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.     

Carbon dioxide on the satellites of Saturn: Results from the Cassini VIMS investigation and revisions to the VIMS wavelength scale

Several of the icy satellites of Saturn show the spectroscopic signature of the asymmetric stretching mode of C-O in carbon dioxide (CO₂) at or near the nominal solid-phase laboratory wavelength of 4.2675 μm (2343.3 cm⁻¹), discovered with the Visible-Infrared Mapping Spectrometer (VIMS) on the Cassini spacecraft. We report here on an analysis of the variation in wavelength and width of the CO₂ absorption band in the spectra of Phoebe, Iapetus, Hyperion, and Dione. Comparisons are made to laboratory spectra of pure CO₂, CO₂ clathrates, ternary mixtures of CO₂ with other volatiles, implanted and adsorbed CO₂ in non-volatile materials, and ab initio theoretical calculations of CO₂ * nH₂O. At the wavelength resolution of VIMS, the CO₂ on Phoebe is indistinguishable from pure CO₂ ice (each molecule’s nearby neighbors are also CO₂) or type II clathrate of CO₂ in H₂O. In contrast, the CO₂ band on Iapetus, Hyperion, and Dione is shifted to shorter wavelengths (typically ∼4.255 μm (∼2350.2 cm⁻¹)) and broadened. These wavelengths are characteristic of complexes of CO₂ with different near-neighbor molecules that are encountered in other volatile mixtures such as with H₂O and CH₃OH, and non-volatile host materials like silicates, some clays, and zeolites. We suggest that Phoebe’s CO₂ is native to the body as part of the initial inventory of condensates and now exposed on the surface, while CO₂ on the other three satellites results at least in part from particle or UV irradiation of native H₂O plus a source of C, implantation or accretion from external sources, or redistribution of native CO₂ from the interior.The analysis presented here depends on an accurate VIMS wavelength scale. In preparation for this work, the baseline wavelength calibration for the Cassini VIMS was found to be distorted around 4.3 μm, apparently as a consequence of telluric CO₂ gas absorption in the pre-launch calibration. The effect can be reproduced by convolving a sequence of model detector response profiles with a deep atmospheric CO₂ absorption profile, producing distorted detector profile shapes and shifted central positions. In a laboratory blackbody spectrum used for radiance calibration, close examination of the CO₂ absorption profile shows a similar deviation from that expected from a model. These modeled effects appear to be sufficient to explain the distortion in the existing wavelength calibration now in use. A modification to the wavelength calibration for 13 adjacent bands is provided. The affected channels span about 0.2 μm centered on 4.28 μm. The maximum wavelength change is about 10 nm toward longer wavelength. This adjustment has implications for interpretation of some of the spectral features observed in the affected wavelength interval, such as from CO₂, as discussed in this paper.     

Detection and discrimination of sulfate minerals using reflectance spectroscopy

A suite of sulfate minerals were characterized spectrally, compositionally, and structurally in order to develop spectral reflectance-compositional-structural relations for this group of minerals. Sulfates exhibit diverse spectral properties, and absorption-band assignments have been developed for the 0.3-26 μm range. Sulfate absorption features can be related to the presence of transition elements, OH, H₂O, and SO₄ groups. The number, wavelength position, and intensity of these bands are a function of both composition and structure. Cation substitutions can affect the wavelength positions of all major absorption bands. Hydroxo-bridged Fe³⁺ results in absorption bands in the 0.43, 0.5, and 0.9 μm regions, while the presence of Fe²⁺ results in absorption features in the 0.9-1.2 μm interval. Fundamental SO bending and stretching vibration absorption bands occur in the 8-10, 13-18, and 19-24 μm regions (1000-1250, 550-770, and 420-530 cm⁻¹). The most intense combinations and overtones of these fundamentals are found in the 4-5 μm (2000-2500 cm⁻¹) region. Absorption features seen in the 1.7-1.85 μm interval are attributable to HOH/OH bending and translation/rotation combinations, while bands in the 2.1-2.7 μm regions can be attributed to H₂O- and OH-combinations as well as overtones of SO bending fundamentals. OH- and H₂O-bearing sulfate spectra are fundamentally different from each other at wavelengths below ∼6 μm. Changes in H₂O/OH content can shift SO band positions due to change in bond lengths and structural rearrangement. Differences in absorption band wavelength positions enable discrimination of all the sulfate minerals used in this study in a number of wavelength intervals. Of the major absorption band regions, the 4-5 μm region seems best for identifying and discriminating sulfates in the presence of other major rock-forming minerals.     

