Latitudinal variations of HCN, HC3N, and C2N2 in Titan's stratosphere derived from Cassini CIRS data

Mid- and far-infrared spectra from the Composite InfraRed Spectrometer (CIRS) have been used to determine volume mixing ratios of nitriles in Titan's atmosphere. HCN, HC₃N, C₂H₂, and temperature were derived from 2.5 cm⁻¹ spectral resolution mid-IR mapping sequences taken during three flybys, which provide almost complete global coverage of Titan for latitudes south of 60° N. Three 0.5 cm⁻¹ spectral resolution far-IR observations were used to retrieve C₂N₂ and act as a check on the mid-IR results for HCN. Contribution functions peak at around 0.5-5 mbar for temperature and 0.1-10 mbar for the chemical species, well into the stratosphere. The retrieved mixing ratios of HCN, HC₃N, and C₂N₂ show a marked increase in abundance towards the north, whereas C₂H₂ remains relatively constant. Variations with longitude were much smaller and are consistent with high zonal wind speeds. For 90°-20° S the retrieved HCN abundance is fairly constant with a volume mixing ratio of around 1 × 10⁻⁷ at 3 mbar. More northerly latitudes indicate a steady increase, reaching around 4 × 10⁻⁷ at 60° N, where the data coverage stops. This variation is consistent with previous measurements and suggests subsidence over the northern (winter) pole at approximately 2 × 10⁻⁴ m s⁻¹. HC₃N displays a very sharp increase towards the north pole, where it has a mixing ratio of around 4 × 10⁻⁸ at 60° N at the 0.1-mbar level. The difference in gradient for the HCN and HC₃N latitude variations can be explained by HC₃N's much shorter photochemical lifetime, which prevents it from mixing with air at lower latitude. It is also consistent with a polar vortex which inhibits mixing of volatile rich air inside the vortex with that at lower latitudes. Only one observation was far enough north to detect significant amounts of C₂N₂, giving a value of around 9 × 10⁻¹⁰ at 50° N at the 3-mbar level.     

Kinetic studies at room temperature of the cyanide anion CN with cyanoacetylene (HC3N) reaction

Rate coefficient of the cyanide anion (CN⁻) with cyanoacetylene (HC₃N) reaction, has been studied in gas phase at room temperature using a Flowing Afterglow Langmuir Probe - Mass Spectrometer (FALP-MS) apparatus. The rate constant for the CN⁻ + HC₃N reaction is k = 4.8 × 10⁻⁹ cm³/s with an uncertainty of 30%.     

Electrostatic ion-cyclotron waves in a plasma with heavy negative ions

Results of a laboratory study of electrostatic ion-cyclotron (EIC) waves in a plasma containing K⁺ (39 amu) positive ions, electrons and C₇F₁₄⁻ (350 amu) negative ions are presented. Excitation of the fundamental and higher harmonic light and heavy ion EIC modes was observed. The presence of heavy negative ions in the plasma has a significant effect on the excitation of the light ion EIC modes. The results may be relevant to the understanding of plasma wave properties in plasmas containing negative ions, such as those found in the Earth's ionosphere, the solar system, and, in particular, near Saturn's moon Titan, where an abundance of heavy negative ion species has recently been discovered [Coates, et al., 2007. Discovery of heavy negative ions in Titan's ionosphere. Geophys. Res. Lett. 34, L22103].     

