminosity of the Sun ∼4 Gyr ago. Here, we show that heterogeneous (gas-solid) reactions on freshly-recondensed dust in the impact cloud may provide a plausible nonbiological mechanism for reducing CO to CH₄ before and during the emergence of life on Earth, and perhaps Mars as well. These encouraging results emphasize the importance of future research into the kinetics and catalytic properties of astrophysical condensates or “smokes” and also more detailed models to determine the conditions in impact-generated dust clouds.     

Mineralogy of Terra Meridiani and western Arabia Terra from OMEGA/MEx and implications for their formation

Analyses of Mars Express OMEGA hyperspectral data (0.4-2.7 μm) for Terra Meridiani and western Arabia Terra show that the northern mantled cratered terrains are covered by dust that is spectrally dominated by nanophase ferric oxides. Dark aeolian dunes inside craters and dark streaks extending from the dunes into the intercrater areas in mantled cratered terrains in western Arabia Terra have similar pyroxene-rich signatures demonstrating that the dunes supply dark basaltic material to create dark streaks. The dissected cratered terrains to the south of the mantled terrains are dominated spectrally by both low-calcium and high-calcium pyroxenes with abundances of 20-30% each retrieved from nonlinear radiative transfer modeling. Spectra over the hematite-bearing plains in Meridiani Planum are characterized by very weak but unique spectral features attributed to a mixture of a dark and featureless component (possibly gray hematite) and minor olivine in some locations. Hydrated minerals (likely hydrous ferric sulfates and/or hydrous hydroxides) associated with poorly ferric crystalline phases are found in the etched terrains to the north and east of the hematite-bearing plains where erosion has exposed ∼1 km of section of layered outcrops with high thermal inertias. These materials are also found in numerous craters in the northern Terra Meridiani and may represent outliers of the etched terrain materials. A few localized spots within the etched terrain also exhibit the spectral signature of Fe-rich phyllosilicates. The ensemble of observations show that the evidence for aqueous processes detected by the Opportunity Rover in Meridiani Planum is widespread and confirms the extended presence of surface or near-surface water over this large region of Mars. The scenarios of formation of Terra Meridiani (“dirty” acidic evaporite, impact surge or weathering of volcanic ash) cannot satisfactorily explain the mineralogy derived from the OMEGA observations. The formation of the etched terrains is consistent with leaching of iron sulfides and formation of sulfates and hydrated iron oxides, either in-place or via transport and evaporation of aqueous fluids and under aqueous conditions less acidic than inferred from rocks examined by Opportunity.     

The 506 nm absorption feature in pyroxene spectra: Nature and implications for spectroscopy-based studies of pyroxene-bearing targets

High-resolution (0.34 nm) reflectance spectra of a suite of terrestrial ortho- and clinopyroxenes were characterized in the 506-nm region. This region exhibits absorption bands attributed to spin-forbidden transitions in Fe²⁺ located in the M2, and possibly M1, crystallographic site(s). The most intense absorption bands (up to 3.8% deep in <45 μm fractions) are present in low Ca-content orthopyroxene spectra. This region exhibits two (spectral Group I) or more (spectral Group II) absorption bands in the 500-515 nm interval. Group I spectra are associated with the lowest Ca-content samples. For orthopyroxenes, the number of constituent absorption bands and band depths vary as a function of Ca content; increasing Ca content results the appearance of more than two absorption bands and a general reduction in band depths, offsetting an expected increase in band depth with increasing Fe²⁺ content; band depths may also be reduced due to the long wavelength wing of ultraviolet region Fe-O charge transfer absorptions. Band depths and shapes in this region are also a function of grain size, with the strongest bands appearing for larger grain sizes - in the 90-250 μm range. The number and position of constituent absorption bands can be used to constrain factors such as cooling rates, as expressed in the formation of Guinier-Preston zones versus coarser-grained augite exsolution lamellae. Band depths in the spectra of fine-grained (<45 μm) clinopyroxenes do not exceed 1% and are generally lowest for spectral type A clinopyroxenes, where most of the Fe²⁺ is present in the M1 crystallographic site. The appearance of the 506 nm band in the spectra of pyroxene-bearing asteroids can be used to constrain pyroxene composition and structure. The results of this study suggest that detailed analysis of absorption features in the 506 nm region is a powerful tool for determining the composition and structure of pyroxenes. The spectral resolution of the VIR-MS spectrometer aboard the Dawn spacecraft - which will examine Asteroid 4 Vesta, a body possessing surficial pyroxenes - will be sufficient to provide some constraints on pyroxene composition.     