Near-infrared spectra of laboratory H2O-CH4 ice mixtures

We present 1.25-19 μm infrared spectra of pure solid CH₄ and H₂O/CH₄=87, 20, and 3 solid mixtures at temperatures from 15 to 150 K. We compare and contrast the absorptions of CH₄ in solid H₂O with those of pure CH₄. Changes in selected peak positions, profiles, and relative strength with temperature are presented, and absolute strengths for absorptions of CH₄ in solid H₂O are estimated. Using the two largest (ν₃+ν₄) and (ν₁+ν₄) near-IR absorptions of CH₄ at 2.324 and 2.377 μm (4303 and 4207 cm⁻¹), respectively, as examples, we show that peaks of CH₄ in solid H₂O are at slightly shorter wavelength (higher frequency) and broader than those of pure solid CH₄. With increasing temperature, these peaks shift to higher frequency and become increasingly broad, but this trend is reversible on re-cooling, even though the phase transitions of H₂O are irreversible. It is to be hoped that these observations of changes in the positions, profiles, and relative intensities of CH₄ absorptions with concentration and temperature will be of use in understanding spectra of icy outer Solar System bodies.     

Physisorption of CO2 on non-ice materials relevant to icy satellites

CO₂ is known to adsorb onto clay and other minerals when a significant atmospheric pressure is present. We have found that CO₂ can also adsorb onto some clays when the CO₂ partial pressure is effectively zero under ultra-high vacuum (UHV) if cooled to the surface temperatures of the icy satellites of Jupiter and Saturn. The strength of adsorption and the spectral characteristics of the adsorbed CO₂ infrared (IR) ν₃ absorption band near 4.25 μm depend on the composition and temperature of the adsorbent. CO₂ remains adsorbed onto the clay mineral montmorillonite for >10 s of min when exposed to a vacuum of ∼1×¹⁰⁻⁸ Torr at ∼125 K. CO₂ does not adsorb onto serpentine, goethite, or palagonite under these conditions. A small amount may adsorb onto kaolinite. When heated above 150 K under vacuum, the CO₂ desorbs from the montmorillonite within a few minutes. The ν₃ absorption band of CO₂ adsorbed onto montmorillonite at 125 K is similar to that of the CO₂ detected on the saturnian and Galilean satellites and is markedly different from CO₂ adsorbed onto montmorillonite at room temperature. We infer the adsorption process is physisorption and postulate that this mechanism may explain the presence and spectral characteristics of the CO₂ detected in the surfaces of these outer satellites.     

Prebiotic organic synthesis in early Earth and Mars atmospheres: Laboratory experiments with quantitative determination of products formed in a cold plasma flow reactor