Titan's stratospheric C2N2, C3H4, and C4H2 abundances from Cassini/CIRS far-infrared spectra

Far-IR (25-50 μm, 200-400 cm⁻¹) nadir and limb spectra measured during Cassini's four year prime mission by the Composite InfraRed Spectrometer (CIRS) instrument have been used to determine the abundances of cyanogen (C₂N₂), methylacetylene (C₃H₄), and diacetylene (C₄H₂) in Titan's stratosphere as a function of latitude. All three gases are enriched at northern latitudes, consistent with north polar subsidence. C₄H₂ abundances agree with those derived previously from mid-IR data, but C₃H₄ abundances are about 2 times lower, suggesting a vertical gradient or incorrect band intensities in the C₃H₄ spectroscopic data. For the first time C₂N₂ was detected at southern and equatorial latitudes with an average volume mixing ratio of 5.5±1.4×¹⁰−11 derived from limb data (>3-σ significance). This limb result is also corroborated by nadir data, which give a C₂N₂ volume mixing ratio of 6±3×¹⁰−11 (2-σ significance) or alternatively a 3-σ upper limit of 17×¹⁰−11. Comparing these figures with photochemical models suggests that galactic cosmic rays may be an important source of N₂ dissociation in Titan's stratosphere. Like other nitriles (HCN, HC₃N), C₂N₂ displays greater north polar relative enrichment than hydrocarbons with similar photochemical lifetimes, suggesting an additional loss mechanism for all three of Titan's main nitrile species. Previous studies have suggested that HCN requires an additional sink process such as incorporation into hazes. This study suggests that such a sink may also be required for Titan's other nitrile species.     

Spatially-resolved high-resolution spectroscopy of Venus 2. Variations of HDO, OCS, and SO2 at the cloud tops

While CO, HCl, and HF, that were considered in the first part of this work, have distinct absorption lines in high-resolution spectra and were detected four decades ago, the lines of HDO, OCS, and SO₂ are either very weak or blended by the telluric lines and have not been observed previously by ground-based infrared spectroscopy at the Venus cloud tops. The H₂O abundance above the Venus clouds is typically below the detection limit of ground-based IR spectroscopy. However, the large D/H ratio on Venus facilitates observations of HDO. Converted to H₂O with D/H ≈ 200, our observations at 2722 cm⁻¹ in the Venus afternoon show a H₂O mixing ratio of ∼1.2 ppm at latitudes between ±40° increasing to ±60° by a factor of 2. The observations in the early morning reveal the H₂O mixing ratio that is almost constant at 2.9 ppm within latitudes of ±75°. The measured H₂O mixing ratios refer to 74 km. The observed increase in H₂O is explained by the lack of photochemical production of sulfuric acid in the night time. The recent observations at the P-branch of OCS at 4094 cm⁻¹ confirm our detection of OCS. Four distributions of OCS along the disk of Venus at various latitudes and local times have been retrieved. Both regular and irregular components are present in the variations of OCS. The observed OCS mixing ratio at 65 km varies from ∼0.3 to 9 ppb with the mean value of ∼3 ppb. The OCS scale height is retrieved from the observed limb darkening and varies from 1 to 4 km with a mean value of half the atmospheric scale height. SO₂ at the cloud tops has been detected for the first time by means of ground-based infrared spectroscopy. The SO₂ lines look irregular in the observed spectra at 2476 cm⁻¹. The SO₂ abundances are retrieved by fitting by synthetic spectra, and two methods have been applied to determine uncertainties and detection limits in this fitting. The retrieved mean SO₂ mixing ratio of 350 ± 50 ppb at 72 km favors a significant increase in SO₂ above the clouds since the period of 1980-1995 that was observed by the SOIR occultations at Venus Express. Scale heights of OCS and SO₂ may be similar, and the SO₂/OCS ratio is ∼500 and may be rather stable at 65-70 km under varying conditions on Venus.     