Generation and performance of automated jarosite mineral detectors for visible/near-infrared spectrometers at Mars

We have developed two automated detectors that can recognize the sulfate mineral jarosite in unknown visible to near-infrared spectra (350-2500 nm). The two detectors are optimized for use within the terrestrial and martian atmospheres. The detectors are built from Support Vector Machines trained using a generative model to create linear mixtures of library mineral spectra. Both detectors performed with an average ∼90% accuracy on laboratory spectra of single minerals and the laboratory and field spectra of rocks collected in a hydrothermal environment. This type of algorithm will contribute to the efficiency of onboard data analysis of landed and orbital visible/near-infrared spectrometers at Mars.     

Composite models (shock and photoionization) for the interpretation of AGN spectra

AGN spectra are investigated by comparing model calculations with observations. Line intensity ratios show that the emitting gas is heated by shocks. Therefore, composite models which consistently account for both shocks, accompanying the radial motion of the gaseous clouds, and a photoionizing radiation flux are used. Liners are ambiguous objects between AGN and Starburst galaxies, therefore, power-law or black body radiations are considered in the models, depending on the characteristics of the line spectra. The SUMA code is used.The results show that shocks definitively play an important role, even if a photoionizing flux is generally present. Particularly, the heterogeneous nature of the objects, which are classified as Liners, is confirmed.     

Characteristics of Saturn's polar atmosphere and auroral electrons derived from HST/STIS, FUSE and Cassini/UVIS spectra

Ultraviolet (UV) spectra of Saturn's aurora obtained with the Hubble Space Telescope Imaging Spectrograph (STIS), the Cassini Ultraviolet Imaging Spectrograph (UVIS) and the Far Ultraviolet Spectroscopic Explorer (FUSE) have been analyzed. Comparisons between the observed spectra and synthetic models of electron-excited H₂ have been used to determine various auroral characteristics. Far ultraviolet (FUV: 1200-1700 Å) STIS and UVIS spectra exhibit, below 1400 Å, weak absorption due to methane, with a vertical column ranging between 1.4×¹⁰¹⁵ and . Using the low-latitude Moses et al. [Moses, J.I., Bézard, B., Lellouch, E., Feuchtgruber, H., Gladstone, G.R., Allen, M., 2000. Icarus, 143, 244-298] atmospheric model of Saturn and an electron energy-H₂ column relationship, these methane columns are converted into the mean energy of the primary precipitating electrons, estimated to lie in the range 10-18 keV. This result is confirmed by the study of self-absorption with UVIS and FUSE extreme ultraviolet (EUV: 900-1200 Å) spectra. Below 1200 Å, it is seen that transitions connecting to the v^″<2 vibrational levels of the H₂ electronic ground state are partially self-absorbed by H₂ molecules overlying the auroral emission. Because of its low spectral resolution (∼5.5 Å), the UVIS EUV spectrum we analyzed does not allow us to unequivocally determine reasonable ranges of temperatures and H₂ columns. On the other hand, the high spectral resolution (∼0.2 Å) of the FUSE LiF1a and LiF2a EUV spectra we examined resolve the H₂ rotational lines and makes it possible to determine the H₂ temperature. The modeled spectrum best fitting the FUSE LiF1a observation reveals a temperature of 500 K and self-absorption by a H₂ vertical column of . When converted to energy of precipitating electrons, this H₂ column corresponds to primary electrons of ∼10 keV. The model that best fits the LiF2a spectrum is characterized by a temperature of 400 K and is not self-absorbed, making this segment ideal to determine the H₂ temperature at the altitude of the auroral emission. The latter value is in agreement with temperatures obtained from infrared polar spectra. Self-absorption is detectable in the LiF2a segment for H₂ columns exceeding , which sets the maximum mean energy determined from the FUSE observations to ∼15 keV. The total electron energy range of 10-18 keV deduced from FUV and EUV observations places the auroral emission peak between the 0.1 and 0.3 μbar pressure levels. These values should be seen as an upper limit, since most of the Voyager UVS spectra of Saturn's aurora examined by Sandel et al. [Sandel, B.R., Shemansky, D.E., Broadfoot, A.L., Holberg, J.B., Smith, G.R., 1982. Science 215, 548] do not exhibit methane absorption. The auroral H₂ emission is thus likely located above but close to the methane homopause. The H₂ auroral brightness in the 800-1700 Å bandwidth varies from 2.9 kR to 139 kR, comparable to values derived from FUV Faint Object Camera (FOC) and STIS images.     