The goal of this study was to explore prebiotic chemistry in a range of plausible early Earth and Mars atmospheres. To achieve this laboratory continuous flow plasma irradiation experiments were performed on N₂/H₂/CO/CO₂ gas mixtures chosen to represent mildly reducing early Earth and Mars atmospheres derived from a secondary volcanic outgassing of volatiles in chemical equilibrium with magmas near present day oxidation state. Under mildly reducing conditions (91.79% N₂, 5.89% H₂, 2.21% CO, and 0.11% CO₂), simple nitriles are produced in the gas phase with yield (G in molecules per 100 eV), for the key prebiotic marker molecule HCN at G∼1×¹⁰⁻³ (0.1 nmol J⁻¹). In this atmosphere localized HCN concentrations possibly could approach the 10⁻² M needed for HCN oligomerization. Yields under mildly oxidizing conditions (45.5% N₂, 0.1% H₂, 27.2% CO, 27.2% CO₂) are significantly less as expected, with HCN at G∼3×¹⁰⁻⁵ (). Yields in a Triton atmosphere which can be plausibly extrapolated to represent what might be produced in trace CH₄ conditions (99.9% N₂, 0.1% CH₄) are significant with HCN at G∼1×¹⁰⁻² (1 nmol J⁻¹) and tholins produced. Recently higher methane abundance atmospheres have been examined for their greenhouse warming potential, and higher abundance hydrogen atmospheres have been proposed based on a low early Earth exosphere temperature. A reducing (64.04% N₂, 28.8% H₂, 3.60% CO₂, and 3.56% CH₄), representing a high CH₄ and H₂ abundance early Earth atmosphere had HCN yields of G∼5×¹⁰⁻³ (0.5 nmol J⁻¹). Tholins generated in high methane hydrogen gas mixtures is much less than in a similar mixture without hydrogen. The same mixture with the oxidizing component CO₂ removed (66.43% N₂, 29.88% H₂, 0% CO₂, and 3.69% CH₄) had HCN yields of G∼1×¹⁰⁻³ (0.1 nmol J⁻¹) but more significant tholin yields.     

Identification of a new band system of isotopic CO2 near 3.3 μm: Implications for remote sensing of biomarker gases on Mars

We present the discovery of a new vibrational band system of isotopic CO₂ (carbon dioxide) near 3.3 μm, with multiple strong P, Q and R lines in the prime spectral region used to search for Mars CH₄ (methane). The band system was discovered on Mars using high-resolution spectrometers (λ/δλ>40,000, CSHELL and NIRSPEC) at telescopes (NASA-IRTF and Keck-2) atop Mauna Kea, HI. The observed line intensities and frequencies agree very well with values predicted by a vibrational band model that we developed using known parameters for the molecular levels involved. Using this model, we synthesized spectra for different observing conditions (from Space and ground-based telescopes) and for different spectral resolving powers (5000 to 40,000). Although the total atmospheric burden on Mars is more than 150 times smaller than on Earth, the greater mixing ratio of CO₂ ensures that its column abundance on Mars is almost 20 times greater than on Earth. Thus, weak telluric CO₂ band systems appear much stronger on Mars. Many molecules of possible biological and geothermal interest have strong signatures at these wavelengths, in particular hydrocarbons owing to their strong ro-vibrational CH stretching modes. For example, the new isotopic CO₂ band-system encompasses lines of CH₄, C₂H₆ (ethane), CH₃OH (methanol) and H₂O (water). Implications for previous and future searches of biomarker gases are presented.     

Titan’s atmosphere from ISO mid-infrared spectroscopy

We have analyzed Titan observations performed by the Infrared Space Observatory (ISO) in the range 7-30 μm. The spectra obtained by three of the instruments on board the mission (the short wavelength spectrometer, the photometer, and the camera) were combined to provide new and more precise thermal and compositional knowledge of Titan’s stratosphere. With the high spectral resolution achieved by the SWS (much higher than that of the Voyager 1 IRIS spectrometer), we were able to detect and separate the contributions of most of the atmospheric gases present on Titan and to determine disk-averaged mole fractions. We have also tested existing vertical distributions for C₂H₂, HCN, C₂H₆, and CO₂ and inferred some information on the abundance of the first species as a function of altitude. From the CH₃D band at 1161 cm⁻¹ and for a CH₄ mole fraction assumed to be 1.9% in Titan’s stratosphere, we have obtained the monodeuterated methane-averaged abundance and retrieved a D/H isotopic ratio of 8.7−1.9+3.2 × 10⁻⁵. We discuss the implications of this value with respect to current evolutionary scenarios for Titan. The ν₅ band of HC₃N at 663 cm⁻¹ was observed for the first time in a disk-averaged spectrum. We have also obtained a first tentative detection of benzene at 674 cm⁻¹, where the fit of the ISO/SWS spectrum at R = 1980 is significantly improved when a constant mean mole fraction of 4 × 10⁻¹⁰ of C₆H₆ is incorporated into the atmospheric model. This corresponds to a column density of ∼ 2 × 10¹⁵ molecules cm⁻² above the 30-mbar level. We have also tested available vertical profiles for HC₃N and C₆H₆ and adjusted them to fit the data. Finally, we have inferred upper limits of a few 10⁻¹⁰ for a number of molecules proposed as likely candidates on Titan (such as allene, acetonitrile, propionitrile, and other more complex gases).     