Vertical profiles of HCN, HC3N, and C2H2 in Titan's atmosphere derived from Cassini/CIRS data

Mid-infrared limb spectra in the range 600-1400 cm⁻¹ taken with the Composite InfraRed Spectrometer (CIRS) on-board the Cassini spacecraft were used to determine vertical profiles of HCN, HC₃N, C₂H₂, and temperature in Titan's atmosphere. Both high (0.5 cm⁻¹) and low (13.5 cm⁻¹) spectral resolution data were used. The 0.5 cm⁻¹ data gave profiles at four latitudes and the 13.5 cm⁻¹ data gave almost complete latitudinal coverage of the atmosphere. Both datasets were found to be consistent with each other. High temperatures in the upper stratosphere and mesosphere were observed at Titan's northern winter pole and were attributed to adiabatic heating in the subsiding branch of a meridional circulation cell. On the other hand, the lower stratosphere was much colder in the north than at the equator, which can be explained by the lack of solar radiation and increased IR emission from volatile enriched air. HC₃N had a vertical profile consistent with previous ground based observations at southern and equatorial latitudes, but was massively enriched near the north pole. This can also be explained in terms of subsidence at the winter pole. A boundary observed at 60° N between enriched and un-enriched air is consistent with a confining polar vortex at 60° N and HC₃N's short lifetime. In the far north, layers were observed in the HC₃N profile that were reminiscent of haze layers observed by Cassini's imaging cameras. HCN was also enriched over the north pole, which gives further evidence for subsidence. However, the atmospheric cross section obtained from 13.5 cm⁻¹ data indicated a HCN enriched layer at 200-250 km, extending into the southern hemisphere. This could be interpreted as advection of polar enriched air towards the south by a meridional circulation cell. This is observed for HCN but not for HC₃N due to HCN's longer photochemical lifetime. C₂H₂ appears to have a uniform abundance with altitude and is not significantly enriched in the north. This is consistent with observations from previous CIRS analysis that show increased abundances of nitriles and hydrocarbons but not C₂H₂ towards the north pole.     

Meridional distribution of CH3C2H and C4H2 in Saturn’s stratosphere from CIRS/Cassini limb and nadir observations

Limb and nadir spectra acquired by Cassini/CIRS (Composite InfraRed Spectrometer) are analyzed in order to derive, for the first time, the meridional variations of diacetylene (C₄H₂) and methylacetylene (CH₃C₂H) mixing ratios in Saturn’s stratosphere, from 5 hPa up to 0.05 hPa and 80°S to 45°N. We find that the C₄H₂ and CH₃C₂H meridional distributions mimic that of acetylene (C₂H₂), exhibiting small-scale variations that are not present in photochemical model predictions. The most striking feature of the meridional distribution of both molecules is an asymmetry between mid-southern and mid-northern latitudes. The mid-southern latitudes are found depleted in hydrocarbons relative to their northern counterparts. In contrast, photochemical models predict similar abundances at north and south mid-latitudes. We favor a dynamical explanation for this asymmetry, with upwelling in the south and downwelling in the north, the latter coinciding with the region undergoing ring shadowing. The depletion in hydrocarbons at mid-southern latitudes could also result from chemical reactions with oxygen-bearing molecules.Poleward of 60°S, at 0.1 and 0.05 hPa, we find that the CH₃C₂H and C₄H₂ abundances increase dramatically. This behavior is in sharp contradiction with photochemical model predictions, which exhibit a strong decrease towards the south pole. Several processes could explain our observations, such as subsidence, a large vertical eddy diffusion coefficient at high altitudes, auroral chemistry that enhances CH₃C₂H and C₄H₂ production, or shielding from photolysis by aerosols or molecules produced from auroral chemistry. However, problems remain with all these hypotheses, including the lack of similar behavior at lower altitudes.Our derived mean mixing ratios at 0.5 hPa of (2.4 ± 0.3) × 10⁻¹⁰ for C₄H₂ and of (1.1 ± 0.3) × 10⁻⁹ for CH₃C₂H are compatible with the analysis of global-average ISO observations performed by Moses et al. (Moses, J.I., Bézard, B., Lellouch, E., Gladstone, G.R., Feuchtgruber, H., Allen, M. [2000a]. Icarus 143, 244-298). Finally, we provide values for the ratios [CH₃C₂H]/[C₂H₂] and [C₄H₂]/[C₂H₂] that can constrain the coupled chemistry of these hydrocarbons.     