Synthetic high-resolution near-IR spectra of the Sun for planetary data reductions made from ATMOS/Spacelab-3 and Atlas-3 data

We have constructed synthetic solar spectra for the 2302-4800 cm⁻¹ (2.08-4.34 μm) range, a spectral range where planetary objects mainly emit reflected sunlight, using ATMOS (Atmospheric Trace Molecule Spectroscopy)/Spacelab-3 and Atlas-3 spectra, of which resolution is 0.01 cm⁻¹. We adopted Voigt line profiles for the modeling of line shapes based on an atlas of line identifications compiled by Geller [Geller, M., 1992. Key to Identification of Solar Features. A High-Resolution Atlas of the Infrared Spectrum of the Sun and the Earth Atmosphere from Space. NASA Reference Publ. 1224, vol. III. NASA, Washington, DC, pp. 1-22], who derived solar line positions and intensities from contaminated high-resolution solar spectra obtained by ATMOS/Spacelab-3. Because the ATMOS spectra in these wavelength ranges are compromised by absorption lines of molecules existing in Earth's high-altitude atmosphere and in the compartment of the spacecraft, the direct use of these high-resolution solar spectra has been inconvenient for the data reductions of planetary spectra. We compared the synthetic solar spectra with the ATMOS spectra, and obtained satisfactory fits for the majority of the solar lines with the exception of abnormal lines, which do not fit with Voigt line profiles. From the model fits, we were able to determine Voigt line parameters for the majority of solar lines; and we made a list of the abnormal lines. We also constructed telluric-line-free solar spectra by manually eliminating telluric lines from the ATMOS spectra and filling the gaps with adjacent continua. These synthetic solar spectra will be useful to eliminate solar continua from spectra of planetary objects to extract their own intrinsic spectral features.     

Vertical abundance profiles of hydrocarbons in Titan's atmosphere at 15° S and 80° N retrieved from Cassini/CIRS spectra

Limb spectra recorded by the Composite InfraRed Spectrometer (CIRS) on Cassini provide information on abundance vertical profiles of C₂H₂, C₂H₄, C₂H₆, CH₃C₂H, C₃H₈, C₄H₂, C₆H₆ and HCN, along with the temperature profiles in Titan's atmosphere. We analyzed two sets of spectra, one at 15° S (Tb flyby) and the other one at 80° N (T3 flyby). The spectral range 600-1400 cm⁻¹, recorded at a resolution of 0.5 cm⁻¹, was used to determine molecular abundances and temperatures in the stratosphere in the altitude range 100-460 km for Tb and 170-495 km for T3. Both temperature profiles show a well defined stratopause, at around 310 km (0.07 mbar) and 183 K at 13° S, and 380 km (0.01 mbar) with 207 K at 80° N. Near the north pole, stratospheric temperatures are colder and mesospheric temperatures are warmer than near the equator. C₂H₂, C₂H₆, C₃H₈ and HCN display vertical mixing ratio profiles that increase with height at 15° S and 80° N, consistent with their formation in the upper atmosphere, diffusion downwards and condensation in the lower stratosphere, as expected from photochemical models. The CH₃C₂H and C₄H₂ mixing ratios also increase with height at 15° S. But near the north pole, their profiles present an unexpected minimum around 300 km, observed for the first time thanks to the high vertical resolution of the CIRS limb data. C₂H₄ is the only molecule having a vertical abundance profile that decreases with height at 15° S. At 80° N, it also displays a minimum of its mixing ratio around the 0.1-mbar level. For C₆H₆, an upper limit of 1.1 ppb (in the 0.3-10 mbar range) is derived at 15° S, whereas a constant mixing ratio profile of is inferred near the north pole. At 15° S, the vertical profile of HCN exhibits a steeper gradient than other molecules, which suggests that a sink for this molecule exists in the stratosphere, possibly due to haze formation. All molecules display a more or less pronounced enrichment towards the north pole, probably due, in part, to subsidence of air at the north (winter) pole that brings air enriched in photochemical compounds from the upper atmosphere to lower levels.