The composition of Titan's stratosphere from Cassini/CIRS mid-infrared spectra

We have analyzed data recorded by the Composite Infrared Spectrometer (CIRS) aboard the Cassini spacecraft during the Titan flybys T0-T10 (July 2004-January 2006). The spectra characterize various regions on Titan from 70° S to 70° N with a variety of emission angles. We study the molecular signatures observed in the mid-infrared CIRS detector arrays (FP3 and FP4, covering roughly the 600-1500 cm⁻¹ spectral range with apodized resolutions of 2.54 or 0.53 cm⁻¹). The composite spectrum shows several molecular signatures: hydrocarbons, nitriles and CO₂. A firm detection of benzene (C₆H₆) is provided by CIRS at levels of about 3.5×¹⁰⁻⁹ around 70° N. We have used temperature profiles retrieved from the inversion of the emission observed in the methane ν₄ band at 1304 cm⁻¹ and a line-by-line radiative transfer code to infer the abundances of the trace constituents and some of their isotopes in Titan's stratosphere. No longitudinal variations were found for these gases. Little or no change is observed generally in their abundances from the south to the equator. On the other hand, meridional variations retrieved for these trace constituents from the equator to the North ranged from almost zero (no or very little meridional variations) for C₂H₂, C₂H₆, C₃H₈, C₂H₄ and CO₂ to a significant enhancement at high northern (early winter) latitudes for HCN, HC₃N, C₄H₂, C₃H₄ and C₆H₆. For the more important increases in the northern latitudes, the transition occurs roughly between 30 and 50 degrees north latitude, depending on the molecule. Note however that the very high-northern latitude results from tours TB-T10 bear large uncertainties due to few available data and problems with latitude smearing effects. The observed variations are consistent with some, but not all, of the predictions from dynamical-photochemical models. Constraints are set on the vertical distribution of C₂H₂, found to be compatible with 2-D equatorial predictions by global circulation models. The D/H ratio in the methane on Titan has been determined from the CH₃D band at 1156 cm⁻¹ and found to be . Implications of this deuterium enrichment, with respect to the protosolar abundance on the origin of Titan, are discussed. We compare our results with values retrieved by Voyager IRIS observations taken in 1980, as well as with more recent (1997) disk-averaged Infrared Space Observatory (ISO) results and with the latest Cassini-Huygens inferences from other instruments in an attempt to better comprehend the physical phenomena on Titan.     

The 1.10- and 1.18-μm nightside windows of Venus observed by SPICAV-IR aboard Venus Express

Observations of the 1.10- and 1.18-μm nightside windows by the SPICAV-IR instrument aboard Venus Express were analyzed to characterize the various sources of gaseous opacity and determine the H₂O mole fraction in the lower atmosphere of Venus. We showed that the line profile model of Afanasenko and Rodin (Afanasenko, T.S., Rodin, A.V. [2007]. Astron. Lett. 33, 203–210) underestimates the CO₂ absorption in the high-wavelength wing of the 1.18-μm window and we derived an empirical lineshape that matches this wing well. An additional continuum opacity is required to reproduce the variation of the 1.10- and 1.18-μm radiances with surface elevation as observed by the VIRTIS-M instrument aboard Venus Express. A constant absorption coefficient of 0.7 ± 0.2 × 10⁻⁹ cm⁻¹ am⁻² best reproduces the observed variation. We compared spectra calculated with different CO₂ and H₂O line lists. We found that the CDSD line list lacks the 5ν₁ + ν₃ series of CO₂ bands, which provide significant opacity in Venus’ deep atmosphere, and we have constructed a composite line list that best reproduces the observations. We also showed for the first time that HDO brings significant absorption at 1140–1190 nm. Using the best representation of the atmospheric opacity we could reach, we retrieved a water vapor mole fraction of ppmv, pertaining to the altitude range 5–25 km. Combined with previous measurements in the 1.74- and 2.3-μm windows, this result provides strong evidence for a uniform H₂O profile below 40 km, in agreement with chemical models.     