Molecular hydrogen in Titan’s atmosphere: Implications of the measured tropospheric and thermospheric mole fractions

The third most abundant species in Titan’s atmosphere is molecular hydrogen with a tropospheric/lower stratospheric mole fraction of 0.001 derived from Voyager and Cassini infrared measurements. The globally averaged thermospheric H₂ mole fraction profile from the Cassini Ion Neutral Mass Spectrometer (INMS) measurements implies a small positive gradient in the H₂ mixing ratio from the tropopause region to the lower thermosphere (∼950-1000 km), which drives a downward H₂ flux into Titan’s surface comparable to the H₂ escape flux out of the atmosphere (∼2 × 10¹⁰ cm⁻² s⁻¹ referenced to the surface) and requires larger photochemical production rates of H₂ than obtained by previous photochemical models. From detailed model calculations based on known photochemistry with eddy, molecular, and thermal diffusion, the tropospheric and thermospheric H₂ mole fractions are incompatible by a factor of ∼2. The measurements imply that the downward H₂ surface flux is in substantial excess of the speculative threshold value for methanogenic life consumption of H₂ (McKay, C.P., Smith, H.D. [2005], Icarus 178, 274-276. doi:10.1016/j.icarus.2005.05.018), but without the extreme reduction in the surface H₂ mixing ratio.     

FT-IR measurements of cold C3H8 cross sections at 7–15 μm for Titan atmosphere

We present absorption cross sections of propane (C₃H₈) at temperatures from 145 K to 297 K in the 690–1550 cm⁻¹ region. Pure and N₂-broadened spectra were measured at pressures from 3 Torr to 742 Torr using a Bruker IFS125 FT-IR spectrometer at JPL. The gas absorption cell, developed at Connecticut College, was cooled by a closed-cycle helium refrigerator. The cross sections were measured and compiled for individual spectra recorded at various experimental conditions covering the planetary atmosphere and Titan. In addition to the cross sections, a propane pseudoline list with a frequency grid of 0.005 cm⁻¹, was fitted to the 34 laboratory spectra. Line intensities and lower state energies were retrieved for each line, assuming a constant width. Validation tests showed that the pseudoline list reproduces discrete absorption features and continuum, the latter contributed by numerous weak and hot band features, in most of the observed spectra within 3%. Based on the pseudoline list, the total intensity in the 690–1550 cm⁻¹ region was determined to be 52.93 (±3%) × 10⁻¹⁹ cm⁻¹/(molecule cm⁻²) at 296 K; this value is within 3% of the average from four earlier studies. Finally, the merit of the pseudoline approach is addressed for heavy polyatomic molecules in support of spectroscopic observation of atmospheres of Titan and other planets. The cold cross sections will be submitted to the HITRAN database (hitran.harvard.edu), and the list of C₃H₈ pseudolines will be available from a MK-IV website of JPL (http://mark4sun.jpl.nasa.gov/data/spec/Pseudo).     