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

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

Experimental impact shock chemistry on planetary icy satellites

We present new experimental results on impact shock chemistry into icy satellites of the outer planets. Icy mixtures of pure water ice with CO₂, Na₂CO₃, CH₃OH, and CH₃OH/(NH₄)₂SO₄ at 77 K were ablated with a powerful pulsed laser—a new technique used to simulate shock processes which can occur during impacts. New products were identified by GC-MS and FTIR analyses after laser ablation. Our results show that hydrogen peroxide is formed in irradiated H₂O/CO₂ ices with a final concentration of 0.23%. CO and CH₃OH were also detected as main products. The laser ablation of frozen H₂O/Na₂CO₃ generates only CO and CO₂ as destruction products from the salt. Pulsed irradiation of water ice containing methanol leads also to the formation of CO and CO₂, generates methane and more complex molecules containing carbonyl groups like acetaldehyde, acetone, methyl formate, and a diether, dimethyl formal. The last three compounds are also produced when adding ammonium sulfate to H₂O/CH₃OH ice, but acetone is more abundant. The formation of two hydrocarbons, CH₄ and C₂H₆ is observed as well as the production of three nitrogen compounds, nitrous oxide, hydrogen cyanide, and acetonitrile.     

Photochemistry of minor constituents in the troposphere

Altitude profiles for the number densities of NO, NO₂, NO₃, N₂O₅, HNO₂, CH₃O, CH₃O₂, H₂CO, OH, and HO₂ are calculated as a function of time of day with a steady-state photochemical model in which the altitude profiles for the number densities of H₂O, CH₄, H₂, CO, O₃, and the sum of NO and NO₂ are fixed at values appropriate to a summer latitude of 34°. Average daily profiles are calculated for the long-lived species, HNO₃, H₂O₂, and CH₃O₂H.The major nitrogen compound HNO₃ may have a number density approaching 5 × 10¹¹ molecules cm^?3 at the surface, although an effective loss path due to collisions with particulates could greatly reduce this value.The number density of OH remains relatively unchanged in the first 6 km and reaches 1 × 10⁷ molecules cm^?3 at noon, while the number density of HO₂ decreases throughout the lower troposphere from its noontime value of 8 × 10⁸ molecules cm^?3 at the surface.H₂O₂ and H₂CO both have number densities in the ppb range in the lower troposphere.Owing to decreasing temperature and water concentration, the production of radicals and their steady-state number densities decrease with altitude, reaching a noontime minimum of 1 × 10⁸ molecules cm^?3 for OH and 3 × 10⁷ molecules cm^?3 for HO₂ at the tropopause. The related minor species show even sharper decreases with increasing altitude.The primary path for interconverting OH and HO₂ serves as the major sink for CO and leads to a tropospheric lifetime for CO of ~0.1 yr.Another reaction cycle, the oxidation of CH₄, is quite important in the lower troposphere and leads to the production of H₂CO along with the destruction of CH₄ for which a tropospheric lifetime of ~2 yr is estimated.The destruction of H₂CO that was produced in the CH₄ oxidation cycle provides the major source of CO and H₂ in the atmosphere.     