A spatially resolved high spectral resolution study of Neptune’s stratosphere

Using TEXES, the Texas Echelon cross Echelle Spectrograph, mounted on the Gemini North 8-m telescope we have mapped the spatial variation of H₂, CH₄, C₂H₂ and C₂H₆ thermal-infrared emission of Neptune. These high-spectral-resolution, spatially resolved, thermal-infrared observations of Neptune offer a unique glimpse into the state of Neptune’s stratosphere in October 2007, L_S = 275.4° just past Neptune’s southern summer solstice (L_S = 270°). We use observations of the S(1) pure rotational line of molecular hydrogen and a portion of the ν₄ band of methane to retrieve detailed information on Neptune’s stratospheric vertical and meridional thermal structure. We find global-average temperatures of 163.8 ± 0.8, 155.0 ± 0.9, and 123.8 ± 0.8 K at the 7.0 × 10⁻³-, 0.12-, and 2.1-mbar levels with no meridional variations within the errors. We then use the inferred temperatures to model the emission of C₂H₂ and C₂H₆ in order to derive stratospheric volume mixing ratios (hence forth, VMR) as a function of pressure and latitude. There is a subtle meridional variation of the C₂H₂ VMR at the 0.5-mbar level with the peak abundance found at −28° latitude, falling off to the north and south. However, the observations are consistent within error to a meridionally constant C₂H₂ VMR of at 0.5 mbar. We find that the VMR of C₂H₆ at 1-mbar peaks at the equator and falls by a factor of 1.6 at −70° latitude. However, a meridionally constant VMR of at the 1-mbar level for C₂H₆ is also statistically consistent with the retrievals. Temperature predictions from a radiative-seasonal climate model of Neptune that assumes the hydrocarbon abundances inferred in this paper are lower than the measured temperatures by 40 K at 7 × 10⁻³ mbar, 30 K at 0.12 mbar and 25 K at 2.1 mbar. The radiative-seasonal model also predicts meridional temperature variations on the order of 10 K from equator to pole, which are not observed. Assuming higher stratospheric CH₄ abundance at the equator relative to the south pole would bring the meridional trends of the inferred temperatures and radiative-seasonal model into closer agreement.We have also retrieved observations of C₂H₄ emission from Neptune’s stratosphere using TEXES on the NASA Infrared Telescope Facility (IRTF) in June 2003, L_S = 266°. Using the observations from the middle of the planet and an average of the middle three latitude temperature profiles from the 2007 observations (9.5° of L_S later, the seasonal equivalent of 9.5 Earth days within Earth’s seasonal cycle), we infer a C₂H₄ VMR of at 1.5 × 10⁻³ mbar, a value that is 3.25 times that predicted by global-average photochemical models.     

Venus night airglow: Ground-based detection of OH, observations of O2 emissions, and photochemical model

Venus nightglow was observed at NASA IRTF using a high-resolution long-slit spectrograph CSHELL at LT = 21:30 and 4:00 on Venus. Variations of the O₂ airglow at 1.27 μm and its rotational temperature are extracted from the observed spectra. The mean O₂ nightglow is 0.57 MR at 21:30 at 35°S-35°N, and the temperature increases from 171 K near the equator to ∼200 K at ±35°. We have found a narrow window that covers the OH (1-0) P1(4.5) and (2-1) Q1(1.5) airglow lines. The detected line intensities are converted into the (1-0) and (2-1) band intensities of 7.2 ± 1.8 kR and <1.4 kR at 21:30 and 15.5 ± 2 kR and 4.7 ± 1 kR at 4:00. The f-component of the (1-0) P1(4.5) line has not been detected in either observation, possibly because of resonance quenching in CO₂. The observed Earth’s OH (1-0) and (2-1) bands were 400 and 90 kR at 19:30 and 250 and 65 kR at 9:40, respectively. A photochemical model for the nighttime atmosphere at 80-130 km has been made. The model involves 61 reactions of 24 species, including odd hydrogen and chlorine chemistries, with fluxes of O, N, and H at 130 km as input parameters. To fit the OH vibrational distribution observed by VEX, quenching of OH (v > 3) in CO₂ only to v ? 2 is assumed. According to the model, the nightside-mean O₂ emission of 0.52 MR from the VEX and our observations requires an O flux of 2.9 × 10¹² cm⁻² s⁻¹ which is 45% of the dayside production above 80 km. This makes questionable the nightside-mean O₂ intensities of ∼1 MR from some observations. Bright nightglow patches are not ruled out; however, the mean nightglow is ∼0.5 MR as observed by VEX and supported by the model. The NO nightglow of 425 R needs an N flux of 1.2 × 10⁹ cm⁻² s⁻¹, which is close to that from VTGCM at solar minimum. However, the dayside supply of N at solar maximum is half that required to explain the NO nightglow in the PV observations. The limited data on the OH nightglow variations from the VEX and our observations are in reasonable agreement with the model. The calculated intensities and peak altitudes of the O₂, NO, and OH nightglow agree with the observations. Relationships for the nightglow intensities as functions of the O, N, and H fluxes are derived.     