Solar-wind interactions: Nature and composition of lunar atmosphere

The solar wind interacts directly with the lunar surface material resulting in an essentially complete absorption of the corpuscles producing no upstream bowshock but a cavity downstream from the Moon. The main source of most neutral species of the atmosphere, except probably⁴⁰Ar, is the solar-wind interaction products. The other sources which appear to be minor contributors to the atmosphere are the interaction products of cosmic rays, planetary degassing, effects of meteorite impacts and radioactive decays. Most of the hydrogen atoms derived from the solar-wind protons contribute to the atmosphere as hydrogen molecules rather than atoms. Only on the basis of the solar-wind protons, alpha particles and ions of oxygen and carbon, the atmospheric species concentration (cm^–3) near the lunar surface at 300K are as follows: H₂ 3.3 to 9.9 × 10³; He 2.4 to 4.7 × 10³; H 3.7; OH 0.25; H₂O 0.24; and O₂, O, CO, CO₂ and CH₄ in concentrations smaller than H₂. Whatever the source, the OH and H₂O concentrations in the atmosphere are about the same. The calculated concentrations are in good agreement with the observations by the Apollo 17 lunar surface mass spectrometer and the Apollo 17 orbital UV spectrometer. At the time of sample collection from the Moon, the hydrogen content in the trapped gas layer of the lunar surface material was partly as hydrogen atoms and partly as hydrogen molecules, but at the time of sample analysis hydrogen was mostly in molecular form. The H₂O content at the time of sample analysis was only a few parts per million by weight.Paper presented at the Conference on Interactions of the Interplanetary Plasma with the Modern and Ancient Moon, sponsored by the Lunar Science Institute, Houston, Texas and held at the Lake Geneva Campus of George Williams College, Wisconsin, between September 30 and October 4, 1974.     

Atomic oxygen distribution in the Venus mesosphere from observations of O2 infrared airglow by VIRTIS-Venus Express

This VIRTIS instrument on board Venus Express has collected spectrally resolved images of the Venus nightside limb that show the presence of the (0,0) band of the infrared atmospheric system of O₂ at 1.27 μm. The emission is produced by three-body recombination of oxygen atoms created by photodissociation of CO₂ on the dayside. It is consistently bright so that emission limb profiles can be extracted from the images. The vertical distribution of O₂() may be derived following Abel inversion of the radiance limb profiles. Assuming photochemical equilibrium, it is combined with the CO₂ vertical distribution to determine the atomic oxygen density. The uncertainties on the O density caused by the Abel inversion reach a few percent at the peak, increasing to about 50% near 120 km. We first analyze a case when the CO₂ density was derived from a stellar occultation observed with the SPICAV spectrometer simultaneously with an image of the O₂ limb airglow. In other cases, an average CO₂ profile deduced from a series of ultraviolet stellar occultations is used to derive the O profile, leading to uncertainties on the O density less than 30%. It is found that the maximum O density is generally located between 94 and 115 km with a mean value of 104 km. It ranges from less than 1×¹⁰¹¹ to about 5×¹⁰¹¹ cm⁻³ with a global mean of 2.2×¹⁰¹¹ cm⁻³. These values are in reasonable agreement with the VIRA midnight oxygen profile. The vertical O distribution is generally in good agreement with the oxygen profile calculated with a one-dimensional chemical-diffusive model. No statistical latitudinal dependence of the altitude of the oxygen peak is observed, but the maximum O density tends to decrease with increasing northern latitudes. The latitudinal distribution at a given time exhibits large variations in the O density profile and its vertical structure. The vertical oxygen distribution frequently shows multiple peaks possibly caused by waves or variations in the structure of turbulent transport. It is concluded that the O₂ infrared night airglow is a powerful tool to map the distribution of atomic oxygen in the mesosphere between 90 and 115 km and improve future Venus reference atmosphere models.     