Condensed species in Titan's stratosphere: Confirmation of crystalline cyanoacetylene (HC3N) and evidence for crystalline acetylene (C2H2) on Titan

Infrared spectra of crystalline HC₃N and C₂H₂ were investigated at several temperatures between 15 and 150 K. The characteristics of the 505 and 753 cm⁻¹ bands of HC₃N are in complete agreement with the emission spectral data on Titan obtained by the Voyager IRIS instrument, thus confirming the identification of crystalline HC₃N on Titan. A composite spectrum in the 720-800 cm⁻¹ region, with contributions from HC₃N and C₂H₂ in crystalline phases, reproduces the Voyager emission data in that region, thus providing a suggestion for the identification of crystalline C₂H₂ on Titan.     

Clouds, haze, and CH4, CH3D, HCN, and C2H2 in the atmosphere of Titan probed via 3 μm spectroscopy

Using synthetic spectra derived from an updated model atmosphere together with a continuum model that includes contributions from haze, cloud and ground, we have re-analyzed the recently published (Geballe et al., 2003, Astrophys. J. 583, L39-L42) high-resolution 3 μm spectrum of Titan which contains newly-detected bands of HCN (in emission) and C₂H₂ and CH₃D (in absorption), in addition to previously detected bands of CH₄. In the 3.10-3.54 μm interval the analysis yields strong evidence for the existence of a cloud deck or optically thick haze layer at about the 10 mbar (∼ 100 km) level. The haze must extend well above this altitude in order to mask the strong CH₄ lines at 3.20-3.50 μm. These cloud and haze components must be transparent at 2.87-2.92 μm, where analysis of the CH₃D spectrum demonstrates that Titan's surface is glimpsed through a second cloud deck at about the 100 mbar (∼ 50 km) level. Through a combination of areal distribution and optical depth this cloud deck has an effective transmittance of ∼ 20%. The spectral shape of Titan's continuum indicates that the higher altitude cloud and haze particles responsible for suppressing the CH₄ absorptions have a largely organic make-up. The rotational temperature of the HCN ranges from 140 to 180 K, indicating that the HCN emission occurs over a wide range of altitudes. This emission, remodeled using an improved collisional deactivation rate, implies mesospheric mixing ratio curves that are consistent with previously predictions. The stratospheric and mesospheric C₂H₂ mixing ratios are ∼¹⁰⁻⁵, considerably less than previous model predictions (Yung et al., 1984), but approximately consistent with recent observational results. Upper limits to mixing ratios of HC₃N and C₄H₂ are derived from non-detections of those species near 3.0 μm.     

Deep Impact, Stardust-NExT and the behavior of Comet 9P/Tempel 1 from 1997 to 2010

We present observational data for Comet 9P/Tempel 1 taken from 1997 through 2010 in an international collaboration in support of the Deep Impact and Stardust-NExT missions. The data were obtained to characterize the nucleus prior to the Deep Impact 2005 encounter, and to enable us to understand the rotation state in order to make a time of arrival adjustment in February 2010 that would allow us to image at least 25% of the nucleus seen by the Deep Impact spacecraft to better than 80 m/pixel, and to image the crater made during the encounter, if possible. In total, ∼500 whole or partial nights were allocated to this project at 14 observatories worldwide, utilizing 25 telescopes. Seventy percent of these nights yielded useful data. The data were used to determine the linear phase coefficient for the comet in the R-band to be 0.045 ± 0.001 mag deg⁻¹ from 1° to 16°. Cometary activity was observed to begin inbound near r ∼ 4.0 AU and the activity ended near r ∼ 4.6 AU as seen from the heliocentric secular light curves, water-sublimation models and from dust dynamical modeling. The light curve exhibits a significant pre- and post-perihelion brightness and activity asymmetry. There was a secular decrease in activity between the 2000 and 2005 perihelion passages of ∼20%. The post-perihelion light curve cannot be easily explained by a simple decrease in solar insolation or observing geometry. CN emission was detected in the comet at 2.43 AU pre-perihelion, and by r = 2.24 AU emission from C₂ and C₃ were evident. In December 2004 the production rate of CN increased from 1.8 × 10²³ mol s⁻¹ to Q_CN = 2.75 × 10²³ mol s⁻¹ in early January 2005 and 9.3 × 10²⁴ mol s⁻¹ on June 6, 2005 at r = 1.53 AU.     

Analysis of Cassini/CIRS limb spectra of Titan acquired during the nominal mission: I. Hydrocarbons, nitriles and CO2 vertical mixing ratio profiles

Observations of the Composite InfraRed Spectrometer (CIRS) during the entire nominal Cassini mission (2004-2008) provide us with an accurate global view of composition and temperature in the middle atmosphere of Titan (between 100 and 500 km). We investigated limb spectra acquired at resolution at nine different latitudes between 56°S and 80°N, with a better sampling in the northern hemisphere where molecular abundances and temperature present strong latitudinal variations. From this limb data acquired between February 2005 and May 2008, we retrieved the vertical mixing ratio profiles of C₂H₂, C₂H₄, C₂H₆, C₃H₈, CH₃C₂H, C₄H₂, C₆H₆, HCN, HC₃N and CO₂. We present here for the first time, the latitudinal variations of the C₂H₆, C₃H₈, CO₂, C₂H₄ and C₆H₆ vertical mixing ratios profiles. Some molecules, such as C₂H₆ or C₃H₈ present little variations above their condensation level. The other molecules (except CO₂) show a significant enhancement of their mixing ratios poleward of 50°N. C₂H₄ is the only molecule whose mixing ratio decreases with height at latitudes below 46°N. Regions depleted in C₂H₂, HCN and C₄H₂ are observed around 400 km (0.01 mbar) and 55°N. We also inferred a region enriched in CO₂ located between 30 and 40°N in the 2-0.7 mbar pressure range. At 80°N, almost all molecules studied here present a local minimum of their mixing ratio profiles near 300 km (∼0.07 mbar), which is in contradiction with Global Circulation Models that predict constant-with-height vertical profiles due to subsidence at the north pole.     

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.     

Minimum estimates of the amount and timing of gases released into the martian atmosphere from volcanic eruptions

Volcanism has been a major process during most of the geologic history of Mars. Based on data collected from terrestrial basaltic eruptions, we assume that the volatile content of martian lavas was typically ∼0.5 wt.% water, ∼0.7 wt.% carbon dioxide, ∼0.14 wt.% sulfur dioxide, and contained several other important volatile constituents. From the geologic record of volcanism on Mars we find that during the late Noachian and through the Amazonian volcanic degassing contributed ∼0.8 bar to the martian atmosphere. Because most of the outgassing consisted of greenhouse gases (i.e., CO₂ and SO₂) warmer surface temperatures resulting from volcanic eruptions may have been possible. Our estimates suggest that ∼1.1 × 10²¹ g (∼8 ± 1 m m⁻²) of juvenile water were released by volcanism; slightly more than half the amount contained in the north polar cap and atmosphere. Estimates for released CO₂ (1.6 × 10²¹ g) suggests that a large reservoir of carbon dioxide is adsorbed in the martian regolith or alternatively ∼300 cm cm⁻² of carbonates may have formed, although these materials would not occur readily in the presence of excess SO₂. Up to ∼120 cm cm⁻² (2.2 × 10²⁰ g) of acid rain (H₂SO₄) may have precipitated onto the martian surface as the result of SO₂ degassing. The hydrogen flux resulting from volcanic outgassing may help explain the martian atmospheric D/H ratio. The amount of outgassed nitrogen (∼1.3 mbar) may also be capable of explaining the martian atmospheric ¹⁵N/¹⁴N ratio. Minor gas constituents (HF, HCl, and H₂S) could have formed hydroxyl salts on the surface resulting in the physical weathering of geologic materials. The amount of hydrogen fluoride emitted (1.82 × 10¹⁸ g) could be capable of dissolving a global layer of quartz sand ∼5 mm thick, possibly explaining why this mineral has not been positively identified in spectral observations. The estimates of volcanic outgassing presented here will be useful in understanding how the martian atmosphere evolved over time.     