Cratering of icy targets by different impactors: Laboratory experiments and implications for cratering in the Solar System

Studies of impacts (impactor velocity about 5 km s⁻¹) on icy targets were performed. The prime goal was to study the response of solid CO₂ targets to impacts and to find the differences between the results of impacts on CO₂ targets with those on H₂O ice targets. The crater dimensions in CO₂ ice were found to scale with impact energy, with little dependence on projectile density (which ranged from nylon to copper, i.e., 1150-8930 kg m⁻³). At equal temperatures, craters in CO₂ ice were the same diameter as those in water ice, but were shallower and smaller in volume. In addition, the shape of the radial profiles of the craters was found to depend strongly on the type of ice and to change with impact energy. The impact speed of the data is comparable to that for impacts on many types of icy bodies in the outer Solar System (e.g., the satellites of the giant planets, the cometary nuclei and the Kuiper Belt objects), but the size and thus energy of the impactors is lower. Scaling with impact energy is demonstrated for the impacts on CO₂ ice. The issue of impact disruption (rather than cratering) is discussed by analogy with that on water ice. Expressions for the critical energy density for the onset of disruption rather than cratering are established for water ice as a function of porosity and silicate content. Although the critical energy density for disruption of CO₂ ice is not established, it is argued that the critical energy to disrupt a CO₂ ice body will be greater than that for a (non-porous) water ice body of the similar mass.     

The first detection of propane on Saturn

We report the first detection of propane, C₃H₈, in Saturn's stratosphere. Observations taken on September 8, 2002 UT at NASA's IRTF using TEXES, show multiple emission lines due to the 748 cm⁻¹ν₂₁ band of C₃H₈. Using a line-by-line radiative transfer code, we are able to fit the data by scaling the propane vertical mixing ratio profile from the photochemical model of Moses et al. [2000. Icarus 143, 244-298]. Multiplicative factors of 0.7 and 0.65 are required to fit the −20° and −80° planetocentric latitude spectra. The resultant profiles are characterized by a 5 mbar mixing ratio of 2.7±0.8×¹⁰⁻⁸ at −20° and at −80° latitude. These results suggest that the time scale for meridional circulation lies between the net photochemical lifetimes of C₂H₂ and C₃H₈, ≈30-600 years.     

Water vapour in sunspots

The line intensities are calculated at temperatures of 263 K and 3500 K for the H₂O band 201 at 0.94 m. The possibility of detecting these lines in sunspots is discussed. The amount of H₂O is estimated to be 4.2 × 10²⁰ molecules or 0.013 g cm^–2 above optical depth equal to unity. However, other bands at longer wavelengths are more favourable for detection of H₂O.     

Detection of C2HD and the D/H ratio on Titan

We report here the first detection of mono-deuterated acetylene (acetylene-d1, C₂HD) in Titan's atmosphere from the presence of two of its emission bands at 678 and 519 cm⁻¹ as observed in CIRS spectral averages of nadir and limb observations taken between July 2004 and mid-2007. By using new laboratory spectra for this molecule, we were able to derive its abundance at different locations over Titan's disk. We find the C₂HD value () to be roughly constant with latitude from the South to about 45° N and then to increase slightly in the North, as is the case for C₂H₂. Fitting the 678 cm⁻¹ν₅ band simultaneously with the nearby C₂H₂ 729 cm⁻¹ν₅ band, allows us to infer a D/H ratio in acetylene on Titan with an average of the modal values of 2.09±0.45×¹⁰⁻⁴ from the nadir observations, the uncertainties being mainly due to the vertical profile used for the fit of the acetylene band. Although still subject to significant uncertainty, this D/H ratio appears to be significantly larger than the one derived in methane from the CH₃D band (upper limit of 1.5×¹⁰⁻⁴; Bézard, B., Nixon, C.A., Kleiner, I., Jennings, D.E., 2007. Icarus, 191, 397-400; Coustenis, A., Achterberg, R., Conrath, B., Jennings, D., Marten, A., Gautier, D., Bjoraker, G., Nixon, C., Romani, P., Carlson, R., Flasar, M., Samuelson, R.E., Teanby, N., Irwin, P., Bézard, B., Orton, G., Kunde, V., Abbas, M., Courtin, R., Fouchet, Th., Hubert, A., Lellouch, E., Mondellini, J., Taylor, F.W., Vinatier, S., 2007. Icarus 189, 35-62). From the analysis of limb data we infer D/H values of (at 54° S), (at 15° S), (at 54° N) and (at 80° N), which average to a mean value of 1.63±0.27×¹⁰⁻⁴.     

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.