The Unusual Absorption Line Spectrum of Quasar SDSS J2220+0109

We report the Balmer broad absorption lines (BALs) in the quasar SDSS J2220 + 0109 discovered from the SDSS data, and present a detailed analysis of the peculiar absorption line spectrum, including the He I* multiplet at λλ3189, 3889 arising from the metastable 2³s-state helium and the Balmer Hα and Hβ lines from the excited hydrogen H I of n = 2 level, which are rarely seen in quasar spectra, as well as many absorption lines arising from the excited Fe II* of the levels 7 955 cm⁻¹, 13 474 cm⁻¹ and 13 673 cm⁻¹ in the wavelength range 3100∼3300 Å. Ca II H, K absorption line doublets also clearly appear in the SDSS spectrum. All absorption lines show a similar blueshifted velocity structure of Δv ≈ − 1500 ∼ 0 km·s⁻¹ relative to the quasar's systematic redshift determined from the emission lines. Detailed analysis suggests that the Balmer absorption lines should arise from the partially ionized region with a column density of N_HI ≈ 10²¹ cm⁻² for an electron density of ne ∼ 10⁶ cm⁻³; and that the hydrogen n = 2 level may be populated via collisional excitation with Lyα pumping.     

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).     

Adsorptive fractionation of HDO on JSC MARS-1 during sublimation with implications for the regolith of Mars

A chamber was constructed to simulate the boundary between the ice table, regolith and atmosphere of Mars and to examine fractionation between H₂O and HDO during sublimation under realistic martian conditions of temperature and pressure. Thirteen experimental runs were conducted with regolith overlying the ice. The thickness and characteristic grain size of the regolith layer as well as the temperature of the underlying ice was varied. From these runs, values for the effective diffusivity, taking into account the effects of adsorption, of the regolith were derived. These effective diffusivities ranged from 1.8 × 10⁻⁴ m² s⁻¹ to 2.2 × 10⁻³ m² s⁻¹ for bare ice and from 2.4 × 10⁻¹¹ m² s⁻¹ to 2.0 × 10⁻⁹ m² s⁻¹ with an adsorptive layer present. From these, latent heats of adsorption of 8.6 ± 2.6 kJ mol⁻¹ and 9.3 ± 2.8 kJ mol⁻¹ were derived at ice-surface temperatures above 223 ± 8 K and 96 ± 28 kJ mol⁻¹ and 104 ± 31 kJ mol⁻¹ respectively for H₂O and HDO were derived at colder temperatures. For temperatures below 223 K, the effective diffusivity of HDO was found to be lower than the diffusivity of H₂O by 40% on average, suggesting that the regolith was adsorptively fractionating the sublimating gas with a fractionation factor of 1.96 ± 0.74. Applying these values to Mars predicts that adsorbed water on the regolith is enriched in HDO compared to the atmosphere, particularly where the regolith is colder. Based on current observations, the D/H ratio of the regolith may be as high as 21 ± 8 times VSMOW at 12°S and L_S = 357° if the regolith is hydrated primarily by the atmosphere, neglecting any hydration from subsurface ice.